JPH10158646A - Antioxidant composition and food or feed containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antioxidant composition showing antioxidant effect more excellent than that of a conventional antioxidant when used in food or feed by adding shell membranes to an antioxidant. SOLUTION: Soluble shell membranes or a powder of shell membranes are added to a liquid obtained by emulsifying an oil-soluble antioxidant such as tocopherol or an ascorbic ester with an emulsifier or dissolving them in water- containing ethanol or to an aqueous solution of a water-soluble antioxidant such as ascorbic acid. Alternatively, the membranes are added when a solution of each antioxidant is prepared. To this solution-like composition or during its preparation, an excipient for powder formation such as a protein (e.g. casein) and/or milk sugar or a saccharide (e.g. dextrin) is added, and the resulting mixture is freeze-dried or spray-dried to obtain a powdery composition. It is desirable that the soluble shell membranes are those obtained by treating shell membranes obtained from egg shells or a powder of shell membranes by acid hydrolysis alone or in combination with another hydrolysis such as alkali hydrolysis or enzymatic hydrolysis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antioxidant composition and a food or feed containing the same.
The present invention relates to an antioxidant composition containing an antioxidant and an eggshell membrane for the purpose of improving antioxidant power, and a food or feed containing the composition and having excellent oxidative stability.

[0002]

2. Description of the Related Art In recent years, polyunsaturated fatty acids such as linoleic acid, eicosapentaenoic acid and docosahexaenoic acid have an epidemiological antithrombotic effect and an effect of lowering serum cholesterol level. Came to be blended.

[0003] However, foods or feeds containing such polyunsaturated fatty acids, if stored poorly, are oxidized with time, resulting in deterioration of flavor, generation of oxidized odor, and the like, resulting in loss of commercial value. Dropping is a problem.

In order to prevent such oxidation, conventionally, tocopherol, ascorbic acid, ascorbate, ascorbate, various protein hydrolysates, and antioxidant compositions combining these have been used. ing.

[0005]

However, the effects of the conventional antioxidant compositions are not sufficient, and a more effective antioxidant composition is desired. An object of the present invention is to provide a novel antioxidant composition having a more excellent antioxidant effect than conventional antioxidant compositions, and a food or feed containing the same.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention. That is, the present invention provides (1) an antioxidant composition comprising an antioxidant and an eggshell membrane, and (2) an antioxidant comprising tocopherol, ascorbic acid, ascorbate, and ascorbic acid. The antioxidant composition according to claim 1, which is a combination of one or more esters, and (3) the eggshell membrane is a soluble eggshell membrane obtained by acid hydrolysis in at least one step. The antioxidant composition according to claim 1 or 2, and
(4) A food or feed characterized by containing the antioxidant composition according to any one of claims 1 to 3.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, "%" means "% by weight". In the present invention, the "antioxidant" is a substance having antioxidant power by itself, for example, α-tocopherol, β
-Tocopherol, γ-tocopherol, δ-tocopherol or a mixture thereof tocopherol, ascorbate such as sodium ascorbate, ascorbate such as ascorbate palmitate or stearate ascorbate, ascorbic acid, erythorbic acid, egg white Or a protein hydrolyzate such as soybean; gallic acid esters such as gallic acid and propyl gallate; and polybasic organic acids such as citric acid, succinic acid, tartaric acid, fumaric acid and malic acid. Among these antioxidants, tocopherol, ascorbic acid, ascorbate and ascorbate are preferable because they exhibit a more antioxidant effect than other antioxidants when combined with eggshell membranes.

[0008] In the present invention, the term "egg membrane" refers to a powdered egg shell membrane obtained by drying and then pulverizing an eggshell membrane collected from a bird egg (typically a chicken egg). Alternatively, it refers to a soluble eggshell membrane obtained by hydrolyzing an eggshell membrane with an acid, an alkali, an oxidizing agent, a reducing agent, an enzyme, or the like to make it soluble in water.

