JPH0898647A - Nourishing composition containing metal-binding casein blended therein - Google Patents

Abstract

PURPOSE: To obtain a nourishing composition, containing iron and copper binding to casein therein, capable of suppressing the decomposition due to oxidizing reaction with other nourishing ingredients and hardly deteriorating the quality. CONSTITUTION: This nourishing composition contains iron-binding casein and copper-binding casein in an amount so as to that about 0.01-30mg% each of the iron and copper may exist based on the solid content thereof. The oxidizing reaction of other substances such as an oil and a fat, vitamin A or carotene in the nourishing composition is suppressed and physiological effects of the iron and copper as a minor metallic elements are not deteriorated.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a nutritional composition containing iron-bound casein and copper-bound casein (hereinafter referred to as "metal-bound casein"). The present invention particularly relates to a nutritional composition that is stable against oxidation and hardly deteriorates in quality by incorporating a metal-bound casein.

[0002]

2. Description of the Related Art In recent years, research on breast milk has progressed, and components contained in breast milk have been elucidated in great detail. Along with this, in the development of nutritional compositions such as infant formula and infant formula, the approximation to breast milk is being pursued. The nutritional composition is generally protein,
It is composed of lipids, carbohydrates, ash, and other trace components, and improvements in these components and addition of new components are becoming increasingly popular. However, various nutritionally or physiologically important components contained in the nutritional composition are not always stable against oxidation. For example, unsaturated fatty acids in fats and oils mixed as a fat source are very likely to be oxidized, and hydroperoxides produced by oxidation of the fatty acids have a problem of acting as a stronger oxidizing agent. Also, when proteins are oxidized and damaged,
Affects hardness and mouth feel, and browning occurs during storage.

Further, reducing substances such as ascorbic acid, tocopherol, glutathione and uric acid contained in the nutritional composition are easily oxidatively decomposed, and vitamin A and carotene having many conjugated double bonds are easily oxidatively decomposed. . When oxidation occurs in the nutritional composition in this way, it is said that not only the quality is deteriorated due to decomposition of the components, but also in extreme cases, there is a risk of causing poisoning (Yukiro Matsushita, “ Oil Chemistry ", Vol. 36, pp. 3-9, 1987). The rate of oxidation of a substance varies depending on the structure unique to the substance such as double bond and conjugated double bond, and is promoted by oxygen, temperature rise, light, radiation, organometallic compounds, trace metal catalysts (transition metals), etc. To be done.

In the nutritional composition, as essential trace elements,
Metals such as copper, iron and zinc are mixed, but there is a problem that these may act as an oxidation catalyst for other components. Conventionally, these metals are copper sulfate, ferrous sulfate,
Although it is incorporated in the form of a metal salt of ferrous sodium citrate, ferric pyrophosphate, zinc sulfate, etc., it retains its oxidation catalytic ability in the nutritional composition. That is, the oxidation reaction in the nutritional composition accelerates the reaction rate due to the catalytic action of these metals, and as a result, there is a risk of degrading the quality of the nutritional composition in a short time. For this reason, various attempts have hitherto been made to suppress the oxidation catalytic ability of metals added as essential trace elements. For example milk protein,
It has been disclosed that a protein such as soybean protein and egg white is bound to an iron salt and then hydrolyzed by an enzyme to form an iron-binding peptide, which suppresses the oxidation catalytic ability of iron (JP-A-63-63).
290827).

[0005]

It is known that some proteins have the property of binding to divalent metal ions due to their electrical properties, but they are simply milk protein, soy protein, egg. Only by reacting a protein such as protein with an aqueous solution of an iron salt, only a trace amount of metal is bound, and the metal remains in a state of retaining the oxidation catalytic ability. Therefore, when the iron-binding peptide obtained by the method described in JP-A-63-290827 is added to the nutritional composition, the iron-binding peptide is contained in the nutritional composition rather than in the metal salt form. There is a problem in that the effect of suppressing the oxidation catalytic activity of the metal cannot be obtained, although the oxidation catalytic activity of the oil and fat is suppressed to some extent. Furthermore,
There is also a problem that in the production of iron-binding peptides, complicated and time-consuming operations such as enzyme treatment and peptide recovery are required. Therefore, the present invention solves the problems of the prior art as described above, by incorporating the metal-bonded casein obtained by a simpler method into the nutritional composition, the oil or fat blended in the nutritional composition or It is an object of the present invention to provide a nutritional composition that suppresses the oxidation of other substances such as vitamin A and carotene and that does not easily deteriorate in quality. That is, an object of the present invention is to provide a nutritional composition in which quality deterioration is suppressed by suppressing decomposition of components constituting the nutritional composition due to an oxidation reaction.

