JPH02167036A - Natural gum and its manufacturing method - Google Patents

Abstract

PURPOSE:To obtain a gummy matter useful as a thickener, densifier, stabilizer, etc., for foods, cosmetics, pharmaceuticals, etc., utilizing waste shell of cacao nuts by adding water or hot water to shell of cacao nut and extracting soluble components from the shell. CONSTITUTION:The objective gummy matter resistant to precipitation even by the addition of (A) 0.5 pts.wt. of dioxane, (B) 1 pt.wt. of ethanol, (C) 1 pt.wt. of ethanol hydrochloride or (D) 1 pt.wt. of trichloroacetic acid (based on 1 pt.wt. of the gummy matter) is produced by adding 3-50 pts.wt. of water or hot water to 1 pt.wt. of the shell of cacao nut preferably after deactivating the action of enzymes in the shell and extracting the soluble components of the shell.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Fields" The present invention is suitable as a thickener, 4II4 densifier, stabilizer, etc. in the fields of food, medicine, cosmetics, etc.

It also relates to the natural gum substance obtained from the shell of cocoa fruit, which can also be used as water-soluble gummy fiber, and its production method.

"Prior Art" A cacao fruit is composed of an outer shell, seeds contained inside the shell, and a soft substance surrounding the seeds. The molluscum and the soft substance surrounding the seeds undergo a fermentation process using wild yeast, acetic acid bacteria, etc., and the molluscum is used as a raw material for chocolate and cocoa.

However, the reality is that most of the outer shells are currently incinerated and discarded.

The shell of this cacao fruit contains a large amount of carbohydrates as shown in Table 1, and has the potential to become an effective resource.

Table 1 [Problems to be Solved by the Invention] As described above, although cacao fruit shells have the potential to become an effective resource that can be used industrially,
The reality is that there has not been much research into how to use it.

Therefore, one object of the present invention is to provide a technique for effectively utilizing the shells of cacao fruits, which have not been utilized effectively in the past.

[Means for Solving the Problems] As a result of various studies on how to effectively utilize cacao fruit shells, the present inventors noticed that the liquid extracted from crushed shells with water becomes extremely viscous. However, it was discovered that this viscosity is caused by the natural gum contained in cacao fruit, and based on these facts, the present invention was completed.

That is, the present invention provides a natural gum characterized by being obtained from the shell of cacao fruit.

The present invention also provides a method for producing natural gum, which is characterized by adding water or hot water to the shells of cacao fruits to extract soluble components.

Hereinafter, the present invention will be explained in more detail by giving preferred specific examples.

In the present invention, the shell of a cacao fruit refers to the part of the cacao fruit from which the seeds and the mucilage surrounding the seeds are removed. These shells are obtained in large quantities as waste left after collecting the soft substance that envelops the pods and seeds during the processing of cacao beans, which are the raw materials for chocolate and cocoa.

This shell can be left as is for further processing, but
Preferably cut into appropriate size. Cutting improves the efficiency of extracting viscous substances from the shell and speeds up heat transfer inside the shell during the next heating process. 'm
Cutting can be done using commonly used cooking utensils, such as a slicer. Note that the black skin inside the shell has little gum, so it is best to remove it.

Next, blanching is preferably performed by adding water or hot water to the upper shell.The main purpose of blanching is to deactivate the enzyme polyphenol oxidase, which is contained in cocoa fruits and causes browning reaction. , This operation can also improve extraction efficiency. Blanching conditions depend on the size of the shell, but for example,
It is preferable to heat the mixture for 20 minutes, 4 times boiling water for 3 to 5 minutes or more.

Direct heating with steam can also be performed.

If the operation up to blanching is not done quickly and thoroughly,
As the browning reaction of the polyphenol compound progresses, the shell and the extract in the subsequent process turn brown, and the final gum quality obtained also becomes poor in color.

Furthermore, in order to prevent browning reactions, the equipment used should preferably be one that does not elute iron (for example, made of stainless steel), and the water used for blanching should preferably be iron-free. This is to prevent the compound from reacting with iron and causing browning of the extract.

For the extraction of gummy matter, the amount of water or hot water added to the shell is preferably 3 to 50 times the weight of the shell, more preferably 5 times the weight of the shell.
~30 times the weight. If the amount of water added is small, the concentration of the extracted gummy substance will be high, and the viscosity of the extract will be high (which makes it very difficult to separate the solid and liquid).On the other hand, if the amount of water added is large,
This is not preferable because the concentration of the extracted gummy substance is low, so the viscosity of the extract is also low, and a special solvent is required when drying and powdering.

