JPS605267B2 - Soy sauce manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing soy sauce, and more particularly, to a method for producing soy sauce that is light in color, deep red in color, and with little oxidative color gain by contacting soy sauce with cellulose-immobilized tannins.

The color of soy sauce, along with its taste and aroma, is an important element in stimulating the appetite, and it has been called ``purple'' since the Edo period due to its deep red color.

In Japanese cuisine, many efforts have been made to take advantage of the color characteristics of this soy sauce.
Dishes expressed using the color of soy sauce, such as yellow-brown tea rice, are known, and in recent years, colors have been used to preserve the natural flavors and colors of fish and vegetables used in cooking, as well as for reasons of cooking necessity. Soy sauce with a light and deep red color has come to be used favorably. in this way,
Soy sauce is a traditional naturally colored seasoning that is used in cooking not only for its taste and aroma, but also for its color, but the deep reddish bright color represented by this purple soy sauce is unstable in the presence of oxygen.
As time passes after manufacturing, the product undergoes browning due to oxidation, changing to a dark blackish color (hereinafter referred to as "oxidation color increase"), reducing its value as a product. For this reason, it has become an important issue for the soy sauce brewing industry to obtain soy sauce that is light in color, deep red in color, and with little oxidative color gain.

Therefore, in view of the above-mentioned current situation, the present inventors have conducted various studies and have developed a water-insoluble tannin preparation (hereinafter referred to as "cellulose-immobilized tannin") consisting of a tannin component covalently bonded to cellulose. ) was found to act specifically on soy sauce, decolorizing it, enhancing its reddish color, and suppressing oxidative discoloration of soy sauce.Based on this knowledge, the present invention was finally completed. did. That is, the present invention is a method for producing a light-colored soy sauce with a deep red tinge and less color increase due to acid P, which is characterized by subjecting soy sauce and cellulose-immobilized tannin to a brush treatment. The present invention will be explained in detail below. The soy sauces used in the present invention include soy sauces such as dark soy sauce, light soy sauce, tamed soy sauce, white soy sauce, and saininkomi soy sauce, which are manufactured according to the usual soy sauce brewing method, as well as soy sauces that brown and darken due to long-term storage after manufacture. Examples include soy sauce.

Furthermore, the cellulose-immobilized tannin used in the present invention contains one or more tannin compounds selected from the group consisting of tannins, activated tannins, and tannin amino/derivatives or carboxyl derivatives;
It is produced by covalently bonding one or more celluloses selected from the group consisting of cellulose, activated cellulose, and amino derivatives or carboxyl derivatives of cellulose to make the tannin compound insoluble in water.

The tannin used here may be pyrogallol tannin or catechol tannin.

Examples of pyrogallol tannin include gallic tannin,
For example, catechol tannins include catechol polymers obtained from tea, cacao, etc. These tannins do not necessarily have to be purified, such as those commercially available as persimmon juice. It may even be impure evening nin.

Activated tannins include the above tannins treated with cyanogen halides (e.g. cyanogen bromide), and amino derivatives and carboxy derivatives of tannins include alkylene diamines and tannins such as the above activated tannins. Examples include aminoalkylated tannins and carboxyalkylated tannins obtained by reacting aminoalkylcarboxylic acids (for example, aminocaproic acid). Similarly, activated cellulose includes cellulose as described above treated with cyanogen halide (e.g. cyanogen bromide), and amino derivatives and carboxy derivatives of cellulose include alkylene diamines and amino derivatives of the activated cellulose. Examples include aminoalkylated cellulose and carboxyalkylated cellulose obtained by reacting an alkylcarboxylic acid (for example, aminocaproic acid).

Next, as a means of halogenation treatment in the preparation of activated tannin or activated cellulose, the tannin or cellulose is suspended in water, the pH is adjusted to 8 to 12, and then an appropriate amount of cyanogen bromide is added. This is carried out by reacting at about 5 to 30q0 for about 5 to 30 minutes while maintaining the pH at 8 to 12.

In addition, amino derivatives of tannin or cellulose can be prepared by mixing activated tannin or activated cellulose as described above with water or a hydrophilic organic solvent such as methyl alcohol or ethyl alcohol, and adding sodium hydroxide to pH 8.
After adjusting to ~11, ethylenediamine, diaminobutane,
A diamino compound such as diamino/hexane, diaminooctane, and diaminodecane is added and reacted for about 1 to 2 hours at about 5 to 40 oo, thereby intervening a methylene group (this is called a substrate) in tannin or cellulose. be.

Next, in order to covalently bond tannin compounds and cellulose, a known method used for preparing immobilized enzymes [for example, Chibata ed., "Immobilized Enzymes", p. 11-40 "Published by Kodansha (March 20, 1975), see "Affinity Chromatography" edited by Yamazaki et al. p. 19-32, Published by Kodansha (February 1, 1975)] can.

