JPH08107772A - Production of calcium dispersion and food containing the same - Google Patents

Abstract

PURPOSE: To obtain a calcium dispersion, good in stability and hardly forming precipitates even when preserved for a long period by preparing fine calcium oxide particles from a sparingly water-soluble or water-insoluble calcium salt and a hydroxy acid, adding a hydrophilic emulsifying agent thereto and carrying out the dispersing treatment. CONSTITUTION: This stable calcium dispersion is obtained by mixing and stirring a sparingly water-soluble or a water-insoluble calcium salt (calcium carbonate, etc.) and a hydroxy acid (citric acid) in a dispersion medium, producing a hydroxy acid salt of calcium having <=1μm average particle diameter, then adding a hydrophilic emulsifying agent having >=10HLB thereto and carrying out the dispersing treatment for 20-30min with a usual dispersing machine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a calcium dispersion and a food containing the same.

[0002]

2. Description of the Related Art Calcium is a main component of animal bones and teeth and is an essential element for living organisms. For humans, in adults
Calcium intake of 1.0 g / day and even 0.6 g / day of infants are required. In order to ingest the required amount of calcium as described above, it is sufficient to eat small fish, milk, soybeans, green leafy vegetables, etc. having a high calcium content, but in recent years, in order to efficiently ingest calcium, , Foods to which calcium is added, that is, calcium-fortified foods have been developed. For example, it has been conventionally practiced to add a water-soluble organic acid calcium salt to a beverage such as milk. However, by adding such a water-soluble organic acid calcium salt, the flavor of the beverage is impaired, and when protein is contained in the beverage, coagulation of the protein in the sterilizer is performed when the beverage is sterilized. There was an inconvenience that it happened and the passage of liquid became impossible.

As a method for solving the above problems, a technique for adding an inorganic salt calcium such as calcium carbonate to a beverage has been developed. Japanese Unexamined Patent Publication No. 64-69513 discloses a slurry of calcium carbonate to which a sucrose fatty acid ester (generally referred to as a sugar ester) is added, which is irradiated with ultrasonic waves to make calcium carbonate particles fine, which is then added to milk or milk. It discloses a method of adding to dispersed butter or the like and dispersing. However, in the method disclosed by this publication, since the finely divided calcium carbonate particles have a large particle size, good dispersibility of calcium carbonate in the product cannot be obtained, and the product after passing through the clarifier is not obtained. It has the drawback of low calcium retention. Furthermore, in this method, in order to disperse calcium carbonate in milk or butter, a high-speed stirrer such as a homogenizer or homomixer had to be used. The use of such special equipment complicates the manufacturing process of the product.

[0004]

The object of the present invention is therefore to provide a process for the production of calcium dispersions which does not have the abovementioned disadvantages. That is, the present invention provides a method capable of refining calcium particles to an extent sufficient to disperse the calcium particles using an ordinary disperser, by utilizing a chemical reaction rather than by mechanical impact. The purpose is to Another object of the present invention is to provide a food containing a calcium dispersion having good dispersibility.

[0005]

The inventors of the present invention can easily obtain calcium particles having an average particle size of 1 μm or less by reacting a poorly water-soluble or water-insoluble calcium salt with an oxy acid, and further, HLB It was found that the calcium particles can be stably dispersed by adding a hydrophilic emulsifier having a ratio of 10 or more, and the present invention has been completed. That is, the present invention comprises a step of adjusting the average particle size of calcium particles to 1 μm or less by mixing and stirring a sparingly water-soluble or water-insoluble calcium salt and an oxyacid in a dispersion medium, and a hydrophilic property with HLB of 10 or more. The present invention provides a method for producing a calcium dispersion, which comprises the step of adding a strong emulsifier. The present invention also provides a food containing the calcium dispersion produced by the above production method.

Without being bound to a particular theory, calcium carbonate (a sparingly water-soluble or water-insoluble calcium salt)
Taking citric acid (oxy acid) as an example, the reaction mechanism between the sparingly water-soluble or water-insoluble calcium salt and oxy acid in the present invention will be described below.

