WO2018190310A1 - Quality improver and use thereof - Google Patents

Quality improver and use thereof Download PDF

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Publication number
WO2018190310A1
WO2018190310A1 PCT/JP2018/014976 JP2018014976W WO2018190310A1 WO 2018190310 A1 WO2018190310 A1 WO 2018190310A1 JP 2018014976 W JP2018014976 W JP 2018014976W WO 2018190310 A1 WO2018190310 A1 WO 2018190310A1
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glucan
mass
starch
quality
molecular weight
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PCT/JP2018/014976
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French (fr)
Japanese (ja)
Inventor
誠一郎 岸下
亜希子 安田
晶子 溝手
学 宮田
知代 吉實
毅弘 西田
三宅 正樹
山本 拓生
仁志 三皷
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株式会社林原
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Priority to JP2019512505A priority Critical patent/JPWO2018190310A1/en
Publication of WO2018190310A1 publication Critical patent/WO2018190310A1/en

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    • 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
    • A23L2/38Other non-alcoholic beverages
    • 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
    • A23L11/00Pulses, i.e. fruits of leguminous plants, for production of food; Products from legumes; Preparation or treatment thereof
    • A23L11/60Drinks from legumes, e.g. lupine drinks
    • A23L11/65Soy drinks
    • 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
    • A23L29/20Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/212Starch; Modified starch; Starch derivatives, e.g. esters or ethers
    • 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
    • A23L7/104Fermentation of farinaceous cereal or cereal material; Addition of enzymes or microorganisms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A21BAKING; EDIBLE DOUGHS
    • A21DTREATMENT, e.g. PRESERVATION, OF FLOUR OR DOUGH, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS; PRESERVATION THEREOF
    • A21D13/00Finished or partly finished bakery products
    • AHUMAN NECESSITIES
    • A21BAKING; EDIBLE DOUGHS
    • A21DTREATMENT, e.g. PRESERVATION, OF FLOUR OR DOUGH, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS; PRESERVATION THEREOF
    • A21D2/00Treatment of flour or dough by adding materials thereto before or during baking
    • A21D2/08Treatment of flour or dough by adding materials thereto before or during baking by adding organic substances
    • A21D2/14Organic oxygen compounds
    • A21D2/18Carbohydrates
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23CDAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00Milk preparations; Milk powder or milk powder preparations
    • A23C9/152Milk preparations; Milk powder or milk powder preparations containing additives
    • 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
    • A23L13/00Meat products; Meat meal; Preparation or treatment 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
    • A23L17/00Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
    • A23L17/50Molluscs
    • 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
    • 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
    • A23L7/109Types of pasta, e.g. macaroni or noodles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • 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
    • C12P19/18Preparation of compounds containing saccharide radicals produced by the action of a glycosyl transferase, e.g. alpha-, beta- or gamma-cyclodextrins

Definitions

  • the present invention relates to a quality improving agent and various uses thereof, and in particular, relates to a quality improving agent containing an edible material as an active ingredient and uses thereof.
  • Edible materials are used mainly for the purpose of improving quality such as aging control, flavor improvement, texture improvement, etc., depending on the various properties of the material.
  • the material include starch and derivatives thereof, carbohydrates such as alginic acid, pectin, and gum arabic, and proteins such as gelatin, casein, soy protein, milk protein, gluten, and zein.
  • lipids such as paraffin, carnauba wax, beeswax, candelilla wax, polyethylene wax, monoglycerides of various fatty acids, and resins such as shellac, rosin, and copal may be used.
  • edible materials that are useful in that they can be formed into films and capsules include, for example, wafers made from starch, collagen, gelatin, pullulan, and carrageenan.
  • gelatinized starch is water-soluble without reducing the molecular weight of raw starch, and can be used as an adhesive or thickener in various foods and beverages by taking advantage of the adhesiveness and thickening of starch.
  • it has an advantage that it can be used, it has a drawback that it is difficult to handle because of its high viscosity, and it is easy to age and form an insoluble precipitate.
  • dextrin starch partially decomposed product
  • starch which is a raw material, is hydrolyzed and reduced in molecular weight by acid, alkali, enzyme, etc.
  • the reducing power is increased by hydrolysis, there is a problem that when it is mixed and heated with protein or amino acid, it is colored by Maillard reaction.
  • dextrin has a disadvantage that it is difficult to form a strong film because it has a low molecular weight.
  • Films made from starch-based edible materials are manufactured by blending plasticizers such as glycerol, sorbitol, and sorbitol esters for the purpose of improving vulnerability at low temperatures and increasing flexibility. In many cases, it is said that when a plasticizer such as a polyhydric alcohol is added, the strength of the film may be significantly reduced (see Patent Document 1).
  • the present invention is an edible material prepared from starch, which has an appropriate molecular weight, an appropriate viscosity, and cold water solubility, an aging regulator, a flavor improver, a shape retention agent, a foam property improver, a texture It is an object of the present invention to provide a quality improver that can be advantageously used in the fields of food, cosmetics, quasi-drugs, pharmaceuticals, industrial products and the like as various quality improvers such as an improver.
  • the present applicant has obtained a low glucose equivalent (DE), a low reducing power, and an appropriate molecular weight when gelatinized waxy starch and liquefied by the action of a small amount of amylase.
  • DE glucose equivalent
  • An unprecedented excellent ⁇ -glucan mixture having a moderate viscosity is obtained, and the ⁇ -glucan mixture is used as an edible material, as a raw material for edible films, as well as a binder for food materials, It has been found that it can be suitably used as a texture improving agent for bread, confectionery, etc., a flaw improving agent for noodle products, a preservability improving agent, and the like.
  • the application was filed as PCT / JP2016 / 85946 (International Publication No. WO2017 / 094895).
  • a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) ( Mw / Mn) having a specific range and having an isomaltose structure at the non-reducing end is particularly suitable as a quality improver, specifically an aging regulator, a flavor improver, a physical property improver, etc.
  • a quality improver specifically an aging regulator, a flavor improver, a physical property improver, etc.
  • the present invention is an ⁇ -glucan mixture obtained by a production method including a step of gelatinizing waxy starch, allowing amylase to act and liquefying, and a step of allowing ⁇ -glucosyltransferase to act, comprising the following (1) to Solving the above problems by providing a quality improver comprising an ⁇ -glucan mixture having the characteristics of (3) (hereinafter sometimes simply referred to as “ ⁇ -glucan” or “present ⁇ -glucan”) as an active ingredient
  • ⁇ -glucan the weight average molecular weight
  • Mw weight average molecular weight
  • Mn The value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less
  • An ⁇ -glucan molecule having an isomaltose structure at the non-reducing end is included.
  • the present invention solves the above-mentioned problems by providing various uses as an aging regulator, a flavor improver, a physical property improver and the like of the quality improver.
  • this invention solves the said subject by providing the food / beverage products, cosmetics, quasi-drugs, pharmaceuticals, and industrial goods which contain the said quality improvement agent.
  • the quality-improving agent according to the present invention basically has an ⁇ -glucan mixture, which is an active ingredient, having an appropriate molecular weight and viscosity and high solubility in water. It has the advantages of excellent water solubility and excellent handling properties.
  • the quality improver of the present invention has excellent functions such as aging control ability, flavor improvement ability, physical property improvement ability, etc., and is excellent as an aging control agent, flavor improvement agent, physical property improvement agent, etc. It is useful for improving the quality of industrial products, cosmetics, quasi drugs and pharmaceuticals.
  • 5 is a graph showing the viscosity measured after repeated cold thawing for an aqueous solution of this ⁇ -glucan.
  • 3 is a graph showing the turbidity measured after refrigerated storage of a mixture of this ⁇ -glucan solution and starch liquor.
  • 3 is a graph showing the results of a sensory test on the change in flavor of soymilk prepared using this ⁇ -glucan.
  • 2 is a photograph showing the shape retention of a gelatin gel prepared using this ⁇ -glucan.
  • 6 is a graph showing the time taken for the present ⁇ -glucan aqueous solution to warm to the target temperature after heating.
  • 4 is a graph showing the degree of stickiness of a gelatinized starch gel prepared using this ⁇ -glucan.
  • starch In general, starch (starch) is composed of amylose having a structure in which glucose, which is a constituent sugar, is linked in a straight chain via ⁇ -1,4 bonds, and ⁇ -1,6 bonds at the location of glucose inside the amylose. It is known that it is in a mixed form with amylopectin having a structure branched via a.
  • “Waxy starch” as used herein refers to a plant of waxy (rice cake) variety, for example, waxy rice (rice), barley, wheat, wheat, corn, millet, whey, corn Means starch. Waxy starch has almost no amylose and has only amylopectin.
  • Waxy corn starch is a starch obtained from waxy corn and is easy to gelatinize. Transparent gel has excellent storage stability. Therefore, it is most widely used and is suitable as a raw material for ⁇ -glucan, which is an active ingredient of the quality improver of the present invention.
  • gelatinization means a phenomenon in which, when starch granules are heated in the presence of water, the hydrogen bonds of the starch granules are broken and the grains irreversibly swell (or hydrate or dissolve). Starch loses crystallinity and birefringence with gelatinization, increases in viscosity, and reacts rapidly with enzymes (amylases) and chemicals. Gelatinization is also called alpha.
  • “Liquefaction” as used in the present specification means liquefaction by causing amylase to act on gelatinized starch and partially hydrolyzing it.
  • the liquefied starch ( ⁇ -glucan) obtained by liquefying the gelatinized starch becomes lower in molecular weight as the degree of hydrolysis increases, and exhibits a lower molecular weight and lower viscosity.
  • Mw / Mn weight average molecular weight / number average molecular weight
  • Mw / Mn is an index representing the spread (dispersion degree) of the molecular weight distribution. The larger the value, the wider the molecular species range, and the closer the value, the more uniform the molecular species in molecular weight. Means.
  • Mw / Mn is subjected to gel filtration high performance liquid chromatography (gel filtration HPLC), and its chromatogram is analyzed by molecular weight distribution analysis software to obtain weight average molecular weight (Mw) and number average molecular weight (Mn). It can be calculated by
  • cold water solubility means that a test sample is added to deionized water so as to have a solid concentration of 20% by mass, and stirred at a liquid temperature of 30 ° C. to visually determine the degree of dissolution. Sometimes means the property of completely dissolving within 15 minutes to give a homogeneous solution.
  • the quality improver comprising ⁇ -glucan having cold water solubility as an active ingredient is easy to handle because it does not need to be dissolved by heating when blended into various compositions, although it depends on the proportion of ⁇ -glucan contained. There is an advantage of being.
  • gelatinized starch pregelatinized starch
  • liquefied starch changes to a water-insoluble state like natural starch over time.
  • Aging is a state change in which starch molecules naturally associate and partially move into a densely assembled state, and the association of molecules is thought to be mainly due to hydrogen bonding by hydroxyl groups (OH groups) of glucose residues.
  • OH groups hydroxyl groups
  • starch is composed of amylose and amylopectin, it is known that linear amylose that is not branched is more likely to age. In addition, aging is known to occur not only in starch but also in polysaccharides such as partially decomposed starch (dextrin), and in general, it is said that the smaller the glucose equivalent (DE) described later, the easier it is to age. .
  • DE glucose equivalent
  • anti-aging means that a material such as the quality improver of the present invention or the composition itself does not easily cause aging, which is a change in the state of the starchy polysaccharide.
  • aging control refers to the degree of aging, which is a change in the state of the starchy polysaccharide, and the ease of aging, by allowing a material or composition such as the quality improver of the present invention to coexist. It means to adjust, and is different from “aging resistance” in this specification.
  • “flavor improvement” refers to bitterness, pungent taste, astringency, savory taste, astringent taste, etc. of target foods and beverages, oxidation odor, heated odor, processed odor, raw odor, blue odor, etc. It means to improve off-flavors and the like that people feel unpleasant, and it means that the quality improver of the present invention exerts the effect of flavoring.
  • the “flavor” here is not limited to the “flavor” of foods and drinks, but includes odors of cosmetics, quasi drugs, pharmaceuticals, industrial products, and the like.
  • “improvement of physical properties” literally means that various physical properties of a target product or the like are improved, such as adhesiveness, formability, shine, moisture retention, viscosity, osmotic pressure.
  • improvements of physical properties such as syrup and preventing the precipitation of sugar from syrup, etc., curing control, flow control, fogging control, shelf life improvement, adhesion improvement, improvement over the throat, oxidation prevention, collapse Prevent and improve browning prevention, water separation prevention, water retention, moisture controllability, moldability, shape retention, refrigeration resistance, freezing resistance, ice crystal stability, etc. Means.
  • ⁇ -Glucosyltransferase refers to an enzyme that acts on a partially degraded starch and has an activity to transfer ⁇ -1,6 glucosyl to its non-reducing terminal glucose residue. By allowing ⁇ -glucosyltransferase to act on ⁇ -glucan, ⁇ -glucan having an isomaltose structure at the non-reducing end can be obtained. Examples of ⁇ -glucosyltransferase include ⁇ -glucosidase, ⁇ -glucosyltransferase, and dextrin dextranase.
  • isomaltodextranase digestion means that isomaltdextranase is allowed to act on a test sample to hydrolyze the bond on the reducing end side of the isomaltose structure in the test sample. If isomaltdextranase (EC 3.2.1.94) is a glucan having an isomaltose structure at the non-reducing end, such as dextran, the bond adjacent to the reducing end of the isomaltose structure is ⁇ -1,2, ⁇ -1,3, ⁇ -1,4, and ⁇ -1,6 linkages are enzymes that have hydrolytic activity.
  • the test sample contains ⁇ -glucan having an isomaltose structure at the non-reducing end by subjecting the digestion product to HPLC analysis and examining whether or not isomaltose is observed in the sugar composition. It can be confirmed whether or not.
  • the test sample is an aqueous solution having a concentration of 1 w / v%, and isomaltdextranase derived from Arthrobacter globiformis (manufactured by Hayashibara Co., Ltd.) per gram of the test sample solid. 100 units were added and allowed to act at 50 ° C. and pH 5.0 for 16 hours. The obtained digest was subjected to sugar composition analysis HPLC under the following conditions to quantitate isomaltose.
  • Glucose equivalent (DE) is an index indicating the degree of hydrolysis in starch sugar (starch partially decomposed product) obtained by hydrolyzing starch using an acid or an enzyme. It means the numerical value expressed by the formula.
  • the glucose equivalent (DE) is a relative scale when the reducing power of D-glucose (dextrose, glucose) is 100, and the closer to 0, the lower the degree of hydrolysis and the closer to starch. , The closer to 100, the higher the degree of hydrolysis and the closer to glucose.
  • the amount of reducing sugar is determined according to the conventional modified Park-Johnson method (see Takusaku et al., “Carbohydrate Research”, Vol. 94, pages 205 to 213 (1981)). Quantify glucose as standard. The total amount of solids is determined by a conventional drying method.
  • amylose content can be used as one of the indices for specifying the starch species.
  • “amylose content” refers to starch or a partial degradation product ( ⁇ -glucan) by amylase, or a starch sample such as ⁇ -glucan obtained by allowing ⁇ -glucosyltransferase to act on them. Means the amylose content of the sample measured based on the color reaction of amylose and iodine in accordance with the amylose content measurement method shown in Ministry of Agriculture, Forestry and Fisheries Notification No. 332, Standard Measurement Method.
  • the absorbance at a wavelength of 620 nm is measured using a spectrophotometer; (4) The absorbance and an amylose standard separately prepared using reagent grade amylose The amylose content in the analytical sample is obtained based on a calibration curve measured and prepared in the same manner for the solution, and the amylose content is calculated.
  • the quality improving agent of the present invention is an ⁇ -glucan mixture obtained by a production method comprising gelatinizing waxy starch, allowing amylase to act and liquefying, and ⁇ -glucosyltransferase to act, and
  • the present invention relates to a quality improver comprising an ⁇ -glucan mixture having the following characteristics (1) to (3) as an active ingredient: (1) the weight average molecular weight (Mw) is in the range of 150 kDa to 3,000 kDa; (2) The value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less; and (3) An ⁇ -glucan molecule having an isomaltose structure at the non-reducing end is included.
  • the ⁇ -glucan containing the quality improving agent of the present invention as an active ingredient is obtained by a production method including a step of gelatinizing waxy starch, causing amylase to act and liquefying, and a step of allowing ⁇ -glucosyltransferase to act Usually, it is in the form of a mixture of various ⁇ -glucan molecules having different molecular weights and structures.
  • Waxy starch is a starch that is substantially free of amylose, which is a linear ⁇ -1,4 glucan, and is composed only of an amylopectin having a substantially branched structure.
  • Waxy starch is also superior in film-forming properties (film forming ability) compared to starch containing amylose other than waxy starch.
  • the present ⁇ -glucan obtained by using such waxy starch as a starting material is characterized as the whole ⁇ -glucan mixture by the features (1) to (3), which will be sequentially described below. It is difficult to directly define the structural characteristics of various ⁇ -glucan molecules contained in this ⁇ -glucan.
  • amylase has an advantage that the degree of hydrolysis can be controlled more easily than acid.
  • the present ⁇ -glucan is characterized in that (1) the weight average molecular weight (Mw) is in the range of 150 kDa to 3,000 kDa, and more preferably in the range of 200 kDa to 3,000 kDa.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is less than 150 kDa, the proportion of ⁇ -glucan molecules having a small molecular weight increases, the viscosity and film-forming property (film forming ability) decrease, and coloring occurs due to an increase in reducing power.
  • the weight average molecular weight exceeds 3,000 kDa, it is difficult to dissolve in water, and since it exhibits a high viscosity, it is difficult to handle and difficult to use.
  • the ⁇ -glucan is characterized in that (2) a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less.
  • Mw / Mn a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less.
  • the present ⁇ -glucan is an ⁇ -glucan having the characteristics of (1) and (2) above and (3) including an ⁇ -glucan molecule having an isomaltose structure at the non-reducing end.
  • ⁇ -glucan with an isomaltose structure at the non-reducing end gelatinizes waxy starch and liquefies it with amylase, then acts on a partially degraded starch and ⁇ -1,6-glucosyl transfer to the non-reducing end glucose residue It can be obtained by further acting an ⁇ -glucosyltransferase having the activity of
  • This ⁇ -glucan contains an ⁇ -glucan molecule having an isomaltose structure at the non-reducing end. This can be confirmed by examining whether or not isomaltose is contained in the digest.
  • the ⁇ -glucan used in the present invention is preferably one that produces isomaltose more than 3% by mass and less than 22% by mass by solid digestion by digestion with isomalt dextranase.
  • This ⁇ -glucan contains an ⁇ -glucan molecule having a special structure that does not inherently exist in the starch hydrolyzate having an isomaltose structure at the non-reducing end. (Partially decomposed product) and a linear ⁇ -1,4 glucan in which glucose is linked via an ⁇ -1,4 bond, have a property that is not easily aged (aging resistance).
  • aging resistance For example, the ⁇ -glucan that produces isomaltose of more than 3% by mass and less than 22% by mass of the digested solid in the isomalt-dextranase digestion has a solid concentration of 30% by mass. Even when kept as an aqueous solution at 6 ° C.
  • the aging resistance is such that even if the step of natural thawing after freezing an aqueous solution with a solid concentration of 30% by mass at ⁇ 20 ° C. is repeated five times, the viscosity is not changed.
  • Have sex. Therefore, among the present ⁇ -glucans, ⁇ -glucans that produce more than 3% by weight and less than 22% by weight of isomaltose in the digestion of isomaltodextranase have a relatively high concentration prior to use. In the case of a quality improver containing ⁇ -glucan as an active ingredient, the same can be said.
  • the glucose equivalent (DE) of the ⁇ -glucan is not particularly limited, the glucose equivalent (DE) can be used as an indicator of the degree of decomposition of waxy starch. Depending on the use of the quality improver, it is desired that the color improver is less likely to be colored or browned due to the Maillard reaction or the like when mixed with protein or amino acid and heated. In such a case, it is desirable that the ⁇ -glucan has a low glucose equivalent (DE). When the glucose equivalent (DE) exceeds 2.0, the reducing power increases and causes coloring, so the glucose equivalent (DE) is usually 2.0 or less, preferably 1.8 or less, more preferably Is preferably 1.6 or less.
  • the waxy starch for obtaining the present ⁇ -glucan is not limited by the plant from which it is derived, but a waxy corn starch that is mass-produced and easily available is widely used.
  • Waxy starch is generally said to contain substantially no amylose, which is a linear molecule in which glucose is linearly linked via ⁇ -1,4 bonds. In the measurement method of the amylose content based on this, an amylose content of about 25% by mass or less is usually shown.
  • amylose content of the ⁇ -glucan used in the present invention obtained from a waxy starch as a raw material and subjected to the ⁇ -glucosyl transfer reaction after the decomposition reaction with amylase may vary depending on the type of the waxy starch used as a raw material, In the measurement method of amylose content based on the coloration method, a value of 25% by mass or less is usually shown.
  • This ⁇ -glucan is soluble in cold water, and when added to deionized water to a solids concentration of 20% by mass and stirred at a temperature of 30 ° C., it completely dissolves within 15 minutes, A uniform solution can be obtained.
  • the present ⁇ -glucan can be produced by a production method including a step of gelatinizing waxy starch, causing amylase to act and liquefying, and a step of causing ⁇ -glucosyltransferase to act.
  • the method is not particularly limited by the origin of the waxy starch used, the conditions for gelatinization, and the types and origins of amylase and ⁇ -glucosyltransferase.
  • the method of gelatinizing the raw waxy starch can be performed by a conventional method of heating a waxy starch aqueous suspension. Specifically, for example, a method in which a waxy starch water suspension is placed in a jacketed reactor and heated indirectly, a method in which steam is mixed with the waxy starch water suspension and heated directly, a hot roll of a drum dryer The method of heating above is mentioned.
  • the gelatinized waxy starch is liquefied by adding amylase and hydrolyzing.
  • amylase is added to starch milk (starch suspension) in advance, and the gelatinization and liquefaction proceed simultaneously by heating the starch.
  • a conventional method may be selected as appropriate, and it is usually performed in either a batch system or a continuous system.
  • thermostable liquefied ⁇ -amylase examples include “Spitase HK” (manufactured by Nagase ChemteX Corporation), “Tarmamyl 60L” (manufactured by Novozyme Japan), “Amylase AD“ Amano ”” (Amano Enzyme) Manufacturing Co., Ltd.), “Christase T10S” (manufactured by Amano Enzyme Co., Ltd.), “Sumiteam L” (manufactured by Shin Nippon Chemical Industry Co., Ltd.), and the like.
  • an ⁇ -glucosyltransferase that introduces an isomaltose structure at the non-reducing end acts on a partial degradation product of starch, as long as it has an activity to transfer glucose to the non-reducing end glucose residue by ⁇ -1,6. It is not limited by origin or physicochemical properties. Examples of the ⁇ -glucosyltransferase having such an activity include transglucosidase derived from Aspergillus niger ( ⁇ -glucosidase), dextrin dextranase derived from Acetobacter capsuratam, International Publication No. WO2008 / “ ⁇ -glucosyltransferase” derived from Bacillus or Arthrobacter microorganisms disclosed in US Pat.
  • the ⁇ -glucosyltransferase disclosed in International Publication No. WO2008 / 136331 pamphlet acts on a maltose and / or ⁇ -1,4 glucan having a glucose polymerization degree of 3 or more as a substrate and other non-reducing terminal glucose residues.
  • ⁇ -1,4 or ⁇ -1,6 glucosyl transfer mainly to the non-reducing terminal glucose residue of the ⁇ -1,4-glucan of -It has an activity to produce bound glucan, and it is complicated from maltose and / or ⁇ -1,4 glucan having a degree of glucose polymerization of 3 or more by acting the ⁇ -glucosyltransferase and repeating the glucosyltransferase reaction.
  • a branched ⁇ -glucan having a simple branched structure can be produced.
  • the ⁇ -glucosyltransferase is ⁇ -1,3 glucosyltransferase or ⁇ -1,4 linked to ⁇ -1,6 linked glucose residues in the interior of glucan, although it is less frequently.
  • 1,3-glucosyl transfer it also has an activity to produce ⁇ -glucan having ⁇ -1,3 bond, ⁇ -1,4,6 bond and ⁇ -1,3,6 bond. Yes.
  • this ⁇ -glucosyltransferase is used, an isomaltose structure can be introduced into the non-reducing end thereof, and this ⁇ -glucan can be preferably produced.
  • the ⁇ -glucosyltransferase derived from the genus Bacillus or Arthrobacter disclosed in the pamphlet of International Publication No. WO2008 / 136331 has the following properties (A) to (F).
  • B Molecular weight In SDS-polyacrylamide gel electrophoresis, 90,000 ⁇ 10,000 daltons;
  • ⁇ -Isomaltosylglucosaccharide-forming enzyme disclosed in the pamphlet of International Publication No. WO02 / 010361, that is, ⁇ -glucosyltransferase has ⁇ -1 having a maltose and / or glucose polymerization degree of 3 or more as a substrate.
  • 4-glucan and the non-reducing terminal glucose residue is transferred to the non-reducing terminal glucose residue of other ⁇ -1,4-glucan by ⁇ -1,6-glucosyl transfer, thereby It has an activity to produce glucan in which glucose is ⁇ -linked to a hydroxyl group.
  • this ⁇ -glucosyltransferase has no activity to transfer glucose further to a glucan having an isomaltose structure at the non-reducing end once produced, the branched ⁇ having a complex branching enzyme as described above -Although glucan cannot be produced, even with this ⁇ -glucosyltransferase, the isomaltose structure can be introduced into the non-reducing end without greatly changing Mw / Mn (dispersion degree), and this ⁇ -glucan is suitable. Can be manufactured.
  • the “ ⁇ -isomaltosylglucosaccharide-forming enzyme” derived from the microorganisms of the genus Bacillus or Arthrobacter disclosed in the pamphlet of International Publication No. WO02 / 010361 has the following properties (G) to (M). is doing.
  • (G) Action As a non-reducing end-binding mode, a glucose having a degree of polymerization of ⁇ -1,4 glucosyl bonds of 2 or more undergoes ⁇ -glucosyl transfer without substantially increasing the reducing power.
  • H molecular weight having a molecular weight in the range of about 74,000 to 160,000 daltons by SDS-gel electrophoresis;
  • I isoelectric point having an isoelectric point in the range of pI of about 3.8 to 7.8 by an ampholine-containing electrophoresis method;
  • J Optimal temperature, having an optimal temperature in the range of about 40 to 50 ° C.
  • the feed concentration of the raw waxy starch is usually 10% by mass or more, preferably about 20 to 50% by mass, more preferably 30 to 35% by mass.
  • the waxy starch was partially decomposed by adjusting the amount of amylase added, and the weight average molecular weight (Mw) of the waxy starch liquefied product ( ⁇ -glucan) in the reaction solution was 150 kDa to It can be controlled within the range of 3,000 kDa.
  • the weight average molecular weight (Mw) of the liquefied product can be measured by gel filtration HPLC, the correlation between the weight average molecular weight of the liquefied product and glucose equivalent (DE) is preliminarily determined, and the weight average molecular weight of the liquefied product is The correlation with the viscosity of the liquefied liquid can be examined and grasped by measuring the glucose equivalent (DE) of the liquefied product, the viscosity of the liquefied liquid, etc., instead of the weight average molecular weight measurement.
  • the DE is usually less than 1.0, preferably 0.62 or less. Good.
  • the gelatinization and liquefaction reaction should be terminated in as short a time as possible.
  • the gelatinization and liquefaction methods are based on starch suspension. The continuous method in which the liquid (starch milk) can be heated more uniformly and rapidly is more preferable than the batch method.
  • the amount of the isomaltose structure of the ⁇ -glucan can be adjusted by the amount of ⁇ -glucosyltransferase added, and may be appropriately adjusted according to the physical properties required for the ⁇ -glucan to be produced.
  • ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the action of ⁇ -glucosyltransferase has a larger Mw / Mn value than the ⁇ -glucan used as a raw material, and has a glucose equivalent (DE ) May increase slightly, but as shown in the experimental section described later, the Mw / Mn range obtained by adjusting the amount of action of ⁇ -glucosyltransferase is 35.1 or less, glucose equivalent (DE ) Is less than 2.8, for example, ⁇ -glucan is not only an excellent edible film material that can be used without problems when formed into a film, but also a quality improver, in particular, aging control It can also be advantageously used as an agent, flavor improver, physical property improver and the like.
  • the solution containing the ⁇ -glucan obtained by the enzyme reaction can be used as it is as a quality improver, but is generally used after further purification.
  • a purification method a normal method used for sugar purification may be appropriately employed. For example, decolorization with activated carbon, desalting with H-type or OH-type ion exchange resin, fractionation with an organic solvent such as alcohol and acetone, and the like.
  • One or more purification methods such as separation by a membrane having separation performance can be appropriately employed.
  • This ⁇ -glucan is in the form of a mixture of ⁇ -glucan having a relatively large molecular weight and contains almost no low molecular weight oligosaccharide. Therefore, it is necessary to fractionate the obtained reaction product by means such as column chromatography. Although there is no particular limitation, it is optional to perform further fractionation according to the purpose of use. When ion exchange chromatography is employed for fractionation, for example, column chromatography using a strongly acidic cation exchange resin disclosed in JP-A-58-23799 and JP-A-58-72598 is advantageously used. Can be used. At this time, it is optional to adopt any of a fixed floor method, a moving floor method, and a simulated moving floor method.
  • the ⁇ -glucan obtained in this way can be used as it is in solution, it is preferable to dry it into a powder so that it is advantageous for storage and easy to use depending on the application.
  • a dryer such as a drum dryer, a spray dryer (spray dryer), a hot air dryer, a vacuum dryer, a flash dryer, a freeze dryer, a fluidized bed dryer, or the like can be used.
  • a drum dryer or a spray dryer it is preferable to use a drum dryer or a spray dryer.
  • the dried product can be pulverized into a powder, or the powder can be screened or granulated to adjust to a specific particle size range.
  • the quality improvement in the present invention refers to improving the quality of products such as food, cosmetics, quasi-drugs, pharmaceuticals and industrial products, or intermediate products thereof. Means aging control ability, flavor improvement ability, physical property improvement ability, and the like.
  • the quality-improving agent of the present invention includes aging control, flavor improvement, physical property improvement, adhesion, osmotic pressure control, shaping, shine imparting, water retention, moisture retention, viscosity imparting, other sugars Since it has properties such as anti-crystallizing properties, not only aging regulators, flavor improvers, and physical property improvers, but also quality improvers, stabilizers, excipients, fogging modifiers, shelf life improvers, walkers Retention improver, cure modifier, flow modifier, viscoelasticity improver, adhesion improver, throat improver, antioxidant, browning inhibitor, water separation inhibitor, intestinal, molding agent, shape retainer, refrigeration resistant agent Also, as a freezing tolerant, an ice crystal stabilizer, etc., it can be advantageously used in various compositions such as foods, foods, feeds, feeds, cosmetics, pharmaceutical
  • the ⁇ -glucan which is an active ingredient of the quality improver of the present invention, has a special structure that does not inherently exist in the hydrolyzate of starch, that is, the non-reducing end isomaltose structure. Unlike a mixture (a partially decomposed starch) or a linear ⁇ -1,4 glucan in which glucose is linked via ⁇ -1,4 bonds, it has the ability to control aging of coexisting starchy polysaccharides.
  • an ⁇ -glucan having an isomaltose structure at the non-reducing end, and isomalt dextranase digestion, more than 3 mass% and less than 22 mass% per solid of digest The ⁇ -glucan that produces isomaltose is aged with the starch liquefaction solution even when it is kept at 4 ° C. for 5 days as a solution containing a solid concentration of 5% by mass. It has aging control properties so as to remarkably suppress white turbidity.
  • ⁇ -glucan having an isomaltose structure at the non-reducing end, and in the isomalt dextranase digestion, more than 3% by weight and more than 22% by weight per solid product
  • ⁇ -glucan that produces less isomaltose it has the advantage that the quality of the product containing starchy polysaccharides can be remarkably controlled to maintain the quality, and is extremely suitable as an aging regulator. is there.
  • the ⁇ -glucan which is an active ingredient of the quality improving agent of the present invention, has a glucose equivalent (DE) of usually about 2.0 and hardly gives sweetness, so that it is not preferable that sweetness is given. It can be added to and used for products without worrying about the effect on taste. Furthermore, since the ⁇ -glucan, which is an active ingredient of the quality improving agent of the present invention, has a flavor improving action, for example, by appropriately adding it to commercially available soy milk, the delicious taste and blue odor of soy milk can be reduced. Can be suppressed. Therefore, the quality improving agent of the present invention has the advantage that the flavor can be improved with almost no sweetness to a product having an off-flavor or off-flavor, which may cause off-flavor. Suitable as an improving agent.
  • DE glucose equivalent
  • ⁇ -glucan which is an active ingredient of the quality improving agent of the present invention, is characterized by having a weight average molecular weight (Mw) in the range of 150 kDa to 3,000 kDa, and has an appropriate viscosity.
  • Mw weight average molecular weight
  • the quality improving agent of the present invention is suitable as a physical property improving agent that imparts thickness and improves viscosity to a liquid product, for example.
  • the present ⁇ -glucan is, for example, gelatin, collagen, pectin, agar, carrageenan, xanthan gum, locust bean gum, gellan gum, gum arabic, guar gum, tara gum, tamarind seed gum, curdlan, psyllium seed gum, alginic acid, hyaluronic acid , Starch, modified starch, dextrin, dextran, carboxyvinyl polymer, cross-linked polyacrylic acid, hydroxyethylcellulose, carboxymethylcellulose, sodium acrylate, etc.
  • the quality improving agent of the present invention has an advantage that the gel strength can be adjusted, for example, for a product containing a high molecular weight gelling agent, and is suitable as a physical property improving agent.
  • ⁇ -glucan which is an active ingredient may be used alone, but other materials such as polysaccharides, extenders, and excipients are used depending on the use.
  • the quality improving agent of the present invention includes, for example, flour, glucose, fructose, isomerized sugar, sugar, maltose, trehalose, honey, maple sugar, sorbitol, maltitol, dihydrochalcone, Stevioside, ⁇ -glycosyl stevioside, Rakanka sweet, glycyrrhizin, thaumatin, sucralose, L-aspartylphenylalanine methyl ester, dulcin, monelin, acesulfame potassium, cyclamate, aspartame, neotame, alitame, advantame, luznum, saccharin, glycine, alanine And a sweetener such as dextrin, starch, pullulan, dextran, lactose and the like.
  • a sweetener such as dextrin, starch, pullulan, dextran, lactose and the
  • the quality improver of the present invention can be molded into various shapes such as granules, spheres, short bars, plates, cubes, etc., as they are or as necessary, mixed with extenders, excipients, binders, etc. It is also optional to use.
  • excipients include polysaccharides such as pullulan, carrageenan, xanthan gum, carboxymethylcellulose, cellulose, hemicellulose, gum arabic, guar gum, pectin, chitin, agarose, dextran, dextrin, amylose and modified starch, or their Macromolecules such as derivatives, proteins such as gelatin or casein, saccharides such as sorbitol, mannitol, maltitol, sucrose, maltose, lactose, ⁇ , ⁇ -trehalose, ⁇ , ⁇ -trehalose, gum arabic, corn starch, crystalline cellulose, Aluminum hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium sulfate, calcium sulfite, calcium carbonate, silica, calcium silicate, basic magnesium carbonate, Kaori It includes inorganic substances such as talc.
  • polysaccharides such as pullulan, carrageenan,
  • ⁇ , ⁇ -trehalose can be advantageously used as a stabilizer because it has the action of suppressing the denaturation of active ingredients due to oxidative degradation and keeping the activity stable.
  • Plasticizers include sugar alcohols such as sorbitol, maltitol, mannitol, erythritol, lactitol, xylitol, and reduced starch syrup, monosaccharides such as glucose, fructose, galactose, xylose, rhamnose, and psicose, maltose, sucrose, trehalose, lactose, and tulanose.
  • Disaccharides such as cellobiose, maltotriose, panose, raffinose, melezitose, maltotetraose, stachyose, cyclodextrins and other oligosaccharides, glycerol, polyvinyl alcohol, polyethylene glycol, propylene glycol and other polyhydric alcohols, triethyl citrate , Triacetin, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, dibuphthalate And esters such as dibutyl sebacate, diethyl phthalate, vinyl pyrrolidone glycol triacetate, paraoxybenzoic acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, and the like.
  • Disaccharides such as cellobiose, maltotriose, panose, raffinose, melezitos
  • the plasticizer can be used for, for example, a film, a sheet, a capsule film and the like containing the quality improver of the present invention, and can be advantageously used in combination with a soft capsule film. It is not limited to products.
  • the quality improving agent of the present invention can be used advantageously as a food material, among others.
  • Use in food is not particularly limited, and using the binding property of the quality improving agent of the present invention, molded snacks, molded cheese, molded dried fruit, fish molded products, fish egg molded products, fish food, livestock meat foods, It can be used for simulated meat foods and molded delicacy foods.
  • it can also be used for food loosening agents, food anti-sticking agents, processed rice, etc. by utilizing the film-forming (coating) property.
  • it can be used for starchy polysaccharide-containing foods, chilled chilled products, frozen products, etc. by utilizing the aging controllability.
  • beverages such as soft drinks and alcoholic beverages
  • desserts such as frozen desserts have an excellent richness, rich taste, milky feeling, fruit juice feeling, etc.
  • powdered foods such as vinegar, powdered soy sauce, powdered seasoning, powdered fragrance, and powdered tea, in addition to excellent flavor retention, effects such as masking of miscellaneous taste, expression of flavor, etc. can be expected.
  • emulsified liquid nutritional foods such as enteric nutrients, and retort pouch foods such as curry, stew, cooked rice, sugar beet, side dish, soup and pasta sauce
  • stabilization of emulsification suppression of oil-off, prevention of protein aggregation
  • seasonings such as dressing and mayonnaise, it can be expected to have excellent richness, impart rich body, and express flavor, etc. Effect as a fat substitute for fats and oils can also be expected.
  • the quality improver of the present invention can be used for improving the texture, improving the storage stability of the food and improving the yield by adding it to bread, rice flour bread, confectionery, and noodle strip products.
  • a preferred method of using the quality improver of the present invention for foods is to mix and knead with other raw materials such as flour, salt, sugar, water, and knead to form and cook the dough. Can be mentioned.
  • the blending ratio in the food is greater than 0% by mass and 30% by mass or less, preferably 10% by mass or less, and particularly preferably 5% by mass or less per solid as a ratio at the time of preparing the dough.
  • the quality improver of the present invention uses waxy starch as a raw material, so it gives bread, rice flour bread, confectionery, noodle strip products a moist feeling, sticky feeling, softness, good mouthfeel, crispness, etc. be able to.
  • confectionery it can be used mainly for the dough prepared and then baked, steamed, fried, dried, etc., for example, buns, rice cakes, daifuku, dumplings, fertilizers, seaweeds, carcass, in the middle Grilled, Yokan, Kintsuba, Imagawa-yaki, rice cracker, Japanese confectionery such as hail, okoshi, biscuits, cookies, crackers, wafers, sponge cakes (roll cake, castella), butter cakes (pound cake, madeleine, gateau chocolate, financier) , Cream candy, Baumkuchen, muffin, souffle, pie, tart, donut, waffle, pudding and other Western confectionery, moon cake, Chinese confectionery, chips, puffs, fries and other snacks.
  • buns, rice cakes, daifuku, dumplings, fertilizers, seaweeds, carcass in the middle Grilled, Yokan, Kintsuba, Imagawa-yaki, rice cracker, Japanese confectionery such as hail, okoshi, biscuits, cookies, crackers, wafers, sponge cakes
  • creams such as butter cream and custard cream, hard candy such as jasper, drop, toffee and butterscotch, soft candy such as caramel, nougat, marshmallow, gummy, jelly beans and Bontang rice cake
  • hard candy such as jasper, drop, toffee and butterscotch
  • soft candy such as caramel, nougat, marshmallow, gummy, jelly beans and Bontang rice cake
  • chocolates chewing gums, and the like.
  • noodle strip products include noodles such as udon, somen, Chinese noodles, buckwheat noodles, rice noodles, pho, etc.
  • Examples include skins such as wonton, gyoza, shumai, and spring rolls.
  • the quality improving agent of the present invention has an excellent solubility in water for the present ⁇ -glucan as an active ingredient, and therefore it can be easily added to beverages depending on the content of the present ⁇ -glucan. It can be suitably used for the purpose of dissolving and improving the texture over the throat and improving the storage stability.
  • any other beverage material such as water, tea, coffee, fruit juice, alcohol, dairy products, extracts, carbonic acid and the like can be mentioned.
  • the blending ratio in the beverage is more than 0% by mass and 30% by mass or less, preferably 10% by mass or less, particularly preferably 5% by mass or less per solid, as the amount of the ⁇ -glucan. Since this ⁇ -glucan is made from waxy starch, it can impart rich physical properties such as body, thickness, mellowness and body feeling.
  • beverages examples include water beverages, green tea, gyokuro, roasted tea, kobu tea, black tea, oolong tea, barley tea, mate tea, and other coffee beverages, cocoa beverages, fruit juice beverages, carbonated beverages, functional beverages.
  • Soft drinks such as sports drinks, jelly drinks, and non-alcoholic drinks, beer, sparkling wine, wine, fruit liquor, sake, shochu, liqueur, brandy, whiskey and other liquor drinks, processed milk, yogurt and other milk drinks , Soy milk, soups, energy drinks, beauty drinks and the like.
  • the quality improving agent of the present invention can be advantageously used for other general foods and drinks.
  • seasonings such as Nomoto, Dashi-no-moto, compound seasonings, mirin, new mirin, table sugar, coffee sugar, and syrup.
  • pastes such as flower paste, peanut paste, fruit paste, processed foods of fruits and vegetables such as jam, marmalade, syrup pickles, sugar cane, sesame tofu, konjac, pickles such as Fukujin pickles, bedara pickles, thousand pickles Pickles, takuwanzuke, pickled vegetables such as Chinese cabbage, livestock meat products such as ham and sausage, fish ham, fish sausage, fish products such as sea urchin, chikuwa, tempura, sea urchin, squid salty, vinegar kombu , Various delicacies such as rice fields such as sakisume, cod, thai, shrimp, boiled seaweeds made with seaweed, wild vegetables, seaweed, small fish, shellfish, bean products such as boiled beans, natto, tofu, steamed tea Egg products such as egg tofu, side dish foods such as potato salad, rolls of konbu, dairy products, fish meat, livestock meat, fruits, bottled and canned vegetables, pudding mix,
  • ⁇ -glucan which is an active ingredient, has good solubility in water and high strength when formed into a film or the like, as well as an aging-controlling effect and flavor improvement.
