JPH02190169A - Calcium water solution composition - Google Patents

Abstract

PURPOSE:To contain Ca dissolved in water and capable of readily being absorbed into human body at large quantities and make it possible not to cause abnormality such as diarrhea in proper phosphoric acid content by dissolving calcium phosphate ingredient in an aqueous solution of a specific organic carboxylic acid component. CONSTITUTION:Calcium phosphate is subjected to dehydration and thermal decomposition at >=1200 deg.C to afford (B) calcium phosphate consisting of a mixture of alpha-tricalcium phosphate and tetracalcium phosphate. Then the component B is dissolved in (A) an aqueous solution of at least one organic carboxylic selected from citric acid, malic acid, gulconic acid, lactic acid, acetic acid and water soluble salt thereof to provide the Ca water solution composition having 12.5-250m mol/l Ca concentration, >=37.5m mol/l carboxyl group concentration and 8.2-170m mol/l phosphoric acid radical concentration and being 1:3.6-6 in mol ratio of Ca with phosphoric acid radical and 1.5-2.0:1 in mol ratio of Ca with phosphoric acid radical.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an aqueous calcium solution composition. More specifically, the present invention relates to an aqueous calcium solution composition useful as a component of soft drinks.

[Prior art and problems to be solved by the invention] Calcium is one of the important nutrients for the human body and animals.
Its deficiency causes weakened bones or hypertension. Calcium is preferably ingested through daily meals, but
Depending on our food habits, we are often deficient. Additionally, calcium in foods is difficult to dissolve in water and is difficult to absorb even when ingested. However, the exception is calcium in milk, which is already dissolved in water and has the property of being easily absorbed by the human or animal body.

However, not all calcium dissolved in water is as easily absorbed as in milk.

For example, milk contains about 11,000 pp of calcium, but if water contains the same amount of calcium, the calcium in the water is free, so it is difficult for the human body to absorb it even if you drink it. Not only does it taste unpleasant and induce diarrhea. Such water is called hard water and is not suitable for drinking.

Milk contains a lot of calcium and is suitable for drinking because
This is because the calcium in this is bound to proteins. Unlike free calcium, this calcium in milk is easy to drink, easily absorbed, and does not cause diarrhea. However, conventionally, it has been considered difficult to ingest calcium in a dissolved state, that is, in the form of beverages other than milk or processed products thereof.

Additionally, the presence of phosphoric acid is essential for calcium absorbed into the body to be deposited in bones. However, since phosphoric acid forms a poorly soluble salt with calcium, the presence of phosphoric acid in calcium drinks was thought to inhibit calcium absorption. Therefore, it has been considered extremely difficult to improve calcium absorption while simultaneously ingesting phosphoric acid and calcium.

Foods with high calcium content are defined as those containing 50 mg or more of calcium per 100 g of food. In the case of beverages, a beverage containing 500 mg of calcium per liter, that is, a concentration of 12.5 mmol/1 or more, can be said to be a beverage with a high calcium content. On the other hand, phosphoric acid has a calcium:phosphoric acid molar ratio of 1.5:1 to 2.0:
It is said that it is preferably within the range of 1.

An aqueous solution with a high calcium content and a well-balanced ratio of cicaphosphoric acid to calcium can only exist in a strongly acidic region with a pH of about 2 or less; , not suitable as a beverage. Generally, the pH range suitable for beverages is 3 to 8, but in such a pH range, there is a problem in that calcium and phosphoric acid react to form a precipitate.

The present invention has been made in view of the above circumstances, and has a composition different from that of milk or its processed products, which contains a large amount of calcium that is easily absorbed by dissolving in water, and has an appropriate phosphoric acid content. The present invention aims to provide an aqueous calcium solution composition that does not cause inconveniences such as diarrhea when used as a beverage component.

[Means to solve the problem]

The calcium aqueous solution composition of the present invention includes at least one organic carboxylic acid component consisting of at least one member selected from citric acid, malic acid, gluconic acid, lactic acid, acetic acid, and water-soluble salts of the aforementioned carboxylic acids. It is characterized by being obtained by dissolving a calcium phosphate component consisting of seeds of calcium phosphate.

The calcium aqueous solution composition of the present invention contains calcium and phosphate radical dissolved in water, and is useful as a component of soft drinks.

One component necessary to obtain the calcium aqueous solution composition of the present invention is selected from citric acid, malic acid, gluconic acid, lactic acid, and acetic acid, and water-soluble salts of the aforementioned carboxylic acids, such as sodium salts, potassium salts. It is an aqueous solution of an organic carboxylic acid component consisting of at least one member.