[0007] by reaction of calcium carbonate and citric acid, calcium citrate is formed, which is the chelate compound of soluble _{^{[- OOCCH 2 C (OH) (}} COO -) CH 2 CO
O ^-] is a [Ca ^2+] chelates CO ₃ and a sparingly soluble salt ^[- OO
_{CCH 2 C (OH) (COO} -) CH 2 COO -] is believed to be a mixture of ^{_{2 Ca 2+ 3 · 4H 2 O}} . However, the ratio of both differs depending on the concentration of calcium carbonate, the concentration of citric acid, the concentration ratio of calcium carbonate and citric acid, the solution temperature, and the like. In the present invention,
By reacting calcium carbonate with citric acid under appropriate reaction conditions, precipitation of calcium citrate containing the chelate compound of the above-mentioned sparingly soluble salt as a main component is caused. The resulting precipitate of calcium citrate is made into fine particles, which can be used to prepare a stable calcium dispersion.

The present invention will be described in detail below. In the present invention, a sparingly water-soluble or water-insoluble calcium salt and an oxyacid are mixed and stirred in a dispersion medium to adjust the average particle size of calcium particles to 1 μm or less. As the sparingly water-soluble or water-insoluble calcium salt, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium hydroxide, calcium sulfate, and calcium citrate can be used, and calcium carbonate is preferably used.

As the oxyacid, there can be used those capable of reacting with a sparingly water-soluble or water-insoluble calcium salt to form a sparingly water-soluble or water-insoluble calcium oxyacid salt, such as citric acid, tartaric acid, lactic acid and glucon. Examples thereof include acids and malic acid, but citric acid having a plurality of carboxyl groups is preferable. Water is preferably used as the dispersion medium.

While the dispersion medium is being stirred with a homomixer, mycoloider or the like, a sparingly water-soluble or water-insoluble calcium salt and oxyacid are added and mixed to adjust the average particle size of calcium particles to 1 μm or less. Good. Specification of sparingly water-soluble or water-insoluble calcium salt and oxyacid (normal)
The ratio is preferably 1: 1 to 1: 1.2, and 1: 1 to
1: 1.15 is more preferable. If the defined ratio of the oxyacid to the poorly water-soluble or water-insoluble calcium salt is less than 1, there is a problem that the unreacted poorly water-soluble or water-insoluble calcium salt remains as coarse particles. The pH of the obtained calcium dispersion becomes high, which causes a problem that the pH must be adjusted when it is added to food. The concentration of the sparingly water-soluble or water-insoluble calcium salt in the dispersion medium is preferably 5 to 13% by weight, more preferably 10 to 13% by weight. When the concentration of the sparingly water-soluble or water-insoluble calcium salt in the dispersion medium is lower than 5% by weight, the calcium concentration of the obtained calcium dispersion becomes low, and the original purpose cannot be achieved when adding and strengthening calcium to foods. A problem occurs, and if it is higher than 13% by weight, the production rate of the chelate compound of the poorly soluble salt becomes excessive, and the degree of dispersion of calcium particles decreases. For example, when the sparingly water-soluble or water-insoluble calcium salt is calcium carbonate, the concentration of calcium carbonate in the dispersion medium is preferably 5 to 13% by weight, and 10 to 13% by weight.
Is more preferable. The concentration of oxyacid in the dispersion medium is 10-
20 wt% is preferable, and 15-20 wt% is more preferable. When the concentration of the oxyacid in the dispersion medium is lower than 10% by weight, the calcium concentration of the obtained calcium dispersion becomes low, which causes a problem that the original purpose cannot be achieved when adding and strengthening calcium to foods. When the content is higher than the weight%, the composition ratio of the chelate compound of the sparingly soluble salt does not change even if the concentration is higher than this, and thus there is a problem that it is economically disadvantageous. For example, when the oxyacid is citric acid, the citric acid concentration in the dispersion medium is preferably 10 to 20% by weight, more preferably 15 to 20% by weight. Further, the dispersion may be carried out until the average particle diameter of the calcium particles becomes 1 μm or less, preferably 0.6 μm or less.
When the average particle size of the calcium particles is larger than 1 μm, there is a problem that the degree of dispersion of the calcium particles decreases. For example, a mixture of a sparingly water-soluble or water-insoluble calcium salt in a dispersion medium and an oxyacid is added at a solution temperature of 20 to 30 ° C.,
By stirring at a rotation speed of 10,000 to 12,000 rpm for 10 to 30 minutes, the average particle diameter of calcium particles in the dispersion medium can be 1 μm or less. Preferably, the above mixture is 2
2 at a temperature of 0 to 25 ° C and a rotation speed of 10,000 to 12,000 rpm
Stir for 0 to 30 minutes.

