WO2008044588A1 - Branched starch derivative, process for production thereof, and molded article comprising the branched starch derivative - Google Patents

Abstract

Disclosed are: a novel branched starch derivative having an anti-aging property; a process for producing the derivative; and a molded article comprising the derivative. Specifically disclosed are: a branched starch derivative which has a 6-α-maltosyl branch structure and/or a 6-α-maltotetraosyl branch structure and has a significant anti-aging property; a process for producing the derivative; and a molded article comprising the derivative.

Description

 Specification

 Branched starch derivative and method for producing the same, and molded product containing branched starch derivative

 Technical field

 [0001] 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.

 Background art

 [0002] 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 α-1,4 glucan having a structure in which dalose is linearly bonded with α-1,4 bonds. On the other hand, amylopectin is a linear part of α-1, 4 glucan, and usually has a structure in which α-1, 4 glucan having a glucose polymerization degree of 6 or more is branched by α-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. In addition, starch is liquefied and industrially used as a raw material for dulose, isomerized sugar, maltooligosaccharide, chickenpox and the like. However, 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.

[0003] Proposals have also been made to enzymatically modify vegetal starch that ameliorates these deficiencies and to prevent aging. In JP-A-8-134104, a branching enzyme (branching enzyme; EC 2 · 6) is synthesized in a starch liquefaction solution by cleaving α 1, 4 bonds of starch and synthesizing α-1,6 bonds by transfer reaction. 4. 1. 18), 4-α-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. However, this macrocyclic structure dulcan has a problem in that the physical properties of the raw material liquefied starch are lost because the molecular weight is greatly reduced and the viscosity is lowered with the formation of the cyclic structure. 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. 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. However, the Neuros Bora Classa is a special mold, and its safety has not been confirmed in the production of food and drink. Furthermore, 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. A method of forming a branched starch having a branched structure is proposed. However, it is extremely difficult to use barley-derived branching enzyme (SBE II), phosphorylase, and the substrate glucose 1-phosphate for industrial production. Under such circumstances, it has been desired to provide starchy materials having improved physical properties such as aging properties, while hardly reducing the molecular weight of starchy materials. In recent years, the same applicant proposed in Japanese Patent Application No. 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.

 Disclosure of the invention

 [0004] 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. .

[0005] In order to solve the above-mentioned problems, the present inventors paid attention to the use of various glycosyltransferases, and in the process of intensive research, disclosed in JP 2005-95148 A by the same applicant as the present invention. Cyclo {→ 6) α D-Darkopyranosyl 1 (1 → 4)-a-D-Darkopyranosyl 1 (1 → 6)-a-D-Darkoviranosi disclosed in Japanese Patent Application No. 2004-174880 Lu (1 → 4) a D Dalcoviranosyl (1 →) cyclic maltosyl manretose (hereinafter abbreviated as “cyclic maltosyl maltose” in this specification) from α — 1, 4 glucan When the resulting cyclic maltosyl maltose-forming enzyme was allowed to act on a high concentration of liquefied starch or partially decomposed starch, a new branched starch having a 6-a maltosyl branched structure and / or a 6a maltotetraosyl branched structure In the present specification, it has been found that the branched starch may be referred to simply as “branched starch.” Then, various enzymes known in the art such as cyclomaltodextrin glucanotran are produced. 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. In addition to these enzyme reaction systems, a 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. According to these reaction methods, it has been found that various substituents other than glycosyl groups can be selectively introduced, and the physical properties of the branched starch can be arbitrarily modified. According to the present invention, osmotic pressure controllability, shaping, shine imparting, moisture retention, viscosity, water separation prevention, consolidation Stopping property, Inclusion property, Aroma retaining property, Stability, Anti-crystallization of other sugars, Anti-starch aging property, Anti-protein denaturation property, Anti-lipid degradation property, Acid resistance, Aminocarbonyl reactivity, Dielectric property, Physical properties of branched starch such as polarizability, electrical conductivity, etc. can be modified arbitrarily, for example, derivatives having a strong hydrophobic substituent make it possible to impart fat solubility to the branched starch and have high reactivity. 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. In addition, it is possible to modify the physical properties of an organic compound by using this property and bonding it to another organic compound.

That is, 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.

[0007] According to the present invention, 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. Moreover, a novel organic compound can be obtained by combining with branched starches or other compounds. Furthermore, by combining with other compounds, the physical properties of this branched starch can be imparted to the compounds.

 Brief Description of Drawings

 [0008] 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.

 Explanation of symbols

 [0009] a: Control liquefied starch (rice corn starch liquefied liquid)

 b: Branched starch 1 (acting amount of cyclic maltosyl maltose producing enzyme 0.001 unit) c: Branched starch 2 (acting amount of cyclic maltosyl maltose producing enzyme 0.025 unit)

 d: Branched starch 3 (acting amount of cyclic maltosyl maltose producing enzyme 0.05 unit)

e: Branched starch 4 (Amount of cyclic maltosyl maltose producing enzyme 0.1 unit) In Figure 4

 A: Schematic diagram of liquefied starch

 B: Schematic diagram of the branched starch used in the present invention

1: A chain structure in which glucose is linked by _α -1 and 4 bonds (amylose structure)

 Branching part of chain structure by 2: 6 bond

 3: Reducing end glucose

 4: 6-a-maltosyl branched structure

 5: 6-a maltotetraosyl branched structure

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0010] 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. Thus, 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. 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.

[0011] Branched starch having a 6-a maltosyl branched structure and / or a 6-a maltotetraosyl branched structure used in the present invention is an α-1, 6 bond in the molecule with maltose units and / or maltotetraose units. This means starch in general that has a branched structure due to maltose and / or maltotetraose at the 6-position of the non-reducing end glucose as well as inside the α — 1, 4 glucan chain in the starch. Also includes those having a 6-linked structure. There is no limitation in particular in the manufacturing method and origin of this branched starch. The molecular weight of the branched starch is not particularly limited, but is preferably 1.0 × 10 ⁴ daltons or more. In addition, when this starch is digested with pullulanase, a kind of starch debranching enzyme that specifically hydrolyzes α-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.

 [0012] In addition, in the branched starch having a 6-a maltosyl branched structure and / or 6-a maltotetraosyl branched structure used in the present invention, the number of branches branched by α-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. It can be judged from showing 4% or more. In addition, a degradation test with β-amylase (/ 3-amylolysis) is conducted, and the degradation limit of β-amylase of this branched starch can be determined from that of the raw starch.

 [0013] Further, 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!

[0014] As 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. Specifically, for example, 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 Α-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 α-maltosyl transfer to a hydroxyl group. For example, 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.

[0015] 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.

 1) Acts on α-1,4 glucan with a degree of glucose polymerization of 3 or more as a substrate, and converts the maltosyl residue at the non-reducing end of the non-reducing end glucose residue of other α-1, 1 glucan molecules to 6 By catalyzing the 6a maltosyl transfer between the molecules that transfer to the hydroxyl group, the degree of glucose polymerization with 6-a maltosyl group at the non-reducing end increased by 2, and the degree of polymerization of 6-a maltosinomalto-oligosaccharides and 2 To produce reduced maltooligosaccharides.

 2) Furthermore, it acts on 6-a-maltosyl-malto-oligosaccharide and cyclizes by intramolecular α-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.

