JP3651642B2 - Iron-casein complex oil and fat solution and emulsion - Google Patents

Description

【００３１】
これによると、本発明の液状形態で安定な炭酸及び／又は重炭酸−鉄−カゼイン複合体の油脂溶液は、加熱後も沈澱したり分離することなく安定な状態を維持しており、さらに、鉄の収斂味やざらつきも全く感じない良好なものであった。
【００３２】
【実施例５】
（Ａ溶液）1,200mM 重炭酸ナトリウムを含む溶液 1 L
（Ｂ１溶液）鉄濃度 10mM の塩化第二鉄を含む溶液 0.2 L
（Ｂ２溶液）0.1mM 乳酸カゼイン（ニュージーランドデイリーボード製）を含む溶液 0.8 L
【００３３】
上記のＡ溶液及びＢ１溶液、Ｂ２溶液を調製した。なお、Ｂ２溶液のモル濃度の調整は実施例１と同様に行った。次に、Ｂ１溶液とＢ２溶液を混合してＢ溶液を調製した後、Ａ溶液にＢ溶液を加え、重炭酸−鉄−カゼイン複合体を調製した。この重炭酸−鉄−カゼイン複合体溶液を分子量 5,000カットの限外濾過膜で加水しながら脱塩した後、20分静置し、生成した沈澱を遠心分離機で回収し、室温で水分含量が19％になるまで風乾した。
【００３４】
この重炭酸−鉄−カゼイン複合体の乾燥粉末を65％(W/W) となるようオリーブ油に分散させたところ、数分で容易に溶解し、ざらつきの全くない液状形態で安定な重炭酸−鉄−カゼイン複合体の油脂溶液を得ることができた。
この液状形態で安定な重炭酸−鉄−カゼイン複合体の油脂溶液を12mM/200mlとなるよう脱脂乳に配合し、ホモジナイザーで乳化した後、 120℃で２秒間プレート殺菌して鉄強化乳飲料を製造した。
【００３５】
【発明の効果】
本発明の炭酸及び／又は重炭酸−鉄−カゼイン複合体溶液あるいはそれを水中油型(O/W) としたエマルションは、加熱しても沈澱したり分離することもなく、また、鉄の収斂味やざらつきも全く感じさせないという特徴を有するので、鉄強化を目的とする各種の飲食品、医薬、飼料等に配合する素材として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention, carbonate and / or bicarbonate - about Casein fat complexes dry燥粉end of dispersed dissolved in oil solutions and oil-in-water to the oil solution and the oil phase (O / W) emulsion - iron.
[0002]
The oil / fat solution and oil-in-water (O / W) emulsion of the present invention have the characteristics that they do not exhibit iron astringent taste and are stable without agglomeration (precipitation). Therefore, it is useful as a raw material for foods, pharmaceuticals, feeds, etc. for the purpose of preventing or treating anemia and strengthening iron, and also in the production process of these foods, it causes a decrease in yield and clogging of lines. Absent.
[0003]
[Prior art]
The amount of iron intake by Japanese people has been leveling off around 100% of the required rate since 1975, and iron can be said to be one of the nutrients that must be taken carefully in the diet. Also, globally, in many industrialized countries, iron is often regarded as a nutrient that tends to be deficient, and it is particularly desirable to supply iron-enriched foods and medicines for people with anemia and for pregnant women. . However, iron salts such as iron sulfate and iron citrate, which are generally used for iron strengthening, are added from the viewpoint of feeling the astringent taste peculiar to iron when added to foods, etc., and side effects such as damaging the gastrointestinal mucosa. There is a limit to the amount. In addition, even organic heme iron has problems in flavor such as metal taste and raw odor, and there are many restrictions on addition to foods and the like.
[0004]
In order to promote the absorption of iron, attempts have been made to add milk casein, amino acid, or casein phosphopeptide (Japanese Patent Laid-Open No. 59-162843). However, these methods cannot eliminate the astringent taste of iron, and cannot reduce the amount of iron added to the extent that the astringent taste of iron is lost.
The present inventors have already succeeded in developing an iron agent that has weakened the astringent taste unique to iron by combining iron and casein (JP-A-2-83400). However, this iron casein has poor heat resistance, and has the disadvantage of exhibiting a unique astringent taste when subjected to heat sterilization at 90 ° C for 10 minutes, heat sterilization at 120 ° C for 2 to 3 seconds, retort sterilization, etc. Yes. The cause of this defect is considered to be that iron is released from casein by heating and iron hydroxide and the like are generated due to weak binding between iron and casein.
