WO2020050152A1 - Composition - Google Patents

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Publication number
WO2020050152A1
WO2020050152A1 PCT/JP2019/034043 JP2019034043W WO2020050152A1 WO 2020050152 A1 WO2020050152 A1 WO 2020050152A1 JP 2019034043 W JP2019034043 W JP 2019034043W WO 2020050152 A1 WO2020050152 A1 WO 2020050152A1
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Prior art keywords
organic solvent
composition
particles
mass
less
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PCT/JP2019/034043
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French (fr)
Japanese (ja)
Inventor
翔 大高
和恵 上村
高志 阿久津
宮田　壮
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リンテック株式会社
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Priority to JP2020541176A priority Critical patent/JPWO2020050152A1/en
Publication of WO2020050152A1 publication Critical patent/WO2020050152A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives

Definitions

  • the present invention relates to a composition.
  • Patent Document 1 describes a filter medium for an air filter in which cellulose nanofibers having a number average fiber diameter of 1 to 50 nm are adhered at a predetermined ratio to a support having air permeability.
  • Patent Document 1 describes that the cellulose nanofiber used for the air filter material has a particle collecting performance.
  • the organic solvent has the property of gradually releasing the organic solvent to the outside with time (slow release) while taking in the organic solvent.
  • the formation of capsule-like particles may be required.
  • the composition containing such particles generally supplies the organic solvent to the outside by suppressing the release of the organic solvent to the outside, and by applying pressure when necessary to break the outer shell of the particles. Therefore, the present invention can be applied to applications where such characteristics are required.
  • General cellulose fibrils have a function of replacing a surfactant and are amphiphilic materials having a hydrophilic group and a hydrophobic site. Therefore, it is possible to adsorb an organic solvent by using cellulose fibrils.
  • an organic solvent is adsorbed using a general cellulose fibril, it does not have a property of gradually releasing the adsorbed organic solvent to the outside over time, that is, a sustained release property. Further, the organic solvent is in a state of being adsorbed on the surface of the fibrous material of the cellulose fibrils, and particles such as capsules incorporating the organic solvent are not formed.
  • the present invention is a particle incorporating an organic solvent, has a sustained release property of gradually releasing the organic solvent to the outside over time, the outer shell is broken when a certain or more pressure is applied It is an object of the present invention to provide a composition containing particles capable of supplying an organic solvent to the outside.
  • the present inventors have conducted various studies, and as a result, blended cellulose nanofiber, water, and an organic solvent having a distance Ra of the Hansen solubility parameter calculated from a predetermined formula of 5.80 MPa 1/2 or less. As a result, it has been found that a composition containing particles having an outer shell containing cellulose nanofibers can be obtained. The present invention has been completed based on this finding.
  • the present invention relates to the following [1] to [12].
  • [1] Cellulose nanofiber (A), water (B), and an organic solvent represented by the following formula (1) and having a distance Ra of a Hansen solubility parameter at 25 ° C. of 5.80 MPa 1/2 or less ( A composition comprising C), Containing particles having an outer shell containing cellulose nanofibers (A), A composition in which at least a part of the organic solvent (C) is in a state of being incorporated in the particles.
  • ⁇ D is a dispersion component of the Hansen solubility parameter of the organic solvent (C)
  • ⁇ P is the polar component of the Hansen solubility parameter of the organic solvent (C)
  • ⁇ H indicates the hydrogen bonding component of the Hansen solubility parameter of the organic solvent (C).
  • [2] At least one of a state in which at least a part of the organic solvent (C) is included in the particles and a state in which the organic solvent (C) is adsorbed on the cellulose nanofibers (A) forming the outer shell of the particles.
  • the composition according to the above [1] which is: [3]
  • the composition according to the above [1] or [2], wherein the solid content in the composition is 80 to 100% by mass relative to the total amount of the composition.
  • the organic solvent (C) contains an organic solvent (C1) having less than 20 carbon atoms.
  • the content of the surfactant is less than 10 parts by mass relative to 100 parts by mass of the total amount of the cellulose nanofiber (A). object.
  • the content of the polysaccharide other than the cellulose nanofiber (A) is less than 10 parts by mass based on 100 parts by mass of the total amount of the cellulose nanofiber (A).
  • the particles contained in the composition of the present invention are particles incorporating an organic solvent, have a sustained release property of gradually releasing the organic solvent to the outside over time, and maintain a constant or higher pressure. When applied, the outer shell is broken and the organic solvent can be supplied to the outside.
  • FIG. 9 is an image obtained when the composition prepared in Example 7 was observed with a digital microscope.
  • 9 is an image obtained when the composition prepared in Comparative Example 3 was observed with a digital microscope.
  • It is a schematic diagram of the measurement sample for observing the composition prepared by the Example and the comparative example with a digital microscope, (a) is a schematic plan view of the measurement sample in the middle of manufacture, (b) is the manufacture
  • FIG. 5 is a schematic front view of a measurement sample obtained.
  • the composition of the present invention comprises cellulose nanofiber (A), water (B), and an organic solvent (C), and comprises particles having an outer shell containing cellulose nanofiber (A). contains.
  • the cellulose nanofiber (A), water (B), and organic solvent (C) may be collectively referred to as “components (A) to (C)”.
  • FIG. 1 is an image obtained when the composition prepared in Example 7 described below was observed with a digital microscope. As shown in FIG. 1, the composition of the present invention contains particles, which are composed of an outer shell containing cellulose nanofibers (A).
  • the organic solvent (C) is in a state of being taken in by the particles, and specifically, in a state of being included in the particles, and in an outer shell of the particles. It is preferable that at least one of the state in which the cellulose nanofiber (A) is adsorbed is present.
  • the state in which the organic solvent (C) is included in the particles means that hollow particles are formed from the outer shell containing the cellulose nanofiber (A), and the organic solvent (C) is formed in the hollow portion of the hollow particles. ) Means the state is taken in. At this time, the organic solvent (C) is separated from the outside of the hollow particles by the outer shell constituting the hollow particles.
  • the particles contain the organic solvent (C), and the cellulose nanofibers (A) constituting the outer shell of the particles adsorb the organic solvent (C). It may be in the state where it is.
  • the outer shell composed of the cellulose nanofiber (A) adsorbs the organic solvent (C) means that the organic solvent is contained in the network structure of the outer shell composed of the cellulose nanofiber (A). (C) means that it exists.
  • Cellulose nanofibers (A) contained in the outer shell of the particles have a fine structure as compared with general cellulose fibrils such as pulp, and therefore have a large surface area per unit mass.
  • the amount of the organic solvent (C) attracted to the surface of the cellulose nanofiber (A) also increases. Further, the cellulose nanofiber (A) has a large force to attract the organic solvent (C) to the surface because a plurality of fibers are entangled with each other to form an outer shell. It is easy to maintain the state where the organic solvent (C) is taken into the network structure (that is, the state where the organic solvent (C) is adsorbed).
  • the organic solvent (C) is incorporated into the particles (ie, within the network structure of the outer shell, unless intentionally applying a constant or higher pressure).
  • the state in which the organic solvent (C) is present in the space inside the outer shell) is maintained, and it becomes difficult for a large amount of the organic solvent (C) to be released to the outside.
  • the organic solvent (C) taken in the particles is not completely sealed with the outside of the particles, but can be gradually released to the outside of the particles over time. That is, the particles contained in the composition of the present invention have the outer shell containing the cellulose nanofiber (A) as described above. Since the cellulose nanofiber (A) is a fibrous material, the outer shell containing the cellulose nanofiber (A) has many voids. Then, the organic solvent (C) taken into the particles can be released to the outside of the particles over time from the void.
  • the outer shell of the particles contains the cellulose nanofibers (A), the film strength is high, and it is difficult to break under normal conditions of no load or low load.
  • the particles can be easily broken by applying a certain or more pressure, and the captured organic solvent (C) can be supplied to the outside at once. Note that in the composition of one embodiment of the present invention, an organic solvent (C) that is not incorporated into the particles may be present.
  • water (B) may be incorporated into the particles together with the organic solvent (C).
  • a gas such as air may be taken into the particles.
  • a gas such as air is mixed into the composition, but it is conceivable that a gas such as air is taken into the inside of the outer shell constituting the particles.
  • the cellulose nanofiber (A) forms a hydrogen bond with water (B), and thus has a high affinity for water (B). Therefore, the outer shell containing the cellulose nanofibers (A) of the particles may be in a state of adsorbing water (B). That is, the particles may be in a state where the organic solvent (C) is taken in and the water (B) is adsorbed on the outer shell.
  • the particles having the outer shell containing the cellulose nanofibers, and the cellulose nanofibers that do not form the particles and are dispersed in water retain water so that the water interacts with a large number of water molecules as a dispersion medium. Therefore, it is considered that the amount of liquid composed of water (B) present separately from the cellulose nanofiber (A) is reduced.
  • the solid content ratio in the composition is preferably as large as possible.
  • the solid content in the composition of one embodiment of the present invention is preferably from 80 to 100% by mass, more preferably from 90 to 100% by mass, and still more preferably from 95 to 100% by mass, based on the total amount (100% by mass) of the composition. -100% by mass, more preferably 98-100% by mass.
  • the “solid content ratio” in the composition refers to the ratio of the solid content remaining on the tetron mesh after the composition is applied on a tetron mesh (# 200 mesh) and allowed to stand. And specifically, a value measured by the method described in Examples.
  • the solid content remaining on the tetron mesh described above includes not only the cellulose nanofiber (A), but also the organic solvent (C) incorporated in the particles, and the water ( B), and the mass of water (B) and the like retained in the cellulose nanofibers (A) that are not involved in the formation of the outer shell of the particles. Therefore, a composition having a high solid content means at least one of the following [A] and [B].
  • a large amount of at least one of water (B) and the organic solvent (C) is taken into the three-dimensional network structure of the outer shell constituted by the cellulose nanofiber (A) and the space inside the outer shell. ing.
  • At least one of a large amount of water (B) and an organic solvent (C) is held in the cellulose nanofiber (A) which is not involved in the formation of the outer shell of the particles.
  • the average particle diameter of the particles contained in the composition of one embodiment of the present invention is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and still more preferably 7 ⁇ m or more, from the viewpoint of suppressing aggregation of the particles in the composition. And still more preferably 10 ⁇ m or more, particularly preferably 15 ⁇ m or more, and from the viewpoint of suppressing the floating of particles in the composition, preferably 60 ⁇ m or less, more preferably 50 ⁇ m or less, still more preferably 40 ⁇ m or less, and even more. Preferably it is 35 ⁇ m or less, particularly preferably 30 ⁇ m or less.
