JP2020003165A - Production method and production apparatus for organism-derived water-soluble polymer dried product - Google Patents

Abstract

To provide a production method and a production apparatus for an organism-derived water-soluble polymer, the method capable of shortening a drying time compared with a conventional method, and the dried product being excellent in solubility.SOLUTION: A method of producing an organism-derived water-soluble polymer dried product uses a production apparatus 10 comprising: a chamber 11 where an unsaturated solution containing water and organism-derived water-soluble polymer is arranged inside thereof; temperature detecting means 12 that detects a temperature of the unsaturated solution; pressure reducing means 13 that reduces a pressure inside the chamber 11 to a pressure-reduced state; microwave heating means 14 that radiates a microwave to heat the unsaturated solution; and controlling means 15 that controls the pressure reducing means 13 and the microwave heating means 14 on the basis of temperature data acquired by the temperature detecting means 12; the method including: radiating the microwave to the unsaturated solution under a pressure-reduced condition; causing the water to be boiled at a lower temperature than a denaturation temperature of the water-soluble polymer; and performing drying treatment to remove the water while causing the unsaturated solution to expand in a foamy state by means of vapor generated by boiling such that an apparent volume becomes 10 times or more of the original volume, thereby producing the product.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a dried water-soluble polymer derived from a living body and an apparatus for producing the same.

In recent years, with the advance of biotechnology, pharmaceuticals using water-soluble polymers derived from living organisms such as water-soluble proteins and water-soluble polysaccharides (hereinafter simply referred to as water-soluble polymers) have been increasing. In many cases, it is difficult to ensure the stability in an unsaturated solution containing water and a water-soluble polymer, and the storage period is short. Therefore, many water-soluble polymers are freeze-dried (hereinafter referred to as “FD”). ) And stored in a dried state.
However, FD takes a long time (about 1 to 3 days) due to drying accompanied by sublimation of ice, and requires large energy. Further, the water-soluble polymer may be deactivated or aggregated due to a change in the hydration state due to freeze concentration or physical damage from ice crystals or the like.

Therefore, as a new drying method replacing the FD, for example, a microwave room temperature drying method (hereinafter, also referred to as “MVD”) described in Non-Patent Document 1 has been proposed. As described in Patent Document 1, this MVD is a method of lowering the boiling point of water under reduced pressure conditions to promote the evaporation of water, supplying only latent heat taken off during evaporation by microwaves, and consequently drying at room temperature. It is.
This makes it possible to shorten the drying time due to the effect of draining moisture from the inside and to dry at room temperature as compared with the FD, so that physical damage of the water-soluble polymer can be expected to be prevented.

Japanese Patent No. 4474506

Ryuji Tsuruta and 3 others, "Study on Dry Storage of Protein Preparations Using Microwave", Proc. Of the 53rd Japan Heat Transfer Symposium, May 2016

Although the drying time of the water-soluble polymer can be shortened by MVD as compared with FD, a further drastic reduction has been required.
In addition, when using a water-soluble polymer, it is necessary to dissolve the dried and stored water-soluble polymer in a liquid (water), but the water-soluble polymer dried by MVD is a thick film. Therefore, the dissolution rate was slow and the dissolution time was long as compared with the porous water-soluble polymer dried by FD. The solubility can be improved by combining MVD and FD. However, since FD is used, there is a problem that the drying time of the water-soluble polymer is longer than that of MVD alone.

  The present invention has been made in view of the above circumstances, and provides a method of manufacturing a water-soluble polymer-derived dried product derived from a living body, which can drastically reduce the drying time and has good solubility compared to the related art, and an apparatus for manufacturing the same. With the goal.

  The method for producing a biologically-derived dried water-soluble polymer according to the present invention according to the present invention, which irradiates a microwave to an unsaturated solution containing water and a biologically-derived water-soluble polymer under reduced pressure conditions, The water in the unsaturated solution is boiled at a temperature lower than the denaturation temperature of the water-soluble polymer, and the unsaturated solution is bubbled by steam generated by the boiling so that the apparent volume becomes 10 times or more the initial volume. Drying is performed to remove water while swelling.

  In the method for producing a biologically-derived dried water-soluble polymer according to the present invention, in the drying treatment, after reducing the water contained in the unsaturated solution to a predetermined amount, the pressure and the unsaturated solution are reduced. It is preferred that the temperature of the unsaturated solution is raised above the pressure at which the water contained in the unsaturated solution has decreased to a preset amount and the temperature of the unsaturated solution, and the unsaturated solution is sterilized.

  In the method for producing a dried water-soluble polymer derived from a living body according to the present invention, it is preferable that the dried product obtained by performing the drying treatment is crushed and powdered.

  In the method for producing a dried biologically-derived water-soluble polymer according to the present invention, the drying treatment is preferably performed in a state where the unsaturated solution is contained in a hydrophobic container.

