JPH08198803A - Composition of amorphous citric acid, organic acid, calcium and magnesium and its production - Google Patents

Abstract

PURPOSE: To obtain a stable easily water-soluble composition comprising amorphous citric acid, an organic acid, calcium and magnesium, and to provide the method for producing the composition. CONSTITUTION: This composition is obtained by reacting a magnesium source (at least one kind selected from magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium chloride and magnesium sulfate) and a calcium source (at least one kind selected from calcium carbonate, calcium hydroxide, a calcined calcium derived from a living thing and its hydrate) with at least one kind of organic carboxylic acid selected from citric acid, malic acid, succinic acid, lactic acid, gluconic acid, etc., wherein at least one organic acid is citric acid, in an aqueous medium at a temperature of <=30 deg.C and aging the reaction product followed by spray drying or lyophilization. The obtained product is a stable easily water-soluble composition comprising amorphous citric acid, an organic acid, calcium and magnesium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stable and readily water-soluble amorphous citric acid / organic acid / calcium / magnesium composition capable of simultaneously supplying magnesium and calcium, and a method for producing the same.

[0002]

2. Description of the Related Art Magnesium is important as a mineral with a large amount of living body, and the required amount is 200 to 30 in humans.
It is said to be 0 mg. However, recently, the intake of magnesium has become chronically insufficient due to changes in eating habits. Recently, it was pointed out that the relative deficiency of magnesium with respect to ingested calcium correlates with ischemic heart disease, and the intake ratio of calcium and magnesium (Ca / M
(g ratio) is drawing attention. In addition, magnesium stabilizes the amorphous calcium phosphate of bone (Calcif
Tissue, Vol. 23, p. 245-250, 1977
It has been reported that bone formation, bone resorption, bone calcification, etc. are reduced by magnesium deficiency (Ca
lcif Tissue Int, Vol. 31, p. 231
238, 1980). As a magnesium supplement method, a method of administering magnesium oxide tablets (Magn
esium Res, vol. 6, p. 155-163, 19
1993), a method of administering magnesium lactate, a method of controlling magnesium in food, and the like have been reported. Also,
Chewable tablets made of a composition containing precipitated calcium carbonate and magnesium carbonate are commercially available. However,
Since the above conventional products, for example, chewable tablets, use water-insoluble calcium carbonate and magnesium carbonate, there is a problem in solubility, and there is a drawback that it is difficult to be absorbed in, for example, patients with hypoxia or hypoxia. . In addition, when trying to ingest magnesium from food, it is necessary to ingest a considerable amount.

It has been desired to develop a calcium-magnesium composition which can efficiently and simultaneously supplement calcium and magnesium, is stable in water, is easily soluble in water, and has a pleasant texture and taste.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to provide a stable amorphous calcium carbonate which can supplement magnesium and calcium at the same time, is easily soluble in water, has a pleasant texture and taste, and is suitable for oral administration. To provide an acid / organic acid / calcium / magnesium composition and a method for producing the same.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that a magnesium source, a calcium source and a group of citric acid, malic acid, succinic acid, lactic acid, gluconic acid or the like. An organic acid in which at least one of the one or more organic acids selected from the group is citric acid is reacted in an aqueous medium so that the temperature of the reaction solution does not exceed 30 ° C., and then spray-dried or It was found that by freeze-drying, an amorphous citric acid / organic acid / calcium / magnesium composition which is stable and easily soluble in water can be obtained, and the present invention was completed. The composition of the present invention is extremely stable and can be stored for a long period of time.

The amorphous citric acid / organic acid / calcium / magnesium composition of the present invention and a method for producing the same will be described below.

That is, the first aspect of the present invention is to use at least one selected from the group consisting of magnesium source, calcium source, citric acid, malic acid, succinic acid, lactic acid, gluconic acid and the like, or at least one organic acid. Is an amorphous citric acid / organic acid / calcium / magnesium composition obtained by reacting a citric acid with an organic acid in a temperature range of 30 ° C. or lower in an aqueous medium and then spray-drying.

