JP7404233B2 - Crystalline starch decomposition products, food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, fertilizers, and modifiers thereof, and the crystalline starch decomposition products using the crystalline starch decomposition products. Methods for producing products, food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, and fertilizers - Google Patents

Description

This technology provides crystalline starch decomposition products, food and drink compositions using the crystalline starch decomposition products, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, fertilizers, and modifiers thereof; The present invention relates to a method for producing the crystalline starch decomposition product, compositions for food and drink products, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, and fertilizers.

BACKGROUND ART Starch decomposition products have traditionally been used in the food and beverage field for applications such as sweeteners, taste adjustment, osmotic pressure adjustment, humectants, and powdered base materials. Starch decomposition products are also used in the pharmaceutical field as carbohydrate sources for enteral nutrients, excipients for drugs, and the like. Furthermore, in the field of cosmetics, starch decomposition products are used as binders for solidifying cosmetics and for adjusting the viscosity of creamy cosmetics.

In this way, starch decomposition products can be used for the various purposes mentioned above by adjusting their basic physical properties such as sweetness, taste, osmotic pressure, viscosity, and hygroscopicity. For example, those with a high degree of sweetness are suitable for use as sweeteners, while those with a low degree of sweetness are suitable as taste regulators, osmotic pressure regulators, powdered base materials, etc. In addition, the hygroscopicity of the starch decomposition product itself is also an important factor in selecting the application. For example, if the hygroscopicity of starch decomposition products is too high, they may solidify or become sticky during storage or distribution, making them unsuitable for use in powdered foods or powdered base materials. do not have.

Crystalline starch decomposition products obtained by crystallizing these starch decomposition products are also utilized in various fields by taking advantage of their characteristics such as low hygroscopicity. For example, Patent Document 1 discloses that cyclomaltodextrin glucanotransferase is caused to act on an aqueous solution containing cyclodextrin or starch to generate amylose particles insoluble in the aqueous solution, and the amylose particles are collected. , a technique for producing amylose particles that can be used in the pharmaceutical field, cosmetic field, etc. is disclosed.

Patent Document 2 also discloses melting 1,4-α-D-polyglucan or polysaccharide in water, leading the melted product to precipitation, cooling the mixture, and separating the particles formed. Microsphere-like crystals can thereby be used as additives for cosmetics, carriers of active substances in pharmaceutical and other applications, food additives, fillers for biodegradable or industrial polymers, etc. Techniques for manufacturing lights are disclosed.

Japanese Patent Application Publication No. 04-85301 Special Publication No. 2004-512405

Crystalline substances used in a wide range of fields, including the food and medical fields, include crystalline glucose and trehalose, which are soluble in water, and crystals of cellulose and high-molecular amylose, which are insoluble in water. Depending on the presence or absence, there are certain restrictions on how it can be used. Crystalline glucose and trehalose, for example, cannot be used for suspension applications because they are soluble in both low-temperature and high-temperature water. Furthermore, crystals of cellulose and high-molecular amylose are insoluble in both low-temperature water and high-temperature water, so it is difficult to mix them uniformly in an aqueous solution. As a result, there are restrictions on the processing methods for products such as food and beverage compositions, food and beverages, pharmaceuticals, cosmetics, industrial products, feed, culture media, and fertilizers, making it difficult to achieve the desired effects. be.

Therefore, the main objective of the present technology is to provide a novel crystalline starch decomposition product whose solubility varies depending on the temperature.

In order to solve the above object, the inventors of the present application conducted extensive research on specific components contained in starch decomposition products. As a result, the present inventors developed a new crystalline starch decomposition product characterized by a high content of very high molecular weight components among oligosaccharides and low molecular weight components of dextrin, and the crystalline starch decomposition product has the following characteristics: They discovered that while it contains a portion that is insoluble in low-temperature water, it completely dissolves in high-temperature water, leading to the completion of this technology.

That is, in the present technology, first, the content of glucose polymerization degree (DP) 8 to 19 is 40% or more;
The content of glucose polymerization degree (DP) of 20 or more is 55% or less,
A crystalline starch decomposition product having a crystallization ratio calculated from the results of X-ray diffraction of 1% or more is provided.
The crystallization ratio of the crystalline starch decomposition product according to the present technology can be 10% or more.
Furthermore, the crystalline starch decomposition product according to the present technology can have a supernatant Brix value of 2.0% or less when dispersed in water at 20°C.

Since the crystalline starch decomposition product according to the present technology has different solubility depending on the temperature, it can be suitably applied to food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, fertilizers, etc. is possible.

The composition of the crystalline starch decomposition product according to the present technology is new, and the method for obtaining it is not particularly limited. For example, after obtaining a starch decomposition product by appropriately combining a starch raw material with a treatment using general acids or enzymes, various chromatography, membrane separation, ethanol precipitation, etc., A starch decomposition product can be obtained by subjecting it to a general crystallization process.

That is, the present technology is a method for producing a crystalline starch decomposition product, in which a debranching enzyme and a debranching enzyme are added to starch or a starch decomposition intermediate (for example, a liquefied liquid) obtained by mildly decomposing starch. , by acting a branching enzyme simultaneously or after the action of a branching enzyme,
The content of glucose polymerization degree (DP) 8 to 19 is 32% or more,
an enzymatic reaction step for obtaining a starch decomposition product having a glucose polymerization degree (DP) of 20 or more and a content of 30% or less;
a crystallization step of crystallizing the starch decomposition product;
Provided is a method for producing a crystalline starch decomposition product.
In addition, in this technology, after adding acid to starch or starch decomposition intermediates and liquefying them, debranching enzymes are applied to
The content of glucose polymerization degree (DP) 8 to 19 is 32% or more,
an enzymatic reaction step for obtaining a starch decomposition product having a glucose polymerization degree (DP) of 20 or more and a content of 30% or less;
a crystallization step of crystallizing the starch decomposition product;
Provided is a method for producing a crystalline starch decomposition product.
In the crystallization step in the production method according to the present technology, the starch decomposition product can be crystallized by maintaining the solution of the starch decomposition product at a predetermined concentration or higher and/or by lowering the temperature to a predetermined temperature or less. .
In the production method according to the present technology, a separation step of separating the crystalline starch decomposition product can also be performed after the crystallization step.

The quality of the crystalline starch decomposition product according to the present technology can be improved by including it in a composition for food and drink, food and drink, medicine, cosmetics, industrial product, feed, culture medium, or fertilizer.
That is, the present technology provides a modifier for food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, or fertilizers, which contains the crystalline starch decomposition product according to the present technology.

In this technology, the content of glucose polymerization degree (DP) 8 to 19 is 32% or more,
A composition for food or drink, a food or drink, a pharmaceutical, a cosmetic, an industrial product, a feed, a culture medium, or Provide fertilizer.
These food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, or fertilizers are
The content of glucose polymerization degree (DP) 8 to 19 is 32% or more,
It can be produced by performing a crystallization step of crystallizing part or all of a starch decomposition product having a glucose polymerization degree (DP) of 20 or more and 30% or less.

Here, technical terms used in this technology will be explained. “Debranching enzyme” is a general term for enzymes that catalyze a reaction that hydrolyzes α-1,6-glucoside bonds, which are branching points in starch. For example, "Isoamylase, glycogen 6-glucanohydrolase", "Pullulanase, pullulan 6-glucan hydrolase", "amylo-1,6-glucosidase/4-α glucanotransferase" /4-α glucanotransferase)” is known. Note that these debranching enzymes may be used in combination depending on the purpose.