  • it has physical properties improving action such as action, shape retention and viscoelasticity, antioxidant ability and browning prevention ability, and the molecular weight distribution of ⁇ -glucan contained as an active ingredient is within a specific range. Can be expected to always give a constant strength, dissolution rate, and disintegration rate to the molded product.
  • the quality improving agent of the present invention can be used not only for foods but also for cosmetics, pharmaceutical products for which the pharmacokinetics of active ingredients are always required to be constant, quasi drugs, sheets, As a molded article such as a capsule, soft capsule, microcapsule, fiber used for gauze or surgical thread, etc., or as an excipient, binder or coating agent when preparing tablets or granules, and further It can be a solid preparation of a dissolution type.
  • the molded product is a cosmetic or quasi-drug or an intermediate product thereof, lotion, milky lotion, cosmetic liquid, cream, gel, makeup base, foundation, teak, funny, concealer, lipstick, lip balm, mascara, Eyeshadow, Eyeliner, Eyebrow, Facial Cleanser, shampoo, Rinse, Conditioner, Hair Conditioner, Hair Nourishing, Scalp, Hair Coloring, Shaving Agent, Sunscreen, Nail Cosmetic, Body Powder, Ointment, Pack, Mask, Bath Agent, oral refreshing film, etc., for example, preservatives such as paraoxybenzoic acid ester, benzalkonium chloride, pentanediol, arbutin, ellagic acid, kojic acid, tranexamic acid, nicotinamide, vitamin C Derivatives, placenta extract, t
  • the molded product when it is a pharmaceutical product, a quasi-drug or an intermediate product thereof, it can be in the form of a solid such as a granule, a tablet, a sugar-coated tablet, a liquid, or a paste.
  • the quality improver of the present invention can also be used as a material for industrial products.
  • Industrial products here are agricultural chemicals, fertilizers, feeds, paper products, abrasives, glues, adhesives (binders), gelling agents, water separation preventing agents, excipients, water retention agents, moisturizing agents, moisture permeation agents.
  • the agricultural chemicals and fertilizers as excipients when granulating and tableting using the adhesion improving ability of the quality improving agent.
  • this ⁇ -glucan Utilizing the ability of this ⁇ -glucan to control aging, it can be used as a fertilizer, feed viscoelasticity improver, flavor improver, stabilizer, antioxidant, and shelf life improver.
  • it can be used as a surface coating agent and a reinforcing agent for paper products by utilizing the binding property and film forming ability of a quality improving agent, and also as a material for nonwoven fabrics and packaging materials.
  • it can also be used as a substitute for polyvinyl alcohol (PVA), a substitute for carboxymethyl cellulose (CMC), a gypsum board, cement, a binder for battery separators, and the like.
  • waxy corn starch (trade name “waxy corn starch Y”, manufactured by J-Oil Mills Co., Ltd.) is suspended in deionized water to a solids concentration of 30% by mass, and calcium chloride is adjusted to a concentration of 0.1% by mass. After the addition, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension.
  • Heat-resistant ⁇ -amylase (trade name “Spitase HK”, manufactured by Nagase ChemteX Corporation) was added to this waxy corn starch suspension at 0 (no addition), 0.001, 0.002, 0.004 per waxy corn starch solid. , 0.008 or 0.02% by mass, heated at pH 6.5, 100 ° C.
  • ⁇ -glucan powder is set by spray drying and setting the disk rotation speed at 18,000 rpm and the raw material supply speed at 23 kg / hour. Each prepared by about 2 kg, and a test sample 1-6.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are the same chromatogram of the test sample based on a calibration curve prepared based on a gel filtration HPLC chromatogram of a pullulan standard product for molecular weight measurement (manufactured by Hayashibara Co., Ltd.). Was obtained by analyzing with molecular weight distribution analysis software.
  • test samples 1 to 6 glucose equivalent (DE) was measured as an index for knowing the degree of hydrolysis. Further, each of the test samples 1 to 6 was dissolved in deionized water so as to have a solid concentration of 20% by mass, and the solubility in cold water was determined. Furthermore, test samples 1 to 6 were made into aqueous solutions having a solid concentration of 30% by mass, and each solution was measured at 35 ° C. using a dynamic viscoelastic rheometer (trade name “MCR102” manufactured by Anton Pearl Japan Co., Ltd.). The viscosity was measured. The viscosity of an aqueous solution having a solid concentration of 30% by mass was expressed as a shear viscosity under conditions of 35 ° C. and a shear rate of 10.8 / sec. The results are summarized in Table 1.
  • test sample 1 that is, the gelatinized waxy corn starch not treated with thermostable ⁇ -amylase, has a viscosity of 26,700 mPa ⁇ S showed high viscosity and had difficulty in handling.
  • pretreatment for high molecular weight distribution analysis by gel filtration HPLC could not be performed, and weight average molecular weight (Mw) and number average molecular weight (Mn) could not be measured.
  • test sample 1 was inferior in water solubility and did not have cold water solubility.
  • test samples 2 to 5 prepared by the action of a small amount of thermostable ⁇ -amylase, as the amount of amylase increases, the degree of degradation of gelatinized waxy corn starch increases, and the weight average molecular weight (Mw), The number average molecular weight (Mn) decreased and Mw / Mn decreased.
  • Test samples 2 to 5 have a weight average molecular weight (Mw) in the range of 2,560 to 183 kDa and Mw / Mn in a range of 3.95 to 8.09. Unlike test sample 1, the test samples 2 to 5 have cold water solubility. Was.
  • the viscosity of the aqueous solution having a solid concentration of 30% by mass in the test samples 2 to 5 shows a lower value as the amount of amylase acting increases, that is, as the degree of hydrolysis increases, 2,330 to 220 mPa ⁇ s. Met.
  • the test sample 6 prepared by acting 0.02% by mass of heat-resistant ⁇ -amylase per waxy corn starch solid has a small weight average molecular weight (Mw) of 39.1 kDa and a large value of Mw / Mn of 35.9.
  • Mw weight average molecular weight
  • ⁇ Experiment 2 Suitability of various ⁇ -glucans as edible film materials> Using the test samples 1 to 6 obtained in Experiment 1 as raw materials, each was formed into a film without adding a plasticizer, and the properties of the obtained films were examined, whereby various ⁇ -glucans as edible film materials were used. Suitability (film suitability) was examined.
  • test samples 1 to 6 obtained in Experiment 1 were uniformly dissolved in deionized water so that the solid concentration would be 30% by mass, and defoamed by centrifugation (3,000 rpm, 10 minutes).
  • a baker applicator trade name “YBA”, manufactured by Yoshimitsu Seiki Co., Ltd.
  • YBA baker applicator
  • the test samples 1 to 5 could be formed into films, a film having a thickness of about 40 ⁇ m was prepared from each of the test samples 1 to 5 as film samples 1 to 5.
  • each of the obtained film samples 1 to 5 was visually observed, ( ⁇ ): a good film having a uniform thickness and a smooth surface; and ( ⁇ ): a non-uniform thickness.
  • the film suitability was evaluated in two stages: a film with uneven surface.
  • the transparency of each film sample was visually observed and evaluated in two stages: ( ⁇ ): transparent; and (x): turbid.
  • the film cut into 1 cm square for each film sample was put into 200 mL of deionized water maintained at 30 ° C., and the time until the film was completely dissolved visually was measured under stirring.
  • the film was evaluated for water solubility in two stages: complete dissolution within 1 minute; The results are shown in Table 2.
  • film sample 1 prepared from test sample 1 simply gelatinized waxy corn starch is a film with uneven surface and lacking transparency, and does not completely dissolve in the water solubility test. It was inferior in nature.
  • film samples 2 to 5 were films having a uniform thickness, a smooth surface, and excellent transparency and water solubility.
  • the viscosity was low and it was difficult to shape
  • test samples 2 to 5 have suitability as a material for preparing a good edible film without using a plasticizer, while test samples 1 and 6 lack suitability. Met.
  • the weight average molecular weight (Mw) obtained by subjecting test samples 2 to 5 and film samples 2 to 5, ie, waxy starch, to amylase and partially decomposing it is 150 kDa to 3,000 kDa.
  • ⁇ -glucan having a range of Mw / Mn of less than 10 is excellent in cold water solubility and has a property of maintaining an appropriate viscosity. Also, by molding the ⁇ -glucan, it is uniform, transparent and water-soluble. It was found that an edible film having excellent properties can be obtained.
  • the amount of heat-resistant ⁇ -amylase (trade name “Spitase HK”, manufactured by Nagase ChemteX Corporation) per waxy corn starch solid was 0.002% by mass, and the other operations were the same as in Experiment 1.
  • An ⁇ -glucan-containing solution was obtained.
  • 1 g of solid ⁇ -glucan was obtained by purifying a purified preparation of ⁇ -glucosyltransferase derived from Bacillus circulans PP710 disclosed in the pamphlet of International Publication No. WO2008 / 136331 by the same applicant as the present application.
  • reaction was stopped by adding 0.25, 0.5, 2.5, 10 or 25 units per unit, acting at pH 6.0, 50 ° C. for 24 hours and heating at 140 ° C. for 10 minutes.
  • about 2 kg each of ⁇ -glucan was prepared by spray drying using a disk type spray drying apparatus (manufactured by Niro Co., Ltd.), and used as test samples 7 to 11.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn), and Mw / Mn were determined in the same manner as in Experiment 1.
  • the above-described isomalt-dextranase digestion test was carried out using a 1 w / v% aqueous solution of test samples 7-11. The isomaltose content in the obtained digest was measured.
  • test samples 7 to 11 obtained by allowing 0.002% by mass of thermostable ⁇ -amylase to act on waxy corn starch and further causing ⁇ -glucosyltransferase to act on the isomaltodextranase Digestion confirmed that 1.57% to 25.4% by weight of isomaltose was produced per solid of digested material, and although the degree was different, all of them had an isomaltose structure at the non-reducing end. It was confirmed to be an ⁇ -glucan mixture containing ⁇ -glucan molecules having
  • test samples 7-11 the greater the amount of action of ⁇ -glucosyltransferase, the greater the Mw / Mn (dispersity) of the obtained test sample, and the test sample with the largest amount of action of 25 units / g-substrate. In the case of 11, it increased to 62.3. Although the test samples 7 to 11 had no significant change in the weight average molecular weight (Mw) compared to the test sample 3, Mw / Mn was clearly increased by the action of ⁇ -glucosyltransferase, and the ⁇ -glucan Variation in molecular weight of molecular species occurred.
  • Mw weight average molecular weight
  • the viscosities of the aqueous solutions of the test samples 7 to 11 having a solid concentration of 30% by mass were 651 to 990 mPa ⁇ s, which were slightly lower than those of the test sample 3 to which no ⁇ -glucosyltransferase was allowed to act. I could't.
  • the test sample 7 showed white turbidity in the aging resistance test in which an aqueous solution with a solid concentration of 30% by mass was held at 6 ° C. for 1 week. Although no aging property was observed, it was found in the same aging resistance test that the test samples 8 to 11 had remarkable aging resistance that maintained the state of a transparent aqueous solution at the time of storage for 1 week.
  • ⁇ -glucan having an isomaltose structure at the non-reducing end was prepared from ⁇ -glucan having a weight average molecular weight (Mw) smaller than that in Experiment 3, and examined in the same manner as in Experiment 3.
  • Mw weight average molecular weight
  • Treatment was performed in the same manner as in Experiment 1 except that the amount of heat-resistant ⁇ -amylase used per waxy corn starch solid was changed to 0.004% by mass to obtain ⁇ -glucan having a further reduced molecular weight.
  • a purified preparation of ⁇ -glucosyltransferase derived from Bacillus circulans PP710 strain was added to the ⁇ -glucan at 0.5, 1.0, 2.5 or 5. The reaction was stopped by adding 0 units, acting at pH 6.0, 50 ° C. for 24 hours and heating at 140 ° C. for 10 minutes.
  • about 2 kg each of ⁇ -glucan was prepared by spray drying using a disk type spray drying apparatus (manufactured by Niguchi Co., Ltd.), and used as test samples 12 to 15.
  • Test Samples 12 to 15 as in Experiment 3, the weight average molecular weight (Mw), number average molecular weight (Mn), Mw / Mn, isomaltose content in isomaltdextranase digest, glucose equivalent (DE) was measured, and the viscosity and aging resistance of a solution with solubility in cold water and a solid concentration of 30% by mass were evaluated.
  • the results are summarized in Table 4.
  • the results of Test Sample 4 prepared by adding 0.004% by mass of heat-resistant ⁇ -amylase per waxy corn starch solid to the waxy corn starch suspension obtained in Experiment 1 are also shown in Table 4 as a control.
  • test samples 12 to 15 obtained by allowing 0.004% by mass of thermostable ⁇ -amylase to act on waxy corn starch and further causing ⁇ -glucosyltransferase to act on the isomaltodextranase Since it was confirmed that the digestion produced 1.5% to 20.6% by mass of isomaltose per solid of the digested product, the same as in the case of test samples 7 to 11 obtained in Experiment 3 In addition, it was confirmed that both included an ⁇ -glucan molecule having an isomaltose structure at the non-reducing end.
  • test samples 12 to 15 the weight average molecular weight (Mw) is 365 to 449 kDa, about 1/3 that of Test Samples 7 to 11 obtained in Experiment 3, and ⁇ -glucan having a lower molecular weight. It was confirmed that. Mw / Mn of test samples 12 to 15 showed values of 8.3 to 37.5. Although the test samples 12 to 15 did not change much in the weight average molecular weight (Mw) as compared to the test sample 4, Mw / Mn was clearly increased as the amount of action of ⁇ -glucosyltransferase increased. The glucose equivalent (DE) of test samples 12 to 15 was in the range of 0.46 to 2.76.
  • the viscosity of the aqueous solution of the test samples 12 to 15 having a solid concentration of 30% by mass was 294 to 525 mPa ⁇ s, which was not significantly different from that of the test sample 4 in which no ⁇ -glucosyltransferase was allowed to act.
  • the test sample 12 showed white turbidity in the aging resistance test in which an aqueous solution having a solid concentration of 30% by mass was maintained at 6 ° C. for 1 week. Although no aging property was observed, it was found in the same aging resistance test that the test samples 13 to 15 had remarkable aging resistance that maintained the state of a transparent aqueous solution at the time of storage for 1 week.
  • the isomaltose dextranase digest is digested with a low isomaltose content of 1.57% by mass or 1.50% by mass.
  • Test sample 7 and test sample 12 having low isomaltose content contained in the digest of isomaltdextranase of ⁇ -glucan having an isomaltose structure at the reducing end did not have aging resistance.
  • test samples 8 to 11 and test samples 13 to 15 having an isomaltose content of 3.83% by mass or more have aging resistance, and the above experimental results indicate that ⁇ -glucan is converted to ⁇ -glucosyltransferase.
  • ⁇ Experiment 5 Suitability of ⁇ -glucan having isomaltose structure at non-reducing end as edible film material> Films having a thickness of about 40 to 50 ⁇ m were prepared using test samples 7 to 15 obtained in Experiments 3 and 4 as raw materials in the same manner as in Experiment 2, and designated as film samples 7 to 15, respectively. Next, as in Experiment 2, the film samples 7 to 15 were evaluated for appearance (film suitability), transparency, and water solubility, and puncture breaking strength was measured.
  • Table 5 shows the results of film samples 7 to 11 using ⁇ -glucan having a weight average molecular weight (Mw) of 1,210 kDa or more as a raw material, and film samples using ⁇ -glucan having a weight average molecular weight (Mw) of less than 500 kDa as a raw material.
  • Mw weight average molecular weight
  • the results of 12 to 15 are summarized in Table 6, respectively.
  • film samples 7 to 10 prepared using ⁇ -glucan having an isomaltose structure at the non-reducing end and having a weight average molecular weight (Mw) of 1,210 kDa or more are as follows: Similar to film sample 3 prepared using ⁇ -glucan obtained by partially degrading waxy corn starch with amylase, it was excellent in transparency and water solubility, and puncture strength was as strong as 2.0 N / mm 2 or more. Had properties. However, the test sample 11, that is, the film sample 11 prepared from ⁇ -glucan whose Mw / Mn value increased to 62.3 by the action of ⁇ -glucosyltransferase, becomes very brittle and obtains a film. It was difficult.
  • Mw weight average molecular weight
  • film samples 12 to 14 prepared using ⁇ -glucan having an isomaltose structure at the non-reducing end and having a weight average molecular weight (Mw) of less than 500 kDa Similar to film sample 4 prepared using ⁇ -glucan obtained by partially degrading waxy corn starch with amylase, it is excellent in transparency and water solubility, and has a strong puncture and break strength of 2.0 N / mm 2 or more. Had the same properties. However, the test sample 15, that is, the film sample 15 prepared from ⁇ -glucan whose Mw / Mn value increased to 37.5 by the action of ⁇ -glucosyltransferase, becomes very brittle and obtains a film. It was difficult.
  • Mw weight average molecular weight
  • amylose content of commercially available corn starch (trade name “Showa Corn Starch”, manufactured by Shikishima Starch Co., Ltd.) and high amylose corn starch (trade name “starch corn derived”, code number: S4180, manufactured by Sigma Aldrich) It measured similarly about.
  • amylose content of each sample was measured based on the color reaction of amylose and iodine according to the amylose content measurement method shown in the Ministry of Agriculture, Forestry and Fisheries Notification No. 332, Standard Measurement Method.
  • an amylose standard solution was prepared using a reagent grade amylose (trade name “Potatoamylose Type III” manufactured by Sigma Aldrich), and a calibration curve was prepared. The results are shown in Table 7.
  • the amylose content (% by mass) of waxy corn starch and ⁇ -glucan obtained in Example 3 was measured to be 13.4% by mass and 10.3% by mass, respectively, in this measurement method.
  • the amylose content of commercially available corn starch and high amylose corn starch was measured to be 35.9% by mass and 46.9% by mass, respectively.
  • the amylose content is said to be higher in the order of high amylose corn starch> corn starch> waxy corn starch, and the above measured values support this conventional knowledge.
  • ⁇ -glucan which is an active ingredient of the quality improving agent of the present invention, is obtained by partially decomposing waxy starch with amylase and then allowing ⁇ -glucosyltransferase to act to produce ⁇ -glucan having an isomaltose structure at the non-reducing end. It is manufactured by generating. Since amylase and ⁇ -glucosyltransferase are not enzymes that degrade the branched structure through ⁇ -1,6 bonds in waxy starch like starch debranching enzyme, the action of amylase and ⁇ -glucosyltransferase Does not produce linear amylose from waxy starch and does not increase the amylose content in the reaction product.
  • ⁇ -glucan containing the quality improving agent of the present invention as an active ingredient showed an amylose content equal to or lower than that of waxy corn starch.
  • This ⁇ -glucan was produced using waxy corn starch as a raw material. It tells that it is a thing.
  • ⁇ -glucan having a weight average molecular weight (Mw) of 150 kDa or more and having an amylose content of less than 15% by this measurement method is obtained at least from waxy starch. It can be said that there is.
  • Example 6 Aging resistance of this ⁇ -glucan during freezing storage>
  • the freezing tolerance of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improver of the present invention, obtained by the method of Example 1 described later was examined and evaluated.
  • the ⁇ -glucan obtained by the method of Example 1 was dissolved in deionized water so as to have a solid concentration of 30% by mass to obtain a test carbohydrate solution, which was a sample with 0 cold thawing cycles. 3 g of this test carbohydrate solution was dispensed into a test tube, frozen at ⁇ 20 ° C., and then naturally thawed to obtain a sample with one cold thawing.
  • the test carbohydrate solution prepared by using the ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has a viscosity of about 1,400 mPa ⁇ s before freezing. This viscosity was maintained with almost no change even after repeated cold thawing 5 times. That is, it has been found that ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has very excellent aging resistance against cold thawing.
  • Example 7 Aging control of ⁇ -glucan to liquefied starch> Comparison of aging control of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 and comparison with two commercially available dextrins derived from waxy corn starch evaluated. Two dextrins derived from ⁇ -glucan and waxy corn starch obtained by the method of Example 1 (trade name “Paindex # 100”, manufactured by Matsutani Chemical Industry Co., Ltd., and trade name “Sandeck # 30”, Sanwa Starch Co., Ltd.
  • test solutions 1 to 3 The compositions of the test solutions 1 to 3 are shown in Table 8. Each test solution was dispensed into a test tube, stored in a sealed state at 4 ° C. for 5 days, and then turbidity (Abs 720 nm) was measured as an index for aging control. The results are summarized in FIG.
  • test solutions 2 and 3 prepared using the control and two commercially available waxy corn starch-derived dextrins showed a turbidity of 0.9 or more after refrigerated storage, and became markedly cloudy.
  • test solution 1 prepared by using the ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 maintains the turbidity after refrigerated storage at 0.19, which is extremely low. It had been. From these results, ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, remarkably suppresses aging of coexisting starchy polysaccharides, and exhibits excellent aging control. It was found to have the ability.
  • ⁇ Experiment 8 Flavor improvement of soymilk of this ⁇ -glucan>
  • the taste improving property of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated by a sensory test.
  • the ⁇ -glucan obtained by the method of Example 1 was commercialized with soymilk (trade name “delicious unadjusted soymilk”, Kikkoman, so that the solids concentration would be 0.5 mass%, 1.0 mass%, and 2.0 mass%. Added to and dissolved in Beverage Co., Ltd. to obtain test soybean milk 1 to 3 for flavor improvement test.
  • the sensory test by 12 panelists was implemented about the flavor of each prepared soymilk, and it evaluated using VAS method.
  • VAS method For the four items of blue odor, savory taste, sweet taste, and deliciousness, the flavor of the control soymilk without the addition of ⁇ -glucan is 0, the imaginable highest flavor state is 10, and the lowest flavor state is -10.
  • the flavor of the test soymilk was expressed as a numerical value, and the average value was evaluated. The results are summarized in FIG.
  • the test soymilk 1 to 3 prepared using ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 was used in the items of blue odor, savory taste, and deliciousness. All showed values of 0.4 or more, and the effect increased in a dose-dependent manner.
  • the ⁇ -glucan had little effect on sweetness. Therefore, the test soymilk 1 to 3 prepared using the ⁇ -glucan has almost no change in sweetness, the blue odor and the savory taste are remarkably reduced as compared with the additive-free soymilk.
  • ⁇ Experiment 9 Shape retention of gelatin gel of this ⁇ -glucan>
  • the property improvement property of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention obtained by the method of Example 1 was examined using the shape retention of gelatin gel as an index. evaluated.
  • a gelatin solution was prepared by dissolving commercially available gelatin (trade name “Gelatin 21”, manufactured by Nitta Gelatin Co., Ltd.) having a solid concentration of 2.4% by mass in water heated to 65 ° C.
  • the saccharide solution 1 or 2 and the gelatin solution were mixed in equal amounts, respectively, and then placed in a container and refrigerated at 4 ° C. for 16 hours to prepare test gelatin gels 1 and 2.
  • a control gelatin gel was prepared in the same manner except that water heated to 65 ° C. was used instead of the saccharide solution.
  • the gelatin gel was taken out of the container and stored at 20 ° C. for 4 hours, and then each gelatin gel was photographed to evaluate the shape retention. The results are shown in FIG.
  • the test gelatin gel 2 prepared using the control gelatin gel and the commercially available dextrin derived from waxy corn starch was deformed immediately after removal from the container, and the degree of deformation further increased after 4 hours.
  • the test gelatin gel 1 prepared using ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 was taken out from the container. Immediately after, the shape of the container was maintained, and even after 4 hours, it was a gelatin gel that hardly collapses so as to maintain the shape of the container, indicating that the shape retention was high. That is, it was found that ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent shape retention ability.
  • ⁇ Experiment 10 Ability of this ⁇ -glucan to improve foam physical properties of meringue>
  • the property improvement property of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated using meringue foam property as an index. .
  • To 100 parts by weight of egg white 45 parts by weight of sugar and 5 parts by weight of ⁇ -glucan obtained by the method of Example 1 were added and dissolved, and a test meringue was prepared with a whisk.
  • a control meringue was prepared in the same manner except that 50 parts by weight of sugar was added to 100 parts by weight of egg white.
  • the control meringue was evaluated as “+” immediately after preparation and the foam was fine, but was evaluated as “ ⁇ ” after 18 hours of refrigeration, and the foam became coarse and almost disappeared.
  • the test meringue prepared by using the ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has finer and smoother bubbles immediately after the preparation than the control meringue. It was elastic, creamy and rich, and was rated “++”.
  • the test meringue foam was less likely to disappear, and was evaluated as “ ⁇ ” even after 18 hours as compared with the control meringue, and the foam was maintained. That is, the meringue blended with the ⁇ -glucan has improved foam quality, and its bubbles are stabilized over time. It has been found that the ⁇ -glucan possessed has an excellent ability to improve foam physical properties.
  • test bracken was obtained by adding 1%, 2.5%, 5.0%, 10.0% by weight of sugar to ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1.
  • Test warabimo 1 to 4 were prepared in the same manner as the control except that it was replaced.
  • Table 10 shows the compositions of the control bracken and the test bracken 1 to 4.
  • a sensory test was conducted on the texture of each of the prepared warabimochi with five panelists, with + as the standard softness (control), +: slightly soft, ++: soft, +++: fairly soft, +++: very It was evaluated in four grades: soft.
  • the average values of the five panelists are summarized in Table 11.
  • test bracken koji 1 to 4 prepared using ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has a blending amount of ⁇ -glucan. As it increased, it had a softer texture. That is, it was found that ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent texture improvement ability.
  • ⁇ Experiment 12 Examination of temperature stability of ⁇ -glucan>
  • the property improving property of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated using the heat retaining property of an aqueous solution as an index.
  • the ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 or a commercially available dextrin derived from waxy corn starch (trade name “Sandeck # 30”, manufactured by Sanwa Starch Co., Ltd.)
  • Test aqueous solutions 1 and 2 were prepared by dissolving in water to 10.0 mass%, and the control was water.
  • the time required for the control and the test aqueous solution 2 to decrease to each set temperature was short, and the temperature decrease was rapid.
  • the test aqueous solution 1 prepared by using the ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has a gradual temperature decrease, and decreases to each set temperature. It was revealed that the time required was long. That is, it was found that ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, is excellent in heat retention and temperature stability.
  • ⁇ Experiment 13 Examination of the viscosity of gelatinized starch of this ⁇ -glucan> The property improvement property of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention obtained by the method of Example 1, was examined using the viscosity of gelatinized starch gel as an index. evaluated.
  • Corn starch (trade name “Showa Corn Starch”, manufactured by Shikishima Starch Co., Ltd.) having a solid concentration of 15.0% by mass was heated in a boiling bath to prepare a starch gelatinization solution, which was then kept warm in the boiling bath.
  • Example 1 the ⁇ -glucan obtained by the method of Example 1 or a commercially available dextrin derived from waxy corn starch (trade name “Sandeck # 30”, manufactured by Sanwa Starch Co., Ltd.) so that the solid concentration is 10.0% by mass, Each was dissolved in water and then heated in a boiling bath to prepare carbohydrate solutions 1 and 2, which were kept warm in the boiling bath. Next, an equal amount of starch gelatinization liquid heated and kept in a boiling bath and sugar solution 1 or 2 heated and kept in a boiling bath are mixed, put into a container, and allowed to stand at room temperature for 1.5 hours. Test gelatinized starch gels 1-2 were formed.
  • Loss tangent (used as an index of stickiness) using a rheometer (trade name “MCR102”, manufactured by Anton Pearl Japan Co., Ltd.) immediately after gel formation and after storage for 5 days at 4 ° C. tan ⁇ ) was determined and the degree of stickiness of each gel was evaluated and is shown in FIG.
  • the degree of viscosity of the test gelatinized starch gel 1 prepared using ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 was 0.12.
  • the value was about 1.2 times. 5 days after the preparation, although the degree of stickiness of the test gelatinized starch gel 1 decreased to about 0.05, it showed a value of 1.7 times or more as compared with the test gelatinized starch gel 2, The reduction rate was lower than that of the test gelatinized starch gel 2.
  • the ⁇ -glucan having an isomaltose structure at the non-reducing end which is an active ingredient of the quality improving agent of the present invention, is prepared by gelatinizing starch gel after 5 days of refrigeration compared to commercially available dextrin. It has been found that it is excellent in maintaining a high degree of stickiness and suppressing a decrease in stickiness accompanying a change with time.
  • aqueous solution After 78 g of each aqueous solution was dispensed into a plastic cup, the upper part of the cup was covered with a plastic paraffin film (trade name “Parafilm M”, manufactured by Bemis Company) to prevent evaporation of water, and 20 ° C. at room temperature (22 ° C.).
  • a gel containing ⁇ -carrageenan at a final concentration of 0.8% (w / w) was prepared by standing for a minute.
  • a control carrageenan gel was prepared in the same manner except that only ⁇ -carrageenan and sugar were used. The three kinds of prepared carrageenan gels were each stored at 4 ° C. for 2 weeks in a state filled in a container.
  • the amount of water separation after storage at 4 ° C. for 2 weeks reached 3.0% of the total gel weight in the case of the control gel, while 1.6% in the commercial dextrin-containing gel.
  • the gel in which ⁇ -glucan having an isomaltose structure was blended at the non-reducing end obtained by the method of Example 1 it remained at 0.8%.
  • the water separation amount of the present ⁇ -glucan-containing gel was remarkably reduced to about 1/4 of the water separation amount of the control gel. That is, it was found that ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent ability to suppress water separation.
  • ⁇ Experiment 15 Improving the texture of this ⁇ -glucan bread>
  • the property improving property of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated using the elasticity of bread as an index.
  • Each component was mixed with the composition shown in Table 14, and bread was baked using a home bakery (SD-BMT1000 type, manufactured by Panasonic Corporation) with a bread bread program (menu 4) built in the main body.
  • the amount of ⁇ -glucan obtained by the method of Example 1 was set to 5% of the weight of the flour, and the amount of water was reduced by the amount of this ⁇ -glucan.
  • the control bread was prepared using the same method except that the ⁇ -glucan was not added.
  • the center part of the inner phase of the baked bread was cut into a 2 cm square, and the cut out part was subjected to a condition using a rheometer (CR-500DX type, manufactured by Sun Kagaku Co., Ltd.) with a plunger diameter of 15 mm and a pedestal rising speed of 5 mm / sec.
  • a rheometer CR-500DX type, manufactured by Sun Kagaku Co., Ltd.
  • the test bread prepared by blending ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 showed an elasticity of 0.42N and an elasticity of 0.21N. Compared to the control bread shown, the value was doubled. It was shown that an elastic bread can be prepared by blending this ⁇ -glucan. In other words, the bread blended with the present ⁇ -glucan has a greater elasticity than the control bread without the present ⁇ -glucan, and when eaten, it is a bread that gives a resilient and comfortable texture. . From this, it was found that ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent texture improvement ability.
  • ⁇ Experiment 16 Effect of the ⁇ -glucan on the texture of gummi> About the physical property improvement property of ⁇ -glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention obtained by the method of Example 1, for sensory evaluation using gummy texture as an index And evaluated.
  • the components shown in Table 16 those obtained by removing gelatin and citric acid solution were mixed in a glass container, and maintained at 121 ° C. using an electric stove (SK-65, 600 W, manufactured by Ishizaki Electric Manufacturing Co., Ltd.). While being heated, it was boiled until Brix was 90.
  • the gummy prepared by blending ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has almost the same hardness as the control gummy.
  • the number of respondents who responded that this was the most (8/10 out of 10) was higher, but when chewing quickly, the panel that responded that this ⁇ -glucan-containing gummy was firmer than the control gummy. (7 out of 10 people).
  • the gummi containing the ⁇ -glucan gave a soft texture equivalent to that of the control gummi when chewed slowly and a firm texture when chewed quickly.
  • the gummi containing the ⁇ -glucan is a dilatancy-like gummy that gives a unique texture that cannot be obtained with conventional gummi, and is an active ingredient of the quality improver of the present invention, at the non-reducing end. It has been found that ⁇ -glucan having an isomaltose structure has an excellent texture improvement ability.
  • ⁇ -glucan which is an active ingredient of the quality improving agent of the present invention, has a shape retention effect, a foam property improvement effect, a texture improvement effect, a heat retention effect / temperature stabilization effect, and a stickiness degree adjustment effect. Excellent effects such as water separation inhibiting effect were exhibited. That is, it was found that the quality improver of the present invention has an excellent ability to improve physical properties.
  • the quality improving agent of the present invention comprising ⁇ -glucan having an isomaltose structure at the non-reducing end used in the present invention as an active ingredient and its use will be described in detail by way of examples. It is not limited at all by an example.
  • waxy corn starch (trade name “waxy corn starch Y” manufactured by J-Oil Mills Co., Ltd.) is suspended in deionized water to a solids concentration of 30% by mass, so that calcium chloride has a concentration of 0.1% by mass. After the addition, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension. To this waxy corn starch suspension, a heat-resistant ⁇ -amylase (trade name “Spitase HK / R”, manufactured by Nagase ChemteX Corporation) was added in an amount of 0.005% by mass per waxy corn starch solid, at pH 6.5 and 100 ° C. By heating for 20 minutes, gelatinization and liquefaction were carried out.
  • a heat-resistant ⁇ -amylase (trade name “Spitase HK / R”, manufactured by Nagase ChemteX Corporation) was added in an amount of 0.005% by mass per waxy corn starch solid, at pH 6.5 and 100 ° C.
  • ⁇ -glucosyltransferase derived from Bacillus circulans PP710 strain disclosed in International Publication No. WO2008 / 136331 was added to 1.25 per gram of waxy corn starch solids. After adding the unit and allowing it to act at pH 6.0 and 50 ° C. for 24 hours, the reaction was stopped by heating at 140 ° C. for 10 minutes, and the mixture was supplied to a spray dryer and spray-dried at 135 ° C. The dried product was pulverized through a pulverizer to obtain powdery ⁇ -glucan having an isomaltose structure at the non-reducing end.
  • the ⁇ -glucan has a weight average molecular weight (Mw) of 1,070 kDa, a number average molecular weight (Mn) of 63.1 kDa, Mw / Mn (dispersity) of 16.9, and has cold water solubility,
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw / Mn disersity
  • the viscosity of the aqueous solution having a solid concentration of 30% by mass was 861 mPa ⁇ s.
  • the glucose equivalent (DE) of the ⁇ -glucan was 0.89, and the isomaltose content of the ⁇ -glucan digested with isomaltose dextranase was 5.6% by mass.
  • the ⁇ -glucan is an ⁇ -glucan having an isomaltose structure at the non-reducing end, and is transparent when stored for 1 week in an aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C. for 1 week. It had remarkable aging resistance that maintained the state of the aqueous solution.
  • the ⁇ -glucan is suitable as an active ingredient of the quality improving agent of the present invention.
  • the quality improving agent containing the ⁇ -glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
  • waxy corn starch Y Commercially available waxy corn starch (trade name “waxy corn starch Y” manufactured by J-Oil Mills Co., Ltd.) was suspended in deionized water to a solids concentration of 30% by mass, and calcium chloride was added to a concentration of 0.1% by mass. After that, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension.
  • heat-resistant ⁇ -amylase trade name “Spitase HK”, manufactured by Nagase ChemteX Corporation
  • the ⁇ -glucan had a weight average molecular weight (Mw) of 1,270 kDa, Mw / Mn of 22.1, was soluble in cold water, and the viscosity of an aqueous solution having a concentration of 30% by mass was 896 mPa ⁇ s.
  • the isomaltose content of the digest obtained by allowing isomaltdextranase to act on the ⁇ -glucan was 9.3% by mass.
  • the ⁇ -glucan is an ⁇ -glucan having an isomaltose structure at the non-reducing end, and in an aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C.
  • the ⁇ -glucan is suitable as an active ingredient of the quality improving agent of the present invention.
  • the quality improving agent containing the ⁇ -glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
  • waxy corn starch (trade name “waxy corn starch Y” manufactured by J-Oil Mills Co., Ltd.) was suspended in deionized water to a solids concentration of 35% by mass, and calcium chloride was added to a concentration of 0.1% by mass. After that, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension.
  • Heat-resistant ⁇ -amylase (trade name “Termamyl 60L”, manufactured by Novozymes Japan Co., Ltd.) is added to this waxy corn starch suspension in an amount of 0.004% by mass per waxy corn starch solid, and heated at 100 ° C. for 20 minutes.
  • the ⁇ -glucan had a weight average molecular weight (Mw) of 566 kDa, Mw / Mn of 13.2, was soluble in cold water, and the viscosity of an aqueous solution having a concentration of 30% by mass was 483 mPa ⁇ s.
  • the isomaltose content of the digest obtained by allowing isomaltdextranase to act on the ⁇ -glucan was 7.0% by mass.
  • the ⁇ -glucan is an ⁇ -glucan having an isomaltose structure at the non-reducing end, and in an aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C.
  • the ⁇ -glucan is suitable as an active ingredient of the quality improving agent of the present invention.
  • the quality improving agent containing the ⁇ -glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
  • the ⁇ -glucosyltransferase derived from Arthrobacter globiformis PP349 strain disclosed in International Publication No. WO2008 / 136331 is further solidified into waxy rice starch.
  • the same procedure as in Example 3 was performed except that 2.5 units per gram was added and the mixture was allowed to act at pH 6.0 and 50 ° C. for 24 hours. Glucan was obtained.
  • the ⁇ -glucan had a weight average molecular weight (Mw) of 1,360 kDa, Mw / Mn of 22.4, was soluble in cold water, and the viscosity of an aqueous solution having a concentration of 30% by mass was 840 mPa ⁇ s.
  • the isomaltose content of the digest obtained by allowing isomaltdextranase to act on the ⁇ -glucan was 17.5% by mass.
  • the ⁇ -glucan is an ⁇ -glucan having an isomaltose structure at the non-reducing end, and in the aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C.
  • the ⁇ -glucan is suitable as an active ingredient of the quality improving agent of the present invention.
  • the quality improving agent containing the ⁇ -glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
  • ⁇ Frozen cooked rice> Using ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 as a quality improver, water is added to this and completely dissolved to obtain a carbohydrate solution having a concentration of 25% Was prepared. 600 parts by mass of raw rice was washed, immersed in water at 15 ° C. for 60 minutes, cooked in a conventional manner, and steamed for 5 minutes. While stirring the steamed cooked rice, the sugar solution heated to 80 ° C. is 2.5% as ⁇ -glucan having an isomaltose structure at the non-reducing end with respect to the mass of raw rice used for cooking rice.
  • ⁇ Cooked rice for chilled use> ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 was used as a quality improver, and water was added to this to completely dissolve it.
  • a 5% sugar solution was prepared. 600 parts by mass of raw rice was washed, immersed in water at 15 ° C. for 60 minutes, cooked with 800 parts by mass of the carbohydrate solution, and steamed for 10 minutes to obtain cooked rice. After cooling this cooked rice, divide it into containers one by one, store it in chilled for 48 hours, and test it after returning it to room temperature.
  • the quality-improving agent demonstrates the ability to control aging, and tastes comparable to that immediately after production.
  • Was holding With this cooked rice, rice balls were made, stored at 5 ° C for 24 hours, 36 hours, and 48 hours, then returned to room temperature and sampled. It was confirmed that the quality-improving agent exhibited excellent aging control ability.
  • This product was stored at -20 ° C for 1 week, thawed at chilled for 24 hours at 5 ° C, returned to room temperature, and tasted, and the aging control ability, physical property improvement ability, and flavor improvement ability of the quality improver were demonstrated. The taste was inferior to that immediately after.
  • This product can be used as it is or refrigerated and used as sushi rice when making nigiri sushi, roll sushi, chirashi sushi, inari sushi, pressed sushi, etc. It can also be used as sushi rice when manufacturing nigiri sushi. In addition, it can be frozen and stored in the state of nigiri sushi with sushi seeds on it.
  • ⁇ Spaghetti> An ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 4 was used as a quality improver, and an appropriate amount of water was added thereto to completely dissolve it.
  • a saccharide solution was prepared. 100 parts by weight of commercially available spaghetti (dried product) is boiled with hot water in a conventional manner, and the noodles immediately after being boiled from hot water are placed in a heat-retaining container and heated to 75 ° C. while stirring gently. 5 parts by mass was added and held for 30 minutes to allow the carbohydrates to penetrate. The product was returned to room temperature after 48 hours of chilled storage or frozen storage, and the noodles were evaluated for looseness. As a result, the quality-improving agent exhibited aging control and physical properties, and it was manufactured in any storage method. It had the same looseness immediately after that.
  • ⁇ Spaghetti> 2,000 parts by weight of a saccharide solution in which ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 is used as a quality improving agent and dissolved in 0.5% by mass was used to prepare 100 parts by weight of commercially available spaghetti (dried product).
  • the product was returned to room temperature after 48 hours of chilled storage or frozen storage, and the noodles were evaluated for looseness.
  • the quality-improving agent exhibited aging control and physical properties, and it was manufactured in any storage method. It had the same looseness immediately after that.
  • ⁇ Taste reduction inhibitor of starch gelatinized food> ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 was used as a quality improver and water-containing crystal ⁇ , ⁇ -trehalose (trade name “ Toreha ”, Hayashibara Co., Ltd.), hydrous crystal maltose (trade name“ San Mart ”, Hayashibara Co., Ltd.), maltotetraose-rich syrup (trade name“ Tetrap H ”, Hayashibara Co., Ltd.) And dissolved in a mass ratio of 1: 1: 1: 1, containing an ⁇ -glucan, ⁇ , ⁇ -trehalose, maltose, and maltotetraose-rich carbohydrate having an isomaltose structure at the non-reducing end in terms of anhydride.
  • a syrup-like taste reduction inhibitor having a sugar concentration of 30% by mass was prepared. This product was further spray-dried by a conventional method to prepare a powdery taste
  • These taste reduction inhibitors can be used as they are or dissolved in water, and further used as a taste reduction inhibitor for starch gelatinized foods in combination with other starch aging inhibitors or food quality improvers. it can.
  • the present taste lowering inhibitor coexists with and is in contact with starch gelatinized food immediately after starch is gelatinized by heating, and maintains the starch gelatinized food at room temperature, at a relatively high temperature for a certain period of time. It can control the aging of starch that may progress when stored and distributed in chilled, refrigerated or frozen state, and can suppress the generation of curing and off-flavors.
