HK1253285B - Capsules containing two phases and method for their preparation - Google Patents

Description

The present invention refers to capsules coated with a calcium alginate film which contain two mutually immiscible or partly miscible phases, such as an aqueous phase and a hydrophobic phase. Moreover, the present invention also refers to the method by which said two phases can be encapsulated and kept stable within the formed capsule.

The preparation of polysaccharide capsules containing two immiscible phases in the interior thereof is known in the state of the art, for example the production of seamless capsules comprising a polysaccharide gel membrane wherein said capsule encapsulates an emulsion is disclosed in patent application EP 2289494 A1 . Furthermore, patent application US 4702921 A discloses a method for preparing fish-egg-like capsules consisting of membranes of calcium alginate containing separate aqueous and oil phases comprising the steps of: a) preparing an emulsion, b) surrounding said emulsion droplets with membranes of calcium alginate, and c) separating said emulsion by heating to at least 45ºC. Finally, the patent application GB 2480361 A discloses core shell capsules comprising a hydrophilic core A, a polymer shell C, and an intermediate oil layer B containing hydrophobic particles. In addition to the said patent applications, Thorsten Brandau (Chapter 10: "Annular Jet-Based Processes" In: "Microencapsulation in Food Industry: A Practical Implementation Guide", 2014 Elsevier Science, ISBN: 978-0-12-404735-8) discloses a series of annular jet-based processes suitable for the encapsulation of various active species such as flavours.

Biphasic capsules can be obtained by a method usually known as "spherification", either by direct or reverse spherification.

In industrial-scale direct spherification, for example, the substance to be encapsulated and a non-calcium alginate are pumped through two concentric tubes with flow volumes that allow a drop of the substance to be encapsulated to be formed covered by a film of non-calcium alginate solution, which acts as a gelling agent. It is also possible to mix the alginate with the substance to be encapsulated. Said drop falls into a bath containing a source of calcium ions, forming a layer of gel which contains the material to be encapsulated. Said film is formed almost instantaneously on the outside and is semi-solid and gelatinous, while holding the encapsulated substance inside, in solid form if the calcium ions can migrate and in liquid form if the calcium ions cannot migrate.

An industrial spherification method is disclosed in patent application PCT WO 2009/109681 A1 , for example, in which food products such as fruit pulp are encapsulated, said food products for encapsulation always being aqueous based, in other words, the substance to be encapsulated is hydrophilic.

However, in reverse spherification, the substance to be encapsulated is mixed with a source of calcium ions or magnesium ions, for example calcium chloride or other calcium salt. Next, a drop or other shape is formed with said mixture of the substance to be encapsulated and calcium ions or magnesium ions, and is introduced in a solution containing a non-calcium alginate, such as sodium alginate, for example. When the drop formed containing calcium ions is put in contact with the solution containing the alginate, a semi-solid, calcium alginate gelatinous film forms almost instantaneously, which holds within it the substance to be encapsulated.

Following exhaustive research, the inventor of the present invention has developed a spherification method by which capsules containing two substances which form two mutually immiscible or partly miscible phases can be obtained on an industrial scale, and which surprisingly are spherical shaped. While it is possible with this method for the diameter of said capsules to be up to 50 mm without affecting the sphericity thereof, such as within a range from 5 mm to 50 mm, the capsules obtained by the method of the present invention which fall within the scope of the claimed invention have a diameter from 10 mm to 50 mm, yet more preferably from 15 mm to 50 mm, from 20 mm to 50 mm, from 25 mm to 50 mm and most preferably from 30 mm to 50 mm.

The method according to the present invention is based on the use of two concentric tubes which form the two-phase drop to be encapsulated and the gelling solution, it being necessary that the substance applied through the outer tube should comprise a source of calcium ions or magnesium ions. The production of the biphasic capsules takes place using a method known as reverse spherification with some variations.

The present invention therefore relates to a method for producing spherical capsules formed at the outer portion thereof by a film of calcium alginate characterised in that it comprises in its interior two liquid substances that form two mutually immiscible or partly miscible phases J Z characterised in that it comprises the following steps:

1. a) preparation of the aqueous non-calcium alginate solution in which the concentration of alginate is within the range 0.05% to 5% by weight of the solution;
2. b) preparation of the substances that will form the two mutually immiscible or partly miscible J phases to be encapsulated in which one of said substances comprises a source of calcium ions or magnesium ions;
3. c) application of the substances that will form the two phases to be encapsulated through concentric tubes, it being necessary to apply the substance that comprises the source of calcium ions or magnesium ions through the outer tube;
4. d) introduction of the drop or drops formed in step (c) into an aqueous solution that contains alginate, in which the outer layer of the drop reacts forming at least one sphere which contains both phases;
5. e) washing, draining and packing of the capsules formed in step (d).

