WO2022102664A1 - Liquide saccharifié de céréales, et procédé de fabrication de celui-ci - Google Patents

Liquide saccharifié de céréales, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2022102664A1
WO2022102664A1 PCT/JP2021/041370 JP2021041370W WO2022102664A1 WO 2022102664 A1 WO2022102664 A1 WO 2022102664A1 JP 2021041370 W JP2021041370 W JP 2021041370W WO 2022102664 A1 WO2022102664 A1 WO 2022102664A1
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Prior art keywords
grain
saccharified
saccharified solution
dietary fiber
solution
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PCT/JP2021/041370
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English (en)
Japanese (ja)
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舜 渡辺
亮平 福本
真也 木村
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群栄化学工業株式会社
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Publication of WO2022102664A1 publication Critical patent/WO2022102664A1/fr

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • A23L2/60Sweeteners
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/30Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/20Reducing nutritive value; Dietetic products with reduced nutritive value
    • A23L33/21Addition of substantially indigestible substances, e.g. dietary fibres
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L7/00Cereal-derived products; Malt products; Preparation or treatment thereof
    • A23L7/10Cereal-derived products
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/14Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/44Preparation of O-glycosides, e.g. glucosides
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13KSACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00Glucose; Glucose-containing syrups
    • C13K1/06Glucose; Glucose-containing syrups obtained by saccharification of starch or raw materials containing starch

Definitions

  • the present invention relates to a cereal saccharified liquid and a method for producing the cereal saccharified liquid.
  • the saccharified solution is obtained from a reaction of converting high molecular weight carbohydrates such as starch and cellulose into low molecular weight saccharides by the action of enzymes and the like, and is widely used as a sweetener for foods.
  • grains are often used as a raw material for saccharified liquids, and methods for treating grains are being studied.
  • Patent Document 1 contains a large amount of starch and insoluble fiber in brown rice. Therefore, the insoluble component of brown rice is decomposed by enzymatic treatment to make brown rice water-soluble as a raw material.
  • An invention aimed at providing a beverage composition according to the above is described. Specifically, in Patent Document 1, protease, cellulase and pectinase are mixed with an aqueous dispersion of finely crushed brown rice, enzymatically decomposed, and then heated to obtain a pregelatinized swollen rice powder liquid, and then amylases are mixed.
  • a method of enzymatic decomposition has been proposed, and it is described that the liquid derived from brown rice obtained by the method contains extremely few substances insoluble in water.
  • Patent Document 2 describes a method for producing a rice saccharified solution.
  • water is added to raw rice, and the raw rice is subjected to high-temperature and high-pressure treatment to sterilize the raw material microorganisms, pregelatinize starch, promote swelling of rice, and then cool to 45 to 50 ° C. suitable for enzymatic reaction.
  • the enzyme as amylase center
  • the homogenizer micronization
  • Patent Document 3 grains are used as raw materials, and amylase is charged into a pulverizer as the raw materials, hot water and liquefied enzyme, and the raw materials are pulverized in a mixed solution obtained in the pulverizer. ⁇ Dispersion, dissolution, pregelatinization, and liquefaction are performed all at once, and the obtained fluid treatment liquid flows through the liquid passage tube connected to the crusher and is provided in front of the treatment liquid by a heating device.
  • a method for continuously producing a cereal stock solution which is characterized by deactivating the enzymes in the grain, is described, whereby a stable grain stock solution suitable for beverages and the like can be continuously produced in a short time from the input of raw materials with high efficiency. Can be done.
  • Japanese Unexamined Patent Publication No. 5-137545 Japanese Patent Application Laid-Open No. 2003-250485 Japanese Unexamined Patent Publication No. 2009-207359
  • the present inventor used oats or barley as a raw material and diligently studied the treatment method thereof.
  • the contents of insoluble dietary fiber, water-soluble dietary fiber and isomaltooligosaccharide were high, and the intestine was regulated. It has been found that it is possible to provide a grain saccharified solution with less roughness by adjusting the particle size distribution of insoluble components in the grain saccharified solution, in addition to being expected to have an effect and an intestinal regulating effect.
  • the content of insoluble dietary fiber contained in the solid content in the cereal saccharified solution is 1.0 wt% or more, and the content of water-soluble dietary fiber contained in the solid content in the grain saccharified solution is contained.
  • a cereal saccharified solution which is a cereal saccharified solution characterized in that the grain that is the raw material of the grain saccharified solution contains at least one of oat and barley.
  • the grain is oat.
  • the water-soluble dietary fiber content is 2.0 wt% or more.
  • a second aspect of the present invention is a method for producing a saccharified liquid from a grain, wherein the grain contains at least one of oats and barley, and the saccharified liquid is contained in the solid content in the grain saccharified liquid.
  • the content of insoluble dietary fiber contained is 1.0 wt% or more
  • the content of water-soluble dietary fiber contained in the solid content of the grain saccharified solution is 0.6 wt% or more
  • It is a method for producing a cereal saccharified liquid, characterized in that the ratio of sugar is 10.0 wt% or more and the average particle size of insoluble components in the cereal saccharified liquid is 30 to 70 ⁇ m.