  • the standard deviation with respect to the average particle size of the particles contained in the composition of one embodiment of the present invention is incorporated into the particles when the outer shell of the particles is broken by applying a certain or more pressure. From the viewpoint of stabilizing the amount of organic solvent released to the outside, it is preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, still more preferably 15 ⁇ m or less, even more preferably 12 ⁇ m or less, and usually 1 ⁇ m or more.
  • the average particle size of the particles and the standard deviation with respect to the average particle size are calculated from images obtained when the target composition is observed at a magnification of 500 to 1000 using a digital microscope. can do.
  • the average value of the particle diameters (outer diameters of the outer shells constituting the particles) of the 36 particles arbitrarily selected among the particles displayed in the image is defined as the “average particle diameter”. it can.
  • the “standard deviation with respect to the average particle size” can be calculated from the value of the particle size of each of the 36 particles.
  • the standard deviation is the standard deviation of the population. In the above calculation, the standard deviation is calculated for all 36 particle size values.
  • the average thickness of the outer shell of the particles contained in the composition of one embodiment of the present invention is preferably 10 nm or more, more preferably 50 nm or more, and still more preferably, from the viewpoint of improving the shape stability of the particles. Is 75 nm or more, and from the viewpoint of easily breaking the outer shell of the particle by applying a constant or more pressure, preferably 2000 nm or less, more preferably 1750 nm or less, still more preferably 1500 nm or less, even more preferably It is 1250 nm or less.
  • the thickness of the outer shell of the particles, the target composition, after coating and drying on a support material such as a polyethylene terephthalate film to form a coating, the cross-section of the coating can be calculated based on an image obtained when observed using a scanning electron microscope (SEM) or the like.
  • SEM scanning electron microscope
  • the average value of the outer shells of the particle diameters of the 36 particles arbitrarily selected among the particles shown in the image can be the above-mentioned “average of outer shell thickness”.
  • the viscosity of the composition of one embodiment of the present invention at 23 ° C. and a rotation speed of 50 rpm is preferably 500 mPa ⁇ s or more, and more preferably, from the viewpoint of improving storage stability and suppressing sedimentation when stored in a container. 1000 mPa ⁇ s or more, more preferably 1200 mPa ⁇ s or more, and from the viewpoint of improving the ease of stirring and taking out of the container, preferably 20,000 mPa ⁇ s or less, more preferably 15000 mPa ⁇ s or less, and still more preferably. Is 12000 mPa ⁇ s or less.
  • the TI value of the composition of one embodiment of the present invention at 23 ° C. indicates good storage stability and suppresses sedimentation when stored in a container. From the viewpoint, it is preferably 1.2 or more, more preferably 2 or more, still more preferably 3 or more, and still more preferably 4 or more, and preferably 20 or less from the viewpoint of improving the removability from the container. It is more preferably 15 or less, further preferably 10 or less, and still more preferably 8 or less.
  • the viscosity of the composition means a value measured using a B-type viscometer according to JIS Z 8803: 2011.
  • the pH of the composition of one embodiment of the present invention is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more, from the viewpoint that the formed particles are stable and the dispersion state is easily maintained in the composition. And preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
  • the pH of a composition means the value measured based on the method of an Example in 23 degreeC and 50% of relative humidity environment.
  • the composition of one embodiment of the present invention may contain components other than the above components (A) to (C).
  • the total content of the cellulose nanofiber (A), water (B), and organic solvent (C) is preferably based on the total amount of the composition (100% by mass). Is from 60 to 100% by mass, more preferably from 65 to 100% by mass, further preferably from 70 to 100% by mass, even more preferably from 80 to 100% by mass.
  • the active ingredient concentration of the composition of one embodiment of the present invention is preferably such that the particles are easily formed and the film strength of the formed particles is improved with respect to the total amount of the composition (100% by mass). It is preferably at least 0.5% by mass, more preferably at least 0.7% by mass, still more preferably at least 1.0% by mass, and still more preferably at least 1.5% by mass. From the viewpoint of appropriately adjusting the viscosity of the composition, the content is preferably 50% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and further more preferably 10% by mass or less.
  • active ingredient means the component except water (B) and organic solvent (C) among the components contained in a composition, and specifically, a cellulose nanofiber ( A), polysaccharides other than cellulose nanofiber (A), and various additives. In other words, it differs from the above-mentioned “solid content” in that the mass of the organic solvent (C) and water (B) taken into the cellulose nanofiber (A) is not included.
  • Particles having an outer shell containing the cellulose nanofiber (A) and incorporating the organic solvent (C) are used to mix the cellulose nanofiber (A) with the organic solvent (C).
  • the type of the organic solvent (C), and the like formation can be facilitated.
  • the particles are formed by blending an organic solvent (C) having a distance Ra of the Hansen solubility parameter of 5.80 MPa 1/2 or less. .
  • the particles can be easily formed by appropriately setting the compounding ratio and the like.
  • each component will be described in detail, focusing on a specific method for forming the particles.
  • ⁇ Cellulose nanofiber (A)> As a raw material of the cellulose nanofiber (A) used in one embodiment of the present invention, for example, wood-derived kraft pulp or sulfite pulp; powdered cellulose obtained by grinding kraft pulp or sulfite pulp with a high-pressure homogenizer or a mill; Microcrystalline cellulose powder obtained by purifying pulp by chemical treatment such as acid hydrolysis; bast fiber pulp such as mulberry, ganpi, mitsumata, etc .; cellulosic raw material derived from plants such as cotton pulp, kenaf, hemp, rice, bacas, bamboo; Cellulose-based raw materials.
  • wood-derived kraft pulp or sulfite pulp powdered cellulose obtained by grinding kraft pulp or sulfite pulp with a high-pressure homogenizer or a mill
  • Microcrystalline cellulose powder obtained by purifying pulp by chemical treatment such as acid hydrolysis
  • bast fiber pulp such as mulberry, ganpi, mitsumata
  • a cellulose-based raw material obtained by removing lignin from these raw materials is preferable. Further, the above-mentioned cellulose-based raw material may be used as finely divided by a high-speed rotation type, colloid mill type, high pressure type, roll mill type, ultrasonic type or other dispersing device, wet type high pressure or ultra high pressure homogenizer, or the like.
  • these cellulosic raw materials may be those having improved functionality by chemical modification and / or physical modification.
  • the chemical modification includes acetylation, carboxylation, carboxysodiumation, esterification, cyanoethylation, acetalization, etherification, arylation, alkylation, acryloylation, addition of a functional group by isocyanation, etc.
  • an inorganic substance such as silicate or titanate is compounded or coated by a chemical reaction, a sol-gel method, or the like.
  • a metal or ceramic raw material is subjected to a physical vapor deposition method (PVD method) such as vacuum deposition, ion plating, and sputtering, a chemical vapor deposition method (CVD method), and a plating method such as electroless plating and electrolytic plating.
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • plating method such as electroless plating and electrolytic plating.
  • Surface coating may be performed either at the time of defibrating the cellulose-based material or before or after defibrating.
  • the above-mentioned cellulose-based material can be made into cellulose nanofibers by defibrating and forming nanofibers.
  • a shear force is applied to the cellulose-based material to obtain a dispersion containing cellulose nanofibers.
  • a shearing force is applied to the cellulosic material, after adding the cellulosic material to a dispersion medium such as water, using a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, an ultrasonic type or the like, The method of preparation is preferred.
  • the pressure applied to the dispersion is preferably 50 MPa or more, more preferably 100 MPa or more, and still more preferably 140 MPa or more. From the viewpoint of applying a strong shearing force to the cellulosic material under such a high pressure, it is preferable to use a wet high-pressure or ultra-high-pressure homogenizer.
  • the average of the diameter (thickness) of the cellulose nanofiber (A) used in one embodiment of the present invention is preferably 1. from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. 0 nm or more, more preferably 1.5 nm or more, still more preferably 2.0 nm or more, even more preferably 2.5 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less, and still more preferably 200 nm or less. More preferably, it is 100 nm or less.
  • the average of the fiber length of the cellulose nanofiber (A) used in one embodiment of the present invention is preferably 0.01 ⁇ m or more from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. It is more preferably at least 0.1 ⁇ m, further preferably at least 0.2 ⁇ m, even more preferably at least 0.3 ⁇ m, and preferably at most 10 ⁇ m, more preferably at most 7.0 ⁇ m, even more preferably at most 5.0 ⁇ m, Even more preferably, it is 2.5 ⁇ m or less.
  • the average aspect ratio of the cellulose nanofiber (A) used in one embodiment of the present invention is preferably 5 or more, more preferably 5 or more, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. It is 10 or more, more preferably 15 or more, and preferably 10,000 or less, more preferably 5,000 or less, further preferably 3,000 or less, still more preferably 1,000 or less, and particularly preferably 500 or less.
  • the “aspect ratio” is a ratio of the length to the thickness of the target cellulose nanofiber [length / thickness], and the “length” of the cellulose nanofiber is the most of the cellulose nanofiber. Refers to the distance between two distant points. If a part of the target cellulose nanofiber is in contact with another cellulose nanofiber and it is difficult to determine the “length”, only the part of the target cellulose nanofiber whose thickness can be measured can be used. Is measured, and the aspect ratio of the portion may be within the above range.
  • the diameter (thickness) and fiber length of the cellulose nanofiber (A) can be measured using a transmission electron microscope.
  • the average of the diameter (thickness) and the average of the fiber length of the cellulose nanofibers (A) are obtained by measuring the diameter (thickness) and the fiber length of a plurality of arbitrarily selected cellulose nanofibers, and calculating the average value of each. It is obtained by calculating.
  • the average aspect ratio of the cellulose nanofiber (A) can be calculated using the thus obtained average of the diameter (thickness) and the average of the fiber length.
  • the diameter (thickness), fiber length, average value, and average aspect ratio of the cellulose nanofiber (A) can be specifically calculated by the methods described in Examples.
  • the blending amount of the cellulose nanofiber (A) facilitates the formation of the particles with respect to the total amount (100% by mass) of the composition, and a film of the formed particles. From the viewpoint of improving the strength, it is preferably at least 0.7% by mass, more preferably at least 0.8% by mass, still more preferably at least 1.0% by mass, even more preferably at least 1.2% by mass, and From the viewpoint of appropriately adjusting the viscosity of the composition so as to facilitate the formation of the particles, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less, and still more preferably It is at most 5% by mass, particularly preferably at most 3% by mass.
