JP3131898B2 - Bread making method using ferrous sulfate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing bread and an agent for improving bread dough, and more particularly to a method for preventing potassium bromate added as an oxidizing agent in dough from remaining in a finished bread. About technology.

[0002]

2. Description of the Related Art Potassium bromate has been widely used worldwide since it was recommended in the United States in the 1910s as a bread making improver. However, in Japan, the amount of potassium bromate used for bread making is limited. In addition, the bromic acid must be not more than 0.03 g per 1 kg of flour, and there is a use standard that potassium bromate used must not remain in the product.

[0003] Conventionally, as a method for preventing potassium bromate from remaining in bread, a fermentation time or baking time for bread dough is sufficient to complete the chemical reaction of potassium bromate, Either the addition amount has been reduced, or a combination thereof has been used. In addition, the inventors have already developed a method for preventing potassium bromate from remaining in bread by adding ascobic acid (Japanese Patent Application Laid-Open No. Hei 8-116857).

[0004]

However, according to the high-performance liquid chromatographic measurement method described below, which was developed by the inventors, a method of preparing a fermentation time and a baking time that is very short, and using a large amount of potassium bromate as an improving agent. In the case of making bread by a manufacturing method such as a short process method or a no-time method performed in other countries, and further, in the case of a method of making some confectionery bread or a method of making bread using frozen dough, the reaction of potassium bromate is a chemical reaction. It has been found that the reaction may not be complete due to the reaction, and the possibility of remaining even a little remains. This is because the detection limit of potassium bromate in the measurement method is as large as 3 ppb in bread, which is larger than the detection limit of 30 ppb in the conventional measurement method developed by the inventors (see the above publication and JP-A-7-83890). Although confirmed by the lowering of the limit value, the present invention was newly developed in order to eliminate the minute residual.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and the problem is that even if potassium bromate is added in an amount sufficient to obtain an effect as an oxidizing agent, it does not remain in the final product. Another object of the present invention is to provide a method for producing bread of good quality, and an improving agent therefor.

[0006]

In order to solve the above-mentioned problems, a method for producing bread according to the present invention is directed to a method for producing bread using potassium bromate, wherein ferrous sulfate is added to the dough. Do not leave potassium bromate in the bread obtained by baking, or reduce the residual amount, further complete ferrous sulfate potassium bromate It is characterized in that it is an active ingredient that does not remain in the bread, which is a product, or that reduces the remaining amount.

In the present invention, it is desirable to use ferrous sulfate together with ascorbic acid in both the method for producing bread and the agent for improving bread dough.

[0008]

[Function] Ferrous sulfate added to bread dough (including sponge) functions as a good iron fortifier in relation to bread dough, but a reducing agent or the like in relation to potassium bromate. Works to complete the chemical reaction of potassium bromate. The present invention has been basically completed based on such knowledge.

Further, when ferrous sulfate and ascorbic acid are used in combination, bread-making properties can be improved while the effect of reducing potassium bromate is completed.

[0010]

The present invention will be described in detail below with reference to working examples of the production method and the improving agent according to the present invention. Note that ferrous sulfate is represented by the chemical formula of FeSO ₄ ,
Water salt) and dried products (1-1.5 water salt), which are called ferrous sulfate (crystal) and ferrous sulfate (dry), respectively. Ferrous sulfate (crystal) was designated as a food additive in 1957, and ferrous sulfate (dried) was added in 1964.
These two are collectively referred to as ferrous sulfate.
The production method is as follows by adding iron and dilute sulfuric acid. F
_{e + H 2 SO 4 + 7H} 2 O → FeSo 4 · 7H 2 O
(Crystal) + H ₂ dried product is obtained by drying the crystal obtained above at 40 ° C. to obtain a powder. The ferrous sulfate in the present invention may be either a crystalline product or a dried product, but in the examples, a higher purity crystalline FeSO
Using the ₄ · 7H ₂ O.

