JPWO2018116936A1 - Fiberized paramylon, additive, and method for producing the additive - Google Patents

Abstract

  A fiberized paramylon derived from Euglena is provided. Also provided is an additive comprising fiberized paramylon. Moreover, the manufacturing method of an additive provided with the shearing process which forms a paramylon granule in a fiber form by fiberizing a paramylon granule with a shearing force is provided.

Description

Cross-reference of related applications

  This application claims the priority of Japanese Patent Application No. 2006-245593 and Japanese Patent Application No. 2017-171267, and these applications are incorporated in the description of the present specification by reference.

  The present invention relates to fiberized paramylon. The present invention also relates to, for example, an additive used in the food field and a method for producing the additive.

  Conventionally, the additive added as a filler to the composition containing resin is known. As this type of additive, an additive containing paramylon granules is known (Patent Document 1).

  The additive described in Patent Document 1 can be obtained by taking out paramylon granules stored by Euglena from the cells. The additive described in Patent Document 1 is blended as a filler in a composition not containing water, for example. Thereafter, the composition is formed into a composite by being formed into a plate shape and used in various industrial fields.

  However, since the additive described in Patent Document 1 contains paramylon granules, its dispersibility in water is not good, so that it is difficult to blend it into a composition for food use containing water, for example. Thus, the additive described in Patent Document 1 has a problem that dispersibility in water is not good.

Japanese Unexamined Patent Publication No. 2013-091716

  In view of such problems, the present invention provides a fiberized paramylon having relatively good dispersibility in water, an additive containing the fiberized paramylon, and a method for producing the additive. And

  In order to solve the above problems, the present invention provides a fiberized paramylon derived from Euglena. The fiberized paramylon may be in a state where a plurality of fibrous materials are gathered together by being entangled with each other. Since such fiberized paramylon is relatively uniformly and easily dispersed in water, it has a relatively good dispersibility in water, and thus has a performance of being dispersed in a liquid containing water. Such fiberized paramylon usually does not dissolve in 0.1M NaOH aqueous solution. Such fiberized paramylon has been subjected to a defibrating treatment with a shearing force.

  Moreover, in order to solve the said subject, the additive which concerns on this invention is characterized by including said fiberized paramylon. Since the additive contains a fibrous material of paramylon, the additive is relatively uniformly and easily dispersed in water, so that the dispersibility in water is relatively good.

  The additive according to the present invention may be in a solid state. The solid-state additive according to the present invention preferably further contains a water-soluble polymer compound. By further including a water-soluble polymer compound, the additive has better dispersibility in water. The additive in the solid state according to the present invention may be for dispersing in a solvent containing water.

  The method for producing an additive according to the present invention is characterized by comprising a shearing step of forming paramylon granules into fibers by fiberizing the paramylon granules with a shearing force.

Electron micrograph of fiberized paramylon. An electron micrograph of the fiberized paramylon (a partially enlarged view of FIG. 1). Electron micrograph of fiberized paramylon. Schematic showing an example of an apparatus for applying a shearing force to paramylon granules. Schematic showing the other example of the apparatus which applies a shear force to a paramylon granule. Schematic showing the other example of the apparatus which applies a shear force to a paramylon granule. Schematic showing the other example of the apparatus which applies a shear force to a paramylon granule. The external appearance photograph of the composition containing a fiberized paramylon and a paramylon granule, respectively. X-ray diffraction (XRD) chart of fiberized paramylon and paramylon granules. Optical micrograph of fiberized paramylon and cellulose dispersed in water. The photograph showing the external appearance of the composition which disperse | distributed the additive and cellulose of this embodiment to water. A photograph showing an evaluation result of a submerged settling volume. The graph showing the evaluation result of the settling volume in water. Optical micrograph of fiberized paramylon dispersed in water. The graph showing the evaluation result of the settling volume in water. Optical micrograph of fiberized paramylon dispersed in water. The graph showing the evaluation result of water retention ability. The graph showing the result (measurement result of glucose production amount) of the degradability test by (beta) -1, 3- glucanase enzyme. A photograph showing the appearance after mixing an alkaline aqueous solution with fiberized paramylon and the like. The graph showing the evaluation result of the dispersion | distribution (emulsification) stability of the composition containing an oil component. The photograph showing the external appearance of the composition containing cocoa powder.

  Hereinafter, an embodiment of the fiberized paramylon (paramylon fiber) according to the present invention will be described in detail.

  The fiberized paramylon of the present embodiment is one in which a plurality of fibrous materials are formed by fiberizing Euglena-derived paramylon granules. The fiberized paramylon includes an aggregate of a plurality of fibrous materials. The fibrous material has β-1,3-glucan microfibrils. Paramylon granules are stored in cells by the microalgae Euglena. Paramylon granules are produced by forming paramylon, which is one of β-1,3-glucans, in the form of granules in cells. Euglena will be described later.

  The fiberized paramylon includes a plurality of fibrous materials. In the above-mentioned fiberized paramylon, usually, a plurality of fibrous materials are gathered together by being entangled with each other. The above-mentioned fiberized paramylon has a network structure in which a plurality of fibrous materials are gathered to form a network. The above-mentioned fiberized paramylon has a performance of dispersing in a liquid containing water. Since the above-mentioned fiberized paramylon is relatively uniformly and easily dispersed in water, the dispersibility in water is relatively good. The submerged settling volume of the fiberized paramylon is usually 35 mL / g or more and 200 mL / g or less. The subsidence volume in water is measured by the method described in the examples.

  In addition, the settling volume in water of the fiberized paramylon in a state dispersed in water without passing through a drying step described later is usually 70 mL / g or more and 200 mL / g or less. On the other hand, the subsidence volume in water of the fiberized paramylon once in a solid state through a drying step described later is usually 35 mL / g or more and 200 mL / g or less. As for the latter, the fibrotic paramylon submerged in volume is as described in <Evaluation of dispersibility (2) Submerged subsidence volume> in the examples described later by adding the fibrotic paramylon that has become solid to water. Measured using a fiberized paramylon re-dispersed by stirring using a stirrer or the like. The method for measuring the settling volume in water will be described in detail in Examples.

  When the submerged settling volume of the above-mentioned fiberized paramylon is in the above numerical range, the above-mentioned fiberized paramylon can sufficiently hold a solution such as water in the network structure.

  The thickness of each fibrous material of the above-mentioned fiberized paramylon is usually 10 nm or more and 500 nm or less. Such thickness is preferably 20 nm or more and 300 nm or less, and more preferably 100 nm or more and 200 nm or less. Thereby, there exists an advantage that the fibrous substance of paramylon formed in the fiber form becomes easy to disperse | distribute to water more. When observed with an electron microscope (SEM), a fibrous material having a branched structure (branched structure) is observed, and a state in which the fibrous material is formed into a mesh shape is observed. The shape of the fiberized paramylon is confirmed, for example, by observing the fiberized paramylon with a microscope. In addition, said thickness is the average of the length (thickness) in the direction orthogonal to the length direction at each point at any five points in the length direction when the fibrous material is observed with a microscope. It is determined by the value.

  Specifically, the thickness of the fibrous material is measured by observing the fiberized paramylon by the following method. The mixture in which fiberized paramylon and water coexist is subjected to a treatment for replacing water with t-butanol (tert-butyl alcohol). Specifically, 0.5 to 9 times volume t-butanol of the mixture is added to the mixture of fiberized paramylon and water, and the fiberized paramylon is dispersed by a vortex mixer or the like. When a relatively large amount (for example, 9 times volume) of t-butanol is added, the solid-liquid separation treatment is then performed by centrifugation or the like, the supernatant is removed to obtain a solid content, and the solid content is converted to t-butanol. By repeating the same operation about 3 to 5 times, a test solution in which the fiberized paramylon is dispersed in t-butanol and hardly contains water is prepared. A part of the test solution is dropped on a flat plate (for example, a glass plate), and the dropped test solution is placed at a low temperature (for example, −20 ° C.) and frozen. Further, t-butanol is volatilized by a reduced pressure treatment. Thereafter, osmium plasma ion coating (thickness 20 nm) is applied, and the fiberized paramylon is observed by a general observation method using a scanning electron microscope.

