JP2003070424A - Protein stabilizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protein stabilizer capable of significantly preventing protein coagulation within a weak acidic region of pH 4.5-6.3, and to provide a stabilized protein-containing composition through significantly protecting protein coagulation within the weak acidic region. SOLUTION: This protein stabilizer comprises using chondroitin sulfuric acid or its salt. The chondroitin sulfuric acid or its salt as the protein stabilizer is used especially for a protein-containing composition of a weak acidic region of pH 4.5-6.3.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a protein stabilizer capable of significantly preventing protein aggregation in a weakly acidic region. Furthermore, the present invention relates to a protein-containing composition that contains the protein stabilizer to significantly prevent protein aggregation and has excellent stability.

[0002]

2. Description of the Related Art Conventionally, there has been no material capable of significantly preventing protein from aggregating and stabilizing it in a weakly acidic region such as pH 4.5 to 6.3. Therefore, there are almost no foods using protein as a raw material in this pH region. There wasn't. For example,
In strawberry milk drinks containing protein derived from milk,
After adding strawberry juice, etc., using a pH adjuster, it was previously known that it is possible to impart a good flavor having both a milky feel and a fruit juice sensation by adjusting the pH to a weakly acidic range and producing it. Since blending milk in the pH range causes a problem of aggregation of milk protein, a milk beverage product having a good flavor having both milk feeling and fruit juice feeling has not been obtained.

In the preparation of such a milk drink containing fruit juice (weakly acidic milk drink), as a method for preventing the aggregation of proteins derived from milk, conventionally, the amount of fruit juice (acid component) added to milk is kept low. Alternatively, a method of adjusting the pH to pH higher than 6.3 using sodium bicarbonate or the like is adopted. However, although these methods have a milky feel, the flavor and sourness derived from fruit juice cannot be sufficiently imparted to the milk drink.

In Japanese Patent Publication No. 1-50383,
As a method for preventing coagulation and precipitation of casein powder in an acidic aqueous solution, there is described a method in which cyclic phosphates and chondroitin sulfate are mixed with sodium casein, dissolved in a liquid medium, and powdered by a spray drying method. However, this method has a problem in that it requires a complicated process such as once dissolving the casein powder together with a predetermined compound and then drying it again, which is troublesome.

On the other hand, conventionally known stabilizers for sour milk drinks include pectin, soybean polysaccharide, sodium carboxymethyl cellulose, propylene glycol alginate, and the like. The region where these stabilizers can stabilize proteins is pH3. It is a region such as ~ 4, and there was no method to sufficiently stabilize the protein in a higher pH region. Therefore, most of the conventional sour milk drinks suppress the milk content and lower the pH, and as a result,
The milky feeling is not fully exhibited. When adding a lot of milk, it is necessary to lower the pH, so that the sourness is strongly expressed and consumers who do not like strong sourness,
For example, they tended to be shunned by small children.

[0006]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a protein stabilizer capable of significantly suppressing aggregation of a protein in a weakly acidic region by applying it to a composition containing the protein. And More specifically, the present invention provides a protein stabilizer capable of suppressing protein aggregation and stabilizing the dispersion of a protein even when a protein-containing composition such as a dairy product is adjusted to a weakly acidic region. The purpose is to do. Another object of the present invention is to provide a protein-containing composition having excellent stability, in which protein aggregation is significantly suppressed even in a weakly acidic region by containing such a protein stabilizer.

[0007]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above-mentioned conventional problems. As a result, by using chondroitin sulfate or a salt thereof,
It was found that protein aggregation in the weakly acidic region of 4.5 to 6.3 can be significantly suppressed and the protein can be well dispersed and stabilized. A similar effect was also observed with shark fin extract containing chondroitin sulfate at a high concentration. As described above, the use of chondroitin sulfate or a salt thereof and a shark fin extract containing them can satisfactorily disperse and stabilize a protein in a weakly acidic region. It was confirmed that it is possible to develop a protein-containing acidic product in such a weakly acidic region, and that it is possible to prepare a food with particularly excellent palatability when applied to food. The present invention was developed based on such findings.