After cooling, the blanched shells are crushed in a mixture of water or hot water to extract the gum, and the solid and liquid are separated from the extract. The coarse crushing can be carried out using a coarse crusher commonly used for fruit processing, such as a grater, finisher, or working blender, and the separation of heat into solids and liquids can be carried out using a centrifugal dehydrator, filter press, or the like. ,
ffl When the viscosity of the crushed liquid is low, a filter, centrifuge, etc. can also be used. In addition, since the shell remaining as a residue after solid/liquid separation also contains gum, the extraction rate can be increased by adding more water and repeating the re-extraction if necessary. In this case, if complete solid/liquid separation is not performed, the product will become gummy and contain insoluble solids, which is not preferable.

The cacao fruit shell extract thus obtained has a high concentration of gum and has a considerable viscosity, and this extract alone can be used for various purposes. Therefore, the natural gum of the present invention may be this extract, but it is more preferable to powder the extract to make it easier to use.

As a method for powderizing the extract, for example, methods such as spray drying or freeze drying the extract can also be adopted.
Preferably, a method is employed in which a hydrophilic organic solvent is used to precipitate a gum substance from the extract. Next, the powdering method using a hydrophilic organic solvent will be explained in more detail.

As the hydrophilic organic solvent, lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol, acetone, etc. can be used, but ethyl alcohol is preferably used. The following explanation is based on an example in which ethylalfur is used as the hydrophilic organic solvent.

When ethyl alcohol is added to the extract to make an ethyl alcohol aqueous solution, the ethyl alcohol concentration is 50% fV/V1
In the above process, gummy substances precipitate. However, 60% (V/
Below V1, it retains its tackiness in an aqueous solution and has a viscosity of 65%.
Since a non-sticky precipitate is formed only at IV/V1 or higher, it is preferable to set the concentration to 65% IV/V1 or higher.When making this one-time ethyl alcohol aqueous solution, ethyl alcohol is added while stirring the extract. Otherwise, vigorous mixing immediately after addition will result in a fine precipitate. On the other hand, when the extract is brought into contact with ethyl alcohol and gently stirred and mixed, a fibrous precipitate is obtained. When these precipitates are collected, drained, washed with ethyl alcohol if necessary, replaced with diethyl ether, etc., and dried, a powdery or fibrous gum substance (1) is obtained. This gum substance is dissolved in an aqueous solution. Then it will show viscosity as shown later,
Further, by subjecting this aqueous solution to the above-mentioned operation, it can be made into a dry product again.

As mentioned above, even if acetone is used in place of ethyl alcohol, a dry gummy substance can be similarly obtained. However, since the polyphenol compounds contained in the extract are easily soluble in water, soluble in ethyl alcohol, and insoluble in acetone, it is preferable to treat with ethyl alcohol rather than acetone because the polyphenol compounds can be easily removed from the gum. If the precipitate is sufficiently washed with ethyl alcohol of 70% (V/V1 or more, preferably 70-80% IV/Vl), the polyphenol substance is washed away, and then drying is performed, pure white with an even higher degree of purification can be obtained. These washing and drying operations are easier and can be obtained in higher yields when the precipitate is in the form of fibers than in the form of fine powder.

In addition, if you obtain a fibrous gum like konbu,
By pulverizing it by physical means, it can be made into a powder that is easy to use. In this case, 0 particles become hard (
This is because it becomes more difficult to dissolve when used, and significant heat generation leads to a decrease in viscosity due to decomposition of the gum substance.

For this reason, it is preferable to use an impact-type or shredding-type pulverizer to crush the particles to a desired particle size.

The natural gum material of the present invention thus obtained has an infrared absorption spectrum shown in FIG. 1, and has the property of not causing precipitation when the following chemicals are added.

A, 0.5 mmf @ dioxane, the same weight of ethanol, the same weight of ethanol, hydrochloric acid, and the same weight of trichloroacetic acid The natural gum of the present invention can be used, for example, in dressings, mayonnaise, ketchup, jam, sauce for grilled meat, etc. It can be used in the same way as other natural thickeners in the production of food products such as sauces and thick sauces. In addition, it can be used as is, or by taking advantage of its properties of being susceptible to heat and acid to reduce its viscosity, it can be used as a food supplying natural dietary fiber. Furthermore, by utilizing the thickening and dispersing effects of this natural gum, it can be used as a densifying agent in drug softeners, as a densifying agent or bubble stabilizer in toothpaste, and as a densifying agent in lotions and creams in cosmetics. can. Yet again. It can also be used in industrial applications such as abrasives and pigment dispersion/suspension agents in the same way as other thickeners.

"Example" Example 1 (Extraction of natural gum) Six Malaysian cacao fruits (3216 g in total), which were collected from cacao trees and then frozen, were placed in hot water in a double pot and boiled for 15 minutes. The seeds were thawed, cut into two, and the seeds, the mucilage surrounding the seeds, and the black skin inside the shell were removed. The remaining shell portion weighed 2054 g in total.

Add purified water to this shell and boil it for 15 minutes in a double boiler to completely inactivate polyphenol oxidase, then add l
I cut it to about ca+angle.