"Branching enzyme" is a general term for enzymes that act on linear glucans connected by α-1,4-glucosidic bonds to form α-1,6-glucosidic bonds. . Although it exists in animals and bacteria, it can also be purified from plants such as potatoes, rice seeds, and corn seeds.

The crystalline starch decomposition product according to this technology contains a large amount of high molecular weight components of oligosaccharides and low molecular weight components of dextrin (glucose polymerization degree; DP8-19), so linear sugar molecules that do not occur with low molecular weight oligosaccharides As a result of interactions between the two, crystallinity increases, and it exhibits properties that include a portion that is insoluble in cold water. Further, since the crystalline starch decomposition product according to the present technology has a content of DP20 or higher of 55% or less, it exhibits appropriate crystallinity and exhibits the property of dissolving in hot water. Therefore, it is easy to purify it in a heated solution state, and it can be used by dissolving it by heating when processing a wide range of products.

2 is a graph substituted for a drawing showing a powder X-ray diffraction chart of Example 1. 2 is a graph substituted for a drawing showing a powder X-ray diffraction chart of Example 2. 3 is a graph substituted for a drawing showing a powder X-ray diffraction chart of Comparative Example 4. 3 is a photograph substituted for a drawing showing the icing donut manufactured in Experimental Example 2. 2 is a photograph substituted for a drawing showing the edible plastic-like substance produced in Experimental Example 2. This is a photograph substituted for a drawing showing characters written with a character pen using this technology.

Hereinafter, a preferred form for implementing the present technology will be described. Note that the embodiment described below shows an example of a typical embodiment of the present technology, and therefore the scope of the present technology should not be interpreted narrowly.

<About crystalline starch decomposition products>
The crystalline starch decomposition product according to the present technology is derived from starch raw materials, such as starch (terrestrial starch) such as corn starch, waxy corn starch, rice starch, and wheat starch, underground stems or roots such as potato starch, tapioca starch, sweet potato starch, etc. It is obtained by crystallizing a starch decomposition product obtained by decomposing (saccharifying) starch (underground starch) or these processed starches. The starch raw material used is not particularly limited, and any starch raw material can be used.

The compositional characteristics of the crystalline starch decomposition product according to the present technology are that the content of glucose polymerization degree (hereinafter referred to as "DP") 8 to 19 is 40% or more, and the content of DP 20 or more is 55% or less, The crystallization ratio calculated from the results of X-ray diffraction is 1% or more. Since the crystalline starch decomposition product according to the present technology has a content of 45% or more with a DP of less than 20, it is easy to redissolve in a boiling bath or purify in a solution state.

Further, the crystalline starch decomposition product according to the present technology includes a portion that is insoluble in cold water, unlike crystalline glucose, sugar, trehalose, and the like. Specifically, it begins to dissolve in water at about 40°C, and some parts are insoluble in cold water at 20°C or lower. Therefore, it can also be used to suspend products such as food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, and fertilizers.

Furthermore, the crystalline starch decomposition product according to the present technology is soluble in hot water, unlike crystalline cellulose or polymeric amylose. Specifically, it exhibits the property that it is almost soluble in water at 60 to 80°C, and completely soluble in hot water at 100°C. Therefore, it can be melted and used by heating when processing into various products.

In addition, the crystalline starch decomposition product according to the present technology is digestible, unlike crystalline cellulose, polymer amylose, etc., which are indigestible. Therefore, it can also be used as a source of carbohydrates (calories) that can be digested and absorbed.

The crystallization ratio of the crystalline starch decomposition product according to the present technology may have an upper limit of 100%, and may be 80% or less or 60% or less. In powder X-ray diffraction analysis, the crystal fraction in the crystalline starch decomposition product according to the present technology has a 2-θ of "5°-6.5°", "8.5°-12.5°", and "13 °-16°", "16°-19°", "19°-21°", "21°-25.5°", "25.5°-27.5°", "27.5°- Since positive peaks are measured in each section of 32°, 32°-35.5°, and 37°-40°, crystal starch decomposition can be calculated based on the area values of each section. It is possible to determine the crystallization ratio of a substance.

More specifically, the "total area" and "crystal area" are calculated according to the following criteria in the Y axis: diffraction intensity/X axis: 2-θ chart of the powder X-ray diffraction measurement results, and the following (3) The crystallization ratio can be determined by the calculation formula.
(1) Total area (area in the section where 2-θ is "3°-40°");
The straight line connecting the measured values when 2-θ is 3° and 40° is used as the reference line, and the area of the region surrounded by the reference line and the diffraction intensity curve, where the diffraction intensity is stronger than the reference line, is defined as the "total area." ” is calculated as
(2) Crystal area;
2-θ is "5°-6.5°", "8.5°-12.5°", "13°-16°", "16°-19°", "19°-21°", "21°-25.5°", "25.5°-27.5°", "27.5°-32°", "32°-35.5°", "37°-40°" The area in each section is calculated in the same manner as (1) overall area, and the total value of the areas of all the sections is calculated as the "crystal area."
(3) Calculation formula: Crystallization ratio = (crystal area/total area) x 100

The "crystallization ratio" in this technology was calculated using powder X-ray diffraction measurement results analyzed using MiniFlex 600 (manufactured by Rigaku Co., Ltd.) with an X-ray wavelength of Cu Kα and an X-ray output of 40 kV and 15 mA. It is a value.

In other words, the crystalline starch decomposition product according to the present technology is a crystallized starch decomposition product in which the content of DP8 to 19 is 32% or more and the content of DP20 or more is 30% or less. That is, the starch decomposition product before crystallization of the crystalline starch decomposition product according to the present technology is characterized in that the content of DP 8 to 19 is 32% or more, and the content of DP 20 or more is 30% or less.

The sweetness of the crystalline starch decomposition product according to the present technology can be reduced by performing a separation step. By having low sweetness, it can be suitably applied to applications that do not require sweetness. Therefore, it can be used, for example, in food additives, drinks, and drugs where crystalline carbohydrates with high sweetness cannot be used.

In addition, since the crystalline starch decomposition product according to the present technology also contains a portion that is insoluble in cold water below 20°C, by performing a separation step to separate the insoluble portion and remove soluble carbohydrate components, A crystalline starch decomposition product exhibiting low hygroscopicity can be obtained. By having low hygroscopicity, products such as food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, and fertilizers that use the crystalline starch decomposition products related to this technology may absorb moisture. It has low properties and can prevent it from leaching out of the product.

Among the crystalline starch decomposition products according to the present technology, the crystalline starch decomposition products with low sweetness and low hygroscopicity have a crystallization ratio of 10% or more and are dispersed in water at 20°C. The actual supernatant Brix value is 2.0% or less. Here, in this technology, "supernatant Brix value when dispersed in 20°C water" specifically means that 10% by mass of crystalline starch decomposition product is dispersed in 20°C water and stirred well. This refers to the Brix value of the supernatant.

Among the crystalline starch decomposition products according to the present technology, the crystalline starch decomposition products having low sweetness and low hygroscopicity can be obtained by precipitating the crystalline starch decomposition products according to the present technology, followed by a separation process (for example, at 20 °C It can be easily taken out by washing with the following water.

