JPH0947253A - Composition containing easily absorbable calcium and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition containing easily absorbable calcium and simultaneously a chondroitin sulfate in a prescribed total concentration range and capable of increasing the absorption of the calcium into bodies. SOLUTION: A food composition contains an easily absorbable calcium product comprising a calcium salt and a chondroitin sulfate in a range of 0.2-5wt.% based on the calcium content. The calcium salt preferably used in the composition is obtained e.g. by calcining the shells of echinoids in an oven, hydrating the obtained calcium oxide, and subsequently reacting the obtained calcium hydroxide with an organic carboxylic acid. The addition of the chondroitin sulfate in a prescribed concentration range remarkably promotes the absorption of the calcium component in bodies. The sources for the calcium include various kinds of natural and synthetic calcium products.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition containing easily absorbable calcium and a method for producing the same.

[0002]

2. Description of the Related Art Calcium is a constituent of bones and teeth and is important for maintaining biological functions as a regulator of muscle, nervous system and hormone secretion, and it has been clarified that it is involved in immune functions. Insufficient intake of calcium is known to be involved in the development of adult diseases such as hypertension, ischemic heart disease and endocrine disease in addition to bone disease, and there is generally increasing interest in calcium, but The intake is not always sufficient in the diet. Therefore, various calcium preparations and health foods containing calcium have been proposed and marketed in order to make up for the deficiency.

Conventionally, for example, calcium compounds obtained by chemical synthesis, calcium compounds derived from shells, shellfish, eggshells, animal bones and plant-derived calcium from seaweeds have been used. Has not been widely used due to its poor absorbability and, in many cases, the problem of taste and flavor when used as a preparation or as a food additive.

The present inventors can obtain a calcium preparation which is well absorbed into the body and has a good taste and flavor when ingested or a food additive containing such calcium. Focusing on obtaining from natural animal raw materials, as a result of experiments and research, it was discovered that a calcium compound obtained by firing an outer shell consisting of sea urchin spines and shells fulfills such purpose, Further, research and development were carried out on the practical production method thereof and the formulation of the composition containing the sea urchin-derived calcium compound obtained as a main component.

In this process, the present inventor has found that the amount of calcium absorbed in the living body is remarkably increased by adding an appropriate amount of chondroitin sulfate belonging to the sulfomucopolysaccharide to the calcium compound thus obtained. The result was filed as Japanese Patent Application No. 6-260996. As a result of further research and development, absorption of calcium into the living body by the addition of chondroitin sulfate was not limited to the case of sea urchin shell calcium, but other animal calcium or synthetic calcium salts such as calcium lactate and calcium carbonate by synthesis. It has been found that the case is also significantly accelerated. Further, as described above, it has been discovered that the absorption of calcium in vivo is promoted by the combined use with chondroitin sulfate, but the absorption has a unique dependence on the concentration of chondroitin sulfate.

The above chondroitin sulfate remarkably promotes the absorption of calcium into the living body, but there is no possibility that the calcium concentration in the blood will be rapidly increased and the calcium balance will be lost.

[0007]

The present invention has been completed based on the above findings of the present inventors. The first feature of the present invention is that the calcium salt and the calcium content of the calcium salt are 0%. A food composition containing easily absorbable calcium, characterized in that it contains chondroitin sulfate in the range of 2 to 5% by weight. The ratio of the chondroitin sulfate to the calcium content is more preferably 0.3.
To 2.5% by weight.

A more specific feature of the second invention, in which the present invention is applied to the use of a natural calcium source, is a calcium salt of an organic carboxylic acid obtained by treating a shell of sea urchin and a calcium content of this calcium salt. And 0.2 to 5% by weight of chondroitin sulfate in the food composition containing easily absorbable calcium.

