Water-soluble glucan, glucan aqueous solution, molded body containing water-soluble glucan, packaging material containing molded body, and production method for water-soluble glucan

Abstract

The present invention relates to a water-soluble glucan containing an α-1,3 bond, an α-1,4 bond, and an α-1,6 bond.

Description

Water-soluble glucan, aqueous solution of glucan, molded article containing water-soluble glucan, packaging material containing the molded article, and method for producing water-soluble glucan

[0001] The present invention relates to a water-soluble glucan, an aqueous solution of glucan, a molded article containing a water-soluble glucan, a packaging material containing a molded article, and a method for producing a water-soluble glucan.

[0002] Conventionally, starch has been used in a variety of applications. For example, molded articles such as films obtained by molding a starch-containing composition, and laminates obtained by coating a support with a starch-containing composition are known. For example, Patent Document 1 discloses a starch-containing wafer (a film-like material with a thickness of about 10 μm).

[0003] Japanese Patent Publication No. 2002-155163

[0004] However, the inventors have found that when attempting to produce a film using the method described in Patent Document 1, the viscosity of the starch aqueous solution is very high, posing challenges to the handling and / or productivity of the aqueous solution. Therefore, the present invention aims to provide a water-soluble glucan that yields a low-viscosity aqueous solution.

[0005] The present inventors have conducted detailed studies on water-soluble glucans in order to solve the above problems and have completed the present invention. That is, the present invention encompasses the following preferred embodiments: [1] A water-soluble glucan comprising α-1,3-bonds, α-1,4-bonds, and α-1,6-bonds. [2] The water-soluble glucan according to [1], wherein the content of α-1,3-bonds is 0.5 to 10 mol% relative to the total number of moles of glucose units constituting the water-soluble glucan. [3] The water-soluble glucan according to [1] or [2], wherein the viscosity of the aqueous glucan solution measured at 80°C at a concentration of 10% by mass is 10 to 120,000 mPa·sec. [4] The water-soluble glucan according to any one of [1] to [3], wherein the water-soluble glucan is derived from one or more materials selected from the group consisting of potato, tapioca, corn, sweet potato, lily bulb, taro, yam, lotus root, wheat, rice, kudzu, water chestnut, and pea. [5] The water-soluble glucan is one or more selected from the group consisting of unmodified starch derived from bulbs and its derivatives, as described in any of [1] to [4]. [6] The water-soluble glucan is one or more selected from the group consisting of modified starch and its derivatives, as described in any of [1] to [4]. [7] The water-soluble glucan is one or more selected from the group consisting of starch derived from seeds and its derivatives, as described in any of [1] to [4]. [8] A water-soluble composition comprising the water-soluble glucan described in any of [1] to [7] and a polysaccharide. [9] The water-soluble composition according to [8], wherein the polysaccharide is at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum and their derivatives.

[10] An aqueous glucan solution comprising the water-soluble glucan described in any of [1] to [7] and water.

[11] The aqueous glucan solution according to

[10] , wherein the water-soluble glucan content is 0.1 to 50% by mass.

[12] The aqueous glucan solution according to

[10] or

[11] , further comprising 4-α-glucanotransferase.

[13] The aqueous glucan solution according to any one of

[10] to

[12] , further comprising polysaccharides.

[14] The aqueous glucan aqueous solution according to

[13] , wherein the polysaccharide is at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum, and derivatives thereof.

[15] A molded article comprising the water-soluble glucan according to any one of [1] to [7].

[16] The molded article according to

[15] , further comprising a polysaccharide.

[17] The molded article according to

[16] , wherein the polysaccharide is at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum, and derivatives thereof.

[18] The molded article according to any one of

[15] to

[17] , wherein the molded article is a film, a coating film, a fiber, a pellet, a foam, a disc, or a rod.

[19] A molded article according to any one of

[15] to

[18] , wherein the water content is 30% by mass or less.

[20] A molded article according to any one of

[15] to

[19] , wherein the tensile elongation at break measured in accordance with ASTM D 882 is 20 to 1000%.

[21] A molded article according to any one of

[18] to

[20] , wherein the molded article, which is a film or coating, is integrated with a support, and the support is a fiber.

[22] A molded article according to any one of

[18] to

[20] , wherein the molded article, which is a film or coating, is integrated with a support, and the support is one or more selected from the group consisting of textile products, paper, film and metal foil.

[23] A molded article according to any one of

[18] to

[20] , wherein the molded article, which is a film or coating, is integrated with a support, and the support is one or more selected from the group consisting of paper, film and metal foil, and the molded article integrated with the support is a packaging material.

[24] A molded article according to any one of

[18] to

[20] , wherein the film is a packaging material. A packaging material comprising a molded body according to any one of

[25]

[15] to

[20] . A method for producing a water-soluble glucan according to any one of

[26] [1] to [7], wherein (1) 1 × 10. ４ ~1 x 10 １０A method comprising the step of reacting a raw material glucan having a weight-average molecular weight with 4-α-glucanotransferase to obtain a water-soluble glucan.

[27] The method according to

[26] , wherein the mass ratio of the raw material glucan to 4-α-glucanotransferase is 99.999:0.001 to 90:10.

[28] The method according to

[26] or

[27] , comprising the step (0) of preparing a solution of the raw material glucan before step (1), wherein the reaction in step (1) is carried out in the solution obtained in step (0), and the solution after the reaction is dried to obtain a water-soluble glucan.

[29] The method according to

[28] , wherein the concentration of the raw material glucan in the solution in step (0) is 1 to 50% by mass.

[30] A water-soluble composition comprising the water-soluble glucan described in [1] and a polyvinyl alcohol-based resin.

[0006] According to the present invention, it is possible to provide a water-soluble glucan that yields a low-viscosity aqueous solution.

[0007] Embodiments of the present invention will be described in detail below. However, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without impairing the spirit of the invention.

[0008] [Water-soluble glucan] The water-soluble glucan of the present invention contains α-1,3-links, α-1,4-links, and α-1,6-links. In this specification, water-soluble glucan means that the solubility of the glucan in water, determined by the following procedure, is 80% or more. Prepare an aqueous solution of glucan with a concentration of approximately 10% by mass, heat the aqueous solution to 95°C and stir for 1 hour, then cool to room temperature. Next, take a portion of the aqueous solution and dry it, and determine the concentration of the aqueous solution (concentration A, approximately 10% by mass) from the change in mass. Then, centrifuge this aqueous solution at 3000 rpm for 10 minutes (centrifuge: Kubota Corporation, model number: 2410, rotor: RS-240), take a solution (supernatant) from within 1 cm of the liquid surface, dry it, and determine the concentration of the supernatant (concentration B) from the change in mass. Calculate the solubility of the glucan in water using the following formula. The solubility of glucan in water (%) = (Concentration B / Concentration A) × 100 In the present invention, the solubility of water-soluble glucan in water is 80% or more, preferably 90% or more, more preferably 95% or more, even more preferably 97% or more, and preferably 100% or less. The solubility of water-soluble glucan in water can be adjusted to above the above lower limit by, for example, reacting the raw material glucan with an enzyme, particularly by reacting it according to the embodiment described as preferred in the method for producing water-soluble glucan described later.

[0009] The glucan in this invention contains two or more unit chains. More specifically, it contains one unit chain having a reducing end (main chain) and one or more unit chains not having a reducing end (branched chains). The unit chain contained in the glucan refers to a structure in which glucose molecules are linked in a chain by α-1,4- bonds. The branched chain branches off from the 6th position of the glucose molecules contained in the main chain or other branched chains, that is, it is linked to the glucose molecules contained in the main chain or other branched chains by α-1,6- bonds. The degree of polymerization of a unit chain corresponds to the number of glucose molecules that make up the unit chain. That is, a degree of polymerization of a unit chain of 4 means that the number of glucose molecules that make up the unit chain is 4. One or more of the unit chains contained in the glucan (i.e., one main chain and one or more branched chains) is linked to another branched chain via α-1,3- bonds. The degree of polymerization of the other branched chain is not limited, but is usually between 1 and 30. The inventors have found that by including α-1,3-links, α-1,4-links, and α-1,6-links in the water-soluble glucan, a low-viscosity aqueous solution of water-soluble glucan can be obtained. The low-viscosity aqueous solution is easy to handle. Furthermore, since a low-viscosity water-soluble glucan solution can be prepared using less solvent, high productivity can be expected when removing the solvent after forming a molded article using the solution, for example, when producing a film (molded article) by casting and drying the solution. Moreover, in one embodiment of the present invention, the water-soluble glucan can result in a molded article with improved toughness. When the water-soluble glucan has improved toughness, a molded article containing such a water-soluble glucan can also have improved toughness, and such a molded article can be suitably used as a film or packaging material on its own, or as a packaging material, fiber, or textile product when integrated with a support.

[0010] From the viewpoint of obtaining a lower viscosity aqueous solution, the α-1,3-bond content in water-soluble glucans is preferably 0.5 to 10 mol%, more preferably 1 to 8 mol%, even more preferably 2 to 6 mol%, and particularly preferably 2.5 to 5.5 mol%, relative to the total number of glucose units constituting the water-soluble glucans. The α-1,3-bond content in water-soluble glucans can be adjusted to the above range, for example, by reacting the raw material glucan with an enzyme, particularly according to the embodiments described as preferred in the method for producing water-soluble glucans described later. The α-1,3-bond content in water-soluble glucans can be measured by the method described in the examples below.

[0011] From the viewpoint of obtaining a lower viscosity aqueous solution, the α-1,4-bond content in water-soluble glucans is preferably 20 to 99.9 mol%, more preferably 80 to 99.5 mol%, even more preferably 90 to 99 mol% (e.g., 92 to 99 mol% or 93 to 99 mol%), and particularly preferably 94 to 98 mol%, relative to the total number of moles of glucose units constituting the water-soluble glucan. The α-1,4-bond content in water-soluble glucans can be adjusted to the above range, for example, by reacting the raw material glucan with an enzyme, particularly according to the embodiments described as preferred in the method for producing water-soluble glucans described later. The α-1,4-bond content in water-soluble glucans can be measured by the method described in the examples below.

[0012] The α-1,6-bond content in water-soluble glucans is preferably 0.1 to 50 mol%, more preferably 0.3 to 30 mol%, even more preferably 0.5 to 10 mol%, and particularly preferably 1 to 4 mol%, relative to the total number of glucose units constituting the water-soluble glucan, from the viewpoint of providing an aqueous solution that is more stable against heat, acids, and / or alkalis. The α-1,6-bond content in water-soluble glucans can be adjusted to the above range, for example, by reacting the raw material glucan with an enzyme, particularly according to the embodiments described as preferred in the method for producing water-soluble glucans described later. The α-1,6-bond content in water-soluble glucans can be measured by the method described in the examples below.

[0013] The ratio of α-1,3-bond content to α-1,6-bond content in water-soluble glucan ([α-1,3-bond content] / [α-1,6-bond content ratio]) is preferably 0.1 to 10, more preferably 0.3 to 5, even more preferably 0.5 to 3, and particularly preferably 1 to 2.5, from the viewpoint of providing a lower viscosity aqueous solution and a more stable aqueous solution with respect to heat, acids, and / or alkalis. The ratio of α-1,3-bond content to α-1,6-bond content in water-soluble glucan can be adjusted to the above range, for example, by reacting the raw material glucan with an enzyme, particularly according to the embodiment described as preferred in the method for producing water-soluble glucan described later. The ratio of α-1,3-bond content to α-1,6-bond content in water-soluble glucan can be determined by the method described in the examples below.

[0014] The viscosity of the glucan aqueous solution measured at 80°C when the concentration is 10% by mass is preferably 10 to 120,000 mPa·sec, more preferably 100 to 100,000 mPa·sec, still more preferably 100 to 50,000 mPa·sec, even more preferably 500 to 15,000 mPa·sec, and particularly preferably 1,000 to 15,000 mPa·sec. The above viscosity can be measured with a B-type viscometer, and more specifically, by the method described in the examples below. If the viscosity of the aqueous solution is too high, the concentration of the water-soluble glucan has to be lowered during processing, and it tends to take a long time for drying and the processability deteriorates. On the other hand, if the viscosity of the aqueous solution is too low, the liquid easily flows when coated, and unevenness in thickness is likely to occur. The viscosity within the above range can be obtained, for example, by reacting the raw material glucan with an enzyme, particularly by reacting according to the embodiment described as preferable in the method for manufacturing the molded body described below. When the raw material glucan is reacted with an enzyme, particularly the enzyme described as preferable in the method for manufacturing the molded body described below, at least one of the α-1,4-linkages in at least one of the unit chains contained in the raw material glucan is cleaved, and a branched chain having a degree of polymerization of 1 or more is separated, thereby generating an intermediate glucan; it is considered that the separated branched chain having a degree of polymerization of 1 or more binds to the unit chain contained in the intermediate glucan or another raw material glucan via an α-1,3-linkage. The water-soluble glucan produced by treating the raw material glucan with an enzyme can provide a solution (particularly an aqueous solution) with a lower viscosity compared to the solution (particularly an aqueous solution) of the raw material glucan.

[0015] The weight average molecular weight of the water-soluble glucan is preferably 1×10 ３ to 1×10 １０ and more preferably 1×10 ４ to 1×10 ８ and particularly preferably 1×10 ５ to 1×10 ７ When the water-soluble glucan is subjected to gel permeation chromatography (GPC) analysis under conditions using a dimethyl sulfoxide solvent, at least one of the peak tops of the weight average molecular weight is preferably 1×10 ３ to 1×10 １０ and more preferably 1×10４ ~5 x 10 ９ More preferably 1 x 10 ５ ~1 x 10 ９ Particularly preferably 1 x 10 ６ ~1 x 10 ８ Observed in the range of . When water-soluble glucan is subjected to gel permeation chromatography (GPC) analysis using dimethyl sulfoxide solvent, at least one of the peak tops of the number-average molecular weight is preferably 1 × 10 ３ ~1 x 10 １０ , more preferably 5 × 10 ３ ~1 x 10 ９ More preferably 5 × 10 ４ ~5 x 10 ８ , particularly preferably 5 × 10 ５ ~5 x 10 ７ It is observed in the range of . The peak top with the highest number-average molecular weight is preferably 1 × 10 ４ ~1 x 10 １０ , more preferably 1 × 10 ５ ~5 x 10 ８ More preferably 1 x 10 ６ ~1 x 10 ８ Particularly preferably 1 x 10 ７ ~5 x 10 ７ These are observed within the range described above. When the weight-average molecular weight, the peak position of the weight-average molecular weight, and / or the peak position of the number-average molecular weight are within the range described above, the water-soluble glucan can yield a lower viscosity aqueous solution. The weight-average molecular weight, the peak position of the weight-average molecular weight, and the peak position of the number-average molecular weight can be adjusted to within the range described above, for example, by reacting the raw material glucan with an enzyme, particularly according to embodiments described as preferred in the method for producing water-soluble glucan described later.

[0016] The weight-average molecular weight, the peak top of the weight-average molecular weight, and the peak top of the number-average molecular weight mentioned above can be determined by the following method. 20 μg of glucan is subjected to gel filtration HPLC under the following conditions: Eluent: 5 mM sodium nitrate / DMSO Column: One TSK GEL α-M column Column temperature: 60°C Flow rate: 0.8 mL / min Glucan concentration: 0.2 w / v% Preparation of measurement sample: After letting the mixture of glucan and eluent stand overnight, the mixture is stirred at 60°C for 1 hour, and then stirred at 65°C for 1.5 hours to dissolve the glucan and obtain the measurement sample. Filtration: 0.45 μm PP filter (Whatman) Injection volume: 100 μL Standard: PMMA-R, Y, G Measurement time: 18 minutes Liquid delivery unit: GPC-101 (Shodex) Detector: RI If multiple peaks are present in the chromatogram, the weight-average molecular weight is determined by including all peaks. The peak positions of the weight-average molecular weight and the number-average molecular weight are determined from the peak top position of the weight-average molecular weight and the peak top position of the number-average molecular weight, respectively.

