WO2006016713A1

WO2006016713A1 - Microcapsule using pectin as wall material

Info

Publication number: WO2006016713A1
Application number: PCT/JP2005/014975
Authority: WO
Inventors: Yukiko Takakura; Kentarou Maruyama
Original assignee: Ajinomoto Co., Inc.
Priority date: 2004-08-11
Filing date: 2005-08-10
Publication date: 2006-02-16
Also published as: JP2006050946A

Abstract

Disclosed is a microcapsule. After forming an O/W emulsion with a water phase containing pectin and an oil phase, polyvalent cations are mixed into the O/W emulsion, thereby producing a microcapsule containing an oil-soluble substance and having a median diameter of 0.01-100 μm.

Description

Microcapsules with pectin as a wall material

The present invention relates to a microcapsule using pectin as a wall material. Background art

In recent years, health foods such as dietary supplements and functional foods have attracted attention due to the growing health consciousness. Capsules are used for document protection, stabilization, and taste / odor masking of the ingredients contained in these foods. There are various types of capsules, but hard capsules such as tablets, soft capsules, seamless capsules, and conventional microcapsules have a particle size of 0.3 mm to 2 cm. is there. Therefore, when these capsules are added to food, the texture changes. Emulsion-type foods such as mayonnaise have a particle size of 5 m or less and cannot be perceived by the tongue when eating. However, emulsion-type foods have problems in terms of heat stability / storage stability, difficulty in masking, and cost.

In addition, in conventional microcapsules, protein derived from animals such as cattle, pigs, birds and fish has been used as the wall material, but the market demand for non-animal materials is also increasing.

As a method for producing micro-force cells using non-animal materials as a wall material, polysaccharides and oily emulsions are dropped into an aqueous polycation salt solution to form a crosslink between the polysaccharide and polyvalent ions. A microcapsule that is formed and solidified is known (see Patent Document 1).

However, in the dropping method in which emulsion is dropped into a polyvalent cation salt aqueous solution, since the particle size depends on the wettability of the nozzle diameter, only a comparatively large capsule of millimeter order can be produced. In addition, it is a multi-core capsule with multiple oil droplets in one capsule Therefore, there is a problem that the amount of inclusion per capsule is small.

A microcapsule having a median diameter of 3 or less without using an emulsifier is also known (see Patent Document 2).

However, in the invention, it is essential to use protein as a wall material. In addition, the manufacturing method is complicated, such as operations such as preliminary emulsification and pressure treatment.

Fine particles containing a natural polysaccharide and having an average particle size of 0.1 to 50 im are known (see Patent Document 3).

However, since the present invention is a method for producing a multi-core pushcell, complicated steps such as membrane emulsification with a porous glass membrane, concentration adjustment step, and insolubilization step are required. In addition, since it is a multi-core capsule, the amount of encapsulation per capsule is reduced.

A WZOZW composite emulsion in which a water-soluble polymer such as a water-soluble polysaccharide is blended in an outer aqueous phase is known (see Patent Document 4). .

However, the emulsions of the invention include those having a median diameter as small as 20 to 200 nm, but the invention is characterized by the composition ratio of water, an oily component, and a lipophilic emulsifier. For this reason, an emulsifier is not only an essential component, but also the oily components that can be used are limited.

There is known a microcapsule in which a fragrance is encapsulated by an edible gum-like film (see Patent Document 5).

Although the coacervate method and the seamless method are mentioned as the capsule production method of the invention, in the case of the coacervate method, polymer droplets (coacervate) are collected and formed on the surface of the core material (oil). Therefore, the thickness of the force cell is always larger than that of a single cell drop (see: Multi-layered gel at in / acacia microcapsules by compl ex coaservat ion me thod, Journal of chemical engineering of Japan, 793-798 vol. 30 No. 5 199 7). In the case of the seamless method, since the capsule particle diameter depends on the wettability of the nozzle diameter, it is difficult for the microcapsules of the present invention to have a particle diameter of several hundreds um or less. In the present invention, the coacervate method (coacervation method) means that insoluble core substance particles (oil, etc.) are dispersed in a polymer solution in advance, and then the concentration of the polymer Adjust the temperature, pH, and other variables to the values in the region where coacervation occurs to generate coacervate droplets, collect them on the surface of the core material particles, and manufacture micro force cells.