  • the present taste reduction inhibitor when applied to the production of noodles such as udon, soba noodles, Chinese noodles and spaghetti, it can also be used for the purpose of improving the looseness of the noodles.
  • the immersion liquid consisting of After removing the immersion liquid, it was stored frozen at ⁇ 20 ° C. to prepare a frozen squid.
  • the quality improver demonstrates the ability to improve physical properties such as resistance to freezing and water separation prevention, and the ability to improve flavor, whitening does not occur even during long-term frozen storage, and there is little drip when thawing, It is a high-quality frozen squid with no odor.
  • Nonfat powdered milk (milk fat content: 0.8%, non-fat milk solid content: 96.2%) 8 parts by weight, egg yolk 2 parts by mass, sugar 12 parts by mass, non-obtained by the method of Example 4 5 parts by mass of ⁇ -glucan having an isomaltose structure at the reducing end as a quality improver, 5 parts by mass of trehalose (trade name “Treha” manufactured by Hayashibara Co., Ltd.) and 60 parts by mass of water were added and dissolved with stirring. . Next, 8 parts by weight of fresh cream (milk fat content: 47.0%, non-fat milk solid content: 4.0%) was added, and further heated and stirred, and then homogenized with a homogenizer.
  • This product is a high-quality ice milk with a good taste, taste and mouth-melting properties, and a quality-improving agent that exhibits improved physical properties such as ice crystal stability and curability control, and improved flavor.
  • 2-O- ⁇ -D-glucosyl-L-ascorbic acid trade name “ASCOFRESH” manufactured by Hayashibara Co., Ltd.
  • An orange jelly was obtained by filling this solution in a container and storing it in a refrigerator.
  • This product is a high-quality orange jelly with a quality-improving agent that improves physical properties and flavor, such as shape retention, stability and water separation prevention, and has a beautiful appearance, good texture and good flavor. It is.
  • ⁇ Lactic acid bacteria beverage 175 parts by weight of skim milk powder, 100 parts by weight of ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 and a powder containing high lactosucrose (trade name “milk Oligo ", manufactured by Hayashibara Co., Ltd.) in 1,500 parts by mass of water, sterilized at 65 ° C. for 30 minutes, cooled to 40 ° C., and then inoculated with 30 parts by mass of a starter of lactic acid bacteria. And culturing at 37 ° C. for 8 hours to obtain a lactic acid bacteria beverage.
  • This product contains oligosaccharides and has not only an intestinal regulating action, but also a quality improver that can improve the physical properties such as stability and formability and the ability to improve flavor to keep lactic acid bacteria stable. It is a high quality lactic acid bacteria beverage that can be made.
  • ⁇ Green juice powder> With respect to 25 parts by mass of barley young leaf powder and 25 parts by mass of kale powder, 40 parts by mass of ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 3 as a quality improver and Trehalose powder (trade name “Treha”, manufactured by Hayashibara Co., Ltd.) 5 parts by mass, water-soluble dietary fiber (trade name “Fiber Rixa”, manufactured by Hayashibara Co., Ltd.) 5 parts by mass, 2-O- ⁇ -glucosyl-L-ascorbic acid (Product name “ASCOFRESH”, manufactured by Hayashibara Co., Ltd.) 1 part by mass was thoroughly mixed and stirred, pulverized into a fine powder, weighed and packaged to obtain a product.
  • a quality improver and Trehalose powder trade name “Treha”, manufactured by Hayashibara Co., Ltd.
  • water-soluble dietary fiber trade name “Fiber Rixa”, manufactured by Hayashibara
  • This product exhibits the ability to improve the physical properties of quality improvers and is excellent in dispersibility, color development and stability of young barley leaf powder and kale powder, and it can be dissolved or suspended in an appropriate amount of water.
  • the flavor improving ability of the quality improving agent is exerted, there is no off-flavor, and the product value is high as a high quality green juice.
  • the corn starch is completely gelatinized. When the whole became translucent, the fire was turned off, cooled, added with an appropriate amount of vanilla fragrance, weighed, filled and packaged to obtain a product.
  • This product is a high quality custard cream that has a smooth luster and texture, with a quality improving agent that exerts the ability to control starch aging and improve flavor, and has a smooth luster and texture.
  • ⁇ Strawberry> water was added to 10 parts by mass of raw material red beans, boiled, astringent and extracted, and water-soluble impurities were removed to obtain about 21 parts by mass of red bean grains.
  • 14 parts by mass of sucrose, and 5 parts by mass and 10 parts by mass of water were added as a quality improver with ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 and boiled.
  • a small amount of salad oil was added and kneaded so as not to break the granule, and about 35 parts by mass of the product koji was obtained.
  • the quality improver exhibits starch aging control ability, physical property improvement ability, flavor improvement ability, color burning, water separation, stable, good taste, rice cake bread, manju, dumpling, middle, ice confectionery, etc. It is suitable as a confectionery material.
  • Ui-no-Moto, an appropriate amount of Matcha and water were kneaded, and the mixture was placed in a container and steamed for 60 minutes to produce Matcha Uiro.
  • This product contains maltitol and is not only low in calories, but also exhibits the ability to improve the physical properties and flavor of the quality improver, and has good shine, mouthfeel, and good flavor.
  • the starch aging control ability of the quality improver is demonstrated, and it is a long-lasting Uro.
  • This product exhibits the ability to improve the physical properties of starch, the ability to control starch aging, and the ability to improve flavor, and it has good hue and durability, moderate elasticity, good shelf life, and good flavor.
  • the bread 100 parts by weight of wheat flour, 2 parts by weight of yeast, 5 parts by weight of sucrose, 1 part by weight of ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 3 and 0 inorganic food .1 part by mass was kneaded with water according to a conventional method, the
  • the product was soaked in a pickled solution in a cold room for 7 days, then washed with cold water, wound with a string, smoked, cooked, cooled and packaged according to a conventional method to obtain a product.
  • This product is a high-quality ham that exhibits the ability to improve the physical properties and flavor of the quality improver, has a good color, and has a good flavor.
  • the open-boiled dried mackerel of the present invention is a product that not only has excellent taste, but also has an acidity and fish odor, and has a strong appetite in color and luster. It is.
  • the pickle of the present invention is a high-quality pickle that is not only excellent in texture and taste, but also has a stable color and appetite, because the physical properties improving ability and flavor improving ability of the quality improver are demonstrated. is there.
  • ⁇ Mayonnaise> Quality improvement of ⁇ -glucan having 20 parts by mass of egg yolk, 2.5 parts by mass of salt, 5 parts by mass of water, 12.5 parts by mass of vinegar and non-reducing end obtained by the method of Example 3 After adding 5 parts by mass as an agent in a container and stirring, it was further stirred while gradually adding 200 parts by weight of edible oil to prepare mayonnaise.
  • the mayonnaise of the present invention exhibits the ability to improve the physical properties and flavor of the quality improver and not only has a good texture and taste, but also has high stability, gloss, good mouthfeel, and good appetite. It is a high quality mayonnaise.
  • This product is not only useful for confectionery materials such as premixes and frozen desserts, because the flavor improving ability of the quality improving agent is demonstrated, and it is useful as a confectionery material for premixes, frozen desserts, etc. It is also useful as an intestinal adjustment material for foods and tube feeding fluids.
  • This product is a high-quality edible film that exhibits the ability to improve the physical properties of a quality improver, is supple and stretchable, has little stickiness, and has a good transparency.
  • ⁇ Cosmetic cream > 2 parts by weight of polyoxyethylene glycol monostearate, 5 parts by weight of self-emulsifying glyceryl monostearate, 1 part by weight of liquid paraffin, 10 parts by weight of glyceryl trioctanoate and appropriate amounts of preservatives are heated and dissolved according to a conventional method.
  • This product is a stable formulation that exhibits the ability to improve physical properties such as stability and moisture retention of quality improvers, and does not impair functions such as detergent detergency. The feeling after use is also good.
  • ⁇ Food Edible Solid Formulation 100 parts by mass of ⁇ -glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 4 as a quality improver, 200 parts by mass of hydrous crystals of trehalose, 200 parts by mass of powder containing high maltotetraose Parts, powdered egg yolk 270 parts, skim milk powder 209 parts, sodium chloride 4.4 parts, potassium chloride 1.8 parts, magnesium sulfate 4 parts, thiamine 0.01 parts, sodium L-ascorbate A blend consisting of 1 part by weight, 0.6 part by weight of vitamin E acetate and 0.04 part by weight of nicotinamide is prepared, and 25 grams of this blend is filled into a moisture-proof laminate sachet and heat sealed to obtain a product.
  • This product is a liquid food that is stable and excellent in regulating the intestine due to its ability to improve the physical properties such as stability and formability of the quality improver and the ability to regulate the intestine. It can be used for the intestine and the like by a method of tube use, and can be advantageously used for energy supply to a living body.
  • This product has the strength suitable for full-layer fertilization because the ⁇ -glucan exhibits easy-to-handle properties, such as binding, shape retention, shaping, and releasability.
  • the elution rate of the fertilizer component can be adjusted by changing the blending ratio. Further, if necessary, it is also possible to advantageously carry out blending of plant hormones, agricultural chemicals, soil improvers and the like with this fertilizer bar.
  • the quality improver of the present invention comprises an ⁇ -glucan having an isomaltose structure at the non-reducing end as an active ingredient, exhibits an appropriate molecular weight range, is excellent in cold water solubility, retains an appropriate viscosity, various raw materials, and intermediate materials
  • the composition is excellent in aging control, flavor improvement, and physical property improvement, and therefore can be advantageously used in the fields of food, cosmetics, pharmaceuticals, and industrial products.
  • it can be advantageously used as an aging control agent for starch-containing foods, a flavor improving agent for foods having a nasty smell, a physical property improving agent, and the like, and has a great industrial significance.

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Abstract

The present invention addresses the problem of providing: a quality improver which has a proper molecular weight, a proper viscosity and solubility in cold water and can be used advantageously in the fields of foods, cosmetics, quasi drugs, drugs, industrial products, etc.; and a use of the quality improver. The problem can be solved by: a quality improver which can be produced by a production method involving a step of gelatinizing a waxy starch and then allowing an amylase to act on a gelatinized product to liquefy the gelatinized product and a step of allowing an α-glucosyltransferase to act on a liquefied product, and which contains an α-glucan mixture having the below-mentioned characteristic properties as an active ingredient; and a use of the quality improver: (1) the weight average molecular weight (Mw) falls within the range from 150 kDa to 3,000 kDa; (2) a value (Mw/Mn) obtained by dividing the weight average molecular weight (Mw) with a number average molecular weight (Mn) is 35.1 or less; and (3) an α-glucan molecule having an isomaltose structure at a non-reducing terminal is contained.

Description

品質改善剤並びにその用途Quality improver and its use
 本発明は、品質改善剤並びにその各種用途に関し、詳細には、可食性素材を有効成分とする品質改善剤とその用途に関する。 The present invention relates to a quality improving agent and various uses thereof, and in particular, relates to a quality improving agent containing an edible material as an active ingredient and uses thereof.
 可食性素材は、その素材が持っている種々の特性に応じて、主として食品の老化調節、風味改良、食感改良等の品質改善を目的として使用されており、実際に使われている可食性素材としては澱粉及びその誘導体、アルギン酸、ペクチン、アラビアガムなどの炭水化物、ゼラチン、カゼイン、大豆タンパク、乳タンパク、グルテン、ツェインなどのタンパク質がある。この他には、パラフィン、カルナバワックス、ミツロウ、キャンデリラワックス、ポリエチレンワックス各種脂肪酸のモノグリセライド等の脂質及びセラック、ロジン、コーパルなどの樹脂が用いられる場合もある。また、中でも、フィルムやカプセルに成形できる点で有用とされる可食性素材としては、例えば、澱粉から製造されるオブラート、コラーゲン、ゼラチン、プルラン、カラギーナンなどがある。 Edible materials are used mainly for the purpose of improving quality such as aging control, flavor improvement, texture improvement, etc., depending on the various properties of the material. Examples of the material include starch and derivatives thereof, carbohydrates such as alginic acid, pectin, and gum arabic, and proteins such as gelatin, casein, soy protein, milk protein, gluten, and zein. Other than these, lipids such as paraffin, carnauba wax, beeswax, candelilla wax, polyethylene wax, monoglycerides of various fatty acids, and resins such as shellac, rosin, and copal may be used. Among them, edible materials that are useful in that they can be formed into films and capsules include, for example, wafers made from starch, collagen, gelatin, pullulan, and carrageenan.
 しかし、これら従来から使用されている可食性素材には、その素材自体が有している特性に基づいて、一長一短のあるものが多い。例えば、同じく澱粉から調製される可食性素材であっても、糊化澱粉とデキストリン(澱粉部分分解物)とは、互いに相反する特性を有しており、可食性素材としての用途にも向き不向きがある。すなわち、糊化澱粉は、原料澱粉を低分子化することなく水溶性を持たせたものであり、澱粉の持つ接着性、増粘性を生かして、接着剤や増粘剤などとして各種飲食品に利用できるという利点を備えているが、反面、高粘度であるため、ハンドリングし難い上に、老化し易く、不溶性の沈澱を形成し易いという欠点を有している。因みに、糊化澱粉をフィルム状に成形した可食性素材としてはオブラートがあり、従来から、薬を包み飲むための補助製品として汎用されているが、糊化澱粉の水溶液からオブラートを成形するには、水溶液中の糊化澱粉濃度を低くして粘度を下げる必要があり、必然的に得られるフィルムは薄く、強度に欠けるという欠点がある。 However, many of these conventionally used edible materials have advantages and disadvantages based on the characteristics of the materials themselves. For example, even if it is an edible material prepared from starch, gelatinized starch and dextrin (partially decomposed starch) have mutually contradictory properties and are not suitable for use as an edible material. There is. In other words, gelatinized starch is water-soluble without reducing the molecular weight of raw starch, and can be used as an adhesive or thickener in various foods and beverages by taking advantage of the adhesiveness and thickening of starch. Although it has an advantage that it can be used, it has a drawback that it is difficult to handle because of its high viscosity, and it is easy to age and form an insoluble precipitate. Incidentally, there is an oblate as an edible material in which gelatinized starch is formed into a film, and it has been widely used as an auxiliary product for wrapping and drinking medicine. It is necessary to lower the viscosity by reducing the gelatinized starch concentration in the aqueous solution, and there is a drawback that the film obtained inevitably is thin and lacks in strength.
 一方、デキストリン(澱粉部分分解物)は、その製造の過程で原料である澱粉が酸、アルカリ、酵素などによって加水分解され低分子化しているので、水への溶解性は高く、粘度が低いという利点は有しているものの、加水分解により還元力が増加しているため、タンパク質やアミノ酸などと混合して加熱する場合には、メイラード反応により着色するという問題点を有している。また、デキストリンには、低分子化されているが故に、強度のあるフィルムに成形することが困難であるという不都合もある。 On the other hand, dextrin (starch partially decomposed product) has high solubility in water and low viscosity because starch, which is a raw material, is hydrolyzed and reduced in molecular weight by acid, alkali, enzyme, etc. Although it has an advantage, since the reducing power is increased by hydrolysis, there is a problem that when it is mixed and heated with protein or amino acid, it is colored by Maillard reaction. In addition, dextrin has a disadvantage that it is difficult to form a strong film because it has a low molecular weight.
 なお、澱粉系の可食性素材から成形されるフィルムには、低温での脆弱性を改善し、柔軟性を増大させる目的で、グリセロール、ソルビトールや、ソルビトールエステル等の可塑剤を配合し製造される場合が多いが、多価アルコール等の可塑剤を添加すると、フィルムの強度が著しく低下する場合があるとされている(特許文献1を参照)。 Films made from starch-based edible materials are manufactured by blending plasticizers such as glycerol, sorbitol, and sorbitol esters for the purpose of improving vulnerability at low temperatures and increasing flexibility. In many cases, it is said that when a plasticizer such as a polyhydric alcohol is added, the strength of the film may be significantly reduced (see Patent Document 1).
 このような状況下、古来から食経験があり、安全であるとともに、比較的多量かつ安価に入手できる澱粉から得られる可食性素材であって、しかも、上述した糊化澱粉とデキストリンの両者の利点、すなわち、低い還元力、適度な分子量、適度な粘度、冷水可溶性を併せ持つ新規な可食性素材が得られれば、それらの特性を生かして、可食性フィルムとしてはもとより、老化調節剤、風味改良剤、保形性付与剤、泡特性改良剤、食感改良剤等の種々の品質改善剤として、飲食品や化粧品、医薬品、医薬部外品等を含めた各種分野に幅広く使用することができるので極めて有用である。 Under such circumstances, it is an edible material obtained from starch that has been eaten since ancient times, is safe, is available in a relatively large amount, and is inexpensive, and has the advantages of both gelatinized starch and dextrin described above. In other words, if a new edible material having both low reducing power, moderate molecular weight, moderate viscosity, and cold water solubility is obtained, it will be possible to take advantage of these properties to develop an aging regulator and flavor improver as well as an edible film. Because it can be widely used in various fields including food and drink, cosmetics, pharmaceuticals, quasi-drugs, etc., as various quality improvers such as shape retention agents, foam property improvers, texture improvers, etc. Very useful.
特開2008-79525号公報JP 2008-79525 A
 本発明は、澱粉から調製される可食性素材であって、適度な分子量、適度な粘度、冷水可溶性を併せ持ち、老化調節剤、風味改良剤、保形性付与剤、泡特性改良剤、食感改良剤等の種々の品質改善剤として、食品、化粧品、医薬部外品、医薬品、工業用品などの分野で有利に利用できる品質改善剤並びにその用途を提供することを課題とする。 The present invention is an edible material prepared from starch, which has an appropriate molecular weight, an appropriate viscosity, and cold water solubility, an aging regulator, a flavor improver, a shape retention agent, a foam property improver, a texture It is an object of the present invention to provide a quality improver that can be advantageously used in the fields of food, cosmetics, quasi-drugs, pharmaceuticals, industrial products and the like as various quality improvers such as an improver.
 本出願人は、上記課題を解決するために鋭意研究を重ねた結果、ワキシースターチを糊化し、少量のアミラーゼを作用させて液化すると、グルコース当量(DE)が小さく、低い還元力、適度な分子量範囲、適度な粘度を有するこれまでにない優れたα-グルカン混合物が得られること、さらに当該α-グルカン混合物が可食性素材として、可食性フィルムの原料としては勿論、食品材料の結着剤、パン、菓子などの食感改良剤、麺製品のほぐれ改良剤、保存性向上剤などとして好適に用いることができることを見出し、先に、国際出願No.PCT/JP2016/85946(国際公開第WO2017/094895号)として出願した。 As a result of intensive research to solve the above-mentioned problems, the present applicant has obtained a low glucose equivalent (DE), a low reducing power, and an appropriate molecular weight when gelatinized waxy starch and liquefied by the action of a small amount of amylase. An unprecedented excellent α-glucan mixture having a moderate viscosity is obtained, and the α-glucan mixture is used as an edible material, as a raw material for edible films, as well as a binder for food materials, It has been found that it can be suitably used as a texture improving agent for bread, confectionery, etc., a flaw improving agent for noodle products, a preservability improving agent, and the like. The application was filed as PCT / JP2016 / 85946 (International Publication No. WO2017 / 094895).
 本発明者らは、その後、さらに研究を重ね、上記先願で見出された新規なα-グルカン混合物の中でも、特に、重量平均分子量(Mw)を数平均分子量(Mn)で除した値(Mw/Mn)が特定の範囲にあり、かつ、非還元末端にイソマルトース構造を有するものが、品質改善剤、詳細には、老化調節剤、風味改良剤、物性改良剤などとして特に好適であることを見出し、本発明を完成するに至った。 The inventors then conducted further research, and among the novel α-glucan mixture found in the above-mentioned prior application, in particular, a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) ( Mw / Mn) having a specific range and having an isomaltose structure at the non-reducing end is particularly suitable as a quality improver, specifically an aging regulator, a flavor improver, a physical property improver, etc. As a result, the present invention has been completed.
 即ち、本発明は、ワキシースターチを糊化し、アミラーゼを作用させ液化する工程、及びα-グルコシル転移酵素を作用させる工程を含む製造方法により得られるα-グルカン混合物であって、下記(1)乃至(3)の特徴を有するα-グルカン混合物(以下、単に「α-グルカン」又は「本α-グルカン」というときがある。)を有効成分とする品質改善剤を提供することにより上記課題を解決するものである:
  (1)重量平均分子量(Mw)が150kDa乃至3,000kDaの範囲にある;

  (2)重量平均分子量(Mw)を数平均分子量(Mn)で除した値(Mw/Mn)が35.1以下である;及び、
  (3)非還元末端にイソマルトース構造を有するα-グルカン分子を含む。
That is, the present invention is an α-glucan mixture obtained by a production method including a step of gelatinizing waxy starch, allowing amylase to act and liquefying, and a step of allowing α-glucosyltransferase to act, comprising the following (1) to Solving the above problems by providing a quality improver comprising an α-glucan mixture having the characteristics of (3) (hereinafter sometimes simply referred to as “α-glucan” or “present α-glucan”) as an active ingredient What to do:
(1) the weight average molecular weight (Mw) is in the range of 150 kDa to 3,000 kDa;

(2) The value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less; and
(3) An α-glucan molecule having an isomaltose structure at the non-reducing end is included.
 また、本発明は、上記品質改善剤の老化調節剤、風味改良剤、物性改良剤などとしての多彩な用途を提供することにより、上記課題を解決するものである。 In addition, the present invention solves the above-mentioned problems by providing various uses as an aging regulator, a flavor improver, a physical property improver and the like of the quality improver.
 さらに、本発明は、上記品質改善剤を含有してなる飲食品、化粧品、医薬部外品、医薬品、工業用品を提供することにより上記課題を解決するものである。 Furthermore, this invention solves the said subject by providing the food / beverage products, cosmetics, quasi-drugs, pharmaceuticals, and industrial goods which contain the said quality improvement agent.
 本発明に係る品質改善剤は、有効成分であるα-グルカン混合物が、適度な分子量及び粘度を有し、水への溶解性が高いので、混合する他の成分にもよるが、基本的に水溶性に優れ、且つ、ハンドリング性に優れるという利点を有する。また、本発明の品質改善剤は、老化調節能、風味改良能、物性改良能などの優れた機能を有し、老化調節剤、風味改良剤、物性改良剤などとして優れており、各種飲食品、工業用品、化粧品、医薬部外品及び医薬品の品質改善に有用である。 The quality-improving agent according to the present invention basically has an α-glucan mixture, which is an active ingredient, having an appropriate molecular weight and viscosity and high solubility in water. It has the advantages of excellent water solubility and excellent handling properties. The quality improver of the present invention has excellent functions such as aging control ability, flavor improvement ability, physical property improvement ability, etc., and is excellent as an aging control agent, flavor improvement agent, physical property improvement agent, etc. It is useful for improving the quality of industrial products, cosmetics, quasi drugs and pharmaceuticals.
本α-グルカンの水溶液について、冷解凍を繰り返した後に測定した粘度を示したグラフである。5 is a graph showing the viscosity measured after repeated cold thawing for an aqueous solution of this α-glucan. 本α-グルカン溶液と澱粉液化液との混合液を冷蔵保存した後、測定した濁度を示したグラフである。3 is a graph showing the turbidity measured after refrigerated storage of a mixture of this α-glucan solution and starch liquor. 本α-グルカンを用いて調製した豆乳の風味変化を官能試験で調べた結果を示したグラフである。3 is a graph showing the results of a sensory test on the change in flavor of soymilk prepared using this α-glucan. 本α-グルカンを用いて調製したゼラチンゲルの保形性を示す写真である。2 is a photograph showing the shape retention of a gelatin gel prepared using this α-glucan. 本α-グルカン水溶液を加温後、目的の温度に低下するまでに要した時間を示したグラフである。6 is a graph showing the time taken for the present α-glucan aqueous solution to warm to the target temperature after heating. 本α-グルカンを用いて調製した糊化澱粉ゲルの粘り度合いを示したグラフである。4 is a graph showing the degree of stickiness of a gelatinized starch gel prepared using this α-glucan.
1.用語の定義
 本明細書において以下の用語は以下の意味を有している。
1. Definition of Terms In this specification, the following terms have the following meanings.
<ワキシースターチ>
 澱粉(スターチ)は、一般に、構成糖であるグルコースがα-1,4結合を介して直鎖状に連なった構造を有するアミロースと、アミロースがその内部のグルコースのところどころでα-1,6結合を介して分岐した構造を有するアミロペクチンとが混合した形態にあることが知られている。本明細書でいう「ワキシースターチ」とは、ワキシー(もち(糯))種の植物、例えば、ワキシー種の稲(米)、大麦、小麦、はと麦、トウモロコシ、きび、あわ、もろこしから得られる澱粉を意味する。ワキシースターチは、アミロースを殆ど含まず、ほぼアミロペクチンのみからなるという特徴を有しており、中でもワキシーコーンスターチは、ワキシーコーンから得られる澱粉で、糊化しやすく、透明なゲルは保存安定性に優れていることから最も汎用されており、本発明の品質改善剤の有効成分であるα-グルカンの原料として好適である。
<Waxy starch>
In general, starch (starch) is composed of amylose having a structure in which glucose, which is a constituent sugar, is linked in a straight chain via α-1,4 bonds, and α-1,6 bonds at the location of glucose inside the amylose. It is known that it is in a mixed form with amylopectin having a structure branched via a. “Waxy starch” as used herein refers to a plant of waxy (rice cake) variety, for example, waxy rice (rice), barley, wheat, wheat, corn, millet, whey, corn Means starch. Waxy starch has almost no amylose and has only amylopectin. Waxy corn starch is a starch obtained from waxy corn and is easy to gelatinize. Transparent gel has excellent storage stability. Therefore, it is most widely used and is suitable as a raw material for α-glucan, which is an active ingredient of the quality improver of the present invention.
<糊化>
 本明細書でいう「糊化」とは、澱粉粒を水の存在下で加熱すると、澱粉粒の水素結合が破壊され粒が不可逆的に膨潤(又は水和、溶解)する現象を意味する。澱粉は糊化とともに結晶性、複屈折性を失い、粘度が上昇し、酵素(アミラーゼ)や化学薬品に対する反応性が急激に増大する。糊化は別名アルファ化とも呼ばれる。
<Gelatinization>
As used herein, “gelatinization” means a phenomenon in which, when starch granules are heated in the presence of water, the hydrogen bonds of the starch granules are broken and the grains irreversibly swell (or hydrate or dissolve). Starch loses crystallinity and birefringence with gelatinization, increases in viscosity, and reacts rapidly with enzymes (amylases) and chemicals. Gelatinization is also called alpha.
<液化>
 本明細書でいう「液化」とは、糊化澱粉にアミラーゼを作用させ、部分的に加水分解することにより、液状化することを意味する。糊化澱粉を液化して得られる液化澱粉(α-グルカン)は、加水分解の程度が大きいほど低分子化し、低い分子量、低い粘度を示す。
<Liquefaction>
“Liquefaction” as used in the present specification means liquefaction by causing amylase to act on gelatinized starch and partially hydrolyzing it. The liquefied starch (α-glucan) obtained by liquefying the gelatinized starch becomes lower in molecular weight as the degree of hydrolysis increases, and exhibits a lower molecular weight and lower viscosity.
<Mw/Mn(重量平均分子量/数平均分子量)>
 本明細書でいう「Mw/Mn」とは、重量平均分子量(Mw)を数平均分子量(Mn)で除した値を意味する。なお、Mw/Mnは分子量分布の拡がり(分散度)を表わす指標であり、値が大きいほど分子種が幅広い分子量範囲に及んでおり、値が1に近いほど分子種が分子量において均一であることを意味する。因みに、Mw/Mnは被験試料をゲル濾過高速液体クロマトグラフィー(ゲル濾過HPLC)に供し、そのクロマトグラムを分子量分布解析ソフトウェアにより解析し、重量平均分子量(Mw)と数平均分子量(Mn)を求めることによって算出することができる。
<Mw / Mn (weight average molecular weight / number average molecular weight)>
As used herein, “Mw / Mn” means a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). Mw / Mn is an index representing the spread (dispersion degree) of the molecular weight distribution. The larger the value, the wider the molecular species range, and the closer the value, the more uniform the molecular species in molecular weight. Means. By the way, Mw / Mn is subjected to gel filtration high performance liquid chromatography (gel filtration HPLC), and its chromatogram is analyzed by molecular weight distribution analysis software to obtain weight average molecular weight (Mw) and number average molecular weight (Mn). It can be calculated by
<冷水可溶性>
 本明細書でいう「冷水可溶性」とは、被験試料を固形物濃度20質量%となるよう脱イオン水に添加し、液温30℃の条件下で攪拌して溶解の程度を目視で判定した時、15分間以内に完全に溶解して均一な溶液を与える性質を意味する。冷水可溶性を有するα-グルカンを有効成分とする品質改善剤は、含まれるα-グルカンの割合にもよるが、各種組成物に配合する際などに加熱溶解する必要がないため、取扱いが容易であるという利点がある。
<Cool water soluble>
As used herein, “cold water solubility” means that a test sample is added to deionized water so as to have a solid concentration of 20% by mass, and stirred at a liquid temperature of 30 ° C. to visually determine the degree of dissolution. Sometimes means the property of completely dissolving within 15 minutes to give a homogeneous solution. The quality improver comprising α-glucan having cold water solubility as an active ingredient is easy to handle because it does not need to be dissolved by heating when blended into various compositions, although it depends on the proportion of α-glucan contained. There is an advantage of being.
<老化>
 本明細書でいう「老化(retrogradation)」とは、糊化澱粉(アルファ化澱粉)又は液化澱粉が時間の経過とともに天然澱粉のように水に不溶性の状態に変化することを意味する。老化は澱粉分子が自然に会合し、部分的に密な集合状態に移行する状態変化であり、分子の会合は主にグルコース残基の水酸基(OH基)による水素結合によると考えられている。糊化澱粉又は液化澱粉の水溶液は時間の経過により白濁する現象が認められるが、これは、糊化澱粉又は液化澱粉が老化し不溶化するために起こるものである。なお、澱粉はアミロースとアミロペクチンとで構成されているが、枝分かれしていない直鎖状のアミロースの方が老化し易いことが知られている。また、老化は、澱粉のみならず澱粉部分分解物(デキストリン)などの多糖でも起こることが知られ、一般的には、後述するグルコース等量(DE)の小さい方が老化し易いとされている。
<Aging>
The term “retrogradation” as used herein means that gelatinized starch (pregelatinized starch) or liquefied starch changes to a water-insoluble state like natural starch over time. Aging is a state change in which starch molecules naturally associate and partially move into a densely assembled state, and the association of molecules is thought to be mainly due to hydrogen bonding by hydroxyl groups (OH groups) of glucose residues. A phenomenon in which an aqueous solution of gelatinized starch or liquefied starch becomes clouded over time is observed, but this occurs because gelatinized starch or liquefied starch is aged and insolubilized. Although starch is composed of amylose and amylopectin, it is known that linear amylose that is not branched is more likely to age. In addition, aging is known to occur not only in starch but also in polysaccharides such as partially decomposed starch (dextrin), and in general, it is said that the smaller the glucose equivalent (DE) described later, the easier it is to age. .
<耐老化>
 本明細書でいう「耐老化」とは、本発明の品質改善剤などの素材又は組成物自体が上記澱粉性多糖の状態変化である老化を起こしにくいことを意味している。
<Aging resistance>
The term “anti-aging” as used in the present specification means that a material such as the quality improver of the present invention or the composition itself does not easily cause aging, which is a change in the state of the starchy polysaccharide.
<老化調節>
 本明細書でいう「老化調節」とは、本発明の品質改善剤などの素材又は組成物を共存させることによって、上記澱粉性多糖の状態変化である老化の程度や、老化のし易さを調節することを意味しており、本明細書でいう「耐老化」とは異なる。
<Aging control>
The term “aging control” as used herein refers to the degree of aging, which is a change in the state of the starchy polysaccharide, and the ease of aging, by allowing a material or composition such as the quality improver of the present invention to coexist. It means to adjust, and is different from “aging resistance” in this specification.
<風味改良>
 本明細書でいう「風味改良」とは、対象となる飲食品等の苦味、辛味、渋味、えぐ味、収斂味等、さらに酸化臭、加熱臭、加工臭、生臭み、青臭み等といった、人が不快に感じる異味異臭等を改良することを意味し、本発明の品質改善剤が矯味矯臭の効果を発揮することを意味している。ここでいう「風味」とは、飲食品の「風味」に限られるものではなく、化粧品、医薬部外品、医薬品、工業用品等の臭い等も含むものである。
<Flavor improvement>
As used herein, “flavor improvement” refers to bitterness, pungent taste, astringency, savory taste, astringent taste, etc. of target foods and beverages, oxidation odor, heated odor, processed odor, raw odor, blue odor, etc. It means to improve off-flavors and the like that people feel unpleasant, and it means that the quality improver of the present invention exerts the effect of flavoring. The “flavor” here is not limited to the “flavor” of foods and drinks, but includes odors of cosmetics, quasi drugs, pharmaceuticals, industrial products, and the like.
<物性改良>
 本明細書でいう「物性改良」とは、文字どおり、対象となる製品等における様々な物性が改良されることを意味し、例えば接着性、賦形性、照り性、保湿性、粘度、浸透圧などの物性が改良されたり、シラップなどからの糖の析出が防止されたりすることに加え、硬化調節、流動調節、曇化調節、日持向上、付着性改良、喉越し改良、酸化防止、崩壊防止、褐変防止、離水防止、保水性、水分調節性、成形性、保形性、冷蔵耐性、冷凍耐性、氷結晶安定性など、対象となる製品等の物性に効果を発揮して改良することを意味している。
<Improvement of physical properties>
As used herein, “improvement of physical properties” literally means that various physical properties of a target product or the like are improved, such as adhesiveness, formability, shine, moisture retention, viscosity, osmotic pressure. In addition to improving physical properties such as syrup and preventing the precipitation of sugar from syrup, etc., curing control, flow control, fogging control, shelf life improvement, adhesion improvement, improvement over the throat, oxidation prevention, collapse Prevent and improve browning prevention, water separation prevention, water retention, moisture controllability, moldability, shape retention, refrigeration resistance, freezing resistance, ice crystal stability, etc. Means.
<α-グルコシル転移酵素>
 本明細書でいう「α-グルコシル転移酵素」とは、澱粉部分分解物に作用し、その非還元末端グルコース残基にα-1,6グルコシル転移する活性を有する酵素を意味する。α-グルコシル転移酵素をα-グルカンに作用させることにより、非還元末端にイソマルトース構造を有するα-グルカンを得ることができる。α-グルコシル転移酵素としては、例えば、α-グルコシダーゼ、α-グルコシルトランスフェラーゼ、デキストリンデキストラナーゼなどが挙げられる。
<Α-Glucosyltransferase>
As used herein, “α-glucosyltransferase” refers to an enzyme that acts on a partially degraded starch and has an activity to transfer α-1,6 glucosyl to its non-reducing terminal glucose residue. By allowing α-glucosyltransferase to act on α-glucan, α-glucan having an isomaltose structure at the non-reducing end can be obtained. Examples of α-glucosyltransferase include α-glucosidase, α-glucosyltransferase, and dextrin dextranase.
<イソマルトデキストラナーゼ消化>
 本明細書でいう「イソマルトデキストラナーゼ消化」とは、被験試料にイソマルトデキストラナーゼを作用させ、被験試料中のイソマルトース構造の還元末端側の結合を加水分解することを意味する。イソマルトデキストラナーゼ(EC 3.2.1.94)は、デキストランなどの、非還元末端にイソマルトース構造を有するグルカンであれば、当該イソマルトース構造の還元末端側に隣接する結合が、α-1,2、α-1,3、α-1,4及びα-1,6結合のいずれの結合であっても加水分解する活性を有する酵素であることから、被験試料にイソマルトデキストラナーゼを作用させ、得られる消化物をHPLC分析に供し、糖組成中にイソマルトースが認められるか否かを調べることにより、被験試料が非還元末端にイソマルトース構造を有するα-グルカンを含有するか否かを確認することができる。後述する実験の項では、具体的には、被験試料を濃度1w/v%の水溶液とし、アルスロバクター・グロビホルミス由来のイソマルトデキストラナーゼ(株式会社林原製造)を被験試料固形物1グラム当たり100単位加え、50℃、pH5.0で16時間作用させ、得られた消化物を下記条件による糖組成分析用HPLCに供してイソマルトースを定量した。
(糖組成分析用HPLC条件)
カラム:MCI GEL CK04SS(株式会社三菱化学製造)を2本連結
溶離液:水
カラム温度:80℃
流 速:0.4mL/分
検 出:示差屈折計RID-10A(株式会社島津製作所製造)
<Isomalt dextranase digestion>
The term “isomaltodextranase digestion” as used herein means that isomaltdextranase is allowed to act on a test sample to hydrolyze the bond on the reducing end side of the isomaltose structure in the test sample. If isomaltdextranase (EC 3.2.1.94) is a glucan having an isomaltose structure at the non-reducing end, such as dextran, the bond adjacent to the reducing end of the isomaltose structure is α -1,2, α-1,3, α-1,4, and α-1,6 linkages are enzymes that have hydrolytic activity. The test sample contains α-glucan having an isomaltose structure at the non-reducing end by subjecting the digestion product to HPLC analysis and examining whether or not isomaltose is observed in the sugar composition. It can be confirmed whether or not. In the experimental section described below, specifically, the test sample is an aqueous solution having a concentration of 1 w / v%, and isomaltdextranase derived from Arthrobacter globiformis (manufactured by Hayashibara Co., Ltd.) per gram of the test sample solid. 100 units were added and allowed to act at 50 ° C. and pH 5.0 for 16 hours. The obtained digest was subjected to sugar composition analysis HPLC under the following conditions to quantitate isomaltose.
(HPLC conditions for sugar composition analysis)
Column: Two MCI GEL CK04SS (Mitsubishi Chemical Corporation) coupled Eluent: Water Column temperature: 80 ° C
Flow rate: 0.4 mL / min Detection: Differential refractometer RID-10A (manufactured by Shimadzu Corporation)
<グルコース当量(Dextrose Equivalent,DE)>
 本明細書でいう「グルコース当量(DE)」とは、澱粉を酸又は酵素を用いて加水分解して得られる澱粉糖(澱粉部分分解物)における加水分解の進行程度を示す指標であり、次式で表わされる数値を意味する。なお、グルコース当量(DE)はD-グルコース(デキストロース、ブドウ糖)の還元力を100とした場合の相対的な尺度であり、0に近いものほど加水分解の程度が低く澱粉に近い特性を有し、100に近いものほど加水分解の程度が高くグルコースに近い特性を有することとなる。
<Glucose equivalent (Dextrose Equivalent, DE)>
“Glucose equivalent (DE)” as used herein is an index indicating the degree of hydrolysis in starch sugar (starch partially decomposed product) obtained by hydrolyzing starch using an acid or an enzyme. It means the numerical value expressed by the formula. The glucose equivalent (DE) is a relative scale when the reducing power of D-glucose (dextrose, glucose) is 100, and the closer to 0, the lower the degree of hydrolysis and the closer to starch. , The closer to 100, the higher the degree of hydrolysis and the closer to glucose.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
 なお、上記還元糖量は、常法である改良Park-Johnson法(檜作ら、「カーボハイドレートリサーチ(Carbohydrate Research)」、第94巻、205乃至213頁(1981年)を参照)により、D-グルコースを標準物質として定量する。全固形物量は、常法の乾燥法にて求める。 The amount of reducing sugar is determined according to the conventional modified Park-Johnson method (see Takusaku et al., “Carbohydrate Research”, Vol. 94, pages 205 to 213 (1981)). Quantify glucose as standard. The total amount of solids is determined by a conventional drying method.
<アミロース含有率>
 澱粉は、コーンスターチ、ポテトスターチ、タピオカスターチなど種類が異なれば、それぞれアミロースの含有率が異なっているため、「アミロース含有率」は、澱粉種を特定する指標の一つとして使用することができる。本明細書でいう「アミロース含有率」とは、澱粉若しくはそのアミラーゼによる部分分解物(α-グルカン)、又は、それらにα-グルコシル転移酵素を作用させて得られるα-グルカンなどの澱粉質試料において、農林水産省告示第332号、標準計測方法に示されているアミロース含有率測定法に準じてアミロースとヨウ素の呈色反応に基づき測定される、試料のアミロース含有率を意味する。当該測定法は、具体的には、(1)分析試料100mgに、エタノール1mLと1M水酸化ナトリウム試液9mLを加え沸騰水中で10分間加熱し、水を加え正確に100mLとして試料液を調製する;(2)次いで、当該試料液5mLと1M酢酸試液1mLを混合し、次にヨウ素・ヨウ化カリウム試液2mLを加え混合した後に、水を加えて正確に100mLとして測定液とする;(3)当該測定液を27℃で30分間保持することにより温度調整した後、分光光度計を用いて波長620nmの吸光度を測定する;(4)当該吸光度と、別途、試薬級アミロースを用いて調製したアミロース標準溶液について同様に測定し作成した検量線に基づき、分析試料中のアミロース含量を求め、アミロース含有率を算出する;という方法である。
<Amylose content>
Since starch has different amylose contents if different types such as corn starch, potato starch, tapioca starch, etc., the “amylose content” can be used as one of the indices for specifying the starch species. As used herein, “amylose content” refers to starch or a partial degradation product (α-glucan) by amylase, or a starch sample such as α-glucan obtained by allowing α-glucosyltransferase to act on them. Means the amylose content of the sample measured based on the color reaction of amylose and iodine in accordance with the amylose content measurement method shown in Ministry of Agriculture, Forestry and Fisheries Notification No. 332, Standard Measurement Method. Specifically, (1) 1 mL of ethanol and 9 mL of 1M sodium hydroxide reagent solution are added to 100 mg of an analysis sample, heated in boiling water for 10 minutes, and water is added to prepare exactly 100 mL of the sample solution; (2) Next, 5 mL of the sample solution and 1 mL of 1M acetic acid test solution are mixed, then 2 mL of iodine / potassium iodide test solution is added and mixed, and then water is added to make exactly 100 mL to obtain a measurement solution; (3) After adjusting the temperature by holding the measurement solution at 27 ° C. for 30 minutes, the absorbance at a wavelength of 620 nm is measured using a spectrophotometer; (4) The absorbance and an amylose standard separately prepared using reagent grade amylose The amylose content in the analytical sample is obtained based on a calibration curve measured and prepared in the same manner for the solution, and the amylose content is calculated.