[0017] The amylose content in water-soluble glucan is preferably 0 to 90% by mass, more preferably 5 to 30% by mass, even more preferably 5 to 28% by mass, and even more preferably 6 to 25% by mass, from the viewpoint of being able to produce a low-viscosity aqueous solution, or a molded article having improved toughness, and may be, for example, 10 to 25% by mass, 15 to 23% by mass, or 18 to 22% by mass. The amylose content in water-soluble glucan can be measured, for example, from the absorbance at a wavelength of 620 nm when iodine is adsorbed onto water-soluble glucan, according to the method described in "Standard Measurement Method No. 332 of the Ministry of Agriculture, Forestry and Fisheries Notification of March 14, 2001". When water-soluble glucan is a mixture of two or more types, the amylose content refers to the average amylose content, which is a weighted average value that takes into account the proportion of the two or more types of water-soluble glucan.

[0018] The water content in the water-soluble glucan is preferably 0 to 20% by mass, more preferably 5 to 15% by mass. The water content in the water-soluble glucan can be measured by, for example, a halogen moisture meter, a Karl Fischer moisture meter, etc. The protein content in the water-soluble glucan is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, even more preferably 0 to 0.5% by mass, and may be 0% by mass. The protein content of the water-soluble glucan can be determined by, for example, the Kjeldahl method, the Dumas method, etc. The lipid content in the water-soluble glucan is preferably 0 to 2% by mass, more preferably 0 to 1% by mass, even more preferably 0 to 0.2% by mass, and may be 0% by mass. The lipid content in the water-soluble glucan can be determined by, for example, liquid chromatography, gas chromatography, etc. The α-1,6-bond content in the glucan is preferably 0.1 to 50% by mass, more preferably 0.3 to 30% by mass, even more preferably 0.5 to 10% by mass, and particularly preferably 1 to 4 mol%. The α-1,6-bond content in the glucan is, for example １３ This can be determined by methods such as C-NMR and methylation analysis.

[0019] In one embodiment of the present invention, from the perspective that the water-soluble glucan can provide an aqueous solution with reduced viscosity, or that it can provide an aqueous solution with reduced viscosity and can provide a molded body having improved toughness, preferably, it is derived from one or more materials selected from the group consisting of potato, tapioca, corn, sweet potato, Jerusalem artichoke, taro, yam, lotus root, wheat, rice, kudzu, Chinese radish, and pea. More preferably, it is derived from one or more materials selected from the group consisting of potato, tapioca, corn, wheat, and pea. Even more preferably, it is derived from one or more materials selected from the group consisting of potato, tapioca, corn, and wheat. This embodiment is also preferable because the water-soluble glucan is derived from a plant material rather than an animal material. Incidentally, as to what the water-soluble glucan is derived from, that is, the raw material of the water-soluble glucan, the type of the origin of the glucan can be determined by examining the presence or absence of DNA bands specific to the raw material by, for example, the PCR method. Even in the case of a composition containing multiple types of water-soluble glucan, the type of each water-soluble glucan can be determined by the PCR method. Also, the content of each water-soluble glucan can be measured, for example, by measuring the amylose content after identifying the type of each water-soluble glucan by the PCR method. Further, as the raw material of the water-soluble glucan, a commercially available raw material glucan with a known origin may be used.

[0020] In one embodiment of the present invention, the water-soluble glucan is one or more selected from the group consisting of unmodified starch derived from bulbs and its derivatives. In another embodiment of the present invention, the water-soluble glucan is one or more selected from the group consisting of modified starch and its derivatives. The modified starch may or may not be derived from bulbs. In one embodiment, it is preferable that the modified starch is derived from bulbs. In one embodiment of the present invention, the water-soluble glucan is one or more selected from the group consisting of unmodified starch derived from bulbs, its derivatives, modified starch, and its derivatives. A bulb is a fleshy root or rhizome of a plant that stores nutrients. When the water-soluble glucan is, for example, derived from bulbs, it means that the raw material for the water-soluble glucan is a bulb. Derivatives of starch include etherified, esterified, cationized, anionic, and crosslinked starch derivatives, and such derivatives are known in the art. Modified starch is starch having a modified group. Examples of modifying groups include hydroxyalkyl groups having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), hydroxypropyl groups having 1 to 15 carbon atoms, carboxymethyl groups, and / or phosphate ester groups. The degree of substitution in the modified starch is preferably 0.01 to 0.5, more preferably 0.1 to 0.4, and even more preferably 0.15 to 0.3, from the viewpoint of being able to produce a low-viscosity aqueous solution, or a molded article having improved toughness, preferred examples of bulbs include potatoes, tapioca, sweet potatoes, lily bulbs, taro, yams, lotus roots, kudzu, and arrowhead, with more preferred examples of bulbs being potatoes and tapioca. Examples of modified starches not derived from bulbs include modified starches derived from seeds or fruit pulp.

[0021] In one embodiment of the present invention, the water-soluble glucan is one or more selected from the group consisting of starch derived from seeds and derivatives thereof. Derivatives of starch include etherified starch, esterified starch, cationized starch, anionized starch, and crosslinked starch, and such derivatives are known in the art. From the viewpoint of providing an aqueous solution with reduced viscosity, or from the viewpoint of providing an aqueous solution with reduced viscosity and a molded body having improved toughness, examples of preferred seeds include corn, wheat, rice, and pea, more preferred examples of seeds include corn, wheat, and pea, and particularly preferred examples of seeds include corn.

[0022] In one embodiment of the present invention, from the viewpoint of providing an aqueous solution with reduced viscosity, or from the viewpoint of providing an aqueous solution with reduced viscosity and a molded body having improved toughness, the water-soluble glucan contains one or more starch derivatives selected from the group consisting of etherified starch, esterified starch, cationized starch, anionized starch, and crosslinked starch. In this embodiment, the water-soluble glucan may contain one or more starches and one or more starch derivatives, may contain one or more starch derivatives without containing one or more starches, or may consist of one or more starch derivatives. In this one embodiment, the proportion of the one or more starch derivatives in the water-soluble glucan of the present invention may preferably be 1 to 100% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 50% by mass with respect to the total mass of the water-soluble glucan.

[0023] Examples of etherified starch include alkyl etherified starch such as methyl etherified starch; carboxyalkyl etherified starch such as carboxymethyl etherified starch; hydroxyalkyl etherified starch such as etherified starch having a hydroxyalkyl group with 2 to 6 carbon atoms; allyl etherified starch; aminoalkyl etherified starch, ammonium alkyl etherified starch, and the like. Examples of the hydroxyalkyl group with 2 to 6 carbon atoms include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and the like.

[0024] Examples of esterified starches include esterified starches having structural units derived from carboxylic acids, such as esterified starches having structural units derived from acetic acid; esterified starches having structural units derived from dicarboxylic acid anhydrides, such as esterified starches having structural units derived from maleic anhydride, esterified starches having structural units derived from phthalic anhydride, and esterified starches having structural units derived from octenylsuccinic acid anhydride; and esterified starches having structural units derived from oxoacids, such as nitrate esterified starch, sulfate esterified starch, carbonate esterified starch, phosphate esterified starch, and urea phosphate esterified starch.

[0025] Examples of cationized starches include reaction products of starch with 2-diethylaminoethyl chloride and reaction products of starch with 2,3-epoxypropyltrimethylammonium chloride. Examples of anionized starches include reaction products of starch with phosphoric acid, reaction products of starch with chloroacetic acid or its salts, and reaction products of starch with octenyl succinic acid. Examples of cross-linked starches include formaldehyde-crosslinked starch, epichlorohydrin-crosslinked starch, phosphate-crosslinked starch, acrolein-crosslinked starch, and electron beam-crosslinked starch. These starch derivatives can be obtained by methods conventional in the art.

[0026] In one embodiment of the present invention, the water-soluble glucan preferably contains one or more modified starches having a modifying group, from the viewpoint of being able to provide a low-viscosity aqueous solution, or from the viewpoint of being able to provide a low-viscosity aqueous solution and a molded article having improved toughness. Examples of modifying groups include hydroxyalkyl groups having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) (preferably hydroxypropyl groups), alkyl ester groups having 1 to 15 carbon atoms, carboxymethyl groups, and / or phosphate ester groups. When the water-soluble glucan contains modified starch, the crystallinity of the water-soluble glucan may decrease, and the recrystallization of the molded article containing the water-soluble glucan after molding may be moderately inhibited, thereby increasing the toughness of the molded article, or the toughness and solubility in water. In this embodiment, the water-soluble glucan preferably contains hydroxyalkylated starch having 1 to 10 carbon atoms or starch having a carboxymethyl group, more preferably hydroxyethylated starch, hydroxypropylated starch, or starch having a carboxymethyl group, and even more preferably hydroxypropylated starch. In this embodiment, the proportion of one or more modified starches in the water-soluble glucan may be preferably 1 to 100% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 50% by mass, based on the total mass of the water-soluble glucan.

[0027] The degree of substitution in the modified starch is preferably 0.01 to 0.5, more preferably 0.1 to 0.4, and even more preferably 0.15 to 0.3, from the viewpoint of being able to produce a low-viscosity aqueous solution, or a molded article that is able to produce a low-viscosity aqueous solution and has improved toughness. The degree of substitution in the modified starch can be determined, for example, by using a nuclear magnetic resonance apparatus. １ This can be determined by measuring 1H-NMR and analyzing the ratio of the peak area of ​​the denatured region to the peak area of ​​glucose units in the obtained spectrum. For example, if the denatured starch is hydroxypropylated starch, a nuclear magnetic resonance spectrometer can be used to determine DMSO-d ６ Hydroxypropylated starch in solvent at room temperature １By measuring 1H-NMR, the degree of substitution can be determined from the ratio of the peak area of ​​the denatured region appearing at 1.04 ppm to the peak area of ​​the glucose unit appearing at 5.13 ppm ((peak area of ​​the denatured region appearing at 1.04 ppm / 3) / peak area of ​​the glucose unit).

[0028] In the present invention, from the viewpoint of biodegradability, it is preferable that the water-soluble glucan does not contain monomers such as (meth)acrylic acid, and especially grafted starch formed by grafting acrylic monomers. The proportion of grafted starch in the water-soluble glucan is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less, based on the total mass of the water-soluble glucan.

[0029] Furthermore, it is preferable that the water-soluble glucan does not contain oxidized starch, from the viewpoint of being able to produce a low-viscosity aqueous solution, or from the viewpoint of being able to produce a low-viscosity aqueous solution and a molded article having improved toughness. The proportion of oxidized starch in the water-soluble glucan is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less, based on the total mass of the water-soluble glucan.

[0030] [Molded Articles] The present invention also covers molded articles comprising the above-mentioned water-soluble glucan. In the present invention, a molded article means a solid object molded to a desired shape. The dimensions of a molded article in the present invention are not limited. In one embodiment of the present invention, the minimum dimensions of the molded article are preferably 1 cm or less, more preferably 0.1 μm to 1 cm, even more preferably 0.5 μm to 1 mm, and particularly preferably 1 μm to 200 μm. The minimum dimensions refer to the smallest dimensions of the external shape of the molded article. For example, if the molded article is a rectangular parallelepiped, it refers to the smallest value among the length, width, and height; if the molded article is a sealed pouch, it refers to the smallest value among the length, width, height, and thickness of the film constituting the pouch; and if the molded article is a partially open pouch, for example, a cup with a circular bottom, it refers to the smallest value among the diameter of the bottom, the height of the cup, the thickness of the cup bottom, and the thickness of the cup side. In one embodiment of the present invention, the maximum dimension of the molded body is preferably 0.5 cm or more, more preferably 1 cm or more, even more preferably 10 cm to 10,000 m, and particularly preferably 1 cm to 1,000 m. The maximum dimension refers to the largest dimension of the outer shape of the molded body. For example, if the molded body is a film and the film is wound in a roll, it refers to the dimension that represents the largest value among the width of the film (width of the roll), the thickness of the wound film, and the length. Dimensions such as length, diameter, height, and thickness can be measured using a contact-type measuring method such as a caliper or thickness gauge, or an optical measuring method such as a laser displacement meter.

[0031] The moisture content of the molded article in the present invention is usually 30% by mass or less, preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably 3 to 15% by mass. The moisture content of the molded article can be adjusted within the above range by subjecting the molded article to heating and / or vacuum treatment as necessary, and / or by adding additives such as plasticizers. The moisture content of the molded article can be measured, for example, by a halogen moisture meter or a Karl Fischer moisture meter. Alternatively, it can be determined by the change in mass before and after vacuum drying, as described in the examples below. Note that, as described later, in the case of a molded article in which the molded article is integrated with a support and / or has an arbitrary layer, the above moisture content of the molded article means the moisture content of the molded article excluding the integrated support and / or the arbitrary layer. For example, in the case of a molded article in which a coating film and a paper support are integrated and which has an arbitrary layer, the above moisture content of the molded article means the moisture content of the coating film excluding the paper and the arbitrary layer. Similarly, with respect to the solubility in 80°C hot water, protein content, and lipid content of the molded body described later, in the case of a molded body integrated with a support and / or a molded body having an arbitrary layer, the above-mentioned solubility in 80°C hot water, protein content, and lipid content of the molded body refer to the solubility in 80°C hot water, protein content, and lipid content of the molded body excluding the integrated support and / or arbitrary layer, respectively.

[0032] In one embodiment of the present invention, the molded body is preferably water-soluble. In this specification, a molded body being water-soluble means that its solubility in 80°C hot water is preferably 50% by mass or more. That is, if the amount of solids that do not pass through the filter (pore size: 21 μm) after adding the molded body to 80°C hot water and stirring the molded body for 60 minutes is less than 50% by mass, it can be evaluated as water-soluble. The mass of the molded body to be dissolved in 80°C hot water is 0.1 parts by mass per 100 parts by mass of 80°C hot water. If the maximum dimensions of the molded body are 2 mm or more, it should be reduced to less than 2 mm by cutting with scissors or using a pulverizer before being subjected to the test. The solubility of the molded body in 80°C hot water is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. Because the molded body is water-soluble, it can be suitably used in applications such as agents used in contact with water or water-containing liquids (e.g., cleaning agents, softeners, medicines, cosmetics, colorants, fragrances, pesticides, insecticides, fungicides, viscosity modifiers, preservatives, and / or antistatic agents), packaging materials for food or food additives (e.g., films, pouches (sealed pouches or partially open pouches, e.g., cups, tubes, trays, bottles, boxes, lids, or containers)), tapes, seed tapes, embroidery bases, transfer substrates, seed coatings, and release films. In this case, the molded body dissolves during use, releasing its contents. The contents may be, for example, a liquid, solid, or gel.

[0033] The protein content or lipid content of the molded article in the present invention is usually 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.3% by mass or less, and may even be 0% by mass. The protein content or lipid content of the molded article can be adjusted to be below the above upper limit by changing the raw material used, such as the raw material glucan. From the viewpoint of water solubility of the molded article, a lower protein content or lipid content is preferable. The protein content of the molded article can be determined by, for example, the Kjeldahl method, the Dumas method, etc. The lipid content of the molded article can be determined by, for example, liquid chromatography, gas chromatography, etc.

[0034] In one embodiment of the present invention, the molded body is preferably a non-food item or an edible packaging material. Non-food items refer to articles that are not edible. Edible packaging materials refer to packaging materials that are edible or can be eaten, and include, for example, edible films and pouches (pouches that are sealed inside or partially open, such as cups, tubes, trays, bottles, boxes, lids, or containers). The items to be packaged in the edible packaging material are preferably items that can be eaten or ingested, such as foods containing beverages like water or juice, medicines, supplements, or food additives containing seasonings. If the molded body is a water-soluble edible packaging material, from the viewpoint of stable packaging before eating or ingesting, the water content of the packaged items is preferably 20% by mass or less, and more preferably 5% by mass or less.