  The above-mentioned fiberized paramylon has been subjected to a defibrating treatment with a shearing force. Specifically, the above-mentioned fiberized paramylon is formed by pulverizing and defibrating paramylon granules by a shearing force in the production method described later. As described above, the above-mentioned fiberized paramylon is obtained by a physical defibrating process using a shearing force.

  The paramylon granules may be subjected to chemical treatment before the above-described defibrating treatment. In this chemical treatment, treatment under conditions in which the paramylon granules are not completely dissolved (for example, treatment with a 0.25 M NaOH aqueous solution) can be performed, followed by neutralization treatment with a hydrochloric acid aqueous solution.

  The observation image of the fiberized paramylon observed with a scanning electron microscope is shown in FIGS. FIG. 2 is an enlarged view of a rectangular portion in FIG. FIG. 3 is an observation image of the fiberized paramylon produced by a production method different from the production method of the fiberized paramylon shown in FIG. In FIG. 1 to FIG. 3, 10 scales (from one end to the other end) of the lower right scale are the lengths described in each figure. In FIG. 1 to FIG. 3, it is observed that the fibrous materials of the fiberized paramylon are entangled with each other and the fibrous materials are gathered together to form a three-dimensional network. In other words, the fiberized paramylon has a network structure in which the fibrous materials are intertwined in a complex manner. In each fibrous product of fiberized paramylon, the ratio of the length in the longitudinal direction to the thickness is usually 5 to 5000. The length in the longitudinal direction of each fibrous material of fiberized paramylon is usually 3 μm or more and 100 μm or less.

  The above-mentioned fiberized paramylon usually has a crystallinity of 45% or more and 60% or less. Such a degree of crystallinity is obtained by obtaining an X-ray diffraction chart by the method described in the Examples, and further by the method described in the Examples based on the chart. The degree of crystallinity is determined by the ratio of the strength of the amorphous part to the strength of the crystal part at 2θ = 5 to 80 ° in the X-ray diffraction chart. The relative value of the degree of crystallinity of the above-mentioned fiberized paramylon relative to the degree of crystallinity of the paramylon granules (before producing the fiberized paramylon) may be 0.60 or more and 0.90 or less, and 0.60 or more and 0. .85 or less, or 0.65 or more and 0.80 or less. Note that the relative value of the crystallinity as described above is calculated from each crystallinity based on the X-ray diffraction chart measured under the same measurement conditions.

  The volume-based median diameter (D50) of the above-mentioned fiberized paramylon is usually 0.9 times or more and less than 3 times, preferably 1.0 or more times and 2.0 times or less that of the raw material paramylon granules, More preferably, it is 1.2 times or less. The median diameter is obtained by measuring the particle size with a laser diffraction / scattering particle size distribution analyzer after dispersing the sample by ultrasonic irradiation in advance. The median diameter is usually 6 μm or less. The median diameter may be 4 μm or less.

  The fibrotic paramylon is not easily decomposed into glucose by β-1,3-glucanase. In other words, the above-mentioned fibrotic paramylon is less sensitive to β-1,3-glucanase, and is less likely to be degraded by β-1,3-glucanase than, for example, chemically treated (described later) paramylon. The sensitivity to β-1,3-glucanase (easiness of being decomposed into glucose) is, for example, glucose produced by bringing β-1,3-glucanase and the above-mentioned fibrotic paramylon into contact with water at a predetermined temperature for a predetermined time. The above sensitivities can be compared based on the results. The glucose production amount of the above-mentioned fiberized paramylon can be represented by the glucose production amount [mg / g] per 1 g of fiberized paramylon. According to the method described in the examples, the glucose production amount is 30 mg / g (glucose / fibrinated paramylon) or less, preferably 10 mg / g or less. The glucose production amount is measured by the method described in the examples using a commercially available glucose determination kit described in the examples. The fiberized paramylon is less susceptible to degradation by microorganisms because it is less sensitive to β-1,3-glucanase than chemically treated paramylon.

  Moreover, said fiberized paramylon is not dissolved in an aqueous solution having a relatively high pH. For example, the above fiberized paramylon does not dissolve in a 0.1 M NaOH aqueous solution and does not dissolve in a 0.3 M NaOH aqueous solution. After mixing 250 mg of the above powdered paramylon dried powder and 10 mL of 0.3 M NaOH aqueous solution and stirring at 20 ° C. for 1 hour, the mixture is suspended (not transparent) By observing the above, it can be confirmed that the fiberized paramylon does not dissolve. On the other hand, paramylon precipitated after the paramylon granules are once dissolved in an aqueous NaOH solution or dimethyl sulfoxide is dissolved in an aqueous 0.1 M NaOH solution or an aqueous 0.3 M NaOH solution. It is confirmed whether it melt | dissolved by observing visually whether said liquid mixture is transparent or a suspension state. If it is difficult to visually confirm, it is desirable to measure the absorbance of the above mixed solution at 660 nm using a spectrophotometer, and to determine that it is dissolved if the measured value is 0.1 or less. The absorbance of pure water measured under the same conditions is used as a blank value, and the final absorbance of the mixed solution is obtained by subtracting the blank value from the absorbance of the mixed solution.

  In addition, since the chemically treated paramylon has been subjected to a treatment such as once dissolved by an alkaline aqueous solution, DMSO, or the like, β-1, It is thought that hydrogen bonds between 3-glucans are reduced. Thereby, it is considered that the chemically treated paramylon is easily decomposed by β-1,3-glucanase or easily dissolved in an alkaline aqueous solution as described above.

  The fiberized paramylon may be in a state of being dispersed in a liquid containing water, or may be in a state of being aggregated into particles without being dispersed in water. Even when the fiberized paramylon is not dispersed in water, the fiberized paramylon is relatively uniformly and easily redispersed in water, so that the dispersibility in water is relatively good. Since the fiberized paramylon dispersed in water can maintain the dispersed state for a relatively long period of time, the dispersibility in water is relatively good.

  Next, an embodiment of the additive according to the present invention will be described in detail.

  The additive of this embodiment contains the above-mentioned fiberized paramylon.

  The additive of this embodiment may be liquid (slurry or the like). The liquid additive usually contains water and the above-mentioned fiberized paramylon. Since the liquid additive contains the above-mentioned fiberized paramylon, it is usually viscous. Since the liquid additive is in a state in which the above-mentioned fiberized paramylon is already dispersed in water, the dispersibility in water is relatively good when further dispersed in water.

  The additive may be a solid. The additive in a solid state may be in the form of a tablet, for example. The additive may be, for example, a powder containing a large amount of particles. The fiberized paramylon is agglomerated into particles and contained in the additive. The size of the particles and tablets constituting the additive may be 0.4 μm or more and 10 mm or less. The additive may be composed of, for example, at least one tablet containing particles containing the above-mentioned fiberized paramylon. The water content in the solid additive is usually less than 5% by weight. The above-mentioned additive in a solid state has better redispersibility in water than a powdery additive containing, for example, cellulose fibers.

  The additive in the solid state may contain 20% by mass or more of the above-mentioned fiberized paramylon, may contain 50% by mass or more, and may contain 80% by mass. Moreover, all the additives in the above-mentioned solid state may be composed of fiberized paramylon.

  The additive in the solid state may further contain a water-soluble polymer compound. The additive in a solid state may contain 100% by mass or more of a water-soluble polymer compound with respect to the fiberized paramylon, and contains 200% by mass or more of the water-soluble polymer compound with respect to the fiberized paramylon. But you can. The content of the water-soluble polymer compound can be appropriately changed depending on the use of the additive.

