CN114616191A

CN114616191A - Method for generating and using ultra-fine air bubbles and generating device

Info

Publication number: CN114616191A
Application number: CN202080073863.5A
Authority: CN
Inventors: 木下耕一; 藤山泰三; 武知美和
Original assignee: Shiseido Co Ltd
Current assignee: Shiseido Co Ltd
Priority date: 2019-11-01
Filing date: 2020-10-30
Publication date: 2022-06-10
Also published as: WO2021085628A1; JPWO2021085628A1

Abstract

The object is to obtain a method for easily producing and using a liquid containing ultrafine bubbles. The solution is a method for adhering and using a liquid containing ultra-fine bubbles to a predetermined use surface, for example, the back of the right hand (1R), wherein the liquid and a jet gas are stored in an aerosol container (10) having a jet button (11) with a flow rate adjusting mechanism, and the jet liquid is jetted from the aerosol container (10) by operating the jet button (11). The ejection liquid is applied to the back of the right hand (1R) and used as a liquid containing ultra fine bubbles.

Description

Method for generating and using ultra-fine air bubbles and generating device

Technical Field

The present invention relates to a method for generating and using ultra fine bubbles and an apparatus for generating ultra fine bubbles.

Background

Conventionally, as shown in patent documents 1 to 3, for example, there is known a technique of attaching a liquid containing extremely fine bubbles to a body surface part of a human body by coating or the like, and embodying a specific function of such a liquid.

Specifically, patent document 1 shows that plasma discharge treated water, which is high-concentration ozone water, can be used as cosmetic water as it is, or can be used as raw water for various cosmetic liquids such as cosmetic moisturizing water and cosmetic emulsions, and that the plasma discharge treated water is excellent in permeability to the skin and has a high moisturizing effect on the skin (see paragraphs 0040 and 0043). Patent document 1 also discloses a method of blowing ozone into water while forming numerous ultrafine bubbles called microbubbles, nanobubbles, etc. as a method of obtaining high-concentration ozone water (see paragraph 0002).

Further, patent document 2 relating to the method of generating fine bubbles shows that, as an effect of using hot water containing many fine bubbles, the penetration is high, and therefore, dirt inside pores can be removed, and dirt and grease of hair can be removed (see paragraph 0027). Further, patent document 2 shows that in hot water exhibiting the above-described effects, minute bubbles having a diameter of 500nm or less, particularly about 100 to 300nm, are generated, and such minute bubbles are in the concept of micro bubbles including micro bubbles, micro-nano bubbles, and the like (see paragraphs 0030 and 0031).

Further, patent document 3 describes, as a method for providing a dispersion without containing a surfactant in a mixture of a dispersoid and a liquid dispersion medium by an ultrafine bubble generating apparatus, a method for producing a composition containing ultrafine bubbles having a mode particle diameter of 500nm or less, a hydrophobic drug and water, and describes that in such a composition, the effect of the drug is more exhibited because the ultrafine bubbles coexist, and for example, in the case where the drug is evaporable, the evaporability is improved, and in the case where the drug is a fungicide or the like, the permeability is improved (see paragraphs 0015 and 0016). Patent document 3 describes that various pharmaceutical products and cosmetics are mentioned as the above-mentioned drug (see paragraph 0021).

In the above-mentioned patent documents 1 to 3, the terms micro bubbles, micro nano bubbles, and nano bubbles are used for micro bubbles or ultra fine bubbles contained in a liquid such as water, but at present, micro bubbles having a particle size of 1000nm or less are defined as "ultra fine bubbles" according to ISO/TC281 (micro bubble technology). Since the present invention relates to fine bubbles having a particle diameter of 1000nm or less, the fine bubbles are hereinafter referred to as ultrafine bubbles.