The apparatus for producing a dried biologically-derived water-soluble polymer according to the present invention according to the present invention includes a chamber in which an unsaturated solution containing water and a biologically-derived water-soluble polymer is disposed,
Temperature detection means for detecting the temperature of the unsaturated solution in the chamber,
Pressure reducing means for reducing the pressure in the chamber to a reduced pressure state;
Microwave heating means for irradiating the unsaturated solution in the chamber with microwaves for heating,
Based on the temperature data obtained by the temperature detecting means, the pressure reducing means controls the temperature at which the water in the unsaturated solution boils below the denaturation temperature of the water-soluble polymer and the microwave heating. Means for boiling the water of the unsaturated solution, and controlling the apparent volume to be at least 10 times the initial volume by the steam generated by the boiling so that the unsaturated solution expands in a bubble-like manner. .

  In the apparatus for producing a dried water-soluble polymer derived from a living body according to the present invention, the control means reduces the pressure reduction means and the microwave heating means to a predetermined amount of water contained in the unsaturated solution. It is preferable that the temperature of the unsaturated solution is controlled so as to increase to a temperature at which the unsaturated solution can be sterilized.

  The apparatus for producing a dried water-soluble polymer derived from a living body according to the present invention preferably further includes a hydrophobic container that accommodates the unsaturated solution and is disposed in the chamber.

The method for producing a biologically-derived dried water-soluble polymer according to the present invention and the apparatus for irradiating the unsaturated solution with microwaves under reduced pressure conditions, the water content of the unsaturated solution is less than the denaturation temperature of the water-soluble polymer. Boil, and remove the moisture while swelling the unsaturated solution in a bubble by the steam generated by the boiling, so that the gas-liquid boundary area of the unsaturated solution expands with the boiling, and the evaporation of the moisture is promoted. In comparison, the drying time can be shortened. Further, the dried product of the water-soluble polymer derived from a living body obtained in this manner becomes a foamed thin film, so that the area in contact with the liquid (water) is larger than that of a conventional thick film dried by MVD. The dissolution rate can be increased, and the dissolution time can be shortened, because the dissolution rate can be increased and the dissolution can be facilitated.
Therefore, it is possible to shorten the drying time (less than half) and to provide a dried water-soluble polymer derived from a living body with good solubility as compared with the conventional case.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the manufacturing apparatus of the water-soluble dried polymer derived from living body which concerns on one Embodiment of this invention. (A) is a plan view of a dried egg white product produced using the apparatus for producing a water-soluble polymer dried product derived from the same organism, (B) is a side view of the dried egg white product, (C) () Is a photograph of the dried egg white on a petri dish, and (D) is a photograph of the dried egg white according to the conventional example. It is a graph which shows the result of having performed the molecular structure analysis of egg white. It is a graph which shows the time change of the moisture content of egg white at the time of drying. It is a graph which shows the drying speed of egg white at the time of drying. It is a graph which shows the solubility of the dried egg white product.

Next, embodiments of the present invention will be described with reference to the accompanying drawings to provide an understanding of the present invention.
First, a biologically-derived water-soluble polymer dried product (hereinafter simply referred to as “water-soluble Polymer dried product or dried product).
The dried biologically-derived water-soluble polymer is obtained by drying an unsaturated solution containing water and a biologically-derived water-soluble polymer (hereinafter, also simply referred to as a water-soluble polymer). The water-soluble polymers derived from living organisms include water-soluble proteins and water-soluble polysaccharides. Among them, egg white protein and egg yolk protein (egg white and egg yolk), albumin, lysozyme, placenta extract, collagen (gelatin), hyaluronic acid Glucosaminoglycan, fucodine, alginate, pectin and the like (a mixture of any two or more of these may be used).

A dried egg white product A (Example) which is an example of the dried water-soluble polymer derived from a living body will be described with reference to FIGS. 2 (A) to 2 (C). FIG. 2A is a plan view of a dried egg white product (an example of a biologically-derived dried water-soluble polymer) in a beaker immediately after production, and FIG. 2B is a side view of the dried egg white product. (C) shows a dried egg white product in a Teflon (registered trademark, the same applies hereinafter) container immediately after production, and the egg white dried product dropped on a petri dish by inverting the container to give an impact. A. The reason why the glass beaker is used in FIGS. 2A and 2B is to make it easier to confirm the foaming state of the dried egg white product. In FIG. 2C, a Teflon container is used. The reason for this is to make it easy to remove dried egg whites produced from unsaturated solutions having high viscosity from containers. As described above, a glass beaker and a Teflon container are used when producing a dried egg white product, but the quality of the produced dried product is the same.
Since the unsaturated solution has a high viscosity, the dried egg white product immediately after the production is such that the unsaturated solution swells greatly in the form of bubbles in the production process (becomes a foamed state), and as shown in FIGS. 2 (A) and 2 (B). As shown, a large number of large bubbles having a diameter of several centimeters are present, and the apparent volume is several tens times (10 times or more) the volume (initial volume) of the unsaturated solution before drying. And dried.