Next, add purified water 10 times the weight of the cut shells.

After boiling for 5 minutes, coarse crushing and extraction were performed. This treatment was carried out by first crushing the shells with a 5+++a+ screen grater manufactured by Seiken Co., Ltd., and then roughly crushing the pieces by washing with water the pieces of equipment that had adhered to the inside of the machine.

The crushed liquid was separated into solid and liquid by filtration using a nylon filter cloth and centrifugation using a Marusan centrifuge at 3.00 rpm for 10 minutes. Approximately 17.7 kg of the extract having a refractometer reading of 0.7 was obtained.

In addition, the extract obtained by adding 10 times the weight of purified water to the shell remaining as a residue after solid/liquid separation, heating for 5 minutes, filtering and centrifuging again, has a refractometer reading of 0.3 It was showing.

Example 2 (Powderization of extract) Add 1 pharmacopoeia ethyl alcohol to the first extract in Example 1 so that the alcohol concentration is 67% iV/Vl, stir gently, and turn into a white powder like kelp. A precipitate formed and was removed and collected in another pharmacopoeia of ethyl alcohol. Then, in order to flush out the polyphenol compound, it was washed three times with 75% ethyl alcohol.

In order to remove moisture from this washed precipitate, it was replaced with special grade ethyl alcohol and then diethyl ether, and then air-dried to leave 31.5 g of a white dried product (hereinafter referred to as "cocoa bod gum"). .

As mentioned above, precipitation can be performed not only with ethyl alcohol but also with other lower alcohols and acetone, but ethyl alcohol is more common, easier to handle, and is said to be suitable for removing polyphenol compounds that exist as impurities. It has advantages.

The dried product thus obtained can be pulverized to an appropriate particle size using a commonly used impact type or shredding type pulverizer.

On the other hand, the method of dropping alcohol or acetone little by little into a vigorously stirred extract produces fine precipitates, so by drying the precipitates, it can be powdered without using mechanical means.

Test Examples The components and properties of the cacao bod gum obtained in Example 2 were subjected to various measurements as shown below.

+1+- Shell component analysis value The general component analysis values of the cacao bod gum are as shown in Table 2, and most of them were carbohydrates.

Table 2 Also, assuming that it will be used in beverages, an aqueous solution containing 10% by weight of high fructose sugar, 0.35% by weight of citric acid, and 05% by weight of cacao bod gum is prepared. When dietary fiber was quantified by methods A and C (enzyme-gravimetric method), 75% by weight of the cacao bod gum was determined as dietary fiber.

Cacao bod gum (dry product) is a starch-like substance that dissolves in both cold and hot water, has little pasty feel, and exhibits high viscosity. Note that compatibility (gel-forming ability) with locust bean gum, xanthan gum, and guar gum was not observed.

An investigation of the characteristics of cacao bod gum as a thickener revealed the following. All of the viscosity measurements shown below were performed using a B-type viscometer manufactured by Shitokyo Keiki.

(2) Relationship between concentration and viscosity of gummy substances When we measured the relationship between the viscosity and the concentration of guar gum, xanthan gum, and cacao bod gum, we found that cacao bod gum, like other natural gum substances, has a The viscosity showed a tendency to increase depending on the temperature. Note that the measurement was performed using rotor No.
, 2 at 30 rpm and 20°C. The results are shown in FIG. In the figure, a is guar gum, b is xanthan gum, and C is cacao bod gum.

(3) Relationship between temperature and viscosity When an aqueous solution containing 0.3% by weight of cacao bod gum was prepared and the change in viscosity as the temperature increased, the viscosity tended to decrease as the temperature increased.

The viscosity was measured using rotor No. 092 at 60 rpm.
I went with m. The results are shown in FIG.

(4) Relationship between salt concentration and viscosity (salt tolerance) Salt was added to various concentrations to an aqueous solution of 0.3% by weight of cacao bod gum, and changes in viscosity as the salt level increased by 4% were investigated. . The viscosity was measured using rotor No. 2 at 60 rpm.
I went there. The results are shown in FIG.

As is clear from this figure, the viscosity of cacao bod gum hardly changes with one degree of salt.

This means that cacao bod gum can also be effectively used in foods such as sauces, dressings, and ketchup.

(5) Relationship between sterilization temperature and viscosity (heat resistance) fal Aqueous solution of 0.3% by weight of cacao bod gum fbl Aqueous solution of 0.3% by weight of cacao bod gum, 3% by weight of common salt fCl 0.3% by weight of cacao bod gum , pH 2,50
Aqueous solutions (adjusted by adding citric acid) were prepared, and the viscosity of these aqueous solutions was measured after holding them at various sterilization temperatures for 30 minutes. The viscosity was measured using rotor No. 1 at 60 rpm and 20°C. The results are shown in FIG. 6, where a, b, and c correspond to the above-mentioned fat, fbl, and fat.