On the other hand, as a device for generating such ultrafine bubbles in a liquid such as water, a device exemplified in patent document 3 has been known. These exemplified apparatuses are apparatuses to which a static mixing type, a venturi type, a cavitation type, a steam coagulation type, an ultrasonic type, a swirling flow type, a pressure dissolution type, a micropore type, and a gas-liquid mixing shear type are applied. Further, devices such as those shown in patent documents 4 and 5 are also known. The apparatuses disclosed in these documents are configured such that a rotating shaft body having a plurality of triangular columnar projections or rectangular blades attached to an outer peripheral surface thereof is disposed in a storage pipe such as a water pipe through which a liquid can flow.

Documents of the prior art

Patent document 1: japanese patent laid-open publication No. 2006-289236

Patent document 2: japanese laid-open patent publication No. 2010-201397

Patent document 3: japanese re-listing 2011/16529

Patent document 4: japanese patent No. 6077627

Patent document 5: japanese patent No. 6490317

Disclosure of Invention

Referring to patent documents 1 to 3, it is considered that a skin preparation for external use such as a cosmetic containing a specific component is applied to the skin to obtain a specific effect by ultrafine bubbles. However, conventionally, a method for easily producing and using a liquid containing ultrafine bubbles has not been known, including the descriptions of patent documents 1 to 3. The apparatuses disclosed in patent documents 4 and 5 have a complicated structure, and cannot easily produce a liquid containing ultrafine bubbles. In addition, in the conventional methods disclosed in patent documents 1 to 5, when the viscosity of the liquid containing the ultrafine bubbles is low, it is difficult to retain the ultrafine bubbles in the liquid at a high concentration for a long period of, for example, 3 years or longer.

Accordingly, an object of the present invention is to provide a method for producing and using microbubbles, which can easily produce and use a liquid containing microbubbles at a high concentration. Further, an object of the present invention is to provide an apparatus for generating ultrafine bubbles, which can generate ultrafine bubbles at a high concentration in a liquid.

The method for producing and using microbubbles according to the present invention is a method for attaching a liquid containing microbubbles to a predetermined surface for use,

storing a liquid and a propellant gas in an aerosol container having a spray button with a flow adjustment mechanism,

operating a spray button of the aerosol container to spray the liquid from the aerosol container,

the ejected liquid is attached to a use surface, and the liquid is used as a liquid containing ultrafine bubbles.

In the method for producing and using the ultrafine bubbles according to the present invention, it is particularly preferable that the liquid containing the ultrafine bubbles contains water as a main component. The "main component" refers to the largest component by weight among the plurality of components.

In the method for producing and using ultrafine bubbles according to the present invention, the pressure of the gas to be ejected is preferably set to 0.3 to 1.0MPa, more preferably 0.6 to 0.9 MPa.

The ultrafine bubble generating apparatus according to the present invention is characterized by including an aerosol container having a spray button with a flow rate adjusting mechanism.

In the method for generating and using ultra fine bubbles according to the present invention, it is known that a large amount of ultra fine bubbles are generated in a liquid ejected from an ejection button with a flow rate adjustment mechanism, by storing the liquid and an ejection gas in the aerosol container having the ejection button with the flow rate adjustment mechanism, operating the ejection button of the aerosol container, and ejecting the liquid from the aerosol container. As described above, according to the method for generating and using ultrafine bubbles of the present invention, ultrafine bubbles can be easily generated, in other words, a liquid containing ultrafine bubbles can be easily generated and used, simply by operating the spray button of the aerosol container.

Further, according to the method of generating and using ultrafine bubbles of the present invention, and according to the ultrafine bubble generating apparatus of the present invention, ultrafine bubbles can be generated from the start of ejection by an ejection button operation using an aerosol container to the end of the ejection, and therefore, a liquid containing ultrafine bubbles at a high concentration can be generated at all times.

Drawings

Fig. 1 is a schematic view showing a method for generating and using ultrafine bubbles according to an embodiment of the present invention.

Fig. 2 is a schematic diagram showing the structure of an apparatus for generating ultrafine bubbles.

Fig. 3 is a graph illustrating the generation of ultrafine bubbles for the number of aerosol emissions.

Fig. 4 is a graph illustrating generation of ultrafine bubbles by aerosol injection.