The phrase "comprising an antioxidant and an eggshell membrane" means that the antioxidant and the eggshell membrane are contained in some state. For example, a powdered eggshell membrane or a soluble eggshell membrane mixed with a powdered antioxidant, or a powdered eggshell membrane dispersed in a solution or emulsion of an antioxidant, or a soluble eggshell membrane And the like are dissolved.

"Soluble eggshell membrane obtained by subjecting eggshell membrane to acid hydrolysis in at least one step" means that the eggshell membrane is subjected to acid hydrolysis only or other hydrolysis such as acid hydrolysis, alkali hydrolysis and enzymatic hydrolysis. Is a soluble eggshell membrane obtained by a treatment using a combination of the above. The soluble eggshell membrane obtained by acid hydrolysis in at least one step was combined with an antioxidant, compared to the non-hydrolyzed powdery eggshell membrane and the soluble eggshell membrane obtained by hydrolysis other than acid hydrolysis. In such a case, the antioxidant effect is more exhibited, which is preferable. Examples of the acid agent used for acid hydrolysis include hydrochloric acid, sulfuric acid, nitric acid, and acetic acid. When a generally used hydrochloric acid is used, the eggshell membranes have a hydrochloric acid concentration of less than 0.5 N (normality). Since it takes time to decompose the compound, it is preferable to set it to 0.5 N (normality) or more from the viewpoint of productivity.

"Food or feed containing the antioxidant composition" refers to a state in which the food or feed contains an antioxidant and eggshell membranes as a result. A method of adding an antioxidant composition containing an antioxidant and an eggshell membrane to foods and the like, and a method of separately adding an antioxidant and an eggshell membrane.

"Food" includes, for example, Japanese confectionery such as oysters, rice crackers, rice crackers, buns, candy, cookies, biscuits, crackers, pies, castella, donuts, puddings, sponge cakes, waffles, butter cream, custard cream, cream puffs , Chocolate, chocolate confectionery, caramel, candy, queuing gum, jelly, various Western confectionery such as hot cake, bread, confectionery bread, snack confectionery such as potato chips, ice cream, popsicles, ice confectionery such as sherbet, lactic acid beverage, lactic acid beverage, rich Milk drinks, juice drinks, pulp drinks, functional drinks, soft drinks such as carbonated drinks, green tea, black tea, coffee,
Cocoa and other luxury items and their beverages, fermented milk, processed milk,
Dairy products such as cheese, soy milk, processed soybean foods such as tofu, jams, fruit syrup pickles, flower pastes, peanut pastes, pastes such as fruit pastes, pickles, ham, sausage, bacon, dry sausage, beef jerky, etc. Meat products, fish ham, fish sausage, fish and shellfish products such as kamaboko, chikuwa, and starch, fish,
Dried fish such as shellfish, various nodes such as bonito, mackerel, aji, salted sea urchin, squid, etc. Retort foods such as boiled-in boiled rice, curry, stew, miso, soy sauce, sauce, ketchup,
Various types of seasonings such as mayonnaise, dressing, bouillon, grilled meat sauce, curry roux, stew ingredients, soup ingredients, dashi ingredients, cooked rice, various ranges containing oils and fats, frozen foods, etc., require oxidative stability. Refers to food.

The term "feed" refers to feed for chickens, cows, pigs, etc., raised for food, feed for pets such as dogs and cats, goldfish,
It refers to bait for ornamental fish such as carp and guppy, and bait for cultured fish such as hamachi and eel.

It is not clear why the antioxidant composition of the present invention exerts a more excellent antioxidant effect as compared with the conventional product, but it is not clear why it depends on the amino acid composition of the eggshell membrane or the sequence of the constituent amino acids. It is presumed that the combination of the oxidizing agent and the eggshell membrane promotes the antioxidant effect of the antioxidant by the eggshell membrane.

