JPS6236668B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is capable of containing acetic acid, which is a volatile component, in a high yield and in a high content in a dry powder when powdering an acetic acid-containing seasoning liquid containing acetic acid as a main component, and also improves the quality of the obtained powder. This invention relates to an excellent method of powderizing acetic acid-containing seasoning liquid. Previously, the method for powderizing acetic acid-containing seasoning liquid was patented.
The method according to No. 929540 is already known. This method involves adding and dissolving a water-soluble substance containing one or more starch derivatives such as dextrin and gelatinizable oxidized starch as main components to an acetic acid-containing seasoning solution.
The amount of water-soluble substances is at least 70% of the water content in the acetic acid-containing seasoning liquid, and the types of water-soluble substances that can be sprayed are selected and mixed, and the mixed solution is made as much as possible. This is a powdering method by spray drying at a relatively low temperature, but this method has several issues such as spray suitability during manufacturing, acetic acid content retention, caking resistance of the produced powder,
It has been difficult to obtain an excellent acetic acid-containing seasoning powder as a powder due to various defects in the stability, solubility, and viscosity of the acetic acid content. In other words, for example, in order to prevent the caking phenomenon of products containing acetic acid at a high content of at least 10%, it is recommended to use polymeric dextrin or oxidized starch, but these are essentially has a high viscosity, and when it dissolves at least 70% of the water content in the acetic acid aqueous solution, it becomes even more viscous, making spraying extremely difficult, and the resulting product also becomes viscous when used after being dissolved in water. This has caused various problems in terms of usage, and the quality of acetic acid content such as yield, stability of acetic acid content, and caking resistance has not always been excellent. Furthermore, since oxidized starch is a starch that is insoluble in cold water, it is very inconvenient to prepare a mixed solution before spray drying. Therefore, the present inventors first used starch hydrolysates to improve these drawbacks, and among starch hydrolysates that vary depending on the degree of starch hydrolysis, starch hydrolysates are generally used. They attempted to produce high-yield, high-quality acetic acid-containing seasoning liquid powder by regulating the DE value, which is said to indicate the properties of a product, but the yield and quality of the acetic acid content of the product varied. However, it was not possible to obtain satisfactory results. For example, we prepared various starch hydrolysates with a DE of around ₁₄ , which were considered to be good based on experience, and tried producing acetic acid-containing seasoning liquid powder using each, but the same DE ₁₄
It was found that even though the previous and previous products were used, the yield of acetic acid content in the product varied, and the quality of the acetic acid content, such as stability, caking resistance, and solubility, also varied. Furthermore, in order to improve the many drawbacks in the production of acetic acid-containing seasoning liquid powder, the present inventors conducted research to overcome the DE value and found that starch composed of carbohydrates with various degrees of glucose polymerization was obtained. Among the hydrolysates, glucose with a degree of polymerization of 1 to 3 has no performance as a powdered base material at all in drying a mixed solution consisting of the three main components of powdered base material, acetic acid, and water, and approximately Glucose with a degree of polymerization of 4 to 5 has significantly inferior performance as a powdered base material;
In addition, as the proportion of these glucose polymerization degrees of 5 or less, especially glucose polymerization of 3 or less, in the starch hydrolyzate increases, the drying properties, acetic acid content retention, and quality tend to deteriorate in proportion to this. was found to be visible. On the other hand, in cases where the degree of glucose polymerization is approximately 6 or more, the higher the degree of polymerization, the higher the performance of the acetic acid content as a powder base material, and the greater the storage stability such as the caking resistance of the produced powder. However, if the degree of polymerization becomes too large, the viscosity will increase and cause trouble in spraying, and adding water to lower the viscosity (reducing the amount of starch hydrolyzate added to water) will reduce the yield. Therefore, it was found that there is a limit to the degree of glucose polymerization, and it was found that the suitable range of the degree of polymerization of the starch hydrolyzate used is approximately 6 to 18 as the average degree of polymerization of glucose. That is, when a starch hydrolyzate is added to and mixed with an acetic acid-containing seasoning liquid and the resulting mixed solution is spray-dried, the acetic acid content retention and quality of the acetic acid-containing seasoning liquid powder depend on the degree of glucose polymerization of the starch hydrolyzate. The proportion of oligosaccharides with a degree of glucose polymerization of 5 or less is 20% or less, the proportion of saccharides with a degree of glucose polymerization of 3 or less is 7% or less, and the average degree of glucose polymerization of the whole is 6. If a starch hydrolyzate composed of ~18 is selected and used, a high acetic acid seasoning liquid powder containing at least 10% of acetic acid can be produced with a high acetic acid content of at least 70%. It has been found that this method is effective in obtaining acetic acid-containing seasoning liquid powder with low yield and excellent quality. Furthermore, the present inventors conducted research and found that within the above-mentioned range of glucose polymerization degree composition, the way of glucose polymerization is special, that is, starch consisting of cyclic oligosaccharides and amylopectin polymerized in a cyclic manner is relatively mild. It has also been found that it is suitable to use starch hydrolyzed alone or in combination with other starch hydrolysates. The present invention was completed based on these findings, and contains 20% oligosaccharides with a degree of glucose polymerization of 5 or less.