  • the liquefied enzyme and the saccharified enzyme used for producing the saccharified solution each have a ⁇ -glucanase activity of 0 to 80%.
  • the homogenizer treatment is performed on the saccharified liquid at a pressure of 10 MPa or more.
  • the cereal is oat.
  • the water-soluble dietary fiber content is 2.0 wt% or more.
  • the third aspect of the present invention is a beverage using the above-mentioned grain saccharified liquid.
  • the fourth aspect of the present invention is a sweet product using the above-mentioned grain saccharified liquid.
  • the first and second aspects of the present invention it is possible to provide a cereal saccharified solution having a novel composition expected to have an intestinal regulating effect and an intestinal regulating effect and having less roughness. Further, according to the third and fourth aspects of the present invention, it is possible to provide a beverage and a sweet product using such a saccharified solution.
  • the "cereal saccharified liquid” is a liquid produced by using grains as a raw material and undergoing liquefaction and saccharification of grains, and can be used as, for example, a sweetener.
  • the main raw materials for the grain saccharified liquid are grains and water (preferably pure water).
  • the grain is not particularly limited as long as it is a grain capable of containing insoluble dietary fiber, water-soluble dietary fiber and isomaltooligosaccharide in the saccharified solution, and is not particularly limited, and is, for example, rice, wheat, corn, and the like. Examples include great millet, hie, corn, millet, barley, oats, and rye.
  • the grain as a raw material preferably contains at least one of oats and barley, and more preferably oats.
  • Oats and barley contain a large amount of ⁇ -glucan, which is a water-soluble dietary fiber, and are preferable from the viewpoint of providing a health-oriented saccharified solution. While barley has acidity and bitterness, oats have no habit, so oats are suitable from the viewpoint of providing a delicious saccharified solution.
  • the total amount of oats and barley in the grain is preferably at least 50 wt% or more, more preferably 80 to 100 wt%.
  • the grain saccharified solution of the present invention contains dietary fiber.
  • Dietary fiber is a substance contained in food that cannot be digested by human digestive enzymes, and is usually roughly classified into insoluble dietary fiber that is insoluble in water and water-soluble dietary fiber that is soluble in water.
  • the effectiveness of dietary fiber is explained, for example, in the revised and expanded edition of the Handbook of Functional Food Materials (Yakuji Nippo Co., Ltd., published in 2006).
  • Insoluble dietary fiber has the effect of adjusting bowel movements and preventing constipation, and ingestion of insoluble dietary fiber increases bifidobacteria and improves the intestinal environment.
  • the grain saccharified solution of the present invention can be expected to have an intestinal regulating effect by containing insoluble dietary fiber.
  • the insoluble dietary fiber include cellulose, hemicellulose, chitin, chitosan and the like.
  • the insoluble dietary fiber is preferably the insoluble dietary fiber derived from the above-mentioned grains.
  • a grain saccharified liquid having a high content of insoluble dietary fiber can be obtained by producing the saccharified liquid without removing the insoluble dietary fiber after the liquefaction step and the saccharification step. Further, by using oats as a raw material of the grain saccharified liquid, the content of insoluble dietary fiber can be increased.
  • the content of insoluble dietary fiber contained in the solid content in the grain saccharified liquid is preferably 1.0 wt% or more, more preferably 2.0 wt% or more, still more preferably 4.0 wt% or more.
  • the content of insoluble dietary fiber contained in the solid content in the grain saccharified liquid is, for example, 8.0 wt% or less, preferably 6.0 wt% or less.
  • Water-soluble dietary fiber has the effect of increasing blood glucose level and reducing cholesterol, slowing down the absorption of carbohydrates, suppressing the rapid increase of postprandial blood glucose level, and also having an intestinal regulation effect.
  • the grain saccharified solution of the present invention can also be expected to have an intestinal regulating effect even if it contains water-soluble dietary fiber.
  • the water-soluble dietary fiber include glucan, pectin, glucomannan, alginic acid, agarose, agaropectin, carrageenan, polydextrose and the like.
  • the water-soluble dietary fiber is preferably the water-soluble dietary fiber derived from the above-mentioned grains.
  • the water-soluble dietary fiber derived from oats and barley is preferable from the viewpoint of providing a health-oriented saccharified solution.
  • the content of water-soluble dietary fiber is high by liquefying and saccharifying the water-soluble dietary fiber contained in the raw material, particularly ⁇ -glucan, without enzymatically decomposing it. A grain saccharified solution is obtained. Further, by using oats as a raw material for the grain saccharified liquid, the content of water-soluble dietary fiber can be increased.
  • the content of water-soluble dietary fiber contained in the solid content in the grain saccharified liquid is preferably 0.6 wt% or more, more preferably 1.0 wt% or more, still more preferably 2.0 wt% or more.