A typical method for producing the antioxidant composition of the present invention will be described below. A. Preparation of Eggshell Membrane Preparation of Powdered Eggshell Membrane Eggshell membrane is collected from egg shell. For collection, the membrane usually attached to the inside of the eggshell is separated from the eggshell using humans or machines. If the eggshell adhered or mixed into the eggshell membrane during separation is difficult to remove by hand or machine, the attached eggshell (mainly composed of calcium carbonate) is dissolved with an acid such as hydrochloric acid and then washed with water to remove it. Next, the eggshell membrane containing the water is dried in the sun or in a drier, and then pulverized by a pulverizer such as a hammer mill (produced by Fuji Paudal Co., Ltd.) or a new speed mill (produced by Okada Seiko Co., Ltd.). , To obtain a powdery eggshell membrane. Further, when a fine powder is desired, it is pulverized with a fine pulverizer such as a New Cosmomizer (manufactured by Nara Machinery Co., Ltd.).

Preparation of Soluble Eggshell Membrane Eggshell membrane or powdered eggshell membrane obtained from egg shell is treated to be soluble. That is, examples of the treatment method include hydrolysis using an acid, an alkali, an oxidizing agent, a reducing agent, an enzyme, or the like. These may be used alone or in combination of two or more. Especially,
A soluble eggshell membrane using acid hydrolysis alone or in combination with another hydrolysis method is preferable because the antioxidant composition of the present invention exhibits a more antioxidant effect. The following is an example of these processing methods.

Acid hydrolysis method 5 to 40 parts of 0.5 to 6 N (normal) hydrochloric acid or 0.5 to 6 parts per 1 part of the dry matter of the eggshell membrane or the powdery eggshell membrane obtained from the shell of eggs. 15N (normality) sulfuric acid is added, for example, under normal pressure at 50-100 ° C for 30 minutes-2.
After treatment for 4 hours, neutralization, filtration, and further desalting as needed, a soluble eggshell membrane aqueous solution is obtained.

5 to 40 parts of 0.5 to 3 N (normality) sodium hydroxide or 30 to 30 parts with respect to 1 part of the dry matter of the eggshell membrane or the powdery eggshell membrane obtained from the shell part of the alkali-hydrolyzed egg. 0.5 to 3N (normality) sodium hydroxide containing 70% by volume of ethanol is added, and the mixture is treated, for example, under normal pressure at 40 to 100 ° C. for 30 minutes to 8 hours. The salt is further desalted to obtain a soluble eggshell membrane aqueous solution.

Enzyme hydrolysis 10 parts to 40 parts of water is added to 1 part of the dry matter of the eggshell membrane or the powdery eggshell membrane obtained from the shell part of the eggs, and the protease is added with papain, pancreatin or the like. 0.5 to 20% of the dry matter of the eggshell membrane is added, and the enzyme is treated at the optimum pH and temperature for 5 to 40 hours. Get.

Combination of acid hydrolysis method and enzymatic hydrolysis method 5 to 40 parts of 0.5 to 6 N (normality) with respect to 1 part in terms of dry matter of eggshell membrane or powdery eggshell membrane obtained from egg shell. Hydrochloric acid or sulfuric acid of 0.5 to 15 N (normality), for example, at 50 to 100 ° C. for 30 minutes under normal pressure.
After treating for 24 hours, and then adjusting the pH of the protease to an optimum pH, the protease is added to the eggshell membranes in a dry matter of 0.1 to 2%.
The solution is treated so as to have a concentration of 0%, and treated at the optimum temperature of the enzyme for 5 to 40 hours.

The aqueous solution of the soluble eggshell membrane obtained by various hydrolysis methods may be dried as required by a drying method such as freeze drying (freeze drying) or spray drying (spray drying).

B. Preparation of antioxidant composition Preparation of solution-type antioxidant composition Tocopherol, oil-soluble antioxidant such as ascorbic acid ester, emulsified with emulsifier or dissolved in aqueous ethanol, or water-soluble ascorbic acid A soluble eggshell membrane or a powdery eggshell membrane is added to an aqueous solution of the antioxidant, or is added at the time of preparing a solution of these antioxidants to obtain a solution-type antioxidant composition. If desired, thickeners such as xanthan gum and guar gum and / or other additives can be added.