[0035] The shape of the molded article is not particularly limited. In one embodiment of the present invention, the molded article is a film, a coating, a fiber, a pellet, a foam, a disc, or a rod.

[0036] If the molded body is a film, its average thickness is usually 1 to 500 μm, preferably 5 to 300 μm, and more preferably 10 to 100 μm, from the viewpoint of the film's mechanical strength (e.g., elongation at break) and water solubility. The film may be a sheet or have other shapes, such as a pouch or tape. The film may also be integrated into all or part of a support. In this case, the thickness of the film refers to the thickness of the film excluding the integrated support. The film may be a single layer or multiple layers. If the film is multiple layers, each layer may be the same or different, and the average thickness refers to the thickness per layer. A molded body that is a film may have any additional layers, as described later, at any point in its layer structure. If the molded body has a protective layer or a heat-seal layer as an additional layer, the layer is preferably located on the outermost surface of the molded body.

[0037] When the molded body is a coating film, its average thickness is usually 1 to 500 μm, preferably 5 to 100 μm, and more preferably 10 to 50 μm, from the viewpoint of the mechanical strength and water solubility of the coating film. A coating film refers to a film-like material integrated with a support by coating. The coating film may coat the entire support or only a part of the support. The coating film may be a single layer or multiple layers. If the coating film is multiple layers, each layer may be the same or different, and the above average thickness refers to the thickness of each layer. A molded body that is a coating film may have any additional layers, as described later, at any point in its layer structure. If the molded body has a protective layer or a heat-seal layer as an additional layer, the layer is preferably located on the outermost surface of the molded body.

[0038] When the molded body is a fiber, the single-fiber fineness is preferably 0.01 to 10,000 dtex, more preferably 0.3 to 5,000 dtex, and even more preferably 1 to 10 dtex. When the single-fiber fineness is within the above range, the fiber can have excellent break elongation and texture. The single-fiber fineness can be adjusted within the above range by appropriately adjusting, for example, the size of the spinneret during spinning; the draw ratio; the draw speed, etc. The single-fiber fineness can be calculated from the value obtained by measuring the total fineness of the fiber in accordance with JIS L 1013 and dividing it by the number of filaments. The total fineness of the fiber is preferably 10 to 100,000 dtex, more preferably 100 to 10,000 dtex, and even more preferably 1,000 to 5,000 dtex. When the total fineness is below the above upper limit, the fiber can have excellent handling properties. The total fineness can be adjusted within the above range by appropriately adjusting, for example, the fineness of the single filament during spinning; the number of filaments, etc. The total fineness can be determined in accordance with JIS L 1013. The cross-sectional shape of the fiber is not particularly limited and may be, for example, round, elliptical, flower-shaped, leaf-shaped, polygonal, star-shaped, Y-shaped, snowman-shaped, hollow, and cross-shaped. The fiber may be in the form of a continuous fiber (monofilament, multifilament), short fiber, yarn, string, rope, etc. It may also be in the form of a textile product such as a woven fabric, knitted fabric, or nonwoven fabric containing the fiber. Furthermore, these forms may consist only of the fiber of the present invention, or they may be composed in combination with other fibers other than the fiber of the present invention. In one embodiment, the textile product of the present invention is preferably in the form of a nonwoven fabric.

[0039] When the molded body is a pellet, the pellet may have one or more shapes selected from the group consisting of, for example, spherical, ellipsoidal, cylindrical, elliptic prism, polygonal prism, rugby ball shape, flattened, and cylindrical, and these shapes may have parts missing or convex. The pellet usually has an average external dimension of 0.1 to 20 mm, preferably 1 to 10 mm, and more preferably 2 to 8 mm. The average external dimension of the pellet refers to the average value of the external dimensions such as diameter, length, and width of the pellet, and can be determined by measuring the external dimensions at at least four points for each of any 10 pellets and calculating the average value.

[0040] If the molded body is a foam, the bubble (cell) size of the foam is preferably 0.1 to 500 μm in diameter, more preferably 1 to 300 μm, even more preferably 5 to 100 μm, and particularly preferably 10 to 80 μm.

[0041] When the molded body is a disc, its average thickness is typically 10 to 10,000 μm, preferably 100 to 1,000 μm, and more preferably 200 to 500 μm, and the average diameter of the disc is typically 1 to 10 mm, preferably 2 to 8 mm, and more preferably 3 to 5 mm.

[0042] When the molded body is a rod, its diameter is typically 0.1 to 10 mm, preferably 0.2 to 5 mm, more preferably 0.5 to 2 mm, and the average length of the rod is typically 1 to 10 mm, preferably 2 to 8 mm, more preferably 3 to 5 mm.

[0043] The average thickness of the film, the average thickness of the coating, the average external dimensions of the pellets, the average thickness and diameter of the discs, and the average diameter and length of the rods can be determined using contact-type measurement methods such as calipers or thickness gauges, or optical measurement methods such as laser displacement meters. The average thickness of the coating can also be determined by measuring the dimensions of the support using contact-type measurement methods such as calipers or thickness gauges, and then measuring the dimensions of the coating integrated with the support, and calculating the difference between these two values.

[0044] Examples of supports when a molded body which is a film or coating is integrated with a support include fibers, textile products, paper, film (hereinafter also referred to as "support film"), or metal foil. Accordingly, the present invention also covers molded bodies in which one or more molded bodies selected from the group consisting of films and coatings are integrated with a support, and the support is a fiber. The present invention further covers molded bodies in which one or more molded bodies selected from the group consisting of films and coatings are integrated with a support, and the support is one or more selected from the group consisting of textile products, paper, support film, and metal foil. The molded body which is a film (hereinafter also referred to as "molded body film") or coating may be integrated with the whole or a part of the support. For example, when the support is a textile product, paper, support film, or metal foil, one or more films and / or one or more coatings may be integrated with one or both sides of the support, across the entire surface or on a part of the surface. If the molded body includes two or more molded body films, two or more coating films, and / or two or more supports, the two or more molded body films, two or more coating films, and / or two or more supports may be the same or different from each other.

[0045] When the support is a fiber, examples of the fiber include spun yarn, staples, and filament yarn. The average fiber diameter of the fiber is, for example, 0.1 to 500 μm, preferably 0.5 to 100 μm, and more preferably 1 to 50 μm. The fiber may be in the form of continuous fibers (monofilaments, multifilaments), short fibers, threads, strings, ropes, etc. When the support is a textile product, examples of the textile product include woven fabrics, knitted fabrics, nonwoven fabrics, and fiber-reinforced plastics. The fibers constituting the textile product are, for example, the fibers listed above as examples of fibers when the support is a fiber. The plastic included in the fiber-reinforced plastic is not particularly limited and may be, for example, epoxy resin, polyester resin, or phenolic resin. The average thickness of the textile product is, for example, 1 to 500 μm, preferably 5 to 300 μm, and more preferably 10 to 100 μm. When the support is a fiber or a textile product, the molded body, which is a film or coating, can act as an adhesive for the fiber or textile product. In this case, the molded body, which is a film or coating, can improve the lubricity of the support surface and prevent thread breakage or fraying.

[0046] When the support material is paper, examples of such paper include kraft paper, glossy kraft paper, glossy bleached kraft paper, bleached kraft paper, unbleached kraft paper, fine paper, medium-quality paper, coated paper, glossy paper, imitation paper, glassine paper, Graphan paper, parchment paper, synthetic paper, white cardboard, Manila cardboard, milk carton base paper, cup base paper, ivory paper, silver paper, tissue paper, cardboard, rayon paper, wax paper, liner paper, etc. From the viewpoint of suitability for packaging applications, the basis weight of the paper should be 20 to 400 g / m². ２ Preferably, it is 25 to 150 g / m². ２ It is more preferable that the basis weight of the paper be 30 to 100 g / m², from the viewpoint of suitability for flexible packaging applications, which will be discussed later. ２ It is more preferable that the concentration be 40-70 g / m². ２ It is even more preferable that this be the case. The basis weight of the paper is measured in accordance with JIS P 8124:2011.

[0047] The above-mentioned paper can generally be manufactured by papermaking using a pulp stock containing pulp, fillers, and various auxiliary agents. Examples of pulp include chemical pulps such as bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), unbleached hardwood kraft pulp (LUKP), unbleached softwood pulp (NUKP), and sulfite pulp; mechanical pulps such as stone-ground pulp and thermomechanical pulp; wood fibers such as deinked pulp and recycled paper pulp; and non-wood fibers obtained from kenaf, bamboo, hemp, etc. These can be used individually or in combination of two or more. Among these, it is preferable to use wood fiber chemical pulp and mechanical pulp, and more preferably chemical pulp, from the viewpoint of reducing the possibility of foreign matter contamination in the base paper and the possibility of discoloration over time when recycled after use, and from the viewpoint of achieving good printing due to high whiteness and thus increasing its value (especially when used as packaging material). Other materials besides pulp can also be incorporated as auxiliary paper materials, as long as they do not impair the effects of the present invention. Examples of such materials include synthetic fibers such as rayon fibers and nylon fibers.

[0048] Examples of fillers include white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium dioxide, zeolite, and synthetic resin fillers. These can be used individually or in combination of two or more. Examples of various additives include aluminum sulfate, various anionic, cationic, nonionic, or amphoteric yield enhancers, water drainage enhancers, paper strength enhancers, and internal sizing agents, which can be used individually or in combination of two or more. Optionally, dyes, fluorescent whitening agents, pH adjusters, defoamers, pitch control agents, slime control agents, and two or more of these additives can also be used.

[0049] The method for manufacturing paper is not particularly limited, and paper can be manufactured, for example, by following the procedure below. First, a pulp stock is prepared by mixing a pulp slurry with fillers and various auxiliary agents. The pulp slurry can be prepared by beating pulp in the presence of water. The method and apparatus for beating the pulp are not particularly limited, and known beating methods and apparatus can be used. The pulp content in the pulp stock is not particularly limited. For example, it is 60% by mass or more and less than 100% by mass of the total mass of the pulp stock. Next, the prepared pulp stock is used to make paper using known wire mesh formers, on-top hybrid formers, gap former machines, etc., using acidic papermaking, neutral papermaking, or alkaline papermaking methods. After dewatering, multiple sheets of the wet paper obtained are stacked as needed, and one or more sheets of wet paper are pressed and dried to obtain paper. In this case, if multiple sheets of wet paper are not stacked, single-layer paper is obtained, and if multiple sheets of wet paper are stacked, multi-layer paper is obtained. When stacking multiple sheets of wet paper, adhesive may be applied to the surface of each sheet of wet paper (the side that will be stacked with the other sheets).

[0050] The paper may have its surface treated with various chemicals. Examples of usable chemicals include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agents, water-resistant agents, water-retaining agents, thickeners, lubricants, etc. These can be used individually or in combination of two or more. Furthermore, these various chemicals may be used in combination with pigments. Examples of pigments include inorganic pigments such as kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicates, colloidal silica, and satin white, as well as organic pigments such as solid, hollow, or core-shell types, which can be used individually or in combination of two or more.

[0051] The method of surface treatment of paper is not particularly limited. For example, it can be treated using known coating equipment such as a rod metering size press, a pound size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater.

[0052] When the support is a film, examples of such films include films (polyolefin films such as polyethylene, polypropylene, and norbornene polymers; polyvinyl alcohol films; polyethylene terephthalate (PET) films; poly(meth)acrylic acid ester films; cellulose ester films such as triacetylcellulose, diacetylcellulose, and cellulose acetate propionate; polylactic acid films; ethylene-vinyl alcohol copolymer films, etc.), sheets, etc. When the support is a metal foil, examples of such metal foils include aluminum foil, copper foil, nickel foil, etc. The average thickness of the paper, film, or metal foil used as the support is, for example, about 1 to 500 μm or 10 to 300 μm.

[0053] A molded body in which one or more molded bodies selected from the group consisting of films and coatings are integrated with one or more supports selected from the group consisting of paper, support films and metal foils corresponds to a laminate including the molded body and the support. The laminate may have one or more layers selected from the group consisting of barrier layers, protective layers and heat seal layers, as any layer at any location in its layer configuration. If the laminate has a protective layer and / or a heat seal layer, it is preferable that the layer be located on the outermost surface of the laminate. The barrier layer may be a gas barrier layer or a water vapor barrier layer, and such barrier layers are known in the art. Examples of barrier layers include resin layers and metal foils, and more specifically, resin layers containing polyvinyl alcohol, ethylene-vinyl alcohol copolymer and / or polyvinylidene chloride, layers containing glucan but not corresponding to the molded article of the present invention, aluminum foil, aluminum vapor-deposited film (aluminum vapor-deposited on a substrate such as polyethylene, polypropylene, nylon, polyethylene terephthalate, or ethylene-vinyl alcohol copolymer), alumina vapor-deposited film (alumina vapor-deposited on a substrate such as polyethylene, polypropylene, nylon, polyethylene terephthalate, or ethylene-vinyl alcohol copolymer), and silica vapor-deposited film (silica vapor-deposited on a substrate such as polyethylene, polypropylene, nylon, polyethylene terephthalate, or ethylene-vinyl alcohol copolymer). The protective layer is a layer that exists as at least a part of the outermost layer of the laminate, thereby reducing the influence of the surrounding environment on the components below the protective layer (deterioration of the components). Therefore, the protective layer may have one or more functions selected from the group consisting of barrier properties, oil resistance, solvent resistance, heat resistance, abrasion resistance, impact resistance, weather resistance, and light resistance. The protective layer can better perform the above functions by covering the entire outermost layer of the laminate. Examples of protective layers include resin layers, paper layers, and metal foils. As the heat seal layer, any known in the art can be used. The heat seal layer is preferably a resin layer having heat sealability. The heat seal layer preferably contains a water-dispersible resin and optionally additives.Examples of water-dispersible resins include polyolefin resins, styrene / acrylic copolymers, acrylic resins such as ethylene-(meth)acrylic acid copolymers, ethylene-vinyl acetate copolymers, polyester resins, rubber resins, urethane resins, polyamide resins, and combinations thereof. Examples of optional additives include lubricants such as paraffin wax, carnauba wax, and polyolefin waxes, pigments such as silica and kaolin, and combinations thereof. The heat-seal layer may have barrier properties, in which case it can function as both a heat-seal layer and a barrier layer. If the support is a film with barrier or protective properties, the film can also function as a barrier or protective layer.

[0054] One or more molded bodies selected from the group consisting of films (molded body films) and coating films are integrated with one or more supports selected from the group consisting of paper, films (support films), and metal foils, and may have any layers (barrier layer, protective layer, heat seal layer). Specific layer configurations of the molded body (laminated body) in the present invention include, for example, the following configurations. The following configurations are described starting from the outermost layer (the layer opposite to the layer that comes into contact with the contents) when used, for example, as a packaging material. Molded film or coating film / paper or support film or metal foil, gas barrier layer or water vapor barrier layer / molded film or coating film / paper or support film or metal foil, water vapor barrier layer / gas barrier layer / molded film or coating film / paper or support film or metal foil, gas barrier layer / water vapor barrier layer / molded film or coating film / paper or support film or metal foil, protective layer / molded film or coating film / paper or support film or metal foil, protective layer / gas barrier layer or water vapor barrier layer / molded film or coating film / paper or support film or metal foil, protective layer / water vapor barrier layer / gas barrier layer / molded film or coating film / paper or support film or metal foil, protective layer / gas barrier layer / water vapor barrier layer / molded film or coating film / paper or support film or metal foil, protective layer / molded film or coating film / gas barrier layer or water vapor barrier layer / paper or support film or metal foil, Protective layer / molded film or coating film / water vapor barrier layer / gas barrier layer / paper or support film or metal foil, Protective layer / molded film or coating film / gas barrier layer / water vapor barrier layer / paper or support film or metal foil, Protective layer / gas barrier layer or water vapor barrier layer / molded film or coating film / paper or support film or metal foil / gas barrier layer or water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / molded film or coating film / paper or support film or metal foil / gas barrier layer or water vapor barrier layer,Protective layer / gas barrier layer / water vapor barrier layer / molded film or coating film / paper or support film or metal foil / gas barrier layer or water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / molded film or coating film / paper or support film or metal foil / gas barrier layer / water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / molded film or coating film / paper or support film or metal foil / water vapor barrier layer / gas barrier layer, Protective layer / gas barrier layer / water vapor barrier layer / molded film or coating film / paper or support film or metal foil / gas barrier layer / water vapor barrier layer, Protective layer / gas barrier layer / water vapor barrier layer / molded film or coating film / paper or support film or metal foil / water vapor barrier layer / gas barrier layer, Layer configuration comprising a heat seal layer on the opposite side of the outermost layer in the above layer configuration, Layer configuration comprising a heat seal layer instead of a protective layer in the above layer configuration, for example, heat seal layer / molded film or coating film / paper or support film or metal foil, The aforementioned layer configuration includes one or more adhesive layers between each layer, for example, a heat seal layer / adhesive layer / molded film or coating film / paper or support film or metal foil. Known adhesives can be used for the adhesive layers described above and below, and examples include two-component reactive polyurethane adhesives containing a polyisocyanate component and a polyol portion.