  • Water (B)> In the composition of one embodiment of the present invention, most of the water (B) is adsorbed on the outer shell of the particle, or is present outside the particle. However, a part of the water (B) may be included together with the organic solvent (C) inside the particles.
  • the blending amount of water (B) is determined based on the total amount of the composition (100% by mass). ), Preferably 15% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and preferably 99% by mass or less, more preferably Is 98.7% by mass or less, more preferably 98.5% by mass or less.
  • the mixing ratio of water (B) to 100 parts by mass of the cellulose nanofiber (A) Is preferably 500 parts by mass or more, more preferably 1000 parts by mass or more, still more preferably 2000 parts by mass or more, still more preferably 3000 parts by mass or more, and preferably 20,000 parts by mass or less, more preferably 15,000 parts by mass. Parts by mass, more preferably 10,000 parts by mass or less.
  • the composition of one embodiment of the present invention is preferably formed by mixing an organic solvent (C) with an aqueous dispersion containing cellulose nanofibers (A) and water (B).
  • an organic solvent (C) By preparing the aqueous dispersion in advance and blending the organic solvent (C), the cellulose nanofiber (A) can easily take in the organic solvent (C), and the particles can be easily formed.
  • the aqueous dispersion is prepared by blending the respective components such that the blending ratio of the cellulose nanofiber (A) and the water (B) is within the above range.
  • the aqueous dispersion may contain components other than the components (A) to (C) together with the cellulose nanofiber (A) and the water (B).
  • the organic solvent (C) used in the present invention is an organic solvent represented by the following formula (1) and having a distance Ra of the Hansen solubility parameter at 25 ° C. of 5.80 MPa 1/2 or less.
  • ⁇ D is a dispersion component of the Hansen solubility parameter of the organic solvent (C)
  • ⁇ P is the polar component of the Hansen solubility parameter of the organic solvent (C)
  • ⁇ H indicates the hydrogen bonding component of the Hansen solubility parameter of the organic solvent (C).
  • the Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components of Hansen, ⁇ D (dispersion component), ⁇ P (polar component), and ⁇ H (hydrogen bonding component). It is shown in a dimensional space. Note that the values of ⁇ D, ⁇ P, and ⁇ H are values specific to each organic solvent, and are values calculated from specific calculations. More specifically, the definition and calculation method of the Hansen solubility parameter are as described in "Hansen Solubility Parameters: A Users Handbook (by Charles M. Hansen, CRC Press, 2007)".
  • ⁇ D, ⁇ P, and ⁇ H are calculated in a database included in calculation software “Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03” (Steven Abbott, Charles M. Hansen, Hiroshi Yamamoto). Was used.
  • Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03 (Steven Abbott, Charles M. Hansen, Hiroshi Yamamoto).
  • the values of ⁇ D, ⁇ P, and ⁇ H of typical organic solvents used in Examples and Comparative Examples described later, and the distance Ra calculated from the above formula (1) (all units are “MPa 1/2 ”) ) Are shown in Table 1.
  • ⁇ D, ⁇ P, and ⁇ H of the organic solvent other than those shown in Table 1 can be calculated from the molecular structure of the organic solvent or the like, or ⁇ D, ⁇ P, and The value of ⁇ H can also be calculated by conducting an experiment on the solubility with an organic solvent known from various literatures.
  • the present inventors have paid attention to the case where the particles are formed and the case where the particles are not formed, depending on the type of the organic solvent (C) to be blended.
  • the organic solvents used when the particles are formed are densely distributed in a certain area in the three-dimensional space. I understand. Therefore, when plotting the largest sphere such that the plot of the organic solvent in which the particles are formed is all included inside and the plot of the organic solvent in which the particles are not formed is outside, the radius of the sphere is "5.80 MPa 1/2 ".
  • the distance Ra calculated from Expression (1) means the distance between the plot of the target organic solvent and the center of the sphere in the three-dimensional space of the Hansen solubility parameter. That is, if the distance Ra is equal to or less than the radius of the sphere, “5.80 MPa 1/2 ”, the plot of the target organic solvent is located inside the sphere, and the particles can be formed. I can judge. On the other hand, an organic solvent having a distance Ra of more than 5.80 MPa 1/2 is considered to be difficult to form the particles.
  • the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is heptane, n-hexadecane, toluene, cyclohexanone, methyl ethyl ketone, or n-dodecane.
  • Table 2 when these organic solvents were used, the result that the particles could be formed was obtained.
  • the particles can be formed with an organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less, other than the organic solvents shown in Table 1.
  • the organic solvent (C) used in the composition of the present invention may be used alone or as a mixed solvent using two or more kinds.
  • the organic solvent (C) is a mixed solvent
  • the values of the three components ( ⁇ D, ⁇ P, ⁇ H) of the weighted average Hansen solubility parameter are determined from the mixing ratio (volume ratio) of the mixed solvent, and calculated from the above equation (1). It is sufficient that the determined distance Ra is equal to or less than 5.80 MPa 1/2 .
  • the organic solvent (C) when using a mixed solvent composed of an organic solvent ⁇ and beta, 3-component [delta] D m Hansen parameter of the mixed solvent, [delta] P m, delta] H m can be calculated as follows . That is, the three components of Hansen parameters of the organic solvent ⁇ ⁇ D ⁇ , ⁇ P ⁇ , and delta] H alpha, the three components of Hansen parameters of the organic solvents beta [delta] D beta, [delta] P beta, and delta] H beta, the volume of the organic solvent alpha the rate v alpha, if the volume fraction of organic solvents beta was v ⁇ , ⁇ D m, ⁇ P m , ⁇ H m can be calculated from the following equation.
  • organic solvent (C) capable of forming the particles can be obtained by mixing the mixture at an appropriate volume ratio and preparing a mixed solvent prepared so that the distance Ra is 5.80 MPa 1/2 or less.
  • a composition containing particles incorporating an organic solvent having a distance Ra of more than 5.80 MPa 1/2 by one type alone another organic solvent having a distance Ra of 5.80 MPa 1/2 or less It is thought that it can be prepared by using the above-mentioned mixed solvent prepared by mixing with.
  • the Hansen solubility parameter represented by a vector in three-dimensional space as described above the first organic solvent alone distance Ra of 5.80MPa 1/2 than alone distance Ra is 5.80MPa 1 / a second organic solvent comprising a 2 exceeds even by mixing a second organic solvent which is positioned on the opposite side of the first organic solvent with respect to the center of the sphere in the 3-dimensional space as described above, A mixed solvent having a distance Ra of 5.80 MPa 1/2 or less can be prepared.
  • the particles are more easily formed than in the case of using another organic solvent. It is considered that particles can be more easily formed by adjusting the amounts of the components (A), (B) and (C) and selecting the shape of the component (A) and the modifying group. Therefore, in the present invention, the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is used, and the particles are more easily obtained by appropriately considering the items described in the item of each component in the present specification. Is preferably prepared so that
  • the organic solvent (C) used in one embodiment of the present invention preferably contains an organic solvent (C1) having less than 20 carbon atoms.
  • the organic solvent (C1) having less than 20 carbon atoms is easily taken into the cellulose nanofiber (A), and the particles are easily formed. That is, in an organic solvent having a large number of carbon atoms, molecules of the organic solvent are likely to collect with each other, and since the viscosity is high, it is difficult to form particles close to a true sphere. As a result, it is considered that such an organic solvent is not taken into the cellulose nanofiber (A), but remains at a higher rate outside the particles.
  • the carbon number of the organic solvent (C1) is preferably less than 20, more preferably 1 to 18, and still more preferably 1 to 16.
  • the blending ratio of the organic solvent (C1) in the organic solvent (C) is preferably 20% by mass or more, more preferably 35% by mass or more based on the total amount (100% by mass) of the organic solvent (C). , More preferably 50% by mass or more, even more preferably 70% by mass or more.
  • the viscosity of the organic solvent (C) at 25 ° C is preferably 0.1 mPa ⁇ s or more, more preferably 0.15 mPa ⁇ s. s or more, more preferably 0.2 mPa ⁇ s or more, even more preferably 0.25 mPa ⁇ s or more, and preferably 30 mPa ⁇ s or less, more preferably 10 mPa ⁇ s or less, and still more preferably 6.0 mPa ⁇ s or less. s or less, more preferably 2.8 mPa ⁇ s or less.
  • the amount of the organic solvent (C) is preferably 0.05% by mass based on the total amount (100% by mass) of the composition. % Or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass. %, More preferably 45% by mass or less, further preferably 42% by mass or less, further preferably 40% by mass or less, and still more preferably 38% by mass or less.
  • the blending ratio of the organic solvent (C) to 100 parts by mass of the cellulose nanofiber (A) is preferably 1 part by mass or more, and more preferably from the viewpoint of facilitating the formation of the particles. Is at least 5 parts by mass, more preferably at least 10 parts by mass, even more preferably at least 50 parts by mass, particularly preferably at least 75 parts by mass, most preferably at least 90 parts by mass, and also preferably at most 6000 parts by mass. It is preferably at most 4,500 parts by mass, more preferably at most 4,000 parts by mass, even more preferably at most 3,500 parts by mass.
  • the blending ratio [(B) / (C)] of water (B) and the organic solvent (C) is expressed by mass ratio, It is preferably at least 0.1, more preferably at least 0.5, further preferably at least 1.0, even more preferably at least 1.5, and preferably at most 1,000, more preferably at most 700, still more preferably It is at most 500, more preferably at most 300, particularly preferably at most 100.
  • composition of one embodiment of the present invention may contain components other than the components (A) to (C) as long as the effects of the present invention are not impaired.
  • Such other components are appropriately selected according to the use of the composition, and include, for example, a colorant, an antioxidant, a pH adjuster, a sweetener, a flavor, a preservative, an ultraviolet absorber, and a polymerization inhibitor.
  • a surfactant may be contained.
  • the content of the surfactant is preferably as small as possible.
  • the content of the surfactant is preferably less than 10 parts by mass, more preferably 1 part by mass, based on 100 parts by mass of the total amount of the cellulose nanofiber (A). Less than 0.1 part by mass, more preferably less than 0.01 part by mass, particularly preferably less than 0.001 part by mass, and most preferably 0 part by mass.
  • the composition of one embodiment of the present invention may contain a polysaccharide other than the cellulose nanofiber (A), but from the viewpoint of improving the thermal stability of the particles and facilitating the formation of the particles.
