WO2015163064A1 - Edible film and method for manufacturing same - Google Patents

Edible film and method for manufacturing same Download PDF

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Publication number
WO2015163064A1
WO2015163064A1 PCT/JP2015/058567 JP2015058567W WO2015163064A1 WO 2015163064 A1 WO2015163064 A1 WO 2015163064A1 JP 2015058567 W JP2015058567 W JP 2015058567W WO 2015163064 A1 WO2015163064 A1 WO 2015163064A1
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Prior art keywords
water
soluble
polysaccharide
film
oligosaccharide
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PCT/JP2015/058567
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French (fr)
Japanese (ja)
Inventor
聖 以倉
伊藤　久義
隆弘 平邑
左枝 板谷
智仁 岡林
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株式会社ダイセル
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Publication of WO2015163064A1 publication Critical patent/WO2015163064A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/0012—Galenical forms characterised by the site of application
    • A61K9/0053—Mouth and digestive tract, i.e. intraoral and peroral administration
    • A61K9/0056—Mouth soluble or dispersible forms; Suckable, eatable, chewable coherent forms; Forms rapidly disintegrating in the mouth; Lozenges; Lollipops; Bite capsules; Baked products; Baits or other oral forms for animals
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor

Definitions

  • the present invention relates to an edible film that can be rapidly dissolved with a smooth feel and a method for producing the edible film.
  • Edible films are often used in confectionery for the prevention of bad breath and oral care, but in recent years the number of people who have difficulty swallowing has increased in the medical field due to the aging trend, and it is difficult to swallow medicines.
  • a preparation that is easy to administer orally In addition, a preparation for absorbing a drug through the oral mucosa or a preparation for treating a disease in the oral cavity has been proposed by taking advantage of its ability to rapidly disintegrate or dissolve in the oral cavity and elute a medicinal component.
  • the edible film used for these applications is an oblate obtained by gelatinizing and drying starch, or a film prepared by dissolving a water-soluble component such as a water-soluble polymer in water and casting it. Yes.
  • Patent Document 1 a solution containing a water-soluble polysaccharide mainly composed of carrageenan, a polyhydric alcohol, and water is formed into a film shape, and then dried to obtain a moisture content. It is described that a heat-sealable edible film having a weight ratio of 25% by weight or less and having a polyhydric alcohol to water-soluble polysaccharide ratio of 0.2 to 1 is produced. However, in the method of this document, since the affinity between the water-soluble polysaccharide and water is high, only a high edible film having a water content of about 15% by weight can be obtained even after drying.
  • Patent Document 2 JP 2000-342193 A (Patent Document 2) describes an edible film obtained by molding and drying an aqueous solution containing hydroxypropylated starch having a hydroxypropyl group concentration of 2 to 10% and a predetermined aqueous solution viscosity.
  • hydroxypropylated starch may further contain a component selected from polyhydric alcohol, sugar alcohol, monosaccharide, disaccharide, oligosaccharide and starch degradation product.
  • this edible film also has a high moisture content of about 10 to 15% by weight.
  • Patent Document 3 describes a film-form preparation containing a film-forming agent, a gel-forming agent, and a neuroleptic agent.
  • a film-forming agent sugar, sugar alcohol and derivatives thereof, In particular, sucrose, sorbitol, mannitol, xylitol, glucose, fructose, lactose and galactose are described.
  • a solution containing the above components is cast on a peelable substrate and dried to remove the solvent.
  • the film forming agent and the gel forming agent having high affinity for water are also used in the method of this document, the water content of the film cannot be reduced.
  • Such a film with a high water content is likely to be adversely affected in terms of stability.
  • the film and the packaged body may be in close contact with each other, or the films may be in close contact with each other to be solidified, resulting in a decrease in storage stability.
  • lumps (strength) of an edible film are easy to fall, it adheres to each other in an oral cavity, and it is easy to solidify in a lump shape, and solubility may be impaired.
  • the effect of the medicinal ingredients on the storage stability is also a concern.
  • JP-A-4-51852 (Claims, Examples) JP 2000-342193 A (Claims, Examples) JP-T 2009-501752 (Claims, Examples)
  • an object of the present invention is to provide an edible film having excellent storage stability (or storage stability) and a method for producing the same even if it contains a water-soluble polysaccharide.
  • Another object of the present invention is to provide an edible film which is excellent in touch in the oral cavity and can be rapidly dissolved, and a method for producing the edible film.
  • Still another object of the present invention is to provide a method for producing an edible film industrially advantageously with high production efficiency.
  • the present inventors have been able to heat-melt a composition containing a predetermined water-soluble component such as an oligosaccharide and form such a composition by extrusion molding, etc. It has been found that an edible film with a low water content can be produced by melt film formation according to the present invention, and the present invention has been completed.
  • the edible film of the present invention contains a water-soluble film-forming component (A), and the water-soluble film-forming component (A) is composed of an oligosaccharide (B1) and a polysaccharide (B2) having a cyclic structure. It contains at least one selected water-soluble polysaccharide (B).
  • the edible film is formed by melt film formation.
  • Such an edible film has a low water content, and may be, for example, 5% by weight or less.
  • the water-soluble film forming component (A) may contain a water-soluble polysaccharide (B) and a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B),
  • the water-soluble plasticizing component (C) may be at least one selected from sugar and sugar alcohol.
  • the oligosaccharide (B1) was selected from starch sugar, maltooligosaccharide, isomaltooligosaccharide, galactooligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, dairy oligosaccharide, chitin oligosaccharide and chitosan oligosaccharide At least one kind may be sufficient, and the polysaccharide (B2) which has a cyclic structure may be cluster dextrin and / or cycloamylose.
  • the sugar alcohol may be at least one selected from erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbitol, dulcitol, mannitol, maltitol, lactitol and the like.
  • the present invention melts and forms a water-soluble film-forming component (A) containing at least one water-soluble polysaccharide (B) selected from an oligosaccharide (B1) and a polysaccharide (B2) having a cyclic structure. Also included is a method of producing an edible film. In this method, the water-soluble film-forming component (A) containing the water-soluble polysaccharide (B) and the water-soluble plasticizing component (C) may be melt-kneaded and extruded into a sheet or film.
  • the edible film of the present invention melt-forms a composition containing the predetermined water-soluble film-forming component (A), even if it contains a water-soluble polysaccharide, the water content can be reduced, and the storability (or Excellent storage stability). Moreover, since there is little water content, it is excellent in the touch in an oral cavity, and it can melt
  • the water-soluble film-forming component (A) that forms the edible film contains at least one water-soluble polysaccharide (B) selected from oligosaccharides (B1) and polysaccharides having a cyclic structure (B2),
  • B water-soluble polysaccharide
  • the oligosaccharide (B1) may be either a homo-oligosaccharide or a hetero-oligosaccharide, or may be an anhydride. In oligosaccharides, monosaccharides and sugar alcohols may be bonded.
  • the oligosaccharide may be an oligosaccharide composition composed of a plurality of sugar components. In this specification, even such an oligosaccharide composition may be simply referred to as an oligosaccharide. Oligosaccharides (or oligosaccharide compositions) can be used alone or in combination of two or more. Oligosaccharides are not limited to oligosaccharides of about disaccharide to decasaccharide, but include polysaccharides having a degree of polymerization of 10 or more (especially 15 or more, especially 20 or more).
  • disaccharides examples include homo-oligosaccharides such as trehalose, maltose, isomaltose, and cellobiose; and hetero-oligosaccharides such as lactose, sucrose, and palatinose.
  • homo-oligosaccharides such as trehalose, maltose, isomaltose, and cellobiose
  • hetero-oligosaccharides such as lactose, sucrose, and palatinose.
  • Trisaccharides include homo-oligosaccharides such as maltotriose, isomaltotriose, panose and cellotriose; hetero-oligosaccharides such as manninotriose, solatriose, melezitose, planteose, gentianose, umbelliferose, lactosucrose and raffinose It is done.
  • tetrasaccharides examples include homo-oligosaccharides such as maltotetraose and isomalttetraose; and hetero-oligosaccharides such as tetraose in which sugar or sugar alcohol is bonded to the reducing end of stachyose, cellotetraose, scorodose, liquinose, or panose.
  • tetraose in which a monosaccharide or a sugar alcohol is bonded to the reducing end of panose is disclosed, for example, in JP-A-10-215892, and glucose, fructose, mannose
  • examples include tetraose to which monosaccharides such as xylose and arabinose and sugar alcohols such as sorbitol, xylitol and erythritol are bonded.
  • pentasaccharides examples include homo-oligosaccharides such as maltopentaose and isomaltopentaose; and hetero-oligosaccharides such as pentaose in which a disaccharide is bonded to the reducing end of panose.
  • Pentaose in which a disaccharide is bonded to the reducing end of panose is disclosed, for example, in JP-A-10-215892, and pentaose in which a disaccharide such as sucrose, lactose, cellobiose, trehalose is bonded to the reducing end of panose. It can be illustrated.
  • hexasaccharides examples include homo-oligosaccharides such as maltohexaose and isomaltohexaose.
  • Oligosaccharide (B1) may be an oligosaccharide composition produced by degradation of a polysaccharide.
  • examples of the oligosaccharide composition include starch sugar (starch saccharified product), galacto-oligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, chitin oligosaccharide, chitosan oligosaccharide and the like. It can be used alone or in combination of two or more.
  • the starch sugar may be a mixture of oligosaccharides having a plurality of glucose bound thereto.
  • an oligosaccharide composition (oligosaccharide mixture) may be bonded to a sugar alcohol in the same manner as described above. That is, the oligosaccharide composition (or the oligosaccharide constituting the oligosaccharide composition) may have an oligosaccharide unit and a sugar alcohol unit bonded to the oligosaccharide unit. Such sugar alcohol units are usually often located at the end of oligosaccharide units. That is, the oligosaccharide constituting the oligosaccharide composition may have a sugar alcohol unit whose terminal is reduced. In addition, the oligosaccharide composition having such a sugar alcohol unit can be obtained, for example, by reducing an oligosaccharide composition (such as starch sugar).
  • starch sugar examples include reduced starch saccharified product (trade name: PO-10) manufactured by Mitsubishi Corporation Foodtech.
  • the oligosaccharide may be a non-reducing type (trehalose type), but a reducing type (maltose type) oligosaccharide is preferred because of its excellent heat resistance.
  • the reduced oligosaccharide is not particularly limited as long as it has a free aldehyde group or a ketone group and exhibits reducing properties.
  • the oligosaccharide composition may contain a large amount of relatively large multimeric oligosaccharides.
  • the content ratio of oligosaccharides of 20 or more saccharides is 30% by weight or more (for example, 40% To 100% by weight), preferably 50% by weight or more (eg, 50 to 95% by weight), more preferably about 65 to 90% by weight, and particularly about 50 to 85% by weight.
  • the oligosaccharide (B1) has a high viscosity. Specifically, when measured at a temperature of 25 ° C. using a B-type viscometer, the viscosity of a 50% by weight aqueous solution of oligosaccharide (B1) is 0.1 Pa ⁇ s or more (eg, 0.2 to 2 Pa ⁇ s). Degree), preferably 0.3 Pa ⁇ s or more (eg, about 0.4 to 1.5 Pa ⁇ s, particularly about 0.45 to 1 Pa ⁇ s), more preferably 0.5 Pa ⁇ s or more (eg, 0.5 About 0.9 Pa ⁇ s).
  • oligosaccharide (B1) for example, starch sugar such as reduced starch saccharified product
  • it may be decomposed (thermally decomposed) without showing a melting point or a softening point.
  • the decomposition temperature may be the “melting point or softening point” of the oligosaccharide (B1).