The third aspect of the present invention is characterized in that the shell of sea urchin is calcined and hydrated to give calcium hydroxide, which is then reacted with an organic carboxylic acid for neutralization to give calcium of the organic carboxylic acid. A method for producing a food composition containing easily absorbable calcium, which comprises adding a chondroitin sulfate in the range of 0.2 to 5% by weight to the calcium of the calcium salt as a salt.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The easily absorbable calcium-containing food composition of the present invention contains 0.2 to 5% by weight of chondroitin sulfate with respect to the calcium content of the calcium salt, thereby ingesting calcium into the living body. Is significantly promoted. Chondroitin sulphate belongs to the sulfomucopolysaccharides that are widely present in the animal kingdom along with heparin, kerato sulphate, hyalurono sulphate, etc. Especially chondroitin sulphate and its salts are already safe as food additives (emulsification stabilizers, fish odor removers). Has been proven.

Chondroitin sulphate has a molecular weight of about 500 in which sulfuric acid is ester-bonded to a repeating conjugate of a disaccharide in which D-glucuronic acid is β-glycoside-bonded to a chondrosamine derivative.
00 is a water-soluble polymer, the aqueous solution of which exhibits viscous properties, for example, from chondroitin sulfate C
Obtained as isomers.

When chondroitin sulfate or the like is added to the calcium salt, the absorbability of calcium into the living body is remarkably improved as described above. Although the reason for this is not clear, in general, sulfomucopolysaccharides are easily bound to proteins, so that calcium from the cell surface of the intestinal tract membrane becomes Ca.
It is considered that when it is absorbed into cells in the form of a binding protein, it promotes absorption of calcium under the influence of interaction with lactic acid, which is a constituent acid of calcium salt.

Regarding the blending amount of chondroitin sulfate with respect to the above-mentioned calcium salt, an improvement in calcium absorbability has already been recognized by the addition of a very small amount of 0.01% by weight with respect to the calcium content. In addition, its absorbability is significantly reduced. The effect of chondroitin sulfate becomes remarkable from around 0.2% by weight with respect to the calcium content, and exhibits particularly excellent absorbability around 0.3 to 2.5%. On the other hand, if it exceeds 1%, the above-mentioned effect tends to gradually decrease, and if it exceeds 5%, the effect of promoting absorption of calcium is remarkably reduced.

Therefore, in the present invention, chondroitin sulfate is added in the range of about 0.2 to 5% by weight, preferably 0.3 to 2.5% by weight, based on the calcium content.

Calcium is preferably used in the form of an inorganic salt such as a carbonate or an organic carboxylic acid salt from the viewpoint of safety when incorporated into a living body. Synthetic calcium lactate, calcium citrate, calcium carbonate and the like can be used as the calcium source, but especially natural calcium sources such as calcium salts of various carboxylic acids obtained by baking and hydrating sea urchin, shellfish and egg shells. Is preferred. In the present invention, of the natural calcium sources, calcium obtained by firing the shell of sea urchin is particularly preferable.

Sea urchins accumulate calcium carbonate crystals in their body walls, which are combined as a calcareous plate to form an outer shell. Sea urchins are mainly used for edible ovaries, and the outer shell is partly discarded except as part of the fertilizer used for upland farming, causing problems as fishery waste. However, sea urchin shell is mostly a calcium component and is a well-balanced calcium source containing a relatively large amount of trace mineral components such as magnesium, potassium, sodium, phosphorus and zinc. Also from the viewpoint of industrial use, it is economically easy to obtain as a large amount of fishery waste as described above.

The sea urchins used in the present invention belong to the phylum Echinodermata and the sea urchin net, and typical ones to be used for food are, for example, Bahun sea urchins and Ezo bafun sea urchins, Murasaki sea urchins of the family Naga sea urchin, and Shirahige sea urchins of the family Rappa sea urchin. However, various sea urchins have been imported in large quantities from overseas such as North America and South Korea in recent years.

In the present invention, as a raw material, for example, the shell of sea urchin from which ovaries are collected is first washed with water and appropriately dried. Then, it is put into a usual heat-resistant heating furnace and heated. In this case, the calcium carbonate in the sea urchin shell is about 1000-
By heating at 1200 ° C., most of it is converted into calcium oxide, and the firing work is completed.

