JPH1175707A - Dried powder of iron casein complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an iron casein complex not exhibiting an astringent taste peculiar to iron, and stable as a liquid state. SOLUTION: This iron casein complex is a dried powder of a carbonic acid and/or bicarbonic acid-iron-caseins complex containing 1-1000 atom iron and >=1 molecule carbonic acid and/or bicarbonic acid per 1 molecule of caseins, a stable oil and fat solution obtained by dispersing and dissolving the dried powder in the oil and fat, or a stable oil in water type (O/W) emulsion obtained by using the oil and fat solution as an oil phase. Since the oil and fat solution or a water in oil type (O/W) emulsion does not form precipitation by heating, is stable, and does not have an astringent taste, it is useful as a raw material of a food, a medicine, a feed, etc., for iron enrichment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dry powder of a carbonate and / or bicarbonate-iron-casein complex. Also,
The present invention relates to a fat and oil solution in which the dry powder is dispersed and dissolved in fat and oil, and an oil-in-water (O / W) emulsion using the fat and oil solution as an oil phase.

[0002] The fat and oil solution and the oil-in-water (O / W) emulsion of the present invention do not exhibit the astringent taste peculiar to iron and are stable without aggregation (precipitation). Therefore,
It is useful as a raw material for foods, medicines, feeds and the like for the purpose of preventing or treating anemia and fortifying iron, and does not cause a decrease in yield or clogging of lines in the production process of these foods and the like.

[0003]

2. Description of the Related Art Since 1975, the iron intake of Japanese people has been flat at around 100% of the required amount, and iron is a dietary nutrient that must be taken with care. One can say. In addition, in many industrialized nations, iron is often regarded as a nutrient that tends to be deficient in the world, and there is a demand for the supply of iron-enriched foods and medicines especially for people with anemia and pregnant women. . However, iron salts such as iron sulfate and iron citrate, which are generally used for iron fortification, are added in view of problems such as a feeling of astringent taste unique to iron when added to foods, and side effects such as damaging the gastrointestinal mucosa. The amount is limited. Further, even heme iron, which is an organic iron, has problems in flavor, such as metallic taste, fresh smell, and the like, and there are many restrictions on its addition to foods and the like.

Attempts have been made to add milk casein, amino acids, or casein phosphopeptide (JP-A-59-162284) to promote the absorption of iron. However, in these methods, the astringent taste of iron cannot be eliminated, and the amount of added iron cannot be reduced so as to eliminate the astringent taste of iron. The present inventors have already succeeded in developing an iron agent having a reduced astringent taste unique to iron by binding iron and casein (JP-A-2-83400). However, this iron casein has poor heat resistance, and has the drawback of exhibiting a unique astringent taste when subjected to heat sterilization at 90 ° C. for 10 minutes, heat sterilization at 120 ° C. for 2-3 seconds, and retort sterilization. I have. It is considered that the cause of this drawback is that the bond between iron and casein is weak, so that iron is released from casein by heating to produce iron hydroxide and the like.

Accordingly, the present inventors have further studied and found that the use of carbonic acid and / or bicarbonate can strengthen the binding between iron and casein. -An iron-casein complex was obtained (JP-A-9-77793). This carbonic acid and / or bicarbonate-iron-
The casein complex has heat resistance, and has the characteristic of not exhibiting the unique astringent taste of iron even when sterilized by heating.Therefore, prevention or treatment of anemia, foods, pharmaceuticals, It is useful as a raw material for feeds and the like. However, this carbonate and / or bicarbonate-iron-casein complex is formed by mixing a solution of carbonate or bicarbonate, an iron compound and casein to form a complex in the solution, ultrafiltration and desalting. It is concentrated and the concentrated liquid is diluted and used in a liquid state. As described above, when the liquid is made liquid, the complex tends to aggregate and precipitate, and there has been a problem that the yield is reduced or the line is clogged in the production process, or that the texture during eating is poor.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to develop an iron casein complex in which iron and casein are combined without exhibiting the unique astringent taste of iron and causing no aggregation during the production process. The carbonic acid and / or bicarbonate-iron-casein complex previously proposed (JP-A-9-77793)
) Is dried to obtain a dry powder, and the dry powder is dispersed and dissolved in fats and oils to obtain an extremely stable fat and oil solution of carbonic acid and / or bicarbonate-iron-casein complex which does not cause aggregation even in a liquid form. I found that I can do it. An oil-in-water (O / W) emulsion obtained by dispersing an emulsified solution of the carbonic acid and / or bicarbonate-iron-casein complex in an aqueous phase as an oil phase and emulsifying it is also extremely stable. To complete the present invention. Accordingly, the present invention provides a dry powder of a carbonated and / or bicarbonate-iron-casein complex that does not exhibit the unique astringent taste of iron and does not cause cohesive precipitation even in a liquid form. Make it an issue. Also,
The present invention relates to a stable carbonic acid and / or bicarbonate-iron-casein complex oil or fat solution or an oil-in-water (O
/ W) The task is to provide an emulsion.

