JPS6161782B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel artificial granule for oral intake and a method for producing the same. In particular, the present invention relates to an artificial granular material for oral intake in which water is separated from the inside of the granular material of artificial fish eggs such as artificial salmon roe, and the shape of the granular material does not change, and a method for producing the same.

Soft capsules (so-called pearl-shaped capsules) are conventionally known as orally ingestible granular substances whose contents are kept in a fluid state. However, in conventional soft capsules, the contents constituting the homogeneous fluid phase are granular substances encapsulated by a solid film-forming layer that is different from the contents, and nothing is known about the substance that is brought into contact with the diaphragm.

A well-known similar orally ingestible particulate material is so-called artificial fish roe. There are many proposals for artificially producing foods similar to these fish roe (Special Publication No. 15088-15088, Special Publication No. 15088, No. 46
−51772, Special Publication No. 13697, Special Publication No. 13697, Special Publication No. 53-
31933, and Japanese Patent Application Laid-Open No. 1983-79755).

However, although the artificial fish roe produced by the above-mentioned conventional method has characteristics such as hue and strength, if left for a long time, water will separate from the roe, the particle shape will change, and the shape will shrink. The texture and appearance change significantly, and if the amount of separated water increases, the fish roe particles become immersed in water, which significantly reduces the commercial value.

In other words, conventionally proposed methods for producing artificial granules, especially methods for producing artificial fish roe, can be roughly divided into methods of hardening granulated fish roes through physical treatment, methods of hardening them through chemical treatment, or methods that involve hardening granulated fish roe through physical treatment. It can be divided into methods that are used together.

Physical methods mainly involve processing at low temperatures, and chemical processing methods include processing with a chemical gelling agent, such as a polyvalent metal compound, to chemically gel it. . As can be easily guessed by these granulation methods, when artificial fish roe produced by physical treatment is heated to a temperature higher than the treatment temperature (usually 5°C or less), the thermal stability of the fish roe decreases markedly, and eventually the fish roe becomes a sol. It reaches the point where the fish eggs become unable to maintain their shape. Of course, it is possible to blend the grains so that they maintain their shape at the normal edible temperature (30°C to 40°C), but with such a blend, the grains will be hard and have a poor texture, especially for salmon roe-like. Granules with a soft texture cannot be obtained, and the commercial value as artificial fish roe is inferior.

In addition, even if appropriate reaction conditions are selected for artificial fish roe produced by treatment with a chemical gelling agent, the moisture retained in the roe separates from the roe, significantly reducing its commercial value.

In order to compensate for the drawbacks of the physical and chemical treatments described above, it is conceivable to use both methods in combination, but even if they are used in combination, it is not possible to prevent the moisture retained in the granules from separating from the granules.

However, the present inventors have conducted various studies to improve the above-mentioned properties desired in artificial particulate materials for oral ingestion, and have developed a processing agent containing aldehydes that substantially removes the above-mentioned particulate materials and formaldehyde. It has been discovered that the above-mentioned problems can be solved all at once by contacting with.

Therefore, an object of the present invention is to bring a part of the outer surface of the edible granules containing an edible sol or/and an edible gel into contact with a processing agent containing aldehydes that substantially excludes formaldehyde. Or, by forming a film on the entire surface, part of the inner surface, or the entire surface, the color, strength, texture, stability, and appearance of the granules are superior, and liquids such as moisture are separated for a long period of time compared to edible granules. The purpose of the present invention is to provide artificial granules for oral ingestion that can be taken orally.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The artificial granules of the present invention and the method for producing the same include (i) an edible granule containing an edible sol or/and an edible gel; (ii) a treatment agent in which at least one layer contains aldehydes substantially excluding formaldehyde; (iii) A novel artificial granular material for oral ingestion, characterized in that it is a substance formed by contacting with. and (iii) for oral ingestion, characterized in that (i) edible granules comprising an edible sol or/and edible gel are brought into contact with (ii) a treatment agent containing aldehydes substantially excluding formaldehyde. Method for producing artificial granules.

It is.

The above (i) edible granules include granules of edible gel substances or edible sol substances containing a liquid such as water and having a gel coating.
No. 15088, Special Publication No. 1972-21772, Special Publication No. 13697, No. 1973
No. 53-31933, JP-A-51-79755, JP-A-48-8587, JP-A-52-59079, JP-A-52
−117282, etc., and Japanese Patent Application No. 18363, Japanese Patent Application No.
It is applicable to the granular materials proposed in No. 53-77395, Japanese Patent Application No. 53-79853, etc.

To give a concrete example, (a) Gel particles whose entire particle is made of the same substance.