When using this dried egg white product, the above-mentioned dried foam and the like can be used as they are, but it can also be used in a state where the container is turned upside down and dropped as described above. It can also be used by crushing and pulverizing (eg, storage of dried egg white products may be performed in the state of dry foam etc. as it is, or may be performed in a state where the container is turned upside down and dropped, Further, it may be performed in a powdered state.)
The dried egg white product A shown in FIG. 2 (C) is a thin foamed piece (the moisture content of the unsaturated solution before drying (initial moisture content) is 1, and the moisture content after drying (final moisture content)). Is 0.05 or less). Here, the thickness of the thin film is, for example, about 500 μm or less (further, 300 μm or less). The same applies to the dried egg white product in the beaker shown in FIGS. 2 (A) and 2 (B).
FIG. 2 shows a photograph of a dried egg white product B (Comparative Example) obtained by drying without foaming using the microwave room temperature drying method (MVD) described in Non-Patent Document 1 described above. D). The dried egg white product B is a thick film of several mm.
Thus, the form of the dried egg white product A is different from that of the dried egg white product B.

Next, with reference to FIG. 1, a description will be given of a manufacturing apparatus (hereinafter, also simply referred to as a manufacturing apparatus) 10 for producing a dried biologically-derived water-soluble polymer according to the present embodiment.
The manufacturing apparatus 10 includes a decompression container (an example of a chamber) 11, an optical fiber thermometer (an example of a temperature detection unit) 12, a decompression pump (an example of a decompression unit) 13, a microwave heating unit 14, and a control unit 15. ing.

The decompression container 11 has an unsaturated solution disposed therein, and is closed by reducing the pressure in the decompression container 11. A suction pipe 16 for supplying external air into the pressure reducing vessel 11 is connected to the pressure reducing vessel 11, and a flow meter 17 and a flow regulating valve 18 are provided in the suction pipe 16.
The optical fiber thermometer 12 immerses (contacts) the temperature detecting section in the unsaturated solution, and detects the temperature of the unsaturated solution in the decompression vessel 11.
The depressurizing pump 13 (for example, a vacuum pump) is connected to the depressurizing container 11 and reduces the pressure in the depressurizing container 11 to a depressurized state. Note that an oil / water separator 19 is connected to the pressure reducing pump 13.

The microwave heating means 14 has a microwave transmitter 20 provided with a magnetron (microwave generating element), and irradiates the unsaturated solution in the depressurized container 11 with, for example, a microwave having a frequency of 2.45 GHz. It is to be heated. Microwave is a general term of electromagnetic waves indicating a wavelength range of 1 to 30 cm and a frequency range of 1 to 30 GHz, for example, and has a property of being reflected by metal but easily absorbed by water and the like. .
The microwave heating means 14 has an isolator 21 and protects the magnetron in the microwave transmitter 20 by absorbing the reflected wave returning from the decompression vessel 11.

The unsaturated solution heated by the microwave heating means 14 is placed inside a reduced-pressure container 11 in a state of being put in a container (not shown) (the manufacturing apparatus 10 has a container).
The material of the container is not particularly limited as long as it is not deformed or deteriorated by the use of the microwave heating means 14. For example, the glass beaker described above can be used, but in consideration of the releasability (peelability) of the manufactured water-soluble polymer such as egg white from the container, a hydrophobic container, specifically, It is preferable to use the container made of Teflon (polytetrafluoroethylene (PTFE)) described above. Other materials include fluororesins such as tetrafluoroethylene / hexafluoropropylene copolymer (FEP) and tetrafluoroethylene / perfluoroalkylvinyl ether copolymer (PFA), or polyethylene terephthalate (PET) or polypropylene. (PP) and the like.
Further, a sheet material of the above-described material may be disposed on the inner surface of the glass container.

The control unit 15 includes a measuring unit 22, an operation unit 23, and a computer 24.
The temperature data obtained by the optical fiber thermometer 12 and the pressure data obtained by a pressure gauge (pressure sensor) 25 provided in the decompression container 11 are transmitted to the measurement unit 22.
The operation unit 23 performs each operation (for example, ON / OFF and / or Output adjustment).
The computer 24 issues a command to the operation unit 23 based on the temperature data and the pressure data received by the measurement unit 22.