Example 1 The bread to be manufactured was rolled bread (confectionery bread) by a medium-class production method. First, the blending of the raw material of the bread to be a sample is based on 100 parts of flour (second-strength flour for bread, 14.0% moisture-based, 0.52% ash, 13.2% protein). -3.5% of strike, 0.1% of fast food (containing no oxidizing agent), 0.15 pp of potassium bromate
m, ferrous sulfate 5, 10, 15, 20, or 37 mg / 1
00g powder, water 54.0%, granulated sugar 28.0%,
Salt 0.7%, shortening 5.0%, egg 4.0%.

[0012] 70% of the flour has 2.5% yeast, 0.1% yeast food, 0, 15 pp potassium bromate.
m, ferrous sulfate 5, 10, 15, 20, or 37 mg / 1
00g powder, 3.0% of granulated sugar and 40.0% of water were added and the medium speed (200 rpm) at low speed (100 rpm) for 3 minutes.
m) for 2 minutes and knead to 26 ° C. to make a medium seed. The sponge was fermented at 27 ° C. (75% relative humidity) for 2 hours. The dough is mixed with all the remaining ingredients except for the shorting, and mixed at a low speed (100 rpm) for 2 minutes and at a medium speed (200 rpm) for 2 minutes 30 seconds.
m) for 2 minutes and at a medium speed (200 rpm) for 3 minutes and 30 seconds, and kneaded to 28 ° C. The dough was aged for 50 minutes, weighed and weighed to 80 g, and the dough was aged for another 20 minutes, molded as it was, and placed on a top plate. Then 38 ° C
(85% relative humidity) for 60 minutes with a proofer, 220 ℃
For 9 minutes.

Example 2 A fermented bread made by the middle-class method was prepared by adding ferrous sulfate to 15 mg / 100 g powder and using the same raw material composition as in Example 1, except for the same steps as in Example 1. 2 whole
The dough kneaded at 8 ° C is aged for 50 minutes, weighed and weighed to 55 g, then aged for 20 minutes, wrapped in 55 g of bean paste, placed on a top plate, and then placed at 38 ° C (85% relative humidity).
And baked at 220 ° C. for 10 minutes.

Comparative Example 1 Example 1 was repeated except that ferrous sulfate was removed from the raw material mixture of Example 1 above.
A roll bread baked by the same manufacturing method as in Comparative Example 1 was used.

Comparative Example 2 An anpan baked by the same manufacturing method as in Example 2 except that ferrous sulfate was removed from the raw material mixture of Example 2 was used.
And

Example 3 The bread using frozen dough to be manufactured was rolled bread (confectionery bread) by a direct kneading method. First, the ingredients of the bread to be sampled were wheat flour (first-class strong flour, 14.0% moisture base).
With 0.37% ash and 11.8% protein)
The amount of yeast is 5.0%, the amount of yeast food is 0.5% (containing no oxidizing agent), the amount of potassium bromate is 0, 15 ppm, and the amount of ferrous sulfate is 10, 15, 20, or 30.
mg / 100 g powder, ascorbic acid 100 ppm, water 50.0%, granulated sugar 25.0%, salt 0.7%,
Shortening is 5.0% and eggs are 4.0%. The dough is
Low speed (100 rpm) for 2 minutes, medium speed (200 rpm)
For 3 minutes, then add shorting and mix for 2 minutes at low speed (100 rpm) and 5 minutes at medium speed (200 rpm), knead to 24 ° C, bake the dough for 10 minutes and weigh to 80 g. The mixture was rolled, aged for another 15 minutes, molded as it was, and rapidly frozen at -25 ° C. 1
Thaw the dough stored frozen for 0 days at 24 ° C. for 50 minutes.
Remove the stove at 0 ° C (75% relative humidity) for 90 minutes,
Baking at 5 ° C. for 10 minutes.

Comparative Example 3 A roll bread which was frozen and baked by the same production method as in Example 3 except that ferrous sulfate was excluded from the raw material mixture of Example 3 was designated as Comparative Example 3.

