JP3180846B2 - Milk-derived calcium agent and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calcium preparation containing casein-binding calcium and colloidal calcium recovered from casein of milk as active ingredients, and a method for producing the same. The calcium agent of the present invention can be used as a calcium enhancer by blending it in foods and drinks, medicines or feeds.

[0002]

2. Description of the Related Art The calcium intake of Japanese people has been below the nutritional requirement for many years, and the average dietary habit of Japanese people is that it is considerable to continue menus containing sufficient calcium. It takes effort. Therefore, intake of calcium having good absorbability is desired. As calcium having good absorbability, it is reported that calcium contained in milk is particularly excellent in absorbability. There are three forms of calcium in milk, soluble calcium, casein-binding calcium and colloidal calcium. One-third of the soluble calcium is ionic and the rest is calcium citrate, and the casein-bound calcium is calcium bound to the casein micelles.
Colloidal calcium is incorporated into casein micelles in the form of calcium apatite. Regarding the absorption of calcium by form, it has been reported that the soluble form has good absorbability, but the form of casein-binding calcium and colloidal calcium is more useful than that (Nutr. Rep. Int., 21, 6738 (1980)]. And nearly 60-70% of these calcium in milk is in the form of casein binding and colloidal calcium.

Various methods for separating and recovering calcium contained in milk have been studied in the past, and most of them have been recovered in the form of minerals containing calcium (Japanese Patent Laid-Open No. 59-78644). JP-A-60-232052, JP-A-63-87944, JP-A-2-107152, JP-A-2-107156). The raw materials used in these conventional methods are all whey, and are obtained from whey by removing acid by adding acid to whole milk or skim milk, or by precipitating and removing casein by lactic acid fermentation or rennet treatment.

[0004]

Calcium contained in milk is dissociated from casein micelles and transferred to whey when an acid is added to milk or lactic acid fermentation is performed. Casein-binding calcium and colloidal calcium transferred to this whey
Once mixed with whey protein, lactose or soluble calcium, it is extremely difficult to separate it from whey as casein-binding calcium or colloidal calcium. In addition, the form of calcium present in whey is unstable and tends to form calcium phosphate crystals and precipitate. Therefore, the calcium agent obtained by the above-described conventional method using whey as a raw material does not have a calcium content sufficient for use as a calcium enhancer. As another method, there is a method of precipitating as a calcium phosphate salt by bringing a mineral solution in an acidic state obtained from acid whey to near neutrality in order to increase the calcium content,
The form of calcium obtained by this method is different from the form contained in milk and has a problem in absorbability. As described above, at present, a milk-derived calcium agent that is closest to the form of calcium contained in milk, has a high calcium content, and has good absorbability has not yet been obtained. Accordingly, an object of the present invention is to provide a milk-derived calcium agent having a high calcium content and good absorbability and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a calcium preparation containing casein-binding calcium and colloidal calcium recovered from casein of milk as an active ingredient. The present invention has been completed based on the finding that it is closest to the form of calcium contained in, and has a high calcium content and good absorbability. In milk, these calcium are present in the form of a calcium phosphate-casein complex or a calcium phosphate-citrate-casein complex or colloidal calcium phosphate present between the casein micelles. It refers to the casein which most of casein has been removed. And as a method of obtaining this calcium agent, an acid is added to casein to pH 5.
4 or less to selectively recover casein-binding calcium and colloidal calcium from the casein. Casein may be rennet casein obtained by treating milk with rennet at pH 5.5 or higher, or casein obtained by dialysis of milk at pH 5.5 or higher with an ultrafiltration membrane or reverse osmosis membrane to remove lactose and soluble minerals. preferable.

