JP6754072B2 - Viscous bubble liquid - Google Patents

Description

The present invention relates to a viscous bubble liquid capable of holding bubbles for a long period of time.

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

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

Non-Patent Document 1 cites the following points as the reasons. (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 a living tissue or water that is abundant in a living body is a gas. (4) The amount of ultrasonic reflection is proportional to the sixth power of the diameter of the bubble.

From the above description (4), it can be seen that a material containing large bubbles is suitable for inspecting the lumen in the living body.

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

The oral ultrasonic contrast medium contains a liquid having high ultrasonic permeability such as water and castor oil, and a composition composed of alginate and the like for adjusting the viscosity of the contrast medium in the digestive organs.

Alginate has the property of increasing the viscosity of the liquid in the digestive tract in an acidic environment or a polyatomic ion acidic environment. Therefore, by adding the above composition to the above liquid, the viscosity is low and easy to swallow at the time of oral injection, but in the digestive organs, the viscosity can be increased to the extent that it stays in the digestive organs. Can be obtained.

According to Patent Document 1, the oral ultrasonic contrast medium is contained in an appropriate container and stirred and shaken by hand or a predetermined instrument, or microbubbles are generated using a homogenizing pump such as a homogenizer. By forming the oral ultrasonic contrast medium, microbubbles are contained.

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

In addition to detecting abnormalities in the human body in medical ultrasonic diagnosis, ultrasonic echo inspection technology is a technology that non-invasively visualizes parts that cannot be seen with the naked eye, such as detection of abnormalities in pipes in nondestructive inspection. It is widely used in the medical and industrial fields.

Japanese Patent Publication "Japanese Patent Laid-Open No. 10-306042 (published on November 17, 1998)"

Koji Tsuchiya, "Development of Ultrasound Contrast Microbubbles for Early Medical Diagnosis", Proceedings of the 12th Applied Technology Lecture on Fine Bubbles, June 28, 2013, pp. 16-31 Seiji Hirai, Makoto Kamura, "High-concentration microbubble generator and its application", Shape material, March 2008, pp. 44-47

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

In addition, Patent Document 1 actually increases the viscosity of the oral ultrasonic contrast medium in the digestive organs after oral injection, and causes the oral ultrasonic contrast medium to stay in the digestive organs to perform ultrasonic image diagnosis. It is what you do.

However, as described in Patent Document 1, even if the viscosity of the oral ultrasonic contrast agent containing bubbles is increased experimentally under an acidic environment or a polyatomic ion acidic environment, the life of the bubbles is not so long. It cannot be extended. Patent Document 1 describes that when a 0.5% sodium alginate aqueous solution containing bubbles was used as the oral ultrasonic contrast medium, the life of the microbubbles could be extended to about 5 minutes to about 10 minutes. ing.

However, if the life of the bubbles is extended to this extent, even if the ultrasonic contrast medium contains the bubbles, the bubbles disappear at the stage of preparing for the ultrasonic examination.

Further, when the manufactured oral ultrasonic contrast medium is not used, it is necessary to store it, but there is no method for stably containing bubbles in the oral ultrasonic contrast medium for a long time. For this reason, it is necessary to manufacture an oral ultrasonic contrast medium each time an ultrasonic examination is performed, which complicates the examination work.

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 period of time, a method for producing the same, an apparatus for producing the same, and a method for storing the same.

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

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

In addition, the inventors of the present application have described that a viscous foam liquid in which a gas is encapsulated in a coating film containing a surfactant and a gelling agent and is dispersed in an aqueous solution containing a thickener has a life of bubbles. The present invention has been completed by finding that the bubbles can be retained for a long period of time.

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

That is, in the viscous bubble liquid according to one aspect of the present invention, bubbles formed by encapsulating a gas in a coating film containing a surfactant and a gelling agent are dispersed as bubbles in a viscous liquid composed of an aqueous solution containing a thickener. Has been done.

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

Further, the device for producing a viscous bubble liquid according to one aspect of the present invention is a device for producing a viscous bubble liquid used in the above method for producing a viscous bubble liquid, and contains warm water containing a surfactant and a gelling agent. A first container, a second container containing a viscous liquid consisting of an aqueous solution containing a thickener, a gas introducer for introducing a gas into hot water in the first container, the first container, and the first container. A foam moving portion for connecting the two containers and introducing a gas into the hot water in the first container to move the foam formed on the liquid surface of the hot water to the second container is provided. ing.

Further, in the method for storing the viscous bubble liquid according to one aspect of the present invention, the viscous bubble liquid is stored under pressure.

According to one aspect of the present invention, it is possible to provide a viscous bubble liquid capable of holding bubbles for a long period of time, a method for producing the same, an apparatus for producing the same, and a method for storing the viscous bubble liquid.

It is sectional drawing which shows typically an example of the viscous bubble liquid production apparatus which concerns on Embodiment 1 of this invention. It is sectional drawing which shows typically an example of the viscous bubble liquid production apparatus which concerns on Embodiment 2 of this invention. (A)-(c) are sectional views which show the manufacturing method of the viscous bubble liquid which concerns on one Embodiment of this invention in the order of steps. It is sectional drawing which shows the apparatus used for measuring the physical property of the bubble in the viscous bubble liquid obtained in the Example of this invention. (A) is a diagram showing an optical micrograph of the viscous bubble liquid immediately after production in the examples of the present invention, and (b) is a diagram after 3 days have passed from production when refrigerated at 5 ° C. after production. In the optical micrograph of the viscous bubble liquid, it is a figure which superimposes a circle for measuring a bubble diameter on the edge of a bubble. It is a graph which shows the volume distribution of the viscous bubble liquid immediately after production in the Example of this invention. It is a graph which shows the volume distribution of the viscous bubble liquid 3 days after the manufacture in the Example of this invention. It is a graph which shows the volume distribution of the viscous bubble liquid 7 days after the manufacture in the Example of this invention. It is a graph which shows the volume distribution of the viscous bubble liquid 35 days after the manufacture in the Example of this invention. It is a graph which shows the transition of the void ratio of the viscous bubble liquid in the Example of this invention. It is a graph which shows the cell diameter distribution of the viscous bubble liquid after 3 days from the manufacture in the Example of this invention. It is a graph which shows the rising speed and the moving time of a normal bubble having a diameter of 1 mm in each liquid having a different viscosity. 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 the transition of the void ratio of the viscous bubble liquid in the case where the internal pressure is applied to the pressure storage container in the third embodiment of the present invention, and the case where it is not applied. It is a graph which shows the reduction rate of the void ratio of the viscous bubble liquid after 7 days from the manufacture in the case of changing the internal pressure of the pressurized storage container 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 a surfactant and a gelling agent in Embodiment 4 of this invention. It is a graph which shows the transition of the void ratio of the viscous bubble liquid in the viscous bubble liquid containing hydrogen gas as a bubble which concerns on Embodiment 5 of this invention.