  • the melting point or softening point of the oligosaccharide (B1) can be selected in the range of 70 to 300 ° C., for example, 90 to 290 ° C., preferably 100 to 280 ° C. (eg 110 to 270 ° C.), more preferably 120 to 260. It may be about 0 ° C. (for example, 130 to 260 ° C.).
  • the polysaccharide (B2) having a cyclic structure has at least one cyclic structure, has a relatively high molecular weight and higher melt viscosity than the oligosaccharide (B1), etc., and is also due to the cyclic structure? Shows water solubility.
  • a polysaccharide it is possible to maintain a higher shear viscosity in melt kneading as compared with oligosaccharide (B1) and the like, and melt film formation is possible.
  • a plurality of glucose units (particularly D-glucose) constituting the polysaccharide has a glucoside bond (or glucosylation) in the cyclic structure (cyclic skeleton, cyclic unit, cyclic portion).
  • Any ring formed may be used. That is, in this specification, a cyclic structure means a ring formed of a plurality of glucose units (and glucoside bonds), not a monosaccharide ring such as a glucose ring.
  • the cyclic structure only needs to be composed of a plurality of glucoside bonds ( ⁇ -glucoside bonds and / or ⁇ -glucoside bonds), and may generally be composed of ⁇ -glucoside bonds.
  • the cyclic structure is a cyclic structure containing a 1,4-glucoside bond (eg, ⁇ -1,4-glucoside bond) or a 1,6-glucoside bond (eg, ⁇ -1,6-glucoside bond).
  • it may be a cyclic structure having a 1,4-glucoside bond (especially an ⁇ -1,4-glucoside bond) and a 1,6-glucoside bond (particularly an ⁇ -1,6-glucoside bond). May be.
  • the polysaccharide (B2) having a cyclic structure has an ⁇ -1,4-glucoside bond and an ⁇ -1,6-glucoside bond, and a glucose unit has a predetermined average polymerization degree per one cyclic structure. It may be composed of a polysaccharide having a cyclic structure polymerized in (i) and an acyclic structure bonded to the cyclic structure and having an average degree of polymerization (total average degree of polymerization) of 50 or more.
  • the average degree of polymerization of the cyclic structure (per one cyclic structure) (number average degree of polymerization, average number of glucoside bonds forming the cyclic structure, average degree of polymerization of glucose units forming the cyclic structure) is, for example, 10 or more (for example, It may be about 10 to 500), preferably 12 or more (for example, about 12 to 300), and more preferably 14 or more (for example, about 14 to 100).
  • the average number of 1,6-glucoside bonds in the cyclic structure may be 1 or more (for example, about 1 to 700). It may be 1 to 300 (eg 1 to 200), preferably 1 to 100 (eg 1 to 50), more preferably 1 to 20 (eg 1 to 10).
  • the water-soluble polysaccharide having a cyclic structure may have at least one cyclic structure (cyclic unit), and may have a plurality of cyclic structures.
  • the average degree of polymerization (number average degree of polymerization, total average degree of polymerization, average degree of polymerization of the whole polysaccharide) of the polysaccharide (B2) having a cyclic structure is, for example, 14 or more (for example, 14 to 15000), preferably It may be 17 or more (for example, 17 to 10000), more preferably 20 or more (for example, about 20 to 8000).
  • the polysaccharide (B2) having a cyclic structure may be modified or derivatized (or modified).
  • a polysaccharide having a cyclic structure has a hydroxyl group (alcoholic hydroxyl group) modified or derivatized [eg, etherification (eg, alkyl etherification such as methyl etherification; hydroxyethyl etherification, hydroxypropyl etherification, etc. Hydroxyalkyl etherification; glycerylation, etc.), esterification, grafting, cross-linking, etc.].
  • etherification eg, alkyl etherification such as methyl etherification; hydroxyethyl etherification, hydroxypropyl etherification, etc. Hydroxyalkyl etherification; glycerylation, etc.
  • esterification grafting, cross-linking, etc.
  • the water-soluble polysaccharide having a cyclic structure may be used alone or in combination of two or more.
  • the water-soluble polysaccharide having a typical cyclic structure has a cyclic structure (or cyclic unit) and an acyclic structure (acyclic skeleton, acyclic unit acyclic part) bonded to the cyclic structure, and an average Polysaccharides having a degree of polymerization of 50 or more (sometimes referred to as polysaccharides (1)), polysaccharides having one cyclic structure formed by ⁇ -1,4-glucoside bonds of 14 or more (polysaccharides (2 ))).
  • the cyclic structure may be a ring formed by an ⁇ -1,4-glucoside bond and an ⁇ -1,6-glucoside bond.
  • the average degree of polymerization (number average degree of polymerization) of one cyclic structure may be, for example, 10 to 500, preferably 12 to 300, and more preferably 14 to 100.
  • the average number of ⁇ -1,6-glucoside bonds in the cyclic structure (per one cyclic structure) is, for example, 1 or more (for example, 1 to 200), preferably 1 to 100, and more preferably about 1 to 50. May be.
  • the average degree of polymerization (number average degree of polymerization, total number average degree of polymerization) of the polysaccharide (1) may be 50 or more, for example, 50 to 10,000, preferably 60 to 7000, more preferably about 70 to 5000. Good.
  • the polysaccharide (1) may have one or a plurality of acyclic structures, usually a plurality of (for example, about 2 to 1000, preferably about 3 to 500) acyclic structures.
  • the average degree of polymerization (number average degree of polymerization) per such acyclic part (or part other than the cyclic structure of the polysaccharide (1)) is, for example, 10 or more (for example, 10 to 30), preferably 10 It may be about ⁇ 20.
  • the average degree of polymerization (number average degree of polymerization) of the entire non-cyclic moiety may be 10 or more, for example, 40 or more (for example, about 50 to 5000), preferably about 100 to 3000.
  • the acyclic moiety is often branched from a glucose unit of an ⁇ -1,6-glucoside bond.
  • the hydroxyl group (alcoholic hydroxyl group) may be modified or derivatized (for example, etherification, esterification, grafting, etc.).
  • Such a polysaccharide (1) includes a polysaccharide known as a “cluster dextrin”.
  • Such polysaccharides (1) are synthesized by, for example, saccharides (for example, starch, partially decomposed starch, amylopectin, glycogen, waxy starch, high amylose starch, soluble starch, dextrin, starch hydrolyzate, and phosphorylase). It may be obtained by reacting an enzyme (branching enzyme, D enzyme, cyclodextrin glucanotransferase, etc.) capable of forming a cyclic structure by acting on a saccharide with at least one substrate selected from amylopectin. . JP-A-8-134104 and the like can be referred to for details of such cluster dextrin and the production method thereof.
  • saccharides for example, starch, partially decomposed starch, amylopectin, glycogen, waxy starch, high amylose starch, soluble
  • the cyclic structure may be a ring formed of at least an ⁇ -1,4-glucoside bond, and includes an ⁇ -1,4-glucoside bond and an ⁇ -1,6-glucoside bond. It may be a ring formed.
  • the average degree of polymerization (number average degree of polymerization) of the cyclic structure may be 14 or more, for example, 14 to 5000, preferably 15 or more (for example, about 15 to 3000), more preferably 17 or more (for example, 17 to 1000).
  • the average number of ⁇ -1,6-glucoside bonds in the cyclic structure is, for example, about 1 to 500, preferably about 1 to 300, and more preferably about 1 to 100 It may be.
  • the polysaccharide (2) may have an acyclic structure (for example, a straight chain structure) as long as it has the cyclic structure, but is usually composed (or formed) of only the cyclic structure. It may be a cyclic polysaccharide.
  • the hydroxyl group (alcoholic hydroxyl group) may be modified or derivatized (for example, etherified, esterified, grafted, crosslinked).
  • Such polysaccharide (2) includes a polysaccharide known as “cycloamylose (or cycloamylose)”.
  • a polysaccharide (2) is, for example, a linear ⁇ -1,4-glucan or a saccharide containing this glucan (for example, maltooligosaccharide, amylose, amylopectin, glycogen, starch, waxy starch, high amylose starch, Soluble starch, dextrin, starch debranch, partially hydrolyzed starch, enzyme synthesized amylose by morpholase, and at least one selected from these derivatives) and an enzyme capable of forming polysaccharide (2) (for example, D enzyme and the like) can be obtained by reacting in the presence of phosphorylase and glucose 1-phosphate, if necessary.
  • an enzyme capable of forming polysaccharide (2) for example, D enzyme and the like
  • an enzyme capable of cleaving the ⁇ -1,6-glucoside bond eg, isoamylase, pullulanase, etc.
  • JP-A-8-311103 and the like can be referred to for details on such cycloamylose and its production method.
  • Polysaccharides having a cyclic structure may be used alone or in combination of two or more.
  • the polysaccharide (1) or cluster dextrin
  • the polysaccharide (1) can be suitably used.
  • the water-soluble polysaccharide (B) can be composed of an oligosaccharide (B1) and / or a polysaccharide having a cyclic structure, and the melt viscosity can be adjusted by properly using these components and adjusting the ratio of both components. .
  • the water-soluble film forming component (A) may further contain a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B).
  • a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B).
  • the water-soluble plasticizing component (C) is not particularly limited as long as it is a compound that plasticizes the water-soluble polysaccharide (B), and is composed of saccharides (for example, monosaccharides, disaccharides, etc.) or sugar alcohols. Alternatively, such saccharides may be composed of reducing sugars.
  • the monosaccharide may be composed of triose, tetrose, pentose, hexose, heptose, octose, nonose, decose, dodecose, etc., and examples thereof include glucose, galactose, fructose, mannose, and xylose.
  • the disaccharide may be composed of homo- and hetero-disaccharides of the monosaccharides, and examples thereof include sucrose, lactose, maltose, trehalose, cellobiose and the like.
  • Sugar alcohols include tetritol (eg, erythritol), pentitol (eg, pentaerythritol, arabitol, ribitol, xylitol, etc.), hexitol (eg, sorbitol, dulcitol, mannitol, galactitol, etc.), heptitol, octitol, nonitol, dexitol. , Dodecitol may be used.
  • the sugar alcohol may be a sugar alcohol obtained by reducing a reducing sugar, for example, maltitol by catalytic reduction of maltose, reduced lactose (lactitol), or the like.
  • sugars such as trehalose, maltose, and lactose and sugar alcohols are widely used, and sugar alcohols are preferred.
  • sugar alcohols erythritol, pentaerythritol, arabitol, ribitol, xylitol, dulcitol, mannitol, sorbitol, lactitol, maltitol (particularly pentitol such as xylitol and / or hexitol such as sorbitol) are preferable.
  • the details of the oligosaccharide and sugar alcohol are described in JP-A No. 2004-51942 and JP-A No. 2005-162841.
  • the edible film may contain polysaccharides such as alginic acid or a salt thereof, pullulan and carrageenan as necessary, and various additives such as colorants, sweeteners, flavoring agents, stabilizers (antioxidants). Agents, ultraviolet absorbers, heat stabilizers, etc.), preservatives, antibacterial agents and the like.
  • polysaccharides such as alginic acid or a salt thereof, pullulan and carrageenan as necessary
  • various additives such as colorants, sweeteners, flavoring agents, stabilizers (antioxidants). Agents, ultraviolet absorbers, heat stabilizers, etc.), preservatives, antibacterial agents and the like.
  • the water-soluble film forming component (A) often does not contain a water-soluble and / or water-insoluble cellulose derivative, starch or a derivative thereof (for example, hydroxypropylated starch, starch, gelatinized starch, etc.).
  • the water-soluble film forming component (A) forms a dispersion form (for example, a dispersion form such as a particulate form, a sea-island form, a fiber form, a layer form) by kneading with a non-edible organic polymer.