[0006]

The present inventors have found that, out of the metals to be incorporated in the nutritional composition, particularly iron and copper act particularly strongly as a catalyst for the oxidation reaction of other components, Furthermore, they have found that the oxidation catalytic activity is remarkably suppressed when these metals are blended in a state of being bound to casein, and have completed the present invention. That is, the present invention
It consists of a nutritional composition containing metal-bound casein. The present invention also provides that the amount of the metal-bound casein is 0.01 to 30 mg per solid content of the nutritional composition.
% Of the nutritional composition.

The present invention will be described in detail below. The nutritional composition according to the present invention includes infant formula, infant formula, follow-up formula, formula-specific formula, enteral nutritional supplement, and the like. The nutritional composition of the present invention may be in any form of liquid, powder and solid. The nutritional composition of the present invention generally contains proteins, lipids, carbohydrates, ash and the like as main components, and contains metals such as iron, copper, zinc and manganese as essential trace components, vitamins and the like. However, it may further contain other components that can be incorporated into the nutritional composition. In the present invention, as described above, among the above-mentioned metals, in particular, focusing on the fact that the oxidation catalytic ability of iron and copper is high, iron and copper are the forms of metal-bonded casein of iron-bonded casein and copper-bonded casein. Is added to the nutritional composition in order to suppress the oxidation catalytic ability with respect to other components. Moreover, the iron and copper compounded in the form of metal-bound casein are
Similar to the case where it is mixed in the form of salt or the like, it can also function as a trace element. That is, the nutritional composition of the present invention, by incorporating iron and copper as metal-bound casein, while having the function as an essential trace element thereof, at the same time, is particularly formulated as a fat source in the nutritional composition. It is possible to effectively suppress the oxidation of fats and oils (particularly, fats and oils containing a large amount of unsaturated fatty acids in the fatty acids constituting the fats and oils), vitamin A, carotene, ascorbic acid and the like.

The metal-bound casein to be incorporated in the nutritional composition of the present invention may be produced by any method. For example, the method described in JP-A-2-83400 is preferred. It can be manufactured. The method described in the publication is shown below for reference. Milk or processed milk as a raw material is desalted by an electrodialyzer or an ultrafiltration membrane while keeping the pH at 6.0 or more with an alkali to remove calcium bound to casein in the milk.
Remove 0% or more. Rennet was added to the desalted milk to remove κ-casein in casein from para-κ-
It is converted to casein to give soluble casein. When the iron-bound casein is prepared, the casein concentration of the soluble casein solution is adjusted to 5 to 25%, and, for example, sulfuric acid having a concentration of 0.1 to 25% by weight, preferably about 10% by weight is added. When an aqueous solution of a divalent iron salt such as ferrous iron is added, it solidifies to produce an iron-bound casein curd. This can be used as it is as a raw material for a nutritional composition. Also,
If necessary, the iron-bound casein curd is collected, washed with ion-exchanged water or tap water, dehydrated by means such as centrifugation, and the obtained curd is subjected to a drying treatment such as freeze-drying or spray-drying. By doing so, the iron-bound casein can also be pulverized. When preparing copper-bound casein, the soluble casein is adjusted to the same concentration as above, and then copper sulfate (pentahydrate) is added to the solution at a concentration of 0.12 to 2
When added as an aqueous solution of 0% by weight, preferably 2% by weight, the curd produces a curd of copper-bound casein, and thus the curd may be used as it is as a raw material of a nutritional composition. It is also possible to collect and treat it in the same manner as the iron-bound casein, and then mix it into the nutritional composition in powder form.