[0005]
Accordingly, the present inventors have further studied and found that the binding property of iron and casein can be strengthened by using carbonic acid and / or bicarbonate, and carbonic acid and / or bicarbonate-iron- A casein complex was obtained (Japanese Patent Laid-Open No. 9-77793). Since this carbonic acid and / or bicarbonate-iron-casein complex has heat resistance and has a characteristic that it does not exhibit astringent taste unique to iron even when heat-sterilized, the prevention or treatment of anemia, It is useful as a raw material for foods, pharmaceuticals, feeds, etc. for the purpose of strengthening iron. However, this carbonate and / or bicarbonate-iron-casein complex is mixed with a solution of carbonate or bicarbonate, iron compound and casein to form a complex in the solution, and ultrafiltered to desalinate. It is concentrated and used in the liquid state after being diluted. Thus, when it is made liquid, the complex tends to agglomerate and precipitate, and there is a problem in that the yield is reduced and the line is clogged during the production process, or the texture is inferior when eaten.
[0006]
[Problems to be solved by the invention]
The inventors of the present invention have been diligently researching to develop an iron casein complex in which iron and casein are combined without exhibiting the astringent taste unique to iron or causing aggregation in the production process. The carbonic acid and / or bicarbonate-iron-casein complex (Japanese Patent Laid-Open No. 9-77793) is dried to form a dry powder, and this dry powder is dispersed and dissolved in fats and oils so that no aggregation occurs even in liquid form. It has been found that an oil / fat solution of a stable carbonic acid and / or bicarbonate-iron-casein complex can be obtained. In addition, an oil-in-water (O / W) emulsion obtained by dispersing and emulsifying a solution of the carbonic acid and / or bicarbonate-iron-casein complex, which is stable in this liquid form, as an oil phase in an aqueous solution is also in an extremely stable state. As a result, the present invention has been completed. Accordingly, the present invention is not exhibit iron characteristic astringent taste, also, carbonate and / or bicarbonate also has the property of no aggregation sedimentation as the liquid form - iron - casein complexes oil fat solution or this oil It is an object to provide an oil-in-water (O / W) emulsion as a phase.
[0007]
[Means for Solving the Problems]
In the present invention, the following treatment is performed in order to obtain a dry powder of carbonic acid and / or bicarbonate-iron-casein complex that is stable even in liquid form. That is, a carbonic acid and / or bicarbonate-iron-casein complex is prepared according to the method disclosed in JP-A-9-77793. Next, the carbonate and / or bicarbonate-iron-casein complex is desalted while being added with water, and then allowed to stand. As a result, a precipitate of high-purity carbonic acid and / or bicarbonate-iron-casein complex is formed. The precipitate is recovered by a process such as centrifugation or decantation, and sufficiently air-dried, and then carbonated and / or heavy. A dry powder of carbonate-iron-casein complex is obtained. Alternatively, the carbonic acid and / or bicarbonate-iron-casein complex prepared in the same manner is freeze-dried or spray-dried to obtain a dry powder of carbonic acid and / or bicarbonate-iron-casein complex. The moisture content of these dry powders is preferably 20% or less. If the water content exceeds 20%, the carbonic acid and / or bicarbonate-iron-casein complex is difficult to dissolve in the oil and fat, and the mouth feels uncomfortable.
[0008]
Then, by dispersing the dry powder of this carbonic acid and / or bicarbonate-iron-casein complex in oil and fat, carbonic acid and / or bicarbonate-iron- until a high concentration of 65% (W / W) is obtained at room temperature. The casein complex can be dissolved, and a stable carbonic acid and / or bicarbonate-iron-casein complex oil solution in a liquid form can be obtained. About this oil and fat solution, stability is not impaired even if it heat-sterilizes.
