JP2022027274A - Liquid for liquid marbles, liquid marble, method and device for producing liquid marble, and bioreactor - Google Patents

Abstract

To provide a liquid for liquid marbles that has high production efficiency of valuable material, suppresses the union of droplets for a variety of liquids, and has excellent durability against external force.SOLUTION: A liquid for liquid marbles has a biocatalyst, water, and a thickener, the content of the water being 15 mass% or more and 98 mass% or less, and the viscosity at 25°C being 400 mPa s or more and 4,000 mPa s or less.SELECTED DRAWING: Figure 1A

Description

The present invention relates to a liquid for liquid marble, a liquid marble, a method and apparatus for producing the liquid marble, and a bioreactor.

The bioreactor generally means a device that utilizes a biological reaction by a biocatalyst such as an enzyme. Immobilized enzymes, immobilized microorganisms, and other living cells are used for biological reactions used in bioreactors. Bioreactors are used for the production of amino acids, peptide organic acids, etc., isomerization of sugars, and the like. Bioreactors that utilize enzyme catalysts are also applied to some processes in the petrochemical industry. Further, some bioreactors are used for analytical purposes such as various diagnoses. Many bioreactors are large-sized devices, which are difficult to carry, and many of them are complicated to handle. Therefore, a small bioreactor that can be easily used is desired.

Industrially used materials can be stably handled in any of the gas phase, liquid phase, and solid phase by changing the pressure and temperature. However, from the viewpoint of handleability such as transportation and transportation of materials, it is difficult to handle gas efficiently because it requires measures to prevent leakage and its low density. In addition, it is difficult to handle the liquid efficiently because it requires measures to prevent leakage and contaminates the transport path. Therefore, it is preferable that the material is solid in terms of handling. Therefore, in the prior art, for example, a method of cooling a gas or liquid to solidify it or adsorbing the gas or liquid to a porous material to treat it as a solid is known, but energy for cooling is known. Is required, and the range that can be used industrially is limited.

In recent years, for example, liquid marbles produced by aphids have been attracting attention as a technique for handling materials without changing their phases. Aphids are known to coat the surface of nectar droplets secreted from the body with hydrophobic particles and move them out of the nest, treating liquids like solids (eg,). , See Non-Patent Document 1).

On the other hand, in general, the substance production process using microorganisms that produce valuable products is carried out in a large culture tank under strict control of the culture solution. However, such a culture device requires appropriate stirring and gas supply such as oxygen, which complicates the process and management. In addition, it may be guided by the dead microorganisms in the large culture tank, and the killing of the surrounding microorganisms may be induced, resulting in poor substance production.

As a liquid marble forming technique that imitates this liquid marble and is industrially applied, for example, a droplet is encapsulated with particles, and the encapsulated droplet contains a biocatalyst such as a microorganism, so that the inside of the liquid-encapsulated particles is contained. A technique for culturing microorganisms has been reported (see, for example, Non-Patent Document 2).

An object of the present invention is to provide a liquid for liquid marble, which has high resource production efficiency, suppresses the coalescence of droplets with respect to various liquids, and has excellent durability against external forces.

The liquid for liquid marble of the present invention as a means for solving the problem contains a biocatalyst, water, and a thickener, and the content of the water is 15% by mass or more and 98% by mass or less. The viscosity at 25 ° C. is 400 mPa · s or more and 4,000 mPa · s or less.

According to the present invention, it is possible to provide a liquid for liquid marble having high resource production efficiency, suppressing the coalescence of droplets with respect to various liquids, and having excellent durability against external forces.

FIG. 1A is a schematic diagram showing an example of composite particles. FIG. 1B is a schematic view showing an example of a cross section in the XZ plane in FIG. 1A.

(Liquid for liquid marble)
The liquid for liquid marble of the present invention contains a biocatalyst, water, a thickener, and if necessary, other components.
The liquid for liquid marble of the present invention contains a biocatalyst, water, and a thickener, and the content of the water is 15% by mass or more and 98% by mass or less, and the viscosity at 25 ° C. is 400 mPa · s. It is 4,000 mPa · s or less.

In the case of conventional technology for culturing microorganisms using particles containing liquid, the size of the particles used is several mm or more, so the durability (strength) is low and it is easy to unite, so it is within the same system. There was a problem that it was difficult to handle a large number of particles. Further, since the size of the particles used is large, there is a problem that it is difficult to stir to circulate the liquid inside the particles and to supply gas.

Therefore, the present inventor investigated a liquid for liquid marble having high resource production efficiency, suppressing the coalescence of droplets with respect to various liquids, and having excellent durability against external forces, and obtained the following findings.

Liquid marbles are formed when the "hydrophilicity" and "hydrophobicity" of liquid and solid particles are reversed. Therefore, even when the liquid is hydrophobic, if the solid particles are hydrophilic, a liquid marble can be formed. Normally, there is no material that can maintain hydrophilicity, and it becomes hydrophobic over time. This is due to deterioration of the material itself and adsorption of impurities. On the other hand, it is not known that the hydrophobicity of a hydrophobic material becomes hydrophilic over time. It is considered that all stains and deterioration proceed in the hydrophobic direction. Therefore, liquid marbles have usually been used in a system where liquids are hydrophilic and solid particles are hydrophobic. From the viewpoint of hydrophilicity and hydrophobicity, the liquid is preferably hydrophilic as much as possible, and ideally, 100% of water is used. However, it has been found that when the water content is 100%, there is a problem that the viscosity is low and the water is weak against external force. There has been no knowledge about the physical characteristics of liquids that can achieve both biocatalytic activity and the environment in which liquid marble can be maintained.

Therefore, the present inventor has the liquid for liquid marble containing a biocatalyst, water, and a thickener, and the content of the water is 15% by mass or more and 98% by mass or less at 25 ° C. It has been found that when the viscosity is 400 mPa · s or more and 4,000 mPa · s or less, the resource production efficiency is high, the coalescence of droplets is suppressed with respect to various liquids, and excellent durability against external force is exhibited. ..

The viscosity of the liquid for liquid marble at 25 ° C. is 400 mPa · s or more and 4,000 mPa · s or less, preferably 500 mPa · s or more and 3,000 mPa · s or less, and 1,000 mPa · s or more and 2,000 mPa · s. The following are more preferable. If the viscosity at 25 ° C. is less than 400 mPa · s, the coalescence of droplets cannot be suppressed, the durability of the liquid marble against external force is lowered, and the liquid marble may not be manufactured. 4 If it exceeds 000 mPa · s, it may be difficult to produce droplets and liquid marble may not be produced. On the other hand, when the viscosity at 25 ° C. is 400 mPa · s or more and 4,000 mPa · s or less, it is advantageous in that the coalescence of droplets can be suppressed and the liquid marble is excellent in durability against external force.

<Biocatalyst>
The biocatalyst is not particularly limited as long as it is a living body itself or a catalyst derived from a living body and can change the reaction rate when the substance changes to a different substance, and there is no particular limitation, depending on the purpose. It can be selected as appropriate.
Examples of the living body itself include animal cells, plant cells, and microorganisms.
Examples of the biological catalyst include proteins, enzymes, organelles, hormone receptors, antibodies and the like.
These may be used alone or in combination of two or more. Among these, the biocatalyst is preferably one that can be produced by using the biocatalyst.
As the biocatalyst, a biocatalyst collected from nature may be used, a synthetic catalyst may be used, or a commercially available product may be used.

The valuable resources are not particularly limited as long as they can be produced using a biocatalyst, and can be appropriately selected depending on the intended purpose. For example, ethanol, acetic acid, lactic acid, butyric acid, propionic acid, etc. Formic acid and the like can be mentioned.

The content of the biocatalyst is not particularly limited and may be appropriately selected depending on the type of biocatalyst, the desired activity and the like.

The method for measuring the catalytic activity of the biocatalyst is not particularly limited, and can be appropriately selected from known methods according to the type of biocatalyst, the desired activity, and the like.

<Water>
The water is not particularly limited and may be appropriately selected depending on the intended purpose. For example, pure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, fresh water, purified water, hot water, etc. Examples thereof include ion-exchanged water, physiological saline, phosphate buffer, phosphate buffered physiological saline and the like. These may be used alone or in combination of two or more.

The content of the water is 15% by mass or more and 98% by mass or less, preferably 50% by mass or 98% by mass, and more preferably 85% by mass or 98% by mass or less with respect to the entire liquid for liquid marble. If the water content is less than 15% by mass, problems may occur from the viewpoint of biocatalytic activity such as microbial growth, and if it exceeds 98% by mass, it may be difficult to maintain the viscosity. On the other hand, when the content of the water is 15% by mass or more and 98% by mass or less, it is preferable from the viewpoint that the strength of the liquid marble and the production of valuable resources can be balanced.

The content of the water in the liquid for liquid marble can be analyzed with a Karl Fischer moisture meter.

<Thickener>
The thickener is not particularly limited as long as the viscosity of the liquid for liquid marble at 25 ° C. can be 400 mPa · s or more and 4,000 mPa · s or less, and is appropriately selected depending on the intended purpose. This can be done, for example, polysaccharides, synthetic resins, derivatives thereof and the like. These may be used alone or in combination of two or more. Among these, polysaccharides are preferable as the thickener.

Examples of the polysaccharide include pregelatinized or partially pregelatinized starch of gums and starches, dextrin, alginic acid, alginate, alginate ester, gelatin, seaweed extract powder, cellulose and the like.
Examples of the gums include gum arabic, guar gum, xanthan gum, gellan gum, locust bean gum, tamarind seed gum, psyllium seed gum and the like.
Examples of the pregelatinized or partially pregelatinized starch of the starch include pregelatinized or partially pregelatinized starch of starches such as potato starch, corn starch, tapioca starch, rice starch, wheat starch and sweet potato starch.
Examples of the cellulose include hydroxypropyl cellulose (HPC), hydroxypropimethyl cellulose (HPMC), methyl cellulose (MC), hydroxymethyl cellulose (HMC), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), fermented cellulose and the like. ..
As the polysaccharide, a purified one may be used, or one containing the polysaccharide such as honey may be used.

Examples of the synthetic resin include polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA).

The content of the thickener is not particularly limited as long as the viscosity of the liquid marble liquid at 25 ° C. is 400 mPa · s or more and 4,000 mPa · s or less, and is appropriately selected according to the purpose. However, it is preferably 0.1% by mass or more, more preferably 0.1% by mass or more and 10% by mass or less, based on the total amount of the liquid for liquid marble. If the content of the thickener is less than 0.1% by mass, the viscosity of the liquid marble liquid at 25 ° C. may not be 400 mPa · s or more. On the other hand, when the content of the thickener is 0.1% by mass or more, it is preferable in that the coalescence of droplets can be suppressed and the liquid marble is excellent in durability against external force.

The content of the thickener in the liquid for liquid marble can be measured by liquid chromatography, NMR analysis, mass spectrometry, elemental analysis and the like alone or in combination.

<Other ingredients>
The other components in the liquid for liquid marble are not particularly limited as long as the effects of the present invention can be exhibited, and can be appropriately selected depending on the intended purpose, but are necessary for the catalytic activity of the biocatalyst. It preferably contains an ingredient, and examples thereof include additives (eg, pH adjusters, preservatives), physiologically active substances, water-soluble compounds, water-insoluble compounds, and the like. These may be used alone or in combination of two or more.

Examples of the additive include antioxidants such as sodium L-ascorbic acid, fungicides and the like.