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

(Manufacturing method of viscous bubble liquid and viscous bubble liquid)
The viscous bubble liquid according to this embodiment is a bubble liquid in which gas is encapsulated in a coating film containing a surfactant and a gelling agent and is dispersed as bubbles in a viscous liquid composed of an aqueous solution containing a thickener. is there.

Further, in the method for producing a viscous foam liquid according to this embodiment, foams formed by introducing a gas into warm water containing a surfactant and a gelling agent are put into a viscous liquid composed of an 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 as a medical contrast agent (oral contrast agent), the surfactant is extracted from, for example, lecithin (for example, plant lecithin extracted from soybeans, rapeseed, etc., egg yolk). Egg yolk lecithin), glycerin fatty acid ester, sucrose fatty acid ester, stearoyl lactate calcium, sorbitan fatty acid ester, propylene glycol fatty acid ester, etc. As an emulsifier, a surfactant mainly used as a food additive is used. As the above-mentioned surfactant, only one kind may be used, or two or more kinds may be appropriately mixed and used.

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.

As for these gelling agents, only one kind may be used, or two or more kinds may be appropriately mixed and used. As an example of a gelling agent obtained by mixing two or more of these gelling agents, for example, "Gel Up WM" (trade name, manufactured by Saneigen FFI Co., Ltd., composition: carrageenan 28% by weight, locust bean gum 17) .4%, calcium lactate (stabilizer) 6.6%, food material 48%) and the like.

Further, as the gelling agent, alginate and calcium can be used. When alginate and calcium ions are cross-linked, they gel. Therefore, by using alginate in combination with a calcium compound such as calcium chloride or calcium carbonate, it can be used as a gelling agent. Further, the calcium used in the gelling agent may be a food material containing calcium.

As the alginate, for example, sodium alginate or the like can be used. Further, as the alginate, for example, "Kimika algin" (trade name) manufactured by Kimika Co., Ltd. can be used.

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

However, when the viscous bubble liquid is used on the human body such as a contrast medium for medical use, 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 medium in non-destructive inspection of piping, it may be any one that does not damage the 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 (carboxymethyl cellulose) and "Thickening Up Perfect" (trade name, manufactured by Nisshin Oillio).

The gas is not particularly limited, and can be appropriately selected depending on the intended use and the like. For example, when the viscous bubble liquid is used as a medical contrast medium, a gas harmless to the human body is used as the gas. Examples of such a gas include atmosphere, oxygen, nitrogen, hydrogen, carbon dioxide and the like.

According to this embodiment, by introducing a gas into warm water containing a surfactant and a gelling agent and mixing air bubbles in the warm water, the gas is contained in a coating film containing the surfactant and the gelling agent. Foam is formed.

As a result of diligent studies by the inventors of the present application, both a surfactant and a gelling agent are required for the formation of the foam in order to produce the viscous foam liquid having a long bubble life, which is the object of the present embodiment.

From this, the foams constituting the bubbles in the viscous bubble liquid contain a gas like a normal soap bubble, and are arranged with hydrophobic groups on the inside (gas side) and hydrophilic groups on the outside. It is considered that the gelling agent plays a role of connecting the double-arranged surfactants, because it has a structure in which the surfactants are doubly arranged.

In the present 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 used, and is not particularly limited, but as an example. For example, it is in the range of 0.1 to several% by weight.

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

As the above-mentioned surfactant and gelling agent, for example, a surfactant (emulsifier) and a gelling agent commercially available as food supplements can be used, and for example, as described in the instruction manual. It can be used within the range of the amount.

Further, the blending ratio of the surfactant and the gelling agent may be appropriately set so as to obtain a desired foam according to the type of the surfactant and the gelling agent used. For example, the above-mentioned example may be used. It can be changed as appropriate within the range.

Therefore, the blending ratio of the surfactant and the gelling agent is not particularly limited, but for example, by using the surfactant and the gelling agent in a ratio of 1: 1 in the examples described later. As shown, it is possible to form foams that can obtain long-lived bubbles.

Further, the hot water may be capable of uniformly dispersing or dissolving the surfactant and the gelling agent.

Tap water, drinking water, or the like can be used as the hot water, and pure water or ion-exchanged water does not necessarily have to be used. In other words, the main component of the hot water may be water.

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

Further, the time from the addition of the surfactant and the gelling agent to the warm water to the introduction of the gas is not particularly limited, and the surfactant and the gelling agent are uniformly dispersed or dissolved in the warm water. I just need to be able to do it.

However, the temperature of the hot water is, for example, about 85 ° C. (particularly 85 ° C. from the viewpoint of sterilization) because of the meaning of sterilization and the property that the surfactant and the gelling agent are difficult to dissolve or disperse in water. ), And after adding the surfactant and gelling agent to the warm water, it is desirable to stir at about 85 ° C. for about several minutes.

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 flow bubble generator can be used as the gas introducer.

Specifically, the foam is formed by generating bubbles by a bubble generator in a liquid obtained by uniformly dissolving or dispersing a surfactant and a gelling agent in warm water.

When a gas was introduced into the liquid in which the surfactant and the gelling agent were uniformly dispersed in this way to generate bubbles, the gas was contained inside the film formed by the surfactant and the gelling agent. State foam is formed. Then, the formed foam accumulates on the liquid surface of the liquid.

The viscous bubble liquid according to the present embodiment can be obtained by dispersing the foam as bubbles in a viscous liquid consisting of an aqueous solution containing a thickener.

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

The lifetime of submillimeter-class bubbles in an aqueous solution generally depends on the viscosity of the aqueous solution. The cell life is long in a high-viscosity aqueous solution, but if the viscosity is too high, it becomes difficult to introduce the viscous bubble solution into the object to be introduced.

For example, when the viscous bubble liquid is used as a contrast medium 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 lengthened, but there is a risk of suffocation. Therefore, when the viscous bubble liquid is used as a medical contrast medium, it is necessary to adjust the viscosity to be suitable for the medical contrast medium.

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

When the viscous bubble liquid is used as a contrast medium for non-destructive inspection of pipes, for example, the inner diameter of the pipe and the configuration state of the pipe (for example, whether the pipe is connected to a pump or the like, whether the pipe is in a closed state or not). Or, the conditions for flowing at an appropriate speed differ depending on the number of bends, angle, etc.).