[0009]
In addition, an oil-in-water type (O / W) It can also be made into an emulsion-like stable liquid form. About this oil-in-water (O / W) emulsion, stability is not impaired even if heat-sterilized. When emulsifying, the carbonic acid and / or bicarbonate-iron-casein complex itself has an emulsifying power, so there is no need to add an emulsifier, but by adding an emulsifier or a stabilizer, carbonic acid and The bicarbonate-iron-casein complex can be easily dispersed in an aqueous solution at a high concentration.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention, carbonate and / or bicarbonate - iron - casein complexes obtained by the dry燥粉late (JP-A 9 77793 JP) is dispersed and dissolved in fat, very stable carbonate and / or in liquid form It is in an oil / fat solution of a bicarbonate-iron-casein complex. The oil and fat solution of carbonic acid and / or bicarbonate-iron-casein complex which is stable in this liquid form is a dry powder of carbonic acid and / or bicarbonate-iron-casein complex disclosed in JP-A-9-77793. And this dry powder can be obtained by dispersing and dissolving in fats and oils. In addition, there is no restriction | limiting in particular about the fats and oils used when disperse-dissolving the dry powder of a carbonic acid and / or bicarbonate-iron-casein complex, Soybean oil, rapeseed oil, cottonseed oil, sesame oil, safflower oil which is liquid at normal temperature Vegetable oils such as olive oil and corn oil, and animal oils such as fish oil, milk fat and pork fat may be used.
[0011]
In addition, the oil and fat solution of carbonic acid and / or bicarbonate-iron-casein complex which is stable in a liquid form, obtained by dispersing and dissolving the dry powder of this carbonic acid and / or bicarbonate-iron-casein complex in oil and fat. In addition, by dispersing this in an aqueous solution and further emulsifying it, a stable carbonic acid and / or bicarbonate-iron-casein complex oil-in-water (O / W) emulsion using this oil / fat solution as an oil phase may be obtained. it can. In addition, there is no restriction | limiting in particular about the emulsifier used for emulsification, What is necessary is just to use emulsifiers, such as sodium caseinate, a lecithin, and a sugar ester.
[0012]
In this way, a stable carbonic acid and / or bicarbonate-iron-casein complex oil and fat solution in a liquid form in which carbonic acid and / or bicarbonate-iron-casein complex is dissolved at a high concentration, and an oil phase thereof. An oil-in-water (O / W) emulsion can be obtained. Oil and fat solutions and oil-in-water (O / W) emulsions of carbonic acid and / or bicarbonate-iron-casein complex that are stable in this liquid form are not precipitated or separated by heating, and the astringent taste of iron It has the feature of not letting you feel any roughness. 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 strengthening, medicine, feed, etc. It can be used as a material for blending.
[0013]
Hereinafter, the present invention will be specifically described with reference to test examples and examples.
[Example 1]
(Solution A) Solution containing 1,200 mM sodium bicarbonate 1 L
(B1 solution) Solution containing ferric chloride with an iron concentration of 10 mM 0.2 L
(B2 solution) 0.8 L solution containing 0.1 mM lactate casein (New Zealand Daily Board)
[0014]
The above A solution, B1 solution, and B2 solution were prepared. The average molecular weight was used to adjust the molar concentration of the B2 solution. Further, the average molecular weight was calculated from the constituent ratio of α-casein, β-casein and κ-casein determined from urea-sodium dodecyl sulfate (SDS) -electrophoresis and the theoretical molecular weight of each casein. Next, the B solution was mixed with the B1 solution to prepare the B solution, and then the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. This bicarbonate-iron-casein complex solution was desalted while adding water through an ultrafiltration membrane with a molecular weight of 5,000 cut, and then allowed to stand for 20 minutes. The resulting precipitate was collected by a centrifuge, and had a water content at room temperature. Air dried until 20%.
[0015]
When the dry powder of this 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 stable in a liquid form with no roughness. An oil-and-fat solution of iron-casein complex could be obtained. This liquid fat and oil solution of the stable bicarbonate-iron-casein complex is diluted with olive oil until the iron concentration reaches 3.6 mM, heat-sterilized at 90 ° C for 10 minutes, and then kept at 15 ° C. Then, the presence or absence of precipitation was observed, but no precipitation was observed even after 2 months.
[0016]
[Example 2]
(Solution A) Solution containing 1,200 mM sodium bicarbonate 1 L
(B1 solution) Solution containing ferric sulfate with iron concentration of 9 mM 0.2 L
(B2 solution) Solution containing 0.1 mM lactate casein (Sigma) 0.8 L
[0017]
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, the B solution was mixed with the B1 solution to prepare the B solution, and then the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. This bicarbonate-iron-casein complex solution was desalted while adding water through an ultrafiltration membrane with a molecular weight of 5,000 cut, and then allowed to stand for 20 minutes. The resulting precipitate was recovered with a centrifuge, and the water content was 9%. Lyophilization was performed until
[0018]
When the dry powder of this 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 stable in a liquid form with no roughness. An oil-and-fat solution of iron-casein complex could be obtained. This oily solution of stable bicarbonate-iron-casein complex in this 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 then kept at 15 ° C. Then, the presence or absence of precipitation was observed, but no precipitation was observed even after 2 months.