Examples of the physiologically active substance include vitamins such as vitamin B1 and folic acid; amino acids such as arginine and alanine; soybean flour, wheat germ, pressed barley, peptone, cottonseed starch, yeast extract, meat extract, and corn steep liquor. , Nitrogen sources such as ammonium sulfate, sodium nitrate, urea; tomato paste, glycerin, starch, glucose, galactose, dextrin, bacto (registered trademark) soyton, carbohydrates such as glucose, sucrose, carbon sources such as fat; salt, calcium carbonate Inorganic salts such as: bovine fetal serum (BSA) and the like; growth regulators such as auxin and kinetin and the like can be mentioned.

Examples of the water-soluble compound include glucose, ascorbic acid, Japanese Pharmacopoeia honey, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM] [CF ₃ SO ₃ ]), 1-butyl-3-. Methylimidazolium trifluoromethanesulfonate ([BMIM] [CF ₃ SO ₃ ]), (1-butyl-3-methylimidazolium = chloride ([BMIM] [Cl])), glycerin, polyglycerin, lactose, etc. may be mentioned. ..

Examples of the water-insoluble compound include inorganic fillers such as titanium oxide, activated carbon, zeolite, and silica.

The content of the other components in the liquid for liquid marble is not particularly limited as long as the effect of the present invention can be obtained, and can be appropriately selected depending on the intended purpose.

(Liquid Marble)
The liquid marble of the present invention is formed by encapsulating the liquid for liquid marble of the present invention with external particles.
The liquid marble means particles in which the surface of the liquid for liquid marble is covered with the external particles. Therefore, in the present specification, "the liquid for liquid marble is encapsulated by the external particles" is synonymous with "the state where the surface of the liquid for liquid marble is covered with the external particles".
The liquid marble is not particularly limited as long as it is coated to the extent that the effects of the present invention can be exhibited, and the surface of the liquid for liquid marble may be completely covered with the external particles. , May be partially covered.

The liquid marble contains a liquid for liquid marble, an external additive, and if necessary, other components.

<Liquid for liquid marble>
The liquid for liquid marble is the above-mentioned liquid for liquid marble of the present invention, and contains a biocatalyst, water, a thickener, and if necessary, other components.
The properties of the biocatalyst, the water, and the thickener are as described in the item "(Liquid for liquid marble)".

The content of the water in the liquid for liquid marble is such that a plurality of the liquid marbles are collected, subjected to a centrifuge, separated into external particles and an inclusion liquid (the liquid for liquid marble), and then the inclusion liquid is curled. It can be analyzed with a Fisher Moisture Analyzer.

The content of the thickener in the liquid for liquid marble is determined by collecting a plurality of the liquid marbles, subjecting them to a centrifuge, separating them into external particles and an encapsulating liquid (the liquid for liquid marble), and then the encapsulating liquid. Can be measured by liquid chromatography, NMR analysis, mass analysis, elemental analysis and the like alone or in combination.

<External particles>
The external particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, composite particles containing two kinds of hydrophobic materials, composite particles containing an amphipathic material and a hydrophobic material, and the like. Can be mentioned. These may be used alone or in combination of two or more. Among these, composite particles containing two kinds of hydrophobic materials and composite particles containing an amphipathic material and a hydrophobic material are preferable in that they suppress coalescence of droplets and are excellent in durability against external force.

The number average particle size d50e of the external particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 nm or more and 10 μm or less, and more preferably 500 nm or more and 5 μm or less. When the number average particle size d50e of the external particles is 1 nm or more and 10 μm or less, the amount of the external particles adsorbed on the droplets made of the liquid marble liquid can be increased, so that the liquid marble liquid can be used. Can be stabilized.
The number average particle size d50e of the external particles is the average value of the longest diameters of each of the 10 arbitrarily selected particles in the scanning electron microscope image obtained by observing the external particles in bulk.

When the present inventor manufactures a liquid marble using only particles having a large particle size, the contact area between the particles covering the droplets of the liquid for liquid marble and the droplets becomes small, and the droplets are exposed. There will be some spots. As a result, we have found that the strength is very weak against external force and it is difficult to improve the durability.
Further, if the liquid marble is manufactured using only particles having a small particle size, the durability against an external force is improved, but the deformation is likely to occur, and there is a problem that the liquid marbles may be united with each other due to the capillary phenomenon. I found that.

Therefore, in order to suppress the coalescence of droplets, the present inventor has two kinds of solid particles having specific physical characteristics and different particle sizes (hydrophobic solid particles A having a large particle size and hydrophobicity having a small particle size). It has been found that it is more preferable to use composite particles containing solid particles B) in that the coalescence of liquid marbles can be suppressed.
Furthermore, the present inventor can further suppress the coalescence of liquid marbles by forming composite particles in which the hydrophobic solid particles B are arranged on the surface of the hydrophobic solid particles A, and more various liquids can be liquid. It has been found that the surface of drops can be coated and a more durable liquid marble can be formed.

ただし、式２中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｂは、疎水性固体粒子Ｂの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｂは、疎水性固体粒子Ｂの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｂは、疎水性固体粒子Ｂの体積（μｍ^３）を表す。 << Composite particles >>
The composite particles contain hydrophobic solid particles A and hydrophobic solid particles B, preferably have solid particles C, and further contain other components, if necessary.
The composite particles further have the hydrophobic solid particles B on the surface of the hydrophobic solid particles A, and the contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less. The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less, and the number average particle size d50a of the hydrophobic solid particles A and the number average particle size d50b of the hydrophobic solid particles B. The ratio (d50a / d50b) is 10 or more and 100 or less, and the coverage rate CR ₂ represented by the following formula 2 is 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ).

ただし、式１中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｃは、固体粒子Ｃの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｃは、固体粒子Ｃの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｃは、固体粒子Ｃの体積（μｍ^３）を表す。 The composite particles further have solid particles C on the surface of the hydrophobic solid particles A, and the contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less, and the solid particles. The contact angle CAc1 of C with water is less than 110 °, the contact angle CAc2 of the solid particles C with n-hexane is less than 110 °, and the number average particle size d50a of the hydrophobic solid particles A The ratio (d50a / d50c) of the solid particles C to the number average particle size d50c is 10 or more and 100 or less, and the coverage CR ₁ represented by the following formula 1 is 0.3% or more and 18% or less. It is preferable to have.

However, in the formula 1, Xa represents the mass (g) of the hydrophobic solid particle A, Xc represents the mass (g) of the solid particle C, and Ya represents the density (g / μm) of the hydrophobic solid particle A. ³ ), Yc represents the density of the solid particle C (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zc represents the volume of the solid particle C (μm ³ ). ).

-Hydrophobic solid particles A-
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less. If the contact angle CAa of the hydrophobic solid particles A with water is less than 110 °, the liquid marbles are difficult to form and may coalesce. On the other hand, when the contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less, the coalescence of the liquid marbles can be suppressed.
As used herein, the term "hydrophobic" means that the contact angle (CAa or CAb) with water measured by the contact angle measuring method described later is 110 ° or more and 180 ° or less.

The contact angle CAa of the hydrophobic solid particles A with water can be measured according to a conventionally known contact angle measuring method (θ / 2 method). Specifically, a plate-like body obtained by heat-pressing the constituent material of the hydrophobic solid particle A or a plate-shaped body obtained by casting a dispersion liquid of the constituent material of the hydrophobic solid particle A onto a substrate by a casting method. Is used as a measurement sample, and the angle formed by the liquid level when 10 μL of water is placed on the plate-shaped body with a microsyringe and the surface of the plate-shaped body can be measured as the contact angle CAa with the water. can.

The conditions of the hot press in producing a plate-like body obtained by hot pressing the constituent material of the hydrophobic solid particles A are as follows.
[Hot press conditions]
・ Temperature: 200 ℃
・ Total pressure: 30kN
-Time: 5 minutes from the time of reaching 30 kN-Work content: Sample (constituent material of hydrophobic solid particles A) Powder is placed in a powder molding die (depth: 20 mm) with an inner diameter (φ) of 10 mm, and the height from the bottom. Fill to 10 mm and set in a press machine (device name: SA-302 desktop test press, manufacturing company name: Tester Sangyo Co., Ltd.). After confirming that the mold has reached a predetermined temperature (200 ° C.), the press is started and pressed to a predetermined pressure (30 kN). Press for 5 minutes from the time when the predetermined pressure is reached to prepare a measurement sample (plate-shaped body) of the contact angle.

Further, the plate-like body obtained by casting the dispersion liquid of the constituent material of the hydrophobic solid particle A onto the substrate by the casting method first has a diameter in the production of the plate-like body obtained by hot-pressing the constituent material of the hydrophobic solid particle A. PTFE (polytetrafluoroethylene, average thickness: 200 μm) punched to 10 mm was placed in the powder molding mold, and the sample (component of the hydrophobic solid particle A) powder was sprinkled substantially uniformly on the powder molding mold, and the heat was applied. It can be obtained by pressing.

The method for sprinkling the sample (constituent material of the hydrophobic solid particles A) powder substantially uniformly is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method for sprinkling dry sample powder, a sample dispersion liquid. There is a method of sprinkling.
The solvent used for the sample dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanol. When the sample dispersion is used, it is possible to easily handle a sample having a small bulk density.

When the hydrophobic solid particle A as a constituent material in the composite particle is used as a measurement sample, the material of the hydrophobic solid particle A in the composite particle is gas chromatography (GC-MS) or nuclear magnetic resonance (GC-MS). The material is obtained by specifying by NMR), infrared spectroscopy (IR), etc., and the contact angle CAa with the water is measured using the obtained material, or the hydrophobic solid particle A is obtained from the composite particles. The plate-like body can be prepared from the isolated and isolated hydrophobic solid particles A, and the contact angle CAa between the plate-like body and water can be measured.

The method for isolating the hydrophobic solid particles A from the composite particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alcohol is added to the composite particles to add the hydrophobic solid particles A. Examples thereof include a method of filtering the liquid in which the particles are dispersed.
The alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanol and isopropanol. These may be used alone or in combination of two or more. Among these, ethanol is particularly preferable because it is highly volatile and can be easily dried after filtration.

The number average particle size d50a of the hydrophobic solid particles A is not particularly limited as long as the effect of the present invention can be obtained, and can be appropriately selected depending on the intended purpose, but is 0.1 μm or more and 10 μm or less. It is preferably 0.5 μm or more and 5 μm or less, more preferably. When the number average particle size d50a of the hydrophobic solid particles A is 0.1 μm or more and 10 μm or less, the amount of the hydrophobic solid particles A adsorbed on the droplets made of the liquid for liquid marble can be increased. , The liquid for liquid marble can be more stabilized.
The number average particle size d50a of the hydrophobic solid particles A is 10 particles arbitrarily selected in a scanning electron microscope image obtained by observing the hydrophobic solid particles A isolated by the above method in bulk. This is the average value of the longest diameter.

The material of the hydrophobic solid particles A is not particularly limited as long as the contact angle CAa of the hydrophobic solid particles A with water satisfies 110 ° or more and 180 ° or less, and is appropriately selected according to the purpose. Examples thereof include organic materials and inorganic materials. These may be used alone or in combination of two or more.

Examples of the organic material include polymer materials.
Examples of the polymer material include resins and the like.
Examples of the resin include fluororesin, silicone resin, cellulose, and a copolymer containing at least one resin selected from these.
Examples of the fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF). Examples thereof include polychlorotrifluoroethylene (PCTFE) and ethylene chlorotrifluoroethylene copolymer (ECTFE).
Examples of the silicone resin include methyl silicone resin and urethane-modified silicone resin.