As the soluble casein for binding metals, acid casein, soda casein or potassium casein can be used in addition to the desalted casein obtained by the above-mentioned method. One of these casein or Two or more kinds can be mixed and used. Incidentally, when the soluble casein is added to the metal salt, by using a nozzle having a fine caliber or the like and injecting the metal salt into the soluble casein solution, the particle size of the obtained metal-bonded casein becomes fine, and the particle The diameter can be adjusted, which is convenient for use. Whole milk powder, skim milk powder, milk raw materials such as whey protein concentrate, fat raw materials, carbohydrates, ash and other trace components such as metal salts and vitamins, and the like are prepared in liquid form. Alternatively, the nutritional composition is prepared by mixing in a powder form. When the obtained nutritional composition is filled in a container and packaged, if air is replaced with an inert gas such as nitrogen gas in accordance with a conventional method, the stability against oxidation is further improved.

The content of metal-bound casein in the nutritional composition of the present invention varies depending on the intended nutritional composition, but in the case of the nutritional composition intended for infants, based on the weight of the metal alone, Usually, it is 0.01 to 25 mg% per solid content of the final product, especially 0.1 to 10 mg.
mg% is preferred. Further, in the case of a nutritional composition for pregnant women, based on the weight of the metal alone, usually,
It is respectively 0.02 to 30 mg%, and particularly preferably 0.15 to 25 mg%, based on the solid content of the final product. The protein content in the nutritional composition of the present invention is 0 to 30% by weight, particularly 7 to 15% by weight, based on the solid content of the final product, and the lipid content is 0 to 60% based on the solid content of the final product. weight%,
In particular, 20 to 40% by weight, the content of carbohydrate is 0 to 90% by weight, based on the solid content of the final product, particularly 40 to 60% by weight, and the content of ash is 0 to 10% by weight, the solid content of the final product. %, Particularly 0.5 to 4% by weight, and the amount of vitamins to be added is 0 to 2% by weight, especially 0.0
It is preferably 1 to 0.5% by weight.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

【Example】

Example 1 (Preparation of infant formula containing metal-bound casein) Sodium casein (1.0 kg) was dissolved in warm water (4.0 kg), and ferric sulfate (anhydrous) having a solid content of 10% by weight was stirred under stirring. Stuff)
22.6 g of an aqueous solution of the above was injected through a nozzle having a diameter of 0.5 mm. Further, 6.45 g of a 2 wt% copper sulfate (pentahydrate) aqueous solution was injected through a nozzle having a diameter of 0.5 mm in the same manner to produce a casein curd to which iron or copper was bound.
In the metal-bound casein solution thus obtained, 8.8 kg of whey powder (75% protein content), 8.8 kg of whole milk powder, 3.9 kg of acid casein, 51.6 kg of lactose, vitamins and mineral components (iron, copper) 1.5 kg and water 695 kg are added,
After dissolving and mixing, 25.1 kg of vegetable oil and fat was added and mixed, and 1
The mixture was homogenized at 75 kgf / cm ² and then sterilized at 120 ° C. for 3 seconds to obtain about 800 kg of infant formula. This infant formula contains reduced ascorbic acid 0.2 mg / ml,
The iron and copper contents are 6 mg% of iron and
It was 320 μg%.

Comparative Example 1 (Preparation of infant formula containing iron-binding peptide) To 9.0 kg of water, 20 g of K ₂ CO _{3 and} 20 g of Na ₂ CO ₃ were added, and further 1.0 kg of acid casein was added. The solution was heated to 60 ° C to dissolve it, then cooled to 50 ° C and held. An aqueous solution of ferrous sulfate (anhydrous) having a solid content of 0.06% by weight was added to this.
The mixture was mixed with kg, 100 ml of a 4N sodium hydroxide aqueous solution was added to adjust the pH to 8.0 to 9.0, and the mixture was kept at 50 ° C. Into this solution, 7.0 g of pancreatin (manufactured by Amano Pharmaceutical Co., Ltd.) dissolved or suspended in an appropriate amount of water and 15.0 g of protease N derived from Bacillus subtilis (manufactured by Amano Pharmaceutical Co., Ltd.) were separately separated. Sequential addition, 16 at 50 ℃
The enzyme reaction was performed for a time. After the reaction, the mixture was heated at 85 ° C. for 15 minutes to inactivate the enzyme, remove insoluble matter, and then concentrated and dried to obtain 850 g of iron-binding peptide powder. The iron content of this iron-binding peptide powder was about 15 mg per 100 g. Sodium casein 1.0kg is dissolved in warm water 4.0kg, whey powder (protein mass 75%) 8.8kg, whole milk powder 8.8
kg, acid casein 3.9 kg, lactose 51.6 kg, vitamin and mineral components 1.5 kg [including iron binding peptide powder 40.0 g and copper sulfate (pentahydrate) 1.29 g] and water 695 k.
After adding g and dissolving and mixing, 25.1 kg of vegetable oils and fats were added and mixed, and homogenized at 175 kgf / cm ² , and then 120 ° C, 3
It was sterilized for 2 seconds to obtain about 800 kg of infant formula. This infant formula contains 0.2 mg / ml of reduced ascorbic acid, and the content of iron and copper is 6 mg of iron per solid content.
%, And copper was 320 μg%.