Another component necessary to obtain the calcium aqueous solution composition of the present invention is a calcium phosphate component consisting of at least one type of calcium phosphate.

The calcium phosphate component preferably consists of a mixture of α-tricalcium phosphate and tetracalcium phosphate, but may also consist of a reaction product of a water-soluble calcium compound, such as calcium hydroxide, and phosphoric acid. It may be something.

A mixture of α-tricalcium phosphate and tetracalcium phosphate can be obtained by dehydrating and thermally decomposing tricalcium phosphate, which is used as a food additive, at a high temperature of 1200°C or higher, or by using a food additive. Calcium carbonate and/or calcium hydroxide is added to at least one member selected from phosphoric acid, monocalcium phosphate, and dibasic calcium phosphate used as a compound, and the molar ratio of calcium to phosphate groups is It can be obtained by blending and mixing at a ratio of 1.5:1 to 2.0:1 and heat-treating this mixture at a high temperature of 1200° C. or higher.

When the above-mentioned calcium phosphate component is mixed with the above-mentioned organic carboxylic acid component aqueous solution, both components are mutually dissolved to obtain the calcium aqueous solution composition of the present invention.

The specific calcium phosphate component of the present invention is extremely easily soluble in the aqueous solution of the specific organic carboxylic acid component of the present invention, and although the composition of this composition is not fully clear, calcium is chelated with the organic carboxylic acid anion. A water-soluble organic complex is formed and dissolved in water, and it is thought that this complex does not precipitate even if it comes into contact with a phosphate anion in a neutral state. Such a water-soluble calcium organic complex is easy to drink as a beverage ingredient and does not cause inconveniences such as diarrhea. When drunk, it is easily absorbed into the human or animal body along with phosphate ions, and is quickly deposited in bones. It has properties.

In the composition of the present invention, total calcium content! Ca
degree) is 12.5 to 250 mmol/l, the total content of carboxyl groups is 37.5 mmol/l or more, and the total content of phosphate groups is 8.2 to 170 mm.
Preferably it is ol/1.

In the composition of the present invention, the total calcium content is 1
If it is less than 2.5 mmol/L, the calcium content is too low and the usefulness of the composition is reduced, and if it is more than 250 mmol/It, the content of free calcium is too high, resulting in poor absorption of calcium. Efficiency may be reduced.

In addition, the total content I (concentration) of carboxyl groups is 37.5 m
If it is lower than mol/12, the stability of the calcium organic complex may become insufficient. Generally, the total content of carboxyl groups is 37.5 to 1000+y+mol
/ It is preferred. More preferably, the total content of carboxyl groups is within the range of 40 to 750 mrno I/It.

Furthermore, if the content of phosphate radicals is less than 8.2 mmol/n or more than 170 mmol/It, the balance with the calcium content may be lost and the stability of the composition may be reduced.

Generally, in the composition of the present invention, the molar ratio of calcium to carboxyl groups is preferably 1:3 or more, and more preferably within the range of 1:3.6 to 1:6. That is, 3 or more moles of carboxyl groups are coordinated to 1 mole of calcium to form a stable complex structure.

When the molar ratio of calcium to carboxyl groups is less than 1:3, the stability of the calcium complex decreases, the content of free calcium increases, and therefore the usefulness of the compositions of the invention in drinking applications decreases.

In the composition of the present invention, the molar ratio of calcium to phosphate radical is preferably within the range of 1.5:1 to 2.0:1. Calcium/phosphate mole ratio is 1.5:
When the ratio is lower than 1, precipitation due to the reaction between calcium and phosphate radicals tends to be formed, and when the ratio is higher than 2.0:1, the deposition of calcium in bones tends to decrease.

The calcium aqueous solution composition of the present invention can be evaporated to saturation to form a precipitate, and this precipitate can be separated and dried. The calcium aqueous solution composition of the present invention can be obtained by dissolving this dried precipitate in water.

The calcium aqueous solution composition of the present invention may be used as a component of a soft drink, and desired sweeteners, flavors, colorants, etc. may be mixed therein. Such a drink is useful as a calcium supplement drink.

〔Example〕

The invention will be further illustrated by examples.

Example 1 Tricalcium phosphate used as a food additive,
The mixture was heated to 1500° C. for dehydration and thermal decomposition to obtain a mixture of α tricalcium phosphate and tetracalcium phosphate. After dissolving 2.5 g of this mixture in 1000 cc of a mixed solution of 0.2% citric acid and 0.7% trisodium citrate, sugar and flavoring were added thereto to prepare a soft drink.