Examples of the inorganic material include silica and calcium carbonate.
Examples of the silica include fumed silica and silica spherical fine particles (QSG series: manufactured by Shin-Etsu Chemical Co., Ltd.).

The surface of the organic material and the inorganic material may be further hydrophobized. As the organic material and the inorganic material, even if the physical properties of the materials do not have hydrophobicity, those having a hydrophobic surface imparted by the hydrophobic treatment can be used.

Examples of the hydrophobized organic material include hydrophobized starch. Examples of the hydrophobized starch include octenyl succinate corn starch ester aluminum (trade name: Octier, manufactured by Nissho Chemical Co., Ltd.).
It can be confirmed by measuring the contact angle that the organic material is hydrophobized. It is confirmed that the organic material is hydrophobized by measuring the contact angle of the sample compression-molded (heat press, etc.) by the above-mentioned method and confirming that the contact angle with water is 110 ° or more. can do.

Examples of the hydrophobized inorganic material include stearic acid-treated calcium carbonate. Examples of the stearic acid-treated calcium carbonate include those obtained by mixing 100 g of calcium carbonate with 10 g of stearic acid and 500 mL of methanol, distilling off methanol under reduced pressure, and then heating and drying at 50 ° C.
It can be confirmed by measuring the contact angle that the inorganic material is hydrophobized. For example, in the case of stearic acid treatment as the hydrophobization, the contact angle of the compression-molded (heat-pressed, etc.) sample is measured to confirm that the contact angle with water is 110 ° or more. It can be confirmed that the stearic acid treatment has been performed.

The shape of the hydrophobic solid particle A is not particularly limited as long as the effect of the present invention can be obtained, and can be appropriately selected depending on the intended purpose. For example, spherical, true sphere, flat, needle-shaped, etc. Examples include columnar, amorphous, and rectangular parallelepiped.

The structure of the hydrophobic solid particles A is not particularly limited as long as the effects of the present invention can be obtained, and can be appropriately selected depending on the intended purpose. Examples thereof include porous, hollow, and layered. ..

-Hydrophobic solid particles B-
The hydrophobic solid particles B exist on the surface of the hydrophobic solid particles A and cover the surface of the hydrophobic solid particles A.
In the present specification, the fact that the hydrophobic solid particles B coat the surface of the hydrophobic solid particles A is not particularly limited as long as it can be coated to the extent that the effects of the present invention can be exhibited, and the coverage rate described later is not particularly limited. It is preferable to cover in a range that satisfies CR ₂ .
As used herein, the term "surface of hydrophobic solid particles A" means an exposed surface of hydrophobic solid particles A.

The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less. If the contact angle CAb of the hydrophobic solid particles B with water is less than 110 °, the liquid marbles are difficult to form and may coalesce. On the other hand, when the contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less, the coalescence of the liquid marbles can be satisfactorily suppressed.

The contact angle CAb of the hydrophobic solid particles B with water is measured according to a conventionally known contact angle measuring method (θ / 2 method), similarly to the contact angle CAa of the hydrophobic solid particles A with water. can do. Specifically, a plate-like body obtained by hot-pressing the constituent material of the hydrophobic solid particle B, or a plate-shaped body obtained by casting a dispersion liquid of the constituent material of the hydrophobic solid particle B onto a substrate by a casting method. Is used as a measurement sample, and the angle formed by the liquid level when 10 μL of water is placed on the plate-shaped body with a microsyringe and the surface of the plate-shaped body can be measured as the contact angle CAb with the water. can.

The method for producing a plate-like body obtained by hot-pressing the constituent material of the hydrophobic solid particle B and a dispersion liquid of the constituent material of the hydrophobic solid particle B on a substrate by a casting method is described above. The same is true for the hydrophobic solid particles A.
Further, a method for measuring the contact angle CAb when the hydrophobic solid particle B as a constituent material in the composite particle is used as a measurement sample, and a method for isolating the hydrophobic solid particle B from the composite particle are also described as hydrophobic. This is the same as in the case of the sex solid particle A.

The number average particle size d50b of the hydrophobic solid particles B is not particularly limited as long as the effect of the present invention can be obtained, and can be appropriately selected depending on the intended purpose, but is 0.01 μm or more and 0.5 μm or more. The following is preferable, and 0.01 μm or more and 0.05 μm or less is more preferable. When the number average particle size d50b of the hydrophobic solid particles B is 0.01 μm or more and 0.5 μm or less, the amount of the hydrophobic solid particles B adsorbed on the droplets made of the liquid for liquid marble can be increased. Therefore, the liquid marble can be more stabilized.
The number average particle size d50b of the hydrophobic solid particles B is 10 particles arbitrarily selected in a scanning electron microscope image obtained by observing the hydrophobic solid particles B isolated by the above method in bulk. This is the average value of the longest diameter.

The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B (also referred to as “particle size ratio (d50a / d50b)”). There is no particular limitation, and it can be appropriately selected depending on the intended purpose, but it is preferably 10 or more and 100 or less, and more preferably 10 or more and 30 or less. If the ratio (d50a / d50b) is less than 10, it may be difficult to form composite particles, and if the ratio (d50a / d50b) exceeds 100, composite particles can be formed, but the liquid marble is formed. It may be difficult to manufacture stably. On the other hand, when the ratio (d50a / d50b) is 10 or more and 100 or less, it is advantageous in that a liquid marble having excellent coalescence inhibitory property and durability against external force can be formed.

The material of the hydrophobic solid particles B is not particularly limited as long as the contact angle CAb of the hydrophobic solid particles B with water satisfies 110 ° or more and 180 ° or less, and is appropriately selected according to the purpose. Examples thereof include organic materials and inorganic materials. These may be used alone or in combination of two or more.

Examples of the organic material include polymer materials.
Examples of the polymer material include resins and the like.
Examples of the resin include fluororesin, silicone resin, cellulose, and a copolymer containing at least one resin selected from these.
Examples of the fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF). Examples thereof include polychlorotrifluoroethylene (PCTFE) and ethylene chlorotrifluoroethylene copolymer (ECTFE).
Examples of the silicone resin include methyl silicone resin and urethane-modified silicone resin.

Examples of the inorganic material include silica and calcium carbonate.
Examples of the silica include fumed silica and silica spherical fine particles (QSG series: manufactured by Shin-Etsu Chemical Co., Ltd.).

The surface of the organic material and the inorganic material may be further hydrophobized. As the organic material and the inorganic material, even if the physical properties of the materials do not have hydrophobicity, those having a hydrophobic surface imparted by the hydrophobic treatment can be used.
As the hydrophobized organic material and the hydrophobized inorganic material, the same materials as those mentioned in the hydrophobic solid particles A can be used, and the organic material is hydrophobized. As a method for confirming that the inorganic material is hydrophobic, the same method as that described for the hydrophobic solid particles A can be used.

The shape of the hydrophobic solid particles B is not particularly limited as long as the effect of the present invention can be obtained, and can be appropriately selected depending on the intended purpose. For example, spherical, true sphere, flat, needle-shaped, etc. Examples include columnar, amorphous, and rectangular parallelepiped.

The structure of the hydrophobic solid particles B is not particularly limited as long as the effects of the present invention can be obtained, and can be appropriately selected depending on the intended purpose. Examples thereof include porous, hollow, and layered. ..

The material, shape, or structure of the hydrophobic solid particle B may be the same material, shape, or structure as the hydrophobic solid particle A, or may be different as long as the effect of the present invention is exhibited. However, it is preferable that at least one of the hydrophobic solid particles A and the hydrophobic solid particles B is at least one of a fluororesin, silica, stearic acid-treated calcium carbonate, and hydrophobicized starch.

ただし、式２中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｂは、疎水性固体粒子Ｂの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｂは、疎水性固体粒子Ｂの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｂは、疎水性固体粒子Ｂの体積（μｍ^３）を表す。 The coverage CR ₂ represented by the following formula 2 of the composite particles is not particularly limited, and is not particularly limited as long as the effect of the present invention can be obtained, and can be appropriately selected depending on the intended purpose. , 50% or more and 500% or less are preferable, and 100% or more and 200% or less are more preferable. When the coverage CR ₂ is less than 50%, contact with water may be dominated by the hydrophobic solid particles A, making it difficult to obtain a coalescence suppressing effect, and the coverage CR ₂ is 500. If it exceeds%, the hydrophobic solid particles B will be aggregated and deposited on the surface of the hydrophobic solid particles A, and the contact with water will be dominated by the hydrophobic solid particles B. (1) It may be difficult to obtain the inhibitory effect. On the other hand, when the coverage CR ₂ is 50% or more and 500% or less, it is preferable that the liquid marble having excellent coalescence inhibitory property and durability against external force can be formed.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ).

The mass (g) and the volume (μm ³ ) may be per unit particle, but may be per bulk as long as the mass and volume of the composite particle to be used are numerical values obtained by the same standard. As the volume of each particle, the average value of the volumes of the used particles may be used, or the volume when the volume is assumed to be a true sphere having the obtained number average particle diameter as the diameter may be calculated and used. ..
The coverage CR ₂ means the abundance of the hydrophobic solid particles B present on the surface of the hydrophobic solid particles A.

The coverage CR ₂ is obtained as follows.
First, when the composite particles are true spheres (the hydrophobic solid particles A and the hydrophobic solid particles B are also true spheres), the number average particle size d50a of the hydrophobic solid particles A and the hydrophobic solid particles B The sum of the numbers obtained by dividing each of the number average particle size d50b by 2 (d50a / 2 + d50b / 2) is taken as the radius of the composite particle, and the surface surface of the composite particle (4π (d50a / 2 + d50b / 2) ² ) is calculated.
Next, the area of the hydrophobic solid particle B covering the surface of the hydrophobic solid particle A is a line segment connecting the center of one hydrophobic solid particle A and the center of the hydrophobic solid particle B. When the area of the cross section of the hydrophobic solid particle B including the center of the hydrophobic solid particle B (hereinafter referred to as cross-sectional area Sb) is defined as It is obtained by multiplying the number of the hydrophobic solid particles B to be coated. The cross-sectional area Sb is expressed as π (d50b / 2) ² using the number average particle size d50b of the hydrophobic solid particles B. Further, the number of the hydrophobic solid particles B to be coated on one of the hydrophobic solid particles A is the mass Xa, the density Ya, and the volume Za of the hydrophobic solid particles A, and the hydrophobic solid particles B. Using the mass Xb, the density Yb, and the volume Zb, {Xb (g) / Yb (g / μm ³ ) / Zb (g / μm ³ )} / {Xa (g) / Ya (g / μm ³ ) ) / Za (g / μm ³ )}.

FIG. 1A is a schematic diagram showing an example of the composite particles. FIG. 1B is a schematic view showing an example of a cross section in the XZ plane in FIG. 1A.
As shown in FIG. 1A, the composite particle 10 of the present invention contains the hydrophobic solid particle A11 and the hydrophobic solid particle B12, and the hydrophobic solid particle B12 covers the surface of the hydrophobic solid particle A11. When calculating the coverage rate CR ₁ , the surface area of the composite particles 10 is calculated from the number average particle size d50a of the hydrophobic solid particles A11 and the number average particle size d50b of the hydrophobic solid particles B12, and the area of the composite particles 10 is calculated. It is calculated as the ratio of the area occupied by the hydrophobic solid particles B12 to the surface area. As shown in FIG. 1B, the area occupied by the hydrophobic solid particles B12 is orthogonal to the line connecting the center of the hydrophobic solid particles A11 and the center of the hydrophobic solid particles B12, and is a hydrophobic solid. It is obtained by multiplying the cross-sectional area Sb of the hydrophobic solid particles B12 including the center of the particles B12 by the number of the hydrophobic solid particles B12 to be coated on one hydrophobic solid particle A11.