[0007]

In the present invention, the following treatment is carried out to obtain a dry powder of a carbonic acid and / or bicarbonate-iron-casein complex which is stable even in a liquid form. That is, according to the method disclosed in JP-A-9-77793,
A carbonate and / or bicarbonate-iron-casein complex is prepared. Next, the carbonate and / or bicarbonate-iron-casein complex is desalted while being hydrolyzed, and then left to stand. As a result, a precipitate of a highly pure carbonic acid and / or bicarbonate-iron-casein complex is formed, and the precipitate is collected by a treatment such as centrifugation or decantation and air-dried sufficiently to remove carbonic acid and / or heavy carbonic acid. A dry powder of the carbonate-iron-casein complex is obtained.
Alternatively, similarly prepared carbonic and / or bicarbonate-
The iron-casein complex is lyophilized or spray-dried to obtain a dry powder of the carbonate and / or bicarbonate-iron-casein complex. The moisture content of these dry powders is preferably 20% or less. If the water content exceeds 20%, carbonic acid and / or bicarbonate
The iron-casein complex hardly dissolves in fats and oils, making it hard to feel.

The carbonic acid and / or bicarbonate-iron-
By dispersing the dry powder of the casein complex in fats and oils, the carbonate and / or bicarbonate-iron-casein complex can be dissolved at room temperature to a high concentration of 65% (W / W),
It is possible to obtain a stable solution of carbonic acid and / or bicarbonate-iron-casein in a liquid form. The stability of the fat and oil solution is not impaired even by heat sterilization.

The oil-in-water type in which the oil-and-fat solution containing the oil-and-fat solution is dispersed in an aqueous solution and then emulsified by dispersing the oil-and-fat solution of the carbonated and / or bicarbonate-iron-casein complex stable in a liquid form. (O / W) A stable liquid form of an emulsion form can also be obtained. The stability of the oil-in-water (O / W) emulsion is not impaired even by heat sterilization. In the case of emulsification, since the carbonic acid and / or bicarbonate-iron-casein complex itself has emulsifying power,
There is no particular need to add an emulsifier, but by adding an emulsifier or stabilizer, the carbonate and / or bicarbonate-iron-casein complex can be easily dispersed in an aqueous solution at a high concentration.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention can be obtained by drying carbonic acid and / or bicarbonate-iron-casein complex (JP-A-9-77793), and dispersing and dissolving this dry powder in fats and oils. , An extremely stable solution of carbonic acid and / or bicarbonate-iron-casein complex in a liquid form. The oil / fat solution of the carbonic acid and / or bicarbonate-iron-casein complex which is stable in the liquid form can be obtained by drying the carbonic acid and / or bicarbonate-iron-casein complex disclosed in Japanese Patent Application Laid-Open No. 9-77793. The dry powder can be obtained by dispersing and dissolving this dry powder in fats and oils. There is no particular limitation on the fats and oils used when dispersing and dissolving the dry powder of the carbonic acid and / or bicarbonate-iron-casein complex, and soybean oil, rapeseed oil, cottonseed oil, sesame oil, sesame oil, and safflower oil that are liquid at room temperature. And vegetable oils such as olive oil and corn oil, and animal oils such as fish oil, milk fat and lard.

Also, the stable oil and fat of the carbonic acid and / or bicarbonate-iron-casein complex in liquid form obtained by dispersing and dissolving the dry powder of the carbonate and / or bicarbonate-iron-casein complex in the oil and fat. The solution is dispersed in an aqueous solution and further emulsified to obtain a stable oil-in-water (O / W) emulsion of a stable carbonic acid and / or bicarbonate-iron-casein complex having the oil solution as an oil phase. You can also.
The emulsifier used for emulsification is not particularly limited, and an emulsifier such as sodium caseinate, lecithin, and sugar ester may be used.