Therefore, even if the case where the viscous bubble liquid is used as a contrast medium is taken up, for example,
Optimization is required depending on the system to be observed.

Therefore, the viscosity of the aqueous solution is not particularly limited, but is, for example, in the range of 1 × 10 ² to 1 × 10 ⁶ mPa · s at room temperature (for example, a viscosity equivalent to that of sauces, yogurt, mayonnaise, etc.). ) Is set.

The concentration of the thickener in the aqueous solution is appropriately set so that the viscosity of the aqueous solution becomes a desired viscosity, and is not particularly limited.

Further, the mixing conditions such as the time and temperature for mixing the foam with the aqueous solution are not particularly limited, and may be appropriately set 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 pressure, and if necessary, the aqueous solution is heated and easily stirred and mixed in order to uniformly disperse the foam in the aqueous solution. You may adjust to and mix.

Further, the aqueous solution may contain, for example, a known additive or the like used as a food supplement or the like, if necessary.

(Production equipment for viscous bubble liquid)
[Embodiment 1]
Next, as an example of the viscous bubble liquid manufacturing apparatus according to the present embodiment, the viscous bubble liquid manufacturing apparatus using the porous fine bubble generator will be described below with reference to FIG.

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

The viscous foam liquid producing 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 portion 10 in the viscous bubble liquid producing apparatus 1 shown in FIG. 1 includes a heating / stirring device 11 (first container), a compressor 12, a porous fine bubble generator 13 (gas introducer), and stirring. It includes a child 14, a pressure gauge 15, and a relief valve 16.

The heating / stirring device 11 is composed of a hermetically sealed container having a heating function and a stirring function such as an electromagnetic stirrer. The heating / stirring device 11 agitates the material supplied into the heating / stirring device 11 by rotating the stirrer 14 arranged in the heating / stirring device 11 by an electromagnetic stirrer or the like.

The heating / stirring device 11 includes a container portion 11a which is a main body of the heating / stirring device, and a lid portion 11b provided so as to be able to seal the container portion 11a.

Inside the heating / stirring device 11, a porous fine bubble generator 13 connected to a compressor 12 arranged outside the heating / stirring device 11 is arranged as a fine bubble generator. The porous fine bubble generator 13 is provided with a porous material (not shown) inside, and by introducing a gas into the liquid in the container portion 11a through the porous material, the porous material is introduced into the liquid in the container portion 11a. Fine bubbles are generated and mixed.

Therefore, the porous fine bubble generator 13 is provided so as to be located 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 as to generate bubbles having a desired size, and are not particularly limited.

Further, on the lid portion 11b of the heating / stirring device 11, the pressure gauge 15 for measuring the pressure in the heating / stirring device 11 and the pressure in the heating / stirring device 11 are equal to or higher than the 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.

Further, 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 which is a main body of the heating device, and a lid portion 31b provided so as to be able to seal the container portion 31a.

In the example shown in FIG. 1, the heating device 31 shows a case where the liquid 43 in the heating device 31 is agitated by the stirrer 32 attached to the lid portion 31b.

However, the viscous bubble liquid producing apparatus 1 according to the present embodiment is not limited to this, and like the foam forming portion 10, heating / stirring having a heating function and a stirring function instead of the heating apparatus 31. The device may be used. In this case, the liquid 43 in the heating / stirring device can be agitated by using the stirrer as in the foam forming unit 10.

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

The foam 41 containing the introduced gas, which is formed by the foam forming portion 10, accumulates on the liquid surface of the liquid 42 in the heating / stirring device 11. The foam moving portion 20 moves the foam 41 on the liquid surface of the liquid 42 from the foam forming portion 10 to the foam mixing portion 30 through the connecting pipe 21 whose cooling is prevented by the heat insulating material 22 or the like.

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

Further, the connecting pipe 21 is provided so as to descend from the foam forming portion 10 toward the foam mixing portion 30 in order to smoothly move the foam 41 from the foam forming portion 10 to the foam mixing portion 30. ..

Therefore, the opening 21b of the connecting pipe 21 in the foam mixing portion 30 is located higher than the liquid level of the liquid 43 in the heating device 31 and lower than the opening 21a of the connecting pipe 21 in the foam forming portion 10. It is formed.

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

First, water is charged into the heating / stirring device 11 in the foam forming portion 10, the temperature is raised to 85 ° C., and then the surfactant and the gelling agent are added to the obtained warm water. Then, the stirrer 14 stirs the surfactant and the gelling agent until they 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 section 30, a thickening polysaccharide is added, and the mixture is stirred and dissolved. 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 viscous bubble liquid is used, for example, as an oral contrast medium, 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. Is desirable.

Next, the gas is passed from the compressor 12 to the porous fine bubble generator 13. As a result, the gas is introduced from the porous fine bubble 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 as described above. To generate fine bubbles.

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 Nack Co., Ltd.) is used for the porous fine bubble generator 13, the porous material is a monoraton film. A polymer film called is used. The monoraton film is a film having a thickness of 50 to 200 μm, and porous portions having a width of 4 to 10 μm are processed at intervals of 20 to 30 μm, and holes (voids) having a diameter of 5 to 20 nm are formed in the porous portions. ) Is provided. When a compressed gas of 0.03 to 0.3 MPa is added to the monoraton film, the gas passes through the voids in the porous portion to generate micro-nano bubbles.

However, the porous type 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 the porous glass of Shirasu include a porous glass film of Shirasu (SPG film, pore size variation of 0.05 to 50 μm) manufactured by SPG Techno Co., Ltd.

When bubbles are generated in a state where the surfactant and the gelling agent are uniformly dispersed or dissolved in the liquid 42 in this way, a gas is contained inside the film formed by the surfactant and the gelling agent. The foam 41 in the 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 whose cooling is prevented by a heat insulating material or the like.

As a result, the foam 41 is dispersed in the liquid 43 in the heating device 31, whose viscosity has been adjusted in advance with a thickening polysaccharide. As a result, it is possible to generate a viscous bubble liquid having a high bubble concentration and a slow bubble extinction rate.

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

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

Like the viscous bubble liquid manufacturing apparatus 1 shown in FIG. 1, the viscous bubble liquid manufacturing apparatus 1 shown in FIG. 2 includes a foam forming portion 10, a foam moving portion 20, and a foam mixing portion 30.