In the present invention, milk refers to whole milk such as cow's milk, goat's milk, buffalo milk and sheep's milk, or defatted or dried powder of these milks, which is dissolved in warm water and reduced. Reduced milk is targeted. 60% of calcium in milk
7070% is casein-binding calcium bound to casein and colloidal calcium incorporated into casein micelles. An object of the present invention is to separate and recover casein-binding calcium and colloidal calcium from casein. There is no particular limitation on the method of obtaining casein from milk in the present invention. To obtain rennet casein, first, an appropriate amount of rennet is added to skim milk having a pH of 5.5 or more and coagulated according to a conventional method, and coagulation is performed. Slice with a knife and remove whey after warming and standing. Next, water is added to the curd, the mixture is stirred for a few minutes, and then allowed to stand still to drain the washing water. Wash the card two or three times to obtain rennet casein. In order to obtain casein from which lactose and soluble minerals have been removed from milk, the pH must be adjusted.
Easily remove most of lactose or soluble minerals by passing whole milk or skim milk of 5.5 or more through an ultrafiltration membrane device (fraction molecular weight: 50,000 Da or more), a reverse osmosis membrane device, or an electrodialysis device. As a result, dialyzed casein is obtained. Casein obtained by performing these treatments at a pH of 5.5 or more contains casein-binding calcium and colloidal calcium. These caseins can be used even if they are commercially available as long as they are treated as described above. In the present invention, these case
Inn is called "milk casein."

Next, casein ( milk
The pH is lowered to 5.4 or less while adding an inorganic acid such as hydrochloric acid or an organic acid such as acetic acid, lactic acid, or citric acid to casein ).
At this time, the solution is sufficiently stirred, kneaded, and crushed by a homomixer or a colloid mill to prevent the formation of nodules of casein and to uniformly distribute the acid. And pH
When the pH is gradually reduced to 5.4 or less, calcium bound to casein is cleaved, and when the pH is around 4.8, it is completely dissociated from casein. Further, when this acidic solution is dispersed by a high-speed stirrer or the like and allowed to stand, casein-binding calcium and colloidal calcium are separated from casein, and casein precipitates insoluble, while casein-binding calcium and colloidal calcium are separated from the supernatant. Contains in fractions. By collecting only the supernatant fraction, casein-binding calcium and colloidal calcium can be easily separated and collected.

It is also possible to separate and collect casein-binding calcium and colloidal calcium from casein using an ultrafiltration membrane. That is, casein ( milk
An acid was added to zein ) to adjust the pH to 5.4 or less, and the solution that had been homogenized by stirring was passed through an ultrafiltration apparatus having a membrane with a molecular weight cut-off of 50,000 Da or less. Colloidal calcium can be separated and recovered. Since the casein-binding calcium and colloidal calcium obtained as described above contain anions such as chloride ions, the calcium content is further increased by subjecting the anion to an electrodialysis device to remove the anions. You should increase it. Then, the casein-binding calcium and colloidal calcium obtained by performing these treatments are concentrated by an evaporator or the like as necessary, and then powdered by spray drying to improve the storage stability and handleability during use. Can be planned. And the obtained casein-binding calcium and colloidal calcium are, for example, beverages, cheeses, jellies, bread, noodles, soups or sausages, etc.
It can be used for orally administrable drugs such as liquid preparations or feed additives such as feed additives, compound feeds and pet foods.

[0009]

The calcium agent of the present invention has good calcium absorption since it is separated and recovered from casein as casein-binding calcium and colloidal calcium.
And the calcium agent obtained by the method of the present invention,
High calcium content. Therefore, it is particularly useful for healthy people, children or elderly people as functional foods and health foods, for patients with osteoporosis and various bone diseases as pharmaceuticals, and for animal health as animal feed.

Next, the production method and absorption effect of the calcium agent of the present invention will be described with reference to examples.

[0011]

Example 1 100 kg of water was added to 15 kg of commercially available powdered rennet casein (manufactured by Snow Brand Milk Products Co., Ltd.), and the pH was adjusted to 4.8 by adding 3.6% hydrochloric acid while suspending with a homomixer. Stirring was continued for another 30 minutes to obtain an extract having an increased calcium concentration. This extract was filtered with a 30-mesh stainless filter to obtain 85 kg of a filtrate. Then, the filtrate was concentrated under reduced pressure by a rotary evaporator, and 17 kg of a concentrated solution was recovered. Further, the concentrated liquid was filtered through a milk filter paper (mil pup) to remove insolubles, and then spray-dried to obtain 500 g of an off-white calcium agent powder. Table 1 (A) shows the component composition of the thus-obtained calcium powder.