In general, the crystal structure of starch can be divided into type A, in which a unit cell contains 4 molecules of water between the double helices, and type B, in which 36 molecules of water are contained between the double helices, based on the results of powder X-ray diffraction. The crystal structure of the crystalline starch decomposition product according to the technique is not limited as long as it does not impair the effects of the present technique, and may be type A or type B.

In the crystalline starch decomposition product according to the present technology, the content is not particularly limited as long as the content of DP8 to 19 is 40% or more, but the content is preferably 50% or more, more preferably 55% or more. As the content of DP8 to 19 increases, the quality of the crystalline starch decomposition product, such as solubility and crystal size, becomes more stable.

Further, the content of the crystalline starch decomposition product according to the present technology is not particularly limited as long as the content of DP20 or higher is 55% or less, but it is preferably 50% or less, more preferably 45% or less. The lower the content of DP20 or more, the easier the crystalline starch decomposition product will dissolve in water at 60 to 80°C.

The crystalline starch decomposition product according to the present technology can be pulverized and used as a fine powder product.

<About food and drink compositions and food and drink compositions containing crystalline starch decomposition products>
The crystalline starch decomposition product according to this technology takes advantage of its solubility that varies depending on temperature and its digestibility, etc. to impart richness to foods and drinks, impart whiteness (emphasizing whiteness, etc.), and provide carbohydrate sources ( It can be suitably used as a calorie source).

In addition, the crystalline starch decomposition product according to the present technology can improve the quality of the composition or the food or drink by including it in the composition or the food or drink. Specifically, qualities such as hygroscopicity, solidification, gelation, shape retention, whiteness, and water repellency of the composition for food and drink products or food and drink products can be modified.

Foods and drinks that can contain the crystalline starch decomposition product according to the present technology are not particularly limited, and include, for example, juices, sports drinks, beverages such as tea, coffee, and black tea, seasonings such as soy sauce and sauces, and soups. , creams, various dairy products, frozen desserts such as ice cream, various powdered foods (including beverages), preserved foods, frozen foods, breads, sweets, processed foods such as cooked rice, noodles, water paste products, meat products, etc. etc. can be mentioned. In addition, it is used in foods and beverages with health claims (including foods with specified health claims, foods with functional claims, and foods with nutritional claims), so-called health foods (including beverages), liquid foods, infant and toddler foods, diet foods, and diabetic foods. It is also possible to contain the crystalline starch decomposition product according to the present technology.

There are no particular limitations on the method of incorporating the crystalline starch decomposition product according to the present technology into a food or drink composition or a food or drink composition. For example, a method of incorporating the crystalline starch decomposition product according to the present technology into a food/drink composition or a food/beverage composition, or a method of incorporating the crystalline starch decomposition product according to the present technology into a food/beverage composition in a state in which it is dissolved or dispersed in an arbitrary solvent. or a method in which the crystalline starch decomposition product according to the present technology is included in a food or drink composition and then recrystallized as necessary; After that, a method of crystallizing the starch decomposition product, etc. can be mentioned.

When the crystalline starch decomposition product according to the present technology is used in food and drink products, a form in which it is distributed as a composition for food and drink products can also be adopted. Specifically, for example, various food mixes (pancake mix, bakery mix, confectionery mix, noodle wrapper mix, etc.), various food flours (tempura flour, karaage flour, okonomiyaki flour, takoyaki flour, etc.) (roasted flour, etc.), various food and drink sources (confectionery sources, donut sources, cake sources, ice cream sources, soup sources, beverage sources, etc.).

In addition, the crystalline starch decomposition products according to this technology can be used as food additives such as concentrated nutrients, bulking agents for foods such as livestock meat, powdered base materials, taste regulators, suspending agents, and osmotic pressure regulators. It is also possible.

<About medicines containing crystalline starch decomposition products>
The crystalline starch decomposition product according to the present technology can be suitably applied to all kinds of pharmaceuticals by taking advantage of its solubility that varies depending on temperature, digestibility, etc.

Moreover, the quality of the crystalline starch decomposition product according to the present technology can be improved by incorporating it into a pharmaceutical product. Specifically, it is possible to modify the qualities of pharmaceuticals, such as hygroscopicity, solidification, gelation, shape retention, whiteness, and water repellency.

Application methods for pharmaceuticals are not particularly limited, but include, for example, powdered base materials for powders and granules, excipients for tablets, suspensions for liquid preparations, semi-solid preparations, ointment preparations, etc. It can be applied to carbohydrate sources (calorie sources) such as agents, osmotic pressure regulators, colorants (white), and enteral nutrients.

The method of incorporating the crystalline starch decomposition product according to the present technology into a pharmaceutical product is not particularly limited, and is the same as the method of incorporating it into the food/beverage composition or food/beverage product described above, so a description thereof will be omitted here.

<About cosmetics containing crystalline starch decomposition products>
The crystalline starch decomposition product according to the present technology can be suitably applied to all kinds of cosmetics by taking advantage of the property that its solubility varies depending on the temperature. In addition, the crystalline starch decomposition product according to this technology has relatively uniform particle shapes and sizes and is biodegradable, so these properties can be utilized to suitably apply it to various cosmetics. be able to.

Moreover, the quality of the crystalline starch decomposition product according to the present technology can be improved by incorporating it into a cosmetic. Specifically, it is possible to modify the qualities of cosmetics, such as hygroscopicity, solidification, gelation, shape retention, whiteness, and water repellency.

The method of application to cosmetics is not particularly limited, but for example, powdered base materials and excipients for powdered cosmetics, solid cosmetics, etc., liquid, milky, gel-like, cream-like cosmetics, etc. It can be applied as a suspending agent, an osmotic pressure adjusting agent, a coloring (whitening) agent, etc.

The method of incorporating the crystalline starch decomposition product according to the present technology into cosmetics is not particularly limited, and is the same as the method of incorporating it into the food/beverage composition or food/beverage product described above, so a description thereof will be omitted here.

<About industrial products containing crystalline starch decomposition products>
The crystalline starch decomposition product according to the present technology can be suitably applied to all kinds of industrial products by taking advantage of the property that its solubility varies depending on the temperature. In addition, the crystalline starch decomposition product according to this technology has a linear molecular structure, the shape and size of its particles are relatively uniform, and it is biodegradable, so by utilizing these properties, It can be suitably applied to various industrial products.

Furthermore, the crystalline starch decomposition product according to the present technology can improve the quality of industrial products by incorporating them into the products. Specifically, it is possible to modify the qualities of industrial products such as hygroscopicity, solidification, gelation, shape retention, whiteness, and water repellency.

Industrial products to which the crystalline starch decomposition product according to the present technology can be applied include, for example, carriers, various films, fibers, capsules, adhesives, mold release agents, anti-adhesion agents, fillers, abrasives, excipients, etc. can be mentioned.

The method of incorporating the crystalline starch decomposition product according to the present technology into an industrial product is not particularly limited, and is the same as the method of incorporating it into the food/beverage composition or food/beverage product described above, so a description thereof will be omitted here.

<About feed, culture medium, and fertilizer containing crystalline starch decomposition products>
The crystalline starch decomposition product according to this technology can be used for livestock mammals such as cows, horses, and pigs, poultry such as chickens and quail, reptiles, birds, and small mammals by taking advantage of the property that its solubility varies depending on temperature. It can also be included in feed for pets, farmed fish, insects, etc. Moreover, it is also possible to include it in a medium or fertilizer for culturing microorganisms.