  • the content of water-soluble dietary fiber contained in the solid content in the grain saccharified liquid is, for example, 6.0 wt% or less, preferably 4.0 wt% or less.
  • the grain saccharified solution of the present invention contains isomaltooligosaccharide.
  • Isomaltose oligosaccharides are saccharides having a degree of polymerization of 2 to 10, in which glucose is bound by ⁇ -1,4 bonds and ⁇ -1,6 bonds, and glucose is bound only by ⁇ -1,6 bonds. , Isomaltose, Panose, Isomaltotriose, Isomalttetraose, Isopanose and the like.
  • Isomaltooligosaccharides are less likely to cause diarrhea than sugar alcohols and can be expected to have an intestinal regulating effect.
  • the effectiveness of isomaltooligosaccharides is explained, for example, in the revised and expanded edition of the Handbook of Functional Food Materials (Yakuji Nippo Co., Ltd., published in 2006).
  • a cereal saccharified solution having a high proportion of isomaltooligosaccharide can be obtained.
  • the ratio of isomaltooligosaccharides to the total saccharides contained in the grain saccharified solution is preferably 10.0 wt% or more, more preferably 13.0 wt% or more, still more preferably 15.0 wt% or more.
  • the ratio of isomaltooligosaccharides to the total saccharides contained in the grain saccharified solution is, for example, 30.0 wt% or less, preferably 25.0 wt% or less.
  • the "solid content in the grain saccharified solution” is a component obtained by removing water from the components constituting the grain saccharified solution, and is mainly composed of dietary fiber and sugar.
  • the content of insoluble dietary fiber contained in the solid content of the cereal saccharified solution and “the content of water-soluble dietary fiber contained in the solid content of the grain saccharified solution” are appropriately measured by known measurement methods. Can be measured using. For example, it can be measured by the modified Proski method of the Standard Tables of Food Composition in Japan 2015 (7th edition) Analysis Manual (published by the Ministry of Education, Culture, Sports, Science and Technology).
  • the "ratio of isomaltooligosaccharides to the total saccharides contained in the cereal saccharified solution" can be measured by appropriately using a known measuring method.
  • the monosaccharide, maltose, maltooligosaccharide, and sucrose contents obtained by liquid chromatography using an exclusion type ion exchange column and a normal layer column from the total sugar content obtained by liquid chromatography using an exclusion type ion exchange column. can be obtained by subtracting.
  • the grain saccharified solution is pretreated with activated carbon, ion exchange resin, solid layer extraction, membrane filter, etc., and high performance liquid chromatography (HPLC: trade name “Alliance (registered trademark) HPLC system” (Japan Waters). )) was used to analyze the total sugar content under the following conditions, and high performance liquid chromatography (HPLC: trade name “Promindence” (manufactured by Shimadzu GLC)) was used to perform simple sugar under the following conditions. , Martose, maltooligosaccharide, sucrose content can be analyzed.
  • the grain saccharified solution of the present invention contains various saccharides such as monosaccharides, disaccharides, trisaccharides, and tetrasaccharides and above.
  • the total content of saccharides contained in the solid content in the grain saccharified solution of the present invention is, for example, 30 to 95 wt%.
  • the cereal saccharified solution of the present invention contains a large amount of isomaltooligosaccharides, in many cases, the proportion of trisaccharides or more in the sugar composition is high.
  • the ratio of saccharides of trisaccharides or more to the total saccharides contained in the grain saccharified solution of the present invention is preferably 30 wt% or more, more preferably 40 wt% or more, still more preferably 50 wt% or more. ..
  • the ratio of saccharides of trisaccharides or more to the total saccharides contained in the grain saccharified solution of the present invention is, for example, 70.0 wt% or less, preferably 60.0 wt% or less.
  • the ratio of monosaccharides and disaccharides to the total saccharides contained in the grain saccharified solution of the present invention is in the range of 15 to 30 wt%, respectively.
  • the composition of saccharides contained in the grain saccharified solution can be appropriately measured by using a known measuring method.
  • a known measuring method As an example, after purifying the grain saccharified solution by activated carbon, ion exchange resin, solid layer extraction, membrane filter, etc., high performance liquid chromatography (HPLC: for example, trade name "Alliance (registered trademark) HPLC system” (Nippon Waters Co., Ltd.) Can be measured by)).
  • HPLC high performance liquid chromatography
  • An example of the analysis conditions is as follows. (Analysis conditions) Column: ULTRON PS80-N (manufactured by Shimadzu GLC) Solvent: Pure water Temperature: 60 ° C Flow velocity: 0.6 ml / min Detection: RI (Differential Refractometer)
  • the average particle size of the insoluble component in the grain saccharified solution is preferably 30 to 70 ⁇ m, more preferably 50 to 70 ⁇ m, and even more preferably 55 to 65 ⁇ m. Since the grain saccharified solution of the present invention contains a relatively large amount of dietary fiber, it is preferable to adjust the particle size distribution in the grain saccharified solution.
  • the average particle size of the insoluble component in the grain saccharified liquid is within the above-specified range, it is possible to provide a grain saccharified liquid having less roughness.