  The water-soluble polymer compound is, for example, solid particles other than paramylon. The water-soluble polymer compound may be, for example, a liquid impregnated with fiberized paramylon in a solid state. Examples of the water-soluble polymer compound include cellulose derivatives (carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, etc.), xanthan gum, xyloglucan, dextrin, dextran, carrageenan, locust bean gum, alginic acid, alginate, pullulan, starch (hard starch, Scrap flour, corn starch), modified starch (cationized starch, phosphorylated starch, phosphoric acid crosslinked starch, phosphoric acid monoesterified phosphoric acid crosslinked starch, hydroxypropyl starch, hydroxypropylated phosphoric acid crosslinked starch, acetylated adipic acid crosslinked starch, acetylated phosphoric acid Cross-linked starch, acetylated oxidized starch, octenyl sodium succinate starch, acetate starch, oxidized starch), gum arabic, locust bean gum, gellan gum, polydextrose, pectin, ki , Chitosan, casein, albumin, soy protein lysate, peptone, polyvinyl alcohol, polyacrylamide, sodium polyacrylate, polyvinyl pyrrolidone, polyvinyl acetate, polyamino acid, polylactic acid, polymalic acid, polyglycerin, latex, rosin size Agent, petroleum resin sizing agent, urea resin, melamine resin, epoxy resin, polyamide resin, polyamide / polyamine resin, polyethyleneimine, polyamine, vegetable gum, polyethylene glycol, hydrophilic cross-linked polymer, polyacrylate, starch polyacrylic acid Examples thereof include at least one selected from the group consisting of a copolymer, tamarind gum, guar gum, and colloidal silica. When the additive in a solid state contains a water-soluble polymer compound, redispersibility in water can be improved.

  When an additive that is in a solid state and contains a water-soluble polymer compound is observed with an optical microscope, usually the particulate water-soluble polymer compound is not observed. Since the water-soluble polymer compound is dissolved and mixed with the fibrous material of the fiberized paramylon, the additive in the solid state in the observation image of the optical microscope has a shape of the water-soluble polymer. Does not contain polymer compounds.

  Next, an embodiment of the method for producing fiberized paramylon and additives according to the present invention will be described in detail.

  The method for producing an additive according to the present embodiment includes a shearing step of forming paramylon granules into fibers by fiberizing the paramylon granules with a shearing force. Paramylon granules can be fiberized by a shearing process.

  The additive manufacturing method according to the present embodiment includes a drying process for drying the additive obtained in the shearing process and a pulverized additive subjected to the drying process in order to manufacture a solid additive. And a pulverization process step for obtaining an additive in a solid state by performing a treatment.

  In the shearing process, for example, fiberized paramylon is obtained by applying shear force in the presence of water to paramylon granules (size of about 1 to 5 μm) stored in cells by Euglena to produce a liquid additive. .

  Further, the liquid additive is dried in the drying process, and then pulverized in the pulverization process, thereby producing the solid additive.

  The additive produced as described above can be produced relatively simply by physical treatment without chemical treatment using alkali or acid. The additive of the present embodiment does not include paramylon fiberized only by chemical treatment, but includes fiberized paramylon fiberized by physical treatment such as shearing force. The shearing step is usually performed in the presence of water, but may be performed in the presence of a solvent other than water.

  In the shearing process, the above-mentioned fiberized paramylon is prepared by defibrating the paramylon granules by physical treatment with a shearing force. In the physical treatment, the fibrillation treatment is performed without substantially breaking the hydrogen bonds of β-1,3-glucan constituting the paramylon granules. On the other hand, in the chemical treatment, paramylon is once completely dissolved in a solution such as an alkaline aqueous solution or DMSO, so that the hydrogen bond between β-1,3-glucans disappears and single-stranded β-1,3- It is thought to produce glucan. From this, the fiberized paramylon of the present embodiment is relatively likely to be relatively chemically stable because it retains the original crystal structure of the paramylon granules rather than the chemically treated paramylon. . As described above, the fiberized paramylon of the present embodiment is less soluble in an alkaline aqueous solution or the like and more difficult to be decomposed by β-1,3-glucanase than the chemically treated paramylon. Therefore, the above-mentioned fiberized paramylon is difficult to be decomposed by β-1,3-glucanase in the body when used as, for example, food, and functions due to maintaining a fibrous state (for example, the function of dietary fiber). ) Can be expected.

  In the shearing process, by applying a shear force to the paramylon granules, the paramylon granules are defibrated. Paramylon granules contain microfibrils with a thickness of a few nm. Paramylon granules have a relatively flat shape, and microfibrils are arranged in the granules so that their longitudinal directions are aligned. Inside the granule, the microfibrils are aligned and the microfibrils are bundled so that the circumferential direction of the flat shape is the longitudinal direction of the microfibrils. When a shearing force is applied to such paramylon granules, a bundle of microfibrils is separated in a direction perpendicular to the longitudinal direction of the microfibrils, and the paramylon granules are defibrated. The fiberized paramylon that has been subjected to the defibrating treatment is usually composed of microfibrils gathered together.

  In the shearing process, as shown in FIGS. 4 and 5, as a device for applying a shearing force, paramylon taken out from Euglena cells between the first member Y1 and the second member Y2 that slide relative to each other. An apparatus configured to put the raw material liquid A containing granules and water and slide the first member Y1 and the second member Y2 relative to each other can be given. Moreover, as an apparatus which applies a shear force, as shown in FIG. 6, the apparatus which injects the raw material liquid A containing a paramylon granule, and collides the raw material liquids A is mentioned. Moreover, as shown in FIG. 7, the apparatus comprised so that the raw material liquid A containing a paramylon granule may be injected and the raw material liquid A may be made to collide with the to-be-collised body X4 is mentioned. In the shearing process, each device is operated under the condition that the paramylon granules are made into a fiber (a predetermined sliding part rotation speed, sliding surface clearance, pressure, etc.).

  As shown in FIGS. 4 and 5, the first member Y1 and the second member Y2 slide relative to each other, as shown in FIGS. 4 and 5, the first member Y1 and the second member Y2 that slides with the first member Y1. With. For example, as shown in FIG. 4, the first member Y1 and the second member Y2 are both cylindrical and have the same size. One of the surfaces perpendicular to the cylinder axis direction of the first member Y1 and one of the surfaces perpendicular to the cylinder axis direction of the second member Y2 face each other. Such an apparatus is configured such that the first member Y1 and the second member Y2 rotate about the respective cylindrical axes as rotation axes. The rotation directions of the first member Y1 and the second member Y2 are opposite to each other. One member may be fixed without rotating, and the other member may be rotated. In such a device, the one surface (sliding surface) of each of the first member Y1 and the second member Y2 slides between the first member Y1 and the second member Y2 by the rotation. It is comprised so that a shear force may be added with respect to the paramylon granule in the raw material liquid A put, and a paramylon granule may be made into a fiber.

  As the above apparatus, a commercially available apparatus can be adopted. Examples of such a commercially available device include “Supermass colloider” manufactured by Masuko Sangyo Co., Ltd.

  As shown in FIG. 5, the device in which the first member and the second member slide relative to each other includes a first member Y1 and a second member Y2, and the first member Y1 and the second member Y2, respectively. The first member Y1 and the second member Y2 may be configured to slide relative to each other by the member Y2 reciprocating in one direction and the opposite direction to move relative to each other. Such an apparatus is configured so that the first member Y1 and the second member Y2 move relative to each other in the opposite directions and slide, whereby paramylon in the raw material liquid A placed between the first member Y1 and the second member Y2. It is comprised so that a shear force may be applied with respect to a granule and the paramylon granule may be made into a fiber.

  As shown in FIG. 6, the apparatus for colliding the raw material liquids A includes a first pipe X1 for injecting the raw material liquid A passing through the inside and a second pipe X2 for injecting the raw material liquid A passing through the inside. With. Nozzles are attached to the respective downstream ends of the first pipe X1 and the second pipe X2. Such an apparatus is configured to collide the raw material liquids A ejected from the nozzles through the pipes. Such an apparatus is configured such that the angle (the angle between one injection direction and the other injection direction) when the raw material liquids A collide with each other is adjusted. Such an apparatus is configured to apply a shearing force to the paramylon granules in the raw material liquid A to cause the paramylon granules to be fiberized when the raw material liquids A collide with each other.

  A commercially available device can be used. Examples of such commercially available devices include “Starburst” manufactured by Sugino Machine, “Microfluidizer” manufactured by Mizuho Industries, Ltd., and the like.