The term magnesium source means, for example, magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium chloride, magnesium sulfate and the like. In the present invention, one kind or two or more kinds selected from the above group may be used in combination.

The term calcium source means, for example, calcium carbonate, calcium hydroxide, calcined calcium of biological origin or hydrates thereof. Examples of the above-mentioned baked calcium derived from organisms include baked shell calcium derived from oyster shells, scallops, abalone and the like, and baked sea urchin shell calcium derived from sea urchin shells. In the present invention, one kind or two or more kinds selected from the above group may be used in combination.

The term organic acid means citric acid, malic acid, lactic acid, gluconic acid and the like. The organic acids include optical isomers, eg malic acid is an optically active d
It means an isomer such as a-, 1- or dl-form, and any isomer can be used in the reaction of the present invention.

The reaction temperature range is preferably 30 ° C. or lower, more preferably −8 to 30 ° C., further preferably 0 to 30 ° C.
26 ° C. If the temperature is higher than 30 ° C, crystals tend to precipitate,
Not suitable.

The combination of organic acids of the above composition of the present invention includes citric acid and malic acid, citric acid and succinic acid,
Citric acid and lactic acid, citric acid and gluconic acid or citric acid,
Mention may be made of compositions such as malic acid and lactic acid.

The magnesium content of the above composition of the present invention varies depending on the type of magnesium source, calcium source, organic acid, etc. used, reaction temperature, aging temperature, etc., as shown in Examples described later, but it is preferable. 1.0 to 9.0
%, And more preferably 3.0 to 7.0.

The calcium content varies depending on the conditions such as the organic acid used, the calcium source, the magnesium source, the reaction temperature, and the aging temperature, as shown in Examples described later, but it is preferably 10 to 21%. It is preferably 13 to 19%.

The composition ratio (molar ratio) of citric acid, organic acid, calcium and magnesium of the above composition is not particularly limited as long as it is within the above pH range, but preferably,
The organic acid is 0.5 to 3.5 mol, the calcium is 0.8 to 3.7 mol, preferably 1.5 to 3.0, and the magnesium is 0.1 to 1 mol of citric acid. 1-1.5
The molar amount is preferably 0.3 to 1.3. Needless to say, some excess or deficiency is acceptable within the range in which the object of the present invention can be achieved.

The above composition is stable and readily soluble in water. The solubility varies depending on the conditions such as the type of magnesium source, calcium source, organic acid, etc. used, the amount used, the reaction temperature, etc. In general, 1 g of the above composition is 20 ml of water.
It dissolves within 5 minutes. The details will be described in a test example described later.

The first amorphous citric acid / organic acid / calcium / magnesium composition can be produced by the method described below.

That is, a magnesium source, a calcium source, and one or more organic acids selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid, gluconic acid, etc., in which at least one is citric acid, A method for producing an amorphous citric acid / organic acid / calcium / magnesium composition, which comprises reacting in an aqueous medium at a temperature range of 30 ° C. or lower and then spray-drying.

The aqueous medium may be cooled in advance to an appropriate temperature of 30 ° C. or lower in order to react in the temperature range of 30 ° C. or lower, or when a magnesium source, a calcium source, an organic acid or the like is added. Alternatively, the reaction may be performed while controlling the temperature with a cooling device or the like.

The reaction temperature can be controlled by a conventional method, for example, by externally cooling the reaction in the case of an exothermic reaction and heating it in the case of an endothermic reaction.

The reaction temperature varies depending on the type of magnesium source, calcium source, organic acid, etc. used, the amount used, etc. and is not particularly limited, but is preferably in a suitable temperature range of 30 ° C. or less, and more preferably − It is 8 to 30 ° C, and more preferably 0 to 26 ° C.