Furthermore, the quality of the crystalline starch decomposition product according to the present technology can be improved by including it in feed, culture medium, or fertilizer. Specifically, it is possible to modify the qualities of feed, culture medium, fertilizer, such as hygroscopicity, solidification, gelation, shape retention, whiteness, and water repellency.

The method of incorporating the crystalline starch decomposition product according to this technology into feed, culture medium, and fertilizer is not particularly limited, and is the same as the method of incorporating it into the food and drink compositions or food and drink products described above, so the explanation is omitted here. do.

<About modifiers containing crystalline starch decomposition products>
As mentioned above, the crystalline starch decomposition product according to this technology can be incorporated into food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, or fertilizers to improve their quality. It can be used as a modifier for various products.

The modifier according to the present invention may be composed only of the crystalline starch decomposition product described above, as long as it contains the crystalline starch decomposition product according to the present technology as an active ingredient, and as long as the effects of the present invention are not impaired. , one or more other components may be freely selected and included. Other components that can be used include, for example, excipients, pH adjusters, coloring agents, flavoring agents, disintegrants, lubricants, stabilizers, and emulsifiers that are commonly used in formulations. Furthermore, components having functions that are known or that will be discovered in the future may be used in combination depending on the purpose. Since the crystalline starch decomposition product described above is classified as a food, the modifier according to the present invention can be treated as a food depending on the selection of components other than the crystalline starch decomposition product.

The method of blending the modifier according to the present technology into each product is not particularly limited. For example, the modifier according to the present technology may be blended into each product as is, or the modifier according to the present technology may be dissolved or dispersed in any solvent and then added to each product, and then reused as necessary. A method of crystallization, etc. can be mentioned.

<About the manufacturing method of crystalline starch decomposition product>
The composition of the crystalline starch decomposition product according to the present technology is new, and the method for obtaining it is not particularly limited. For example, after obtaining a starch decomposition product by appropriately combining a starch raw material with a treatment using general acids or enzymes, various chromatography, membrane separation, ethanol precipitation, etc., A starch decomposition product can be obtained by subjecting it to a general crystallization process. Furthermore, when producing the starch decomposition product, by using water at a temperature of 60 to 100°C depending on the solubility, precipitation in the saccharification solution, etc. during production can be prevented, and high-quality crystals can be obtained.

As a method for efficiently obtaining a starch decomposition product before crystallization of a crystalline starch decomposition product according to the present technology, there is a method in which at least a debranching enzyme and a branching enzyme are allowed to act on starch or a starch decomposition intermediate. Branching enzymes are enzymes involved in decomposing branched chains of starch, and branching enzymes are enzymes used to synthesize branched chains of starch. Therefore, the two are usually not used together. However, by using a combination of both enzymes that have completely opposite effects, it is possible to reliably produce the starch decomposition product according to the present technology.

In this case, the order of action of both enzymes is either simultaneously or after the action of the branching enzyme, the debranching enzyme is brought into action.

The debranching enzyme is not particularly limited. For example, pullulanase (pullulanase, pullulan 6-glucan hydrolase), amylo-1,6-glucosidase/4-α glucanotransferase (amylo-1,6-glucosidase/4-α glucanotransferase) can be mentioned, and more preferred As an example, isoamylase (glycogen 6-glucanohydrolase) can be used.

Furthermore, the branching enzyme is not particularly limited. For example, enzymes purified from animals, bacteria, etc., those purified from plants such as potatoes, rice seeds, and corn seeds, and commercially available enzyme preparations can be used.

Another method of obtaining a starch decomposition product before crystallization of the crystalline starch decomposition product according to the present technology is to add an acid to starch or a starch decomposition intermediate to liquefy it, and then apply a debranching enzyme to the starch decomposition product. . At this time, the acids that can be used are those that can liquefy starch or starch decomposition intermediates, and one or more general acids can be freely used as long as they do not impair the effects of the present technology. It can be selected and used. Examples include hydrochloric acid, oxalic acid, and sulfuric acid.

In the crystallization step in the method for producing a crystalline starch decomposition product according to the present technology, the starch decomposition product is crystallized. The crystallization step can be performed after the enzyme reaction step, or can be performed simultaneously with the enzyme reaction step.

The crystallization method in the crystallization step is not particularly limited, and one or more known crystallization methods can be freely selected and used. In the present technology, for example, the starch decomposition product can be crystallized by maintaining the solution of the starch decomposition product at a predetermined concentration or higher and/or by lowering the temperature to a predetermined temperature or lower.

In this case, the concentration of the solution of the starch decomposition product is not particularly limited and can be set freely as long as it does not impair the effects of the present technology. For example, by maintaining the concentration of the starch decomposition product at 10% by mass or more, Can be crystallized. In addition, the temperature of the starch decomposition product in this case is not particularly limited and can be set freely as long as it does not impair the effects of the present technology. can be converted into Furthermore, the holding time is not particularly limited, and can be freely set as long as it does not impair the effects of the present technology.

In the method for producing a crystalline starch decomposition product according to the present technology, a separation step of separating the crystalline starch decomposition product can be performed on the precipitate after the crystallization step or the powder product after dehydration and drying. The separation process is a process of separating components with low solubility in water from the crystalline starch decomposition product, and may be performed, for example, by washing with an organic solvent such as water or alcohol, filtration, centrifugation, or a combination thereof. Can be done. By performing the separation process, low sweetness and low hygroscopic crystals with a crystallization ratio of 10% or more and a supernatant Brix value of 2.0% or less when dispersed in water at 20°C are obtained. It is possible to obtain starch decomposition products.

In the method for producing a crystalline starch decomposition product according to the present technology, it is also possible to perform a step of removing impurities after the enzyme reaction step, after the crystallization step, or after the separation step. The method for removing impurities is not particularly limited, and one or more known methods can be used in combination. For example, methods such as filtration, activated carbon decolorization, and ion purification can be used.

Furthermore, the crystalline starch decomposition product according to the present technology can be used as a liquid product containing crystals after the crystallization process, but it can also be dehydrated and powdered by vacuum drying, spray drying, freeze drying, etc. It is possible.

<About the manufacturing method of food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, or fertilizers>
The crystallization step in the method for producing a crystalline starch decomposition product according to the present technology is performed as one step in a method for producing a composition for food and beverages, a food and beverage, a pharmaceutical, a cosmetic, an industrial product, a feed, a culture medium, or a fertilizer. Compositions for food and beverages, foods and beverages, pharmaceuticals, cosmetics, and industrial products containing crystallized starch decomposition products with a content of DP8 to 19 of 32% or more and a content of DP20 or higher of 30% or less. A product, feed, culture medium, or fertilizer can be manufactured.

The timing of performing the crystallization step in the manufacturing method of each product can be freely set according to the manufacturing process of each product, as long as the effects of the present invention are not impaired. For example, a method of manufacturing each product and a crystalline starch decomposition product according to this technology, and then blending the crystalline starch decomposition product according to this technology into each product, or manufacturing each product and a crystalline starch decomposition product according to this technology, respectively. After that, the crystalline starch decomposition product according to the present technology is dissolved or dispersed in any solvent and then incorporated into each product, and then recrystallized as necessary. After manufacturing each product, A method of crystallizing the starch decomposition product after incorporating the starch decomposition product in the state before crystallization into each product, a crystalline starch decomposition product according to the present technology and/or a starch decomposition product in the pre-crystallization state in each product Examples include a method in which the starch decomposition product is crystallized at any timing in the manufacturing process of each product after being blended with the raw material.