  • organic solid components such as dispersed resin particles incompatible with the water-soluble film-forming component (A)
  • an unpleasant feeling such as a rough feeling may be given in the mouth of the edible film.
  • the edible film of the present invention is characterized by being formed by melt film formation. Therefore, even if it contains a water-soluble film-forming component (A), the moisture content of the edible film can be greatly reduced, and it is excellent not only in storage stability (or storage stability) but also in the oral cavity and quickly. It can be dissolved.
  • A water-soluble film-forming component
  • the moisture content of the edible film is, for example, 5% by weight or less (for example, 0 to 4% by weight), preferably 0.1 to 3% by weight (for example, 0.2 to 2. 5 wt%), more preferably about 0.2 to 2 wt% (for example, 0.2 to 1 wt%).
  • the thickness (average thickness) of the edible film is not particularly limited, and may be, for example, about 1 to 5000 ⁇ m (for example, 10 to 4000 ⁇ m), preferably about 30 to 3000 ⁇ m (for example, 50 to 1000 ⁇ m).
  • the edible film of the present invention can be prepared by melting the water-soluble film-forming component (A) to form a film.
  • the melt film-forming method is, for example, by extruding a melt of the water-soluble film-forming component (A) in a film or sheet form on a peelable substrate or drum, laminating and cooling, and then peeling the peelable substrate.
  • the edible film may be produced by peeling the film or sheet from the material or drum.
  • the edible film may be produced by an extrusion method or an inflation method in which the water-soluble film-forming component (A) is melt-kneaded with an extruder and extruded from a die into a sheet or film.
  • the extrusion method a T die is often used, and in the inflation method, a cylindrical die is used.
  • the melt kneading temperature can be selected from the range of, for example, about 90 to 300 ° C. (for example, 110 to 260 ° C.), and may be about 150 to 250 ° C. (for example, 170 to 230 ° C.).
  • the extruded film or sheet is cooled to obtain an edible film. If necessary, the film or sheet may be stretched.
  • the moisture content was measured using a moisture vaporizer (VA-100 model, manufactured by Mitsubishi Chemical Corporation) under the conditions of a heating temperature of 150 ° C. and a nitrogen flow rate of 300 ml / min.
  • the thickness was measured with a digital indicator (“ID-C112” manufactured by Mitutoyo Corporation).
  • Example 1 Oligosaccharide (starch sugar, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., reduced starch saccharified product “PO-10”) 0.77 g and sugar alcohol (sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit) 0.63 g are ground.
  • Example 2 0.83 g of oligosaccharide (starch sugar, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., reduced starch saccharified product “PO-10”) and 0.68 g of sugar alcohol (xylitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., xylit) are used.
  • a transparent film having a thickness of 0.48 to 0.55 mm and a water content of 0.79% by weight was obtained in the same manner as in Example 1. When the solubility of this film in the oral cavity was examined, it quickly dissolved in the oral cavity with a smooth feel.
  • Example 3 Same as Example 1 except that 0.83 g of oligosaccharide (Maltotriose, manufactured by Mitsubishi Chemical Foods Corporation, “Oligotose”) and 0.68 g of sugar alcohol (sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit) were used. Thus, a transparent film having a thickness of 0.4 to 0.5 mm and a water content of 2.2% by weight was obtained. When the solubility of this film in the oral cavity was examined, it quickly dissolved in the oral cavity with a smooth feel.
  • oligosaccharide Maltotriose, manufactured by Mitsubishi Chemical Foods Corporation, “Oligotose”
  • sugar alcohol sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit
  • Comparative Example 1 In 13.5 g of water, 0.77 g of oligosaccharide (starch sugar, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., reduced starch saccharified product “PO-10”) and sugar alcohol (sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit ) Add 0.63 g and dissolve, cast this solution on a peelable substrate, evaporate the moisture with a ventilator, thickness 0.2-0.4mm, moisture content 7.5wt% A transparent film was obtained.
  • oligosaccharide starch sugar, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., reduced starch saccharified product “PO-10”
  • sugar alcohol sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit
  • the present invention relates to confectionery for the prevention of bad breath and oral care, film preparations containing or sandwiching medicinal components that can be rapidly dissolved in the oral cavity and absorbed into the digestive organs, oral mucosal absorption and oral diseases It can be used for preparations for treatment.

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Abstract

A water-soluble film forming component (A) including a water-soluble plasticizing component (C) such as sugar alcohol and at least one type of water-soluble polysaccharide (B) selected from an oligosaccharide (B1) and a polysaccharide (B2) having a cyclic structure is used to melt-form a film by a method such as extrusion molding, and an edible film having a low moisture content is obtained. The resultant edible film dissolves rapidly and has excellent shelf life (or storage stability) and texture in the mouth despite including a water-soluble polysaccharide.

Description

可食性フィルム及びその製造方法Edible film and method for producing the same
　本発明は、滑らかな感触で迅速に溶解可能な可食性フィルム及びその製造方法に関する。 The present invention relates to an edible film that can be rapidly dissolved with a smooth feel and a method for producing the edible film.
　可食フィルムは口臭予防・口腔ケアを目的とした菓子類でよく用いられているが、近年医療分野においても高齢化の傾向に伴って嚥下困難者が増加し、薬を飲み込みにくい患者に対して経口投与し易い製剤として強く要望されている。また、口腔内で速やかに崩壊または溶解し、薬効成分を溶出させる性能を活かし、口腔内粘膜を通して薬剤を吸収させるための製剤又は口腔内の疾患の治療を目的とする製剤も提案されている。これらの用途に用いられる可食フィルムは、デンプンを糊化して乾燥させたオブラートであったり、水溶性ポリマーなどの水溶性成分を水に溶解させて流延して乾燥させたフィルムが提案されている。 Edible films are often used in confectionery for the prevention of bad breath and oral care, but in recent years the number of people who have difficulty swallowing has increased in the medical field due to the aging trend, and it is difficult to swallow medicines. There is a strong demand for a preparation that is easy to administer orally. In addition, a preparation for absorbing a drug through the oral mucosa or a preparation for treating a disease in the oral cavity has been proposed by taking advantage of its ability to rapidly disintegrate or dissolve in the oral cavity and elute a medicinal component. The edible film used for these applications is an oblate obtained by gelatinizing and drying starch, or a film prepared by dissolving a water-soluble component such as a water-soluble polymer in water and casting it. Yes.
　特開平４－５１８５２号公報（特許文献１）には、カラギーナンを主成分とする水溶性多糖類と多価アルコールと水とを含む溶液をフィルム状に賦形した後、乾燥し、水分率が２５重量％以下であり、多価アルコールと水溶性多糖類との重量比が０．２～１であるヒートシール可能な可食性フィルムを製造することが記載されている。しかし、この文献の方法では、水溶性多糖類と水との親和性が高いため、乾燥しても水分含有量が１５重量％程度の高い可食性フィルムしか得られない。 In JP-A-4-51852 (Patent Document 1), a solution containing a water-soluble polysaccharide mainly composed of carrageenan, a polyhydric alcohol, and water is formed into a film shape, and then dried to obtain a moisture content. It is described that a heat-sealable edible film having a weight ratio of 25% by weight or less and having a polyhydric alcohol to water-soluble polysaccharide ratio of 0.2 to 1 is produced. However, in the method of this document, since the affinity between the water-soluble polysaccharide and water is high, only a high edible film having a water content of about 15% by weight can be obtained even after drying.
　特開２０００－３４２１９３号公報（特許文献２）には、ヒドロキシプロピル基濃度が２～１０％であり、かつ所定の水溶液粘度を有するヒドロキシプロピル化澱粉を含む水溶液を成形乾燥した可食性フィルムが記載され、ヒドロキシプロピル化澱粉には、さらに多価アルコール、糖アルコール、単糖類、二糖類、オリゴ糖及び澱粉分解物から選択された成分を含有させてもよいことが記載されている。しかし、この可食性フィルムも水分含量が１０～１５重量％程度と多い。 JP 2000-342193 A (Patent Document 2) describes an edible film obtained by molding and drying an aqueous solution containing hydroxypropylated starch having a hydroxypropyl group concentration of 2 to 10% and a predetermined aqueous solution viscosity. In addition, it is described that hydroxypropylated starch may further contain a component selected from polyhydric alcohol, sugar alcohol, monosaccharide, disaccharide, oligosaccharide and starch degradation product. However, this edible film also has a high moisture content of about 10 to 15% by weight.
　特表２００９－５０１７５２号公報（特許文献３）には、フィルム形成剤、ゲル形成剤、並びに神経弛緩薬を含むフィルム型製剤が記載され、フィルム生成剤として、糖、糖アルコール及びそれらの誘導体、特にサッカロース、ソルビトール、マンニトール、キシリトール、グルコース、フルクトース、ラクトース及びガラクトースが記載されている。また、この文献でも前記成分を含む溶液を剥離性基材に流延し、乾燥させて溶媒を除去している。しかし、この文献の方法でも水に対する親和性の高いフィルム形成剤及びゲル形成剤を用いるため、フィルムの水分含有量を低減できない。 JP 2009-501752 A (Patent Document 3) describes a film-form preparation containing a film-forming agent, a gel-forming agent, and a neuroleptic agent. As a film-forming agent, sugar, sugar alcohol and derivatives thereof, In particular, sucrose, sorbitol, mannitol, xylitol, glucose, fructose, lactose and galactose are described. Also in this document, a solution containing the above components is cast on a peelable substrate and dried to remove the solvent. However, since the film forming agent and the gel forming agent having high affinity for water are also used in the method of this document, the water content of the film cannot be reduced.
　このような水分含有量の多いフィルムは、安定性の面で悪影響が懸念される。特に、環境湿度及び温度によっては、フィルムと被包装体とが密着したり、フィルム同士が密着して固化する場合があり、保存性が低下する。さらには、水分含有量が多いため、可食性フィルムの腰（強度）が低下しやすく、口腔内で互いに付着して塊状に固化し易く、溶解性が損なわれる場合がある。また、薬効成分の保存安定性への影響も危惧される。 Such a film with a high water content is likely to be adversely affected in terms of stability. In particular, depending on the environmental humidity and temperature, the film and the packaged body may be in close contact with each other, or the films may be in close contact with each other to be solidified, resulting in a decrease in storage stability. Furthermore, since there is much water content, the waist | lumps (strength) of an edible film are easy to fall, it adheres to each other in an oral cavity, and it is easy to solidify in a lump shape, and solubility may be impaired. In addition, the effect of the medicinal ingredients on the storage stability is also a concern.
　さらに、前記文献の方法では、水を含む水性溶液を流延して乾燥する必要があるとともに、低水分含量のフィルムを調製するために、水溶性多糖類から水を脱離させるのに多くのエネルギーを必要とする。そのため、可食性フィルムの生産効率を高めることができない。 Furthermore, in the method of the above literature, it is necessary to cast and dry an aqueous solution containing water, and in order to prepare a film having a low moisture content, it is necessary to remove a lot of water from the water-soluble polysaccharide. Requires energy. Therefore, the production efficiency of edible films cannot be increased.
特開平４－５１８５２号公報（特許請求の範囲、実施例）JP-A-4-51852 (Claims, Examples) 特開２０００－３４２１９３号公報（特許請求の範囲、実施例）JP 2000-342193 A (Claims, Examples) 特表２００９－５０１７５２号公報（特許請求の範囲、実施例）JP-T 2009-501752 (Claims, Examples)
　従って、本発明の目的は、水溶性多糖類を含んでいても、保存性（又は保存安定性）に優れた可食性フィルム及びその製造方法を提供することにある。 Therefore, an object of the present invention is to provide an edible film having excellent storage stability (or storage stability) and a method for producing the same even if it contains a water-soluble polysaccharide.