A starch hydrolyzate containing the following and containing 7% or less of oligosaccharides with a degree of glucose polymerization of 3 or less is added to the acetic acid-containing seasoning solution and mixed so that the water content in the acetic acid-containing seasoning solution is 70% or more of the water content in the acetic acid-containing seasoning solution. This is a method of powderizing an acetic acid-containing seasoning liquid, which is characterized by drying and spray-drying. More preferably, the starch hydrolyzate used in the present invention has an average degree of polymerization of 6 to 18, a viscosity of 300 cps or less in an aqueous solution at 40°C at 50% concentration, and a degree of glucose polymerization of 15% or less of oligosaccharides with a glucose polymerization degree of 3 or less, and 5% or less of oligosaccharides with a degree of glucose polymerization of 3 or less. In addition, the starch hydrolyzate used in the present invention is: a) a hydrolyzate of starch consisting of amylopectin and amylose; b) a hydrolyzate of starch consisting of amylopectin; c) a hydrolyzate of starch consisting of amylopectin and amylose containing cyclic oligosaccharides; A hydrolyzate of starch consisting of amylopectin containing a cyclic oligosaccharide A hydrolyzate of starch consisting of amylopectin containing a cyclic oligosaccharide A hydrolyzate of starch consisting of one or more types selected from the group consisting of a, b, c and d. It is a mixture. Furthermore, the starch hydrolyzate used in the present invention may contain α, β, or γ cyclic oligosaccharides. In addition, in the case of a starch hydrolyzate that does not contain cyclic oligosaccharides, the average degree of polymerization referred to in the present invention is based on the value obtained by dividing the total amount of the starch hydrolyzate by the amount of reducing sugar in the starch hydrolyzate. In the case of starch hydrolyzate containing cyclic oligosaccharides, the average value of the degree of polymerization of cyclic oligosaccharides multiplied by the proportion of cyclic oligosaccharides in the starch hydrolyzate and the non-cyclic portion can be determined by the above method. It is based on the total value of the average degree of polymerization multiplied by the proportion of the acyclic portion in the starch hydrolyzate. In addition, G represents glucose, and the number after that represents the degree of polymerization, for example
_G1 is glucose, _G2 is maltose, _G3 is maltotriose, _G4 is an oligosaccharide with a degree of polymerization of 4, and _{G9 to n} are sugars with a degree of polymerization of 9 or more. In the starch hydrolyzate used in the present invention, when starch consisting of normal amylopectin and amylose is hydrolyzed, 20% or less has a glucose polymerization degree of 5 or less, and 7% or less has a glucose polymerization degree of 3 or less. and the average degree of polymerization is 6 to 18
The following methods are used to obtain the starch hydrolyzate, and the products obtained by these methods may be used singly or in combination. Furthermore, starch hydrolysates obtained by methods other than these may also be used as long as they meet the purpose of use of the present invention. [A] Starch hydrolyzate hydrolyzed with an enzyme or acid in a conventional manner (it is preferable to use a starch hydrolyzate with a DE6 to 20 that has been hydrolyzed mainly with an enzyme or acid) and fractionated using alcoholic water. A method in which unnecessary portions are separated and removed so that the glucose polymerization degree composition falls within the above range. [B] Special two-stage liquefaction of starch (in two-stage liquefaction of starches, the decomposition liquid of the first stage is
A method of obtaining a starch hydrolyzate by first heating and steaming until the DE reaches 3, and in the second step, adding α-amylase to hydrolyze the starch to a DE of about 6 to 16. [C] Starch hydrolyzate obtained by conventional methods (mainly enzyme-hydrolyzed DE of about 10~
A method of assimilating glucose, maltose, and maltotriose (preferably using a starch hydrolyzate of 20%) using microorganisms such as yeast. Next, in the present invention, a starch hydrolyzate having an average degree of polymerization of glucose of 6 to 18, 20% or less of glucose with a degree of polymerization of 5 or less, and 7% or less of glucose with a degree of polymerization of 3 or less is powdered. When used as a base material, in particular (I) a cyclic oligosaccharide with a degree of polymerization of 6 to 8 obtained by special hydrolysis of starch, and (II) an average degree of polymerization obtained by hydrolyzing starch consisting of amylopectin. A starch hydrolyzate having a polymerization degree of 6 to 50 is used alone or in combination with (III) a starch hydrolyzate having an average degree of polymerization of 6 to 18 obtained by hydrolyzing ordinary starches, that is, (I) + (II). ),
(I)+(III), (II)+(III), or (I)+(II)+
It is characterized in that it is used in combination with the specific combination (III), which can further enhance the intended effect. The properties of these specific starch hydrolysates and their combinations are described below. (I) Regarding cyclic oligosaccharides: Glucose obtained by applying a cyclic oligosaccharide producing enzyme to starch that is gelatinized or liquefied is 6 to 7
Alternatively, a starch hydrolyzate (cyclic oligosaccharide) consisting of a cyclic oligosaccharide (degree of polymerization 6 to 8) in which 8 oligosaccharides form a cyclic structure and an acyclic starch hydrolyzate
(I) + acyclic starch hydrolyzate (II) mixture)
Since it is easy to mix and dissolve in acetic acid water and has low viscosity, we added it to acetic acid water and mixed it, and the resulting mixed solution was spray-dried. It has good suitability, and furthermore, it is possible to further improve the technology of increasing the amount of powdered base material added to the water content in acetic acid water as much as possible, at least 70%, which is one of the basic techniques of the present invention. As a result, the yield of acetic acid in the produced powder improved. It was also found that the acetic acid-containing powder produced had excellent storage stability. Cyclic oligosaccharides with glucose polymerization degrees of 6, 7, and 8 obtained by separating and refining a starch hydrolyzate containing cyclic oligosaccharides obtained by applying a cyclic oligosaccharide-producing enzyme to starch to be gelatinized or liquefied are treated with acetic acid. Although it cannot be used alone as a powder base material because of its low solubility in water, it is a starch hydrolyzate obtained by hydrolyzing starch in accordance with the spirit of the present invention.