(b) Gel particles consisting of two or more types of gel layers.

(c) Particles with a sol phase encapsulated in a gel layer.

(d) Particles in which a sol phase is encapsulated with multiple gel layers.

(e) Particles containing solid or oil particles among the particles (a) to (d).

(f) Particles in which all or part of the gel layer in (a) to (e) has been chemically gelled.

can be mentioned.

The process of producing these edible granules is arbitrary, and there are no limitations on the process for applying the present invention.
Examples of commonly used processes include placing a sol in a suitable physical or chemical gelling agent to create gel particles, or encapsulating a sol or soft gel in a gel-like coating. Here are some ways to do it. The aldehyde may be added to the material used in advance, or may be added during the granulation process, or may be treated with the aldehyde after granulation.

Incidentally, each model of (a) to (e) is shown in FIG. In the figure, S indicates sol, G indicates gel, and O indicates oily substance.

The above-mentioned sol is not particularly limited as long as it is an edible sol-like substance, and the gel is not particularly limited as long as it forms an edible gel, but generally the above-mentioned sol substance and As the gelable substance, polysaccharides (including starch), proteins, polypeptides, etc. are selected and used at appropriate concentrations.

For example, "Large Organic Chemistry" edited by Mr. Funio Kotake, Volume 21 "Natural Polymer Compounds" (published by Asakura Shoten Co., Ltd.)
Proteins and polypeptides described in
28 and pages 356-457), polysaccharides (see pages 177-234), starch and its derivatives (see pages 177-234), which are also described in "Great Organic Chemistry" Volume 20 "Natural Polymer Compounds" (See pages 81 to 176), synthetic glues listed in Attached Table 5 of the Enforcement Regulations of the Food Sanitation Act, etc. can be used.

More specifically, pectin substances such as pectin and petatinic acid, vegetable gum substances such as gum arabic and gum tragacanth, polysaccharides such as carob seed mucilage (locust bean gum) and guar seed mucilage (guaran), and algae. Examples of polysaccharides include alginic acid and its salts, which are cell membrane components, and seaweed stickies such as agar and carrageenan. Specific examples of starches and their derivatives include natural starches such as arrowroot starch and wheat starch, and dextrins obtained by hydrolyzing them. Furthermore, specific examples of proteins and polypeptides include seed proteins such as wheat protein and soybean protein, milk proteins such as casein (milk), gelatin, which is a denatured substance of natural protein, metaprotein, and derivatives of denatured proteins that are further degraded. Examples include proteins. In addition, the synthetic glues listed in Attached Table 5 of the Food Sanitation Construction Regulations include sodium alginate, propylene glycol alginate, sodium cellulose glycolate, calcium cellulose glycolate, sodium starch glycolate, and sodium starch phosphate ester. , sodium polyacrylate, methylcellulose, etc. are used.

Further suitable edible sol substances and gelatinable substances include pectin, gelatin, agar,
Carrageenan, zein, starch, gluten, dextrin, konjac flour, guar gum, gum arabic, locust bean gum, tragacanth gum,
xanthan gum, tamarind gum, albumin,
casein, sodium alginate, alginate propylene glycol ester, cellulose sodium glycolate, cellulose calcium glycolate,
These include sodium starch glycolate, sodium starch phosphate, sodium polyacrylate, and methylcellulose. Particularly preferred are pectin, carrageenan, casein, gelatin, dextrin, sodium alginate, methylcellulose, and the like.

The desired granules can be obtained by appropriately selecting these edible substances depending on the properties, purpose, etc. of the granules and forming a sol phase or gel layer.

These edible substances can be used alone or as a mixture of several kinds in aqueous solution, but in some cases, various physical properties can be improved by combining several kinds.

These edible substances generally range from 0.01 to 50%.
It is preferably used in an aqueous solution of about 0.1 to 30%. The viscosity of these aqueous solutions is appropriately selected depending on the method of forming the granules, the size of the granules, etc., but preferably the viscosity during treatment with a chemical gelling agent (viscosity at treatment temperature) is 40~ A range of 2500 centivoise is used, particularly preferably a range of 50 to 2000 centivoise, even more preferably a range of 60 to 1500 centivoise. Especially in the case of artificial fish eggs, they are generally used at a moisture content of about 80 to 99%.