Hereinafter, the present technology will be described in more detail based on examples. Note that the embodiment described below shows one example of a typical embodiment of the present technology, and therefore the scope of the present technology should not be interpreted narrowly.

<Experiment example 1>
In Experimental Example 1, we investigated how the specific sugar composition and crystallization ratio of the crystalline starch decomposition product affect solubility, sweetness, and hygroscopicity.

(1) Test method [Branch-forming enzyme]
In this experiment, as an example of a branch-forming enzyme, a potato-derived enzyme purified according to the method of Eur. J. Biochem. 59, p615-625 (1975) (hereinafter referred to as "potato-derived branch-forming enzyme") was used. and Branchzyme (manufactured by Novozymes Co., Ltd., hereinafter referred to as "bacterial branching enzyme").

Note that the activity of the branching enzyme was measured by the following method.
As the substrate solution, an amylose solution in which 0.1% by mass of amylose (manufactured by Sigma-Aldrich, A0512) was dissolved in 0.1M acetate buffer (pH 5.2) was used. Add 50 μL of enzyme solution to 50 μL of substrate solution, react at 30°C for 30 minutes, and then add 2 mL of iodine-potassium iodide solution (0.39 mM iodine-6 mM potassium iodide-3.8 mM hydrochloric acid mixed solution). was added to stop the reaction. A blank solution was prepared by adding water instead of the enzyme solution. Absorbance at 660 nm was measured 15 minutes after the reaction was stopped. One unit of enzyme activity of the branching enzyme was defined as the amount of enzyme activity that lowered the absorbance at 660 nm by 1% per minute when tested under the above conditions.

[Content of DP8 to 19 and DP20 or higher]
Analysis was performed by high performance liquid chromatography (HPLC) under the conditions shown in Table 1 below, and the content of DP 8 to 19 and DP 20 or higher was determined based on the detected peak area ratio.

[Powder X-ray diffraction]
Powder X-ray diffraction analysis was performed using MiniFlex600 (manufactured by Rigaku Co., Ltd.) at an X-ray wavelength of Cu Kα and an X-ray output of 40 kV and 15 mA. The type of crystal was determined from the analysis chart.

[Crystallization ratio]
The "total area" and "crystal area" were calculated based on the following criteria in the Y axis: diffraction intensity/X axis: 2-θ chart of the powder X-ray diffraction measurement results, and were determined using the formula (3) below. .
(1) Total area (area in the section where 2-θ is "3°-40°");
The straight line connecting the measured values when 2-θ is 3° and 40° is used as the reference line, and the area of the region surrounded by the reference line and the diffraction intensity curve, where the diffraction intensity is stronger than the reference line, is defined as the "total area." ” was calculated.
(2) Crystal area;
2-θ is "5°-6.5°", "8.5°-12.5°", "13°-16°", "16°-19°", "19°-21°", "21°-25.5°", "25.5°-27.5°", "27.5°-32°", "32°-35.5°", "37°-40°" The area in each section was calculated in the same manner as (1) overall area, and the total value of the areas of all the sections was calculated as the "crystal area."
(3) Calculation formula: Crystallization ratio (%) = (crystal area/total area) x 100

[Evaluation of solubility]
[Solubility at 20°C]
The crystalline starch decomposition product was dispersed in 20° C. water at 10% by mass and stirred well, and the residue of insoluble matter and the transparency of the solution were evaluated based on the following criteria. Further, the Brix value of the supernatant excluding the precipitate was measured using a refractometer.

[Solubility at 100℃]
The crystalline starch decomposition product was dispersed in water at 10% by mass, heated in a boiling bath for 10 minutes with thorough stirring, and the precipitation of insoluble matter and the transparency of the solution were evaluated based on the following criteria.

〔Evaluation criteria〕
Dissolved: Completely dissolved, resulting in a transparent solution. Cloudy: Dissolved to some extent, with almost no precipitate, but the liquid is cloudy. Insoluble: Most of the solution is not dissolved and is precipitated.

[Sweetness]
The sweetness of the crystalline starch decomposition product when eaten in powder form was evaluated by a panel of five experts according to the following evaluation criteria, and the evaluation was determined by a consensus.

〔Evaluation criteria〕
○: No sweetness, good △: Slightly sweetness ×: Strong sweetness

[Hygroscopicity]
The state of the crystalline starch decomposition product after being stored for one week at 25° C. and 95% relative humidity was evaluated using a temperature/humidity tester HIFLEX TH401 (manufactured by Kusumoto Kasei Co., Ltd.) according to the following evaluation criteria.

〔Evaluation criteria〕
○: Maintained powder state △: Part or all of the powder solidified ×: Powder became candy-like

(2) Manufacturing method of Examples and Comparative Examples [Example 1]
To a 30% by mass cornstarch slurry adjusted to pH 5.8 with 10% calcium hydroxide, 0.2% by mass per solid content (g) of α-amylase (Ricozyme Supra, manufactured by Novozymes Co., Ltd.) was added and It was liquefied in a cooker (temperature 110°C). This liquefied liquid was kept at 95° C., DE was measured over time, and when DE reached 8, the pH was adjusted to 4.0 with 10% hydrochloric acid and the reaction was stopped by boiling. After the reaction was stopped, the pH of the sugar solution was adjusted to 5.8, and then 1000 units of bacterial branching enzyme was added per solid content (g), and the reaction was carried out at 50° C. for 24 hours. Thereafter, 1.5% by mass of a branch cutting enzyme (GODO-FIA, manufactured by Godo Shusei Co., Ltd.) was added based on the solid content (g), and the mixture was reacted at 50°C for 24 hours. This starch decomposition product solution was subjected to activated carbon decolorization, ion purification, and concentrated to a solid content concentration of 60% by mass. The concentrated solution was maintained at 60° C. for 7 days, and the resulting precipitate was separated by repeated washing with water and centrifugation until no solid content was dissolved out, and then lyophilized to powder the crystalline starch of Example 1. A decomposition product was obtained.

[Example 2]
To a 30% by mass corn starch slurry adjusted to pH 5.8 with 10% calcium hydroxide, 0.2% by mass of α-amylase (Clistase T10S, manufactured by Amano Enzyme Co., Ltd.) was added per solid content (g), It was liquefied in a jet cooker (temperature 110°C). This liquefied liquid was kept at 95° C., DE was measured over time, and when DE reached 9, the pH was adjusted to 4.0 with 10% hydrochloric acid and the reaction was stopped by boiling. After adjusting the pH of the sugar solution after stopping the reaction to 5.8, the bacterial branching enzyme was added to 800 units per solid content (g), and the branching enzyme (GODO-FIA, manufactured by Godo Shusei Co., Ltd.) was added to the solid content (g). 1.0% by mass per g) was added and reacted at 50°C for 60 hours. This starch decomposition product solution was decolorized with activated carbon, ion-purified, and concentrated to a solid content concentration of 50% by mass. The concentrated solution was kept at 4°C for 3 days, and the resulting precipitate was separated by repeating water washing and centrifugation until no solid content was dissolved out, and then freeze-dried and powdered to obtain the crystalline starch of Example 2. A decomposition product was obtained.