  The control means 15 controls the output of the decompression pump 13 based on the temperature data transmitted from the optical fiber thermometer 12 and the pressure data transmitted from the pressure gauge 25 to adjust the pressure in the decompression container 11 and The output of the microwave transmitter 20 of the microwave heating means 14 is controlled to adjust the temperature of the unsaturated solution. The output of the pressure reducing pump 13 can be controlled based on the temperature data from the optical fiber thermometer 12, but should be controlled based on the pressure data from the pressure gauge 25 without using this temperature data (optical fiber thermometer 12). You can also. In this case, since the boiling point of water is determined by the atmospheric pressure condition, the relationship between the temperature and the pressure is graphed in advance, and the pressure condition is calculated from this graph so that the boiling point is lower than the denaturation temperature of the water-soluble polymer.

The output control of the decompression pump 13 reduces the pressure in the decompression container 11 (to a reduced pressure state), and the temperature at which the moisture of the unsaturated solution boils (hereinafter also referred to as the boiling point) becomes lower than the denaturation temperature of the water-soluble polymer. Is done as follows.
This is because, when heating the unsaturated solution, if the influence of heat increases (if the temperature exceeds the denaturation temperature), the molecular structure of the water-soluble polymer is broken, and the required function cannot be obtained.
It is preferable to confirm the denaturation temperature of the water-soluble polymer by performing a molecular structure analysis (for example, an analysis using a circular dichroism dispersometer) in advance.

The output control of the microwave transmitter 20 of the microwave heating means 14 is performed by heating the unsaturated solution in the depressurized container 11 to boil the water of the unsaturated solution, and by using steam (gas) locally generated by the boiling. The unsaturated solution is foamed so as to have an apparent volume of 10 times or more the initial volume. As described above, since the temperature at which the unsaturated solution is foamed is lower than the denaturation temperature of the water-soluble polymer, the molecular structure of the water-soluble polymer can be maintained without breaking.
As described above, when the unsaturated solution is dried while being foamed, it has a large number of large bubbles having a diameter of several cm, and the apparent volume is at least 10 times the volume of the unsaturated solution before drying. By doing so, the obtained dried water-soluble polymer becomes a thin film (see FIGS. 2A to 2C) without becoming a thick film (see FIG. 2D). In addition, as the apparent volume increases, the drying time can be further shortened by reducing the thickness of the foam by foaming, and the solubility of the obtained water-soluble polymer in a liquid described below is improved by reducing the thickness of the obtained dried water-soluble polymer. Therefore, the apparent volume with respect to the volume of the unsaturated solution before drying is preferably 30 times or more, more preferably 50 times or more. On the other hand, the upper limit value is not particularly limited for the above-mentioned reason, but it is, for example, about 500 times since a remarkable increase in the effect cannot be expected with an increase in the apparent volume.

Further, the control means 15 preferably controls the output of the vacuum pump 13 and the microwave transmitter 20 so that the unsaturated solution can be sterilized. The output control of the pressure-reducing pump 13 and the microwave transmitter 20 is performed on the condition that the moisture contained in the unsaturated solution (hereinafter, also referred to as moisture content) decreases to a preset amount.
When an unsaturated solution having a high water content is heated, as described above, the water-soluble polymer is easily denatured by the influence of heat. For this reason, it is preferable that the preset water content of the unsaturated solution be 60% by mass or less, and more preferably 50% by mass or less, with the initial water content of the unsaturated solution being 100% by mass. As described above, if the drying is advanced to some extent (unless the water content of the unsaturated solution is small), the water-soluble polymer is not denatured even if exposed to high temperature for a short time (it is hardly denatured). Is not specified, but for effective sterilization, the water content of the unsaturated solution is preferably 20% by mass, more preferably 30% by mass.

The output control of the decompression pump 13 is performed so that the pressure in the decompression vessel 11 becomes higher than the current pressure (the pressure at the time when the water content becomes a predetermined amount) (preferably, in a range below the atmospheric pressure). Done. That is, outside air is supplied from the intake pipe 16 into the decompression container 11, and the decompression pump 13 is operated so that the pressure is stabilized.
When controlling the output of the microwave transmitter 20 to increase the output and heating the unsaturated solution, the pressure in the depressurized container 11 sets the temperature of the unsaturated solution to the current value (the water content is set in advance). The temperature is adjusted to a temperature at which the unsaturated solution can be sterilized (for example, a denaturation temperature or higher).
After raising the temperature of the unsaturated solution in this way, the output of the vacuum pump 13 is again controlled so that the boiling point of the unsaturated solution is lower than the denaturation temperature of the water-soluble polymer, and the microwave transmitter is used. The output of 20 is controlled to remove moisture while foaming the unsaturated solution.

As described above, when removing moisture while foaming the unsaturated solution, the gas (moisture) generated from the swollen unsaturated solution is discharged to the outside by a gas stream to dry the unsaturated solution. It is preferred to promote. This will be described below.
In order to keep the inside of the decompression container 11 in a decompressed state, the air in the decompression container 11 sucked by the decompression pump 13 and the outside air supplied into the decompression container 11 from the intake pipe 16 are respectively pressure-regulated valves (not shown). And the flow is adjusted by the flow control valve 18.
The water in the decompression container 11 evaporated by the microwave irradiation can be discharged to the outside of the decompression container 11 via the decompression pump 13 (a gas discharge port of the decompression container 11 and a decompression pipe). As described above, by removing the water in the decompression container 11, the humidity in the decompression container 11 can be reduced, and the drying can be further promoted.