  As shown in FIG. 7, the apparatus for causing the raw material liquid A to collide with the collision object X4 has a collision with which the injection pipe X3 for injecting the raw material liquid A passing therethrough and the injected raw material liquid A collide. A body X4. A nozzle is attached to the downstream end of the injection pipe X3. The collision object X4 is formed of a material that does not absorb the injected raw material liquid A and jumps off the surface. Such an apparatus is configured to cause the raw material liquid A injected from the nozzle through the injection pipe X3 to collide with the collision target X4. Such an apparatus is configured to apply a shearing force to the paramylon granules in the raw material liquid A to cause the paramylon granules to be fiberized when the raw material liquid A collides with the collision target X4.

  Examples of devices that can be used in the shearing process other than the above devices include a twin screw kneader, a high pressure homogenizer, a high pressure emulsifier, a twin screw extruder, and a bead mill. A defibrating device or the like that performs freeze pulverization can also be used.

  In the shearing process, the additive is produced by applying a shearing force to the paramylon granules. Therefore, the fiberized paramylon and the additive can be produced relatively easily by physical treatment (defibration treatment by shearing force) without performing chemical treatment using alkali or acid.

  In the shearing process, first, a raw material liquid A containing at least paramylon granules and water is prepared. Paramylon granules are mainly composed of β-1,3-glucan made by Euglena, for example. Paramylon granules made by Euglena are usually granular. In addition, before preparing the raw material liquid A, a pretreatment using an alkali such as sodium hydroxide may be performed so that the paramylon granules are not dissolved.

Euglena is a microalgae with a size of about several micrometers to several tens of micrometers. Euglena usually lives in the water while floating in the water. Euglena is not particularly limited as long as it is a microalgae that stores paramylon granules inside cells. Examples of Euglena that stores paramylon granules inside cells include Euglena genus microalgae.

Examples of the Euglena (Euglena) genus microalgae, for example, Euglena gracilis, Euglena longa, Euglena caudata, Euglena oxyuris, Euglena tripteris, Euglena proxima, Euglena viridis, Euglena sociabilis, Euglena ehrenbergii, Euglena deses, Euglena pisciformis, Euglena spirogyra, Euglena acus , Euglena geniculata , Euglena intermedia , Euglena mutabilis , Euglena sanguinea , Euglena stellata , Euglena terricola , Euglena klebsi , Euglena rubra , or Euglena cyclopicola .

As the Euglena gracilis, for example, and the like (storage strains in later to Independent Administrative Institution National Institute for Environmental Studies microorganism strain preservation facility) Euglena gracilis NIES-48 and Euglena gracilis EOD-1.

  The above Euglena spp. Microalgae are stored in the National Institute of Environmental Studies, National Institute for Environmental Studies, Japan Patent Evaluation Microorganism Deposit Center (Postal Code 292-0818, Kisarazu-shi, Chiba Prefecture) Facility (zip code 305-8506, 16-2 Onagawa, Tsukuba, Ibaraki) or The Culture Collection of Algae at the University of Texas at Austin, USA (http://web.biosci.utexas.edu/utex/default. aspx).

  Euglena contains valuable substances such as paramylon granules, vitamins, carotenoids, and nutritious proteins in cells. Paramylon granules are usually produced in a granular state in Euglena cells.

  In the shearing step, it is preferable to prepare the raw material solution A using paramylon granules isolated from Euglena. Thereby, the density | concentration of the paramylon granule in the raw material liquid A becomes high, and the impurity in the raw material liquid A becomes comparatively few. The raw material solution A may include Euglena cells grown by culture or the like. That is, the raw material liquid A may include Euglena cells in which paramylon granules are encapsulated. As a result, the product obtained by applying the shearing force contains the components constituting Euglena cells.

  Although the density | concentration of the paramylon granule in the raw material liquid A is not specifically limited, Usually, it is 0.1-50 mass%, Preferably it is 0.5-30 mass%, More preferably, it is 1-20 mass%.

  Next, in the shearing process, for example, the raw material liquid A containing paramylon granules is put between the first member Y1 and the second member Y2 that move relative to each other while sliding, and the first member Y1 and the second member Y2 are placed. By sliding them relative to each other, a shearing force is applied to the paramylon granules in the raw material liquid A in the presence of water. As a result, a relatively large shear force can be applied to the paramylon granules, and fiberized paramylon can be obtained in a relatively short time.

  When performing a shearing process using the above-mentioned super mass colloider, for example, 500 to 3000 rpm, more preferably 1000 to 2500 rpm is employed as the rotation speed of the first member Y1 and the second member Y2. In addition, the gap between the first member and the second member (for example, a grindstone) is not particularly limited, but when using a super mass collider, the state of the gap where the grindstones are in light contact with each other (the tips of the grindstones are in slight contact with each other) For example, −10 μm to −800 μm, preferably −50 μm to −500 μm.

  The shearing force applied to the paramylon granules before being fiberized (granular) is at least a shearing force that is strong enough to defibrate the paramylon granules. By applying a shearing force as described above, the paramylon granules are defibrated and fiberized paramylon is obtained.

  Then, in the manufacturing method of the additive of this embodiment, in order to obtain the additive in a solid state, a drying treatment step and a pulverization treatment step are performed. Specifically, the additive containing fiberized paramylon in a state of being fiberized by shearing force and dispersed in water is subjected to a drying treatment. Examples of the drying process include a heat drying process, a reduced pressure drying process, a freeze drying process, and a spray drying process. In addition, a grinding process is performed. Examples of the pulverization process include a pulverization process using a ball mill and a pulverization process using a stone mortar or a mortar. Thus, the additive in the state of a solid substance is manufactured by performing a drying process and a grinding | pulverization process. The additive in a solid state may be produced by mixing the pulverized paramylon after the pulverization treatment with the above-described water-soluble polymer compound. For example, after adding the above-mentioned water-soluble polymer compound to a mixed solution containing water and fiberized paramylon dispersed in water, the above-described drying treatment step and pulverization treatment step are performed to obtain a solid matter. You may obtain the additive of the state.

  The above-mentioned solid additive is used, for example, for dispersion in a solvent containing water. Specifically, the solid additive is used, for example, by being added to food in a state where it is mixed with water and dispersed in water. Further, the solid additive is used, for example, by being added to cosmetics in a state of being mixed with water and dispersed in water. The solid additive is used by being orally administered as a pharmaceutical or applied to the skin in a state where it is mixed with water and dispersed in water, for example. The solid additive can be used by oral administration as it is.

  The solid additive produced as described above is used as follows.

  For example, the fiberized paramylon contained in the additive is dispersed in the solvent by mixing the solid additive and a solvent containing water (for example, water). The fiberized paramylon and water in the additive are mixed, for example, simply by stirring, so that the fiberized paramylon is dispersed in water relatively easily and uniformly.

  At the time of the mixing, water may be used as a solvent containing water. In addition, after preparing the organic solvent which melt | dissolves in water, and water, you may mix such a solvent and said additive. Further, oil or powder may be mixed.

  Examples of the organic solvent that can be used in the above mixing and that dissolves in water include monohydric alcohols such as ethanol, polyhydric alcohols such as glycerin, and the like.

  At the time of the mixing, the additive and the solvent containing water are usually mixed by stirring. As a means for stirring, for example, a stirring bar, a stirring blade, or the like is employed. The temperature at the time of mixing is not specifically limited, Usually, it is room temperature.

  At the time of the above mixing, the concentration of the fiberized paramylon in the composition prepared after the mixing is not particularly limited, but the concentration of the fiberized paramylon is usually 0.25% by mass or more and 40.0% by mass or less, preferably 0.8. A composition is prepared by mixing an additive and a solvent containing water so as to be 5% by mass or more and 10.0% by mass or less, more preferably 1.0% by mass or more and 5.0% by mass or less. To do. Mixing so that the concentration is 0.25% by mass or more and 40.0% by mass or less, preferably 0.5% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and 5.0% by mass or less. By doing so, there is an advantage that the fiberized paramylon can be more easily and more uniformly dispersed.

  In addition, a composition containing a predetermined concentration of fiberized paramylon (dispersion) is obtained by adding a solvent such as water to the liquid composition in which the fiberized paramylon obtained by mixing as described above is dispersed and stirring. Liquid).