After cooling, water is added to the calcium oxide to produce white powdery calcium hydroxide, which is then neutralized with various acids to form a calcium salt form that can be safely taken into the body. In this case, calcium hydroxide does not generate CO ₂ during the neutralization reaction unlike calcium carbonate, so that handling operation in an aqueous solution is extremely easy. The amount of organic acid with respect to calcium hydroxide is stoichiometrically used in an excessive amount so that free calcium hydroxide does not exist in the aqueous solution after the reaction. Although the exact amount varies depending on the type of acid and the use of the resulting composition, the p of the aqueous solution after the reaction is
It is used in an amount such that H is about 5-6.

As the acid used for neutralization, an organic carboxylic acid which is generally used in the food field in terms of safety when ingested, solubility, absorbability of calcium into the body, taste and flavor, etc. is used. Depending on the application, L-lactic acid, citric acid, malic acid, succinic acid, gluconic acid, acetic acid, L-ascorbic acid and the like are used.

The mixture thus obtained in the form of an aqueous solution is then spray-dried to give a powder or granule, and a powder or tablet product or a drink as an aqueous solution depending on the application. Used as. In order to facilitate the granulation treatment, it is preferable to use an excipient such as a sugar alcohol, particularly reduced maltose or erythritol. The chondroitin sulfate is added to the calcium mixture of this form in a ratio within the above range with respect to the calcium content.

The ur shell calcium preferably used in the present invention is subjected to a subsequent treatment such as a neutralization reaction in order to temporarily convert the calcium oxide obtained by firing the sea urchin shell at a high temperature into calcium hydroxide. It will be easier.
Further, since it is in the form of a calcium salt of an organic acid by the neutralization reaction with the organic carboxylic acid, calcium can be safely ingested into the body with a high absorption rate. The type of the organic acid may be appropriately selected in consideration of the solubility and the like depending on the application in addition to the above-mentioned safety and absorbability.

The sea urchin shell calcium, as a single product, has a significantly higher absorbability into the body than other chemically synthesized calcium carbonate, egg shell calcium, and shell-derived calcium. As described above, in the sea urchin shell, in addition to calcium as the main component (50% or more), specifically, the content of magnesium is high (about 2%). It is known to be a substance involved in. In addition, sodium,
Minor components such as potassium, sulfur, phosphorus, iron, and zinc are contained in a good balance, and it is considered that these also contribute to the absorption of calcium into the body. Hg,
Heavy metals such as Cd, Pb and As are below about 1 ppm or not detected at all.

The present invention will be described in detail below with reference to examples.

Example 1 Method for producing sea urchin shell calcium The outer shell of the sea urchin after collecting the ovaries of sea urchin was washed with water and
The mixture was naturally dried and calcined in a calcination furnace at a temperature of about 1100 ° C. for about 10 hours to give calcium oxide, which was then sufficiently hydrated to be converted into calcium hydroxide. 1000 g of the calcium hydroxide thus obtained was dissolved in 10 liters of water, about 5000 g of 50% L-lactic acid was added, and the mixture was reacted at a temperature of 75 ° C. for 15 minutes to produce sea urchin shell calcium lactate. In this case, lactic acid is added in a stoichiometrically slightly excessive amount such that the pH of the aqueous solution after the reaction becomes a predetermined value in the range of about 5 to 6, and the reaction is terminated when the pH value is stabilized. Was. To this aqueous solution, 150 g of reduced maltose and about 15 g of a 20% pure composition of chondroitin sulfate (ratio of chondroitin sulfate (100%) to calcium:
(About 0.6%) was added, and the mixture was dried by a spray dryer to obtain almost white fine particles having an average particle size of 60 μm or less, which are odorless and have a slightly unique taste and high water solubility.

Example 2 A calcium-containing fine particle was produced by the same procedure as in Example 1 except that chondroitin sulfate was added to an aqueous solution of calcium carbonate and calcium lactate by synthesis in the same proportion as in Example. did.