2.本発明の品質改善剤
 本発明は、ワキシースターチを糊化し、アミラーゼを作用させ液化する工程、及びα-グルコシル転移酵素を作用させる工程を含む製造方法により得られるα-グルカン混合物であって、且つ、下記(1)乃至(3)の特徴を有するα-グルカン混合物を有効成分とする品質改善剤に係るものである:
  (1)重量平均分子量(Mw)が150kDa乃至3,000kDaの範囲にある;
  (2)重量平均分子量(Mw)を数平均分子量(Mn)で除した値(Mw/Mn)が35.1以下である;及び、
  (3)非還元末端にイソマルトース構造を有するα-グルカン分子を含む。
2. The quality improving agent of the present invention is an α-glucan mixture obtained by a production method comprising gelatinizing waxy starch, allowing amylase to act and liquefying, and α-glucosyltransferase to act, and The present invention relates to a quality improver comprising an α-glucan mixture having the following characteristics (1) to (3) as an active ingredient:
(1) the weight average molecular weight (Mw) is in the range of 150 kDa to 3,000 kDa;
(2) The value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less; and
(3) An α-glucan molecule having an isomaltose structure at the non-reducing end is included.
 本発明の品質改善剤が有効成分とするα-グルカンは、ワキシースターチを糊化し、アミラーゼを作用させ液化する工程、及びα-グルコシル転移酵素を作用させる工程を含む製造方法により得られることを特徴とし、通常、異なる分子量や構造を有する種々のα-グルカン分子の混合物の形態にある。ワキシースターチは、直鎖状のα-1,4グルカンであるアミロースを実質的に含まず、ほぼ分岐構造を有するアミロペクチンのみで構成される澱粉であり、ワキシースターチ以外のアミロースを含む澱粉に比べ糊化し易く本来的に老化し難い性質を有しており、その分解物についても同様である。また、ワキシースターチは、ワキシースターチ以外のアミロースを含む澱粉に比べると造膜性(フィルム形成能)にも優れている。このようなワキシースターチを始発原料とすることにより得られる本α-グルカンは、以下で順次説明する、上記(1)乃至(3)の特徴により、α-グルカン混合物全体としては特徴付けられるものの、本α-グルカンに含まれる種々のα-グルカン分子の構造的特徴で直接規定することは困難である。ちなみに、糊化澱粉を液化する方法としては酸を用いる方法もあるものの、アミラーゼの方が酸に比べ加水分解の程度をコントロールし易いという利点がある。 The α-glucan containing the quality improving agent of the present invention as an active ingredient is obtained by a production method including a step of gelatinizing waxy starch, causing amylase to act and liquefying, and a step of allowing α-glucosyltransferase to act Usually, it is in the form of a mixture of various α-glucan molecules having different molecular weights and structures. Waxy starch is a starch that is substantially free of amylose, which is a linear α-1,4 glucan, and is composed only of an amylopectin having a substantially branched structure. Compared with starch containing amylose other than waxy starch, It has the property of being easily aging and not inherently aging, and the same applies to the decomposition products. Waxy starch is also superior in film-forming properties (film forming ability) compared to starch containing amylose other than waxy starch. The present α-glucan obtained by using such waxy starch as a starting material is characterized as the whole α-glucan mixture by the features (1) to (3), which will be sequentially described below. It is difficult to directly define the structural characteristics of various α-glucan molecules contained in this α-glucan. Incidentally, although there is a method using an acid as a method for liquefying gelatinized starch, amylase has an advantage that the degree of hydrolysis can be controlled more easily than acid.
 本α-グルカンは、(1)重量平均分子量(Mw)が150kDa乃至3,000kDaの範囲にあることを特徴とし、200kDa乃至3,000kDaの範囲にあるものがより好ましい。重量平均分子量(Mw)が150kDa未満になると、分子量の小さいα-グルカン分子の割合が増加して、粘度や造膜性(フィルム形成能)が低下し、また、還元力の増加することで着色の原因となる。重量平均分子量が3,000kDa超になると、水に溶解し難く、高粘度を示すためハンドリングが悪く使用が困難となる。 The present α-glucan is characterized in that (1) the weight average molecular weight (Mw) is in the range of 150 kDa to 3,000 kDa, and more preferably in the range of 200 kDa to 3,000 kDa. When the weight average molecular weight (Mw) is less than 150 kDa, the proportion of α-glucan molecules having a small molecular weight increases, the viscosity and film-forming property (film forming ability) decrease, and coloring occurs due to an increase in reducing power. Cause. When the weight average molecular weight exceeds 3,000 kDa, it is difficult to dissolve in water, and since it exhibits a high viscosity, it is difficult to handle and difficult to use.
 また、本α-グルカンは、(2)重量平均分子量(Mw)を数平均分子量(Mn)で除した値(Mw/Mn)が35.1以下にあることを特徴とする。Mw/Mnの値が35.1超になると、分子量の小さなα-グルカン分子の割合が増加し、造膜性に劣るものとなるだけでなく、還元力が増加することで着色の原因となるという不都合が生じる。 The α-glucan is characterized in that (2) a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less. When the value of Mw / Mn exceeds 35.1, the proportion of α-glucan molecules having a small molecular weight increases, which results in not only poor film-forming properties, but also causes reduction due to increased reducing power. The inconvenience arises.
 また、本α-グルカンは、上記(1)及び(2)の特徴を有するとともに、(3)非還元末端にイソマルトース構造を有するα-グルカン分子を含むα-グルカンである。非還元末端にイソマルトース構造を有するα-グルカンは、ワキシースターチを糊化し、アミラーゼを作用させ液化した後、澱粉部分分解物に作用しその非還元末端グルコース残基にα-1,6グルコシル転移する活性を有するα-グルコシル転移酵素をさらに作用させることによって得ることができる。 In addition, the present α-glucan is an α-glucan having the characteristics of (1) and (2) above and (3) including an α-glucan molecule having an isomaltose structure at the non-reducing end. Α-glucan with an isomaltose structure at the non-reducing end gelatinizes waxy starch and liquefies it with amylase, then acts on a partially degraded starch and α-1,6-glucosyl transfer to the non-reducing end glucose residue It can be obtained by further acting an α-glucosyltransferase having the activity of
 本α-グルカンが、非還元末端にイソマルトース構造を有しているα-グルカン分子を含んでいることは、当該α-グルカンを水溶液とし、イソマルトデキストラナーゼを作用させて消化し、その消化物中にイソマルトースが含まれるか否かを調べることにより確認することができる。本発明で用いるα-グルカンは、イソマルトデキストラナーゼ消化により、消化物の固形物当たりイソマルトースを3質量%超22質量%未満生成するものが好ましい。 This α-glucan contains an α-glucan molecule having an isomaltose structure at the non-reducing end. This can be confirmed by examining whether or not isomaltose is contained in the digest. The α-glucan used in the present invention is preferably one that produces isomaltose more than 3% by mass and less than 22% by mass by solid digestion by digestion with isomalt dextranase.
 本α-グルカンは、非還元末端にイソマルトース構造を有するという澱粉の加水分解物に本来的に存在しない特殊な構造を有するα-グルカン分子を含むがゆえに、その原料となるα-グルカン(澱粉部分分解物)や、グルコースがα-1,4結合を介して連結した直鎖状のα-1,4グルカンに比べ、顕著に老化し難い性質(耐老化性)を有している。例えば、本α-グルカンであって、イソマルトデキストラナーゼ消化において、消化物の固形物当たり3質量%超22質量%未満のイソマルトースを生成するα-グルカンは、固形物濃度30質量%の水溶液として6℃で1週間保持した場合でも老化による溶液の白濁が認められないほどの耐老化性を有する。さらには、後述する実験例に示すように、固形物濃度30質量%の水溶液を-20℃で冷凍後に自然解凍する工程を5回繰り返しても、その粘度に変化が認められないほどの耐老化性を有する。したがって、本α-グルカンのうち、イソマルトデキストラナーゼ消化において、消化物の固形物当たり3質量%超22質量%未満のイソマルトースを生成するα-グルカンは、使用に先立ち予め比較的高濃度の水溶液の形態や、凍結状態で保存しておくことができるという利点を有しており、これは当該α-グルカンを有効成分とする品質改善剤においても同様である。 This α-glucan contains an α-glucan molecule having a special structure that does not inherently exist in the starch hydrolyzate having an isomaltose structure at the non-reducing end. (Partially decomposed product) and a linear α-1,4 glucan in which glucose is linked via an α-1,4 bond, have a property that is not easily aged (aging resistance). For example, the α-glucan that produces isomaltose of more than 3% by mass and less than 22% by mass of the digested solid in the isomalt-dextranase digestion has a solid concentration of 30% by mass. Even when kept as an aqueous solution at 6 ° C. for 1 week, it has an aging resistance such that no cloudiness of the solution due to aging is observed. Furthermore, as shown in an experimental example to be described later, the aging resistance is such that even if the step of natural thawing after freezing an aqueous solution with a solid concentration of 30% by mass at −20 ° C. is repeated five times, the viscosity is not changed. Have sex. Therefore, among the present α-glucans, α-glucans that produce more than 3% by weight and less than 22% by weight of isomaltose in the digestion of isomaltodextranase have a relatively high concentration prior to use. In the case of a quality improver containing α-glucan as an active ingredient, the same can be said.
 本α-グルカンのグルコース当量(DE)は特に限定されないものの、グルコース当量(DE)はワキシースターチの分解程度の指標として使用することができる。品質改善剤の用途によっては、タンパク質やアミノ酸などと混合して加熱する場合にメイラード反応などによる着色、褐変を起こし難いものが望まれる。そのような場合には、本α-グルカンのグルコース当量(DE)は低い方が望ましい。グルコース当量(DE)が2.0超となると、還元力が増加することで着色の原因となるため、グルコース当量(DE)を、通常、2.0以下、好ましくは1.8以下、さらに好ましくは1.6以下とするのが望ましい。 Although the glucose equivalent (DE) of the α-glucan is not particularly limited, the glucose equivalent (DE) can be used as an indicator of the degree of decomposition of waxy starch. Depending on the use of the quality improver, it is desired that the color improver is less likely to be colored or browned due to the Maillard reaction or the like when mixed with protein or amino acid and heated. In such a case, it is desirable that the α-glucan has a low glucose equivalent (DE). When the glucose equivalent (DE) exceeds 2.0, the reducing power increases and causes coloring, so the glucose equivalent (DE) is usually 2.0 or less, preferably 1.8 or less, more preferably Is preferably 1.6 or less.
 本α-グルカンを得るためのワキシースターチとしては、その由来植物によって限定されるものではないが、大量製造され、入手し易く汎用されているワキシーコーンスターチが好適に用いられる。ワキシースターチは、一般に、グルコースがα-1,4結合を介して直鎖状に連結した直鎖状分子であるアミロースを実質的に含有しないと言われているものの、前記したヨウ素呈色法に基づくアミロース含有率の測定法においては、通常、約25質量%以下のアミロース含有率を示す。ワキシースターチを原料とし、アミラーゼによる分解反応後にα-グルコシル転移反応させて得られる本発明で用いるα-グルカンのアミロース含有率は、原料とするワキシースターチの種類によって異なる場合があるものの、前記したヨウ素呈色法に基づくアミロース含有率の測定法において、通常、25質量%以下の値を示す。 The waxy starch for obtaining the present α-glucan is not limited by the plant from which it is derived, but a waxy corn starch that is mass-produced and easily available is widely used. Waxy starch is generally said to contain substantially no amylose, which is a linear molecule in which glucose is linearly linked via α-1,4 bonds. In the measurement method of the amylose content based on this, an amylose content of about 25% by mass or less is usually shown. Although the amylose content of the α-glucan used in the present invention obtained from a waxy starch as a raw material and subjected to the α-glucosyl transfer reaction after the decomposition reaction with amylase may vary depending on the type of the waxy starch used as a raw material, In the measurement method of amylose content based on the coloration method, a value of 25% by mass or less is usually shown.
 本α-グルカンは、冷水可溶性を有しており、固形物濃度20質量%となるよう脱イオン水に添加し、温度30℃の条件下で攪拌した場合、15分間以内に完全に溶解し、均一な溶液とすることができる。 This α-glucan is soluble in cold water, and when added to deionized water to a solids concentration of 20% by mass and stirred at a temperature of 30 ° C., it completely dissolves within 15 minutes, A uniform solution can be obtained.
3.本α-グルカンの製造方法
 本α-グルカンは、ワキシースターチを糊化し、アミラーゼを作用させ液化する工程、及びα-グルコシル転移酵素を作用させる工程を含む製造方法によって製造することができ、当該製造方法は、使用するワキシースターチの由来、糊化の条件、アミラーゼ及びα-グルコシル転移酵素の種類や由来によって特に限定されるものではない。
3. Production method of the present α-glucan The present α-glucan can be produced by a production method including a step of gelatinizing waxy starch, causing amylase to act and liquefying, and a step of causing α-glucosyltransferase to act. The method is not particularly limited by the origin of the waxy starch used, the conditions for gelatinization, and the types and origins of amylase and α-glucosyltransferase.
 原料のワキシースターチを糊化する方法は、ワキシースターチ水懸濁液を加熱する常法で行うことができる。具体的には、例えば、ワキシースターチ水懸濁液をジャケット付反応器に入れて間接的に加熱する方法、ワキシースターチ水懸濁液に蒸気を混合して直接加熱する方法、ドラムドライヤーのホットロール上で加熱する方法などが挙げられる。糊化したワキシースターチは、アミラーゼを加えて加水分解することにより液化される。今日では、アミラーゼを予め澱粉乳(澱粉懸濁液)に添加しておき、これを加熱することにより、糊化と液化を同時に進行させる方法が一般に行われている。糊化・液化は慣用の方法を適宜選択すればよく、通常、バッチ方式または連続方式のいずれかで行われる。 The method of gelatinizing the raw waxy starch can be performed by a conventional method of heating a waxy starch aqueous suspension. Specifically, for example, a method in which a waxy starch water suspension is placed in a jacketed reactor and heated indirectly, a method in which steam is mixed with the waxy starch water suspension and heated directly, a hot roll of a drum dryer The method of heating above is mentioned. The gelatinized waxy starch is liquefied by adding amylase and hydrolyzing. Nowadays, a method is commonly used in which amylase is added to starch milk (starch suspension) in advance, and the gelatinization and liquefaction proceed simultaneously by heating the starch. For gelatinization and liquefaction, a conventional method may be selected as appropriate, and it is usually performed in either a batch system or a continuous system.
 糊化澱粉を液化するためのアミラーゼとしては、市販の耐熱性液化型α-アミラーゼが好適に用いられる。市販の耐熱性液化型α-アミラーゼとしては、例えば、「スピターゼ HK」(ナガセケムテックス株式会社製造)、「ターマミル 60L」(ノボザイム・ジャパン株式会社製造)、「アミラーゼAD“アマノ”」(天野エンザイム株式会社製造)、「クライスターゼ T10S」(天野エンザイム株式会社製造)、「スミチーム L」(新日本化学工業株式会社製造)などが挙げられる。 As the amylase for liquefying the gelatinized starch, a commercially available heat-resistant liquefied α-amylase is preferably used. Examples of commercially available thermostable liquefied α-amylase include “Spitase HK” (manufactured by Nagase ChemteX Corporation), “Tarmamyl 60L” (manufactured by Novozyme Japan), “Amylase AD“ Amano ”” (Amano Enzyme) Manufacturing Co., Ltd.), “Christase T10S” (manufactured by Amano Enzyme Co., Ltd.), “Sumiteam L” (manufactured by Shin Nippon Chemical Industry Co., Ltd.), and the like.
 さらに、非還元末端にイソマルトース構造を導入するα-グルコシル転移酵素は、澱粉部分分解物に作用し、その非還元末端グルコース残基にグルコースをα-1,6転移する活性を有する限り、その由来、理化学的性質などによって限定されるものではない。斯かる活性を有するα-グルコシル転移酵素としては、例えば、アスペルギルス・ニガー由来のトランスグルコシダーゼ(α-グルコシダーゼ)、アセトバクター・カプスラタム由来のデキストリンデキストラナーゼ、本願と同じ出願人による国際公開第WO2008/136331号パンフレットに開示されたバチルス属又はアルスロバクター属微生物由来の「α-グルコシル転移酵素」や、同じく、本願と同じ出願人による国際公開第WO02/010361号パンフレットに開示されたバチルス属又はアルスロバクター属微生物由来の「α-イソマルトシルグルコ糖質生成酵素」などが挙げられ、とりわけ、バチルス属又はアルスロバクター属微生物由来の、α-グルコシル転移酵素、及び、α-イソマルトシルグルコ糖質生成酵素がより好適に使用できる。 Furthermore, an α-glucosyltransferase that introduces an isomaltose structure at the non-reducing end acts on a partial degradation product of starch, as long as it has an activity to transfer glucose to the non-reducing end glucose residue by α-1,6. It is not limited by origin or physicochemical properties. Examples of the α-glucosyltransferase having such an activity include transglucosidase derived from Aspergillus niger (α-glucosidase), dextrin dextranase derived from Acetobacter capsuratam, International Publication No. WO2008 / “Α-glucosyltransferase” derived from Bacillus or Arthrobacter microorganisms disclosed in US Pat. No. 136331, or Bacillus or Al disclosed in International Publication No. WO 02/010361 by the same applicant as the present application. Examples include “α-isomaltosylglucosaccharide-producing enzyme” derived from microorganisms belonging to the genus Slobacter, and in particular, α-glucosyltransferase and α-isomaltosylglucose derived from microorganisms belonging to the genus Bacillus or Arthrobacter. More sugar-generating enzymes It can be used to apply.
 国際公開第WO2008/136331号パンフレットに開示されたα-グルコシル転移酵素は、基質としてマルトース及び/又はグルコース重合度が3以上のα-1,4グルカンに作用し、非還元末端グルコース残基を他のα-1,4グルカンの非還元末端グルコース残基に主としてα-1,4又はα-1,6グルコシル転移することにより、非還元末端グルコース残基の4位又は6位水酸基にグルコースがα-結合したグルカンを生成する活性を有しており、当該α-グルコシル転移酵素を作用させグルコシル転移反応を繰り返すことにより、マルトース及び/又はグルコース重合度が3以上のα-1,4グルカンから複雑な分岐構造を有する分岐α-グルカンを製造することができる。また、当該α-グルコシル転移酵素は、さらに、頻度は低いながらも、α-1,3グルコシル転移やグルカンの内部にあるα-1,6結合したグルコース残基に対するα-1,4又はα-1,3グルコシル転移を触媒することにより、α-1,3結合、α-1,4,6結合及びα-1,3,6結合をも有するα-グルカンを生成する活性をも有している。このα-グルコシル転移酵素を用いれば、その非還元末端にイソマルトース構造を導入でき、本α-グルカンを好適に製造することができる。 The α-glucosyltransferase disclosed in International Publication No. WO2008 / 136331 pamphlet acts on a maltose and / or α-1,4 glucan having a glucose polymerization degree of 3 or more as a substrate and other non-reducing terminal glucose residues. By α-1,4 or α-1,6 glucosyl transfer mainly to the non-reducing terminal glucose residue of the α-1,4-glucan of -It has an activity to produce bound glucan, and it is complicated from maltose and / or α-1,4 glucan having a degree of glucose polymerization of 3 or more by acting the α-glucosyltransferase and repeating the glucosyltransferase reaction. A branched α-glucan having a simple branched structure can be produced. In addition, the α-glucosyltransferase is α-1,3 glucosyltransferase or α-1,4 linked to α-1,6 linked glucose residues in the interior of glucan, although it is less frequently. By catalyzing 1,3-glucosyl transfer, it also has an activity to produce α-glucan having α-1,3 bond, α-1,4,6 bond and α-1,3,6 bond. Yes. If this α-glucosyltransferase is used, an isomaltose structure can be introduced into the non-reducing end thereof, and this α-glucan can be preferably produced.
 因みに、国際公開第WO2008/136331号パンフレットに開示されたバチルス属又はアルスロバクター属由来のα-グルコシル転移酵素は、下記(A)乃至(F)の性質を有している。
(A)作用
 マルトース及び/又はグルコース重合度3以上のα-1,4グルカンに作用し、主としてα-1,4グルコシル転移又はα-1,6グルコシル転移を触媒し、非還元末端グルコース残基の4位又は6位水酸基にグルコースを転移する;
(B)分子量
 SDS-ポリアクリルアミドゲル電気泳動法において、90,000±10,000ダルトン;
(C)至適温度
 pH6.0、30分間反応の条件下で、約50℃;
(D)至適pH
 40℃、30分間反応の条件下で約6.0;
(E)温度安定性
 pH6.0、60分間保持の条件下で40℃まで安定;及び、
(F)pH安定性
 4℃、24時間保持の条件下でpH4.0乃至8.0の範囲で安定。
Incidentally, the α-glucosyltransferase derived from the genus Bacillus or Arthrobacter disclosed in the pamphlet of International Publication No. WO2008 / 136331 has the following properties (A) to (F).
(A) Action It acts on α-1,4 glucan having a degree of polymerization of maltose and / or glucose of 3 or more, mainly catalyzing α-1,4 glucosyl transfer or α-1,6 glucosyl transfer, and non-reducing terminal glucose residue Transfer glucose to the 4- or 6-position hydroxyl group of
(B) Molecular weight In SDS-polyacrylamide gel electrophoresis, 90,000 ± 10,000 daltons;
(C) Optimum temperature, pH 6.0, about 50 ° C. under reaction conditions for 30 minutes;
(D) Optimum pH
About 6.0 under reaction conditions at 40 ° C. for 30 minutes;
(E) Temperature stability pH 6.0, stable to 40 ° C. under 60 minutes hold condition; and
(F) pH stability Stable in the range of pH 4.0 to 8.0 under conditions of 4 ° C. and 24 hours holding.
 国際公開第WO02/010361号パンフレットに開示された「α-イソマルトシルグルコ糖質生成酵素」、すなわち、α-グルコシル転移酵素は、基質としてマルトース及び/又はグルコース重合度が3以上のα-1,4グルカンに作用し、非還元末端グルコース残基を他のα-1,4グルカンの非還元末端グルコース残基にα-1,6グルコシル転移することにより、非還元末端グルコース残基の6位水酸基にグルコースがα-結合したグルカンを生成する活性を有している。このα-グルコシル転移酵素は、一旦生成した、非還元末端にイソマルトース構造を有するグルカンにさらにグルコースを転移する活性を有していないため、前記した酵素のように複雑な分岐酵素を有する分岐α-グルカンを製造することはできないものの、このα-グルコシル転移酵素によっても、Mw/Mn(分散度)を大きく変えることなく、その非還元末端にイソマルトース構造を導入でき、本α-グルカンを好適に製造することができる。 “Α-Isomaltosylglucosaccharide-forming enzyme” disclosed in the pamphlet of International Publication No. WO02 / 010361, that is, α-glucosyltransferase has α-1 having a maltose and / or glucose polymerization degree of 3 or more as a substrate. , 4-glucan, and the non-reducing terminal glucose residue is transferred to the non-reducing terminal glucose residue of other α-1,4-glucan by α-1,6-glucosyl transfer, thereby It has an activity to produce glucan in which glucose is α-linked to a hydroxyl group. Since this α-glucosyltransferase has no activity to transfer glucose further to a glucan having an isomaltose structure at the non-reducing end once produced, the branched α having a complex branching enzyme as described above -Although glucan cannot be produced, even with this α-glucosyltransferase, the isomaltose structure can be introduced into the non-reducing end without greatly changing Mw / Mn (dispersion degree), and this α-glucan is suitable. Can be manufactured.
 因みに、国際公開第WO02/010361号パンフレットに開示されたバチルス属又はアルスロバクター属微生物由来の「α-イソマルトシルグルコ糖質生成酵素」は、下記(G)乃至(M)の性質を有している。
(G)作用
 非還元末端の結合様式としてα-1,4グルコシル結合を有するグルコース重合度が2以上の糖質から、還元力を実質的に増加することなくα-グルコシル転移することによって、非還元末端の結合様式としてα-1,6グルコシル結合を有し、この非還元末端以外の結合様式としてα-1,4グルコシル結合を有するグルコース重合度が3以上の糖質を生成する;
(H)分子量
 SDS-ゲル電気泳動法により、約74,000乃至160,000ダルトンの範囲内に分子量を有する;
(I)等電点
 アンフォライン含有電気泳動法により、pI約3.8乃至7.8の範囲内に等電点を有する;
(J)至適温度
 pH6.0、60分間反応で、約40乃至50℃の範囲内に至適温度を有する;
 pH6.0、60分間反応で、1mMCa2+存在下、約45乃至55℃の範囲内に至適温度を有する;
 pH8.4、60分間反応で、60℃に至適温度を有する;又は、
 pH8.4、60分間反応で1mMCa2+存在下、65℃に至適温度を有する。
(K)至適pH
 35℃、60分間反応で、pH約6.0乃至8.4の範囲内に至適pHを有する。
(L)温度安定性
 pH6.0、60分間保持する条件で、約45℃以下に温度安定域を有する;
 pH6.0、60分間保持する条件で、1mMCa2+存在下、約50℃以下に温度安定域を有する;
 pH8.0、60分間保持する条件で、約55℃以下に温度安定域を有する;又は、
 pH8.0、60分間保持する条件で、1mMCa2+存在下、約60℃以下に温度安定域を有する;
(M)pH安定性
4℃、24時間保持する条件で、pH約4.5乃至10.0の範囲内に安定pH域を有する。
Incidentally, the “α-isomaltosylglucosaccharide-forming enzyme” derived from the microorganisms of the genus Bacillus or Arthrobacter disclosed in the pamphlet of International Publication No. WO02 / 010361 has the following properties (G) to (M). is doing.
(G) Action As a non-reducing end-binding mode, a glucose having a degree of polymerization of α-1,4 glucosyl bonds of 2 or more undergoes α-glucosyl transfer without substantially increasing the reducing power. A carbohydrate having an α-1,6 glucosyl bond as a binding mode at the reducing end and an α-1,4 glucosyl bond as a binding mode other than the non-reducing end and having a glucose polymerization degree of 3 or more;
(H) molecular weight having a molecular weight in the range of about 74,000 to 160,000 daltons by SDS-gel electrophoresis;
(I) isoelectric point having an isoelectric point in the range of pI of about 3.8 to 7.8 by an ampholine-containing electrophoresis method;
(J) Optimal temperature, having an optimal temperature in the range of about 40 to 50 ° C. at a reaction of pH 6.0 for 60 minutes;
having an optimum temperature in the range of about 45-55 ° C. in the presence of 1 mM Ca 2+ at a reaction of pH 6.0 for 60 minutes;
pH 8.4, reaction for 60 minutes, with optimal temperature at 60 ° C; or
It has an optimum temperature of 65 ° C. in the presence of 1 mM Ca 2+ at pH 8.4 for 60 minutes.
(K) Optimum pH
It has an optimum pH in the range of about 6.0 to 8.4 after reaction at 35 ° C. for 60 minutes.
(L) Temperature stability Under a condition of holding at pH 6.0 for 60 minutes, it has a temperature stable region at about 45 ° C. or lower;
has a temperature stability range of about 50 ° C. or lower in the presence of 1 mM Ca 2+ under conditions of holding at pH 6.0 for 60 minutes;
has a temperature stability range of about 55 ° C. or lower under conditions of pH 8.0 and 60 minutes; or
has a temperature stability range of about 60 ° C. or lower in the presence of 1 mM Ca 2+ under the condition of holding at pH 8.0 for 60 minutes;
(M) pH stability Under the condition of maintaining at 4 ° C. for 24 hours, it has a stable pH range in the range of about pH 4.5 to 10.0.
 本α-グルカンの製造において、原料のワキシースターチの仕込み濃度、液化(部分分解)に使用するアミラーゼ、当該アミラーゼの添加量、イソマルトース構造を導入するのに使用するα-グルコシル転移酵素、当該α-グルコシル転移酵素の添加量、糊化、液化、及びα-グルコシル転移の反応温度及び反応時間、これら反応の停止温度、反応の方式(バッチ方式、連続方式)等は、製造する本α-グルカンに求める物性に応じ、適宜選択すればよい。原料のワキシースターチの仕込み濃度は、通常、10質量%以上、望ましくは、約20乃至50質量%、より望ましくは30乃至35質量%とするのが好適である。後述の実験の項でも示すとおり、上述したアミラーゼの添加量を調節することによりワキシースターチを部分分解し、反応液中のワキシースターチ液化物(α-グルカン)の重量平均分子量(Mw)を150kDa乃至3,000kDaの範囲にコントロールすることができる。液化物の重量平均分子量(Mw)は、ゲル濾過HPLCにて測定することもできるものの、予備的に液化物の重量平均分子量とグルコース当量(DE)の相関性や、液化物の重量平均分子量とその液化液の粘度との相関性を調べておき、重量平均分子量測定に代えて、液化物のグルコース当量(DE)や液化液の粘度などを測定することで把握することができる。後述する実験の項でも示すように、ワキシースターチ液化物の重量平均分子量(Mw)を150kDa以上とするには、そのDEを、通常、1.0未満、好ましくは0.62以下に抑えればよい。ワキシースターチ液化物のDEを、比較的低い1.0未満に抑えるためには、糊化、液化の反応をできる限り短時間で終結させるのがよく、糊化、液化の方式は、澱粉懸濁液(澱粉乳)をより均一、急激に加熱昇温させることのできる連続方式の方がバッチ方式よりもより望ましい。 In the production of this α-glucan, the feed concentration of the raw waxy starch, the amylase used for liquefaction (partial decomposition), the addition amount of the amylase, the α-glucosyltransferase used to introduce the isomaltose structure, the α -Addition amount of glucosyltransferase, gelatinization, liquefaction, reaction temperature and reaction time of α-glucosyl transfer, stop temperature of these reactions, reaction method (batch method, continuous method), etc. Depending on the physical properties required, it may be selected as appropriate. The feed concentration of the raw waxy starch is usually 10% by mass or more, preferably about 20 to 50% by mass, more preferably 30 to 35% by mass. As shown in the experimental section described later, the waxy starch was partially decomposed by adjusting the amount of amylase added, and the weight average molecular weight (Mw) of the waxy starch liquefied product (α-glucan) in the reaction solution was 150 kDa to It can be controlled within the range of 3,000 kDa. Although the weight average molecular weight (Mw) of the liquefied product can be measured by gel filtration HPLC, the correlation between the weight average molecular weight of the liquefied product and glucose equivalent (DE) is preliminarily determined, and the weight average molecular weight of the liquefied product is The correlation with the viscosity of the liquefied liquid can be examined and grasped by measuring the glucose equivalent (DE) of the liquefied product, the viscosity of the liquefied liquid, etc., instead of the weight average molecular weight measurement. As shown in the experimental section to be described later, in order to set the weight average molecular weight (Mw) of the waxy starch liquefied product to 150 kDa or more, the DE is usually less than 1.0, preferably 0.62 or less. Good. In order to keep the DE of waxy starch liquefied products to a relatively low value of less than 1.0, the gelatinization and liquefaction reaction should be terminated in as short a time as possible. The gelatinization and liquefaction methods are based on starch suspension. The continuous method in which the liquid (starch milk) can be heated more uniformly and rapidly is more preferable than the batch method.
 また、本α-グルカンのイソマルトース構造の量は、α-グルコシル転移酵素の添加量によって調整することができ、製造する本α-グルカンに求める物性に応じて適宜調整すればよい。 In addition, the amount of the isomaltose structure of the α-glucan can be adjusted by the amount of α-glucosyltransferase added, and may be appropriately adjusted according to the physical properties required for the α-glucan to be produced.
 なお、α-グルコシル転移酵素を作用させて得られる、非還元末端にイソマルトース構造を有するα-グルカンは、原料としたα-グルカンに比べMw/Mnの値が大きくなり、またグルコース当量(DE)が若干増大する場合があるけれども、後述する実験の項でも示すように、α-グルコシル転移酵素の作用量を調節して得られる、Mw/Mnが35.1以下の範囲、グルコース当量(DE)が2.8未満にあるα-グルカンは、例えばフィルムに成形して問題なく使用することができる優れた可食性フィルム素材であるのみならず、更には、品質改善剤、詳細には老化調節剤、風味改良剤、物性改良剤などとしても有利に使用することができる。 Note that α-glucan having an isomaltose structure at the non-reducing end obtained by the action of α-glucosyltransferase has a larger Mw / Mn value than the α-glucan used as a raw material, and has a glucose equivalent (DE ) May increase slightly, but as shown in the experimental section described later, the Mw / Mn range obtained by adjusting the amount of action of α-glucosyltransferase is 35.1 or less, glucose equivalent (DE ) Is less than 2.8, for example, α-glucan is not only an excellent edible film material that can be used without problems when formed into a film, but also a quality improver, in particular, aging control It can also be advantageously used as an agent, flavor improver, physical property improver and the like.
 酵素反応によって得られた本α-グルカンを含有する溶液は、そのまま品質改善剤とすることもできるものの、一般的にはさらに精製して用いられる。精製方法としては、糖の精製に用いられる通常の方法を適宜採用すればよく、例えば、活性炭による脱色、H型、OH型イオン交換樹脂による脱塩、アルコール及びアセトンなど有機溶媒による分別、適度な分離性能を有する膜による分離などの1種又は2種以上の精製方法が適宜採用できる。 The solution containing the α-glucan obtained by the enzyme reaction can be used as it is as a quality improver, but is generally used after further purification. As a purification method, a normal method used for sugar purification may be appropriately employed. For example, decolorization with activated carbon, desalting with H-type or OH-type ion exchange resin, fractionation with an organic solvent such as alcohol and acetone, and the like. One or more purification methods such as separation by a membrane having separation performance can be appropriately employed.
 本α-グルカンは、比較的分子量が大きいα-グルカンの混合物の形態にあり、低分子オリゴ糖をほとんど含有していないので、得られる反応生成物をカラムクロマトグラフィーなどの手段で分画する必要は特にないものの、用途など目的に応じてさらに分画することも随意である。分画にイオン交換クロマトグラフィーを採用する場合、例えば、特開昭58-23799号公報、特開昭58-72598号公報などに開示されている強酸性カチオン交換樹脂を用いるカラムクロマトグラフィーを有利に用いることができる。この際、固定床方式、移動床方式、擬似移動床方式のいずれの方式を採用することも随意である。 This α-glucan is in the form of a mixture of α-glucan having a relatively large molecular weight and contains almost no low molecular weight oligosaccharide. Therefore, it is necessary to fractionate the obtained reaction product by means such as column chromatography. Although there is no particular limitation, it is optional to perform further fractionation according to the purpose of use. When ion exchange chromatography is employed for fractionation, for example, column chromatography using a strongly acidic cation exchange resin disclosed in JP-A-58-23799 and JP-A-58-72598 is advantageously used. Can be used. At this time, it is optional to adopt any of a fixed floor method, a moving floor method, and a simulated moving floor method.
 このようにして得られた本α-グルカンは溶液のままでも利用できるものの、保存に有利で、且つ、用途によっては利用しやすいように、乾燥し、粉末とするのが望ましい。乾燥には、例えば、ドラムドライヤー、噴霧乾燥機(スプレードライヤー)、熱風乾燥機、真空乾燥機、気流乾燥機、凍結乾燥機、流動層乾燥機などの乾燥機を使用することができる。生産性、コストを考慮すれば、ドラムドライヤー又は噴霧乾燥機を用いるのが好ましい。乾燥物は、必要に応じて、粉砕し粉末とすることも、また、粉末を篩別又は造粒して、特定粒度の範囲に整えることも有利に実施できる。 Although the α-glucan obtained in this way can be used as it is in solution, it is preferable to dry it into a powder so that it is advantageous for storage and easy to use depending on the application. For drying, for example, a dryer such as a drum dryer, a spray dryer (spray dryer), a hot air dryer, a vacuum dryer, a flash dryer, a freeze dryer, a fluidized bed dryer, or the like can be used. In consideration of productivity and cost, it is preferable to use a drum dryer or a spray dryer. If necessary, the dried product can be pulverized into a powder, or the powder can be screened or granulated to adjust to a specific particle size range.
4.本発明の品質改善剤の機能並びに用途
 本発明でいう品質改善とは、食品、化粧品、医薬部外品、医薬品、工業用品等製品あるいはその中間製品の品質を改善することを指し、具体的には、老化調節能、風味改良能、物性改良能などを意味する。
4). Function and use of the quality improver of the present invention The quality improvement in the present invention refers to improving the quality of products such as food, cosmetics, quasi-drugs, pharmaceuticals and industrial products, or intermediate products thereof. Means aging control ability, flavor improvement ability, physical property improvement ability, and the like.
 本発明の品質改善剤が粉末である場合には、白色で流動性に優れ、水に対して良好な溶解性を示しているので、種々の用途に用いることができる。本発明の品質改善剤は、老化調節性、風味改良性、物性改良性、接着性、浸透圧調節性、賦形性、照り付与性、保水性、保湿性、粘度付与性、他の糖の結晶防止性などの性質を具備しているので、老化調節剤、風味改良剤、物性改良剤のみならず、品質改良剤、安定剤、賦形剤、曇化調節剤、日持向上剤、歩留向上剤、硬化調節剤、流動調節剤、粘弾性改善剤、付着改良剤、喉越し改良剤、酸化防止剤、褐変防止剤、離水防止剤、整腸剤、成形剤、保形剤、冷蔵耐性剤、冷凍耐性剤、氷結晶安定化剤などとしても、食品、嗜好物、飼料、餌料、化粧品、医薬品、工業用品などの各種組成物に有利に利用できる。 When the quality improver of the present invention is a powder, it is white and excellent in fluidity, and exhibits good solubility in water, so that it can be used for various applications. The quality-improving agent of the present invention includes aging control, flavor improvement, physical property improvement, adhesion, osmotic pressure control, shaping, shine imparting, water retention, moisture retention, viscosity imparting, other sugars Since it has properties such as anti-crystallizing properties, not only aging regulators, flavor improvers, and physical property improvers, but also quality improvers, stabilizers, excipients, fogging modifiers, shelf life improvers, walkers Retention improver, cure modifier, flow modifier, viscoelasticity improver, adhesion improver, throat improver, antioxidant, browning inhibitor, water separation inhibitor, intestinal, molding agent, shape retainer, refrigeration resistant agent Also, as a freezing tolerant, an ice crystal stabilizer, etc., it can be advantageously used in various compositions such as foods, foods, feeds, feeds, cosmetics, pharmaceuticals, and industrial products.
 本発明の品質改善剤の有効成分であるα-グルカンは、非還元末端のイソマルトース構造という澱粉の加水分解物に本来的に存在しない特殊な構造を有するがゆえに、その原料となるα-グルカン混合物(澱粉部分分解物)や、グルコースがα-1,4結合を介して連結した直鎖状のα-1,4グルカンと異なり、共存する澱粉性多糖の老化調節能を有している。後述した実験項で示したように、例えば、非還元末端にイソマルトース構造を有するα-グルカンであって、イソマルトデキストラナーゼ消化において、消化物の固形物当たり3質量%超22質量%未満のイソマルトースを生成するα-グルカンは、澱粉液化液と共存させた場合、それぞれ固形物濃度5質量%を含有する溶液として4℃で5日間保持した場合でも、共存させた澱粉液化液の老化による白濁を顕著に抑制するほどの老化調節性を有する。したがって、本発明の品質改善剤の有効成分として、非還元末端にイソマルトース構造を有するα-グルカンであって、イソマルトデキストラナーゼ消化において、消化物の固形物当たり3質量%超22質量%未満のイソマルトースを生成するα-グルカンを用いる場合には澱粉性多糖を含有する製品の老化を顕著に調節して品質を保持することができるという利点を有し、老化調節剤として極めて好適である。 The α-glucan, which is an active ingredient of the quality improver of the present invention, has a special structure that does not inherently exist in the hydrolyzate of starch, that is, the non-reducing end isomaltose structure. Unlike a mixture (a partially decomposed starch) or a linear α-1,4 glucan in which glucose is linked via α-1,4 bonds, it has the ability to control aging of coexisting starchy polysaccharides. As shown in the experimental section to be described later, for example, an α-glucan having an isomaltose structure at the non-reducing end, and isomalt dextranase digestion, more than 3 mass% and less than 22 mass% per solid of digest The α-glucan that produces isomaltose is aged with the starch liquefaction solution even when it is kept at 4 ° C. for 5 days as a solution containing a solid concentration of 5% by mass. It has aging control properties so as to remarkably suppress white turbidity. Therefore, as an active ingredient of the quality improving agent of the present invention, α-glucan having an isomaltose structure at the non-reducing end, and in the isomalt dextranase digestion, more than 3% by weight and more than 22% by weight per solid product When α-glucan that produces less isomaltose is used, it has the advantage that the quality of the product containing starchy polysaccharides can be remarkably controlled to maintain the quality, and is extremely suitable as an aging regulator. is there.
 本発明の品質改善剤の有効成分であるα-グルカンは、上記したようにグルコース当量(DE)が通常2.0程度であり甘味をほとんど与えないことから、甘味が付与されることが好ましくない製品に対しても、その呈味に与える影響を懸念することなく添加、使用することが可能である。さらに、本発明の品質改善剤の有効成分である本α-グルカンは、風味改良作用を有していることから、例えば、市販の豆乳に適宜添加することで、豆乳のえぐ味や青臭みを抑制することができる。したがって、本発明の品質改善剤は、異味異臭を有する、あるいは異味異臭を発生する恐れのある製品に対して、甘味をほとんど与えることなく、風味を改良することができるという利点を有し、風味改良剤として好適である。 As described above, the α-glucan, which is an active ingredient of the quality improving agent of the present invention, has a glucose equivalent (DE) of usually about 2.0 and hardly gives sweetness, so that it is not preferable that sweetness is given. It can be added to and used for products without worrying about the effect on taste. Furthermore, since the α-glucan, which is an active ingredient of the quality improving agent of the present invention, has a flavor improving action, for example, by appropriately adding it to commercially available soy milk, the delicious taste and blue odor of soy milk can be reduced. Can be suppressed. Therefore, the quality improving agent of the present invention has the advantage that the flavor can be improved with almost no sweetness to a product having an off-flavor or off-flavor, which may cause off-flavor. Suitable as an improving agent.