However, the foam forming portion 10 in the viscous bubble liquid producing apparatus 1 shown in FIG. 2 includes a heating apparatus 51 (first container), a water flow pump 52, a swirling flow type fine bubble generator 53 (gas introducer), and the like. It includes a pressure gauge 15 and a relief valve 16.

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

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

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

The swirling flow type fine bubble generator 53 includes an intake port 53a and a liquid suction port 53b, and circulates the gas self-primingly taken into the swirling flow type fine bubble generator 53 from the intake port 53a by a water flow pump 52. As a result, the liquid 42 taken in from the liquid suction port 53b is mixed to generate a gas-liquid mixed liquid. In the swirling flow type fine bubble generator 53, the gas is refined by the centrifugal force acting on the gas and liquid by spirally introducing the gas and liquid mixture into the cylindrical cylinder. The finely divided gas-liquid mixed liquid is discharged from the discharge port 53c into the liquid 42 in the heating device 51.

The lid 51b of the heating device 51 has a pressure gauge 15 that measures the pressure inside the heating device 51, and discharges excess gas when the pressure inside the heating device 51 reaches a set pressure (threshold) or higher. 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.

The configuration of the foam mixing section 30 in the viscous bubble liquid manufacturing apparatus 1 shown in FIG. 2 is the same as the configuration of the foam moving portion 20 in the viscous foam manufacturing apparatus 1 shown in FIG. Further, the configuration of the foam moving portion 20 in the viscous bubble liquid manufacturing apparatus 1 shown in FIG. 2 is the same as the configuration of the foam moving portion 20 in the viscous foam 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 shall be read as the heating device 51, and the description thereof will be omitted here.

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

First, water is charged into the heating device 51 in the foam forming portion 10, the temperature is raised to 85 ° C., and then the surfactant and the gelling agent are added to the obtained warm water. Next, the liquid 42 in the heating device 51 is circulated by the water flow pump 52 and stirred to uniformly disperse or dissolve the surfactant and the gelling agent in the warm water.

Next, a gas-liquid mixture is generated by the gas self-priming 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. By introducing the gas into a fine shape, the gas is atomized and discharged from the discharge port 53c into the liquid 42 in the heating device 51.

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

In this example as well, on the other hand, water is charged into the heating device 31 in the foam mixing section 30, a thickening polysaccharide is added, and the mixture is stirred and dissolved. 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 viscous bubble liquid is used, for example, as an oral contrast medium, 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. 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 whose cooling is prevented by a heat insulating material or the like.

As a result, also in this example, the foam 41 is dispersed in the liquid 43 in the heating device 31, whose viscosity has been adjusted in advance with a thickening polysaccharide. As a result, it is possible to generate a viscous bubble liquid having a high bubble concentration and a slow bubble extinction rate.

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

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

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

After that, 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 swirling flow fine bubble generator 53. To generate. As a result, also in this example, the foam 41 in a state of containing gas is formed inside the film formed by 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 foam 41 is dispersed in the liquid 43 in the heating device 31, whose viscosity has been adjusted in advance with a thickening polysaccharide. As a result, it is possible to generate a viscous bubble liquid having a high bubble concentration and a slow bubble extinction rate.

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

The following shows the results of simply producing (generating) a viscous bubble liquid on a small scale and evaluating the performance of the obtained viscous bubble liquid.

3 (a) to 3 (c) are cross-sectional views showing a method for producing a viscous bubble liquid in order of steps.

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

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

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

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

After that, when the temperature of the aqueous solution 81 in the beaker 65 fell below 65 ° C., bubbles were generated by the bubble generator 69 connected to the compressor 68. As the bubble generator 69, a column-type "Fomest" (registered trademark), which is a porous micro-nano bubble generator manufactured by Nack Co., Ltd., was used.

As a result, a foam portion 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 bubbles 41 accumulated on the liquid surface of the aqueous solution 81 in the beaker 65 were collected in another beaker 71 as shown in FIG. 3 (c).

On the other hand, in yet another beaker 72, as a liquid 43 (viscous liquid), the thickening polysaccharide "thickening up perfect" was dissolved in water (tap water) at a concentration of 1% by weight, and "thickening up perfect" was dissolved. A thickening liquid 82 composed of an aqueous solution was prepared. The viscosity of the thickening liquid 82 was 0.8 Pa · s.

Next, as shown in FIG. 3 (c), the entire amount of the foam 41 collected in the beaker 71 was added to the thickened liquid 82 and mixed. As a result, the viscous foam liquid according to this example was obtained in which the foam 41 was dispersed as bubbles in the thickening liquid 82.

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

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

To measure the physical properties of bubbles in the viscous bubble liquid, first, a petri dish 92 containing the viscous bubble liquid as a sample 93 is placed on the turntable 91, and the sample 93 is irradiated with laser light. Then, the projected image of the bubbles in the sample 93 is imaged by a camera 95 attached to an optical microscope and image analysis is performed to measure the physical properties of the bubbles in the viscous bubble liquid.

Since the light transmittance decreases as the thickness of the sample 93 increases, in this embodiment, in order to reduce the thickness of the sample 93, the laser 94 and the camera 95 are arranged in the vertical direction for measurement. ..

The method for measuring each of the above physical properties will be described below.

(Bubble diameter)
The image captured by the camera 95 was displayed by a paint application, and a circle was superimposed on the edge of each bubble as shown in (b) of FIG. 5, for example. Then, the diameter of the overlapped circles was measured as the bubble diameter.

(Volume of bubbles)
The volume of all the bubbles in the image was calculated by calculating the volume of the imaged portion from the two-dimensional size (vertical and horizontal size) and the focal length of the single image captured by the camera 95. ..

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

(Void rate of bubbles)
From the total volume of the viscous bubble liquid in the imaging portion and the sum of the volumes of all the bubbles calculated by the above method, the ratio of the volume of the bubbles to the unit volume of the viscous bubble liquid (volume content of the bubbles). Was calculated as the void ratio 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 the production, 3 days after the production, 7 days after the production, and 35 days after the production. The elapsed days and the void rate were represented in a graph, and an approximate line was drawn by the following formula to obtain the disappearance rate per day.

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

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

B = B ₀ × exp (−λt) ・ ・ ・ (2)
Here, when Eq. (2) is obtained from the plot of the measured values using an approximate straight line, B ₀ = 0.3756 and λ = 0.049. At this time, t was set to a daily unit.

(Measurement result)
FIG. 5 (a) is a diagram showing an optical micrograph of the viscous bubble liquid immediately after production, and FIG. 5 (b) is a diagram after 3 days have passed from the production when the viscous bubble liquid was stored refrigerated at 5 ° C. after production. In the optical micrograph of the above-mentioned viscous bubble liquid, it is a figure which superimposes a circle for measuring a bubble diameter on the edge of a bubble.