(III), starch hydrolyzate (II) obtained by hydrolyzing starch specifically composed of amylopectin, and a mixture of cyclic oligosaccharides and acyclic starch hydrolyzate obtained by reacting starch with a cyclic oligosaccharide-forming enzyme ( I+
The object of the present invention can be achieved if used in combination with one or more of II) within a range where cyclic oligosaccharides can be mixed and dissolved and within a range where the average degree of polymerization of the mixture is 6 to 18. Therefore, the amount of cyclic oligosaccharide used as the powdered base material of the present invention is within the range in which the cyclic oligosaccharide can be dissolved, but it is approximately 5% in the powdered base material.
The above is preferable. (II) Regarding starch hydrolysates obtained by hydrolyzing starches consisting of amylopectin: When starches consisting of amylopectin, such as waxy corn starch and waxy rice starch, are hydrolyzed using α-amylase. The amylopectin polymer breaks down from the α-1,4 glucoside bond, but in the early stages, the decomposition starts from the middle position of the linear part of amylopectin.
It gradually changes into a smaller polymer while retaining its branched polymer structure. The hydrolyzate of amylopectin by α-amylase has an average degree of polymerization.
The viscosity begins to drop rapidly at around 50 to 70 degrees, but in the average polymerization degree range of 6 to 50, the viscosity is lower than that of ordinary starch hydrolysates containing amylose and amylopectin, and it is difficult to dissolve in acetic acid water. It has good mixing solubility and is non-aging. In the present invention, when using starch hydrolyzate (II) of amylopectin hydrolyzed to an average degree of polymerization of 6 to 50, when this is used alone as a powder base material, the average degree of polymerization is 6 to 18 and the sugar composition is The branched structure of amylopectin is selected and used within the range of 20% or less with a glucose polymerization degree of 5 or less, and 7% or less with a glucose polymerization degree of 3 or less. secured,
It has a lower viscosity than amylose-containing starches that have been hydrolyzed to the same degree, so it is easier to spray, and it can be mixed thickly with acetic acid water, so the yield of acetic acid content is high and the produced powder is stable in storage. The sex will also be excellent. In addition, when using this starch hydrolyzate derived from amylopectin in combination with other starch hydrolysates, the starch hydrolyzate derived from amylopectin should be mainly used with an average degree of polymerization of 10 to 50 among those hydrolyzed to an average degree of polymerization of 6 to 50.
Starch hydrolyzate (III), cyclic oligosaccharide (I), cyclic oligosaccharide (I) and acyclic starch hydrolyzate are used.
When used in combination with one or more of the mixtures in (III), the average degree of polymerization is 6 as a powder base material.
~18, the intended purpose of the present invention can be achieved if the oligosaccharides with a glucose polymerization degree of 5 or less are 20% or less, and the oligosaccharides with a glucose polymerization degree of 3 or less are 7% or less. be. In the present invention, water-soluble polymeric substances such as gum arabic, gelatin, and CMC may be added. In the present invention, the above-mentioned starch hydrolyzate is added to and mixed with an acetic acid-containing seasoning solution within a range of 70% to 200% of the water content in the acetic acid-containing seasoning solution, and then spray-dried. It is. The acetic acid-containing seasoning liquid used in the present invention is rice vinegar, lees vinegar, alcoholic vinegar, malt vinegar, grape vinegar, apple cider vinegar,
Acidic seasonings containing acetic acid as a main component, such as synthetic vinegar, sauces, aqueous acetic acid solutions, their concentrates, acetic acid-added solutions, and processing solutions. In addition, in the present invention, when powdering the acetic acid-containing seasoning liquid, various aroma components other than acetic acid are also powdered, but the yield of low-boiling aroma components such as the above-mentioned brewed vinegar ( Since the aroma retention rate is almost proportional to the yield of acetic acid, improving the yield of acetic acid is extremely important in order to obtain aroma components. Next, test examples and examples of the present invention will be shown. Test Example 1 Samples A, B, C, having the analysis values shown in Table 1,
Using the starch hydrolysates (dry products) of D, E, F, G, H and I, starch hydrolysates were prepared as shown in Table 2.
