JP2729390B2 - Natural gum and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial application field" The present invention is suitable as a thickener, a thickener, a stabilizer and the like in the fields of food, medicine, cosmetics, etc., and as a water-soluble dietary fiber. The present invention also relates to a natural gum obtained from cocoa fruit shells and a method for producing the same.

"Prior Art" Cocoa fruit is composed of an outer shell, seeds contained in the shell, and a soft material wrapping the seeds. The seed and the soft material surrounding the seed are subjected to a fermentation process using a wild yeast, an acetic acid bacterium, or the like, and the seed is used as a raw material for chocolate or cocoa. However, most of the outer shells are currently incinerated and discarded.

The cocoa fruit shell contains a large amount of carbohydrates as shown in Table 1 and has the potential to be an effective resource.

"Problems to be Solved by the Invention" As described above, although cocoa fruit husks have the potential to be an effective resource that can be used industrially, there has been little research on how to use them. Is the actual situation.

Therefore, the present invention has been made to provide a technique for effectively using cocoa fruit shells, which has been hardly used conventionally.

"Means for Solving the Problems" The present inventors have conducted various studies on the effective use of cocoa fruit shells, and as a result, have noticed that the liquid obtained by extracting coarsely crushed shells with water is very viscous. Found that this viscosity is due to the natural gum quality of the cocoa fruit,
Based on these facts, the present invention has been completed.

That is, the present invention provides a natural gum which is obtained from cocoa fruit shells.

The present invention also provides a method for producing a natural gum, wherein soluble components are extracted by adding water or hot water to cocoa fruit shells.

Hereinafter, the present invention will be described in more detail with reference to preferred specific examples.

In the present invention, the shell of the cocoa fruit means a portion of the cocoa fruit from which seeds and various kinds of soft materials are wrapped. This husk is obtained in large quantities as a residual waste from the collection of seeds and various kinds of soft materials in the process of processing cocoa beans, which are raw materials for chocolate and cocoa.

This shell can be subjected to subsequent processing as it is, but is preferably cut to an appropriate size. By cutting, the extraction efficiency of the viscous substance from the shell is improved, and heat transfer inside the shell in the next heating step can be accelerated.
The cutting can be performed using commonly used cooking utensils such as slicers. It should be noted that the black scale inside the shell has less gum because it has less gum.

Next, water or hot water is preferably added to the shell to perform blanching. The main purpose of blanching is to inactivate an enzyme, polyphenol oxidase, which is contained in cocoa fruits and causes a browning reaction, but the operation can also improve extraction efficiency. The conditions for blanching depend on the size of the shell, but for example, 10 to 20 at 80 ° C.
It is preferable to apply heat with boiling water for 3 to 5 minutes or more. Also, direct heating by steam can be performed.

If the operation up to blanching is not performed promptly and sufficiently, the browning reaction of the polyphenol compound proceeds, the shell and the extract in the subsequent step brown, and the finally obtained gum has poor color. Further, in order to prevent the browning reaction, the equipment used is preferably one which does not elute iron or the like (for example, made of stainless steel), and the water used for blanching is preferably iron-free. This is to prevent the polyphenol compound contained in the shell from reacting with iron to cause browning of the extract.

For gum extraction, 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.
Up to 30 times the weight. If the amount of water is small, the concentration of the extracted gum will be high, so the viscosity of the extract will be high and it will be very difficult to separate solids and liquids. Since the concentration is low, the viscosity of the extract is also low, and furthermore, a large amount of solvent is required for dry powdering, which is not preferable.

After cooling, the blanched shell is crushed in a state where water or hot water is mixed, to extract gum, and to separate solid and liquid from the extract. Crushing is a Greater, Finisher,
It can be carried out by a crusher usually used for fruit processing or the like such as a working blender, and the solid / liquid separation can be carried out by a centrifugal dehydrator, a filter press or the like.
When the viscosity of the crushed liquid is low, a filter, a centrifuge or the like can be used. In addition, the gum remaining in the shell remaining as a residue after the solid / liquid separation contains gum, so that the extraction rate can be increased by further adding water as necessary and repeating re-extraction. In this case, if the solid-liquid separation is not performed completely, a gum containing insoluble solids is formed, which is not preferable.

The cocoa fruit shell extract thus obtained has a high viscosity, including a high concentration of gum, and can be used for various purposes by itself.
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 of pulverizing the extract, for example, a method of spray-drying the extract, or a method of freeze-drying can be adopted, but preferably, a method of precipitating gum from the extract using a hydrophilic organic solvent is employed. Is done. Next, a powdering method using a hydrophilic organic solvent will be described in more detail.