Fig. 5 is a graph illustrating generation of ultrafine bubbles by aerosol injection.

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Fig. 1 is a view schematically showing one step in a method for generating and using ultrafine bubbles according to an embodiment of the present invention. In the present embodiment, for example, a cosmetic containing adenosine is applied to the back of the right hand 1R of a person who is to be made up. Before the cosmetic is applied, as shown in fig. 1, the aerosol container 10 is used to spray the aerosol spray liquid a on the back of the right hand 1R. As an example, the aerosol spray liquid a is sprayed by pressing the spray button 11 of the aerosol container 10 with a finger of the left hand 1L.

Here, as the injection button 11, an injection button with a flow rate adjustment mechanism is used. Specifically, in the present embodiment, a button "D391" with a flow rate adjusting mechanism, manufactured by mitsubishi corporation, a valley valve, is applied. The detailed structure of the push button with a flow rate adjusting mechanism and the aerosol container using the push button is described in, for example, japanese patent No. 4217049, japanese patent No. 4350970, and japanese patent No. 4974175. In the present embodiment, the push button and the container described in these publications can be suitably used as the spray button 11 and the aerosol container 10.

When the liquid is ejected from the ejection button 11 and the aerosol container 10, it is confirmed through experiments that ultrafine bubbles are generated in the liquid. The confirmation result will be described in detail below. In this experiment, in order to confirm the generation of ultrafine bubbles, a laser diffraction particle size distribution measuring apparatus "SALD-7100 HH" manufactured by Shimadzu corporation was used. The measurement principle of the particle size distribution measuring apparatus will be described with reference to FIG. 2.

In the present apparatus, a laser beam L emitted from a laser light source 21 is collimated by a collimator lens 22 and then irradiated onto a particle group 23 to be measured. In this example, if many ultrafine bubbles are generated in the liquid, the many ultrafine bubbles become the particle group 23. When the laser light L is irradiated onto the particle group 23, diffracted and scattered light is generated from the particle group 23 toward the rear (the laser light source 21 side), the side, and the front. The diffracted/scattered light shows a certain spatial pattern (light intensity distribution pattern) in a plane intersecting the traveling direction thereof. Since it is known that the light intensity distribution pattern shows various shapes depending on the particle size, by detecting and analyzing the light intensity distribution pattern, it is possible to determine the degree of size of particles (particle size distribution) contained at a certain degree of proportion.

More specifically, in the present apparatus, the light from the particle group 23 is condensed by the condenser lens 24 to obtain the diffraction/scattering image 25. Then, the back scattered light from the particle group 23 is detected by a back scattered light sensor 26, the side scattered light is detected by a side scattered light sensor 27, and the front scattered light is detected by a front scattered light sensor 28, and the light intensity of each light is obtained. In fig. 2, the forward scattering light sensor 28 is shown as a single plane, but actually a plurality of sensors are arranged in a predetermined arrangement pattern in such a plane. A plurality of the back scattering light sensors 26 and the side scattering light sensors 27 are similarly arranged, and these

sensors

26 and 27 detect diffracted/scattered light mainly caused by particles having a relatively small particle diameter in the particle group 23. On the other hand, the front scattered light sensor 28 detects diffracted/scattered light mainly caused by particles having a relatively large particle diameter in the particle group 23.

The light intensity measured by each of the

sensors

26, 27, and 28 is a value that increases as the concentration of the ultrafine bubbles in the particle group 23 increases. Fig. 3 shows an example of the measurement results of light intensity when ultra fine bubbles are generated by aerosol spraying using a button with a flow rate adjustment mechanism. In this case, aerosol injection was performed for the 1 st, 2 nd, and 3 rd times, and the light intensity was measured for each time. The horizontal axis of the graph indicates the number of times the aerosol was ejected, and the light intensity indicated by the vertical axis indicates a relative value obtained by calculating the difference from the stock solution (liquid not ejected from the aerosol) containing no ultrafine bubbles.

