JP3131385B2 - Composition containing easily absorbable calcium and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 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 It has been clarified that calcium is a constituent of bones and teeth, and is important as a regulator of muscle, nervous system and hormone secretion to maintain biological functions, and is also involved in immune functions. Insufficient calcium intake 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.In general, interest in calcium has been increasing, but in Japan, In the diet, the intake is not always sufficient. 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, crustaceans, eggshells, bones of animals and calcium derived from plants 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.

[0004] The present inventors have proposed a calcium source which can obtain a calcium preparation or a food additive containing such calcium which has a good absorption into the body and a good taste and flavor upon ingestion. Focusing on obtaining from natural animal raw materials, experiments and research have found that calcium compounds obtained by firing the outer shell consisting of sea urchin spines and shells satisfy such purposes, Furthermore, research and development were proceeded on the practical production method and the composition of a composition containing a sea urchin-derived calcium compound as a main component obtained by the method.

[0005] In this process, the present inventor has found that by adding an appropriate amount of chondroitin sulfate belonging to the sulfomcopolysaccharide to the calcium compound thus obtained, the amount of calcium absorbed into the living body is significantly increased. The result was filed as Japanese Patent Application No. 6-260996. As a result of further research and development, the absorption of calcium into the living body by the addition of chondroitin sulfate is not only in the case of sea urchin shell calcium, but also in other animal calcium or synthetic calcium lactate or calcium carbonate such as calcium carbonate. It has been found that the case is also significantly accelerated. Further, as described above, absorption of calcium into the living body is promoted by the combined use with chondroitin sulfate, and it has been discovered that the absorption has a specific dependence on the concentration of chondroitin sulfate.

[0006] The chondroitin sulfate remarkably promotes the absorption of calcium into the living body as described above, but there is no possibility that the calcium concentration in the blood rapidly increases and the calcium balance is lost.

[0007]

The present invention has been completed on the basis of the above findings of the present inventors, and the first aspect of the present invention is characterized in that the calcium salt and the calcium content of the calcium salt are 0%. A food composition containing easily absorbable calcium, wherein the food composition comprises chondroitin sulfate in the range of 2 to 5% by weight. The ratio of chondroitin sulfate to calcium 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 utilization of a natural calcium source is that a calcium salt of an organic carboxylic acid obtained by treating a shell of sea urchin and a calcium component of the calcium salt are obtained. And chondroitin sulfate in the range of 0.2 to 5% by weight of the food composition containing easily absorbable calcium.

A feature of the third invention according to the present invention is that the outer shell of sea urchin is calcined and hydrated to form calcium hydroxide, which is then reacted with an organic carboxylic acid to neutralize the calcium hydroxide. A method for producing a food composition containing easily absorbable calcium, which comprises adding chondroitin sulfate in the range of 0.2 to 5% by weight based on the calcium of the calcium salt.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The food composition containing easily absorbable calcium according to the present invention contains 0.2 to 5% by weight of chondroitin sulfate with respect to the calcium content of a calcium salt, thereby ingesting calcium into a living body. Is significantly promoted. Chondroitin sulfate belongs to the sulfomcopolysaccharides that widely exist in the animal kingdom together with heparin, keratosulfate, hyaluronosulfate, etc. In particular, chondroitin sulfate and its salts are already safe as food additives (emulsion stabilizers, fish odor removers). Proven.

Chondroitin sulfate has a molecular weight of about 500, in which sulfuric acid is ester-bonded to a repeating disaccharide in which D-glucuronic acid is β-glycosidically linked 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 blended with the calcium salt, the absorption of calcium into the living body is significantly improved as described above. Although the reason is not always clear, since sulfomcopolysaccharides generally tend to bind to proteins, calcium is found to be Ca from the cell surface of the intestinal membrane.
It is considered that when absorbed into cells in the form of a binding protein, it promotes the absorption of calcium under the influence of interaction with lactic acid or the like, which is a constituent acid of the calcium salt.

With respect to the blending amount of chondroitin sulfate with respect to the calcium salt, an improvement in calcium absorption is already observed when a very small amount of, for example, 0.01% by weight is added to the calcium content. In addition, its absorbability is significantly reduced. Chondroitin sulfate has a remarkable effect at around 0.2% by weight based on the calcium content, and exhibits particularly excellent absorbability at around 0.3 to 2.5%. On the other hand, if it exceeds 1%, the above effect tends to gradually decrease. In particular, if it exceeds 5%, the effect of promoting calcium absorption 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 and an organic carboxylate from the viewpoint of safety during incorporation into a living body. As the calcium source, synthetic calcium lactate, calcium citrate, calcium carbonate and the like can be used. In particular, natural calcium sources, for example, calcium salts of various carboxylic acids obtained by calcining and hydrating sea urchin, shellfish and eggshell, etc. Is preferred. In the present invention, among the natural calcium sources, calcium obtained by calcining the sea urchin shell is particularly preferable.