  • the saccharified liquid can be adjusted to a desired particle size distribution by subjecting the saccharified liquid to a homogenizer treatment after the liquefaction step and the saccharification step.
  • the "insoluble component in the grain saccharified solution” is a component that is not dissolved in the saccharified solution among the components constituting the grain saccharified solution, and is a component for which the particle size distribution is to be measured.
  • the "insoluble component in the grain saccharified solution” is mainly composed of insoluble dietary fiber.
  • the "average particle size of the insoluble component in the grain saccharified solution” refers to the 50% particle size (D50) of the volume-based particle size distribution, and is based on the particle size distribution measured by the laser diffraction / scattering method (microtrack method). You can ask.
  • the particle size distribution of the microtrack method is to obtain the particle size and its frequency close to a sphere by irradiating a non-spherical substance with a laser and detecting and arithmetically processing the scattered light at regular angles.
  • the grain saccharified solution of the present invention has a Brix of, for example, 15.0 to 25.0.
  • Brix is a soluble solid content concentration (%), and in the present specification, the refractive index of the sucrose solution at 20 ° C. is measured, and the conversion table provided by ICUMSA (International Communication for Uniform Methods of Sugar Analysis) is used. Based on this, it is a value converted into mass / mass percent of a pure sucrose solution.
  • Brix is measured in order to adjust the concentration when concentrating or diluting the saccharified solution.
  • Brix can be measured by appropriately using a known measuring method that is already known, and generally, a commercially available sugar content meter (for example, a digital refractometer trade name "RX-5000 ⁇ " (manufactured by Atago)) can be used. Can be measured using.
  • a commercially available sugar content meter for example, a digital refractometer trade name "RX-5000 ⁇ " (manufactured by Atago)
  • RX-5000 ⁇ manufactured by Atago
  • the cereal saccharified solution of the present invention has a pH at 25 ° C., for example, 3.5 to 7.0, preferably 4.5 to 6.5.
  • the pH of the saccharified solution is measured by appropriately using a known measuring method.
  • a commercially available pH meter for example, a desktop pH meter model: F-74 (manufactured by HORIBA) can be used for measurement.
  • Another aspect of the present invention is a method for producing a cereal saccharified liquid.
  • the method for producing a cereal saccharified liquid of the present invention is a method for producing a saccharified liquid from grains using grains as a raw material, and is a method for producing a saccharified liquid from the grains.
  • the content of insoluble dietary fiber contained in the grain is 1.0 wt% or more
  • the content of water-soluble dietary fiber contained in the solid content of the grain saccharified solution is 0.6 wt% or more
  • the content of the water-soluble dietary fiber is 0.6 wt% or more.
  • the production method of the present invention typically includes a preparation step, a liquefaction step, and a saccharification step, and the saccharified liquid can be produced from grains as a raw material through these steps.
  • the main raw materials of the grain saccharified liquid are grains and water.
  • the grain used as a raw material preferably contains at least one of oats and barley, and is more preferably oats.
  • the crushed grain is used as a raw material, and the crushed product of the grain is mixed with an aqueous medium such as pure water to obtain a preparation liquid.
  • an aqueous medium such as pure water
  • the ratio of the grain and the water medium at that time can be appropriately selected according to the ratio of the desired sugar.
  • the amount of water medium such as pure water is adjusted so that the ratio of grain to the total of grain and water is 10 to 50 wt%, preferably 15 to 40 wt%, and more preferably 20 to 30 wt%.
  • ⁇ -glucan which is a water-soluble dietary fiber
  • ⁇ -glucan degrading enzyme for example, before the liquefaction step.
  • enzymatic decomposition is performed under the product name "Fizym 250L” (manufactured by Novozymes Japan Co., Ltd.).
  • a liquefaction step is carried out in order to obtain a liquefied liquid containing low molecular weight saccharides by cleaving the sugar chain of starch contained in the above-mentioned preparation liquid.
  • the step is performed by adding a liquefying enzyme to the charging liquid.
  • the concentration of the grain in the charging liquid is preferably 5 to 35 wt%, particularly preferably 15 to 25 wt% in consideration of the yield and the like.
  • the pH of the charged liquid is preferably 3.5 to 7.0, and particularly preferably 4.5 to 6.5, from the optimum pH range of the liquefiing enzyme. Since a general charged liquid has a pH in the range of 3.5 to 7.0, the liquefaction reaction can proceed without intentionally adjusting the pH of the charged liquid. Further, in one embodiment of the production method of the present invention, it is not necessary to adjust the pH of the liquefied liquid before the saccharification step described later. That is, since most of the saccharifying enzymes used in the saccharification step also have an optimum pH in the range of pH 3.5 to 7.0, the pH conditions of the liquefaction step and the saccharification step can be set in the same range.