 3) 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.

[0016] Although the 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.

 [0017] 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. In the case of an immobilized enzyme, the reaction format may be batch, semi-continuous or continuous. Examples of 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.

 [0018] 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 In addition, underground starch such as waste starch can be advantageously used industrially. Furthermore, 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.

 [0019] For example, a method of allowing a cyclic maltosyl maltose producing enzyme to act on liquefied starch can be preferably carried out under the following conditions. First, 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. On the other hand, if it exceeds 45%, it is difficult to dissolve starch in water.

[0020] In producing the branched starch used in the present invention, 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 μmol 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.

 [0021] 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.

 [0022] 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. Although 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.

 [0023] Although a 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. Can be used. Further, if necessary, such oligosaccharide can be removed and purified to be used advantageously for the preparation of branched starch derivatives. As a purification method, a conventional polysaccharide purification method such as gel filtration chromatography may be appropriately selected as necessary.

[0024] 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. In general, starch is insoluble in cold water. The branched starch used in the present invention dissolves in cold water to at least 20%. In addition, 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.

 [0025] 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. Specifically, for example, one or more of enzymes having transglycosylation ability such as cyclomaltodextrin glucanotransferase, / 3-galatatosidase, α-galactosidase, lysozyme, etc. are added to the branched starch as a substrate of the enzyme. In the presence of monosaccharides, oligosaccharides and / or polysaccharides, one or two or more arbitrary hydroxyl groups of the branched molecule are bonded to one or two or more α D —dalcobilanosyl groups, β-D galactopyrano A saccharide obtained by transferring one or more of a glycosyl group such as a syl group and a β-D chitosaminyl group, and further an α-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, α D gnolecopyranosinole group, β D galactoviranosinore group, β—D It refers to a reaction system to transfer one or two or more one or more of the Dali cosyl groups such Kitosamininore group.

 [0026] 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. For example, methyl group, ethyl group, ethynino group, propyl group, cyclopropyl group, isopropenyl group, 1 propenyl group, 1-propyl group, 2-propenyl group, butyl group, isobutyl group , S butyl group, t-butynol group, bur group, 1,3-butagenyl group, 2-butul group, pentyl group, isopentyl group, neopentyl group, t pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentyl group 2 pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, etc., an aliphatic hydrocarbon group having 1 to 18 carbon atoms, cyclopropyl group, cyclobutyl group, Cyclopentyl, cyclohexyl, cyclohexyl and other alicyclic hydrocarbon groups, and benzene rings as the basic skeleton, such as phenyl and naphthyl groups. Monocyclic or polycyclic aromatic hydrocarbon group can enumerate the

[0027] 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. For example, glucose, sulphatose and its multimers, caproic acid, strength prillic acid, strength purine acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, hebenic 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. For example, amino group, hydroxylamino group, oxime group, carbamic acid group, strong rubamic acid ester group, thiocarbamic acid O-ester group, thiocarbamic acid S-ester group, imine group, azirine group, nitro group, nitroso group, List of functional groups such as azide group, diazo group, nitrile group, isonitrile group, cyano group, isocyanato group, isothiocyanate group, cyanuric chloride group, substituents having them, and various nitrides it can.

 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. For example, mercapto group, sulfone group, sulfonic acid group, sulfide group, disulfide group, sulfoxide group, sulfonylumide group, sulfenic acid group, sulfinic acid group, thiolsulfinate group, thiolsulfonate group, sulfilimine group, List functional groups such as sulfoximine group, p-toluenesulfonyl group or substituents having them, and various sulfurated products.

Yes

[0030] 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. example For example, functional groups such as fluorine group, black mouth group, bromo group, and iodine group, or substituents having these, and various halides can be listed.

 [0031] 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.

[0032] 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, 1,2-dichloroethane, 1,2-dibromoethane, tetrachloroethane , Dichloroethylene, trichloroethylene, nocturnal ethylene, dichloropropane, salt 匕 aminole, dichloropentane, monochrome benzene, o halogen solvents such as dichlorobenzene, trichlorobenzene, bromobenzene, methanol, ethanol, n-pill pill alcohol , Isopropyl alcohol, n butyl alcohol, isobutyl alcohol, s butyl alcohol, t butyl alcohol, isoamyl alcohol, synthetic amino alcohol, fusenol? , 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 glycolenole, ethyleneglycololemonomethenoatenore, Ethylene glycol monoethanolino etherate, ethylene glycol monobutinoate ethere, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl etherate Methyl acetate, ethylene glycol nole methylate, diethylene glycol monol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol nole methylate, triethylene glycol nore, propylene glycol nore, hexylene glycol, glycerin, etc. Monohydric alcohols or their ethers or ester solvents, furfural, methylal, acetal, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisoptyl ketone, mesityloxide, acetylacetone, diacetone ethanolone, cyclohexanone, methylol cyclohexane Aldehydes such as hexanone and isophorone, acetal or ketone solvents, nitromethane, nitroethane, 1 12 troprono , 2-nitropronone, nitrobenzene, acetonitorinole, jetinoreamine, triethylamine, cyclohexylamine, ethylenediamine, aniline, pyridine, picoline, quinoline, monoethanolamine, diethanolamine, morpholine, dimethylformamide, dimethylacetamide Nitrogen-containing compound solvents such as hexamethylphosphortriamide and N-methylpyrrolidone, sulfur compound solvents such as anhydrous sulfite, carbon disulfide, thiophene, sulfolane, and dimethyl sulfoxide. Among these, branched starch Alternatively, 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. In addition, when the reaction under anhydrous conditions is preferable, it is preferable to remove moisture from the solvent using an appropriate dehydrating agent as necessary. In the case where 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! [0033] Further, when a branched starch derivative is prepared using a branched starch, 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 μm or less, preferably from 0.1 μm to 250 μm, more preferred (between 1 μm and 100 μm).

[0034] 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 Examples include 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%).

[0035] 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. Means one or more of acid, base, alcohol, aldehyde, ketone, halogen, amine, cyanine, nitrinole, oxolan, isocyanate, isothiocyanate, cinnole, snorephone and their reactive derivatives . The molar ratio of the reactive reagent to branched starch may ίί 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 ί or 0.5 1, 000 is selected from the range of Monore _^0/0. [0036] 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. If a higher purity branched starch derivative is required, for example, sugar or 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.

 [0037] Hereinafter, a typical method for producing a branched starch derivative of the present invention will be described in more detail.

 [0038] 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. For example, 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. Cabronic acid, strong prillic acid, strong purine acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, hebenic acid, lignoceric acid, zomarinic acid, oleic acid, linolinoleic acid, linolenic acid, cadrenic acid 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.

[0039] The production method by the sulfonylation reaction is useful for producing a reaction intermediate for obtaining various derivatives. After adding tosyl group (4 methylbenzenesulfonyl), mesyl group (methanesulfonyl), and other related arylsulfonyl groups to the branched starch, 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. Further, in order to produce a fermented carboxylic acid branched branched starch, 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. In order to produce aminated 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.

 [0040] The production by 2, 2, 6, 6 tetramethyl-1-piperidinyloxylation reaction can be applied to the production of a carboxylated branched starch. When 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. For example, 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.