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 are shown in FIGS. 6 to 9 in order. Further, the transition of the void rate at this time is shown in FIG. 10, and the elapsed days and the transition of the void rate are shown in Table 1. In each case, the viscous bubble liquid after production was stored in a refrigerator at 5 ° C.

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

According to this example, as shown in FIGS. 6 to 9 and 11, bubbles having a diameter of 2 mm or less, for example, a maximum diameter of 1.6 mm could be stably obtained.

Further, according to this embodiment, as can be seen from FIG. 10, assuming that a void ratio of 10% or more is required, a viscous bubble liquid that is easy to handle can be obtained because it has a life of about 25 to 30 days. It turns out that it can be done.

Here, for comparison, ordinary bubbles having a diameter of 1 mm (that is, bubbles having a diameter of 1 mm generated by blowing air into a liquid such as water) obtained by a usual method in the above liquid. The ascending speed and the traveling time are shown in FIG. 12 and Table 2.

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

(Rising speed of bubbles)
The bubble rise rate is a balance of buoyancy, gravity, and Stokes resistance, where V∞ is the bubble rise rate, r is the bubble radius, g is the gravitational acceleration, μ is the liquid viscosity, ρf is the liquid density, and ρb is the gas density in the bubble. Therefore, the following equation V∞ = (ρf−ρb) / 6πμr × (4 / 3πr ³ ) × g ・ ・ ・ (3)
(See Non-Patent Document 2).

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

As shown in FIGS. 12 and 2, a normal bubble having a diameter of 1 mm takes 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 escapes. As shown in FIGS. 12 and 2, even if the viscosity of the liquid is increased to 10 Pa · s, it takes about 30 minutes for the 10 cm bubbles to move, and the bubbles are formed in about several tens of minutes at most. It turns out that it will come off.

As described above, based on the results shown in Patent Document 1 and FIGS. 12 and 2, in the conventional contrast medium, bubbles disappear at a speed that is not an exaggeration to say instantaneously.

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

Therefore, the viscous bubble liquid is very suitable for ultrasonic examination, and by using the viscous bubble liquid as a contrast medium, it is possible to provide a contrast medium which is remarkably easier to handle than the conventional one. Further, by using the viscous bubble liquid as a contrast medium, it is possible to prepare a large amount of a contrast medium containing bubbles in advance, which was not possible in the past. Therefore, for example, in a group health diagnosis, inspection efficiency Can be greatly improved. Further, by using the viscous bubble liquid as a contrast medium, it is possible to take a longer time for one ultrasonic examination than before. Furthermore, it is possible to expand the inspection target, such as enabling inspection of an inspection target having a length that cannot be maintained until the time of contrast with the conventional contrast medium.

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 so as to secure the void ratio required at the time of use according to the application. Well, it is 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.

In addition, FIG. 13 is a contrast image when a tube is passed through water, viscous bubble water is passed through the tube, and an ultrasonic examination is performed from the outside.

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 can be seen that the ultrasonic resolution is at least about 1 mm.

As described above, according to the above embodiments and examples, it is possible to provide a viscous bubble liquid capable of holding bubbles for a long period of time, a method for producing the same, and an apparatus for producing the viscous bubble liquid.

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 and the like of parts that cannot be seen from the outside, such as inside various pipes.

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

Further, since the method and apparatus for producing the viscous bubble liquid according to the above embodiments and examples can change the texture of food by containing bubbles, the method and apparatus for changing the texture of foodstuffs. It can also be used as.

[Embodiment 3]
In the present embodiment, the method of storing (preserving) the viscous bubble liquid will be described below with reference to FIGS. 3 (a) to 3 (c), FIGS. 14 and 15. In the following, for convenience of explanation, the components having the same functions as the components in the first and second embodiments are designated by the same reference numerals, and the description thereof will be omitted.

The viscous bubble liquid produced by the methods according to the first and second embodiments can stably store bubbles in the liquid for a long time, unlike the conventional ones. 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 the present embodiment, in order to improve the decrease in the void ratio, the viscous bubble liquid is stored under pressure (that is, pressure storage). Therefore, 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 in this way to increase the internal pressure, a decrease in the void ratio of the viscous bubble liquid during storage is suppressed, and the bubbles are stably contained for a long time. Can be done. Therefore, according to the present embodiment, the frequency of producing the viscous bubble liquid can be reduced, and the complexity of the inspection work can be eliminated.

The material and shape of the storage container are not particularly specified, and any storage container that can withstand the pressure inside the container (hereinafter referred to as "pressurized storage container") may be used. 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 the atmospheric pressure. In the present embodiment, for example, when the gauge pressure of the pressurizing device at normal pressure (atmospheric pressure) is 0 MPa when the pressurized storage container is not pressurized, the internal pressure of the pressurized storage container is, for example, 0 in gauge pressure. The viscous bubble liquid was stored under pressure so as to be 1 MPa or more (that is, atmospheric pressure + 0.1 MPa or more).

In the viscous bubble liquid, the higher the internal pressure of the pressurized storage container, the lower the reduction rate of the void ratio. Therefore, the upper limit 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. Therefore, in the present 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 set to, for example, 0.5 MPa or less in 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.

However, it goes without saying that when a pressurized storage container having high pressure resistance is used, the internal pressure of the pressurized storage container can be set even higher.

(Pressurized storage method of viscous bubble liquid)
The method for pressurizing and storing the viscous bubble liquid will be described in more detail below.

First, a viscous bubble liquid to be stored was produced. The viscous bubble liquid was produced according to the production method shown in FIGS. 3 (a) to 3 (c) described in the above [Example].

Specifically, first, in the step shown in FIG. 3A, the water in the electromagnetic cooking pot 62 was heated to about 85 ° C. by the electromagnetic heater 61. Then, while stirring the water (warm water) in the electromagnetic cooking pot 62 with the stirrer 64, lecithin as a surfactant and "gel-up WM" as a gelling agent were added to the water at 0. The mixture was added at a ratio of 3% by weight and stirred for 10 minutes. As a result, 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 are generated by the bubble generator 69 connected to the pressurizing device while keeping the temperature constant at 65 ° C. , Foam 41 was formed. For the bubble generator 69, "Fomest" (registered trademark) was used. A compressor 68 was used as the pressurizing device, and the pressure was 0.2 MPa. All the bubbles 41 accumulated on the liquid surface of the aqueous solution 81 in the beaker 65 were collected in another beaker 71 shown in FIG. 3 (c).