Preparation of Powdered Antioxidant Composition The above-mentioned solution-type antioxidant composition or, when prepared, is used for powdering proteins such as casein and / or sugars such as lactose and dextrin. After adding the excipients used,
Freeze drying or spray drying is performed to obtain a powdered antioxidant composition.

Although the representative examples of the antioxidant composition of the present invention have been described above, the present invention is, of course, not limited to these production methods.

Next, the present invention will be described in more detail based on Examples and Test Examples.

Example 1 Preparation of Eggshell Membrane After eggs of shell eggs were broken to remove egg fluid, the obtained eggshell with an eggshell membrane was pulverized. The pulverized material was placed in clear water and stirred, and the eggshell membrane that had separated and floated from the eggshell was collected. Next, it was dried with hot air to obtain a dried eggshell membrane. This dried eggshell membrane 1
100 L (liter) of 1.5 N (normality) hydrochloric acid solution was added to 0 kg, and the mixture was treated at 90 ° C. for 8 hours. Next, the mixture was neutralized with a 4N (normal degree) aqueous sodium hydroxide solution, filtered, desalted by electrodialysis, and the resulting solution was spray-dried to obtain a powdery soluble eggshell membrane. Preparation of antioxidant composition 50 g of the above powdery soluble eggshell membrane and 40 g of decaglycerin monooleate (trade name “Poem J-91F” manufactured by Riken Vitamin Co., Ltd.) are dissolved in 800 g of fresh water, and homomixed. 60 g of tocopherol (manufactured by Yoshihara Oil Co., Ltd., trade name “Golden Tocopherol 70”) gradually while stirring at 10,000 rpm for 30 minutes using (trade name “TK homomixer” manufactured by Tokushu Kika Kogyo Co., Ltd.) In addition, an emulsified antioxidant composition was obtained.

Example 2 To 5 kg of the dried eggshell membrane of Example 1, 100 L (liter) of 2N (normal) sodium hydroxide was added and treated at 70 ° C. for 3 hours. After neutralization with 3N (normal) hydrochloric acid, the solution was desalted by electrodialysis and freeze-dried to obtain a powdery soluble eggshell membrane.
Next, an emulsified antioxidant composition was obtained in the same manner as in the production of the antioxidant composition of Example 1.

Example 3 50 g of the powdery soluble eggshell membrane of Example 1, 40 g of decaglycerin stearate (manufactured by Riken Vitamin Co., Ltd., trade name "Poem J-0081H") and dextrin (manufactured by Matsutani Chemical Industry Co., Ltd.) , Product name "Paindex 1") 100
g was dissolved in 740 g of Shimizu and tocopherol (trade name, manufactured by Yoshihara Oil Co., Ltd.) while stirring at 10,000 rpm for 30 minutes using a homomixer (trade name “TK homomixer” manufactured by Tokushu Kika Kogyo Co., Ltd.) 60 g of “golden tocopherol 70”) is gradually added and emulsified. This emulsion was spray-dried to obtain a powdery antioxidant composition.

Example 4 100 g of the powdery soluble eggshell membrane of Example 1 and 20 g of powdery tocopherol (manufactured by Riken Vitamin Co., Ltd., trade name "RIKEN Dry E Mix-20") were uniformly mixed. An antioxidant composition was obtained.

Example 5 The dried anti-oxidant composition obtained in Examples 1 and 2 was immersed for 15 minutes in a 0.1% saline solution containing 1% of the emulsified antioxidant composition for 15 minutes. Draining was carried out to obtain whole dried shishamo covered with the antioxidant composition. As a control, a tocopherol preparation obtained by the same method as in the preparation of the antioxidant composition of Example 1 without adding a soluble eggshell membrane was used. The whole dried shishamo obtained was stored at −20 ° C. for 5 months, baked, and tasted. As a result, Shishamo coated with the antioxidant composition containing the soluble eggshell membranes of Example 1 and Example 2 maintained a good flavor after storage, whereas the control tocopherol preparation was used. The other had a slight oxidizing odor. In particular, when the antioxidant composition of Example 1 was used, the same good flavor as before storage was maintained.

