JPS6099336A - Preparation of spherical material - Google Patents

Abstract

PURPOSE:To prepare a spherical material with high efficiency by extruding a soln. contg. polysaccharide from an outermost layer of a multilayered tubular nozzle, extruding simultaneously a soln. contg. a gelling agent from an inner layer of the nozzle to gel the polysaccharide layer. CONSTITUTION:Aq. soln. contg. 0.5-20wt% polysaccharide such as carrageenan, sodium alginate, or low methoxyl pectin, etc. is extruded from the outermost layer of a multilayered tubular nozzle. also, aq. soln. contg. 0.1-10wt% gelling agent such as Ca ion, Al ion, or quat. ammonium ion, and water-miscible org. solvent such as methanol, ethanol, isopropanol, etc. is discharged from inner layers of the nozzle to form liquid drops, and the polysaccharide is gelled forming the outermost layer of the particle.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a spherical article, particularly a spherical article in which the outermost layer and the inner layer have different compositions. More specifically, the present invention relates to a method for producing a spherical material that can encapsulate foods, aromatics, medicines, agricultural chemicals, fertilizers, enzymes, etc. in a manner that maintains their efficacy.

Suspension polymerization is a well-known method for producing simple capsule-like spherical materials, but this method allows food, fragrances, medicines, pesticides, enzymes, etc. to be encapsulated to maintain their efficacy. It is extremely difficult to obtain spheres. Therefore, an aqueous solution of a gelling polysaccharide is dropped from a nozzle having an appropriate shape, and the polysaccharide is contacted from the outer periphery with an aqueous solution containing a substance capable of gelling, so that the polysaccharide is gelled in droplet form. A method to do this is being tried. When carrying out this method, it is preferable that the droplets exhibit a sol state at a relatively low temperature of 30 to 50°C, and that the transition from sol to gel occurs easily. Therefore, carrageenan, sodium alginate, etc. are used as the polysaccharide. Water-soluble salts such as calcium, aluminum, and potassium are used as substances for gelling polysaccharide aqueous solutions. When making spherical objects using this method, the substances contained in the spherical objects include water-soluble and water-insoluble substances, such as silica, oil, etc., and these are dissolved or dispersed in an aqueous polysaccharide solution depending on their properties. A method is to use a droplet F from a nozzle to gel the polysaccharide, or to form a solution of these encapsulated substances using a compound nozzle so that these substances enter inside the polysaccharide droplet. The former method has the convenience of being able to easily create spherical objects, but has the disadvantage that the substance to be encapsulated escapes from the droplets during the gelation process of the polysaccharide, resulting in large losses. .

In the latter method, if the surface tension of the substance encapsulated in these spherical objects is lower than the surface tension of the aqueous polysaccharide solution, the substance to be encapsulated moves to the outer layer of the droplet during droplet formation, and the outermost layer of the spherical object moves to the outer layer of the spherical object. A phase inversion occurs in which the aqueous polysaccharide phase that should become the solution moves to the inner layer of the droplet, and the intended purpose is often not achieved. Even if a droplet phase is formed that can still achieve the desired purpose, it is difficult to increase the gelation rate of the polysaccharide in the outermost layer to a sufficiently high rate using currently developed methods. Substances that should be added to the gas leak into the external phase, making it difficult to achieve the intended purpose.

The inventors of the present invention have conducted extensive studies to find an efficient method for manufacturing spherical objects without the above-mentioned drawbacks, and as a result, have achieved the intended purpose and completed the present invention based on an idea completely different from those methods. did.

The gist of the present invention is to encapsulate liquid droplets containing a substance capable of gelling a polysaccharide solution in a polysaccharide solution that is to become the outermost layer of a spherical object, thereby gelling the polysaccharide. The method for producing a spherical object is characterized in that the outermost layer of the spherical object is formed by: ejecting an aqueous solution of a polysaccharide to form the outermost layer of the spherical object from the outermost layer of a multi-tube composite nozzle; From the inner layer nozzle, a solution containing a substance capable of gelling an aqueous polysaccharide solution (hereinafter referred to as a gelling agent) is released, thereby forming droplets and gelling the polysaccharide to form a spherical object. It's in the manufacturing method. Other substances to be encapsulated in the resulting spherical material may be dissolved or dispersed in a solution containing a gelling agent, or may be embedded in a gelling agent-containing solution to efficiently form the inner layer of the spherical material. It can be captured well.

