JPS587262B2 - Greta - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a fibrous high-protein food, and more particularly to a method for producing a fibrous high-protein food with excellent heat softening resistance.

In recent years, research on artificial fibrous proteins such as so-called artificial meat has progressed, and some attempts have been made to put them into practical use.

The present inventors also previously treated non-fibrous protein with a proteolytic enzyme under certain conditions, stretched it and modified it into fibrous protein, and produced a fibrous protein food with a meat-like texture. He invented a method to do so (% Kosho No. 46-29870).

In this method, a non-fibrous protein, such as casein, is micelle-formed with calcium, treated with a proteolytic enzyme to form a gel, and this gel is stretched to form an oriented fibrillar composition, which is then fixed with acid. The fibrous composition obtained by such a method has low heat resistance, so when heated during cooking,
There is a risk of softening and loss of fiber form.

It has been found that such softening due to heat can be prevented by using acetic anhydride for its fixation (see Japanese Patent, supra).

However, this acetic anhydride has safety problems as a food additive, and has a strong pungent odor, which causes problems in handling and product purification, so it cannot be used in practice.

Under these circumstances, the present inventors have discovered a fixing method for producing an excellent fibrous high-protein food that has excellent anti-thermal softening properties and does not cause heat softening even when mixed with other fish and livestock meats. As a result of extensive research, we have found that an aqueous solution containing at least one type of condensed or esterified phosphoric acid compound having two or more phosphoric acid groups in one molecule, or a small number of the above phosphoric acid compounds, can be used as a fixing bath. It has been found that by using a mixed aqueous solution containing acetic acid and sulfuric acid, it is possible to produce a fibrous protein that has significantly better anti-thermal softening properties than the above method.

These phosphoric acid compounds are widely present in natural foods and are also widely used as additives, and have the advantage of being almost tasteless and odorless, and are
Not only is it easy to handle, but even if some remains in the product, there is no need to purify it.

For example, 20% casein solution (% indicates weight %).

The same applies hereinafter) is added with an aqueous calcium chloride solution, and then treated with protease to form a gel obtained by spreading it into an oriented fibrillar composition, which is then treated with a normal acid and the above-mentioned phosphoric acid compound, When the heat softening resistance was investigated, the results shown in Table 1 below were obtained.

In addition, the heat softening resistance in the table indicates that the treated fibrous material is
The results are shown when heated for 0 minutes, +++: No fibrous change, ++: Most of the fibrous remains, +: A little fibrous remains, Soil: Almost no fibrous, -: No fibrous at all. None (used in the same manner hereafter).

As is clear from the results in Table 1, fixation with acetic anhydride shows excellent anti-heat softening properties with no change in fiber properties even after heat treatment at 80°C for 20 minutes, but acetic acid shows remarkable anti-heat softening properties. It is inferior, and after heat treatment at 80° C. for 20 minutes, the fibrous material completely disappears.

Next, regarding phosphoric acid compounds, as is clear from conventional knowledge and Table 1, it is clear that orthophosphoric acid does not impart anti-thermal softening properties, and is not a problem at all as a fixed bath. It wasn't.

However, we unexpectedly discovered that sodium pyrophosphate with a degree of phosphoric acid condensation of 2 has anti-thermal softening properties as shown in Table 1, and as a result of further tests, It has been discovered that the heat softening resistance of this phosphoric acid compound is improved as the degree of condensation increases.

In addition, this effect is the same for phosphoric acid ester compounds; when the number of phosphoric acid groups in one molecule becomes 2, anti-thermal softening properties are discovered, and as the number of phosphoric acid groups increases beyond that, the anti-thermal softening properties are further improved.
In particular, it has been found that when phytic acid, which is a hexanoic acid ester of inosyte, is used, excellent anti-thermal softening properties equivalent to those of acetic anhydride are exhibited.

That is, in order to improve the heat softening resistance of a fibrous composition, a compound having two or more phosphoric acid groups in one molecule is effective, and a compound having six or more phosphoric acid groups is particularly preferable. Acid condensation or esterification compounds are very effective.