Thus, carbonic acid and / or bicarbonate
Obtaining a stable carbonic acid and / or bicarbonate-iron-casein complex oil or fat solution in a liquid form in which an iron-casein complex is dissolved in a high concentration, and an oil-in-water (O / W) emulsion using the same as an oil phase. Can be. This liquid form of stable carbonic acid and / or bicarbonate-iron-casein complex oil solution or oil-in-water (O /
W) Emulsions have the characteristics that they do not precipitate or separate upon heating, and that they do not have any astringent taste or roughness of iron. And, in this liquid form, stable carbonic acid and / or bicarbonate-iron-casein complex oil and fat solution, oil-in-water (O / W) emulsion, various foods and drinks for the purpose of iron enhancement, medicine, feed, etc. It can be used as a compounding material.

Hereinafter, the present invention will be described in detail with reference to Test Examples and Examples.

Example 1 (A solution) 1 L solution containing 1,200 mM sodium bicarbonate (B1 solution) Solution containing ferric chloride having an iron concentration of 10 mM 0.2
L (B2 solution) 0.8 L solution containing 0.1 mM casein lactate (New Zealand Daily Board)

The above A solution, B1 solution and B2 solution were prepared. The molar concentration of the B2 solution was adjusted using the average molecular weight. The average molecular weight was calculated from the composition ratio of α-casein, β-casein, and κ-casein determined by urea-sodium dodecyl sulfate (SDS) -electrophoresis and the theoretical molecular weight of each casein. Next, B solution is prepared by mixing B1 solution and B2 solution, and B solution is added to A solution.
The solution was added to prepare a bicarbonate-iron-casein complex.
The bicarbonate-iron-casein complex solution was desalted while being hydrolyzed by an ultrafiltration membrane having a molecular weight of 5,000, and then allowed to stand for 20 minutes.The resulting precipitate was collected by a centrifugal separator, and the water content at room temperature was reduced. Air dried to 20%.

When the dried powder of the bicarbonate-iron-casein complex was dispersed in olive oil to a concentration of 65% (W / W), it was easily dissolved in a few minutes, and was stable in a liquid form without any roughness. A bicarbonate-iron-casein complex oil solution was obtained. This liquid form of stable bicarbonate-iron-casein complex oil solution was diluted with olive oil until the iron concentration reached 3.6 mM, sterilized by heating at 90 ° C for 10 minutes, and kept at 15 ° C. Then, the presence or absence of precipitate formation was observed, but no precipitate formation was observed even after 2 months.

[0016]

Example 2 (A solution) 1 L of a solution containing 1,200 mM sodium bicarbonate (B1 solution) 0.2 L of a solution containing ferric sulfate having an iron concentration of 9 mM (B2 solution) 0.1 mM casein lactate (manufactured by Sigma) 0.8 L containing solution

The above A solution, B1 solution and B2 solution were prepared. The molar concentration of the B2 solution was adjusted in the same manner as in Example 1. Next, B1 solution and B2 solution are mixed and B
After the solution was prepared, the solution B was added to the solution A to prepare a bicarbonate-iron-casein complex. The bicarbonate-iron-casein complex solution was desalted while being hydrolyzed with an ultrafiltration membrane having a molecular weight of 5,000, and then allowed to stand for 20 minutes. The resulting precipitate was collected by a centrifugal separator, and the water content was 9%. Lyophilization was carried out until.

When the dried powder of the bicarbonate-iron-casein complex was dispersed in olive oil so as to have a concentration of 65% (W / W), it was easily dissolved in a few minutes and was stable in a liquid form without any roughness. A bicarbonate-iron-casein complex oil solution was obtained. This oily solution of bicarbonate-iron-casein complex, which is stable in liquid form, is diluted with olive oil until the iron concentration reaches 3.6 mM, sterilized by heating at 120 ° C for 15 minutes, and kept at 15 ° C. Then, the presence or absence of precipitate formation was observed, but no precipitate formation was observed even after 2 months.

[0019]

Example 3 (A solution) 1 L of a solution containing 1,200 mM sodium bicarbonate (B1 solution) 0.2 L of a solution containing ferric sulfate having an iron concentration of 9 mM (B2 solution) 0.1 mM casein lactate (manufactured by Sigma) 0.8 L containing solution The above A solution, B1 solution and B2 solution were prepared. The molar concentration of the B2 solution was adjusted in the same manner as in Example 1. Next, after mixing the B1 solution and the B2 solution to prepare a B solution, the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. The bicarbonate-iron-casein complex solution was desalted while being hydrated with an ultrafiltration membrane having a molecular weight of 5,000, and then allowed to stand for 20 minutes. The resulting precipitate was collected by a centrifuge, and the water content was 8%. Lyophilization was carried out until.