That is, in the conventional method, gelation of the polysaccharide that forms the outermost layer of the spherical object is performed from the outside of the spherical object, so the time required to form the outermost layer is longer, and the outermost layer is usually formed in a fluid. In particular, it is restricted in that it must be carried out in liquid. On the other hand, in the formation of spherical objects by the method of the present invention, the gelation of polysaccharides when forming the outermost layer is caused from inside the spherical object, so the formation of the outermost layer is extremely difficult. Formation of the outermost layer, that is, gelation of the polysaccharide, does not necessarily need to be carried out in the liquid phase, as the process can proceed rapidly.
This process can be carried out by dropping the spherical object directly onto a wire mesh or belt, and the handling is significantly improved compared to the conventional method. Furthermore, in the method for forming spherical objects of the present invention using multiple tubular nozzles, the polysaccharide-containing solution starts contacting the outer periphery of the gelling agent-containing liquid layer and gelation progresses, so that the outermost polysaccharide layer is Formation is extremely rapid, and undesirable phase inversion phenomena can be completely eliminated.

Therefore, in conventional methods for producing similar spherical objects, elution or leakage of the substance to be contained in the spherical objects has hardly been observed.

In the production of the spherical objects of the present invention, a method is employed in which droplets containing a gelling agent are dropped into a polysaccharide solution, a method in which a polysaccharide solution is sprayed around the outer periphery of droplets containing a gelling agent, or a multi-tubular nozzle is used. A method of discharging a polysaccharide solution from the outermost nozzle of a multi-tube nozzle, discharging a gelling agent-containing solution from the inner side of a multi-tube nozzle to form droplets, and promoting gelation of the polysaccharide. However, from an industrial standpoint, the most efficient method for producing spherical objects is using a multi-tube nozzle.

When encapsulating flavoring substances, flavoring substances, medicinal ingredients, enzymes, etc. into gelled polysaccharide spherules, from the nozzles arranged inside other than the nozzle that releases the aqueous solution containing the gelling agent. These substances, components, etc., or a liquid containing them may be discharged, or a mixed liquid of a gelling agent aqueous solution and a liquid containing these substances/components may be discharged from a nozzle arranged inside. If the droplets are still gelling in the middle of falling and falling onto a wire mesh, etc., and the substance to be encapsulated does not have excessive volatility, dissolve or disperse the substance to be encapsulated in an aqueous polysaccharide solution. It may also be discharged from the outermost nozzle of a multi-tube nozzle.

Polysaccharides with gelling ability used in the present invention include wax methoxyl pectin, carrageenan, sodium alginate, agar, 7-arselan, guar, and locust pea gum. In order to prevent loss and denaturation of aroma substances, medicinal substances, etc., polysaccharides must be able to maintain a sol state even at relatively low temperatures such as 30 to 50°C, and be easily gelled.
Particularly preferred are wax methoxyl pectin, carrageenan, and sodium alginate because non-toxic substances can be used as gelling agents. The concentration of the polysaccharide aqueous solution is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight! It is preferable that If the weight ratio is less than 0.5, gelation is insufficient;
If it exceeds % by weight, it will be difficult to obtain a homogeneous solution, and the high viscosity will make handling difficult.

As the gelling agent, water-soluble salts containing cation species or water-miscible organic solvents described below are used, and in the case of water-soluble salts, the type of cation may be appropriately selected depending on the type of polysaccharide used. Examples of these salts include water-soluble salts containing calcium, aluminum, and quaternary ammonium, such as calcium chloride, calcium acetate, calcium lactate, aluminum chloride, aluminum sulfate, epitylpyridinium chloride, alkyldimethylbenzylammonium chloride, wax methoxyl pectin, and carrageenan. , sodium alginate, agar, and furseleran, and can be used as a gelling agent for these polysaccharides.