[Example 3]
To a 30% by mass corn starch slurry adjusted to pH 5.8 with 10% calcium hydroxide, 0.2% by mass of α-amylase (Clistase T10S, manufactured by Amano Enzyme Co., Ltd.) was added per solid content (g), It was liquefied in a jet cooker (temperature 110°C). This liquefied liquid was kept at 95° C., DE was measured over time, and when DE reached 11, the pH was adjusted to 4.0 with 10% hydrochloric acid and the reaction was stopped by boiling. After the reaction was stopped, the pH of the sugar solution was adjusted to 5.8, and then 600 units of bacterial branching enzyme was added per solid content (g), and the reaction was carried out at 65° C. for 15 hours. Thereafter, 0.5% by mass of a branch cutting enzyme (GODO-FIA, manufactured by Godo Shusei Co., Ltd.) was added based on the solid content (g), and the mixture was reacted at 50°C for 40 hours. This starch decomposition product solution was decolorized with activated carbon, ion-purified, and concentrated to a solid content concentration of 50% by mass. The concentrate was kept at 50° C. for 5 days, and the resulting sugar solution containing the precipitate was pulverized using a spray dryer. The powder was separated by repeated washing with water and centrifugation until no solid content was dissolved out, and then lyophilized to obtain a powdered crystalline starch decomposition product of Example 3.

[Example 4]
A 30% by mass cornstarch slurry adjusted to pH 2.0 with 10% hydrochloric acid was decomposed to DE8 at a temperature of 130°C. After returning to normal pressure, the reaction was stopped using sodium hydroxide, and the pH of the sugar solution was adjusted to 5.8. After that, 300 units of potato-derived branching enzyme was added per solid content (g), and the mixture was heated at 35°C. After reacting for 48 hours, the reaction was stopped by boiling. Thereafter, the pH was adjusted to 4.2, and 1.0% by mass of a debranching enzyme (isoamylase, manufactured by Sigma-Aldrich Japan Co., Ltd.) was added based on the solid content (g), and the mixture was reacted at 45° C. for 40 hours. Example 4 This starch decomposition product solution was kept at 4°C for 3 days, and the resulting precipitate was separated by repeating water washing and centrifugation until no solid content was dissolved, and then freeze-dried and powdered. A crystalline starch decomposition product was obtained.

[Example 5]
To a 30% by mass tapioca starch slurry adjusted to pH 5.8 with 10% calcium hydroxide, 0.2% by mass of α-amylase (Clistase T10S, manufactured by Amano Enzyme Co., Ltd.) was added per solid content (g). , and liquefied in a jet cooker (temperature 110°C). This liquefied liquid was kept at 95° C., DE was measured over time, and when DE reached 15, the pH was adjusted to 4.0 with 10% hydrochloric acid and the reaction was stopped by boiling. After the reaction was stopped, the pH of the sugar solution was adjusted to 5.8, and then 2000 units of potato-derived branch-forming enzyme per solid content (g) was added, and the mixture was reacted at 35° C. for 30 hours. Thereafter, 1.0% by mass of a branch cutting enzyme (GODO-FIA, manufactured by Godo Shusei Co., Ltd.) was added based on the solid content (g), and the mixture was reacted at 50°C for 20 hours. This starch decomposition product solution was decolorized with activated carbon, ion-purified, and concentrated to a solid content concentration of 40% by mass. The concentrated solution was maintained at 65° C. for 10 days, and the resulting precipitate was separated by repeated washing with water and centrifugation until no solid content was dissolved out, and then lyophilized to form the crystalline starch of Example 5. A decomposition product was obtained.

[Example 6]
A 30% by mass waxy cornstarch slurry adjusted to pH 2.0 with 10% hydrochloric acid was decomposed to DE6 at a temperature of 130°C. After returning to normal pressure, the pH of the sugar solution that had stopped the reaction was adjusted to 5.8 using sodium hydroxide, and then 500 units of bacterial branching enzyme per solid content (g) and branching enzyme (GODO) were added. -FIA, manufactured by Godo Shushu Co., Ltd.) was added in an amount of 0.5% by mass based on the solid content (g), and the mixture was reacted at 50°C for 72 hours. The solution of this starch decomposition product was decolorized with activated carbon and subjected to ion purification. The purified sugar solution was kept at 4°C for 10 days, and the resulting precipitate was separated by repeating water washing and centrifugation until no solid content dissolved out, and then powdered with a spray dryer to obtain the crystalline starch of Example 6. A decomposition product was obtained.

[ Reference example 7]
The concentrated sugar solution of Example 2 was held at 4° C. for 3 hours, and the resulting sugar solution containing the precipitate was pulverized using a spray dryer to obtain a crystalline starch decomposition product of Reference Example 7.

[ Reference example 8]
As the crystalline starch decomposition product of Reference Example 8, the spray-dried powder of Example 3 was used.

[Example 9]
A 20% by mass cornstarch slurry adjusted to pH 2.0 with 10% hydrochloric acid was decomposed to DE17 at a temperature of 130°C. After returning to normal pressure, the pH of the sugar solution was adjusted to 5.8 by neutralizing the reaction with 10% by mass sodium hydroxide, and then a debranching enzyme (isoamylase, Sigma-Aldrich Japan Co., Ltd.) was added. 1.0% by mass based on the solid content (g) was added and reacted at 45°C for 50 hours. This starch decomposition product solution was decolorized with activated carbon, ion-purified, and concentrated to a solid content concentration of 45% by mass. The concentrated solution was kept at 4° C. for 3 days, and the resulting precipitate was washed with water and centrifuged repeatedly until no solid content was dissolved out, followed by freeze-drying to obtain the crystal-containing starch decomposition product of Example 9.

[Comparative example 1]
To a 30% by mass waxy corn starch slurry adjusted to pH 5.8 with 10% sodium hydroxide, 0.2% by mass of α-amylase (Ricozyme Supra, manufactured by Novozymes Inc.) was added per solid content (g), It was liquefied in a jet cooker (temperature 110°C). This liquefied liquid was kept at 95° C., DE was measured over time, and when DE reached 6, the pH was adjusted to 4.0 with 10% hydrochloric acid and the reaction was stopped by boiling. After adjusting the pH of the sugar solution after stopping the reaction to 5.8, debranching enzyme (GODO-FIA, manufactured by Godo Shusei Co., Ltd.) was added at 2.0% by mass per solid content (g), and the pH was adjusted to 48% at 50°C. Allowed time to react. A large amount of precipitate was observed during the reaction, and after the reaction was completed, the mixture was left to cool at room temperature for one day. The precipitate obtained during the reaction and during cooling was separated by repeating water washing and centrifugation until no solid content dissolved out, and then freeze-dried to obtain a powdered crystalline starch decomposition product of Comparative Example 1.

[Comparative example 2]
As the crystalline carbohydrate in Comparative Example 2, "Treha" (registered trademark) (trehalose) manufactured by Hayashibara Co., Ltd. was used.

[Comparative example 3]
As the crystalline carbohydrate in Comparative Example 3, "Endurance MCC VE-050" (crystalline cellulose) manufactured by Koyo Shokai Co., Ltd. was used.

[Comparative example 4]
The solution of the starch decomposition product of Example 1 was subjected to activated carbon decolorization and ion purification, and then powdered as it was by spray drying without concentrating to obtain the starch decomposition product of Comparative Example 4.