Prepare a mixed solution (40°C) with different amounts of water for 100 parts and 25 parts of acetic acid, and spray this mixed solution at a chamber temperature of 87°C while heating it to 60°C with a plate heater just before spraying. When a drying experiment was conducted, acetic acid-containing powder was obtained under the conditions shown in Table 2. The starch hydrolyzate used as a sample was obtained by the following method. Sample A: DE17.9 hydrolyzed by acid-enzyme
commercially available starch hydrolyzate. Sample B: Enzyme - hydrolyzed by the enzyme
Commercial starch hydrolyzate with DE14.5. Sample C: Add α-amylase to a starch emulsion of cornstarch and heat to hydrolyze it. When the DE reached 1.5, the decomposition solution was heated to 130°C, kept for 10 minutes, cooled, and α-amylase was added again.
After hydrolysis to DE16.8, the glucose, maltose, and maltotriose in the resulting decomposition solution were assimilated by yeast.
Starch hydrolyzate of DE14.1. Sample D: Commercially available starch hydrolyzate with DE13.9 hydrolyzed with acid. Sample E: Prepared by decomposing cornstarch starch emulsion in two steps using α-amylase in the same manner as sample C, decomposing it to DE1.5 in the first step and hydrolyzing it to DE11 in the second step. starch hydrolyzate. Sample F: A starch hydrolyzate prepared in the same manner as Sample E by hydrolyzing it to DE8.2 in the second step. Sample G: A starch hydrolyzate prepared in the same manner as Sample E by hydrolyzing it to DE6.4 in the second step. Sample H: A starch hydrolyzate prepared in the same manner as Sample E by hydrolyzing it to DE5.6 in the second step. Sample I: Starch hydrolyzate prepared in the same manner as Sample E by hydrolyzing to DE4.5 in the second step. Next, maltotriose (maltotriose) was prepared by decomposing commercially available glucose, commercially available maltose (sugar composition of 95% maltose and 5% glucose), and pullulan (Hayashibara KK Pullulan PF-10) with pullulanase (Amano Pharmaceutical KKKC20-L). 90% maltohexaose and 5% maltohexaose) and a malt obtained by assimilating glucose, maltose, and a part of maltotriose from the starch hydrolyzate of Sample A using yeast bacteria, and then fractionating and preparing the mixture with alcoholic water. Starch hydrolyzate mainly composed of tetraose and maltopentaose (G ₁ 0.4%, G ₂ 1.3%, G ₃ 15.4%,
G ₄ 25.2%, G ₅ 20.6%, G ₆ 15.8%, G ₇ 9.5%, G ₈ 4.2
%, G _9-7.6 %) to prepare a mixed solution shown in Table 3 and spray-dry it at a chamber temperature of 87° C., and the results shown in Table 3 were obtained. In addition, the calculation method of sugar composition, viscosity, and acetic acid content yield in the present invention is as follows. Sugar composition: Qualitative and quantitative determination was carried out using a liquid chromatograph using PNH ₂ -10/S2504 (Shimadzu KK) as the column, acetonitrile-water system as the mobile phase, and a differential refractometer as the detector. Viscosity: The viscosity of the aqueous solution of starch hydrolyzate is sample 500.
g was dissolved in 500 g of water, and the viscosity at 40°C was measured using a cylindrical rotational viscometer. The viscosity of the mixed solution before drying was measured in the same manner as the viscosity at 40°C. Acetic acid yield calculation method: Amount of acetic acid used (A), amount of starch hydrolyzate (solid content) used (B), % solid content in the produced acetic acid-containing powder (C), production If the acetic acid content % (D) in the acetic acid-containing powder is the acetic acid content percentage (residual rate) % = B/C x D x 100/A.

【table】

[Table] As shown in Table 2, (a) the average degree of polymerization is as low as 5.6, and G ₁ to G ₃ are
In an experiment using sample A containing 16.1% and 27.1% of _G1 to _G5 , the drying performance and yield were very poor.
Moreover, the obtained powder was very easy to caking. (b) Samples B, C, and D all have a DE value of approximately 14.
However, when comparing the acetic acid content retention and caking resistance of the obtained powder, G ₁ to _{G 3} is 13.0%,
When sample B containing 23.2% of G ₁ to _{G 5} was used, both yield and caking resistance were poor, and G ₁ to _{G 3}
When using sample D, which contains 12.4% of starch and 20.5% of _G1 to _G5 , the acetic acid content retention is secured when the amount of water per 100 parts of starch hydrolyzate is 100 parts, but the solidification resistance is Poor cohesion, G ₁ to G ₃ 7.3%,
When sample C containing 20.7% of G ₁ to _{G 5} is used, the yield and caking resistance are improved compared to sample D, but there is still some difficulty in caking resistance. (c) The proportion of G ₁ to _{G 5} is within 20%, and the average degree of polymerization of the starch hydrolyzate is 9.1, 12.2, and 15.6.