  The composition prepared after the mixing includes at least the additive and water. In the above composition, the fiberized paramylon contained in the additive is dispersed in water. In addition, said composition may further contain the organic solvent, oil component, powder, etc. which melt | dissolve in water. When the above composition contains oil or powder, the oil or powder is sufficiently dispersed in water by the fiberized paramylon as an additive.

  Said additive can be utilized as a dispersing agent for disperse | distributing a to-be-dispersed material in water. The present invention also relates to such a dispersant and a composition comprising the above-described dispersant, a material to be dispersed, and water. Hereinafter, an embodiment of the composition according to the present invention will be described in detail.

  The composition of this embodiment contains said dispersing agent, to-be-dispersed material, and water. The composition of the present embodiment is a composition in which the object to be dispersed is dispersed in water by the above-described fiberized paramylon. In the composition, it is considered that the dispersion is dispersed by entanglement of the dispersion with the fibrous material between the fibrous materials of the fiberized paramylon. In addition, the composition of this embodiment may further contain the water-soluble organic solvent which melt | dissolves in water. The composition of this embodiment is usually liquid. The composition of this embodiment may be in a viscous state.

  The composition of the present embodiment can keep the state in which the dispersion is dispersed in water for a relatively long time. In other words, the composition of the present embodiment has sufficient dispersion stability by allowing the above-mentioned dispersant to maintain the state in which the dispersion is dispersed in water for a relatively long time.

  A to-be-dispersed material will not be specifically limited if it does not melt | dissolve in water. Examples of the material to be dispersed include oil or powder.

  The oil component is usually liquid at room temperature (20 ° C.). The oil may be solid at room temperature (20 ° C.). Examples of the oil include ester oil and hydrocarbon oil.

  Examples of ester oils include natural fats and oils such as vegetable oils and animal oils, and synthetic ester oils. On the other hand, examples of the hydrocarbon oil include mineral oil such as liquid paraffin.

  The above powder is an aggregate of particles. The powder is not particularly limited as long as it does not dissolve in water. Examples of the powder include inorganic powder and organic powder. Examples of the material of the inorganic powder include metal oxides (including silica and the like), clay minerals, and ceramics. Examples of the material of the organic powder include synthetic resins and polysaccharides. Examples of the organic powder include food ingredients such as kinako powder, cocoa powder, curry powder, sesame, green tea powder, and turmeric.

  When said composition contains a to-be-dispersed material, it may contain 0.01 mass% or more of fiberized paramylon. Such a composition preferably contains 0.05 mass% or more and 40.0 mass% or less of fiberized paramylon, and more preferably contains 0.1 mass% or more and 20 mass% or less.

  In the above composition, the mass ratio of the dispersion to water is preferably 0.01 or more and 70.0 or less. When the mass ratio is 0.01 or more and 70.0 or less, there is an advantage that the state in which the object to be dispersed is dispersed in water can be kept longer.

  In the above composition, the mass ratio of the fiberized paramylon to the material to be dispersed is preferably 0.000001 or more and 100 or less. When the mass ratio is 0.000001 or more and 100 or less, there is an advantage that the state in which the object to be dispersed is dispersed in water can be kept longer.

  Said composition is manufactured by mixing said dispersing agent, to-be-dispersed material, and the solvent containing water, for example. In the production of the above composition, at least water and the material to be dispersed are stirred and mixed in the presence of the above fiberized paramylon to obtain a composition in which the material to be dispersed is dispersed in water. Can do.

  Specifically, in the production of the above composition, for example, a dispersion is added to a dispersant containing a water-containing solvent such as water and fiberized paramylon, and the mixture is stirred using a mixer or the like. Get. The temperature at the time of mixing is not specifically limited, Usually, it is room temperature.

  When mixing the object to be dispersed, the water-containing solvent may contain a water-soluble organic solvent such as monohydric alcohol or polyhydric alcohol other than water. Examples of the monohydric alcohol include ethanol, and examples of the polyhydric alcohol include glycerin.

  The dispersion may be added to a dispersant containing water and mixed to disperse the dispersion in water, and then the above water-soluble organic solvent may be further added to produce the composition.

  In the production of the above composition, it is preferable that the fiberized paramylon before being mixed with the material to be dispersed is in a state of being dispersed in water. Specifically, it is preferable that the dispersant containing fiberized paramylon is in a state where moisture is not volatilized and the fiberized paramylon is dispersed in water after the paramylon granules are fiberized by the above-described method. Thereby, in the dispersing agent, since the fiberized paramylon is suppressed from aggregating with each other, the object to be dispersed can be more sufficiently dispersed in water by the fiberized paramylon.

  Said composition is used for uses, such as a foodstuff, cosmetics, or a pharmaceutical, for example. Examples of the food include beverages, supplements, confectionery, seasonings, processed meat foods, dressings, and noodles. Examples of the cosmetics include skin external cosmetics, hair cosmetics, and bathing agents. Examples of the above-mentioned pharmaceuticals include oral preparations (such as swallows), external preparations for skin (such as coatings), and skin patches (such as patches).

  The fiberized paramylon, the additive (dispersant), the method for producing the additive (dispersant), and the composition of the present embodiment are as exemplified above, but the present invention is not limited to those exemplified above.

  In addition, various modes used in general additives (dispersing agents), additive (dispersing agent) manufacturing methods, and compositions can be employed as long as the effects of the present invention are not impaired.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.

An additive (fibrinated paramylon-containing additive) was produced as follows. Specifically, by applying shear force to the paramylon granules produced by Euglena microalgae in the presence of water, the paramylon granules are fibrillated and the slurry in which the fiberized paramylon is dispersed in water (liquid addition Agent). Furthermore, an additive in a solid state (powder) was manufactured by performing a drying process and a pulverization process.
Example 1
Paramylon granules stored in cells by Euglena microalgae after culture were isolated. Paramylon granules and water were mixed so that the concentration of the isolated paramylon was 5% by mass to prepare a raw material solution containing paramylon granules.

  By using an apparatus as shown in FIG. 4 (specifically, a stone mill grinder manufactured by Masuko Sangyo Co., Ltd., product name “Supermass colloider”), between the first member (grinding stone) and the second member (grinding stone). The raw material liquid is added to the first member and the first member and the second member are slid against each other, thereby applying shearing force to the paramylon granules, fiberizing the paramylon granules, and slurry containing the fiberized paramylon (liquid additive). Manufactured.

In the production of the additive, the wet defibrating treatment in the shearing process using the above-mentioned millstone mill was performed under the following conditions.
[Defibration processing]
・ Grinder type: MKGC type ・ Clearing (gapstone clearance): −100 μm
-Grinding wheel rotation speed: 1200 rpm
A slurry containing fiberized paramylon is obtained by collecting the slurry obtained with a stone mill and obtaining a slurry by subjecting the collected slurry to defibrating again and repeating the same operation 20 times in total (20 passes). Got.

  Furthermore, this slurry (liquid additive) was subjected to freeze-drying treatment and pulverization treatment with a ball mill in order to produce a solid-state additive.

Each appearance photograph of the raw material liquid containing the slurry (liquid additive) containing fiberized paramylon and the paramylon granule before making it into fiber is shown in FIG. In addition, the observation image which observed the fiberized paramylon of Example 1 with the scanning electron microscope is already shown FIG.1 and FIG.2.
(Example 2)
A slurry-like additive containing fiberized paramylon (like in Example 1) except that the number of repetitions of the defibrating treatment described above was changed to 10 times (10 passes) instead of 20 times (20 passes). A liquid additive) was produced.
Example 3
A slurry-like additive containing fiberized paramylon (similar to Example 1) except that the number of repetitions of the defibrating process described above was changed to 5 (5 passes) instead of 20 (20 passes). A liquid additive) was produced.
(Example 4)
A slurry-like additive containing fiberized paramylon (except for the point that the number of repetitions of the defibrating process described above was changed to 15 times (15 passes) instead of 20 times (20 passes) ( A liquid additive) was produced.
(Example 5)
A shear force was applied to the paramylon granules used in Example 1 by a bead mill to fiberize the paramylon granules to produce a slurry (liquid additive) containing fiberized paramylon. The defibrating treatment with a bead mill was performed under the general operating conditions used for submicron grinding. The raw material solution containing 10% by mass of paramylon granules was defibrated by a bead mill. The observation image obtained by observing the fiberized paramylon in Example 5 with a scanning electron microscope is already shown in FIG.
(Example 6)
An additive containing a water-soluble polymer compound was produced using the slurry of Example 1 containing fiberized paramylon and dextrin (water-soluble polymer compound). In detail, dextrin was added to the slurry of Example 1, the dextrin was dissolved, and the additive in the solid state was produced by sublimating water by freeze-drying from the mixed solution after dissolution. In terms of solid content, 2 parts by mass of dextrin was mixed with 1 part by mass of fiberized paramylon.