  • the liquefiing enzyme has an optimum pH of 3.5 to 7.0, particularly 4.5 to 6.5, and can cleave a sugar chain such as starch to decompose it into a small molecule saccharide. If there is, any of them can be preferably used, and among them, ⁇ -amylase (EC 3.2.1.1) is preferable. Enzymes with high heat resistance are preferable, and specific examples thereof include the product name "Crystase SD8", the product name "Crystase T10S" (above, manufactured by Amano Enzyme), and the product name "Tarmamil SC” (Novozymes Japan).
  • the ⁇ -glucanase activity of the liquefied enzyme is preferably 0 to 80%, more preferably 0 to 40%, still more preferably 0 to 20%. , 0-10% is particularly preferred.
  • a grain saccharified solution having a high content of water-soluble dietary fiber can be obtained, especially when grains containing a large amount of ⁇ -glucan (oats, barley, etc.) are used as raw materials. Can be done. Details of the method for measuring ⁇ -glucanase activity will be described later.
  • the amount of the liquefiing enzyme added is, for example, 1 unit to 150 units, preferably 10 units to 100 units, more preferably 1 unit, with respect to 1 g of the raw material grain, when the 1 liquefaction force unit (JLU) measured by JIS K7001: 1990 is 1 unit. Is 20 units to 70 units. If it is 1 unit or more, the liquefaction reaction proceeds sufficiently, and if it is 150 units or less, it is economical.
  • JLU liquefaction force unit
  • the reaction temperature and reaction time in the liquefaction step can be appropriately adjusted depending on the type of liquefiing enzyme to be added.
  • the reaction temperature is 65 ° C. to 120 ° C., preferably 80 ° C. to 110 ° C.
  • the reaction time is 0.01 to 24 hours, preferably 0.1 to 12 hours. More preferably, the reaction time can be 0.1 to 2 hours.
  • endogenous enzymes such as ⁇ -amylase that acts on starch to liquefy, dextrinase that acts on dextrin to produce oligosaccharides, and enzymes that act on polysaccharides such as ⁇ -glucan.
  • the action of these endogenous enzymes can optionally lead to the loss of all or any of the preferred components of the invention: insoluble dietary fiber, water-soluble dietary fiber and isomaltooligosaccharides. Therefore, it may be a preferable aspect that the endogenous enzyme is not allowed to act in the liquefaction step.
  • the charged liquid is heated to the reaction temperature range and then the liquefied enzyme is added to keep the charged liquid within the reaction temperature range during the reaction.
  • the liquefaction reaction is carried out in a temperature range.
  • the charging liquid is heated to the reaction temperature range as quickly as possible to inactivate the endogenous enzyme and suppress its action as much as possible.
  • a jet cooker capable of instantly heating and mixing by directly applying a steam jet to the charging liquid can be used.
  • a trade name "Noritake Cooker / Steam Mixer” (manufactured by Noritake Co., Ltd.), a trade name “Jet Cooker” (manufactured by Hydrothermal Co., Ltd.) and the like are commercially available, and can also be used in the present embodiment.
  • the added liquefied enzyme can be sufficiently allowed to act by mixing under high pressure.
  • the liquefied liquid after the liquefaction reaction by the jet cooker is maintained in a batch tank, for example, in a temperature range optimum for the liquefied enzyme, and the liquefaction reaction is further aged. It is also possible to make it.
  • the liquefied liquid after the liquefaction reaction may be appropriately filtered using diatomaceous earth or the like as an auxiliary agent to remove impurities as appropriate.
  • Saccharification step A saccharification step is carried out in order to further decompose the low molecular weight saccharides in the liquefied solution to obtain a saccharified solution containing monosaccharides, disaccharides, trisaccharides, tetrasaccharides and the like.
  • the step is performed by adding a saccharifying enzyme to the liquefied liquid.
  • saccharifying enzymes examples include ⁇ -amylase (EC 3.2.1.2), saccharified ⁇ -amylase (EC 3.2.1.1), glucoamylase (EC 3.2.2.13), and pullulanase (ECEC 3. 2.1.41), transglucosidase (EC 3.2.1.20), glucanase (EC 3.2.1.6) and the like can be mentioned. Although these enzymes can be used alone, it is also preferable to use a combination of a plurality of enzymes.
  • the saccharifying enzyme may be commercially available, and specific examples thereof include the trade name " ⁇ -amylase L / R" (manufactured by Nagase ChemteX Corporation) and the trade name " ⁇ -amylase F Amano” (Amano Enzyme). ), Product name "Hymaltocin GL” (manufactured by HBI), etc., and saccharified ⁇ -amylase, product name "Fangamil” (manufactured by Novozymes), etc.
  • Examples of commercially available pullulanase include the trade name “pullanase” Amano "3” (manufactured by Amano Enzyme), and examples of transglucosidase include the trade name “transglucosidase L” Amano "” (manufactured by Amano Enzyme).
  • the product name “transglucosidase L-500” (manufactured by Genecoa) and the like can be mentioned, and the trade name “Fizym250L” (manufactured by Novozymes Japan) and the like can be mentioned as glucanase.
  • These enzymes are generally active at pH 3.5-7.0 and have an optimum pH of pH 4.5-6.5.