A hydrophilic emulsifier having an HLB of 10 or more is added to the calcium suspension obtained as described above. HL
As the hydrophilic emulsifier having B of 10 or more, sucrose fatty acid ester and polyglycerin fatty acid ester can be used. The addition amount of the emulsifier is preferably 0.5 to 2 and more preferably 0.8 to 1.5 with respect to the sparingly water-soluble or water-insoluble calcium salt. If the amount of the emulsifier added is more than 2% by weight, there is a problem that the effect on the amount used is small and it is not economical, and if it is less than 0.5% by weight, the problem of insufficient dispersion of calcium particles occurs. When adding the emulsifier, water is added in a weight ratio of 3 to 5 with respect to the mixed stirring liquid of the calcium salt and the oxy acid. By adding water, the emulsifier can be sufficiently dispersed and a calcium dispersion can be efficiently produced.

After adding a hydrophilic emulsifier having an HLB of 10 or more, the calcium suspension is further dispersed. The variance is
It can be carried out using a homomixer, mycoloider or the like as described above, and is preferably carried out for 20 to 30 minutes. Thereby, a stable calcium dispersion can be obtained.

A calcium-fortified food can be produced by adding and dispersing the above calcium dispersion in food. Foods to which the calcium dispersion is added include milk, soy milk, milk drink, fruit juice, juice, soft drink,
Examples thereof include beverages such as tea, soups and foods such as stews. In the calcium dispersion, the amount of calcium added to 100 g of food is 50 to 200 mg, preferably 100 to 1
It can be added to foods in an amount to give 50 mg. Since the milk calcium dispersion produced by the method of the present invention has good dispersion stability, it can be dispersed in foods using a line mixer, a batch type mixing tank or the like.

The calcium-fortified food thus produced may be sterilized by applying high temperature or high pressure,
Further, when the calcium-enriched food is a beverage, foreign substances may be removed using a clarifier or the like. Hereinafter, the present invention will be specifically described with reference to Examples, but the scope of the present invention is not limited thereto.

[0015]

【Example】

Example 1 (1) Preparation of Calcium Suspension Calcium carbonate (Shiroishi Calcium trade name Corocarn) 150 g Citric acid (Takeda Pharmaceutical Co., Ltd.) 210 g Water (tap water) 1140 g 1500 g At room temperature, a homomixer (tabletop type) Calcium carbonate and citric acid were added while stirring the water at 10,000 rpm), and the particle size distribution was measured over time. The following Table 1 shows the relationship between the stirring time after adding calcium carbonate and citric acid to water and the average particle size of calcium particles.

[0016]

[Table 1] Table 1 ───────────────────────────── Agitation time (min) 1 10 20 30 Particle size (μm) 6.5 6.3 0.4 0.3 ───────────────────────────── Calcium particles with an average particle size of 1 μm or less were obtained after stirring for 20 minutes. .

(2) Preparation of calcium dispersion liquid Calcium suspension prepared in (1) (stirring time 30 minutes) 20% sugar ester F-160 (Daiichi Kogyo Seiyaku Co., Ltd.) 3% water (tap water) 77 % Total 100% Using the above mixture, use a homomixer (tabletop type) as in (1).
When dispersed at 10,000 rpm for 20 minutes, an average particle size of 0.4
μm calcium particles were obtained.

(3) Addition of calcium dispersion to foods Skim milk (SNF 9.0% by weight) so that the calcium dispersion prepared in (2) has a concentration of 10% (corresponding to 120 mg% Ca fortification) In addition, the milk bottle was allowed to stand and stored for 3 days, and the presence or absence of precipitate formation was observed. The results are shown in Table 2.

[0019]

[Table 2] Table 2 ────────────────── Stationary days (days) 1 2 3 ────────────────── ─ Presence or absence of precipitate formation − − ± ────────────────── −: There is no precipitation at all. ±: Slight precipitation is observed.

Example 2 (1) Preparation of Calcium Suspension The same procedure as in (1) of Example 1 was carried out. (2) Preparation of Calcium Dispersion Liquid Calcium suspension prepared in (1) (stirring time 30 minutes) 20% Polyglycerin fatty acid ester (manufactured by Taiyo Kagaku Co., HLB12) 2% Water (tap water) 78% Total 100% Use the homomixer (tabletop type) in the same manner as in step (1) above for the mixed solution.
When dispersed at 10,000 rpm for 20 minutes, an average particle size of 0.2
μm calcium particles were obtained. (3) Addition of calcium dispersion to foods Skim milk (9.0% by weight of SNF) was added with the calcium dispersion prepared in (2) to a concentration of 10% (corresponding to 120 mg% of Ca fortification), The milk bottle was allowed to stand and stored, and the presence or absence of precipitate formation was observed for 3 days. Table 3 shows the results.