 [0041] Production by an oxidation reaction is used when producing oxidized branched starch. In general, 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. In this case, suitable oxidizing agents used for oxidation are, for example, sodium hypochlorite, hydrogen peroxide and the like.

[0042] In the production by grafting reaction, in the same manner as usual starch grafting reaction, a butyl monomer such as acrylic acid or methacrylic acid is added to enzymatically synthesized amylose in the presence of iron or cerium ion. Another example is a method of adding a carboxylic acid having a hydroxyl group such as lactic acid in a branched manner by polycondensation. In order to maintain high biodegradability, it is preferable to select a monomer that itself has biodegradability, such as lactic acid and force prolatatone. In this case, 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

[0043] In addition, 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. As 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. As 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. As 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.

[0044] 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. Further, 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. Further, 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.

[0045] 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. Furthermore, 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 is introduced 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. In addition, 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.

[0046] Since these derivatives also change the affinity with living tissue, they are also effective in controlling cell adhesion in applications such as medical materials. In addition, the 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. In addition, 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. Furthermore, 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.

 [0047] Since 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. Hereinafter, the use of the branched starch derivative of the present invention will be described in more detail.

 [0048] 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.

 [0049] Specifically, for example, when the branched starch derivative of the present invention is 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.

[0050] 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.

[0051] 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.

[0052] The molded product containing the branched starch derivative of the present invention is particularly suitable as a molded product that requires biodegradability. Specifically, 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. In addition, there are no particular restrictions on the form of these molded products, which may be solutions, semi-solids, solids, pastes, foams, films, sheets, tubes, capsules, short bars, plates, chips. What was shape | molded etc. may be sufficient.

 [0053] More specifically, these molded products can be used in the field where plastic foam has been used. In particular, 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. .

 [0054] In addition, the high foam is particularly effective as an alternative material for polystyrene foam, which currently has a problem in disposal. For example, 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.

[0055] In addition to the above, the molded product containing the branched starch derivative of the present invention includes 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. Cards that are consumed in large quantities, such as telephone cards, orange cards, pachinko cards, and library cards, various credit cards, library card, and various membership cards, and are regularly discarded due to their deadlines. It is optional to use it as a class.

[0056] Further, 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.

[0057] When it is desired to further improve the water resistance, chemical resistance, heat resistance, mechanical strength, etc. of these molded products, it is optional to treat the surface of the molded products with various materials. For example, metal, non-plastics such as aluminum, and other biodegradable plastics such as polylactic acid having a higher melting point, such as coating, laminating, deving, or vapor deposition, are effective. In addition, when treating the surface with metals or non-biodegradable plastics, to prevent the biodegradability after use from being deteriorated, surface treatment is applied only to parts that require water resistance, etc. It is also optional to take measures such as partially leaving unprocessed parts.

 [0058] Further, as 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%.

[0059] 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. In the molded product containing the branched starch derivative of the present invention, 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 Such as mucopolysaccharides, polylactic acid and its derivatives, polyalginic acid and the like can be used in combination. At that time, a plasticizer or a gelling agent can be advantageously added to adjust the plasticity of the molded product. Examples of plasticizers include water and various polyols, for example, polyalcohols such as glycerin and polybutal alcohol, sugar alcohols such as erythritol, xylitole, sonorebitol, multitole, α, a-trehalose, cyclodextrin, international publication WO 02 / Cyclo disclosed in the specification of No. 10361 etc. → (→ 6)-a—D—Dalcoviranosinore-(1 → 3)-a—D Gnorecopyranosinore (1 → 6)-a—D Gnoreco Pyranosinole (1 → 3)-α D Dalcobilanosyl (1 →) cyclic tetrasaccharide (Cyclonigerosylnigelose), cyclic maltosyl maltose, international patent application PCT / JP2005 / 17642 The structure of the cyclo {→ 6) [α D-Darcopyrano Silou (l → 4)] n—a D Darcoviranosil (1 →} (n means 4 or 5) disclosed in the specification Having ring Non-reducing carbohydrates such as sugars, cyclic hexasaccharides, and sugar derivatives of these cyclic oligosaccharides, natural fats and oils such as urea, soybean oil and castor oil, and alkyl esters of organic acids S. 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 In addition, in addition to the above-mentioned components, this branched starch derivative-containing molded product can also be advantageously made into a biodegradable starch-based plastic molded product. Other inorganic components can be added as appropriate, including talc, titanium dioxide, calcium carbonate, sand, clay, limestone, diatomaceous earth, mica, glass, quartz, alumina, silica, glass, kaolin and ceramics. Organic components include chitin, chitosan, collagen, hive mouth-in, keratin, rosin, dammar, copal, ί 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 the like. In addition, it is optional to add biologically active substances such as nutrients, physiologically active substances, animal and plant extracts, enzymes, herbicides, fungicides, fungicides, antibiotics, insecticides, repellents, etc. is there.

 [0061] Hereinafter, the branched starch used in the present invention will be described more specifically by experiments.

 <Experiment 1: Preparation of cyclic maltosyl maltose producing enzyme>

 Prior to the experiment, Alsulopactor 'Globiformis M6 (FERM BP-8448) was cultivated, and a cyclic maltosyl maltose-producing enzyme in the culture supernatant was purified to prepare an enzyme preparation.

 [0063] <Experiment 1-1—Cultivation of alsulopactor 'Globiformis M6>

 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. lw / v%, monosodium phosphate · 2 water 100 ml each of two 500 ml Erlenmeyer flasks with a liquid medium consisting of Japanese 0.06 w / v%, magnesium sulfate heptahydrate 0.05 h / v%, calcium carbonate 0.3 w / v%, and water Sterilized in an autoclave at 121 ° C for 20 minutes, cooled, inoculated with ALSU ROBACTA globiformis M6 (FERM BP-8448), and cultured at 27 ° C and 230 rpm for 48 hours with shaking. . Place about 20L of liquid medium with the same composition as the seed culture in a 30L capacity mentor, heat sterilize, cool to 27 ° C, inoculate with about 200ml of seed culture, temperature 27 ° C, pH5 The culture was aerated and stirred for 96 hours while maintaining at 5 to 8.0. After culturing, the culture solution was extracted from the fermenter, centrifuged (8,000 rpm, 20 minutes) to remove the cells, and about 18 L of culture supernatant was obtained.

[0064] 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 α-dalcosidase (“Trans-Dalcosidase L” was used to degrade the remaining soluble starch and contaminating oligosaccharides. "Amano" (manufactured by Amano Enzym Co., Ltd.) 4000 units per gram of solids and darcoamylase ("Dalco Team", sold by Nagase Seikagaku Corporation) 250 units per gram of solids added at 50 ° C Treat for 1 hour and quantify the amount of cyclic maltosyl maltose in the treated solution by high performance liquid chromatography (hereinafter abbreviated as “HPLC”). One unit of cyclic maltosyl maltose producing enzyme activity is defined as the amount of enzyme that produces 1 μmol of cyclic maltosyl maltose per minute under the above conditions. Η 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).