[0012]

Example 2 Commercially available powdered rennet casein 7.5 kg
Then, 50 kg of water and 2.5 kg of 3.6% hydrochloric acid were added, kneaded and crushed for 10 minutes while circulating in a colloid mill to obtain an extract having an increased calcium concentration. And this extract is 5000r
Solid-liquid separation was performed using a decanter at pm, and 45 kg of an extract having a further increased calcium concentration was obtained. The pH of the extract was 5.2. Then, 7 kg of rennet casein was added to this extract to secure the concentration for powdering,
The pH was again adjusted to 5.2 with 5% hydrochloric acid, extracted with a colloid mill and separated into solid and liquid with a decanter in the same manner as described above. After repeating this operation twice, the mixture was filtered through a 0.45 μm micron filter and spray-dried to obtain about 200 g of an off-white calcium agent powder. The component composition of the calcium agent powder thus obtained is shown in Table 1 (B). In addition, (%) shows all weight%.

[0013]

[Table 1] (%) 成分 Component composition Calcium agent (A) Calcium agent (B)水分 Water 20.6 9.0 Fat 0.3 0.2 Protein 4.3 6.5 Carbohydrate 14.2 29.5 Ash 60.6 54.8 ──── ─────────────────────────── Calcium 22.0 19.9 Phosphorus 6.8 3.7 Sodium 0.3 0.5 Potassium 0.2 1.1 Magnesium 1.0 1.1 Iron (mg%) 9.0 31.0 Zinc (mg%) 2.7 3.5 Copper (mg%) 1.2 3.8 Manganese (mg%) 0.6 0.2 ────────────────────────────── ──

[0014]

Example 3 10 l of raw milk was centrifuged at 5,000 xg for 10 minutes to obtain 9.5 l of skim milk. This skim milk has a molecular weight cutoff of 50,000
The solution was passed through an ultrafiltration apparatus having a Da membrane to remove lactose and soluble minerals. 4.5 liters of the mixture was adjusted to pH 4.6 with 3.6% hydrochloric acid to coagulate casein and centrifuged at 5,000 xg for 10 minutes with a cooling centrifuge to remove casein. Casein-binding calcium and colloidal calcium were collected in the supernatant solution, and this solution was concentrated under reduced pressure using a rotary evaporator and lyophilized to obtain a powdered calcium agent.
The yield of the obtained powdered calcium agent was 29.7 g, and the component composition was as shown in (C) of Table 2.

[0015]

Example 4 10 kg of commercially available powdered rennet casein was added to 10
%, And the pH was adjusted to 5.2 with 3.6% hydrochloric acid to release casein-binding calcium and colloidal calcium from casein. The solution was passed through an ultrafiltration apparatus having a membrane with a molecular weight cut-off of 50,000 Da and passed through a permeate. I got The permeate was concentrated under reduced pressure by a rotary evaporator and then freeze-dried to obtain a powdered calcium agent. The yield of the obtained powdered calcium agent was 136 g, and the composition of the components was as shown in (D) of Table 2.