  • the content of the polysaccharide other than the cellulose nanofibers (A) is preferably less than 10 parts by mass relative to 100 parts by mass of the total amount of the cellulose nanofibers (A). , More preferably less than 1 part by mass, further preferably less than 0.1 part by mass, still more preferably less than 0.01 part by mass, particularly preferably 0 part by mass.
  • the method for producing the composition of the present invention is not particularly limited, but a method having the following steps (1) and (2) is preferable from the viewpoint of facilitating the formation of the particles.
  • Step (1) a step of preparing an aqueous dispersion containing the cellulose nanofiber (A) and water (B).
  • Step (2) a step of adding an organic solvent (C) to the aqueous dispersion obtained in Step (1).
  • the details of the components (A) to (C) used in the steps (1) and (2) are as described above.
  • Step (1) is a step of preparing an aqueous dispersion containing cellulose nanofibers (A) and water (B).
  • the step may be omitted.
  • the cellulose nanofiber (A) or water (B) is added to the commercially available aqueous dispersion, and a desired blending is performed. It may be prepared in a volume of aqueous dispersion.
  • components other than the components (A) to (C) When components other than the components (A) to (C) are blended, they may be blended in the preparation of the aqueous dispersion in the step (1), and the steps (1) and (2) May be added during the step (2), may be added during the step (2), or may be added after the step (2).
  • the pH of the aqueous dispersion obtained in the step (1) is preferably from the viewpoint of suppressing aggregation of the cellulose nanofibers (A) in the aqueous dispersion and reducing variations in the shape and size of the formed particles. It is 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
  • Step (2) is a step of adding an organic solvent (C) to the aqueous dispersion obtained in step (1).
  • organic solvent (C) it is preferable to add the organic solvent (C) while stirring the aqueous dispersion using a stirrer equipped with a stirring blade such as a homodisper, a mixer, or a paddle blade.
  • the stirring speed (rotation speed) when stirring the aqueous dispersion is preferably 500 rpm or more, from the viewpoint of suppressing aggregation of the cellulose nanofibers (A) and reducing variations in the shape and size of the formed particles. It is preferably at least 1,000 rpm, more preferably at least 1500 rpm, even more preferably at least 2,000 rpm, and preferably at most 5,000 rpm, more preferably at most 4,500 rpm, more preferably at most 4,000 rpm, further preferably at most 3,500 rpm, even more preferably at 3,000 rpm. It is as follows.
  • the temperature of the aqueous dispersion is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of suppressing aggregation of the cellulose nanofibers (A) and reducing the variation in the shape and size of the formed particles. It is more preferably at least 15 ° C, and from the viewpoint of suppressing the volatilization of the added organic solvent (C), preferably at most 45 ° C, more preferably at most 40 ° C, even more preferably at most 35 ° C.
  • the addition amount of the organic solvent (C) every 10 seconds is preferably at least 0.1 part by mass, more preferably at least 1 part by mass, further preferably at least 3 parts by mass based on 100 parts by mass of the total amount of the aqueous dispersion. It is at least 5 parts by mass, more preferably at least 5 parts by mass, and preferably at most 20 parts by mass, more preferably at most 15 parts by mass, further preferably at most 10 parts by mass, even more preferably at most 7 parts by mass. .
  • the stirring time from the start of the addition of the organic solvent (C) is preferably 3 minutes or more, more preferably 5 minutes or more, and still more preferably 10 minutes or more, from the viewpoint of reducing the variation in the shape and size of the formed particles.
  • the time is preferably 180 minutes or less, more preferably 120 minutes or less, further preferably 60 minutes or less, still more preferably 40 minutes or less, and particularly preferably 20 minutes or less.
  • the stirring time refers to the time from the addition of the organic solvent (C) to the end of the stirring.
  • the particles contained in the composition of the present invention are particles containing an organic solvent, and have a sustained release property that is capable of gradually releasing the organic solvent to the outside over time, and at least a certain amount or more.
  • a composition containing particles having such properties can be used in the fields of agriculture, food, cosmetics, medicine, and the like. Specifically, a liquid fragrance supplied according to the pressure, a liquid fragrance supplied according to the temperature, a foodstuff whose taste changes on the tongue according to the temperature, a coolant gradually released according to the temperature , A pressure-sensitive adhesive, a drug delivery system, and the like.
  • a mixture of the active ingredients (flavors, nutrients, functional substances, drugs, etc.) for each of the above uses in an appropriate organic solvent is incorporated into the hollow particles formed of the outer shell containing the cellulose nanofibers described above.
  • the composition can be prepared and used for each application.
  • Viscosity and TI value of composition According to JIS Z 8803: 2011, the viscosity of the composition was measured using a B-type viscometer at 23 ° C, rotation speed of 5 rpm and 50 rpm. The ratio of [viscosity at 5 rpm] / [viscosity at 50 rpm] was defined as the TI value.
  • Aqueous dispersion (1) Product name "BiNFi-s AMa 10002", manufactured by Sugino Machine Co., Ltd.
  • the aqueous dispersion (1) contained 4900 parts by mass of water with respect to 100 parts by mass of the cellulose nanofiber, and the pH of the aqueous dispersion (1) was 7.0.
  • -Aqueous dispersion (2) Product name "TEMPO oxidized CNF", manufactured by Nippon Paper Industries. An aqueous dispersion containing 1% by mass of chemically treated cellulose nanofibers having an average diameter (thickness) of 3.8 nm, an average length of 0.7 ⁇ m, and an average aspect ratio of 184. The aqueous dispersion (2) contained 9900 parts by mass of water with respect to 100 parts by mass of the cellulose nanofibers, and the pH of the aqueous dispersion (2) was 7.0.
  • the amount of the organic solvent shown in Table 2 is added to the aqueous dispersion (1) or (2) with respect to 100 parts by mass of the cellulose nanofiber in the aqueous dispersion (1) or (2).
  • stirring blade homodisper (manufactured by the company, blade diameter 35 mm)).
  • the organic solvents shown in Table 2 were added at a rate of 5 parts by mass every 10 seconds to 100 parts by mass of the total amount of the aqueous dispersion (1) or (2). Stirring was continued after the addition of the organic solvent, and the stirring was stopped 10 minutes after the start of stirring to prepare a composition.
  • compositions prepared in Examples and Comparative Examples were measured and calculated for viscosity (viscosity at 5 rpm and 50 rpm, TI value), and evaluated and measured as follows. Table 3 shows the results.
  • test sample was prepared by putting 100 g of the prepared composition in a cylindrical transparent glass container having a diameter of 4.2 cm.
  • a comparative sample was prepared by putting an organic solvent having a mass contained in 100 g of the composition to be measured in the same type of transparent container as described above. Then, the test sample and the comparative sample were left uncovered at 23 ° C. and a relative humidity of 50%, and allowed to stand in a continuously operated draft for 6 hours. Five evaluators confirmed the odor of the test sample and the comparative sample taken out of the draft after standing still. Table 3 shows the number of evaluators who judged that the test sample smelled better than the comparative sample. It can be said that the larger the number of the evaluators, the higher the accuracy of the particles in the sustained release.
  • FIG. 1 is an image obtained when the composition of Example 7 was observed with a digital microscope, and it can be seen that particles were present. In the compositions of Examples 1 to 6 and 8 to 13, the presence of similar particles was confirmed. And it was also confirmed that these particles have a sustained release property.
  • the composition of Example 7 had a pH of 7.0.
  • each of the compositions prepared in Examples 7 and 10 was applied onto the surface of an easily adhesive layer of a PET film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 ⁇ m) as a support material. And dried at 120 ° C. for 10 minutes to form a coating film having a thickness of 50 ⁇ m, and an image obtained by observing a cross section of the coating film with a scanning electron microscope (SEM) (S-4700 manufactured by Hitachi, Ltd.) I got Then, among the particles projected on the image, the thicknesses of the outer shells of 36 particles arbitrarily selected are measured, and the average value thereof is calculated as the above-mentioned “average of outer shell thickness”. did. As a result, the average of the outer shell thickness of the particles in the composition was “1202 nm” in Example 7 and “93 nm” in Example 10.
  • SEM scanning electron microscope
  • FIG. 2 is an image obtained when the composition of Comparative Example 3 was observed with a digital microscope, but the presence of particles could not be confirmed. Similarly, in the compositions of Comparative Examples 1, 2, 4, and 5, the presence of particles could not be confirmed.

Abstract

A composition that contains particles into which an organic solvent has been taken in, and which have sustained release properties, while being capable of supplying the organic solvent to the outside by having shells that are broken when a pressure of a predetermined value or higher is applied thereto. This composition is obtained by blending (A) cellulose nanofibers, (B) water and (C) an organic solvent which has a Hansen solubility parameter distance Ra of 5.80 MPa1/2 or less at 25°C, said Hansen solubility parameter distance Ra being represented by formula (1). This composition contains particles which are provided with shells that contain the cellulose nanofibers (A), and into which at least some of the organic solvent (C) has been taken in. (In the formula, δD represents the dispersion term of the Hansen solubility parameter of the organic solvent (C); δP represents the polarity term of the Hansen solubility parameter of the organic solvent (C); and δH represents the hydrogen bonding term of the Hansen solubility parameter of the organic solvent (C).)

Description

組成物Composition
　本発明は、組成物に関する。 The present invention relates to a composition.
　繊維状多糖の一つであるセルロース原繊維は、農業、食品、化粧品、薬剤、フィルタ等の広範な用途への適用が検討されている。特に、近年、このセルロース原繊維を種々の方法で微細化したセルロースナノファイバーが、新材料として注目されている。
　例えば、特許文献１には、通気性を有する支持体に、数平均繊維径が１～５０ｎｍのセルロースナノファイバーを所定の割合で付着させた、エアフィルタ用濾材について記載されている。
　特許文献１には、当該エアフィルタ用濾材に用いるセルロースナノファイバーは、粒子捕集性能を有する旨の記載がある。 Cellulose fibrils, one of the fibrous polysaccharides, have been studied for application to a wide range of uses such as agriculture, food, cosmetics, drugs, and filters. In particular, in recent years, cellulose nanofibers obtained by miniaturizing the cellulose fibrils by various methods have attracted attention as new materials.
For example, Patent Document 1 describes a filter medium for an air filter in which cellulose nanofibers having a number average fiber diameter of 1 to 50 nm are adhered at a predetermined ratio to a support having air permeability.
Patent Document 1 describes that the cellulose nanofiber used for the air filter material has a particle collecting performance.