<Experiment 1 2: Purification of cyclic maltosyl maltose producing enzyme>

About 9.2 L of the culture supernatant was added ammonium sulfate to a final concentration of 60% saturation, and left to stand at 4 ° C. for 24 hours for salting out. The produced salting-out precipitate was collected by centrifugation (11, OOOrpm, 30 minutes), dissolved in 10 mM Tris-HCl buffer (pH 7.5), dialyzed against the same buffer, and crude enzyme. About 240 ml was obtained as a liquid. This crude enzyme solution was subjected to anion exchange chromatography (gel volume: 100 ml) using “DEAE Toyopearl 650S” gel 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 (ρ · 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. (Phenyl-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.

[0066] [Table 1]

 [0067] 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.

 <Experiment 2: Preparation of Branched Starch>

 In order to investigate the structure and physical properties of the reaction product produced when cyclic maltosyl maltose-forming enzyme was allowed to act on liquefied starch, the following experiment was conducted.

 [0069] <Experiment 2-1: Enzyme reaction>

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. Prepared. Add 20,000 units of α-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. for 5 minutes in a continuous liquefaction apparatus to prepare 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. After stopping the enzyme reaction by heating at 100 ° C for 10 minutes, the cyclic maltosyl maltose content in each reaction solution was measured by HPLC. In addition, the raw material liquefied starch which does not make cyclic maltosyl maltose production enzyme act As a control.

 [0070] 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).

 [0071] [Table 2]

[0072] As is clear from Table 2, the cyclic maltosyl maltose content tended to increase as the amount of action of the cyclic maltosyl maltose producing enzyme increased in each reaction solution. However, its content is about 5% at the maximum enzyme action amount examined this time, 0.1 unit per gram of solid content of corn corn starch liquefied liquid! There were few.

 [0073] <Experiment 2-2: Purification of branched starch>

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. While maintaining the internal temperature of the column at 60 ° C, add 5% v / v% of corn starch liquefied liquid to the resin, flow it at 60 ° C with SV0. The composition was monitored by HPLC, and a polymer fraction free from cyclic maltosyl maltose was collected. The obtained polymer fraction was concentrated to 25% and then vacuum-dried. Each branched starch powder was obtained at a rate of 90% or more. These branched starches were subjected to the same HPLC analysis as in Experiment 2-1 and confirmed that they did not contain cyclic maltosyl maltose!

[0074] <Experiment 3: Structural analysis of branched starch>

 The branched starch obtained by the method of Experiment 2 was subjected to the following test to examine the structure of the branched starch.

 [0075] <Experiment 3-1: Molecular weight distribution of branched starch 0>

The molecular weight distribution of the branched starch obtained by the method of Experiment 2 was examined by gel filtration analysis. 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. As a control, 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. In the figure below, “ _a” is a control (oxyxy corn starch liquefied liquid), and “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. Hereinafter, 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. In addition, the elution patterns of the gel filtration analysis of branched starches 1, 2, 3, and 4 showed almost the same pattern when treated with any of the four types of enzyme units. Only the elution pattern of branched starch 4 (e in Fig. 1) treated with a) in 1 and the maximum amount of enzyme action (0.1 unit) is shown.

[0076] As is apparent from FIG. 1, 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.ヮ Kishiko Elution of branched starch 4 (e in Fig. 1) by gel filtration chromatography by reacting cyclic maltosyl maltose-producing enzyme with 0.1 unit per gram of solid content of corn starch liquefied liquid in starch starch liquefied liquid It was found that even when a cyclic maltosyl maltose producing enzyme, which is significantly different from that of the control (a), was allowed to act on the pattern, the molecular weight distribution did not change significantly.

 [0077] <Experiment 3-2: Hydrolysis rate of branched starch>

 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). ))), And the hydrolysis rate, which means the ratio (%) of the reducing sugar amount in the total sugar amount, is expressed by the following formula: hydrolysis rate (%) = (reducing sugar amount / total sugar amount) Calculated with X100. The results are shown in Table 3.

 [0078] [Table 3]

[0079] As is apparent from Table 3, the amount of action of the cyclic maltosyl maltose-producing enzyme is 0.1% per gram of xylocon starch liquefied solid, and the highest amount of branched starch is 0.1 unit per gram. In comparison, the increase in hydrolysis rate was only about 0.5%, and hydrolysis caused by the reaction of cyclic maltosyl maltose producing enzyme was almost negligible.

 [0080] <Experiment 3-3: Methylation analysis of branched starch>

In order to examine the binding mode of glucose, which is a constituent sugar, for the above four branched starches 1, 2, 3, and 4 obtained in Experiment 2-2, or the control oxy corn starch liquefied liquid, a conventional method was used. Accordingly, after methylation, hydrolysis with an acid, followed by reduction and acetylation, and the resulting partial methyl-acetylylditol (hereinafter sometimes referred to as “partially methylated product”) is gas chromatographed. The composition of the partially methylated product was examined by a graphic method (hereinafter abbreviated as “GLC”). The results are shown in Table 4.

[Table 4]

4 Since no trimethylated product is detected, it is considered that there is no glucose residue bonded to other glucose at the 1- and 6-positions. On the other hand, 2, 3, 4 trimethylated products were detected in the branched starch obtained by the action of cyclic maltosyl maltose-producing enzyme, and the ratio increased as the amount of action of the enzyme increased. This result indicates that as the amount of action of the enzyme increases, the structure in which the glucose residue is bonded to the 6-position of the glucose residue by another glucose force, that is, the branched structure increases. In addition, since the ratio of 2,3 dimethyl compounds is also increasing, the glucose residues bound to other glucose at the 1st, 4th and 6th positions are thought to have increased slightly. . This is because the 6a maltosyl transfer due to the action of cyclic maltosyl maltose synthase is 6% of the glucose residues located inside the glucose chain that constitutes the starch consisting only of the 6th position of the non-reducing terminal glucose residue of the substrate starch. It also suggests that it happens to the place.

 [0083] <Experiment 3-4: Products in digestion of branched starch with pullulanase>

In order to investigate the branched structure of the above four branched starches 1, 2, 3 and 4 obtained by the method of Experiment 2-2, or the control starch corn corn liquefaction solution, the _α -1 and 6 bonds of starch were specifically identified. Hydrolyzed pullulanase (EC 3.2.1.41) was allowed to act, and the sugar composition of each of the prananese digests was examined.

 [0084] The four branched starches obtained by the method of Experiment 2-2 or the control oxy-starch liquefied liquor were dissolved in deionized water to a final concentration of lw / v%, and acetate buffer (pH 6.0) was obtained. ) Was added to a final concentration of 20 mM, then 20 units of pullulanase (reagent crystal product, manufactured by Hayashibara Biochemical Laboratories Co., Ltd.) was added per gram of substrate solids, and reacted at 40 ° C for 24 hours. . After the reaction, heat treatment was performed at 100 ° C. for 10 minutes to inactivate pullulanase, and then the sugar composition of the reaction solution was measured by the same HPLC method as in Experiment 2. The results are shown in Table 5. In addition, the results of the control xy corn starch liquefied liquid and branched starch 3 (the amount of cyclic maltosyl maltose producing enzyme: 0.05 units / g oxy corn starch liquefied liquid) in Table 5 are shown as the degree of glucose polymerization. Figure 2 shows the graph with the horizontal axis and the content (%) in the digest of pullulanase on the vertical axis. The symbols a and d in FIG. 2 mean the control starch corn liquefied liquor and the branched starch 3, respectively.