Next, the water placed in another beaker 72 is kept at about 85 ° C. with an electromagnetic heater 61, and "thickening up perfect" is added as a thickener at a ratio of 1% by weight to water and stirred for 10 minutes. The thickener 82 shown in FIG. 3 (c) was produced.

Next, as shown in FIG. 3C, the foam 41 was mixed with the thickening liquid 82 and stirred to disperse the foam 41 in the thickening liquid 82 to produce a viscous foam liquid.

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

As storage samples, three pressurized storage samples in which the internal pressure of the pressure storage container was pressurized to 0.3 MPa by the atmosphere and one non-pressurized normal pressure storage sample were produced.

At the same time, the pressure storage container is pressurized with one pressure storage sample each so that the internal pressure thereof becomes 0.1 MPa, 0.3 MPa, and 0.5 MPa in gauge pressure. No normal pressure storage sample was produced.

Each physical property of the pressure-stored sample was measured by opening the pressure-stored sample one by one immediately after the production, and after 7 days and 14 days from the production. On the other hand, each physical property of the atmospheric storage sample was measured immediately after the production, and after 7 days and 14 days from the 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. The measurement items and measurement methods for 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 bubbles, the bubble diameter distribution, the void ratio of the bubbles, and so on. The rate of disappearance of air 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 the internal pressure is not applied.

In addition, Table 3 shows the void porosity of the viscous bubble liquid immediately after production and after 7 days and 14 days have passed since the internal pressure was applied to the pressurized storage container and when the internal pressure was not applied for 14 days. It is shown together with the rate of disappearance of air bubbles per day during the storage period of.

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

Further, in the same manner as in the above [Example], the rate of disappearance of air bubbles per day was measured. That is, assuming that the void ratio of the viscous bubble liquid is B and the disappearance rate is λ, the relationships of the above equations (1) and (2) are established. Therefore, with the y-axis as the void ratio B (that is, y = B) and the x-axis as the number of elapsed days t (that is, x = t), from the plot of the measured values shown in FIG. In the case of the pressurized storage sample, B ₀ = 0.6171 and λ = 0.034. In the case of a sample stored at normal pressure, B ₀ = 0.5374 and λ = 0.066.

Therefore, as shown in Table 3, the rate of disappearance of air bubbles per day of the atmospheric storage sample during the storage period of 14 days was 3.4% / day for the pressurized storage sample, and 6. for the atmospheric storage sample. It will be 6% / day.

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

Further, for the sample in which the internal pressure of the pressurized storage container is changed, the bubble diameter, the volume of the bubbles, the bubble diameter distribution, and the void ratio of the bubbles are separately measured in the same manner as in the above [Example], and the bubbles disappear. As the rate, the rate of decrease in the void rate when the internal pressure of the pressurized storage container was changed was measured.

FIG. 15 is a graph showing the reduction 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.

In addition, Table 4 shows the changes in the void ratio of the viscous porosity immediately after production and after 7 days from production when the internal pressure of the pressurized storage container was changed. It is shown together with the reduction rate of the void rate of.

When the internal pressure of the pressurized storage container is changed as shown in Table 4 and FIG. 15, the reduction 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% (= 57.8% -55%) at 0.3 MPa, 1.3% (= 57.8% -56) at 0.5 MPa It was 5.5%). In addition, the reduction rate of the void ratio of the sample stored under atmospheric pressure after 7 days from the production was 28.5% (= 57.8% -29.3%).

From the above results, the higher the internal pressure of the pressurized storage container, the lower the reduction rate of the void ratio, 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 ratio can be reduced by storing under pressure as compared with the case of storing at normal pressure.

[Embodiment 4]
Other embodiments of the present invention will be described below based on FIGS. 3 (a) to 3 (c) and FIG. In the following, for convenience of explanation, the components having the same functions as the components in the first to third embodiments are designated by the same reference numerals, and the description thereof will be 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 with reference to an experimental example.

(Void ratio of viscous bubble liquid when the water temperature of the 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 changing the temperature of an aqueous solution 81 containing a surfactant and a gelling agent to generate bubbles is used. Let's take an example. 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.

The method for producing the viscous bubble liquid according to the present embodiment will be described below. As described above, also in this embodiment, the viscous bubble liquid was produced according to the production method shown in FIGS. 3 (a) to 3 (c) described in the above [Example].

Specifically, first, in the step shown in FIG. 3A, the water in the electromagnetic cooking pot 62 was heated to about 85 ° C. by the electromagnetic heater 61. Then, while stirring the water (warm water) in the electromagnetic cooking pot 62 with the stirrer 64, lecithin as a surfactant and "gel-up WM" as a gelling agent were added to the water at 0. The mixture was added at a ratio of 3% by weight and stirred for 10 minutes. As a result, 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 the beaker 65, and the bubbles 41 are generated by the bubble generator 69 connected to the pressurizing device while keeping the temperature constant. Was formed. In the present 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 foam 41 accumulated on the liquid surface of the aqueous solution 81 in each of the obtained beakers 65 was collected in another beaker 71.

Also in this embodiment, "Fomest" (registered trademark) is used for the bubble generator 69. A compressor 68 was used as the pressurizing device, and the pressure was set to 0.2 MPa.

Next, the water placed in another beaker 72 is kept at about 85 ° C. with an electromagnetic heater 61, and "thickening up perfect" is added as a thickener at a ratio of 1% by weight to water and stirred for 10 minutes. The thickener 82 shown in FIG. 3 (c) was produced.

Then, as shown in FIG. 3C, each thickening liquid 82 put in separate beakers 72 and the foam 41 generated at each temperature collected in each beaker 71 are mixed and stirred. Each of the foams 41 was dispersed in the thickening liquid 82 in each beaker 72 to produce each viscous foam liquid. The mixing ratio of each thickened liquid 82 and each foam 41 was set to 500 cc of foam 41 with respect to 300 cc of thickened liquid 82.

Then, the physical properties of each viscous bubble liquid produced in this manner immediately after production were measured. The measurement items and measurement methods for each physical property of the sample are the same as those in the above [Example], and the bubble diameter, the volume of the bubbles, the bubble diameter distribution, and the void ratio of the bubbles are determined in the same manner as in the above [Example]. It was measured.

(Measurement result)
16 and 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 observed 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 heat retention temperature of the aqueous solution 81 set to 60 ° C, and at 50 ° C, 55 ° C, 65 ° C, and 70 ° C before and after that. When the foam 41 is produced, the void ratio is slightly reduced. Further, when the heat retention temperature of the aqueous solution 81 was 45 ° C. and 75 ° C., the void ratio tended to be extremely lowered as compared with the case where the heat retention temperature of the aqueous solution 81 was 60 ° C.