特開２０１７－１７７０９１号公報JP 2017-177091 A
　ところで、例えば、農業、食品、化粧品、薬剤等の分野において、有機溶剤を取り込みつつ、経時的に当該有機溶剤を少しずつ外部へ放出する性質（徐放性）を有し、有機溶剤を取り込んだカプセルのような粒子の形成が求められる場合がある。
　また、このような粒子を含む組成物は、通常は有機溶剤の外部への放出を抑えつつも、必要時に圧力が加えられて粒子の外殻が破られることで、有機溶剤を外部へ供給することもできるため、このような特性が必要とされる用途への適用も可能である。 By the way, for example, in the fields of agriculture, food, cosmetics, pharmaceuticals, etc., the organic solvent has the property of gradually releasing the organic solvent to the outside with time (slow release) while taking in the organic solvent. The formation of capsule-like particles may be required.
In addition, the composition containing such particles generally supplies the organic solvent to the outside by suppressing the release of the organic solvent to the outside, and by applying pressure when necessary to break the outer shell of the particles. Therefore, the present invention can be applied to applications where such characteristics are required.
　一般的なセルロース原繊維は、界面活性剤を代替し得る機能を有し、親水基と疎水性部位とを有する両親媒性材料である。そのため、セルロース原繊維を用いることによって、有機溶剤を吸着することは可能である。
　しかしながら、一般的なセルロース原繊維を用いて有機溶剤を吸着させた場合、吸着した有機溶剤を経時的に徐々に外部へ放出する性質、つまり徐放性までは有していない。また、当該有機溶剤は、セルロース原繊維の繊維状物の表面に吸着された状態であって、当該有機溶剤を取り込んだカプセルのような粒子は形成されない。 General cellulose fibrils have a function of replacing a surfactant and are amphiphilic materials having a hydrophilic group and a hydrophobic site. Therefore, it is possible to adsorb an organic solvent by using cellulose fibrils.
However, when an organic solvent is adsorbed using a general cellulose fibril, it does not have a property of gradually releasing the adsorbed organic solvent to the outside over time, that is, a sustained release property. Further, the organic solvent is in a state of being adsorbed on the surface of the fibrous material of the cellulose fibrils, and particles such as capsules incorporating the organic solvent are not formed.
　本発明は、有機溶剤を取り込んだ粒子であって、経時的に有機溶剤を少しずつ外部へ放出する性質である徐放性を有すると共に、一定又はそれ以上の圧力をかけると外殻が破れて有機溶剤を外部へ供給することができる粒子を含む組成物を提供することを目的とする。 The present invention is a particle incorporating an organic solvent, has a sustained release property of gradually releasing the organic solvent to the outside over time, the outer shell is broken when a certain or more pressure is applied It is an object of the present invention to provide a composition containing particles capable of supplying an organic solvent to the outside.
　本発明者らは、様々な検討を行った結果、セルロースナノファイバー、水、及び、所定の式から算出されるハンセン溶解度パラメータの距離Ｒａが５．８０ＭＰａ１／２以下となる有機溶剤を配合することで、セルロースナノファイバーを含む外殻を備える粒子を含む組成物が得られるという知見を得た。
　本発明は、当該知見に基づき完成されたものである。 The present inventors have conducted various studies, and as a result, blended cellulose nanofiber, water, and an organic solvent having a distance Ra of the Hansen solubility parameter calculated from a predetermined formula of 5.80 MPa 1/2 or less. As a result, it has been found that a composition containing particles having an outer shell containing cellulose nanofibers can be obtained.
The present invention has been completed based on this finding.
　すなわち、本発明は、下記［１］～［１２］に関する。
［１］セルロースナノファイバー（Ａ）、水（Ｂ）、及び、下記式（１）で表される、２５℃における、ハンセン溶解度パラメータの距離Ｒａが５．８０ＭＰａ１／２以下である有機溶剤（Ｃ）を配合してなる組成物であって、
　セルロースナノファイバー（Ａ）を含む外殻を備える粒子を含有し、
　有機溶剤（Ｃ）の少なくとも一部が、前記粒子に取り込まれている状態である、組成物。
Figure JPOXMLDOC01-appb-M000002
（前記式中、δＤは、有機溶剤（Ｃ）のハンセン溶解度パラメータの分散成分、
　δＰは、有機溶剤（Ｃ）のハンセン溶解度パラメータの極性成分、
　δＨは、有機溶剤（Ｃ）のハンセン溶解度パラメータの水素結合成分を示す。）
［２］有機溶剤（Ｃ）の少なくとも一部が、前記粒子に内包されている状態、及び、前記粒子の外殻を形成しているセルロースナノファイバー（Ａ）に吸着されている状態の少なくとも一方である、上記［１］に記載の組成物。
［３］前記組成物中の固形分率が、当該組成物の全量に対して、８０～１００質量％である、上記［１］又は［２］に記載の組成物。
［４］前記組成物の２３℃、５０ｒｐｍにおける粘度が、５００～２００００ｍＰａ・ｓである、上記［１］～［３］のいずれか一つに記載の組成物。
［５］前記組成物の２３℃でのＴＩ値（回転数５ｒｐｍにおける粘度／回転数５０ｒｐｍにおける粘度）が、１．２～２０である、上記［１］～［４］のいずれか一つに記載の組成物。
［６］セルロースナノファイバー（Ａ）の直径（太さ）の平均が、１～１０００ｎｍである、上記［１］～［５］のいずれか一つに記載の組成物。
［７］セルロースナノファイバー（Ａ）の繊維長の平均が、０．０１～１０μｍである、上記［１］～［６］のいずれか一つに記載の組成物。
［８］有機溶剤（Ｃ）の配合量が、前記組成物の全量に対して、０．０５～８０質量％である、上記［１］～［７］のいずれか一つに記載の組成物。
［９］水（Ｂ）と有機溶剤（Ｃ）との配合量比〔（Ｂ）／（Ｃ）〕が、質量比で、０．１～１０００である、上記［１］～［８］のいずれか一つに記載の組成物。
［１０］有機溶剤（Ｃ）が、炭素数２０未満の有機溶剤（Ｃ１）を含む、上記［１］～［９］のいずれか一つに記載の組成物。
［１１］界面活性剤の含有量が、セルロースナノファイバー（Ａ）の全量１００質量部に対して、１０質量部未満である、上記［１］～［１０］のいずれか一つに記載の組成物。
［１２］セルロースナノファイバー（Ａ）以外の多糖類の含有量が、セルロースナノファイバー（Ａ）の全量１００質量部に対して、１０質量部未満である、上記［１］～［１１］のいずれか一つに記載の組成物。 That is, the present invention relates to the following [1] to [12].
[1] Cellulose nanofiber (A), water (B), and an organic solvent represented by the following formula (1) and having a distance Ra of a Hansen solubility parameter at 25 ° C. of 5.80 MPa 1/2 or less ( A composition comprising C),
Containing particles having an outer shell containing cellulose nanofibers (A),
A composition in which at least a part of the organic solvent (C) is in a state of being incorporated in the particles.
Figure JPOXMLDOC01-appb-M000002
(Wherein δD is a dispersion component of the Hansen solubility parameter of the organic solvent (C),
δP is the polar component of the Hansen solubility parameter of the organic solvent (C),
δH indicates the hydrogen bonding component of the Hansen solubility parameter of the organic solvent (C). )
[2] At least one of a state in which at least a part of the organic solvent (C) is included in the particles and a state in which the organic solvent (C) is adsorbed on the cellulose nanofibers (A) forming the outer shell of the particles. The composition according to the above [1], which is:
[3] The composition according to the above [1] or [2], wherein the solid content in the composition is 80 to 100% by mass relative to the total amount of the composition.
[4] The composition according to any one of [1] to [3], wherein the composition has a viscosity at 23 ° C. and 50 rpm of 500 to 20,000 mPa · s.
[5] The composition according to any one of [1] to [4], wherein the composition has a TI value at 23 ° C. (viscosity at a rotation speed of 5 rpm / viscosity at a rotation speed of 50 rpm) of 1.2 to 20. A composition as described.
[6] The composition according to any one of [1] to [5], wherein the average of the diameter (thickness) of the cellulose nanofiber (A) is 1 to 1000 nm.
[7] The composition according to any one of [1] to [6], wherein the average fiber length of the cellulose nanofiber (A) is 0.01 to 10 μm.
[8] The composition according to any one of [1] to [7], wherein the amount of the organic solvent (C) is 0.05 to 80% by mass based on the total amount of the composition. .
[9] The composition of any of the above-mentioned [1] to [8], wherein the mixing ratio of the water (B) and the organic solvent (C) [(B) / (C)] is 0.1 to 1000 in terms of mass ratio. A composition according to any one of the preceding claims.
[10] The composition according to any one of [1] to [9], wherein the organic solvent (C) contains an organic solvent (C1) having less than 20 carbon atoms.
[11] The composition according to any one of [1] to [10] above, wherein the content of the surfactant is less than 10 parts by mass relative to 100 parts by mass of the total amount of the cellulose nanofiber (A). object.
[12] Any of the above-mentioned [1] to [11], wherein the content of the polysaccharide other than the cellulose nanofiber (A) is less than 10 parts by mass based on 100 parts by mass of the total amount of the cellulose nanofiber (A). A composition according to any one of the preceding claims.
　本発明の組成物に含まれる粒子は、有機溶剤を取り込んだ粒子であって、経時的に有機溶剤を少しずつ外部へ放出する性質である徐放性を有すると共に、一定又はそれ以上の圧力をかけると外殻が破れて有機溶剤を外部へ供給することができる。 The particles contained in the composition of the present invention are particles incorporating an organic solvent, have a sustained release property of gradually releasing the organic solvent to the outside over time, and maintain a constant or higher pressure. When applied, the outer shell is broken and the organic solvent can be supplied to the outside.
実施例７で調製した組成物をデジタル顕微鏡で観察した際に取得した画像である。9 is an image obtained when the composition prepared in Example 7 was observed with a digital microscope. 比較例３で調製した組成物をデジタル顕微鏡で観察した際に取得した画像である。9 is an image obtained when the composition prepared in Comparative Example 3 was observed with a digital microscope. 実施例及び比較例で調製した組成物をデジタル顕微鏡で観察するための測定サンプルの模式図であって、（ａ）は、作製途中の測定サンプルの平面模式図であり、（ｂ）は、作製した測定サンプルの正面模式図である。It is a schematic diagram of the measurement sample for observing the composition prepared by the Example and the comparative example with a digital microscope, (a) is a schematic plan view of the measurement sample in the middle of manufacture, (b) is the manufacture FIG. 5 is a schematic front view of a measurement sample obtained.