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

The sea urchin used in the present invention belongs to the phylum Echinoderm and the sea urchin reticulum, and as edible ones, for example, the sea urchins of the family Paragonidae include the sea urchins and the sea urchins; In recent years, various types of sea urchins have been imported in large quantities from overseas such as North America and Korea.

In the present invention, the outer shell of sea urchin from which ovaries or the like are collected as a raw material is first washed with water and dried as appropriate. 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., it is almost converted into calcium oxide, and the firing operation is completed.

After cooling, water is added to the calcium oxide to form calcium hydroxide in the form of a white powder, which is then neutralized with various acids to form a calcium salt which 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 the organic acid relative to calcium hydroxide is used in a slight stoichiometric excess so that no free calcium hydroxide is present in the aqueous solution after the reaction. The exact amount depends on the type of acid and the intended use of the resulting composition, but the p
It is used in such an amount that H becomes about 5-6.

As the acid used for neutralization, an organic carboxylic acid generally used in the food field in terms of safety upon ingestion, solubility, absorption of calcium into the body, taste and flavor, and the like are 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 thus-obtained formulation in the form of an aqueous solution is then formed into a powdery or granular form by spray-drying, and depending on the use, a powdery or tablet-like product or a further aqueous solution such as a drink. 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. Chondroitin sulfate is added to the calcium compound in this form at a ratio within the above range with respect to the calcium content.

In the ur shell calcium which is preferably used in the present invention, a subsequent treatment such as a neutralization reaction is carried out in order to once convert the calcium oxide obtained by firing the sea urchin shell at a high temperature to calcium hydroxide. It will be easier.
In addition, since calcium is in the form of a calcium salt of an organic acid by a neutralization reaction with the organic carboxylic acid, calcium can be safely taken into the body at 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.

In addition, sea urchin shell calcium, even when used alone, has remarkably high absorbability into the body as compared with other chemically synthesized calcium carbonate, eggshell calcium and shell-derived calcium. As described above, in the sea urchin shell, in addition to calcium (50% or more) as a main component, the content of magnesium is specifically high (about 2%). It is known to be a substance involved in In addition, sodium,
Trace components such as potassium, sulfur, phosphorus, iron and zinc are contained in a well-balanced manner, and these are also considered to contribute to the absorption of calcium into the body. In addition, Hg,
Heavy metals such as Cd, Pb, As, etc. are less than about 1 ppm or are not detected at all.

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

Example 1 Method for Producing Sea Urchin Shell Calcium The outer shell after collecting the ovary of sea urchin shell was washed with water and
The material was naturally dried and calcined in a calciner at a temperature of about 1100 ° C. for about 10 hours to obtain calcium oxide, which was then sufficiently hydrated and converted to 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 so 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. About 15 g of a 20% pure composition of reduced maltose and 150 g of chondroitin sulfate (a ratio of chondroitin sulfate (100%) to calcium:
(Approximately 0.6%) and dried with a spray drier to obtain almost white odorless fine particles having an average particle diameter of 60 μm or less having a slightly unique taste and high water solubility.

Example 2 Calcium-containing fine particles were produced in the same procedure as in Example 1 except that chondroitin sulfate was added to an aqueous solution of synthesized calcium carbonate and calcium lactate in the same ratio as in Example. did.

Comparative Example A composition containing calcium lactate derived from sea urchin shell obtained in the production process of Example 1, and calcium lactate and calcium carbonate by synthesis in the same proportions as in the Examples, respectively, and containing no chondroitin sulfate was prepared. .

EXPERIMENTAL EXAMPLE 1 Calcium Absorption Test Using the compositions containing calcium salts obtained in the above Examples, an intestinal absorption test of calcium in rats was conducted. For comparison, a test was performed on a composition containing a calcium salt according to a comparative example. Test calcium salt Abbreviation ・ Calcium carbonate CaCO ₃・ Calcium lactate LaCAL ・ Sea urchin shell calcium 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 (calculated as 12 m
g) containing 100 ml of artificial intestinal juice having a pH of 6.5,
About 8 weeks old (200 g body weight) rats (Wister:
Male) was circulated at a temperature of 37 ° C. at a perfusion rate of 1 ml per minute at a temperature of 37 ° C. to absorb calcium by using a 6 cm lower part of the pylorus of the small intestine excluding the influence of bile. For each of the test calcium salts, the above five 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 calcium absorption 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 horizontal axis represents the passage of circulation time (Circulation Time) (min), and the vertical axis represents the intestinal absorption rate ABS (%) of calcium.