　本発明の他の目的は、口腔内での感触に優れ、迅速に溶解可能な可食性フィルム及びその製造方法を提供することにある。 Another object of the present invention is to provide an edible film which is excellent in touch in the oral cavity and can be rapidly dissolved, and a method for producing the edible film.
　本発明のさらに他の目的は、高い生産効率で工業的に有利に可食性フィルムを製造する方法を提供することにある。 Still another object of the present invention is to provide a method for producing an edible film industrially advantageously with high production efficiency.
　本発明者らは、前記課題を達成するため鋭意検討した結果、オリゴ糖などの所定の水溶性成分を含む組成物が熱溶融して製膜可能であり、このような組成物を押し出し成形などにより溶融製膜すると、水分含有量の少ない可食性フィルムを製造できることを見いだし、本発明を完成した。 As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have been able to heat-melt a composition containing a predetermined water-soluble component such as an oligosaccharide and form such a composition by extrusion molding, etc. It has been found that an edible film with a low water content can be produced by melt film formation according to the present invention, and the present invention has been completed.
　すなわち、本発明の可食性フィルムは、水溶性フィルム形成成分（Ａ）を含んでおり、前記水溶性フィルム形成成分（Ａ）は、オリゴ糖（Ｂ１）及び環状構造を有する多糖類（Ｂ２）から選択された少なくとも一種の水溶性多糖類（Ｂ）を含んでいる。そして、可食性フィルムは、溶融製膜により形成されている。このような可食性フィルムは水分含有量が少なく、例えば、５重量％以下であってもよい。また、水溶性フィルム形成成分（Ａ）は、水溶性多糖類（Ｂ）と、水溶性多糖類（Ｂ）を可塑化するための水溶性可塑化成分（Ｃ）とを含んでいてもよく、水溶性可塑化成分（Ｃ）は、糖及び糖アルコールから選択された少なくとも一種であってもよい。オリゴ糖（Ｂ１）は、デンプン糖、マルトオリゴ糖、イソマルトオリゴ糖、ガラクトオリゴ糖、カップリングシュガー、フルクトオリゴ糖、キシロオリゴ糖、大豆オリゴ糖、乳果オリゴ糖、キチンオリゴ糖及びキトサンオリゴ糖から選択された少なくとも一種であってもよく、環状構造を有する多糖類（Ｂ２）は、クラスターデキストリン及び／又はシクロアミロースであってもよい。さらに、糖アルコールは、エリスリトール、ペンタエリスリトール、アラビトール、リビトール、キシリトール、ソルビトール、ズルシトール、マンニトール、マルチトール、ラクチトールなどから選択された少なくとも一種であってもよい。なお、水溶性多糖類（Ｂ）と水溶性可塑化成分（Ｃ）との重量割合は、前者（Ｂ）／後者（Ｃ）＝９９／１～３０／７０程度であってもよい。 That is, the edible film of the present invention contains a water-soluble film-forming component (A), and the water-soluble film-forming component (A) is composed of an oligosaccharide (B1) and a polysaccharide (B2) having a cyclic structure. It contains at least one selected water-soluble polysaccharide (B). The edible film is formed by melt film formation. Such an edible film has a low water content, and may be, for example, 5% by weight or less. The water-soluble film forming component (A) may contain a water-soluble polysaccharide (B) and a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B), The water-soluble plasticizing component (C) may be at least one selected from sugar and sugar alcohol. The oligosaccharide (B1) was selected from starch sugar, maltooligosaccharide, isomaltooligosaccharide, galactooligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, dairy oligosaccharide, chitin oligosaccharide and chitosan oligosaccharide At least one kind may be sufficient, and the polysaccharide (B2) which has a cyclic structure may be cluster dextrin and / or cycloamylose. Furthermore, the sugar alcohol may be at least one selected from erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbitol, dulcitol, mannitol, maltitol, lactitol and the like. The weight ratio between the water-soluble polysaccharide (B) and the water-soluble plasticizing component (C) may be about the former (B) / the latter (C) = 99/1 to 30/70.
　本発明は、オリゴ糖（Ｂ１）及び環状構造を有する多糖類（Ｂ２）から選択された少なくとも一種の水溶性多糖類（Ｂ）を含む水溶性フィルム形成成分（Ａ）を溶融して製膜し、可食性フィルムを製造する方法も包含する。この方法において、水溶性多糖類（Ｂ）と水溶性可塑化成分（Ｃ）とを含む水溶性フィルム形成成分（Ａ）を溶融混練して、シート状又はフィルム状に押し出し成形してもよい。 The present invention melts and forms a water-soluble film-forming component (A) containing at least one water-soluble polysaccharide (B) selected from an oligosaccharide (B1) and a polysaccharide (B2) having a cyclic structure. Also included is a method of producing an edible film. In this method, the water-soluble film-forming component (A) containing the water-soluble polysaccharide (B) and the water-soluble plasticizing component (C) may be melt-kneaded and extruded into a sheet or film.
　本発明の可食性フィルムは、所定の水溶性フィルム形成成分（Ａ）を含む組成物を溶融製膜するため、水溶性多糖類を含んでいても、水分含有量を低減でき、保存性（又は保存安定性）に優れる。また、水分含有量が少ないため、口腔内での感触に優れ、塊状などの形態に固化することなく、迅速に溶解可能である。さらには、溶融成形可能であるため、高い生産効率で工業的に有利に可食性フィルムを製造できる。 Since the edible film of the present invention melt-forms a composition containing the predetermined water-soluble film-forming component (A), even if it contains a water-soluble polysaccharide, the water content can be reduced, and the storability (or Excellent storage stability). Moreover, since there is little water content, it is excellent in the touch in an oral cavity, and it can melt | dissolve rapidly, without solidifying into forms, such as a lump. Furthermore, since it can be melt-molded, an edible film can be produced industrially advantageously with high production efficiency.
　可食性フィルムを形成する水溶性フィルム形成成分（Ａ）は、オリゴ糖（Ｂ１）及び環状構造を有する多糖類（Ｂ２）から選択された少なくとも一種の水溶性多糖類（Ｂ）を含んでおり、前記水溶性多糖類（Ｂ）は溶融製膜可能である。 The water-soluble film-forming component (A) that forms the edible film contains at least one water-soluble polysaccharide (B) selected from oligosaccharides (B1) and polysaccharides having a cyclic structure (B2), The water-soluble polysaccharide (B) can be melt-formed.
　（オリゴ糖（Ｂ１））
　オリゴ糖（Ｂ１）は、ホモオリゴ糖とヘテロオリゴ糖とのいずれであってもよく、無水物であってもよい。また、オリゴ糖では、単糖類と糖アルコールとが結合していてもよい。また、オリゴ糖は複数の糖成分で構成されたオリゴ糖組成物であってもよい。本明細書では、このようなオリゴ糖組成物であっても単にオリゴ糖という場合がある。オリゴ糖（又はオリゴ糖組成物）は単独で又は二種以上組み合わせて使用できる。オリゴ糖には、二糖類～十糖類程度のオリゴ糖に限らず、重合度が１０以上（特に、１５以上、中でも２０以上）の多糖類などが含まれる。 (Oligosaccharide (B1))
The oligosaccharide (B1) may be either a homo-oligosaccharide or a hetero-oligosaccharide, or may be an anhydride. In oligosaccharides, monosaccharides and sugar alcohols may be bonded. The oligosaccharide may be an oligosaccharide composition composed of a plurality of sugar components. In this specification, even such an oligosaccharide composition may be simply referred to as an oligosaccharide. Oligosaccharides (or oligosaccharide compositions) can be used alone or in combination of two or more. Oligosaccharides are not limited to oligosaccharides of about disaccharide to decasaccharide, but include polysaccharides having a degree of polymerization of 10 or more (especially 15 or more, especially 20 or more).
　二糖類としては、トレハロース、マルトース、イソマルトース、セロビオースなどのホモオリゴ糖；ラクトース、スクロース、パラチノースなどのヘテロオリゴ糖が挙げられる。 Examples of disaccharides include homo-oligosaccharides such as trehalose, maltose, isomaltose, and cellobiose; and hetero-oligosaccharides such as lactose, sucrose, and palatinose.
　三糖類としては、マルトトリオース、イソマルトトリオース、パノース、セロトリオースなどのホモオリゴ糖；マンニノトリオース、ソラトリオース、メレジトース、プランテオース、ゲンチアノース、ウンベリフェロース、ラクトスクロース、ラフィノースなどのヘテロオリゴ糖が挙げられる。 Trisaccharides include homo-oligosaccharides such as maltotriose, isomaltotriose, panose and cellotriose; hetero-oligosaccharides such as manninotriose, solatriose, melezitose, planteose, gentianose, umbelliferose, lactosucrose and raffinose It is done.
　四糖類としては、マルトテトラオース、イソマルトテトラオースなどのホモオリゴ糖；スタキオース、セロテトラオース、スコロドース、リキノース、パノースの還元末端に糖又は糖アルコールが結合したテトラオースなどのヘテロオリゴ糖が挙げられる。 Examples of tetrasaccharides include homo-oligosaccharides such as maltotetraose and isomalttetraose; and hetero-oligosaccharides such as tetraose in which sugar or sugar alcohol is bonded to the reducing end of stachyose, cellotetraose, scorodose, liquinose, or panose.
　これらの四糖類のうち、パノースの還元末端に単糖類又は糖アルコールが結合したテトラオースは、例えば、特開平１０－２１５８９２号公報に開示されており、パノースの還元末端に、グルコース、フルクトース、マンノース、キシロース、アラビノースなどの単糖類や、ソルビトール、キシリトール、エリスリトールなどの糖アルコールが結合したテトラオースが例示できる。 Among these tetrasaccharides, tetraose in which a monosaccharide or a sugar alcohol is bonded to the reducing end of panose is disclosed, for example, in JP-A-10-215892, and glucose, fructose, mannose, Examples include tetraose to which monosaccharides such as xylose and arabinose and sugar alcohols such as sorbitol, xylitol and erythritol are bonded.
　五糖類としては、マルトペンタオース、イソマルトペンタオースなどのホモオリゴ糖；パノースの還元末端に二糖類が結合したペンタオースなどのヘテロオリゴ糖が挙げられる。パノースの還元末端に二糖類が結合したペンタオースは、例えば、特開平１０－２１５８９２号公報に開示されており、パノースの還元末端に、スクロース、ラクトース、セロビオース、トレハロースなどの二糖類が結合したペンタオースが例示できる。 Examples of pentasaccharides include homo-oligosaccharides such as maltopentaose and isomaltopentaose; and hetero-oligosaccharides such as pentaose in which a disaccharide is bonded to the reducing end of panose. Pentaose in which a disaccharide is bonded to the reducing end of panose is disclosed, for example, in JP-A-10-215892, and pentaose in which a disaccharide such as sucrose, lactose, cellobiose, trehalose is bonded to the reducing end of panose. It can be illustrated.
　六糖類としては、マルトヘキサオース、イソマルトヘキサオースなどのホモオリゴ糖などが挙げられる。 Examples of hexasaccharides include homo-oligosaccharides such as maltohexaose and isomaltohexaose.