That is, the present invention relates to the following item 1. The protein stabilizer according to item 1. A protein stabilizer comprising chondroitin sulfate or a salt thereof.

The active ingredient of the protein stabilizer of the present invention consists essentially of chondroitin sulfate or its salt. That is, the protein stabilizer of the present invention contains chondroitin sulfate or a salt thereof as a main functional component for stabilizing a protein, and in that sense, chondroitin sulfate or a salt thereof is used as an auxiliary in stabilizing the protein. Can be distinguished from Therefore, the above item 1. The described invention can be rephrased as follows. Item 1-1. A protein stabilizer consisting essentially of chondroitin sulfate or a salt thereof. Item 1-2. A protein stabilizer whose main functional component is chondroitin sulfate or a salt thereof.

Further, the present invention is the protein-containing composition described in the following items 2 and 3 .: Item 1. A protein-containing composition comprising the protein stabilizer according to claim 1. Item 3. Item 3. The protein-containing composition according to Item 2, wherein protein aggregation is suppressed in a weakly acidic range of pH 4.5 to 6.3.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention significantly reduces protein aggregation in the region of pH 4.5 to 6.3, which is difficult to solve by weakly acidic stabilizers, which are conventionally known as stabilizers, by using chondroitin sulfate or a salt thereof. It is based on the finding that a protein-containing composition having excellent stability in the pH range can be obtained.

Examples of the salt of chondroitin sulfate used in the present invention include alkali metal salts of chondroitin sulfate such as sodium chondroitin sulfate and potassium chondroitin sulfate.

Such chondroitin sulphate or a salt thereof can be prepared from animal cartilage of sharks (shark fins), whales, cattle, pigs, birds, etc. by neutral salt method, alkali method, enzyme method, autoclave method, etc. It can be purified and prepared by a method. Further, a product having a high chondroitin content such as a shark fin extract obtained by extracting shark fins can also be used. A shark fin extract or a dried product thereof, which can be mentioned as an example of such a chondroitin-containing substance, is available, for example, from San-Ei Gen FFI Co., Ltd. under the trade name of shark fin extract C or shark fin extract powder, respectively.

The protein targeted by the present invention is a protein having a property of aggregating in a weakly acidic region. In addition,
Here, the protein targeted by the present invention does not need to aggregate in all weakly acidic regions, as long as it aggregates in one region. Further, the presence or absence of aggregation in the pH region outside this range is not particularly limited.

Proteins having such properties include
Although not particularly limited, examples thereof include milk protein, whey protein, ovalbumin, and other animal proteins derived from seafood, poultry meat, etc .; plant proteins such as soybean protein and wheat protein. From
Preferred are milk protein, whey protein and soy protein.

The main functional component of the protein stabilizer of the present invention is chondroitin sulfate or its salt. Therefore, the protein stabilizer of the present invention only needs to contain chondroitin sulfate or a salt thereof as an active ingredient, even if it is composed of chondroitin sulfate or a salt thereof, a chondroitin-containing material containing them at a high concentration, For example, it may be a shark fin extract or the like or a dry product thereof.

Further, these components may be blended with excipients, carriers or additives which are acceptable in terms of food hygiene, as long as the effects are not impaired. Such a protein stabilizer usually contains 0.05 to 10 proteins.
The composition can be used in a proportion of 0.1% by weight or more of chondroitin sulfate or its salt in 100% by weight of the final composition, relative to the composition in the weakly acidic region contained at a concentration by weight. Preferably 0.1 to 5% by weight, more preferably
The proportion is 0.3 to 3% by weight.

More specifically, according to the protein stabilizer of the present invention, pH of milk protein is in the range of 4.5 to 6.3, preferably pH 5 to 6, and whey protein is in the range of pH 4.5.
-6.3, preferably pH 5-6, ovalbumin pH 4-5, preferably pH 4.5-4.8 range, soy protein pH 4.8-6.3, preferably pH 5-6 range It is possible to preferably prevent protein aggregation and enhance dispersion stability.

In milk protein, clarification of milk protein is observed specifically in the pH range of 5.3 to 6.

