JP2981595B2 - Sterile calcium carbonate composition, aqueous suspension composition thereof and methods for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to sterilized calcium carbonate having a high suspension stability which is added to foods to enhance calcium and impart soft abrasiveness to cosmetics such as toothpaste bases. Compositions, especially aqueous suspension compositions thereof, and methods for their preparation.

[0002]

2. Description of the Related Art Calcium is a mineral that forms bones and teeth and is indispensable to living organisms. However, recently, a lack of calcium intake is associated with an increase in osteoporosis in elderly people and frequent occurrence of fractures in young people. Is considered a problem. In order to make up for this insufficient intake of calcium, attempts have been made to fortify calcium in foods. In particular, calcium fortification, which is considered to have relatively good calcium bioabsorbability, has been increasing.

[0003] For example, calcium enhancers added to milk include organic acid calcium such as calcium lactate and calcium gluconate. However, since organic acid calcium is water-soluble, it reacts with proteins in milk to sterilize by heating. Occasionally a coagulum is formed. Further, since the calcium component ratio of the organic acid calcium itself is small, the amount added to the milk is inevitably increased, and there is a problem in taste.

On the other hand, poorly water-soluble calcium salts such as calcium carbonate and calcium phosphate do not cause coagulation with proteins in milk, are tasteless and odorless, have little effect on taste, and have a higher calcium content than organic acid calcium. Therefore, it is preferable as a calcium enhancer, for example, calcium can be strengthened with a small amount of addition. For this reason,
Recently, applications of adding calcium carbonate to milk as a calcium enhancer have been increasing, but calcium carbonate precipitates in a liquid in a short time, and there is a problem in suspension stability. As a method for solving this problem, a method of adding crystalline cellulose to calcium carbonate or a method of adding a hydrophilic emulsifier having an HLB of 10 or more such as sucrose fatty acid ester has been proposed. However, when crystalline cellulose is used, the viscosity of milk increases, which affects the taste. When a hydrophilic emulsifier is used, a special dispersing method such as ultrasonic irradiation is required, and there is a problem that the production efficiency is poor.

[0005] When a sterilized calcium carbonate aqueous suspension is used as a food additive, it is particularly important to manage hygiene to prevent the generation of general bacteria and the like, and heat sterilization must be performed as a treatment method. However, sodium metaphosphate, which is most effective as a dispersant for calcium carbonate, reacts when heated in the presence of calcium carbonate to form insoluble calcium phosphate, and the dispersing effect is significantly reduced.

The present invention, when used as a calcium enhancer for adding foods, especially beverages such as milk, hardly precipitates in a liquid, has excellent suspension stability and storage stability, and is used for cosmetics such as toothpaste. It is an object of the present invention to provide a sterilized calcium carbonate aqueous suspension composition having excellent soft abrasiveness without damaging the tooth structure.

[0007]

Means for Solving the Problems As a result of repeated studies in view of the above problems, the present inventor has found that a water suspension of calcium carbonate and an aqueous solution of sodium metaphosphate are individually heat-sterilized beforehand, mixed, and wet pulverized. Or, by separately heating and sterilizing an aqueous suspension of calcium carbonate and an aqueous solution of sodium metaphosphate to which the polypeptide has been added, and then mixing and wet-grinding, it is difficult to settle in the liquid,
It has been found that a sterilized aqueous calcium carbonate suspension having excellent suspension stability and storage stability can be obtained.

That is, the present invention relates to the following sterilized calcium carbonate composition, an aqueous suspension composition thereof, and a method for producing them.

Item 1. A sterilized calcium carbonate composition comprising calcium carbonate and sodium metaphosphate, substantially free of calcium phosphate.

Item 2. A sterilized calcium carbonate aqueous suspension composition containing calcium carbonate and sodium metaphosphate and substantially free of calcium phosphate.

Item 3. A sterilized aqueous calcium carbonate suspension composition comprising calcium carbonate, a polypeptide and sodium metaphosphate.

Item 4. Item 4. The sterilized aqueous calcium carbonate suspension according to Item 3, wherein the polypeptide is at least one selected from the group consisting of casein phosphopeptide and casein calcium peptide.

Item 5. A method for producing a sterilized calcium carbonate aqueous suspension composition, which comprises subjecting an aqueous suspension of calcium carbonate and an aqueous solution of sodium metaphosphate to heat sterilization separately and then mixing and wet grinding.

Item 6. A method for producing a sterilized calcium carbonate aqueous suspension composition, comprising heat-sterilizing an aqueous suspension of calcium carbonate, wet-milling, adding an aqueous solution of sodium metaphosphate separately sterilized by heat, and mixing with stirring.