-Solid particle C-
The solid particles C exist on the surface of the hydrophobic solid particles A and cover the surface of the hydrophobic solid particles A together with the hydrophobic solid particles B.
In the present specification, the fact that the solid particles C coat the surface of the hydrophobic solid particles A together with the hydrophobic solid particles B is not particularly limited as long as they can be coated to the extent that the effects of the present invention can be exhibited. , It is preferable to cover in a range that satisfies the coverage rate CR ₁ described later.

The present inventor has found that when a liquid marble coated with composite particles made of only the hydrophobic material is used in water, it floats on the water surface and the shape of the liquid marble cannot be maintained. In order to produce valuable resources from the biocatalyst, it may be desired that the liquid marble can be put into water and its shape can be maintained for a long period of time.

Therefore, the present inventor has a contact angle CAa of the hydrophobic solid particle A with water, a contact angle CAc1 of the solid particle C with water, and a contact angle CAc2 of the solid particle C with n-hexane. It has been found that a liquid marble that can be used in water can be formed by setting a specific range.
Therefore, when the composite particles contain the solid particles C, the liquid marble is advantageous in that it suppresses the coalescence of droplets, has excellent durability against external force, and can be used even in water. ..

The contact angle CAc1 of the solid particles C with water is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably less than 110 °. When the contact angle CAc1 of the solid particles C with water is 110 ° or more, the liquid marble may not be used in water because it floats on the water surface, and the liquid marbles are united. It may end up. On the other hand, when the contact angle CAc1 of the solid particles C with water is less than 110 °, the liquid marble can be used in water and the coalescence of the liquid marble can be suppressed.

The contact angle CAc1 of the solid particles C with water shall be measured according to a conventionally known contact angle measuring method (θ / 2 method), similarly to the contact angle CAa of the hydrophobic solid particles A with water. Can be done. Specifically, a plate-like body obtained by hot-pressing the constituent material of the solid particle C or a plate-shaped body obtained by casting a dispersion liquid of the constituent material of the solid particle C onto a substrate by a casting method is used as a measurement sample. The angle formed by the liquid level when 10 μL of water is placed on the plate-shaped body with a microsyringe and the surface of the plate-shaped body can be measured as the contact angle CAc1 with the water.

The contact angle CAc2 of the solid particles C with n-hexane is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably less than 110 °. When the contact angle CAc2 of the solid particles C with n-hexane is 110 ° or more, the liquid marble floats on the water surface and cannot be used in water, and the hydrophobic solid particles A and the hydrophobic solid particles A cannot be used. Since the affinity is lost, the liquid marbles are united. On the other hand, when the contact angle CAc2 of the solid particles C with n-hexane is less than 110 °, the liquid marble can be used in water and the affinity with the hydrophobic solid particles A can be ensured. Therefore, it is possible to suppress the union of the liquid marbles.

The contact angle CAc2 of the solid particles C with n-hexane is measured according to a conventionally known contact angle measuring method (θ / 2 method), similarly to the contact angle CAa of the hydrophobic solid particles A with water. can do. Specifically, a plate-like body obtained by hot-pressing the constituent material of the solid particle C or a plate-shaped body obtained by casting a dispersion liquid of the constituent material of the solid particle C onto a substrate by a casting method is used as a measurement sample. The angle formed by the liquid level when 10 μL of n-hexane is placed on the plate-shaped body with a microsyringe and the surface of the plate-shaped body can be measured as the contact angle CAc2 with water.

The method for producing a plate-like body obtained by hot-pressing the constituent material of the solid particle C and a dispersion liquid of the constituent material of the solid particle C on a substrate by a casting method to form a plate-like body is the hydrophobic solid particle. This is the same as in the case of A.
Further, the method for measuring the contact angle CAc when the solid particle C as a constituent material of the composite particle is used as a measurement sample, and the method for isolating the solid particle C from the composite particle are also the hydrophobic solid particle A. It is the same as the case of.

The number average particle size d50c of the solid particles C is not particularly limited as long as the effect of the present invention can be obtained, and can be appropriately selected depending on the intended purpose, but is preferably 0.01 μm or more and 5 μm or less. More preferably, it is 0.1 μm or more and 1 μm or less. When the number average particle size d50c of the solid particles C is 0.01 μm or more and 5 μm or less, the amount of the solid particles C adsorbed on the droplets made of the liquid marble liquid can be increased, and the solid particles can be adsorbed. Since C is easily adsorbed to the hydrophobic solid particles A, the liquid marble can be further stabilized.
The number average particle size d50c of the solid particles C is the average of the longest diameters of 10 arbitrarily selected particles in a scanning electron microscope image obtained by observing the solid particles C isolated by the above method in bulk. The value.

The ratio (d50a / d50c) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50c of the solid particles C is 10 or more and 100 or less, but 10 or more and 50 or less is preferable. When the ratio (d50a / d50c) is less than 10, it becomes difficult to form the composite particles, and when the ratio (d50a / d50c) exceeds 100, the composite particles can be formed but the liquid marble is stable. It becomes difficult to manufacture the particles. On the other hand, when the ratio (d50a / d50c) is 10 or more and 100 or less, it is advantageous in that it can form the liquid marble which is excellent in coalescence inhibitory property and durability against external force and can be used in water. Is.

The ratio of the average particle size d50a of the hydrophobic solid particles A to the average particle size d50b of the hydrophobic solid particles B and the average particle size d50c of the solid particles C (d50a / [(d50b + d50c)). / 2]) (also referred to as "particle size ratio (d50a / [(d50b + d50c) / 2)") is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 or more and 100 or less. More preferably, it is 10 or more and 30 or less. If the ratio (d50a / [(d50b + d50c) / 2]) is less than 10, it may be difficult to form composite particles, and the ratio (d50a / [(d50b + d50c) / 2]) exceeds 100. Although composite particles can be formed, it may be difficult to stably produce the liquid marble. On the other hand, when the ratio (d50a / [(d50b + d50c) / 2]) is 10 or more and 100 or less, it is advantageous in that the liquid marble having excellent coalescence inhibitory property and durability against external force can be formed. be.

The content of the solid particles C (% by mass) with respect to the total amount of the content (% by mass) of the hydrophobic solid particles A and the content (% by mass) of the solid particles C in the composite particles (hereinafter, ". The content of solid particles C (sometimes referred to as 1) is not particularly limited as long as the coverage CR ₁ can be satisfied, and can be appropriately selected depending on the intended purpose, but is 0.1 mass. % Or more and less than 5.5% by mass is preferable, and 0.6% by mass or more and 1.1% by mass or less is more preferable. The content 1 of the solid particles C can be adjusted by the amount of the hydrophobic solid particles A and the solid particles C added when the composite particles are produced.

Further, the total of the content (mass%) of the hydrophobic solid particles A, the content (mass%) of the solid particles C, and the content (mass%) of the hydrophobic solid particles B described later in the composite particles. The content (% by mass) of the solid particles C with respect to the amount (hereinafter, may be referred to as “content rate 2 of the solid particles C”) is not particularly limited as long as the coverage rate CR ₁ can be satisfied. However, it can be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass or more and less than 5% by mass, and more preferably 0.5% by mass or more and 1.0% by mass or less. The content 2 of the solid particles C can be adjusted by the amount of the hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B added when the composite particles are produced.

The ratio of the content 2 (mass%) of the solid particles C to the content (% by mass) of the hydrophobic solid particles B (content 2 of the solid particles C / content of the hydrophobic solid particles B) There is no particular limitation, and it can be appropriately selected depending on the intended purpose, but it is preferably more than 1.8 and 96.0 or less, and more preferably 9.5 or more and 96.0 or less. When the ratio (content 2 of solid particles C / content of hydrophobic solid particles B) is more than 1.8 and 96.0 or less, the liquid marble does not float on the water surface and can be suitably used in water. can. On the other hand, if it exceeds 96.0, the hydrophobic solid particles A and the solid particles C may be decomposed in water, and the shape of the liquid marble may not be maintained, which is 1.8 or less. Then, the liquid marble floats on the surface of the water, and the liquid marble may not be used in water.

As the material of the solid particles C, the contact angle CAc1 of the solid particles C with water is less than 110 °, and the contact angle CAc2 of the solid particles C with n-hexane is less than 110 °. If there is, there is no particular limitation, and it can be appropriately selected depending on the intended purpose, and examples thereof include organic materials and inorganic materials. These may be used alone or in combination of two or more. Among these, a material having amphipathic properties is preferable.

Examples of the organic material include hydroxypropyl cellulose, hydroxypropyl methyl cellulose, poly (N-isopropylacrylamide), polyethylene oxide, polyethylene glycol, phospholipids and the like. Among these, it is preferable that the organic material is at least one of hydroxypropyl cellulose and hydroxypropyl methyl cellulose from the viewpoint of not impairing the function of the biocatalyst.
Examples of the inorganic material include calcium carbonate and the like.

The surface of the organic material and the inorganic material has a contact angle CAc1 of the solid particles C with water of less than 110 ° and a contact angle CAc2 of the solid particles C with n-hexane of 110 °. It may be processed so as to be less than. The surface of the organic material and the inorganic material has physical characteristics such that the contact angle CAc1 is less than 110 ° and the contact angle CAc2 is less than 110 °. By the treatment, a material having a physical property such that the contact angle CAc1 is less than 110 ° and the contact angle CAc2 is less than 110 ° can be used on the surface of the material.

Examples of the surface-treated organic material include ozone-oxidized polycarbonate resin and the like.

It is confirmed by measuring the contact angle that the organic material or the inorganic material is provided with physical properties such that the contact angle CAc1 is less than 110 ° and the contact angle CAc2 is less than 110 °. be able to. Measure the contact angle of the sample compression-molded (heat press, etc.) by the method described above to confirm that the contact angle with water is less than 110 ° and the contact angle with n-hexane is less than 110 °. Thereby, it can be confirmed that the organic material or the inorganic material is imparted with physical properties such that the contact angle CAc1 is less than 110 ° and the contact angle CAc2 is less than 110 °.

The shape of the solid particles C is not particularly limited as long as the effects of the present invention can be obtained, and can be appropriately selected depending on the intended purpose. Examples include amorphous and rectangular parallelepiped.

The structure of the solid particles C is not particularly limited as long as the effects of the present invention can be exhibited, and can be appropriately selected depending on the intended purpose. Examples thereof include porous, hollow, and layered.

ただし、式１中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｃは、固体粒子Ｃの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｃは、固体粒子Ｃの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｃは、固体粒子Ｃの体積（μｍ^３）を表す。 The composite particles have a coverage CR ₁ represented by the following formula 1 of 0.3% or more and 18% or less, but preferably 0.3% or more and 10% or less. When the coverage CR ₁ is less than 0.3%, the hydrophobic solid particles A dominate the contact with water, and when used in water, they float on the water surface and cannot be used in water. Further, it becomes difficult to obtain the effect of suppressing coalescence, and when the coverage rate CR ₁ exceeds 18%, the solid particles C are aggregated and deposited on the surface of the hydrophobic solid particles A, and come into contact with water. However, since the solid particles C become dominant, it becomes difficult to obtain the effect of suppressing coalescence, and the hydrophobic solid particles A and the solid particles C are decomposed in water, so that the shape of the liquid marble is changed. Can't be maintained. On the other hand, when the coverage CR ₁ is 0.3% or more and 18% or less, the liquid marble which is excellent in coalescence inhibitory property and durability against external force and can be used in water can be formed. It is advantageous in that.