[0019]
[Example 3]
(Solution A) Solution containing 1,200 mM sodium bicarbonate 1 L
(B1 solution) Solution containing ferric sulfate with iron concentration of 9 mM 0.2 L
(B2 solution) Solution containing 0.1 mM lactate casein (Sigma) 0.8 L
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, the B solution was mixed with the B1 solution to prepare the B solution, and then the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. This bicarbonate-iron-casein complex solution was desalted while adding water through an ultrafiltration membrane with a molecular weight of 5,000 cut, and then allowed to stand for 20 minutes. The resulting precipitate was recovered with a centrifuge and had a water content of 8%. Lyophilization was performed until
[0020]
When the dry powder of this 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 stable in a liquid form with no roughness. An oil-and-fat solution of iron-casein complex could be obtained. For this oil and fat solution of bicarbonate-iron-casein complex that is stable in liquid form, a buffer solution that mimics liquid food containing 0.05 M imidazole and 0.05 M sodium chloride until the iron concentration reaches 3.6 mM (simulated buffer; pH 7.5), emulsified with a disperser, sterilized by heating at 90 ° C for 10 minutes, and kept at 15 ° C to observe the presence or absence of precipitate formation and the emulsified state. No precipitate formation was observed and the emulsification was not broken.
[0021]
[Example 4]
(Solution A) Solution containing 1,200 mM sodium bicarbonate 1 L
(B1 solution) Solution containing ferric sulfate with iron concentration of 9 mM 0.2 L
(B2 solution) Solution containing 0.1 mM lactate casein (Sigma) 0.8 L
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, the B solution was mixed with the B1 solution to prepare the B solution, and then the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. This bicarbonate-iron-casein complex solution was desalted while adding water through an ultrafiltration membrane with a molecular weight of 5,000 cut, and then allowed to stand for 20 minutes. The resulting precipitate was recovered with a centrifuge and had a water content of 8%. Freeze drying was performed until.
[0022]
When the dry powder of this bicarbonate-iron-casein complex was dispersed in olive oil to a concentration of 50% (W / W), it was easily dissolved in a few minutes and was stable in a liquid form with no roughness. An oil-and-fat solution of iron-casein complex could be obtained. This oil and fat solution of a stable bicarbonate-iron-casein complex is suspended in a simulated buffer solution (pH 7.5) containing 1% sodium caseinate until the iron concentration reaches 3.6 mM, and emulsified with a disperser. After sterilization at 120 ° C for 15 minutes, the mixture was kept at 15 ° C and the presence or absence of precipitation and the emulsified state were observed. However, the formation of precipitate was not observed even after 2 months, and the emulsification was broken. There wasn't.
[0023]
[Comparative Example 1]
(Solution A) Solution containing 1,200 mM sodium bicarbonate 1 L
(B1 solution) Solution containing ferric chloride with an iron concentration of 10 mM 0.2 L
(B2 solution) 0.8 L solution containing 0.1 mM lactate casein (New Zealand Daily Board)
[0024]
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, the B solution was mixed with the B1 solution to prepare the B solution, and then the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. This bicarbonate-iron-casein complex solution was desalted while adding water through an ultrafiltration membrane with a molecular weight of 5,000 cut, and then allowed to stand for 20 minutes. The resulting precipitate was collected by a centrifuge, and had a water content at room temperature. Air dried until 17%.
When this dry powder of bicarbonate-iron-casein complex was dispersed in distilled water, physiological saline, or ethanol, the suspension of rough bicarbonate-iron-casein complex did not dissolve and was rough. It became. These suspensions of bicarbonate-iron-casein complex were diluted with a simulated buffer solution (pH 7.5) until the iron concentration reached 3.6 mM, subjected to heat sterilization at 90 ° C. for 10 minutes, and then 15 ° C. When the presence or absence of precipitate formation was observed, the formation of a precipitate was observed after 5 minutes.
