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WO2008044588A1 - Dérivé d'amidon ramifié, procédé d'obtention et article moulé contenant le dérivé d'amidon ramifié - Google Patents

Dérivé d'amidon ramifié, procédé d'obtention et article moulé contenant le dérivé d'amidon ramifié Download PDF

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Publication number
WO2008044588A1
WO2008044588A1 PCT/JP2007/069442 JP2007069442W WO2008044588A1 WO 2008044588 A1 WO2008044588 A1 WO 2008044588A1 JP 2007069442 W JP2007069442 W JP 2007069442W WO 2008044588 A1 WO2008044588 A1 WO 2008044588A1
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Prior art keywords
starch
branched
branched starch
derivative
group
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PCT/JP2007/069442
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English (en)
Japanese (ja)
Inventor
Tomoyuki Nishimoto
Hiroto Chaen
Shigeharu Fukuda
Toshio Miyake
Original Assignee
Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo
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Priority to JP2008538685A priority Critical patent/JP5349050B2/ja
Publication of WO2008044588A1 publication Critical patent/WO2008044588A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B35/00—Preparation of derivatives of amylopectin
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, 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
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/732—Starch; Amylose; Amylopectin; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations

Definitions

  • the present invention relates to a novel derivative of a branched starch, a method for producing the same, and a molded article containing the derivative of the branched starch, and more specifically, a 6-a maltosyl branched structure and / or a 6a maltotetraosyl branched
  • the present invention relates to a branched starch derivative having a structure, a production method thereof, and a molded product containing the branched starch derivative.
  • Starch is a high molecular weight gnolecan stored mainly in the cells of higher plant seeds and rhizomes, and is generally a mixture of amylose and amylopectin.
  • Amylose is an ⁇ -1,4 glucan having a structure in which dalose is linearly bonded with ⁇ -1,4 bonds.
  • amylopectin is a linear part of ⁇ -1, 4 glucan, and usually has a structure in which ⁇ -1, 4 glucan having a glucose polymerization degree of 6 or more is branched by ⁇ -1, 6 bonds. Yes.
  • Starch swells when heated in an aqueous dispersion to form a viscous gelatinized starch, but has the property of aging and causing gelation when allowed to cool.
  • Starch has been gelatinized since long ago, and is used for food, and because it has excellent processability, low cost, and storability, it is used as the main ingredient of foods.
  • Colloid stabilizers are also widely used for the purpose of improving the physical properties and maintaining the quality of food.
  • starch is liquefied and industrially used as a raw material for dulose, isomerized sugar, maltooligosaccharide, chickenpox and the like.
  • gelatinized starch and liquefied starch have problems such as aging during storage, gelation easily occurs and water retention is lost and hardened, and processing suitability is lowered.
  • JP-A-8-134104 a branching enzyme (branching enzyme; EC 2 ⁇ 6) is synthesized in a starch liquefaction solution by cleaving ⁇ 1, 4 bonds of starch and synthesizing ⁇ -1,6 bonds by transfer reaction. 4. 1. 18), 4- ⁇ -glucanotransferase (D enzyme; EC 2. 4. 1. 25) or CGTase (EC 2. 4. 1. 19) A method for forming an artificial glucan has been proposed.
  • JP 2001-294601 also discloses a branched structure compared to starch, which is a raw material that uses a branching enzyme derived from Neurospora crassa to reduce molecular weight from gelatinized starch.
  • a branching enzyme derived from Neurospora crassa has been proposed for forming highly branched starches having a dense structure and a branched structure centered on a degree of glucose polymerization of 4 to 7.
  • the Neuros Bora Classa is a special mold, and its safety has not been confirmed in the production of food and drink.
  • JP-A-2002-78497 discloses a branching enzyme (SBE II) and phosphorylase derived from barley, with glucose 1-phosphate and maltooligosaccharide as reaction substrates, with a glucose polymerization degree of 6 or 7 as the center.
  • SBE II branching enzyme
  • phosphorylase derived from barley
  • a method of forming a branched starch having a branched structure is proposed.
  • SBE II barley-derived branching enzyme
  • phosphorylase phosphorylase
  • the substrate glucose 1-phosphate for industrial production.
  • 2005-298253 a method for producing a novel branched starch having improved aging resistance using an enzyme derived from a microorganism, and its application development has been promoted. It has been.
  • the branched starch has high aging resistance and excellent water solubility, but depending on the application, there may be problems in terms of mechanical strength and hydrophilicity. Needed to modify its physical properties.
  • the present invention aims to provide a derivative having a modified physical property, a method for producing the same, and a molded product containing the derivative of the branched starch. .
  • branched starch a D Dalcoviranosyl (1 ⁇ ) cyclic maltosyl manretose (hereinafter abbreviated as “cyclic maltosyl maltose” in this specification) from ⁇ — 1, 4 glucan
  • Carbohydrate-related enzymes such as phrerase, a galactosidase, 13 galactosidase, lysozyme and other glycosyltransferases, sugar hydrolases, and glycosylphosphates It has been found that by using the enzyme reaction system according to the present invention, it is possible to prepare a carbohydrate derivative of a branched starch in which the hydroxyl group is substituted with an O-glycosyl group or a modified O-glycosyl group in which a glycosyl group is further bonded to this O-glycosyl group.
  • branched starch derivative in which a hydroxyl group of a branched starch is substituted with a substituent other than a hydroxyl group and a glycosyl group by reacting a reactive reagent with the branched starch.
  • Derivatives having substituents are excellent in binding properties to the branched starch itself or to other compounds, and therefore can be advantageously used for binding to other organic compounds for the purpose of crosslinking and grafting of the branched starch.
  • the present invention relates to a derivative of a branched starch having a 6-a maltosyl branched structure and / or a 6-a maltotetraosyl branched structure (hereinafter referred to simply as “branched” in the present specification). Sometimes referred to as “starch derivatives”. ) And a method for producing the same, and a molded article containing a branched starch derivative.
  • the physical properties such as mechanical strength and hydrophobicity of the novel branched starch can be modified, so that the uses of this branched starch can be expanded.
  • a novel organic compound can be obtained by combining with branched starches or other compounds.
  • the physical properties of this branched starch can be imparted to the compounds.
  • FIG. 1 is a diagram showing elution patterns in gel filtration chromatography of various branched starches obtained by allowing a cyclic maltosyl maltose-producing enzyme to act on liquefied starch (rice corn starch liquefied liquid).
  • FIG. 2 Glucose polymerization in pullulanase digests of various branched starches obtained by allowing cyclic maltosyl maltose-forming enzyme to act on liquefied starch (rice corn starch liquor). It is the figure compared separately.
  • FIG. 3 is a graph showing absorption spectra of iodine-starch complexes of various branched starches obtained by allowing cyclic maltosyl maltose-forming enzyme to act on liquefied starch (soybean corn starch liquefied liquid).
  • FIG. 4 is a diagram schematically showing the structure of a raw material liquefied starch (rice corn starch liquefied liquid) and a branched starch used in the present invention.
  • FIG. 5 The branched starch and raw material liquefied starch used in the present invention (25% concentrated corn starch liquefied solution) were dispensed into glass test tubes and refrigerated at a temperature of 5 ° C for 10 days. It is a photograph.
  • Branched starch 1 (acting amount of cyclic maltosyl maltose producing enzyme 0.001 unit)
  • Branched starch 2 (acting amount of cyclic maltosyl maltose producing enzyme 0.025 unit)
  • Branched starch 3 (acting amount of cyclic maltosyl maltose producing enzyme 0.05 unit)
  • A Schematic diagram of liquefied starch
  • the branched starch derivative referred to in the present invention is a reaction of an enzyme and its substrate or a reactive reagent with a branched starch having a 6a maltosyl branched structure and / or a 6a maltotetraosyl branched structure.
  • a product obtained by substituting at least one hydroxyl group of the branched starch with a substituent other than the hydroxyl group is used.
  • the reaction system used for obtaining the branched starch derivative of the present invention means an enzyme reaction system or a chemical reaction system using a reactive reagent, and in the case of a chemical reaction system, in a normal enzyme reaction system, Even modified O-glycosyl groups that are difficult to introduce can be introduced.
  • esterification As the chemical reaction system, esterification, etherification, sulfonylation, amination reaction, oxidation reaction, etc., which are usually used in the manufacture of carbohydrate derivatives such as starch, can be adopted.
  • the method can be widely adopted.
  • Branched starch having a 6-a maltosyl branched structure and / or a 6-a maltotetraosyl branched structure used in the present invention is an ⁇ -1, 6 bond in the molecule with maltose units and / or maltotetraose units.
  • the molecular weight of the branched starch is not particularly limited, but is preferably 1.0 ⁇ 10 4 daltons or more.
  • a kind of starch debranching enzyme that specifically hydrolyzes ⁇ -1,6 bonds, maltose per solid is 1.8% by mass or more. It is characterized by producing 0.7% by mass or more of maltotetraose (hereinafter, unless otherwise specified, mass% is expressed as “%” in the present specification). Since the chain length (degree of glucose polymerization) of ordinary starch generally has a peak at 9 to 10, this branched starch has a branched structure having a specific chain length that is extremely short. It can be clearly distinguished from existing starch used as a raw material. In addition, this branched starch has a relatively low molecular weight, although the number of branches is increased and the straight chain portion is short compared to normal starch.
  • the number of branches branched by ⁇ -1 and 6 bonds is increased compared to the existing starch. This indicates that the presence of glucose in which the 1-position and 6-position hydroxyl groups are involved in the dalcoside bond in a partially methylated product by performing a known methylation analysis. 2, 3, 4 Trimethylolene 1, 5, 6
  • the content of cetinoregenosito monole (hereinafter abbreviated as “2, 3, 4 trimethylated product”) is higher than that of the raw starch, and is usually 0 per part of solid methylated product.