[0055] Furthermore, an example of a specific layer configuration for the molded article (laminated article) in the present invention is layer (A) / layer (B) / layer (C) / layer (D) / layer (E). Layers (B), (D), and (E) may or may not be included in the laminate. The " / " indicated between layers in the example layer configuration (for example, between layer (A) and layer (B)) indicates that the layers on either side are directly laminated or laminated via an adhesive layer. Examples of layer (A) include paper, LLDPE (linear low-density polyethylene), LDPE (low-density polyethylene), HDPE (high-density polyethylene), CPE (unoriented polyethylene), polyethylene formed from polyethylene emulsion, uniaxially oriented polyethylene, biaxially oriented polyethylene, unoriented polypropylene, uniaxially oriented polypropylene, biaxially oriented polypropylene, PLA (polylactic acid), PHA (polyhydroxyalkanoic acid), PHBH®, PCL (polycaprolactone), PBAT (polybutylene adipate terephthalate), and PBS (polybutylene succinate). Examples of layer (B) include aluminum foil, aluminum vapor-deposited film, alumina vapor-deposited film, silica vapor-deposited film, PVOH (polyvinyl alcohol), EVOH (ethylene-vinyl alcohol copolymer), PVDC (polyvinylidene chloride), and nylon MXD6 (metoxylendiamine-adipic acid copolymer). Layer (C) is a molded film or coating film in the present invention. Examples of layer (D) include aluminum foil, aluminum vapor-deposited film, alumina vapor-deposited film, silica vapor-deposited film, PVOH, EVOH, PVDC, and nylon MXD6. Examples of layer (E) include paper, LLDPE, LDPE, HDPE, CPE (unoriented polyethylene), polyethylene formed from polyethylene emulsion, uniaxially oriented polyethylene, biaxially oriented polyethylene, unoriented polypropylene, uniaxially oriented polypropylene, biaxially oriented polypropylene, PLA, PHA, PHBH, PCL, PBAT, and PBS.

[0056] A more specific layer structure could be, for example, the following: Coating film / paper, LLDPE / coating film / paper, LLDPE / adhesive layer / coating film / paper, LDPE / coating film / paper, LDPE / adhesive layer / coating film / paper, HDPE / coating film / paper, HDPE / adhesive layer / coating film / paper, CPE (unoriented polyethylene) / coating film / paper, CPE (unoriented polyethylene) / adhesive layer / coating film / paper, polyethylene / coating film / paper formed from polyethylene emulsion, polyethylene / adhesive layer / coating film / paper formed from polyethylene emulsion, uniaxially oriented polyethylene / coating film / paper, uniaxially oriented polyethylene / adhesive layer / coating film / paper, biaxially oriented polyethylene / coating film / paper, biaxially oriented polyethylene / adhesive layer / coating film / paper, polypropylene / coating film / paper, polypropylene / adhesive layer / coating film / paper, uniaxially oriented polypropylene / coating film / paper, Uniaxially oriented polypropylene / adhesive layer / coating film / paper, Biaxially oriented polypropylene / coating film / paper, Biaxially oriented polypropylene / adhesive layer / coating film / paper, PLA / coating film / paper, PLA / adhesive layer / coating film / paper, PHA / coating film / paper, PHA / adhesive layer / coating film / paper, PHBH / coating film / paper, PHBH / adhesive layer / coating film / paper, PCL / coating film / paper, PCL / adhesive layer / coating film / paper, PBAT / coating film / paper, PBAT / adhesive layer / coating film / paper, PBS / coating film / paper, PBS / adhesive layer / coating film / paper.

[0057] In one embodiment of the present invention, the molded body can be preferably used as a packaging material, either on its own or integrated with a support. Accordingly, the present invention also relates to a packaging material comprising the molded body of the present invention. Here, "comprising the molded body" includes embodiments comprising a molded body (a molded body without an integrated support, or a molded body including an integrated support), and embodiments comprising a molded body and an optional component (for example, any of the above-mentioned layers). The packaging material is preferably a flexible packaging material. A flexible packaging material refers to a thin and flexible packaging material made of a highly flexible material. For example, the film (molded body film) in the present invention can be preferably used as a packaging material on its own, and in this case the film is a packaging material. For example, the molded body in the present invention, in which one or more molded bodies selected from the group consisting of films and coatings are integrated with a support, and the support is one or more selected from the group consisting of paper, film, and metal foil, can be preferably used as a packaging material. Accordingly, the present invention also covers molded bodies in which a molded body, which is one or more selected from the group consisting of films and coatings, is integrated with a support, the support is one or more selected from the group consisting of paper, films and metal foils, and the molded body is a packaging material. The packaging material may have a sheet-like shape, or it may have the shape of, for example, a tape or a pouch. The pouch is not particularly limited as long as it is capable of packaging a substance (preferably contents), and may be sealed inside or partially open. The pouch may be in the form of, for example, a two-sided pouch, a three-sided pouch, a four-sided pouch, a flat pouch, a standing pouch, a gusset pouch, a bottom gusset pouch, a twin pouch, a spout pouch, a side-seal pouch, an envelope-type seal pouch, a pillow-seal pouch, a pleated seal pouch, a flat-bottom seal pouch, a square-bottom seal pouch, or a bottom-seal pouch, or it may be in the form of a cup, tube, tray, bottle, box, lid, or container.

[0058] The molded film and the molded body in which the molded film and / or coating film are integrated with a support can be suitably used as packaging materials as described above, and can also be suitably used as packaging materials in combination with other packaging materials. Other packaging materials are not particularly limited as long as they are packaging materials other than the packaging material of the present invention. For example, if the other packaging material has the shape of a bottle, the packaging material of the present invention (e.g., in the shape of a film or a lid) can be used as a lid for the bottle into which the contents have been introduced. For example, if the other packaging material has the shape of a film, the packaging material of the present invention can be used as packaging material for packaging contents by sealing the edges of the other packaging material and the packaging material of the present invention (e.g., in the shape of a film) to form a bag-like object, introducing the contents into it, and sealing the opening.

[0059] When the molded article is a film or coating, it can have high mechanical strength, as well as excellent gas barrier properties (especially oxygen barrier properties) and / or water vapor barrier properties, due to the inclusion of specific glucans. A molded article in which a film or coating is integrated with a support can have even better gas barrier properties (especially oxygen barrier properties) and / or water vapor barrier properties, in addition to high mechanical strength, due to the film or coating. If at least one layer of the support has gas barrier properties and / or water vapor barrier properties, the molded article can have even better gas barrier properties and / or water vapor barrier properties. When a molded article having gas barrier properties and / or water vapor barrier properties is used as packaging material, the contents can be protected from deterioration due to oxidation or moisture, thereby extending the shelf life of the contents, and the emission of aromas (odors) from the contents or the transfer of aromas to the contents can be reduced. If at least one layer of the support has another function (for example, heat-sealability in the case of a heat-sealable resin film), the molded article can be given that function provided by the support.

[0060] In one embodiment of the present invention, the surface of the molded body may be flat, and from the viewpoint of preventing the molded bodies from sticking together, a part or the entire surface of the molded body may be subjected to a textured finish such as an embossed pattern or a raised and recessed pattern. Such textured finishes can be performed using methods known in the art.

[0061] The content of water-soluble glucan in a molded article containing water-soluble glucan is preferably 3 to 98% by mass, more preferably 15 to 95% by mass, even more preferably 20 to 90% by mass, even more preferably 25 to 85% by mass, particularly preferably 30 to 80% by mass, even more preferably 32 to 78% by mass, extremely preferably 40 to 75% by mass, even more preferably 50 to 75% by mass, 55 to 73% by mass, 57 to 70% by mass, 60 to 70% by mass, 61 to 70% by mass, or 62 to 69% by mass, based on the total mass of the molded article. When the content of water-soluble glucan is within the above range, the molded article can have better toughness and / or solubility in water. The content of water-soluble glucan in a molded article containing water-soluble glucan can be determined from the amount blended when manufacturing the molded article. Alternatively, it can be determined using the following formula from the concentration and amount of aqueous solution remaining inside the dialysis membrane after dissolving the molded article in water and purifying it by dialysis. Glucan content (mass%) = {[Concentration of aqueous solution remaining inside the dialysis membrane (mass%)] × [Mass of aqueous solution remaining inside the dialysis membrane (g)] / [Mass of molded body used (g)]} Note that in the case of a molded body integrated with a support, the above glucan content in the molded body refers to the glucan content in the molded body excluding the integrated support.

[0062] <Plasticizer> The molded article of the present invention may further contain a plasticizer. When the material for forming the molded article (water-soluble glucan or a composition containing water-soluble glucan, hereinafter referred to as the "material for forming the molded article") contains a plasticizer, the processability of the molded article obtained from the material for forming the molded article may be improved (for example, film formation, pouching, or spinning may be facilitated).

[0063] The plasticizer is preferably one or more selected from the group consisting of polyhydric alcohols, hydroxy acids, monosaccharides, and disaccharides. These compounds can reduce the interactions between water-soluble glucans. Furthermore, they can form a higher-order network by forming hydrogen bonds with water-soluble glucans, thereby improving the processability of the material for forming molded articles, and in particular, increasing the elongation of the molded articles obtained from the material, which can result in superior toughness.

[0064] Examples of the aforementioned polyhydric alcohols include glycerin, polyglycerin (e.g., diglycerin, triglycerin, glycerin pentamer, glycerin decamer), sorbitol, alkylene glycol (e.g., alkylene glycols having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, and neopentyl glycol), polyalkylene glycol (e.g., diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol up to 400 molecular weight, polypropylene glycol up to 400 molecular weight, etc.), trimethylolpropane, erythritol, xylitol, 2-methyl-1,3-propanediol, maltitol, mannitol, and pentaerythritol.

[0065] Examples of the aforementioned hydroxy acids include lactic acid, glycolic acid, malic acid, and tartaric acid.

[0066] Examples of the aforementioned monosaccharides include glucose, mannose, galactose, fructose, and xylose.

[0067] Examples of the aforementioned disaccharides include maltose, trehalose, sucrose, and lactose.

[0068] Among these, from the viewpoint of further increasing the stress and elongation of the resulting molded article, the plasticizer is preferably at least one selected from the group consisting of glycerin, polyglycerin (e.g., diglycerin, triglycerin, glycerin pentamer, glycerin decamer), sorbitol, alkylene glycol, neopentyl glycol, trimethylolpropane, erythritol, 2-methyl-1,3-propanediol, lactic acid, glucose, fructose, maltose, and trehalose; more preferably at least one selected from the group consisting of glycerin, polyglycerin, ethylene glycol, sorbitol, fructose, and trehalose; and even more preferably glycerin, polyglycerin, sorbitol, or trehalose.

[0069] When the molded article contains disaccharides as a plasticizer, the plasticizer content is preferably 1 to 60% by mass, more preferably 3 to 50% by mass, even more preferably 5 to 40% by mass, and particularly preferably 10 to 35% by mass or 10 to 30% by mass, based on the total mass of the molded article. When the molded article contains plasticizers other than disaccharides, the plasticizer content is preferably 2 to 90% by mass, more preferably 5 to 85% by mass, even more preferably 10 to 80% by mass, even more preferably 15 to 75% by mass, particularly preferably 20 to 70% by mass, even more preferably 22 to 68% by mass, extremely preferably 25 to 60% by mass, even more preferably 25 to 50% by mass, 25 to 45% by mass, 25 to 43% by mass, 25 to 40% by mass, 25 to 39% by mass, 28 to 35% by mass or 28 to 33% by mass, based on the total mass of the molded article. When a molded article contains a plasticizer, if the plasticizer content is within the aforementioned range, the processability and elongation of the molded article may be further improved.

[0070] In one embodiment of the present invention, where the molded article contains a plasticizer, the ratio (mass ratio) of glucan to plasticizer in the molded article is preferably 90:10 to 10:90, more preferably 85:15 to 15:85, even more preferably 80:20 to 20:80, and even more preferably 75:25 to 25:75. When the ratio is within the above range, the elongation at break and water solubility of the molded article can be further improved.

[0071] <Other Components> In addition to glucan and plasticizers, if present, the molded article may further contain other components, to the extent that they do not impede the effects of the present invention. Examples of such components include polysaccharides, polyvinyl alcohol-based resins, fillers and additives (e.g., dispersants, water, antioxidants, UV absorbers, lubricants, colorants, preservatives, surfactants, anti-adhesion agents, release agents, dyes, crosslinking agents, etc.). These components may be used individually or in combination of two or more.

[0072] In this invention, polysaccharides refer to hydrated carbonized polysaccharides other than glucans, which are composed of 10 or more monosaccharides linked together. When a molded article contains polysaccharides, it can form a higher-order network by hydrogen bonding with glucans, and in particular, the stress of the resulting molded article can be improved. Examples of polysaccharides include chitin, chitosan, cellulose, hemicellulose, dextrin, gum arabic, carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, carboxyalkylcellulose, tamarind seed gum, locust bean gum, tara gum, karaya gum, succinoglycan, and their derivatives. These polysaccharides may be used individually or in combination of two or more. Among these, from the viewpoint of further increasing the elongation at break of the molded article, the polysaccharide is preferably at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum, and their derivatives, and more preferably at least one selected from the group consisting of carrageenan and its derivatives.

[0073] Carrageenan is a polysaccharide obtained from red algae, containing repeating units of D-galactose or 3,6-anhydro-D-galactose, and also possessing sulfate groups. Carrageenan is classified into κ (kappa)carrageenan, ι (iota)carrageenan, and λ (lambda)carrageenan. These can be used individually or in combination of two or more types. As carrageenan, commercially available products such as "GENUGEL carrageenan type JPE-126" (manufactured by Sansho Co., Ltd.), "GENUTINE VCS-J" (manufactured by Sansho Co., Ltd.), "GENUVISCO CF02" (manufactured by Sansho Co., Ltd.), the "Soagina" series such as "Soagina MW210 (purified carrageenan)" and "Soagina MV320" (manufactured by Mitsubishi Chemical Corporation, purified carrageenan), and the "Soaace" series such as "Soaace MW-952 (carrageenan preparation)" (manufactured by Mitsubishi Chemical Corporation, purified carrageenan preparation) may be used.

[0074] Alginic acid is a polysaccharide obtained from brown algae and other sources, and has a structure in which D-mannuronic acid and L-guluronic acid are randomly polymerized. Commercially available products such as "Kimika Acid G" and "Kimika Acid SA" (manufactured by Kimika Co., Ltd.) may be used as alginic acid.

[0075] Guar gum is a polysaccharide obtained from the endosperm of the guar bean (Cyamopsis tetragonoloba), and has a structure in which mannose is attached to the main chain and galactose is attached to the side chains. Commercially available guar gums such as "Guapac (registered trademark)" (manufactured by MP Gokyo Food & Chemical Co., Ltd.), "RG100" (manufactured by Mitsubishi Chemical Corporation), "JAGUAR C 17K" (manufactured by Sansho Co., Ltd., cationized guar gum), and "MEYPRO-BOND 111" (manufactured by Sansho Co., Ltd., cationized guar gum) may be used.