  • the ⁇ -glucanase activity of the saccharifying enzyme is preferably 0 to 80%, more preferably 0 to 40%, still more preferably 0 to 20%. , 0-10% is particularly preferred.
  • a saccharifying enzyme having a low ⁇ -glucanase activity is used, a grain saccharified solution having a high content of water-soluble dietary fiber can be obtained, especially when a grain containing a large amount of ⁇ -glucan (oat, barley, etc.) is used as a raw material. Can be done.
  • the ⁇ -glucanase activity of each saccharifying enzyme is within the above-specified range, but the ⁇ -glucanase activity of some of the saccharifying enzymes is preferable. Even when the degree is low, it is possible to suppress the decomposition of ⁇ -glucan. For example, if the ⁇ -glucanase activity of one of the plurality of saccharifying enzymes is 0 to 10%, it is possible to sufficiently suppress the decomposition of ⁇ -glucan.
  • ⁇ -glucanase activity for saccharifying enzymes and liquefiing enzymes is measured by the following method.
  • a ⁇ -glucan solution is prepared by dissolving the ⁇ -glucan standard in pure water so as to be 5 mg / ml.
  • a ⁇ -glucan solution was prepared using ⁇ -glucan derived from barley manufactured by Sigma.
  • the enzyme sample is diluted with pure water to 10 mg / ml.
  • the ⁇ -glucan solution and the diluted enzyme sample are mixed in a test tube, incubated in a constant temperature bath at 60 ° C. for 3 hours, and then ice-cooled.
  • the ⁇ - glucan concentration in the solution having a molecular weight of 105 or more is measured by the Congo red method (Tochigi Agricultural Experiment Research Bulletin, No. 47, 57-64, 1998). Instead of the enzyme sample, the one obtained by performing the same operation with pure water is used as a blank.
  • Table 1 below shows the ⁇ -glucanase activity for some liquefied and saccharifying enzymes.
  • the ⁇ -glucanase activity can be obtained from the following equation.
  • ⁇ -Glucanase activity (%) (1-B / B0) ⁇ 100
  • B ⁇ -glucan concentration in the case of enzyme sample diluent
  • B0 ⁇ -glucan concentration in the case of blank
  • the amount of the saccharifying enzyme added is, for example, relative to 1 g of the raw material grain when the amount of the enzyme that produces 1 mg of glucose as a result of adding and reacting with amylose at pH 4.5 at 40 ° C. for 30 minutes is 1 unit. It is 10 units to 1000 units, preferably 20 units to 900 units, and more preferably 500 units to 700 units. If it is 1000 units or less, the unpleasant flavor can be suppressed, and if it is 10 units or more, the saccharification reaction proceeds sufficiently.
  • the reaction temperature and reaction time in the saccharification step can be appropriately adjusted depending on the type of saccharifying enzyme to be added.
  • the reaction temperature is 30 ° C. to 65 ° C., preferably 40 ° C. to 65 ° C., more preferably 45 ° C. to 65 ° C.
  • the reaction time is 1 hour to 24 hours, preferably 1.
  • the reaction time can be from 5 hours to 10 hours, more preferably from 2 hours to 4 hours.
  • enzymes such as protease and lipase may be added together as desired during the saccharification step.
  • the insoluble dietary fiber contained in the saccharified solution is refined by shearing, and the desired particle size distribution can be adjusted.
  • the treatment conditions by the homogenizer are not particularly limited as long as it is possible to smooth the texture when the saccharified solution is eaten by refining the insoluble dietary fiber, and the treatment pressure is, for example, 5 MPa or more, preferably 5 MPa or more. It is 10 MPa or more.
  • the processing pressure is typically 90 MPa or less, preferably 20 MPa or less.
  • the homogenizer a commercially available product can be used, and examples thereof include the trade name “homogenizer H20 type” (manufactured by Sanwa Engineering Co., Ltd.).
  • the saccharified solution may be appropriately filtered using diatomaceous earth or the like as an auxiliary agent to remove impurities as appropriate.
  • the cereal saccharified solution obtained by the production method of the present invention has an insoluble dietary fiber content of 1.0 wt% in the solid content of the cereal saccharified solution of the present invention, specifically, the grain saccharified solution.
  • the content of water-soluble dietary fiber contained in the solid content of the grain saccharified liquid is 0.6 wt% or more, and the ratio of isomaltooligosaccharide to the total saccharides contained in the grain saccharified liquid is 10.0 wt% or more.
  • the cereal saccharified solution has an average particle size of an insoluble component in the grain saccharified solution of 30 to 70 ⁇ m.
  • the grain as a raw material preferably contains at least one of oats and barley, and is more preferably oats.
  • the content of insoluble dietary fiber contained in the solid content of the grain saccharified liquid is preferably 1.0 wt% or more, more preferably 2.0 wt% or more, still more preferably 4.0 wt% or more.