[0025]
[Comparative Example 2]
(Solution A) Solution containing 1,200 mM sodium bicarbonate 1 L
(B1 solution) Solution containing ferric chloride with an iron concentration of 10 mM 0.2 L
(B2 solution) 0.8 L solution containing 0.1 mM lactate casein (New Zealand Daily Board)
[0026]
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, the B solution was mixed with the B1 solution to prepare the B solution, and then the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. This bicarbonate-iron-casein complex solution was desalted while adding water through an ultrafiltration membrane with a molecular weight of 5,000 cut, and then allowed to stand for 20 minutes. The resulting precipitate was collected by a centrifuge, and had a water content at room temperature. Air dried until 18%.
[0027]
When this dry powder of bicarbonate-iron-casein complex was dispersed in distilled water containing 1% sugar ester, physiological saline, simulated buffer, 5% ethanol, or ethanol, respectively, A rough suspension of bicarbonate-iron-casein complex was obtained. These suspensions of bicarbonate-iron-casein complex were diluted with a simulated buffer solution (pH 7.5) until the iron concentration reached 3.6 mM, subjected to heat sterilization at 90 ° C. for 10 minutes, and then 15 ° C. When the presence or absence of precipitate formation was observed, the formation of a precipitate was observed after 5 minutes.
[0028]
[Test Example 1]
6 months of the oil / fat solution of each bicarbonate-iron-casein complex obtained in Examples 1 to 4 and the suspension of each bicarbonate-iron-casein complex obtained in Comparative Examples 1 and 2 Sensory evaluation was performed about the taste after storage. That is, 20 male panelists, 10 males and 10 females, feel the astringency and roughness of each sample using a simulated buffer solution (pH 7.5) in which ferrous sulfate is dissolved so that the iron concentration is 3.6 mM. Whether or not.
[0029]
Each panel was blindfolded so as not to give judgment factors based on appearance. Moreover, the test for one sample was made to test in order of a control and a sample, and after evaluating one sample, the test for evaluating the next sample at intervals of the minimum day was implemented. Furthermore, in order to eliminate the daily deviation in sample evaluation, the order of sample evaluation was randomized for each panel. Table 1 shows the number of panelists who felt astringency and roughness among the 20 panelists.
[0030]
[Table 1]

[0031]
According to this, the oil and fat solution of the carbonic acid and / or bicarbonate-iron-casein complex which is stable in the liquid form of the present invention maintains a stable state without being precipitated or separated even after heating. The astringent taste and roughness of iron were not found at all.
[0032]
[Example 5]
(Solution A) Solution containing 1,200 mM sodium bicarbonate 1 L
(B1 solution) Solution containing ferric chloride with an iron concentration of 10 mM 0.2 L
(B2 solution) 0.8 L solution containing 0.1 mM lactate casein (New Zealand Daily Board)
[0033]
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, the B solution was mixed with the B1 solution to prepare the B solution, and then the B solution was added to the A solution to prepare a bicarbonate-iron-casein complex. This bicarbonate-iron-casein complex solution was desalted while adding water through an ultrafiltration membrane with a molecular weight of 5,000 cut, and then allowed to stand for 20 minutes. The resulting precipitate was collected with a centrifuge and had a water content at room temperature. Air dried until 19%.
[0034]
When this dry powder of 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 with no roughness. An oil-and-fat solution of iron-casein complex could be obtained.
This oily solution of a stable bicarbonate-iron-casein complex in this liquid form is blended into skim milk to 12 mM / 200 ml, emulsified with a homogenizer, and then sterilized on a plate at 120 ° C. for 2 seconds to produce an iron-enriched milk beverage. Manufactured.
[0035]
【The invention's effect】
Carbonate and / or bicarbonate of the present invention - iron - casein complexes soluble liquid or it oil-in-water (O / W) and the emulsion, it without separating or precipitation even when heated, also, the iron Since it has a characteristic that it does not give any astringent taste or roughness, it is useful as a material to be blended in various foods, medicines, feeds, etc. for the purpose of strengthening iron.

Claims (2)

Fat and oil obtained by dispersing and dissolving a dry powder of carbonic acid and / or bicarbonate-iron-casein complex containing 1 to 1,000 atoms of iron and one or more molecules of carbonic acid and / or bicarbonate per molecule of casein. Solution . Claim 1 Symbol a dry powder of mounting the oil solution obtained by dispersing soluble in fats and oil phase oil-in-water (O / W) emulsion.