　オリゴ糖（Ｂ１）は、多糖類の分解により生成するオリゴ糖組成物であってもよい。オリゴ糖組成物としては、例えば、デンプン糖（デンプン糖化物）、ガラクトオリゴ糖、カップリングシュガー、フルクトオリゴ糖、キシロオリゴ糖、大豆オリゴ糖、キチンオリゴ糖、キトサンオリゴ糖などが挙げられ、これらの成分は単独で又は二種以上組み合わせて使用できる。例えば、デンプン糖は、複数個のグルコースが結合したオリゴ糖の混合物であってもよい。また、このようなオリゴ糖組成物（オリゴ糖混合物）は、前記と同様に、糖アルコールと結合していてもよい。すなわち、オリゴ糖組成物（又はオリゴ糖組成物を構成するオリゴ糖）は、オリゴ糖単位と、このオリゴ糖単位に結合した糖アルコール単位とを有していてもよい。このような糖アルコール単位は、通常、オリゴ糖単位の末端に位置する場合が多い。すなわち、オリゴ糖組成物を構成するオリゴ糖は、末端が還元された糖アルコール単位を有していてもよい。なお、このような糖アルコール単位を有するオリゴ糖組成物は、例えば、オリゴ糖組成物（デンプン糖など）を還元することにより得られる。 Oligosaccharide (B1) may be an oligosaccharide composition produced by degradation of a polysaccharide. Examples of the oligosaccharide composition include starch sugar (starch saccharified product), galacto-oligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, chitin oligosaccharide, chitosan oligosaccharide and the like. It can be used alone or in combination of two or more. For example, the starch sugar may be a mixture of oligosaccharides having a plurality of glucose bound thereto. Further, such an oligosaccharide composition (oligosaccharide mixture) may be bonded to a sugar alcohol in the same manner as described above. That is, the oligosaccharide composition (or the oligosaccharide constituting the oligosaccharide composition) may have an oligosaccharide unit and a sugar alcohol unit bonded to the oligosaccharide unit. Such sugar alcohol units are usually often located at the end of oligosaccharide units. That is, the oligosaccharide constituting the oligosaccharide composition may have a sugar alcohol unit whose terminal is reduced. In addition, the oligosaccharide composition having such a sugar alcohol unit can be obtained, for example, by reducing an oligosaccharide composition (such as starch sugar).
　デンプン糖としては、例えば、三菱商事フードテック（株）製の還元デンプン糖化物（商品名：ＰＯ－１０）などが挙げられる。 Examples of starch sugar include reduced starch saccharified product (trade name: PO-10) manufactured by Mitsubishi Corporation Foodtech.
　オリゴ糖は、非還元型（トレハロース型）であってもよいが、還元型（マルトース型）のオリゴ糖は、耐熱性に優れるため好ましい。還元型のオリゴ糖は、遊離のアルデヒド基又はケトン基を有し、還元性を示す糖であれば、特に限定されない。 The oligosaccharide may be a non-reducing type (trehalose type), but a reducing type (maltose type) oligosaccharide is preferred because of its excellent heat resistance. The reduced oligosaccharide is not particularly limited as long as it has a free aldehyde group or a ketone group and exhibits reducing properties.
　オリゴ糖組成物は、比較的大きい多量体のオリゴ糖を多く含んでいてもよく、例えば、オリゴ糖組成物において、二十糖類以上のオリゴ糖の含有割合は、３０重量％以上（例えば、４０～１００重量％）、好ましくは５０重量％以上（例えば、５０～９５重量％）、さらに好ましくは６５～９０重量％程度であってもよく、特に５０～８５重量％程度であってもよい。 The oligosaccharide composition may contain a large amount of relatively large multimeric oligosaccharides. For example, in the oligosaccharide composition, the content ratio of oligosaccharides of 20 or more saccharides is 30% by weight or more (for example, 40% To 100% by weight), preferably 50% by weight or more (eg, 50 to 95% by weight), more preferably about 65 to 90% by weight, and particularly about 50 to 85% by weight.
　オリゴ糖（Ｂ１）の粘度は高いのが望ましい。具体的には、Ｂ型粘度計を用いて温度２５℃で測定したとき、オリゴ糖（Ｂ１）の５０重量％水溶液の粘度は、０．１Ｐａ・ｓ以上（例えば、０．２～２Ｐａ・ｓ程度）、好ましくは０．３Ｐａ・ｓ以上（例えば、０．４～１．５Ｐａ・ｓ、特に０．４５～１Ｐａ・ｓ程度）、さらに好ましくは０．５Ｐａ・ｓ以上（例えば、０．５～０．９Ｐａ・ｓ程度）であってもよい。 It is desirable that the oligosaccharide (B1) has a high viscosity. Specifically, when measured at a temperature of 25 ° C. using a B-type viscometer, the viscosity of a 50% by weight aqueous solution of oligosaccharide (B1) is 0.1 Pa · s or more (eg, 0.2 to 2 Pa · s). Degree), preferably 0.3 Pa · s or more (eg, about 0.4 to 1.5 Pa · s, particularly about 0.45 to 1 Pa · s), more preferably 0.5 Pa · s or more (eg, 0.5 About 0.9 Pa · s).
　なお、オリゴ糖（Ｂ１）の種類（例えば、還元デンプン糖化物などのデンプン糖など）によっては、融点又は軟化点を示さず、分解（熱分解）する場合がある。このような場合、分解温度をオリゴ糖（Ｂ１）の「融点又は軟化点」としてもよい。 In addition, depending on the type of oligosaccharide (B1) (for example, starch sugar such as reduced starch saccharified product), it may be decomposed (thermally decomposed) without showing a melting point or a softening point. In such a case, the decomposition temperature may be the “melting point or softening point” of the oligosaccharide (B1).
　オリゴ糖（Ｂ１）の融点又は軟化点は、７０～３００℃の範囲で選択でき、例えば、９０～２９０℃、好ましくは１００～２８０℃（例えば、１１０～２７０℃）、さらに好ましくは１２０～２６０℃（例えば、１３０～２６０℃）程度であってもよい。 The melting point or softening point of the oligosaccharide (B1) can be selected in the range of 70 to 300 ° C., for example, 90 to 290 ° C., preferably 100 to 280 ° C. (eg 110 to 270 ° C.), more preferably 120 to 260. It may be about 0 ° C. (for example, 130 to 260 ° C.).
　（環状構造を有する多糖類（Ｂ２））
　環状構造を有する多糖類（Ｂ２）は、少なくとも１つの環状構造を有しており、オリゴ糖（Ｂ１）などに比べて比較的高分子量であり溶融粘度が高く、しかも、その環状構造によるためか、水溶性を示す。このような多糖類を使用することにより、オリゴ糖（Ｂ１）などに比べて溶融混練において高い剪断粘度を保持でき、溶融製膜可能である。 (Polysaccharide having a cyclic structure (B2))
The polysaccharide (B2) having a cyclic structure has at least one cyclic structure, has a relatively high molecular weight and higher melt viscosity than the oligosaccharide (B1), etc., and is also due to the cyclic structure? Shows water solubility. By using such a polysaccharide, it is possible to maintain a higher shear viscosity in melt kneading as compared with oligosaccharide (B1) and the like, and melt film formation is possible.
　環状構造を有する多糖類（Ｂ２）において、環状構造（環状骨格、環状ユニット、環状部位）は、多糖類を構成する複数のグルコース単位（特にＤ－グルコース）がグルコシド結合（又はグルコシル化）して形成された環であればよい。すなわち、本明細書において、環状構造とは、グルコース環などの単糖類の環ではなく、複数のグルコース単位（およびグルコシド結合）で形成された環を意味する。 In the polysaccharide (B2) having a cyclic structure, a plurality of glucose units (particularly D-glucose) constituting the polysaccharide has a glucoside bond (or glucosylation) in the cyclic structure (cyclic skeleton, cyclic unit, cyclic portion). Any ring formed may be used. That is, in this specification, a cyclic structure means a ring formed of a plurality of glucose units (and glucoside bonds), not a monosaccharide ring such as a glucose ring.
　環状構造は、複数のグルコシド結合（α－グルコシド結合及び／又はβ－グルコシド結合）で構成されていればよく、通常、α－グルコシド結合で構成されていてもよい。例えば、前記環状構造は、１，４－グルコシド結合（例えば、α－１，４－グルコシド結合）又は１，６－グルコシド結合（例えば、α－１，６－グルコシド結合）を含む環状構造であってもよく、例えば、１，４－グルコシド結合（特に、α－１，４－グルコシド結合）と１，６－グルコシド結合（特に、α－１，６－グルコシド結合）とを有する環状構造であってもよい。代表的には、環状構造を有する多糖類（Ｂ２）は、α－１，４－グルコシド結合およびα－１，６－グルコシド結合を有し、１つの環状構造あたりグルコース単位が所定の平均重合度で重合した環状構造と、この環状構造に結合した非環状構造とを有し、かつ平均重合度（総平均重合度）５０以上である多糖類で構成されていてもよい。環状構造（１つの環状構造あたり）の平均重合度（数平均重合度、環状構造を形成する平均グルコシド結合数、環状構造を形成するグルコース単位の平均重合度）は、例えば、１０以上（例えば、１０～５００程度）、好ましくは１２以上（例えば、１２～３００程度）、さらに好ましくは１４以上（例えば、１４～１００程度）であってもよい。 The cyclic structure only needs to be composed of a plurality of glucoside bonds (α-glucoside bonds and / or β-glucoside bonds), and may generally be composed of α-glucoside bonds. For example, the cyclic structure is a cyclic structure containing a 1,4-glucoside bond (eg, α-1,4-glucoside bond) or a 1,6-glucoside bond (eg, α-1,6-glucoside bond). For example, it may be a cyclic structure having a 1,4-glucoside bond (especially an α-1,4-glucoside bond) and a 1,6-glucoside bond (particularly an α-1,6-glucoside bond). May be. Typically, the polysaccharide (B2) having a cyclic structure has an α-1,4-glucoside bond and an α-1,6-glucoside bond, and a glucose unit has a predetermined average polymerization degree per one cyclic structure. It may be composed of a polysaccharide having a cyclic structure polymerized in (i) and an acyclic structure bonded to the cyclic structure and having an average degree of polymerization (total average degree of polymerization) of 50 or more. The average degree of polymerization of the cyclic structure (per one cyclic structure) (number average degree of polymerization, average number of glucoside bonds forming the cyclic structure, average degree of polymerization of glucose units forming the cyclic structure) is, for example, 10 or more (for example, It may be about 10 to 500), preferably 12 or more (for example, about 12 to 300), and more preferably 14 or more (for example, about 14 to 100).
　さらに、１，６－グルコシド結合を含む環において、環状構造（１つの環状構造あたり）における１，６－グルコシド結合の平均数は、１以上（例えば、１～７００程度）であればよく、例えば、１～３００（例えば、１～２００）、好ましくは１～１００（例えば、１～５０）、さらに好ましくは１～２０（例えば、１～１０）であってもよい。 Further, in the ring containing 1,6-glucoside bond, the average number of 1,6-glucoside bonds in the cyclic structure (per one cyclic structure) may be 1 or more (for example, about 1 to 700). It may be 1 to 300 (eg 1 to 200), preferably 1 to 100 (eg 1 to 50), more preferably 1 to 20 (eg 1 to 10).
　また、環状構造を有する水溶性多糖類は、少なくとも１つの環状構造（環状ユニット）を有していればよく、複数の環状構造を有していてもよい。 Moreover, the water-soluble polysaccharide having a cyclic structure may have at least one cyclic structure (cyclic unit), and may have a plurality of cyclic structures.
　なお、環状構造を有する多糖類（Ｂ２）の平均重合度（数平均重合度、総平均重合度、多糖類全体の平均重合度）は、例えば、１４以上（例えば、１４～１５０００）、好ましくは１７以上（例えば、１７～１００００）、さらに好ましくは２０以上（例えば、２０～８０００程度）であってもよい。 The average degree of polymerization (number average degree of polymerization, total average degree of polymerization, average degree of polymerization of the whole polysaccharide) of the polysaccharide (B2) having a cyclic structure is, for example, 14 or more (for example, 14 to 15000), preferably It may be 17 or more (for example, 17 to 10000), more preferably 20 or more (for example, about 20 to 8000).