 本発明の品質改善剤の有効成分であるα-グルカンは、重量平均分子量(Mw)が150kDa乃至3,000kDaの範囲にあることを特徴とし、適度な粘度を有していることから、これを粘度の小さな水溶液に添加すると、当該水溶液に粘性を付与し水溶液にボディ感を与えることができる。したがって、本発明の品質改善剤は、例えば、液状の製品に対して、とろみを付与し粘性を改良する物性改良剤として好適である。 Α-glucan, which is an active ingredient of the quality improving agent of the present invention, is characterized by having a weight average molecular weight (Mw) in the range of 150 kDa to 3,000 kDa, and has an appropriate viscosity. When added to an aqueous solution having a low viscosity, viscosity can be imparted to the aqueous solution and a body feeling can be imparted to the aqueous solution. Therefore, the quality improving agent of the present invention is suitable as a physical property improving agent that imparts thickness and improves viscosity to a liquid product, for example.
 さらに、本α-グルカンは、例えば、ゼラチン、コラーゲン、ペクチン、寒天、カラギーナン、キサンタンガム、ローカストビーンガム、ジェランガム、アラビアガム、グアーガム、タラガム、タマリンドシードガム、カードラン、サイリウムシードガム、アルギン酸、ヒアルロン酸、澱粉、加工デンプン、デキストリン、デキストラン、カルボキシビニルポリマー、架橋ポリアクリル酸、ヒドロキシエチルセルロース、カルボキシメチルセルロース、アクリル酸ソーダなどの高分子量のゲル化剤と併用することによって、ゲルの強度を調節する性質を有する。したがって、本発明の品質改善剤は、例えば、高分子量のゲル化剤を含有する製品に対して、ゲル強度を調節できるという利点を有し、物性改良剤として好適である。 Further, the present α-glucan is, for example, gelatin, collagen, pectin, agar, carrageenan, xanthan gum, locust bean gum, gellan gum, gum arabic, guar gum, tara gum, tamarind seed gum, curdlan, psyllium seed gum, alginic acid, hyaluronic acid , Starch, modified starch, dextrin, dextran, carboxyvinyl polymer, cross-linked polyacrylic acid, hydroxyethylcellulose, carboxymethylcellulose, sodium acrylate, etc. Have. Therefore, the quality improving agent of the present invention has an advantage that the gel strength can be adjusted, for example, for a product containing a high molecular weight gelling agent, and is suitable as a physical property improving agent.
 本発明の品質改善剤は、有効成分であるα-グルカンを単独で使用してもよいことは勿論であるが、その用途に応じて、その他の材料、例えば、多糖類、増量剤、賦形剤、充填剤、増粘剤、界面活性剤、発泡剤、消泡剤、pH調節剤、安定剤、難燃剤、離形剤、抗菌剤、着色剤、着香剤、栄養物、嗜好物、呈味物、薬効物質及び生理活性物質から選ばれる1種又は2種以上の、食品、化粧品、医薬品及び工業用品の分野で一般に使用される成分と混合して使用することも随意である。 In the quality improving agent of the present invention, α-glucan which is an active ingredient may be used alone, but other materials such as polysaccharides, extenders, and excipients are used depending on the use. Agent, filler, thickener, surfactant, foaming agent, antifoaming agent, pH adjuster, stabilizer, flame retardant, mold release agent, antibacterial agent, coloring agent, flavoring agent, nutrition, taste, It is optional to use a mixture with one or more kinds of ingredients generally used in the fields of foods, cosmetics, pharmaceuticals and industrial products selected from taste products, medicinal substances and physiologically active substances.
 本発明の品質改善剤は、有効成分であるα-グルカン以外に、例えば、粉飴、ブドウ糖、果糖、異性化糖、砂糖、麦芽糖、トレハロース、蜂蜜、メープルシュガー、ソルビトール、マルチトール、ジヒドロカルコン、ステビオシド、α-グリコシルステビオシド、ラカンカ甘味物、グリチルリチン、ソーマチン、スクラロース、L-アスパラチルフェニルアラニンメチルエステル、ズルチン、モネリン、アセスルファムカリウム、チクロ、アスパルテーム、ネオテーム、アリテーム、アドバンテーム、ルグズナム、サッカリン、グリシン、アラニンなどのような甘味料と、また、デキストリン、澱粉、プルラン、デキストラン、乳糖などのような増量剤と混合して使用することもできる。また、本発明の品質改善剤は、そのままで、又は必要に応じて、増量剤、賦形剤、結合剤などと混合して、顆粒、球状、短棒状、板状、立方体など各種形状に成形して使用することも随意である。 In addition to α-glucan, which is an active ingredient, the quality improving agent of the present invention includes, for example, flour, glucose, fructose, isomerized sugar, sugar, maltose, trehalose, honey, maple sugar, sorbitol, maltitol, dihydrochalcone, Stevioside, α-glycosyl stevioside, Rakanka sweet, glycyrrhizin, thaumatin, sucralose, L-aspartylphenylalanine methyl ester, dulcin, monelin, acesulfame potassium, cyclamate, aspartame, neotame, alitame, advantame, luznum, saccharin, glycine, alanine And a sweetener such as dextrin, starch, pullulan, dextran, lactose and the like. In addition, the quality improver of the present invention can be molded into various shapes such as granules, spheres, short bars, plates, cubes, etc., as they are or as necessary, mixed with extenders, excipients, binders, etc. It is also optional to use.
 本発明の品質改善剤を含有してなる各種成形物又はその中間製品には、柔軟性や強度をさらに改良することを目的として、必要に応じて、食品、化粧品、医薬部外品及び医薬品などの分野で通常使用される他の高分子物質、適宜の賦形剤、又は、可塑剤等の他の成分を併用することも随意であり、他の賦形剤を主体とする成形物においては本発明の品質改善剤を結着剤として用いることも可能である。他の賦形剤としては、プルラン、カラギーナン、キサンタンガム、カルボキシメチルセルロース、セルロース、ヘミセルロース、アラビアガム、グァーガム、ペクチン、キチン、アガロース、デキストラン、デキストリン、アミロース及び化工澱粉を含む澱粉などの多糖類又はそれらの誘導体、ゼラチン又はカゼインなどの蛋白質などの高分子、ソルビトール、マンニトール、マルチトール、スクロース、マルトース、ラクトース、α,α-トレハロース、α,β-トレハロース、アラビアゴム、コーンスターチ、結晶セルロースなどの糖質、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化バリウム、硫酸カルシウム、亜硫酸カルシウム、炭酸カルシウム、シリカ、ケイ酸カルシウム、塩基性炭酸マグネシウム、カオリン、タルクなどの無機物が挙げられる。とりわけ、α,α-トレハロースは、有効成分の酸化分解などによる変性を抑制し、活性を安定に保つ作用を有するので、安定化剤としても有利に利用できる。可塑剤としては、ソルビトール、マルチトール、マンニトール、エリトリトール、ラクチトール、キシリトール、還元水飴などの糖アルコール、グルコース、フルクトース、ガラクトース、キシロース、ラムノース、プシコースなどの単糖類、マルトース、スクロース、トレハロース、ラクトース、ツラノース、セロビオースなどの二糖類、マルトトリオース、パノース、ラフィノース、メレジトース、マルトテトラオース、スタキオース、シクロデキストリンなどのオリゴ糖類、グリセロール、ポリビニルアルコール、ポリエチレングリコール、プロピレングリコールなどの多価アルコール類、トリエチルシトラート、トリアセチン、トリブチルシトラート、アセチルトリエチルシトラート、アセチルトリブチルシトラート、フタル酸ジブチル、セバシン酸ジブチル、フタル酸ジエチル、ビニルピロリドングリコールトリアセタート、パラオキシ安息香酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、グリセリン脂肪酸エステルなどのエステル類などが挙げられ、これらの1種又は2種以上を適宜組み合わせて用いることができる。可塑剤は、本発明の品質改善剤を含有してなる、例えば、フィルム、シート、カプセル皮膜などにも用いることができ、とりわけ、ソフトカプセル皮膜に有利に併用できるが、これらの成形物又はその中間製品に限定されるものではない。 Various molded products containing the quality improver of the present invention or intermediate products thereof, for the purpose of further improving flexibility and strength, food, cosmetics, quasi-drugs, pharmaceuticals, etc., if necessary It is also optional to use other polymeric substances, appropriate excipients, or other components such as plasticizers that are usually used in the field of It is also possible to use the quality improving agent of the present invention as a binder. Other excipients include polysaccharides such as pullulan, carrageenan, xanthan gum, carboxymethylcellulose, cellulose, hemicellulose, gum arabic, guar gum, pectin, chitin, agarose, dextran, dextrin, amylose and modified starch, or their Macromolecules such as derivatives, proteins such as gelatin or casein, saccharides such as sorbitol, mannitol, maltitol, sucrose, maltose, lactose, α, α-trehalose, α, β-trehalose, gum arabic, corn starch, crystalline cellulose, Aluminum hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium sulfate, calcium sulfite, calcium carbonate, silica, calcium silicate, basic magnesium carbonate, Kaori It includes inorganic substances such as talc. In particular, α, α-trehalose can be advantageously used as a stabilizer because it has the action of suppressing the denaturation of active ingredients due to oxidative degradation and keeping the activity stable. Plasticizers include sugar alcohols such as sorbitol, maltitol, mannitol, erythritol, lactitol, xylitol, and reduced starch syrup, monosaccharides such as glucose, fructose, galactose, xylose, rhamnose, and psicose, maltose, sucrose, trehalose, lactose, and tulanose. , Disaccharides such as cellobiose, maltotriose, panose, raffinose, melezitose, maltotetraose, stachyose, cyclodextrins and other oligosaccharides, glycerol, polyvinyl alcohol, polyethylene glycol, propylene glycol and other polyhydric alcohols, triethyl citrate , Triacetin, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, dibuphthalate And esters such as dibutyl sebacate, diethyl phthalate, vinyl pyrrolidone glycol triacetate, paraoxybenzoic acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, and the like. They can be used in appropriate combinations. The plasticizer can be used for, for example, a film, a sheet, a capsule film and the like containing the quality improver of the present invention, and can be advantageously used in combination with a soft capsule film. It is not limited to products.
 本発明の品質改善剤は、とりわけ、食品素材として有利に利用できる。食品への使用は特に限定されず、本発明の品質改善剤の結着性を利用して、成形スナック菓子、成形チーズ、成形ドライフルーツ、魚肉成形物、魚卵成形物、魚肉食品、畜肉食品、疑似肉食品、成形珍味食品などに用いることができる。また、造膜(コーティング)性を利用して、食品ほぐれ剤、食品用粘着防止剤、加工米などに用いることもできる。また、老化調節性を利用して、澱粉性多糖含有食品、冷蔵チルド製品、冷凍製品などに用いることができる。さらには、風味改良性や物性改良性を利用して、清涼飲料、アルコール飲料などの飲料類、冷菓などのデザート類においては、優れた濃厚感、こく味が付与され乳感、果汁感等が強調され、酢、粉末醤油、粉末調味料、粉末香料、粉末茶等の粉末食品においては、優れた風味保持に加え、雑味のマスキング、風味発現等の効果が期待でき、濃厚流動食や経腸栄養剤などの乳化液状栄養食品類や、カレー、シチュー、米飯、粥、惣菜、スープ、パスタソースなどのレトルトパウチ食品類においては、乳化の安定化、オイルオフの抑制、タンパク質の凝集防止、殺菌後のレトルト臭のマスキング等の効果が期待でき、ドレッシングやマヨネーズなどの調味料類においては、優れた濃厚感やこく味の付与、及び風味発現等の効果が期待でき、合わせて油脂等の脂肪代替としての効果も期待できる。 The quality improving agent of the present invention can be used advantageously as a food material, among others. Use in food is not particularly limited, and using the binding property of the quality improving agent of the present invention, molded snacks, molded cheese, molded dried fruit, fish molded products, fish egg molded products, fish food, livestock meat foods, It can be used for simulated meat foods and molded delicacy foods. Moreover, it can also be used for food loosening agents, food anti-sticking agents, processed rice, etc. by utilizing the film-forming (coating) property. In addition, it can be used for starchy polysaccharide-containing foods, chilled chilled products, frozen products, etc. by utilizing the aging controllability. Furthermore, with the use of flavor improving properties and physical property improving properties, beverages such as soft drinks and alcoholic beverages, and desserts such as frozen desserts have an excellent richness, rich taste, milky feeling, fruit juice feeling, etc. Emphasized, in powdered foods such as vinegar, powdered soy sauce, powdered seasoning, powdered fragrance, and powdered tea, in addition to excellent flavor retention, effects such as masking of miscellaneous taste, expression of flavor, etc. can be expected. In emulsified liquid nutritional foods such as enteric nutrients, and retort pouch foods such as curry, stew, cooked rice, sugar beet, side dish, soup and pasta sauce, stabilization of emulsification, suppression of oil-off, prevention of protein aggregation, The effect of masking of retort odor after sterilization can be expected, and in seasonings such as dressing and mayonnaise, it can be expected to have excellent richness, impart rich body, and express flavor, etc. Effect as a fat substitute for fats and oils can also be expected.
 また、本発明の品質改善剤は、パン、米粉パン、菓子、麺帯製品に含有させることによって、食感の改良、食品の保存性向上や歩留向上に用いることができる。本発明の品質改善剤の食品への好適な使用方法としては、小麦粉、食塩、砂糖、水など他の原料素材と混合し、混練することで生地を作成して、その生地を成形、調理することが挙げられる。食品中への配合割合は、生地作成時の割合で固形物当たり0質量%を超え30質量%以下、好ましくは10質量%以下、特に好ましくは5質量%以下である。本発明の品質改善剤は、ワキシースターチを原料としているので、パン、米粉パン、菓子、麺帯製品にしっとり感、もちもち感、やわらかさ、口どけの良さ、歯切れ良さなどの食感を付与することができる。 Further, the quality improver of the present invention can be used for improving the texture, improving the storage stability of the food and improving the yield by adding it to bread, rice flour bread, confectionery, and noodle strip products. A preferred method of using the quality improver of the present invention for foods is to mix and knead with other raw materials such as flour, salt, sugar, water, and knead to form and cook the dough. Can be mentioned. The blending ratio in the food is greater than 0% by mass and 30% by mass or less, preferably 10% by mass or less, and particularly preferably 5% by mass or less per solid as a ratio at the time of preparing the dough. The quality improver of the present invention uses waxy starch as a raw material, so it gives bread, rice flour bread, confectionery, noodle strip products a moist feeling, sticky feeling, softness, good mouthfeel, crispness, etc. be able to.
 菓子としては、主に生地を調製後、焼く、蒸す、揚げる、乾燥するなどして製造されるものに利用でき、例えば、饅頭、餅、大福、団子、求肥、ういろう、かるかん、最中、どら焼き、羊羹、きんつば、今川焼き、煎餅、あられ、おこしなどの和菓子、ビスケット、クッキー、クラッカー、ウエハース、スポンジケーキ類(ロールケーキ、カステラ)、バターケーキ類(パウンドケーキ、マドレーヌ、ガトーショコラ、フィナンシェ)、シュークリーム、バウムクーヘン、マフィン、スフレ、パイ、タルト、ドーナツ、ワッフル、プディングなどの洋菓子、月餅などの中華菓子、チップス、パフ、フライなどのスナック菓子などが挙げられる。また、上記に限らず、バタークリーム、カスタードクリームなどのクリーム類、飴玉、ドロップ、タフィ、バタースコッチなどのハードキャンディー類、キャラメル、ヌガー、マシュマロ、グミ、ゼリービーンズ、ボンタン飴などのソフトキャンディー類、チョコレート類、チューインガム類などにも利用することができる。さらには、アイスクリーム、アイスミルク、ラクトアイス、シャーベット、かき氷、アイスキャンディー、アイスポップ、パフェ、サンデー、フラッペなどの氷菓、ゼリー、プリン、ムース、ババロア、パンナコッタ、ヨーグルト、杏仁豆腐などの冷菓にも利用することが可能である。 As confectionery, it can be used mainly for the dough prepared and then baked, steamed, fried, dried, etc., for example, buns, rice cakes, daifuku, dumplings, fertilizers, seaweeds, carcass, in the middle Grilled, Yokan, Kintsuba, Imagawa-yaki, rice cracker, Japanese confectionery such as hail, okoshi, biscuits, cookies, crackers, wafers, sponge cakes (roll cake, castella), butter cakes (pound cake, madeleine, gateau chocolate, financier) , Cream candy, Baumkuchen, muffin, souffle, pie, tart, donut, waffle, pudding and other Western confectionery, moon cake, Chinese confectionery, chips, puffs, fries and other snacks. Also, not limited to the above, creams such as butter cream and custard cream, hard candy such as jasper, drop, toffee and butterscotch, soft candy such as caramel, nougat, marshmallow, gummy, jelly beans and Bontang rice cake It can also be used for chocolates, chewing gums, and the like. It can also be used for ice cream, ice milk, lacto ice, sorbet, shaved ice, ice candy, ice pop, parfait, sundae, frappe and other frozen desserts, jelly, pudding, mousse, bavaroa, panna cotta, yogurt, apricot tofu, etc. Is possible.
 麺帯製品としては、例えば、うどん、そうめん、中華麺、蕎麦、ビーフン、フォーなどの麺類、スパゲッティ、リングイネ、ブカティーニ、フェットチーネ、ペンネ、コンキリエ、マカロニ、フジッリ、ラザニア、ニョッキ、クスクスなどのパスタ類、ワンタン、ギョウザ、シューマイ、春巻きなどの皮などが挙げられる。 Examples of noodle strip products include noodles such as udon, somen, Chinese noodles, buckwheat noodles, rice noodles, pho, etc. Examples include skins such as wonton, gyoza, shumai, and spring rolls.
 また、本発明の品質改善剤は、その有効成分とする本α-グルカンが水に対する良好な溶解性を有するため、本α-グルカンの含有量にもよるが、飲料に添加しても容易に溶解し、喉越し食感の改良や保存性向上などの目的で好適に用いることができる。本発明の品質改善剤の飲料への好適な使用方法としては、水、茶、コーヒー、果汁、アルコール、乳製品、エキス類、炭酸など任意の他の飲料素材と混合することが挙げられる。飲料中への配合割合は、本α-グルカンの量として、固形物当たり0質量%を超え30質量%以下、好ましくは10質量%以下、特に好ましくは5質量%以下である。本α-グルカンは、ワキシースターチを原料としているので、こく、とろみ、まろやかさ、ボディ感などの豊かな物性を付与することができる。 In addition, the quality improving agent of the present invention has an excellent solubility in water for the present α-glucan as an active ingredient, and therefore it can be easily added to beverages depending on the content of the present α-glucan. It can be suitably used for the purpose of dissolving and improving the texture over the throat and improving the storage stability. As a preferred method of using the quality improver of the present invention for beverages, mixing with any other beverage material such as water, tea, coffee, fruit juice, alcohol, dairy products, extracts, carbonic acid and the like can be mentioned. The blending ratio in the beverage is more than 0% by mass and 30% by mass or less, preferably 10% by mass or less, particularly preferably 5% by mass or less per solid, as the amount of the α-glucan. Since this α-glucan is made from waxy starch, it can impart rich physical properties such as body, thickness, mellowness and body feeling.
 飲料としては、例えば、水飲料類、緑茶、玉露、ほうじ茶、こぶ茶、紅茶、ウーロン茶、麦茶、マテ茶などの茶飲料類、コーヒー飲料類、ココア飲料類、果汁飲料、炭酸飲料、機能性飲料、スポーツ飲料、ゼリー飲料、ノンアルコール飲料などの清涼飲料類、ビール、発泡酒、ワイン、果実酒、清酒、焼酎、リキュール、ブランデー、ウイスキーなどの酒飲料類、加工乳、ヨーグルトなどの乳飲料類、豆乳類、スープ類、栄養ドリンク類、美容ドリンク類などが挙げられる。 Examples of beverages include water beverages, green tea, gyokuro, roasted tea, kobu tea, black tea, oolong tea, barley tea, mate tea, and other coffee beverages, cocoa beverages, fruit juice beverages, carbonated beverages, functional beverages. , Soft drinks such as sports drinks, jelly drinks, and non-alcoholic drinks, beer, sparkling wine, wine, fruit liquor, sake, shochu, liqueur, brandy, whiskey and other liquor drinks, processed milk, yogurt and other milk drinks , Soy milk, soups, energy drinks, beauty drinks and the like.
本発明の品質改善剤は、その他一般の飲食物などにも有利に利用できる。例えば、醤油、粉末醤油、味噌、粉末味噌、もろみ、ひしお、ふりかけ、食酢、三杯酢、粉末すし酢、中華の素、天つゆ、麺つゆ、ソース、ケチャップ、焼き肉のタレ、カレールウ、シチューの素、スープの素、ダシの素、複合調味料、みりん、新みりん、テーブルシュガー、コーヒーシュガー、シロップなどの各種調味料への品質改善剤などとして使用することも有利に実施できる。また、例えば、フラワーペースト、ピーナッツペースト、フルーツペーストなどのペースト類、ジャム、マーマレード、シロップ漬、糖果、胡麻豆腐、こんにゃくなどの果実や野菜の加工食品類、福神漬け、べったら漬、千枚漬などの漬物類、たくわん漬の素、白菜漬の素などの漬物の素、ハム、ソーセージなどの畜肉製品類、魚肉ハム、魚肉ソーセージ、カマボコ、チクワ、天ぷらなどの魚肉製品、ウニ、イカの塩辛、酢コンブ、さきするめ、タラ、タイ、エビなどの田麩などの各種珍味類、海苔、山菜、するめ、小魚、貝などで製造される佃煮類、煮豆、納豆、豆腐などの豆製品類、茶碗蒸し、玉子豆腐などの卵製品類、ポテトサラダ、コンブ巻などの惣菜食品、乳製品、魚肉、畜肉、果実、野菜の瓶詰・缶詰類、プリンミックス、ホットケーキミックス、即席ジュース、即席コーヒー、即席汁粉、即席スープなどの即席食品、更には、離乳食、治療食、ペプチド食品、冷凍食品などの各種飲食物に配合可能な品質改善剤として有利に利用でき、何ら限定されることはない。 The quality improving agent of the present invention can be advantageously used for other general foods and drinks. For example, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hashio, sprinkle, vinegar, three cups of vinegar, powdered sushi vinegar, Chinese soup, tenyuyu, noodle soup, sauce, ketchup, grilled meat sauce, curry roux, stew of soup, soup It can also be advantageously used as a quality improver for various seasonings such as Nomoto, Dashi-no-moto, compound seasonings, mirin, new mirin, table sugar, coffee sugar, and syrup. Also, for example, pastes such as flower paste, peanut paste, fruit paste, processed foods of fruits and vegetables such as jam, marmalade, syrup pickles, sugar cane, sesame tofu, konjac, pickles such as Fukujin pickles, bedara pickles, thousand pickles Pickles, takuwanzuke, pickled vegetables such as Chinese cabbage, livestock meat products such as ham and sausage, fish ham, fish sausage, fish products such as sea urchin, chikuwa, tempura, sea urchin, squid salty, vinegar kombu , Various delicacies such as rice fields such as sakisume, cod, thai, shrimp, boiled seaweeds made with seaweed, wild vegetables, seaweed, small fish, shellfish, bean products such as boiled beans, natto, tofu, steamed tea Egg products such as egg tofu, side dish foods such as potato salad, rolls of konbu, dairy products, fish meat, livestock meat, fruits, bottled and canned vegetables, pudding mix, hot It can be advantageously used as a quality improver that can be incorporated into various foods such as cake mix, instant juice, instant coffee, instant juice powder, instant soup, and baby food, therapeutic food, peptide food, frozen food, There is no limitation.
 また、本発明の品質改善剤は、その有効成分であるα-グルカンが、上記のとおり、水に対する良好な溶解性とフィルム等に成形されたときの高い強度に加え、老化調節作用、風味改良作用、保形能、粘弾性改良能といった物性改良作用、酸化防止能や褐変防止能などを併せ持ち、しかも、有効成分として含まれるα-グルカン自体の分子量分布が特定の範囲内にあるので、これを成形物に用いる場合には、当該成形物に常に一定した強度や溶解速度、崩壊速度をもたらすことが期待できる。したがって、本発明の品質改善剤は、食品のみならず化粧品、有効成分の体内動態が常に一定であることが要求される医薬品、医薬部外品などに用いることができ、フィルムはもとより、シート、カプセル、ソフトカプセル、マイクロカプセル、ガーゼや手術糸などに用いられる繊維などの成形物として、或いは、錠剤や顆粒剤を調製する際の賦形剤、結着剤又はコーティング剤などとして、さらには、用時溶解型の固形製剤とすることができる。 In addition, the quality improver of the present invention, as described above, α-glucan, which is an active ingredient, has good solubility in water and high strength when formed into a film or the like, as well as an aging-controlling effect and flavor improvement. In addition, it has physical properties improving action such as action, shape retention and viscoelasticity, antioxidant ability and browning prevention ability, and the molecular weight distribution of α-glucan contained as an active ingredient is within a specific range. Can be expected to always give a constant strength, dissolution rate, and disintegration rate to the molded product. Therefore, the quality improving agent of the present invention can be used not only for foods but also for cosmetics, pharmaceutical products for which the pharmacokinetics of active ingredients are always required to be constant, quasi drugs, sheets, As a molded article such as a capsule, soft capsule, microcapsule, fiber used for gauze or surgical thread, etc., or as an excipient, binder or coating agent when preparing tablets or granules, and further It can be a solid preparation of a dissolution type.
 本発明の品質改善剤を少なくとも原料の一部に用いて製造される成形物には、本発明の品質改善剤以外に、それぞれの分野で汎用されている各種成分を適宜配合することができる。上記成形物が化粧品又は医薬部外品或いはその中間製品である場合には、化粧水、乳液、美容液、クリーム、ジェル、化粧下地、ファンデーション、チーク、おしろい、コンシーラー、口紅、リップクリーム、マスカラ、アイシャドウ、アイライナー、アイブロウ、洗顔料、シャンプー、リンス、コンディショナー、整髪料、養毛料、頭皮料、毛髪着色料、シェービング剤、日焼け止め、爪化粧料、ボディパウダー、軟膏、パック、マスク、浴用剤、口中清涼フィルムなどの形態とすることができ、例えば、パラオキシ安息香酸エステル、塩化ベンザルコニウム、ペンタンジオールなどの防腐剤、アルブチン、エラグ酸、コウジ酸、トラネキサム酸、ニコチン酸アミド、ビタミンC誘導体、プラセンタエキス、テトラヒドロクルクミノイド、ビタミンPなどの美白剤、アラントイン、イソプロピルメチルフェノール、グリチルリチン酸、カンゾウ抽出物などの抗炎症剤、ラクトフェリン、コンドロイチン硫酸、ヒアルロン酸、感光素101号、感光素301号などの細胞賦活剤、エラスチン、ケラチン、尿素、セラミドなどの保湿剤、スクワラン、ワセリン、トリ-2-エチルヘキサン酸セチルなどの油剤、カラギーナン、カルボキシメチルセルロース、ローカストビーンガム、カルボキシビニルポリマーなどの水溶性高分子、1,3-ブチレングリコール、ポリエチレングリコール、プロピレングリコール、ソルビトール、マルチトールなどのアルコール類などを、それぞれ1種又は2種以上、単独又は適宜組み合わせて配合することができ、その有効成分や活性を失うことなく、使用感が良く、安定で高品質の化粧品又は医薬部外品或いはその中間製品などを容易に製造することができる。 In addition to the quality improver of the present invention, various components widely used in the respective fields can be appropriately blended in the molded product produced using the quality improver of the present invention as at least a part of the raw material. When the molded product is a cosmetic or quasi-drug or an intermediate product thereof, lotion, milky lotion, cosmetic liquid, cream, gel, makeup base, foundation, teak, funny, concealer, lipstick, lip balm, mascara, Eyeshadow, Eyeliner, Eyebrow, Facial Cleanser, Shampoo, Rinse, Conditioner, Hair Conditioner, Hair Nourishing, Scalp, Hair Coloring, Shaving Agent, Sunscreen, Nail Cosmetic, Body Powder, Ointment, Pack, Mask, Bath Agent, oral refreshing film, etc., for example, preservatives such as paraoxybenzoic acid ester, benzalkonium chloride, pentanediol, arbutin, ellagic acid, kojic acid, tranexamic acid, nicotinamide, vitamin C Derivatives, placenta extract, tetrahydrocurcuminoids, Whitening agents such as Tamine P, anti-inflammatory agents such as allantoin, isopropylmethylphenol, glycyrrhizic acid, licorice extract, lactoferrin, chondroitin sulfate, hyaluronic acid, cell activators such as Photosensitive Element 101, Photosensitive Element 301, elastin, Moisturizers such as keratin, urea, ceramide, oils such as squalane, petrolatum, cetyl tri-2-ethylhexanoate, water-soluble polymers such as carrageenan, carboxymethylcellulose, locust bean gum, carboxyvinyl polymer, 1,3-butylene Alcohols such as glycol, polyethylene glycol, propylene glycol, sorbitol, maltitol, etc., can be blended individually or in combination of one or more, without losing their active ingredients or activity Good feeling, and stable and high-quality cosmetic or quasi drug or its intermediate products can be easily manufactured.
 また、上記成形物が医薬品又は医薬部外品或いはその中間製品である場合には、顆粒、錠剤、糖衣錠などの固状や、液状、ペースト状などの形態とすることができる。例えば、アザチオプリン、シクロスポリン、シクロフォスファミド、メソトレキサート、タクロリムス水和物、ブスルファンなどの免疫抑制剤、カペシタビン、リツキシマブ、トラスツズマブ、ベバシズマブ、ドセタキセル、イマチニブメシル酸塩、5-フルオロウラシル、アナストロゾール、タキソール、タモキシフェン、ドテタキセル、ヒドロキシカルバミドなどの抗がん剤、アバカビル硫酸塩、ザルシタビン、ジダノシン、ファムシクロビル、リバビリンなどの抗ウイルス剤、アモキシシリン、タランピシリン、セフィキシム、スルファミチゾール、レボフロキサシン水和物、セフカペンピボキシル塩酸塩水和物、セフシトレンピボキシル、クラリスロマイシンなどの抗生物質、アセトアミノフェン、アスピリン、エテンザミド、サリチル酸メチルなどの解熱鎮痛剤、プレドニゾロン、デキサメサゾン、ベタメサゾンなどのステロイド剤、インターフェロン-α、-β、インスリン、オキシトシン、ソマトロピン、などの蛋白又はペプチド、BCGワクチン、日本脳炎ワクチン、はしかワクチン、ポリオワクチン、痘苗、破傷風トキソイド、ハブ抗毒素、ヒト免疫グロブリンなどの生物学的製剤、レチノール、チアミン、リボフラビン、ピリドキシン、シアノコバラミン、L-アスコルビン酸、カロチノイド、エルゴステロール、トコフェロール、ビオチン、カルシトニン、コエンザイムQ、α-リポ酸、ニコチン酸、メナキノン、ユビキノン、ピロロキノンキノリンなどのビタミン剤やそれらの誘導体、高麗人参エキス、アロエエキス、プロポリスエキス、カンゾウエキス、ケイヒエキス、センブリエキスなどの生薬エキスなどを、それぞれ1種又は2種以上、単独又は適宜組み合わせて配合することができ、その有効成分、活性を失うことなく、安定で高品質の医薬品又は医薬部外品或いはその中間製品などを容易に製造することができる。 In addition, when the molded product is a pharmaceutical product, a quasi-drug or an intermediate product thereof, it can be in the form of a solid such as a granule, a tablet, a sugar-coated tablet, a liquid, or a paste. For example, azathioprine, cyclosporine, cyclophosphamide, methotrexate, tacrolimus hydrate, immunosuppressive agents such as busulfan, capecitabine, rituximab, trastuzumab, bevacizumab, docetaxel, imatinib mesylate, 5-fluorouracil, anastrozole, taxol, Anticancer agents such as tamoxifen, dotetaxel, hydroxycarbamide, antiviral agents such as abacavir sulfate, sarcitabine, didanosine, famciclovir, ribavirin, amoxicillin, tarampicillin, cefixime, sulfamitisol, levofloxacin hydrate, cefuka Antibiotics such as penpivoxil hydrochloride hydrate, cefcitrene pivoxil, clarithromycin, acetaminophen, aspirin, etenzamide, sari Antipyretic analgesics such as methyl lurate, steroids such as prednisolone, dexamethasone, betamethasone, proteins or peptides such as interferon-α, -β, insulin, oxytocin, somatropin, BCG vaccine, Japanese encephalitis vaccine, measles vaccine, polio Biologics such as vaccine, seedling, tetanus toxoid, hub antitoxin, human immunoglobulin, retinol, thiamine, riboflavin, pyridoxine, cyanocobalamin, L-ascorbic acid, carotenoid, ergosterol, tocopherol, biotin, calcitonin, coenzyme Q, α -Vitamin preparations such as lipoic acid, nicotinic acid, menaquinone, ubiquinone, pyrroloquinone quinoline and their derivatives, ginseng extract, aloe extract, propolis extract, licorice extract, Herbal extracts such as baboon extract, assembly extract, etc., can be blended alone or in combination of two or more, alone or in combination as appropriate, without losing their active ingredients and activities, stable and high-quality pharmaceuticals or quasi-drugs Products or intermediate products thereof can be easily manufactured.
 本発明の品質改善剤は、工業用品の素材として使用することもできる。ここでいう工業用品とは、農薬、肥料、飼料、紙工品、研磨剤、糊剤、接着剤(バインダー)、ゲル化剤、離水防止剤、賦形剤、保水剤、保湿剤、透湿剤、吸水剤、吸収剤、吸着剤、脱臭剤、増粘剤、粘結剤、潤滑剤、光沢付与剤、滑沢剤、皮膜剤、難燃剤、消泡剤、起泡剤、親水化剤、帯電防止剤、乳化剤、界面活性剤、分散剤、懸濁剤、調整剤、濾過助剤、溶解助剤、溢泥防止剤、製紙用添加剤、安定化剤、分離防止剤、被膜剤、浸透剤、希釈剤、等張化剤、崩壊剤、緩衝剤、増量剤、歩留向上剤、強化剤、撥油剤、耐油剤、保護剤、固化剤、土壌改良剤、充填剤、塗料、染料、顔料、インク、洗浄剤、柔軟剤、トイレタリー製品、生分解性樹脂(バイオプラスチック)、ガスバリアー樹脂などを指す。例えば、農薬、肥料、飼料などの分野では、品質改善剤の付着改良能を利用して、農薬、肥料を造粒、錠剤化する際の賦形剤として使用することができる。本α-グルカンの老化調節能を利用して、肥料、飼料の粘弾性改良剤、風味改良剤、安定化剤、酸化防止剤、日持向上剤として使用することができる。また、例えば、製紙分野では、品質改善剤の結着性や皮膜形成能を利用して紙工品の表面塗工剤、増強剤として、また、不織布の材料、包装材料としても使用することができる。さらに、ポリビニルアルコール(PVA)の代替品、カルボキシメチルセルロース(CMC)の代替品、石膏ボード、セメント、電池セパレーター用のバインダーなどとしても使用することができる。 The quality improver of the present invention can also be used as a material for industrial products. Industrial products here are agricultural chemicals, fertilizers, feeds, paper products, abrasives, glues, adhesives (binders), gelling agents, water separation preventing agents, excipients, water retention agents, moisturizing agents, moisture permeation agents. , Water absorbent, absorbent, adsorbent, deodorant, thickener, binder, lubricant, gloss imparting agent, lubricant, film agent, flame retardant, antifoaming agent, foaming agent, hydrophilizing agent, Antistatic agent, Emulsifier, Surfactant, Dispersant, Suspending agent, Conditioning agent, Filter aid, Dissolving aid, Overflow agent, Paper additive, Stabilizer, Separation agent, Coating agent, Penetration Agent, diluent, tonicity agent, disintegrating agent, buffering agent, bulking agent, yield improver, reinforcing agent, oil repellent, oil proofing agent, protective agent, solidifying agent, soil improver, filler, paint, dye, It refers to pigments, inks, cleaning agents, softeners, toiletry products, biodegradable resins (bioplastics), gas barrier resins, etc. For example, in the fields of agricultural chemicals, fertilizers, feeds, etc., it is possible to use the agricultural chemicals and fertilizers as excipients when granulating and tableting using the adhesion improving ability of the quality improving agent. Utilizing the ability of this α-glucan to control aging, it can be used as a fertilizer, feed viscoelasticity improver, flavor improver, stabilizer, antioxidant, and shelf life improver. Also, for example, in the papermaking field, it can be used as a surface coating agent and a reinforcing agent for paper products by utilizing the binding property and film forming ability of a quality improving agent, and also as a material for nonwoven fabrics and packaging materials. . Furthermore, it can also be used as a substitute for polyvinyl alcohol (PVA), a substitute for carboxymethyl cellulose (CMC), a gypsum board, cement, a binder for battery separators, and the like.
 以下、実験1乃至5及び参考実験例において、本発明の有効成分であるα-グルカンを選択するに至った経緯を説明する。 Hereinafter, the background to the selection of α-glucan, which is the active ingredient of the present invention, in Experiments 1 to 5 and Reference Experiment Examples will be described.
<実験1:ワキシースターチを原料とした分解度が異なる各種α-グルカンの調製>
 ワキシースターチとしてワキシーコーンスターチを用い、加水分解の程度が種々異なる各種α-グルカンを調製し、その物性を調べた。
<Experiment 1: Preparation of various α-glucans with different degrees of decomposition using waxy starch>
Using waxy corn starch as a waxy starch, various α-glucans having different degrees of hydrolysis were prepared and their physical properties were examined.
 市販のワキシーコーンスターチ(商品名「ワキシーコーンスターチ Y」、株式会社J-オイルミルズ製造)を固形物濃度30質量%になるよう脱イオン水に懸濁し、塩化カルシウムを濃度0.1質量%になるよう添加した後、pH6.0に調製し、ワキシーコーンスターチ懸濁液を得た。このワキシーコーンスターチ懸濁液に耐熱性α-アミラーゼ(商品名「スピターゼHK」、ナガセケムテックス株式会社製造)をワキシーコーンスターチ固形物当たり0(無添加)、0.001、0.002、0.004、0.008又は0.02質量%添加し、pH6.5、100℃で20分間加熱することにより、糊化及び液化を行い、140℃で30分間加熱することにより反応を停止させ、活性炭処理による脱色、イオン交換樹脂による脱塩、メンブランフィルターによるろ過を行った後、ディスク型噴霧乾燥装置(ニ口社製造)を用い入口温度205℃、出口温度103℃、風量12.4m/分、ディスク回転数18,000rpm、原料供給速度23kg/時間になるように設定し、噴霧乾燥することによりα-グルカン粉末をそれぞれ約2kgずつ調製し、被験試料1~6とした。 Commercially available waxy corn starch (trade name “waxy corn starch Y”, manufactured by J-Oil Mills Co., Ltd.) is suspended in deionized water to a solids concentration of 30% by mass, and calcium chloride is adjusted to a concentration of 0.1% by mass. After the addition, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension. Heat-resistant α-amylase (trade name “Spitase HK”, manufactured by Nagase ChemteX Corporation) was added to this waxy corn starch suspension at 0 (no addition), 0.001, 0.002, 0.004 per waxy corn starch solid. , 0.008 or 0.02% by mass, heated at pH 6.5, 100 ° C. for 20 minutes to gelatinize and liquefy, and heated at 140 ° C. for 30 minutes to stop the reaction, and activated carbon treatment , Desalting with an ion exchange resin, filtration with a membrane filter, and then using a disk-type spray drying device (manufactured by Niguchi Co., Ltd.), an inlet temperature of 205 ° C., an outlet temperature of 103 ° C., an air volume of 12.4 m 3 / min, The α-glucan powder is set by spray drying and setting the disk rotation speed at 18,000 rpm and the raw material supply speed at 23 kg / hour. Each prepared by about 2 kg, and a test sample 1-6.
 被験試料1~6について、それぞれ約20μgを下記条件によるゲル濾過HPLCに供し、重量平均分子量(Mw)及び数平均分子量(Mn)を測定するとともに、Mw/Mnを求めた。なお、重量平均分子量(Mw)と数平均分子量(Mn)は、分子量測定用プルラン標準品(株式会社林原製)のゲル濾過HPLCクロマトグラムに基づき作成した検量線に基づき、被験試料の同クロマトグラムを、分子量分布解析ソフトウェアで解析することにより求めた。
(ゲル濾過HPLC条件)
カラム:TSK GEL α-M(東ソー株式会社製造)を2本連結
溶離液:10mM リン酸緩衝液(pH7.0)
流 速:0.3mL/分
カラム温度:40℃
検出器:示差屈折計(RID10A、株式会社島津製作所製造)
解析ソフトウェア:データ解析ソフトウェア(商品名「LCソリューションGPCソフトウェア」、株式会社島津製作所社製造)
About 20 μg of each of the test samples 1 to 6 was subjected to gel filtration HPLC under the following conditions, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured, and Mw / Mn was determined. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are the same chromatogram of the test sample based on a calibration curve prepared based on a gel filtration HPLC chromatogram of a pullulan standard product for molecular weight measurement (manufactured by Hayashibara Co., Ltd.). Was obtained by analyzing with molecular weight distribution analysis software.
(Gel filtration HPLC conditions)
Column: TSK GEL α-M (manufactured by Tosoh Corporation), 2 linked eluent: 10 mM phosphate buffer (pH 7.0)
Flow rate: 0.3 mL / min Column temperature: 40 ° C
Detector: differential refractometer (RID10A, manufactured by Shimadzu Corporation)
Analysis software: Data analysis software (trade name “LC Solution GPC Software”, manufactured by Shimadzu Corporation)
 また、被験試料1~6について、加水分解の程度を知るための指標としてグルコース当量(DE)を測定した。さらに、被験試料1~6をそれぞれ固形物濃度20質量%になるよう脱イオン水に溶解し、冷水可溶性を判定した。またさらに、被験試料1~6を固形物濃度30質量%の水溶液とし、それぞれの溶液について、動的粘弾性レオメーター(商品名「MCR102」、株式会社アントンパールジャパン製造)を用いて35℃で粘度を測定した。なお、固形物濃度30質量%の水溶液の粘度は、35℃、せん断速度10.8/秒の条件下でのせん断粘度として表した。結果を表1にまとめた。 In addition, for the test samples 1 to 6, glucose equivalent (DE) was measured as an index for knowing the degree of hydrolysis. Further, each of the test samples 1 to 6 was dissolved in deionized water so as to have a solid concentration of 20% by mass, and the solubility in cold water was determined. Furthermore, test samples 1 to 6 were made into aqueous solutions having a solid concentration of 30% by mass, and each solution was measured at 35 ° C. using a dynamic viscoelastic rheometer (trade name “MCR102” manufactured by Anton Pearl Japan Co., Ltd.). The viscosity was measured. The viscosity of an aqueous solution having a solid concentration of 30% by mass was expressed as a shear viscosity under conditions of 35 ° C. and a shear rate of 10.8 / sec. The results are summarized in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表1に見られるとおり、被験試料1、すなわち、耐熱性α-アミラーゼを作用させていない、ワキシーコーンスターチを単に糊化したものは、固形物濃度30質量%の糊化液の粘度が26,700mPa・sと高粘度を示し、ハンドリングに難があった。また、高粘度でゲル濾過HPLCによる分子量分布分析に供するための前処理が行えず、重量平均分子量(Mw)、数平均分子量(Mn)を測定することはできなかった。さらに、被験試料1は水溶性に劣り、冷水可溶性を有していなかった。 As can be seen from Table 1, the test sample 1, that is, the gelatinized waxy corn starch not treated with thermostable α-amylase, has a viscosity of 26,700 mPa・ S showed high viscosity and had difficulty in handling. In addition, pretreatment for high molecular weight distribution analysis by gel filtration HPLC could not be performed, and weight average molecular weight (Mw) and number average molecular weight (Mn) could not be measured. Furthermore, test sample 1 was inferior in water solubility and did not have cold water solubility.