Capsules using natural polymers are also known (see Patent Document 6)

However, since the invention is a seamless capsule, the particle size is large.

Patent Literature 1

Japanese Unexamined Patent Publication No. 7-145045

Patent Document 2

JP 2003-240 17 Gazette

Patent Document 3

Japanese Patent Laid-Open No. 2004-2582

Patent Document 4

International Publication WO 02/43698

Patent Document 5 ^

Japanese Unexamined Patent Publication No. 2000-342186

Patent Document 6

JP 2001-245660 A DISCLOSURE OF THE INVENTION

The present invention has been made to solve the above-described problems. An object of the present invention is to provide a microcapsule. As a result of studying to solve the above problems, O ZW emulsion was prepared with an aqueous phase containing pectin and an oil phase, and then mixed with polyvalent cations to encapsulate an oil-soluble substance, resulting in a median diameter. The inventors have found that microcapsules having a diameter of 0.01 to 100 m can be produced, and have completed the present invention. More specifically, the inclusions are oil-soluble, the capsules are non-animal vectin, the surfactant-emulsifier is not essential as the capsule material, and the preparation is simple and stable. Good and oil per capsule It has been found that microcapsules with a large amount of inclusion are preferable. The present invention is particularly useful in the fields of pharmaceuticals, foods, health foods, animal feeds, cosmetics, bath / toiletries, and the like.

That is, the present invention relates to a wall material obtained by mixing 1) OZW emulsion with an aqueous phase and an oil phase containing 0.01 to 10% by weight of pectin, and then mixing polyvalent cations. A microcapsule containing a cutin polyvalent cation gel, containing an oil-soluble substance, and having a median diameter of 0.01 to 100 m, and 2) 0.01 to 10% by weight After preparing an O / W emulsion with an aqueous phase containing cutin and an oil phase, the wall material contains pectin calcium gel obtained by mixing calcium ions, contains oil-soluble substances, and has a median diameter of 0. Including microcapsules of 0 1 to 100 m, and 3) including microcapsules of 1) or 2), characterized in that no emulsifier is used when preparing OZW emulsions, and 4) The microcapsules of 1) to 3), characterized in that pectin has an amide group 5) Including the microcapsule of 1) to 4), characterized in that the oil-soluble substance contained is W / O emulsion. 6) OZW emulsion is prepared and mixed with polyvalent cations. 1) to 5) of the mic mouth capsule characterized by adding pectin methylesterase, and 7) adding polyvalent cation after adding pectin methyl esterase 6) including microcapsules.

According to the present invention, it is possible to manufacture a microcapsule having a size not perceived during eating, specifically, a median diameter of 100 m or less. In addition, the inclusion is oil-soluble, the capsule wall material is non-animal vectin, a surfactant / emulsifier is not essential as the capsule material, preparation is simple, and stability is good In addition, it is possible to provide a microcapsule with a large amount of oil inclusion per force pushell.

In the present invention, the microcapsule means a capsule having a median diameter of 0.0 1 to 100 ηι. The median diameter is preferably small from the viewpoint of the stability of the capsule and the fact that it can be ingested by humans. For ingestion by humans, the median diameter is preferably 10 0 ΠΙ より or less, more preferably 10 xm or less. In the present invention In this case, the active ingredient can be introduced into the microcapsule, but the median diameter is preferably 0.1 m or more from the viewpoint of the encapsulation efficiency. In addition, the manufacturing method of the force pussel in the present invention is not limited as long as it can manufacture capsules having a median diameter of 0.01 to 100 m, and examples thereof include a method using ultrasonic waves, a stirring method, and a high pressure extrusion method. The Capsules with a median diameter of 0.01 to 100 m cannot be manufactured by the seamless capsule manufacturing method using multi-tube nozzles, the coacervate manufacturing method, and the capsule manufacturing method by tableting. It cannot be used in the present invention.

In the present invention, it is important that the material used as the wall of the capsule is pectin. The pectin concentration is 0.11 to 10% in the aqueous solution, more preferably 0.1 to 3%, and still more preferably 1 to 3%. If the pectin concentration is too high, it is not preferable in that the capsules aggregate, and if the pectin concentration is too low, the stability of the capsule is low, and it is not preferable in that the contained oil is separated.