That is, cellulose, which has a free hydroxyl group in its molecule, cannot directly covalently bond the hydroxyl group to a tannin compound, so cellulose and at least one of the tannin compounds are combined with a cyanogen halide (for example, cyanogen bromide). After being brought into contact and activated once as a diamino compound,
Suspend each in water and adjust the - to about 8 to 11 to give about 5
-4,000 for about 1 hour to 2 days to obtain cellulose-immobilized tannins, which are then separated and isolated by washing.

Note that, prior to the cyanogen halide treatment, the cellulose is preferably soaked in an aqueous sodium hydroxide solution in advance. Next, in the present invention, the cellulose-immobilized evening nin obtained as described above can be brought into contact with soy sauce using a conventional solid-liquid contact treatment means.

Namely, examples include a method of mixing cellulose-immobilized tannin and soy sauce in a container and then separating the cellulose-immobilized tannin, or a method of passing the soy sauce through a column filled with the cellulose-immobilized tannin. The continuous method is easy to operate. The fixed tannins used at this time vary depending on the type of soy sauce, but usually one of the soy sauces is
'50 to 1/400 times the capacity, preferably 1/50 to 1/
20 times the ship's capacity is sufficient. It is necessary to bring the cellulose-immobilized tannin into contact with the soy sauce until the soy sauce has the desired luster. For example, when soy sauce is brought into contact with S. V. =2
~40, preferably S. V. =2~20 Processing temperature 20~
8,000 oo, preferably 35 to 45 oo, is passed through the column filled with the cellulose-immobilized tannin. By bringing soy sauce and cellulose-immobilized tannin into contact in this manner, a light-colored soy sauce with enhanced redness and suppressed oxidative color gain can be obtained.

Here, the effects of the present invention will be explained in detail by giving experimental examples.
Experimental Example 1 400% of immobilized tannin consisting of a tannin component covalently bonded to a polymer having a group of the following notation 1 in its molecule.
Take 9 pieces of soy sauce, add it to 20 pieces of raw soy sauce produced according to the normal soy sauce brewing method, heat it at 30 qC for 30 minutes to thoroughly contact it, and then cover it with a paper towel to get the obtained product. When the soy sauce was examined for changes in color and changes in component analysis values, the results shown in Table 1 were obtained.

As is clear from this result, there are a wide range of types of immobilized tannins, but only cellulose-immobilized tannins, unlike other immobilized tannins, react specifically with soy sauce and decolorize it. It is also found that this product has the effect of enhancing the redness of soy sauce and significantly suppressing the oxidative color increase of soy sauce.

Furthermore, even if cellulose-immobilized tannin specifically reacts with soy sauce, it hardly adsorbs nitrogen components, ring sugars, etc., which are useful components in soy sauce. The measured value of chromaticity is 0.5 m (corresponding to a 10-legged cell) of 55 m (Gilford microscopic spectrophotometer). D. value, and the decolorization rate is 0 before and after treatment.
．． D. Each value is shown as a rate of decrease. The depth (degree) of redness was determined by measuring the degree of blackening of the soy sauce, that is, by measuring [(logarithm of absorbance at 50 m) - (logarithm of absorbance at 55 m)] x 2. The larger this value is, the smaller the ratio of dark colors to bright colors becomes, indicating that the overall color is bright with a deep red tinge. (Hiroshi Motai;
See Japan Brewing Association Magazine, Vol. 72, No. 1, pp. 18-20. ) Also, for oxidation color increase, first add soy sauce to 8000 and 3
Heated for ~4 hours and measured 55 m (1
0 side cell). Dilute it with distilled water so that the D value is about 3.40 (No. 11 in the standard soy sauce color number), and inject it into a test tube with a diameter of 2 arcs and a length of 20 skins.
Close the checkpoint with Parafilm (trade name of American Can Company) and leave it for 300mm for 7 days. D
．． Expressed as an increase in value. This severe test was conducted by heating at 80CO for 3 to 4 hours, diluting, and then leaving at 3030 for 7 days.
This corresponds to when the product is left at room temperature for more than 6 months.

Furthermore, the soy sauce analysis was carried out according to the standard soy sauce analysis method published on March 31, 1966, published by the Japan Soy Sauce Technical Association, Green.
In addition, the measured values of chromaticity, decolorization rate, red bead density, oxidative color increase, and soy sauce analysis shown in the experimental examples and examples shown below are values obtained according to the above-mentioned methods, respectively.

Further, various types of immobilized tannins in each category in Table 1 were prepared as follows.