Comparative Example A composition was prepared in which the sea urchin shell-derived calcium lactate obtained in the production process of Example 1, and synthetic calcium lactate and calcium carbonate in the same proportions as in each of the Examples, and no chondroitin sulfate was added. .

Experimental Example 1 Calcium Absorption Test A rat intestinal absorption test for calcium was carried out using the composition containing the calcium salt obtained in each of the above Examples. For comparison, a composition containing a calcium salt according to a comparative example was tested. Test calcium salt abbreviation ・ Calcium carbonate CaCO ₃・ Calcium lactate LaCAL ・ Sea urchin shell lactate UCAL ・ Calcium lactate + Chondroitin LaCAL * ・ Calcium carbonate + Chondroitin CaCO ₃ * ・ Sea urchin shell lactate + Chondroitin UCAL *

Test Method Composition of each of the above calcium salts (calcium conversion 12 m
100 ml of artificial intestinal fluid of pH 6.5 containing g) was prepared,
About 8 weeks old (200 g body weight) rat (Wister:
6 cm below the pyloric part of the small intestine excluding the influence of bile (male) was circulated as a perfusion region at a temperature of 37 ° C. at a perfusion rate of 1 ml / min to absorb calcium. For each sample calcium salt, 5 rats were used as a group, and these rats were subjected to parathyroidectomy except that they were fasted for 24 hours.
No calcium absorption promoting load such as vitamin D administration was added. The absorption rate of calcium was measured for each test calcium salt by decreasing the amount of calcium in the circulating fluid. The results are shown in Table 1 and FIG. In FIG. 1, the abscissa indicates the passage of circulation time (Circulation Time) (min), and the ordinate indicates the intestinal absorption rate ABS (%) of calcium.

[0030]

[Table 1]

As shown in Table 1 and FIG. 1, the calcium absorption rate in the 60-minute perfusion was higher in the compositions of Examples 1 and 2 to which chondroitin sulfate was added than in the composition of Comparative Example without addition. Is also clearly high, showing the excellent effect of the addition of chondroitin sulfate. Among them, the sample in which chondroitin sulfate was added to sea urchin shell calcium showed a high calcium absorption rate. The sea urchin shell calcium lactate composition to which chondroitin sulfate was not added also had a relatively high absorption rate, which indicates that the sea urchin shell itself is a calcium source having excellent absorbability. In addition, the composition obtained by substituting succinic acid for lactic acid in Example 1 also showed almost the same calcium absorbability as the composition containing UCAL *. On the other hand, the calcium absorption rate of the calcium carbonate composition obtained by treating the egg shell by a usual method was about 1/5 of that of the composition containing UCAL *.

Experimental Example 2 Change in Calcium Absorption Rate with Addition of Chondroitin Sulfate The same as in Example 1 in which the ratio of chondroitin sulfate (100%) to calcium was changed to 6 concentrations between 0.6 and 6% by weight. The same calcium absorption test as in Experimental Example 1 was conducted using a composition containing the test compound UCAL *. Further, in order to confirm the lower limit of the amount of chondroitin sulfate added, the same experiment was conducted with the respective ratios to calcium being 0.15% and 0.3% by weight. The results are shown in Table 2 and FIG. In FIG. 2, the vertical axis of the graph shows the calcium absorption rate (%), and the horizontal axis shows the circulation time (min).

[0033]

[Table 2]

As is clear from the above results, the calcium absorption rate is high and the concentration of chondroitin sulfate is high when the ratio of chondroitin sulfate to calcium is 0.2 to 5.0% by weight, particularly 0.3 to 2.5% by weight. From 2% by weight to 5
Absorption rate gradually decreases with increasing weight% and concentration is 5% by weight
Then, the value was reduced to about 1/2 as compared with the case of 1% of the maximum absorption concentration value. On the other hand, chondroitin sulfate shows a sufficient Ca absorption rate even at a concentration of around 0.3% by weight, but 0.1
At 5% by weight, the value sharply decreases, and about 0.2% by weight is considered to be the practical lower limit of the concentration of chondroitin sulfate with respect to calcium.