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

[Embodiment 5]
Yet another embodiment of the present invention will be described with reference to FIGS. 3 (a) to 3 (c) and FIG. 17 as follows. In the following, for convenience of explanation, the components having the same functions as the components in the first to fourth embodiments are designated by the same reference numerals, and the description thereof will be omitted.

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

(Functional food)
When the viscous bubble liquid is used as food, as described above, a gas 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 a gas having a function such as an antioxidant action as the gas, the viscous bubble liquid can be used as a functional food. Examples of the functional food include hydrogen gas-containing foods containing hydrogen gas as bubbles.

Hereinafter, in the present embodiment, a case where hydrogen gas is used as the gas will be described as an example. Also in this embodiment, the viscous bubble liquid was produced according to the production method shown in FIGS. 3 (a) to 3 (c) described in the above [Example].

Specifically, first, in the step shown in FIG. 3A, the water in the electromagnetic cooking pot 62 was heated to about 85 ° C. by the electromagnetic heater 61. Then, while stirring the water (warm water) in the electromagnetic cooking pot 62 with the stirrer 64, lecithin as a surfactant and "gel-up WM" as a gelling agent were added to the water at 0. The mixture was added at a ratio of 3% by weight and stirred for 10 minutes. As a result, 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 hydrogen gas-containing bubbles are generated by the bubble generator 69 connected to the pressurizing device while keeping the temperature constant at 65 ° C. By allowing the foam 41 to be formed, a foam 41 containing hydrogen gas was formed.

In this embodiment, since hydrogen gas is used, an experiment was conducted while covering the upper part of the beaker 65, installing an exhaust line, and monitoring the leakage state of hydrogen gas with a hydrogen detector.

For the bubble generator 69, "Fomest" (registered trademark) was used. A compressor 68 was used as the pressurizing device, and the pressure was set to 0.2 MPa. All the bubbles 41 accumulated on the liquid surface of the aqueous solution 81 in the beaker 65 were collected in another beaker 71 shown in FIG. 3 (c).

Next, the water placed in another beaker 72 is kept at about 85 ° C. with an electromagnetic heater 61, and "thickening up perfect" is added as a thickener at a ratio of 1% by weight to water and stirred for 10 minutes. The thickener 82 shown in FIG. 3 (c) was produced.

Next, as shown in FIG. 3C, the foam 41 is mixed with the thickening liquid 82, and the foam 41 is dispersed in the thickening liquid 82 by stirring to contain hydrogen gas as bubbles. A viscous foam 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 300 cc of the thickened liquid 82.

Then, the physical properties of the viscous bubble liquid produced in this manner immediately after production and after 7 days from production were measured. The measurement items and measurement methods for 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 bubbles, the bubble diameter distribution, the void ratio of the bubbles, and so on. The rate of disappearance of air bubbles per day was measured.

(Measurement result)
FIG. 17 and Table 6 show changes in the void porosity of the viscous cell solution in the viscous bubble solution 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% 7 days after production.

Further, as described above, assuming that the void ratio of the viscous bubble liquid is B and the disappearance rate is λ, the relationship between the above equations (1) and (2) is established. Therefore, the y-axis is the void ratio B (that is, that is). When equation (2) is obtained from the plot of the measured values shown in FIG. 17 with y = B) and the x-axis as the number of elapsed days t (that is, x = t), B ₀ = 0.425, λ = 0.085.

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

As described above, the foam 41 in which hydrogen gas is contained as a gas in the coating film containing the surfactant and the gelling agent is an aqueous solution containing a thickener, and is a viscous bubble dispersed in the thickening liquid 82. It was found that the liquid can maintain the hydrogen gas in the bubbles in a high concentration state for a long time by converting the gas introduced into the aqueous solution 81 containing the surfactant and the gelling agent into hydrogen gas.

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

[Summary]
In the viscous foam liquid according to the first aspect of the present invention, the foam 41 in which a gas is encapsulated in a coating film containing a surfactant and a gelling agent is contained in a viscous liquid (liquid 43, thickening) composed of an aqueous solution containing a thickener. It is dispersed as bubbles in the liquid 82).

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

However, in the viscous bubble liquid of the above aspect 1, the rate of disappearance of bubbles is very slow, and the life of bubbles can be remarkably extended as compared with the conventional case.

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

Further, in the viscous bubble liquid according to the third aspect of the present invention, in the above aspect 1 or 2, the void ratio of the bubbles in the viscous bubble liquid is 5% or more (as an example, according to the experimental result shown in FIG. 10, for example. It has a composition of 5% or more and a maximum of 42.8%).

The viscous bubble liquid according to the fourth aspect of the present invention has a configuration in which the diameter of the bubbles is 2 mm or less in any of the first to third aspects.

Therefore, the viscous bubble liquid according to aspects 1 to 4 of the present invention can be suitably used as, for example, an ultrasonic contrast medium. By using the viscous bubble liquid as a contrast medium, it is possible to provide a contrast medium that is remarkably easier to handle than the conventional one.

The viscous bubble liquid according to the fifth aspect of the present invention has a configuration in which the viscous bubble liquid is a functional food in any one of the above aspects 1 to 4.

Examples of the functional food include hydrogen gas-containing foods 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 above aspects 1 to 5.

The viscous foam liquid in which hydrogen gas is contained as a gas in the film containing the surfactant and the gelling agent is dispersed in the aqueous solution (liquid 43, thickening liquid 82) containing the thickener. By changing the gas to 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 antiaging, arteriosclerosis, diabetes, spots, wrinkles, cataracts, etc.

Further, in the method for producing a viscous foam liquid according to the seventh aspect of the present invention, the foam 41 formed by introducing a gas into warm water (liquid 42, aqueous solution 81) containing a surfactant and a gelling agent is increased. This is a method of dispersing as bubbles in a viscous liquid (liquid 43, thickening liquid 82) composed of an aqueous solution containing a viscous agent.

Further, the method for producing a viscous bubble liquid according to the eighth aspect of the present invention is the method in which the blending ratio of the surfactant and the gelling agent is 1: 1 in the above aspect 7.

Further, in the method for producing a viscous bubble liquid according to the ninth aspect of the present invention, in the seventh or eighth aspect, the hot water is formed in a state where the temperature of the hot water is maintained within the range of 50 ° C. to 70 ° C. This is a method performed by introducing the above gas into the water.