In addition, by opening the flow control valve 18, outside air is supplied into the decompression container 11 through the intake pipe 16 (for example, about several hundred cc / min). At this time, as described above, since the inside of the decompression container 11 is depressurized by the decompression pump 13, the gas in the decompression container 11 is substantially equal to the outside air flowing into the decompression container 11 through the intake pipe 16. By discharging the steam from the inside of the depressurized container 11 to the outside, the degree of vacuum in the depressurized container 11 is maintained, and the room temperature drying is maintained.
As a result, an airflow is generated around the unsaturated solution, and the vapor that has accumulated and filled around the unsaturated solution is discharged to the outside of the depressurized container 11 in the airflow, thereby promoting the drying of the unsaturated solution. You.

When the unsaturated solution is sterilized, the amount of outside air flowing into the decompression container 11 is increased from the amount of air discharged from the decompression container 11 by the decompression pump 13 to increase the pressure in the decompression container 11. be able to. As a result, the boiling point can be raised to a sterilizable temperature, and the unsaturated solution can be sterilized.
As the above-mentioned outside air, air can be generally used, but it is preferable to use an inert gas such as nitrogen gas or argon gas (rare gas). Can be prevented from being altered by oxygen contained in the steel. In particular, by using outside air in a dry state (low humidity) from which water has been removed, drying of the unsaturated solution can be further promoted.

Next, a method for producing a dried biologically-derived water-soluble polymer according to an embodiment of the present invention will be described with reference to FIG.
First, the molecular structure of the unsaturated solution to be dried is analyzed to confirm the denaturation temperature of the water-soluble polymer. In this molecular structure analysis, a circular dichroism dispersometer (hereinafter, circular dichroism is also referred to as CD) can be used, but the present invention is not limited to this.
Next, the unsaturated solution contained in the container is charged into the reduced pressure container 11. At this time, the temperature detector of the optical fiber thermometer 12 is immersed in the unsaturated solution.

The pressure reducing pump 13 is operated by the control means 15 to reduce the pressure in the pressure reducing vessel 11 until the boiling point of the unsaturated solution becomes lower than the denaturation temperature of the water-soluble polymer. The pressure in the pressure reducing container 11 can be detected by the pressure gauge 25.
Here, the pressure in the decompression container 11 is, for example, 20 kPa or less, though it depends on the type of the unsaturated solution. In consideration of the fact that foaming is easily caused by lowering the boiling point of water, the pressure is preferably 10 kPa or less, more preferably 5 kPa or less. On the other hand, the lower limit is not specified, but it is not necessary to lower the pressure to a vacuum state in consideration of the capacity of the pressure reducing pump (the time required for pressure reduction) and the like.

As described above, after the inside of the decompression vessel 11 is depressurized, the microwave heating means 14 is operated by the control means 15 to irradiate the unsaturated solution with microwaves, and the unsaturated solution is unsaturated at a temperature lower than the denaturation temperature of the water-soluble polymer. Bring the water of the solution to a boil. Here, the output of the microwave transmitter 20 of the microwave heating means 14 is controlled such that the apparent volume is at least 10 times the initial volume by steam generated by boiling (further shortening of the drying time and the solubility in liquids are reduced). Considering this, the lower limit is preferably set to 30 times, and more preferably 50 times, while the upper limit is set to about 500 times since the effect cannot be remarkably increased.
As described above, the drying treatment for removing moisture while foaming the unsaturated solution under reduced pressure conditions is performed by setting the moisture content (initial moisture content) of the unsaturated solution before drying to 1 and then the moisture content after drying (final moisture content). By doing so until the ratio becomes 0.05 or less, a water-soluble polymer dried product that is a thin-film foam piece is obtained.

Further, in the course of the above-mentioned drying treatment, a sterilization treatment can be performed on the unsaturated solution.
In this sterilization process, the output of the pressure reducing pump 13 and the microwave transmitter 20 is controlled by the control means 15 after reducing the moisture contained in the unsaturated solution to a preset amount.
Here, the preset water content of the unsaturated solution is, as described above, 60% by mass or less, and further 50% by mass or less (lower limit value, with the initial water content of the unsaturated solution being 100% by mass). Is preferably 20% by mass, more preferably 30% by mass. The moisture content of the unsaturated solution in the course of this drying treatment can be estimated, for example, by previously measuring the change in mass of the unsaturated solution over time, but is particularly limited if the moisture content is known. Not something.