When the dried powder of the bicarbonate-iron-casein complex was dispersed in olive oil so as to have a concentration of 65% (W / W), it was easily dissolved in a few minutes, and was stable in a liquid form without any roughness. A bicarbonate-iron-casein complex oil solution was obtained. A buffer solution that simulates a liquid food containing 0.05 M imidazole and 0.05 M sodium chloride until the iron concentration reaches 3.6 mM with respect to the oil / fat solution of the bicarbonate-iron-casein complex that is stable in the liquid form (simulated buffer; pH 7.5), emulsified with a disperser, sterilized by heating at 90 ° C for 10 minutes, and then kept at 15 ° C to observe the presence of precipitate formation and the state of emulsification. No precipitate was formed and the emulsification was not broken.

[0021]

Example 4 (A solution) 1 L of a solution containing 1,200 mM sodium bicarbonate (B1 solution) 0.2 L of a solution containing ferric sulfate having a concentration of 9 mM of iron (B2 solution) 0.1 mM casein lactate (manufactured by Sigma) 0.8 L containing solution The above A solution, B1 solution and B2 solution were prepared. The molar concentration of the B2 solution was adjusted in the same manner as in Example 1. Next, after mixing the B1 solution and the B2 solution to prepare a B solution, the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. The bicarbonate-iron-casein complex solution was desalted while being hydrated with an ultrafiltration membrane having a molecular weight of 5,000, and then allowed to stand for 20 minutes. The resulting precipitate was collected by a centrifuge, and the water content was 8%. Lyophilization was carried out until.

When the dried powder of the bicarbonate-iron-casein complex was dispersed in olive oil so as to have a concentration of 50% (W / W), it was easily dissolved in a few minutes, and was stable in a liquid form without any roughness. A bicarbonate-iron-casein complex oil solution was obtained. A simulated buffer (pH 7.5) containing 1% sodium caseinate until the iron concentration reaches 3.6 mM is obtained for the fat / oil solution of the bicarbonate-iron-casein complex which is stable in the liquid form.
The mixture was emulsified with a disperser, sterilized by heating at 120 ° C for 15 minutes, and kept at 15 ° C to observe the presence or absence of precipitate formation and the state of emulsification. No formation was observed and the emulsification was not broken.

[0023]

[Comparative Example 1] (A solution) 1 L of solution containing 1,200 mM sodium bicarbonate (B1 solution) Solution containing ferric chloride having an iron concentration of 10 mM 0.2
L (B2 solution) 0.8 L solution containing 0.1 mM casein lactate (New Zealand Daily Board)

The above A solution, B1 solution and B2 solution were prepared. The molar concentration of the B2 solution was adjusted in the same manner as in Example 1. Next, B1 solution and B2 solution are mixed and B
After the solution was prepared, the solution B was added to the solution A to prepare a bicarbonate-iron-casein complex. The bicarbonate-iron-casein complex solution was desalted while being hydrated with an ultrafiltration membrane having a molecular weight of 5,000 and then allowed to stand for 20 minutes.The resulting precipitate was collected by a centrifuge, and the water content was reduced to room temperature. Air dried to 17%. When the dried powder of the bicarbonate-iron-casein complex was dispersed in distilled water, physiological saline, or ethanol, each of the powders did not dissolve, and the coarse bicarbonate-
A suspension of the iron-casein complex was obtained. The suspension of these bicarbonate-iron-casein complexes had an iron concentration of 3.6
After diluting with a simulated buffer solution (pH 7.5) until the concentration reached mM, the mixture was sterilized by heating at 90 ° C for 10 minutes, and kept at 15 ° C to observe the presence or absence of precipitate formation. Was observed.

[0025]

[Comparative Example 2] (Solution A) 1 L of solution containing 1,200 mM sodium bicarbonate (Solution B1) Solution containing ferric chloride having an iron concentration of 10 mM 0.2
L (B2 solution) 0.8 L solution containing 0.1 mM casein lactate (New Zealand Daily Board)

The above A solution, B1 solution and B2 solution were prepared. The molar concentration of the B2 solution was adjusted in the same manner as in Example 1. Next, B1 solution and B2 solution are mixed and B
After the solution was prepared, the solution B was added to the solution A to prepare a bicarbonate-iron-casein complex. The bicarbonate-iron-casein complex solution was desalted while being hydrated with an ultrafiltration membrane having a molecular weight of 5,000 and then allowed to stand for 20 minutes.The resulting precipitate was collected by a centrifuge, and the water content was reduced to room temperature. Air dried to 18%.

The dried powder of the bicarbonate-iron-casein complex was dispersed in distilled water containing 1% sugar ester, physiological saline, a simulated buffer, 5% ethanol, or ethanol. Instead, a suspension of a rough bicarbonate-iron-casein complex was obtained. These bicarbonate-iron-casein complex suspensions were diluted with a simulated buffer solution (pH 7.5) until the iron concentration reached 3.6 mM, sterilized by heating at 90 ° C for 10 minutes, and then cooled to 15 ° C. As a result, the formation of a precipitate was observed after 5 minutes.