[0085] [Table 5]

[0086] As is apparent from the results in Table 5 and FIG. 2, in the case of the control oxy-corn starch liquefied liquid, malto-oligosaccharides of DP6 or more were produced, whereas malto-oligosaccharides of DP5 or less were not recognized. In the branched starch used in the present invention prepared by the action of a cyclic maltosyl maltose-producing enzyme, malto-oligosaccharides of DP5 or less, particularly maltose (DP2) and maltotetraose (DP4) in the digest of pullulanase are significantly increased. Was. From these results, it was found that a new branched starch having a 6-α maltosyl branched structure and / or a 6a maltotetraosyl branched structure was generated by the action of the cyclic maltosyl maltose-producing enzyme.

 [0087] <Experiment 3-5: Degradation limit of / 3-amylase in branched starch (/ 3-amylase lysis)>

 The above four types of branched starch 1, 2, 3 and 4 obtained in Experiment 2-2, or the control xy-corn starch liquefaction solution were each finished at lw / v% and acetate buffer (pH 5.5). Add 100 units of / 3-amylase (from soybeans, manufactured by Nagase Seikagaku Corporation) to lg solids to a substrate solution prepared to a concentration of 20 mM, and let it act at 50 ° C for 24 hours. The enzyme reaction was stopped by heat treatment for a minute. The amount of enzyme that produces a reducing power equivalent to 1 mol of maltose per minute under the condition of pH 5.5 and 40 ° C, with 1 unit of soluble starch as the substrate. It was defined as The content of maltose and / 3-amylase that was not degraded by / 3-amylase in the / 3-amylase digest of each branched starch and control oxy-cone starch liquefaction solution was measured under the same HPLC conditions as in Experiment 1. The results are shown in Table 6.

 [0088] [Table 6]

表 6の結果から明らかなように、分岐澱粉は、作用させた環状マルトシルマルトース 生成酵素の量が多いほど、 /3—アミラーゼ消化により生成するマルトースの含量が低 い値を示し、逆に /3—リミットデキストリンの含量は高い値を示した。 β—アミラーゼは 澱粉を非還元末端からマルトース単位で加水分解し、 α - 1 , 6結合による分岐点の 手前で加水分解反応を停止する酵素であることから、上記結果は、環状マルトシノレ マルトース生成酵素がヮキシ一コーンスターチ液化液に作用し、その α—1 , 6マルト シル転移により分岐構造が形成され、環状マルトシルマルトース生成酵素の作用量 が多いほど分岐澱粉における分岐構造の割合も増加する（分岐が密になる）ことを物 語っている。

As is clear from the results in Table 6, the content of maltose produced by digestion of 3-3-amylase in the branched starch increases with the amount of cyclic maltosyl maltose-forming enzyme that is acted on. On the contrary, the content of / 3-limit dextrin was high. β-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 α-1, 6 bond. Acts on the liquefied liquor of corn starch and forms a branched structure due to its α-1,6 maltosyl transition, and the greater the amount of cyclic maltosyl maltose producing enzyme, the greater the proportion of branched structure in the branched starch (branch structure). Talking about becoming dense).

 [0090] <Experiment 3-6: Iodine coloration of branched starch>

 The above four types of branched starch 1, 2, 3 and 4 obtained in Experiment 2-2, or the control oxy-starch liquefied liquor was dissolved in deionized water to a concentration of 0-15%. Add 0.5 ml of 0.02N sulfuric acid to 0.5 ml of solution, 0.5 ml of 0.1 N potassium monoiodide solution, leave at 25 ° C for 25 minutes, and then add iodine-starch complex in the range of 450 to 700 nm. The absorption vector was measured. The results are shown in Figure 3. The symbols a, b, c, d, and e in FIG. 3 are the same as those described in Experiment 31 and FIG. As is apparent from the results in FIG. 3, 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 reason for this is thought that the branched starch having a larger amount of cyclic maltosyl maltose-producing enzyme has a lower abundance ratio of the linear structure of starch that forms a complex with iodine, and the amount of iodine bound to the starch has decreased. It was.

[0091] Based on the results of Experiment 3, 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. 4, 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. In the schematic diagram shown in FIG. 4, 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 α-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.

 [0092] <Experiment 4: Aging resistance of branched starch>

 The aging resistance of the above four types of branched starches 1, 2, 3, and 4 obtained by the method of Experiment 2 or the control coconut corn starch liquefied liquid was examined. Each sample, heated and dissolved in water to a concentration of 25%, was dispensed into glass test tubes, stored in a sealed state at 10 ° C for 10 days, and the degree of starch aging was observed. . The results are shown in FIG. The symbols a, b, c, d, and e in FIG. 5 are the same as those described in Experiment 31 and FIG. As is clear from the results of FIG. 5, the control oxy-starch liquefied liquid (a) became cloudy under the above-mentioned storage conditions, and partly solidified, and starch aging was remarkable. On the other hand, all of the branched starches (b to e) prepared by the action of cyclic maltosyl maltose-producing enzyme maintain a transparent solution state. 6-a maltosyl branched structure and / or 6a maltotetraosyl It has been found that the branched starch used in the present invention having a branched structure has remarkable aging resistance.

 [0093] <Production Example 1 of Branched Starch>

ヮ Kishi corn starch (manufactured by Sanwa Starch Co., Ltd.) was suspended in tap water, and calcium chloride was added to this so that the final concentration was ImM, and adjusted to pH 6.0 to prepare starch milk with a concentration of about 10%. . Add 0.05 mg of heat-resistant α-amylase (trade name “Spitase HS”, sold by Nagase Seikagaku Corporation) to this starch milk per gram of starch solid, stir for 30 minutes, and then add it to the continuous liquefaction equipment. The liquid was passed at 1 L / min. Starch milk was heated in a continuous liquefaction device at 100 ° C for 25 minutes and then at 140 ° C for 5 minutes to prepare liquefied starch. Next, after concentrating the liquefied starch solution under reduced pressure to obtain a liquefied starch solution having a concentration of about 25%, 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. The resulting branched starch pullulanase digestion contained 3.7% maltose and 1.7% maltotetraose. Further, 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.

 [0094] <Production Example 2 of Branched Starch>

 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. For fractionation, 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. By this operation, a branched starch powder containing about 10% of water and having a low hygroscopic property and excellent particle size characteristics was obtained. This product can be advantageously used for the production of branched starch derivatives.

 [0095] <Production Example 3 of Branched Starch>

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. To this, add 1 unit of purified cyclic maltosyl maltose-producing enzyme obtained in the method of Experiment 1 per gram of substrate solid, react at 40 ° C for 48 hours, then heat to 100 ° C and hold for 10 minutes The reaction was stopped. 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.

 [0096] When the raw starch partial degradation product was digested with pullulanase, it was insolubilized due to aging of the produced amylose, whereas this product pullulanase digested product exhibited aging resistance and maintained a clear solution. It contained 26.3% of maltose and 15.4% of maltotetraose.