It is preferable that the pectin as the capsule wall material is amidated in that the gel strength is increased by hydrophobic bonding. 'The solution to be mixed with the aqueous phase is not particularly limited as long as it is an oil-soluble substance, but handling is more preferably edible oil from the viewpoint of cost and safety. Producing microcapsules containing the target substance at one time without separately manufacturing the microcapsules and their inclusions by mixing the target substances such as drugs and edible nutritional components in advance with oil-soluble substances This is preferable. The oil-soluble substance may be WZO emulsion, which is preferable in that it can contain a water-soluble drug, an edible nutritional component, and the like. In the text, unless otherwise noted, the contents of the microphone mouth capsule will be explained using hydrophobic examples.

In the present invention, it is important to prepare an OZW emulsion with an aqueous phase containing pectin and an oil phase, and then mix with a polyvalent cation. Further, from the viewpoint of stability, the polyvalent cation is preferably a calcium ion.

The calcium ion concentration is from 0.01 to 100 OmM, more preferably 0.01. ˜10-0 mM, more preferably 1 to 1 OmM. If the polyvalent cation concentration is too high, it is not preferable in terms of agglomeration of force capsules, and if the polyvalent cation concentration is too low, it is not preferable in terms of low capsule stability and separation of the encapsulated oil.

In general, it is known to add an emulsifier when producing an emulsion or suspension. Even in the present invention, microcapsules can be formed by adding an emulsifier such as sugar ester, monodaliselide, sorbitan ester, etc., but in the present invention, the reason for safety, odor, cost, etc. when ingesting as a food or medicine Therefore, it is also characterized in that microcapsules can be formed stably even if the material for the capsule film does not contain an emulsifier.

In the present invention, the structure stability and inclusion stability against the heating load of the capsule are improved by reacting with pectin methylesterase (hereinafter sometimes referred to as PME) after preparation of the capsule. By adding a polyvalent cation, preferably calcium ion, to PME, the structural stability and inclusion stability of the capsule against heating load are further improved. The PME concentration is 2-30 OmP EU / ^ m 1, preferably 20-300 m PE UZml. If the PME concentration is too high, it is not preferable in that the capsules aggregate, and if the PME concentration is too low, it is not preferable in that the effect of improving the stability is small. Here, PEU is an abbreviation for Pectin Esterase Unit, which is a unit that indicates the ability of PME 1 m 1 to decompose methine methyl ester and produce lm mo 1 acid per minute.

In addition, it is not essential to add polyvalent cations, specifically calcium ions, etc. to PME, but when adding calcium ions to increase the stability against heating load, The concentration is 20 mM, more preferably 1 to 1 OmM. If the calcium ion concentration is too high, it is not preferable in that the capsules aggregate, and if the calcium ion concentration is too low, it is not preferable in that the effect of improving the stability is small. If calcium ions are not added, free force lupoxyl groups that are not chelated to calcium ions become excessive, and force cells are aggregated or force wall surfaces are weakened.

In addition, if PME treatment is performed before capsule preparation, the entire gelation will occur during capsule preparation. A psel is not formed. Therefore, the capsule wall is further strengthened by PME treatment and calcium chloride addition after capsule preparation.

(Example 1)

Production of pectin capsules using an ultrasonic device

Pectin (trade name “LM-104AS”, manufactured by CPKelco JAPAN) and deionized water were mixed to prepare a 2% aqueous pectin solution. Next, add 27 ml of 2% pectin aqueous solution and 3 ml of soybean oil (Ajinomoto Oil Co., Ltd.) to a 50 ml stainless steel tube, and heat the sonicator with the ice around the stainless steel tube S on ifier 2 50 (manufactured by BRANSON) was used for 2 minutes at an output of 145 W. After 30 seconds from the start of ultrasonic treatment, 7.3 mM calcium chloride 2m 1 was added at a rate of 127 m 1 / h using a micro syringe pump IC 3100 (manufactured by KD Scientific), and a milky white dispersion was obtained. It was.

When the dispersion liquid obtained by fluorescently staining soybean oil with Ni 1 e Red and pectin with Rhode am ine was observed with a confocal laser scanning microscope LSM510 (manufactured by Carl Zeiss), soybean oil was observed. The formation of encapsulated microcapsules was confirmed. The particle size distribution of the microcapsule dispersion was measured with a laser diffraction particle size analyzer LA 920 (manufactured by Horiba Ltd.). It was a single peak and the median diameter of the outer diameter of the microcapsule was 1.3 m. It was.