The reaction time varies depending on the type of magnesium source, calcium source, organic acid, etc. used, the amount used, the setting of the reaction temperature, etc. and is not particularly limited, but it is usually from 1 hour to 7 hours.
Time.

After reacting the magnesium source, the calcium source and the organic acid, the reaction solution may be aged if necessary.

The aging temperature varies depending on the type of magnesium source, calcium source, organic acid, etc. used, the amount used, the setting of the reaction temperature and the like, and is not particularly limited, but preferably a temperature range not exceeding 30 ° C. And more preferably -8
-30 degreeC, More preferably, it is 0-26 degreeC.

The aging time varies depending on the aging temperature, the type of organic acid to be combined with the citric acid used, the amount of citric acid, the organic acid, the calcium source, the magnesium source, etc., and is not particularly limited, but is from several minutes to It is 7 hours, preferably several minutes to several hours.

The pH of the reaction solution during aging is preferably 3.0.
To 5.5, more preferably 3.5 to 5.0,
More preferably, it is 4.0-4.5. After aging the reaction solution, insoluble matter can be removed by filtration if necessary.

The spray drying can be carried out according to a conventional method, for example, by a conventional spray drying granulator or a fluidized bed built-in spray dryer. The spray drying temperature or spraying conditions vary depending on the type of machine used, the aging temperature, the type of organic acid to be combined with citric acid used, the amount of organic acid such as citric acid, the calcium source, the magnesium source, etc. Type, the inlet temperature is 200 ℃, the outlet temperature is 80-100
C, disk rotation speed 10,000 to 25,000 rp
m conditions.

In the above-mentioned production method of the present invention, the order of adding the magnesium source, the calcium source, the organic acid such as citric acid and the like to the aqueous medium is not particularly limited, and they may be added simultaneously to the reaction aqueous solution.

In the second aspect of the present invention, a magnesium source, a calcium source, and at least one organic acid selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid, gluconic acid and the like are used. An amorphous citric acid / organic acid / calcium / magnesium composition obtained by reacting an organic acid, which is an acid, in a water medium at a temperature range of 30 ° C. or lower and then freeze-drying.

The magnesium, calcium and organic acid contents of the second composition are the same as those obtained by the first production method.

As the combination of the organic acids of the second composition, citric acid and malic acid, citric acid and succinic acid, citric acid and lactic acid, citric acid and gluconic acid or citric acid, malic acid and lactic acid, etc. I can list things.

The above composition is stable and readily soluble in water. The solubility varies depending on conditions such as the type of magnesium source, calcium source, organic acid, etc. used, the amount used, the reaction temperature, etc., but generally 1 g of the above composition is 20 ml as shown in the test examples described later. Dissolves in water within 5 minutes.

The second amorphous citric acid / organic acid / calcium / magnesium composition can be produced by the method described below.

That is, a magnesium source, a calcium source, and one or more selected from the group of citric acid, malic acid, succinic acid, lactic acid or gluconic acid, and at least one organic acid being citric acid, A method for producing an amorphous citric acid / organic acid / calcium / magnesium composition, which comprises reacting in a medium in a temperature range of 30 ° C. or lower and then freeze-drying.

In a water medium, a magnesium source, a calcium source and an organic acid in which at least one selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid or gluconic acid is at least one citric acid is used in an aqueous medium. The process is the same as that of the first method described above until the reaction is performed in the temperature range of 30 ° C. or lower.

After the magnesium source, the calcium source and the organic acid are reacted, the reaction solution may be aged if necessary.

The aging temperature and aging time, and the pH of the reaction solution during aging are the same as those in the above-mentioned first production method.

After aging, if necessary, insoluble matter in the reaction solution may be removed by filtration.

Freeze-drying can be obtained by freezing the above reaction solution in a conventional manner and drying it in a freeze dryer.