  • the branched starch having a 6-a maltosinole branched structure and / or 6-a maltotetraosyl branched structure used in the present invention is specifically described later in the experimental section. Even when it is kept at 5 ° C for 10 days, it does not substantially show white turbidity due to aging of starch, and shows remarkable aging resistance compared to raw material liquefied starch! / Has features!
  • a method for producing a branched starch having a 6-a maltosyl branched structure and / or a 6-a maltotetraosyl branched structure used in the present invention its origin, production method, etc., unless the object of the present invention is impaired. Regardless of the method, it may be produced by a method such as an enzymatic method, a fermentation method, or a synthesis method with no particular restrictions.
  • a method is preferred in which liquefied starch is used as a raw material and an enzyme that acts on this to produce a 6a maltosyl branched structure and / or a 6a maltotetraosyl branched structure in the starch molecule is suitable.
  • Such an enzyme acts on liquefied starch, recognizes the maltose structure present at the non-reducing end, and converts this maltose into ⁇ -maltosyl transfer force to the other non-reducing terminal glucose residue of starch molecule or 6-position hydroxyl group of glucose residue inside starch molecule, or this maltose to 4-position of other non-reducing terminal glucose residue of starch molecule
  • Any enzyme can be used as long as it catalyzes the reaction of ⁇ -maltosyl transfer to a hydroxyl group.
  • the cyclic maltosyl maltose producing enzyme disclosed in Japanese Patent Application Laid-Open No. 2005-95148 by the same applicant as the present applicant can be suitably used.
  • the cyclic maltosyl maltose producing mechanism of the cyclic maltosyl maltose producing enzyme that can be used in the production of the branched starch used in the present invention is as follows.
  • 6-a-maltosyl-malto-oligosaccharide acts on 6-a-maltosyl-malto-oligosaccharide and cyclizes by intramolecular ⁇ -maltosyl transition to cyclo ⁇ 6)-a-D-darcopyranosyl mono (1 ⁇ 4)-a-D gno Lecopyranosinole (1 ⁇ 6)-a—D Gnolecopyranosinole (1 ⁇ 4)-a—D Cyclomalosyl maltose (1 ⁇ and a degree of glucose polymerization of 4 Produces reduced maltooligosaccharides.
  • the enzyme also catalyzes a slight intermolecular 4a maltosyl transfer, and produces a few malto-oligosaccharides with an increased glucose polymerization degree of 2 and malto-oligosaccharides with a decreased glucose polymerization degree of 2.
  • Enzymes that catalyze the above reactions are included in cyclic maltosyl maltose-producing enzymes that can be used in the preparation of branched starches used in the present invention, regardless of their source, form, crude enzyme or purified enzyme.
  • cyclic maltosyl maltose-producing enzyme used in the present invention is not limited by its source, a preferred source is a microorganism, such as Alslopacter globiformis M6 (National Institute of Advanced Industrial Science and Technology) A cyclic maltosyl manreose-producing enzyme produced by the biological deposit center, accession number FERM BP-8448) is preferably used.
  • the microorganism having the ability to produce cyclic maltosyl maltose producing enzyme includes not only the above-mentioned bacteria, but also mutants thereof, and other microorganisms including recombinant microorganisms having the ability to produce cyclic maltosyl maltose producing enzyme, and Those mutants are also included.
  • the cyclic maltosyl maltose producing enzyme used in the production of the branched starch used in the present invention may be a purified enzyme or a crude enzyme as long as it can be used for the preparation of the branched starch, and a free enzyme. Even an immobilized enzyme can be used.
  • the reaction format may be batch, semi-continuous or continuous.
  • the immobilization method include a carrier bonding method (for example, a covalent bonding method, an ionic bonding method, or a physical adsorption method), and a crosslinking method! /, A comprehensive method (lattice type or microcapsule type), Known methods can be used.
  • Starch used as a raw material for producing the branched starch used in the present invention is, for example, corn starch, potato starch, rice starch, ground starch such as glutinous starch, potato starch, sweet potato starch, tapio starch
  • underground starch such as waste starch can be advantageously used industrially.
  • amylose obtained from starch, amylopectin, a partially degraded starch, etc. can be used as a raw material.
  • Starch Power In producing this branched starch it is preferable to use the raw material starch as described above, usually gelatinized and / or liquefied. Starch gelatinization • A known method can be adopted as the liquefaction method itself.
  • a method of allowing a cyclic maltosyl maltose producing enzyme to act on liquefied starch can be preferably carried out under the following conditions.
  • the concentration of liquefied starch is usually 10% to 45%. If the concentration of the liquefied starch is less than 10%, the cyclic maltosyl maltose-producing enzyme is more likely to catalyze the intramolecular maltosyl transfer reaction, and cyclic maltosyl maleretose is produced rather than the branched starch, resulting in a decrease in the yield of the branched starch.
  • it exceeds 45% it is difficult to dissolve starch in water.
  • the cyclic maltosyl maltose-producing enzyme is 0.01 unit to 10 units, preferably 0.02 units to 1 unit, per gram of liquefied starch solids. Used to be One unit of enzyme here refers to the cyclic malto described later
  • the amount of enzyme that produces 1 ⁇ mol of cyclic maltosyl maltose per minute under the conditions of the activity measurement method for sylmaltose-producing enzyme is defined as 1 unit. If the amount of cyclic maltosyl maltose-producing enzyme used is less than 0.01 units, the reaction will be insufficient and the meaning of adding the enzyme will be meaningless. Is also not preferred.
  • the reaction temperature in the enzyme reaction may be a temperature at which the reaction proceeds, that is, up to around 60 ° C. Preferably a temperature in the vicinity of 30 ° C to 50 ° C is used.
  • the reaction pH is usually adjusted to a range of 5 to 9, preferably 5 to 7.
  • the amount of enzyme used and the reaction time are closely related, and may be appropriately selected depending on the progress of the target enzyme reaction.
  • a reaction product obtained by the reaction can be used as a raw material for producing a branched starch derivative as it is. If necessary, the product obtained by the reaction is centrifuged, filtered to remove insoluble matters, and the water-soluble fraction is concentrated to prepare a solution for preparing the desired branched starch derivative of the present invention. It can also be obtained.
  • the obtained branched starch solution can be used as it is for the preparation of branched starch derivatives, it is advantageous for storage and handling, and depending on its use, it is desirable to dry and obtain a powder. For drying, freeze drying or spray drying or drum drying can be used. It is desirable to grind the dried product if necessary.
  • reaction product obtained by allowing a cyclic maltosyl maltose-producing enzyme to act on liquefied starch usually contains a small amount of cyclic maltosyl maltose together with the branched starch
  • this reaction product can be used as it is for preparing a branched starch derivative.
  • oligosaccharide can be removed and purified to be used advantageously for the preparation of branched starch derivatives.
  • a conventional polysaccharide purification method such as gel filtration chromatography may be appropriately selected as necessary.
  • the branched starch obtained in this manner has the characteristics that, even when the solution is left at a low temperature, white turbidity due to aging is not observed and remarkable aging resistance is observed as compared with ordinary starch. is doing.
  • starch is insoluble in cold water.
  • the branched starch used in the present invention dissolves in cold water to at least 20%.
  • this branched starch has a lower viscosity compared to the raw starch liquefaction solution, and it is easy to handle when preparing branched starch derivatives. Is excellent.
  • the enzyme reaction system used for obtaining the starch derivative of the present invention refers to a reaction system capable of substituting the hydroxyl group of the branched starch with an O-glycosyl group, and the O-daricosyl group substituted by this reaction. And a reaction system in which the hydroxyl group is further substituted with an O-glycosyl group.
  • one or more of enzymes having transglycosylation ability such as cyclomaltodextrin glucanotransferase, / 3-galatatosidase, ⁇ -galactosidase, lysozyme, etc. are added to the branched starch as a substrate of the enzyme.
  • one or two or more arbitrary hydroxyl groups of the branched molecule are bonded to one or two or more ⁇ D —dalcobilanosyl groups, ⁇ -D galactopyrano
  • a saccharide obtained by transferring one or more of a glycosyl group such as a syl group and a ⁇ -D chitosaminyl group, and further an ⁇ -D-darcobilanosyl group transferred to a carbohydrate derivative of these cyclic tetrasaccharides, / 3— D galactoviranosyl group and / or / 3— D chitosaminyl group and other glycosyl groups, ⁇ D gnolecopyranosinole group, ⁇ D galactoviranosinore group, ⁇ —D It refers to a reaction system to transfer one or two or more one or more of the
  • the hydrocarbon group referred to in the present invention is a group composed of one or more carbon atoms and hydrogen atoms, and includes a saturated or unsaturated hydrocarbon group.
  • the substituent having an oxygen other than a hydroxyl group as used in the present invention means all substituents having an oxygen atom excluding a hydroxyl group, and generally an oxygen atom and another atom such as hydrogen or carbon. , This means a substituent composed of nitrogen, sulfur, halogen or the like.
  • glucose, sulphatose and its multimers caproic acid, strength prillic acid, strength purine acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, ariaic acid, lignoceric acid, zomarinic acid
  • Fatty acid esters acetic acid, propionic acid with saturated or unsaturated, branched or straight chain fatty acids such as lenic acid, linoleic acid, linolenic acid, cadrenic acid, erucic acid, ceracoleic acid, etc.
  • Carboxylic acid ester with benzoic acid, sulfuric acid ester, phosphoric acid ester, and fragrance such as alkyl ether with C1-C18 alkyl alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, benzyl alcohol, phenol, etc.
  • Various esters or ethers such as aromatic ethers with aromatic alcohols, Hexyl group, can be enumerated an aldehyde group, a functional group other than hydroxyl group having an oxygen atom such as a ketone group, a carboxyl group, an aldehyde group, a ketone group, hydrocarbon group having a functional group such as a hydroxyl group, and various oxides and the like.