The method of the present invention can be used both in the food industry and in the cosmetic, intraceutical, chemical or pharmaceutical industries, or any other industry that requires this type of capsule.

in the present disclosure, biphasic substances are understood to be two substances that are mutually immiscible or partly miscible. They may be organic or inorganic substances provided they comply with the above.

In addition, in the context of the present disclosure but without falling under the claimed scope of the present invention, the term biphasic is understood in the present document to refer to two phases that are mutually immiscible or partly miscible, and may contain both two liquid phases, a liquid-solid phase where the solid can be obtained with or without a reaction, a liquid-gas phase, and in addition a person skilled in the art could use additives to emulsify the encapsulated solutions and obtain biphasic spheres that are more stable over time. Finally, biphasic spheres obtained by freezing one of the two phases and a subsequent direct or reverse spherification reaction, by means of a method known as frozen spherification are also disclosed herein without falling under the claimed scope of the present invention. Also disclosed herein but not falling under the claimed scope of the present invention are two phases which are separated by a film of alginate, or even an alginate sphere formed earlier and incorporated with the sphere that will be formed subsequently by the method of the present invention. For example, a sphere of oil obtained by direct spherification can be included in a solution of vinegar with a source of calcium, which after contact with the alginate creates a sphere surrounded by a film of alginate which has within it said sphere of oil. It may also include a solid phase of a frozen or gelled product which is incorporated in said calcium-rich solution for subsequent gelling.

In the cosmetic industry, liquid paraffins or paraffin waxes, petroleum jellies, plant oils, waxes, fatty alcohols and their esters, lanolin and silicon and mixtures thereof can be used as the oleous phase.

In the food industry, biphasic spheres can be obtained such as vinegar-oil, soy sauce-sesame oil, mustard-olive oil, honey-olive oil and coffee-chocolate, among others. A person skilled in the art will understand that any combination of liquid substances that form two mutually immiscible or partly miscible phases can be used for encapsulation according to the method of the present invention. Preferably, the substances that form the two mutually immiscible or partly miscible phases are vinegar-oil, soy sauce-sesame oil, mustard-olive oil, honey-olive oil or coffee-chocolate.

Moreover, said mutually immiscible or partly miscible liquid substances can be mixed with seasonings, perfumes, flavourings and other oil-soluble additives.

The aqueous solution containing calcium ions used in the method of the present invention could be any source of calcium ions, provided it can form a calcium alginate gel which forms the outer film of the capsule. Preferably, the aqueous solution that contains calcium ions is selected from solutions of calcium chloride, calcium lactate, calcium gluconate, or a mixture thereof. Preferably, the source of calcium ions is calcium chloride.

Furthermore, said solution of calcium ions may contain any type of additive or may be mixed with any raw material that allows the organoleptic characteristics of the capsule obtained to be modified.

The alginate solution of the method of the present invention may be any non-calcium alginate salt, provided it reacts in the presence of calcium ions and forms the outer film of calcium alginate of the capsules. Preferably, the alginate used is sodium alginate. The pH of the alginate solution is preferably between 2 and 14.

An additional advantage of the method of the present invention is that all the steps are carried out at ambient temperature. An increase or reduction in temperature, as well as increasing the production cost of the capsules, may affect the viscosity, density and surface tension of the oleous and aqueous phases present in the method, and it would therefore be necessary to modify various process parameters to obtain the same results as at ambient temperature.

EXAMPLES

Example 1. Production of biphasic vinegar-olive oil capsules according to the method of the present invention.

Commercial vinegar was taken, and 1.2% by weight of xanthan gum and 3% by weight of calcium lactate were added. A solution of sodium alginate 0.4% by weight was also prepared. Extra virgin olive oil was used for the second phase.

Drops were produced through two concentric tubes, and said drops containing olive oil in the inside tube and the prepared vinegar solution in the outer tube were introduced into a bath of the sodium alginate solution at ambient temperature. Said drops were collected and placed in a bath of water for washing. They were drained and packed. At least one capsule 45 mm in diameter was obtained, which contained two phases of olive oil and vinegar.

Example 2. Production of biphasic capsules of soya-sesame oil according to the method of the present invention.

Commercial soy sauce was taken, and 1% by weight of xanthan gum and 1% by weight of calcium chloride were added. A solution of sodium alginate 0.5% by weight was also prepared. Sesame oil was used for the second phase.

Drops were produced through two concentric tubes, and said drops containing sesame oil in the inside tube and the prepared soy sauce solution in the outer tube were introduced into a bath of the sodium alginate solution at ambient temperature. Said drops were collected and placed in a bath of water for washing. They were drained and packed. Capsules 22 mm in diameter were obtained, which contained two phases of sesame oil and soy sauce.