　なお、環状構造を有する多糖類（Ｂ２）は、修飾又は誘導体化（又は変性）されていてもよい。例えば、環状構造を有する多糖類は、ヒドロキシル基（アルコール性ヒドロキシル基）が修飾又は誘導体化［例えば、エーテル化（例えば、メチルエーテル化などのアルキルエーテル化；ヒドロキシエチルエーテル化、ヒドロキシプロピルエーテル化などのヒドロキシアルキルエーテル化；グリセリル化など）、エステル化、グラフト化、架橋化など］されていてもよい。 The polysaccharide (B2) having a cyclic structure may be modified or derivatized (or modified). For example, a polysaccharide having a cyclic structure has a hydroxyl group (alcoholic hydroxyl group) modified or derivatized [eg, etherification (eg, alkyl etherification such as methyl etherification; hydroxyethyl etherification, hydroxypropyl etherification, etc. Hydroxyalkyl etherification; glycerylation, etc.), esterification, grafting, cross-linking, etc.].
　環状構造を有する水溶性多糖類は、単独で又は２種以上組み合わせてもよい。代表的な環状構造を有する水溶性多糖類には、環状構造（又は環状ユニット）とこの環状構造に結合した非環状構造（非環状骨格、非環状ユニット非環状部位）とを有し、かつ平均重合度５０以上の多糖類（多糖類（１）という場合がある）、１４以上のα－１，４－グルコシド結合で形成された環状構造を分子内に一つ有する多糖類（多糖類（２）という場合がある）などが挙げられる。 The water-soluble polysaccharide having a cyclic structure may be used alone or in combination of two or more. The water-soluble polysaccharide having a typical cyclic structure has a cyclic structure (or cyclic unit) and an acyclic structure (acyclic skeleton, acyclic unit acyclic part) bonded to the cyclic structure, and an average Polysaccharides having a degree of polymerization of 50 or more (sometimes referred to as polysaccharides (1)), polysaccharides having one cyclic structure formed by α-1,4-glucoside bonds of 14 or more (polysaccharides (2 ))).
　（多糖類（１））
　前記多糖類（１）において、環状構造は、通常、α－１，４－グルコシド結合とα－１，６－グルコシド結合とで形成された環であってもよい。また、１つの環状構造の平均重合度（数平均重合度）は、例えば、１０～５００、好ましくは１２～３００、さらに好ましくは１４～１００であってもよい。環状構造（１つの環状構造あたり）におけるα－１，６－グルコシド結合の平均数は、例えば、１以上（例えば、１～２００）、好ましくは１～１００、さらに好ましくは１～５０程度であってもよい。 (Polysaccharide (1))
In the polysaccharide (1), the cyclic structure may be a ring formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond. The average degree of polymerization (number average degree of polymerization) of one cyclic structure may be, for example, 10 to 500, preferably 12 to 300, and more preferably 14 to 100. The average number of α-1,6-glucoside bonds in the cyclic structure (per one cyclic structure) is, for example, 1 or more (for example, 1 to 200), preferably 1 to 100, and more preferably about 1 to 50. May be.
　なお、多糖類（１）の平均重合度（数平均重合度、総数平均重合度）は、５０以上、例えば、５０～１００００、好ましくは６０～７０００、さらに好ましくは７０～５０００程度であってもよい。 The average degree of polymerization (number average degree of polymerization, total number average degree of polymerization) of the polysaccharide (1) may be 50 or more, for example, 50 to 10,000, preferably 60 to 7000, more preferably about 70 to 5000. Good.
　多糖類（１）は、１又は複数の非環状構造、通常、複数（例えば、２～１０００、好ましくは３～５００程度）の非環状構造を有していてもよい。このような非環状部位（又は多糖類（１）の環状構造以外の部位）１つあたりの平均重合度（数平均重合度）は、例えば、１０以上（例えば、１０～３０）、好ましくは１０～２０程度であってもよい。また、非環状部位全体の平均重合度（数平均重合度）は、１０以上であればよく、例えば、４０以上（例えば、５０～５０００程度）、好ましくは１００～３０００程度であってもよい。なお、非環状部位は、特に、α－１，６－グルコシド結合のグルコース単位から分岐している場合が多い。 The polysaccharide (1) may have one or a plurality of acyclic structures, usually a plurality of (for example, about 2 to 1000, preferably about 3 to 500) acyclic structures. The average degree of polymerization (number average degree of polymerization) per such acyclic part (or part other than the cyclic structure of the polysaccharide (1)) is, for example, 10 or more (for example, 10 to 30), preferably 10 It may be about ~ 20. Further, the average degree of polymerization (number average degree of polymerization) of the entire non-cyclic moiety may be 10 or more, for example, 40 or more (for example, about 50 to 5000), preferably about 100 to 3000. In particular, the acyclic moiety is often branched from a glucose unit of an α-1,6-glucoside bond.
　なお、多糖類（１）において、ヒドロキシル基（アルコール性ヒドロキシル基）は、修飾又は誘導体化（例えば、エーテル化、エステル化、グラフト化など）されていてもよい。 In the polysaccharide (1), the hydroxyl group (alcoholic hydroxyl group) may be modified or derivatized (for example, etherification, esterification, grafting, etc.).
　このような多糖類（１）には、いわゆる「クラスターデキストリン」として知られている多糖類が含まれる。このような多糖類（１）は、例えば、糖類（例えば、澱粉、澱粉の部分分解物、アミロペクチン、グリコーゲン、ワキシー澱粉、ハイアミロース澱粉、可溶性澱粉、デキストリン、澱粉加水分解物、およびホスホリラーゼによる酵素合成アミロペクチンから選択された少なくとも１種の基質など）に、糖類に作用して環状構造を形成可能な酵素（枝作り酵素、Ｄ酵素、サイクロデキストリングルカノトランスフェラーゼなど）を反応させることにより得てもよい。このようなクラスターデキストリンおよびその製造方法についての詳細は、特開平８－１３４１０４号公報などを参照できる。 Such a polysaccharide (1) includes a polysaccharide known as a “cluster dextrin”. Such polysaccharides (1) are synthesized by, for example, saccharides (for example, starch, partially decomposed starch, amylopectin, glycogen, waxy starch, high amylose starch, soluble starch, dextrin, starch hydrolyzate, and phosphorylase). It may be obtained by reacting an enzyme (branching enzyme, D enzyme, cyclodextrin glucanotransferase, etc.) capable of forming a cyclic structure by acting on a saccharide with at least one substrate selected from amylopectin. . JP-A-8-134104 and the like can be referred to for details of such cluster dextrin and the production method thereof.
　（多糖類（２））
　前記多糖類（２）において、環状構造は、少なくともα－１，４－グルコシド結合で形成された環であればよく、α－１，４－グルコシド結合とα－１，６－グルコシド結合とで形成された環であってもよい。また、環状構造の平均重合度（数平均重合度）は、１４以上であればよく、例えば、１４～５０００、好ましくは１５以上（例えば、１５～３０００程度）、さらに好ましくは１７以上（例えば、１７～１０００程度）であってもよい。環状構造がα－１，６－グルコシド結合を有する場合、環状構造におけるα－１，６－グルコシド結合の平均数は、例えば、１～５００、好ましくは１～３００、さらに好ましくは１～１００程度であってもよい。 (Polysaccharide (2))
In the polysaccharide (2), the cyclic structure may be a ring formed of at least an α-1,4-glucoside bond, and includes an α-1,4-glucoside bond and an α-1,6-glucoside bond. It may be a ring formed. Further, the average degree of polymerization (number average degree of polymerization) of the cyclic structure may be 14 or more, for example, 14 to 5000, preferably 15 or more (for example, about 15 to 3000), more preferably 17 or more (for example, 17 to 1000). When the cyclic structure has an α-1,6-glucoside bond, the average number of α-1,6-glucoside bonds in the cyclic structure is, for example, about 1 to 500, preferably about 1 to 300, and more preferably about 1 to 100 It may be.
　多糖類（２）は、前記環状構造を有している限り、非環状構造（例えば、直鎖状構造）を有していてもよいが、通常、前記環状構造のみで構成（又は形成）された環状多糖類であってもよい。 The polysaccharide (2) may have an acyclic structure (for example, a straight chain structure) as long as it has the cyclic structure, but is usually composed (or formed) of only the cyclic structure. It may be a cyclic polysaccharide.
　なお、多糖類（２）において、ヒドロキシル基（アルコール性ヒドロキシル基）は、修飾又は誘導体化（例えば、エーテル化、エステル化、グラフト化、架橋化など）されていてもよい。 In the polysaccharide (2), the hydroxyl group (alcoholic hydroxyl group) may be modified or derivatized (for example, etherified, esterified, grafted, crosslinked).
　このような多糖類（２）には、いわゆる「シクロアミロース（又はサイクロアミロース）」として知られている多糖類が含まれる。このような多糖類（２）は、例えば、直鎖状のα－１，４－グルカン又はこのグルカンを含む糖類（例えば、マルトオリゴ糖、アミロース、アミロペクチン、グリコーゲン、澱粉、ワキシー澱粉、ハイアミロース澱粉、可溶性澱粉、デキストリン、澱粉枝切り物、澱粉部分加水分解物、ホルホリラーゼによる酵素合成アミロース、およびこれらの誘導体から選択された少なくとも１種など）と、多糖類（２）を形成可能な酵素（例えば、Ｄ酵素など）とを、必要に応じて、ホスホリラーゼおよびグルコース１－リン酸の存在下で反応させることにより得ることができる。また、前記反応は、基質としてα－１，６－グルコシド結合を有する基質を用いる場合には、α－１，６－グルコシド結合を切断可能な酵素（例えば、イソアミラーゼ、プルラナーゼなど）の存在下で行ってもよい。このようなサイクロアミロースおよびその製造方法についての詳細は、特開平８－３１１１０３号公報などを参照できる。 Such polysaccharide (2) includes a polysaccharide known as “cycloamylose (or cycloamylose)”. Such a polysaccharide (2) is, for example, a linear α-1,4-glucan or a saccharide containing this glucan (for example, maltooligosaccharide, amylose, amylopectin, glycogen, starch, waxy starch, high amylose starch, Soluble starch, dextrin, starch debranch, partially hydrolyzed starch, enzyme synthesized amylose by morpholase, and at least one selected from these derivatives) and an enzyme capable of forming polysaccharide (2) (for example, D enzyme and the like) can be obtained by reacting in the presence of phosphorylase and glucose 1-phosphate, if necessary. In the above reaction, when a substrate having an α-1,6-glucoside bond is used as a substrate, an enzyme capable of cleaving the α-1,6-glucoside bond (eg, isoamylase, pullulanase, etc.) is present. You may go on. JP-A-8-311103 and the like can be referred to for details on such cycloamylose and its production method.
　環状構造を有する多糖類は、単独で又は２種以上組み合わせてもよい。本発明では、環状構造を有する多糖類のうち、特に、前記多糖類（１）（又はクラスターデキストリン）を好適に用いることができる。 Polysaccharides having a cyclic structure may be used alone or in combination of two or more. In the present invention, among the polysaccharides having a cyclic structure, in particular, the polysaccharide (1) (or cluster dextrin) can be suitably used.
　水溶性多糖類（Ｂ）は、オリゴ糖（Ｂ１）及び／又は環状構造を有する多糖類で構成でき、これらの成分の使い分けや、両者の成分の割合を調整することにより、溶融粘度を調整できる。 The water-soluble polysaccharide (B) can be composed of an oligosaccharide (B1) and / or a polysaccharide having a cyclic structure, and the melt viscosity can be adjusted by properly using these components and adjusting the ratio of both components. .