[0016]

[Table 2] (%) ─────────────────────────────── Component composition Calcium agent (C) Calcium agent (D)水分 Moisture 6.18 8.76 Fat 0.34 0.29 Protein 45.21 15.23 Carbohydrate 11.02 24.60 Ash 37.25 51.12 ──── ─────────────────────────── Calcium 10.48 13.54 Phosphorus 5.22 5.28 Sodium 0.68 0.67 Potassium 0.48 2.71 Magnesium 0.39 0.74 Iron (mg%) 1.6 1.1 Zinc (mg%) 1.1 8.6 ────────────────────────────────

[0017]

Example 5 Absorption Test by Oral Administration to Rats The calcium absorption test was performed using 10-week-old SD male rats. The milk-derived calcium preparations of A, B, C, and D obtained in Examples 1 to 4 as a group of 6 animals, the calcium preparation (Whey Ca) obtained from whey, and dicalcium phosphate were prepared as follows. Was subjected to an absorption test. The calcium preparation was suspended so as to contain a calcium content of 5 mg / ml, and the suspension was orally administered to rats fasted for 24 hours. At this time, phosphorus and magnesium were made to have the same composition, and protein and saccharide were made to have the same composition with purified casein dialyzed whey protein and lactose. Four hours later, the stomach and intestine were removed and each was ashed as it was. The digestive absorption was determined by subtracting the residual calcium in the stomach and intestine from the administered calcium. The result is shown in FIG.
From FIG. 1, the milk-derived calcium agent showed higher absorbency than Whey Ca and calcium phosphate, and it was proved that the casein-binding calcium and colloidal calcium obtained this time had high bioavailability.

[0018]

Example 6 Apple juice was prepared by adding 10% by weight of apple juice, 15% by weight of mixed isomerized sugar, 0.5% by weight of citric acid and 0.1% by weight of flavor to 74% by weight of water. Example 1
Add the powdered calcium agent (A) obtained in
For 30 minutes to obtain apple juice enriched in milk-derived calcium. The obtained apple juice was inferior in flavor and tongue texture to beverages to which no calcium agent was added.

[0019]

Example 7 125 g of the powdered calcium agent (A) obtained in Example 1 was dissolved in 2 kg of warm water at 60 ° C., added to 25 kg of raw milk, and stirred. This was sterilized at 120 ° C. for 2 seconds, concentrated by a concentrator, and spray-dried to obtain 3 kg of calcium-enriched milk powder.
Further, this powdered milk was granulated to a particle size of 200 to 350 μm by a fluid bed granulator.

[0020]

Example 8 34 kg of Cheddar cheese and 200 kg of Goder cheese were ground and mixed to obtain 1.1 kg of molten salt (mixed molten salt composed of 80% sodium polyphosphate and 20% sodium diphosphate) and obtained in Example 2. 1.1kg of powdered calcium agent (B) was added and Stefan cutter (750rpm)
After heating and melting to 85-90 ° C. in the flask, it was filled and cooled. The obtained calcium-enhanced processed cheese was comparable in flavor, texture, and taste to the conventional calcium-containing additive-free product.

[0021]

Example 9 Jelly was produced according to the following compounding ratio. 58.4% by weight of water at 40 ° C., 20.0% by weight of fruit juice, 15.0% by weight of granulated sugar, 5.0% by weight of starch syrup, 1.0% by weight of agar powder, 0.5% by weight of the powdered calcium preparation obtained in Example 4
And 0.1% by weight of fragrance were mixed to form a mix. The mixture was sterilized at 130 ° C. for 2 seconds, filled in a container with a filling machine, and further cooled to 10 ° C. in a refrigerator to obtain jelly. The obtained jelly was comparable in flavor, texture and taste as compared with the conventional calcium agent-free product.

[0022]

Example 10 In order to convert the calcium preparation of the present invention into a tablet form calcium preparation, 220 g of the powdered calcium preparation (A) obtained in Example 1, 163 g of corn starch,
10 g of crystalline cellulose and 6.8 g of calcium carboxymethylcellulose were mixed in a kneader, and then kneaded while spraying 50 ml of water dropwise. The kneaded material is granulated with a single-axis oscillator set with a 20-mesh screen,
It was dried in a fluid bed dryer. The dried product was pulverized and sized with a flash mill to obtain a powder for tableting. Then, 8 g of sucrose fatty acid ester as a lubricant was mixed with a V-type mixer, and the mixture was tableted with a tableting machine equipped with a punch having a diameter of 11 mm to obtain a tablet having an average weight of 0.35 g. The component composition of this tablet was 55% by weight of a calcium agent, 40.8% by weight of corn starch, 2.5% by weight of crystalline cellulose, and 1.7% by weight of calcium carboxymethylcellulose. This calcium agent is used as a calcium enhancer.