In addition, the additive which does not contain a particulate water-soluble high molecular compound (dextrin) can be manufactured by sublimating a water | moisture content after dissolving dextrin in water, and manufacturing an additive. That is, an additive containing no dextrin in the form of particles can be produced.
(Example 7)
An additive in a solid state was produced in the same manner as in Example 6 except that 1 part by mass of dextrin was mixed with 1 part by mass of fiberized paramylon in terms of solid content.
(Example 8)
An additive in a solid state was produced in the same manner as in Example 6 except that 0.5 part by mass of dextrin was mixed with 1 part by mass of fiberized paramylon in terms of solid content.
Example 9
An additive in a solid state was produced in the same manner as in Example 6 except that 0.25 part by mass of dextrin was mixed with 1 part by mass of fiberized paramylon in terms of solid content.
(Example 10)
An additive containing a water-soluble polymer compound was produced using the slurry of Example 5 containing fiberized paramylon (prepared by a bead mill) and dextrin (water-soluble polymer compound). In detail, dextrin was added to the slurry of Example 5, the dextrin was dissolved, and the additive in the solid state was produced by sublimating water by freeze-drying from the mixed solution after dissolution. In addition, 2 mass parts dextrin was mixed with respect to 1 mass part fiberized paramylon in conversion of solid content.
(Reference example)
After sublimating moisture from the slurry of Example 1 containing fiberized paramylon to obtain a solid material of fiberized paramylon, the solid material of fiberized paramylon and dextrin powder were mixed in a dry state to obtain a solid state The additive was manufactured.
(Comparative Example 1)
The paramylon granule before performing a shearing process in Example 1 was used.
(Comparative Example 2)
The paramylon granule before performing a shearing process in Example 1 was prepared. This paramylon granule was chemically treated using the method described in JP2011-184593A. Specifically, 15 g of paramylon granules were added to 600 mL of 1M NaOH aqueous solution and dissolved with stirring for 1 hour. After dissolution, neutralization treatment was performed by adding an aqueous hydrochloric acid solution. A gel-like material was generated by the neutralization treatment. The supernatant obtained by the separation process by centrifugation was removed to obtain a solid content. Since the solid content contains a salt (NaCl) obtained by the neutralization treatment, a large amount of water is added to the obtained solid content to disperse the solid content to form a gel-like material. By performing the separation process by separation, the salt contained in the gel-like material was removed. The salt removal treatment was repeated until the dry mass of NaCl contained in the gel-like material was 0.1% by mass or less per dry weight of the paramylon granules dissolved in the 1M NaOH aqueous solution to produce chemically treated paramylon. The dry weight of NaCl contained in the gel was determined by calculating the NaCl concentration of the supernatant after centrifugation from the electrical conductivity of the supernatant. In addition, according to the following literature, as a result of observing this chemically treated paramylon with an electron microscope, the chemically treated paramylon was not in the form of a fiber but a mass having an indefinite shape or size.
・ Literature title “2014 Strategic Substrate Technology Advancement Support Research and Development on Advanced Culture Production Technology and Utilization of Polysaccharide Paramylon (Report on Research and Development Results March 2015)”
<Crystallinity of fiberized paramylon>
For the fiberized paramylon of the additive produced in Example 1 and the paramylon granules of Comparative Example 1, the crystallinity was measured by X-ray diffraction (XRD). The measurement conditions are as follows.

Measuring instrument: PANalytical X'Pert ³ Powder
Tube voltage: 45kV
Tube current: 40mA
Measurement range: 5-80 °
Analysis software: HighScore (product name)
An X-ray diffraction chart obtained by the measurement is shown in FIG. The degree of crystallinity of the fiberized paramylon and the paramylon granules is to analyze the ratio (B / A) between the strength (A) of the amorphous part and the strength (B) of the crystalline part at 2θ = 5 to 80 °. Sought by. In the analysis, the background of each chart was removed (background setting: Auto, bending factor: 0, granularity: 100), and then a curve representing an amorphous part was determined. The curve representing the amorphous part was determined so as to pass through the tangent of the chart at 2θ = 14 ° and 29 °. The values of the bending factor and granularity employed to determine the curve representing the amorphous part were 0/30 (fibrinated paramylon) and 0/20 (paramylon granules). As a result, the crystallinity of the fiberized paramylon was 51.0%, and the crystallinity of the paramylon granules was 66.2%. Therefore, the relative value (ratio) of the crystallinity of the fiberized paramylon relative to the crystallinity of the paramylon granules was 0.77. The crystallinity of the chemically treated paramylon of Comparative Example 2 was 37.6%.
<Evaluation of dispersibility (1)>
A composition was produced by mixing the solid additive of Example 1 produced as described above and water, and the dispersibility of the fiberized paramylon was evaluated.

Specifically, fiberized paramylon and water were mixed in a sample bottle by stirring with a stirrer and a stirrer so that the concentration of paramylon in the composition was 3% by mass. Stirring with a stir bar and stirrer was performed under the following conditions. Dispersibility was evaluated by continuing stirring for a predetermined time (1, 3, 5, 24 hours) and visually observing the appearance of the composition after standing.
[Stirring]
・ Stirrer: PTFE, total length 15mm x diameter 1.5mm
・ Rotation speed: 300 to 1000 rpm (stirrer display value)
In addition, the thing which performed the drying process and the grinding | pulverization process similar to the above to the commercially available fibrous cellulose dispersion liquid (what disperse | distributed fibrous cellulose in water) was used as a comparison object. Details are as follows.

Example 1: Additives obtained from the slurry (in the state of solids)
Cellulose 1: Dispersion manufactured by Sugino Machine Co., Ltd. Product name “BiNFi-s FMa-10002” subjected to drying treatment and grinding treatment (fiber length is about 1 μm)
Powdered Cellulose 2: Dispersion manufactured by Sugino Machine Co., Ltd. Product name “BiNFi-s WMa-10002” subjected to drying and pulverization (fiber length is longer than FMa-10002 above) Not semi-solid)
FIG. 10 shows optical micrographs of fiberized paramylon and cellulose after stirring for 24 hours in the above evaluation using Example 1, and cellulose 1 and cellulose 2, respectively.

  A photograph of the appearance of the composition when the above evaluation is performed is shown in FIG. As can be seen from FIG. 11, when the additive of Example 1 (including the solid state fiberized paramylon) was dispersed in water, it was more uniform than the solid comparative object containing cellulose. It could be easily dispersed. That is, with the additive of Example 1, uniform and good dispersion was confirmed when the composition was produced by mixing with water. When the viscosities of the compositions were compared, the case where the fiberized paramylon was dispersed was sufficiently higher than the case where the cellulose was dispersed.

Next, in order to evaluate the dispersibility, an experiment was conducted as follows using the settled volume in water as an index. In addition, the measuring method of the settling volume in water is generally known as a method for evaluating the performance of insoluble dietary fiber. Details of the measurement of the settling volume in water are shown in <Evaluation of dispersibility (2)> below.
<Evaluation of dispersibility (2) Settling volume in water>
The measurement was performed according to the method of Takeda-Kiriyama “Satoshi Inami, Shuhachi Kiriyama (1995) Dietary Fiber, p. 64 Daiichi Shuppan, Tokyo”.

  Specifically, 250 mg of each slurry-like test sample was weighed out into a 25 mL plastic tube in terms of dry mass, and the plastic tube was shaken vigorously by hand to stir the contents. Thereafter, the contents were transferred to a graduated cylinder having a volume of 25 mL, and pure water was added to 25 mL. The liquid in the graduated cylinder was stirred and then allowed to stand at 37 ° C. for 24 hours. In addition, in the slurry-like test sample of Example 1, since the interface was not visible, 125 mg was measured in terms of dry mass to measure the interface, and the dispersibility was evaluated by the same method as described above. .