When carrageenan is used as the polysaccharide, it is preferable to use water-soluble salts containing potassium, magnesium, and ammonium as gelling agents, such as potassium chloride, potassium sulfate, potassium phosphate, magnesium chloride, magnesium sulfate, ammonium chloride, and ammonium sulfate. . Two or more types of these salts can be combined. These salts are preferably used as an aqueous solution having a concentration of 0.1 to 10% by weight; if the concentration is too low, the gelling ability of the polysaccharide solution will be insufficient, which is not preferred.

Examples of water-miscible organic solvents include methanol, ethanol, ingropanol, ethylene glycol, glopylene glycol, chrycerin, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, and dimethylformamide. It can be used in common regardless of the

Both the gelling agent and the water-soluble organic solvent must be non-toxic if the spherical material is to be used for food. The liquid containing substances that gel these polysaccharides may include taste substances, flavoring substances, etc. depending on the intended use of the spherical product.
Medicinal ingredients, enzymes, etc. may be dissolved or dispersed.

Preferably, the liquid containing the substance that causes the polysaccharide to gel is in the range of 10 to 90 percent of the total volume of the sphere. In other words, a solution containing less gelling agent than the above range would require an extremely long time for gelation to proceed throughout the droplet, making it impractical; on the other hand, when using a solution containing a large amount of gelling agent, The thickness of the wall of the spherical object is insufficient to achieve the intended purpose. The droplets may be dropped into a liquid such as water or directly onto a wire mesh or plate.

In order to prevent leakage of the substance to be added, which is one of the objects of the present invention, it is preferable to drop the substance directly onto a wire mesh or plate rather than dropping it into a liquid such as water. However, in this case, it is necessary that gelation from the inside progresses sufficiently throughout the droplet, so a sufficient amount of time, at least 1 second, is allowed for the droplet to reach the wire mesh or plate that receives the droplet from the nozzle. For example, it is preferable to set the distance between the nozzle and the wire mesh or plate to be 5 meters or more, and allow free fall between the nozzle and the wire mesh or plate.

Furthermore, it is also possible to adopt a method in which the droplet is caused to fall into a liquid containing a substance that causes polysaccharide to gel, thereby causing gelation from both the inside and outside of the droplet.

Thus, the method of the present invention differs from known methods in the formation mechanism of the outermost layer, improves various drawbacks of known methods, and is an extremely efficient method for producing desired spherical objects. It is clear that the spherical material produced can be dried depending on the purpose.

The present invention will be described in more detail below with reference to Examples.

Example 1 An aqueous polysaccharide solution was prepared by adding 10% by weight of sugar as a taste substance to an aqueous solution of 3% by weight of carrageenan, and an aqueous solution of 2% by weight of potassium chloride. Diameter 1
．． A polysaccharide aqueous solution is applied from the nozzle on the 91 side of a double tubular nozzle in which 0 mm and 0.2 mm nozzles are arranged concentrically, and a potassium chloride aqueous solution is applied from the inner nozzle.The liquid ratio of the polysaccharide aqueous solution and the potassium chloride aqueous solution is The mixture was discharged at a ratio of 65:35 and dropped onto a wire mesh set 6 meters below the double tubular nozzle to obtain a spherical substance (Sample IA).

On the other hand, the polysaccharide aqueous solution was discharged from another nozzle with a diameter of LO mm and dropped into potassium chloride aqueous centric fluid to obtain spherical particles (
Sample IB Comparative Example).

The sugar d contained in the white spherical material is the same as shown in Table 1, and it is clear that there is no elution loss of sugar according to the method of the present invention.

Example 2 Sample 2A (of the present invention) consisting of spherical objects was produced in exactly the same manner as in Example 1 except that a 3% by weight aluminum chloride aqueous solution was used instead of the potassium chloride aqueous solution used in Example 1. 2o (comparative example) was obtained, and the sugar content was measured in the same manner, and the results were as shown in Table 1.