The broken line in FIG. 3 shows an example of the measurement result when the button with the flow rate adjusting mechanism "D391" and the outlet diameter φ 0.3 is used, and the solid line shows an example of the measurement result when the button with the flow rate adjusting mechanism "D391" and the outlet diameter φ 0.2 is used. In either case, the aerosol container 10 was filled with the preparation 1 described below and nitrogen gas as a propellant and used for measurement. As shown in the figure, it was confirmed that the ultrafine bubbles were sufficiently contained after the 2 nd button, regardless of the button used. Although not shown in fig. 3, it was confirmed that buttons other than the button with the flow rate adjustment mechanism (for example, a single mechanical break up button or a double mechanical break up button) hardly included ultrafine bubbles after the 2 nd time, and thus an effective ultrafine bubble concentration could not be provided.

As described above, the light intensities shown by the

sensors

26, 27, and 28 are measured. In this example, a total of 70 sensors were disposed as the

sensors

26, 27, and 28, and the element numbers "1 to 70" were given to the respective sensors, and the light intensities indicated by the respective sensors were measured. The measurement results are shown in fig. 4. The sensor element number on the horizontal axis of the measurement result shown in fig. 4 is the number of the sensor that detects the intensity distribution pattern of the diffracted/scattered light, and satisfies the correspondence relationship with the particle diameter.

The particle size distribution obtained by the laser diffraction/scattering method may vary greatly depending on sample conditions and the like. On the other hand, in the case of the same microbubble generation condition, the local maximum value and the distribution of the scattered light intensity faithfully reflect the density of the microbubbles, and therefore the local maximum value of the scattered light intensity is used as an index for evaluating the relative density of the microbubbles contained therein. In both the case of generating ultrafine bubbles by aerosol jetting and the case of generating ultrafine bubbles using a pressurized dissolution type generator, the scattering light distribution is extremely large in the vicinity of the sensors of element numbers 43 to 45. In general, element numbers 43 to 45 reflect scattered light caused by particles of 100 to 200nm, which represent the maximum value of the number distribution of the ultrafine bubbles, regardless of the method of generating the ultrafine bubbles.

Therefore, based on the measurement results shown in fig. 4, the light intensity detected by the sensor of element number 43 was extracted, and the concentration of the ultrafine bubbles contained in the liquid was relatively evaluated. In fig. 4, the horizontal axis shows the light intensity indicated by each sensor as a relative value, as described above. The total of 70 forward scattering light sensors 28 are arranged closer to the center side as the number of elements is smaller, that is, closer to the extension of the optical axis of the condenser lens 24 in fig. 2.

The measurement of the light intensity was performed by changing the state of the aerosol container 10 to 4 types described below, and ejecting the preparation 1 described below from the aerosol container 10 for each case. The above 4 states are as follows. In fig. 4, the line shape was changed for 4 kinds of states to show the measurement results, and the correspondence between each state and the line shape is shown outside the upper right column. The injection buttons applied to the aerosol container 10 are changed to nos. 1 to 3, where No.1 indicates that the button "D391" with the flow rate adjustment mechanism is applied, No.2 indicates that the "two-machine scattering button" is applied, and No.3 indicates that the "one-machine scattering button" is applied. In these cases, nitrogen gas is used as the propellant to be filled into the aerosol container 10 together with the preparation 1. The term (stock solution) refers to a case where the preparation 1 is not applied to the back of the hand by the spray button. The measurement results at this time are shown in the lowermost curve in fig. 4.

As shown in fig. 4, it is found from the experiment that when the button "D391" with the flow rate adjusting mechanism is used, a light intensity distribution pattern in which the light intensity is extremely large is obtained by the forward scattering light sensor 28 in the vicinity of the element numbers 43 to 45. In the laser diffraction particle size distribution measuring apparatus "SALD-7100 HH" used in advance in this experiment, it was known that the forward scattering light sensor 28 having the element number of around 43 to 45 mainly detects diffracted/scattered light from particles having a particle size of 50 to 1000nm, and thus it was confirmed that ultrafine bubbles having a particle size of about 50 to 1000nm were generated.