Comparative Example 2 (Preparation of infant formula formulated in the form of metal salt) 1.0 kg of sodacasein was dissolved in 4.0 kg of warm water to obtain 8.8 kg of whey powder (75% protein content), whole milk powder. 8.8 kg, acid casein 3.9 kg, lactose 51.6 kg, vitamin and mineral components 1.5 kg [ferrous sulfate (anhydrous) 2.26 g, copper sulfate (5
Hydrate) 1.29 g] and 695 kg of water are added and dissolved and mixed, and then 25.1 kg of vegetable oils and fats are added and mixed.
After homogenized at 5 kgf / cm ² , it was sterilized at 120 ° C for 3 seconds to obtain about 800 kg of infant formula. This infant formula contains 0.2 mg / ml of reduced ascorbic acid, and the iron and copper contents are 6 mg% of iron and 320% of copper per solid content.
It was μg%.

Control Example 1 (Preparation of infant formula containing no iron or copper) Sodacasein (1.0 kg) was dissolved in warm water (4.0 kg), and whey powder (protein content 75%) 8.8 kg, whole milk powder 8 0.8 kg, acid casein 3.9 kg, lactose 51.6 kg, vitamins and mineral components (excluding iron and copper) 1.5 kg, and water 695 kg are added, dissolved and mixed, and then vegetable oil and fat 25.1 kg are added and mixed, 17
After homogenized at 5 kgf / cm ² , it was sterilized at 120 ° C for 3 seconds to obtain about 800 kg of infant formula. This infant formula contained 0.2 mg / ml of reduced ascorbic acid.

Test Example 1 (Comparison of Oxidation Inhibition of Powdered Milk Prepared by Examples, Comparative Examples and Control Examples) The infant formulas prepared in Example 1, Comparative Examples 1 and 2 and Control Example 1 (Formulated Milk A) The progress of the oxidation of D) was compared by measuring the time course of the reduction and reduction of the reduced ascorbic acid contained therein. The contents of iron and copper in the modified milk (A, B and C) are the same. Formulated milk for child-rearing containing the metal-bound casein prepared in Example 1 (Formulation A) Formulated milk for child-rearing containing the metal-binding peptide prepared in Comparative Example 1 (Formulation B) Metal salt prepared in Comparative Example 2 Formulated milk for child-rearing (formulated milk C) Formulated for child-rearing prepared without the metal salt prepared in Comparative Example 1 (formulated milk D) 500 ml of each of the above-mentioned milk formulas A to D is gently stirred at 25 ° C. Then, 5 ml of each was collected over time, and the content of reduced ascorbic acid in the prepared milk was measured. At this time, the temperature and stirring conditions of each formula were set to be the same. The reduced ascorbic acid was measured by the indophenol / xylene method (Japan Agricultural Standards Association, fruit drink, test method). The time course of the reduced ascorbic acid content in each formula is shown in FIG. As is clear from FIG. 1, in the modified milk D, the reduced ascorbic acid is hardly reduced, whereas in the modified milk C, the reduced amount is remarkably decreased, and it is understood that the oxidation progresses quickly. Also in the modified milk B, the reduced ascorbic acid decreases rapidly, and the oxidation progresses quickly. On the other hand, in formula A, the rate of reduction of reduced ascorbic acid is slow, and the progress of oxidation is obviously slower than formulas B and C.