Category 1. (Biogel P.10-immobilized tannin)
;Biogel P-10 (Bio Butterfly 11P-10, product name of Bio-Rad Co., Ltd.) 1 part 2N hydrochloric acid 25 parts
and 20% of 14% sodium nitrate solution,
After reacting for 1 hour, a reaction product was obtained by washing with water, which was then suspended in 50% of distilled water, and diaminohexane 2.
Add 9 of 50 and adjust the pH with 1N sodium hydroxide solution.
After adjusting the pH to 9.5, the mixture was reacted at 2500 for 20 hours, washed with water, and separated to obtain active biogel P.10.

On the other hand, add 1 part of tannin to 5 parts of 0.1N sodium carbonate solution.
Suspend at a pH of 0.0 and adjust the pH to 1N with 1N sodium hydroxide solution.
was adjusted to 11.0, then 200% cyanogen bromide was added and reacted at about 20% for 8 minutes to obtain active tannins. Next, after suspending the above-mentioned activated biogel P-10 and activated tannin in 50 parts of water, the pH was adjusted to 10.5 with a 0.1N sodium hydroxide solution, and the pH was adjusted to 2000 for 2 hours. It is obtained by reacting, separating and drying. Category 2. (Cowhide powder solidified tannins): This product was obtained by processing in exactly the same manner as in Category 1 except that cowhide powder (trade name of Wako Pure Chemical Industries, Ltd.) was used instead of Biogel P-10.

Category 3. (Polyamide C-200-immobilized tannin): In the above Category 1, it was treated in exactly the same way except that Polyamide C-200 (trade name of Wako Pure Chemical Industries, Ltd.) was used instead of Biogel P-10. That's what I got.

Category 4. (Nylon-immobilized tannin): This product was obtained by processing in exactly the same manner as in Category 1 except that powdered nylon (manufactured by Toray Industries, Inc.) was used instead of Biogel P.10.

Category 5. (cellulose-immobilized tannin); cellulose 1
Suspend the solution in 50% of 0.1N sodium carbonate solution and add 1
Adjust - to 11.0 with normal sodium hydroxide solution,
Next, add 200 parts of cyanogen bromide and make about 2000 parts of 1 part.
After reacting for 2 minutes, it was separated after washing with water, suspended on 50% distilled water, 250% diaminohexane was added, the pH was adjusted to 9.5 with 1N sodium hydroxide, and the mixture was heated at 250 °C.
The reaction mixture was reacted for 2 hours at 100 mL of water and separated to obtain activated cellulose.

On the other hand, 1 ton of tannin was suspended in 50 g of 0.1N sodium carbonate solution, and the pH was adjusted to 11 with 1N sodium hydroxide.
．． 0, add 200 parts of cyanogen bromide, and add about 20 parts of cyanogen bromide.
qo for 8 minutes to obtain activated tannins. next,
The activated cellulose and active tannins obtained as above were suspended in 50°C of water, adjusted to pH 10.5 with 1N sodium hydroxide solution, reacted at 20°C for 2 hours, and then washed with water. The mixture was separated and dried to obtain cellulose-immobilized tannin.

・Category 6. (Sephadex G 25 immobilized tannin); Category 5. , Cephadex G instead of cellulose.

25 (trade name of Aalmacia Co., Ltd.) was treated in exactly the same manner.

Category 7. (C.P. 10-immobilized tannin); Category 5. It was obtained in exactly the same manner except that CP 10 (trade name of Electron Eucleonics Co., Ltd.) was used instead of cellulose.

Category 8. (Celite-immobilized tannin); Category 5. It was obtained by the same process except that celite was used instead of cellulose.

Table 1 Experimental Example 2 Preliminarily add 25% sodium hydroxide solution to 500 min.
100 grams of cellulose obtained by splitting was suspended in 500 grams of 0.1N sodium carbonate solution, the pH was adjusted to 11.0 with 1N sodium hydroxide solution, and 20 grams of cyanogen bromide was added. Add and react for 12 minutes at about 20q0,
Separate and divide into 6 sections of 10 minutes each, and add 1 portion of distilled water to each section.
00', added various alkylene diamines of the second notation, adjusted the axis to 9.5 with 1N sodium hydroxide solution, and reacted at 20q0 for 2 feeding hours to obtain 6 types of active cellulose. Ta.

On the other hand, 10 ml of tannin was suspended in 100 ml of 0.1 N sodium carbonate solution, the pH was adjusted to 11.0, 2 ml of cyanogen bromide was added, and the reaction was carried out at about 20 ml for 8 minutes to dissolve active tannins. Obtained.

Next, after suspending the active cellulose and active evening nin obtained in the above manner in 300 ml of water, the spots were adjusted to 10.5 with 0.1 N sodium hydroxide solution, and fed 2 times at 20:00. The mixture was reacted for a period of time, then washed with water, and separated and dried to obtain six types of cellulose-immobilized evening nins each having a different number of methylene groups in the baser.