 <Production Example 4 of Branched Starch>

 When the cyclic maltosyl maltose producing enzyme was allowed to react, it was reacted in the same manner as in Example 3 except that 2,500 units of isoamylase was allowed to act per gram of substrate solids. The solution was purified by filtration, and further concentrated to obtain a branched starch partial degradation product solution having a concentration of 30% in a yield of about 90% per solid. This branched starch partial hydrolyzate-containing solution was dehydrated, dried and powdered with a Norus combustion drying system PULCO (sold by Partec Co., Ltd.). 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.

 [0098] 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.

 [0099] <Example 5 of production of branched starch>

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. For fractionation, 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.

 [0100] Hereinafter, the present invention will be described more specifically by way of examples. Production examples of the branched starch derivative used in the present invention are shown in Examples 1 to 13, and molded products containing the branched starch derivative of the present invention are shown in Examples 14 to 38. However, the present invention is not limited by these examples.

 Example 1

 [0101] <Benzylated branched starch>

 Branched starch powder 5 mass parts obtained by the method of Production Example 2 and 7 parts by mass of potassium hydroxide were dissolved in 64 parts by mass of benzyl chloride, and then heated at 140 ° C. for 3 hours. After cooling to room temperature, 200 parts by weight of distilled water and 400 parts by weight of ethyl acetate were added and mixed, and the mixture was allowed to stand until the aqueous layer and the ethyl acetate layer separated, and then the ethyl acetate layer was recovered. According to a conventional method, dehydration was performed with an appropriate amount of anhydrous magnesium sulfate, followed by drying under reduced pressure to obtain benzylated branched starch. Since this product is fat-soluble, it can be advantageously used in combination with oily cosmetics in general.

 Example 2

 [0102] <Methylated branched starch>

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. To this, 50 parts by mass of distilled water was added and mixed, allowed to stand, and then the black mouth form layer was collected again. This operation was repeated 10 times, dehydrated with an appropriate amount of anhydrous magnesium sulfate according to a conventional method, concentrated, added with 100 parts by mass of saturated saline, stirred at 60 ° C for 30 minutes, cooled on ice, and then the supernatant was removed. . This operation was repeated once more. This was redissolved in 300 parts by mass of black mouth form, stirred at 60 ° C. for 30 minutes, dehydrated with an appropriate amount of anhydrous magnesium sulfate according to a conventional method, and concentrated to obtain syrupy methylated branched starch. Since this product is fat-soluble, it can be used advantageously in oily cosmetics in general.

 Example 3

 [0103] <Linoleic acid ester of branched starch>

 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. This was purified by silica gel chromatography to prepare a branched starch linoleic acid ester. This product is tasteless and odorless, and can be advantageously used in foods, cosmetics, pharmaceuticals and the like. Example 4

 [0104] <Myristate ester of branched starch>

Branched starch production example 200 parts by weight of the branched starch powder obtained by the method in Example 5 was dissolved in 800 parts by weight of N, N'-dimethyl honolemamide, 60 parts by weight of myristic acid methyl ester and 4 parts by weight of carbonic acid lucium were added, and lOOmmHg The reaction was carried out at 85 ° C to 95 ° C for 24 hours with stirring under reduced pressure of 200mmHg. Thereafter, the solvent is distilled off from the reaction mixture under reduced pressure, the residue is immersed twice in 300 parts by weight of acetone, the leachate is concentrated, and the viscous oil obtained by washing with benzene and petroleum ether is again added to 300 parts of acetone. Immerse in the part. Ice-cold leachate The precipitate was collected and dried to obtain a myristate ester of branched starch. This product is tasteless and odorless, and can be advantageously used in foods, cosmetics, and pharmaceuticals.

 Example 5

 [0105] <Dodecyl ether of branched starch>

 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. Separately, 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. Thereafter, the 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.

 Example 6

 [0106] <Sulfuric ester of branched starch>

 Take 1 part by weight of the branched starch powder obtained by the method of Production Example 5 in a reaction vessel, add 5 parts by weight of a sulfur trioxide-dimethylformamide complex separately prepared according to a conventional method under a nitrogen stream, and drop it at room temperature. The reaction was allowed to proceed for 4 hours and then at 70 ° C for an additional hour. An appropriate amount of 5N sodium hydroxide was added for neutralization, 5 volumes of methyl alcohol was added, and the mixture was allowed to stand for a while, and then the precipitate was collected by suction filtration to obtain a sulfate ester of branched starch. This product can be used advantageously in cosmetics as a moisturizer and skin beautifier.

 Example 7

[0107] <Sulfuric ester of branched starch>

 100 parts by mass of the 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.

 Example 8

 [0108] <Cyanuric chloride derivative of branched starch>

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.

 Example 9

 [0109] <Tosylated derivatives of branched starch>

 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.

 Example 10

 [0110] <Phenylsulfide derivative of branched starch>

 7 parts by mass of potassium t-butoxide was dissolved in 20 parts by weight of dimethylformamide, 7 parts by mass of thiophenol was added dropwise at 0 ° C, and the mixture was further stirred at 0 ° C for 10 minutes. After 14 parts by weight of the tosylated derivative prepared in Example 9 was dissolved in dimethylformamide, it was added and stirred at room temperature for 1 hour. Extracted with ethyl acetate, washed with brine and concentrated. The residue was purified by silica gel chromatography to obtain a phenylsulfide derivative. This product has fat-solubility and can be applied to cosmetics and pharmaceuticals.

 Example 11

[0111] <Aminated derivative of branched starch>

10 parts by mass of the tosylated derivative prepared in Example 9 was dissolved in 20 parts by mass of anhydrous dimethylformamide in the presence of nitrogen gas, 1 part by mass of anhydrous sodium azide was added, and 65 ° C in the presence of nitrogen gas. After stirring for 18 hours, the mixture was cooled to room temperature, and 150 parts by mass of ice-cooled water was added. The precipitate was collected by filtration and resuspended in 150 parts by weight of water. The precipitate was collected and dried to obtain a diazotized derivative. Further, 1 part by mass of 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.

 Example 12

 [0112] <Acetylated branched starch>

 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.

 [0113] 10 g of this acetylated branched starch and 60 g of ε-force prolatatone were added, and graft polymerization was performed at 120 ° C for about 102 minutes in the presence of tin (II) octylate. This product had a graft rate of about 60%, and the thermal fluidization temperature was lower by 200 ° C or more than the branched starch used as a raw material.

 [0114] Using this acetylated branched starch derivative, a 30 m thick hot-press molded sheet was prepared with an ordinary plastic molding machine, a 1 cm x 3 cm piece was cut out, and its tensile strength was measured. The strength characteristics corresponding to general-purpose polyolefin having the same thickness were exhibited. Example 13

 [0115] <Cross-linked product of branched starch>

 Branched starch production example After preparing 32 g of 2.5% aqueous solution of branched starch powder prepared by the method of 5 to ρΗ12 · 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%.

 [0116] An aqueous solution of the above-mentioned branched starch cross-linked product is placed on a polystyrene plate at 37 ° C for 1 hour, further at 40 ° C,

Cast for 24 hours to make a film. 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.