The chemical gelling agent is preferably a solution of an edible substance capable of gelling an aqueous solution of the edible substance, such as polyvalent metals, sugars, sugar alcohols, etc.
Examples include organic acids and esters of organic acids. Specifically, as the polyvalent metals, organic and inorganic salts of polyvalent metals such as calcium and iron are used. More specifically, representative examples include calcium acetate, calcium lactate, calcium chloride, magnesium chloride, barium chloride, aluminum chloride, and iron chloride. Examples of sugars include glucose, galactose, xylose, sutucarose, etc., and examples of sugar alcohols include sorbitol, mannitol,
Examples of organic acids include citric acid, oxalic acid, succinic acid, tartaric acid,
Examples include lactic acid and glycidic acid, and representative examples of organic acid esters include methyl citrate, ethyl citrate, and ethyl succinate.

In addition, the sol phase or gel layer contains drugs, nutrients, appetite stimulants, attractants for fish or animals, etc.
It is also possible to support useful ingredients such as seasonings, fragrances, sweeteners, and colorants.

The oily substances contained in the particles include, for example, vegetable oils such as olive oil, safflower oil, corn oil, sunflower oil, cottonseed oil, camellia oil, rice bran oil, or mixtures thereof, and animal oils such as squid oil and cod oil. Fish oils such as oil, liver oils such as shark liver oil and carp liver oil, marine animal oils such as seal oil and blue whale oil, shellfish oils such as abalone oil and oyster oil, or mixtures thereof can be used. It is also an oily substance that can be used as a medicinal ingredient. cod liver oil,
Castor oil, fatty acid glycerides, vitamin E, etc. can also be used.

The oily substance can also carry useful ingredients such as medicines, health agents, flavoring agents, appetite stimulants, fish or animal attractants, seasonings, colorants, fragrances, and sweeteners.

In the expression "edible sol" used herein, "edible" refers not only to humans, but also to humans.
It means that it can be orally ingested by any one or more animals such as cows, horses, fish, birds, etc. without causing physiological problems, and "sol" means a solution or a colloidal solution. Furthermore, the term "gel" as used herein refers to a state in which a solute or dispersoid in a solution or colloid solution is physically or chemically gelled or solidified.

As the aldehyde in the above (ii) treatment agent containing aldehydes other than formaldehyde, any compound having an aldehyde group can be used, but generally acetaldehyde, butyraldehyde, octylaldehyde, propylaldehyde, benzaldehyde, cinnamic aldehyde, etc. Aldehydes listed in Attached Table 2 of the Food Sanitation Enforcement Regulations can be used.
Preferred examples include acetaldehyde, propylaldehyde, butyraldehyde, and valeraldehyde.

The aldehyde contained in the treatment agent used in the present invention is 0.001% to 100%, preferably 0.01%
% to 50%, more preferably 0.01% to 20%, and the pH of the treatment liquid is 1 to 11, preferably 2 to 10, and more preferably 3 to 10. Methods for bringing the processing agent and edible granules into contact include adding the processing agent containing aldehydes to part or all of the raw materials, and adding the processing agent containing aldehydes to the granules or intermediate molding. Examples of methods include immersing the object, spraying the processing agent onto the granular material, and entraining the granular material into the flow of the processing agent. It goes without saying that the treatment of aldehydes of the present invention can be used in combination with other gelling methods, such as chemical gelling using metal salts and physical gelling using drying or heating.

One important aspect of the novel orally ingestible particles (iii) above is that it can be used as a novel pharmaceutical dosage form. That is, if the medicinal ingredient is oil-soluble, it can be dissolved alone or mixed with other oily ingredients and encapsulated in a sol phase or gel layer, and if the medicinal ingredient is water-soluble, it can be encapsulated in a sol phase or gel layer. A pharmaceutical drug type granule can be obtained by mixing and dissolving in a gel layer. In this way, one or both of oily or water-soluble medicinal ingredients can be supported on the granules. These granular pharmaceutical preparations are much softer than conventional solid preparations, and their surfaces are smooth and spherical, making them extremely easy to use for elderly people, young children, and patients who complain of difficulty swallowing. It can be taken orally. Moreover, since the material is mostly natural, unexpected problems caused by absorption into the human body can be avoided compared to conventional capsules that frequently use synthetic chemicals.

In another embodiment of the present invention, fish roe (salmon roe type)-like granules can be obtained. In this case, in order to improve the fish egg-like appearance, the colorant concentration of the oily substance should be higher than the sol phase or gel layer that encapsulates the oily substance, thereby approaching the presence of the natural egg yolk part (commonly known as the eyeball). I can do it. For example, the granules obtained by coloring an oily substance orange-red with a commercially available oil-soluble edible natural dye and coloring the sol phase or gel layer pale yellow-orange with a commercially available water-soluble edible natural dye are very similar to salmon roe. be similar.