However, in the formula 1, Xa represents the mass (g) of the hydrophobic solid particle A, Xc represents the mass (g) of the solid particle C, and Ya represents the density (g / μm) of the hydrophobic solid particle A. ³ ), Yc represents the density of the solid particle C (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zc represents the volume of the solid particle C (μm ³ ). ).

The mass (g) and the volume (μm ³ ) may be per unit particle, but may be per bulk as long as the mass and volume of the composite particle to be used are numerical values obtained by the same standard. As the volume of each particle, the average value of the volumes of the used particles may be used, or the volume when the volume is assumed to be a true sphere having the obtained number average particle diameter as the diameter may be calculated and used. ..
The coverage CR ₁ means the abundance of the solid particles C present on the surface of the hydrophobic solid particles A.

The coverage rate CR ₁ is obtained in the same manner as the coverage rate CR ₂ as follows.
First, when the composite particles are true spheres (the hydrophobic solid particles A and the solid particles C are also true spheres), the number average particle size d50a of the hydrophobic solid particles A and the number average grains of the solid particles C are used. The sum of the numbers obtained by dividing the diameter d50c by 2 (d50a / 2 + d50c / 2) is used as the radius of the composite particle, and the surface area of the composite particle (4π (d50a / 2 + d50c / 2) ² ) is calculated.
Next, the area of the solid particles C covering the surface of the hydrophobic solid particles A is orthogonal to the line connecting the center of one hydrophobic solid particle A and the center of the solid particles C. Then, when the area of the cross section of the solid particles C including the center of the solid particles C (hereinafter referred to as “cross-sectional area Sc”), the solid particles C to be coated on one of the hydrophobic solid particles A. It is calculated by multiplying the number of particles. The cross-sectional area Sc is expressed as π (d50c / 2) ² using the number average particle size d50c of the solid particles C. The number of the solid particles C to be coated on one hydrophobic solid particle A is the mass Xa, the density Ya, and the volume Za of the hydrophobic solid particle A, and the mass Xc, the density of the solid particle C. Using Yc and volume Zc, {Xc (g) / Yc (g / μm ³ ) / Zc (g / μm ³ )} / {Xa (g) / Ya (g / μm ³ ) / Za ( It can be expressed as g / μm ³ )}.

ただし、式３中、被覆率ＣＲ_１は、前記式１により求められる値を表し、被覆率ＣＲ_２は、前記式２により求められる値を表す。 The coverage CR ₃ represented by the following formula 3 of the composite particles is not particularly limited, and is not particularly limited as long as the effects of the present invention can be obtained, and can be appropriately selected depending on the intended purpose. , 50% or more and 518% or less are preferable, and 100% or more and 210% or less are more preferable. When the coverage CR ₃ is less than 50%, contact with water may be dominated by the hydrophobic solid particles A, making it difficult to obtain a coalescence suppressing effect, and the coverage CR ₃ is 518. When it exceeds%, the solid particles C and the hydrophobic solid particles B are aggregated and deposited on the surface of the hydrophobic solid particles A, and contact with water is caused by the solid particles C and the hydrophobic solid. Since the particles B become dominant, it may be difficult to obtain the effect of suppressing coalescence. On the other hand, when the coverage CR ₃ is 50% or more and 518% or less, it is preferable that the liquid marble having excellent coalescence inhibitory property and durability against external force can be formed.
The coverage rate CR ₃ means the abundance of the solid particles C and the hydrophobic solid particles B present on the surface of the hydrophobic solid particles A.

However, in the formula 3, the coverage rate CR ₁ represents the value obtained by the above formula 1, and the coverage rate CR ₂ represents the value obtained by the above formula 2.

The ratio (CR ₂ / CR ₁ ) between the coverage rate CR ₁ and the coverage rate CR ₂ is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 or more and 300 or less, preferably 20 or more. 290 or less is more preferable. When the ratio (CR ₂ / CR ₁ ) is 5 or more and 300 or less, the liquid marble does not float on the water surface and can be suitably used in water. On the other hand, if it is 5 or less, the hydrophobic solid particles A and the solid particles C may be decomposed in water, and the shape of the liquid marble may not be maintained. If it exceeds 300, the liquid may not be maintained. The marble may float on the surface of the water and the liquid marble may not be usable in water.

-Other ingredients-
The other components in the composite particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, other than the hydrophobic solid particles A and the hydrophobic solid particles B forming the composite particles. Hydrophobic solid particles, additives and the like can be mentioned.

The hydrophobic solid particles other than the hydrophobic solid particles A and the hydrophobic solid particles B forming the composite particles include hydrophobic solid particles other than the hydrophobic solid particles A and the hydrophobic solid particles B forming the composite particles. The sex solid particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, those having the same material as the hydrophobic solid particles A and the hydrophobic solid particles B can be used.

The additive is not particularly limited as long as it can exert the effect of the present invention, and can be appropriately selected depending on the intended purpose. Examples thereof include zinc stearate.

The content of the other components in the composite particles is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected depending on the intended purpose.

－－Manufacturing method of composite particles －－
The method for producing the composite particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the hydrophobic solid particles A, the hydrophobic solid particles B, and further, if necessary, said. Examples thereof include a method in which the solid particles C and the other components are added to a mixer under an inert gas and stirred at 10 rpm for 12 hours.

The method for analyzing the properties of the composite particles is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the following methods.
The obtained composite particles are dispersed by adding alcohol (for example, ethanol, isopropanol, etc.) to separate the hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B, and then filtered off. The mass (g), density (g / μm ³ ), and volume (μm ³ ) of the hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B were determined by the following methods, respectively. Measure.
The mass (g) of the hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B can be measured by a precision balance.
The densities (g / μm ³ ) of the hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B are measured values of true density and are measured by a Gerusac type specific gravity bottle (pycnometer method). be able to. As the density (g / μm ³ ) of the hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B, the catalog value or the literature value of the solid particles used can also be used.
The volumes (μm ³ ) of the hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B can be calculated from the number average particle size of each solid particle.

The isolated number average particle size d50a of the hydrophobic solid particles A, the number average particle size d50c of the solid particles C, and the number average particle size d50b of the hydrophobic solid particles B are the isolated hydrophobic solid particles. A, the solid particle C, and the hydrophobic solid particle B are each photographed using an electron microscope, and the average value of 10 arbitrarily selected longest diameters in the obtained electron microscope image is calculated. be able to.

The contact angle CAa of the isolated hydrophobic solid particle A, the contact angles CAc1 and CAc2 of the isolated solid particle C, and the contact angle CAb of the isolated hydrophobic solid particle B are the composite particles. The isolated hydrophobic solid particles A, the solid particles C, and the hydrophobic solid particles B, which are the constituent materials of the above, are cast on a substrate by a hot-pressed plate-like body or a dispersion liquid casting method to form a plate-like material. A body can be used as a measurement sample, and measurement can be performed from the angle formed by the water or n-hexane and the smooth surface of the measurement sample when 10 μL of water or n-hexane is placed on the measurement sample with a microsyringe. The hot press and the casting method are the same as those described above.

<Other ingredients>
The other components in the liquid marble are not particularly limited and may be appropriately selected depending on the intended purpose.
Further, the content of the other components is not particularly limited and may be appropriately selected depending on the intended purpose.

The number average particle size d50d of the liquid marble is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 15 μm or more and 2.5 mm or less, and more preferably 15 μm or more and 1.0 mm or less. When the number average particle size d50d of the liquid marble is 15 μm or more, the drying of the liquid marble during the droplet processing can be controlled, and the liquid marble can be efficiently manufactured. Further, when the number average particle size d50d of the liquid marbles is 2.5 mm or less, spontaneous identification or bursting of the liquid marbles can be suppressed due to the influence of gravity.
The number average particle diameter d50d of the liquid marble is an average value of the longest diameters of each of the 10 arbitrarily selected liquid marbles in the optical microscope image obtained by observing the liquid marble in bulk.

The method for analyzing the components of the droplets contained in the liquid marble is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the liquid marble is exposed to ethanol vapor, filtered and used for the liquid marble. Examples thereof include a method of separating a liquid (droplet) and the composite particle and analyzing the liquid for liquid marble.

The method for analyzing the liquid for liquid marble is not particularly limited and can be appropriately selected from known methods according to the purpose, and examples thereof include liquid chromatography.

(Liquid marble manufacturing method and liquid marble manufacturing equipment)
The method for producing a liquid marble of the present invention is a method for obtaining a liquid marble by encapsulating the liquid for liquid marble of the present invention with external particles.
The method for producing the liquid marble is not particularly limited as long as the liquid for liquid marble can be encapsulated with the external particles, and can be appropriately selected depending on the intended purpose. It is preferable to include a coating step, and if necessary, other steps are included.

The liquid marble manufacturing apparatus of the present invention is an apparatus for obtaining a liquid marble by encapsulating the liquid for liquid marble of the present invention with external particles.
The liquid marble manufacturing apparatus is not particularly limited as long as the liquid for liquid marble can be encapsulated with the external particles, and can be appropriately selected depending on the intended purpose. It is preferable to have a covering means, and if necessary, other means.

The method for producing a liquid marble is preferably performed by the liquid marble manufacturing apparatus.
Hereinafter, the liquid marble manufacturing apparatus of the present invention will be described together with the description of the liquid marble manufacturing method of the present invention.

<Droplet forming step and droplet forming means>
The droplet forming step is a step of forming droplets from the liquid marble liquid.
The droplet forming means is a means for forming a droplet from the liquid marble liquid.
The droplet forming step can be preferably carried out by the droplet forming means.

The liquid for liquid marble is the above-mentioned liquid for liquid marble of the present invention, and contains a biocatalyst, water, a thickener, and if necessary, other components.
The properties of the biocatalyst, the water, and the thickener are as described in the "<Thickening agent>" item of the "(Liquid for liquid marble)".

The droplet forming means is not particularly limited as long as it can form droplets from the liquid for liquid marble, and can be appropriately selected from known droplet forming means according to the purpose, for example, inkjet. Examples include a method, a dispenser method, and a spray dry method. Among these, a dispenser method is preferable because it has a wide characteristic range in which droplets can be formed, is versatile, and can control the size of droplets by the size of the hole diameter of the head and the extrusion pressure of the filling liquid.

<Surface coating process and surface coating means>
The surface coating step is a step of surface-coating the liquid for liquid marble with external particles having a number average particle size of 1 nm or more and 10 μm or less.
The surface coating means is a means for surface-coating the liquid for liquid marble with external particles having a number average particle diameter of 1 nm or more and 10 μm or less.
The surface coating step can be preferably carried out by the surface coating means.
As used herein, the term "surface coating" is not particularly limited as long as it is coated to the extent that the effects of the present invention can be exhibited, and the surface of the droplets is completely covered with the composite particles. It may be present or may be partially covered.

<< External particles >>
The external particles are not particularly limited and may be appropriately selected depending on the intended purpose, and the same particles as those described in the "<External particles>" item of the "(Liquid Marble)" shall be used. Can be done. Among these, composite particles containing two kinds of hydrophobic materials are preferable in that they suppress the coalescence of droplets and are excellent in durability against external force.