In fig. 5, the light intensity shown in fig. 4 is shown by taking the difference from the light intensity measured similarly for the 30% ethanol aqueous solution. In fig. 5, the upper graph shows an example of the measurement result when the button "D391" with the flow rate adjustment mechanism is used, and the lower graph shows an example of the measurement result when the "two-mechanical break button" is used. Since this difference also indicates that the element numbers of the forward scattering light sensors 28 in the vicinity of 43 to 45 have a very large light intensity distribution pattern, it is understood that the light intensity distribution pattern shown in fig. 4 reflects the concentration distribution of the ultra fine bubbles.

Further, the method of using the ultrafine bubbles of the present invention can significantly improve the permeability of the skin particularly when the specific component contained in the external preparation for skin is adenosine. The results of this confirmation by experiment are described below. For comparison of permeability, preparation 1 and preparation 2 containing adenosine were prepared. The formulation of each preparation is as follows, and the component ratio is expressed in mass%.

Preparation 1

90 percent of water

7.0 percent of ethanol

DPG 1.0％

DPG-2-decanol polyether-120.5%

Proper amount of citric acid

Proper amount of sodium citrate

Proper amount of preservative

Proper amount of spice

Other trace components 0.3%

Preparation 2

95 percent of ethanol 20.0 percent

1.0 percent of squalane

Butanediol 5.0%

Polyoxyethylene hardened castor oil 0.2%

5.0 percent of glycerin

Adenosine 0.2%

The balance of purified water

In order to obtain a preparation 1 containing ultrafine air bubbles on the skin, the preparation 1 was filled in an aerosol container 10, the internal pressure thereof was set to 0.9MPa with nitrogen gas, and a button "D391" with a flow rate adjusting mechanism, manufactured by mitsunobu valve, manufactured by kokko corporation, was applied as the spray button 11. On the other hand, in order to obtain a preparation 1 containing no ultrafine air bubbles on the skin, the preparation 1 was used as a stock solution.

That is, the spray of the aerosol container 10 and the stock solution of the preparation 1 were treated at different positions on the forearm 2 of the subject. Then, the preparation 2 containing adenosine was treated for 10 minutes for each site. Then, the horny layer of each part treated as described above was peeled off in a size of 1cm × 1cm to extract the horny layer components, and the adenosine content was quantitatively analyzed by an LC-MS method (liquid chromatography mass spectrometry). The amount of adenosine in the stratum corneum after the quantitative analysis was 1.6 times that in the case of the treatment of preparation 1 containing ultrafine bubbles, compared to the case of the treatment of preparation 1 containing ultrafine bubbles. This shows that the effect of enhancing the adenosine permeability by the ultrafine bubbles is significantly improved.

As described above, when the preparation 1 is ejected from the aerosol container 10 by using the button "D391" with a flow rate adjusting mechanism as the ejection button 11, the aerosol ejection liquid becomes a liquid containing a large amount of ultra fine bubbles, which are fine bubbles having a particle diameter of 1000nm or less. Thus, when the preparation 2 is applied to the back of the right hand 1R after the liquid jet containing the ultrafine bubbles is applied to the back, the effect of promoting penetration of a specific component of the preparation 2, for example, adenosine, into the skin can be obtained. Further, since the ejection liquid containing the ultrafine bubbles is generated only by operating the ejection button 11 of the aerosol container 10, the liquid containing the ultrafine bubbles can be easily generated, in other words, the ultrafine bubbles can be easily generated and used.

As described above, the spray liquid containing the ultrafine bubbles may be sprayed and applied directly from the aerosol container 10 to the liquid application surface (the back of the hand of the right hand 1R in the present embodiment), or may be sprayed and applied to a cosmetic cotton or the like first and then applied to the application surface using the cosmetic cotton or the like. Such a coating method is particularly suitable in the case where the liquid application surface is a portion of the scalp, eyes, nose, or the vicinity of ears.