As the hydrophilic organic solvent, lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol, acetone, and the like can be used, and ethyl alcohol is preferably used. The following description is an example in which ethyl alcohol is used as the hydrophilic organic solvent.

When ethyl alcohol is added to the extract to make an aqueous solution of ethyl alcohol, gum is precipitated at an ethyl alcohol concentration of 50% (v / v) or more. However, if it is less than 60% (v / v), it retains tackiness in aqueous solution, and 65% (v / v)
It becomes a sticky precipitate for the first time, so 65%
(V / v) or more is preferable. In preparing an aqueous solution of ethyl alcohol of this concentration, a fine precipitate can be obtained by adding ethyl alcohol while stirring the extract or by vigorous mixing immediately after the addition. On the other hand, when ethyl alcohol is brought into contact with the extract and gently stirred and mixed, a fibrous precipitate is obtained. These precipitates are collected, drained, washed with ethyl alcohol if necessary, replaced with diethyl ether or the like, and dried to obtain a powdery or fibrous gum. This gum substance has the following viscosity when converted to an aqueous solution, and can be dried again by adding the above operation to the aqueous solution.

As described above, a dry gum can be obtained similarly by using acetone instead of ethyl alcohol.
However, since the polyphenol compound contained in the extract is easily soluble in water, soluble in ethyl alcohol, and insoluble in acetone, it is preferable to treat the polyphenol compound with ethyl alcohol rather than acetone since the polyphenol compound is easily removed from the gum. Further, the precipitate is sufficiently washed with 70% (v / v) or more, preferably 70 to 80% (v / v) ethyl alcohol,
If the polyphenol substance is washed away and then subjected to a drying treatment, a pure white gum having a further improved purification degree can be obtained. These washing and drying operations are easier and higher yields can be obtained when the precipitate is fibrous than fine powder.

When fibrous gum like corn is obtained, it can be made into an easy-to-use powder by pulverizing by physical means. In this case, pulverization in which particles become hard or heat is generated, such as vibration pulverization, is not preferable. This is because the harder the particles, the more difficult it is to dissolve during use, and significant heat generation causes a decrease in viscosity due to decomposition of the gum. For this reason, it is preferable to perform pulverization to a desired particle size by a pulverizer such as an impact type or a shredding type.

The thus obtained natural gum substance of the present invention has an infrared absorption spectrum shown in FIG. 1, and has a property of not causing precipitation by the addition of the following agents.

A. 0.5 times by weight of dioxane b. Ethanol of the same weight c. Ethanol hydrochloride of the same weight d. Trichloroacetic acid of the same weight The natural gum of the present invention is, for example, dressings, mayonnaise, ketchup, jam, sauces such as sauteed meat, sauces such as thick sauces, in the production of foods such as thick sauces and other natural thickeners You can use it in the same way. Also,
Alternatively, it can be used as a natural dietary fiber supply food by reducing the viscosity by utilizing the property of being weak to heat and acid. Furthermore, utilizing the effects of thickening and dispersing of the natural gum, it is also used as a thickener for softener in medicine, a thickener or foam stabilizer for dentifrice, and a thickener for lotion and cream in cosmetics. it can. Furthermore, it can be used for industrial uses such as an abrasive and a pigment dispersion / suspension as well as other thickeners.

"Examples" Example 1 (extraction of natural gum) After collecting from a cocoa tree, 6 pieces of Malaysian cocoa fruits (3216 g in total) frozen as they are were placed in hot water of a double kettle and boiled for 15 minutes. Thawed, cut into two pieces, and the seeds, the soft material surrounding the seeds, and the black scale inside the shell were removed.
The remaining shell was 2054 g in total.

After adding purified water to the shell and boiling in a double kettle for 15 minutes to completely inactivate polyphenol oxidase, 1c
It was cut to about m square.

Then, purified water 10 times the weight of the cut shell was added, and the mixture was boiled for 5 minutes, followed by crushing and extraction. This process
The crushing was performed by crushing into shells using a 5 mm screen grater manufactured by SEIKEN Co., Ltd., and then crushing the shell pieces attached to the inside of the machine by washing with water.

The crushed liquid is solidified by filtration through a nylon filter cloth and centrifugation at 3,000 rpm for 10 minutes using a centrifuge manufactured by Marusan Co., Ltd.
The liquid was separated. Then, extract the extract with a refractometer reading of 0.7 for approximately 17.
7 kg was obtained.