The amorphous citric acid / organic acid / calcium / magnesium composition of the present invention can be dried by either spray drying or freeze drying, but spray drying is more suitable for mass production between the two. It is more economical because the manufacturing cost is also low.

The physicochemical properties of the above composition of the present invention can be confirmed by a conventional method, for example, by an X-ray diffraction spectrum method.

The organic acid was quantified by liquid chromatography according to a conventional method.

Regarding the solubility in water, the sample to be tested was accurately weighed according to a conventional method, and then the sample was dissolved or suspended in water, stirred for a certain period of time, and then filtered, and the magnesium and calcium contents in the filtrate were measured by an atomic absorption method. The solubility can be determined from the difference between the magnesium and calcium contents in the test sample and the filtrate.

The amorphous citric acid / organic acid / calcium / magnesium compositions obtained in the respective examples of the present invention are shown in FIG.
As shown in the X-ray diffraction spectrum, which indicates that all are amorphous.

The amorphous citric acid / organic acid / calcium / magnesium composition of the present invention is extremely stable and easy to store.

The invention is described in more detail in the examples below.

【Example】

Example 1 Citric acid monohydrate 52.5 in 150 ml of water under stirring and cooling.
g and malic acid 33.5 g were added and dissolved, then cooled to −5 ° C., calcium hydroxide 23.0 g and magnesium hydroxide 8.6 g were added little by little to the solution, and then aged for 30 minutes. The liquid temperature during the reaction was -5 to 23 ° C, and the pH of the final solution was 3.7. Thereafter, the solution was filtered, and the filtrate was spray-dried and granulated [model Mobile Miner, manufactured by Niro Co., Ltd.] at an inlet temperature of 200 ° C. and an outlet temperature of 80 to 8
98.7 g of a granulated product was obtained by spray-drying under the conditions of 5 ° C. and disk rotation speed of 25,000 rpm. The obtained granulated product had a Ca content of 11.9%, a magnesium content of 5.9% and a bulk density of 0.58 g / ml.

Example 2 52.0 Citric acid monohydrate in 800 ml of water under stirring and cooling
g, 30.0 g of succinic acid were added and dissolved, then cooled to -7 ° C, 21.3 g of calcium hydroxide and 16.7 g of magnesium hydroxide were added little by little to the solution, and then aged for 30 minutes. The liquid temperature during the reaction was -7 to 26 ° C, and the pH of the final solution was 4.9. Then, the same treatment as in Example 1 was carried out and spray drying was carried out to obtain 90.8 g of a granulated product.
The obtained granulated product had a Ca content of 10.7%, a magnesium content of 8.2% and a bulk density of 0.64 g / ml.

Example 3 52.0% of citric acid monohydrate in 150 ml of water under stirring and cooling
g, 50% lactic acid 45.0 g. Then, the mixture was cooled to 0 ° C., 35.0 g of calcium hydroxide and 15.1 g of magnesium chloride hexahydrate were added little by little to the solution, and then 3
Aged for 0 minutes. The liquid temperature during the reaction was 0 to 28 ° C, and the pH of the final solution was 4.2. Thereafter, the same treatment as in Example 1 was carried out and spray drying was carried out to obtain 78.6 g of a granulated product. The obtained granulated product had a Ca content of 21.5%, a magnesium content of 3.6% and a bulk density of 0.51 g / ml.

Example 4 Citric acid monohydrate 5 was added to 150 ml of water at 5 ° C. with stirring and cooling.
After 2.0 g and 50% gluconic acid 78.0 g were charged and dissolved, 35.0 g of calcium hydroxide and 20.2 g of magnesium chloride hexahydrate were added little by little to the solution, followed by aging for 30 minutes. The liquid temperature during the reaction was 5 to 23 ° C., and the pH of the final solution was 4.0. Thereafter, the same treatment as in Example 1 was carried out and spray drying was carried out to obtain 102.8 g of a granulated product. The obtained granulated product had a Ca content of 16.1%, a magnesium content of 4.0% and a bulk density of 0.57 g / ml.