(Example 2)

Examination of wall material of microcapsule

The following combinations were used as wall materials and cations for micro-force cells.

1) Pectin 0.02-5%, calcium chloride 0-70 OmM,

2) Alginic acid 0.25 ~; L%, calcium chloride 0 ~ 0.1M,

3) PGA 1 ~ 40%, Alum 2 ~ 200mM,

4) K-carrageenan 0.1 to 1%, potassium chloride 0 to 0.2M,

5) -Carrageenan 0.1-1%, calcium chloride 0-0.2M,

6) Gelatin-gum arabic (1 to 1 mixture) 0.01-0.1% We examine each optimum condition with these combinations,

1) Pectin 2%, calcium chloride 7mM,

2) Alginic acid 25%, calcium chloride 0.05M,

3) PGA 1%, Alum 5mM,

4) κ-carrageenan 0.5%, potassium chloride 0.02Μ,

5) Carrageenan 0.5%, calcium chloride 0.2%,

6) Gelatin-Gum Arabic 0. 0 1%

Was selected. Then, a microcapsule dispersion produced by the same method as in Example 1 using each wall material and each cation was prepared.

Oil encapsulation rate of each microcapsule (%) (Each sample was centrifuged to separate the oil not contained in the capsule, and the amount of oil contained was measured, and the ratio of the amount of oil contained in the total oil amount was obtained. The content was determined by the Soxhlet method), the median diameter (; m), and the number of capsules (X10 ¹² / L). The results are shown in Table 1. Table 1: Effect of wall materials on microcapsules

Table 1 shows that PGA, κ-carrageenan, carrageenan, gelatin and arabic gum have small oil inclusion ratios of 30% or less, while pectin has an oil inclusion ratio of 9 7% and alginic acid has It was found that the encapsulation rate of oil was 94% and the encapsulation rate was large and preferable. In particular, vectin is preferable because it has a median diameter as small as 1 m, and the number of capsules is as large as 150 × 10 ¹² / L, which proves promising as a microcapsule material. (Example 3)

Production of pectin capsules using an ultra-high shearing machine

Pectin (trade name: LM-104AS, manufactured by CPKelco JAPAN) and deionized water were mixed to prepare a 2% aqueous pectin solution. Next, add 8 ml of 2% aqueous pectin solution and 9 ml of soybean oil (manufactured by Ajinomoto Oil Co., Ltd.) to the stirring vessel of the ultra-high shearing machine (Nippon Seiki Seisakusho Co., Ltd.). In the cooled state, it was treated at 9500 rpm for 3 minutes with an ultra-high shearing machine. One minute after the start of stirring, 7.3 mM calcium chloride 6 ml 1 was added for 1 minute to obtain a milky white dispersion. When the particle size distribution of the microcapsule dispersion was measured with a laser diffraction particle size distribution analyzer L A 920 (manufactured by Horiba Ltd.), it was a single peak and the median diameter of the outer diameter of the microcapsule was 4.

(Example 4)

Effects of Pectin Concentration and Calcium Concentration on Microcapsule Particle Size Concentration of pectin (LM—104 AS CPKelco JAPAN)

Microcapsules were prepared in the same manner as in Example 1, except that they were changed to%, 0.2%, 2%, and 5%.

For each concentration of pectin, 2 ml of calcium chloride was added 30 seconds later, but the calcium chloride concentration was changed to 0 mM, 7 mM, 70 mM, and 700 mM.

Table 2 shows the particle size of each microcapsule. The numbers shown in the table indicate the median diameter (^ m) unless otherwise specified. In addition, the gel was severely gelled and the sample became one lump, and the particle size distribution measurement impossible was indicated as “aggregation”. Table 2: Capsule median diameter using pectin

As shown in Table 2, there was a tendency for particles to aggregate as the pectin concentration and calcium chloride concentration increased. Capsules with the least aggregation and a small median diameter were obtained under the conditions of 2% pectin and 7 mM calcium chloride.