The protein-containing composition targeted by the present invention refers to a general product containing a protein, but in view of the action and effect of the protein stabilizer of the present invention, a product containing a protein in a weakly acidic region. Can be preferably illustrated.

Examples of such products include weakly acidic foods and drinks containing proteins, pharmaceuticals, and various products such as quasi drugs. Specifically, lactic acid bacteria beverages, fermented milk, acidic milk beverages that acidify dairy products, protein-enhanced weakly acidic beverages, weakly acidic frozen desserts, weakly acidic desserts, and protein drinks such as milk and soymilk, fruit juices, fruits, vegetables or Examples include weakly acidic beverages prepared by adding an organic acid or an inorganic acid. In particular, liquid products such as acidic milk drinks and weakly acidic drinks are preferable in terms of their effects.

The protein-containing composition according to the present invention comprises the above-mentioned proteins (milk protein, animal protein,
In addition to the vegetable protein, chondroitin sulfate or a salt thereof which is a functional component of the protein stabilizer may be contained, but as another component, in a range that does not impair the effect of the protein stabilizer of the present invention, Sucrose, fructose, liquid sugar, glucose, oligosaccharides and other sugars, aspartame, sucralose, acesulfame K, thaumatin, stevia, alitame, neotame, depending on the type of the above-mentioned various products (food and drink, pharmaceuticals, quasi drugs) High intensity sweeteners such as: Minerals such as magnesium and calcium: Vitamins such as vitamin A, vitamin C and vitamin K: Xanthan gum, gellan gum, carrageenan (κ, λ,
ι) etc. Thickening polysaccharides: Glycerin fatty acid esters, sucrose fatty acid esters, lecithin etc. Emulsifiers: Strawberry, melon, peach, pineapple, grape, apple juice etc.
Fruit: fragrance: pigment may be mixed.

The mixing ratio of the chondroitin sulfate or its salt contained in the protein-containing composition of the present invention is such that the aggregation of the protein, which can be caused in the weakly acidic region by the action of chondroitin sulfate or its salt, can be substantially suppressed. If there is no particular limitation. Specifically, in the case of a composition containing a protein at a concentration of 0.05 to 10% by weight, the mixing ratio of chondroitin sulfate or its salt is 0.1% by weight or more, preferably 0.1 to 5% by weight, more preferably 0.3 to 3 wt% can be exemplified.

The protein-containing composition of the present invention is usually prepared according to the method for producing various products to which the present invention is applied, except that the protein-containing composition of the present invention is well dispersed in the composition using chondroitin sulfate or its salt. It can be manufactured by the method. For example, chondroitin sulfate or its salt dissolved in an aqueous solution at room temperature or under heating,
Addition of protein, stirring by a known method, if necessary, pH is adjusted with citric acid, sodium bicarbonate, etc., homogenized using a homogenizer, etc., and a method of producing by sterilizing by a conventionally known method is exemplified. it can.

[0025]

EXAMPLES The contents of the present invention will be specifically described below with reference to the following experimental examples and examples. However, the present invention is not limited to these. In addition, the unit of the prescription described below means part by weight unless otherwise specified. In the experimental examples and examples, shark fin extract (trade name: shark fin extract C, manufactured by San-Ei Gen FFI Co., Ltd.) was used as chondroitin sulfate.

Experimental Example 1 Effect of Chondroitin Sulfate to Prevent Protein Aggregation (1) (1) Chondroitin sulfate as a protein stabilizer, or various known stabilizers (water-soluble soybean hemicellulose (SSHC), pectin, carboxymethylcellulose) (CMC)) and skimmed milk powder as a protein material, various pH values (4.8, 5, 5.5)
An acidic milk drink having the following formula was prepared, and the protein aggregation preventing effect of chondroitin sulfate was evaluated.