〔組成物〕
　本発明の組成物は、セルロースナノファイバー（Ａ）、水（Ｂ）、及び、有機溶剤（Ｃ）を配合してなるものであって、セルロースナノファイバー（Ａ）を含む外殻を備える粒子を含有する。以下、セルロースナノファイバー（Ａ）、水（Ｂ）、及び、有機溶剤（Ｃ）をまとめて「成分（Ａ）～（Ｃ）」と称することがある。
　図１は、後述の実施例７で調製した組成物をデジタル顕微鏡で観察した際に取得した画像である。
　図１に示すように、本発明の組成物は、粒子を含有し、当該粒子は、セルロースナノファイバー（Ａ）を含む外殻から構成されている。
　本発明の組成物において、有機溶剤（Ｃ）の少なくとも一部は、当該粒子に取り込まれた状態であり、具体的には、前記粒子に内包されている状態、及び、前記粒子の外殻を形成しているセルロースナノファイバー（Ａ）に吸着されている状態の少なくとも一方であることが好ましい。
　ここで、「有機溶剤（Ｃ）が前記粒子に内包されている状態」とは、セルロースナノファイバー（Ａ）を含む外殻から中空粒子が形成され、当該中空粒子の中空部分に有機溶剤（Ｃ）が取り込まれた状態を意味する。この際、中空粒子を構成する外殻によって、有機溶剤（Ｃ）は、中空粒子の外側とは隔てられた状態となっている。 〔Composition〕
The composition of the present invention comprises cellulose nanofiber (A), water (B), and an organic solvent (C), and comprises particles having an outer shell containing cellulose nanofiber (A). contains. Hereinafter, the cellulose nanofiber (A), water (B), and organic solvent (C) may be collectively referred to as “components (A) to (C)”.
FIG. 1 is an image obtained when the composition prepared in Example 7 described below was observed with a digital microscope.
As shown in FIG. 1, the composition of the present invention contains particles, which are composed of an outer shell containing cellulose nanofibers (A).
In the composition of the present invention, at least a part of the organic solvent (C) is in a state of being taken in by the particles, and specifically, in a state of being included in the particles, and in an outer shell of the particles. It is preferable that at least one of the state in which the cellulose nanofiber (A) is adsorbed is present.
Here, "the state in which the organic solvent (C) is included in the particles" means that hollow particles are formed from the outer shell containing the cellulose nanofiber (A), and the organic solvent (C) is formed in the hollow portion of the hollow particles. ) Means the state is taken in. At this time, the organic solvent (C) is separated from the outside of the hollow particles by the outer shell constituting the hollow particles.
　本発明の一態様の組成物において、前記粒子は、有機溶剤（Ｃ）を内包しつつ、且つ、当該粒子の外殻を構成するセルロースナノファイバー（Ａ）は、有機溶剤（Ｃ）を吸着している状態であってもよい。本明細書において、「セルロースナノファイバー（Ａ）によって構成される外殻が有機溶剤（Ｃ）を吸着する」とは、セルロースナノファイバー（Ａ）によって構成される外殻の網目構造内に有機溶剤（Ｃ）が存在することを意味する。 In the composition of one embodiment of the present invention, the particles contain the organic solvent (C), and the cellulose nanofibers (A) constituting the outer shell of the particles adsorb the organic solvent (C). It may be in the state where it is. In this specification, "the outer shell composed of the cellulose nanofiber (A) adsorbs the organic solvent (C)" means that the organic solvent is contained in the network structure of the outer shell composed of the cellulose nanofiber (A). (C) means that it exists.
　前記粒子の外殻に含まれるセルロースナノファイバー（Ａ）は、パルプ等の一般的なセルロース原繊維に比べて、微細な構造を有しているため、単位質量あたりの表面積が大きく、結果として、セルロースナノファイバー（Ａ）の表面に引きつけられる有機溶剤（Ｃ）の量も多くなる。
　更に、セルロースナノファイバー（Ａ）は、複数の繊維が互いに絡み合って外殻を形成するため、表面に有機溶剤（Ｃ）を引きつける力が大きく、セルロースナノファイバー（Ａ）によって構成される外殻の網目構造内に有機溶剤（Ｃ）を取り込んだ状態（つまり、有機溶剤（Ｃ）を吸着した状態）を保ち易い。
　そのため、前記粒子の形成時及び形成からしばらくの間は、意図的に一定又はそれ以上の圧力を加えない限り、有機溶剤（Ｃ）の当該粒子への取り込み（すなわち、外殻の網目構造内、及び、外殻より内側の空間に有機溶剤（Ｃ）が存在する状態）が保たれ、多量の有機溶剤（Ｃ）が外部へ放出され難くなる。 Cellulose nanofibers (A) contained in the outer shell of the particles have a fine structure as compared with general cellulose fibrils such as pulp, and therefore have a large surface area per unit mass. The amount of the organic solvent (C) attracted to the surface of the cellulose nanofiber (A) also increases.
Further, the cellulose nanofiber (A) has a large force to attract the organic solvent (C) to the surface because a plurality of fibers are entangled with each other to form an outer shell. It is easy to maintain the state where the organic solvent (C) is taken into the network structure (that is, the state where the organic solvent (C) is adsorbed).
Therefore, during and for a while after the formation of the particles, the organic solvent (C) is incorporated into the particles (ie, within the network structure of the outer shell, unless intentionally applying a constant or higher pressure). In addition, the state in which the organic solvent (C) is present in the space inside the outer shell) is maintained, and it becomes difficult for a large amount of the organic solvent (C) to be released to the outside.
　その一方で、前記粒子に取り込まれた有機溶剤（Ｃ）は、粒子の外側と完全に密閉されたわけではなく、経時的に、徐々に粒子の外側へ放出し得る。
　つまり、本発明の組成物に含まれる粒子は、上記のとおり、セルロースナノファイバー（Ａ）を含む外殻を備えている。セルロースナノファイバー（Ａ）は繊維状物であるため、このセルロースナノファイバー（Ａ）を含む外殻は多数の空隙を有する。そして、当該粒子に取り込まれた有機溶剤（Ｃ）は、この空隙から経時的に粒子の外側へ放出し得る。 On the other hand, the organic solvent (C) taken in the particles is not completely sealed with the outside of the particles, but can be gradually released to the outside of the particles over time.
That is, the particles contained in the composition of the present invention have the outer shell containing the cellulose nanofiber (A) as described above. Since the cellulose nanofiber (A) is a fibrous material, the outer shell containing the cellulose nanofiber (A) has many voids. Then, the organic solvent (C) taken into the particles can be released to the outside of the particles over time from the void.
　以上のことから、前記粒子は、形成後に取り込んだ有機溶剤（Ｃ）が短期間もしくは負荷がかからない状態では多量に外部へ放出され難いが、経時的に徐々に有機溶剤（Ｃ）を外部へ放出する性質である徐放性を有するものといえる。 From the above, it is difficult for the particles to release a large amount of the organic solvent (C) taken in after the formation in a short period of time or in a state where no load is applied, but the particles gradually release the organic solvent (C) to the outside over time. It can be said that it has a sustained release property.
　加えて、粒子の外殻は、セルロースナノファイバー（Ａ）を含むため、膜強度は高く、無負荷又は低負荷の通常時には破断し難い。その一方で、当該粒子は、一定又はそれ以上の圧力が加えられることで容易に破断させることができ、取り込まれていた有機溶剤（Ｃ）を外部へ一度に供給させ得ることも可能である。
　なお、本発明の一態様の組成物において、前記粒子に取り込まれない有機溶剤（Ｃ）が存在していてもよい。 In addition, since the outer shell of the particles contains the cellulose nanofibers (A), the film strength is high, and it is difficult to break under normal conditions of no load or low load. On the other hand, the particles can be easily broken by applying a certain or more pressure, and the captured organic solvent (C) can be supplied to the outside at once.
Note that in the composition of one embodiment of the present invention, an organic solvent (C) that is not incorporated into the particles may be present.
　また、前記粒子には、有機溶剤（Ｃ）と共に、水（Ｂ）が取り込まれていてもよい。
　更に、前記粒子には、空気等の気体も取り込まれていてもよい。当該粒子の形成時の撹拌工程にて、組成物中には空気等の気体が混入するが、前記粒子を構成する外殻の内部に、空気等の気体が取り込まれることも考えられる。 Further, water (B) may be incorporated into the particles together with the organic solvent (C).
Further, a gas such as air may be taken into the particles. In the stirring step at the time of the formation of the particles, a gas such as air is mixed into the composition, but it is conceivable that a gas such as air is taken into the inside of the outer shell constituting the particles.
　ところで、セルロースナノファイバー（Ａ）は、水（Ｂ）と水素結合を形成するため、水（Ｂ）との親和性が高い。
　そのため、前記粒子のセルロースナノファイバー（Ａ）を含む外殻は、水（Ｂ）を吸着した状態であってもよい。つまり、前記粒子は、内部に有機溶剤（Ｃ）を取り込みつつ、且つ、水（Ｂ）が外殻に吸着された状態であってもよい。 By the way, the cellulose nanofiber (A) forms a hydrogen bond with water (B), and thus has a high affinity for water (B).
Therefore, the outer shell containing the cellulose nanofibers (A) of the particles may be in a state of adsorbing water (B). That is, the particles may be in a state where the organic solvent (C) is taken in and the water (B) is adsorbed on the outer shell.
　本発明の組成物中において、有機溶剤（Ｃ）が前記粒子に取り込まれる量が多くなるほど、前記粒子とは分離して存在する有機溶剤（Ｃ）から構成される液体の量は少なくなる。
　また、セルロースナノファイバーを含む外殻を備える前記粒子や、前記粒子を形成しておらず水に分散しているセルロースナノファイバーが、分散媒である水分子と多く相互作用する程、水を保持しやすくなるため、セルロースナノファイバー（Ａ）とは分離して存在する水（Ｂ）から構成される液体の量は少なくなると考えられる。粒子から離れて存在する液体の量を少なくすることによって粒子の沈降や凝集を防ぐ観点から、当該組成物中の固形分率は、多いほど好ましい。
　本発明の一態様の組成物中の固形分率は、当該組成物の全量（１００質量％）に対して、好ましくは８０～１００質量％、より好ましくは９０～１００質量％、更に好ましくは９５～１００質量％、より更に好ましくは９８～１００質量％である。 In the composition of the present invention, the larger the amount of the organic solvent (C) incorporated into the particles, the smaller the amount of the liquid composed of the organic solvent (C) present separately from the particles.