[0030]

[Table 1]

As shown in Table 1 and FIG. 1, the calcium absorption rate after 60 minutes of perfusion was greater in the compositions of Examples 1 and 2 to which chondroitin sulfate was added than in the composition of Comparative Example to which chondroitin was not added. Is clearly high, indicating an excellent effect of the addition of chondroitin sulfate. Among them, a 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 exhibited a somewhat high absorption rate, indicating that the sea urchin shell itself was a calcium source having excellent absorbability. In addition, the composition obtained by replacing lactic acid with succinic acid in Example 1 also showed almost the same calcium absorption as the composition containing UCAL *. On the other hand, the calcium carbonate absorption rate of the calcium carbonate composition obtained by treating the eggshell by the usual method was about 1/5 of the composition containing UCAL *.

EXPERIMENTAL EXAMPLE 2 Change in Calcium Absorption Rate Depending on Chondroitin Sulfate Addition The ratio of chondroitin sulfate (100%) to calcium was changed to 6 in the range of 0.6 to 6% by weight. Using the composition containing the test compound UCAL *, the same calcium absorption test as in Experimental Example 1 was performed. Further, in order to confirm the lower limit of the amount of chondroitin sulfate, similar experiments were carried out with the proportions of calcium to 0.15% and 0.3% by weight, respectively. The results are shown in Table 2 and FIG. In FIG. 2, the vertical axis of the graph indicates the calcium absorption rate (%), and the horizontal axis indicates the circulation time (min).

[0033]

[Table 2]

As is clear from the above results, the ratio of chondroitin sulfate to calcium is in the range of 0.2 to 5.0% by weight, particularly 0.3 to 2.5% by weight, so that the calcium absorption is high and the concentration of chondroitin sulfate is high. From 2% by weight to 5
The absorption rate gradually decreases as the concentration increases to 5% by weight.
In this case, the value was reduced to about 値 compared with the case of 1% of the maximum absorption concentration value. On the other hand, chondroitin sulfate shows a sufficient Ca absorption even at a concentration of about 0.3% by weight,
At 5% by weight, the value drops sharply, and about 0.2% by weight is considered to be the practical lower limit of the concentration of chondroitin sulfate relative to calcium.

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

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

The calcium Ca (OH) _{2 in} the sea urchin shell is 0.1%.
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 group (50 animals in total)
Indeed in 3 other groups only were observed death if administrable 5000 mg / kg is because no observed deaths for not be calculated LD ₅₀ values, therefore LD ₅₀
Was temporarily estimated to be 5000 mg / kg or more. On the other hand, in the intravenous administration group, the LD ₅₀ value was 187.0 mg / kg.
From the above results, it is considered that the composition containing calcium in the present invention can be used extremely safely as a calcium preparation or a food additive.

[0038]

As described above, according to the composition containing absorbable calcium to which chondroitin sulfate is added according to the present invention, the absorption of calcium into a living body during their ingestion is remarkably promoted. In particular, when sea urchin shells, which are hardly useful as fishery waste, are used as raw materials, sea urchin shell-derived calcium, which has a very good absorption of calcium components in the body, can be obtained. In addition to calcium preparations, it has applications as various foods and food additives with excellent taste and flavor.

[Brief description of the drawings]

FIG. 1 shows the absorption of calcium in the intestine (Absorption calcium) when the ratio of chondroitin sulfate to calcium in the composition containing various calcium salts obtained according to 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 intestinal absorptivity (%) of calcium in the rat when sea urchin shell-derived calcium lactate obtained in Example 1 was administered, in which the chondroitin sulfate concentration was changed in the range of 0.15 to 6% by weight. Time elapsed for case (min)
FIG.

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Claims (6)

(57) [Claims] 1. A food composition containing easily absorbable calcium, comprising a calcium salt and chondroitin sulfate in the range of 0.2 to 5% by weight based on the calcium content of the calcium salt. 2. The food composition according to claim 1, wherein the chondroitin sulfate content is in the range of 0.3 to 2.5% by weight. 3. The method 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. Food composition containing easily absorbable calcium. 4. The food composition according to claim 1, wherein the calcium salt is a carbonate. 5. An organic carboxylic acid calcium salt obtained by treating a sea urchin shell, and chondroitin sulfate in an amount of 0.2 to 5% by weight based on the calcium content of the calcium salt. A food composition containing an easily absorbable calcium, which is characterized by the following. 6. An outer shell of sea urchin is calcined and hydrated to form calcium hydroxide, which is then reacted with an organic carboxylic acid and neutralized to form a calcium salt of an organic carboxylic acid. A method for producing a food composition containing easily absorbable calcium, comprising adding chondroitin sulfate in an amount of 0.2 to 5% by weight based on calcium.