Specifically, the preparation of an acidic milk drink is carried out by using chondroitin sulfate (final concentration: 0.1, 0.2, 0.3, 0.4, 0.5,
0.8 or 1% by weight) or various known stabilizers (final concentration: 0.4% by weight of chondroitin sulfate + 0.4% by weight of known stabilizer) are heated at 80 ° C for 10 minutes to dissolve them, and this is dissolved in water. The mixture was mixed with skim milk powder (final concentration: 3% by weight) dissolved and the pH was adjusted using citric acid and baking soda. Then, heat this to 80 ℃, 1470 with a homogenizer
An acidic milk drink was prepared by homogenizing at a pressure of 0 kPa (150 kgf / cm ² ), heating again to 93 ° C., and then hot-pack filling. As a control sample,
An acidic milk drink was prepared in the same manner as above, except that the stabilizer was not added. These were stored for 24 hours, and the presence or absence of protein aggregation after storage was evaluated.

The effect of preventing protein aggregation was determined by observing the appearance with a skilled panelist and measuring the precipitation rate. The precipitation rate was 45 g of the acidic milk drink prepared above in a 50 ml capacity centrifuge tube, stored at 4 ° C for 1 day, and then centrifuged with a centrifuge (3000 rpm, 20 min) to accumulate at the bottom of the centrifuge tube. It was determined by measuring the amount of precipitate. (Precipitation rate (%) = [weight of precipitate g / 45 g] × 100) The results are shown in Table 1.

[0029]

[Table 1]

As a result, by using chondroitin sulfate as a stabilizer in an amount of 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.3% by weight or more, at least pH 5.5, preferably pH 5 to pH 5.5. It was found that the aggregation of milk proteins can be prevented more preferably in the range of pH 4.8 to pH 5.5. Also, it was observed that the milk protein was solubilized and clarified at around pH 5.5.

On the other hand, it was found that when chondroitin sulfate was used in combination with water-soluble soybean hemicellulose, pectin or carboxymethylcellulose, which has heretofore been known as a stabilizer for acidic milk drinks, the stability of milk protein is slightly lowered. It is known that water-soluble soybean hemicellulose alone has a pH of 3.3 to 4.3, pectin alone has a pH of 3.7 to 4.4, and carboxymethyl cellulose alone has a pH range of 4 to 4.8 to prevent aggregation and stabilize milk proteins. Has been. (2) Based on the above results, 1% by weight of chondroitin sulfate was used as the protein stabilizer, and skim milk powder was used as the protein material, and various pH values (4.5, 4.
8, 5, 5.5, 6, and 6.3) were prepared, and the effect of chondroitin sulfate on protein aggregation was evaluated in the same manner as above. The results are shown in Table 2.

[0032]

[Table 2]

As a result, it was found that chondroitin sulfate can suppress and prevent the aggregation of milk proteins in the pH range of 4.5 to 6.3, preferably pH 4.8 to 6.3. Also
Milk proteins were solubilized and clarified in the region of pH 5.5-6.

From the results of (1) and (2) above, chondroitin sulfate is useful as a protein stabilizer for acidic milk drinks in the pH range of 4.5 to 6.3, and soybean polysaccharide, pectin or It was suggested that it is preferable to use it without substantially combining it with CMC.

Experimental Example 2 Effect of Chondroitin Sulfate to Prevent Protein Aggregation (2) The effect of chondroitin sulfate and sodium hexametaphosphate, which is a cyclic phosphate, was investigated together to investigate the effect of protein aggregation.

Specifically, chondroitin sulfate alone as a protein stabilizer (final concentration: 1% by weight) or a mixture thereof with sodium hexametaphosphate (final concentration: chondroitin sulfate 1% by weight + Na hexametaphosphate 0.03% by weight). %), And skimmed milk powder (final concentration: 3% by weight) as a protein material for various pH values.
An acidic milk drink having (4.5, 4.8, 5, 5.5, 6) was prepared to evaluate the protein aggregation preventing effect of the above protein stabilizer. In addition, an acidic milk drink was prepared in the same manner as above except that a protein stabilizer was not used as a control sample, and the aggregation of proteins was examined in the same manner.

The protein aggregation preventing effect was determined by observing the appearance of the sample after 24 hours of storage and measuring the precipitation rate, as in Experimental Example 1.