[0076] Pectin is a polysaccharide found in plants, and has a structure in which galacturonic acid and methyl-esterified galacturonic acid (galacturonic acid that has been methyl-esterified) are linked by an α-1,4-bond, and has a carboxyl group based on galacturonic acid as an ionic functional group. As pectin, commercially available products such as "H&F Pectin Classic AM201" (manufactured by MP Gokyo Food & Chemical Co., Ltd.) may be used.

[0077] Xanthan gum is a polysaccharide produced by fermenting starch with the bacterium Xanthomonas campestris. It has a glucose main chain and a side chain containing one glucuronic acid between two mannose molecules. Commercially available xanthan gums such as "Echo Gum (registered trademark)" (manufactured by MP Gokyo Food & Chemical Co., Ltd.) and "Soaxan" (manufactured by Mitsubishi Chemical Corporation) may be used.

[0078] Examples of hydroxyalkylcellulose include hydroxyalkylcellulose having 2 to 10 carbon atoms in the hydroxyalkyl group, such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and hydroxyethylmethylcellulose, preferably hydroxyalkylcellulose having 2 to 6 carbon atoms in the hydroxyalkyl group. Examples of alkylcellulose include alkylcellulose having 2 to 10 carbon atoms in the alkyl group, such as methylcellulose, ethylcellulose, propylcellulose, and butylcellulose, and alkylcellulose having 2 to 6 carbon atoms in the alkyl group. The hydroxyalkylcellulose refers to cellulose in which one or more hydroxyl groups are modified by a hydroxyalkyl group, and the alkylcellulose refers to cellulose in which one or more hydroxyl groups are modified by an alkyl group. The carbon atoms of the hydroxyalkyl group and the carbon atoms of the alkyl group mentioned above refer to the carbon atoms of one hydroxyalkyl group and one alkyl group, respectively.

[0079] Tamarind seed gum is a polysaccharide obtained from the seeds of tamarind (Tamarindus indica), and has a structure in which glucose is the main chain and xylose and galactose are bonded to the side chains. Commercially available tamarind seed gums such as "Gliloid® 6C", "Gliloid® 3S", "Gliloid® 2A", "Glyate®" (manufactured by MP Gokyo Food & Chemical Co., Ltd.) and "TG120" (manufactured by Mitsubishi Chemical Corporation) may be used.

[0080] Locust bean gum is a polysaccharide obtained from the seeds of the carob plant (Celatonia siliqua), and has a structure in which mannose is attached to the main chain and galactose is attached to the side chains. Commercially available products such as "GENU® GUM type RL-200Z" (manufactured by Sansho Co., Ltd.), "Soarocust A120", and "MC1000" (manufactured by Mitsubishi Chemical Corporation) may be used as locust bean gum.

[0081] Tara gum is a polysaccharide obtained from the seeds of Caesalpinia spinosa, and has a structure in which mannose is attached to the main chain and galactose is attached to the side chains. Commercially available tara gum products such as "MT120" (manufactured by Mitsubishi Chemical Corporation) may be used.

[0082] Examples of polysaccharide derivatives include sodium salts, potassium salts, calcium salts, cationized compounds and their salts, anionic compounds and their salts, and acid hydrolysates. Polysaccharides may be used individually or in combination of two or more.

[0083] In one embodiment of the present invention, the number-average molecular weight of the polysaccharide (sometimes denoted as Mn) is preferably 5 kDa to 50,000 kDa, more preferably 10 kDa to 10,000 kDa, and even more preferably 10 kDa to 5,000 kDa, for example, 5 kDa to 1,000 kDa, 10 kDa to 500 kDa, or 15 kDa to 200 kDa. The weight-average molecular weight of the polysaccharide (sometimes denoted as Mw) is preferably 5 kDa to 150,000 kDa, more preferably 10 kDa to 50,000 kDa, and even more preferably 10 kDa to 30,000 kDa, for example, 10 kDa to 5,000 kDa, 30 kDa to 2,000 kDa, or 50 kDa to 1,000 kDa. When the Mn and / or Mw of the polysaccharides are within the aforementioned range, the elongation at break of the molded article can be further increased. If the molded article contains two or more types of polysaccharides, the Mn of the polysaccharides is the weighted average of the Mn of the two or more types of polysaccharides. The same applies to Mw.

[0084] In one embodiment of the present invention, for example, the molded article is a film or coating film, and is integrated with a support which is one or more selected from the group consisting of textile products, paper, film and metal foil, or which is a fiber, if the molded article contains a polysaccharide, the polysaccharide content is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, even more preferably 1 to 30% by mass, even more preferably 1.5 to 20% by mass, even more preferably 2 to 18% by mass, even more preferably 2 to 15% by mass, even more preferably 2 to 10% by mass, and particularly preferably 2 to 6% by mass, based on the total mass of the molded article. When the polysaccharide content is within the above range, the elongation at break of the molded article can be improved. In this embodiment, the polysaccharide is preferably at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum and their derivatives, and more preferably at least one selected from the group consisting of carrageenan and its derivatives.

[0085] Furthermore, in this embodiment, the ratio (mass ratio) of glucan to polysaccharide in the film or coating is preferably 99.5:0.5 to 1:99, more preferably 99:1 to 5:95, even more preferably 98:2 to 10:90, and even more preferably 97:3 to 15:85. When the ratio is within the above range, the elongation at break and flexural resistance of the film or coating can be further increased. In this embodiment, if the film or coating also contains a plasticizer, the ratio (mass ratio) of plasticizer to polysaccharide in the film or coating is preferably 99:1 to 20:80, more preferably 99:1 to 40:60, even more preferably 98:2 to 50:50, and even more preferably 97:3 to 60:40. When the ratio is within the above range, the elongation at break of the film or coating can be further increased.

[0086] In another embodiment of the present invention, for example, an embodiment in which the molded body is not integrated with a support, for example an embodiment in which the molded body exists alone, if the molded body contains a polysaccharide, the polysaccharide content is preferably 0.1 to 40% by mass, more preferably 0.1 to 35% by mass, even more preferably 1 to 30% by mass, even more preferably 5 to 28% by mass, even more preferably 10 to 28% by mass, even more preferably 13 to 25% by mass, and particularly preferably 15 to 22% by mass, based on the total mass of the molded body. When the polysaccharide content is within the above range, the stress and elongation at break of the molded body can be improved. In this embodiment, the polysaccharide is preferably at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum and their derivatives, and more preferably at least one selected from the group consisting of carrageenan and its derivatives.

[0087] In another embodiment, the ratio (mass ratio) of glucan to polysaccharide in the molded article is preferably 99.5:0.5 to 30:70, more preferably 99:1 to 40:60, even more preferably 95:5 to 50:50, and even more preferably 90:10 to 55:45. When the ratio is within the above range, the elongation at break and maximum stress of the molded article can be further increased. In another embodiment, when the molded article further contains a plasticizer, the ratio (mass ratio) of plasticizer to polysaccharide in the molded article is preferably 95:5 to 20:80, more preferably 95:5 to 30:70, even more preferably 90:10 to 35:65, and even more preferably 85:15 to 40:60. When the ratio is within the above range, the elongation at break of the molded article can be further increased.

[0088] A filler refers to a component that is incompatible with glucan. When a molded body contains a filler, it can form a higher-order network by hydrogen bonding with glucan, which can improve the stress of the resulting molded body. Furthermore, especially when a molded body is produced by coating, adding a filler to the coating solution increases the solid content concentration, allowing for a thicker coating film.

[0089] Examples of fillers include kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica (swelling mica, synthetic mica, muscovite, sericite, phlocopite, biotite, fluorinated phlocopite, red mica, soda mica, vanadine mica, illite, tin mica, paragonite, brittle mica, etc.), talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicates, bentonite (montmorillonite, bydelite, saponite, stevensite, hectorite, etc.), colloidal silica, and inorganic pigments such as satin white, as well as organic pigments such as dense, hollow, or core-shell types. Fillers may be used individually or in combination of two or more types.

[0090] When the molded article contains a filler, the total filler content is preferably 0.1 to 50% by mass, more preferably 0.5 to 35% by mass, even more preferably 1 to 30% by mass, even more preferably 1.5 to 20% by mass, even more preferably 2 to 18% by mass, even more preferably 2 to 15% by mass, even more preferably 2 to 10% by mass, and particularly preferably 2 to 6% by mass, relative to the total mass of the molded article. Furthermore, from the viewpoint of increasing the thickness of the coating film, the total filler content is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, even more preferably 10 to 75% by mass, even more preferably 20 to 70% by mass, even more preferably 30 to 65% by mass, even more preferably 40 to 60% by mass, even more preferably 42 to 58% by mass, and particularly preferably 45 to 55% by mass.

[0091] Furthermore, a dispersant may be added separately to the material for forming the molded body. The addition of a dispersant can improve the dispersibility of the filler. Cationic polymers are preferred as dispersants, and examples include polyalkylene polyamines, polyamide compounds, polyamidoamine-epihalohydrin or formaldehyde condensation reaction products, polyamine-epihalohydrin or formaldehyde condensation reaction products, polyamidopolyurea-epihalohydrin or formaldehyde condensation reaction products, polyaminepolyurea-epihalohydrin or formaldehyde condensation reaction products, polyamidoaminepolyurea-epihalohydrin or formaldehyde condensation reaction products, polyamidoaminepolyurea compounds, polyaminepolyurea compounds, polyamidoaminepolyurea compounds and polyamidoamine compounds, polyethyleneimine, polyvinylpyridine, amino-modified acrylamide compounds, polyvinylamine, polydiallyldimethylammonium chloride, and modified polyvinyl alcohol. The dispersant may be used alone or in combination of two or more types. When the molded article contains a dispersant, the dispersant content is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 1 to 5% by mass, based on the total mass of the molded article.

[0092] Examples of crosslinking agents include tannic acid and its salts, tannins other than tannic acid, catechins, anthocyanins, gallic acid and its salts, phenols, hydroquinones, and phosphoric acid.

[0093] If the molded article contains additives, the total amount of additives is, for example, 0 to 10% by mass, preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.1 to 1% by mass, relative to the total mass of the molded article.

[0094] The tensile elongation at break of a molded article, measured according to ASTM D 882, is preferably 20-1000%, more preferably 30-600%, even more preferably 50-300%, and particularly preferably 80-150% when the measurement film is dumbbell-shaped, and preferably 50-2000%, more preferably 60-1000%, even more preferably 70-600%, and particularly preferably 80-300% when the measurement film is rectangular. In the case of a molded article integrated with a support, the above tensile elongation at break of the molded article refers to the tensile elongation at break of the molded article excluding the integrated support.

[0095] [Method for producing water-soluble glucan] The water-soluble glucan of the present invention is, for example, (1) 1 × 10 ４ ~1 x 10 １０ It can be produced by a method that includes the step of reacting a raw material glucan having a weight-average molecular weight with 4-α-glucanotransferase to obtain a water-soluble glucan.

[0096] In step (1), at least a portion of the unit chains contained in the raw material glucan is cleaved by 4-α-glucanotransferase, so the weight-average molecular weight of the glucan contained in the reaction product is smaller than the weight-average molecular weight of the raw material glucan. The weight-average molecular weight of the raw material glucan is preferably 1 × 10⁻⁶. ４ ~1 x 10 １０ , more preferably 1 × 10 ５ ~5 x 10 ９ Particularly preferably 1 x 10 ６ ~1 x 10 ９This is the case. Examples of preferred raw material glucans include those corresponding to the preferred glucans exemplified in the above-mentioned paragraph on [water-soluble glucans]. That is, for example, the raw material glucan is preferably derived from one or more materials selected from the group consisting of potatoes, tapioca, corn, sweet potatoes, lily bulbs, taro, yams, lotus roots, wheat, rice, kudzu, water chestnuts, and peas, and preferably contains one or more starch derivatives selected from the group consisting of etherified starch, esterified starch, cationized starch, anionized starch, and cross-linked starch, and preferably contains modified starch.

[0097] The amylose content in the raw material glucan is preferably 0 to 90% by mass, more preferably 5 to 30% by mass, even more preferably 5 to 28% by mass, and even more preferably 6 to 25% by mass, from the viewpoint of the elongation at break of the molded article, or from the viewpoint of elongation at break and solubility in water. For example, it may be 10 to 25% by mass, 15 to 23% by mass, or 18 to 22% by mass. When two or more raw material glucans are used as raw material glucans, the amylose content refers to the average amylose content, which is a weighted average value considering the proportion of the two or more raw material glucans. The amylose content of the raw material glucan, as well as the water content, protein content, lipid content, α-1,6-bond content, and solubility in 80°C hot water, which will be described later, can be measured in the same way as the glucan measurement methods described above.

[0098] The water content in the raw material glucan is preferably 0 to 20% by mass, more preferably 5 to 15% by mass. The protein content in the raw material glucan is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, even more preferably 0 to 0.5% by mass, and may be 0% by mass. The lipid content in the raw material glucan is preferably 0 to 2% by mass, more preferably 0 to 1% by mass, even more preferably 0 to 0.2% by mass, and may be 0% by mass. The α-1,6-bond content in the raw material glucan is preferably 0.1 to 50% by mass, more preferably 0.3 to 30% by mass, even more preferably 0.5 to 10% by mass, and particularly preferably 1 to 4 mol%.

[0099] The raw material glucan is preferably water-soluble. The solubility of the raw material glucan in 80°C hot water is preferably 90% by mass or more, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and particularly preferably 98 to 100% by mass. When the raw material glucan is water-soluble, the viscosity of the aqueous solution of the raw material glucan measured at 80°C with a concentration of 10% by mass is preferably 10 to 12,000,000 mPas·sec, more preferably 100 to 10,000,000 mPas·sec, even more preferably 5,000 to 5,000,000 mPas·sec, even more preferably 10,000 to 1,000,000 mPas·sec, and particularly preferably 50,000 to 500,000 mPas·sec.

[0100] The raw material glucan may be gelatinized before the reaction in step (1). Gelatinization reduces the molecular regularity of the raw material glucan, making it more susceptible to the effects of 4-α-glucanotransferase. The method of gelatinization is not limited, and methods known in the art can be used.

[0101] 4-α-glucanotransferase is commercially available, and in this invention, commercially available 4-α-glucanotransferase can be used. From the viewpoint of the thermal stability of glucan, it is preferable to use a 4-α-glucanotransferase that produces only a small amount or almost no α-1,6-links during the reaction between the raw material glucan and the 4-α-glucanotransferase. That is, the ratio of the content of α-1,6-links in the glucan obtained by the reaction between the raw material glucan and the 4-α-glucanotransferase to the content of α-1,6-links in the raw material glucan (content of α-1,6-links in the glucan / content of α-1,6-links in the raw material glucan) is preferably 2 or less, more preferably 1.5 or less, even more preferably 1.0 or less, even more preferably less than 1.0, and particularly preferably 0.9 or less. The lower limit of the above ratio is not limited, but for example, it is 0.5 or more.

[0102] The mass ratio of the raw material glucan to 4-α-glucanotransferase is preferably 99.999:0.001 to 90:10, more preferably 99.990:0.01 to 95.000:5.00, even more preferably 99.90:0.10 to 99.000:1.00, and particularly preferably 99.80:0.20 to 99.50:0.50. When the mass ratio is within the above range, the desired water-soluble glucan can be obtained.

[0103] The reaction temperature is preferably 0 to 120°C, more preferably 20 to 100°C, even more preferably 40 to 80°C, and particularly preferably 45 to 75°C, from the viewpoint of reactivity and productivity. If step (0) described later is not included, the reaction temperature is preferably 50 to 150°C, more preferably 80 to 130°C, and particularly preferably 100 to 120°C, from the viewpoint of uniform reactivity. The reaction time can be appropriately determined depending on the type or ratio of raw material glucans, the reaction temperature, and / or the characteristics of the glucans to be produced, and is usually 0.1 to 24 hours, preferably 1 to 6 hours.