　オリゴ糖（Ｂ１）と環状構造を有する多糖類（Ｂ２）とを組み合わせる場合、両者の割合は、前者／後者（重量比）＝１／９９～９９／１、好ましくは５／９５～９５／５、さらに好ましくは１０／９０～９０／１０（例えば、１５／８５～８５／１５）程度であってもよい。 When the oligosaccharide (B1) and the polysaccharide having a cyclic structure (B2) are combined, the ratio of the former is the former / the latter (weight ratio) = 1/99 to 99/1, preferably 5/95 to 95/5. More preferably, it may be about 10/90 to 90/10 (for example, 15/85 to 85/15).
　（水溶性可塑化成分（Ｃ））
　水溶性フィルム形成成分（Ａ）は、さらに、前記水溶性多糖類（Ｂ）を可塑化するための水溶性可塑化成分（Ｃ）を含んでいてもよい。水溶性可塑化成分（Ｃ）の併用により、熱分解する水溶性多糖類（Ｂ）であっても有効に可塑化又は軟化でき、溶融成形可能である。 (Water-soluble plasticizing component (C))
The water-soluble film forming component (A) may further contain a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B). By the combined use of the water-soluble plasticizing component (C), even the water-soluble polysaccharide (B) that is thermally decomposed can be effectively plasticized or softened and can be melt-molded.
　水溶性可塑化成分（Ｃ）は、前記水溶性多糖類（Ｂ）を可塑化する化合物であれば特に制限されず、糖類（例えば、単糖類、二糖類など）や糖アルコールなどで構成してもよく、このような糖類は、還元糖で構成してもよい。単糖類は、トリオース、テトロース、ペントース、ヘキソース、ヘプトース、オクトース、ノノース、デコース、ドデコースなどで構成してもよく、グルコース、ガラクトース、フルクトース、マンノース、キシロースなどが例示できる。二糖類は、前記単糖類のホモ及びヘテロ二糖類で構成してもよく、スクロース、ラクトース、マルトース、トレハロース、セロビオースなどが例示できる。糖アルコールは、テトリトール（例えば、エリスリトールなど）、ペンチトール（例えば、ペンタエリスリトール、アラビトール、リビトール、キシリトールなど）、ヘキシトール（例えば、ソルビトール、ズルシトール、マンニトール、ガラクチトールなど）、ヘプチトール、オクチトール、ノニトール、デキトール、ドデキトールなどで構成してもよい。糖アルコールは、還元糖を還元した糖アルコール、例えば、マルトースの接触還元によるマルチトール、還元乳糖（ラクチトール）などであってもよい。 The water-soluble plasticizing component (C) is not particularly limited as long as it is a compound that plasticizes the water-soluble polysaccharide (B), and is composed of saccharides (for example, monosaccharides, disaccharides, etc.) or sugar alcohols. Alternatively, such saccharides may be composed of reducing sugars. The monosaccharide may be composed of triose, tetrose, pentose, hexose, heptose, octose, nonose, decose, dodecose, etc., and examples thereof include glucose, galactose, fructose, mannose, and xylose. The disaccharide may be composed of homo- and hetero-disaccharides of the monosaccharides, and examples thereof include sucrose, lactose, maltose, trehalose, cellobiose and the like. Sugar alcohols include tetritol (eg, erythritol), pentitol (eg, pentaerythritol, arabitol, ribitol, xylitol, etc.), hexitol (eg, sorbitol, dulcitol, mannitol, galactitol, etc.), heptitol, octitol, nonitol, dexitol. , Dodecitol may be used. The sugar alcohol may be a sugar alcohol obtained by reducing a reducing sugar, for example, maltitol by catalytic reduction of maltose, reduced lactose (lactitol), or the like.
　これらの水溶性可塑化成分のうち、トレハロース、マルトース、ラクトースなどの糖類や糖アルコールが汎用され、糖アルコールが好ましい。糖アルコールのうち、エリスリトール、ペンタエリスリトール、アラビトール、リビトール、キシリトール、ズルシトール、マンニトール、ソルビトール、ラクチトール、マルチトール（特に、キシリトールなどのペンチトール及び／又はソルビトールなどのヘキしトール）が好ましい。 Of these water-soluble plasticizing components, sugars such as trehalose, maltose, and lactose and sugar alcohols are widely used, and sugar alcohols are preferred. Among sugar alcohols, erythritol, pentaerythritol, arabitol, ribitol, xylitol, dulcitol, mannitol, sorbitol, lactitol, maltitol (particularly pentitol such as xylitol and / or hexitol such as sorbitol) are preferable.
　水溶性多糖類（Ｂ）と水溶性可塑化成分（Ｃ）との割合は、前者／後者（重量比）＝９９／１～３０／７０（例えば、９５／５～３０／７０）、好ましくは９０／１０～４０／６０（例えば、８０／２０～５０／５０）程度であってもよく、通常、９９／１～５０／５０（例えば、９０／１０～５０／５０）程度であってもよい。なお、オリゴ糖と糖アルコールの詳細については、特開２００４－５１９４２号公報、特開２００５－１６２８４１号公報に記載されている。 The ratio of the water-soluble polysaccharide (B) to the water-soluble plasticizing component (C) is the former / the latter (weight ratio) = 99/1 to 30/70 (for example, 95/5 to 30/70), preferably It may be about 90/10 to 40/60 (for example, 80/20 to 50/50), and usually about 99/1 to 50/50 (for example, 90/10 to 50/50). Good. The details of the oligosaccharide and sugar alcohol are described in JP-A No. 2004-51942 and JP-A No. 2005-162841.
　前記環状構造を有する多糖類（Ｂ２）と水溶性可塑化成分（Ｃ）との割合は、前者／後者（重量比）＝９９／１～３０／７０、好ましくは９５／５～３０／７０、さらに好ましくは９０／１０～４０／６０程度であってもよい。 The ratio of the polysaccharide (B2) having the cyclic structure to the water-soluble plasticizing component (C) is the former / the latter (weight ratio) = 99/1 to 30/70, preferably 95/5 to 30/70, More preferably, it may be about 90/10 to 40/60.
　なお、可食性フィルムは、必要により、アルギン酸又はその塩、プルラン、カラギーナンなどの多糖類を含んでいてもよく、種々の添加剤、例えば、着色剤、甘味剤、香味剤、安定剤（酸化防止剤、紫外線吸収剤、熱安定剤など）、防腐剤、防菌剤などを含有していてもよい。 The edible film may contain polysaccharides such as alginic acid or a salt thereof, pullulan and carrageenan as necessary, and various additives such as colorants, sweeteners, flavoring agents, stabilizers (antioxidants). Agents, ultraviolet absorbers, heat stabilizers, etc.), preservatives, antibacterial agents and the like.
　なお、デンプン及びセルロース並びにそれらの誘導体は、通常、溶融温度と分解温度とが近接しているため、溶融成形することが困難である。そのため、水溶性フィルム形成成分（Ａ）は、水溶性及び／又は水不溶性セルロース誘導体、デンプン又はその誘導体（例えば、ヒドロキシプロピル化澱粉、デンプン、糊化デンプンなど）を含まない場合が多い。また、可食性とするため、水溶性フィルム形成成分（Ａ）は、非可食性有機高分子、混練により分散形態（例えば、粒子状、海島状、繊維状、層状などの分散形態）を形成する有機固体成分（水溶性フィルム形成成分（Ａ）に対して非相溶な分散樹脂粒子など）を含まない場合が多い。このような非可食性有機高分子及び有機固体成分を含むと、可食性フィルムの口腔内でザラツキ感などの不快な感触を与える場合がある。 Note that starch, cellulose, and derivatives thereof are usually difficult to melt mold because the melting temperature and the decomposition temperature are close to each other. Therefore, the water-soluble film forming component (A) often does not contain a water-soluble and / or water-insoluble cellulose derivative, starch or a derivative thereof (for example, hydroxypropylated starch, starch, gelatinized starch, etc.). Moreover, in order to make it edible, the water-soluble film forming component (A) forms a dispersion form (for example, a dispersion form such as a particulate form, a sea-island form, a fiber form, a layer form) by kneading with a non-edible organic polymer. In many cases, organic solid components (such as dispersed resin particles incompatible with the water-soluble film-forming component (A)) are not included. When such a non-edible organic polymer and an organic solid component are included, an unpleasant feeling such as a rough feeling may be given in the mouth of the edible film.
　本発明の可食性フィルムは、溶融製膜により形成されているという特色がある。そのため、水溶性フィルム形成成分（Ａ）を含んでいても可食性フィルムの水分含有量を大きく低減でき、保存性（又は保存安定性）だけでなく、口腔内での感触に優れ、かつ迅速に溶解可能である。 The edible film of the present invention is characterized by being formed by melt film formation. Therefore, even if it contains a water-soluble film-forming component (A), the moisture content of the edible film can be greatly reduced, and it is excellent not only in storage stability (or storage stability) but also in the oral cavity and quickly. It can be dissolved.
　可食性フィルムの水分含有量は、例えば、可食性フィルム全体に対して５重量％以下（例えば、０～４重量％）、好ましくは０．１～３重量％（例えば、０．２～２．５重量％）、さらに好ましくは０．２～２重量％（例えば、０．２～１重量％）程度であってもよい。 The moisture content of the edible film is, for example, 5% by weight or less (for example, 0 to 4% by weight), preferably 0.1 to 3% by weight (for example, 0.2 to 2. 5 wt%), more preferably about 0.2 to 2 wt% (for example, 0.2 to 1 wt%).
　可食性フィルムの厚み（平均厚み）は特に制限されず、例えば、１～５０００μｍ（例えば、１０～４０００μｍ）、好ましくは３０～３０００μｍ（例えば、５０～１０００μｍ）程度であってもよい。 The thickness (average thickness) of the edible film is not particularly limited, and may be, for example, about 1 to 5000 μm (for example, 10 to 4000 μm), preferably about 30 to 3000 μm (for example, 50 to 1000 μm).
　［可食性フィルムの製造方法］
　本発明の可食性フィルムは、前記水溶性フィルム形成成分（Ａ）を溶融して製膜することにより調製できる。溶融製膜の方法は、例えば、剥離性基材やドラム上に、水溶性フィルム形成成分（Ａ）の溶融物をフィルム状又はシート状の形態で押し出して積層し、冷却した後、剥離性基材やドラムからフィルム又はシートを剥離して可食性フィルムを製造してもよい。 [Method for producing edible film]
The edible film of the present invention can be prepared by melting the water-soluble film-forming component (A) to form a film. The melt film-forming method is, for example, by extruding a melt of the water-soluble film-forming component (A) in a film or sheet form on a peelable substrate or drum, laminating and cooling, and then peeling the peelable substrate. The edible film may be produced by peeling the film or sheet from the material or drum.
　工業的に好ましい方法では、水溶性フィルム形成成分（Ａ）を押出機で溶融混練し、ダイからシート状又はフィルム状に押し出し成形する押出形成法又はインフレーション法により可食性フィルムを製造してもよい。押出成形法ではＴダイを用いる場合が多く、インフレーション法では円筒ダイが使用される。 In an industrially preferred method, the edible film may be produced by an extrusion method or an inflation method in which the water-soluble film-forming component (A) is melt-kneaded with an extruder and extruded from a die into a sheet or film. . In the extrusion method, a T die is often used, and in the inflation method, a cylindrical die is used.
　溶融混練温度は、例えば、９０～３００℃（例えば、１１０～２６０℃）程度の範囲から選択でき、１５０～２５０℃（例えば、１７０～２３０℃）程度であってもよい。 The melt kneading temperature can be selected from the range of, for example, about 90 to 300 ° C. (for example, 110 to 260 ° C.), and may be about 150 to 250 ° C. (for example, 170 to 230 ° C.).
　押出成形されたフィルム又はシートは、冷却され、可食性フィルムが得られる。なお、必要であれば、フィルム又はシートは延伸してもよい。 The extruded film or sheet is cooled to obtain an edible film. If necessary, the film or sheet may be stretched.