Example 2 (Preparation of infant formula containing powdered metal-bound casein) Sodacasein 1.0 kg was dissolved in warm water 4.0 kg,
Under stirring, 500 g of a ferrous sulfate (dry) aqueous solution having a solid content of 10% by weight was injected through a nozzle having a diameter of 0.5 mm to produce an iron-bound casein curd. Apart from
Sodium casein (1.0 kg) was dissolved in warm water (4.0 kg), and with stirring, a 2 wt% aqueous solution of copper sulfate (pentahydrate) 50 was added.
0 g was also injected through a nozzle having a diameter of 0.5 mm,
A card of copper-bound casein was generated. Each solution,
Centrifuge, collect the generated card, wash thoroughly with tap water, then centrifuge again to collect the card,
After dehydration, drying and pulverization, iron-bonded casein powder and copper-bonded casein powder were obtained. The iron content of the iron-bound casein powder was 1020 mg per 100 g and the copper content of the copper-bound casein powder was 2600 mg per 100 g. To the obtained iron-bound casein powder 588g, copper-bound casein powder 12.3g, whey powder (protein mass 75%) 9.4kg,
Sodacasein powder 6.5 kg, lactose 55.0 kg, vitamin and mineral components (excluding iron and copper) 2.0 kg and water 7
After adding 00 kg and dissolving and mixing, 27.4 kg of vegetable oil and fat was added and mixed, and homogenized at 175 kgf / cm ² , and then 120
Sterilization at ℃ for 3 seconds, about 800 kg of infant formula was obtained.
This infant formula is 0.24 mg of reduced ascorbic acid.
/ Ml, and the iron and copper contents were 6 mg% iron and 320 μg% copper, based on solids.

Example 3 (Preparation of infant formula prepared by incorporating metal-bound casein)
1.0 kg of soda casein is dissolved in 4.0 kg of hot water, and ferrous sulfate (anhydrous) with a solid content of 10% by weight is added thereto with stirring.
22.6 g of the aqueous solution was injected through a nozzle having a diameter of 0.5 mm. Further, a 2 wt% copper sulfate (pentahydrate) aqueous solution 6.
45 g were likewise injected through a 0.5 mm caliber nozzle to produce iron or copper bound casein curds.
In the metal-bound casein solution thus obtained, 8.8 kg of whey powder (75% protein mass), 8.8 kg of whole milk powder, 3.9 kg of acid casein, 51.6 kg of lactose, vitamins and mineral components (iron and copper) 1.5 kg and 695 kg of water are added and dissolved and mixed, and then 24.6 kg of vegetable oils and fats and evening primrose oil are added.
1 kg and 0.4 kg of fish oil were added and mixed, homogenized at 175 kgf / cm ² and sterilized at 120 ° C for 3 seconds to about 800
Obtained was kg of infant formula. After concentrating this by a conventional method,
After spray drying, 100 kg of infant formula was obtained. This infant formula has reduced ascorbic acid 1.
It contains 85mg% and the content of iron and copper is 6mg of iron.
%, And copper was 320 μg%.

Comparative Example 4 (Preparation of infant formula powder mixed in the form of metal salt) 1.0 kg of sodacasein was dissolved in 4.0 kg of warm water to obtain 8.8 kg of whey powder (75% protein content), whole milk powder. 8.8 kg, acid casein 3.9 kg, lactose 51.6 kg, vitamin and mineral components 1.5 kg [ferrous sulfate (anhydrous) 2.26 g, copper sulfate (5
Hydrate) 1.29 g] and 695 kg of water were added and dissolved and mixed, and then 24.6 kg of vegetable oil and fat, 0.1 kg of evening primrose oil and 0.4 kg of fish oil were added and mixed, and homogenized at 175 kgf / cm ² . Then, it was sterilized at 120 ° C. for 3 seconds to obtain about 800 kg of infant formula. This was concentrated by a conventional method and then spray-dried to obtain 100 kg of infant formula. This infant formula has 1.8% reduced ascorbic acid per solid content.
5 mg%, and the content of iron and copper is 6 mg% of iron,
The amount of copper was 320 μg%.