  • the substituent having nitrogen as used in the present invention means all substituents having one or more nitrogen atoms, and generally means a substituent composed of a nitrogen atom and other atoms.
  • the substituent having sulfur as used in the present invention means all substituents having one or more sulfur atoms, and generally means a substituent composed of a sulfur atom and other atoms.
  • the halogen-containing substituent in the present invention means all substituents having one or more halogen atoms, and generally means a substituent composed of a halogen atom and another atom.
  • functional groups such as fluorine group, black mouth group, bromo group, and iodine group, or substituents having these, and various halides can be listed.
  • a branched starch derivative of the present invention As a method for producing a branched starch derivative of the present invention, a branched starch is dissolved, suspended or immersed in a solvent described later, and if necessary, a substrate which becomes a donor of a substituent together with a catalyst (including an enzyme). Alternatively, a reactive reagent may be added, mixed and stirred by an appropriate method, and performed under appropriate reaction conditions (temperature, time, pH, pressure, etc.). Furthermore, the produced branched starch derivative can be purified by removing unreacted substrates, reactive reagents, solvents and / or catalysts by an appropriate separation and purification method.
  • Examples of the solvent used in the present invention include propane, butane, pentane, hexane, isohexane, heptane, isoheptane, isooctane, benzine, rubber volatile oil, soybean volatile oil, mineral spirit, cleaning solvent, Petroleum ether, petroleum benzine, lignin, kerosene, cyclohexane, methylcyclohexane, benzene, benzonole, toluene, toluol, xylene, xylol, ethylbenzene, tamen, mesitylene, light sorbent naphtha, heavy solvent naphtha, tetralin, Hydrocarbon solvents such as decalin, creosote oil, turpentine oil, methyl chloride, methylene chloride, black form, carbon tetrachloride, dichlorodifluoromethane, chlorinated chloride, 1,
  • Methinoreisobutinorecanolebinole n-hexanolreconole, 2-ethylbutanol, n-octylalcohol, 2-ethylhexanol, cyclohexanolenole, funolefrinoreanoreconole, tetrahydro Alcohol or phenolic solvents such as funolefurinorenoreconole, bendinoreanolol, phenol, talesol, etc.
  • Ether solvents such as tetrahydropyran and benzylethyl ether, formic acid, acetic acid, acetic anhydride, butyric acid, methyl formate, ethyl formate, Butyl formate, amyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, sbutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, ethyl propionate, butyl propionate, propionic acid Amyl, butyrate butyrate, jetyl carbonate, jetyl oxalate, methyl lactate, ethyl acetate lactate, triethyl phosphate, acid such as butyrolatatane, trifluorobutyric acid or their ester solvents, ethylenic glyco
  • branched starch it is preferable to use a solvent capable of dissolving at least one of the branched starch derivatives of the present invention because the synthesis efficiency is increased.
  • a solvent capable of dissolving at least one of the branched starch derivatives of the present invention because the synthesis efficiency is increased.
  • the reaction system contains water! /, Or may! /
  • Water or other hydrophilic solvents can be used as the solvent. These solvents can be used alone or in combination of two or more. Those substituted with one or more substituents other than hydroxyl groups!
  • a solvent that is hardly soluble or insoluble in the branched starch is used as a solvent for dissolving the branched starch. If it cannot be dissolved sufficiently, it is desirable to increase the efficiency by using powdered branched starch.
  • the particle size of the branched starch powder should be a size suitable for the solvent in which it is suspended and the reaction conditions. Normally, the smaller the particle size, the higher the reaction rate, so the reaction rate can be increased by selecting an appropriate particle size. Can be adjusted.
  • the particle size of the branched starch powder used in the present invention may be appropriately determined according to the target branched starch derivative or reaction system, and is usually 500 ⁇ m or less, preferably from 0.1 ⁇ m to 250 ⁇ m, more preferred (between 1 ⁇ m and 100 ⁇ m).
  • Examples of the catalyst used in the present invention include aluminum chloride, aluminum bromide, zinc chloride, antimony chloride, boron fluoride, copper chloride, tin chloride, phosphorus chloride and other Lewis acids, hydrogen fluoride, phosphoric acid and the like.
  • Basic organics such as alkali or alkaline earth metal hydroxides or oxides such as Bronsted acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, magnesium oxide, potassium oxide, and amines
  • bases such as compounds, heavy metals such as platinum, palladium, nickel, cobalt, copper, chromium, molybdenum, silver, and zinc, or oxides, sulfides, and Raney catalysts, and one or more Can be used in combination.
  • These catalysts are usually Yogu be properly selected by the branch starch derivatives or the reaction system for the purpose, with respect to branched starch, typically, the weight is 0.0001 0/0 or more, preferably (or, 0.001 0 / 0 to 10,000%, more preferably (between 0.01% and 1,000%).
  • the reactive reagent used in the present invention is a branched starch containing a hydrocarbon group, an oxygen-containing substituent, a nitrogen-containing substituent, a sulfur-containing substituent, a halogen-containing substituent, etc. in the branched starch.
  • the molar ratio of the reactive reagent to branched starch may ⁇ be suitably determined in accordance with the branched starch derivatives and the reaction system for the purpose, usually 0.01 to 10, 000 Monore 0/0, 1 or preferably ⁇ or 0.5 1, 000 is selected from the range of Monore 0/0.
  • the reaction product containing the branched starch derivative of the present invention thus obtained is usually an unreacted reactive reagent and / or solvent by filtration, extraction, liquid separation, fractional precipitation, dialysis, distillation, etc. Is used as it is.
  • branched starch derivative for example, sugar or branching such as thin layer chromatography, column chromatography, ion exchange chromatography, high performance liquid chromatography, gas chromatography, distillation, crystallization, etc.
  • branching such as thin layer chromatography, column chromatography, ion exchange chromatography, high performance liquid chromatography, gas chromatography, distillation, crystallization, etc.
  • the conventional methods in the art for purifying starch derivatives may be applied, and these purification methods may be applied in appropriate combination as necessary.
  • the production method of the branched starch derivative by ester-etherification reaction is applied when a hydrophobic group such as an alkyl group, an acyl group or an aromatic hydrocarbon group is introduced.
  • a carboxylic acid ester such as acetic acid, propionic acid or benzoic acid can be obtained by reacting a corresponding acid anhydride or acid halide with a branched starch in a basic organic solvent such as pyridine.
  • the sulfate ester can be obtained by reacting a complex of sulfur trioxide with dimethyl sulfoxide or pyridine with a branched starch in an inert gas or a rare gas stream.
  • Fatty acid esters such as acids, ferroacids, and ceracoleic acid can be obtained by the reaction of a condensation reaction under a basic catalyst and the corresponding fatty acid halide.
  • Ethers such as methyl ether, benzyl ether, trityl ether, methyl silyl ether and dodecyl ether are capable of reacting an excess amount of the corresponding alcohol with the branched starch under an acid catalyst, and the corresponding alkyl halide under a basic catalyst. It can be obtained by reacting with or diolenoquinolate sulfate.
  • the production method by the sulfonylation reaction is useful for producing a reaction intermediate for obtaining various derivatives.
  • substituents such as amino group, azide group and halogen group are added. It can be introduced by nucleophilic reaction. It is also possible to limit the sites for introducing substituents by selecting reaction conditions. Noh. For example, when tosyl chloride is reacted in pyridine, a tosylated branched starch in which the primary hydroxyl group is tosylated is obtained.
  • the fermented carboxylic acid sodium salt may be heated and reacted in dimethyl sulfoxide to introduce a fermented carboxylic acid group into the branched starch.
  • the above-mentioned tosylated branched starch is diazotized with sodium azide, and then reduced to convert it to an amino group to produce an S-linked alkylated branched starch.
  • the alkyl group can be introduced through a sulfide bond by epoxidizing tosylated branched starch under alkaline conditions and reacting with alkyl sulfide.
  • the production by 2, 2, 6, 6 tetramethyl-1-piperidinyloxylation reaction can be applied to the production of a carboxylated branched starch.
  • branched starch is mixed with 2, 2, 6, 6-tetramethyl-1-piperidinyloxy-sodium perchlorate, sodium bromide, sodium chlorite, and reacted at pH 9-11, the first grade of branched starch
  • the hydroxyl group is oxidized to a carboxyl group, and carboxylated branched starch can be obtained.
  • the carboxyl group has the ability to bind to a compound having an amino group by an amide bond.
  • a compound in which a spacer having an amino group such as an aminohexyl group is introduced is allowed to react with 1- (3-dimethylaminopropyl) 3-ethinorenoylimideimide hydrochloride in a phosphate buffer at room temperature. Can be linked through an amide bond.
  • Production by an oxidation reaction is used when producing oxidized branched starch.
  • low-temperature oxidation in an aqueous solution or a water suspension is preferable, but a method in which a powder impregnated with an oxidizing agent is heated by calorie can be mentioned.
  • suitable oxidizing agents used for oxidation are, for example, sodium hypochlorite, hydrogen peroxide and the like.
  • a butyl monomer such as acrylic acid or methacrylic acid is added to enzymatically synthesized amylose in the presence of iron or cerium ion.
  • a carboxylic acid having a hydroxyl group such as lactic acid in a branched manner by polycondensation.
  • a monomer that itself has biodegradability such as lactic acid and force prolatatone.
  • the cross-linking reaction may be performed by, for example, converting a branched starch into formalin, epichlorohydrin, gnoretanolenodehydride, various diglycidyl ethers and esters in the same manner as a normal starch cross-linking reaction. It is also optional to carry out a crosslinking reaction using
  • the branched starch derivative of the present invention in which the hydroxyl group of the branched starch is substituted with another functional group can be used to form a conjugate with another organic compound.
  • Specific examples of the production include, for example, a method of introducing an aldehyde group into the branched starch, a method of adding a halogenated methyl group to the branched starch, and then subjecting it to an oxidation reaction with dimethyl sulfoxide, hexamine or the like.