 一方、耐熱性α-アミラーゼを少量作用させて調製した被験試料2~5においては、アミラーゼの作用量が多くなるにつれて、糊化ワキシーコーンスターチの分解の程度が大きくなり、重量平均分子量(Mw)、数平均分子量(Mn)が低下し、Mw/Mnが小さくなった。また、被験試料2~5は、重量平均分子量(Mw)が2,560~183kDa、Mw/Mnが3.95~8.09の範囲を示し、被験試料1の場合とは異なり冷水可溶性を有していた。さらに、被験試料2~5の固形物濃度30質量%の水溶液の粘度は、アミラーゼの作用量が多いもの、すなわち、加水分解の程度が大きいものほど低い値を示し、2,330~220mPa・sであった。一方、耐熱性α-アミラーゼをワキシーコーンスターチ固形物当たり0.02質量%作用させて調製した被験試料6は重量平均分子量(Mw)が39.1kDaと小さく、Mw/Mnが35.9と大きい値を示し、その粘度は、固形物濃度30質量%の水溶液において、57mPa・sと低い値であった。 On the other hand, in test samples 2 to 5 prepared by the action of a small amount of thermostable α-amylase, as the amount of amylase increases, the degree of degradation of gelatinized waxy corn starch increases, and the weight average molecular weight (Mw), The number average molecular weight (Mn) decreased and Mw / Mn decreased. Test samples 2 to 5 have a weight average molecular weight (Mw) in the range of 2,560 to 183 kDa and Mw / Mn in a range of 3.95 to 8.09. Unlike test sample 1, the test samples 2 to 5 have cold water solubility. Was. Further, the viscosity of the aqueous solution having a solid concentration of 30% by mass in the test samples 2 to 5 shows a lower value as the amount of amylase acting increases, that is, as the degree of hydrolysis increases, 2,330 to 220 mPa · s. Met. On the other hand, the test sample 6 prepared by acting 0.02% by mass of heat-resistant α-amylase per waxy corn starch solid has a small weight average molecular weight (Mw) of 39.1 kDa and a large value of Mw / Mn of 35.9. The viscosity was as low as 57 mPa · s in an aqueous solution having a solid concentration of 30% by mass.
<実験2:各種α-グルカンの可食性フィルム素材としての適性>
 実験1で得た被験試料1乃至6を原材料として、可塑剤を添加することなくそれぞれをフィルムに成形し、得られたフィルムの性質を調べることにより、各種α-グルカンの可食性フィルム素材としての適性(フィルム適性)を調べた。
<Experiment 2: Suitability of various α-glucans as edible film materials>
Using the test samples 1 to 6 obtained in Experiment 1 as raw materials, each was formed into a film without adding a plasticizer, and the properties of the obtained films were examined, whereby various α-glucans as edible film materials were used. Suitability (film suitability) was examined.
 実験1で得た被験試料1~6を、それぞれ固形物濃度30質量%となるよう脱イオン水に均一に溶解し、遠心分離(3,000rpm、10分)して脱泡した後、適量をポリエチレンテレフタレート(PET)製の平板上にベーカーアプリケーター(商品名「YBA」、ヨシミツ精機株式会社製造)を用いて塗布、延伸させ、室温で1夜以上自然乾燥させる方法でフィルム化を試みたところ、被験試料6については、水溶液の粘度が低いためか造膜性が悪く、フィルムに成形することが困難であった。一方、被験試料1~5はフィルム成形が可能であったことから、それぞれから厚さ約40μmのフィルムを調製し、フィルム試料1~5とした。 The test samples 1 to 6 obtained in Experiment 1 were uniformly dissolved in deionized water so that the solid concentration would be 30% by mass, and defoamed by centrifugation (3,000 rpm, 10 minutes). When we tried to form a film on a flat plate made of polyethylene terephthalate (PET) using a baker applicator (trade name “YBA”, manufactured by Yoshimitsu Seiki Co., Ltd.) About the test sample 6, since the viscosity of aqueous solution was low, film forming property was bad, and it was difficult to shape | mold into a film. On the other hand, since the test samples 1 to 5 could be formed into films, a film having a thickness of about 40 μm was prepared from each of the test samples 1 to 5 as film samples 1 to 5.
 得られたフィルム試料1~5について、それぞれ、その外観を目視にて観察し、(○):厚さが均一で表面が滑らかな良好なフィルム;、及び、(×):厚さが不均一で表面にむらがあるフィルム;の2段階でフィルム適性を評価した。また、各フィルム試料について透明性を目視にて観察し、(○):透明;及び(×):濁りあり;の2段階で評価した。さらに、各フィルム試料について1cm角に裁断したフィルムを30℃に保持した200mLの脱イオン水に投入し、撹拌下、フィルムが目視で完溶するまでの時間を測定し、(○):撹拌下で1分間以内に完溶する;及び(×):撹拌下で1分間保持しても溶け残りがある;の2段階でフィルムの水溶性を評価した。結果を表2に示した。 The external appearance of each of the obtained film samples 1 to 5 was visually observed, (◯): a good film having a uniform thickness and a smooth surface; and (×): a non-uniform thickness. The film suitability was evaluated in two stages: a film with uneven surface. In addition, the transparency of each film sample was visually observed and evaluated in two stages: (◯): transparent; and (x): turbid. Furthermore, the film cut into 1 cm square for each film sample was put into 200 mL of deionized water maintained at 30 ° C., and the time until the film was completely dissolved visually was measured under stirring. The film was evaluated for water solubility in two stages: complete dissolution within 1 minute; The results are shown in Table 2.
 また、フィルム試料1~5から、直径20mmの円形に切り取ったものをそれぞれ10枚ずつ調製し、各10枚を前記した突刺し破断強度試験に供し、各フィルム試料の突刺し破断強度の平均値を求めた。結果を表2に併せて示した。 In addition, 10 pieces of each of the film samples 1 to 5 cut into a circle having a diameter of 20 mm were prepared, each 10 pieces were subjected to the piercing break strength test, and the average value of the piercing break strength of each film sample was prepared. Asked. The results are also shown in Table 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表2に見られるとおり、ワキシーコーンスターチを単に糊化した被験試料1から調製したフィルム試料1は、表面にむらがあり透明性に欠けたフィルムであり、上記水溶性試験で完溶せず、水溶性に劣るものであった。一方、フィルム試料2~5は、厚さが均一で表面が滑らかな、透明性、水溶性に優れるフィルムであった。なお、被験試料6については、上述のとおり、粘度が低く、フィルムに成形すること自体が困難でフィルム試料6は得られなかった。 As seen in Table 2, film sample 1 prepared from test sample 1 simply gelatinized waxy corn starch is a film with uneven surface and lacking transparency, and does not completely dissolve in the water solubility test. It was inferior in nature. On the other hand, film samples 2 to 5 were films having a uniform thickness, a smooth surface, and excellent transparency and water solubility. In addition, about the test sample 6, as above-mentioned, the viscosity was low and it was difficult to shape | mold into a film itself, and the film sample 6 was not obtained.
 以上のとおり、被験試料2~5は、可塑剤を用いることなく良好な可食性フィルムを調製するための素材としての適性を有しており、一方、被験試料1及び6はその適性に欠けるものであった。 As described above, test samples 2 to 5 have suitability as a material for preparing a good edible film without using a plasticizer, while test samples 1 and 6 lack suitability. Met.
 実験1及び2の結果から、被験試料2~5及びフィルム試料2~5、すなわち、ワキシースターチにアミラーゼを作用させ部分分解することにより得られる、重量平均分子量(Mw)が150kDa乃至3,000kDaの範囲、Mw/Mnが10未満であるα-グルカンは、冷水可溶性に優れ、適度の粘度を保持する性質を有しており、また、当該α-グルカンを成形することにより、均一、透明で水溶性に優れる可食性フィルムが得られることが判明した。 From the results of Experiments 1 and 2, the weight average molecular weight (Mw) obtained by subjecting test samples 2 to 5 and film samples 2 to 5, ie, waxy starch, to amylase and partially decomposing it is 150 kDa to 3,000 kDa. Α-glucan having a range of Mw / Mn of less than 10 is excellent in cold water solubility and has a property of maintaining an appropriate viscosity. Also, by molding the α-glucan, it is uniform, transparent and water-soluble. It was found that an edible film having excellent properties can be obtained.
<実験3:非還元末端にイソマルトース構造を有するα-グルカンの調製(その1)>
 本実験及び実験4では、上記α-グルカンに、さらに優れた性質を付与することを目的として、α-グルカンに糖転移酵素をさらに作用させ、非還元末端にイソマルトース構造を有するα-グルカンを調製した。
<Experiment 3: Preparation of α-glucan having isomaltose structure at non-reducing end (part 1)>
In this experiment and experiment 4, for the purpose of imparting further superior properties to the α-glucan, a glycosyltransferase is further allowed to act on the α-glucan, and an α-glucan having an isomaltose structure at the non-reducing end is obtained. Prepared.
 すなわち、ワキシーコーンスターチ固形物当たりの耐熱性α-アミラーゼ(商品名「スピターゼHK」、ナガセケムテックス株式会社製造)の使用量を0.002質量%とし、それ以外の操作は実験1と同様にしてα-グルカン含有溶液を得た。このα-グルカン含有溶液に、本願と同じ出願人による国際公開第WO2008/136331号パンフレットにおいて開示したバチルス・サーキュランスPP710株由来α-グルコシル転移酵素の精製標品をα-グルカンの固形物1グラム当たり0.25、0.5、2.5、10又は25単位添加し、pH6.0、50℃で24時間作用させ140℃で10分間加熱することにより反応を停止させた。実験1と同様に精製した後、ディスク型噴霧乾燥装置(ニロ社製造)を用いて噴霧乾燥することによりα-グルカンをそれぞれ約2kgずつ調製し、被験試料7乃至11とした。 That is, the amount of heat-resistant α-amylase (trade name “Spitase HK”, manufactured by Nagase ChemteX Corporation) per waxy corn starch solid was 0.002% by mass, and the other operations were the same as in Experiment 1. An α-glucan-containing solution was obtained. To this α-glucan-containing solution, 1 g of solid α-glucan was obtained by purifying a purified preparation of α-glucosyltransferase derived from Bacillus circulans PP710 disclosed in the pamphlet of International Publication No. WO2008 / 136331 by the same applicant as the present application. The reaction was stopped by adding 0.25, 0.5, 2.5, 10 or 25 units per unit, acting at pH 6.0, 50 ° C. for 24 hours and heating at 140 ° C. for 10 minutes. After purification in the same manner as in Experiment 1, about 2 kg each of α-glucan was prepared by spray drying using a disk type spray drying apparatus (manufactured by Niro Co., Ltd.), and used as test samples 7 to 11.
 被験試料7~11について、実験1と同様に重量平均分子量(Mw)、数平均分子量(Mn)、Mw/Mnを求めた。また、各被験試料において、非還元末端にイソマルトース構造を有するα-グルカンを含有する程度を評価するため、被験試料7~11の濃度1w/v%水溶液を前記したイソマルトデキストラナーゼ消化試験に供し、得られた消化物中のイソマルトース含量を測定した。さらに、被験試料7~11のグルコース当量(DE)、冷水可溶性を評価し、それぞれから調製した固形物濃度30質量%の溶液について、粘度を実験1と同様に評価した。加えて、被験試料7~11について耐老化性を評価した。耐老化性については、それぞれ固形物濃度30質量%の水溶液を6℃で1週間保存し、(×):保存1週間の時点で水溶液に老化による白濁が認められる;(○):保存1週間の時点で透明な水溶液の状態を維持している;の2段階で評価した。結果を表3にまとめた。なお、実験1で得た、ワキシーコーンスターチ懸濁液に耐熱性α-アミラーゼをワキシーコーンスターチ固形物当たり0.002質量%添加して調製した被験試料3の結果を対照として表3に併記した。 For Test Samples 7 to 11, the weight average molecular weight (Mw), the number average molecular weight (Mn), and Mw / Mn were determined in the same manner as in Experiment 1. In addition, in order to evaluate the degree of containing α-glucan having an isomaltose structure at the non-reducing end in each test sample, the above-described isomalt-dextranase digestion test was carried out using a 1 w / v% aqueous solution of test samples 7-11. The isomaltose content in the obtained digest was measured. Furthermore, the glucose equivalent (DE) and cold water solubility of the test samples 7 to 11 were evaluated, and the viscosity of each of the solutions having a solid concentration of 30% by mass prepared from each of the test samples 7 to 11 was evaluated in the same manner as in Experiment 1. In addition, aging resistance of the test samples 7 to 11 was evaluated. For aging resistance, each aqueous solution with a solid concentration of 30% by mass was stored at 6 ° C. for 1 week, (×): White turbidity due to aging was observed in the aqueous solution at 1 week of storage; (◯): Storage for 1 week The state of the clear aqueous solution is maintained at the time of (1); The results are summarized in Table 3. The results of Test Sample 3 prepared by adding 0.002% by mass of heat-resistant α-amylase to the waxy corn starch suspension obtained in Experiment 1 per waxy corn starch solid are also shown in Table 3 as a control.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表3に見られるとおり、ワキシーコーンスターチに0.002質量%の耐熱性α-アミラーゼを作用させ、さらにα-グルコシル転移酵素を作用させて得た被験試料7~11は、そのイソマルトデキストラナーゼ消化により、消化物の固形物当たり1.57質量%~25.4質量%イソマルトースが生成していることが確認できたことから、その程度こそ異なるものの、いずれも非還元末端にイソマルトース構造を有するα-グルカン分子を含むα-グルカン混合物であることが確認された。 As shown in Table 3, test samples 7 to 11 obtained by allowing 0.002% by mass of thermostable α-amylase to act on waxy corn starch and further causing α-glucosyltransferase to act on the isomaltodextranase Digestion confirmed that 1.57% to 25.4% by weight of isomaltose was produced per solid of digested material, and although the degree was different, all of them had an isomaltose structure at the non-reducing end. It was confirmed to be an α-glucan mixture containing α-glucan molecules having
 被験試料7~11においては、α-グルコシル転移酵素の作用量が多くなるほど、得られる被験試料のMw/Mn(分散度)は増加し、作用量が25単位/g-基質と最も多い被験試料11の場合には62.3まで増加した。被験試料7~11は、その重量平均分子量(Mw)において、被験試料3と比べ大きな変化はなかったものの、α-グルコシル転移酵素の作用により、Mw/Mnが明らかに増加し、α-グルカンにおける分子種の分子量のばらつきが生じていた。被験試料7~11の固形物濃度30質量%の水溶液の粘度は、651~990mPa・sと、α-グルコシル転移酵素を作用させていない被験試料3のそれより若干低かったものの、大きな変動は認められなかった。また、被験試料7~11の内、被験試料7は被験試料3と同様に、固形物濃度30質量%の水溶液を6℃で1週間保持する耐老化性試験において、水溶液に白濁が認められ耐老化性が認められなかったものの、被験試料8乃至11は、同耐老化性試験において、保存1週間の時点で透明な水溶液の状態を維持する顕著な耐老化性を有することが判明した。 In test samples 7-11, the greater the amount of action of α-glucosyltransferase, the greater the Mw / Mn (dispersity) of the obtained test sample, and the test sample with the largest amount of action of 25 units / g-substrate. In the case of 11, it increased to 62.3. Although the test samples 7 to 11 had no significant change in the weight average molecular weight (Mw) compared to the test sample 3, Mw / Mn was clearly increased by the action of α-glucosyltransferase, and the α-glucan Variation in molecular weight of molecular species occurred. The viscosities of the aqueous solutions of the test samples 7 to 11 having a solid concentration of 30% by mass were 651 to 990 mPa · s, which were slightly lower than those of the test sample 3 to which no α-glucosyltransferase was allowed to act. I couldn't. In addition, among the test samples 7 to 11, as in the test sample 3, the test sample 7 showed white turbidity in the aging resistance test in which an aqueous solution with a solid concentration of 30% by mass was held at 6 ° C. for 1 week. Although no aging property was observed, it was found in the same aging resistance test that the test samples 8 to 11 had remarkable aging resistance that maintained the state of a transparent aqueous solution at the time of storage for 1 week.
<実験4:非還元末端にイソマルトース構造を有するα-グルカンの調製(その2)> <Experiment 4: Preparation of α-glucan having isomaltose structure at non-reducing end (part 2)>
 実験3の場合よりも重量平均分子量(Mw)が小さいα-グルカンを原料として非還元末端にイソマルトース構造を有するα-グルカンを調製し、実験3と同様に調べた。 Α-glucan having an isomaltose structure at the non-reducing end was prepared from α-glucan having a weight average molecular weight (Mw) smaller than that in Experiment 3, and examined in the same manner as in Experiment 3.
 ワキシーコーンスターチ固形物当たりの耐熱性α-アミラーゼの使用量を0.004質量%とした以外は実験1と同様に処理し、より分子量が低下したα-グルカンを得た。このα-グルカンに、上記と同様にバチルス・サーキュランスPP710株由来α-グルコシル転移酵素の精製標品をα-グルカンの固形物1グラム当たり0.5、1.0、2.5又は5.0単位添加し、pH6.0、50℃で24時間作用させ140℃で10分間加熱することにより反応を停止させた。実験3と同様に精製した後、ディスク型噴霧乾燥装置(ニ口社製造)を用いて噴霧乾燥することによりα-グルカンをそれぞれ約2kgずつ調製し、被験試料12乃至15とした。 Treatment was performed in the same manner as in Experiment 1 except that the amount of heat-resistant α-amylase used per waxy corn starch solid was changed to 0.004% by mass to obtain α-glucan having a further reduced molecular weight. In this α-glucan, a purified preparation of α-glucosyltransferase derived from Bacillus circulans PP710 strain was added to the α-glucan at 0.5, 1.0, 2.5 or 5. The reaction was stopped by adding 0 units, acting at pH 6.0, 50 ° C. for 24 hours and heating at 140 ° C. for 10 minutes. After purification in the same manner as in Experiment 3, about 2 kg each of α-glucan was prepared by spray drying using a disk type spray drying apparatus (manufactured by Niguchi Co., Ltd.), and used as test samples 12 to 15.
 また、被験試料12~15についても実験3と同様に重量平均分子量(Mw)、数平均分子量(Mn)、Mw/Mn、イソマルトデキストラナーゼ消化物中のイソマルトース含量、グルコース当量(DE)を測定し、冷水可溶性、固形物濃度30質量%の溶液についての粘度及び耐老化性を評価した。結果を表4にまとめた。なお、実験1で得た、ワキシーコーンスターチ懸濁液に耐熱性α-アミラーゼをワキシーコーンスターチ固形物当たり0.004質量%添加して調製した被験試料4の結果を対照として表4に併記した。 For Test Samples 12 to 15, as in Experiment 3, the weight average molecular weight (Mw), number average molecular weight (Mn), Mw / Mn, isomaltose content in isomaltdextranase digest, glucose equivalent (DE) Was measured, and the viscosity and aging resistance of a solution with solubility in cold water and a solid concentration of 30% by mass were evaluated. The results are summarized in Table 4. The results of Test Sample 4 prepared by adding 0.004% by mass of heat-resistant α-amylase per waxy corn starch solid to the waxy corn starch suspension obtained in Experiment 1 are also shown in Table 4 as a control.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 表4にみられるとおり、ワキシーコーンスターチに0.004質量%の耐熱性α-アミラーゼを作用させ、さらにα-グルコシル転移酵素を作用させて得た被験試料12~15は、そのイソマルトデキストラナーゼ消化により、消化物の固形物当たり1.5質量%~20.6質量%のイソマルトースが生成していることが確認できたことから、実験3で得た被験試料7~11の場合と同様に、いずれも非還元末端にイソマルトース構造を有するα-グルカン分子を含むことが確認された。 As seen in Table 4, test samples 12 to 15 obtained by allowing 0.004% by mass of thermostable α-amylase to act on waxy corn starch and further causing α-glucosyltransferase to act on the isomaltodextranase Since it was confirmed that the digestion produced 1.5% to 20.6% by mass of isomaltose per solid of the digested product, the same as in the case of test samples 7 to 11 obtained in Experiment 3 In addition, it was confirmed that both included an α-glucan molecule having an isomaltose structure at the non-reducing end.
 また、被験試料12~15においては、重量平均分子量(Mw)が365~449kDaを示し、実験3で得た被験試料7~11の約1/3の値を示し、より低分子のα-グルカンであることが確認された。被験試料12~15のMw/Mnは、8.3~37.5の値を示した。被験試料12~15は、その重量平均分子量(Mw)において、被験試料4と比べ大きな変化はなかったものの、α-グルコシル転移酵素の作用量が多くなるとMw/Mnが明らかに増加した。なお、被験試料12~15のグルコース当量(DE)は0.46~2.76の範囲を示した。被験試料12~15の固形物濃度30質量%の水溶液の粘度は、294~525mPa・sと、α-グルコシル転移酵素を作用させていない被験試料4と大きな変動は認められなかった。また、被験試料12~15の内、被験試料12は被験試料4と同様に、固形物濃度30質量%の水溶液を6℃で1週間保持する耐老化性試験において水溶液に白濁が認められ、耐老化性が認められなかったものの、被験試料13乃至15は、同耐老化性試験において、保存1週間の時点で透明な水溶液の状態を維持する顕著な耐老化性を有することが判明した。 In Test Samples 12 to 15, the weight average molecular weight (Mw) is 365 to 449 kDa, about 1/3 that of Test Samples 7 to 11 obtained in Experiment 3, and α-glucan having a lower molecular weight. It was confirmed that. Mw / Mn of test samples 12 to 15 showed values of 8.3 to 37.5. Although the test samples 12 to 15 did not change much in the weight average molecular weight (Mw) as compared to the test sample 4, Mw / Mn was clearly increased as the amount of action of α-glucosyltransferase increased. The glucose equivalent (DE) of test samples 12 to 15 was in the range of 0.46 to 2.76. The viscosity of the aqueous solution of the test samples 12 to 15 having a solid concentration of 30% by mass was 294 to 525 mPa · s, which was not significantly different from that of the test sample 4 in which no α-glucosyltransferase was allowed to act. In addition, among the test samples 12 to 15, as in the test sample 4, the test sample 12 showed white turbidity in the aging resistance test in which an aqueous solution having a solid concentration of 30% by mass was maintained at 6 ° C. for 1 week. Although no aging property was observed, it was found in the same aging resistance test that the test samples 13 to 15 had remarkable aging resistance that maintained the state of a transparent aqueous solution at the time of storage for 1 week.
 実験3及び4の結果、特に表3及び表4に示すとおり、イソマルトデキストラナーゼ消化物の固形物当たりのイソマルトース含量が1.57質量%又は1.50質量%と低い、すなわち、非還元末端にイソマルトース構造を有するα-グルカンのイソマルトデキストラナーゼ消化物に含まれるイソマルトース含量が低い被験試料7及び被験試料12は耐老化性を有さなかった。一方、当該イソマルトース含量が3.83質量%以上を示す被験試料8~11及び被験試料13~15が耐老化性を有しており、上記実験結果は、α-グルカンにα-グルコシル転移酵素を作用させることにより、非還元末端にイソマルトース構造を3質量%以上導入含有させれば、原料としたα-グルカンが有する性質を維持しつつ、さらに耐老化性を付与することができることが明らかになった。 As a result of Experiments 3 and 4, in particular, as shown in Tables 3 and 4, the isomaltose dextranase digest is digested with a low isomaltose content of 1.57% by mass or 1.50% by mass. Test sample 7 and test sample 12 having low isomaltose content contained in the digest of isomaltdextranase of α-glucan having an isomaltose structure at the reducing end did not have aging resistance. On the other hand, test samples 8 to 11 and test samples 13 to 15 having an isomaltose content of 3.83% by mass or more have aging resistance, and the above experimental results indicate that α-glucan is converted to α-glucosyltransferase. It is clear that if the isomaltose structure is introduced and incorporated at 3% by mass or more at the non-reducing end, the aging resistance can be further imparted while maintaining the properties of the α-glucan used as a raw material. Became.
<実験5:非還元末端にイソマルトース構造を有するα-グルカンの可食性フィルム素材としての適性>
 実験3及び4で得た被験試料7~15を原材料として実験2と同様の操作により厚さ約40~50μmのフィルムをそれぞれ調製し、フィルム試料7~15とした。次いで、実験2と同様に、フィルム試料7~15について、外観(フィルム適性)、透明性、水溶性を評価するとともに、突刺し破断強度を測定した。重量平均分子量(Mw)が1,210kDa以上のα-グルカンを原料としたフィルム試料7~11の結果を表5に、重量平均分子量(Mw)が500kDa未満のα-グルカンを原料としたフィルム試料12~15の結果を表6に、それぞれまとめた。
<Experiment 5: Suitability of α-glucan having isomaltose structure at non-reducing end as edible film material>
Films having a thickness of about 40 to 50 μm were prepared using test samples 7 to 15 obtained in Experiments 3 and 4 as raw materials in the same manner as in Experiment 2, and designated as film samples 7 to 15, respectively. Next, as in Experiment 2, the film samples 7 to 15 were evaluated for appearance (film suitability), transparency, and water solubility, and puncture breaking strength was measured. Table 5 shows the results of film samples 7 to 11 using α-glucan having a weight average molecular weight (Mw) of 1,210 kDa or more as a raw material, and film samples using α-glucan having a weight average molecular weight (Mw) of less than 500 kDa as a raw material. The results of 12 to 15 are summarized in Table 6, respectively.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
 表5に見られるとおり、非還元末端にイソマルトース構造を有するα-グルカンであって、重量平均分子量(Mw)が1,210kDa以上のα-グルカンを用いて調製したフィルム試料7~10は、ワキシーコーンスターチをアミラーゼで部分分解して得たα-グルカンを用いて調製したフィルム試料3と同様に、透明性、水溶性に優れ、突刺し破断強度が2.0N/mm以上と強い優れた性質を有していた。しかしながら、被験試料11、すなわち、α-グルコシル転移酵素を作用させることによりMw/Mnの値が62.3まで増加したα-グルカンから調製したフィルム試料11は、非常に脆いものとなりフィルムを得ることが困難であった。 As seen in Table 5, film samples 7 to 10 prepared using α-glucan having an isomaltose structure at the non-reducing end and having a weight average molecular weight (Mw) of 1,210 kDa or more are as follows: Similar to film sample 3 prepared using α-glucan obtained by partially degrading waxy corn starch with amylase, it was excellent in transparency and water solubility, and puncture strength was as strong as 2.0 N / mm 2 or more. Had properties. However, the test sample 11, that is, the film sample 11 prepared from α-glucan whose Mw / Mn value increased to 62.3 by the action of α-glucosyltransferase, becomes very brittle and obtains a film. It was difficult.
 また、表6に見られるとおり、非還元末端にイソマルトース構造を有するα-グルカンであって、重量平均分子量(Mw)が500kDa未満のα-グルカンを用いて調製したフィルム試料12~14は、ワキシーコーンスターチをアミラーゼで部分分解して得たα-グルカンを用いて調製したフィルム試料4と同様に、透明性、水溶性に優れ、突刺し破断強度が2.0N/mm以上と強く、優れた性質を有していた。しかしながら、被験試料15、すなわち、α-グルコシル転移酵素を作用させることによりMw/Mnの値が37.5まで増加したα-グルカンから調製したフィルム試料15は、非常に脆いものとなりフィルムを得ることが困難であった。 Further, as seen in Table 6, film samples 12 to 14 prepared using α-glucan having an isomaltose structure at the non-reducing end and having a weight average molecular weight (Mw) of less than 500 kDa, Similar to film sample 4 prepared using α-glucan obtained by partially degrading waxy corn starch with amylase, it is excellent in transparency and water solubility, and has a strong puncture and break strength of 2.0 N / mm 2 or more. Had the same properties. However, the test sample 15, that is, the film sample 15 prepared from α-glucan whose Mw / Mn value increased to 37.5 by the action of α-glucosyltransferase, becomes very brittle and obtains a film. It was difficult.
 実験3、4及び5の結果から、ワキシーコーンスターチを糊化し、アミラーゼを作用させて得たα-グルカンに、さらにα-グルコシル転移酵素を作用させ、そのイソマルトデキストラナーゼ消化物におけるイソマルトース含量が3質量%超を示す程度に非還元末端にイソマルトース構造を有するα-グルカンは、顕著な耐老化性を有するものとなることが分かった。また、実験1、2から得られた結果と実験3、4及び5で得られた結果とを総合すると、重量平均分子量(Mw)が150kDa乃至3,000kDaの範囲、Mw/Mnが35.1以下である当該α-グルカンは、冷水可溶性を有し、適度な粘度を有しながらもハンドリングが良く、耐老化性や造膜性に優れ、かつ着色しにくいことから、本発明の品質改善剤の有効成分として適していることが明らかになった。 From the results of Experiments 3, 4 and 5, the α-glucan obtained by gelatinizing waxy corn starch and allowing amylase to act further causes α-glucosyltransferase to act, and the isomaltose content in the digest of isomalt-dextranase It was found that α-glucan having an isomaltose structure at the non-reducing end to an extent of more than 3% by mass has remarkable aging resistance. Further, when the results obtained from Experiments 1 and 2 and the results obtained in Experiments 3, 4 and 5 are combined, the weight average molecular weight (Mw) is in the range of 150 kDa to 3,000 kDa, and Mw / Mn is 35.1. The following α-glucan is soluble in cold water, has an appropriate viscosity, has good handling, is excellent in aging resistance and film-forming property, and is difficult to be colored. It became clear that it was suitable as an active ingredient.
<参考実験例1:α-グルカンのアミロース含有率>
 実験1、3及び4においてα-グルカンの原料として用いたワキシーコーンスターチ(商品名「ワキシーコーンスターチ Y」、株式会社J-オイルミルズ製造)と、後述する実施例3で得たα-グルカン、すなわち、重量平均分子量(Mw)が566kDa、Mw/Mnが13.2、そのイソマルトデキストラナーゼ消化物におけるイソマルトース含量が7.0質量%であるα-グルカンについてアミロース含有率を測定し比較した。さらに、参考値として、市販のコーンスターチ(商品名「昭和コーンスターチ」、敷島スターチ株式会社製造)及びハイアミロースコーンスターチ(商品名「デンプン トウモロコシ由来」、コード番号:S4180、シグマアルドリッチ社製造)のアミロース含有率についても同様に測定した。
<Reference Experimental Example 1: Amylose content of α-glucan>
Waxy corn starch (trade name “waxy corn starch Y”, manufactured by J-Oil Mills Co., Ltd.) used as a raw material for α-glucan in Experiments 1, 3 and 4, and α-glucan obtained in Example 3 described later, The amylose content was measured and compared for α-glucan having a weight average molecular weight (Mw) of 566 kDa, Mw / Mn of 13.2, and an isomaltose dextranase digested isomaltose content of 7.0% by mass. Furthermore, as reference values, amylose content of commercially available corn starch (trade name “Showa Corn Starch”, manufactured by Shikishima Starch Co., Ltd.) and high amylose corn starch (trade name “starch corn derived”, code number: S4180, manufactured by Sigma Aldrich) It measured similarly about.
 各試料のアミロース含有率は、前述のとおり、農林水産省告示第332号、標準計測方法に示されているアミロース含有率測定法に準じ、アミロースとヨウ素の呈色反応に基づき測定した。なお、本実験例では、試薬級アミロース(商品名「ポテトアミロース Type III」、シグマアルドリッチ社製造)を用い、アミロース標準溶液を調製し、検量線を作成した。結果を表7に示す。 As described above, the amylose content of each sample was measured based on the color reaction of amylose and iodine according to the amylose content measurement method shown in the Ministry of Agriculture, Forestry and Fisheries Notification No. 332, Standard Measurement Method. In this experimental example, an amylose standard solution was prepared using a reagent grade amylose (trade name “Potatoamylose Type III” manufactured by Sigma Aldrich), and a calibration curve was prepared. The results are shown in Table 7.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 表7に見られるとおり、ワキシーコーンスターチ及び実施例3で得たα-グルカンのアミロース含有率(質量%)は、本測定法においてそれぞれ、13.4質量%及び10.3質量%と測定された。一方、市販のコーンスターチ及びハイアミロースコーンスターチのアミロース含有率は、それぞれ、35.9質量%及び46.9質量%と測定された。一般に、アミロース含有率は、ハイアミロースコーンスターチ>コーンスターチ>ワキシーコーンスターチの順に高いと言われており、上記の測定値はこの従来からの知見を裏付けるものであった。 As seen in Table 7, the amylose content (% by mass) of waxy corn starch and α-glucan obtained in Example 3 was measured to be 13.4% by mass and 10.3% by mass, respectively, in this measurement method. . On the other hand, the amylose content of commercially available corn starch and high amylose corn starch was measured to be 35.9% by mass and 46.9% by mass, respectively. In general, the amylose content is said to be higher in the order of high amylose corn starch> corn starch> waxy corn starch, and the above measured values support this conventional knowledge.
 因みに、本発明の品質改善剤が有効成分とするα-グルカンは、ワキシースターチをアミラーゼで部分分解した後、α-グルコシル転移酵素を作用させ、非還元末端にイソマルトース構造を有するα-グルカンを生成させることにより製造されるものである。アミラーゼ及びα-グルコシル転移酵素は、いずれも澱粉枝切り酵素のようにワキシースターチにおけるα-1,6結合を介した分岐構造を分解する酵素ではないことから、アミラーゼ及びα-グルコシル転移酵素の作用によりワキシースターチから直鎖状のアミロースが生成することはなく、反応産物においてアミロース含有率が増加することはない。したがって、本測定法において、本発明の品質改善剤が有効成分とするα-グルカンがワキシーコーンスターチと同等以下のアミロース含有率を示したことは、当該α-グルカンがワキシーコーンスターチを原料として製造されたものであることを物語るものである。言い換えれば、重量平均分子量(Mw)が150kDa以上のα-グルカンであって、本測定方法によりアミロース含有率が15質量%未満を示すα-グルカンは、少なくともワキシースターチを原料として得られたものであるということができる。 Incidentally, α-glucan, which is an active ingredient of the quality improving agent of the present invention, is obtained by partially decomposing waxy starch with amylase and then allowing α-glucosyltransferase to act to produce α-glucan having an isomaltose structure at the non-reducing end. It is manufactured by generating. Since amylase and α-glucosyltransferase are not enzymes that degrade the branched structure through α-1,6 bonds in waxy starch like starch debranching enzyme, the action of amylase and α-glucosyltransferase Does not produce linear amylose from waxy starch and does not increase the amylose content in the reaction product. Therefore, in this measurement method, α-glucan containing the quality improving agent of the present invention as an active ingredient showed an amylose content equal to or lower than that of waxy corn starch. This α-glucan was produced using waxy corn starch as a raw material. It tells that it is a thing. In other words, α-glucan having a weight average molecular weight (Mw) of 150 kDa or more and having an amylose content of less than 15% by this measurement method is obtained at least from waxy starch. It can be said that there is.
 以下、実験6乃至16において、本発明の品質改善剤の有効成分であるα-グルカンが有している種々の機能について詳細を説明する。 Hereinafter, in Experiments 6 to 16, various functions of α-glucan, which is an active ingredient of the quality improving agent of the present invention, will be described in detail.
<実験6:本α-グルカンの冷凍保存時の耐老化性>
 後述する実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの冷凍耐性を検討評価した。実施例1の方法で得たα-グルカンを、固形物濃度30質量%になるよう脱イオン水に溶解して、被験糖質溶液とし、冷解凍回数0回の試料とした。本被験糖質溶液を試験管に3gずつ分注し、-20℃下で冷凍した後、自然解凍する工程を経たものを冷解凍回数1回の試料とした。同様にして、冷解凍回数が3回及び5回の試料を調製し、各冷解凍回数の被験糖質溶液の粘度を、動的粘弾性レオメーター(商品名「MCR102」、株式会社アントンパールジャパン製造)を用いて30℃で測定した。結果を図1に示した。
<Experiment 6: Aging resistance of this α-glucan during freezing storage>
The freezing tolerance of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improver of the present invention, obtained by the method of Example 1 described later was examined and evaluated. The α-glucan obtained by the method of Example 1 was dissolved in deionized water so as to have a solid concentration of 30% by mass to obtain a test carbohydrate solution, which was a sample with 0 cold thawing cycles. 3 g of this test carbohydrate solution was dispensed into a test tube, frozen at −20 ° C., and then naturally thawed to obtain a sample with one cold thawing. Similarly, samples with 3 and 5 cold thawing cycles were prepared, and the viscosity of the test carbohydrate solution with each cold thawing cycle was measured using a dynamic viscoelastic rheometer (trade name “MCR102”, Anton Pearl Japan Co., Ltd.). Measured at 30 ° C. The results are shown in FIG.
 図1に示すように、実施例1の方法で得た、非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験糖質溶液は、冷凍前から1,400mPa・s程度の粘度を保有しており、この粘度は、冷解凍を5回繰り返してもほとんど変化することがなく維持されていた。すなわち、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、冷解凍に対して非常に優れた耐老化性を有していることが判明した。 As shown in FIG. 1, the test carbohydrate solution prepared by using the α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has a viscosity of about 1,400 mPa · s before freezing. This viscosity was maintained with almost no change even after repeated cold thawing 5 times. That is, it has been found that α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has very excellent aging resistance against cold thawing.
<実験7:本α-グルカンの液化澱粉に対する老化調節性>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの老化調節性について、市販のワキシーコーンスターチ由来デキストリン2種と比較検討評価した。実施例1の方法で得たα-グルカン及びワキシーコーンスターチ由来のデキストリン2種(商品名「パインデックス#100」、松谷化学工業株式会社製造、及び商品名「サンデック#30」、三和澱粉工業株式会社製造)をそれぞれ固形物濃度10質量%になるよう脱イオン水に溶解して、糖質溶液とした。次いで、タピオカ澱粉を固形物濃度30質量%となるよう純水に懸濁し、これに塩化カルシウムを最終濃度1mMとなるように添加した後、pH6.0に調整し、この澱粉懸濁液に、α-アミラーゼ(商品名「スピターゼHK」、ナガセケムテックス株式会社製造)を、固形物1グラム当たり10単位添加し、連続液化装置に流速1L/分で通液しながら、100℃で25分間、次いで、140℃で5分間加熱して酵素反応を停止し、タピオカ澱粉部分分解物溶液を得た。このタピオカ澱粉部分分解物を固形物濃度10質量%になるよう脱イオン水に溶解して、澱粉液化液として、老化調節試験に供した。各糖質溶液と澱粉液化液を質量で等量混合し、それぞれ被験溶液1~3とした。被験溶液1~3の組成を表8に示した。各被験溶液を試験管に分注し、密閉状態で、4℃で5日間冷蔵保存した後、老化調節の指標として、濁度(Abs720nm)を測定した。結果を図2にまとめた。
<Experiment 7: Aging control of α-glucan to liquefied starch>
Comparison of aging control of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 and comparison with two commercially available dextrins derived from waxy corn starch evaluated. Two dextrins derived from α-glucan and waxy corn starch obtained by the method of Example 1 (trade name “Paindex # 100”, manufactured by Matsutani Chemical Industry Co., Ltd., and trade name “Sandeck # 30”, Sanwa Starch Co., Ltd. (Manufactured by the company) was dissolved in deionized water to a solids concentration of 10% by mass to obtain a saccharide solution. Next, tapioca starch was suspended in pure water so as to have a solid concentration of 30% by mass, and calcium chloride was added thereto so as to have a final concentration of 1 mM, and then adjusted to pH 6.0. α-Amylase (trade name “Spitase HK”, manufactured by Nagase ChemteX Corporation) was added at 10 units per gram of solid matter and passed through a continuous liquefier at a flow rate of 1 L / min for 25 minutes at 100 ° C. Subsequently, the enzyme reaction was stopped by heating at 140 ° C. for 5 minutes to obtain a tapioca starch partial decomposition product solution. This tapioca starch partial decomposition product was dissolved in deionized water so as to have a solid concentration of 10% by mass, and subjected to an aging control test as a starch liquefaction solution. Each carbohydrate solution and starch liquefaction solution were mixed in an equal amount by mass to obtain test solutions 1 to 3, respectively. The compositions of the test solutions 1 to 3 are shown in Table 8. Each test solution was dispensed into a test tube, stored in a sealed state at 4 ° C. for 5 days, and then turbidity (Abs 720 nm) was measured as an index for aging control. The results are summarized in FIG.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
 図2に示すように、対照及び市販のワキシーコーンスターチ由来デキストリン2種を用いて調製した被験溶液2及び3は、冷蔵保存後の濁度がいずれも0.9以上を示し、顕著に白濁した。これに対して、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験溶液1は、冷蔵保存後の濁度は0.19と、きわめて低く維持されていた。斯かる結果から、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、共存する澱粉性多糖の老化を顕著に抑制し、非常に優れた老化調節能を有していることが判明した。 As shown in FIG. 2, the test solutions 2 and 3 prepared using the control and two commercially available waxy corn starch-derived dextrins showed a turbidity of 0.9 or more after refrigerated storage, and became markedly cloudy. In contrast, the test solution 1 prepared by using the α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 maintains the turbidity after refrigerated storage at 0.19, which is extremely low. It had been. From these results, α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, remarkably suppresses aging of coexisting starchy polysaccharides, and exhibits excellent aging control. It was found to have the ability.