Next, various immobilized tannins 40 obtained in this way
9 of 0 is raw soy sauce made according to the normal soy sauce brewing method 2
After adding 7 pieces of soy sauce and keeping it warm for 30 minutes, we made 3 powders to fully contact each other, and then covered them with a piece of paper, and examined the resulting soy sauce for changes in color and component analysis values. The results shown in Table 2 were obtained.

These results show that as the number of methylene groups in immobilized evening nin increases, the effect of decolorizing soy sauce and suppressing the oxidative coloring of soy sauce increases as the number of methylene groups in the subaser increases, and soy sauce with a deep redness can be obtained. Those with a methylene base of 8 or more,
It turns out that the effect is excellent. Furthermore, it can be seen that even when soy sauce is brought into contact with cellulose-immobilized tannins, there is almost no loss of useful components in soy sauce. Table 2 Experimental Example 3 Take 200 pairs of cellulose-immobilized tannins of Category 6 prepared in Experimental Example 2 above, add 1 cup of 20' of raw soy sauce produced according to the usual soy sauce brewing method, and then As shown in Table 3, after incubation at each temperature for 10 minutes, the soy sauce was incubated for 30 minutes and then filtered through thick paper, and the color of the obtained soy sauce was examined, and the results were as shown in Table 3. was gotten.

These results show that the higher the temperature, the greater the inhibitory effect on oxidative discoloration, and that the decolorization rate and redness enhancement effect of soy sauce are 35 to 35%.
It can be seen that the best effect can be obtained at 45oo.

Table 3 As shown, according to the present invention, it is possible to achieve a light color and a deep reddish color by using an extremely simple method without losing most of the useful ingredients in soy sauce, and in addition, it is possible to achieve You will get less soy sauce.

In addition, it is possible to effectively decolorize product soy sauce that has oxidized and turned black due to being left unused for a long time, making it lighter in color and recovering its redness to a level greater than that of product soy sauce that has been heated. Deteriorated incense can be removed. The present invention will be explained in more detail below with reference to Examples. Example 1 10×9 cellulose-immobilized tannins of category 4) obtained in Experimental Example 2 were added to one ingredient of raw soy sauce produced according to the normal soy sauce brewing method, and after preheating to 35q0, it was soaked for 30 minutes. Next, the soy sauce obtained by passing it through a sand cloth, and the soy sauce obtained by heating and pasteurizing this at 8,000 °C for 4 hours and rapidly cooling it to 30 ° C. were compared with the original untreated raw soy sauce and the soy sauce that was pasteurized. After considering it, I got a result similar to the third notation game.

From this result, raw soy sauce (total nitrogen 1.5, reducing sugar 3.50
) has been bleached by 23.7% compared to the original raw soy sauce, and the red color has been noticeably strengthened, and for the hot soy sauce, it has been bleached by 23.5% compared to the original hot soy sauce, and the red color has been significantly strengthened. A soy sauce with a strong flavor and oxidative discoloration suppressed by 26% was obtained.

Table 4 Example 2 The same cellulose-immobilized tannin as in Example 1 was packed into a cylindrical column with an inner diameter of 6 and a length of 100 cm, and 35 q from the top.
150 pieces of raw soy sauce kept warm at S.C. V. When we compared the raw soy sauce obtained by passing the solution at a rate of 5 and the fired soy sauce that was heated and fired at 85q0 for 4 hours with the original untreated raw soy sauce and fired soy sauce, we found that: As shown in Table 5, soy sauces were obtained which were light in color, had a deep reddish tinge, and had little oxidative color gain.

Table 5 Example 3 3000, concentrated □ stored in a plastic container for 7 months
50 pieces of soy sauce A, B and 30q○, 500 pieces of light soy sauce stored in a plastic container for 10 months and C. The same cellulose-immobilized evening nin as in Example 1 was added to each of D for 10 days, heated to 30 qC, heated for 20 minutes, and then filtered through a monkey cloth.The resulting soy sauces were as shown in Table 6 and As shown in Table 7, soy sauce was obtained which was decolorized by 33 to 45% and whose redness was recovered to a level greater than that of the product immediately after pasteurization.

In addition, all of the processed soy sauces had the aroma degraded by oxidation removed, and were almost as good as the products immediately after firing. Table 6 Table 7

Claims (1)

[Scope of Claims] 1. A method for producing soy sauce, which comprises contacting soy sauce and cellulose-immobilized tannin. 2. The method for producing soy sauce according to claim 1, wherein the contacting is carried out at 35 to 45°C. 3. The method for producing soy sauce according to claim 1, wherein the cellulose-immobilized tannin has a spacer having two or more methylene groups.