Example 5 800 ml of 13 ° C. water and 400 parts of citric acid aqueous solution under stirring
ml (208 g as citric acid monohydrate), aqueous malic acid solution (134 g as malic acid), calcium carbonate suspension (165.2 g as calcium carbonate) and 120 ml magnesium carbonate suspension (6 as magnesium carbonate).
6.8 g) respectively, 13.3 ml / min, 6.7 ml
/ Min, 3.3 ml / min, 5 ml / min and 2 ml / min flow rates for 60 minutes at the same time for continuous reaction.
Aged for 30 minutes. The liquid temperature during the reaction was 13 to 25 ° C, and the pH of the final solution was 5.2. Thereafter, the same treatment as in Example 1 and spray drying were carried out to obtain a granulated product 85.2.
g was obtained. The obtained granulated product had a Ca content of 17.2%, a magnesium content of 6.2% and a bulk density of 0.42 g / ml.

Example 6 While stirring and cooling, 2.78 kg of citric acid monohydrate and 5.33 kg of malic acid were put into 20 liters of water at 4 ° C. and dissolved, and then 3.31 kg of calcined oyster shell calcium and 0.3 of magnesium carbonate. After 21 kg was gradually added to the solution, it was aged for 6 hours. The liquid temperature during the reaction was 13 to 25 ° C, and the pH of the final solution was 4.4. After that, the solution is filtered, and the solution is spray-dried granulator (model S-50NR, manufactured by Niro).
Then, 8.60 kg of a granulated product was obtained by spray drying under the conditions of an inlet temperature of 200 ° C., an outlet temperature of 100 ° C. and a disk rotation speed of 10,000 rpm. The obtained granulated product had a Ca content of 17.9%, a magnesium content of 0.8% and a bulk density of 0.46 g / ml.

Example 7 Citric acid monohydrate 27.8 in 150 ml of water under stirring and cooling
g, malic acid 22.3 g, and 50% lactic acid 60.4 g were added and dissolved, then cooled to 3 ° C., and calcined oyster shell calcium 3
After adding 2.4 g (30.6 g as calcium hydroxide) and 16.7 g of magnesium carbonate little by little to the solution,
Aged for 30 minutes. The liquid temperature during the reaction was 13 to 25 ° C, and the pH of the final solution was 4.2. Thereafter, the same treatment as in Example 1 and spray drying were carried out to obtain a granulated product 91.8.
g was obtained. The obtained granulated product had a Ca content of 16.6%, a magnesium content of 4.5% and a bulk density of 0.56 g / ml.

Example 8 58.0 citric acid monohydrate in 400 ml of water under stirring and cooling
g and dl-malic acid 20.0 g were charged and dissolved, and then 3 ° C.
After cooling, 28.5 g of calcium hydroxide and 8.6 g of magnesium hydroxide were added little by little, followed by aging for 30 minutes. The liquid temperature during the reaction is 3 to 29 ° C, and the pH of the final solution is
Was 4.2. After that, the solution was filtered, and the filtrate was frozen with acetone-dry ice, lyophilized with a lyophilizer [Model FD-80 manufactured by Tokyo Scientific Machinery Co., Ltd.], pulverized, and sieved with 100 mesh. , 90.8 g of a granulated product was obtained. The obtained granulated product had a Ca content of 15.
5. %, Magnesium content 4.8%, bulk density 0.33 g
/ Ml.

Example 9 58.3 citric acid monohydrate in 800 ml of water under stirring and cooling
g and 17.5 g of succinic acid were added and dissolved, then cooled to 0 ° C., 28.5 g of calcium hydroxide and 8.6 g of magnesium hydroxide were added little by little, and then aged for 30 minutes. The liquid temperature during the reaction was 0 to 22 ° C., and the pH of the final solution was 4.0.
Met. Then, the same treatment as in Example 8 was carried out to obtain 88.0 g of a granulated product. The obtained granulated product has a Ca content of 1
6.0%, magnesium content 5.8%, bulk density 0.26
It was g / ml.