  • a method for introducing a halogen group into a branched starch for example, in order to introduce a chloro group, there may be mentioned a method in which concentrated hydrochloric acid and zinc chloride are added to a branched starch and reacted in a heated or dry hydrogen chloride gas stream.
  • a method for introducing an amino group into the branched starch there may be mentioned a method in which a halogenated carboxylate or epichlorohydrin is reacted with the branched starch to form a halide and then reacted with ammonia.
  • a method for introducing a mercapto group there may be mentioned a method in which the halogenated branched starch is reacted with a sulfurizing agent such as sodium thiosulfate and reduced with lithium aluminum hydride or the like.
  • Examples of other substances capable of forming a conjugate with the branched starch derivative of the present invention into which these functional groups are introduced include biologically and physiologically active substances.
  • Power S can be. More specifically, for example, physiologically active substances such as interferon, tsumanecrosis factor, erythropoietin, interleukin 2 and the like, hormones such as insulin and steron, amino acids, oligopeptides, polypeptides, proteins , Nucleic acids, carbohydrates, lipids, vitamins, antibiotics, and hapten molecules for inducing antibodies.
  • the branched starch derivative of the present invention binds to a dye or fluorescent substance such as dansyl glycine, N, N dimethylaminobenzoyl group, methyl red, paramethyl red, anthracene-9 carbonyl group, pyrene, or azobenzene. These can also be used as detection reagents. Furthermore, the branched starch derivative of the present invention can bind a 2-hydroxypropyl group, a pyridoxamine residue, p-methoxyphenol, p-nitrophenol, benzofuroxan, metaphorbol, etc., and these can react with other substances. It can be used as a medium.
  • the branched starch derivative of the present invention also binds to a polymer carrier such as polybutyl alcohol, polyacrylamide, polyethylene glycol, polypropylene glycol, polymethyl butyl ether, cellulose, or derivatives thereof. These can be used for analysis and purification of other substances.
  • a polymer carrier such as polybutyl alcohol, polyacrylamide, polyethylene glycol, polypropylene glycol, polymethyl butyl ether, cellulose, or derivatives thereof.
  • Branched starch derivatives obtained by these production methods are used only in the fields of food industry, cosmetic industry, pharmaceutical industry, etc., in various fields such as catalyst, fiber, packaging, architecture, paint, analysis, electricity, communication, etc. Have a wide range of uses.
  • the branched starch derivative of the present invention into which a hydrophobic group such as a phenyl group, an alkyl group, and a acetyl group is introduced is fat-soluble and is useful as a surfactant in foods, cosmetics, pharmaceuticals and the like.
  • the branched starch derivative of the present invention in which a sulfate ester is introduced can be advantageously blended in cosmetics as an excellent moisturizing agent and skin beautifying agent.
  • the branched starch derivative of the present invention into which a functional group having a binding property such as a bur group, an amino group, a carboxyl group, a mercapto group, or a halogen group or a substituent having such a group may contain other organic compounds and / or branched starch. Since it can be bound to itself, it can be used for the production of new organic compounds by forming multimers including homo- or hetero-dimers, and for analysis, detection and purification by binding to other polymer carriers Can be used for carrier preparation, modification of physical properties of other compounds such as proteins, and catalytic reactions of other compounds. Introduced functional groups such as cyano group, nitro group, nitroso group or substituents having these.
  • the branched starch derivative of the present invention can be used as an antibacterial agent, immunostimulant, anticancer agent, etc., as a pharmaceutical, a fiber material, a packaging material, or a building material.
  • the branched starch derivative of the present invention having a dissociative functional group such as a carboxyl group or a halogen group and the branched starch derivative of the present invention having a polarizable functional group such as a hydroxyl group or an amino group have dielectric properties. It can be used as an additive for fuel cells.
  • the derivatives of the present invention having an alkyl alcohol group such as a hydroxymethyl group, a hydroxychetyl group and a hydroxypropyl group are further improved in water solubility.
  • thermoplasticity increases as the number of substituents introduced increases. For example, large substituents introduced by the grafting reaction significantly reduce the heat flow temperature. Therefore, the molding process with a normal plastic molding machine is easier than those without chemical modification. Furthermore, it can be used in the same manner as general-purpose plastics in the fields of films, sheets and molded products that require water resistance.
  • the chemically modified product is converted into an aqueous solution, paste or cream form. It is easy to process and can be stored in a bottle or tube for a long period of time.
  • branched starch can be prepared into a superabsorbent gel by grafting reaction, and can be insolubilized in water and other solvents by subjecting it to a crosslinking reaction. It is also optional to prepare a gel with a wide range of swelling degrees.
  • the basic skeleton of the branched starch derivative of the present invention is the same as that of the branched starch, usually, the characteristics and functions of the branched starch are partially retained. Therefore, the derivative can be used for the same purpose as the branched starch.
  • the use of the branched starch derivative of the present invention will be described in more detail.
  • the branched starch derivative of the present invention usually retains partially the properties and functions of the branched starch, depending on the type and substitution rate of the substituent, and, like the branched starch, Used as materials and base materials in various fields such as cosmetics, quasi-drugs, pharmaceuticals, feed, feed, chemicals, industrial products, civil engineering greenery products, agricultural and forestry products, horticultural materials, powdered products, miscellaneous goods, etc. Ability to rub with S.
  • the branched starch derivative of the present invention when used as a substitute for ordinary starch in foods and drinks containing starch, it has aging resistance itself, so that Foods and beverages in which the above is suppressed are obtained. Therefore, foods and drinks containing the branched starch derivative of the present invention are those in which a decrease in water retention, shape retention, freezing resistance, digestibility and the like due to aging of starch is suppressed. Examples of foods and drinks containing starch include rice cakes, dumplings, rice cakes, breads, potatoes, starch-containing sports drinks, and starch-containing dietary supplements.
  • branched starch derivative of the present invention As a method for incorporating the branched starch derivative of the present invention as described above into various composition forms, it may be contained in the process until the product is completed, for example, mixing, kneading, Known methods such as dissolution, dipping, infiltration, spraying, coating, coating, spraying, pouring and solidification are appropriately selected.
  • the amount is usually 0.1% or more, preferably 1% or more, and more preferably 2% or more, and can be appropriately selected according to the purpose.
  • the branched starch derivative of the present invention has properties such as shaping, irradiating property, moisture retention, viscosity, freezing resistance, drying resistance, heat resistance, and retention. Therefore, the branched starch induction
  • the body is a taste improver, quality improver, water separation inhibitor, stabilizer, discoloration inhibitor, excipient, inclusion agent, binder, adhesive, molding agent, shaping agent, thickener, stabilization Food, food, food, food, food, pet food, cosmetics, quasi-drugs, pharmaceuticals, agricultural chemicals, biocompatible medical materials, miscellaneous goods, civil engineering greening products, etc. It can be advantageously used for the production of various molded products such as agricultural and forestry products, horticultural materials, powder products, industrial products, and chemical products.
  • the molded product containing the branched starch derivative of the present invention is particularly suitable as a molded product that requires biodegradability.
  • paper non-woven fabrics, woven fabrics, knitted fabrics, yarns, fibers including slit fibers, ropes, tubes, ropes, foamed containers, hamburgers, ice cream, ramen, juices, coffee, beer, milk, etc.
  • Containers such as food containers and ice cream corn cups, tableware, trays, dishes, cups, cartons, garbage bag containers, packaging boxes, agricultural and horticultural pots, artificial wood, foam sheets, films, capsules, rose-shaped cushioning materials , Adhesive moldings, agricultural house sheets and construction sheets, such as civil engineering sheets, various packaging films including agricultural films, and coatings such as paint, cement, concrete It can be advantageously used for chemical products such as plastics and industrial products.
  • these molded products may be solutions, semi-solids, solids, pastes, foams, films, sheets, tubes, capsules, short bars, plates, chips. What was shape
  • these molded products can be used in the field where plastic foam has been used.
  • low foams are suitable for packaging materials for electrical appliance cabinets, automobile handles, bumpers, interior parts, and the like.
  • Other uses that require lightness and safety such as home interior items, hotel toothbrushes, spoons for in-flight meals, forks, dishes and trays, toys, air gun balls, stationery, office supplies, etc. .
  • the high foam is particularly effective as an alternative material for polystyrene foam, which currently has a problem in disposal.
  • tableware packaging containers such as food trays and instant potato containers, marine products, transport boxes such as agricultural products boxes, packaging boxes, electrical products, cushioning materials such as cushioning materials for precision equipment, construction, roads Sound insulation and heat insulating materials are suitable.
  • the molded product containing the branched starch derivative of the present invention includes a hat
  • a hat examples include clothing such as ponchos and windbreakers, packaging materials such as garbage bags and souvenir bags, and exercise equipment such as ski poles.
  • the branched starch derivative of the present invention that has been substituted with a hydrophobic substituent to enhance the hydrophobicity can be advantageously used as a biocompatible material, such as a medical thread or gauze.
  • the molded product containing the branched starch derivative of the present invention civil engineering greening products such as piles, piles, gonorefty, agricultural films, seedling pots, agricultural and horticultural pots, agricultural and forestry supplies, horticultural use It is preferable to knead known fertilizers such as chisso, phosphorus, potash, etc., effective fungi, and / or pesticides in advance for the material supplies since they become more effective as fertilizers after biodegradation.
  • the addition ratio is 0% to 80%, preferably 5% to 30%.
  • the molded product containing the branched starch derivative of the present invention can be formed into a desired shape such as a film, a sheet, a tube, or a capsule by using, for example, an ordinary plastic molding machine.
  • the molding method is not particularly limited. For example, extrusion molding, injection molding, pressure molding, mold molding, cast molding, blow molding, stamping molding, cutting molding, thermoforming, and film molding methods are used as appropriate. The method can be used.