Item 7. A method for producing a sterilized aqueous solution of calcium carbonate, comprising subjecting an aqueous suspension of calcium carbonate to which a polypeptide has been added and an aqueous solution of sodium metaphosphate separately to heat and then mixing and wet-grinding.

Item 8. A sterilized aqueous solution of calcium carbonate, wherein the aqueous suspension of calcium carbonate to which the polypeptide is added is heat-sterilized, and an aqueous solution of sodium metaphosphate separately heat-sterilized after wet pulverization is added, followed by stirring and mixing. Manufacturing method.

Item 9. A method for producing a sterilized calcium carbonate composition, wherein calcium carbonate and sodium metaphosphate are individually heat-sterilized in advance and then stirred and mixed.

Item 10. A toothpaste containing the sterilized calcium carbonate composition according to item 1.

The sterilized calcium carbonate composition of the present invention can be easily converted into a stable sterilized calcium carbonate aqueous suspension composition by adding sterilized water such as distilled water. Therefore, the composition may be in the form of a water-free composition at the time of transportation or storage, and may be added with water at the time of use to form a suspension. Further, the sterilized calcium carbonate composition of the present invention can stably contain calcium carbonate even in a paste or a concentrated suspension containing a little water. However, the tooth material is not damaged, the polishing can be performed smoothly, and the toothpaste after the tooth brushing can be easily removed. In addition, the present invention can be applied to a cleanser-type dishwasher and kitchen-use liquid detergent that removes dirt without scratching.

Further, even when the composition of the present invention is added to a solid, liquid or semi-solid food, the fine particles of calcium carbonate are present in a sufficiently dispersed state when the food is ingested. Easy to be absorbed. Foods to which the composition of the present invention is blended include, for example, milk products, milk drinks, dairy products such as ice cream and condensed milk, coffee, drinking water, soy milk and the like.

[0021] The composition of the present invention can be produced by separately heating and sterilizing calcium carbonate and sodium metaphosphate, followed by mixing and stirring.

In the present invention, "substantially free of calcium phosphate" means that the suspension stability of the aqueous calcium carbonate suspension is not impaired by the presence of calcium phosphate. It means that it may contain calcium phosphate as long as the suspension is sufficiently stable.

For example, if 100 ml of the aqueous suspension (calcium carbonate concentration = 0.2%) of the present invention is allowed to stand for 4 weeks and the apparent volume of the sediment is 1 ml or less, "substantially contains no calcium phosphate."".

As the calcium carbonate, a synthetic product or a pulverized product conforming to food additive standards or cosmetic raw material standards is used, and preferably has a BET specific surface area of 7 m ² / g or more and an average particle diameter of 5 μm or less, more preferably. , BET specific surface area of about 7 to 100 m ² / g, average particle size of 0.02 to 5
It is about μm.

The most preferred calcium carbonate is porous calcium carbonate, which is produced, for example, by the following steps (i) to (iii).

(I) A carbon dioxide-containing gas having a carbon dioxide concentration of 15% by volume or more is blown into the aqueous solution of calcium hydroxide at a rate of 25 L / min or more per kg of calcium hydroxide, and the carbonation rate is increased to 60 to 90%. A first carbonation step for carrying out the reaction, (ii) an aqueous suspension of calcium hydroxide is added to the aqueous suspension after the first carbonation step, and a carbon dioxide-containing gas having a carbon dioxide concentration of 10% by volume or more is added Blow at a rate of 15 liters / minute or more per kg of calcium hydroxide, and carbonation rate 70-90.
%, And after the completion of the second carbonation step, the same carbonation step as the second carbonation step is repeated once or more, and then after the completion of the carbonation step. A calcium hydroxide aqueous suspension is added to the water suspension, and a carbon dioxide-containing gas having a carbon dioxide gas concentration of 10% by volume or more is blown at a rate of 15 liter / min or more per 1 kg of calcium hydroxide, and the pH is 6.5 to 7.5. Final carbonation step in which the carbonation reaction is performed until

The carbonation rate in the steps (i) to (iii) is calculated by the following formula:
Carbonation rate (%) = 100 × W / (W + W1) (W
Is the weight of calcium carbonate in the reaction solution, and W1 is the weight of calcium hydroxide in the reaction solution. ).

The solid content of calcium carbonate is about 5 to 50% by weight, preferably about 10 to 45% by weight. When the solid concentration of calcium carbonate is in the above range, the production efficiency is high and the production can be carried out at low cost, which is preferable.

The amount of sodium metaphosphate to be added is about 0.5 to 5 parts by weight, preferably about 0.8 to 4 parts by weight, based on 100 parts by weight of calcium carbonate.

The polypeptide preferably has 10 to 50 amino acid residues. In the case of an associative protein, the number of amino acid residues is the number of monomeric amino acids. The polypeptide is preferably a phosphopeptide containing a phosphate residue in its structure. Examples of such a phosphopeptide include casein phosphopeptide (CPP) and casein calcium peptide (CCP). C
Both PP and CCP are obtained by enzymatic degradation of casein or casein calcium, and are available as commercial products.