Example 10 With stirring, 58.3 g of citric acid monohydrate and 26.8 g of 50% lactic acid were added and dissolved in 400 ml of water, and the mixture was cooled to 15 ° C., and 28.5 g of calcium carbonate and 1 part of magnesium carbonate.
After 2.5 g was added little by little, it was aged for 30 minutes. The liquid temperature during the reaction was 15 to 28 ° C, and the pH of the final solution was 3.
It was 4. Then, the same treatment as in Example 8 was carried out to obtain 82.6 g of a granulated product. The obtained granulated product has a Ca content of 1
2.8%, magnesium content 4.2%, bulk density 0.32
It was g / ml.

Example 11 While stirring, 58.3 g of citric acid monohydrate and 58.0 g of 50% gluconic acid were added and dissolved in 400 ml of water with stirring, and the mixture was dissolved at 16 ° C.
After cooling, 28.5 g of calcium carbonate and 12.6 g of magnesium carbonate were added little by little, followed by aging for 30 minutes.
The liquid temperature during the reaction was 15 to 28 ° C., and the pH of the final solution was 3.3. Then, the same treatment as in Example 8 was carried out to obtain 90.3 g of a granulated product. The obtained granulated product had a Ca content of 11.9%, a magnesium content of 4.3% and a bulk density of 0.
It was 30 g / ml.

Example 12 3.72 kg of citric acid monohydrate and 1.96 kg of malic acid were added to and dissolved in 15 liters of water at 4 ° C. with stirring and cooling, and then, 2.82 kg of calcined oyster shell calcium (as calcium hydroxide) 2.72 kg) and 600 ml of a magnesium chloride hexahydrate solution (solid content 34 w / v%) were added little by little to the solution, followed by aging for 2 hours. Liquid temperature during reaction is -5
~ 23 [deg.] C and pH of final solution was 4.4. Next, 0.6 kg of reduced maltose starch syrup was added, the solution was filtered, and the solution was spray-dried and granulated (model S-50NR, manufactured by Niro) at an inlet temperature of 225 ° C, an outlet temperature of 150 ° C, and a nozzle combination 1 0.5 / SE, spray pressure 10 kg / c
Granules 6.70 by spray drying under m ² conditions
I got kg. The obtained granulated product had a Ca content of 15.2%,
The magnesium content was 0.4% and the bulk density was 0.31 g / ml.

Comparative Example 1 5 ml of citric acid monohydrate was added to 200 ml of water at 40 ° C. under stirring.
2.0 g and malic acid 33.5 g were added and dissolved, and then calcium hydroxide 27.4 g and magnesium hydroxide 9.5 g
Was gradually added and aged for 60 minutes. Liquid temperature during reaction is 40
˜72 ° C., pH of final solution was 4.5. After filtration, the precipitate was washed with 200 ml of methanol and then 70
The mixture was dried by ventilation at 16 ° C. for 16 hours, pulverized, and then sieved with 100 mesh. The obtained citric acid / malic acid / calcium / magnesium composition had a calcium content of 17.2%, a magnesium content of 9.7% and a bulk density of 0.44 (g / ml).

Comparative Example 2 45.0 g of 50% lactic acid was added to 200 ml of water at 35 ° C. with stirring.
Was added and dissolved, 30.0 g of calcium hydroxide and 9.5 g of magnesium hydroxide were gradually added, and the mixture was aged for 60 minutes. The liquid temperature during the reaction was 35 to 74 ° C., and the p of the final solution was p.
H was 4.7. Then, the solution is heated to an inlet temperature of 230
℃, outlet temperature 120 ℃, disk rotation speed 25,000
Spray dried under conditions of rpm. The calcium content of the obtained lactic acid / calcium / magnesium composition was 17.
3%, magnesium content 9.8%, bulk density 0.60
Met.