[0104] In step (1), the reaction between the raw material glucan and 4-α-glucanotransferase is preferably carried out with stirring from the viewpoint of uniform reactivity.

[0105] After the reaction in step (1), the resulting water-soluble glucan may be purified to increase its purity. The purification method is not particularly limited and can be carried out using, for example, a dialysis membrane. The dialysis membrane used should be appropriately selected depending on the target water-soluble glucan.

[0106] When producing a molded article containing a water-soluble glucan, and the molded article contains a plasticizer and / or other components, the reaction system and the plasticizer and / or other components may be mixed either simultaneously with or after step (1). The mixing method is not limited, and methods known in the art can be used. Step (1) and the above mixing yield a reaction product containing glucan, and optionally a composition containing a plasticizer and / or other components. The present invention also covers such compositions, i.e., compositions containing the glucan in the present invention, and optionally a plasticizer and / or other components. When the glucan in the present invention is water-soluble, the composition is preferably a water-soluble composition containing the glucan in the present invention, and optionally a plasticizer and / or other components. When the molded article or composition contains a plasticizer, the ratio (mass ratio) of water-soluble glucan to plasticizer contained in the molded article or composition is preferably 90:10 to 10:90, more preferably 85:15 to 15:85, even more preferably 80:20 to 20:80, and even more preferably 75:25 to 25:75. When the ratio is within the above range, the elongation at break and water solubility of the molded article can be further improved.

[0107] In one embodiment of the present invention, the composition is preferably a composition containing polysaccharides as other components, and more preferably a water-soluble composition containing polysaccharides as other components. Accordingly, the present invention also covers water-soluble compositions containing glucan and polysaccharides, wherein the glucan contains two or more unit chains, and the degree of polymerization of one or more of the two or more unit chains is 1 to 4. In this embodiment, the polysaccharides may be those exemplified in the section on "Other Components" above, or preferably those exemplified as preferred. In an embodiment in which the composition contains polysaccharides, for example, in which a molded article produced using the composition is a film or coating film integrated with a support which is one or more selected from the group consisting of textile products, paper, film and metal foil, or is a fiber, the content ratio (mass ratio) of glucan to polysaccharides contained in the composition is preferably 99.5:0.5 to 1:99, more preferably 99:1 to 5:95, even more preferably 98:2 to 10:90, and even more preferably 97:3 to 15:85. When the aforementioned content ratio is within the aforementioned range, the elongation at break and flexural resistance of the molded article produced using the composition can be further increased. In another embodiment of the present invention, where the composition contains polysaccharides, for example, an embodiment in which the molded article produced using the composition is not integrated with a support, for example, an embodiment in which the molded article exists alone, the content ratio (mass ratio) of glucan to polysaccharides contained in the composition is preferably 99.5:0.5 to 30:70, more preferably 99:1 to 40:60, even more preferably 95:5 to 50:50, and even more preferably 90:10 to 55:45. When the aforementioned content ratio is within the aforementioned range, the elongation at break and maximum stress of the molded article produced using the composition can be further increased. The molded article according to the present invention can be produced using a water-soluble composition containing the glucan according to the present invention, and optionally a plasticizer and / or other components, as described above. Therefore, matters described as preferred with respect to the molded article according to the present invention in this specification are also preferred with respect to the water-soluble composition according to the present invention, unless otherwise specifically stated.

[0108] The reaction in step (1) can also be carried out in solution. In this embodiment, the method includes step (0) of preparing a solution of the raw material glucan before step (1), carrying out the reaction in step (1) in the solution obtained in step (0), and drying the solution after the reaction to obtain a water-soluble glucan.

[0109] In step (0), the concentration of the raw material glucan in the solution is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 20 to 35% by mass, and particularly preferably 23 to 32% by mass, from the viewpoint of reactivity. The temperature when mixing the raw material glucan and the solvent to prepare the solution is usually 30 to 100°C, preferably 40 to 98°C. The mixing method is not particularly limited and may be done by conventionally known methods.

[0110] The solvent is not particularly limited, but it is preferably one or more selected from the group consisting of water, ethanol, methanol, 1-propanol, and 2-propanol, as it can dissolve the raw material glucan and the plasticizer if used, and allows for easy subsequent drying. From the viewpoint of toxicity, it is more preferably water, methanol, or a mixture thereof, and water is particularly preferred.

[0111] When producing a molded article containing a water-soluble glucan, if the method includes step (0) and the molded article contains a plasticizer and / or other components, the reaction system and the plasticizer and / or other components may be mixed simultaneously with step (0), after step (0) and before step (1), simultaneously with step (1), or after step (1). Whether the method includes step (0) or not, from the viewpoint of reactivity, it is preferable to mix the reaction system and the plasticizer and / or other components after step (1).

[0112] Step (1) yields a water-soluble glucan, and by mixing the water-soluble glucan with water, an aqueous glucan solution containing the water-soluble glucan of the present invention is obtained. Furthermore, by steps (0) and (1), when the solvent is water, an aqueous glucan solution containing the water-soluble glucan of the present invention is obtained. The present invention also covers aqueous glucan solutions containing water-soluble glucan and water. The content of water-soluble glucan in the aqueous glucan solution is not limited, but is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 20 to 35% by mass, and particularly preferably 23 to 32% by mass. The aqueous glucan solution may further contain 4-α-glucanotransferase. The mass ratio of water-soluble glucan to 4-α-glucanotransferase is not limited, but is preferably 99.999:0.001 to 90:10, more preferably 99.990:0.01 to 95.000:5.00, even more preferably 99.90:0.10 to 99.000:1.00, and particularly preferably 99.80:0.20 to 99.50:0.50.

[0113] [Method for Manufacturing a Molded Article] A molded article containing the water-soluble glucan of the present invention can be manufactured using the water-soluble glucan of the present invention. Such a molded article can be manufactured, for example, by a method for manufacturing a molded article, which includes a step of molding a molded article forming material containing the water-soluble glucan obtained in step (1). In addition to the water-soluble glucan obtained in step (1), the molded article forming material may optionally contain a plasticizer, a solvent, and other components that may be optionally included in the molded article. The molded article forming material may be the reaction system of step (1), or it may be prepared by mixing the water-soluble glucan obtained in step (1) with the above-mentioned optional components in a known manner. If the molded article does not contain the above-mentioned optional components, the molded article forming material consists of the water-soluble glucan obtained in step (1). When the molded article is a film, the temperature of the molded article forming material can be adjusted as needed, and the molten molded article forming material can be extruded from a T-die or the like onto a known substrate with release properties, and then cooled to form the film. A single-layer molded article can be manufactured, and a multi-layer molded article can also be manufactured by co-extrusion or by laminating the obtained molded articles in a known manner. If the molded body is a film, it can also be molded by adjusting the temperature of the material for forming the molded body as needed, performing inflation molding, and then cooling. Multilayer molded bodies can also be manufactured by employing co-extrusion in inflation molding. In the case of a multilayer molded body, a laminated molded body of two or more layers of the molded body (film) according to the present invention, or a laminated molded body of one or more layers of the molded body (film) according to the present invention and one or more layers other than the molded body (film) (for example, any of the above-mentioned layers) can be manufactured by the above method. If the multilayer molded body includes two or more layers of the molded body (film) according to the present invention, the films may be the same or different from each other. If the multilayer molded body includes two or more layers other than the molded body (film), the two or more layers may be the same or different from each other. If the multilayer molded body includes any of the above-mentioned layers, and the arbitrary layer is a resin layer, the multilayer molded body including the arbitrary layer can also be manufactured by coating with a solution containing the material forming the resin layer and a solvent in a general method, and then removing the solvent.

[0114] When the molded body is made of fibers, the temperature of the molding material is adjusted as needed, the molten molding material is extruded from a nozzle, and then cooled to form the molded body. When the molded body is made of pellets, discs, or rods, the temperature of the molding material is adjusted as needed, the molten molding material is extruded from an extruder into the desired shape, cut, and then cooled to form the molded body.

[0115] The temperature of the material used to form the molded body may be adjusted as needed by known methods, and the temperature should be appropriately selected according to the type of raw material glucan and the type and amount of plasticizer used. When no plasticizer is used, the temperature is preferably adjusted to 150 to 350°C, more preferably to 200 to 300°C, and even more preferably to 170 to 220°C, from the viewpoint of moldability and prevention of deterioration of the material used to form the molded body. When a plasticizer is used, the temperature is preferably adjusted to 80 to 300°C, more preferably to 120 to 250°C, and even more preferably to 150 to 200°C, from the viewpoint of moldability and prevention of deterioration of the material used to form the molded body.

[0116] If the molded body is a single-layer or multi-layer film, one or more of these films may be integrated with one or more supports selected from the group consisting of textile products, paper, film, and metal foil. The method of integration is not limited and includes, for example, a method of integration by applying water to the surface of the molded body and adhering the coated surface to the support, a method of integration of the molded body and the support by thermocompression bonding, a method of integration of the molded body and the support via an adhesive or bonding agent, and an inflation method by co-extruding the material for forming the molded body and the material for forming the support (film). When integration is performed by thermocompression bonding, the conditions can be appropriately selected depending on the type of glucan contained in the molded body and the type and amount of plasticizer if present. For example, integration can be performed by pressing at a temperature of 100 to 200°C and a pressure of 0.1 to 30 MPa for 0.1 to 10 seconds. When integration is performed via an adhesive or bonding agent, such adhesives or bonding agents are known in the art. The molded body integrated with the support may have one or more of the above-mentioned arbitrary layers at any location. Any layer can be integrated in the same manner as the support. Furthermore, if any of the layers is a resin layer, a molded body containing the desired layer and an integrated support can be manufactured by coating the resin layer with a solution containing the material and solvent that form the resin layer using a general method, and then removing the solvent.

[0117] When a molded body that is a film or a molded body integrated with a support has a shape other than a sheet, such as a tape or a pouch, a molded body having a desired shape can be obtained by processing the molded body that is a film or a molded body integrated with a support. For example, if the molded body has the shape of a pouch, it can be manufactured by a method that includes the step of sealing one or more molded bodies that are a film or a molded body integrated with a support to form a bag. A pouch containing contents can be manufactured by a method that includes the steps of putting contents into a molded body formed into a bag shape and sealing the opening; or by a method that includes the steps of forming a recess in a first molded body, putting contents into the recess, and bonding and sealing a second molded body.

[0118] Methods for sealing molded bodies include sealing by applying water to the surface of the molded body and bonding the coated surface (also called water sealing), sealing by heat compression (also called heat sealing), and sealing with an adhesive. From the viewpoint of minimizing thermal degradation of the molded body and avoiding problems caused by harmful components that may be contained in adhesives, water sealing is preferred, while from the viewpoint of versatility of the device, heat sealing is preferred.

[0119] In one embodiment of the present invention, the molded body has high adhesive strength due to moisture, making it suitable for use with water seals. In another embodiment of the present invention, the molded body has high water sealability and low heat sealability. Due to the low heat sealability, when manufacturing a film-type molded body using a roll-to-roll method, the film is less likely to adhere to the roll, effectively suppressing damage during manufacturing. Furthermore, due to the high water sealability, the manufactured molded body can be easily and simply formed into a pouch using moisture.

[0120] When employing a sealing method using heat compression, the molded body may include the heat-seal layer described above.

[0121] If the reaction in step (1) is carried out in solution, a molded body can be formed from the solution containing the reaction product in step (2). Even if the reaction in step (1) is not carried out in solution, a molded body can be formed from a solution in step (2) by preparing a solution containing the reaction product, a solvent, and optionally a plasticizer and / or other components. In this case, the same solvent as exemplified as the solvent that can be used in step (0) can be used. Since the water-soluble glucan of the present invention yields a low-viscosity aqueous solution, the solution containing the reaction product can also be a low-viscosity solution, and therefore, the solution can have excellent handling properties. Furthermore, since a low-viscosity water-soluble glucan solution can be prepared using less solvent, high productivity can be expected when removing the solvent after forming a molded body using the solution. Note that whether the reaction in step (1) is carried out in solution or not, the above solution contains the reaction product containing the glucan of the present invention, a solvent, and optionally a plasticizer and / or other components. The solution corresponds to a composition comprising glucan, solvent, and optionally a plasticizer and / or other components in the present invention.

[0122] If the molded article is a film, the film can be obtained by casting and drying a solution containing the reaction product. Casting can be performed, for example, by applying the solution containing the reaction product onto a substrate that has release properties. Such substrates are known in the art. Examples of methods for applying the solution containing the reaction product to the substrate include known methods such as spin coating, extrusion, bar coating, and applicator coating. As coaters, blade coaters, bar coaters, roll coaters, gravure coaters, reverse gravure coaters, comma coaters, air knife coaters, reverse roll coaters, curtain coaters, spray coaters, size press coaters, or gate roll coaters can be used. After casting, a dried coating is formed by removing the solvent by drying or other means. Drying methods include natural drying, forced-air drying, heat drying, and reduced-pressure drying. As a dryer, a conventional dryer can be used, and examples include steam heaters, gas heaters, infrared heaters, electric heaters, hot-air heaters, microwaves, and cylinder dryers. After that, the film can be obtained by removing the substrate. A laminate containing a film and a support can be manufactured by integrating one or more layers of the obtained film with one or more support selected from textile products, paper, film, and metal foil. As a method for integrating the film and the support, the method for integrating the film and the support exemplified in the previous paragraph can be employed. When laminating one or more of the above-mentioned arbitrary layers, the obtained film or film integrated with the support and one or more of the arbitrary layers can be integrated in any lamination order by the same method. Alternatively, one or more of the arbitrary layers may be laminated onto the support first, and then the support and film may be integrated. If the arbitrary layer is a resin layer, a film containing the arbitrary layers in any lamination order, or a film with an integrated support, can also be manufactured by coating with a solution containing the material forming the resin layer and a solvent by a general method, and then removing the solvent.

[0123] If the molded body is a coated film, the coating film can be obtained by coating a support with a solution containing the reaction product and drying it. The coating film may be single-layer or multi-layer. If it is multi-layer, the layers may be the same or different. Coating the support can be done, for example, by coating the support with a solution containing the reaction product, or by passing the support through a solution containing the reaction product. Such coatings are well known in the art, and such known coatings can be used. In this case, the support may be fibers, textile products, paper, film, or metal foil. When coating using a coater, the coaters exemplified in the previous paragraph as usable in the film manufacturing method can be used. Drying methods include natural drying, forced-air drying, heat drying, and vacuum drying. As for the dryer, the dryers exemplified in the previous paragraph as usable in the film manufacturing method can be used. If the coating film is multi-layer, coating and drying may be performed sequentially, or drying may be performed after multi-layer coating. When laminating one or more of the above-mentioned arbitrary layers, the resulting film integrated with the support and one or more of the arbitrary layers can be integrated in any lamination order using a method similar to the method of integrating the film and support as exemplified in the previous paragraph. Alternatively, one or more of the arbitrary layers may be laminated onto the support first, and then a coating film may be formed. If the arbitrary layer is a resin layer, a film with an integrated support containing the arbitrary layers in any lamination order can also be produced by coating with a solution containing the material and solvent for forming the resin layer using a general method, and then removing the solvent.

[0124] If the molded body is a fiber, the molded body can be manufactured by dry spinning or wet spinning, preferably by dry spinning, and such manufacturing methods are known in the art. For example, it can be manufactured by a method including the steps of obtaining a yarn from the material for forming the molded body by dry spinning, and stretching the obtained yarn.