Example 6 500 g of ground pork contains 9.6 g of salt, 2 g of sugar and 80 crushed ice.
g, and after salting, 1 g of the antioxidant composition obtained in Example 3 was added, mixed well, filled into sheep intestine, and sterilized by heating to obtain sausage. As a control, a tocopherol preparation obtained by the same method as in the preparation of the antioxidant composition of Example 3 without adding a soluble eggshell membrane was used. After the obtained sausage was stored at 4 ° C. for 20 days, the peroxide value (POV) was measured in accordance with the standard fat and oil analysis test method. As a result, the peroxide value of the one to which the control tocopherol preparation was added was 8.6 meq / kg before storage and 24.8 m after storage.
In contrast to eq / kg, when the antioxidant composition was added, the increase in peroxide value was suppressed to 8.3 meq / kg before storage and 9.6 meq / kg after storage.

Example 7 The ingredients including the antioxidant composition obtained in Example 4 were mixed in the following composition, cooled at 10 ° C. for 1 hour, and shaped.
Cookies were prepared by roasting at 0 ° C. for 14 minutes. As a control, powdered tocopherol (RIKEN Vitamin Co., Ltd.)
Manufactured by Riken Dry E Mix-20). Put the obtained cookies in a polyethylene bag,
After tasting for one month, we tasted. As a result, the one using the antioxidant composition containing the soluble eggshell membrane had a good flavor even after storage, whereas the one using the control powdered tocopherol showed a slight oxidative odor. Had. Butter 140 g Shortening 140 g Brown sugar 100 g Granulated sugar 70 g Whole egg 120 g Soft flour 310 g Sodium bicarbonate 2.2 g Salt 2.5 g Antioxidant composition 2 g

Example 8 Preparation of Eggshell Membrane After the eggs with shells were broken to remove egg fluid, the obtained eggshells with eggshell membranes were pulverized. The pulverized material was placed in clear water and stirred, and the eggshell membrane that had separated and floated from the eggshell was collected. Next, it was dehydrated with a centrifugal dehydrator to obtain an infiltrated eggshell membrane having a solid content of 21% by weight. 1 kg of 20 kg of this infiltrated eggshell membrane
(Normality) Add 50 L (liter) of hydrochloric acid solution, 90 ° C
For 15 hours. Next, after adjusting the pH to 5.5 with a 4N (normality) aqueous sodium hydroxide solution, 40 g of a proteolytic enzyme (manufactured by Novo Nordics Bioindustry, trade name "Flavorzyme MG") was added, and 55 ° C was added.
, The pH was adjusted to 7 with a 4N (normality) aqueous sodium hydroxide solution, and 40 g of Flazyme MG was added, followed by treatment at 50 ° C for 4 hours. Next, the enzyme-treated solution was heated at 90 ° C. for 30 minutes to inactivate the enzyme, decolorized with 2 kg of activated carbon, filtered, and the obtained aqueous solution was desalted by electrodialysis and lyophilized to form a powder. A soluble eggshell membrane was obtained. Production of food Mix the ingredients in the following formulation, including the soluble eggshell membrane above,
Baking at 180 ° C for 20 minutes produced a sponge cake.
The control did not contain a soluble eggshell membrane. After the obtained sponge cake was stored at -20 ° C for 6 months, it was tasted. As a result, the compound containing the soluble eggshell membrane had a good flavor even after storage, whereas the control had a slight oxidizing odor. Whole egg 180 g Granulated sugar 200 g Soft flour 190 g Lemon juice 30 g Butter 50 g Soluble eggshell membrane 1 g (The content of ascobic acid in lemon juice is 13.3 mg
Is)