  • the resulting molded product can also be used as a biodegradable molded product.
  • a water-soluble polysaccharide other than the branched starch derivative such as starch, a partially decomposed starch product, amylose, or amylope, is used as a polymer material as necessary. Kuching etc.
  • Starch derivatives esterified, etherified, oxidized and / or cross-linked starch derivatives, punoleran, sodium alginate, agar, pectin, xanthan gum, dextran, carrageenanan, native dielan gum, galatatomannan, chondroitin sulfate
  • a plasticizer or a gelling agent can be advantageously added to adjust the plasticity of the molded product.
  • plasticizers include water and various polyols, for example, polyalcohols such as glycerin and polybutal alcohol, sugar alcohols such as erythritol, xylitole, sonorebitol, multitole, ⁇ , a-trehalose, cyclodextrin, international publication WO 02 / Cyclo disclosed in the specification of No. 10361 etc.
  • Thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, natural rubber, shellac resin, polyethylene resin, polystyrene resin, polyvinyl chloride resin, polypropylene resin, acrylic resin, polyester resin Mix with powder or pellets of thermoplastic polymer material, add emulsifier, heat stabilizer, quality improver, preservative, etc., heat to 150 ° C to 250 ° C, press molding
  • this branched starch derivative-containing molded product can also be advantageously made into a biodegradable starch-based plastic molded product.
  • Organic components include chitin, chitosan, collagen, hive mouth-in, keratin, rosin, dammar, copal, ⁇ powder, cellulose, wood flour, fiber, pulp, lignin, protein and its degradation products, Waxes, fats and oils, lipids, Sugar fatty acid esters, alcohols such as ethanol, saccharides other than the branched starch derivative of the present invention, cyclic saccharides, sugar alcohols, colorants, pigments, preservatives, flavoring agents, flavoring agents, binders, freshness-preserving agents , Surfactants, builders, co-builders, antioxidants, bleaches, brighteners, dispersants, antifoaming agents, water softeners, UV reflectors, UV absorbers and
  • Partially decomposed starch (trade name “Pinedettas # 4”, manufactured by Matsutani Chemical Co., Ltd.) 1.5 w / v (mass / volume)%, yeast extract (trade name “Polypeptone”, manufactured by Nippon Pharmaceutical Co., Ltd.) 0. 5w / v%, yeast extract (trade name "Yeast Extract S”, manufactured by Nippon Pharmaceutical Co., Ltd.) 0. lw / v%, dipotassium phosphate 0.
  • the enzyme activity of the cyclic maltosyl maltose producing enzyme was measured by the following method. Dissolve soluble starch in 50 mM acetate buffer (pH 6.0) containing 2 mM calcium chloride to a concentration of 2 w / v% to make a substrate solution. Add 0.5 ml of enzyme solution to 0.5 ml of the substrate solution. , 40 ° C The reaction solution was heated at about 100 ° C for 10 minutes to stop the reaction, and then ⁇ -dalcosidase (“Trans-Dalcosidase L” was used to degrade the remaining soluble starch and contaminating oligosaccharides.
  • cyclic maltosyl maltose producing enzyme activity is defined as the amount of enzyme that produces 1 ⁇ mol of cyclic maltosyl maltose per minute under the above conditions.
  • the PLC was run using “Shodex SUGAR KS-801” (manufactured by Showa Denko KK) for the column, using water as the eluent, at a column temperature of 60 ° C and a flow rate of 0.5 ml / min.
  • the detection was performed using a differential refractometer RI-8012 (manufactured by Tosoh Corporation).
  • Cyclic maltosyl maltose-producing enzyme activity is adsorbed on a DEAE Toyo pearl 650S gel equilibrated with 10 mM Tris-HCl buffer ( ⁇ ⁇ 7.5), and has a linear gradient from 0 M to 0.4 M salt concentration. Upon elution, it was eluted at a salt concentration of about 0.22M. Collect this active fraction, add ammonium sulfate to a final concentration of 1M and leave it at 4 ° C for 24 hours, then centrifuge to remove insolubles.
  • Phhenyl-Toyopearl 650M gel was used for hydrophobic chromatography (gel volume 10 ml).
  • Cyclic maltosyl maltogenic enzyme activity is adsorbed on a “Phenyl-Toyopearl 650M” gel equilibrated with 20 mM acetate buffer (pH 6.0) containing 1 M ammonium sulfate. And elution with a linear gradient of 0M, the ammonium sulfate concentration was about 0.1M. Cyclic maltosyl maltose producing enzyme activity, cyclic malt in each step of this purification Table 1 shows the specific activity and yield of sylmaltose-producing enzyme.
  • the purified cyclic maltosyl maltose-producing enzyme preparation after hydrophobic chromatography was subjected to 5 to 2 Ow / v% concentration gradient polyacrylamide gel electrophoresis, and the purity of the enzyme preparation was tested. It was a standard product with high purity.
  • 2,500 g of commercially available rice cake corn starch (sold by Sanwa Starch Co., Ltd.) is suspended in 25 L of tap water containing ImM calcium chloride, adjusted to pH 6.0 with 2N hydrochloric acid, and 10% starch starch is added.
  • 20,000 units of ⁇ -amylase (trade name “Neospirase PK 2”, manufactured by Nagase Seikagaku Corporation) to this starch milk, stir for 30 minutes, and then pass through the continuous liquefaction device at a flow rate of 1 L / min. did.
  • the starch milk was heated at 100 ° C. for 25 minutes and then at 140 ° C.
  • liquefied starch a starchy corn starch liquor
  • the obtained liquefied liquid was decolorized with activated carbon, filtered through diatomaceous earth, and concentrated under reduced pressure to a concentration of 25%.
  • This concentrated liquefied solution is divided into 5 equal parts, and the cyclic maltosyl maltose-producing enzyme purified sample obtained in Experiment 1 is divided into 4 liquefied solutions by adding 0.0125, 0, 025, 0.05, or 0.1 unit of harm, calories with U, and allowed to act at 50 ° C, pH 6.0 for 24 hours.
  • HPLC uses “MCIgel CK04SS” (manufactured by Mitsubishi Chemical Corporation) connected in series, using water as the eluent, column temperature of 80 ° C, flow rate of 0.4 ml / The detection was performed using a differential refractometer RI-8012 (manufactured by Tosoh Corporation).
  • Each reaction solution obtained in Experiment 2-1 is filtered, decolorized with activated carbon according to conventional methods, desalted with H-type and OH-type ion exchange resins, purified, and concentrated to 20% solid content with an evaporator. did. Subsequently, in order to remove cyclic maltosyl maltose mixed as a by-product, column fractionation using a strongly acidic cation exchange resin (“Amberlite CR-1310”, Na type, manufactured by Organo Co., Ltd.) was performed. . Resin was packed into four jacketed stainless steel columns with an inner diameter of 5.4 cm and connected in series to a total resin layer length of 240 cm.
  • a strongly acidic cation exchange resin (“Amberlite CR-1310”, Na type, manufactured by Organo Co., Ltd.
  • the branched starch obtained by the method of Experiment 2 was subjected to the following test to examine the structure of the branched starch.
  • Genome filtration analysis was performed by connecting two “TSK-GEL ALPHA-M” columns (manufactured by Tosohichi Co., Ltd.) in series and using lOmM acid buffer (pH 7.0) as the eluent. Detection was performed using a differential refractometer “RI-8012” (manufactured by Tosohichi Corporation) at 40 ° C. under a flow rate of 0.3 ml / min.
  • the branched starch was dissolved in lOmM acid buffer (pH 7.0) and subjected to membrane filtration as a sample for gel filtration analysis.
  • lOmM acid buffer pH 7.0
  • the oxy-starch liquefied liquor before treatment with the cyclic maltosyl maltose-producing enzyme was similarly analyzed.
  • the molecular weight of gnolecan in the sample was calculated based on a molecular weight calibration curve prepared by gel filtration analysis of a pullulan standard product for molecular weight measurement (sales by Hayashibara Biochemicals, Inc.). The elution pattern in gel filtration chromatography is shown in FIG.
  • a is a control (oxyxy corn starch liquefied liquid)
  • “b”, “c”, “d”, and “e” each represent a cyclic manoleorenolease producing enzyme per gram of solid in the liquefied liquid.
  • Branched starch obtained by the action of 0125 units, 0.025 units, 0.05 units and 0.1 units.
  • branched starches obtained by acting 0.0125 units, 0.025 units, 0.05 units and 0.1 units of cyclic maltosyl maltose-producing enzyme per solid of starch corn starch liquefaction are respectively branched. Called starches 1, 2, 3 and 4.
  • the oxy-starch liquefied liquid of the control (a) showed one peak in the gel filtration chromatography.
  • the weight average molecular weight of glucan contained in this peak was calculated to be 1.1 ⁇ 10 6 dalton from the calibration curve data. ⁇ Kishiko Elution of branched starch 4 (e in Fig.
  • the reducing power of the four branched starches 1, 2, 3, and 4 obtained in Experiment 2-2 or the control oxy-starch liquefied liquor was measured.
  • the total sugar content of each sample was determined by the anthrone-sulfuric acid method, and the reduced sugar content was improved by the Park 'Johnson method (Takusaku et al., “Carbohydrate Research”, vol. 94, pages 205-213 (1981). ))),
  • ⁇ -Amylase is an enzyme that hydrolyzes starch in maltose units from the non-reducing end and stops the hydrolysis reaction just before the branching point due to ⁇ -1, 6 bond.
  • the branched starch having a larger amount of cyclic maltosyl maltose producing enzyme has a lower absorbance as a whole.
  • the maximum absorption wavelength was about 520 nm, and no difference was observed between the samples. From the results of Experiment 3-2, hydrolysis due to the action of cyclic maltosyl maltose producing enzyme is hardly observed, but despite this, branch starch with a large amount of cyclic maltosyl maltose producing enzyme has lower absorbance.