The results of the composition analysis values of the citric acid / organic acid / calcium / magnesium composition obtained in the present invention are shown in Table 1.
Shown in The water content is the weight of each sample before drying and 105 ° C.
It was calculated from the difference from the weight after drying for 3 hours. The numbers in the table correspond to the example numbers.

[0062]

[Table 1]

The results of the solubility test of the granules obtained in each example of the present invention are shown below. 1. Test method Take 5 g of the test powder and put it in 100 ml of water at 25 ° C.
Stir for minutes. 2. Test results Test results are shown in Table 2. Column A is immediately after manufacturing. Column B is 25 ° C
Represents after 3 months.

[0064]

[Table 2]

Each sample 1 obtained in Examples 1 to 11
Accurately weigh 0 g into a 50 ml volumetric flask and hold at 25 ° C.
I adjusted the balance line with. After shaking for 5 minutes, the mixture was filtered and the magnesium content in the filtrate was measured to determine the solubility. As a result, the solubility of the test powders of Examples 1, 2, and 8 was 7.
It was 9%, 10.3% and 8.2%.

As is clear from the above results, the amorphous citric acid / organic acid / calcium / magnesium composition of the present invention exhibits excellent properties, and is particularly useful for patients with hypoacidity or hypoxia. It can be widely used as a replenishing agent.

The composition of the present invention can be processed into a form such as powder, granules, tablet confectionery or tablets by dissolving it in water at the time of use as a reinforcing agent of magnesium and calcium or by a conventional method. Therefore, it can be used as a food or a preparation that can simultaneously supplement calcium and magnesium.

The above powders, granules, tablet confectionery or tablets are pharmaceutically or food additives acceptable excipients such as lactose, glucose, mannitol, sucrose and erythritol, disintegrating agents such as starch and sodium alginate, Lubricants such as magnesium stearate, polyvinyl alcohol, hydroxypropyl cellulose, binders such as gelatin, surfactants such as fatty acid esters, plasticizers such as glycerin, masking agents, alanine, aspartame, stevia sweeteners, lemon, etc. Powder, ume extract, flavoring agents such as orange powder, powdered milk and the like can be appropriately added according to a conventional method.

If necessary, as a pH adjusting agent, alkali metal salts of organic acids such as sodium salts and potassium salts of acetic acid, or alkalis such as sodium hydroxide and potassium hydroxide, or hydrochloric acid and acetic acid. Acids, preferably organic acids or salts thereof, can also be added.

If necessary, the above additives may be added to the aqueous reaction solution at the time of spray drying or freeze drying.

By the above method, as a food or medicine,
It was possible to produce a calcium-magnesium-containing tablet confectionery or tablet capable of simultaneously reinforcing magnesium and calcium.

Production Examples 1-2 The production method of tablet confectionery (1,000 mg / 1 tablet) is shown below.

[0073]

[Table 3]

With the above formulation, a powder mixer, a punch, and a mortar 15 m
m and a tableting pressure of 1,500 kg / cm ^{2 under} the conditions of rotary tableting [model HRT-18 manufactured by Hata Tekko Co., Ltd.]
A taste test was performed by 0 persons (5 boys, 5 girls, 24-56 years old). The results were evaluated as delicious in both Production Example 1 and Production Example 2. On the other hand, the comparative product by the conventional method was very bitter.

[0075]

Industrial Applicability According to the present invention, it is possible to provide an amorphous citric acid / organic acid / calcium / magnesium composition which is readily soluble in water, and a method for producing the same. The above-mentioned composition has a feature that it dissolves in water extremely quickly and its solubility is extremely high. In addition, the composition of the present invention is stable, and when it is made into a tablet or a tablet confectionery, it has excellent solubility and disintegrability, has a pleasant texture, has little bitterness, and can be supplemented with calcium and magnesium at the same time. Alternatively, it can be used as a replenishing agent and is extremely useful industrially.