The output control of the decompression pump 13 and the microwave transmitter 20 by the control means 15 increases (pressurizes) the pressure from the current level (the pressure at the time when the water content reaches a predetermined amount), and is unsaturated. The temperature of the solution is set to be higher than the current temperature (the temperature at the time when the water content reaches a predetermined amount).
In order to sterilize the unsaturated solution, it is necessary to increase the output of the microwave transmitter 20 and raise the temperature of the unsaturated solution to a temperature at which the unsaturated solution can be sterilized. For this reason, outside air is supplied into the decompression container 11 from the intake pipe 16 and the decompression pump 13 is operated so that the pressure is stabilized.

When sterilizing the unsaturated solution, it is preferable to perform high-temperature sterilization in a short time in order to suppress and further prevent denaturation of the water-soluble polymer. Hereinafter, a specific description will be given.
The pressure in the decompression vessel 11 is, for example, 50 kPa or more, preferably 70 kPa or more, although it depends on the type of the unsaturated solution. On the other hand, since the boiling point of the unsaturated solution can be increased if the pressure in the depressurized container 11 can be increased, the upper limit is not particularly limited, but considering that the drying treatment is performed under reduced pressure after the sterilization treatment, For example, the pressure is set to 200 kPa, preferably 100 kPa.
The boiling point of the unsaturated solution corresponding to the pressure in the pressure reducing vessel 11 is obtained from a conventionally known vapor pressure curve of water, and is 80 ° C. at 50 kPa, 90 ° C. at 70 kPa, 120 ° C. at 200 kPa, and 100 ° C. at 100 kPa. is there. The pressure in the decompression vessel 11 may be adjusted so that the boiling point of the unsaturated solution is equal to or higher than the denaturation temperature of the water-soluble polymer.

Here, as for the sterilization time, the heating time (microwave irradiation time) is controlled so that the sterilization time becomes shorter as the temperature of the unsaturated solution becomes higher. The sterilization time depends on the type of the unsaturated solution, but may be, for example, about 10 seconds at 90 ° C., about several seconds at 120 ° C., or about 1 second at 150 ° C.
As described above, if the drying has progressed to some extent (if the water content of the unsaturated solution is small), it is exposed to a high temperature for a short time (less than a few minutes, preferably about several tens of seconds, more preferably about several seconds). Even if it is carried out, there is almost no influence by heating, and the water-soluble polymer is not denatured (hardly denatured).
After the sterilizing treatment of the unsaturated solution is performed as described above, the drying treatment is subsequently performed. Specifically, the control of the output of the decompression pump 13 and the microwave transmitter 20 by the control means 15 is performed so that the pressure is reduced (reduced pressure) from the current state (the pressure at the end of the sterilization process) and the unsaturated solution is controlled. The temperature is lowered from the current level (the temperature at the end of the sterilization treatment) so that the water in the unsaturated solution is boiled and foamed at a temperature lower than the denaturation temperature of the water-soluble polymer so that the water can be removed.

As a result, a dried water-soluble polymer that has been subjected to a sterilization treatment (a thin film-like foam having an initial moisture content of 1 and a final moisture content of 0.05 or less) is obtained.
This water-soluble polymer dried product can store dry foam and the like as it is, but can also be stored in a state where the container is turned upside down and dropped as described above. It can be crushed, powdered and stored.
In use, dissolve the dried water-soluble polymer dried product in a liquid such as water or saline (dissolve the manufactured water-soluble polymer dried product in the liquid without storage You can also).

Next, examples performed to confirm the operation and effect of the present invention will be described.
Here, the following tests were performed using egg white (an example of an unsaturated solution containing water and a water-soluble polymer derived from a living body).
First, the results of a molecular structure analysis performed to evaluate a dried product A (a dried product of a biologically-derived water-soluble polymer) obtained by drying the above-mentioned egg white while foaming it into a foam will be described with reference to FIG. . This molecular structure analysis was performed using a circular dichroism dispersometer (J-820, manufactured by JASCO Corporation) under the conditions of a wavelength of 205 to 240 nm and a measurement temperature of 25 ° C. (normal temperature).

In addition to the dried egg white product A (Example: dashed line), the dried egg white dried product B (comparative example: thin solid line) dried without foaming was used at 98 ° C. as a reference sample showing heat damage. Egg white (dotted line) and untreated egg white (thick solid line) which were allowed to stand at 25 ° C. for 20 minutes after heating for 10 minutes were used.
The waveforms of the dried egg white products A and B are slightly different from the waveforms of the untreated egg white, but there is almost no effect of drying, and the helix structure of albumin, the main component of egg white, is broken. It was found that it could be maintained almost without any problem. On the other hand, the egg white that has been heat-treated at 98 ° C. has a reduced CD intensity at 208 to 230 nm as compared with the untreated egg white, and particularly the peaks around 210 nm and 220 nm are reduced and separated, and the helix structure of albumin is reduced. It turned out that it changed to a random structure.