The residual amount of potassium bromate in the bread baked in this manner was measured by a bromate determination method using a high-performance liquid chromatograph equipped with a post-column reaction apparatus as described below. The limit of detection by the quantitative method is 3 ppb as the concentration in bread.

The following instruments and devices were used for inspection. 1) Silver cartridge column: An OnGuard-Ag (trade name) cartridge column manufactured by Dionex, Part No. 039637, which was previously washed with 10 ml of HPLC water was used. 2) Disposal disc filter: Gelman N
ylon acrodisc 0.45 umx 25 mm, Part No. 4438 3) Cation exchange cartridge column: Varian Bon
d Elut PRS Cartridge Column, Part No. 1210-20
39 (500 mg / 3 cc) used was washed in advance with 10 ml of methanol and then with 10 ml of water for HPLC. 4) Solid phase extraction cartridge column: Sep-Pak manufactured by Waters
Plus tC18 Environmental (900mg), Part No.WAT0368
00 in advance in 10 ml of methanol, followed by HPLC
Washed with 10 ml of water for use. 5) Ultrafiltration cartridge filter: manufactured by Millipore
Molcut L Cat. No. UFP2 TTK 6) Refrigeration centrifuge: Model CR20B2 manufactured by Hitachi, Ltd. and an angle rotor of 50 ml × 8 were used. 7) Food processor: CQM-62 manufactured by Toshiba Corporation 8) High-performance liquid chromatograph with post column reactor (H
PLC): Waters Pump 616 LC system, Autosampler Model 717, Detector Model 486, Thermostat Mod
el CHM, reaction coil Model RXN 1000, data processing device Millennium, LaboCo-Tech post column pump
Model MP-311 Inert specification

The following reagents were used. 1) Water: In this embodiment, extraction of bromate ion from the sample and subsequent cleanup use water distilled after ion exchange, and the mobile phase of the post-column high-performance liquid chromatography and the cartridge column. Water for high performance liquid chromatography manufactured by Kanto Chemical Co. was used for washing. 2) Potassium bromate: Reagent grade manufactured by Junsei Chemical Co., Ltd. 3) Methanol: for high performance liquid chromatography manufactured by Kanto Chemical Co., Ltd. 4) o-Dianisidine dihydrochloride: Sigma
Chemical Co. 5) Nitric acid: manufactured by Kanto Chemical Co., Ltd. for precision analysis, 70% 6) Tetrabutylammonium hydroxide (T
BAH): 40% solution, Aldrich Chemical Co., Inc. 7) Potassium bromide: IR manufactured by Oken Kogyo (Oken)
For analysis 8) Other reagents: Reagent grade 9) Bromic acid standard solution: In this example, 130.5 mg of potassium bromate was precisely weighed, dissolved in water and dissolved in 100 ml.
Solution (1 ml of this solution is 1000 μg as bromic acid)
Was appropriately diluted with water to prepare a 1-20 ng / ml solution, which was used as a standard solution. 10) Post-column reaction reagent: 700 mL of distilled water for HPLC
90g of 70% nitric acid (60ml), 10g of potassium bromide
And O-dianisidine dihydrochloride 50
0 mg was added while dissolving using 200 mL of methanol for HPLC (completely dissolved without leaving any precipitate),
The volume was made up to 1000 ml using distilled water for HPLC.

A high performance liquid chromatograph with a post column reactor was measured under the following conditions. The sample extraction solution was introduced into HPLC using an autosampler, and after separating bromic acid and contaminants by a column, the solution was subsequently mixed with a post-column reaction reagent in a reaction coil, and the reagent in the reagent was subjected to an oxidation reaction of bromic acid. O-dianisidine is colored and detected at a detection wavelength of 45.
The measurement was performed using 0 nm. 1) Mobile phase: HPLC in 700 ml of distilled water for HPLC
200 ml of methanol for use, 2 g of glacial acetic acid, 19 g of TBAH
Is adjusted to pH 6.3 to 6.5 with TBAH, and the volume is adjusted to 1000 ml with distilled water for HPLC. The flow rate of this mobile phase was 1 ml / min. 2) Column: Zorbax analytical column SB C-18 Column
(4.6 mm x 25 cm, 5 um) and guard column SB C18
(4 mm x 1.25 cm) 3) Flow rate of post-column reaction solution: 0.3 ml / min 4) Reaction temperature: 60 ° C 5) Injection volume: 250 μl 6) Measurement wavelength: 450 nm 7) Mobile phase and post-column reaction reagent It was always degassed with helium gas (10 ml / min).