In addition, 10 weight times purified water was added to the shell remaining as a residue after solid-liquid separation, heated for 5 minutes, filtered again, and centrifuged. The resulting extract showed a refractometer reading of 0.3. I was

Example 2 (Pulverization of Extract) To the first extract in Example 1 was added pharmacological ethyl alcohol to an alcohol concentration of 67% (v / v), and the mixture was gently stirred to form a corn-like mixture. Yielded a white precipitate which was removed and collected in another local ethyl alcohol. Then, the column was washed three times with 75% ethyl alcohol to allow the polyphenol compound to flow out.

In order to remove water from the washed precipitate, it was replaced with special-grade ethyl alcohol and then with diethyl ether, and then air-dried to obtain 31.5 g of a white dried product (hereinafter, referred to as “cocoa pod gum”).

As described above, precipitation can be performed not only with ethyl alcohol but also with other lower alcohols or acetone, but ethyl alcohol is more general and easier to handle, and is suitable for removing polyphenol compounds present as impurities. Has advantages.

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

On the other hand, in the method in which alcohol or acetone is added dropwise little by little to the vigorously stirred extract, fine precipitates are formed. Therefore, the precipitates can be dried to be powdered without using mechanical means.

Test Examples Various components and properties of the cacao pod gum obtained in Example 2 were measured as described below.

(1) Analytical value of general components The analytical values of general components of cocoa pod gum were as shown in Table 2, and most of them were carbohydrates.

Also, assuming use in beverages, isomerized sugar 10% by weight, citric acid 0.35% by weight, cocoa pod gum 0.5% by weight
AOAC method (enzyme / weight method)
Of dietary fiber by cocoa pod gum
75% by weight was determined as dietary fiber.

The cocoa pod gum (dried product) is a starch-like substance that dissolves in both cold and hot water, and has little paste-like feeling and high viscosity. In addition, locust bean gum,
Compatibility with xanthan gum and guar gum (gel-forming ability)
Was not seen.

The characteristics of the cocoa pod gum as a thickener were examined as follows. The measurements of the viscosity shown below were all performed using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.

(2) Relationship between concentration and viscosity of gum substance When the relationship between each concentration and viscosity of guar gum, xanthan gum, and cocoa pod gum was measured, cocoa pod gum, as with other natural gum substances, responded to the concentration. Viscosity tended to increase. The measurement was performed using the rotor N
O.2 was performed at 20 rpm at 30 rpm. The result is shown in FIG. In the figure, a is guar gum, c is xanthan gum,
c is cocoa pod gum.

(3) Relationship between Temperature and Viscosity A 0.3% by weight aqueous solution of cocoa pod gum was prepared, and the change in viscosity with increasing temperature was examined. As a result, the viscosity tended to decrease with increasing temperature. The viscosity was measured at 60 rpm using a rotor No. 2. The result is shown in FIG.

(4) Relationship between Salt Concentration and Viscosity (Salt Resistance) Salt was added to an aqueous solution of 0.3% by weight of cacao pod gum so as to have various concentrations, and a change in viscosity with an increase in salt concentration was examined. The viscosity was measured using a rotor No. 2 at 60 rp.
m. The result is shown in FIG.

As is clear from this figure, the viscosity of the cocoa pod gum hardly changes with the salt concentration. This means
This means that cocoa pod gum can be effectively used in foods such as sauces, dressings, and ketchup.

(5) Relationship between sterilization temperature and viscosity (heat resistance) (a) 0.3% by weight aqueous solution of cocoa pod gum (b) 0.3% by weight aqueous solution of cocoa pod gum, 3% by weight aqueous solution of salt (c) 0.3% by weight of cocoa pod gum And aqueous solutions of pH 2.50 (adjusted by adding citric acid) were prepared, and these aqueous solutions were prepared at various sterilization temperatures.
The viscosity after holding for 30 minutes was measured. The viscosity was measured at 20 ° C. at 60 rpm using a rotor No. 1. The result is shown in FIG. In the figure, a, b, and c represent the above (a),
These correspond to (b) and (c).

From this result, it is understood that the viscosity of the cocoa pod gum decreases as the sterilization temperature increases, and the viscosity decrease is particularly large under acidic conditions.

(6) Relationship between pH and Viscosity An aqueous solution of 0.3% by weight of cocoa pod gum was prepared, aqueous solutions of various pH were prepared using citric acid and sodium hydroxide, and the relationship between pH and viscosity was examined. The viscosity was measured using a rotor No. 1 at 30 rpm at 20 ° C. The result is shown in FIG.