Next, the result of examining the effect of the foaming of egg white on the drying time under reduced pressure will be described with reference to FIG.
Here, 5 g of egg white was placed as a raw material in a 100 cc peaker, and under reduced pressure (5 kPa), the output of the microwave transmitter was changed to 50 W (x), 100 W (Ｗ), 150 W (□), and The egg white was dried until the final moisture content was adjusted to 200 W (marked with ○) and the final moisture content became 0.05 or less. When the output of the microwave transmitter is 150 W or 200 W, the foaming state of the egg white is maintained from the start to the end of drying. At the output of 50 W, the egg white does not foam (bubbles are generated but does not grow). From the middle to the middle, the foaming state of the egg white was maintained, and from the middle to the end, the egg white did not further foam (the foaming state of the albumen from the middle to the middle) continued.
By setting the output of the microwave transmitter to 50 W, the drying time of the egg white (about 1 to 3 days) can be greatly shortened (drying time: about 85 minutes) as compared with the conventional FD, but the output is further increased. It was found that the moisture content was rapidly reduced in a short time by increasing the temperature and maintaining the foaming state, and the drying time could be further shortened. In particular, at an output of 150 W and 200 W, in which egg white was dried while being foamed from the start of drying to the end of drying, the drying time could be reduced to less than 20 minutes (about 15 minutes).

Here, the effect of the output (50 W, 100 W, 150 W, and 200 W) of the microwave transmitter on the drying process of the egg white will be described in more detail.
When the pressure condition is 20 kPa, the boiling point is 60 ° C. from the conventionally known vapor pressure curve of water. At this time, when the output of the microwave transmitter was set to 100 W, the temperature of the egg white (atmospheric temperature near the egg white, the same applies hereinafter) was 40 ° C. or less (the microwave room temperature drying method described in Non-Patent Document 1 described above). (Equivalent to (MVD)).
When egg white is dried under these conditions, the water has a high boiling point (60 ° C.), so even if the supplied energy is 100 W, the water gradually evaporates without boiling. A film-shaped dried product (thick film-like material) having a thickness of several mm containing bubbles of about millimeters was obtained (see FIG. 2 (D)).

When the pressure condition is 5 kPa, the boiling point is 30 ° C. from the conventionally known vapor pressure curve of water. At this time, when the output of the microwave transmitter was set to 50 W, the temperature of the egg white was 40 ° C. or less.
When the egg white is dried under these conditions, the water in the egg white boils because the boiling point of water (30 ° C.) is low, but the supplied energy is as small as 50 W and large bubbles are generated in the egg white liquid. The egg white was gradually dried, and a dry product in the form of a bubble buffer (Air Cap (registered trademark)) having a thickness of about 5 mm was obtained.
When the output of the microwave transmitter was set to 100 W when the pressure condition was 5 kPa, the temperature of the egg white was 40 ° C. or less.
When the egg white is dried under these conditions, the water in the egg white boils because the boiling point of water (30 ° C.) is low, but the supplied energy is a little less than 100 W and the egg white foams, but the generation of bubbles does not continue. Thus, a dried product in which a foamed portion and a foamed film portion were mixed was obtained.

When the output of the microwave transmitter was set to 150 W when the pressure condition was 5 kPa, the temperature of the egg white was 40 ° C. or less.
When the egg white is dried under these conditions, the water in the egg white boils due to the low boiling point of water (30 ° C.), and the supplied energy is as high as 150 W, so that the egg white is dried while foaming continues, A large foamy dried product was obtained.
When the pressure condition was 5 kPa and the output of the microwave transmitter was set to 200 W, the temperature of the egg white was 40 ° C. or less.
When the egg white is dried under these conditions, the water in the egg white boils due to the low boiling point of water (30 ° C.), and the supplied energy is as high as 200 W. Therefore, the egg white is dried while foaming continues, A large foam-like dried product was obtained (see FIGS. 2A and 2B).

Next, the result of examining the effect of egg white foaming on the drying speed under reduced pressure will be described with reference to FIG.
FIG. 5 shows changes in the water content until a dried egg white product A (marked by □) and a dried egg white product B (marked by ○) are obtained. Like the dried egg white product A, the egg white is dried while foaming it in a foamy form, so that the drying speed is greatly increased as compared with the dried egg white product B which is dried without foaming the egg white. I knew it could be done.

Finally, the results of comparing the dried product A obtained by another drying method to evaluate the solubility of the dried product A of the above-mentioned egg white will be described with reference to FIG.
The solubility test was performed by dissolving 0.05 g of dried egg white in 5 mL of ultrapure water, filtering the solution at predetermined time intervals, and stirring the filtrate to obtain albumin (an egg white protein) which is one of the components of egg white. (Content: 50-60%) in the solution (titer = mg / mL).
The samples include dried egg white product A (Example: 印), dried egg white product B (Comparative Example: 印), freeze-dried product dried by FD (■), and MVD (Implemented for 1 hour) and a dried product (marked with ◆) dried by combining FD.