In the case of roe-like granules, it is often preferable to provide an additional phase outside the sol or gel phase due to the intended use.

In addition, oily substances and edible sol substances may contain salt, seasonings, vitamins, fats, fragrances,
Components such as colorants and preservatives can be supported.

The obtained granules may be eaten by humans as they are, or they may be mixed with natural fish and shellfish or artificially processed products to make food. Such granules can also be used as bait for fishing or farmed fish, or feed for livestock. In that case, depending on the purpose, the outermost shell phase may be coated with an edible sticky liquid to give it mutual adhesion, a viscous process, a seasoning process, a coloring process, etc. In the present invention, the sol phase and gel layer can be added in double or triple layers, if necessary.

Artificial granules for oral intake that have been treated in this way have significantly improved water retention. For example, in the case of artificial fish roe, the water retention has been improved and it has a texture and appearance that closely resembles natural fish roe, significantly increasing its commercial value. It has the effect of increasing

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A 0.8% sodium alginate solution was dropped into a 3% calcium lactate solution using a granulation dropping device having a nozzle with an inner diameter of 6 m/m, and the solution was allowed to stay at room temperature for 3 minutes to cause a chemical reaction, and then the granules were taken out. Washed lightly with water. The obtained granules were immersed in a 10% butyraldehyde solution adjusted to pH 4 and heated at 40℃.
After processing for 60 minutes, the pH was adjusted to 9, and the sample was left immersed for 20 minutes, and then washed with water. The resulting granules were heated at 20°C.
When left for 24 hours, the water separation rate was 18%.

(Note) Method for measuring water separation rate After lightly wiping off the water adhering to the surface of the granules on a cloth, measure the weight of the granules. ( _W1 ).

After being left to stand under certain conditions, the water adhering to the surface of the granules is further gently wiped off with a cloth, and the weight of the granules is measured (W ₂ ).

Calculate the water separation rate using the following formula.

Water separation rate (%) = W ₁ - W ₂ /W ₁ × 100 Comparative Example 1 A granular material obtained by the same operation as in Example 1 except that the 10% butyraldehyde solution treatment step was removed was incubated at 20°C for 24 hours. When left alone, the water separation rate was 50%.

Example 2 Gelatin 5% and sodium alginate 0.8% were produced using a granulation dropping device having a nozzle with an inner diameter of 6 m/m.
While keeping the solution at 40°C, it was dropped into a 3% calcium lactate solution kept at 5°C and allowed to stay there for 3 minutes to undergo physical hardening and chemical reaction, and then the grains were taken out and lightly washed with water. The obtained granules were heated at 40°C in a 1% probilaldehyde solution adjusted to pH 4.
After soaking for 60 minutes at pH 9, the sample was left immersed for 20 minutes, and then washed with water.

When the obtained granules were left at 20°C for 24 hours, the water separation rate was 19%.

Comparative Example 2 The water separation rate after 24 hours at 20° C. of a granular product obtained by the same operation as in Example 2 except that the steps after the 1% propylaldehyde treatment were omitted was 51%.

Example 3 An aqueous solution containing 5% gelatin, 2.0% pectin, and 0.3% sodium alginate was made into a light yellow-orange color using a commercially available water-soluble edible natural coloring agent using a granulation dropping device combining two nozzles with an inner diameter of 6 mm and an inner diameter of 0.5 mm. (Liquid A) and a solution (Liquid B) in which refined corn oil was colored orange-red with a commercially available oil-based natural food dye.
Droplets containing purified corn oil were made in liquid A while keeping the temperature at 20°C, and this was dropped into a 3% aqueous solution of calcium lactate at 20°C to allow a chemical reaction to occur for 3 minutes, then taken out and lightly washed with water. .

The obtained granules were immersed for 2 minutes in an aqueous solution containing 0.8% sodium alginate and 5% gelatin heated to 40°C, and then immersed in a 3% calcium chloride solution for 30 seconds, and then lightly washed with water. Then, spherical particles with an outer diameter of about 7 mm were obtained with an additional gel coating.

The resulting triple-structured fish roe particles were placed in a 1% propylaldehyde solution adjusted to pH 4 at 20℃ for 30 minutes.
After soaking for a minute, it was taken out and lightly dyed with water. When the obtained fish roe granules were dried at 35°C for 40 minutes and left at 20°C for 24 hours, the water separation rate was 5%.

In addition, the strength, hue, texture,
The stability and appearance were excellent and very similar to natural salmon roe.

Comparative Example 3 Fish roe grains obtained by the same procedure as in Example 3 except that the steps after the treatment with 1% propylaldehyde solution were omitted had a water separation rate of 35% after 24 hours at 20°C.