(Example 5)

Evaluation of microcapsule stability by the degree of esterification of pectin and the presence or absence of amide groups As shown in Table 3 below, pectin with varying degree of esterification (DE value) of 3 1, 3 4 and 3 6 Microcapsules were prepared in the same manner as in Example 1 using pectin whose types were changed to LMA and LMC. The prepared microcapsules were heat-treated at 120 ° C. for 30 minutes, and the stability before and after heating was evaluated. Table 3: List of pectin esterification levels and types

MA: Low Methoxyl Amidated Pectin

LMC: Low Methoxyl Conventional Pectin Table 4 shows the median diameter before and after heating and the number of capsules. All of the microcapsule dispersions after preparation were white turbid liquids without separation. After heating, LMA (amidation type) was stably dispersed, but both LCG 12 CG and 13 CG were separated. Table 4: Change in median diameter and number of capsules before and after heating

As shown in Table 4, all the microcapsules aggregated or merged after heating and the median diameter increased. However, the higher the degree of esterification, the lower the median change of LMA pectin, and the 101 AS of DE value 36 has a median change of about 1.5 times, and the particle size distribution remains a single peak. The stability was highest. It was found that LMC pectin is not suitable for the preparation of micro-force cells because the aggregation or coalescence progresses dramatically by heating and the median diameter increases.

(Example 6)

Effects of pectin methyl esterase and calcium concentration on microcapsule stability

Mix 5 mL of microcapsule dispersion prepared by the same method as in Example 1 and 5 mL of PME solution with varying concentration, and shake on a shaker under the conditions of pH 4, reaction temperature 40 ° C, and reaction time 4 hours. Calcium chloride solution with a different concentration after reaction Added. Mixed PME (Product name: NOVO SHAPE, manufactured by NOPOSYM) Concentration is 0, 2.5, 25, 250, 500 mP E UZm 1 and added chloride power Lucium concentration is 7, 10, 15 25, 45 OmM. The results are shown in Table 5.

Table 5: Effect of pectin methylesterase and calcium concentration on microcapsule stability (solution state)

From Table 5, PME concentrations of 50 OmPEU / m 1 are all calcium chloride concentrations, PME concentrations of 25 OmP EU / m 1 are 15 mM or more of calcium chloride, and other PME concentrations are 25 mM or more of chloride. It was found that the whole gelled with calcium.

(Example 7)

Effect of the presence or absence of calcium chloride after P ME treatment on heat resistance

A microcapsule dispersion prepared by the same method as in Example 1 was mixed with a PME solution having a changed concentration, and then a sample added with 7 mM calcium chloride lm 1 and an additive-free sample were prepared (all pH 4). This was heated at 120 ° C for 30 minutes, and the median g before and after heating was measured. Mixed PME (Product name: NOVO SHAPE, manufactured by NOPOSYM) Concentration is 0, 2.5, 25, 25 OmPEU / m 1 Met. The results are shown in Table 6.

The control (Cont.) Used was a micro cab cell produced by the production method of Example 1. Table 6: Median diameter before and after heating with and without calcium chloride (zm)

From Table 6, for those that do not add calcium chloride after PME treatment, the median size increases as the PME concentration increases after heating or coalesce or agglomerate. It was found that the media diameter was maintained even after heating. From the above results, it was found that when PME treatment was performed, the capsule structure was resistant to heating load by adding calcium chloride after PME treatment. In addition, it was found that capsules obtained by adding calcium chloride to PME of 25 OmPEUZm 1 had the highest stability and a PME concentration of 0 to 25 OmPEUZm 1. Industrial applicability

According to the present invention, microcapsules having a size that is not perceived during eating can be produced.

Claims

The scope of the claims

1. After making o / w emulsion with water phase and oil phase containing 0.01 to 10% by weight of vectin, mixed with polyvalent cations. A microcapsule containing gel and containing an oil-soluble substance and having a median diameter of 0.01 to 100 mm

2. O / W emulsion prepared with water phase and oil phase containing 0.01 to 10% by weight of pectin, and then mixed with calcium ions. The wall material contains pectin calcium gel and is oil-soluble. A microcapsule containing a substance and having a median diameter of 0.01 to 100 zm

3. The micro-force process according to claim 1 or 2, wherein an emulsifier is not used when producing the O / W emulsion.

4. The microphone mouth capsule according to claim 1, wherein the pectin has an amide group-

5. The microcapsule according to claim 1, wherein the oil-soluble substance contained therein is WZO emulsion.

6. Microcapsules according to claims 1 to 5, characterized in that pectin methylesterase is added after preparing a ○ / W emulsion and mixing multivalent cations.

7. The microcapsule according to claim 6, wherein a polyvalent cation is added after the addition of pectin methylesterase.