In experiments using Samples E, F, and G, which are Good results were obtained in all aspects of quality, including yield and caking resistance. However, it can be seen that when the amount of starch hydrolyzate relative to water decreases, the yield of acetic acid content decreases considerably. (d) Sample H, which has an average degree of polymerization of 17.9, has a high viscosity, and a mixed solution of 100 parts of water to 100 parts of starch hydrolyzate has a high viscosity and cannot be mechanically sprayed, making it difficult to spray. If the amount of water that falls within the range is 160 parts, the yield of acetic acid will be poor; if the amount of water used is 130 parts, the yield of acetic acid will be
It was 80.8%. Sample I, which has an average degree of polymerization of 22.2, is difficult to spray and has a poor yield.

【table】

[Table] As shown in Table 3 above, when a mixed solution of not only glucose and maltose but also maltotriose (G ₃ ) is spray-dried, the drying properties are extremely poor and the powder adheres to the chamber wall and melts. It cannot be recovered. This can be seen from the fact that maltotriose dissolves in a 97% acetic acid aqueous solution. G ₁
In experiments using starch hydrolyzate, in which G ₄ to G 5 is small and G ₄ to _{G 5} account for nearly 50%, it was found that the drying properties, yield, and caking resistance were very poor, and the degree of glucose polymerization was 4 to 4. It is considered that No. 5 has almost no performance as a powdered base material that coats and contains an acetic acid component. Judging from the above, the degree of glucose polymerization is 5.
The proportion of the following oligosaccharides is 20% or less, and the sugars of glucose, maltose, and maltotriose are 7% or less, and the average degree of polymerization of the entire glucose is 6 to 18. After selecting the starch hydrolyzate, the selected starch hydrolyzate is added to and mixed with an acetic acid aqueous solution so that the water content is approximately 70% or more of the water content of the acetic acid aqueous solution, and the resulting mixed solution is spray-dried at the lowest possible temperature. By doing so, it is possible to produce acetic acid-containing powder with a high acetic acid content and high yield, and the resulting acetic acid-containing powder has properties such as caking resistance, moisture resistance, fragrance retention, and solubility in water. It was found that it has very good properties. Test Example 2 About the starch hydrolyzate used in the test and its sugar composition ☆ α-Cyclodextrin separated and purified from a liquefied liquid containing cyclic oligosaccharides obtained by treating potato starch with a cyclic oligosaccharide-forming enzyme ・Cyclic oligosaccharides Sugar (α: 100%) ...(I)− ☆After allowing α-amylase to act on potato starch,
Hydrolyzed (non-cyclic) starch with 50% cyclic oligosaccharide (a mixture of α: 60%, β: 25%, γ: 15%) and an average degree of polymerization of 11.8 obtained by the action of a cyclic oligosaccharide-forming enzyme. Something that consists of 50% of something.・Cyclic oligosaccharide (α: 60%, β: 25%, γ: 15
%) ...(I)- ・Starch hydrolyzate with an average degree of polymerization of 11.8 ...(III)- ☆Produced by hydrolyzing waxy starch (starch consisting of amylopectin) with α-amylase Each with an average degree of polymerization of 12.5 and 25.0 ・Amylopectin hydrolyzate with an average degree of polymerization of 12.5 (II)− ・Amylopectin hydrolyzate with an average degree of polymerization of 25.0 …(II)− ☆Potato starch (containing amylose and amylopectin) The respective average degrees of polymerization obtained by hydrolyzing (starch) with α-amylase were 5.0, 7.6, 11.8 and
13.3 - Starch hydrolyzate with an average degree of polymerization of 5.0 ... (III) - - Starch hydrolyzate with an average degree of polymerization of 7.6 ... (III) - - Starch hydrolyzate with an average degree of polymerization of 11.8 ... (III)− ・Starch hydrolyzate with an average degree of polymerization of 13.3 ……(III)−

[Table] Use one or more of these starch hydrolysates and create a mixed solution by adding each to a 20% acetic acid aqueous solution in an amount equivalent to 125% of the water content in the acetic acid aqueous solution. Then, set the chamber temperature to 95℃.
A spray drying test was conducted under the following conditions, and Table 5 summarizes the results of observations regarding the spraying conditions, the acetic acid content retention, the stability of the acetic acid content, and the caking resistance of the produced powder. . From this table, it is clear that: (1) As shown in experiments No. 1 to No. 4 using starch hydrolyzate obtained by hydrolyzing ordinary amylose and amylopectin-containing starches, the average degree of polymerization is small, and G ₅ or less is 20. % or more of starch hydrolyzate
No. 1 using (III)- has a low viscosity and there are no problems with sprayability, but its ability to cover acetic acid is poor, it adheres to the dry wall during drying, and acetic acid remains. The rate is bad. Moreover, the stability of the acetic acid content and the caking resistance of the produced product are also very poor. On the other hand, starch hydrolyzate with a high average degree of polymerization
In No. 4 using (III)-, when the amount of powdered base material to water was 125%, the viscosity was so high that spraying was impossible and a product could not be obtained.
In experiment No. 3 using starch hydrolyzate (III), which has a lower viscosity than starch hydrolyzate (III), the viscosity was still somewhat thick and spraying was somewhat poor, but the yield of acetic acid was also compared. When ejected in a well-targeted manner, it is difficult to solidify, and the acetic acid content is relatively stable. However, in the case of starch hydrolyzate (III)-,
Since the amount added to the water in the acetic acid aqueous solution cannot be increased any further, it is extremely difficult to further improve the yield of acetic acid. We used starch hydrolyzate (III), which is intermediate between starch hydrolyzate (III) and starch hydrolyzate (III).