 Example 14

 [0117] <Carrot chip>

 After washing, 50 g of carrots 150 g sliced into slices of about 1 Omm X about 1 Omm X about 2 mm thick, α, α-Trehalose (trade name “Treha”, sold by Hayashibara Corporation), Example 4 The solution was immersed in a solution at about 100 ° C. containing 0.5% of a linoleic acid ester of a branched starch derivative prepared by the above method, and immersed for 15 minutes while maintaining the solution temperature. Dried slice carrots were prepared by draining the sliced carrots after the immersion treatment, placing them in a warm air dryer and drying in an atmosphere heated to 60 ° C for 6 hours. This product is a carrot chip that is vivid and retains the flavor of carrots even when stored for a long time.

 [0118] 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.

 Example 15

 [0119] <Green grass extract powder>

 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, α —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.

[0120] 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>

 To 10 parts by weight of royal jelly extract, 0.5 parts by weight of a branched starch derivative prepared by the method of Example 3 and 1 part by weight of α-trehalose were added as a powdered base, and stirred and dissolved. The powder was lyophilized by a conventional method. This product is excellent in storage stability of useful ingredients contained in royal jelly that can be stored for a long period of time and absorbs moisture and browns.

[0122] This royal jelly powder 27 parts by mass, Coenzyme Q 5 parts by mass, sucrose 5 parts by mass,

 Ten

 Slithorne 55 Mass Sound, Snow Levi, Acid 6.5 Mass Sound, Ghi, Tamin Β 0.1 Mass Sound, Ghi, Tamin Β

 1 2

0. 1 part by weight, vitamin Β 0.1 part by weight, fruit flavor 1. Mix 2 parts by weight, l

 6

 Divided into Nate containers. This product is suitable as a health supplement because its useful components are retained even after long-term storage.

 Example 17

 [0123] <Powdered peppermint oil>

 150 g of water, 70 parts by weight of gum arabic, 4 parts by weight of sucrose fatty acid ester, 2 parts by weight of powdered branched starch derivative obtained by the method of Example 3 as a powdered base, hydrous crystals α, α-trehalose 20 parts by mass was added to dissolve, heated to 85 ° C for sterilization, and maintained for 15 minutes. After cooling to 40 ° C., 10 g of peppermint oil was added and emulsified with a homomixer. This was spray-dried by a conventional method to prepare powdered peppermint oil. In this product, the powder molded product that also absorbs moisture maintained sufficient powder flowability. In addition, since the oxidation and decomposition of peppermint oil is suppressed, the generation of deteriorated odors is suppressed, and even if deteriorated odors are generated, the deteriorated odors are masked, resulting in a stable fragrance of peppermint oil. Held for a long time. In addition, this product can be advantageously used as a fragrance for food and drink, cosmetics, quasi drugs, and pharmaceuticals.

[0124] As a control, 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 was placed in a sealed container and stored in a 50 ° C incubator for 6 months. Using equal parts by weight of the preserved peppermint powder, each gum is prepared by a conventional method, and the flavor of the peppermint is subjected to a sensory test by 10 panelists. As a result, 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! /.

 Example 18

[0125] <Powdered orange oil>

Α, α Trehalose 300 g as powdered base, cyclo disclosed in the specification of WO 02/10361 (→ 6) a—D gnolecopyranosinole (1 → 3) a—D glucopyranosyl ( 1 → 6)-a-D-Darkopyranosyl 1 (1 → 3)-a- D-Darkopyranosyl- (1 →} cyclic tetrasaccharide (manufactured by Hayashibara Biochemical Laboratories, Inc.) 30 0g, a, Sugar containing sugar derivative of trehalose (trade name “Hello Dettas”, sold by Hayashibara Shoji Co., Ltd.) 60 parts by mass and 10 g of the branched starch derivative prepared by the method of Example 4 were dissolved in 200 g of ion-exchanged water. Then, 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燥後, ² 〇 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. As a fragrance for cosmetics, cosmetics, quasi-drugs, and pharmaceuticals, it is advantageously used for IJ.

 Example 19

[0126] <Spinning>

An 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. Further, 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.

 Example 20

 <Laminated polylactic acid film using a branched starch derivative>

 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.

 Example 21

 [0128] <Coating layer molding for printing>

 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. To this slurry, 10 parts by mass (solid content) of styrene-butadiene copolymer latex, 3 parts by mass of the branched starch derivative prepared by the method of Example 12

(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%.

[0129] Using the above coating material were performed base paper, both sides coated with a blade coater so that 20 g / m ² on one surface per dry weight. After drying this paper, supply water with a roll-up applicator Then, it was coated with water and dried. After that, the surface was glossy by super calendering to obtain coated paper for printing. This product has little bleeding of printing ink and pigment, and has sufficient mechanical strength and durability.

 Example 22

[0130] <Paper>

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. Example 23

 [0131] <Nonwoven fabric>

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. Example 24

 [0132] <Gardening sheet>

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.

 Example 25

[0133] <Antimicrobial sheet>

 Carbohydrate containing a carbohydrate derivative of a, a-trehalose (trade name “Hello Dettas”, sold by Hayashibara Corporation) 45 parts by mass, sodium lactate 5 parts by mass, water 30 parts by mass, branched starch prepared by the method of Example 1 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.

 Example 26

[0134] <Sheet>

 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.

 [0135] When a seedling pot was prepared by vacuum forming using this sheet, a beautiful molded product (seedling pot) could be obtained. This product had sufficient water resistance and mechanical strength. Example 27

 [0136] <Foamed material>

100 parts by mass of the branched starch derivative prepared by the method of Example 12, a copolymer of methyl methacrylate and alkyl acrylate, (molecular weight 3.1 million) 1 part by mass, water 30 parts by mass After mixing for 10 minutes at 1000 rpm, pelletized at 100 ° C with a test extruder (Sold by Toyo Seiki Co., Ltd., “Laboplast Mill”). This was dried to a moisture content of 13.5%, and a foam was formed at 190 ° C using the pellets in a rose cushioning material production facility. 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.

 Example 28

[0137] <Tray>

 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.

 Example 29

[0138] <Tray and pile>

 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.

[0139] The appearance of the obtained trays and stakes was good. In addition, the mechanical strength of the tray and piles was sufficient, and washing with water was possible. These moldings were biodegradable and were almost completely decomposed when buried in soil and left at room temperature for 3 months.

 Example 30

[0140] <Tablets> Aspirin is mixed with 50 parts by mass of trehalose hydrous crystal powder, 14 parts by mass, and 4 parts by mass of the branched starch derivative prepared by the method of Example 3. 25mm, 1 tablet 680mg tablet was produced. This product uses the formability of branched starch and trehalose, and has sufficient physical strength to absorb moisture, and disintegrates in water compared to when no branched starch derivative is used. It is good.

 Example 31

[0141] <Treatment for trauma>

 To 400 parts by weight of manoleose, 50 parts by weight of methanol in which 3 parts by weight of iodine were dissolved and mixed, and further, 200 parts by weight of a 10 w / v% aqueous solution of a branched starch derivative-containing powder prepared by the method of Example 4 were added. The mixture was mixed to obtain 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. In addition, 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.

 Example 32

[0142] <Finorem>

 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. Like the pullulan film, 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.

 Example 33

[0143] <Finorem> 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 and water solubility, and is suitable as an edible film capsule film.

 Example 34

 [0144] <Capsenore>

 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. In addition, it is suitable as a filling container for foods and pharmaceuticals because it has an appropriate gradual disintegration property in an aqueous system.