In Experimental Examples 1 and 2 for the absorption rate of various calciums, the calcium concentration in the plasma obtained by blood collection before and after the start of perfusion was different between the groups at any concentration of chondroitin sulfate. There was almost no difference between before and after perfusion, and it was within the normal range as a living body.

Experimental Example 3 Sea urchin shell calcium L and L
D ₅₀ test The acute toxicity of sea urchin shell calcium used as one of the starting materials for the compositions of the examples of the present invention was determined by the rat LD ₅₀ test.

Sea urchin shell calcium Ca (OH) ₂ 0.
The 5% solution is pH 5.0 with 50% L-lactic acid (U-grade).
0, a 7-week-old (200 g body weight) rat (SD
Male) orally (1000-5000 mg / k)
g) and intravenous administration (100-290 mg / kg)
Then, observation was performed over 14 days to determine the LD ₅₀ value. During the observation period, for oral administration, each dose administration group (50 animals in total)
For the case of 5000 mg / kg which was actually administrable, the LD ₅₀ value could not be calculated because only 3 deaths were observed and no deaths were observed in other groups, therefore LD ₅₀
Was estimated to be 5000 mg / kg or more. On the other hand, the LD ₅₀ value in the intravenous administration group was 187.0 mg / kg.
From the above results, it is considered that the calcium-containing composition of the present invention can be used very safely as a calcium preparation, a food additive, or the like.

[0038]

As described above, according to the composition containing absorbable calcium to which chondroitin sulfate according to the present invention is added, the absorbability of calcium into the living body upon ingestion thereof is remarkably promoted. In particular, when sea urchin shell, which has almost no utility value as fishery waste at present, is used as raw material, sea urchin shell-derived calcium with extremely good absorbability into the body of its calcium component is obtained, and the composition obtained by blending this is In addition to calcium preparations, it has applications as various foods and food additives with excellent taste and flavor.

[Brief description of drawings]

FIG. 1 Calcium intestinal absorbability (Absorption calcium) when the ratio of chondroitin sulfate to calcium in the composition containing various calcium salts obtained by each example of the present invention is constant (0.6%). It is a figure which shows (%) with progress (min) of circulation time (Circulation Time).

FIG. 2 shows the rat intestinal absorbability (%) of calcium obtained when sea urchin shell-derived calcium lactate obtained in Example 1 was administered in the range of chondroitin sulfate concentration of 0.15 to 6% by weight. About time (min)
It is a figure shown with.

Claims (6)

[Claims] 1. A food composition containing easily absorbable calcium, comprising calcium salt and chondroitin sulfate in an amount of 0.2 to 5% by weight based on the calcium content of the calcium salt. 2. The food composition containing easily absorbable calcium according to claim 1, wherein the chondroitin sulfate is in the range of 0.3 to 2.5% by weight. 3. The organic carboxylic acid salt according to claim 1, wherein the calcium salt is a salt of an organic carboxylic acid selected from the group consisting of L-lactic acid, citric acid, malic acid, succinic acid, gluconic acid, L-ascorbic acid and acetic acid. A food composition containing easily absorbable calcium. 4. The food composition containing easily absorbable calcium according to claim 1, wherein the calcium salt is a carbonate. 5. A calcium salt of an organic carboxylic acid obtained by treating a shell of sea urchin, and chondroitin sulfate in the range of 0.2 to 5% by weight based on the calcium content of the calcium salt. A food composition containing a characteristic easily absorbable calcium. 6. A sea salt of sea urchin is calcined and hydrated to give calcium hydroxide, which is then reacted with an organic carboxylic acid for neutralization to give a calcium salt of the organic carboxylic acid. A method for producing a food composition containing easily absorbable calcium, which comprises adding chondroitin sulfate in an amount of 0.2 to 5% by weight relative to calcium.