Example 4 The same procedure as in Example 3 was carried out, except that instead of the refined corn oil used in Example 3, a commercially available oil-based vitamin A fatty acid ester dissolved in refined soybean oil at a ratio of 0.3% by weight was used. Artificial granules were obtained in the operation. When the obtained artificial granules were left at 20°C for 24 hours, the water separation rate was 5%.

Example 5 An aqueous solution containing 5% gelatin, 2.0% pectin, 0.5% propyl aldehyde, and 0.3% sodium alginate was prepared using a commercially available water-soluble edible natural powder using a granulating and dropping device combining two nozzles with an inner diameter of 6 mm and an inner diameter of 0.5 mm. A solution colored pale yellow-orange with a dye (A
Using a solution (solution B) in which refined corn oil as an oily substance is colored orange-red with a commercially available oil-based edible natural pigment, refined corn oil is encapsulated in solution A while maintaining solution A at 40°C. A droplet was made and dropped into a 3% aqueous solution of calcium lactate at 20°C to carry out a chemical reaction for 3 minutes, then taken out and lightly washed with water.

The obtained granules were immersed for 2 minutes in an aqueous solution containing 0.8% sodium alginate and 5% gelatin heated to 40°C, and then immersed in a 3% calcium chloride solution for 30 seconds, and then lightly soaked. After washing with water, spherical particles having an outer diameter of about 7 mm and having an additional gel coating were obtained.

The obtained fish roe particles were dried at 35°C for 40 minutes, and then dried at 20°C.
When it was left for 24 hours, the water separation rate was 6°C.

In addition, the strength, hue, texture,
The stability and appearance were excellent and very similar to natural salmon roe.

Example 6 An aqueous solution containing 5% gelatin, 2.0% vectin, and 0.3% sodium alginate was made into a light yellow-orange color using a commercially available water-soluble edible natural coloring agent using a granulating and dropping device combining two nozzles with an inner diameter of 6 mm and an inner diameter of 0.5 mm. (Liquid A) and a solution (Liquid B) in which refined corn oil was colored orange-red with a commercially available oil-based natural food dye.
Droplets containing purified corn oil were made in liquid A while keeping the temperature at 20°C, and this was dropped into a 3% aqueous solution of calcium lactate at 20°C to allow a chemical reaction to occur for 3 minutes, then taken out and lightly washed with water. .

The obtained granules were immersed for 2 minutes in an aqueous solution containing 0.8% sodium alginate and 5% gelatin heated to 40°C, and then immersed in a 1% propylaldehyde solution adjusted to PH4 at 20°C. in
After soaking for 30 minutes, it was taken out and lightly washed with water. The obtained granules were immersed in a 3% solution of calcium chloride for 30 seconds and then lightly washed with water to obtain spherical granules having an additional gel coating and an outer diameter of about 7 mm.

The obtained fish roe particles were dried at 35°C for 40 minutes, and then dried at 20°C.
When it was left for 24 hours, the water separation rate was 6%.

In addition, the strength, hue, texture,
The stability and appearance were excellent and very similar to natural salmon roe.

[Brief explanation of the drawing]

FIG. 1 schematically shows specific examples ((a) to (f)) of granular materials to which the present invention can be applied, in which S represents a sol, G represents a gel, and O represents an oily substance.

Claims (1)

[Scope of Claims] 1. At least one layer of an edible granule containing an edible sol or/and an edible gel is a substance formed by contacting it with a processing agent containing aldehydes that substantially excludes formaldehyde. A novel artificial granule for oral ingestion characterized by: 2. The novel artificial granular material for oral intake according to claim 1, wherein the edible granular material is an edible granular material containing an oily substance. 3. The novel artificial fish roe according to claim 1 or 2, wherein the artificial granular material for oral intake is an artificial fish roe. 4. The artificial salmon roe according to claim 3, wherein the artificial fish eggs are artificial salmon roe. 5. The novel artificial granule for oral intake according to claim 1 or 2, wherein the at least one layer is an outermost shell phase. 6. A method for producing artificial granules for oral ingestion, which comprises contacting edible granules with a processing agent containing aldehydes that substantially exclude formaldehyde. 7. The method for producing an artificial granule for oral intake according to claim 6, wherein the edible granule contains an oily substance. 8. The novel method for producing artificial fish eggs according to claim 6 or 7, wherein the artificial granules for oral intake are artificial fish eggs. 9. The method for producing artificial salmon roe according to claim 8, wherein the artificial fish eggs are artificial salmon roe.