[0028]

Test Example 1 Oil solution of each bicarbonate-iron-casein complex obtained in Examples 1-4 and suspension of each bicarbonate-iron-casein complex obtained in Comparative Examples 1-2 A sensory evaluation was performed on the taste of the solution after storage for 6 months. That is, a simulation buffer (p) in which ferrous sulfate was dissolved so that the iron concentration was 3.6 mM was given to 20 panelists, 10 men and 10 women.
H 7.5) was used as a control sample, and it was determined whether or not each sample felt astringent taste and roughness.

Each panelist was blindfolded so as not to give a judgment factor based on appearance. In addition, the test for one sample was performed in the order of a control and a sample. After evaluating one sample, a test for evaluating the next sample was performed at least one day apart. Furthermore, the order of sample evaluation was randomized for each panelist in order to eliminate the daily deviation of sample evaluation. Table 1 shows the number of panelists who felt astringent taste and roughness among the 20 panelists.

[0030]

[Table 1] 試 料 Sample Astringency Roughness ───────── ──────────────────────── Example 1 0 0 Example 2 0 0 Example 3 0 0 Example 4 0 0 Comparative Example 1 (Physiological 0 20 Comparative Example 2 (diluted with physiological saline) 0 20 Control sample 200 0 ───────────

According to this, the stable oil and fat solution of the carbonated and / or bicarbonate-iron-casein complex in the liquid form of the present invention maintains a stable state even after heating without precipitation or separation. Further, it was good without any astringent taste or roughness of iron.

[0032]

Example 5 (A solution) 1 L of solution containing 1,200 mM sodium bicarbonate (B1 solution) Solution containing ferric chloride having an iron concentration of 10 mM 0.2
L (B2 solution) 0.8 L solution containing 0.1 mM casein lactate (New Zealand Daily Board)

The above A solution, B1 solution and B2 solution were prepared. The molar concentration of the B2 solution was adjusted in the same manner as in Example 1. Next, B1 solution and B2 solution are mixed and B
After the solution was prepared, the solution B was added to the solution A to prepare a bicarbonate-iron-casein complex. The bicarbonate-iron-casein complex solution was desalted while being hydrated with an ultrafiltration membrane having a molecular weight of 5,000 and then allowed to stand for 20 minutes.The resulting precipitate was collected by a centrifuge, and the water content was reduced to room temperature. Air dried to 19%.

When the dried powder of the bicarbonate-iron-casein complex was dispersed in olive oil so as to have a concentration of 65% (W / W), it was easily dissolved in a few minutes, and was stable in a liquid form without any roughness. A bicarbonate-iron-casein complex oil solution was obtained. This liquid form of a stable bicarbonate-iron-casein complex oil solution was blended into skim milk at a concentration of 12 mM / 200 ml, emulsified with a homogenizer, and sterilized on a plate at 120 ° C. for 2 seconds to prepare an iron-enriched milk beverage. Manufactured.

[0035]

The dry powder of the carbonic acid and / or bicarbonate-iron-casein complex of the present invention is easily dissolved and becomes liquid when the powder is dispersed and dissolved in fats and oils. The solution dissolved in the fat or oil or the emulsion in the form of an oil-in-water (O / W) does not precipitate or separate even when heated, and
Since it has the characteristic of not feeling the astringent taste and roughness of iron at all, various foods and beverages, pharmaceuticals,
It is useful as a material to be incorporated into feeds and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hitoshi Aikawa 12-89 Goryo-cho, Higashimatsuyama-shi, Saitama Prefecture 5-503 Park-Town Goryo 5-503 (72) Inventor Akira Tomizawa 5-3-33 Toyooka, Iruma-shi, Saitama Arden 710

Claims (4)

[Claims] (1) Iron is contained in an amount of 1 to 1,00 per casein molecule.
0 atom, carbonic acid and / or bicarbonate containing one or more molecules, and dry powdered carbonic acid and / or bicarbonate-iron-
Dry powder of casein complex. 2. The method according to claim 1, wherein the water content is not more than 20% by weight.
The dry powder as described. 3. An oil or fat solution in which the dry powder according to claim 1 is dispersed and dissolved in an oil or fat. 4. An oil-in-water (O / W) emulsion in which a solution obtained by dispersing and dissolving the dry powder according to claim 1 or 2 in an oil or fat is used as an oil phase.