Example 3 Sample 3A consisting of spherical objects was prepared in the same manner as in Example 1 except that a sodium alginate aqueous solution was used in place of the carrageenan aqueous solution used in Example 1, and a calcium chloride aqueous solution was used in place of the potassium chloride aqueous solution (this invention). Sample 3B (comparative example) was obtained, and the sugar content was measured in the same manner. The results are shown in Table 1.

Example 4 Sample 4A (present invention) and Sample 4B made of spherical objects were prepared in exactly the same manner as in Example 1, except that an aqueous solution of roumetquin lupectin was used instead of an aqueous carrageenan solution and an aqueous calcium chloride solution was used instead of an aqueous potassium chloride solution. (Comparative Example) was obtained and the sugar content was measured in the same manner. The results are as shown in Table 1.

Example 5゜ An aqueous solution containing 4% by weight carrageenan and 10% by weight sugar was discharged from the outer nozzle of the double tubular nozzle used in Example 1, and a 1% by weight potassium chloride aqueous solution was discharged from the inner nozzle to form droplets. At this time, the potassium chloride aqueous solution was adjusted to 40% of the total volume of the droplet. The droplets were placed into a 3 weight percent aqueous potassium chloride solution placed 1 meter below a double tubular nozzle.

The sugar content of the obtained spherical sample 5 was measured and the results were as shown in Table 1.

Table-1 Example 6゜Carrageenan 4 weight percent aqueous solution and potassium chloride 3
A weight percent aqueous solution and spearmint oil were prepared.

A carrageenan aqueous solution and 1 salt were added from the outermost, central, and innermost parts of a triple tubular nozzle in which nozzles with diameters of 1.0 mm, 0.6 mm, and 0.4 mm were arranged concentrically.
All of the 100 spheres produced by dropping the aqueous solution of hypotum and spearmint oil were composite spheres in which the inner layer contained spearmint oil and the outermost layer was made of gelled carrageenan.

For comparison, nozzles with diameters of 1.0 mm and 0.4 mm were arranged concentrically in a double tubular nozzle. Carrageenan aqueous solution was discharged from the outer part and spearmint oil was discharged from the inner part to form spherical droplets, and potassium chloride aqueous solution was discharged. Of the 100 spherical objects produced by adding drops into the inside, 38 were composite spherical objects with spearmint oil in the inner layer and carrageenan gel as the outer layer, and the remaining 62 were spherical objects consisting only of carrageenan. .

Applicant: Mitsubishi Acetate Co., Ltd. Agent Patent Attorney 1) Taketoshi Mura

Claims (1)

[Claims] l) A polysaccharide-containing solution is extruded from the outermost layer of the multi-tubular nozzle, and a liquid containing a substance capable of gelling the polysaccharide is extruded from the inner layer to form droplets. A method for producing a spherical object, which comprises gelling a layer. 2) Claim 1 characterized in that one or more polysaccharides selected from carrageenan, sodium alginate, and wax methoxyl pectin are used as the polysaccharide.
The method for producing a spherical object according to item 1 or 2. 3) Substances that gel polysaccharides include potassium, calcium, magnesium, ammonium, aluminum,
The spherical shape according to claim 1 or 2, characterized in that one or more substances selected from water-soluble salts containing one or more ions selected from 74th grade ammonium are used. How things are manufactured. 4) Production of a spherical article according to claim 1 or 2, wherein the substance that causes the polysaccharide to gel is a water-miscible organic solvent that does not dissolve the polysaccharide constituting the droplets. Method. 5) Methanol, ethanol, as a water-miscible organic solvent
Claim 1, characterized in that one or more solvents selected from inpropatol, ethylene glycol, glopylene glycol, glycerin, acetone, tetrahydrofuran, dioxane, dimethylformamide, and dimethyl sulfoxide are used. A method for producing a spherical object according to item 5.