The amount of the polypeptide to be added is about 0.05 to 1 part by weight, preferably about 0.1 to 0.8 part by weight, per 100 parts by weight of calcium carbonate.

In the production method of the present invention, a colloid mill, a sand mill, a ball mill or the like can be used as a wet pulverizer used in the wet pulverization step.

The stirring and mixing device used in the stirring and mixing step of the present invention includes a homogenizer and a disper. Conditions such as wet pulverization and stirring and mixing are not particularly limited, and can be easily determined by those skilled in the art.

Heat sterilization is carried out at about 60 to 120 ° C. for 15 to 15 hours.
What is necessary is just to carry out on conditions of about 60 minutes.

The production method of the present invention is characterized in that calcium carbonate (which may contain a polypeptide) and sodium metaphosphate are previously heat-sterilized separately and then mixed. When heat sterilization is performed after mixing these, insoluble calcium phosphate is generated,
Not preferred.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Example 1 30% porous calcium carbonate (BET specific surface area 30 m ²
/ G, average particle size 3 μm, pH = 9.5)
Heat sterilization was performed at 5 ° C. for 30 minutes. Separately, a 15% aqueous sodium metaphosphate solution was sterilized by heating at 95 ° C. for 5 minutes. After each of them was cooled to 30 ° C., both were mixed so that sodium metaphosphate was 3 parts by weight with respect to 100 parts by weight of calcium carbonate, and wet-ground with a Dyno mill to obtain a suspension.

Example 2 20% calcium carbonate (BET specific surface area 11 m ² / g,
Average particle diameter 1 μm, pH = 10.5) water suspension at 85 ° C.
And then cooled to 30 ° C. and wet-pulverized with a Dyno mill. Separately, a 15% aqueous solution of sodium metaphosphate was sterilized by heating at 95 ° C for 5 minutes.
Cooled to ° C. Then, both were mixed so that sodium metaphosphate was 4 parts by weight with respect to 100 parts by weight of calcium carbonate to obtain a suspension.

Example 3 35% porous calcium carbonate (BET specific surface area 30 m ²
/ G, average particle size 3 μm, pH = 9.5)
10% CPP was added in an amount of 0.3 part by weight to 100 parts by weight of calcium carbonate, sterilized by heating at 85 ° C. for 30 minutes, and cooled to 30 ° C. Apart from this, 15%
The aqueous sodium metaphosphate solution was heat-sterilized at 95 ° C for 5 minutes and cooled to 30 ° C. Then, calcium carbonate 10
The two were mixed so that the sodium metaphosphate was 3 parts by weight with respect to 0 parts by weight, and the mixture was wet-pulverized with a dyno mill to obtain a suspension.

Example 4 30% porous calcium carbonate (BET specific surface area 30 m ²
/ G, average particle size 3 μm, pH = 9.5)
10% CCP was added in an amount of 0.1 part by weight to 100 parts by weight of calcium carbonate, sterilized by heating at 85 ° C. for 30 minutes, and cooled to 30 ° C. Apart from this, 15%
The aqueous sodium metaphosphate solution was heat-sterilized at 95 ° C for 5 minutes and cooled to 30 ° C. Then, calcium carbonate 10
The two were mixed so that the sodium metaphosphate was 1 part by weight with respect to 0 part by weight, and wet-pulverized with a Dyno mill to obtain a suspension.

Example 5 25% calcium carbonate (BET specific surface area 11 m ² / g,
Average particle diameter 1 μm, pH = 10.5)
% CPP is added to 0.4 parts by weight per 100 parts by weight of calcium carbonate.
It was added so as to be in parts by weight, sterilized by heating at 85 ° C. for 30 minutes, cooled to 30 ° C., and wet-pulverized with a Dyno mill.
Separately, a 15% aqueous sodium metaphosphate solution was added to 9
The solution was sterilized by heating at 5 ° C for 5 minutes and cooled to 30 ° C. Then, both were mixed so that sodium metaphosphate was 2 parts by weight with respect to 100 parts by weight of calcium carbonate to obtain a suspension.

Comparative Example 1 30% calcium carbonate (BET specific surface area 30 m ² / g,
(Average particle diameter 3 μm, pH = 9.5) The water suspension was heat-sterilized at 85 ° C. for 30 minutes. Separately, a 15% aqueous sodium metaphosphate solution was sterilized by heating at 95 ° C. for 5 minutes. After each of them was cooled to 30 ° C., they were mixed so that 0.2 parts by weight of sodium metaphosphate was added to 100 parts by weight of calcium carbonate, and wet-ground with a Dyno mill to obtain a suspension.