Using the above samples, instruments, reagents, and devices,
The amount of residual bromic acid in the bread was measured by the following procedure. First,
Bread sample 1 crushed and homogenized by a food processor
0.0 g was collected in a 100 ml glass beaker, 50 ml of water was added as a solvent, and a magnetic star was added for 30 minutes.
After stirring at room temperature with a mixer, the supernatant was centrifuged at 5 ° C for 15000 r.
Centrifuged at pm for 15 minutes. The supernatant was used as a filter paper No. Filtered through 2. Plastic syringe (1
0 ml), collect about 10 ml of the filtrate, and dispose it.
The liquid was passed through a serially connected Zarudisk filter, solid-phase extraction cartridge column, and silver cartridge column in this order. Discard the first 3 ml and load 3 ml of the subsequent permeate into an ultrafiltration cartridge filter,
The flow-through was loaded onto a cation exchange cartridge column. The first 1 ml was discarded, and the subsequent passing solution was used as a sample solution for HPLC.

The obtained HPLC sample solution (250 μm)
was injected into a high-performance liquid chromatograph equipped with a post-column reactor, bromic acid was separated, and according to the obtained peak height,
Bromic acid in the sample solution was quantified from the regression equation of the calibration curve prepared from the bromate standard solution in advance.

Tables 1 to 3 below show the results of the bromic acid residual test obtained by the above measurement method.

[Table 1]

[Table 2]

[Table 3]

In these tables, potassium bromate (K
The amount of BrO ₃ ) added and the amount remaining are as follows: Bromic acid (HBr)
O ₃ ) content is unified and described as potassium bromate unless otherwise specified. Also, the value of "Remaining amount"
The average value at five repetition points is shown. Further, "not detected" means that the detection limit of the above-mentioned measurement method is 3 ppb.
Means less than.

As a result, the amount of potassium bromate added was 15 p.
At pm, in the case of potassium bromate alone, 11 ppb in Comparative Example 1, 17 ppb in Comparative Example 2, and 3 ppb in Comparative Example 3.
7 ppb potassium bromate was detected from the final product bread, whereas ferrous sulfate was added at 15 mg / 100 g.
When more than powder was added, potassium bromate was not detected in any of Examples 1 to 3.

Example 4 Example 1 In the case of using ascorbic acid in combination with 15 ppm of potassium bromate and 15 mg / 100 g of ferrous sulfate in which no residual potassium bromate was observed in the middle-class method roll bread of Example 1, The effect of improving the baking quality was shown. That is, potassium bromate 1
Add 5ppm and ferrous sulfate 15mg / 100g powder,
Further, 5, 10, and 15 ppm of ascorbic acid were added, and the other conditions were the same as in Example 1 to prepare a roll bread. The results of a comparison of the quality of the resulting bread by evaluation by 20 trained panelists are shown in Table 4 below.

[Table 4]

In Table 4, Comparative Example 4 added only 15 ppm of potassium bromate and did not add ferrous sulfate and ascorbic acid, and Comparative Example 5 added potassium bromate 15 ppm.
ppm and ferrous sulfate 15 mg / 100 g powder were added, and ascorbic acid was not added. Others were prepared under the same conditions as in Example 1.