  • the content of water-soluble dietary fiber contained in the solid content in the grain saccharified liquid is preferably 0.6 wt% or more, more preferably 1.0 wt% or more, still more preferably 2.0 wt% or more.
  • the ratio of isomaltooligosaccharides to the total saccharides contained in the grain saccharified solution is preferably 10.0 wt% or more, more preferably 13.0 wt% or more, still more preferably 15.0 wt% or more.
  • the average particle size of the insoluble component in the grain saccharified solution is preferably 30 to 70 ⁇ m, more preferably 50 to 70 ⁇ m, and even more preferably 55 to 65 ⁇ m.
  • Another aspect of the present invention is a beverage using the grain saccharified solution of the present invention.
  • the beverage of the present invention typically, the above-mentioned grain saccharified solution of the present invention is used as a sweetener, and a beverage containing the grain saccharified solution of the present invention can be mentioned.
  • Another aspect of the present invention is a sweetened product using the grain saccharified solution of the present invention.
  • the sweetener of the present invention typically, the above-mentioned grain saccharified solution of the present invention is used as a sweetener, and a sweetened substance containing the grain saccharified solution of the present invention can be mentioned, and as a specific example thereof, jelly. , Pudding, ice cream, candy, soft candy, gum and other sweets.
  • Example 1 This is an example in which oats are used as the raw material grain.
  • the mixture was added at a concentration of 0.3% (3930 unit / 100 g raw material) based on the mass of the grain as a raw material, and reacted at 90 ° C. for 1 hour to obtain a reaction solution.
  • the above reaction solution is cooled to 60 ° C.
  • the product name "Transglucosidase L Amano” (manufactured by Amano Enzyme), which is a transglucosidase, is 0.20% based on the mass of the grain as a raw material (W / W). It was added to the above reaction solution at a concentration of (60000unit / 100g raw material). Then, the saccharification reaction was carried out at 60 ° C. for 3 hours, and then the mixture was heated to 90 ° C. to inactivate the enzyme. Next, after cooling to room temperature, homogenizer treatment was performed at 15 MPa to obtain an oat-derived saccharified solution. The obtained saccharified solution had a Brix of 20.2 and a pH of 6.1.
  • Example 2 This is an example in which barley is used as a raw material grain.
  • the water was charged into the reaction tank so that the weight ratio of pure water and barley (manufactured by Kyoto Grain) was 75:25, and the trade name "Crystase T10S" (manufactured by Amano Enzyme) was used as the raw material for ⁇ -amylase, which is a liquefiing enzyme.
  • the mixture was added at a concentration of 0.3% (3930 unit / 100 g raw material) based on the mass of the grain (W / W), and reacted at 90 ° C. for 1 hour to obtain a reaction solution.
  • the above reaction solution is cooled to 60 ° C.
  • the product name "Transglucosidase L Amano” (manufactured by Amano Enzyme), which is a transglucosidase, is 0.20% based on the mass of the grain as a raw material (W / W). It was added to the above reaction solution at a concentration of (60000unit / 100g raw material). Then, a saccharification reaction was carried out at 60 ° C. for 3 hours, and then the mixture was heated to 90 ° C. to inactivate the enzyme. Next, after cooling to room temperature, a homogenizer treatment was performed at 15 MPa to obtain a saccharified solution derived from barley. The obtained saccharified solution had a Brix of 22.1 and a pH of 5.5.
  • the product name "Transglucosidase L Amano” (manufactured by Amano Enzyme), which is a transglucosidase, is 0.20% based on the mass of the grain as a raw material (W / W). It was added to the above reaction solution at a concentration of (60000unit / 100g raw material). Then, a saccharification reaction was carried out at 60 ° C. for 3 hours, and then the mixture was heated to 90 ° C. to inactivate the enzyme. Next, after cooling to room temperature, homogenizer treatment was performed at 15 MPa to obtain an oat-derived saccharified solution. The obtained saccharified solution had a Brix of 20.2 and a pH of 6.1.
  • a saccharification reaction was carried out at 60 ° C. for 3 hours, and then the mixture was heated to 90 ° C. to inactivate the enzyme.
  • homogenizer treatment was performed at 15 MPa to obtain an oat-derived saccharified solution.
  • the obtained saccharified solution had a Brix of 20.3 and a pH of 6.1.
  • the product name "Transglucosidase L Amano” (manufactured by Amano Enzyme), which is a transglucosidase, is 0.20% based on the mass of the grain as a raw material (W / W). It was added to the above reaction solution at a concentration of (60000unit / 100g raw material). Then, a saccharification reaction was carried out at 60 ° C. for 3 hours, and then the mixture was heated to 90 ° C. to inactivate the enzyme, and after cooling, a saccharified solution derived from oats was obtained. No homogenizer treatment was performed. The obtained saccharified solution had a Brix of 20.2 and a pH of 6.1.
  • the obtained saccharified solution Brix, pH, the content of insoluble dietary fiber contained in the solid content, the amount of water-soluble dietary fiber contained in the solid content, the ratio of isomaltooligosaccharide to the total sugar, and the average particle size of the insoluble component.