(3) Measurement For Examples 1 to 6, Reference Examples 7 and 8 , Example 9, and Comparative Examples 1 to 4 obtained above, the content of DP 8 to 19 and DP 20 or more was measured by the method described above. In addition, powder X-ray diffraction was performed using the method described above, the crystal type was determined from the results, and the crystallization ratio (%) was calculated using the method described above. In addition, the solubility, sweetness, and hygroscopicity of Examples 1 to 6, Reference Examples 7 and 8 , Example 9, and Comparative Examples 1 to 4 obtained above were also evaluated using the methods described above. The results are shown in Table 2 below. Further, powder X-ray diffraction charts of Example 1 as an example of A-type crystal, Example 2 as an example of B-type crystal, and Comparative Example 4 as an amorphous example are shown in FIGS. 1 to 3, respectively.

As shown in Table 2, Examples 1 to 6, Reference Examples 7 and 8, and Example 9 were all insoluble or cloudy at 20°C, but all showed solubility at 100°C.

Furthermore, when compared among the Examples, Examples 1 to 6 and 9, which were washed with water, had better sweetness evaluation and hygroscopicity evaluation than Reference Examples 7 and 8, which were not washed with water. . Examples 1 to 6 and 9 with good sweetness evaluation and hygroscopicity evaluation have a crystallization ratio of 10% or more and a supernatant Brix value of 2.0% or less when dispersed in water at 20°C. Met. From this result, by performing the separation process, it is possible to achieve a crystallization ratio of 10% or more, a supernatant Brix value of 2.0% or less when dispersed in water at 20°C, low sweetness and low It has been found that a hygroscopic crystalline starch decomposition product can be obtained.

On the other hand, in Comparative Example 1, in which the content of DP8 to 19 was less than 40% and the content of DP20 or more exceeded 55%, the crystallization ratio was 15%, but it did not completely dissolve even at 100 ° C. . This is thought to be caused by undissolved polymer components. Although Comparative Example 2, which is trehalose, was crystalline, it dissolved even at 20°C, had a strong sweet taste, and had poor hygroscopicity evaluation. Comparative Example 3, which is crystalline cellulose, did not dissolve even at 100°C, so it was not possible to measure the content of DP 8 to 19 and the content of DP 20 or higher. In Comparative Example 4, the content of DP8 to 19 was 40% or more, and the content of DP20 or higher was 55% or less, but the crystallization ratio was low and it was considered that it was not a crystal, and it did not dissolve even at 20 ° C. It tasted sweet, and its hygroscopicity was very poor.

In addition, in Examples 2, 4, 6, Reference Example 7, and Example 9, in which crystallization was performed at a temperature lower than room temperature, type B crystals were formed, and in Examples 2, 4, 6, Reference Example 7, and Example 9, in which crystallization was performed at a temperature higher than room temperature. Regarding Examples 1, 3, 5, and Reference Example 8, it was found that type A crystals were formed.

<Experiment example 2>
In Experimental Example 2, the case where the crystalline starch decomposition product or pre-crystallization starch decomposition product produced in Experimental Example 1 was applied to food and drink compositions, food and drink products, pharmaceuticals, cosmetics, and industrial products was verified. .

(1) Cold potato soup Boil 300 parts by mass of potatoes and 50 parts by mass of onions, peeled and cut into appropriate sizes, in 300 parts by mass of water, crush with a mixer, boil with 300 parts of milk, and add salt. Season to taste with pepper. When the temperature reached about 30°C, 80 parts by mass of the crystalline starch decomposition product of Example 1 was added, and the mixture was cooled in a refrigerator to obtain a cold potato soup. The resulting cold potato soup had a texture derived from the crystals and was of good quality with a rich texture.

(2) Milk pudding 6 parts by mass of skim milk powder, 5 parts by mass of sugar, and 1 part by mass of gelatin were added to 19 parts by mass of water, dissolved in a boiling bath, and when the temperature reached about 50°C, the crystals of Example 2 or Example 9 were crystallized. 4 parts by mass of starch decomposition product was added, transferred to a mold, and solidified at 4°C to obtain milk pudding. The obtained milk pudding was of good quality with enhanced whiteness.

(3) Tablets 20 parts by mass of L-ascorbic acid powder was added to 80 parts by mass of the crystalline starch decomposition product of Example 3, and tablets were produced using a tablet molding machine. Vitamin C tablets with good binding and low hygroscopicity were obtained.

(4) Powdered beverage When 100 parts by mass of the crystalline starch decomposition product of Example 4 was added with 50 parts by mass of green tea that had been boiled to a high concentration and then cooled to approximately 20°C and mixed well, the powder state was maintained without becoming a slurry. A good powdered beverage was obtained.

(5) Powdered fat When 20 parts by mass of salad oil was added to 100 parts by mass of the crystalline starch decomposition product of Example 5 and mixed well, a good powdered fat was obtained which maintained a powder state without becoming a slurry.

(6) Cosmetic cream 2 parts by mass of the crystalline starch decomposition product of Example 1, 4 parts by mass of cetostearyl alcohol, 40 parts by mass of squalane, 5 parts by mass of liquid paraffin, 3 parts by mass of beeswax, 5 parts by mass of reduced lanolin, 0 parts by mass of ethylparaben .1 part by mass, 2 parts by mass of glyceride monostearate, 5 parts by mass of glycerin, and 33.9 parts by mass of purified water to produce a cosmetic cream according to a conventional method. As a result, a good cream was obtained.

(7) Abrasive When the crystalline starch decomposition product powder of Example 2 was directly used as an abrasive to polish stains around the kitchen sink using a sponge, the stains were successfully removed. The crystalline starch decomposition product according to this technology is a solid substance that is insoluble in water, has relatively uniform particle shapes and sizes, and is biodegradable, so it can be used as an abrasive. It was able to be used suitably.

(8) Donut icing/glaze Add 6 parts by mass of water to 20 parts by mass of the starch decomposition product before crystallization of Example 1 or Example 9, dissolve it, and pour it over the top of freshly fried donuts and let it stand at room temperature for 1 hour. , manufactured icing donuts. In addition, 15 parts by mass of water was added to 20 parts by mass of the starch decomposition product before crystallization of Example 1 or Example 9, dissolved, and applied to the entire freshly fried donut and allowed to stand at room temperature for 1 hour to form a glazed donut. Manufactured. Each donut produced was stored at 25° C. and 90% relative humidity for 48 hours.

For comparison, dextrin with a DE of 16.5 (trade name "L-SPD" (manufactured by Showa Sangyo Co., Ltd.)) and powdered sugar were used instead of the starch decomposition product, and the dextrin contained 6 ml of water. 4 parts by weight of powdered sugar were added and dissolved in 4 parts by weight of water, and icing donuts were produced in the same manner as described above. Each donut produced was stored at 25° C. and 90% relative humidity for 48 hours.

The whiteness and stickiness of the icing or glaze of each manufactured donut and each donut after storage were evaluated based on the following evaluation criteria.

[Whiteness evaluation criteria]
○: White and opaque, good △: Slightly white and translucent ×: Transparent, no whiteness

[Stickness evaluation criteria]
○: Not sticky, very good △: Slightly sticky, but good ×: Sticky

The results are shown in Table 3 below. Further, FIG. 4 shows photographs of the icing donut using the starch decomposition product before crystallization of Example 1 and the icing donut using powdered sugar before and after storage.