  • the branched starch obtained by reacting liquefied starch (Luxi corn starch liquefied liquid) with a cyclic maltosyl manreose-producing enzyme has 6 a maltosyl branched structure and / or 6 a maltotetraosyl branched structure. It was found to be a novel branched starch having A schematic diagram showing the structure of the branched starch used in the present invention is shown in FIG. 4 together with that of the liquefied starch (oxyl corn starch liquefied liquid). In FIG.
  • a and B are schematic diagrams of a liquefied starch (a liquefied liquid of starch corn starch) and a branched starch used in the present invention, respectively.
  • reference numerals 1, 2 and 3 denote liquefied starch ( In the case of glucose (corn corn starch liquefied liquid), the straight chain structure (amylose structure) in which glucose is linked by -1,4 bonds, the site where the straight chain structure is branched by ⁇ -1,6 bonds, and the reducing end glucose
  • the symbols 4 and 5 mean 6a maltosyl branched structure and 6a maltotetraosyl branched structure in the branched starch used in the present invention.
  • the purified product of cyclic maltosyl maltose-producing enzyme obtained by the method of Experiment 1 was used per 1 starch of the solid starch. 0.1 unit was added, and the mixture was reacted at pH 6.0 and a temperature of 50 ° C for 20 hours. Stop the enzyme reaction by heat treatment at 100 ° C for 20 minutes, then cool and filter the filtrate. According to a conventional method, the product was decolorized with activated carbon and filtered through diatomaceous earth to obtain a branched starch solution having a concentration of about 25% with a yield of about 90% per solid.
  • This branched starch-containing solution was dehydrated with a pulse combustion drying system PULCO (sold by Partec Co., Ltd.), dried and powdered.
  • PULCO pulse combustion drying system
  • the resulting branched starch pullulanase digestion contained 3.7% maltose and 1.7% maltotetraose.
  • the partially methylated product of the obtained branched starch contained 8.2% of 2,3,4-trimethylated product.
  • This product contained 96.7% branched starch and 3.3% cyclic maltosyl maltose per solid. This product can be used for the production of branched starch derivatives.
  • Branched starch production example 1 The solution-like branched starch obtained in Example 1 is filtered, decolorized with activated carbon according to a conventional method, desalted with H-type and OH-type ion exchange resins and purified, and then solid content concentration with an evaporator 20 Concentrated to%. Subsequently, it was subjected to column fractionation using a strongly acidic cation exchange resin (“Amberlite CR-1310”, Na type, manufactured by Organo Corporation) to remove cyclic maltosyl maltose mixed as a by-product.
  • a strongly acidic cation exchange resin (“Amberlite CR-1310”, Na type, manufactured by Organo Corporation
  • the resin was packed into four stainless steel columns with an inner diameter of 5.4 cm and connected in series with a resin layer with a total length of 240 cm, and the starch solution was maintained while maintaining the internal temperature at 60 ° C. 5v / v% was added to the resin, and 60 ° C hot water was added under conditions of SV0.13.
  • a polymer fraction not containing cyclic maltosyl maltose was collected, concentrated to 25%, dehydrated with a pulse combustion drying system PULCO (sold by Partec Co., Ltd.), dried and powdered.
  • PULCO pulse combustion drying system
  • a commercially available starch partial degradation product (trade name “Paindex # 100”, sold by Matsutani Chemical Industry Co., Ltd.) is made into an aqueous solution with a concentration of about 30% (w / v), and calcium chloride is added to a final concentration of ImM, and pH 6. Adjusted to 0.
  • the reaction solution is decolorized with activated charcoal according to a conventional method, purified by diatomaceous earth filtration, and further concentrated to obtain a 30% concentrated branched starch portion.
  • a digest solution was obtained with a yield of about 90% per solid.
  • This branched starch partial decomposition product-containing solution was dehydrated and dried into a powder by using a Norus combustion drying system PULCO (sold by Partec Co., Ltd.).
  • This product contains 90.8% partially degraded starch having a degree of glucose polymerization of 7 or more, 6.7% maltooligosaccharides having a degree of glucose polymerization of 1 to 6, and 2.5% cyclic maltosyl manoleose per solid. It was.
  • This product can be used for the production of branched starch derivatives.
  • This product contains 69.6% of partially degraded starch with a degree of glucose polymerization of 7 or more, 27.3% of maltooligosaccharides with a degree of glucose polymerization of 1 to 6, and 3.1% of cyclic maltosyl maltose per solid. It was. This product can be used to produce branched starch derivatives.
  • the pullulanase digest of this product was a clear solution containing 41.5% maltose and 26.2% maltotetraose.
  • the maltose and maltotetraose content in the pullulanase digest of this product was about 1.5 times higher than that of the partially digested product of the branched starch obtained in Example 3. This indicates that the number of 6-a maltosyl branch structures and / or 6a maltotetraosyl branch structures increases when hydrolyzing a branch with a high degree of polymerization of gnolecose by isoamylase and allowing the action of a cyclic maltosinole maltose-producing enzyme. Suggests that you can.
  • Branched starch production example 4 The solution-like branched starch partial degradation product obtained in Example 4 was filtered and subjected to conventional methods. After decolorization with activated carbon, desalting with H-type and OH-type ion exchange resins and purification, the mixture was concentrated to an solid content of 20% with an evaporator. Subsequently, it was subjected to column fractionation using a strongly acidic cation exchange resin (“Amberlite CR-1310”, Na type, manufactured by Organo Corporation) to remove oligosaccharides containing mixed cyclic maltosyl maltose.
  • a strongly acidic cation exchange resin (“Amberlite CR-1310”, Na type, manufactured by Organo Corporation
  • the resin was packed in four jacketed stainless steel columns with an inner diameter of 5.4 cm and connected in series with a resin layer with a total length of 240 cm. While maintaining the internal temperature at 60 ° C, the starch solution was added to the resin. In addition, 5v / v% was added, and 60 ° C warm water was added under conditions of SV0.13. The polymer fraction containing no oligosaccharide was collected and concentrated to 25%, and then dehydrated and dried into a powder by using the Nors combustion drying system PULCO (Paltec Co., Ltd.). By this operation, a branched starch powder having less hygroscopicity and excellent particle size characteristics was obtained. This product can be advantageously used for the production of branched starch derivatives.
  • Branched Starch Production Example 4 After dissolving 5 parts by weight of the branched starch obtained in the method of 4 in 125 parts by weight of anhydrous dimethyl sulfoxide, 12.5 parts by weight of sodium hydride was added and mixed, and then iced for 10 minutes. After cooling in, it was heated at 60 ° C for 2 hours. Under ice cooling, 21.5 parts by mass of methyl iodide was gradually added and mixed at room temperature for 18 hours. Further, 40 parts by mass of methanol was added and mixed with 200 parts by mass of ice-cooled distilled water. To this, 500 parts by mass of black mouth form was added and mixed, and allowed to stand until the aqueous layer and the chloroform layer were separated, and the black mouth form layer was collected.
  • Branched starch production example 10 parts by weight of the branched starch powder and 200 parts by weight of anhydrous pyridine obtained in the method of Example 2 were placed in a reaction vessel, and 4 parts by weight of thiazolythione-linoleic acid amide dissolved in 5 parts by weight of anhydrous pyridine under an argon stream. added.
  • Add 0.085 parts by mass of 60% (w / w) oily sodium hydride react at room temperature for 2 hours, add 1.5 parts by mass of saturated aqueous ammonium chloride solution to the reaction, and then distill off pyridine under reduced pressure. To obtain 11.2 parts by mass of a residue.
  • n-dodecanol 390 parts by mass of n-dodecanol was placed in a reaction vessel, heated to 125 ° C, 1 part by mass of p-toluenesulfonic acid was added as a catalyst, and the inside of the vessel was depressurized to 5 mmHg to lOmmHg.
  • 100 parts by mass of the branched starch powder obtained by the method of Branched Starch Production Example 2 was suspended in 130 parts by mass of n-dodecanol, and the resulting mixture was kept in a reaction vessel at a rate of 2.3 parts by mass / min for 100 minutes. In addition, it was made to react by adding dropwise.
  • reaction product was neutralized with a saturated aqueous sodium carbonate solution, and unreacted alcohol was distilled off to obtain a dodecyl ether of a branched starch.
  • This product can be advantageously used in detergents and emulsions.
  • branched starch powder obtained by the method of Production Example 2 of Branched Starch was sulfated by the same method as in Example 6 to obtain a molded product containing sulfated ester of branched starch.
  • This product can be advantageously used as a moisturizer and skin beautifier in general cosmetics.
  • Branched starch powder obtained by the method of Production Example 2 of Branched Starch 2 parts by mass of catalytic amount of pyridine, The suspension was suspended in 20 parts by mass of an N, N′-dimethylformamide solution containing 5 w / v% of cyanuric chloride and reacted at room temperature for 3 hours. The reaction mixture was filtered and the residue was washed with acetone and dried to obtain a cyanuric chloride derivative of branched starch. This product can be combined with organic compounds such as peptides, proteins, and nuclear acids.
  • Branched starch powder 15 parts by mass obtained by the method of Production Example 5 of the branched starch was suspended in 50 parts by mass of pyridine, 12 parts by mass of p-toluenesulfuryl chloride was added at 0 ° C., and the mixture was stirred for 18 hours. Extraction with ethyl acetate, washing with dilute hydrochloric acid and brine, drying and concentration gave a tosylated derivative of branched starch. This product is useful as an intermediate for various derivatives.