[0038]

[Table 3]

As shown in Table 3, when chondroitin sulfate was used in combination with sodium hexametaphosphate, almost the same protein aggregation preventing effect as when chondroitin sulfate alone was used was shown. However, the stability in the system in which sodium hexametaphosphate was used in combination tended to be slightly inferior to that in the case of using chondroitin sulfate alone.

Experimental Example 3 Effect of Chondroitin Sulfate on Protein Aggregation (3) The effect of chondroitin sulfate on aggregation was evaluated when another protein was used in place of skim milk powder (milk protein) as a protein material. Specifically, chondroitin sulfate (final concentration:
1% by weight) and whey protein (trade name: Milpro L-1 (manufactured by San-Ei Gen FFI Co., Ltd.)) as protein material, soy protein (trade name: New Fuji Pro)
V (Fuji Oil Co., Ltd.)) or ovalbumin (trade name: Non Whipping Spray DriedEgg White (GF Ovodry S.
(manufactured by rl Co., Ltd.) so that the final concentration becomes 1% by weight, respectively, to prepare protein-containing compositions having various pHs (4.5, 4.8, 5, 5.5, 6, 6.3), and stabilize the above protein. The effect of the agent on preventing protein aggregation was evaluated. Also,
A protein-containing composition was prepared in the same manner as above except that the protein stabilizing agent was not used as a control sample, and protein aggregation was examined in the same manner. The protein aggregation preventing effect was performed by observing the appearance of the state after storage for 24 hours and measuring the precipitation rate. The results are shown in Table 4.

[0041]

[Table 4]

As shown in Table 4, from the results of appearance observation and precipitation rate, whey protein was satisfactorily prevented from aggregating protein by adding chondroitin sulfate at least in the range of pH 4.5 to 6.3. It was possible. Soy protein was able to satisfactorily prevent protein aggregation in the region of pH 4.8 to 6.3 by adding chondroitin sulfate. Ovalbumin has a pH of 4.8 by adding chondroitin sulfate.
Hereafter, it was possible to satisfactorily prevent protein aggregation, particularly at least at pH 4.5 to 4.8. However, no solubilization of any protein was observed in any pH region, as was observed in skim milk powder.

Example 1 Strawberry Milk Beverage According to the formulation shown in Table 5, a strawberry milk beverage (Example 1,
Comparative Examples 1-3) were prepared.

[0044]

[Table 5]

(Production Method) (1) A mixture of sugar and a powder (pectin or chondroitin sulfate) of powder was added to fresh water, and the mixture was stirred and dissolved at 80 ° C. for 10 minutes, and then cooled to room temperature. (2) Milk and strawberry puree were added to this, pH was adjusted with citric acid or baking soda, and the total amount was adjusted to 100 ml with fresh water. (3) Heat this to 70 ℃ and homogenize it with 1470
Homogenization was performed at a pressure of 0 kPa (150 kgf / cm ² ). (4) After heating to 93 ° C., hot pack filling was performed to obtain a strawberry milk beverage. (Evaluation) For the various strawberry milk drinks obtained above,
Stability evaluation and sensory evaluation were performed. Incidentally, the stability evaluation, based on the results of the appearance observation and microscope observation of the state after storage for 24 hours by a skilled panelist,
The sensory evaluation was performed by having 12 panelists drink each beverage and answering a questionnaire about taste (sourness, ease of drinking, etc.). The results are shown in Table 6.

[0046]

[Table 6]

As shown in Tables 5 and 6, the beverage of Comparative Example 1 (pH 6.4) was a neutral milk-milk beverage prepared with a small amount of fruit juice and had good stability. However, no sourness was felt, and the original flavor of strawberries was applied. There were many opinions that the fruit juice and sourness were desired. The beverage (pH 4) of Comparative Example 2 is a sour milk beverage using conventional pectin as a stabilizer. Although the stability was good, 60% of the panelists evaluated that the sourness was strong or slightly strong. The beverage (pH 5.5) of Comparative Example 3 is a sour milk beverage adjusted to pH 5.5 using a conventional pectin as a stabilizer.
Protein aggregation occurred, the stability was very poor, and the commercial value was extremely poor.