[0125] In dry spinning, the volatile solvent used in the spinning stock containing the material for forming the molded body according to the present invention can be one that has been conventionally used in dry spinning, such as water, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These can be used individually or in combination of two or more. The concentration of the material for forming the molded body according to the present invention in the spinning stock may be appropriately adjusted depending on the composition of the material or the solvent used, for example, to about 5 to 85% by mass. The spinning stock is usually discharged from a known dry spinning apparatus into heated gas (e.g., an inert gas such as helium, argon, or nitrogen) or air, and solidified yarn (fiber) can be obtained by the volatilization of the solvent. The cross-sectional shape and diameter of the obtained fiber can be arbitrarily set by the shape and size of the discharge nozzle. In this step, glucan, optionally plasticizers, and other components may be mixed in the dry spinning apparatus.

[0126] The spinning solution may be preheated, preferably to a temperature of 20 to 200°C, and more preferably to 80 to 150°C. When the temperature of the spinning solution is within this range, the spinnability can be stabilized.

[0127] Stretching may be performed either by winding the solidified yarn first and then stretching it, or by performing it immediately after solidification, but in the case of the fibers of the present invention, either method may be used. The stretching operation is usually performed by heat stretching, and may be done using hot air, a hot plate, atmospheric heating, a hot roller, or any other method. The temperature when performing heat stretching is preferably 100 to 300°C, more preferably 200 to 250°C.

[0128] The stretched fibers described above are preferably wound at a speed of 100 to 10,000 m / min, more preferably 500 to 2,000 m / min. When the winding speed is within the above range, stable spinning properties can be achieved.

[0129] After spinning, one or more processing steps may be applied as long as they do not reduce the properties of the fibers (such as elongation at break or water solubility). Examples of such processing steps include applying an oil after stretching to prevent sticking, interlacing to converge the fibers, false twisting, Taslan processing, crimping, mercerization, shrinkage prevention, wrinkle prevention, dye resistance, bulking, softening, or antibacterial processing.

[0130] The composition constituting the molded article comprising the water-soluble glucan of the present invention is a water-soluble composition comprising the water-soluble glucan and other optionally included components, as described above. In one embodiment of the present invention, the composition may be a water-soluble composition comprising polysaccharides as other components, and the water-soluble composition may be a composition as described in the method for producing a molded article comprising the water-soluble glucan. In another embodiment of the present invention, the composition may be a composition comprising a polyvinyl alcohol-based resin as other components. The composition may further be a water-soluble composition comprising polysaccharides. Accordingly, the present invention also covers a water-soluble composition comprising the water-soluble glucan and a polyvinyl alcohol-based resin, wherein the glucan is a water-soluble glucan comprising α-1,3-links, α-1,4-links, and α-1,6-links.

[0131] In this invention, the polyvinyl alcohol-based resin refers to polyvinyl alcohol and modified polyvinyl alcohol. In a molded article composed of a water-soluble composition containing the above-mentioned water-soluble glucan and polyvinyl alcohol-based resin, the water-soluble glucan and the polyvinyl alcohol-based resin can form a higher-order network through hydrogen bonding, and therefore, the stress of the resulting molded article can be improved.

[0132] The viscosity-average degree of polymerization of polyvinyl alcohol-based resins is preferably 300 or higher, more preferably 400 or higher, and even more preferably 500 or higher, from the viewpoint of easily improving the mechanical properties of molded articles obtained from the resin composition. Furthermore, from the viewpoint of water solubility, it is preferably 3,000 or lower, more preferably 2,500 or lower, and even more preferably 2,000 or lower. The viscosity-average degree of polymerization of polyvinyl alcohol-based resins can be measured in accordance with JIS K 6726-1994.

[0133] The degree of saponification of the polyvinyl alcohol-based resin is preferably 60 to 100 mol%, more preferably 70 to 99.9 mol%, and even more preferably 80 to 99.7 mol%, from the viewpoint of easily improving the mechanical properties and water solubility of the molded article obtained from the resin composition. The lower limit of the degree of saponification of the polyvinyl alcohol-based resin may be, for example, 85 mol% or more, 90 mol% or more, 95 mol% or more, etc. The degree of saponification of the polyvinyl alcohol-based resin can be measured in accordance with the description in JIS K 6726-1994.

[0134] Polyvinyl alcohol-based resins are resins having vinyl alcohol constituent units and, optionally, vinyl acetate constituent units, but may also contain other constituent units other than vinyl alcohol constituent units and vinyl acetate constituent units. Other constituent units are not particularly limited, but examples include olefins such as ethylene, propylene, isobutylene, butene, pentene, hexene, heptene, and octene; acrylic acid and unsaturated monomers having acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and octadecyl acrylate; and metha. Unsaturated monomers having methacrylate esters such as lylic acid and methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, diacetoneacrylamide, 2-acrylamide Acrylamides such as do-2-methylpropanesulfonic acid and acrylamidopropyldimethylamine; methacrylamides such as methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid and methacrylamidopropyldimethylamine; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, and 2,3-diacetoxy-1-vinyloxypropane; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidenes such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate, 2,3-diacetoxy-1-allyloxypropane, and allyl chloride; unsaturated dicarboxylic acids and their salts such as maleic acid, itaconic acid, and fumaric acid;Unsaturated dicarboxylic acid esters and their salts such as monomethyl maleate, dimethyl maleate, methyl itaconate, dimethyl itaconate, methyl fumarate, and dimethyl fumarate; vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate; vinylsulfonic acid; p-styrenesulfonic acid; ammonium salts such as diallyldimethylammonium chloride, vinyltrimethylammonium chloride, allyltrimethylammonium chloride, p-vinylbenzyltrimethylammonium chloride, and 3-(methacrylamide)propyltrimethylammonium chloride; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl stearate Examples include vinyl esters such as vinyl benzoate, vinyl trifluoroacetate, vinyl pivalate, and vinyl versatate; hydroxyl group-containing constituent units such as 1,3-diacetoxy-2-methylenepropane (DAMP), 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyronyloxy-2-methylenepropane, 1,3-dihydroxy-2-methylenepropane, allyl alcohol, 3-acetoxy-1-propene, 3,4-dihydroxy-1-butene, 3,4-diacetoxy-1-butene, 4-hydroxy-2-methyl-1-butene, 4-acetoxy-2-methyl-1-butene, metharyl alcohol, and metharyl acetate; and combinations thereof.

[0135] The content of components other than vinyl alcohol components and vinyl acetate components is preferably 0.1 mol% to 40 mol%, more preferably 1 mol% to 20 mol%, and even more preferably 5 mol% to 15 mol%, relative to the total components of the polyvinyl alcohol-based resin. A content of 0.1 mol% or more of components other than vinyl alcohol and vinyl acetate components is preferable from the viewpoint of improving the water solubility of the resulting vinyl alcohol-based resin. A content of 40 mol% or less of components is preferable from the viewpoint of increasing the molecular weight of the resulting vinyl alcohol-based resin and improving the strength of the molded article.

[0136] In one embodiment of the present invention, when the water-soluble composition contains glucan and a polyvinyl alcohol-based resin, the content of the polyvinyl alcohol-based resin is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass, even more preferably 1 to 65% by mass, even more preferably 2 to 60% by mass, even more preferably 5 to 55% by mass, even more preferably 10 to 54% by mass, even more preferably 15 to 53% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the composition.

[0137] In this embodiment, the content ratio (mass ratio) of glucan to polyvinyl alcohol-based resin is preferably 99:1 to 1:99, more preferably 90:10 to 10:90, even more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

[0138] In another embodiment of the present invention, when the molded article further contains a plasticizer, the content ratio (mass ratio) of the plasticizer to the polyvinyl alcohol-based resin in the molded article is preferably 95:5 to 5:95, more preferably 90:10 to 10:90, even more preferably 80:20 to 20:80, and even more preferably 75:25 to 25:75.

[0139] <Applications> [Packaging material] In one embodiment of the present invention, the molded article or the laminate including the molded article and the support can be preferably used as a packaging material.

[0140] The packaging material is a film used for packaging, and may include thin films, thick films, etc., and may take the form of a container, pouch, cup, tube, tray, bottle, etc. In one embodiment of the present invention, the packaging material may contain a substance, preferably at least one selected from the group consisting of cleaning agents, softeners, and fragrances. Furthermore, the packaging material may contain, internally, at least one selected from the group consisting of food, preferably energy drink powder, hydration drink powder, sports drink powder and their concentrates, protein powder, hot cocoa, concentrated tea, tea leaves, mocha, concentrated fruit beverage, coffee, chicory and other beverage powders; instant foods such as flavor and texture improvers, instant noodle spice packs, and concentrated soups; bread; confectionery; kimchi; pickles; salsa; tomato paste; seasonings or preservatives such as taco powder, dried pepper, pepper paste, miso, and spices; liquid, solid, or concentrated bouillon; food ingredients such as yeast, salt, spices, food coloring, texture modifiers, wheat flour, sugar, and powdered milk; egg products such as liquid egg, egg white, and egg yolk; and additives such as cream, gelatin, fruit filling, or soy paste.

[0141] Furthermore, the packaging material is preferably a flexible packaging material. A flexible packaging material refers to a thin and flexible packaging material made of a highly flexible material. For example, the film (molded film) in the present invention can be suitably used as a packaging material on its own, and in this case the film is the packaging material. Also, the laminate in the present invention, which includes a molded body that is a film and a support, wherein the support is one or more selected from the group consisting of paper, film, and metal foil, can be suitably used as a packaging material. The packaging material can have a sheet-like shape, or it can have a shape such as tape or a pouch. The pouch is not particularly limited as long as it is in a form that can package a substance (preferably the contents), and it may be sealed inside or partially open. The pouch may take the form of, for example, a two-sided pouch, a three-sided pouch, a four-sided pouch, a flat pouch, a standing pouch, a gusset pouch, a bottom gusset pouch, a twin pouch, a spout pouch, a side-seal pouch, an envelope-type seal pouch, a pillow-seal pouch, a pleated seal pouch, a flat-bottom seal pouch, a square-bottom seal pouch, or a bottom-seal pouch, or it may take the form of a cup, tube, tray, bottle, box, lid, or container.

[0142] As described above, the molded articles and laminates of the present invention can be suitably used as packaging materials, and can also be suitably used as packaging materials in combination with other packaging materials. The other packaging materials are not particularly limited, as long as they are other than the packaging materials of the present invention. For example, if the other packaging material has the shape of a bottle, the packaging material of the present invention (e.g., in the form of a film or a lid) can be used as a lid for the bottle into which the contents have been introduced. For example, if the other packaging material has the shape of a film, the packaging material of the present invention can be used as packaging material for packaging contents by sealing the edges of the other packaging material and the packaging material of the present invention (e.g., in the form of a film) to form a bag-like object, introducing the contents into it, and sealing the opening.

[0143] [Uses other than packaging materials] The molded articles and laminates of the present invention can be suitably used not only as packaging materials but also as laundry sheets or fabric softener sheets. A laundry sheet is a sheet-shaped detergent in which detergent components are wrapped in a film or impregnated into a film. A fabric softener sheet is a sheet-shaped fabric softener in which fabric softener components are wrapped in a film or impregnated into a film. A laundry sheet or fabric softener sheet may contain one or more layers made of the molded articles of the present invention. A laundry sheet or fabric softener sheet may include one or more layers made of a film containing the water-soluble composition of the present invention and one or more layers of a known water-soluble film or water-dispersible film. A laundry sheet or fabric softener sheet may further contain laundry additives such as detergent, bleach, or bleach components.

[0144] The molded articles and laminates of the present invention can also be suitably used as cosmetic masks. A cosmetic mask is a sheet in which cosmetic ingredients are wrapped in a film or impregnated into a film. Cosmetic masks can be used as various face masks, such as sheets shaped to fit a person's face. Face masks can contain various active ingredients for moisturizing, wrinkle reduction, etc. Face masks deliver the active ingredients to target organs and decompose and dissolve over time with use. Water may be applied to the face mask before application to the face. Face masks may contain one or more personal care compositions.

[0145] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by such examples. The physical properties in the examples, comparative examples, and reference examples were measured according to the following procedure.

[0146] [Evaluation of Water-Soluble Glucan] <Analysis of α-1,3-bonds, α-1,4-bonds, and α-1,6-bonds> The glucan aqueous solution (1) prepared in Example 1 was dried to obtain water-soluble glucan (solid glucan). For examples other than Example 1, as well as comparative examples and reference examples, water-soluble glucan was obtained by drying the glucan aqueous solution prepared in the same procedure as in Example 1. The obtained water-soluble glucans were each dissolved in dimethyl sulfoxide so that the concentration of water-soluble glucan was 10% by mass. At 70°C, with a cumulative number of cycles of 4000 １３ 13C-NMR measurements were performed, and the α-1,3-bond content was quantified from the area ratio between the 83 ppm peak and the 100 ppm peak. Similarly, the α-1,6-bond content was quantified from the area ratio between the 67 ppm peak and the 100 ppm peak. The determined α-1,3-bond content corresponds to the ratio of the carbon content at position 3, which forms the α-1,3-bond, to the total carbon content at position 1, which forms the glycosidic bonds in the water-soluble glucan. Therefore, the determined content essentially corresponds to the α-1,3-bond content relative to the total number of moles of glucose units constituting the water-soluble glucan. Similarly, the determined α-1,6-bond content essentially corresponds to the α-1,6-bond content relative to the total number of moles of glucose units constituting the water-soluble glucan. The presence or absence of α-1,4-bonds can be determined by confirming the 79 ppm peak, but the α-1,4-bond content was determined by the following formula. The α-1,4-bond content shown below also essentially corresponds to the α-1,4-bond content relative to the total number of moles of glucose units constituting the water-soluble glucan. α-1,4-bond content (mol%) = 100 - (α-1,3-bond content [mol%)) Using the obtained α-1,3-bond and α-1,6-bond content, the ratio of α-1,3-bond content to α-1,6-bond content was determined.

[0147] <Solubleness of Glucan> The glucan aqueous solution (1) prepared in Example 1 was heated to 95°C and stirred for 1 hour, then cooled to room temperature. A portion of this aqueous solution was taken, dried, and the concentration of the aqueous solution (concentration A, approximately 10% by mass) was determined from the change in mass. Next, this aqueous solution was centrifuged at 3000 rpm for 10 minutes (centrifuge: Kubota Corporation, model number: 2410, rotor: RS-240), and the solution (supernatant) within 1 cm of the liquid surface was taken, dried, and the concentration of the supernatant (concentration B) was determined from the change in mass. The solubility of glucan in water was calculated using the following formula: Solubility in water (%) = (concentration B / concentration A) × 100 Examples other than Example 1, as well as comparative examples and reference examples, were evaluated in the same manner using glucan aqueous solutions prepared in the same procedure as in Example 1. The more water-soluble a glucan is, the less precipitation occurs, or the less likely precipitation is to occur during centrifugation. Therefore, the difference between concentration A and concentration B is small, and the solubility is high. A solubility of 80% or more in water was determined to be water-soluble.

[0148] <Viscosity of Glucan Aqueous Solution> A 10% by mass aqueous solution of glucan was heated to 80°C, and the viscosity was measured using a B-type viscometer (TVB-10, manufactured by Toki Sangyo Co., Ltd.) at 85°C, 0.5 to 100 rpm, and spindle No. M1 to M4 (the spindle was changed according to the viscosity, and the rotation speed was changed so that the torque was 50 to 80% of the maximum torque). The percentage decrease in viscosity with and without enzyme treatment was calculated using the following formula. For example, the viscosity of Examples 1 and 2 was compared with the viscosity of Comparative Example 1, and the percentage decrease was calculated. Percentage decrease in viscosity (%) = {(Viscosity of Comparative Example - Viscosity of Example) / (Viscosity of Comparative Example)} × 100

[0149] <Moisture Content> The molded bodies prepared in the Examples, Comparative Examples, and Reference Examples were stored for one week at 23°C and 50% RH, and their mass was measured. Then, they were dried under reduced pressure at 40°C and 1000 Pa or less until the mass became constant. The moisture content was calculated using the following formula: Moisture content (mass%) = {1 - [mass after drying (g)] / [mass before drying (g)]} × 100

[0150] <Tensile Elongation at Break, Maximum Stress, and Toughness> Molded bodies prepared in the Examples, Comparative Examples, and Reference Examples were stored for 7 days at 23°C and 50% RH humidity, and then measured according to the method described in ASTM D 882. Specifically, five rectangular test pieces, 25.4 mm wide and 127 mm long, were cut from each molded body. For each test piece, the tensile elongation at break and maximum stress were measured using an Autograph (device name: AG-5000B, manufactured by Shimadzu Corporation) with a chuck distance of 70 mm and a tensile speed of 500 mm / min. For each molded body, the average value of the measured values ​​was calculated and used as the tensile elongation at break and maximum stress of the molded body. Toughness was calculated from tensile elongation at break × maximum stress. The increase rate of toughness with and without enzyme treatment was determined using the following formula. For example, the toughness of Examples 1 and 2 was compared with the toughness of Comparative Example 1, and the increase rate was determined. Increase in toughness (%) = {(Toughness of the example - Toughness of the comparative example) / (Toughness of the comparative example)} × 100

[0151] The properties of the glucan raw materials used are shown in Table 1 below.