  Using each of the test samples of Examples 1 to 3, Example 5, and Comparative Examples 1 and 2 (slurry “before drying”), the above <evaluation of dispersibility (2) settling volume in water> was performed. . The results are shown in Table 1. In addition, FIG. 12 shows the results of the evaluation of the “before drying” sample (external appearance photograph after dispersion, excluding Example 5). “Before drying” indicates the result of evaluation using the slurry-like test sample produced in each example as it is. “After drying” means that a slurry-like test sample produced in each example or the like was once freeze-dried to obtain a solid, and the obtained solid was redispersed in water for evaluation. The results are shown. In the case of the test sample “after drying”, stirring was performed under the conditions described in <Evaluation of Dispersibility (1)>.

  As understood from FIG. 12, in the additives of Examples 1 to 3, the dispersed state of the fiberized paramylon is more uniform and the dispersed state than the comparative object of Comparative Example 1 and Comparative Example 2. It was kept for a relatively long time.

  By the way, without isolating paramylon granules from Euglena microalgae after culture, the Euglena microalgae itself (with paramylon granules in the cells) after culture is 10% by mass in terms of dry mass. Even when mixed with water and fibrillated the paramylon granules in the cells by the method described in Example 5 (using a bead mill), the same fibrillated paramylon as in the above example could be obtained. That is, it was possible to obtain the same fiberized paramylon as in the above examples without isolating the paramylon granules after culturing. The subsidence volume of the fiberized paramylon obtained by such a method was substantially the same as the subsidence volume of the fiberized paramylon obtained in Example 5 in the sample before drying.

<Evaluation of dispersibility (3) Settling volume in water Influence of water-soluble polymer>
Using each test sample of Example 1 (slurry state), Examples 6 to 9 (solid state), and Reference Example (solid state), the above <Evaluation of Dispersibility (2) The same evaluation as in <Settling volume> was performed. However, for each of the test samples of Examples 6 to 9 and the reference example, the solids were not redispersed in water by stirring using a stirrer, and each test sample in a solid state was put in water. Simply mix and keep to water. The graphed results are shown in FIG. FIG. 14 shows an observation image obtained by observing the state in which the fiberized paramylon is dispersed with an optical microscope. In FIG. 14, the state in which the sample of Example 1 “before drying” is dispersed in water is shown on the left side, and the state in which the sample (containing dextrin) of Example 6 “after drying” is dispersed in water is shown on the right side. Is shown in In FIG. 14, the lower right line segment of each photograph indicates a length of 50 μm.

  As can be seen from FIG. 13, in the additives of Examples 6 to 9, the dispersion state of the fiberized paramylon approached more uniformly as the mass ratio of the polymer compound to the fiberized paramylon increased. The additives of Examples 6 to 9 had relatively good dispersibility in water without being actively stirred.

  As can be understood from the results of the reference example in FIG. 13, an additive (reference example) in a solid state containing fiberized paramylon and particulate dextrin is dispersed in water without stirring by a stirrer. When done, the dispersibility in water was not very good. Dispersibility in water without stirring is not so high as in this reference example, but on the other hand, by stirring and dispersing in water, the settling volume in water is greatly improved as in Example 1. To do. From this, also in Examples 6 to 9 dispersed in water without stirring by a stirrer, it is expected that the settling volume in water will be greatly improved if dispersed in water while stirring.

  Using each test sample of Example 5 (slurry state) and Example 10 (solid state) prepared using a bead mill, <Evaluation of Dispersibility (2) Settling Volume in Water> The same evaluation was performed. The graphed results are shown in FIG. FIG. 16 shows an observation image obtained by observing the state in which the fiberized paramylon is dispersed with an optical microscope. In FIG. 16, the state in which the sample of Example 5 “before drying” is dispersed in water is shown on the left side, and the state in which the sample (containing dextrin) of Example 10 “after drying” is dispersed in water is shown on the right side. Is shown in In FIG. 16, the lower right line segment of each photograph shows a length of 50 μm.

  As can be seen from FIG. 15, in the additives of Examples 5 and 10, the dispersion state of the fiberized paramylon was relatively good. That is, the additives of Examples 5 and 10 were relatively good in water dispersibility.

It is considered that the result of the settling volume in water has a positive correlation with the water retention capacity. From the results of the submerged settling volume, it can be confirmed that the fiberized paramylon of the Examples has a greater water holding capacity than the paramylon granules.
<Evaluation of water retention>
Using each test sample of Example 1 and Comparative Examples 1 and 2, water retention was evaluated as follows.

  The constant weight of a glass centrifuge tube (50 mL) was measured. 0.5 g of each test sample in terms of dry mass was put into this glass centrifuge tube, and 40 mL of pure water was further added. After stirring this well, it was allowed to stand for 12 hours or more. Thereafter, centrifugation (1000 G, 5 minutes) was performed twice, and the supernatant was removed to obtain a pellet. The moisture in the pellet was removed by drying at 105 ° C. for 24 hours or more. From the mass change before and after the drying treatment, the water retention amount (water retention [g water / g]) per dry mass was determined. The water retention capacity was determined by the following formula.

Water retention (g water / g) = (Mass change before and after drying treatment (g) / Dry weight of each sample (g))
In addition, the independent test was implemented 3 times and the water retention power was calculated | required by averaging each measured value. However, in the evaluation using Comparative Example 1, the measurement was performed only once.

  The evaluation results of water retention capacity are shown in FIG.

As can be seen from FIG. 17, the additive of Example 1 was superior in water retention capacity to the comparative object of Comparative Example 1 and Comparative Example 2.
<Measurement of particle size distribution>
After diluting the additives of Examples 1, 2, 4 and Comparative Example 1 with water so as to be 0.1 to 0.2% by mass in terms of dry matter, respectively, and then dispersing by ultrasonic irradiation The particle size distribution was measured using a laser diffraction / scattering particle size distribution measuring device (LS200, manufactured by Beckman Coulter, Inc.). The median diameter (D50) and average diameter on a volume basis were determined. The results are shown in Table 2.

  While the fiberized paramylon of the examples has a three-dimensional structure intricately entangled with each other, the median diameter and average diameter of the fiberized paramylon are close to the median diameter and average diameter of the paramylon granules.

  From the results in Table 2, the median diameter of the fiberized paramylon is 4 μm or less, and the ratio of the median diameter of the fiberized paramylon to the median diameter of the paramylon granules (median diameter of the fibrillated product / median diameter of the paramylon granules) is 1. It was confirmed that it was 2 or less.

<Degradability test with β-1,3-glucanase enzyme>
Using the samples of Example 1, Comparative Example 1 and Comparative Example 2 (slurry sample before drying), the degradability of each sample by β-1,3-glucanase (sensitivity to β-1,3-glucanase) )It was confirmed. In addition, as the sample of the comparative example 1, the paramylon granule and the pure water were mixed and stirred to form a slurry. As described below, a reaction solution was prepared using each sample, β-1,3-glucanase was allowed to act on paramylon, and the amount of glucose produced was measured.
-Composition of the reaction solution (prepared to add 10 mL in total volume with pure water)
Buffer: 5 mL / Enzyme: 0.1 mL / Each sample: 30 mg in terms of dry mass
Buffer solution Potassium hydrogen phthalate-sodium hydroxide buffer (pH 4.0) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Enzyme (β-1,3-glucanase)
endo-1,3-β-Glucanase (enzyme content: 50 units / mL) (manufactured by Nippon Biocon)
Specifically, using a constant-temperature shaker, the prepared reaction solution was shaken for 24 hours under the conditions of 40 ° C. and 45 rpm, and paramylon was reacted with the enzyme. Thereafter, using the product name “glucose CII-Test Wako” (manufactured by Wako Pure Chemical Industries, Ltd.), the glucose concentration was measured for each of the sample subjected to the enzyme reaction and the sample not subjected to the enzyme reaction. Thereby, the glucose production amount [mg / g (glucose / paramylon)] of the samples of Example 1, Comparative Example 1, and Comparative Example 2 was calculated.