As shown in Table 3, the icing using dextrin was syrup-like and did not harden. The icing made with powdered sugar was white, opaque, and non-sticky before storage, but as it was stored, it absorbed moisture and deliquesced, losing its transparent whiteness and becoming sticky. decreased (see Figure 4).

On the other hand, the icing using the starch decomposition product before crystallization of Example 1 or Example 9 maintained its good whiteness and stickiness even after storage (Fig. (see 4). In addition, regarding the glaze using the starch decomposition product before crystallization in Example 1 or Example 9, the whiteness was not noticeable because it was a thin film, but the state before storage was maintained even after storage. Also, regarding stickiness, the good condition before storage was maintained even after storage.

These results showed that by using this technology, it was possible to create icing and glaze that did not become sticky due to moisture absorption and maintained their white color. Furthermore, it was found that since the crystalline starch decomposition product according to the present technology has a low degree of sweetness, the taste can be easily adjusted with sweeteners or other seasonings.

(9) Edible plastic-like substance Add 15 g of water to 50 g of the starch decomposition product before crystallization of Example 3, mix well in a bag, put it in a mold, let it stand for 3 hours, and then remove it from the mold. , produced an edible plastic-like material.

For comparison, in place of the starch decomposition product, dextrin with a DE of 16.5 (trade name "L-SPD" (manufactured by Showa Sangyo Co., Ltd.)) was used, and an edible plastic-like material was prepared in the same manner as above. produced the substance.

When the starch decomposition product before crystallization of Example 3 was used, a resin-like edible plastic-like substance as shown in FIG. 5 was obtained. When using Showa Sangyo Co., Ltd.), only a starch syrup-like product was obtained.

From this result, it was found that by using this technology, an edible, biodegradable resin-like molded product can be obtained. The resulting molded product is resistant to water and humidity, and its hardness can be controlled by adjusting the amount of water added, and its flexibility can be controlled by adding plasticizers (sorbitol, glycerin, etc.). I understand. In addition, it was found that because of its beautiful white color, the colors reflected well with the coloring agent. Furthermore, it was found that by applying and layering small amounts in the same manner, it could be applied as a stock solution for character pens and 3D printers (see Figure 6).

Claims (12)

The content of glucose polymerization degree (DP) 8 to 19 is 40% or more,
The content of glucose polymerization degree (DP) 20 or more is 18% or more and 55% or less,
The crystallization ratio calculated from the results of X-ray diffraction is 10% or more,
A crystallized product of starch or a starch decomposition intermediate treated with a debranching enzyme and a debranching enzyme , and/or a crystallized product of a debranching enzyme-treated product of an acid liquefied starch or a starch decomposition intermediate. A composition for food and drink containing the crystalline starch decomposition product according to claim 1. A food or drink product comprising the crystalline starch decomposition product according to claim 1 or the composition for food or drink according to claim 2. A pharmaceutical, cosmetic, industrial product, feed, culture medium, or fertilizer containing the crystalline starch decomposition product according to claim 1. A debranching enzyme and a branching enzyme are applied to starch or a starch decomposition intermediate at the same time or after the action of the branching enzyme,
The content of glucose polymerization degree (DP) 8 to 19 is 45% or more,
an enzymatic reaction step for obtaining a starch decomposition product having a glucose polymerization degree (DP) of 20 or more and a content of 21% or more and 30% or less;
Crystallizing the starch decomposition product ,
The content of glucose polymerization degree (DP) 8 to 19 is 40% or more,
The content of glucose polymerization degree (DP) 20 or more is 18% or more and 55% or less,
a crystallization step of obtaining a crystalline starch decomposition product having a crystallization ratio calculated from the results of X-ray diffraction method of 10 % or more;
A method for producing a crystalline starch decomposition product. After adding acid to starch or starch decomposition intermediates and liquefying them, debranching enzymes are applied,
The content of glucose polymerization degree (DP) 8 to 19 is 45% or more,
an enzymatic reaction step for obtaining a starch decomposition product having a glucose polymerization degree (DP) of 20 or more and a content of 21% or more and 30% or less;
Crystallizing the starch decomposition product ,
The content of glucose polymerization degree (DP) 8 to 19 is 40% or more,
The content of glucose polymerization degree (DP) 20 or more is 18% or more and 55% or less,
a crystallization step of obtaining a crystalline starch decomposition product having a crystallization ratio calculated from the results of X-ray diffraction method of 10 % or more;
A method for producing a crystalline starch decomposition product. According to claim 5 or 6, in the crystallization step, the starch decomposition product is crystallized by maintaining the starch decomposition product solution at a concentration of 10% by mass or more and/or by controlling the temperature to 60 ° C. or less. Method for producing crystalline starch decomposition product. The method for producing a crystalline starch decomposition product according to any one of claims 5 to 7, wherein a separation step of separating the crystalline starch decomposition product is performed after the crystallization step. A modifier for food and drink compositions, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, culture media, or fertilizers, which contains the crystalline starch decomposition product according to claim 1. The content of glucose polymerization degree (DP) 8 to 19 is 45% or more,
The content of glucose polymerization degree (DP) of 20 or more is 21% or more and 30% or less,
A debranching enzyme and a debranching enzyme-treated product of starch or a starch decomposition intermediate, and/or a debranching enzyme-treated product of an acid liquefied starch or a starch decomposition intermediate ,
The content of glucose polymerization degree (DP) 8 to 19 is 40% or more,
The content of glucose polymerization degree (DP) 20 or more is 18% or more and 55% or less,
A food or drink composition, a food or drink, a pharmaceutical, a cosmetic, an industrial product, a feed, a culture medium, or a fertilizer containing a crystalline starch decomposition product with a crystallization ratio of 10% or more calculated from the results of an X-ray diffraction method. The content of glucose polymerization degree (DP) 8 to 19 is 45% or more,
The content of glucose polymerization degree (DP) of 20 or more is 21% or more and 30% or less,
Crystallizing part or all of a starch decomposition product that is a debranching enzyme and a debranching enzyme-treated product of starch or a starch decomposition intermediate, and/or a debranching enzyme-treated product of an acid liquefied starch or a starch decomposition intermediate. hand ,
The content of glucose polymerization degree (DP) 8 to 19 is 40% or more,
The content of glucose polymerization degree (DP) 20 or more is 18% or more and 55% or less,
Compositions for food and drink products, food and drink products, pharmaceuticals, cosmetics, industrial products, feeds, which perform a crystallization process to obtain a crystalline starch decomposition product with a crystallization ratio calculated from the results of X-ray diffraction method of 10% or more; Method for producing culture medium or fertilizer. an enzymatic reaction step in which a debranching enzyme and a debranching enzyme act on starch or a starch decomposition intermediate to obtain a starch decomposition product ;
and/or
An enzymatic reaction step of adding an acid to starch or a starch decomposition intermediate to liquefy it, and then acting on a debranching enzyme to obtain a starch decomposition product ;
Crystallizing the starch decomposition product,
The content of glucose polymerization degree (DP) 8 to 19 is 40% or more,
The content of glucose polymerization degree (DP) 20 or more is 18% or more and 55% or less,
a crystallization step of obtaining a crystalline starch decomposition product having a crystallization ratio calculated from the results of X-ray diffraction method of 10% or more;
A method for producing a crystalline starch decomposition product.