  • this diazotized derivative was suspended in a mixed solution of 100 parts by mass of purified dioxane and 20 parts by mass of distilled methanol, and 4 parts by mass of purified triphenylphosphine was stirred in the presence of nitrogen gas. While stirring, the mixture was stirred for 1 hour. 5 parts by mass of concentrated aqueous ammonia was added dropwise, and the mixture was stirred for 12 hours in the presence of nitrogen gas. The solvent was removed and the product was suspended in 250 parts by weight of water and adjusted to pH 4 with 1N hydrochloric acid. This suspension was washed with 500 parts by mass of benzene three times to remove triphenylphosphine oxide and lyophilized to obtain an aminated derivative. This product has an ability to bind to organic compounds having a carboxyl group, and is useful as an intermediate for introducing other substituents.
  • Branched starch 10 g of the branched starch powder prepared by the method of Production Example 2 was dissolved in 80 g of dimethyl sulfoxide, 2 g of sodium carbonate was added, 16 g of butyl acetate was added, and the mixture was reacted at 80 ° C. for 120 minutes. After the reaction, water was added to precipitate the product, and after filtration, washed several times with water, purified and dried. A powder of acetylated branched starch having a yield of 90%, a water content of about 10%, a degree of substitution (DS) of 2.1, and a heat fluidization temperature of 275 ° C. was obtained.
  • DS degree of substitution
  • Branched starch production example After preparing 32 g of 2.5% aqueous solution of branched starch powder prepared by the method of 5 to ⁇ 12 ⁇ 8 with sodium hydroxide solution, 1.5 g of nonaethylene glycol diglycidyl ether (sold by Nagase) The product was reacted with a trade name “Denacol EX-830”, molecular weight 526.6) to prepare an aqueous solution of a crosslinked product of branched starch. This aqueous solution was dried by a conventional method to prepare a crosslinked starch powder having a water content of about 5%.
  • Denacol EX-830, sodium hydroxide and uncrosslinked branched starch contained in the film were removed by washing with pure water. This The film was transparent and exhibited excellent strength properties that did not dissolve even when heated to 130 ° C.
  • This product was pulverized by a conventional method to prepare Yujin powder.
  • This powder is a carrot powder that retains the flavor of carrots well even when stored for a long period of time, is colorful, does not solidify, and is highly soluble in water.
  • Water extract of cyanobacteria (produced by Hayashibara Biochemical Laboratories, Inc., solid content: 1.4%) 98 parts by mass, branched starch derivative prepared by the method of Example 3 as a powdered base 0.5 parts by mass, ⁇ —Cyclodextrin 1. 5 parts by mass was added and stirred and dissolved, and this was spray-dried by a conventional method to prepare a green grass extract powder.
  • This product is excellent in storage stability of useful components such as tributanthrine and flavonoids contained in the water extract of indigo grass that absorbs moisture and browns even after long-term storage. This product should be used as a raw material for manufacturing food and drink, cosmetics, quasi drugs, etc.
  • a chocolate containing 0.5% of the powder of this cyanobacteria extract was prepared by a conventional method.
  • This product contains a herb extract and retains its useful components even after long-term storage, so it is used for the prevention of periodontal disease, prevention of hyperlipidemia, treatment and improvement of lipid metabolism.
  • Example 16 [0121] ⁇ Royal jelly powder>
  • This royal jelly powder 27 parts by mass, Coenzyme Q 5 parts by mass, sucrose 5 parts by mass,
  • this product can be advantageously used as a fragrance for food and drink, cosmetics, quasi drugs, and pharmaceuticals.
  • a peppermint powder prepared by the same method as in Example 17 and a peppermint powder prepared in Example 17 were used except that only 20 parts by mass of hydrous crystal trehalose was used as a powdered base.
  • each gum is prepared by a conventional method, and the flavor of the peppermint is subjected to a sensory test by 10 panelists.
  • 8 of 10 panelists evaluated that the gum using the peppermint powder prepared in Example 17 had a stronger peppermint scent and higher persistence than the control. This result shows that the branched starch derivative used as a powdered base contributes to the improvement of the storage stability of fragrances! /.
  • the mixture was heated with stirring at 1 OOrpm to a boiling temperature of 135 ° C. to obtain a melt, and 75 g of orange oil was added to the melt while stirring with a high-speed stirrer and emulsified for 20 minutes. Transfer the emulsion to an extrusion kettle and add 25 ° C isopropyl alcohol. Pressurized into a cooling tank containing squeeze, extruded by injection loci, and pulverized while stirring. The obtained pulverized product was dried under reduced pressure at 40 ° C using a rotary evaporator to remove isopropyl alcohol on the particle surface. was.
  • the powder molded product of dry ⁇ , 2 ⁇ passed through the sieve mesh (mesh opening 840 m), subjected to sieving to remain on the sieve of 60 mesh (opening-out 250 mu m), 60 mesh sieve 80 g of the remaining powder molding was obtained, and the powder molding without deterioration of the fragrance maintained sufficient powder fluidity after long-term storage.
  • a fragrance for cosmetics, cosmetics, quasi-drugs, and pharmaceuticals it is advantageously used for IJ.
  • aqueous solution containing 1.5% polyvinylenoleanolone having an average degree of polymerization of 1150 and a degree of saponification of 99.95% and 2% of a branched starch derivative prepared by the method of Example 2 and reactive dye Kay acion A 1% aqueous solution of Red E—SN7B (manufactured by Nippon Kayaku Co., Ltd.) was mixed with 1.5 liters, adjusted to pH 8 with caustic soda, and then reacted by heating.
  • polyvinyl alcohol having an average degree of polymerization of 1150 and a degree of saponification of 99.95% and a branched starch derivative prepared by the method of Example 2 and water were added to this colored aqueous solution, and 26% of polyvinyl alcohol and that of Example 2 were added.
  • a stock spinning solution containing 6% of the branched starch derivative prepared by the method and 0.3% of the dye was prepared. This spinning solution was dry-spun using a nozzle with 50 holes, drawn 4.5 times, and heat-treated at 220 ° C to obtain a red colored yarn having a melting temperature of 93 ° C. This product has sufficient tensile strength and excellent durability.
  • a 5% aqueous solution of a branched starch derivative prepared by the method of Example 2 was applied onto a 2.5 ⁇ 111-thick polylactic acid film using an applicator and then dried to produce a 3111-thick branched starch. Cast film It was created. A dampened paper was placed on the branched starch surface of the resulting laminate film and dried while pressing. As a result, a three-layer laminate of paper and polylactic acid film using a branched starch as an adhesive layer was obtained. In order to measure the adhesive strength, a 90 degree peel test was conducted, and the adhesive strength was extremely excellent and breakage occurred in the paper layer. However, the breakage in the branched starch layer, the branched starch layer and the paper or No interfacial delamination with the polylactic acid film occurred. Since this product is biodegradable, it is an environmentally friendly film.
  • a pigment slurry consisting of 50 parts by weight of heavy calcium carbonate and 50 parts by weight of kaolin was dispersed using a Coreless disperser to obtain a pigment slurry.
  • Solid content 0.2 parts by weight of water-resistant agent, 0.2 part by weight of lubricant, and other auxiliaries were added and dispersed to prepare a paint having a solid content of 58%.
  • Hardwood bleached kraft pulp was beaten with a Niagara beater and an appropriate amount was added to water to prepare a 400 ml suspension.
  • a branched starch derivative prepared by the method of Example 2 was mixed with the pulp as a powder, and hand-pulled with a paper sheet machine having a basis weight of 100 g / m 2 according to a conventional method.
  • the formed wet paper was dried with a rotary dryer at 90 ° C for 1 minute and then conditioned at a temperature of 20 ° C and a humidity of 65% for 24 hours to obtain kraft paper. This product had sufficient mechanical strength and the like.
  • a water content of about 10% of branched starch derivatives containing 60 parts by mass was prepared by the method of Example 12, E Ji Ren 30 mole 0/0 and acetic Bulle 70 mole 0/0 force, Ken was saponified Ranaru copolymer
  • a pellet of a biodegradable resin molded article comprising 40 parts by mass of a hydrolysis copolymer having a degree of conversion of 92% was prepared. The pellet was melt-spun at a spinning temperature of 140 ° C. using a full flight screw having a diameter of 0.8 mm, a hole number of 350, and a compression ratio of 2.0 to obtain a regular yarn. To this yarn, 0.3% of the yarn mass was adhered to the yarn with potassium lauryl phosphate as a surface finish.
  • the undrawn yarn was cold drawn at a draw ratio of 1.2 and then cut with a cutter to obtain a biodegradable fiber having a single yarn fineness of 6 d / f and a fiber length of 38 mm.
  • This biodegradable fiber was carded with a card machine to obtain a card web.
  • This web was further processed into a nonwoven fabric using an embossing roll at a temperature of 130 ° C. to obtain a nonwoven fabric.
  • This product also had sufficient water resistance, mechanical strength and durability.
  • Branched starch derivative (crosslinked product of branched starch) prepared by the method of Example 13 containing about 5% of water 35 parts by weight, 30% by mole of ethylene and 70% by mole of vinyl acetate (saponification degree is 98%) (Partially hydrolysed copolymer) 60 parts by mass and 5 parts by mass of poly-force prolatatone were blended to obtain a biodegradable resin molded product. This was used for fiberization. This fiber and the web After that, a sheet was obtained by the needle punch nonwoven fabric method / through air processing. This product can be used as a gardening sheet. This product has sufficient water resistance and mechanical strength and durability. Since this product is biodegradable, it decomposes naturally even if left in a field after use, so it is environmentally friendly and a sheet.
  • a coating solution was prepared by adding 20 parts by mass of the derivative. This coating solution was applied to a kitchen paper so that the solid content was 0.5% based on the mass of the paper. This product can be used as an antibacterial sheet for packaging fresh food. Since this coating solution contains a branched starch derivative, the coating property to kitchen paper is improved, and the coating solution can be uniformly coated on the paper.