No. 2 has relatively good sprayability and acetic acid content retention, but is inferior in terms of caking resistance and acetic acid content stability. (2) Experiment No. 5 and No. 6 are cyclic oligosaccharides (I)-
and starch hydrolyzate (III) with an average degree of polymerization of 11.8.
and a mixture of these with an average degree of polymerization of 11.8
This is the case when a mixture of starch hydrolyzate (III)- is used, and the cyclic oligosaccharide has no viscosity and has a kind of binding property with the acetic acid content, so it is suitable for spraying. It has excellent acetic acid yield, greatly improved acetic acid stability, and excellent caking resistance. Experiment No.5 and No.6
In formulating the powdered base material, when the amount of the powdered base material mixture added to the water content in the acetic acid aqueous solution was further increased to the extent that it could be sprayed, the acetic acid fraction yield was further improved. (3) Experiment No. 7 is a test example in which a cyclic oligosaccharide (α-cyclodextrin) (I) was attempted to be used alone as a powder base material, but it was not possible to mix and dissolve the cyclic oligosaccharide. , cyclic oligosaccharides were separated by precipitation. (4) Experiments No. 8 to No. 10 were conducted by hydrolyzing waxy starch and adjusting the average degree of polymerization to 12.5 (II)-
However, the viscosity of this product is about the same as that of normal starch containing amylose and amylopectin decomposed to an average degree of polymerization of 9, and the viscosity is low despite the high average degree of polymerization. Moreover, it maintains the branched polymer structure characteristic of amylopectin. This amylopectin hydrolyzate (II) with an average degree of polymerization of 12.5 was used in combination with cyclic oligosaccharide (I) (Experiment No. 8), and this amylopectin hydrolyzate (II) was used alone. (Experiment No. 9) and the hydrolyzate (II) of this amylopectin and the average degree of polymerization used in Experiment No. 3.
The combination of starch hydrolyzate (III) of 11.8 (Experiment No. 10) had good sprayability, acetic acid content retention,
Experiments on all aspects of acetic acid content stability and caking resistance
It was superior to No. 1 to No. 4. Particularly good results were obtained in experiment No. 8. Experiment No. 11 used waxy starch that had been hydrolyzed and adjusted to an average degree of polymerization of 25.0 (II), which has a relatively high viscosity and cannot be used in large quantities, but it may cause defects if used alone. When used in combination with hot starch hydrolyzate (III), a good effect was obtained by compensating for the defects of starch hydrolyzate (III). Experiment No. 12 used a large amount of the above (II)-, but the viscosity was so high that it could not be sprayed. (5) Experiment No. 13 used a combination of cyclic dextrin (I), starch hydrolyzate (III) with an average degree of polymerization of 11.8, and amylopectin hydrolyzate (II), and investigated their properties. It is the best in terms of sprayability, acetic acid content retention, acetic acid content stability, and caking resistance. *The residual rate of acetic acid is the value obtained by multiplying the acetic acid content in the produced powder by the weight of the produced powder, that is, the residual acetic acid content divided by the acetic acid content in the acetic acid water used, multiplied by 100. ※※ Seal 50g of each in a polyethylene bag (thickness 0.05mm) with good permeability to acetic acid gas, and
After storing it in a constant temperature bath at ℃ for 8 days, the acetic acid content contained in the powder was measured, and the acetic acid content in the powder after storage / the acetic acid content in the powder before storage x 100 = stability of the acetic acid content was calculated. . ※※※ The results were observed after being sealed in aluminum foil and stored at 40℃ for 10 days.

【table】

[Table] Example 1 In performing two-stage hydrolysis of starch emulsion of corn starch using α-amylase, it was liquefied using α-amylase (Clistase KD, Daiwa Kasei KK), and the DE of the first-stage decomposition solution was When DE reaches 1.7, it is heated and steamed to deactivate the enzyme and swell and disperse the starch. In the second step, α-amylase (Klystase KD) is added and hydrolyzed until the DE reaches 7.2. The starch hydrolyzate (water content: 4%) was obtained by drying it, but the sugar composition of these products was
G ₁ trace%, G ₂ 1.4%, G ₃ 2.6%, G ₄ 2.4%, G ₅ 2.0
%, _G6 2.3%, _G7 3.9%, _G8 3.7%, G9 _-n 81.7%, and the average degree of polymerization was about 14. 100 kg of the starch hydrolyzate obtained was mixed with 90 kg of water.