Example 3. Preparation of biphasic capsules of jojoba oil and caffeine according to the method of the present invention.

A 0.2% by weight caffeine solution, and 0.8% by weight of calcium chloride was added. A solution of sodium alginate 0.9% by weight was also prepared. Jojoba oil containing vitamin E at 0.5% by weight was used for the second phase.

Drops were produced through two concentric tubes, and said drops containing jojoba oil and vitamin E in the inside tube and the prepared caffeine solution in the outer tube were introduced into a bath of the sodium alginate solution at ambient temperature. Said drops were collected and placed in a bath of water for washing. They were drained and packed. At least one capsule 16 mm in diameter was obtained, which contained two phases of jojoba oil with vitamin E and caffeine.

Example 4. Preparation of solid-liquid biphasic capsules not according to the present invention.

A solution containing coffee and 1% by weight of xanthan gum was prepared and 0.2% by weight of calcium chloride was added. Liquid chocolate was also prepared and sodium alginate 0.2% by weight was added.

Drops were produced through two concentric tubes, and said drops containing the liquid chocolate solution in the inside tube and the prepared coffee solution in the outer tube were introduced into a bath of the 0.3% sodium alginate solution at ambient temperature. In said bath, the outer layer of the coffee solution reacted with the alginate forming a film of calcium alginate on the outside. In turn, the calcium included in the coffee reacted with the sodium alginate included in the chocolate, forming an outer film on the chocolate. This chocolate solidified completely, and at least one capsule 10 mm in diameter was obtained, which contained two phases: a solid chocolate phase and a liquid coffee phase.

Example 5. Production of biphasic capsules of vinegar-olive oil macerated with rosemary according to the method of the present invention.

Commercial vinegar was taken, and 1% by weight of xanthan gum and 0.4% by weight of calcium lactate were added. In addition, olive oil macerated with rosemary was taken for the second phase.

Drops were produced through two concentric tubes, and said drops containing olive oil macerated with rosemary in the inside tube and the prepared vinegar solution in the outer tube were introduced into a bath of 0.3% sodium alginate solution at ambient temperature. Said drops were collected and placed in a bath of water for washing. They were drained and packed. At least one capsule 28 mm in diameter was obtained, which contained two phases of olive oil macerated with rosemary and vinegar.

Although the invention has been described with respect to preferred embodiments, these should not be considered as limiting the invention, which is defined by the following claims.

Claims (11)

1. Method for producing spherical capsules formed at the outer portion thereof by a film of calcium alginate and comprising in its interior two liquid substances that form two mutually immiscible or partly miscible phases characterised in that it comprises the following steps:

   a) preparation of the aqueous non-calcium alginate solution in which the concentration of alginate is within the range 0.05% to 5% by weight of the solution;

   b) preparation of the substances that will form the two mutually immiscible or partly miscible phases to be encapsulated in which one of said substances comprises a source of calcium ions or magnesium ions;

   c) application of the substances that will form the two phases to be encapsulated through concentric tubes, it being necessary to apply the substance that comprises the source of calcium ions or magnesium ions through the outer tube;

   d) introduction of the drop or drops formed in step (c) into an aqueous solution that contains alginate, in which the outer layer of the drop reacts forming at least one sphere which contains both phases;

   e) washing, draining and packing of the capsules formed in step (d).

   wherein the method is a reverse spherification.
2. Method according to claim 1, characterised in that the aqueous solution that contains calcium ions is selected from solutions of calcium chloride, calcium lactate, calcium gluconate or a mixture thereof.
3. Method according to claim 2, characterised in that the source of calcium ions is calcium chloride.
4. Method according to claims 1 to 3, characterised in that the alginate used is sodium alginate.
5. Method according to claims 1 to 4, characterised in that the pH of the alginate solution is between 2 and 14.
6. Spherical capsule obtained by a method according to any one of claims 1 to 5, characterised in that the diameter of said capsule is in the range from 10 mm to 50 mm.
7. Spherical capsule according claim 6, characterised in that the diameter of said capsule is in the range from 15 mm to 50 mm.
8. Spherical capsule according to claim 6, characterised in that the diameter of said capsule is in the range from 20 mm to 50 mm.
9. Spherical capsule according to claim 6, characterised in that the diameter of said capsule is in the range from 25 mm to 50 mm.
10. Spherical capsule according to claim 6, characterised in that the diameter of said capsule is in the range from 30 mm to 50 mm.
11. Spherical capsule according to any one of claims 6 to 10, characterised in that the substances that form the two mutually immiscible or partly miscible phases are vinegar-oil, soy sauce-sesame oil, mustard-olive oil, honey-olive oil or coffee-chocolate.