The calcium concentration in this composition is 25 mmol/
It, and the concentration of carboxyl group of citric acid is 112
．． 5 mmol/42, and the concentration of phosphate radicals is 15. It was Qmmol/i'. Therefore, the content ratio of calcium and carboxyl groups is 1:
4.5, and the ratio of calcium to phosphoric acid is 1.67.
: It was 1. The pH of this composition was 4.3.
Met. Furthermore, when the free calcium ion concentration was measured using an ion electrode, it was 3 mmol/l.

Therefore, the concentration of soluble organic complex is 25-3=5-3=
It is 22/A. Therefore, the composition obtained here was suitable as the calcium-containing soft drink of the present invention.

Example 2 To confirm the effect of the calcium-containing soft drink, 50 mI of the drinking water produced in Example 1 was used! When administered orally to guinea pigs, serum calcium concentration temporarily increased, and no abnormalities such as diarrhea were observed.

Example 3 Calcium hydroxide 25 mmol and phosphoric acid 12.5 mmol
The reaction solution in water with IQmmol of citric acid and 27.5 mmol of trisodium citrate was mixed and dissolved, and the total amount of water was set to It2. The calcium concentration in this composition is 25 mmol/It, and the concentration of carboxyl groups is (10+27.5) x 3 = 11
2.5 m+nol/It, and the phosphate radical concentration was 12.5 mmol/47. Therefore, the molar ratio of calcium to carboxyl group was 1:4.5, and the molar ratio of calcium to phosphate group was 2:1. The pH of this composition was measured and found to be 4.3. Also, when the free calcium ion concentration was measured using an ion electrode, it was 3 mmol/jl! Met. Therefore, the concentration of soluble calcium organic complex is 25-3=5-3=22/l.

Example 4 1 mol of calcium hydroxide, 5 mol of phosphoric acid Q, and 5 mol of a reaction solution in water were mixed with 3 mol of lactic acid and 3 mol of sodium lactate.
The total amount of water was adjusted to 11. Then, a milky white sol was formed. When this sol was further stirred, precipitation occurred. This precipitate was dried in a freeze dryer. When 50 g of the dried product was poured into 1 liter of water, it was completely dissolved. When this solution was analyzed, the calcium concentration was 2.
0 mmol/jl', and the phosphate group concentration is 12 mmol
l/l, and the lactic acid concentration was 120 mmol/l. Also, the molar ratio of calcium and carboxyl groups is 1
:6, and the molar ratio of calcium and phosphate radicals is 1.7:
It was 1.

Example 5 To evaluate the effect of calcium aqueous solution composition,
When the drinking water 50- obtained in Example was orally administered to guinea pigs, the serum calcium concentration temporarily increased, and no abnormalities such as diarrhea were observed.

The embodiments of the calcium aqueous solution composition of the present invention are as follows.

1. Total calcium content is 12.5-250mm
The composition according to claim 1, wherein the total content of carboxyl groups is 37.5 mmol/It or more, and the total content of phosphate groups is 8.2 to 170 mmol/It. .

2. The molar ratio of calcium and carboxyl groups is 1
The composition according to claim 1, wherein: 3 or more.

3. The molar ratio of calcium to phosphate group is 1.5
2. The composition of claim 1, wherein the composition is within the range of :1 to 2.0:1.

4. The composition according to claim 1, wherein the calcium phosphate component consists of a mixture of α-tricalcium phosphate and tetracalcium phosphate.

〔Effect of the invention〕

The calcium aqueous solution composition of the present invention contains calcium as a stable water-soluble organic carboxylic acid complex, and has successfully coexisted with phosphate groups without forming a precipitate, and is easy to drink and is safe for the human body. It does not cause abnormalities such as diarrhea in the animal body.

Therefore, the calcium aqueous solution composition of the present invention is useful as a component of easily absorbed calcium-replenishing beverages or calcium-containing soft drinks.

Claims (1)

[Scope of Claims] 1. An aqueous solution of an organic carboxylic acid component consisting of at least one member selected from citric acid, malic acid, gluconic acid, lactic acid, acetic acid, and water-soluble salts of the above-mentioned carboxylic acids; A calcium aqueous solution composition obtained by dissolving a calcium phosphate component consisting of a calcium phosphate salt. 2. A soft drink containing the calcium aqueous solution composition according to claim 1 as a main component.