ただし、式２中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｂは、疎水性固体粒子Ｂの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｂは、疎水性固体粒子Ｂの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｂは、疎水性固体粒子Ｂの体積（μｍ^３）を表す。 -Composite particles-
The composite particles are not particularly limited and may be appropriately selected depending on the intended purpose, and the same particles as those described in the "<< Composite particles >>" item of the "(Liquid Marble)" shall be used. Can be done.
As a specific example, the composite particle further has the hydrophobic solid particle B on the surface of the hydrophobic solid particle A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less.
The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B is 10 or more and 100 or less.
The coverage CR ₂ represented by the following formula 2 is 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ).

The method for surface-coating the droplets with the composite particles is not particularly limited as long as the droplets can be brought into contact with the composite particles, and can be appropriately selected depending on the intended purpose, for example, during flight. Examples thereof include a method of spraying the composite particles on the droplets, a method of arranging the droplets in a container in which the composite particles are spread, and the like. Among these, a method of arranging the droplets in a container in which the composite particles are spread is preferable from the viewpoint of excellent controllability of the apparatus.

In the case of the method of arranging the droplets in a container in which the composite particles are spread, the composite particles are coated on the entire surface of the droplets after the droplets are arranged in the container in which the composite particles are spread. It is preferable to include a step of shaking the container, a step of tilting the container, and a step of rolling the droplets while supplying the composite particles to the container. These steps may be performed independently, or any step may be performed followed by another step.

As a means for supplying the composite particles to the container, a commercially available powder supply device can be used, and the mechanism and type of the powder supply device can be appropriately selected according to the properties of the composite particles. ..

-Liquid Marble-
The liquid marble obtained by the surface coating step and the surface coating means is the same as the above-mentioned liquid marble of the present invention.

<Other processes and other means>
The other steps are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a separation step and a recovery step.
The other means are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include separation means and recovery means.
The other steps can be suitably carried out by the other steps, the separation step can be preferably carried out by the separation means, and the recovery step can be preferably carried out by the recovery means.
Among these, it is preferable that the method for producing the liquid marble includes the separation step, and it is preferable that the apparatus for producing the liquid marble includes the separation means.

-Separation process and separation means-
The separation step is a step of separating the composite particles that have not been subjected to the surface coating from the liquid marble in the surface coating step.
The separation means is a means for separating the composite particles that have not been applied to the surface coating from the liquid marble by the surface coating means.
The separation step can be preferably carried out by the separation means.

In the surface coating step, the method for separating the composite particles that have not been subjected to the surface coating and the liquid marble is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the liquid marble. Examples thereof include a method of picking up the liquid and a method of separating the mixture of the liquid marble and the composite particles by utilizing the difference in specific gravity and removing the composite particles. These methods may be performed alone, or any method may be performed followed by another step. Among these, the method using the difference in specific density is preferable from the viewpoint of productivity.

Examples of the method of separating the mixture of the liquid marble and the composite particles by utilizing the specific gravity difference and removing the composite particles include a method of passing the mixture through a push-pull type dust collecting system.

-Recovery process and recovery means-
The recovery step is a step of recovering the liquid marble separated in the separation step.
The collecting means is a means for collecting the liquid marble separated by the separating means.

The method for recovering the separated liquid marble is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of dropping the liquid marble from the container and collecting the liquid marble in a collection container may be used. Can be mentioned. In order to cushion the impact of dropping, the collection container is preferably installed within 200 mm from the container, and the collection container is preferably tilted. Further, it is preferable that the wave and the inner wall thereof are treated with a hydrophobic treatment as the collection container, or the material thereof is preferably made of a hydrophobic material.

(Bioreactor)
The bioreactor of the present invention preferably has the liquid marble of the present invention, preferably has a supporting means, and further has other means, if necessary.
The bioreactor is a device that utilizes the biological reaction of the biocatalyst in the liquid marble.

<Supporting means>
The supporting means is a means for supporting the liquid marble.
The structure and shape of the supporting means are not particularly limited as long as they have a structure and shape capable of supporting the liquid marble, and can be appropriately selected depending on the intended purpose.
When the biocatalyst requires a reaction solution such as a culture solution, the supporting means preferably has a structure and a shape capable of satisfying the reaction solution, and the biocatalyst requires a reaction in the atmosphere. In this case, it is preferable that the structure and shape can hold the atmosphere.
The carrier means may have a function as a reaction field of the bioreactor.

<Other means>
The other means are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include temperature control means, oxygen and carbon dioxide concentration control means, separation means, recovery means and the like.

-Temperature control means-
The temperature adjusting means is a means for adjusting the temperature of the supporting means as the reaction field.
The temperature is not particularly limited and may be appropriately selected depending on the type of the biocatalyst, the desired reaction and the like.

-Oxygen and carbon dioxide concentration means-
The oxygen and carbon dioxide concentration means are means for adjusting the oxygen concentration and the carbon dioxide concentration of the supporting means as the reaction field.
The oxygen concentration and the carbon dioxide concentration are not particularly limited and may be appropriately selected depending on the type of the biocatalyst, the desired reaction and the like.

-Separation means-
The separation means is a means for separating valuable resources produced from the liquid marble.
The separation method is not particularly limited and may be appropriately selected depending on the type of valuable resources produced, the reaction system and the like.

-Recovery means-
The recovery means is a means for recovering valuable resources produced from the liquid marble. The valuable material may be recovered as it is from the carrier means by the recovery means, or may be removed by the recovery means after passing through the separation means.
The recovery method is not particularly limited and may be appropriately selected depending on the type of valuable resources produced, the reaction system and the like.

The bioreactor is not particularly limited as long as the biocatalyst in the liquid marble can be reacted, and the liquid marble may be put into a known reaction field of the bioreactor.
Examples of the known bioreactor include those described in Japanese Patent No. 3283982, Japanese Patent No. 3390377, and the like.

The bioreactor is not particularly limited as long as the biocatalyst in the liquid marble can be reacted, and can be appropriately used depending on the type of substrate and the like, in addition to the production of the valuable material. For example, it can be suitably used for treating or purifying sewage, rivers, lake water, various wastewaters, excess sludge, substances causing malodors, and the like.

The present invention will be specifically described below with reference to experimental examples and reference examples, but the present invention is not limited to these experimental examples and reference examples.

(Experimental Example 1)
-Manufacturing of composite particle 1-
As the hydrophobic solid particles A, polytetrafluoroethylene (PTFE, number average particle size d50a: 1.0 μm, contact angle CAa: 120 °, mass Xa: 100.0 g, density Ya: 2.20 × ^10-12 g / μm ³ , volume Za: 0.52 μm ³ , c, trade name: 430935-100G), and as hydrophobic solid particles B, hydrophobic silica (number average particle size d50b: 0.030 μm, contact angle CAb: 170 °, Mass Xb: 10.6 g, Density Yb: 1.80 x ^10-12 g / μm ³ , Volume Zb: 1.4 x ^10-5 μm ³ , manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: QSG-30) In addition to a V-type container rotary mixer (manufactured by Nishimura Kikai Seisakusho Co., Ltd., device name: NV-5) under an inert gas (nitrogen, 25 ° C.), the composite particles are stirred at 10 rpm for 12 hours. I got 1. The volume of each particle was used by calculating the volume when it was assumed that the number average particle size was a true sphere.

-Manufacturing of Liquid 1 for Liquid Marble-
0.5% by mass of yeast (scientific name: Saccharomyces Cerevisiae, manufactured by Nisshin Flour Milling Group, trade name: dry yeast) and 0.50% by mass of fermented cellulose as a thickener (manufactured by Synaptec Co., Ltd.) in water. , And D-glucose (manufactured by Tokyo Kasei Kogyo Co., Ltd., trade name: G0048) added to 20% by mass at room temperature (25 ° C.) under atmospheric pressure using a syringe equipped with a 32 G syringe needle. ), The droplets were formed at a rate of 1 drop per second, and the formed droplets were arranged in a container (manufactured by PTFE) in which the composite particles 1 were spread to produce Liquid Marble 1.

(Experimental Example 2)
-Manufacturing of composite particles 2-
As the hydrophobic solid particles A, polytetrafluoroethylene (PTFE, number average particle size d50a: 1.0 μm, contact angle CAa: 120 °, mass Xa: 100.0 g, density Ya: 2.20 × ^10-12 g / μm ³ , volume Za: 0.52 μm ³ , c, trade name: 430935-100G), as hydrophobic solid particles B, hydrophobic silica (number average particle size d50b: 0.030 μm, contact angle CAb: 170 °, mass) Xb: 10.6 g, density Yb: 1.80 × ^10-12 g / μm ³ , volume Zb: 1.4 × ^10-5 μm ³ , manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: QSG-30), and As solid particles C, hydroxypropyl cellulose (HPC) (manufactured by Sigma-Aldrich, trade name: 19884-100G) is finely divided (number average particle size d50c: 0.1 μm, contact angle CAc 1: 75 °, contact angle). CAc2: 50 °, mass Xc: 0.12 g, density Yc: 1.3 × ^10-12 g / μm ³ , volume Zc: 5.2 × 10 ^-4 μm ³ ), inert gas (nitrogen, The composite particles 2 were obtained by adding to a V-type container rotary mixer (manufactured by Nishimura Kikai Seisakusho Co., Ltd., device name: NV-5) under 25 ° C.) and stirring at 10 rpm for 12 hours. The volume of each particle was used by calculating the volume when it was assumed that the number average particle size was a true sphere.

-Manufacturing of Liquid 2 for Liquid Marble-
In the method for producing the liquid 1 for liquid marble of Experimental Example 1, the liquid 2 for liquid marble is produced by the same method as the method for producing the liquid 1 for liquid marble, except that the composite particles 1 are changed to the composite particles 2. did.

(Experimental Example 3)
-Manufacturing of Liquid 3 for Liquid Marble-
In the method for producing the liquid 1 for liquid marble of Experimental Example 1, the liquid 3 for liquid marble was produced by the same method as the method for producing the liquid 1 for liquid marble, except that yeast was not added.

(Experimental Examples 4 to 13 and Reference Examples 1 to 4)
Composite particles 4 to 4 in the same manner as in Experimental Example 1 except that the compositions and contents shown in Tables 1-1 to 1-5 and Tables 2-1 to 2-3 were changed in Experimental Example 1. 17 and liquids 4 to 17 for liquid marble were produced.

In Tables 1-3 and 1-4, the "content rate (mass%) of the hydrophobic solid particles B" is a value calculated from the following formula 4, and the "content rate 1 (mass%) of the solid particles C". ) ”Is a value calculated from the following formula 5, and“ solid particle C content 2 (mass%) ”is a value calculated from the following formula 6.
Content of hydrophobic solid particles B (% by mass) = Xa / (Xa + Xb + Xc) × 100 ・ ・ ・ Equation 4
Content of solid particles C 1 (mass%) = Xc / (Xa + Xc) × 100 ・ ・ ・ Equation 5
Content of solid particles C 2 (mass%) = Xc / (Xa + Xb + Xc) × 100 ・ ・ ・ Equation 6
However, in the formulas 4, 5, and 6, Xa represents the mass (g) of the hydrophobic solid particles A added in the production of the composite particles, and Xb represents the hydrophobicity added in the production of the composite particles. It represents the mass (g) of the solid particle B, and Xc represents the mass (g) of the solid particle C added in the production of the composite particle.

The details of the materials used in the experimental examples and the reference examples are as follows.