The method for producing and using microbubbles according to the present invention can be applied similarly even when the cosmetic applied to the skin of a human body is a cosmetic other than preparation 2, or when a skin preparation for external use such as a quasi-drug other than a cosmetic is applied to the skin, or when a liquid containing microbubbles is applied to a use surface other than the skin, and the liquid is used, and the effect similar to the above-described effect is obtained in this case.

Here, another example of the liquid containing ultrafine bubbles that can be used in the present invention will be described. The liquid composed of the above-mentioned preparation 1 and preparation 2 is referred to as example 1, and other examples 2 to 8 will be described below. The formulations of the liquids of examples 2 to 4 are shown in Table 1 below. The composition ratio represented by a numeral for each raw material represents mass% with respect to the whole liquid (hereinafter the same).

TABLE 1

	Example 2	Example 3	Example 4
				Water (W)	88.2	86.3	83.8
Glycerol	1	1	1
				DPG	5	5	5
BG	4	4	4
				PEG/PPG-14/7 dimethyl ether	1	1
PPG-13 decyl tetradecyl polyether-24	0.1	0.1	0.5
				Citric acid	Proper amount of	Proper amount of	Proper amount of
Citric acid sodium salt	Proper amount of	Proper amount of	Proper amount of
				EDTA	0.03	0.03	0.03
Preservative agent	Proper amount of	Proper amount of	Proper amount of
				Glycyrrhizic acid dipotassium salt	0.07
4-Methoxysalicylic acid potassium salt		2
				Tocopherol acetate			0.07

Next, the liquid formulations of examples 5 to 8 are shown. In all of examples 5 to 8, the liquid used was obtained by spraying the preparation 1 to obtain a liquid containing ultrafine air bubbles, applying the liquid to the skin and leveling the same, and then applying the preparation 2 to the same part of the skin. That is, the following table 2 shows the component ratios of formulation 1 used in common in examples 5 to 8, and table 3 shows the component ratios of formulation 2 in each of examples 5 to 8.

TABLE 2 formulation 1

Name of raw materials	Examples 5 to 8 in common
		Water (W)	90
Ethanol	7
		DPG	1
DPG-2-decylpolyether-12	0.5
		Citric acid	Proper amount of
Citric acid sodium salt	Proper amount of
		EDTA	Proper amount of
Preservative	Proper amount of

The active ingredient of the specific component in the external preparation for skin may be constituted by a lipophilic compound or a hydrophilic compound. For example, when a permeation enhancer is used for a lipophilic compound, it is generally difficult to incorporate a component that further increases the permeability of the hydrophilic compound in the same formulation system. The method of producing and using ultrafine bubbles according to the present invention uses ultrafine bubbles having low chemical dependency, and therefore can efficiently promote permeation of all of a plurality of active ingredients. From this point of view, the method of producing and using the ultrafine bubbles of the present invention can be applied to a wider range of external preparations for skin than the case of using a permeation enhancer.

Description of the reference numerals

1L left hand

1R Right hand

10 Aerosol container

11 jet button with flow regulating mechanism

21 laser light source

22 collimating lens

23 particle group

24 condensing lens

25 diffraction/scatter image

26 backscattered light sensor

27 side scattered light sensor

28 forward scattering light sensor

Claims

1. A method for producing and using ultra fine bubbles, which is a method for attaching a liquid containing ultra fine bubbles to a predetermined surface to be used,

storing a liquid and a propellant gas in an aerosol container having a propellant button with a flow adjustment mechanism,

operating the spray button of the aerosol container to spray the liquid from the aerosol container,

the liquid thus ejected is allowed to adhere to the use surface, and the liquid is used as the liquid containing the ultrafine bubbles.

2. The method for producing and using ultrafine bubbles according to claim 1, wherein the liquid is a liquid containing water as a main component.

3. The method for producing and using ultrafine bubbles according to claim 1 or 2, wherein the pressure of the gas to be ejected is 0.3 to 1.0 MPa.

4. An ultrafine bubble generating apparatus includes an aerosol container having a spray button with a flow rate adjusting mechanism.