JPH0380541B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to spheres, particularly polysaccharide spheres containing a water-immiscible liquid therein, and a method for producing the same. Gelled polysaccharide spheres are used in various foods such as artificial fish eggs, or as microcapsules containing flavoring ingredients, flavoring ingredients, medicinal ingredients, etc. [Prior art] Conventionally, spherical polysaccharides are produced by dropping an aqueous solution of a polysaccharide with gelling ability through a nozzle of an appropriate shape, and then turning the polysaccharide into an aqueous solution of a substance (hereinafter referred to as a gelling agent) that gels the polysaccharide. It is manufactured using a method that involves contact and gelation. When trying to obtain a polysaccharide sphere containing a water-immiscible liquid inside, a multi-ring nozzle is used as an extension of the conventional technique so that the water-immiscible liquid becomes the inner layer and the polysaccharide aqueous solution becomes the outer layer. For example, Japanese Patent Application Laid-open No. 102373/1983 discloses a method in which the inner layer is a water-immiscible liquid and the outer layer is a polysaccharide aqueous solution. ing. However, this method has the disadvantage that if the surface tension of the water-immiscible liquid is lower than that of the polysaccharide aqueous solution, a reversal phenomenon occurs during droplet formation in which the water-immiscible liquid moves to the outer layer and the polysaccharide aqueous solution moves to the inner layer. There is. In addition, even if droplets are formed in which polysaccharides form the outer layer, the gelation of the polysaccharides is not fast enough, or the droplets cannot completely contact the gelling agent-containing aqueous solution. This has the disadvantage that water-immiscible liquids leak from the bulb. [Purpose of the Invention] The present inventors have conducted repeated studies with the aim of providing a polysaccharide spherical product having a water-immiscible liquid in its inner layer that does not have the above-mentioned drawbacks, and a method for producing the same. The invention has been achieved. [Structure of the Invention] That is, the gist of the present invention is (1) a gelled polysaccharide composition containing a water-immiscible liquid containing a potassium-containing anionic surfactant as an inner layer and containing 30% or more of Katupa carrageenan; (2) A water-immiscible liquid containing potassium-containing anionic surfactant is added from the inner nozzle of the multi-tubular nozzle and contains at least 30% carrageenan. The present invention provides a method for producing a polysaccharide spherical substance, which comprises discharging an aqueous polysaccharide solution from the outermost nozzle of the nozzle to form droplets. The polysaccharide composition used in carrying out the present invention must contain 30% or more of Katupa carrageenan, and if it contains 30% or more of Katupa carrageenan, the remaining components must be It may be carrageenan, landa carrageenan, or other polysaccharide. Although components other than polysaccharides may be included, it is particularly preferable that the polysaccharide composition contains 50% or more of Katupa carrageenan. The reason why it is necessary to include Katupa carrageenan in the polysaccharide composition is that the spherical objects of the present invention have an outer layer of a gelled polysaccharide, and this outer layer consists of an aqueous polysaccharide solution mixed with an anionic surfactant containing potassium. This is because Katupa carrageenan can be efficiently gelled by this anionic surfactant. Anionic surfactants containing potassium include stearic acid, palmitic acid, oleic acid,
Potassium salts of lauric acid and dodecylbenzenesulfonic acid can be mentioned. These anionic surfactants are characterized by excellent solubility in water-immiscible organic solvents. In the present invention, a water-immiscible liquid means a liquid that is substantially immiscible with water under normal conditions, such as low-boiling organic solvents such as chloroform, dichloromethane, and hexane, and high-boiling organic liquids such as vegetable oil. Various liquids can be exemplified. The water-immiscible organic liquid may be selected depending on the use and purpose. For example, if the product is to be used for food, vegetable oil is preferably used, and if a flavoring component is to be encapsulated to impart a sustained release effect, a liquid that is compatible with and dispersible with the flavoring component may be used. The concentration of the potassium-containing anionic surfactant in the water-immiscible liquid may be sufficient to gelatinize Katupa carrageenan, and is preferably 0.1 to 0.05 to 1 mol per 1 water-immiscible liquid. The concentration may be between 1 molar and 1 molar. If the amount is less than 0.05 mol, the gelation of Katupa carrageenan will be insufficient, and if it exceeds 1 mol, no further improvement in the gelling effect will be observed, which will be economically disadvantageous. In addition to the potassium-containing anionic surfactant, flavor components, flavoring components, medicinal components, and the like may be dissolved or dispersed in the water-immiscible liquid. Next, the method for producing the polysaccharide spheres of the present invention will be described. Polysaccharide spheres are produced using multi-ring nozzles. FIG. 1 is a schematic diagram of an example of a multiple ring nozzle, in which A is a side sectional view of a triple ring nozzle, C is a plan view thereof, B is a side sectional view of a double ring nozzle, and D is a side sectional view of a double ring nozzle. is its plan view. The production of the polysaccharide spherical product of the present invention involves releasing a polysaccharide-containing aqueous solution from the outermost tube nozzle, and
When the anionic surfactant-containing immiscible liquid is discharged from the inner tube nozzle, droplets are formed while the outer layer containing the carrageenan-containing polysaccharide and the anionic surfactant-containing liquid inner layer form an interface. At the interface between the water-immiscible liquid and the polysaccharide aqueous solution in the outer layer, the hydrophobic part of the anionic surfactant efficiently coordinates potassium ions to the inner layer and the potassium ions to the outer layer. While gelling the polysaccharide layer, it diffuses into the polysaccharide outer layer, efficiently forming a gelled polysaccharide outer layer. The concentration of the polysaccharide in the aqueous polysaccharide solution used in producing the spherical material having a gelled polysaccharide outer layer of the present invention may be any concentration that does not hinder the formation of droplets, and the optimum concentration is Although it depends on the temperature of the aqueous polysaccharide solution during droplet formation and the content of Katupa carrageenan, it is preferably in the range of 1 to 10%. In order to encapsulate flavoring ingredients, flavoring ingredients, medicinal ingredients, etc. in the inner layer of the polysaccharide spherical material of the present invention, FIGS.
A method of forming droplets by discharging a polysaccharide-containing aqueous solution from an anionic surfactant-containing water-immiscible liquid containing these components from the inside of a double tube nozzle as shown in FIG. A water-immiscible liquid containing an anionic surfactant is introduced from the innermost tube of a triple-tube nozzle as shown in A and C through an intermediate tube nozzle.This liquid contains the same or different flavor components. This can be carried out by discharging an aqueous polysaccharide solution from an outer tubular nozzle to form droplets. [Effects of the present invention] As is clear from the above, in the polysaccharide spheres of the present invention, diffusion of the organic liquid in the inner layer to the outer layer is extremely small, and the escape of the substance encapsulated in the inner layer of the polysaccharide spheres is suppressed to the utmost. It was possible to capture it in the state,
This is because the outer layer of the polysaccharide is efficiently gelled from within, and the phase inversion phenomenon can be prevented by forming an aqueous phase and an oil phase during its production. This is because it was able to prevent substances from moving to the outer layer. The present invention will be explained in more detail with reference to Examples below. Examples 1 to 3 and comparative examples Inner diameter 0.25 mm and inner diameter as shown in Figure 1 B and C
Using a double tube nozzle consisting of a 0.5mm nozzle,
Using a water-immiscible liquid and a polysaccharide aqueous solution having compositions as shown in Table 1, in Examples 1 to 3, the polysaccharide aqueous solution was discharged from an outer tubular nozzle and the water-immiscible liquid was discharged from an inner nozzle. Droplets were thus formed, creating spheres with a gelled polysaccharide outer layer. On the other hand, in a comparative example, a water-immiscible liquid that does not contain a potassium-containing anionic surfactant was used as the water-immiscible liquid discharged from the inside of the tubular nozzle, and the formed droplets were formed into spherical shapes by being dropped in a 3% potassium chloride aqueous solution. Made things form. Table 1 shows the proportion of spheres containing a hydrothertically miscible liquid as an inner layer.