-Hydrophobic solid particles A-
-Polytetrafluoroethylene (PTFE, number average particle size d50a: 1.0 μm, contact angle CAa: 120 °, density Ya: 2.20 × ^10-12 g / μm ³ , manufactured by Sigma-Aldrich, trade name: 430935 -100G)

-Hydrophobic solid particles B-
Hydrophobic silica (number average particle size d50b: 0.030 μm, contact angle CAb: 170 °, density Yb: 1.80 × ^10-12 g / μm ³ , manufactured by Shin-Etsu Chemical Co., Ltd., trade name: QSG-30 )

-Solid particle C-
Finely divided hydroxypropyl cellulose (HPC) (number average particle size d50c: 0.1 μm, contact angle CAc1: 75 °, contact angle CAc2: 50 °, mass Xc: 0.11 g, density Yc: 1.3 × 10 ^-12 g / μm ³ , volume Zc: 5.2 × 10 ^-4 μm ³ ), hydroxypropyl cellulose (HPC) (manufactured by Sigma-Aldrich, trade name: 19884-100G) is immersed in liquid nitrogen for 10 minutes. After freezing, the mixture was crushed for 15 minutes using a freezing and crushing device (JFC-400, manufactured by Nippon Analytical Industry Co., Ltd.). This was prepared by collecting a small amount each time, measuring with a microscope, calculating the number average particle size, and repeating until a predetermined particle size was obtained (in Table 1-1, the finely divided hydroxypropyl cellulose was "HPC". ").

-Biocatalyst-
-Yeast (scientific name: Saccharomyces Cerevisiae, manufactured by Nisshin Seifun Group, trade name: dry yeast)

-Thickener-
・ Hokkaido Honey (manufactured by Nakakita Pharmaceutical Co., Ltd.)
・ HPC (manufactured by Sigma-Aldrich)
・ Fermented cellulose (manufactured by Synaptec Co., Ltd.)
・ PVP (manufactured by Sigma-Aldrich)

-Second component-
・ D-glucose (manufactured by Tokyo Chemical Industry Co., Ltd., product name: G0048)

Next, the "valuable resource production efficiency" of the liquid marbles 1 and 2 obtained in Experimental Examples 1 and 2 was evaluated as follows. The results are shown in Table 3.

<Valuable resource production efficiency>
The efficiency of production of valuable resources by the biocatalyst (yeast) was evaluated by performing the following "valuation of valuable resource production" and "evaluation of substrate consumption".

<< Valuable resource production evaluation >>
After filling 10 g of the produced sample in a 200 mL airtight container (trade name: GL45 series, manufactured by Shibata Scientific Technology Co., Ltd.), the sample was allowed to stand at 35 ° C. in a nitrogen atmosphere for 12 hours. After standing, the container was immersed in a hot water bath at 70 ° C. and allowed to stand for another 2 hours. Then, 100 mL of gas was collected from the container and the ethanol content was measured. As the ethanol content, a Kitagawa gas sampler (AP-20) and a Gastec ethanol detector tube (ethanol 112) were used. This measured value was defined as the production rate A (%).
As a control experiment, the above liquid containing the same amount of biocatalyst used for producing 10 g of the sample was filled in the same container, allowed to stand under the same conditions, and the gas was collected by the same method. The ethanol content was measured. This measured value was defined as the production rate B (%).
The difference between the production rate A and the production rate B was defined by the following formula 7 and evaluated based on the evaluation criteria.
Evaluation C = Production rate A-Production rate B ... Equation 7

[Evaluation criteria]
10 points: Evaluation C is 0.05 or more and 8 points: Evaluation C is 0.01 or more and less than 0.05 5 points: Evaluation C is more than 0 and less than 0.01 0 points: Evaluation C is 0 or less

<< Substrate consumption evaluation >>
After filling 10 g of the produced sample in a 100 mL airtight container (trade name: GL45 series, manufactured by Shibata Kagaku Co., Ltd.) and allowing it to stand at 35 ° C. in a nitrogen atmosphere for 12 hours, from the gas phase part and the sample in the container. The liquid component was extracted, the concentration was measured using a refractometer, and then the amount of the substrate component in the container was measured. The liquid component was extracted by exposing the sample to ethanol vapor and filtering it with a 200 μm filter to separate it into composite particles and droplets (liquid).
The substrate consumption rate A before and after the reaction including the supply amount of the substrate was calculated from the following formula 8.
・ Substrate consumption rate A = {(base mass before reaction + total supply amount of substrate-total base mass after reaction) / (base mass before reaction + total supply amount of substrate)} × 100 ・ ・ ・ Equation 8
As a control experiment, after filling the same container with the liquid containing the same amount of biocatalyst used to produce 10 g of the sample, the substrate flow was supplied under the same conditions, and the temperature, atmosphere, and time were the same. The substrate consumption rate B before and after the reaction including the supply amount of the substrate was calculated from the following formula 9 by the same method as described above except that the substance production reaction was allowed to proceed.
Substrate consumption rate B = {(base mass before reaction + total supply amount of substrate-total base mass after reaction) / (base mass before reaction + total supply amount of substrate)} × 100 ・ ・ ・ Equation 9
The difference between the substrate consumption rate A and the substrate consumption rate B was defined by the following formula 10 and evaluated based on the evaluation criteria.
Evaluation C = Substrate consumption rate A-Substrate consumption rate B ... Equation 10

[Evaluation criteria]
10 points: Evaluation C is 20 or more and 8 points: Evaluation C is 10 or more and less than 20 5 points: Evaluation C is more than 0 and less than 10 0 points: Evaluation C is 0 or less

Next, with respect to the liquid marbles 1 to 17 obtained in Experimental Examples 1 to 13 and Reference Examples 1 to 4, "union inhibitory property" and "durability" were measured and evaluated as follows. The results are shown in Tables 4-1 to 4-3.

<Evaluation of unification inhibitoryness>
-Evaluation 1-
A glass chalet having a diameter (φ) of 30 mm was washed with a neutral detergent, immersed in a saturated aqueous sodium hydroxide solution for 8 hours or more, and then rinsed with pure water for washing. After sufficiently drying, the product was allowed to stand in a closed container filled with hexamethylene disilazane steam for 12 hours and used as a glass petri dish for evaluation 1.
In this evaluation 1 glass petri dish, composite particles are added so as to have a thickness of about 2 mm from the bottom surface, and while swirling and shaking at 20 rpm with a swirling shaker (manufactured by Corning Inc.), 10 μL of liquid for liquid marble is applied with a microsyringe. Dropped. After 1 minute, 10 μL of a liquid for liquid marble was further added dropwise. After further shaking for 1 minute, the evaluation result was set to "E" when the two liquid marbles were united into one particle, and the evaluation 2 was performed when the two liquid marbles were not united.

-Evaluation 2-
In a container made of PTFE with a diameter (φ) 72 mm × height (H) 89 mm, composite particles are added so as to have a thickness of about 50 mm from the bottom surface, and the mixture is swirled and shaken at 200 rpm with a swirling shaker (manufactured by Corning). However, the liquid for liquid marble was discharged as a droplet having a diameter of 1 mm using a dispenser (manufactured by Musashi Engineering Co., Ltd.) at a rate of 1 drop / 1 second.
After discharging 1,000 drops, visually observe the inside of the container, and when the liquid marble bursts together and a film of composite particles is formed on the water surface, it is designated as "D", and a film of composite particles is formed on the water surface. Those that were not discharged further ejected droplets.
After a total of 4,000 drops have been discharged, the inside of the container is visually observed, and the case where the liquid marble bursts together and a film of composite particles is formed on the water surface is defined as "C", and the composite particles are formed on the water surface. Those that did not eject more droplets.
After a total of 6,000 drops have been discharged, the inside of the container is visually observed, and the case where the liquid marble bursts together and a film of composite particles is formed on the water surface is defined as "B", and a film of composite particles is formed on the water surface. Those that did not exist were designated as "A".
Evaluation points were calculated based on the following evaluation criteria.

[Evaluation criteria]
A: 10 points B: 8 points C: 6 points D: 4 points E: 0 points

<Durability evaluation>
The produced liquid marble 500 mg was filled in a 1 mL vial, and the lid was closed to prepare a measurement sample. The measurement sample was freely dropped onto a woodblock from a height of 200 mm, the inside was visually inspected, and the process was repeated until all liquid marbles burst and the particle shape was lost. The evaluation points were calculated based on the following evaluation criteria, using the number of times all liquid marbles were in a ruptured state as measured values.

[Evaluation criteria]
11 times or more: 10 points 9 times or more and 10 times or less: 8 points 7 times or more and 8 times or less: 6 points 5 times or more and 6 times or less: 4 points 2 times or more and 4 times or less: 2 points 1 time or less: 0 points

<Comprehensive evaluation>
The total value of the evaluation points of "union inhibitory property" and "durability" was evaluated based on the following evaluation criteria. In addition, the one with 0 points in any of the evaluations was given as "x" and the lowest evaluation. "E" and "x" cannot be used industrially.

[Evaluation criteria]
A: 19 points or more and 20 points or less B: 15 points or more and 18 points or less C: 9 points or more and 14 points or less D: 7 points or more and 8 points or less E: 6 points or less

ただし、式２中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｂは、疎水性固体粒子Ｂの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｂは、疎水性固体粒子Ｂの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｂは、疎水性固体粒子Ｂの体積（μｍ^３）を表す。
＜９＞ 前記複合粒子が、前記疎水性固体粒子Ａの表面上に更に固体粒子Ｃを有し、
前記疎水性固体粒子Ａの水との接触角ＣＡａが、１１０°以上１８０°以下であり、
前記固体粒子Ｃの水との接触角ＣＡｃ１が、１１０°未満であり、
前記固体粒子Ｃのｎ－ヘキサンとの接触角ＣＡｃ２が、１１０°未満であり、
前記疎水性固体粒子Ａの個数平均粒径ｄ５０ａと、前記疎水性固体粒子Ｂの個数平均粒径ｄ５０ｂ及び前記固体粒子Ｃの個数平均粒径ｄ５０ｃの平均値との比（ｄ５０ａ／［（ｄ５０ｂ＋ｄ５０ｃ）／２］）が、１０以上１００以下であり、
下記式３で表される被覆率ＣＲ_３が、０．３％以上１８％以下である前記＜８＞に記載のリキッドマーブル。

ただし、式３中、被覆率ＣＲ_１は、下記式１により求められる値を表し、被覆率ＣＲ_２は、前記式２により求められる値を表す。

ただし、式１中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｃは、固体粒子Ｃの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｃは、固体粒子Ｃの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｃは、固体粒子Ｃの体積（μｍ^３）を表す。
＜１０＞ 前記＜１＞から＜５＞のいずれかに記載のリキッドマーブル用液体を外添粒子で内包することによりリキッドマーブルを得ることを特徴とするリキッドマーブルの製造方法である。
＜１１＞ 前記リキッドマーブル用液体から液滴を形成する液滴形成工程と、
個数平均粒径が１ｎｍ以上１０μｍ以下の外添粒子で前記リキッドマーブル用液体を表面被覆させる表面被覆工程と、
を含む前記＜１０＞に記載のリキッドマーブルの製造方法である。
＜１２＞ 前記外添粒子が、前記疎水性固体粒子Ａの表面上に更に疎水性固体粒子Ｂを有し、
前記疎水性固体粒子Ａの水との接触角ＣＡａが、１１０°以上１８０°以下であり、
前記疎水性固体粒子Ｂの水との接触角ＣＡｂが、１１０°以上１８０°以下であり、
前記疎水性固体粒子Ａの個数平均粒径ｄ５０ａと、前記疎水性固体粒子Ｂの個数平均粒径ｄ５０ｂとの比（ｄ５０ａ／ｄ５０ｂ）が、１０以上１００以下であり、
下記式２で表される被覆率ＣＲ_２が、５０％以上５００％以下である複合粒子である前記＜１１＞に記載のリキッドマーブルの製造方法である。