Example 5 A combination of 15 ppm of potassium bromate and 15 mg / 100 g of ferrous sulfate, in which no residual potassium bromate was observed in medium-grade bean bread (in the product crumb) of Example 2, was further added to ascorbin. The effect of improving the baking properties when an acid was used in combination was shown. That is, based on flour, 15 ppm of potassium bromate and 15 mg / 100 mg of ferrous sulfate were used.
g, add ascorbic acid in 5, 10, 15p
pm was added, and the other conditions were the same as in Example 2 to prepare an anpan. The results of a comparison of the quality of the resulting bread by evaluation by 20 trained panelists are shown in Table 5 below.

[Table 5]

In Table 5, Comparative Example 6 was prepared by adding only 15 ppm of potassium bromate and not adding ferrous sulfate and ascorbic acid, and was prepared under the same conditions as in Example 2 except for Comparative Example 6. 7 was prepared under the same conditions as in Example 2, that is, potassium bromate 15 ppm
And ferrous sulfate 15 mg / 100 g powder, and no ascorbic acid.

As is clear from Tables 4 and 5, Examples 4 and 5 to which an appropriate amount of ascorbic acid was further added.
The bread according to the present invention exceeded the comparative examples 5 and 7 in which only potassium bromate and ferrous sulfate were used together in the comprehensive evaluation, and obtained a sufficiently high evaluation equivalent to the comparative examples 4 and 6 in which potassium bromate was added alone. . It was also confirmed that the addition of ascorbic acid did not adversely affect the potassium bromate reducing effect of ferrous sulfate.

In each of the above embodiments, potassium bromate, ferrous sulfate and ascorbic acid were added separately, but potassium bromate and ferrous sulfate or all of them were used as constituents. It may be added as an improver or a combination of the improver and a separate additive. When added as an improver, ammonium salts such as ammonium chloride and ammonium sulfate, calcium salts such as calcium carbonate and calcium sulfate, reducing agents such as glutathione and cysteine, enzymatic agents such as amylase and protease, glycerin fatty acid esters and lecithin, etc. Potassium bromate and ferrous sulfate (adding ascorbic acid if necessary) can be used in combination with the emulsifying agent and the dispersant such as dried flour and starch.

In the sponge method, potassium bromate, ferrous sulfate and ascorbic acid may be added either at the time of sponge preparation or at the time of dough preparation, but the effect of reducing potassium bromate is more assured. It is desirable to add potassium bromate and ferrous sulfate at the time of preparing the sponge, and it is performed at the time of preparing the dough in the direct kneading method.

Further, ascorbic acid may be any of bare ascorbic acid without coating, ascorbic acid coated with oil or fat, or ascorbic acid coated with an emulsifier such as oil or fat and a monoglyceride fatty acid ester. You may.

[0035]

As described above, the bread manufacturing method or bread dough improving agent according to the present invention using ferrous sulfate in combination with potassium bromate produces bread without leaving potassium bromate in the final product. It has a novel effect that it can be performed. In addition, by using ascorbic acid in combination, the present invention can provide an excellent effect that the same quality improvement effect of bread can be obtained as when potassium bromate is used alone.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Katsuichi Himata 3-15-6 Chitose, Sumida-ku, Tokyo Yamazaki Baking Co., Ltd. Central Research Laboratory (56) References JP-A-8-116857 (JP, A JP-A-9-233992 (JP, A) JP-A-60-186243 (JP, A) JP-A-9-9859 (JP, A) JP-A-55-9760 (JP, A) Patent 60530 (JP, A) C1) (58) Field surveyed (Int. Cl. ⁷ , DB name) A21D 2/02 A21D 2/22 JICST file (JOIS)

Claims (4)

(57) [Claims] 1. A method for producing bread, wherein potassium bromate is not left in the finished bread or the amount thereof is reduced by adding ferrous sulfate. 2. The method for producing bread according to claim 1, wherein ascorbic acid is further added. 3. A bread dough improver comprising ferrous sulfate as an active ingredient that does not leave potassium bromate in the finished bread or reduces the remaining amount. 4. The bread dough improving agent according to claim 3, which contains ascorbic acid.