　以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
　なお、以下の実施例及び比較例において、水分量は、水分気化装置（三菱化学（株）製、VA-100型）を用い、加熱温度１５０℃、窒素流量３００ｍｌ／分の条件で測定した。また、厚みは、デジタルインジケータ（（株）ミツトヨ製「ＩＤ－Ｃ１１２」）で測定した。 In the following examples and comparative examples, the moisture content was measured using a moisture vaporizer (VA-100 model, manufactured by Mitsubishi Chemical Corporation) under the conditions of a heating temperature of 150 ° C. and a nitrogen flow rate of 300 ml / min. The thickness was measured with a digital indicator (“ID-C112” manufactured by Mitutoyo Corporation).
　実施例１
　オリゴ糖（デンプン糖、三菱商事フードテック（株）製、還元デンプン糖化物「ＰＯ－１０」）０．７７ｇと糖アルコール（ソルビトール、三菱商事フードテック（株）製、ソルビット）０．６３ｇを粉砕混合し、ハンドプレス機（東洋精機（株）製、miniTEST PRESS-10）を用いて１５０℃、１０ｍＰａにて溶融加圧することで、厚み０．２～０．４ｍｍ、水分含有量０．２重量％の透明なフィルムを得た。このフィルムの口腔内での溶解性を調べたところ、滑らかな感触で口腔内で速やかに溶解した。 Example 1
Oligosaccharide (starch sugar, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., reduced starch saccharified product “PO-10”) 0.77 g and sugar alcohol (sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit) 0.63 g are ground. Mixing and melt pressurizing at 150 ° C. and 10 mPa using a hand press machine (manufactured by Toyo Seiki Co., Ltd., miniTEST PRESS-10), thickness 0.2 to 0.4 mm, moisture content 0.2 weight % Transparent film was obtained. When the solubility of this film in the oral cavity was examined, it quickly dissolved in the oral cavity with a smooth feel.
　実施例２
　オリゴ糖（デンプン糖、三菱商事フードテック（株）製、還元デンプン糖化物「ＰＯ－１０」）０．８３ｇと糖アルコール（キシリトール、三菱商事フードテック（株）製、キシリット）０．６８ｇを用いる以外、実施例１と同様にして、厚み０．４８～０．５５ｍｍ、水分含有量０．７９重量％の透明なフィルムを得た。このフィルムの口腔内での溶解性を調べたところ、滑らかな感触で口腔内で速やかに溶解した。 Example 2
0.83 g of oligosaccharide (starch sugar, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., reduced starch saccharified product “PO-10”) and 0.68 g of sugar alcohol (xylitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., xylit) are used. A transparent film having a thickness of 0.48 to 0.55 mm and a water content of 0.79% by weight was obtained in the same manner as in Example 1. When the solubility of this film in the oral cavity was examined, it quickly dissolved in the oral cavity with a smooth feel.
　実施例３
　オリゴ糖（マルトトリオース、三菱化学フーズ株式会社製、「オリゴトース」）０．８３ｇと糖アルコール（ソルビトール、三菱商事フードテック（株）製、ソルビット）０．６８ｇを用いる以外、実施例１と同様にして、厚み０．４～０．５ｍｍ、水分含有量２．２重量％の透明なフィルムを得た。このフィルムの口腔内での溶解性を調べたところ、滑らかな感触で口腔内で速やかに溶解した。 Example 3
Same as Example 1 except that 0.83 g of oligosaccharide (Maltotriose, manufactured by Mitsubishi Chemical Foods Corporation, “Oligotose”) and 0.68 g of sugar alcohol (sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit) were used. Thus, a transparent film having a thickness of 0.4 to 0.5 mm and a water content of 2.2% by weight was obtained. When the solubility of this film in the oral cavity was examined, it quickly dissolved in the oral cavity with a smooth feel.
　比較例１
　水１３．５ｇに、オリゴ糖（デンプン糖、三菱商事フードテック（株）製、還元デンプン糖化物「ＰＯ－１０」）０．７７ｇと糖アルコール（ソルビトール、三菱商事フードテック（株）製、ソルビット）０．６３ｇとを加えて溶解し、この溶液を剥離性基材上に流延し、通風乾燥機で水分を蒸発させ、厚み０．２～０．４ｍｍ、水分含有量７．５重量％の透明なフィルムを得た。 Comparative Example 1
In 13.5 g of water, 0.77 g of oligosaccharide (starch sugar, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., reduced starch saccharified product “PO-10”) and sugar alcohol (sorbitol, manufactured by Mitsubishi Corporation Foodtech Co., Ltd., Sorbit ) Add 0.63 g and dissolve, cast this solution on a peelable substrate, evaporate the moisture with a ventilator, thickness 0.2-0.4mm, moisture content 7.5wt% A transparent film was obtained.
　比較例２
　メチルセルロース０．８ｇ、グリセリン０．３８ｇ、Ｄ－ソルビトール液０．１６ｇ、トレハロース０．１６ｇを混合し、実施例１と同様に溶融加圧したが、フィルムを形成できなかった。 Comparative Example 2
Methyl cellulose 0.8 g, glycerin 0.38 g, D-sorbitol solution 0.16 g and trehalose 0.16 g were mixed and melt-pressed in the same manner as in Example 1, but no film could be formed.
　本発明は、口臭予防・口腔ケアなどのための菓子類や、速やかに口腔内で溶解し消化器吸収可能な薬効成分などを含有又は挟み込んだフィルム製剤、口腔内粘膜吸収や口腔内の疾患の治療のための製剤などに利用できる。 The present invention relates to confectionery for the prevention of bad breath and oral care, film preparations containing or sandwiching medicinal components that can be rapidly dissolved in the oral cavity and absorbed into the digestive organs, oral mucosal absorption and oral diseases It can be used for preparations for treatment.

Claims (8)

  1. 　水溶性フィルム形成成分（Ａ）を含む可食性フィルムであって、水溶性フィルム形成成分（Ａ）が、オリゴ糖（Ｂ１）及び環状構造を有する多糖類（Ｂ２）から選択された少なくとも一種の水溶性多糖類（Ｂ）を含み、かつ溶融製膜により形成された可食性フィルム。 An edible film comprising a water-soluble film-forming component (A), wherein the water-soluble film-forming component (A) is selected from an oligosaccharide (B1) and a polysaccharide (B2) having a cyclic structure. An edible film containing the sexual polysaccharide (B) and formed by melt film formation.
  2. 　水分含有量が５重量％以下である請求項１記載の可食性フィルム。 The edible film according to claim 1, wherein the moisture content is 5% by weight or less.
  3. 　さらに水溶性多糖類（Ｂ）を可塑化するための水溶性可塑化成分（Ｃ）を含む請求項１又は２記載の可食性フィルム。 The edible film according to claim 1 or 2, further comprising a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B).
  4. 　水溶性フィルム形成成分（Ａ）が、水溶性多糖類（Ｂ）と、この水溶性多糖類（Ｂ）を可塑化するための水溶性可塑化成分（Ｃ）とを含み、
    　オリゴ糖（Ｂ１）が、デンプン糖、マルトオリゴ糖、イソマルトオリゴ糖、ガラクトオリゴ糖、カップリングシュガー、フルクトオリゴ糖、キシロオリゴ糖、大豆オリゴ糖、乳果オリゴ糖、キチンオリゴ糖及びキトサンオリゴ糖から選択された少なくとも一種であり、環状構造を有する多糖類（Ｂ２）が、クラスターデキストリン及び／又はシクロアミロースであり、
    　水溶性可塑化成分（Ｃ）が、糖類及び糖アルコールから選択された少なくとも一種である請求項１～３のいずれかに記載の可食性フィルム。     The water-soluble film-forming component (A) includes a water-soluble polysaccharide (B) and a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B),
    The oligosaccharide (B1) was selected from starch sugar, maltooligosaccharide, isomaltooligosaccharide, galactooligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, dairy oligosaccharide, chitin oligosaccharide and chitosan oligosaccharide The polysaccharide (B2) which is at least one kind and has a cyclic structure is a cluster dextrin and / or cycloamylose,
    The edible film according to any one of claims 1 to 3, wherein the water-soluble plasticizing component (C) is at least one selected from sugars and sugar alcohols.
  5. 　水溶性可塑化成分（Ｃ）としての糖アルコールが、エリスリトール、ペンタエリスリトール、アラビトール、リビトール、キシリトール、ズルシトール、マンニトール、ソルビトール、ラクチトール、及びマルチトールから選択された少なくとも一種である請求項３又は４のいずれかに記載の可食性フィルム。 The sugar alcohol as the water-soluble plasticizing component (C) is at least one selected from erythritol, pentaerythritol, arabitol, ribitol, xylitol, dulcitol, mannitol, sorbitol, lactitol, and maltitol. An edible film according to any one of the above.
  6. 　水溶性多糖類（Ｂ）と水溶性可塑化成分（Ｃ）との重量割合が、前者（Ｂ）／後者（Ｃ）＝９９／１～３０／７０である請求項３～５のいずれかに記載の可食性フィルム。 The weight ratio of the water-soluble polysaccharide (B) and the water-soluble plasticizing component (C) is the former (B) / the latter (C) = 99/1 to 30/70. The edible film described.
  7. 　オリゴ糖（Ｂ１）及び環状構造を有する多糖類（Ｂ２）から選択された少なくとも一種の水溶性多糖類（Ｂ）を含む水溶性フィルム形成成分（Ａ）を溶融して製膜し、可食性フィルムを製造する方法。 An edible film is formed by melting and forming a water-soluble film-forming component (A) containing at least one water-soluble polysaccharide (B) selected from oligosaccharide (B1) and polysaccharide (B2) having a cyclic structure. How to manufacture.
  8. 　水溶性多糖類（Ｂ）と、この水溶性多糖類（Ｂ）を可塑化するための水溶性可塑化成分（Ｃ）とを含む水溶性フィルム形成成分（Ａ）を溶融混練してシート状又はフィルム状に押し出し成形する請求項７記載の製造方法。 A water-soluble film-forming component (A) containing a water-soluble polysaccharide (B) and a water-soluble plasticizing component (C) for plasticizing the water-soluble polysaccharide (B) is melt-kneaded to form a sheet or The manufacturing method of Claim 7 which extrudes in a film form.
PCT/JP2015/058567 2014-04-22 2015-03-20 Edible film and method for manufacturing same WO2015163064A1 (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2000342193A (en) * 1999-06-04 2000-12-12 Nippon Starch Chemical Co Ltd Edible film
JP2001322397A (en) * 2000-05-16 2001-11-20 Lion Corp Transfer sheet for membrane
JP2004051942A (en) * 2002-05-29 2004-02-19 Daicel Chem Ind Ltd Dispersion and method for producing molded article using the same
JP2007119674A (en) * 2005-10-31 2007-05-17 Daicel Chem Ind Ltd Water-soluble auxiliary agent and use thereof
JP2007326808A (en) * 2006-06-07 2007-12-20 Matsutani Chem Ind Ltd Edible film for oral hygiene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000342193A (en) * 1999-06-04 2000-12-12 Nippon Starch Chemical Co Ltd Edible film
JP2001322397A (en) * 2000-05-16 2001-11-20 Lion Corp Transfer sheet for membrane
JP2004051942A (en) * 2002-05-29 2004-02-19 Daicel Chem Ind Ltd Dispersion and method for producing molded article using the same
JP2007119674A (en) * 2005-10-31 2007-05-17 Daicel Chem Ind Ltd Water-soluble auxiliary agent and use thereof
JP2007326808A (en) * 2006-06-07 2007-12-20 Matsutani Chem Ind Ltd Edible film for oral hygiene

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