Compounds that fall under this category include phosphoric acid condensates having two or more phosphate groups, such as sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and sodium ultraphosphate, as well as glyceric acid diphosphate esters and fructose diphosphate esters. Examples include esterified compounds having two or more phosphoric acid groups in one molecule such as phytic acid, phytic acid, and phosphorylated starch.

By fixing the oriented fibrillar composition with a 0.1 to 30% aqueous solution of these, a fibrous protein with excellent heat softening resistance can be obtained.

Here, the fixation time can be shortened by increasing the concentration of the aqueous solution, and the fixation time can be adjusted depending on the concentration.

Particularly desirable fixatives include sodium hexametaphosphate, sodium ultraphosphate, and phytic acid having six or more phosphate groups in one molecule.

Next, the pH of each 1% solution of the above three types of phosphoric acid compounds, which exhibit particularly excellent fixation effects, was adjusted with hydrochloric acid or aqueous caustic soda solution to obtain fixative solutions with various pH values, and then a casein fibrillar composition was prepared. When treated and examined for its anti-thermal softening properties, the results shown in Table 2 were obtained.

As is clear from Table 2, when a phosphoric acid compound is used as a fixing bath, the anti-thermal softening property of the obtained fibrous protein is
For phytic acid, which shows the best fixing effect, p
It was found that the anti-heat softening property was highest at pH 0.5 to 5.0, and the best anti-heat softening property was given at pH 1 and 5 to 2.5 for each phosphoric acid compound.

A comparative study of various acids as H-donating components that should be added to achieve these pH values revealed that the addition of sulfuric acid made the product more stable than when each phosphoric acid compound was used alone or when used in combination with other acids. It was discovered that the anti-thermal softening properties of

Some of the above results are shown in Table 3.

When sulfuric acid is used in conjunction with fixation with phosphoric acid compounds,
As shown in Table 3, the heat softening resistance was further improved, and when compared with the results in Table 1, it is clearly recognized that this effect acts as a synergistic effect due to the use of sulfuric acid.

Therefore, if this method is used, it is possible to obtain a product with excellent heat softening resistance even if a phosphoric acid compound with a small number of phosphoric acid groups is used.

Even if sulfuric acid is added as a sulfate salt such as sodium sulfate or magnesium sulfate, the effect remains the same.

The raw material milk protein used in the method of the present invention is usually used as a solution by dissolving it in an aqueous solution of an alkali metal salt such as sodium hydroxide or potassium carbonate, an alkaline phosphate such as sodium phosphate, or ammonia. p
The H value is preferably 6 to 9, and the concentration is preferably about 5 to 30%.

This milk protein may be used in the form of a mixture with other non-fibrous animal and vegetable proteins such as soybean protein and gluten.

Examples of multivalent metal ions used for micellization of milk proteins include calcium ions (Ca 廿) and magnesium ions (Mg 廿), and specific examples include calcium chloride, calcium bromide, calcium nitrate, and calcium acetate. Water-soluble calcium salts such as, water-soluble magnesium salts such as magnesium chloride, magnesium bromide, magnesium nitrate, and magnesium sulfate are used.

A method of destroying the formed micelles and forming a gel is to add a proteolytic enzyme such as bacterial protease, fungal protease, trypsin, gimotrypsin, papain, etc. and vortex the mixture in a room or under heating (usually 40 to 60°C).
Although a method of treatment with a reducing agent is preferred, a method of treatment with a reducing agent may also be adopted instead of this enzyme treatment.

As a method using a reducing agent treatment, a reducing agent such as a sulfite such as sodium bisulfite, β-mercaptoethanol, sodium monothiophosphate, or sodium borohydride is added to an alkaline solution of the protein, usually as a 1 to 10% aqueous solution. , at room temperature or under heating (usually 40-60℃)
) is gelled by stirring.

The obtained gel is subjected to stress such as stretching according to a conventional method to form an oriented fibrillar composition.

As for how to apply these stresses, common mechanical stress methods such as one-roller stretching, roller rolling, screw extrusion, stirring, and high-speed extrusion (jet injection, etc.) are used.

In addition to applying stress to the gel to orient it, the fixing treatment can also be carried out while applying stress to the gel and orienting it. Fibrous proteins can also be obtained.