Control Example 2 (Preparation of infant formula prepared without blending iron and copper) 1.0 kg of sodacasein was dissolved in 4.0 kg of warm water to obtain 8.8 kg of whey powder (75% protein content) and 8 parts of whole milk powder. 0.8 kg, acid casein 3.9 kg, lactose 51.9 kg, vitamins and mineral components (excluding iron and copper) 1.5 kg, and water 695 kg are added and dissolved and mixed, followed by vegetable oil 24.6 kg and evening primrose oil 0.1 kg And 0.4 kg of fish oil were added and mixed, homogenized at 175 kgf / cm ² and sterilized at 120 ° C. for 3 seconds to obtain about 800 kg of infant formula. This was concentrated by a conventional method and then spray-dried to obtain 100 kg of infant formula. This infant formula is 1.85 mg reduced ascorbic acid per solid content.
%.

(Sensory Evaluation) In order to evaluate the oxidation catalytic ability, the infant formula prepared in Example 3, Comparative Example 4 and Comparative Example 2 above had a unique characteristic when oil and fat were oxidized and deteriorated. The return odor was sensory evaluated. Each powdered milk powder 350 obtained in Example 3, Comparative Example 4 and Control Example 2
g was filled in a can, the air in the can was replaced with nitrogen gas, and the container was sealed as it was. After storing at 37 ° C. for 60 days, the cans were opened, and the characteristic fish odor generated when the fish oil was deteriorated by oxidation was sensory-evaluated by 20 expert panelists. The results are shown in Table 1 below.

[0021]

[Table 1] Example of results of sensory evaluation Number of panelists who felt a fishy odor ------------------ Example 3 4 persons Comparative example 4 16 persons Control example 21 1 −−−−−−−−−−−−−−−−−−−−−− (20 persons)

As is clear from the results shown in Table 1,
Compared with the milk powder of Control Example 2, the milk powder of Comparative Example 4 had an overwhelming majority of people who felt a fishy odor, and the oxidation of fish oil contained in the milk powder,
It can be seen that the deterioration is progressing. On the other hand, the milk powder of Example 3 had a slightly greater fishy odor when compared to the milk powder of Control Example 2, but when compared with the milk powder of Comparative Example 4, far less people felt the fishy odor, and Oxidation and deterioration were suppressed. This indicates that in Example 3, the oxidation of fats and oils was suppressed, that is, the progress of oxidation was suppressed by the use of metal-bound casein.

[0023]

As described above in detail, the nutritional composition of the present invention contains the essential metal components such as iron and copper.
As it is combined with casein, the metal's ability to catalyze oxidation to nutritional compositions is significantly reduced, and oxidative degradation such as fats and oils, vitamin A, reduced ascorbic acid, tocopherols, glutathione, uric acid or carotene. It is possible to suppress the oxidation reaction of nutrients that are easily affected, and moreover, iron and copper can also exert the physiological effect as a trace metal element, as in the case of being mixed in the form of a salt or the like. Furthermore, by suppressing the oxidation reaction in this way, it is possible to prevent degradation of quality such as decomposition of effective nutrients, generation of off-flavor, browning, solidification, etc., and to provide an excellent nutritional composition having stable quality. Obtainable.

[Brief description of drawings]

FIG. 1 is a graph showing the time-dependent change in the content of reduced ascorbic acid in prepared milk.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaya Matsunaga Residence 3-1-2 Shinsayama, Sayama City, Saitama Prefecture No. 205 Shinsayama (72) Inventor Masayuki Eto, 1st at 243 Imafuku, Kawagoe City, Saitama Prefecture Maritch A301 (72) Inventor Tadashi Iwata Kawagoe-shi, Saitama Oita 6083-7 Kawagoe Green Park L1-207

Claims (2)

[Claims] 1. A nutritional composition comprising iron-bonded casein and copper-bonded casein. 2. The nutritional composition according to claim 1, wherein the iron-bound casein and the copper-bound casein are blended in such an amount that the weights of the iron and copper are each 0.01 to 30 mg% based on the solid content of the nutritional composition. Stuff.