  • Branched starch derivative powder prepared by the method of Example 13 (branched starch crosslinked product) Add 100 parts by weight of ethylene glycol 40 parts by weight and Metaprene P530A 1.4 parts by weight, and mix with a Henschel mixer at 1000 rpm for 10 minutes. After that, it was pelletized at 150 ° C with a test extruder. After 100 parts by mass of this plasticized molded product and 100 parts by mass of Bionore (# 1001) were tumbler mixed, it was again subjected to an extruder at 150 ° C. to obtain a plasticized starch 'Bionore composite molded product. Using this molded product, a sheet having a meat pressure of lm m was formed with a T-die extruder under a heating temperature of 170 ° C.
  • This product replaces the branched starch used in the foamed material with the above composition, and provides a uniform foaming compared to the foamed material prepared using starch, as well as restoring force, foamability, hygroscopicity, and water resistance. It has excellent physical properties such as stability, shape retention and durability, and can be used advantageously as a cushioning material. Since this product is biodegradable, it is an environmentally friendly foam material.
  • Branched starch derivative (solid content) prepared by the method of Example 2 100 parts by mass, water 20 parts by mass, polyethylene glycol 15 parts by mass, potassium persulfate 0.04 parts by mass in a Henschel mixer (Mitsui Miike Chemical Sales) The mixture was stirred at 600 rpm for 5 minutes. This was pelletized with a lab plastic mill type twin screw extruder and a pelletizer (both sold by Toyo Seiki Co., Ltd.). This pellet was injection molded using a molding die using an injection molding machine (sold by Nissei Plastic Engineering Co., Ltd.) to obtain a tray. This product has sufficient mechanical strength and is excellent in shape retention and water resistance, and can be used as a tray for plant cultivation. In addition, this product is biodegradable, so it is an environmentally friendly tray.
  • a mixture of 47 parts by mass of aliphatic polyester (Bonore 1020, Showa Polymer Co., Ltd.), 47 parts by mass of branched starch prepared by the method of Example 12 and 6 parts by mass of sucrose (sugar) was supplied to an injection molding machine and molded. A molded product was obtained using a tray and a pile mold.
  • a trauma treatment salve that exhibits moderate elongation and adhesion.
  • This product is a salve with high commercial value, with moderate viscosity and moisturizing properties given by branched starch derivatives, and with little change over time.
  • this product is a plaster that is not sticky or rough when used, and has an excellent feeling of use. It not only acts as a bactericidal effect due to iodine, but also acts as an energy replenisher to cells due to maltose. The healing period is shortened and the wound surface is healed cleanly.
  • the branched starch derivative powder solution prepared by the method of Example 2 was adjusted to a concentration of 25% by mass and dropped in an appropriate amount onto a polyethylene terephthalate film fixed on a flat plate, and a YBA-type strength Lee applicator (manufactured by Yoshimitsu Seiki Co., Ltd. 6) And then dried at room temperature for about 4 hours to prepare a film having a thickness of 19111 and a water content of 10.5% by mass.
  • the dried branched starch derivative film was peeled off from the polyethylene terephthalate film, and stored in a desiccator adjusted to RH 52.8% for at least one night to obtain a product.
  • this product is a high-quality film with high transparency, gloss, flexibility and mechanical strength.
  • the tensile strength of this product was 1.760kgf, and the water solubility was good. This product can be advantageously used as an edible film.
  • Branched starch prepared by the method of Example 2 8 parts by weight, carrageenan (trade name “NEWGELI N NC—400”, sold by Chuo Foods Corporation) 2 parts by weight, sucrose stearate (trade name “sugar ester S1670” 0.01 part by mass, 25 parts by mass of glycerin, and 65 parts by mass of deionized water were mixed and dissolved by heating, and this was then applied to an applicator (trade name “Baker Applicator YBA Type” Yoshimitsu Seiki Co., Ltd.) (Sold by a company), a suitable amount of polyethylene terephthalate was dropped on a glass plate, spread, gelled, dried at 50 ° C for 6 hours, and dried with a moisture content of about 18 A branched starch derivative film having a thickness of 0.5 mm and a thickness of 0.5 mm was prepared. This product is excellent in heat sealability, transparency, and mechanical strength, and is excellent in disintegration
  • Branched starch derivative obtained by the method of Example 4 250 parts by mass, carrageenan (trade name “NEW GELIN NC-400”, sold by Chuo Foods Corporation), 20 parts by mass, glycerin 40 parts by mass, and 700 parts by mass of deionized water The parts were mixed and dissolved by heating to prepare an aqueous raw material solution, which was degassed under reduced pressure. This solution was kept at 50 ° C., and the tip of the capsule forming pin was placed in the solution, then taken out and dried to prepare a hard capsule.
  • This capsule had a bright surface, excellent transparency, no oxygen permeability, and excellent stability against changes in humidity.
  • it is suitable as a filling container for foods and pharmaceuticals because it has an appropriate gradual disintegration property in an aqueous system.
  • an emulsion was prepared by a conventional method.
  • This product is useful as a skin external preparation for whitening and / or beautifying skin.
  • this product is excellent in moisture retention, permeability, spreadability, and usability.
  • a shampoo was prepared by a conventional method based on the following formulation.
  • Photosensitive Element 201 0. 002
  • This product has anti-scaling and anti-aging effects on the scalp, and has strong antibacterial properties, so it has excellent hair-growth effects, suppresses hair loss and keeps the scalp clean.
  • it is a shampoo with excellent usability that retains moderate moisture after use and improves hair slippage.
  • This product is excellent in hair growth and moisturizing properties, suppresses dandruff, itchiness and hair loss, and has a good hair feeling.
  • the branched starch derivative of the present invention has a dense branch structure, has aging resistance, and the physical properties of the branched starch can be appropriately changed. Therefore, it is added to a starch-containing molded product as a starch substitute. In the molded product used as a powdered base, various quality deterioration due to aging of starch is reduced.
  • the molded products include food and drink products, cosmetics, quasi-drugs, pharmaceuticals, feed, sheets made only of feed, fibers, foamed molded products, chemicals including adhesives, industrial products, civil engineering greening products, Since it can be used as agricultural / forestry products, horticultural materials, powder products, miscellaneous goods, biodegradable and / or slow-disintegrating molded products, each industrial field of molded products containing the branched starch derivative of the present invention The significance in is extremely high.

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Abstract

Nouveau dérivé d'amidon ramifié à propriété anti-vieillissement, procédé d'obtention de ce dérivé et article moulé contenant ledit dérivé. Plus précisément, dérivé d'amidon ramifié à structure ramifiée 6-α-maltosyle et/ou structure ramifiée 6-α-maltotétraosyle possédant une propriété anti-vieillissement importante, procédé d'obtention du dérivé et article moulé contenant ce dérivé.
PCT/JP2007/069442 2006-10-06 2007-10-04 Dérivé d'amidon ramifié, procédé d'obtention et article moulé contenant le dérivé d'amidon ramifié WO2008044588A1 (fr)

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WO2017094895A1 (fr) * 2015-12-04 2017-06-08 株式会社林原 Mélange d'α-glucane, procédé de production dudit mélange, et application dudit mélange
WO2018061228A1 (fr) * 2016-09-30 2018-04-05 日本コーンスターチ株式会社 Amidon estérifié, et composition de plastique à base d'amidon
WO2018190310A1 (fr) * 2017-04-11 2018-10-18 株式会社林原 Améliorant de qualité et son utilisation
WO2019130959A1 (fr) * 2017-12-25 2019-07-04 株式会社舞昆のこうはら Film comestible, procédé de production d'aliment et cloison pour aliments
CN111961262A (zh) * 2020-09-01 2020-11-20 郑州工业应用技术学院 一种v型直链淀粉正辛醇复合物的生产方法
JPWO2020004506A1 (ja) * 2018-06-27 2021-07-08 グリコ栄養食品株式会社 ワキシー種澱粉及びその製造方法

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JP7532003B2 (ja) 2016-11-09 2024-08-13 三菱ケミカル株式会社 樹脂組成物及びそれを用いた多層構造体

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Publication number Priority date Publication date Assignee Title
WO2017094895A1 (fr) * 2015-12-04 2017-06-08 株式会社林原 Mélange d'α-glucane, procédé de production dudit mélange, et application dudit mélange
JPWO2017094895A1 (ja) * 2015-12-04 2018-11-22 株式会社林原 α−グルカン混合物とその製造方法並びに用途
US11408019B2 (en) 2015-12-04 2022-08-09 Hayashibara Co., Ltd. Alpha-glucan mixture, its preparation and uses
US11203648B2 (en) 2016-09-30 2021-12-21 Japan Corn Starch Co., Ltd. Esterified starch and starch-containing plastic composition
WO2018061228A1 (fr) * 2016-09-30 2018-04-05 日本コーンスターチ株式会社 Amidon estérifié, et composition de plastique à base d'amidon
JP2018053192A (ja) * 2016-09-30 2018-04-05 日本コーンスターチ株式会社 エステル化澱粉及び澱粉系プラスチック組成物
CN109803985A (zh) * 2016-09-30 2019-05-24 日本玉米淀粉株式会社 酯化淀粉以及淀粉系塑料组合物
WO2018190310A1 (fr) * 2017-04-11 2018-10-18 株式会社林原 Améliorant de qualité et son utilisation
WO2019130959A1 (fr) * 2017-12-25 2019-07-04 株式会社舞昆のこうはら Film comestible, procédé de production d'aliment et cloison pour aliments
JPWO2020004506A1 (ja) * 2018-06-27 2021-07-08 グリコ栄養食品株式会社 ワキシー種澱粉及びその製造方法
JP7270624B2 (ja) 2018-06-27 2023-05-10 グリコ栄養食品株式会社 ワキシー種澱粉及びその製造方法
CN111961262A (zh) * 2020-09-01 2020-11-20 郑州工业应用技术学院 一种v型直链淀粉正辛醇复合物的生产方法
CN111961262B (zh) * 2020-09-01 2022-03-11 郑州工业应用技术学院 一种v型直链淀粉正辛醇复合物的生产方法

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