The results are shown in FIG. In addition, about the Example 1 and the comparative example 2, the sample of the state of the solid substance after drying was used for the test similarly to the above. For Example 1 and Comparative Example 2, there was almost no difference in the results of the degradability test with β-1,3-glucanase enzyme before and after drying.
<Solubility test in alkaline aqueous solution>
Using the samples of Example 1, Comparative Example 1 and Comparative Example 2 (solid state), solubility in an alkaline aqueous solution was confirmed. In addition, as a sample of Example 1, the powdery thing after drying was used. As a sample for Comparative Example 1, a paramylon granule before defibration was dried and then pulverized into a powder. As the sample of Comparative Example 2, a sample obtained by freeze-drying and then pulverizing it was used. When 250 mg of each sample in terms of dry mass was added to 10 mL of pure water or 0.5 M HCl aqueous solution and mixed, it was confirmed in advance that none of the samples was dissolved in pure water or HCl aqueous solution.

  Each sample having a dry mass of 250 mg was added to 10 mL of a 0.3 M aqueous sodium hydroxide solution, shaken vigorously, and then stirred with shaking at 80 rpm at room temperature (20 ° C.) for 1 hour.

  Similarly, each sample was added to 10 mL of pure water, 0.1 M NaOH aqueous solution, etc., and stirred for 1 hour. The results of the solubility test are shown in Table 3 and FIG. FIG. 19 is a photograph showing the appearance of the mixed liquid after stirring.

In the sample of Comparative Example 2, paramylon was dissolved in an aqueous NaOH solution immediately after stirring and became transparent. On the other hand, in the samples of Example 1 and Comparative Example 1, even when stirring was continued for 24 hours, the paramylon was not dissolved in the NaOH aqueous solution and was in a suspended state. In addition, it was confirmed separately that neither the fiberized paramylon of Example 1 nor the paramylon granule of Comparative Example 1 was dissolved in a 0.1 M NaOH aqueous solution.
<Evaluation of oil dispersibility (dispersion stability)>
A composition in which the oil was dispersed in water was prepared by mixing the dispersant (additive slurry) of Example 1 containing fiberized paramylon, the oil, and water. Details of the evaluation method are as follows.

Oil: vegetable oil including rapeseed oil and soybean oil Ratio of water to oil: 1 to 1 [mass ratio]
The concentration of fiberized paramylon in the composition [mass%]:
0.25 / 0.5 / 1.0 / 1.5
A dispersant, an oil component, and water were mixed in a test tube by a vortex mixer so that the concentration of the fiberized paramylon was the above-described concentration, thereby preparing a uniform dispersion (composition). Thereafter, the test tube was allowed to stand at room temperature, and after a predetermined time had elapsed (up to 24 hours), the height of the water phase separated downward was measured. The ratio of the height of the aqueous phase to the total height of the liquid was determined, and this ratio was used as an index of dispersion stability. The lower the ratio, the better the dispersion stability. The measurement was performed 6 times per condition, and the dispersion stability was evaluated by the average value.

  In addition, the following were used as a comparative object of the dispersant.

・ Egg-derived lecithin
・ Soybean-derived saponin
-Granular paramylon (paramylon granules) before being fiberized
-Aqueous dispersion of fiberized cellulose (cellulose 2 above)
(Product name “BiNFi-s WMa-10002” manufactured by Sugino Machine)
FIG. 20 shows a graph of the above evaluation results. As can be seen from FIG. 20, the dispersant containing fiberized paramylon was superior in dispersion stability to lecithin and saponin generally used in the food field. In comparison at the same concentration, fiberized paramylon was superior in dispersion stability to fiberized cellulose and paramylon granules.

  In the composition containing fiberized paramylon at a concentration of 0.5% by mass or more, phase separation was not observed even after standing for 24 hours, and high dispersion (emulsification) stability was shown. A composition containing fiberized paramylon at a concentration of 0.5-1.5% by weight had better dispersion (emulsification) stability than a composition containing fiberized paramylon at a concentration of 0.25% by weight. . On the other hand, at the same concentration (0.25% by mass), the composition containing fiberized paramylon had higher dispersion (emulsification) stability than the composition containing fiberized cellulose.

The composition containing fiberized paramylon had higher dispersion (emulsification) stability than the composition containing lecithin or saponin.
<Evaluation of powder dispersibility (dispersion stability)>
The powder dispersed in water was prepared by mixing the dispersant (additive slurry) of each example containing fiberized paramylon, powder (cocoa powder), and water produced as described above. The prepared composition was prepared. After preparing the composition, the dispersion stability was evaluated by observing the appearance after 24 hours. Details of the evaluation method are as follows.

  In a glass bottle, 385 mg of cocoa powder was suspended in 10 mL of pure water or test sample liquid. The suspension was performed by shaking the glass bottle vigorously by hand at room temperature. In addition, solid content except the cocoa powder in each test sample was unified to 1.0 [mass%].

  In addition to the comparative examples 1 and 2, the following were prepared as comparative objects.

Fiberized cellulose (abbreviated as cellulose nanofiber CNF): cellulose 2 above
The state after the evaluation of the dispersibility of the powder is shown in FIG. As can be seen from FIG. 21, in the case of pure water alone, when the PM granule of Comparative Example 1 was used, the cocoa powder was sedimented. In the case of using the chemically treated PM of Comparative Example 2, phase separation was observed. The dispersant containing fiberized paramylon was excellent in dispersion stability.

  The fiberized paramylon of the present invention is dispersed in water relatively uniformly and easily, for example, by mixing with a solvent containing water. The additive of the present invention can disperse fiberized paramylon in water relatively uniformly and simply by mixing with a solvent containing water, for example. The additive (dispersant) of the present invention is suitably used by being blended in a composition such as food, cosmetics and pharmaceuticals. The manufacturing method of the additive of this invention is used suitably, for example in order to manufacture said additive. The above-mentioned composition is suitably used for applications such as foods, cosmetics, and pharmaceuticals.

A: Raw material solution,
X1: 1st piping, X2: 2nd piping, X3: Piping for injection, X4: Impacted body,
Y1: 1st member, Y2: 2nd member.

In order to solve the above-mentioned problems, the present invention is Euglena-derived fiberized paramylon , which has a structure in which a plurality of fibrous materials are gathered together by being entangled with each other, and the fibrous materials are branched. Provide fiberized paramylon .
The present invention also provides Euglena-derived fiberized paramylon that does not dissolve in 0.1 M NaOH aqueous solution.
Since the above-mentioned fiberized paramylon is relatively uniformly and easily dispersed in water, the dispersibility in water is relatively good, so that it has the performance of being dispersed in a liquid containing water . The above-mentioned fiberized paramylon has been subjected to a defibrating treatment with a shearing force.

In order to solve the above-mentioned problems, the present invention is Euglena-derived fiberized paramylon, which has a structure in which a plurality of fibrous materials are gathered together by being entangled with each other, and the fibrous materials are branched. Provide fiberized paramylon .
Since the above-mentioned fiberized paramylon is relatively uniformly and easily dispersed in water, the dispersibility in water is relatively good, so that it has the performance of being dispersed in a liquid containing water. The above-mentioned fiberized paramylon has been subjected to a defibrating treatment with a shearing force.

Claims (10)

  Euglena-derived fiberized paramylon.   The fiberized paramylon according to claim 1, wherein a plurality of fibrous materials are gathered together by being entangled with each other.   The fiberized paramylon according to claim 1 or 2, which has a performance of dispersing in a liquid containing water.   The fiberized paramylon according to any one of claims 1 to 3, which does not dissolve in a 0.1 M NaOH aqueous solution.   The fiberized paramylon according to any one of claims 1 to 4, which has been defibrated by a shearing force.   The additive containing the fiberized paramylon of any one of Claims 1-5.   The additive according to claim 6, which is in a solid state.   The additive according to claim 7, further comprising a water-soluble polymer compound.   The additive according to any one of claims 6 to 8, which is dispersed in a solvent containing water.   A method for producing an additive, comprising a shearing step of forming paramylon granules into fibers by fiberizing the paramylon granules with a shearing force.

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