By further adding appropriate pigments, seasonings, flavors, etc. to the fibrous protein obtained by the method of the present invention, a fibrous high-protein food with excellent appearance, texture, and taste can be obtained.

Next, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 100 g of casein and 10 g of soybean protein are added and dissolved in 400 ml of 20% potassium carbonate aqueous solution at 50°C.

Add 33 ml of a 30% calcium chloride aqueous solution to this to form micelles.

When 200 mg of protease is added to the micelles, the micelles aggregate to form a gel.

This gel was spread, oriented and fibrillated, fixed by immersion in 1% phytic acid, washed with water, and neutralized to obtain about 400 g of fibrous protein with a water content of 75%.

There was no change in the fibrous properties of this fibrous protein even after heat treatment at 80° C. for 20 minutes.

Example 2 90 g of casein in 400 ml of 1.5% KOH solution
30 ml of a 30% aqueous calcium chloride solution is added at 50°C to form micelles, and when 200 ml of protease is added to the micelles, the micelles aggregate to form a gel.

This gel was spread, oriented and fibrillated, fixed by immersing it in a 1% ultrasodium phosphate solution, washed with water, and neutralized to obtain about 280 g of fibrous protein with a moisture content of 70%.

Most of this fibrous protein remained fibrous after heating at 80° C. for 20 minutes.

Example 3 Add 100 g of casein to 400 ml of 50° C. warm water, stir to suspend, and add 4.5 ml of 28% aqueous ammonia to dissolve.

Add 33 ml of 30% calcium chloride solution to this to form micelles.

When 2007% of grotease is added to these micelles, the micelles aggregate and form a gel.

This gel was spread, oriented and fibrillated, fixed by immersing it in a 1% sodium chloride metaphosphate solution adjusted to pH 2.5 with sulfuric acid, washed with water, neutralized, and reduced to 75% water content.
About 3,602 fibrous proteins were obtained.

The fibrous protein obtained by adjusting the pH with hydrochloric acid is heated at 80°C.
After heating for 20 minutes, some fibrous protein remains, whereas the fibrous protein obtained by this method using sulfuric acid has improved heat softening properties, and after heating under the same conditions, most of it remains in fibrous form. The remaining.

Example 4 100 g of casein was suspended in 400 ml of 50°C warm water,
Add 6.0 ml of 28% aqueous ammonia to this and dissolve.

Add calcium chloride aqueous solution (calcium chloride to 1 O
g) to form micelles.

After forming micelles, 200 mg of grotease was added to obtain a gel.

This gel is separated from the syneresis liquid, extruded through a slit under pressure, and further stretched three times between rollers to form an oriented fibrillar composition.

This was immersed in 0.5% phytic acid solution to fix it, washed with water,
After neutralization, about 300 g of fibrous protein with a water content of 70% was obtained.

There was no change in the fibrous properties of this fibrous protein even after heating at 80° C. for 20 minutes.

Example 5 100 g of casein was suspended in 400 ml of 50°C warm water,
Add 6.0 ml of 28% ammonia water to this and dissolve.

Add 33 ml of 30% calcium chloride solution to this to form micelles.

After forming micelles, 200 mg of protease is added to aggregate the micelles to obtain a gel.

This was separated from the syneresis liquid, extruded through a slit, further stretched to 2 times between rollers, then fixed while being stretched to 1.5 times in a 0.5% phytic acid solution, and then 1% phytic acid. Fix in acid solution.

This is washed with water and neutralized to produce approximately 30% fibrous protein with a water content of 72%.
Obtained 0g.

Even when this fibrous protein was heated at 80° C. for 20 minutes, there was no change in its fibrous properties.

Claims (1)

[Claims] 1. Proteolytic enzymes are added to milk protein, a mixture of it and other non-fibrous animal and vegetable proteins, or a micelle obtained by the action of multivalent metal ions to form a gel, and this gel is subjected to stress. An aqueous solution containing at least one condensation or esterification compound of phosphoric acid having two or more phosphoric acid groups in one molecule, or the above-mentioned phosphoric acid A method for producing a fibrous high-protein food having excellent heat-resistant softening properties, which comprises fixing the food at a pH of 0.5 to 5 in a mixed aqueous solution containing at least one acid compound and sulfuric acid.