[0152] [Example 1] 30 g of potato starch was suspended in 90 g of pure water to a starch concentration of 25% by mass, and gelatinized by heating and stirring at 95°C for 2 hours. The temperature of the gelatinized mixture was lowered to 70°C, 0.12 g of 4-α-glucanotransferase was added, and the reaction was carried out for 3 hours. After the reaction, an aqueous solution was prepared to obtain an aqueous glucan solution (1) to a glucan concentration of 10% by mass. Sorbitol was added as a plasticizer to prepare a coating solution to which the mass ratio of glucan to sorbitol was 70:30. The coating solution was applied to a polyethylene terephthalate film with an applicator, dried with hot air for 1 hour, and the resulting dried coating film was peeled off the polyethylene terephthalate film to obtain a molded body (film) with an average thickness of approximately 80 μm.

[0153] [Examples 2-10, 13-16] Glucan aqueous solutions and molded articles (films) were obtained in the same manner as in Example 1, except that the type of raw material glucan used and / or the reaction conditions were changed as shown in Tables 2 and 3 below.

[0154] [Examples 11-12] Gelatinization and enzymatic reaction of the raw material glucan were carried out in the same manner as in Example 1, except that the type of raw material glucan used and the reaction conditions were changed as shown in Table 3 below. Then, the glucan was obtained by drying the solution after the reaction.

[0155] [Comparative Example 1] A glucan aqueous solution and a molded article (film) were obtained in the same manner as in Example 1, except that an enzymatic reaction was not performed.

[0156] [Comparative Examples 2 and 5-14, and Reference Example 1] Except for changing the type of raw material glucan used as shown in Tables 2 and 3, and not performing an enzymatic reaction, a glucan aqueous solution and a molded body (film) were obtained in the same manner as in Example 1.

[0157] [Comparative Examples 3-4] Glucan aqueous solutions and molded articles (films) were obtained in the same manner as in Example 1, except that the reaction conditions were changed as shown in Table 2.

[0158] The properties of the water-soluble glucans and molded articles were measured for the above examples, comparative examples, and reference examples. The results are summarized in Tables 2 and 3 below.

[0159]

[0160]

[0161] [Example A] Gelatinization and enzymatic reaction of the raw material glucan were carried out in the same manner as in Example 5. Next, the solution after the reaction was dried to obtain water-soluble glucan (referred to as water-soluble glucan of Example 5 in Table 4 below). 6 g of the obtained water-soluble glucan and 4 g of sorbitol were added to pure water so that the total concentration of the two was 15% by mass, and the mixture was heated and stirred at 90°C for 1 hour to dissolve. The solution (coating solution) was cooled to 25°C. The obtained coating solution was applied to paper (Solide Lucent 78gsm) as a support using a bar coater so that the thickness of the coating solution after application (hereinafter sometimes simply referred to as "thickness of the coating solution") was 133 μm. The wet coating film on the support was dried in a hot air dryer at 80°C for 30 minutes to obtain a molded body (laminated body) consisting of a coating film integrated with the support.

[0162] [Examples B-P and Comparative Examples A-D] Molded articles (laminated articles) consisting of a coating film integrated with a support were obtained in the same manner as in Example A, except that the materials and manufacturing conditions were as described in Table 4 below. Other polysaccharides (polysaccharides other than glucans) were added to pure water in the same manner as the addition of glucans and plasticizers. When coating was performed twice, the first coating was applied to the dried coating film on the support obtained by the first coating and drying, in the same manner as the first coating, and the resulting wet coating film was dried in a hot air dryer at 80°C for 30 minutes. The glucans contained in the coating films produced in Comparative Examples A-D included α-1,4-links and α-1,6-links, but did not include α-1,3-links. Furthermore, the molded articles of Examples A-P and Comparative Examples A-D, as well as the molded articles of Examples Q-U and Comparative Example E described later, were water-soluble.

[0163] [Thickness of the coating film] The thickness of the coating film was calculated using the following formula: Thickness of the coating film [μm] = Concentration of the coating solution [mass %] × Thickness of the coating solution [μm] / 100 Concentration of the coating solution [mass %] = {(Mass of the coating solution [g] - Mass of water contained in the coating solution [g]) / Mass of the coating solution [g]} × 100 The total thickness of the coating film when the coating was applied twice was calculated by replacing "thickness of the coating solution" with "total thickness of the coating solution" in the above formula.

[0164] [Water solubility of molded body] 0.1 g of molded body was added to 100 g of water and stirred at 80°C for 60 minutes. The mixture was then filtered using a filter (pore size: 21 μm), and the components that did not pass through the filter were collected, dried, and the amount of solids was measured. Solubility was calculated using the following formula. If the maximum dimensions of the molded body were 2 mm or more, it was cut to less than 2 mm using scissors or a pulverizer before being used for the test. Solubility (mass%) = {1 - [Amount of solids that did not pass through the filter (g)] / [Amount of molded body used (g)]} × 100 If the solubility was 50% by mass or more, the molded body was determined to be water soluble.

[0165] [Flexural Resistance] The laminate was bent with the coated side facing inward. A 2 kg rubber roller was passed back and forth once over the bent area (crease) from one end to the other to create a crease. Toluene colored with food coloring was applied to the 10 cm portion of the crease on the coated side, and it was checked for bleed-through to the back side (uncoated side) (small red spots or complete discoloration of the coated surface). If there was no bleed-through, the same process was repeated and checked again. The maximum number of bends without bleed-through was defined as the flexural resistance [cycles], with a maximum value of 5. The larger this value, the better the mechanical strength of the coated layer and the less likely cracks are to occur when bent.

[0166] [Oxygen Permeability (OTR)] Using an oxygen permeability measuring device (OXYSENSE MODEL 8101e manufactured by Systemch illinois), the oxygen permeability (cc / m³) of the laminate was measured under the following conditions. ２ The following measurements were taken: Temperature: 23°C; Humidity on oxygen supply side: 50% RH; Humidity on carrier gas side: 50% RH; Carrier gas flow rate: 10 mL / min; Oxygen pressure: 1.0 atm; Carrier gas pressure: 1.0 atm

[0167]

[0168] [Example Q] The steps up to the enzymatic reaction were carried out in the same manner as in Example 5. Next, the solution after the enzymatic reaction was dried to obtain a water-soluble glucan (referred to as the glucan of Example 5 in Table 5 below). The obtained water-soluble glucan, ι-carrageenan as a polysaccharide, glycerin and sorbitol as plasticizers were mixed in the proportions shown in Table 5, and the resulting mixture was mixed with pure water to prepare a coating solution. The coating solution was applied onto a polyethylene terephthalate film with an applicator and dried with hot air at 60°C for 1 hour. The resulting dried coating film was peeled off the polyethylene terephthalate film to obtain a molded body (film) with an average thickness of approximately 80 μm. The properties of the obtained molded body were measured in the same manner as above, and the results are shown in Table 5.

[0169] [Examples R to U and Comparative Example E] Molded articles (films) with an average thickness of approximately 80 μm were obtained in the same manner as in Example Q, except that the materials used were as described in Table 5 below. The properties of the obtained molded articles were measured in the same manner as above, and the results are shown in Table 5.

[0170]

[0171] [Example of synthesis of polyvinyl alcohol-based resin] 602 g of vinyl acetate, 1.21 g of methyl acrylate, and 254 g of methanol were charged into a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, and initiator addition port. The reactor was then purged with inert gas for 30 minutes while bubbling with nitrogen. The reactor temperature was increased by heating a water bath, and when the internal temperature reached 60°C, 0.16 g of azobisisobutyronitrile (AIBN) was added as an initiator to start polymerization. Sampling was performed as needed, and the progress of polymerization was confirmed from the solid content concentration. The consumption rate, which is the total mass of vinyl acetate and methyl acrylate consumed by polymerization relative to the total mass of vinyl acetate and methyl acrylate charged, was calculated. When the consumption rate reached 4%, the temperature was cooled to 30°C to stop polymerization. The reactor was connected to a vacuum line, and the remaining vinyl acetate was removed by distillation under reduced pressure at 30°C along with methanol. While visually monitoring the reactor, methanol was added as needed as the viscosity increased, and distillation was continued to obtain polyvinyl acetate containing 5.2 mol% acrylic acid constituent units. The content of acrylic acid constituent units was measured using NMR. Next, 1 g of the obtained polyvinyl acetate containing acrylic acid constituent units and 18.2 g of methanol were added to the same reactor as above and dissolved. The water bath was heated and stirred until the internal temperature reached 70°C. 0.78 g of a methanol solution of sodium hydroxide (methacustic, concentration 15% by mass) was added, and saponification was carried out at 70°C for 2 hours. The obtained solution was filtered to obtain polyvinyl alcohol containing 5.2 mol% acrylic acid constituent units. The degree of saponification measured using NMR was 99%, and the viscosity-average degree of polymerization measured from the viscosity of the aqueous solution was 1700. This polyvinyl alcohol resin was added to water, an equimolar amount of sodium hydroxide was added to the acrylic acid constituent units, and the mixture was heated to 90°C to dissolve and dried to obtain the polyvinyl alcohol resin PVOH-1.

[0172] [Example V] The steps up to the enzymatic reaction were carried out in the same manner as in Example 5. Next, the solution after the enzymatic reaction was dried to obtain a water-soluble glucan (referred to as the glucan of Example 5 in Table 6 below). The obtained water-soluble glucan, PVOH-1 as a polyvinyl alcohol-based resin, and sorbitol as a plasticizer were mixed in the proportions shown in Table 6, and a coating solution was prepared by mixing the resulting mixture with pure water. The coating solution was applied onto a polyethylene terephthalate film with an applicator and dried with hot air at 60°C for 1 hour. The resulting dried coating film was peeled off the polyethylene terephthalate film to obtain a molded body (film) with an average thickness of approximately 80 μm. The properties of the obtained molded body were measured in the same manner as above, and the results are shown in Table 6.

[0173] [Examples W, X] Molded articles (films) with an average thickness of approximately 80 μm were obtained in the same manner as in Example V, except that the materials used were as described in Table 6 below. The properties of the obtained molded articles were measured in the same manner as above, and the results are shown in Table 6.

[0174]

[0175] The water-soluble glucan of the present invention can produce a low-viscosity aqueous solution, making the aqueous solution of the water-soluble glucan of the present invention easy to handle. Furthermore, since a low-viscosity water-soluble glucan solution can be prepared using less solvent, high productivity can be expected when removing the solvent after molding a molded body using the solution, for example, when producing a film (molded body) by casting and drying the solution. In addition, the water-soluble glucan of one embodiment of the present invention has improved toughness. A molded body containing such a water-soluble glucan can be suitably used, for example, in fields such as household goods, cosmetics, stationery, food, clothing, medical products, or electronic components, either on its own as a film, packaging material (e.g., a pouch, or film as packaging material), or fiber, or integrated with a support (e.g., fiber, textile product, paper, film, and / or metal foil, etc.) as a packaging material, fiber, or textile product.

Claims

1. A water-soluble glucan containing α-1,3-links, α-1,4-links, and α-1,6-links.

2. The water-soluble glucan according to claim 1, wherein the content of α-1,3-links is 0.5 to 10 mol% relative to the total number of moles of glucose units constituting the water-soluble glucan.

3. The water-soluble glucan according to claim 1, wherein the viscosity of the aqueous glucan solution measured at 80°C when the concentration is 10% by mass is 10 to 120,000 mPa·sec.

4. The water-soluble glucan according to claim 1, wherein the water-soluble glucan is derived from one or more materials selected from the group consisting of potatoes, tapioca, corn, sweet potatoes, lily bulbs, taro, yams, lotus roots, wheat, rice, kudzu, water chestnuts, and peas.

5. The water-soluble glucan according to claim 1, wherein the water-soluble glucan is one or more selected from the group consisting of unmodified starch derived from bulbs and its derivatives.

6. The water-soluble glucan according to claim 1, wherein the water-soluble glucan is one or more selected from the group consisting of modified starch and its derivatives.

7. The water-soluble glucan according to claim 1, wherein the water-soluble glucan is one or more selected from the group consisting of seed-derived starch and its derivatives.

8. A water-soluble composition comprising the water-soluble glucan and polysaccharide described in claim 1.

9. The water-soluble composition according to claim 8, wherein the polysaccharide is at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum, and derivatives thereof.

10. An aqueous glucan solution comprising the water-soluble glucan described in claim 1 and water.

11. The aqueous glucan solution according to claim 10, wherein the water-soluble glucan content is 0.1 to 50% by mass.

12. The aqueous glucan solution according to claim 10, further comprising 4-α-glucanotransferase.

13. The glucan aqueous solution according to claim 10, further comprising a polysaccharide.

14. The aqueous glucan aqueous solution according to claim 13, wherein the polysaccharide is at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum, and derivatives thereof.

15. A molded article comprising the water-soluble glucan described in claim 1.

16. The molded article according to claim 15, further comprising a polysaccharide.

17. The molded article according to claim 16, wherein the polysaccharide is at least one selected from the group consisting of carrageenan, alginic acid, guar gum, pectin, xanthan gum, hydroxyalkylcellulose, alkylcellulose, tamarind seed gum, locust bean gum, tara gum, and derivatives thereof.

18. The molded article according to claim 15, wherein the molded article is a film, a coating, a fiber, a pellet, a foam, a disc, or a rod.

19. The molded article according to claim 15, wherein the water content is 30% by mass or less.

20. The molded article according to claim 15, wherein the tensile elongation at break, measured in accordance with ASTM D 882, is 20 to 1000%.

21. The molded article according to claim 18, wherein the molded article, which is a film or coating, is integrated with a support, and the support is a fiber.

22. The molded body according to claim 18, wherein the molded body, which is a film or coating, is integrated with a support, and the support is one or more selected from the group consisting of textile products, paper, film and metal foil.

23. A molded body according to claim 18, wherein the molded body, which is a film or coating, is integrated with a support, and the support is one or more selected from the group consisting of paper, film and metal foil, wherein the molded body integrated with the support is a packaging material.

24. The molded article according to claim 18, wherein the film is a packaging material.

25. A packaging material comprising the molded body described in claim 15.

26. A method for producing the water-soluble glucan described in claim 1, wherein (1) 1 × 10 ４ ~1 x 10 １０ A method comprising the step of reacting a raw material glucan having a weight-average molecular weight with 4-α-glucanotransferase to obtain a water-soluble glucan.

27. The method according to claim 26, wherein the mass ratio of the raw material glucan to 4-α-glucanotransferase is 99.999:0.001 to 90:

10.

28. The method according to claim 26, comprising step (0) of preparing a solution of raw material glucan before step (1), wherein the reaction in step (1) is carried out in the solution obtained in step (0), and the solution after the reaction is dried to obtain a water-soluble glucan.

29. The method according to claim 28, wherein in step (0), the concentration of the raw material glucan in the solution is 1 to 50% by mass.

30. A water-soluble composition comprising the water-soluble glucan described in claim 1 and a polyvinyl alcohol-based resin.

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