This result shows that the viscosity of cocoa bod gum decreases as the sterilization temperature increases, and the decrease in viscosity is particularly large under acidic conditions.

(61 Relationship between pH and viscosity) We made water WJWi containing 0.3% by weight of cacao bod gum, prepared an aqueous solution with divine pH using citric acid and sodium hydroxide, and investigated the relationship between pl+ and viscosity. The viscosity was measured using rotor No. 1 at 30 rpm and 20°C.
I went there. The results are shown in FIG.

From this figure, it can be seen that the viscosity of cocoa bod gum decreases both on the acidic side and on the alkaline side.

The reduction in viscosity of cacao bod gum due to heat and acid is considered to be rather advantageous in that, for example, when cacao bod gum is added to drinks as a dietary fiber source, the viscosity is reduced and it becomes easier to drink.

(7) Infrared absorption spectrum Next, in order to estimate the components of cacao bod gum, we investigated the infrared absorption spectrum, which is used to qualitatively characterize this type of natural gum. Figure 1 shows the infrared absorption spectrum of cacao bod gum, and for comparison, Figure 2 shows the infrared absorption spectrum of gum tragacanth.

From FIGS. 1 and 2, it can be said that the infrared absorption spectrum of cacao bod gum has a peak position similar to that of gum tragacanth.

(8) Precipitation reaction The precipitation reaction of cacao bod gum and other plant-derived natural gums was investigated. As a precipitant, dioxane, ethanol, ethanol hydrochloric acid, calcium chloride, cetylpyridinium chloride (CPC), trichloroacetic acid ('rCA
) was used.

The results are shown in Table 3. In the table, 10+, shi, ±,
- represents the degree of precipitation, - is not observed and 1+
shows the most obvious precipitation formation.

(Left below) In this precipitation reaction, cacao pond gum showed a similar reaction to gum tragacanth, except that it did not form a precipitate with dioxane at a mixing ratio of 05, ethanol at a mixing ratio of 1, and hydrochloric acid and ethanol at a mixing ratio of 1. A behavior different from that of gum tragacanth was also observed. In addition, gum tragacanth is not salt tolerant, cacao bod gum is derived from fruit, whereas gum tragacanth is resin, and cacao is a member of the Araliaceae family, while tragacanth tree is a member of the Fabaceae family. Considering certain factors, cacao pond gum can be said to be a new gum that is different from gum tragacanth and other known natural gums.

[Operations and Effects of the Invention] As explained above, according to the present invention, the shells of cacao fruit that have been discarded as waste after removing the seeds and the withered material surrounding the seeds, which are raw materials for chocolate and cocoa, can be removed. A new natural gum substance can be obtained using this method. This natural gum substance can be used like other natural gum substances as a thickener, densifying agent, stabilizer, etc. in foods, cosmetics, pharmaceuticals, etc.
It can also be used as water-soluble guietary fiber.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of cacao bod gum obtained in the present invention, Fig. 2 shows the infrared absorption spectrum of gum tragacanth, and Fig. 3 shows the concentrations of cacao bod gum aqueous solution and known natural gum aqueous solution. Figure 4 shows the relationship between viscosity and viscosity. Figure 5 is a diagram showing the relationship between H degree and viscosity, Figure 5 is a diagram showing the relationship between salt concentration and viscosity of a cacao bod gum aqueous solution, and Figure 6 is a diagram showing the relationship between sterilization temperature and viscosity of a cacao bod gum aqueous solution. ,
FIG. 7 is a diagram showing the relationship between pH and viscosity of a cacao bod gum aqueous solution. Patent applicant: Morinaga & Co., Ltd. Patent attorney: Shigeru Matsui

Claims (6)

[Claims] (1) A natural gum characterized by being obtained from the shell of cacao fruit. (2) The natural gum material according to claim 1, which has the infrared absorption spectrum shown in FIG. 1 and has the property of not causing precipitation when the following chemicals are added. A, 0.5 times the weight of dioxane, the same weight of ethanol, the same weight of ethanolic hydrochloric acid, and the same weight of trichloroacetic acid. (3) A method for producing natural gum characterized by adding water or hot water to the shells of cacao fruits to extract soluble components. (4) The method for producing natural gum according to claim 3, wherein the soluble components are extracted after deactivating the action of enzymes contained in the shells of cacao fruits. (5) The method according to claim 3 or 4, wherein the extraction is carried out in a state where the crushed cacao fruit shell is mixed with water or hot water in an amount of 3 to 50 times the weight of the crushed cacao fruit. Natural gum manufacturing method. (6) Any one of claims 3 to 5, wherein a natural gum substance is precipitated from the extract using a hydrophilic organic solvent.
The method for producing natural gum described in .