ただし、式２中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｂは、疎水性固体粒子Ｂの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｂは、疎水性固体粒子Ｂの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｂは、疎水性固体粒子Ｂの体積（μｍ^３）を表す。
＜１３＞ 前記＜１＞から＜５＞のいずれかに記載のリキッドマーブル用液体を内包することを特徴とするリキッドマーブルの製造装置である。
＜１４＞ 前記リキッドマーブル用液体から液滴を形成する液滴形成手段と、
個数平均粒径が１ｎｍ以上１０μｍ以下の外添粒子で前記リキッドマーブル用液体を表面被覆させる表面被覆手段と、
を有する前記＜１３＞に記載のリキッドマーブルの製造装置である。
＜１５＞ 前記外添粒子が、前記疎水性固体粒子Ａの表面上に更に疎水性固体粒子Ｂを有し、
前記疎水性固体粒子Ａの水との接触角ＣＡａが、１１０°以上１８０°以下であり、
前記疎水性固体粒子Ｂの水との接触角ＣＡｂが、１１０°以上１８０°以下であり、
前記疎水性固体粒子Ａの個数平均粒径ｄ５０ａと、前記疎水性固体粒子Ｂの個数平均粒径ｄ５０ｂとの比（ｄ５０ａ／ｄ５０ｂ）が、１０以上１００以下であり、
下記式２で表される被覆率ＣＲ_２が、５０％以上５００％以下である複合粒子である前記＜１４＞に記載のリキッドマーブルの製造方法である。

ただし、式２中、Ｘａは、疎水性固体粒子Ａの質量（ｇ）を表し、Ｘｂは、疎水性固体粒子Ｂの質量（ｇ）を表し、Ｙａは、疎水性固体粒子Ａの密度（ｇ／μｍ^３）を表し、Ｙｂは、疎水性固体粒子Ｂの密度（ｇ／μｍ^３）を表し、Ｚａは、疎水性固体粒子Ａの体積（μｍ^３）を表し、Ｚｂは、疎水性固体粒子Ｂの体積（μｍ^３）を表す。
＜１６＞ 前記＜６＞から＜９＞のいずれかに記載のリキッドマーブルを有することを特徴とするバイオリアクターである。
＜１７＞ 前記リキッドマーブルを担持する担持手段を有する前記＜１６＞に記載のバイオリアクターである。 Examples of aspects of the present invention include the following.
<1> Contains a biocatalyst, water, and a thickener,
The content of the water is 15% by mass or more and 98% by mass or less.
It is a liquid for liquid marble characterized by having a viscosity at 25 ° C. of 400 mPa · s or more and 4,000 mPa · s or less.
<2> The liquid for liquid marble according to <1>, wherein the content of the thickener is 0.1% by mass or more.
<3> The liquid for liquid marble according to any one of the above <1> to <2>, which is a polysaccharide.
<4> The biocatalyst is described in any one of <1> to <3>, wherein the biocatalyst is at least one selected from animal cells, plant cells, microorganisms, proteins, enzymes, organellas, hormone receptors, and antibodies. Liquid marble liquid.
<5> The liquid for liquid marble according to any one of <1> to <4>, which further contains at least one of an additive and a physiologically active substance.
<6> The liquid marble according to any one of <1> to <5> is characterized in that the liquid for liquid marble is encapsulated by external particles.
<7> The liquid marble according to <6>, wherein the number average particle size d50e of the external particles is 1 nm or more and 10 μm or less.
<8> The external particles further have the hydrophobic solid particles B on the surface of the hydrophobic solid particles A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less.
The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B is 10 or more and 100 or less.
The liquid marble according to <7>, which is a composite particle having a coverage CR ₂ represented by the following formula 2 of 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ).
<9> The composite particles further have solid particles C on the surface of the hydrophobic solid particles A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAc1 of the solid particles C with water is less than 110 °.
The contact angle CAc2 of the solid particles C with n-hexane is less than 110 °.
The ratio of the average particle size d50a of the hydrophobic solid particles A to the average particle size d50b of the hydrophobic solid particles B and the average particle size d50c of the solid particles C (d50a / [(d50b + d50c)). / 2]) is 10 or more and 100 or less,
The liquid marble according to <8>, wherein the coverage CR ₃ represented by the following formula 3 is 0.3% or more and 18% or less.

However, in the formula 3, the coverage rate CR ₁ represents the value obtained by the following formula 1, and the coverage rate CR ₂ represents the value obtained by the above formula 2.

However, in the formula 1, Xa represents the mass (g) of the hydrophobic solid particle A, Xc represents the mass (g) of the solid particle C, and Ya represents the density (g / μm) of the hydrophobic solid particle A. ³ ), Yc represents the density of the solid particle C (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zc represents the volume of the solid particle C (μm ³ ). ).
<10> A method for producing a liquid marble, which comprises encapsulating the liquid for liquid marble according to any one of <1> to <5> with external particles to obtain a liquid marble.
<11> A droplet forming step of forming a droplet from the liquid marble liquid,
A surface coating step of surface-coating the liquid for liquid marble with external particles having an average particle size of 1 nm or more and 10 μm or less.
The method for producing a liquid marble according to <10>.
<12> The external particles further have the hydrophobic solid particles B on the surface of the hydrophobic solid particles A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less.
The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B is 10 or more and 100 or less.
The method for producing a liquid marble according to <11>, which is a composite particle having a coverage CR ₂ represented by the following formula 2 of 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ).
<13> A liquid marble manufacturing apparatus comprising the liquid for liquid marble according to any one of <1> to <5>.
<14> A droplet forming means for forming a droplet from the liquid marble liquid, and a droplet forming means.
A surface coating means for surface-coating the liquid for liquid marble with external particles having an average particle size of 1 nm or more and 10 μm or less.
The liquid marble manufacturing apparatus according to <13>.
<15> The external particles further have the hydrophobic solid particles B on the surface of the hydrophobic solid particles A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less.
The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B is 10 or more and 100 or less.
The method for producing a liquid marble according to <14>, which is a composite particle having a coverage CR ₂ represented by the following formula 2 of 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ).
<16> A bioreactor having the liquid marble according to any one of <6> to <9>.
<17> The bioreactor according to <16>, which has a supporting means for supporting the liquid marble.

10 Composite particles 11 Hydrophobic solid particles A
12 Solid particles B

N. Picke et al. , Proc. R. Soc. Land. B, 2002, 269, 1211-1215 J. Tian et al. , Colloids and Surfaces B, Biointerfaces, 2003, 106, 187-190

Claims (17)

Contains a biocatalyst, water, and a thickener,
The content of the water is 15% by mass or more and 98% by mass or less.
A liquid for liquid marble having a viscosity at 25 ° C. of 400 mPa · s or more and 4,000 mPa · s or less. The liquid for liquid marble according to claim 1, wherein the content of the thickener is 0.1% by mass or more. The liquid for liquid marble according to any one of claims 1 to 2, wherein the thickener is a polysaccharide. The liquid for liquid marble according to any one of claims 1 to 3, wherein the biological catalyst is at least one selected from animal cells, plant cells, microorganisms, proteins, enzymes, organellas, hormone receptors, and antibodies. The liquid for liquid marble according to any one of claims 1 to 4, further comprising at least one of an additive and a physiologically active substance. A liquid marble according to any one of claims 1 to 5, wherein the liquid for liquid marble is encapsulated by external particles. The liquid marble according to claim 6, wherein the number average particle size d50e of the external particles is 1 nm or more and 10 μm or less. The external particles further have hydrophobic solid particles B on the surface of the hydrophobic solid particles A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less.
The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B is 10 or more and 100 or less.
The liquid marble according to claim 7, wherein the coverage CR ₂ represented by the following formula 2 is a composite particle having a coverage of 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ). The composite particle further has a solid particle C on the surface of the hydrophobic solid particle A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAc1 of the solid particles C with water is less than 110 °.
The contact angle CAc2 of the solid particles C with n-hexane is less than 110 °.
The ratio of the average particle size d50a of the hydrophobic solid particles A to the average particle size d50b of the hydrophobic solid particles B and the average particle size d50c of the solid particles C (d50a / [(d50b + d50c)). / 2]) is 10 or more and 100 or less,
The liquid marble according to claim 8, wherein the coverage CR ₃ represented by the following formula 3 is 0.3% or more and 18% or less.

However, in the formula 3, the coverage rate CR ₁ represents the value obtained by the following formula 1, and the coverage rate CR ₂ represents the value obtained by the above formula 2.

However, in the formula 1, Xa represents the mass (g) of the hydrophobic solid particle A, Xc represents the mass (g) of the solid particle C, and Ya represents the density (g / μm) of the hydrophobic solid particle A. ³ ), Yc represents the density of the solid particle C (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zc represents the volume of the solid particle C (μm ³ ). ). A method for producing a liquid marble, which comprises encapsulating the liquid for liquid marble according to any one of claims 1 to 5 with external particles to obtain a liquid marble. The droplet forming step of forming a droplet from the liquid for liquid marble and
A surface coating step of surface-coating the liquid for liquid marble with external particles having an average particle size of 1 nm or more and 10 μm or less.
The method for producing a liquid marble according to claim 10. The external particles further have hydrophobic solid particles B on the surface of the hydrophobic solid particles A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less.
The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B is 10 or more and 100 or less.
The method for producing a liquid marble according to claim 11, wherein the coverage CR ₂ represented by the following formula 2 is a composite particle having a coverage of 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ). A liquid marble manufacturing apparatus comprising the liquid for liquid marble according to any one of claims 1 to 5. A droplet forming means for forming a droplet from the liquid for liquid marble,
A surface coating means for surface-coating the liquid for liquid marble with external particles having an average particle size of 1 nm or more and 10 μm or less.
13. The liquid marble manufacturing apparatus according to claim 13. The external particles further have hydrophobic solid particles B on the surface of the hydrophobic solid particles A.
The contact angle CAa of the hydrophobic solid particles A with water is 110 ° or more and 180 ° or less.
The contact angle CAb of the hydrophobic solid particles B with water is 110 ° or more and 180 ° or less.
The ratio (d50a / d50b) of the number average particle size d50a of the hydrophobic solid particles A to the number average particle size d50b of the hydrophobic solid particles B is 10 or more and 100 or less.
The method for producing a liquid marble according to claim 14, wherein the coverage CR ₂ represented by the following formula 2 is a composite particle having a coverage of 50% or more and 500% or less.

However, in the formula 2, Xa represents the mass (g) of the hydrophobic solid particle A, Xb represents the mass (g) of the hydrophobic solid particle B, and Ya represents the density (g) of the hydrophobic solid particle A. / Μm ³ ), Yb represents the density of the hydrophobic solid particle B (g / μm ³ ), Za represents the volume of the hydrophobic solid particle A (μm ³ ), and Zb represents the hydrophobic solid particle. Represents the volume of B (μm ³ ). A bioreactor comprising the liquid marble according to any one of claims 6 to 9. The bioreactor according to claim 16, which has a supporting means for supporting the liquid marble.

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