The mixture was mixed and dissolved in an acetic acid aqueous solution consisting of 30 kg of 99% acetic acid, and then spray-dried in a chamber at 92° C. while being heated to 55° C. with a plate heater. Approximately 125 kg of acetic acid-containing powder containing 20.6% acetic acid was obtained. The obtained acetic acid-containing powder has a high content of acetic acid and is highly resistant to caking, so it is extremely effective as an acidulant for instant seasonings for various sauces and soups. Example 2 DE15 commercially available starch hydrolyzate (sugar composition G ₁ 1.2%,
G ₂ 5.3%, G ₃ 8.2%, G ₄ 5.4%, G ₅ 4.9%, G ₆ 9.3
%, G ₇ 9.9%, G ₈ 5.1%, G _9~n 50.7%) 100kg with water
Dissolve 250kg of magnesium sulfate in this aqueous solution.
10g, 1-potassium phosphate 70g, yeast extract
Add 100 g of peptone, 50 g of peptone, and 200 g of baker's yeast and stir to dissolve. After culturing for about 48 hours at 30°C ± 1°C while blowing sterilized air at 60 ml/min per solution, adjust the pH to 6.5. , sterilized by heating to 90°C, decolorized, desalted, and deodorized, and then spray-dried to obtain 70 kg of starch hydrolyzate (moisture 3.5%). The sugar composition of the obtained starch hydrolyzate is G ₁ trace
%, G ₂ 0.4%, G ₃ 5.4%, G ₄ 6.1%, G ₅ 5.3%
_G6 10.1%, _G7 10.8%, _G8 5.6%, G9 _-n 56.3%, and the average degree of polymerization was about 8.9. 50 kg of starch hydrolyzate thus obtained was added and mixed with 50 kg of wine vinegar (acetic acid content 12.0%, extract content 2.0%), and the resulting mixed solution was heated to 50°C with a plate heater while the chamber temperature was 90°C. When spray-dried under the following conditions, approximately 55 kg of powdered wine vinegar containing 9.5% acetic acid was obtained. This powdered wine vinegar had a unique flavor as wine vinegar, and had excellent qualities such as caking resistance, moisture absorption resistance, and solubility. Example 3 Commercial starch hydrolyzate with DE17.5 (sugar composition G ₁ 4.3
%, G ₂ 5.5%, G ₃ 5.3%, G ₄ 5.6%, G ₅ 6.5%,
G ₆ 5.5%, G ₇ 4.9%, G ₈ 4.3%, G _9~n 58.1%) 50kg
was mixed with 200 kg of 60 w/w% alcohol aqueous solution, and this mixed solution was allowed to stand for 24 hours. After standing still, separate the transparent solution into two layers, upper and lower, and add 70% of the lower layer solution.
kg and 180 kg of upper layer solution were obtained. The alcohol content was distilled and recovered from the resulting lower layer liquid (solid content: 60%, alcohol content: 15%), and then dried, yielding approximately 40 kg of starch hydrolyzate (water content: 4.0%). The sugar composition of this starch hydrolyzate is G ₁ 1.4%,
G ₂ 1.8%, G ₃ 3.4%, G ₄ 4.8%, G ₅ 5.5%, G ₆ 4.6
%, _G7 5.1%, _G8 6.8%, G9 _-n 66.6%, and the average degree of polymerization was about 13.1. 20 kg of the obtained starch hydrolyzate was added to 20 kg of freeze-concentrated rice vinegar (acetic acid content 20%, extract content 2.7%) and mixed, heated to 50°C with a plate heater and kept at a chamber temperature of 92°C. When spray-dried, approximately 24 kg of powdered rice vinegar containing 14.7% acetic acid was obtained. The obtained powder has the characteristic aroma of rice vinegar and has excellent qualities such as caking resistance, solubility, and viscosity when dissolved, so sugar etc. are mixed with it. This makes it extremely convenient to make instant sambai vinegar and powdered sushi base. Example 4 Alcohol vinegar (acetic acid content 15.0%, extract content 0.5%, water content
Cyclic oligosaccharide (α: 60%, β: 25%) obtained by reacting potato starch with α-amylase and then reacting with cyclic oligosaccharide-forming enzyme in a solution consisting of 100 kg of 84.5%) and 20 kg of 99% acetic acid. , and γ: 15% mixture) and powder consisting of 80 kg of starch hydrolyzate consisting of 50% of an acyclic starch hydrolyzate with an average degree of polymerization of 12 and 30 kg of a commercially available starch hydrolyzate with an average degree of polymerization of 11. base material (average degree of polymerization 9.8, G ₁ 0.4%, G ₂ 1.1%,
A mixed solution (viscosity: 105 cps, 40°C) was obtained by adding and mixing 2.1% of G ₃ , 2.3% of G ₄ , and 2.7% of G ₅ . Next, the obtained mixed solution was heated using a plate heater.
When heated to 60℃ and spray-dried using a nozzle-type spray dryer at a chamber temperature of 95℃, approximately
We were able to obtain 140kg of powdered product. The obtained powder is a powdered vinegar containing a high acetic acid content of 23.0%, and by adding and mixing salt, sugar, seasoning powder, etc., products such as instant sushi vinegar, nibai vinegar, and sanbai vinegar can be made. However, when these mixtures are sealed in wrapping paper and stored, the volatile stability and caking resistance of the acetic acid content are superior to those obtained using conventional methods. It was hot. Example 5 Wine vinegar (acetic acid content 12.0%, extract content 2.0%)
%, moisture 86.0%) add waxy starch to 100 kg
- Powdered base material (average degree of polymerization 14.6, G ₁ trace%, G ₂ 1.6%, G ₃ 3.0%, G ₄ 3.2
%, G ₅ 3.2%) and mix to make a mixed solution (viscosity
120cps, 40℃). Next, the resulting mixed solution was heated with a plate heater and heated to a chamber temperature using a spray dryer.