<実験8:本α-グルカンの豆乳の風味改良性>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの風味改良性を官能試験にて検討評価した。実施例1の方法で得たα-グルカンを、固形物濃度0.5質量%、1.0質量%、2.0質量%になるよう市販の豆乳(商品名「おいしい無調整豆乳」、キッコーマン飲料株式会社製造)に添加溶解し、風味改良試験の被験豆乳1~3とした。次いで、調製したそれぞれの被験豆乳の風味について、パネル12名による官能試験を実施し、VAS法を用いて評価した。青臭み、えぐ味、甘味、美味しさの4項目について、当該α-グルカンを添加しない対照豆乳の風味を0とし、想像し得る最高の風味の状態を10、最低の風味の状態を-10とした場合の、被験豆乳の風味を数値で表し、その平均値で評価した。結果を図3にまとめた。
<Experiment 8: Flavor improvement of soymilk of this α-glucan>
The taste improving property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated by a sensory test. The α-glucan obtained by the method of Example 1 was commercialized with soymilk (trade name “delicious unadjusted soymilk”, Kikkoman, so that the solids concentration would be 0.5 mass%, 1.0 mass%, and 2.0 mass%. Added to and dissolved in Beverage Co., Ltd. to obtain test soybean milk 1 to 3 for flavor improvement test. Subsequently, the sensory test by 12 panelists was implemented about the flavor of each prepared soymilk, and it evaluated using VAS method. For the four items of blue odor, savory taste, sweet taste, and deliciousness, the flavor of the control soymilk without the addition of α-glucan is 0, the imaginable highest flavor state is 10, and the lowest flavor state is -10. The flavor of the test soymilk was expressed as a numerical value, and the average value was evaluated. The results are summarized in FIG.
 図3に示すとおり、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験豆乳1~3は、青臭み、えぐ味、美味しさの項目において、いずれも、0.4以上の値を示し、その効果は用量依存的に増加した。また、当該α-グルカンは、甘味にほとんど影響を与えなかった。したがって、当該α-グルカンを用いて調製した被験豆乳1~3は、無添加の豆乳と比較して、甘味にはほとんど変化がなく、青臭み及びえぐ味が顕著に低減されており、美味しさが増大されていることが示された。すなわち、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、異味異臭を低減し、優れた風味改良能を有していることが判明した。 As shown in FIG. 3, the test soymilk 1 to 3 prepared using α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 was used in the items of blue odor, savory taste, and deliciousness. All showed values of 0.4 or more, and the effect increased in a dose-dependent manner. The α-glucan had little effect on sweetness. Therefore, the test soymilk 1 to 3 prepared using the α-glucan has almost no change in sweetness, the blue odor and the savory taste are remarkably reduced as compared with the additive-free soymilk. Was shown to be increased. That is, it has been found that α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an off-flavor odor and an excellent flavor improving ability.
<実験9:本α-グルカンのゼラチンゲルの保形性>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、ゼラチンゲルの保形性を指標にして検討評価した。実施例1の方法で得たα-グルカン又は市販のワキシーコーンスターチ由来デキストリン(商品名「サンデック#30」、三和澱粉工業株式会社製造)を固形物換算で、濃度10.0質量%になるように、65℃に加熱した水に溶解して、それぞれ糖質溶液1及び2を調製した。固形物濃度2.4質量%の市販ゼラチン(商品名「ゼラチン21」、新田ゼラチン株式会社製造)を65℃に加熱した水に溶解して、ゼラチン溶液を調製した。次いで、糖質溶液1又は2とゼラチン溶液をそれぞれ質量で等量混合した後、容器に入れて、4℃、16時間冷蔵保存して、被験ゼラチンゲル1及び2を調製した。対照ゼラチンゲルは、糖質溶液の代わりに、65℃に加熱した水を用いた以外は同じ方法にて調製した。ゼラチンゲル成形後、ゼラチンゲルを容器から取り出して、20℃、4時間保管後に、各ゼラチンゲルを写真撮影し、保形性を評価した。その結果を図4に示した。
<Experiment 9: Shape retention of gelatin gel of this α-glucan>
The property improvement property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention obtained by the method of Example 1, was examined using the shape retention of gelatin gel as an index. evaluated. The α-glucan obtained by the method of Example 1 or a commercially available dextrin derived from waxy corn starch (trade name “Sandeck # 30”, manufactured by Sanwa Starch Co., Ltd.) so that the concentration becomes 10.0% by mass in terms of solid matter. Were dissolved in water heated to 65 ° C. to prepare carbohydrate solutions 1 and 2, respectively. A gelatin solution was prepared by dissolving commercially available gelatin (trade name “Gelatin 21”, manufactured by Nitta Gelatin Co., Ltd.) having a solid concentration of 2.4% by mass in water heated to 65 ° C. Next, the saccharide solution 1 or 2 and the gelatin solution were mixed in equal amounts, respectively, and then placed in a container and refrigerated at 4 ° C. for 16 hours to prepare test gelatin gels 1 and 2. A control gelatin gel was prepared in the same manner except that water heated to 65 ° C. was used instead of the saccharide solution. After forming the gelatin gel, the gelatin gel was taken out of the container and stored at 20 ° C. for 4 hours, and then each gelatin gel was photographed to evaluate the shape retention. The results are shown in FIG.
 図4に示すように、対照ゼラチンゲル及び市販のワキシーコーンスターチ由来デキストリンを用いて調製した被験ゼラチンゲル2は、容器から取り出した直後から変形しており、4時間後にはさらに変形の程度が大きくなり、保形性が低いことが示されたのに対して、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験ゼラチンゲル1は、容器から取り出した直後において、容器の形状を保っており、さらに、4時間後においても、容器の形状をほぼ維持するほどの崩れにくいゼラチンゲルであり、保形性が高いことが示された。すなわち、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、優れた保形能を有していることが判明した。 As shown in FIG. 4, the test gelatin gel 2 prepared using the control gelatin gel and the commercially available dextrin derived from waxy corn starch was deformed immediately after removal from the container, and the degree of deformation further increased after 4 hours. The test gelatin gel 1 prepared using α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 was taken out from the container. Immediately after, the shape of the container was maintained, and even after 4 hours, it was a gelatin gel that hardly collapses so as to maintain the shape of the container, indicating that the shape retention was high. That is, it was found that α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent shape retention ability.
<実験10:本α-グルカンのメレンゲの泡物性改良能>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、メレンゲの泡物性を指標にして検討評価した。卵白100質量部に、砂糖45質量部および実施例1の方法で得たα-グルカン5質量部を添加溶解し、泡立て器で被験メレンゲを調製した。一方、対照として、卵白100質量部に、砂糖50質量部添加した以外は同じ方法にて対照メレンゲを調製した。各メレンゲを容器に同量入れて、4℃、18時間冷蔵保存した。調製直後および18時間後のメレンゲの泡の状態をパネル5名の目視による官能試験を行い、++:非常にきめ細かい、+:細かい、±:普通で泡が保たれている、-:粗く泡が消失している、の4段階で評価した。パネル5名の評価の平均値を表9に示した。
<Experiment 10: Ability of this α-glucan to improve foam physical properties of meringue>
The property improvement property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated using meringue foam property as an index. . To 100 parts by weight of egg white, 45 parts by weight of sugar and 5 parts by weight of α-glucan obtained by the method of Example 1 were added and dissolved, and a test meringue was prepared with a whisk. On the other hand, as a control, a control meringue was prepared in the same manner except that 50 parts by weight of sugar was added to 100 parts by weight of egg white. The same amount of each meringue was put in a container and stored refrigerated at 4 ° C. for 18 hours. The state of meringue foam immediately after preparation and after 18 hours was subjected to a sensory test by visual observation of five panelists. ++: very fine, +: fine, ±: normal and foam maintained,-: coarse foam Evaluation was made on a four-point scale. Table 9 shows the average values of the evaluations of five panelists.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
 表9に示すとおり、対照メレンゲは、調製直後には「+」と評価され、泡は細かかったものの、冷蔵18時間後においては、「-」と評価され、泡は粗くなり、ほとんど消失した。これと比較して、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験メレンゲは、調製直後にはおけるその気泡が対照メレンゲよりもキメ細かく、なめらかで弾力がありクリーミーでリッチな性質を示し、「++」と評価された。さらに被験メレンゲの泡は消失しにくく、対照メレンゲと比較して、18時間後でも、「±」と評価され、泡は維持されていた。すなわち、本α-グルカンを配合したメレンゲは、泡質が改良され、その気泡は経時的にも安定化しており、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、優れた泡物性改良能を有していることが判明した。 As shown in Table 9, the control meringue was evaluated as “+” immediately after preparation and the foam was fine, but was evaluated as “−” after 18 hours of refrigeration, and the foam became coarse and almost disappeared. . In comparison, the test meringue prepared by using the α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has finer and smoother bubbles immediately after the preparation than the control meringue. It was elastic, creamy and rich, and was rated “++”. Furthermore, the test meringue foam was less likely to disappear, and was evaluated as “±” even after 18 hours as compared with the control meringue, and the foam was maintained. That is, the meringue blended with the α-glucan has improved foam quality, and its bubbles are stabilized over time. It has been found that the α-glucan possessed has an excellent ability to improve foam physical properties.
<実験11:本α-グルカンのわらび餅の食感改良>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、わらび餅の食感を指標にして検討評価した。加工デンプン(商品名「SF-1700」、昭和産業株式会社製造)100質量部に、砂糖200質量部及び水400質量部を混合し、600Wの電子レンジで2分加熱した後、被加熱物をさらに混練し、600Wの電子レンジで2分加熱する操作を6回繰り返して、対照わらび餅を調製した。被験わらび餅は、砂糖の1質量%、2.5質量%、5.0質量%、10.0質量%を実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンに置換した以外は対照と同様の方法にて被験わらび餅1~4を調製した。対照わらび餅及び被験わらび餅1~4の組成を表10に示した。調製したそれぞれのわらび餅の状態をパネル5名の食感による官能試験を行い、±を基準の軟らかさ(対照)として、+:少し軟らかい、++:軟らかい、+++:かなり軟らかい、++++:非常に軟らかい、の4段階で評価した。パネル5名の平均値を表11にまとめた。
<Experiment 11: Improving the texture of this α-glucan bracken>
Examination and evaluation of physical properties of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1, using the texture of warabimochi as an index did. 200 parts by weight of sugar and 400 parts by weight of water are mixed with 100 parts by weight of modified starch (trade name “SF-1700”, manufactured by Showa Sangyo Co., Ltd.), heated in a 600 W microwave oven for 2 minutes, and then heated. Further, the operation of kneading and heating in a 600 W microwave oven for 2 minutes was repeated 6 times to prepare a control warabimochi. The test bracken was obtained by adding 1%, 2.5%, 5.0%, 10.0% by weight of sugar to α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1. Test warabimo 1 to 4 were prepared in the same manner as the control except that it was replaced. Table 10 shows the compositions of the control bracken and the test bracken 1 to 4. A sensory test was conducted on the texture of each of the prepared warabimochi with five panelists, with + as the standard softness (control), +: slightly soft, ++: soft, +++: fairly soft, +++: very It was evaluated in four grades: soft. The average values of the five panelists are summarized in Table 11.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
 表11に示すとおり、対照と比べ、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験わらび餅1乃至4は、α-グルカンの配合量が増えるにしたがって、より軟らかい食感を呈した。すなわち、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、優れた食感改良能を有していることが判明した。 As shown in Table 11, in comparison with the control, test bracken koji 1 to 4 prepared using α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has a blending amount of α-glucan. As it increased, it had a softer texture. That is, it was found that α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent texture improvement ability.
<実験12:本α-グルカンの温度安定性に対する検討>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、水溶液の保温性を指標にして検討評価した。実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカン又は市販のワキシーコーンスターチ由来デキストリン(商品名「サンデック#30」、三和澱粉工業株式会社製造)を、それぞれ固形物濃度10.0質量%となるように水に溶解して被験水溶液1及び2を調製し、対照は水とした。対照および各被験水溶液をガラス容器にそれぞれ200mLを入れ、閉栓して沸騰水浴中で加熱した。開栓後、温度ロガーを試料中心部に位置するように設置して、室温条件下において、70℃から目的とする温度に低下するまでに要する時間を計測して保温性を評価し、図5にまとめた。
<Experiment 12: Examination of temperature stability of α-glucan>
The property improving property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated using the heat retaining property of an aqueous solution as an index. . The α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 or a commercially available dextrin derived from waxy corn starch (trade name “Sandeck # 30”, manufactured by Sanwa Starch Co., Ltd.) Test aqueous solutions 1 and 2 were prepared by dissolving in water to 10.0 mass%, and the control was water. 200 mL each of the control and each aqueous test solution was placed in a glass container, capped and heated in a boiling water bath. After opening, a temperature logger was placed so as to be positioned at the center of the sample, and the temperature retention was evaluated by measuring the time required for the temperature to drop from 70 ° C. to the target temperature under room temperature conditions. Summarized in
 図5に示すように、対照や被験水溶液2は、各設定温度まで低下するのに要する時間が短く、温度低下が急であった。これに対して、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験水溶液1は、温度低下が緩やかであり、各設定温度まで低下するのに要する時間が長いことが明らかになった。すなわち、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、保温性や温度安定性に優れていることが判明した。 As shown in FIG. 5, the time required for the control and the test aqueous solution 2 to decrease to each set temperature was short, and the temperature decrease was rapid. In contrast, the test aqueous solution 1 prepared by using the α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has a gradual temperature decrease, and decreases to each set temperature. It was revealed that the time required was long. That is, it was found that α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, is excellent in heat retention and temperature stability.
<実験13:本α-グルカンの糊化澱粉の粘りに対する検討>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、糊化澱粉ゲルの粘りを指標にして検討評価した。固形物濃度15.0質量%のコーンスターチ(商品名「昭和コーンスターチ」、敷島スターチ株式会社製造)を沸騰浴中で加熱して澱粉糊化液を調製し、そのまま沸騰浴中で保温した。また、実施例1の方法で得たα-グルカン又は市販のワキシーコーンスターチ由来デキストリン(商品名「サンデック#30」、三和澱粉工業株式会社製造)を固形物濃度10.0質量%なるように、それぞれ水に溶解し、その後、沸騰浴中で加熱して、糖質溶液1及び2を調製し、そのまま沸騰浴中で保温した。次いで、沸騰浴中で加熱保温した澱粉糊化液と、沸騰浴中で加熱保温した糖質溶液1又は2とを等量混合後、容器に入れ、室温下で1.5時間静置して、被験糊化澱粉ゲル1~2を形成させた。ゲル形成直後、及び、4℃で5日間保存後に、ゲルを容器から取り出して、レオメーター(商品名「MCR102」、株式会社アントンパールジャパン製造)を用いて、粘りの指標として用いられる損失正接(tanδ)を求め、それぞれのゲルの粘り度合いを評価し、図6に示した。
<Experiment 13: Examination of the viscosity of gelatinized starch of this α-glucan>
The property improvement property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention obtained by the method of Example 1, was examined using the viscosity of gelatinized starch gel as an index. evaluated. Corn starch (trade name “Showa Corn Starch”, manufactured by Shikishima Starch Co., Ltd.) having a solid concentration of 15.0% by mass was heated in a boiling bath to prepare a starch gelatinization solution, which was then kept warm in the boiling bath. In addition, the α-glucan obtained by the method of Example 1 or a commercially available dextrin derived from waxy corn starch (trade name “Sandeck # 30”, manufactured by Sanwa Starch Co., Ltd.) so that the solid concentration is 10.0% by mass, Each was dissolved in water and then heated in a boiling bath to prepare carbohydrate solutions 1 and 2, which were kept warm in the boiling bath. Next, an equal amount of starch gelatinization liquid heated and kept in a boiling bath and sugar solution 1 or 2 heated and kept in a boiling bath are mixed, put into a container, and allowed to stand at room temperature for 1.5 hours. Test gelatinized starch gels 1-2 were formed. Loss tangent (used as an index of stickiness) using a rheometer (trade name “MCR102”, manufactured by Anton Pearl Japan Co., Ltd.) immediately after gel formation and after storage for 5 days at 4 ° C. tan δ) was determined and the degree of stickiness of each gel was evaluated and is shown in FIG.
 図6に示すとおり、ゲル形成直後において、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを用いて調製した被験糊化澱粉ゲル1の粘り度合いは、0.12程度であり、被験糊化澱粉ゲル2と比較して、1.2倍程度の値を示した。調製5日後においては、被験糊化澱粉ゲル1の粘り度合いは、0.05程度まで低下したものの、被験糊化澱粉ゲル2と比較して、1.7倍以上の値を示し、粘り度合いの低下率は被験糊化澱粉ゲル2より低かった。すなわち、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有する当該α-グルカンは、市販のデキストリンに比べ、糊化澱粉ゲルを調製して冷蔵保存5日後においても、粘り度合いを高く保持し、経時変化に伴う粘り度合いの低下を抑制することに優れていることが判明した。 As shown in FIG. 6, immediately after gel formation, the degree of viscosity of the test gelatinized starch gel 1 prepared using α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 was 0.12. As compared with Test Gelatinized Starch Gel 2, the value was about 1.2 times. 5 days after the preparation, although the degree of stickiness of the test gelatinized starch gel 1 decreased to about 0.05, it showed a value of 1.7 times or more as compared with the test gelatinized starch gel 2, The reduction rate was lower than that of the test gelatinized starch gel 2. That is, the α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, is prepared by gelatinizing starch gel after 5 days of refrigeration compared to commercially available dextrin. It has been found that it is excellent in maintaining a high degree of stickiness and suppressing a decrease in stickiness accompanying a change with time.
<実験14:本α-グルカンのカラギーナンゲルの離水に対する検討>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、カラギーナンゲルの離水を指標にして検討評価した。約800mLの脱イオン水に、表12で示す配合に従い、κ-カラギーナン(商品名「カラギニンCSK-1」、三栄源エフ・エフ・アイ株式会社販売)、砂糖、実施例1の方法で得たα-グルカン又は市販のワキシーコーンスターチ由来デキストリン(商品名「サンデック#30」、三和澱粉工業株式会社製造)をそれぞれ添加し、電子レンジで80℃以上に加温し、攪拌することにより完全に溶解させた。得られた各水溶液は、50℃の脱イオン水を添加、攪拌し、最終的にそれぞれ1000gとした。それぞれの水溶液を78gずつプラスチックカップに分注した後、水分の蒸発を防ぐためにカップの上部をプラスチックパラフィンフィルム(商品名「Parafilm M」、Bemis Company社製造)で覆い、室温(22℃)で20分間静置することによってκ-カラギーナンを最終濃度0.8%(w/w)で含むゲルを調製した。対照カラギーナンゲルは、κ-カラギーナンと砂糖のみを使用した以外は同じ方法にて調製した。調製した3種のカラギーナンゲルは容器に充填した状態でそれぞれ4℃で2週間保存した。2週間保存後の、各カラギーナンゲルについて、プラスチックパラフィンフィルムを取り、離水によりゲル表面に出てきた水を濾紙に吸収させて秤量し、濾紙の質量を差し引くことで離水量を求めた。離水量は、各種カラギーナンゲルについて5検体ずつ測定し、平均離水量、ゲルの全質量に対する平均離水量の割合、対照ゲルの平均離水量に対する相対離水量を表13にまとめた。
<Experiment 14: Examination of water separation of carrageenan gel of this α-glucan>
The property improvement property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated using carrageenan gel water separation as an index. . In about 800 mL of deionized water, according to the formulation shown in Table 12, κ-carrageenan (trade name “Carrageenin CSK-1”, sold by Saneigen FFI Co., Ltd.), sugar, obtained by the method of Example 1 Add α-glucan or commercially available dextrin derived from waxy corn starch (trade name “Sandeck # 30”, manufactured by Sanwa Starch Co., Ltd.), warm to 80 ° C. or higher with a microwave oven, and completely dissolve by stirring. I let you. Each obtained aqueous solution was added with deionized water at 50 ° C. and stirred to finally make 1000 g each. After 78 g of each aqueous solution was dispensed into a plastic cup, the upper part of the cup was covered with a plastic paraffin film (trade name “Parafilm M”, manufactured by Bemis Company) to prevent evaporation of water, and 20 ° C. at room temperature (22 ° C.). A gel containing κ-carrageenan at a final concentration of 0.8% (w / w) was prepared by standing for a minute. A control carrageenan gel was prepared in the same manner except that only κ-carrageenan and sugar were used. The three kinds of prepared carrageenan gels were each stored at 4 ° C. for 2 weeks in a state filled in a container. For each carrageenan gel after storage for 2 weeks, a plastic paraffin film was taken, the water that emerged on the gel surface by water separation was absorbed into the filter paper, weighed, and the water separation amount was determined by subtracting the mass of the filter paper. The amount of water separation was measured for each of five carrageenan gels, and the average water separation amount, the ratio of the average water separation amount to the total mass of the gel, and the relative water separation amount with respect to the average water separation amount of the control gel are summarized in Table 13.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
 表13に示すとおり、4℃、2週間保存後の離水量が、対照ゲルの場合はゲル全重量の3.0%まで達したのに対して、市販デキストリン配合ゲルでは1.6%、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを配合したゲルでは0.8%に留まった。本α-グルカン配合ゲルの離水量は、対照ゲルの離水量の約1/4程度にまで顕著に減少した。すなわち、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、優れた離水抑制能を有していることが判明した。 As shown in Table 13, the amount of water separation after storage at 4 ° C. for 2 weeks reached 3.0% of the total gel weight in the case of the control gel, while 1.6% in the commercial dextrin-containing gel. In the gel in which α-glucan having an isomaltose structure was blended at the non-reducing end obtained by the method of Example 1, it remained at 0.8%. The water separation amount of the present α-glucan-containing gel was remarkably reduced to about 1/4 of the water separation amount of the control gel. That is, it was found that α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent ability to suppress water separation.
<実験15:本α-グルカンのパンの食感改良>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、パンの弾力を指標にして検討評価した。表14に示す組成で各成分を混合し、ホームベーカリー(SD-BMT1000型、パナソニック株式会社製)を用い、本体内蔵の食パン用プログラム(メニュー4)にて食パンを焼成した。実施例1の方法で得たα-グルカンの添加量は小麦粉の重量の5%に設定し、本α-グルカンの配合量だけ水を減量した。また、対照パンは、本α-グルカンを無添加とした以外は、同様の方法を用いて調製した。焼成した食パンの内相中心部を2cm角に切り出し、切り出した部分について、レオメーター(CR-500DX型、株式会社サン科学製)を用い、プランジャー径15mm、台座の上昇速度5mm/秒の条件下で、切り出したパンの高さを20%圧縮するのに要した力を測定し、弾力とした。その結果を表15にまとめた。
<Experiment 15: Improving the texture of this α-glucan bread>
The property improving property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, obtained by the method of Example 1 was examined and evaluated using the elasticity of bread as an index. Each component was mixed with the composition shown in Table 14, and bread was baked using a home bakery (SD-BMT1000 type, manufactured by Panasonic Corporation) with a bread bread program (menu 4) built in the main body. The amount of α-glucan obtained by the method of Example 1 was set to 5% of the weight of the flour, and the amount of water was reduced by the amount of this α-glucan. The control bread was prepared using the same method except that the α-glucan was not added. The center part of the inner phase of the baked bread was cut into a 2 cm square, and the cut out part was subjected to a condition using a rheometer (CR-500DX type, manufactured by Sun Kagaku Co., Ltd.) with a plunger diameter of 15 mm and a pedestal rising speed of 5 mm / sec. Below, the force required to compress the height of the cut bread by 20% was measured and used as elasticity. The results are summarized in Table 15.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
 表15に示したとおり、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを配合して調製した被験食パンは0.42Nの弾力を示し、0.21Nの弾力を示す対照食パンと比較して、2倍の値を示した。本α-グルカンの配合により、弾力のあるパンが調製できることが示された。すなわち、本α-グルカンを配合したパンは、本α-グルカンを配合しない対照パンに比べて大きな弾力を有しており、これを食したとき、弾力のある心地よい食感を感じさせるパンである。このことより、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、優れた食感改良能を有していることが判明した。 As shown in Table 15, the test bread prepared by blending α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 showed an elasticity of 0.42N and an elasticity of 0.21N. Compared to the control bread shown, the value was doubled. It was shown that an elastic bread can be prepared by blending this α-glucan. In other words, the bread blended with the present α-glucan has a greater elasticity than the control bread without the present α-glucan, and when eaten, it is a bread that gives a resilient and comfortable texture. . From this, it was found that α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention, has an excellent texture improvement ability.
 <実験16:本α-グルカンのグミにおける食感改善効果>
 実施例1の方法で得た、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンの物性改良性について、グミの食感を指標にして官能評価にて検討評価した。表16に示した成分のうち、ゼラチンとクエン酸溶液を除いたものをガラス容器に入れて混合し、電気コンロ(SK-65、600W、株式会社石崎電機製作所製)を用いて121℃を保持するように加熱しつつ、Brixが90になるまで煮詰めた。煮詰めた混合物の温度を60℃まで下げたところで、表16に示した量のゼラチンとクエン酸50%(w/v)溶液を加え、よく攪拌した後、焙焼澱粉で作製したスターチモールドに充填し、直径22mmのグミを成形した。グミがある程度固まった時点でさらに焙焼澱粉を振りかけ、室温(22℃)で一晩静置し、グミを調製した。実施例1の方法で得たα-グルカンを配合したグミと対照グミの食感を比較するために、調製した2種類のグミについて、パネル10名に対して、それぞれ別に口に入れさせ、ゆっくり噛む(毎秒約1回)方法、または、速く噛む(毎秒約2回)方法の2種類の速さで、奥歯で噛んでもらい、対照グミの食感と本α-グルカン配合グミの食感を対比させ、対照グミと比較して本α-グルカン配合グミの方が「固い」、「同等」、「柔らかい」3段階で評価させた。ゆっくり噛んだ場合、速く噛んだ場合の2種類の噛む速さについて実施し、それぞれの評価を下したパネル数を表17にまとめた。
<Experiment 16: Effect of the α-glucan on the texture of gummi>
About the physical property improvement property of α-glucan having an isomaltose structure at the non-reducing end, which is an active ingredient of the quality improving agent of the present invention obtained by the method of Example 1, for sensory evaluation using gummy texture as an index And evaluated. Among the components shown in Table 16, those obtained by removing gelatin and citric acid solution were mixed in a glass container, and maintained at 121 ° C. using an electric stove (SK-65, 600 W, manufactured by Ishizaki Electric Manufacturing Co., Ltd.). While being heated, it was boiled until Brix was 90. When the temperature of the boiled mixture was lowered to 60 ° C., the amount of gelatin and citric acid 50% (w / v) solution shown in Table 16 were added and stirred well, then filled into a starch mold made of roasted starch A gummy with a diameter of 22 mm was formed. When the gummy solidified to some extent, the roasted starch was further sprinkled and allowed to stand overnight at room temperature (22 ° C.) to prepare gummy. In order to compare the texture of the gummy containing α-glucan obtained by the method of Example 1 and the control gummy, the prepared two kinds of gummy were put in their mouths separately for 10 panelists, and slowly The chewing (about 1 time per second) or the fast chewing (about 2 times per second) chewing with the back teeth, the texture of the control gummi and the texture of this α-glucan combination gummi In comparison, this α-glucan-containing gummy was evaluated in three stages, “hard”, “equivalent”, and “soft”, compared to the control gummy. Table 17 summarizes the number of panels that were evaluated for each of the two types of biting speeds when biting slowly and when biting fast.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
 表17に示すように、ゆっくり噛んだ場合、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを配合して調製したグミの固さは対照グミとほぼ同等の固さであると回答したパネルが最も多かった(8人/10人中)のに対し、速く噛んだ場合には、本α-グルカン配合グミの方が対照グミよりも固いと回答したパネルが多かった(7人/10人中)。この結果は、本α-グルカンを配合したグミは、ゆっくり噛むと対照グミと同等の柔らかい食感を与え、速く噛むと固い食感を与えることが明らかになった。すなわち、本α-グルカンを配合したグミは、ダイラタンシー的な、従来のグミでは得られなかった独特の食感を与えるグミであり、本発明の品質改善剤の有効成分である、非還元末端にイソマルトース構造を有するα-グルカンは、優れた食感改良能を有していることが判明した。 As shown in Table 17, when chewed slowly, the gummy prepared by blending α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 has almost the same hardness as the control gummy. The number of respondents who responded that this was the most (8/10 out of 10) was higher, but when chewing quickly, the panel that responded that this α-glucan-containing gummy was firmer than the control gummy. (7 out of 10 people). As a result, it became clear that the gummi containing the α-glucan gave a soft texture equivalent to that of the control gummi when chewed slowly and a firm texture when chewed quickly. That is, the gummi containing the α-glucan is a dilatancy-like gummy that gives a unique texture that cannot be obtained with conventional gummi, and is an active ingredient of the quality improver of the present invention, at the non-reducing end. It has been found that α-glucan having an isomaltose structure has an excellent texture improvement ability.
 実験9乃至16に示したとおり、本発明の品質改善剤の有効成分であるα-グルカンは、保形作用、泡物性改良作用、食感改良作用、保温作用・温度安定作用、粘り度合い調節作用、離水抑制作用などの優れた効果を奏した。すなわち、本発明の品質改善剤は、優れた物性改良能を有していることが判明した。 As shown in Experiments 9 to 16, α-glucan, which is an active ingredient of the quality improving agent of the present invention, has a shape retention effect, a foam property improvement effect, a texture improvement effect, a heat retention effect / temperature stabilization effect, and a stickiness degree adjustment effect. Excellent effects such as water separation inhibiting effect were exhibited. That is, it was found that the quality improver of the present invention has an excellent ability to improve physical properties.
 以下、本発明で用いる非還元性末端にイソマルトース構造を有するα-グルカンを有効成分とする本発明の品質改善剤とその用途を、実施例により詳細に説明するものの、本発明はこれらの実施例によって何ら限定されるものではない。 Hereinafter, the quality improving agent of the present invention comprising α-glucan having an isomaltose structure at the non-reducing end used in the present invention as an active ingredient and its use will be described in detail by way of examples. It is not limited at all by an example.
 市販のワキシーコーンスターチ(商品名「ワキシーコーンスターチ Y」、株式会社J-オイルミルズ製造)を固形物濃度30質量%になるよう脱イオン水に懸濁し、塩化カルシウムを濃度0.1質量%になるよう添加した後、pH6.0に調製し、ワキシーコーンスターチ懸濁液を得た。このワキシーコーンスターチ懸濁液に耐熱性α-アミラーゼ(商品名「スピターゼHK/R」、ナガセケムテックス株式会社製造)をワキシーコーンスターチ固形物当たり0.005質量%添加し、pH6.5、100℃で20分間加熱することにより、糊化及び液化を行い、さらに、国際公開第WO2008/136331号パンフレットにおいて開示したバチルス・サーキュランスPP710株由来α-グルコシル転移酵素をワキシーコーンスターチの固形物1g当たり1.25単位添加し、pH6.0、50℃で24時間作用させた後、140℃で10分間加熱することにより反応を停止させ、スプレードライヤーに供給して135℃で噴霧乾燥した。乾燥品は粉砕機に通して粉砕を行って、粉末状の、非還元末端にイソマルトース構造を有するα-グルカンを得た。 Commercially available waxy corn starch (trade name “waxy corn starch Y” manufactured by J-Oil Mills Co., Ltd.) is suspended in deionized water to a solids concentration of 30% by mass, so that calcium chloride has a concentration of 0.1% by mass. After the addition, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension. To this waxy corn starch suspension, a heat-resistant α-amylase (trade name “Spitase HK / R”, manufactured by Nagase ChemteX Corporation) was added in an amount of 0.005% by mass per waxy corn starch solid, at pH 6.5 and 100 ° C. By heating for 20 minutes, gelatinization and liquefaction were carried out. Further, α-glucosyltransferase derived from Bacillus circulans PP710 strain disclosed in International Publication No. WO2008 / 136331 was added to 1.25 per gram of waxy corn starch solids. After adding the unit and allowing it to act at pH 6.0 and 50 ° C. for 24 hours, the reaction was stopped by heating at 140 ° C. for 10 minutes, and the mixture was supplied to a spray dryer and spray-dried at 135 ° C. The dried product was pulverized through a pulverizer to obtain powdery α-glucan having an isomaltose structure at the non-reducing end.
 当該α-グルカンは、重量平均分子量(Mw)が、1,070kDa,数平均分子量(Mn)が、63.1kDa、Mw/Mn(分散度)が16.9を示し、冷水可溶性を有し、固形物濃度30質量%の水溶液の粘度は861mPa・sであった。当該α-グルカンのグルコース等量(DE)は0.89であり、当該α-グルカンのイソマルトースデキストラナーゼ消化物におけるイソマルトース含量は5.6質量%を示した。当該α-グルカンは非還元末端にイソマルトース構造を有するα-グルカンであり、固形物濃度30質量%の水溶液を6℃で1週間保持する耐老化性試験において、保存1週間の時点で透明な水溶液の状態を維持する顕著な耐老化性を有していた。当該α-グルカンは本発明の品質改善剤の有効成分として好適であり、当該α-グルカンを有効成分とする品質改善剤は、例えば、可食性フィルムの原材料、食品、化粧品、医薬部外品、医薬品または工業用品の増粘剤、バインダー等として好適に利用できる。 The α-glucan has a weight average molecular weight (Mw) of 1,070 kDa, a number average molecular weight (Mn) of 63.1 kDa, Mw / Mn (dispersity) of 16.9, and has cold water solubility, The viscosity of the aqueous solution having a solid concentration of 30% by mass was 861 mPa · s. The glucose equivalent (DE) of the α-glucan was 0.89, and the isomaltose content of the α-glucan digested with isomaltose dextranase was 5.6% by mass. The α-glucan is an α-glucan having an isomaltose structure at the non-reducing end, and is transparent when stored for 1 week in an aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C. for 1 week. It had remarkable aging resistance that maintained the state of the aqueous solution. The α-glucan is suitable as an active ingredient of the quality improving agent of the present invention. Examples of the quality improving agent containing the α-glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
 市販ワキシーコーンスターチ(商品名「ワキシーコーンスターチ Y」、株式会社J-オイルミルズ製造)を固形物濃度30質量%になるよう脱イオン水に懸濁し、塩化カルシウムを濃度0.1質量%になるよう添加した後、pH6.0に調製し、ワキシーコーンスターチ懸濁液を得た。このワキシーコーンスターチ懸濁液に耐熱性α-アミラーゼ(商品名「スピターゼ HK」、ナガセケムテックス株式会社製造)をワキシーコーンスターチ固形物当たり0.002質量%添加し、100℃で20分間加熱することにより、糊化及び液化を行い、さらに、国際公開第WO2008/136331号パンフレットに開示したバチルス・サーキュランスPP710株由来のα-グルコシル転移酵素をワキシーコーンスターチの固形物1g当たり1.0単位添加し、pH6.0、50℃で24時間作用させたさせた以外は実施例1と同様の操作を行うことにより、粉末状の、非還元末端にイソマルトース構造を有するα-グルカンを得た。 Commercially available waxy corn starch (trade name “waxy corn starch Y” manufactured by J-Oil Mills Co., Ltd.) was suspended in deionized water to a solids concentration of 30% by mass, and calcium chloride was added to a concentration of 0.1% by mass. After that, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension. By adding heat-resistant α-amylase (trade name “Spitase HK”, manufactured by Nagase ChemteX Corporation) to this waxy corn starch suspension at 0.002 mass% per waxy corn starch solid, and heating at 100 ° C. for 20 minutes. Then, gelatinization and liquefaction were performed, and 1.0 unit of α-glucosyltransferase derived from Bacillus circulans PP710 disclosed in the pamphlet of International Publication No. WO2008 / 136331 was added per 1 g of waxy corn starch solid, pH 6 A powdery α-glucan having an isomaltose structure at the non-reducing end was obtained by the same operation as in Example 1 except that the mixture was allowed to act at 0.0 and 50 ° C. for 24 hours.
 当該α-グルカンは、重量平均分子量(Mw)が1,270kDa、Mw/Mnが22.1を示し、冷水可溶性を有し、濃度30質量%の水溶液の粘度は896mPa・sであった。当該α-グルカンにイソマルトデキストラナーゼを作用させて得た消化物のイソマルトース含量は9.3質量%を示した。当該α-グルカンは、非還元末端にイソマルトース構造を有するα-グルカンであり、固形物濃度30質量%の水溶液を6℃で1週間保持する耐老化性試験において、保存1週間の時点で老化による白濁を全く示さない耐老化性を有していた。当該α-グルカンは本発明の品質改善剤の有効成分として好適であり、当該α-グルカンを有効成分とする品質改善剤は、例えば、可食性フィルムの原材料、食品、化粧品、医薬部外品、医薬品又は工業用品の増粘剤、バインダー等として好適に利用できる。 The α-glucan had a weight average molecular weight (Mw) of 1,270 kDa, Mw / Mn of 22.1, was soluble in cold water, and the viscosity of an aqueous solution having a concentration of 30% by mass was 896 mPa · s. The isomaltose content of the digest obtained by allowing isomaltdextranase to act on the α-glucan was 9.3% by mass. The α-glucan is an α-glucan having an isomaltose structure at the non-reducing end, and in an aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C. for 1 week, aging occurs at the time of storage for 1 week. It had aging resistance that showed no cloudiness due to. The α-glucan is suitable as an active ingredient of the quality improving agent of the present invention. Examples of the quality improving agent containing the α-glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
 市販ワキシーコーンスターチ(商品名「ワキシーコーンスターチ Y」、株式会社J-オイルミルズ製造)を固形物濃度35質量%になるよう脱イオン水に懸濁し、塩化カルシウムを濃度0.1質量%になるよう添加した後、pH6.0に調製し、ワキシーコーンスターチ懸濁液を得た。このワキシーコーンスターチ懸濁液に耐熱性α-アミラーゼ(商品名「ターマミル 60L」、ノボザイムズ・ジャパン株式会社製造)をワキシーコーンスターチ固形物当たり0.004質量%添加し、100℃で20分間加熱することにより、糊化及び液化を行い、さらに、国際公開第WO2008/136331号パンフレットに開示したバチルス・サーキュランスPP710株由来のα-グルコシル転移酵素をワキシーコーンスターチの固形物1g当たり1.0単位添加し、pH6.0、50℃で20時間作用させた以外は実施例2と同様の操作を行うことにより、粉末状の、非還元末端にイソマルトース構造を有するα-グルカンを得た。 Commercially available waxy corn starch (trade name “waxy corn starch Y” manufactured by J-Oil Mills Co., Ltd.) was suspended in deionized water to a solids concentration of 35% by mass, and calcium chloride was added to a concentration of 0.1% by mass. After that, the pH was adjusted to 6.0 to obtain a waxy corn starch suspension. Heat-resistant α-amylase (trade name “Termamyl 60L”, manufactured by Novozymes Japan Co., Ltd.) is added to this waxy corn starch suspension in an amount of 0.004% by mass per waxy corn starch solid, and heated at 100 ° C. for 20 minutes. Then, gelatinization and liquefaction were performed, and 1.0 unit of α-glucosyltransferase derived from Bacillus circulans PP710 disclosed in the pamphlet of International Publication No. WO2008 / 136331 was added per 1 g of waxy corn starch solid, pH 6 A powdery α-glucan having an isomaltose structure at the non-reducing end was obtained by the same operation as in Example 2 except that the mixture was allowed to act at 0.0 and 50 ° C. for 20 hours.
 当該α-グルカンは、重量平均分子量(Mw)が566kDa、Mw/Mnが13.2を示し、冷水可溶性を有し、濃度30質量%の水溶液の粘度は483mPa・sであった。当該α-グルカンにイソマルトデキストラナーゼを作用させて得た消化物のイソマルトース含量は7.0質量%を示した。当該α-グルカンは、非還元末端にイソマルトース構造を有するα-グルカンであり、固形物濃度30質量%の水溶液を6℃で1週間保持する耐老化性試験において、保存1週間の時点で老化による白濁を全く示さない耐老化性を有していた。当該α-グルカンは本発明の品質改善剤の有効成分として好適であり、当該α-グルカンを有効成分とする品質改善剤は、例えば、可食性フィルムの原材料、食品、化粧品、医薬部外品、医薬品又は工業用品の増粘剤、バインダー等として好適に利用できる。 The α-glucan had a weight average molecular weight (Mw) of 566 kDa, Mw / Mn of 13.2, was soluble in cold water, and the viscosity of an aqueous solution having a concentration of 30% by mass was 483 mPa · s. The isomaltose content of the digest obtained by allowing isomaltdextranase to act on the α-glucan was 7.0% by mass. The α-glucan is an α-glucan having an isomaltose structure at the non-reducing end, and in an aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C. for 1 week, aging occurs at the time of storage for 1 week. It had aging resistance that showed no cloudiness due to. The α-glucan is suitable as an active ingredient of the quality improving agent of the present invention. Examples of the quality improving agent containing the α-glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
 ワキシーコーンスターチをワキシーライススターチに換え、糊化及び液化した後、さらに、国際公開第WO2008/136331号パンフレットに開示したアルスロバクター・グロビホルミス PP349株由来のα-グルコシル転移酵素をワキシーライススターチの固形物1g当たり2.5単位添加し、pH6.0、50℃で24時間作用させた以外は実施例3と同様の操作を行うことにより、粉末状の、非還元末端にイソマルトース構造を有するα-グルカンを得た。 After replacing waxy corn starch with waxy rice starch, gelatinizing and liquefying, the α-glucosyltransferase derived from Arthrobacter globiformis PP349 strain disclosed in International Publication No. WO2008 / 136331 is further solidified into waxy rice starch. The same procedure as in Example 3 was performed except that 2.5 units per gram was added and the mixture was allowed to act at pH 6.0 and 50 ° C. for 24 hours. Glucan was obtained.