[0021]

[Table 3] Table 3 ────────────────── Stationary days (days) 1 2 3 ────────────────── ─Presence or absence of precipitate formation − − − ^** ────────────────── ^** : The precipitate was dispersed by shaking gently.

Example 3 (1) Preparation of Calcium Suspension A calcium suspension having the following composition and rotation speed was prepared at room temperature using a homomixer. Calcium carbonate Citric acid Water rotation speed Citric acid / Colocarn (Corocarn) (weight ratio) (regular ratio) 150 g 150 g 1200 g 3000 rpm 1.0 0.8 〃 〃 〃 6000 rpm 〃 〃 〃 〃 〃 10000 rpm 〃 〃 150 g 180 g 1170 g 10000 rpm 1.2 0.9 150 g 210 g 1140 g 10000 rpm 1.4 1.1 Stirring time after adding calcium carbonate and citric acid to water, average particle size of calcium particles and p of calcium suspension
The relationship with H is shown in Table 4 below.

[0023]

[Table 4] Table 4 ─────────────────────────────────── Stirring time (min) 1 5 10 15 20 25 30 35 40 ─────────────────────────────────── Particle size 3.18-2.66-2.69-2.52- -(μm) 3000rpm pH 3.92 4.35 4.57 4.70 5.57 5.90 5.97--Particle size 4.12-2.84-2.92-2.82--(μm) 6000rpm pH 3.80 4.30 4.53 4.68 4.72 5.94 6.20 6.41 6.54 Particle size 2.71-2.19-2.30--- -(μm) 10000rpm pH 3.90 4.32 4.60 6.34 7.42 7.65 7.66--Particle size 4.20-3.30-3.08----(μm) 10000rpm pH 3.79 4.13 4.31 5.55 7.36 7.78---Particle size 6.52-6.28-0.43 0.34-- -(μm) 10000rpm pH 3.56 3.77 3.91 4.00 3.80 4.23---────────────────────────────────────

(2) Preparation of calcium dispersion liquid Calcium suspension prepared in (1) (stirring time 25 minutes) 10 g Sugar ester F-160 (Daiichi Kogyo Seiyaku Co., Ltd.) 1 g Water (tap water) 89 g Total 100 g When the above mixed liquid was dispersed for 20 minutes with a homomixer, calcium particles having an average particle diameter of 0.4 μm were obtained.

[0025]

According to the present invention, a calcium dispersion having good dispersion stability can be obtained without using a large-scale equipment such as a mill. The food containing the calcium dispersion obtained according to the present invention has advantages such that precipitation does not easily occur even after long-term storage, the calcium content of the food is high, the loss of calcium is small, and it is economical. Furthermore, by using the calcium dispersion of the present invention, it is possible to disperse calcium in a food without using a special disperser such as a homogenizer or a homomixer, which simplifies the manufacturing process of a calcium-fortified food. Is possible
Capital investment can also be minimized.

Claims (11)

[Claims] 1. A step of adjusting the average particle diameter of calcium particles to 1 μm or less by mixing and stirring a sparingly water-soluble or water-insoluble calcium salt and an oxyacid in a dispersion medium, and
A method for producing a calcium dispersion, comprising the step of adding a hydrophilic emulsifier having an HLB of 10 or more. 2. The method according to claim 1, wherein the sparingly water-soluble or water-insoluble calcium salt is calcium carbonate. 3. The production method according to claim 1, wherein the oxyacid is citric acid. 4. The method according to claim 1, wherein the normal (normal) ratio of the sparingly water-soluble or water-insoluble calcium salt and the oxyacid is in the range of 1: 1 to 1: 1.2. 5. The production method according to claim 1, wherein the concentration of the sparingly water-soluble or water-insoluble calcium salt in the dispersion medium is 5 to 13% by weight. 6. The concentration of oxyacid in the dispersion medium is 10 to 20.
The manufacturing method according to any one of claims 1 to 5, which is in% by weight. 7. The production method according to claim 1, wherein the dispersion medium is water. 8. The production method according to claim 1, wherein the average particle diameter of the calcium particles is adjusted to 0.6 μm or less. 9. The method according to claim 1, wherein the hydrophilic emulsifier having an HLB of 10 or more is added in a weight ratio of 0.5 to 2 with respect to calcium carbonate. 10. The method according to claim 1, wherein the calcium dispersion is used for adding a beverage. 11. A food product containing the calcium dispersion produced by the production method according to claim 1.