Approximately 110 kg of powder product was obtained by drying at 100°C. The obtained powder product is a wine vinegar-flavored powder containing 10.2% acetic acid, which can be used as powdered table vinegar and used in various Western-style instant preparations such as dressing mix powder and sauce mix powder. It can be used as a raw material for seasonings. When the obtained powder was mixed with raw materials such as sugar, salt, and amino acids, the acetic acid content was stable and did not solidify. Example 6 Cider vinegar obtained by freeze concentration (acetic acid content
20.0%, extract content 2.5%, moisture 77.5%) 60kg of cyclic oligosaccharides (average degree of polymerization 6.5) obtained by liquefying potato starch with α-amylase and acting on a post-cyclic oligosaccharide-forming enzyme (average degree of polymerization 6.5) 50% and average degree of polymerization 12
Starch hydrolyzate with an average degree of polymerization of 18 obtained by decomposing 40 kg of starch hydrolyzate consisting of 50% acyclic starch hydrolyzate and waxy starch with α-amylase.
Powdered base material consisting of 20 kg (average degree of polymerization 12.2,
G ₁ 0.3%, G ₂ 0.8%, G ₃ 1.8%, G ₄ 2.1%, G ₅ 2.4
%) and dissolve it using a plate heater.
When spray-dried at a chamber temperature of 95°C while heating to 60°C (viscosity 75 cps at 60°C), a powder product of approx.
Although 71 kg was obtained, the acetic acid content contained in the obtained powder product was 15.8%, and the loss of acetic acid content due to drying was extremely small, and the residual rate of acetic acid content was 94%.
The obtained powder is a powdered brewed vinegar having the aroma of apple cider vinegar, and is used as a raw material for various instant seasonings and sweets. Example 7 Apple cider vinegar (acetic acid content 12.0%, extract content 1.5%) 50
kg, alcoholic vinegar (acetic acid content 15.0%, extract content 0.5%) 50
kg, soy sauce (extract 14.5%, salt 16.0%) 60kg
A starch hydrolyzate with an average degree of polymerization of 12.5 (G ₁ 0%, G ₂ 2.6%, G ₃ 2.6 %, G ₄ 2.4%,
_G5 2.2%) 140 kg was added, mixed and dissolved, and heated to 65°C and spray-dried at a chamber temperature of 100°C to obtain about 170 kg of powder product. The obtained powder has an acetic acid content of 7.0% and a salt content of 5.6%.
%, and contains 6.8% of various extracts, and by dissolving it in water, you can obtain bonito-flavored aji ponzu. This powder product contains salt and various extracts in addition to acetic acid, but it has excellent stability in acetic acid and other flavors, and has very good caking resistance.

Claims (1)

[Claims] 1. 20% oligosaccharide with a glucose polymerization degree of 5 or less
A starch hydrolyzate containing the following and containing 7% or less of oligosaccharides with a degree of glucose polymerization of 3 or less is added to the acetic acid-containing seasoning solution and mixed so that the water content in the acetic acid-containing seasoning solution is 70% or more of the water content in the acetic acid-containing seasoning solution. A method for powderizing an acetic acid-containing seasoning liquid, which is characterized by drying and spray-drying. 2. The starch hydrolyzate has an average degree of polymerization of 6 to 18, and has a viscosity of 40°C aqueous solution at 50% concentration.
A method for powderizing an acetic acid-containing seasoning liquid according to claim 1, wherein the acetic acid-containing seasoning liquid is 300 cps or less. 3. The starch hydrolyzate contains 15% or less of oligosaccharides with a degree of glucose polymerization of 5 or less, and 5% or less of oligosaccharides with a degree of glucose polymerization of 3 or less. Powderization method of acetic acid seasoning liquid. 4 Starch hydrolyzate: a Hydrolyzate of starch consisting of amylopectin and amylose b Hydrolyzate of starch consisting of amylopectin c Hydrolyzate of starch consisting of amylopectin and amylose containing cyclic oligosaccharides Decomposition product d Hydrolyzate of starch consisting of amylopectin containing a cyclic oligosaccharide A patent claim which is one or a mixture of two or more selected from the group consisting of a, b, c and d. A method for pulverizing an acetic acid-containing seasoning liquid according to Scope 1. 5. The method for pulverizing an acetic acid-containing seasoning liquid according to claim 1, wherein the starch hydrolyzate contains an α/β or γ cyclic oligosaccharide. 6 The acetic acid-containing seasoning liquid is selected from rice vinegar, lees vinegar, alcoholic vinegar, malt vinegar, grape vinegar, apple cider vinegar, synthetic vinegar, acetic acid aqueous solution, sauce, or concentrated liquid thereof, acetic acid-added liquid, and processing liquid. A method of powderizing an acetic acid-containing seasoning liquid according to claim 1.