【table】

【table】 [Brief explanation of drawings]

Figure 1 is a schematic diagram of the longitudinal section and cross section of a multi-tube nozzle, where A and C are triple-tube nozzles, B and D are double-tube nozzles, A and B are longitudinal sections, and C and D are longitudinal sections. A cross section is shown.

Claims (1)

[Scope of Claims] 1. A polysaccharide sphere having an inner layer made of a water-immiscible liquid and an outer layer made of a polysaccharide containing 30% or more of Katupa carrageenan gelled with a potassium-containing anionic surfactant. 2. The polysaccharide spherical material according to claim 1, wherein the anionic surfactant containing potassium is a potassium salt of an anion having a hydrocarbon substituent having 11 or more carbon atoms. 3. A water-immiscible liquid containing an anionic surfactant containing potassium is discharged from the inner nozzle of a multi-tubular nozzle, and an aqueous polysaccharide solution containing 30% or more of Kazupaka carrageenan is discharged from the outermost nozzle of the nozzle. 1. A method for producing a polysaccharide sphere having a polysaccharide outer layer containing 30% or more of gelled Katupa carrageenan, the method comprising: forming droplets with a polysaccharide outer layer containing 30% or more of gelled carrageenan. 4. The method for producing polysaccharide spheres according to claim 3, characterized in that an anionic potassium salt having a hydrocarbon substituent having 11 or more carbon atoms is used as the potassium-containing anionic surfactant.