[Brief description of drawings]

FIG. 1 shows X-ray diffraction patterns of the powder substances obtained in Examples 1, 2, 8, 9 and Comparative Examples 1-2. The vertical axis represents the intensity, but the graph is shown as being shifted for each example and comparative example as an arbitrary scale for comparison.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C07C 59/265 9450-4H 59/285 9450-4H

Claims (20)

[Claims] 1. A magnesium source, a calcium source, and an organic acid in which at least one of organic acids selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid, and gluconic acid is citric acid. An amorphous citric acid / organic acid / calcium / magnesium composition obtained by reacting the above in a water medium at a temperature range of 30 ° C. or lower and then spray drying. 2. The manesium source according to claim 1, which is selected from the group consisting of magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium chloride and magnesium sulfate.
A composition of two or more species. 3. The composition according to claim 1, wherein the calcium source is one or more selected from the group consisting of calcium carbonate, calcium hydroxide, biogenic calcined calcium and hydrates thereof. 4. The reaction temperature range according to claim 1, is -8 to 3.
A composition that is 0 ° C. 5. The reaction solution according to claim 1, which has a pH of 3.0 to 3.0.
A composition that is 5.5. 6. A magnesium source, a calcium source, and an organic acid selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid, and gluconic acid, wherein at least one of them is citric acid. A method for producing an amorphous citric acid / organic acid / calcium / magnesium composition, which comprises reacting in a medium in a temperature range of 30 ° C. or lower and then spray drying. 7. The magnesium source according to claim 6, wherein the magnesium source is magnesium oxide, magnesium carbonate, magnesium hydroxide,
A method of producing one or more selected from the group consisting of magnesium chloride and magnesium sulfate. 8. The method according to claim 6, wherein the calcium source is one or more selected from the group consisting of calcium carbonate, calcium hydroxide, biologically derived calcined calcium and hydrates thereof. 9. The reaction temperature range according to claim 6 is -8 to 3.
A manufacturing method which is 0 ° C. 10. The pH of the reaction solution according to claim 6, which is 3.0.
The manufacturing method which is -5.5. 11. A magnesium source, a calcium source, an organic acid in which at least one of organic acids selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid, gluconic acid, etc. is at least one citric acid. And an amorphous citric acid / organic acid / calcium / magnesium composition obtained by reacting and in a water medium at a temperature range of 30 ° C. or lower, and then freeze-drying. 12. The composition according to claim 11, wherein the magnesium source is one or more selected from the group consisting of magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium chloride and magnesium sulfate. 13. The composition according to claim 11, wherein the calcium source is one kind or two or more kinds selected from the group consisting of calcium carbonate, calcium hydroxide, biologically derived calcined calcium and hydrates thereof. 14. The reaction temperature range according to claim 11 is −8.
A composition that is -30 ° C. 15. The pH of the reaction solution according to claim 11 is 3.
A composition that is 0 to 5.5. 16. A magnesium source, a calcium source, an organic acid selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid, and gluconic acid, and at least one of which is citric acid, and water. A method for producing an amorphous citric acid / organic acid / calcium / magnesium composition, which comprises reacting in a medium at a temperature range of 30 ° C. or lower and then freeze-drying. 17. The magnesium source according to claim 16,
A method of producing one or more selected from the group consisting of magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium chloride and magnesium sulfate. 18. The method according to claim 16, wherein the calcium source is one or more selected from the group consisting of calcium carbonate, calcium hydroxide, calcined calcium of biological origin and hydrates thereof. 19. The reaction temperature range according to claim 16 is −8.
The manufacturing method which is -30 degreeC. 20. The pH of the reaction solution according to claim 16 is 3.
A manufacturing method which is 0 to 5.5.