[0023]

Example 11 A dog breeding feed (dock food) was manufactured according to the following mixing ratio. The vitamin mixture and the mineral mixture were added to the above-described basic feed for dog breeding in the above amounts in 100 g of the basic feed for dog breeding, and the mixture was produced in a usual manner.

Next, in order to show that the calcium agent of the present invention is superior in terms of flavor and solubility, milk powder was produced using calcium phosphate as a comparative example, and this milk powder and the milk powder produced in Example 7 were produced. And compared.

[0025]

[Comparative Example] 125 g of calcium phosphate powder in warm water 2 at 60 ° C
The mixture was dissolved in kg, and added to 25 kg of raw milk and stirred. This is 120
The solution was sterilized at ℃ for 2 seconds, concentrated by a concentrator, and spray-dried to obtain 3 kg of calcium-enriched milk powder. This milk powder was further granulated to a particle size of 200 to 350 μm by a fluid bed granulator. The flavor and solubility of each of the milk powder obtained in Example 7 and the milk powder obtained in the Comparative Example were evaluated by panelists of 10 adult males. Table 3 shows the results. As is clear from Table 3 above, the calcium agent of the present invention is excellent in both flavor and solubility.

[0026]

[Table 3] Note) The flavor in the above table was evaluated by dissolving powdered milk at a solid content of 11% and drinking. The solubility was determined by dissolving 5% in 100 cc of warm water at 37 ° C., allowing to stand for 10 minutes, measuring the precipitated insoluble matter, and determining that the measured insoluble matter was 1 cc or more.

[Brief description of the drawings]

FIG. 1 shows the results of a calcium absorption test using a rat intestinal tract according to Example 5.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Ken Kato 5-11-3 Shinjuku-cho, Kawagoe-shi, Saitama Prefecture Snow Brand Musashino dormitory (72) Inventor Masatoshi Yahiro 2-8-13, Kumegawa-cho, Higashimurayama-shi, Tokyo ( 72) Inventor: Shomei Nishitani 699-3 Kitaiso, Sayama City, Saitama Prefecture (56) References Nution Reports International, Vol. 5, p. 673-680 (1980) (58) Fields investigated (Int. Cl. ⁷ , DB name) A23L 1/304 A61K 33/06 JICST file (JOIS) JAFIC file (JOIS)

Claims (4)

(57) [Claims] 1. An acid is added to casein of milk to pH 5.4 or less.
Casein binding calcium and colloidal calcium was selectively separated and recovered from the acidic solution and, calcium
Calcium derived from milk containing 10 wt% or more as an arm active ingredient. 2. A casein binding method comprising adding an acid to milk casein to adjust the pH to 5.4 or less, selectively separating casein-binding calcium and colloidal calcium from the casein, and recovering the casein binding calcium and colloidal calcium. A method for producing a milk-derived calcium agent containing 10% by weight or more of basic calcium and colloidal calcium as calcium. 3. A milk casein , which is rennet casein obtained by treating milk with rennet at pH 5.5 or higher, or milk.
3. The method for producing a calcium agent according to claim 2, wherein casein obtained by dialysis treatment with an ultrafiltration membrane or a reverse osmosis membrane at a pH of 5.5 or more to remove lactose and soluble minerals is used. 4. The selective separation of casein-binding calcium and colloidal calcium from milk casein is carried out by separating milk casein as an aqueous solution having a pH of 5.4 or less by separating said calcium from casein, or further comprising such a method. The method for producing a calcium agent according to claim 2 or 3, wherein the calcium-containing separation liquid separated in the above step is passed through an ultrafiltration membrane having a membrane having a molecular weight cut-off of 50,000 or less to collect a permeate. .