Comparative Example 2 30% calcium carbonate (BET specific surface area 30 m ² / g,
3% by weight of a 15% aqueous sodium metaphosphate solution was added to 100 parts by weight of calcium carbonate, and the mixture was sterilized by heating at 85 ° C. for 30 minutes. After cooling to 30 ° C., the suspension was wet-pulverized with a Dyno mill to obtain a suspension.

Suspension stability test The sterilized aqueous solution of calcium carbonate obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was diluted with water until the solid content of calcium carbonate became 0.2%, 1000 rpm with a stirrer
After stirring for mx 7 minutes 30 seconds, 157 G x 4
Centrifugal force was applied for 20 minutes. Next, the centrifuged sediment was evaporated to dryness, calcined in an electric furnace at 950 ° C. for 3 hours, and after cooling, the weight was measured to calculate the suspension rate. In addition, a 0.2% diluted solution prepared in the same manner was placed in a 100-ml stoppered graduated cylinder, and allowed to stand at room temperature to measure the change over time in the height of the suspension surface of the diluted solution and the apparent volume of the sediment. did. The results are shown in Tables 1 to 3. In Table 2, the pH ratio and the viscosity ratio = (value after 1 to 4 weeks) / (value immediately after production).

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

The criteria for evaluating the high suspension stability of the suspension are shown below.

(1) Suspension rate: 60% or more (2) Height of suspension surface: 70 ml or more (after 4 weeks) (3) pH ratio: 0.90 to 1.10 (after 4 weeks) 4) Viscosity ratio: 0.80 to 1.25 (after 4 weeks) According to the above evaluation criteria, it is clear that the suspension composition of the present invention has high suspension stability. This indicates that the suspensions obtained in Examples 1 to 5 are substantially free of calcium phosphate.

Production Example 1 Toothpaste A toothpaste was produced according to a conventional method according to the following formulation.

100 parts by weight of calcium carbonate 2 parts by weight of sodium metaphosphate 4 parts by weight of sodium lauryl sulfate (foaming agent) 20 parts by weight of sorbite (wetting agent) 2 parts by weight of carrageenan (binder) 2 parts by weight of fragrance Suitable amount of preservative Suitable amount of preservative

[0052]

As described above, the aqueous suspension of sterilized calcium carbonate obtained by the present invention has high suspension stability, is suitable as a calcium fortifier for foods, and has good dispersibility and preservation in foods. Excellent stability. It is also excellent in dispersibility and stability in a cosmetic base.

The polypeptide of the present invention is effective when added at any time during the preparation of an aqueous suspension.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C01F 11/18 C01F 11/18 J // A23L 1/304 A23L 1/304 (56) References JP-A-60-11412 (JP) JP-A-52-127499 (JP, A) JP-A-63-233013 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 7/00-7/50 C01F 11/18

Claims (10)

(57) [Claims] 1. A sterilized calcium carbonate composition comprising calcium carbonate and sodium metaphosphate, substantially free of calcium phosphate. 2. A sterilized aqueous calcium carbonate suspension composition containing calcium carbonate and sodium metaphosphate and substantially free of calcium phosphate. 3. A sterilized aqueous calcium carbonate suspension composition comprising calcium carbonate, a polypeptide and sodium metaphosphate. 4. The sterile calcium carbonate aqueous suspension composition according to claim 3, wherein the polypeptide is at least one selected from the group consisting of casein phosphopeptide and casein calcium peptide. 5. A method for producing a sterilized calcium carbonate aqueous suspension composition, comprising separately heating and sterilizing an aqueous suspension of calcium carbonate and an aqueous solution of sodium metaphosphate, followed by mixing and wet grinding. 6. An aqueous suspension of calcium carbonate is heat-sterilized,
A method for producing a sterilized aqueous solution of calcium carbonate, which comprises adding an aqueous solution of sodium metaphosphate separately sterilized by heat after wet pulverization and stirring and mixing. 7. A sterilized calcium carbonate aqueous suspension composition, which comprises subjecting an aqueous suspension of calcium carbonate to which a polypeptide has been added and an aqueous solution of sodium metaphosphate to individual heat sterilization before mixing and wet grinding. Method of manufacturing a product. 8. A sterilized aqueous solution of calcium carbonate, which is obtained by sterilizing an aqueous suspension of calcium carbonate to which a polypeptide has been added, heat-pulverizing, wet-milling, adding an aqueous solution of sodium metaphosphate separately sterilized by heat, and stirring and mixing. A method for producing a suspension composition. 9. A method for producing a sterilized calcium carbonate composition, wherein calcium carbonate and sodium metaphosphate are individually heat-sterilized beforehand and then stirred and mixed. 10. A toothpaste containing the sterilized calcium carbonate composition according to claim 1.