Further, the particles having the outer shell containing the cellulose nanofibers, and the cellulose nanofibers that do not form the particles and are dispersed in water, retain water so that the water interacts with a large number of water molecules as a dispersion medium. Therefore, it is considered that the amount of liquid composed of water (B) present separately from the cellulose nanofiber (A) is reduced. From the viewpoint of preventing the particles from settling or aggregating by reducing the amount of the liquid existing apart from the particles, the solid content ratio in the composition is preferably as large as possible.
The solid content in the composition of one embodiment of the present invention is preferably from 80 to 100% by mass, more preferably from 90 to 100% by mass, and still more preferably from 95 to 100% by mass, based on the total amount (100% by mass) of the composition. -100% by mass, more preferably 98-100% by mass.
　本明細書において、組成物中の「固形分率」とは、テトロンメッシュ（＃２００メッシュ）上に組成物を塗布して静置した後に、テトロンメッシュ上に残存している固形分の割合を指し、具体的には、実施例に記載の方法により測定された値を意味する。
　なお、上述のテトロンメッシュ上に残存している固形分には、セルロースナノファイバー（Ａ）だけでなく、前記粒子に取り込まれた有機溶剤（Ｃ）、前記粒子の外殻に保持された水（Ｂ）、及び、前記粒子の外殻の形成には関与していないセルロースナノファイバー（Ａ）に保持された水（Ｂ）等の質量も含まれる。
　そのため、固形分率が多い組成物は、下記［イ］及び［ロ］のうち、少なくとも一方であることを意味する。
［イ］セルロースナノファイバー（Ａ）により構成される外殻の３次元網目構造内や該外殻より内側の空間内に、多くの水（Ｂ）及び有機溶剤（Ｃ）の少なくとも一方が取り込まれている。
［ロ］前記粒子の外殻の形成には関与していないセルロースナノファイバー（Ａ）に、多くの水（Ｂ）及び有機溶剤（Ｃ）の少なくとも一方が保持されている。 In the present specification, the “solid content ratio” in the composition refers to the ratio of the solid content remaining on the tetron mesh after the composition is applied on a tetron mesh (# 200 mesh) and allowed to stand. And specifically, a value measured by the method described in Examples.
The solid content remaining on the tetron mesh described above includes not only the cellulose nanofiber (A), but also the organic solvent (C) incorporated in the particles, and the water ( B), and the mass of water (B) and the like retained in the cellulose nanofibers (A) that are not involved in the formation of the outer shell of the particles.
Therefore, a composition having a high solid content means at least one of the following [A] and [B].
[A] A large amount of at least one of water (B) and the organic solvent (C) is taken into the three-dimensional network structure of the outer shell constituted by the cellulose nanofiber (A) and the space inside the outer shell. ing.
[B] At least one of a large amount of water (B) and an organic solvent (C) is held in the cellulose nanofiber (A) which is not involved in the formation of the outer shell of the particles.
　本発明の一態様の組成物に含まれる、前記粒子の平均粒子径は、組成物中で粒子同士の凝集を抑制する観点から、好ましくは１μｍ以上、より好ましくは５μｍ以上、更に好ましくは７μｍ以上、より更に好ましくは１０μｍ以上、特に好ましくは１５μｍ以上であり、また、組成物中で粒子の浮上を抑制する観点から、好ましくは６０μｍ以下、より好ましくは５０μｍ以下、更に好ましくは４０μｍ以下、より更に好ましくは３５μｍ以下、特に好ましくは３０μｍ以下である。 The average particle diameter of the particles contained in the composition of one embodiment of the present invention is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 7 μm or more, from the viewpoint of suppressing aggregation of the particles in the composition. And still more preferably 10 μm or more, particularly preferably 15 μm or more, and from the viewpoint of suppressing the floating of particles in the composition, preferably 60 μm or less, more preferably 50 μm or less, still more preferably 40 μm or less, and even more. Preferably it is 35 μm or less, particularly preferably 30 μm or less.
　また、本発明の一態様の組成物に含まれる、前記粒子の平均粒子径に対する標準偏差は、一定又はそれ以上の圧力をかけて粒子の外殻を破断させた際に、粒子に取り込まれている有機溶剤の外部への放出量を一定化させる観点から、好ましくは２０μｍ以下、より好ましくは１８μｍ以下、更に好ましくは１５μｍ以下、より更に好ましくは１２μｍ以下であり、また、通常１μｍ以上である。 In addition, the standard deviation with respect to the average particle size of the particles contained in the composition of one embodiment of the present invention is incorporated into the particles when the outer shell of the particles is broken by applying a certain or more pressure. From the viewpoint of stabilizing the amount of organic solvent released to the outside, it is preferably 20 μm or less, more preferably 18 μm or less, still more preferably 15 μm or less, even more preferably 12 μm or less, and usually 1 μm or more.
　なお、本明細書において、前記粒子の平均粒子径、及び平均粒子径に対する標準偏差は、対象となる組成物をデジタル顕微鏡を用いて倍率５００～１０００倍にて観察した際に取得した画像から算出することができる。
　つまり、当該画像に写し出された前記粒子のうち、任意に選択した３６個の粒子の粒径（粒子を構成する外殻の外径）の平均値を上記の「平均粒子径」とすることができる。また、３６個の各粒子の粒径の値から、「平均粒子径に対する標準偏差」も算出することができる。上記標準偏差は母集団の標準偏差であり、上記計算においては、３６個の粒径の値の全てを対象として標準偏差を算出する。 In this specification, the average particle size of the particles and the standard deviation with respect to the average particle size are calculated from images obtained when the target composition is observed at a magnification of 500 to 1000 using a digital microscope. can do.
In other words, the average value of the particle diameters (outer diameters of the outer shells constituting the particles) of the 36 particles arbitrarily selected among the particles displayed in the image is defined as the “average particle diameter”. it can. In addition, the “standard deviation with respect to the average particle size” can be calculated from the value of the particle size of each of the 36 particles. The standard deviation is the standard deviation of the population. In the above calculation, the standard deviation is calculated for all 36 particle size values.
　本発明の一態様の組成物に含まれる、前記粒子の外殻の厚さの平均は、前記粒子の形状安定性を良好とする観点から、好ましくは１０ｎｍ以上、より好ましくは５０ｎｍ以上、更に好ましくは７５ｎｍ以上であり、また、一定又はそれ以上の圧力をかけて粒子の外殻を破断させ易くする観点から、好ましくは２０００ｎｍ以下、より好ましくは１７５０ｎｍ以下、更に好ましくは１５００ｎｍ以下、より更に好ましくは１２５０ｎｍ以下である。 The average thickness of the outer shell of the particles contained in the composition of one embodiment of the present invention is preferably 10 nm or more, more preferably 50 nm or more, and still more preferably, from the viewpoint of improving the shape stability of the particles. Is 75 nm or more, and from the viewpoint of easily breaking the outer shell of the particle by applying a constant or more pressure, preferably 2000 nm or less, more preferably 1750 nm or less, still more preferably 1500 nm or less, even more preferably It is 1250 nm or less.
　なお、本明細書において、前記粒子の外殻の厚さは、対象となる組成物を、ポリエチレンテレフタレートフィルム等の支持材上に塗布及び乾燥して塗膜を形成した後、当該塗膜の断面を、走査型電子顕微鏡（ＳＥＭ）等を用いて観察した際に取得した画像を基に算出することができる。
　つまり、当該画像に写し出された前記粒子のうち、任意に選択した３６個の粒子の粒径の外殻の平均値を、上記の「外殻の厚さの平均」とすることができる。 In the present specification, the thickness of the outer shell of the particles, the target composition, after coating and drying on a support material such as a polyethylene terephthalate film to form a coating, the cross-section of the coating Can be calculated based on an image obtained when observed using a scanning electron microscope (SEM) or the like.
In other words, the average value of the outer shells of the particle diameters of the 36 particles arbitrarily selected among the particles shown in the image can be the above-mentioned “average of outer shell thickness”.
　本発明の一態様の組成物の２３℃、回転数５０ｒｐｍにおける粘度は、貯蔵安定性を良好とし、容器内に保存した際に沈降を抑制する観点から、好ましくは５００ｍＰａ・ｓ以上、より好ましくは１０００ｍＰａ・ｓ以上、更に好ましくは１２００ｍＰａ・ｓ以上であり、また、撹拌容易性及び容器からの取り出し性を良好とする観点から、好ましくは２００００ｍＰａ・ｓ以下、より好ましくは１５０００ｍＰａ・ｓ以下、更に好ましくは１２０００ｍＰａ・ｓ以下である。 The viscosity of the composition of one embodiment of the present invention at 23 ° C. and a rotation speed of 50 rpm is preferably 500 mPa · s or more, and more preferably, from the viewpoint of improving storage stability and suppressing sedimentation when stored in a container. 1000 mPa · s or more, more preferably 1200 mPa · s or more, and from the viewpoint of improving the ease of stirring and taking out of the container, preferably 20,000 mPa · s or less, more preferably 15000 mPa · s or less, and still more preferably. Is 12000 mPa · s or less.
　また、本発明の一態様の組成物の２３℃でのＴＩ値（回転数５ｒｐｍにおける粘度／回転数５０ｒｐｍにおける粘度）は、貯蔵安定性を良好とし、容器内に保存した際に沈降を抑制する観点から、好ましくは１．２以上、より好ましくは２以上、更に好ましくは３以上、より更に好ましくは４以上であり、また、容器からの取り出し性を良好とする観点から、好ましくは２０以下、より好ましくは１５以下、更に好ましくは１０以下、より更に好ましくは８以下である。
　また、本明細書において、組成物の粘度は、ＪＩＳ　Ｚ　８８０３：２０１１に準拠して、Ｂ型粘度計を用いて測定した値を意味する。 The TI value of the composition of one embodiment of the present invention at 23 ° C. (viscosity at a rotation speed of 5 rpm / viscosity at a rotation speed of 50 rpm) indicates good storage stability and suppresses sedimentation when stored in a container. From the viewpoint, it is preferably 1.2 or more, more preferably 2 or more, still more preferably 3 or more, and still more preferably 4 or more, and preferably 20 or less from the viewpoint of improving the removability from the container. It is more preferably 15 or less, further preferably 10 or less, and still more preferably 8 or less.
In this specification, the viscosity of the composition means a value measured using a B-type viscometer according to JIS Z 8803: 2011.