In the initial stage, the freeze-dried product was the fastest, and the dried product B of egg white was the slowest. This is thought to be due to the fact that the freeze-dried product is porous, whereas the dried egg white product B is a thick film, and the freeze-dried product is more easily dissolved than the dried egg white product B. .
For this reason, it was found that the dried product obtained by combining MVD and FD had good solubility, though slightly inferior to the freeze-dried product.
The dried egg white product A has a higher initial dissolution rate than the dried egg white product B, and its solubility is slightly inferior to that of the freeze-dried product, but is substantially the same as the dried product obtained by combining MVD and FD. Was obtained, and it was found that the solubility was good. This is probably because the dried egg white product A is a thin foam.

  From the above, the method and the apparatus for producing a dried biologically-derived water-soluble polymer of the present invention can significantly reduce the drying time and improve the solubility of the biologically-derived water-soluble polymer. It was confirmed that a dried product was obtained.

  As described above, the present invention has been described with reference to the embodiments. However, the present invention is not limited to the configurations described in the above-described embodiments, and the matters described in the claims are not limited. Other embodiments and modifications that can be considered within the scope are also included. For example, the method of manufacturing a biologically-derived water-soluble polymer-dried product of the present invention and a device for manufacturing the same in combination with some or all of the above-described embodiments and modifications are also included in the scope of the present invention. included.

10: an apparatus for producing a dried water-soluble polymer derived from a living body, 11: a reduced pressure vessel (chamber), 12: an optical fiber thermometer (temperature detecting means), 13: a reduced pressure pump (depressurized means), 14: a microwave heating means, 15: control means, 16: intake pipe, 17: flow meter, 18: flow control valve, 19: oil / water separator, 20: microwave transmitter, 21: isolator, 22: measuring section, 23: operating section, 24 : Computer, 25: Pressure gauge, 26: Microwave power supply

Claims (7)

  Under reduced pressure conditions, the unsaturated solution containing water and a water-soluble polymer derived from a living body is irradiated with microwaves to boil the water in the unsaturated solution at a temperature lower than the denaturation temperature of the water-soluble polymer, and the boiling is performed. Biologically-derived water-soluble, characterized by performing a drying treatment for removing water while expanding the unsaturated solution in a foamy manner so that the apparent volume becomes 10 times or more the initial volume by the generated steam. Method for producing dried polymer.   The method for producing a water-soluble dried polymer derived from a living body according to claim 1, wherein, during the drying treatment, after the water contained in the unsaturated solution is reduced to a predetermined amount, the pressure and the unsaturated water are reduced. Raising the temperature of the solution to be higher than the pressure and the temperature of the unsaturated solution when the water contained in the unsaturated solution is reduced to a predetermined amount, and performing a sterilization treatment on the unsaturated solution. Of producing a dried water-soluble polymer derived from a living body.   3. The method according to claim 1 or 2, wherein the dried product obtained by performing the drying treatment is crushed and powdered. Manufacturing method of dried products.   The method for producing a water-soluble dried polymer derived from a living body according to any one of claims 1 to 3, wherein the drying treatment is performed in a state where the unsaturated solution is contained in a hydrophobic container. A method for producing a dried product of a water-soluble polymer derived from a living body. A chamber in which an unsaturated solution containing water and a biologically-derived water-soluble polymer is placed,
Temperature detection means for detecting the temperature of the unsaturated solution in the chamber,
Pressure reducing means for reducing the pressure in the chamber to a reduced pressure state;
Microwave heating means for irradiating the unsaturated solution in the chamber with microwaves for heating,
Based on the temperature data obtained by the temperature detecting means, the pressure reducing means controls the temperature at which the water in the unsaturated solution boils below the denaturation temperature of the water-soluble polymer and the microwave heating. Means for boiling the water of the unsaturated solution, and controlling the apparent volume to be at least 10 times the initial volume by the steam generated by the boiling so that the unsaturated solution expands in a bubble-like manner. An apparatus for producing a dried biologically-derived water-soluble polymer.   6. The apparatus according to claim 5, wherein the control unit reduces the pressure in the decompression unit and the microwave heating unit to a predetermined amount of water contained in the unsaturated solution. An apparatus for producing a dried biologically-derived water-soluble polymer, wherein the temperature of the unsaturated solution is controlled to rise to a temperature at which the unsaturated solution can be sterilized, provided that the above conditions are satisfied.   7. The apparatus for producing a dried water-soluble polymer derived from a living body according to claim 5 or 6, further comprising a hydrophobic container containing the unsaturated solution and disposed in the chamber. Equipment for producing water-soluble polymer dried products.