On the other hand, the sour milk drink (Example 1) prepared using chondroitin sulfate as a stabilizer had no protein aggregation at pH 5 and had very good stability. Moreover, the original flavor and sourness of strawberry were obtained, and it was possible to prepare a good strawberry milk beverage (acidic milk beverage) that was unprecedented in terms of dispersion stability and flavor. As an evaluation, there is a fruit juice feeling, a milk feeling is also sufficient, and it has just the right sourness,
About 75% of the panelists said that it was easy to drink, and more than half of them were. From this result, it was suggested that by using chondroitin sulfate as a protein stabilizer, it is possible to produce an acidic milk drink that is acceptable to those who have not been satisfied with the conventional sour milk drink.

Example 2 Melon Milk Beverage A melon milk beverage having a pH of 5.5 was prepared according to the following formulation.

Milk 87.5 Sugar 9 1/5 Concentrated melon juice 3 Chondroitin sulfate 1 50 w / v% citric acid solution Appropriate amount 100 mL (production method) (1) Milk mixed with sugar and chondroitin sulfate powder The mixture was charged, dissolved by stirring at 80 ° C. for 10 minutes, and then cooled to room temperature. (2) 1/5 concentrated melon juice was added to this, and the pH was adjusted to 5.5 with a 50 w / v% citric acid solution. (3) Heat this to 70 ℃ and homogenize it with 1470
Homogenization was performed at a pressure of 0 kPa (150 kgf / cm ² ). (4) After heating to 93 ° C., hot pack filling was performed to obtain a melon milk drink. (Evaluation) The prepared melon milk drink had no protein aggregation and the stability was very good. In addition, it was a good melon milk beverage that had a fruit juice feeling, a milk feeling, and a just sour taste, and was unprecedented in terms of dispersion stability and flavor.

[0051] (Production method) (1) A mixture of powder of sugar and chondroitin sulfate (shark fin extract) was added to fresh water, dissolved by stirring at 80 ° C for 10 minutes, and then cooled to room temperature. (2) Add milk and 1/5 concentrated peach juice to this, and add 50w / v%
The pH was adjusted to 5 with a citric acid solution, and the total amount was adjusted to 100 mL with water. (3) Heat this to 70 ℃ and homogenize it with 1470
Homogenization was performed at a pressure of 0 kPa (150 kgf / cm ² ). (4) After heating to 93 ° C., hot pack filling was performed to obtain a peach milk drink. (Evaluation) The peach milk drink prepared by using chondroitin sulfate as a stabilizer showed no significant protein aggregation even in the acidic region of pH 5, and the stability was very good.
In addition, it was a good peach milk beverage that had never before been in view of dispersion stability and flavor because it had a fruit juice feel, a milk feel, and a good sourness.

[0052]

EFFECTS OF THE INVENTION Chondroitin acid or its salt used as a main functional component in the protein stabilizer of the present invention significantly causes protein aggregation at an acidity, particularly at pH 4.5 to 6.3 where it has been difficult to prevent protein aggregation. Can be prevented. Therefore, the protein stabilizer of the present invention is extremely useful as a protein dispersion stabilizer in such an acidic region. In particular, as described above, since there was no conventional material for stabilizing proteins in the pH range of 4.5 to 6.3, particularly in the pH range of 5 to 6, the protein stabilizer of the present invention can widely apply proteins in such pH range. It is possible to prepare a protein-containing composition having excellent stability (food and drink, pharmaceuticals, quasi drugs, etc.). The present invention also provides a composition comprising a protein stably in such an acidic region, pH 4.5 to 6.3, particularly pH 5 to 6 region.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshio Nishio             1-1-11 Sanwa-cho, Toyonaka-shi, Osaka San-ei             Within Gen FFI Co., Ltd. F term (reference) 4B001 AC03 AC44 BC13 DC01 EC53                 4B017 LC07 LG04 LK08 LK18 LL04

Claims (3)

[Claims] 1. A protein stabilizer comprising chondroitin sulfate or a salt thereof. 2. A protein-containing composition comprising the protein stabilizer according to claim 1. 3. The protein-containing composition according to claim 2, wherein protein aggregation is suppressed in a weakly acidic range of pH 4.5 to 6.3.