  • the sugar composition was measured by the following method.
  • the obtained saccharified solution was subjected to a sensory test when eaten by the following method. Table 2 shows the measurement results and evaluation results.
  • the total sugar content of the saccharified solution purified by the pretreatment is analyzed under the following conditions using high performance liquid chromatography (Alliance, manufactured by Japan Waters), and high performance liquid chromatography (Prominence, Shimadzu) is performed.
  • the contents of monosaccharide, maltose, maltooligosaccharide, and sucrose were analyzed under the following conditions using (manufactured by GLC).
  • GLC glycolity
  • the average particle size of the insoluble component in the obtained saccharified solution was measured using Microtrac MT3000II (manufactured by Microtrac Bell Co., Ltd.). Pure water was used as the measurement solvent, and a few drops of the sample were sucked up with a dropper or the like, placed in the sample inlet, and subjected to ultrasonic treatment before measurement.
  • the measurement conditions are distribution display: volume, particle size classification selection: standard, measurement range: 0.021 to 2,000 ⁇ m, number of channels: 132, measurement time: 10 seconds, number of measurements: 1 time, particle permeability: transmission,
  • the refractive index of the particles was 1.81, the shape of the particles was non-spherical, and the refractive index of the solvent was 1.333.
  • the insoluble dietary fiber content contained in the solid content in the saccharified solution As can be seen from Table 2, according to the examples, the insoluble dietary fiber content contained in the solid content in the saccharified solution, the water-soluble dietary fiber content contained in the solid content in the saccharified solution, and the saccharified solution.

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Abstract

L'invention concerne un liquide saccharifié de céréales qui présente une composition nouvelle permettant d'envisager un effet et une action de régulation intestinale, et qui présente peu de dépôts irréguliers. Plus précisément, l'invention concerne un liquide saccharifié de céréales dans lequel la teneur en fibres alimentaires insolubles contenues dans sa matière solide est supérieure ou égale à 1,0% en masse, la teneur en fibres alimentaires hydrosolubles contenues dans sa matière solide est supérieure ou égale à 0,6% en masse, la proportion d'un isomaltooligosaccharide pour l'ensemble des saccharides qu'il contient est supérieure ou égale à 10,0% en masse, et le diamètre particulaire moyen de ses composants insolubles, est compris entre 30 et 70μm. Ce liquide saccharifié de céréales est caractéristique en ce que les céréales constituant sa matière de départ, incluent une avoine et/ou une orge.
PCT/JP2021/041370 2020-11-12 2021-11-10 Liquide saccharifié de céréales, et procédé de fabrication de celui-ci WO2022102664A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006035725A1 (fr) * 2004-09-27 2006-04-06 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Isocyclomaltooligosaccharide, isocyclomaltooligosaccharide synthase, procedes de synthese de ces composes, et utilisation de ces composes
JP2006519612A (ja) * 2003-03-10 2006-08-31 ジェネンコー・インターナショナル・インク プレバイオティックであるイソマルトオリゴ糖を含む穀物組成物、及び、この製造方法、並びに、その用途
JP2012044989A (ja) * 2010-08-24 2012-03-08 Corn Products Internatl Inc イソマルトオリゴ糖の製造及びその使用
CN105925550A (zh) * 2016-06-23 2016-09-07 福州大学 α-葡萄糖苷酶及同步糖化转苷制备低聚异麦芽糖的方法
JP2018046762A (ja) * 2016-09-21 2018-03-29 株式会社林原 分岐α−グルカン混合物シラップとその用途
JP2020039283A (ja) * 2018-09-10 2020-03-19 カゴメ株式会社 穀類液化物の製造方法、穀類液化物及び穀類液化物の遊離糖含量抑制方法

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CN1756769A (zh) * 2003-03-10 2006-04-05 金克克国际有限公司 含有益生的异麦芽-寡糖的谷物组合物及其制造和应用方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006519612A (ja) * 2003-03-10 2006-08-31 ジェネンコー・インターナショナル・インク プレバイオティックであるイソマルトオリゴ糖を含む穀物組成物、及び、この製造方法、並びに、その用途
WO2006035725A1 (fr) * 2004-09-27 2006-04-06 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Isocyclomaltooligosaccharide, isocyclomaltooligosaccharide synthase, procedes de synthese de ces composes, et utilisation de ces composes
JP2012044989A (ja) * 2010-08-24 2012-03-08 Corn Products Internatl Inc イソマルトオリゴ糖の製造及びその使用
CN105925550A (zh) * 2016-06-23 2016-09-07 福州大学 α-葡萄糖苷酶及同步糖化转苷制备低聚异麦芽糖的方法
JP2018046762A (ja) * 2016-09-21 2018-03-29 株式会社林原 分岐α−グルカン混合物シラップとその用途
JP2020039283A (ja) * 2018-09-10 2020-03-19 カゴメ株式会社 穀類液化物の製造方法、穀類液化物及び穀類液化物の遊離糖含量抑制方法

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