From this figure, it is understood that the viscosity of the cocoa pod gum decreases on both the acidic side and the alkaline side.

The decrease in viscosity of cocoa pod gum due to heat or acid is considered to be rather advantageous, for example, when cocoa pod gum is added to a beverage or the like as a dietary fiber source, the viscosity is reduced and the cocoa pod gum becomes easier to drink.

(7) Infrared absorption spectrum Next, for estimating the components of the cocoa pod gum, the infrared absorption spectrum used for qualifying this kind of natural gum was examined. FIG. 1 shows the infrared absorption spectrum of cocoa pod gum, and FIG. 2 shows the infrared absorption spectrum of tragacanth gum for comparison.

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

(8) Precipitation reaction The precipitation reaction was examined for cocoa pod gum and natural gums derived from other plants. Dioxane, ethanol, ethanol hydrochloride, calcium chloride, cetylpyridinium chloride (CPC), and trichloroacetic acid (TCA) were used as precipitants.

Table 3 shows the results. In the table, ++, +,
±,-represents the degree of precipitation,-is not observed,
++ indicates the most pronounced precipitation.

Also in this precipitation reaction, cocoa pod gum showed a reaction similar to tragacanth gum, but different from tragacanth gum in that no precipitate was formed with dioxane at a mixing ratio of 0.5, ethanol at a mixing ratio of 1 and ethanol hydrochloride at a mixing ratio of 1 It was observed. In addition, tragacanth gum is not salt-tolerant, cocoa pod gum is derived from fruit, while tragacanth gum is resin.Furthermore, cacao trees are of the family Aoguiri, whereas tragacanth is of the legume family. Considering things, etc., cocoa pod gum,
It can be said that this is a novel gum substance different from tragacanth gum and other known natural gum substances.

"Action and Effect of the Invention" As described above, according to the present invention, the shell of cacao fruit, which has been discarded as waste after removing the seeds serving as raw materials for chocolate and cocoa and the soft material surrounding the seeds , A new natural gum can be obtained. This natural gum can be used as a thickener, a thickener, a stabilizer, etc. of foods, cosmetics, pharmaceuticals and the like, like other natural gums, and can also be used as a water-soluble dietary fiber. .

[Brief description of the drawings]

FIG. 1 shows an infrared absorption spectrum of cocoa pod gum obtained by the present invention, FIG. 2 shows an infrared absorption spectrum of tragacanth gum, and FIG. 3 shows concentrations of cocoa pod gum aqueous solution and known natural gum aqueous solution. FIG. 4 is a diagram showing the relationship between the temperature and viscosity of the cocoa pod gum aqueous solution, FIG. 5 is a diagram showing the relationship between the salt concentration and the viscosity of the cocoa pod gum aqueous solution, FIG. The figure shows the relationship between the sterilization temperature and the viscosity of the cocoa pod gum aqueous solution, and FIG. 7 shows the relationship between the pH and the viscosity of the cocoa pod gum aqueous solution.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication A61K 47/36 A61K 47/36 J C08B 37/00 C08B 37/00 Q (56) References JP 48-78825 (JP, A) Koji Nakanishi, "Theory and Practice of Chocolate and Cocoa Production" (S40-1-7) Korin Shoin 56-58 Harada Atsuya ed. “Comprehensive Polysaccharide Chemistry (I)” (S49-6-10) Kodansha 22-23

Claims (6)

(57) [Claims] 1. A natural gum obtained from cocoa fruit shells. 2. The natural gum according to claim 1, which has an infrared absorption spectrum shown in FIG. 1 and has a property of not causing precipitation when the following agents are added. A. 0.5 times by weight of dioxane b. Ethanol of the same weight c. Ethanol hydrochloride of the same weight d. Trichloracetic acid of the same weight 3. A method for producing a natural gum, comprising adding water or hot water to a cocoa fruit shell to extract a soluble component. 4. The method for producing a natural gum according to claim 3, wherein the soluble component is extracted after deactivating the action of an enzyme contained in the shell of the cocoa fruit. 5. The extraction according to claim 3, wherein the crushed cocoa fruit shell is mixed with water or hot water 3 to 50 times by weight of the crushed material. The method for producing the natural gum described. 6. The method for producing a natural gum according to any one of claims 3 to 5, wherein natural gum is precipitated from the extract using a hydrophilic organic solvent.