Further, the viscous bubble liquid manufacturing apparatus (viscous bubble liquid manufacturing apparatus 1) according to the tenth aspect of the present invention is the viscous bubble liquid manufacturing apparatus used in the method for producing the viscous bubble liquid of the above aspect 7 or 8. A viscous liquid consisting of a first container (for example, a heating / stirring device 11 or a heating device 51) containing warm water (liquid 43, thickening liquid 82) containing a surfactant and a gelling agent, and an aqueous solution containing a thickener. A second container (for example, a heating device 31) to be put in, and a gas introducer (for example, a porous fine bubble generator 13 or a swirling flow type fine bubble generator 53) for introducing a gas into the hot water in the first container. , The foam 41 formed on the liquid surface of the hot water by connecting the first container and the second container and introducing a gas into the hot water in the first container is formed in the second container. It is provided with a foam moving portion (foam moving portion 20) to be moved to.

Further, in the viscous bubble liquid manufacturing apparatus according to the eleventh aspect of the present invention, in the tenth aspect, the first container and the second container are provided so as to be hermetically sealed, and the pressure in the first container is provided. A pressure control mechanism (for example, a pressure control mechanism including a compressor 12, a water flow pump 52, a pressure gauge 15, and a relief valve 16) is provided.

Further, the apparatus for producing a viscous bubble liquid according to aspect 12 of the present invention has a configuration in which the gas introducer is a porous fine bubble generator (porous fine bubble generator 13) in the above aspect 10 or 11. is there.

Further, the device for producing a viscous bubble liquid according to the thirteenth aspect of the present invention has a configuration in which the gas introducer is a swirling flow type fine bubble generator (swirl flow type fine bubble generator 53) in the above aspect 10 or 11. is there.

Further, the apparatus for producing a viscous bubble liquid according to the 14th aspect of the present invention has a configuration in which the foam moving portion is kept warm by a heat insulating material (heat insulating material 22) in any of the above aspects 10 to 13.

According to the method for producing the viscous bubble liquid according to the above aspects 7 to 9 and the viscous bubble liquid manufacturing apparatus according to any one of the above aspects 10 to 14, the viscous bubble liquid capable of holding the bubbles for a long period of time is obtained. Can be manufactured. In particular, as shown in the ninth aspect, when the foam is formed by introducing the gas while maintaining the temperature of the hot water in the range of 50 ° C. to 70 ° C., the temperature of the hot water is 45 ° C. or 75 ° C. The void ratio can be improved as compared with the case where the foam is formed by introducing the gas while maintaining the temperature at ° C.

Further, the method for storing the viscous bubble liquid according to the fifteenth aspect of the present invention is a method for storing the viscous bubble liquid according to any one of the above aspects 1 to 6 under pressure.

Further, the method for storing the viscous bubble liquid according to the 16th aspect of the present invention is the method of storing the viscous bubble liquid in the above aspect 15 of the pressurizing device when the internal pressure of the storage container for storing the viscous bubble liquid does not pressurize the storage container. When the gauge pressure is 0 MPa, the pressure is increased so that the gauge pressure of the pressurizing device is 0.5 MPa or less, and the viscous bubble liquid is stored.

Further, in the method for storing the viscous bubble liquid according to the 17th aspect of the present invention, in the 16th aspect, the internal pressure of the storage container for storing the viscous bubble liquid is 0.3 MPa or less at the gauge pressure of the pressurizing device. It is a method of storing the viscous bubble liquid by pressurizing so as to become.

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 retained for a long period of time. Therefore, according to the above aspect, it is possible to provide a storage method of a method for storing a viscous bubble liquid that can be stably contained (preserved) for a long period of time.

The viscous bubble liquid of the present invention has a significantly longer cell life than the conventional one, and can be suitably used as a contrast medium in ultrasonic examination and functional viscous water. Further, the method and apparatus for producing a viscous bubble liquid of the present invention can be suitably used as the method and apparatus for producing the contrast medium and functional viscous water, and for example, a method for changing the texture of a food material. It can also be used as a device.

1 Viscous bubble liquid production device 10 Foam forming unit 11 Heating / stirring device (first container)
11a Container part 11b Lid part 12 Compressor (pressure control mechanism)
13 Porous fine bubble generator (gas introducer)
14 Stirrer 15 Pressure gauge (pressure control mechanism)
16 Relief valve (pressure control mechanism)
20 Foam moving part 21 Connecting pipe 21a Opening 21b Opening 22 Insulating material 30 Foam mixing part 31 Heating device (second container)
31a Container part 31b Lid part 32 Stirrer 41 Foam 42 Liquid 43 Liquid 51 Heating device (first container)
51a Container part 51b Lid part 52 Water flow pump (pressure control mechanism)
53 Swirling flow type fine bubble generator (gas introducer)
53a Intake port 53b Liquid suction port 53c Discharge port 61 Electromagnetic heater 62 Electromagnetic cooking pot 63 Thermometer 64 Stirrer 65 Beaker 66 Stirrer 67 Stirrer 68 Compressor 69 Bubble generator 71 Beaker 72 Beaker 81 Aqueous solution 91 Turntable 92 Petri dish 93 Sample 94 Laser 95 Camera

Claims (3)

A thickener used for functional foods or contrast media, which contains a surfactant and a gelling agent, bubbles in which hydrogen gas is contained in the film, and a thickener in which the bubbles are dispersed. An aqueous solution containing , and a viscous bubble liquid containing
The diameter of the bubbles is less than 1 mm, the void ratio is 5 to 42.8%, and the viscosity of the aqueous solution containing the thickener is in the range of 1 × 10 ² to 1 × 10 ⁶ mPa · s.
The void ratio is the ratio of the volume of the bubbles to the unit volume of the viscous bubble liquid (volume content of the bubbles) from the sum of the total volume of the viscous bubble liquid and the volumes of all the bubbles in the imaged portion by the camera. The required viscous bubble liquid. The surfactant is one or more selected from lecithin, glycerin fatty acid ester, sucrose fatty acid ester, stearoyl lactate calcium, sorbitan fatty acid ester, and propylene glycol fatty acid ester.
The gelling agent is one or more selected from gelatin, carrageenan, locust bean gum, and alginate and calcium or a calcium compound.
The thickener is carboxymethyl cellulose or a thickening polysaccharide.
The viscous bubble liquid according to claim 1, wherein the blending ratio of the surfactant and the gelling agent is 1: 1 . The viscous bubble liquid according to claim 1 or 2, wherein the bubble diameter is 200 μm to less than 1 mm.

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