Example 9 The ingredients including the antioxidant composition obtained in Example 4 were mixed in the following formulation to prepare a chicken feed. As a control, powdered tocopherol (manufactured by Riken Vitamin Co., Ltd., trade name “RIKEN Dry E Mix-20”) was used. After storing the obtained feed at 35 ° C. for one month, a flavor test was performed. As a result, when the antioxidant composition was blended, there was almost no difference in flavor before and after storage, whereas the control had an oxidized odor. Corn 730 g Lucan meal 30 g Soybean meal 130 g Fish meal 60 g Calcium carbonate 70 g Salt 2 g Antioxidant composition 1 g

[0034]

[Test Example] Test Example 1 Test method Preparation of measurement sample A 50 mL (milliliter) sample bottle was filled with 56 mg / ml.
2.5 mL of ethanol solution of linoleic acid at a concentration of 2.5 mL, the amount of eggshell membrane and / or antioxidant shown in Table 1 and 0.1 mL of pH7.
A 1 M (molar concentration) citric acid-0.1 M phosphate buffer and ethanol were added so that the ethanol concentration became 20% by volume to prepare a 25 mL measurement sample in total. The eggshell membrane used was the soluble eggshell membrane obtained in the preparation of the eggshell membrane of Example 1. Each of the above measurement samples was stored at 35 ° C., and the peroxide value (POV) was measured over time by the iron-rodan method. That is, 4.7 mL of 75% aqueous ethanol was added to 0.1 mL of the measurement solution.
mL, 0.1 mL of 30% rhodamon ammonium and 0.0
0.1 mL of 2M ferrous chloride / 3.5% hydrochloric acid was added, and after exactly 3 minutes, the absorbance at 500 nm was measured, and the absorbance when purified water was used in place of the measurement solution as a blank was used. The number of days until 0.3 or more was set as the induction period, and the antioxidant power of each measurement sample was compared.

[0035]

[Table 1]

According to Table 1, the eggshell membrane and the antioxidant were simultaneously added (Sample Nos. 4, 5, 6, 8, 10, 12 and 1).
In the case of 4), the antioxidant power was higher than that of the antioxidant alone. In particular, eggshell membrane and tocopherol (Sample No. 4).
4, 5 and 6) or ascorbic acids (samples Nos. 8 and 10), it is understood that the number of induction days is significantly increased as compared with other antioxidants, and the antioxidant power is enhanced.

Test Example 2 Test Method Preparation of Measurement Sample To lard, 0.02% of tocopherol and 1% of a protein hydrolyzate including a soluble eggshell membrane were added and made uniform. 3.5 g of measurement sample was Rancimat (manufactured by Metrohm)
And measurement temperature: 120 ° C, air volume: 20 L / h
Under the above conditions, the induction time was measured, and the antioxidant power of each measurement sample was compared.

[0038]

[Table 2]

From Table 2, it can be seen that the antioxidant composition using a more soluble eggshell membrane than other protein hydrolysates (Sample No. 1)
It is understood that 5) to 18) have a longer induction time and are superior in antioxidant power. Further, among the soluble eggshell membranes, it is understood that the antioxidant composition using the soluble eggshell membrane obtained by acid hydrolysis in at least one step has a further longer induction time and an excellent antioxidant power. Is done.

[0040]

As described above, according to the present invention, a novel antioxidant composition utilizing an antioxidant and an eggshell membrane and having excellent antioxidation, and having excellent oxidation stability containing this antioxidant composition. Food or feed is provided to expand the use of eggshell membranes.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 15/08 C09K 15/08

Claims (4)

[Claims] 1. An antioxidant composition comprising an antioxidant and an eggshell membrane. 2. The antioxidant composition according to claim 1, wherein the antioxidant comprises at least one of tocopherol, ascorbic acid, ascorbate, and ascorbate. 3. The antioxidant composition according to claim 1, wherein the eggshell membrane is a soluble eggshell membrane obtained by acid hydrolysis in at least one step. 4. A food or feed comprising the antioxidant composition according to claim 1.