 当該α-グルカンは、重量平均分子量(Mw)が1,360kDa、Mw/Mnが22.4を示し、冷水可溶性を有し、濃度30質量%の水溶液の粘度は840mPa・sであった。当該α-グルカンにイソマルトデキストラナーゼを作用させて得た消化物のイソマルトース含量は17.5質量%を示した。また、当該α-グルカンは、非還元末端にイソマルトース構造を有するα-グルカンであり、固形物濃度30質量%の水溶液を6℃で1週間保持する耐老化性試験において、保存1週間の時点で老化による白濁を全く示さない耐老化性を有していた。当該α-グルカンは本発明の品質改善剤の有効成分として好適であり、当該α-グルカンを有効成分とする品質改善剤は、例えば、可食性フィルムの原材料、食品、化粧品、医薬部外品、医薬品又は工業用品の増粘剤、バインダー等として好適に利用できる。 The α-glucan had a weight average molecular weight (Mw) of 1,360 kDa, Mw / Mn of 22.4, was soluble in cold water, and the viscosity of an aqueous solution having a concentration of 30% by mass was 840 mPa · s. The isomaltose content of the digest obtained by allowing isomaltdextranase to act on the α-glucan was 17.5% by mass. Further, the α-glucan is an α-glucan having an isomaltose structure at the non-reducing end, and in the aging resistance test in which an aqueous solution having a solid concentration of 30% by mass is maintained at 6 ° C. for 1 week, the time point of 1 week of storage It had aging resistance that showed no turbidity due to aging. The α-glucan is suitable as an active ingredient of the quality improving agent of the present invention. Examples of the quality improving agent containing the α-glucan as an active ingredient include edible film raw materials, foods, cosmetics, quasi drugs, It can be suitably used as a thickener or binder for pharmaceuticals or industrial products.
<冷凍米飯> 実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として、これに水を加えて、完全に溶解して、濃度25%の糖質溶液を調製した。生米600質量部を洗米し、15℃の水に60分間浸漬後、常法により炊飯し、5分間蒸らした。この蒸らした米飯を攪拌しながら、80℃に加温した上記糖質溶液を、炊飯に使用した生米の質量に対して、非還元末端にイソマルトース構造を有するα―グルカンとして2.5%となるように加えて、保温容器に入れ、時々攪拌しながら、さらに45分間保持した。この米飯を冷却して、1食分ずつ容器に小分けし、冷凍して24時間保存後、5℃で24時間チルド解凍した後、常温に戻して試食したところ、品質改善剤が老化調節能を発揮して、製造直後と遜色のない食味を保持していた。 <Frozen cooked rice> Using α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 as a quality improver, water is added to this and completely dissolved to obtain a carbohydrate solution having a concentration of 25% Was prepared. 600 parts by mass of raw rice was washed, immersed in water at 15 ° C. for 60 minutes, cooked in a conventional manner, and steamed for 5 minutes. While stirring the steamed cooked rice, the sugar solution heated to 80 ° C. is 2.5% as α-glucan having an isomaltose structure at the non-reducing end with respect to the mass of raw rice used for cooking rice. In addition, the mixture was placed in a heat insulating container and kept for an additional 45 minutes with occasional stirring. This cooked rice is cooled, subdivided into containers one by one, frozen and stored for 24 hours, then chilled and thawed at 5 ° C for 24 hours, and then sampled at room temperature. And it kept the same taste as it was immediately after production.
<チルド用の炊飯米> 実施例2の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として、これに水を加えて、完全に溶解して、糖質濃度2.5%の糖質溶液を調製した。生米600質量部を洗米し、15℃の水に60分間浸漬後、上記糖質溶液800質量部を用いて炊飯し、10分間蒸らして米飯を得た。この米飯を冷却して、1食分ずつ容器に小分けし、48時間チルド保存した後、常温に戻して試食したところ、品質改善剤が老化調節能を発揮して、製造直後と遜色のない食味を保持していた。この米飯で、おにぎりをつくり、5℃で24時間、36時間及び48時間保存後に、常温に戻して試食したところ、何れの保存時間を経たおにぎりも、製造直後と遜色のない食味を保持しており、品質改善剤が優れた老化調節能を発揮したことが確認された。 <Cooked rice for chilled use> α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 was used as a quality improver, and water was added to this to completely dissolve it. A 5% sugar solution was prepared. 600 parts by mass of raw rice was washed, immersed in water at 15 ° C. for 60 minutes, cooked with 800 parts by mass of the carbohydrate solution, and steamed for 10 minutes to obtain cooked rice. After cooling this cooked rice, divide it into containers one by one, store it in chilled for 48 hours, and test it after returning it to room temperature. As a result, the quality-improving agent demonstrates the ability to control aging, and tastes comparable to that immediately after production. Was holding. With this cooked rice, rice balls were made, stored at 5 ° C for 24 hours, 36 hours, and 48 hours, then returned to room temperature and sampled. It was confirmed that the quality-improving agent exhibited excellent aging control ability.
<寿司飯> 実施例3の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として14質量部、砂糖25質量部、塩6質量部に水道水25質量部を加えて加温しながら、完全に溶解して、室温まで冷却して、これに穀物酢30質量部を加えて、酢入りの糖質溶液を調製した。生米600質量部を洗米後、15℃の水に60分間浸漬し、生米に対して1.35倍の質量となるように加水して、常法により炊飯し、15分間蒸らした。この蒸らした米飯を攪拌しながら、30℃に加温した上記糖質溶液200質量部を加え、さらに5分間冷却することなくその状態を保持した後(最終の米飯の温度55℃)、バットに拡げ、冷却して、寿司飯を調製した。本品を、-20℃で1週間保存後、5℃で24時間チルド解凍し、常温に戻して試食したところ、品質改善剤の老化調節能、物性改良能、風味改良能が発揮され、製造直後と遜色のない食味を保持していた。本品は、そのままで、或いは冷蔵して、にぎり寿司、巻き寿司、ちらし寿司、いなり寿司、押し寿司などを製造する際の寿司飯として使用することができ、冷凍保存後解凍して、例えば、にぎり寿司を製造する際の寿司飯として使用することもできる。また、本品に寿司種をのせたにぎり寿司の状態で凍結して保存することもできる。 <Sushi rice> 14 parts by weight, α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 3 as a quality improving agent, 25 parts by weight of sugar, and 25 parts by weight of tap water are added to 6 parts by weight of salt. While heating, the solution was completely dissolved, cooled to room temperature, and 30 parts by mass of grain vinegar was added thereto to prepare a saccharide solution containing vinegar. After washing 600 parts by mass of raw rice, it was immersed in water at 15 ° C. for 60 minutes, hydrated to 1.35 times the mass of raw rice, cooked in a conventional manner, and steamed for 15 minutes. While stirring the steamed cooked rice, 200 parts by mass of the sugar solution heated to 30 ° C. was added, and the state was maintained without further cooling for 5 minutes (final cooked rice temperature 55 ° C.). Spread and cool to prepare sushi rice. This product was stored at -20 ° C for 1 week, thawed at chilled for 24 hours at 5 ° C, returned to room temperature, and tasted, and the aging control ability, physical property improvement ability, and flavor improvement ability of the quality improver were demonstrated. The taste was inferior to that immediately after. This product can be used as it is or refrigerated and used as sushi rice when making nigiri sushi, roll sushi, chirashi sushi, inari sushi, pressed sushi, etc. It can also be used as sushi rice when manufacturing nigiri sushi. In addition, it can be frozen and stored in the state of nigiri sushi with sushi seeds on it.
<スパゲティー> 実施例4の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として、これに水を適量加えて、完全に溶解して、糖質濃度12.5%の糖質溶液を調製した。市販のスパゲティー(乾燥品)100質量部を、常法により湯を用いて茹で、茹で湯からあげた直後の麺を、保温容器に入れ、軽く攪拌しながら、75℃に加温した上記糖質溶液5質量部を加えて、30分間保持し、糖質を浸透させた。本品をチルド保存或いは冷凍保存48時間後に常温に戻した後、麺のほぐれ性を評価したところ、品質改善剤が老化調節能や物性改良能を発揮して、何れの保存法においても、製造直後と遜色のないほぐれ性を保持していた。 <Spaghetti> An α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 4 was used as a quality improver, and an appropriate amount of water was added thereto to completely dissolve it. A saccharide solution was prepared. 100 parts by weight of commercially available spaghetti (dried product) is boiled with hot water in a conventional manner, and the noodles immediately after being boiled from hot water are placed in a heat-retaining container and heated to 75 ° C. while stirring gently. 5 parts by mass was added and held for 30 minutes to allow the carbohydrates to penetrate. The product was returned to room temperature after 48 hours of chilled storage or frozen storage, and the noodles were evaluated for looseness. As a result, the quality-improving agent exhibited aging control and physical properties, and it was manufactured in any storage method. It had the same looseness immediately after that.
<スパゲティー> 実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として、これを0.5質量%となるように溶解した糖質溶液2,000質量部を用いて、市販のスパゲティー(乾燥品)100質量部を茹で、茹でスパゲティーを調製した。本品をチルド保存或いは冷凍保存48時間後に常温に戻した後、麺のほぐれ性を評価したところ、品質改善剤が老化調節能や物性改良能を発揮して、何れの保存法においても、製造直後と遜色のないほぐれ性を保持していた。 <Spaghetti> 2,000 parts by weight of a saccharide solution in which α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 is used as a quality improving agent and dissolved in 0.5% by mass Was used to prepare 100 parts by weight of commercially available spaghetti (dried product). The product was returned to room temperature after 48 hours of chilled storage or frozen storage, and the noodles were evaluated for looseness. As a result, the quality-improving agent exhibited aging control and physical properties, and it was manufactured in any storage method. It had the same looseness immediately after that.
<澱粉糊化食品の食味低下抑制剤> 実施例2の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として、これと含水結晶α,α-トレハロース(商品名「トレハ」、株式会社林原製造)、含水結晶マルトース(商品名「サンマルト」、株式会社林原製造)、マルトテトラオース高含有シラップ(商品名「テトラップH」、株式会社林原製造)に適量の水を加えて攪拌溶解し、無水物換算で、非還元末端にイソマルトース構造を有するα-グルカン、α,α-トレハロース、マルトース、マルトテトラオース高含有糖質を1:1:1:1の質量比で含有する、糖質濃度30質量%のシラップ状の食味低下抑制剤を調製した。本品を、さらに、常法により噴霧乾燥して、粉末状の食味低下抑制剤を調製した。  <Taste reduction inhibitor of starch gelatinized food> α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 was used as a quality improver and water-containing crystal α, α-trehalose (trade name “ Toreha ”, Hayashibara Co., Ltd.), hydrous crystal maltose (trade name“ San Mart ”, Hayashibara Co., Ltd.), maltotetraose-rich syrup (trade name“ Tetrap H ”, Hayashibara Co., Ltd.) And dissolved in a mass ratio of 1: 1: 1: 1, containing an α-glucan, α, α-trehalose, maltose, and maltotetraose-rich carbohydrate having an isomaltose structure at the non-reducing end in terms of anhydride. A syrup-like taste reduction inhibitor having a sugar concentration of 30% by mass was prepared. This product was further spray-dried by a conventional method to prepare a powdery taste reduction inhibitor. *
これらの食味低下抑制剤は、そのままで、または水に溶解して、さらには、他の澱粉老化抑制剤や食品品質改良剤などと組み合わせて澱粉糊化食品の食味低下抑制剤として使用することができる。本食味低下抑制剤は、加熱して澱粉を糊化した直後の澱粉糊化食品に共存、接触させて、一定時間、比較的高温で維持して浸透させることにより、澱粉糊化食品を常温、チルド、冷蔵、或いは、冷凍状態で保存、流通させる際に進行する恐れのある澱粉の老化を調節し、硬化や異臭の発生を抑制することができる。また、本食味低下抑制剤を、うどん、蕎麦、中華麺、スパゲティーなどの麺類の製造に適用した場合には、前記効果に加えて麺のほぐれをよくするなどの目的で使用することもできる。 These taste reduction inhibitors can be used as they are or dissolved in water, and further used as a taste reduction inhibitor for starch gelatinized foods in combination with other starch aging inhibitors or food quality improvers. it can. The present taste lowering inhibitor coexists with and is in contact with starch gelatinized food immediately after starch is gelatinized by heating, and maintains the starch gelatinized food at room temperature, at a relatively high temperature for a certain period of time. It can control the aging of starch that may progress when stored and distributed in chilled, refrigerated or frozen state, and can suppress the generation of curing and off-flavors. In addition to the above effects, when the present taste reduction inhibitor is applied to the production of noodles such as udon, soba noodles, Chinese noodles and spaghetti, it can also be used for the purpose of improving the looseness of the noodles.
<冷凍イカ> 生イカ100質量部を、実施例3の方法で製造した非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として1質量部、食塩3質量部、トレハロース1質量部、ソルビトール1質量部、マルチトール1質量部、2-O-α-D-グルコシル-L-アスコルビン酸(商品名「アスコフレッシュ」、株式会社林原製造)0.5質量部及び水92.5質量部からなる浸漬液に、4℃、16時間浸漬した。浸漬液を除去した後、-20℃で冷凍保存して、冷凍イカを調製した。本品は、品質改善剤が冷凍耐性性、離水防止性などの物性改良能や風味改良能を発揮して、長期冷凍保存時においても白蝋化が見られず、解凍時のドリップが少なく、生臭み等もない、高品質の冷凍イカである。 <Frozen squid> 100 parts by weight of raw squid, 1 part by weight of α-glucan having an isomaltose structure at the non-reducing end produced by the method of Example 3, 3 parts by weight of salt, 1 part by weight of trehalose, 1 part by weight of sorbitol, 1 part by weight of maltitol, 0.5 part by weight of 2-O-α-D-glucosyl-L-ascorbic acid (trade name “ASCOFRESH” manufactured by Hayashibara Co., Ltd.) and 92.5 parts by weight of water In the immersion liquid consisting of After removing the immersion liquid, it was stored frozen at −20 ° C. to prepare a frozen squid. In this product, the quality improver demonstrates the ability to improve physical properties such as resistance to freezing and water separation prevention, and the ability to improve flavor, whitening does not occur even during long-term frozen storage, and there is little drip when thawing, It is a high-quality frozen squid with no odor.
<アイスミルク> 脱脂粉乳(乳脂肪分:0.8%、無脂乳固形分:96.2%)8重量部、卵黄2質量部、砂糖12質量部、実施例4の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として5質量部およびトレハロース(商品名「トレハ」、株式会社林原製造)5質量部、水60質量部を加えて攪拌しながら加熱溶解した。次いで、生クリーム(乳脂肪分:47.0%、無脂乳固形分:4.0%)8重量部を加えて、さらに加熱撹拌後、ホモジナイザーで均質化した。これを5℃で冷却保存後、容器に充填し、冷凍保存することで、アイスミルクを得た。本品は、品質改善剤が氷結晶安定性、硬化調節性などの物性改良能や風味改良能を発揮して、匙通り、舌触りや口溶けが良く、風味の良い高品質なアイスミルクである。 <Ice milk> Nonfat powdered milk (milk fat content: 0.8%, non-fat milk solid content: 96.2%) 8 parts by weight, egg yolk 2 parts by mass, sugar 12 parts by mass, non-obtained by the method of Example 4 5 parts by mass of α-glucan having an isomaltose structure at the reducing end as a quality improver, 5 parts by mass of trehalose (trade name “Treha” manufactured by Hayashibara Co., Ltd.) and 60 parts by mass of water were added and dissolved with stirring. . Next, 8 parts by weight of fresh cream (milk fat content: 47.0%, non-fat milk solid content: 4.0%) was added, and further heated and stirred, and then homogenized with a homogenizer. This was cooled and stored at 5 ° C., filled into a container, and stored frozen to obtain ice milk. This product is a high-quality ice milk with a good taste, taste and mouth-melting properties, and a quality-improving agent that exhibits improved physical properties such as ice crystal stability and curability control, and improved flavor.
<オレンジゼリー> オレンジジュース500質量部、水291質量部を80℃に加熱し、これにκ-カラギーナン(商品名「カラギニンCSK-1」、三栄源エフ・エフ・アイ株式会社販売)8質量部、砂糖150質量部、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として50質量部を加えて攪拌しながら加熱溶解した。これを50℃まで冷ました後、2-O-α-D-グルコシル-L-アスコルビン酸(商品名「アスコフレッシュ」、株式会社林原製造)1質量部を加えて攪拌しながら溶解した。この溶液を容器に充填し、冷蔵保存することで、オレンジゼリーを得た。本品は、品質改善剤が保形性、安定性、離水防止性などの物性改良能や風味改良能を発揮して、見た目も美しくて、食感もよく、風味の良い高品質なオレンジゼリーである。 <Orange Jelly> 500 parts by weight of orange juice and 291 parts by weight of water are heated to 80 ° C., and 8 parts by weight of κ-carrageenan (trade name “Carrageenin CSK-1”, Saneigen FFI Co., Ltd.) 150 parts by weight of sugar and 50 parts by weight of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 as a quality improver were added and dissolved with stirring. After cooling to 50 ° C., 1 part by mass of 2-O-α-D-glucosyl-L-ascorbic acid (trade name “ASCOFRESH” manufactured by Hayashibara Co., Ltd.) was added and dissolved while stirring. An orange jelly was obtained by filling this solution in a container and storing it in a refrigerator. This product is a high-quality orange jelly with a quality-improving agent that improves physical properties and flavor, such as shape retention, stability and water separation prevention, and has a beautiful appearance, good texture and good flavor. It is.
<乳酸菌飲料> 脱脂粉乳175質量部、実施例2の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として100質量部およびラクトスクロース高含有粉末(商品名「乳果オリゴ」、株式会社林原製造)を水1,500質量部に溶解し、65℃で30分間殺菌し、40℃に冷却後、これに、常法に従って、乳酸菌のスターターを30質量部植菌し、37℃で8時間培養して乳酸菌飲料を得た。本品は、オリゴ糖を含有し、整腸作用を有するだけでなく、品質改善剤が安定性、賦形性などの物性改良能や風味改良能を発揮して、乳酸菌を安定に保つことができ、風味の良い高品質な乳酸菌飲料である。 <Lactic acid bacteria beverage> 175 parts by weight of skim milk powder, 100 parts by weight of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 and a powder containing high lactosucrose (trade name “milk Oligo ", manufactured by Hayashibara Co., Ltd.) in 1,500 parts by mass of water, sterilized at 65 ° C. for 30 minutes, cooled to 40 ° C., and then inoculated with 30 parts by mass of a starter of lactic acid bacteria. And culturing at 37 ° C. for 8 hours to obtain a lactic acid bacteria beverage. This product contains oligosaccharides and has not only an intestinal regulating action, but also a quality improver that can improve the physical properties such as stability and formability and the ability to improve flavor to keep lactic acid bacteria stable. It is a high quality lactic acid bacteria beverage that can be made.
<青汁粉末> 大麦若葉粉末25質量部、ケール粉末25質量部に対して、実施例3の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として40質量部およびトレハロース粉末(商品名「トレハ」、株式会社林原製造)5質量部、水溶性食物繊維(商品名「ファイバリクサ」、株式会社林原製造)5質量部、2-O-α-グルコシル-L-アスコルビン酸(商品名「アスコフレッシュ」、株式会社林原製造)1質量部をよく混合攪拌し、粉砕し微粉末にして、計量し、包装して製品を得た。本品は、品質改善剤の物性改良能が発揮されて、大麦若葉粉末やケール粉末の分散性や発色性、さらには安定性に優れており、また、本品を適量の水に溶解あるいは懸濁した場合、品質改善剤の風味改良能が発揮されて、異味異臭がなく、高品質の青汁として商品価値の高いものである。 <Green juice powder> With respect to 25 parts by mass of barley young leaf powder and 25 parts by mass of kale powder, 40 parts by mass of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 3 as a quality improver and Trehalose powder (trade name “Treha”, manufactured by Hayashibara Co., Ltd.) 5 parts by mass, water-soluble dietary fiber (trade name “Fiber Rixa”, manufactured by Hayashibara Co., Ltd.) 5 parts by mass, 2-O-α-glucosyl-L-ascorbic acid (Product name “ASCOFRESH”, manufactured by Hayashibara Co., Ltd.) 1 part by mass was thoroughly mixed and stirred, pulverized into a fine powder, weighed and packaged to obtain a product. This product exhibits the ability to improve the physical properties of quality improvers and is excellent in dispersibility, color development and stability of young barley leaf powder and kale powder, and it can be dissolved or suspended in an appropriate amount of water. In the case of turbidity, the flavor improving ability of the quality improving agent is exerted, there is no off-flavor, and the product value is high as a high quality green juice.
<カスタードクリーム> コーンスターチ100質量部、実施例4の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として100質量部、トレハロース含水結晶60質量部、蔗糖40質量部、および食塩1質量部を充分に混合し、鶏卵280質量部を加えて攪拌し、これに沸騰した牛乳1,000質量部を徐々に加え、更に火にかけて攪拌を続け、コーンスターチが完全に糊化して全体が半透明になった時に火を止め、これを冷却して適量のバニラ香料を加え、計量、充填、包装して製品を得た。本品は、品質改善剤が澱粉老化調節能や風味改良能を発揮して、なめらかな光沢や舌触りを有し、風味の良い高品質なカスタードクリームである。 <Custard cream> 100 parts by mass of corn starch, 100 parts by mass of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 4 as a quality improver, 60 parts by mass of water containing trehalose, 40 parts by mass of sucrose, And 1 part by weight of salt are thoroughly mixed, 280 parts by weight of hen's egg is added and stirred, 1,000 parts by weight of boiled milk is gradually added thereto, and the mixture is further stirred by heating. The corn starch is completely gelatinized. When the whole became translucent, the fire was turned off, cooled, added with an appropriate amount of vanilla fragrance, weighed, filled and packaged to obtain a product. This product is a high quality custard cream that has a smooth luster and texture, with a quality improving agent that exerts the ability to control starch aging and improve flavor, and has a smooth luster and texture.
<餡> 原料小豆10質量部に、常法に従って、水を加えて煮沸し、渋切り、あく抜きし、水溶性夾雑物を除去して、小豆粒餡約21質量部を得た。この生あんに蔗糖14質量部、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として5質量部と水10質量部を加えて煮沸し、これに少量のサラダオイルを加えて粒餡を壊さないように練り上げ、製品の餡を約35質量部得た。本品は、品質改善剤が澱粉老化調節能、物性改良能、風味改良能を発揮して、色焼け、離水もなく、安定で、風味良好で、餡パン、まんじゅう、団子、最中、氷菓などの製菓材料として好適である。 <Strawberry> According to a conventional method, water was added to 10 parts by mass of raw material red beans, boiled, astringent and extracted, and water-soluble impurities were removed to obtain about 21 parts by mass of red bean grains. To this raw bean paste, 14 parts by mass of sucrose, and 5 parts by mass and 10 parts by mass of water were added as a quality improver with α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 and boiled. A small amount of salad oil was added and kneaded so as not to break the granule, and about 35 parts by mass of the product koji was obtained. As for this product, the quality improver exhibits starch aging control ability, physical property improvement ability, flavor improvement ability, color burning, water separation, stable, good taste, rice cake bread, manju, dumpling, middle, ice confectionery, etc. It is suitable as a confectionery material.
<ういろうの素> 米粉90質量部に、コーンスターチ20質量部、無水結晶マルチトール70質量部、実施例2の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として50質量部、およびプルラン4質量部を均一に混合してういろうの素を製造した。ういろうの素と適量の抹茶と水とを混練し、これを容器に入れて60分間蒸し上げて抹茶ういろうを製造した。本品は、マルチトールを含有し、低カロリーであるだけでなく、品質改善剤の物性改良能や風味改良能が発揮されて、照り、口当たりも良好で、風味も良い。又、品質
改善剤の澱粉老化調節能が発揮され、日持ちの良いういろうである。
<Uiro no Mo> 90 parts by weight of rice flour, 20 parts by weight of corn starch, 70 parts by weight of anhydrous crystalline maltitol, and α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 as a quality improver Mass parts and 4 parts by mass of pullulan were uniformly mixed to produce a waxy element. Ui-no-Moto, an appropriate amount of Matcha and water were kneaded, and the mixture was placed in a container and steamed for 60 minutes to produce Matcha Uiro. This product contains maltitol and is not only low in calories, but also exhibits the ability to improve the physical properties and flavor of the quality improver, and has good shine, mouthfeel, and good flavor. In addition, the starch aging control ability of the quality improver is demonstrated, and it is a long-lasting Uro.
<パン> 小麦粉100質量部、イースト菌2質量部、蔗糖5質量部、実施例3の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として1質量部および無機フード0.1質量部を、常法に従って、水でこね、中種を26℃で2時間発酵させ、その後30分間熟成、焼き上げた。本品は、品質改善剤の物性改良能、澱粉老化調節能、風味改良能が発揮されて、色相、すだちとも良好で、適度の弾力を有し、日持性が良く、風味良好な高品質のパンである。 <Bread> 100 parts by weight of wheat flour, 2 parts by weight of yeast, 5 parts by weight of sucrose, 1 part by weight of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 3 and 0 inorganic food .1 part by mass was kneaded with water according to a conventional method, the middle seed was fermented at 26 ° C. for 2 hours, and then aged and baked for 30 minutes. This product exhibits the ability to improve the physical properties of starch, the ability to control starch aging, and the ability to improve flavor, and it has good hue and durability, moderate elasticity, good shelf life, and good flavor. The bread.
<ハム> 豚もも肉1,000質量部に食塩15質量部および硝酸カリウム3質量部を均一にすり込んで、冷室に1昼夜堆積する。これを水500質量部、食塩100質量部、硝酸カリウム3質量部、実施例4の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として50質量部および香辛料からなる塩漬液に冷室で7日間漬け込み、次いで、常法に従い、冷水で洗浄し、ひもで巻き締め、薫煙し、クッキングし、冷却、包装して製品を得た。本品は、品質改善剤の物性改良能や風味改良能が発揮されて、色合いもよく、風味良好な高品質のハムである。 <Ham> 15 parts by mass of sodium chloride and 3 parts by mass of potassium nitrate are uniformly rubbed into 1,000 parts by mass of pork thigh and deposited in a cold room for one day and night. A salt composed of 500 parts by weight of water, 100 parts by weight of sodium chloride, 3 parts by weight of potassium nitrate, 50 parts by weight of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 4 and a spice The product was soaked in a pickled solution in a cold room for 7 days, then washed with cold water, wound with a string, smoked, cooked, cooled and packaged according to a conventional method to obtain a product. This product is a high-quality ham that exhibits the ability to improve the physical properties and flavor of the quality improver, has a good color, and has a good flavor.
<あじの開き干し> 水1,000質量部に塩化ナトリウム125質量部及び実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として75質量部を溶解した調味液に常法に従って開いたあじを30分間浸漬し、次いで、30℃の温風で1時間乾燥させてあじの開き干しを製造した。本発明のあじの開き干しは、品質改善剤の物性改良能、風味改良能が発揮されて、食味が優れているだけでなく、酸敗臭や魚臭がなく、色、艶ともに食欲をそそる製品である。 <Aji Opening> 125 parts by mass of sodium chloride in 1,000 parts by mass of water and 75 parts by mass of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1 were dissolved. Opened horse mackerel was soaked in the seasoning liquid according to a conventional method for 30 minutes, and then dried with warm air of 30 ° C. for 1 hour to produce a dried horse mackerel. The open-boiled dried mackerel of the present invention is a product that not only has excellent taste, but also has an acidity and fish odor, and has a strong appetite in color and luster. It is.
<漬物> 大根1,000質量部に食塩35質量部、砂糖80質量部、食酢35質量部、クチナシ色素5質量部及び実施例2の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として50質量部を適宜混合し、ビニール袋に入れ、4℃の冷蔵庫内で一週間保存して、大根の漬物を作成した。本発明の漬物は、品質改善剤の物性改良能、風味改良能が発揮されて、食感や食味が優れているだけでなく、色味も安定しており、食欲をそそる高品質の漬物である。 <Pickles> 1,000 parts by mass of radish with 35 parts by mass of salt, 80 parts by mass of sugar, 35 parts by mass of vinegar, 5 parts by mass of gardenia pigment, and α- having an isomaltose structure at the non-reducing end obtained by the method of Example 2 50 parts by mass of glucan as a quality improver was mixed as appropriate, placed in a plastic bag and stored in a refrigerator at 4 ° C. for a week to prepare pickled radish. The pickle of the present invention is a high-quality pickle that is not only excellent in texture and taste, but also has a stable color and appetite, because the physical properties improving ability and flavor improving ability of the quality improver are demonstrated. is there.
<マヨネーズ> 卵黄20質量部に食塩2.5質量部、水5質量部、食酢12.5質量部及び実施例3の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として5質量部を容器に入れて攪拌した後、食用油200質量部を徐々に添加しながら、さらに攪拌して、マヨネーズを作成した。本発明のマヨネーズは、品質改善剤の物性改良能、風味改良能が発揮されて、食感や食味が優れているだけでなく、安定性が高く、艶があり、口当たりも良好で、食欲をそそる高品質のマヨネーズである。 <Mayonnaise> Quality improvement of α-glucan having 20 parts by mass of egg yolk, 2.5 parts by mass of salt, 5 parts by mass of water, 12.5 parts by mass of vinegar and non-reducing end obtained by the method of Example 3 After adding 5 parts by mass as an agent in a container and stirring, it was further stirred while gradually adding 200 parts by weight of edible oil to prepare mayonnaise. The mayonnaise of the present invention exhibits the ability to improve the physical properties and flavor of the quality improver and not only has a good texture and taste, but also has high stability, gloss, good mouthfeel, and good appetite. It is a high quality mayonnaise.
<粉末ペプチド> 40%食品用大豆ペプチド溶液(商品名「ハイニュートS」、不二製油株式会社製造)1質量部に、実施例4の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として2質量部を混合し、プラスチック製バットに入れ、50℃で減圧乾燥し、粉砕して粉末ペプチドを得た。本品は、品質改善剤の風味改良能が発揮されて、風味良好で、プレミックス、冷菓などの製菓材料として有用であるのみならず、品質改善剤の整腸作用が発揮されて、経口流動食、経管流動食のための整腸材料としても有用である。 <Powdered peptide> 40% soy peptide solution for food (trade name “Hi-Nut S”, manufactured by Fuji Oil Co., Ltd.) 1 part by mass, α having an isomaltose structure at the non-reducing end obtained by the method of Example 4 -2 parts by mass of glucan as a quality improver was mixed, placed in a plastic vat, dried under reduced pressure at 50 ° C, and pulverized to obtain a powdered peptide. This product is not only useful for confectionery materials such as premixes and frozen desserts, because the flavor improving ability of the quality improving agent is demonstrated, and it is useful as a confectionery material for premixes, frozen desserts, etc. It is also useful as an intestinal adjustment material for foods and tube feeding fluids.
<可食性フィルム> 実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカン15質量部、グリセロール8質量部、ポリソルベート80 1質量部、脱イオン水76質量部を容器に入れて懸濁し、マグネティックスターラーを用いて、室温で、800rpm、1時間攪拌し、溶解させた。その後、この溶液を室温で6時間減圧脱泡した後、全自動フィルムアプリケーター(商品名「コートマスター510」、エリクセン社製)を用い、フルオロポリマーでコートしたポリエステルフィルム(商品名「Scotchpak 1022 Release liner」、3M社製)上に流延し、湿厚650nm、5mm/秒の条件下でフィルムを作製した。作製したフィルムを、ホットエアオーブン内で60℃で、1.5時間乾燥させることにより、可食性フィルムを得た。本品は、品質改善剤の物性改良能が発揮されて、しなやかで伸びが良く、べたつき感の少ない、透明感が良好な高品質の可食性フィルムである。 <Edible film> 15 parts by mass of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1, 8 parts by mass of glycerol, 1 part by mass of polysorbate 80, and 76 parts by mass of deionized water are placed in a container. The mixture was suspended and dissolved by stirring at 800 rpm for 1 hour at room temperature using a magnetic stirrer. Thereafter, this solution was degassed under reduced pressure for 6 hours at room temperature, and then a polyester film (trade name “Scotchpak 1022 Release liner) coated with a fluoropolymer using a fully automatic film applicator (trade name“ Coat Master 510 ”, manufactured by Eriksen). “3M”), and a film was produced under conditions of a wet thickness of 650 nm and 5 mm / second. The produced film was dried in a hot air oven at 60 ° C. for 1.5 hours to obtain an edible film. This product is a high-quality edible film that exhibits the ability to improve the physical properties of a quality improver, is supple and stretchable, has little stickiness, and has a good transparency.
<化粧用クリーム> モノステアリン酸ポリオキシエチレングリコール2質量部、自己乳化型モノステアリン酸グリセリン5質量部、流動パラフィン1質量部、トリオクタン酸グリセリン10質量部および防腐剤の適量を常法に従って加熱溶解し、これに実施例2の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として2質量部、L-乳酸2質量部、1、3-ブチレングリコール5質量部および精製水66質量部を加え、ホモゲナイザーにかけ乳化し、更にグルコシルヘスぺリジン(商品名「アルファグルコシルヘスぺリジン」、株式会社林原製造)1質量部、香料を適量加えて攪拌混合し、化粧用クリームを製造した。本品は、グルコシルヘスぺリジンを含有し、抗酸化性を有するだけでなく、品質改善剤の物性改良能が発揮されて、安定性が高く、高品質の日焼け止め、美肌剤、色白剤などとして有利に利用できる。 <Cosmetic cream> 2 parts by weight of polyoxyethylene glycol monostearate, 5 parts by weight of self-emulsifying glyceryl monostearate, 1 part by weight of liquid paraffin, 10 parts by weight of glyceryl trioctanoate and appropriate amounts of preservatives are heated and dissolved according to a conventional method. In addition, 2 parts by mass of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 2 as a quality improver, 2 parts by mass of L-lactic acid, 5 parts by mass of 1,3-butylene glycol, and Add 66 parts by weight of purified water, emulsify with a homogenizer, add 1 part by weight of glucosyl hesperidin (trade name “Alpha Glucosyl Hesperidin”, manufactured by Hayashibara Co., Ltd.), add a suitable amount of perfume, and stir and mix. Manufactured. This product contains glucosyl hesperidin and not only has antioxidant properties, but also exhibits the ability to improve the physical properties of quality improvers, has high stability, high quality sunscreen, skin cleanser, fair skin, etc. Can be used as advantageous.
<練歯磨> 第二リン酸カルシウム45質量部、ラウリル硫酸ナトリウム1.5質量部、グリセリン25質量部、ポリオキシエチレンソルビタンラウレート0.5質量部、実施例3の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として15質量部、サッカリン0.02質量部を水18質量部と混合して練歯磨を得た。本品は、品質改善剤の安定性や保湿性などの物性改良能が発揮されて、界面活性剤の洗浄力などの機能を阻害することのない安定な製剤であり、保湿性に優れており、使用後感も良好である。 <Toothpaste> 45 parts by mass of dibasic calcium phosphate, 1.5 parts by mass of sodium lauryl sulfate, 25 parts by mass of glycerin, 0.5 parts by mass of polyoxyethylene sorbitan laurate, and the non-reducing end obtained by the method of Example 3 Toothpaste was obtained by mixing 15 parts by mass of α-glucan having a maltose structure as a quality improver and 0.02 parts by mass of saccharin with 18 parts by mass of water. This product is a stable formulation that exhibits the ability to improve physical properties such as stability and moisture retention of quality improvers, and does not impair functions such as detergent detergency. The feeling after use is also good.
<流動食用固体製剤> 実施例4の方法で得た非還元末端にイソマルトース構造を有するα-グルカンを品質改善剤として100質量部、トレハロース含水結晶200質量部、マルトテトラオース高含有粉末200質量部、粉末卵黄270質量部、脱脂粉乳209質量部、塩化ナトリウム4.4質量部、塩化カリウム1.8質量部、硫酸マグネシウム4質量部、チアミン0.01質量部、L-アスコルビン酸ナトリウム0.1質量部、ビタミンEアセテート0.6質量部およびニコチン酸アミド0.04質量部からなる配合物を調製し、この配合物25グラムずつ防湿性ラミネート小袋に充填し、ヒートシールして製品を得た。本品は、品質改善剤の安定性、賦形性などの物性改良能や整腸作用が発揮されて、安定で、整腸作用に優れた流動食であり、経口的、または鼻腔、胃、腸などへ経管的使用方法により利用され、生体へのエネルギー補給用に有利に利用できる。 <Food Edible Solid Formulation> 100 parts by mass of α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 4 as a quality improver, 200 parts by mass of hydrous crystals of trehalose, 200 parts by mass of powder containing high maltotetraose Parts, powdered egg yolk 270 parts, skim milk powder 209 parts, sodium chloride 4.4 parts, potassium chloride 1.8 parts, magnesium sulfate 4 parts, thiamine 0.01 parts, sodium L-ascorbate A blend consisting of 1 part by weight, 0.6 part by weight of vitamin E acetate and 0.04 part by weight of nicotinamide is prepared, and 25 grams of this blend is filled into a moisture-proof laminate sachet and heat sealed to obtain a product. It was. This product is a liquid food that is stable and excellent in regulating the intestine due to its ability to improve the physical properties such as stability and formability of the quality improver and the ability to regulate the intestine. It can be used for the intestine and the like by a method of tube use, and can be advantageously used for energy supply to a living body.
<肥料棒>
 配合肥料(窒素12%、リン酸8%、カリウム12%)、実施例1の方法で得た非還元末端にイソマルトース構造を有するα-グルカン、硫酸カルシウム及び水をそれぞれ質量比70:10:15:5とし、充分混合した後、押出機(L/D=20、圧縮比=1.8、ダイスの口径=15mm)で80℃に加熱して肥料棒を製造した。本品は、上記α-グルカンが結着性、保形性、賦形性、離形性などの物性改良能を発揮して、取扱い容易であり、全層施肥に適した強度を有し、更に、配合割合を変えることにより肥料成分の溶出速度を調節できるものである。また、必要に応じ、この肥料棒に植物ホルモン、農業用薬剤及び土壌改良剤などを配合することも有利に実施できる。
<Fertilizer bar>
Compound fertilizer (nitrogen 12%, phosphoric acid 8%, potassium 12%), α-glucan having an isomaltose structure at the non-reducing end obtained by the method of Example 1, calcium sulfate, and water were each in a mass ratio of 70:10: The mixture was mixed sufficiently and then heated to 80 ° C. with an extruder (L / D = 20, compression ratio = 1.8, die diameter = 15 mm) to produce a fertilizer bar. This product has the strength suitable for full-layer fertilization because the α-glucan exhibits easy-to-handle properties, such as binding, shape retention, shaping, and releasability. Furthermore, the elution rate of the fertilizer component can be adjusted by changing the blending ratio. Further, if necessary, it is also possible to advantageously carry out blending of plant hormones, agricultural chemicals, soil improvers and the like with this fertilizer bar.
 本発明の品質改善剤は、非還元末端にイソマルトース構造を有するα-グルカンを有効成分とし、適度な分子量範囲を示し、冷水可溶性に優れ、適度な粘度を保持し、各種原料素材、中間素材、組成物などに対して、例えば老化調節性、風味改良性、物性改良性に優れているので、食品、化粧品、医薬品及び工業用品の各分野において有利に用いることができる。とりわけ、澱粉性含有食品の老化調節剤、異味異臭を有する食品の風味改良剤、物性改良剤などとして有利に用いることができ、産業的意義がきわめて大きい。 The quality improver of the present invention comprises an α-glucan having an isomaltose structure at the non-reducing end as an active ingredient, exhibits an appropriate molecular weight range, is excellent in cold water solubility, retains an appropriate viscosity, various raw materials, and intermediate materials For example, the composition is excellent in aging control, flavor improvement, and physical property improvement, and therefore can be advantageously used in the fields of food, cosmetics, pharmaceuticals, and industrial products. In particular, it can be advantageously used as an aging control agent for starch-containing foods, a flavor improving agent for foods having a nasty smell, a physical property improving agent, and the like, and has a great industrial significance.

Claims (9)

  1.  ワキシースターチを糊化し、アミラーゼを作用させ液化する工程、及びα-グルコシル転移酵素を作用させる工程を含む製造方法により得られるα-グルカン混合物であって、下記(1)乃至(3)の特徴を有するα-グルカン混合物を有効成分とする品質改善剤:
      (1)重量平均分子量(Mw)が150kDa乃至3,000kDaの範囲にある;
      (2)重量平均分子量(Mw)を数平均分子量(Mn)で除した値(Mw/Mn)が35.1以下である;及び、
      (3)非還元末端にイソマルトース構造を有するα-グルカン分子を含む。
    An α-glucan mixture obtained by a production method comprising gelatinizing waxy starch, allowing amylase to act and liquefying, and allowing α-glucosyltransferase to act, comprising the following features (1) to (3) A quality improving agent comprising an α-glucan mixture having:
    (1) the weight average molecular weight (Mw) is in the range of 150 kDa to 3,000 kDa;
    (2) The value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 35.1 or less; and
    (3) An α-glucan molecule having an isomaltose structure at the non-reducing end is included.
  2.  前記α-グルカン混合物が、イソマルトデキストラナーゼ(EC 3.2.1.94)消化により、消化物の固形物当たりイソマルトースを3質量%超22質量%未満生成することを特徴とする請求項1記載の品質改善剤。 The α-glucan mixture produces isomaltose in an amount of more than 3% by mass and less than 22% by mass by digestion with isomalt dextranase (EC 3.2.1.94). Item 6. The quality improving agent according to Item 1.
  3.  前記ワキシースターチが、ワキシーコーンスターチである請求項1または2のいずれかに記載の品質改善剤。 The quality improving agent according to claim 1 or 2, wherein the waxy starch is waxy corn starch.
  4. 前記α-グルカン混合物が、固形物濃度20質量%となるよう脱イオン水に添加し、30℃で15分間撹拌した時、完全に溶解して均一な溶液を与える請求項1乃至3のいずれかに記載の品質改善剤。 4. The α-glucan mixture is added to deionized water so as to have a solid concentration of 20% by mass and stirred at 30 ° C. for 15 minutes to completely dissolve and give a uniform solution. The quality improver described in 1.
  5.  老化調節剤としての、請求項1乃至4のいずれかに記載の品質改善剤。 The quality improvement agent in any one of Claims 1 thru | or 4 as an aging regulator.
  6.  風味改良剤としての、請求項1乃至4のいずれかに記載の品質改善剤。 The quality improver according to any one of claims 1 to 4, as a flavor improver.
  7.  物性改良剤としての、請求項1乃至4のいずれかに記載の品質改善剤。 The quality improver according to any one of claims 1 to 4, as a physical property improver.
  8.  請求項1乃至7のいずれかに記載の品質改善剤を含有してなる食品、化粧品、医薬部外品または医薬品。 A food, cosmetic, quasi-drug or pharmaceutical comprising the quality improver according to any one of claims 1 to 7.
  9.  請求項1乃至7のいずれかに記載の品質改善剤を含有してなる工業用品。 Industrial goods containing the quality improving agent according to any one of claims 1 to 7.
PCT/JP2018/014976 2017-04-11 2018-04-09 Quality improver and use thereof WO2018190310A1 (en)

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