 Example 35

 [0145] <Capsenore>

Commercially available pullulan (trade name “Pullan PF-20”, Hayashibara Shoji Co., Ltd.) 200 parts by weight, branched starch obtained by the method of Example 3 50 parts by weight, native dielan gum 0.5 part by weight, sodium alginate 0.5 parts by mass, sugar ester 0.05 parts by mass and 750 parts by mass of deionized water 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 has a glossy surface, excellent transparency, oxygen It did not show permeability and was excellent in stability against changes in humidity. In addition, it is suitable as a filling container for foods and pharmaceuticals because it has an appropriate gradual disintegration property in water.

 Example 36

 <Latex>

 Based on the following formulation, an emulsion was prepared by a conventional method.

 (Prescription) (%)

 Polyoxyethylene (20E. O.) Polyoxypropylene

 (2E.O.) Cetiano Reconole 1

 Silicon KF96 (20cs) (Shin-Etsu Chemical Co., Ltd. sales) 2

 Liquid paraffin (medium viscosity) 3

 1, 3-Butylene glyconole (1,3-BG) 5

 L-asconolevic acid 1 2 -gnorecoside 2

 Glycerin 2

 Branched starch derivative prepared by the method of Example 5 0.6 Ethyl alcohol 15

 Canolepoxy bininole polymer 0.3

2-Aminomethylpropanol 0 · 1

 Indigo extract (trade name "Ai Luros", Hayashibara Biochemical Research Institute, Inc.

 1, 3—Aqueous extract of green grass containing 30% BG) 2 Preservative

 Add purified water to bring the total volume to 100%.

 [0147] This product is useful as a skin external preparation for whitening and / or beautifying skin. In addition, this product is excellent in moisture retention, permeability, spreadability, and usability.

 Example 37

[0148] <Shampoo>

 A shampoo was prepared by a conventional method based on the following formulation.

(Prescription) (%) Pirotaton Olamine 0.5

 Edetate disodium 0.3

 Photosensitive Element 201 0. 002

 0. 3

 Sodium salicylate 0.2

 1, 3-BG 3

 Polyoxyethylene lauryl ether sulfuric acid 6. 75

 Palm oil fatty acid diethanolamide 2

 Lauryl sulfate triethanolamine 10

 Polyoxyethylene lanolinic acid (80Ε · O.) 0.5

 2 Anolequinore N Force Revoloxymethinore N

 Imidazolinium 10 Ammonium chloride ether 0.8

 Branched starch derivative prepared by the method of Example 6 0.5

 Cyanobacteria extract powder prepared by the method of Example 15 1

 Fragrance 0.2

 Add purified water to bring the total volume to 100%.

 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. In addition, it is a shampoo with excellent usability that retains moderate moisture after use and improves hair slippage.

Example 38

 <Hair restorer>

 Powder of cyanobacteria extract prepared by the method of Example 15 2g

 '3. Oml

 0.lg

a, a-Trenolose 0. O lg Seaweed extract 0.75g

 Glycerin 2g

 Branched starch derivative prepared by the method of Example 7 0.lg

 Add purified water, stir and dissolve to make the total volume 100ml.

 This product is excellent in hair growth and moisturizing properties, suppresses dandruff, itchiness and hair loss, and has a good hair feeling.

Industrial applicability

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. In addition, 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.

Replacement paper (Rule 26)

Claims

Billing area  [1] A derivative of a wheat flour having a 6-α-maltosyl branched structure and / or a 6-α-maltotetraosyl branched structure.  [23 One or more hydroxyl groups of the branched starch are substituted with any substituent other than hydroxyl groups. The derivative of branched starch according to claim 1, characterized in that:  [3] The optional substituent is at least one selected from a hydrocarbon group, a substituent having oxygen other than a hydroxyl group, a substituent having nitrogen, a substituent having sulfur, and a substituent having halogen. 3. The branched starch derivative according to claim 2, wherein  4. The branched starch derivative according to claim 1, wherein the branched starch derivative is chemically modified by esterification, etherification, oxidation, grafting or crosslinking reaction. [5] Branched starch is produced by digestion of pullulanase (EC 3.2.1.41) to produce at least 1.8% by mass of maltose and 0.7% by mass of Z or maltotetraose per solid. The branched starch derivative according to any one of claims 1 to ⁴ , wherein the derivative is a branched starch derivative.  [6] Branched starch was subjected to methylation analysis, and partially methylated product contained 0.4 mass% or more of 2,3,4-trimethylmethyl-1,5,6_triacetylgentol per solid. The branched starch derivative according to any one of claims 1 to 5, wherein the derivative is a branched starch derivative. [7] The branched starch has an aging resistance that does not substantially show white turbidity due to aging of the starch when an aqueous solution having a concentration of 25% by mass is kept at 5 ° C for 10 days. The branched starch derivative according to any one of claims 1 to 6, wherein: [8] Branched starch has a 6-a-maltosyl branched structure and / or a 6-α-maltotetraosyl branched structure by allowing a cyclic maltosyl maltose-producing enzyme to act on liquefied starch and starch or partially decomposed starch. 6-a mono-maltosyl branch comprising a step of producing starch and a step of collecting the produced 6-a-maltosyl branched structure and a branched starch having Z or 6-a mono-maltotetraosyl branched structure. The branched starch derivative according to any one of claims 1 to 7, which is produced by a method for producing a branched starch having a structure and Z or 6-α-maltotetraosyl branched structure. [9] A branched starch having a 6-α-maltosyl branched structure and / or a 6-α-maltotetraosyl branched structure is reacted with an enzyme, a substrate thereof, or a reactive reagent, One of them Replacement paper (Rule 26) A method for producing a derivative of a branched starch, wherein the hydroxyl group is substituted with a substituent other than a hydroxyl group. '  [10] Reactive reagents are acids, bases, carbohydrates, alcohols, aldehydes, ketones, ketones, rhogens, cyanides, nitriles, oxolans, isocyanates, isothiocyanates, thiols, sulfones and / or reactive derivatives thereof. 10. The method for producing a branched starch derivative according to claim 9, wherein the number is one or more. [11] A molded article containing the branched starch derivative according to any one of claims 1 to ⁸ . [12] In addition, it should be added to chemical products, industrial products, civil engineering greenery products, agricultural and forestry products, horticultural materials products, powder products, miscellaneous goods, pharmaceuticals, quasi-drugs, cosmetics, foods, foods and foods and drinks. 12. The molded article according to claim 11, wherein the molded article contains one or more components capable of being formed. [13] Chemical products, industrial products, civil engineering planting supplies, agricultural and forestry supplies, horticultural supplies, powder products, pharmaceuticals, 13. The molded article according to claim 11 or 12, which is any one selected from quasi-drugs, cosmetics, feeds, feeds and foods and drinks. [14] Ingredients that can be incorporated into chemical products, industrial products, civil engineering planting products, agricultural and forestry products, horticultural materials products, powder products, quasi-drugs, cosmetics, pharmaceuticals and foods and drinks 14. The powder powder having a branched structure and / or a 6-α-maltotetraosyl branched structure is a high material other than a conductor: a material and / or a plasticizer. 13. Moldings.  [15] The molded product according to any one of [12] to [14], wherein the chemical product or the industrial product is biogenic. Replacement paper (Rule 26)