　本発明の一態様の組成物のｐＨは、形成される粒子が安定し、組成物中で分散状態を維持し易いという観点から、好ましくは４以上、より好ましくは５以上、更に好ましくは６以上であり、また、好ましくは１０以下、より好ましくは９以下、更に好ましくは８以下である。
　なお、本明細書において、組成物のｐＨは、２３℃、相対湿度５０％の環境下にて、実施例に記載の方法に基づき測定した値を意味する。 The pH of the composition of one embodiment of the present invention is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more, from the viewpoint that the formed particles are stable and the dispersion state is easily maintained in the composition. And preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
In addition, in this specification, the pH of a composition means the value measured based on the method of an Example in 23 degreeC and 50% of relative humidity environment.
　本発明の一態様の組成物は、上記成分（Ａ）～（Ｃ）以外の成分を含有してもよい。
　ただし、本発明の一態様の組成物において、セルロースナノファイバー（Ａ）、水（Ｂ）及び有機溶剤（Ｃ）の合計含有量は、前記組成物の全量（１００質量％）に対して、好ましくは６０～１００質量％、より好ましくは６５～１００質量％、更に好ましくは７０～１００質量％、より更に好ましくは８０～１００質量％である。 The composition of one embodiment of the present invention may contain components other than the above components (A) to (C).
However, in the composition of one embodiment of the present invention, the total content of the cellulose nanofiber (A), water (B), and organic solvent (C) is preferably based on the total amount of the composition (100% by mass). Is from 60 to 100% by mass, more preferably from 65 to 100% by mass, further preferably from 70 to 100% by mass, even more preferably from 80 to 100% by mass.
　本発明の一態様の組成物の有効成分濃度は、前記組成物の全量（１００質量％）に対して、前記粒子を形成し易くすると共に、形成された粒子の膜強度を向上させる観点から、好ましくは０．５質量％以上、より好ましくは０．７質量％以上、更に好ましくは１．０質量％以上、より更に好ましくは１．５質量％以上であり、また、前記粒子を形成し易くするように、組成物の粘度を適切に調整する観点から、好ましくは５０質量％以下、より好ましくは２０質量％以下、更に好ましくは１５質量％以下、より更に好ましくは１０質量％以下である。
　なお、本明細書において、「有効成分」とは、組成物に含まれる成分のうち、水（Ｂ）及び有機溶剤（Ｃ）を除いた成分を意味し、具体的には、セルロースナノファイバー（Ａ）、セルロースナノファイバー（Ａ）以外の多糖類、及び各種添加剤等を指す。つまり、セルロースナノファイバー（Ａ）に取り込まれた有機溶剤（Ｃ）及び水（Ｂ）の質量は含まれない点で、上述の「固形分率」とは異なる。 The active ingredient concentration of the composition of one embodiment of the present invention is preferably such that the particles are easily formed and the film strength of the formed particles is improved with respect to the total amount of the composition (100% by mass). It is preferably at least 0.5% by mass, more preferably at least 0.7% by mass, still more preferably at least 1.0% by mass, and still more preferably at least 1.5% by mass. From the viewpoint of appropriately adjusting the viscosity of the composition, the content is preferably 50% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and further more preferably 10% by mass or less.
In addition, in this specification, "active ingredient" means the component except water (B) and organic solvent (C) among the components contained in a composition, and specifically, a cellulose nanofiber ( A), polysaccharides other than cellulose nanofiber (A), and various additives. In other words, it differs from the above-mentioned “solid content” in that the mass of the organic solvent (C) and water (B) taken into the cellulose nanofiber (A) is not included.
　セルロースナノファイバー（Ａ）を含む外殻を備え、有機溶剤（Ｃ）を取り込んだ粒子は、配合するセルロースナノファイバー（Ａ）の配合量、セルロースナノファイバー（Ａ）と有機溶剤（Ｃ）との配合量比、及び有機溶剤（Ｃ）の種類等を適宜調整することで、より形成させ易くすることもできる。
　なお、本発明の組成物においては、後述のとおり、ハンセン溶解度パラメータの距離Ｒａが５．８０ＭＰａ１／２以下となる有機溶剤（Ｃ）を配合することで、前記粒子を形成するようにしている。
　また、上記以外にも、セルロースナノファイバー（Ａ）の形状（直径、繊維長、アスペクト比）、水（Ｂ）及び有機溶剤（Ｃ）の配合量、水（Ｂ）と有機溶剤（Ｃ）との配合量比等を適宜設定することによっても、前記粒子を形成し易くすることができる。
　以下、前記粒子を形成するための具体的な手法を中心に、各成分の詳細について説明する。 Particles having an outer shell containing the cellulose nanofiber (A) and incorporating the organic solvent (C) are used to mix the cellulose nanofiber (A) with the organic solvent (C). By appropriately adjusting the compounding ratio, the type of the organic solvent (C), and the like, formation can be facilitated.
In the composition of the present invention, as described later, the particles are formed by blending an organic solvent (C) having a distance Ra of the Hansen solubility parameter of 5.80 MPa 1/2 or less. .
In addition to the above, the shape (diameter, fiber length, aspect ratio) of the cellulose nanofiber (A), the amount of water (B) and the organic solvent (C), the water (B) and the organic solvent (C) The particles can be easily formed by appropriately setting the compounding ratio and the like.
Hereinafter, each component will be described in detail, focusing on a specific method for forming the particles.
＜セルロースナノファイバー（Ａ）＞
　本発明の一態様で用いるセルロースナノファイバー（Ａ）の原料としては、例えば、木材由来のクラフトパルプ又はサルファイトパルプ；クラフトパルプ又はサルファイトパルプを高圧ホモジナイザーやミル等で粉砕した粉末セルロース；粉末セルロースを酸加水分解などの化学処理により精製した微結晶セルロース粉末；コウゾ、雁皮、三椏等の靭皮繊維パルプ；コットンパルプ、ケナフ、麻、イネ、バカス、竹等の植物由来のセルロース系原料；等のセルロース系原料が挙げられる。 <Cellulose nanofiber (A)>
As a raw material of the cellulose nanofiber (A) used in one embodiment of the present invention, for example, wood-derived kraft pulp or sulfite pulp; powdered cellulose obtained by grinding kraft pulp or sulfite pulp with a high-pressure homogenizer or a mill; Microcrystalline cellulose powder obtained by purifying pulp by chemical treatment such as acid hydrolysis; bast fiber pulp such as mulberry, ganpi, mitsumata, etc .; cellulosic raw material derived from plants such as cotton pulp, kenaf, hemp, rice, bacas, bamboo; Cellulose-based raw materials.
　なお、これらの原料中にリグニンが多く残留してしまうと、当該原料の酸化反応を阻害する恐れがあるため、これらの原料に対して、リグニンの除去を施した、セルロース系原料が好ましい。
　また、上述のセルロース系原料を高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式などの分散装置、湿式の高圧または超高圧ホモジナイザー等で微細化したものを使用することもできる。 If a large amount of lignin remains in these raw materials, the oxidation reaction of the raw materials may be hindered. Therefore, a cellulose-based raw material obtained by removing lignin from these raw materials is preferable.
Further, the above-mentioned cellulose-based raw material may be used as finely divided by a high-speed rotation type, colloid mill type, high pressure type, roll mill type, ultrasonic type or other dispersing device, wet type high pressure or ultra high pressure homogenizer, or the like.
　また、これらのセルロース系原料は、化学修飾及び／又は物理修飾して機能性を高めたものであってもよい。ここで、化学修飾としては、アセチル化、カルボキシ化、カルボキシナトリウム化、エステル化、シアノエチル化、アセタール化、エーテル化、アリール化、アルキル化、アクリロイル化、イソシアネート化等によって官能基を付加させること、及び、シリケートやチタネート等の無機物を化学反応やゾルゲル法等によって複合化や被覆化させること等が挙げられる。
　また、物理修飾としては、金属やセラミック原料を、真空蒸着、イオンプレーティング、スパッタリング等の物理蒸着法（ＰＶＤ法）、化学蒸着法（ＣＶＤ法）、無電解メッキや電解メッキ等のメッキ法等によって表面被覆させることが挙げられる。
　なお、これらの変性処理は、セルロース系原料を解繊時もしくは解繊する前後のいずれに行ってもよい。 In addition, these cellulosic raw materials may be those having improved functionality by chemical modification and / or physical modification. Here, the chemical modification includes acetylation, carboxylation, carboxysodiumation, esterification, cyanoethylation, acetalization, etherification, arylation, alkylation, acryloylation, addition of a functional group by isocyanation, etc. And a method in which an inorganic substance such as silicate or titanate is compounded or coated by a chemical reaction, a sol-gel method, or the like.
In addition, as the physical modification, a metal or ceramic raw material is subjected to a physical vapor deposition method (PVD method) such as vacuum deposition, ion plating, and sputtering, a chemical vapor deposition method (CVD method), and a plating method such as electroless plating and electrolytic plating. Surface coating.
These modification treatments may be performed either at the time of defibrating the cellulose-based material or before or after defibrating.
　上述のセルロース系原料は、解繊してナノファイバー化することで、セルロースナノファイバーとすることができる。
　具体的な方法としては、セルロース系原料が水等の分散媒に分散している分散液を調製した後、セルロース系原料にせん断力を印加することで、セルロースナノファイバーを含む分散液とする方法が挙げられる。
　セルロース系原料にせん断力を印加する方法としては、水等の分散媒にセルロース系原料を添加した後、高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式等の装置を用いて調製する方法が好ましい。
　この際、分散液にかかる圧力は、好ましくは５０ＭＰａ以上、より好ましくは１００ＭＰａ以上、更に好ましくは１４０ＭＰａ以上である。
　このような高圧下で、セルロース系原料に強力なせん断力を印加する観点から、湿式の高圧又は超高圧ホモジナイザーを用いることが好ましい。 The above-mentioned cellulose-based material can be made into cellulose nanofibers by defibrating and forming nanofibers.
As a specific method, after preparing a dispersion in which the cellulose-based material is dispersed in a dispersion medium such as water, a shear force is applied to the cellulose-based material to obtain a dispersion containing cellulose nanofibers. Is mentioned.
As a method of applying a shearing force to the cellulosic material, after adding the cellulosic material to a dispersion medium such as water, using a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, an ultrasonic type or the like, The method of preparation is preferred.
At this time, the pressure applied to the dispersion is preferably 50 MPa or more, more preferably 100 MPa or more, and still more preferably 140 MPa or more.
From the viewpoint of applying a strong shearing force to the cellulosic material under such a high pressure, it is preferable to use a wet high-pressure or ultra-high-pressure homogenizer.
　本発明の一態様で用いる、セルロースナノファイバー（Ａ）の直径（太さ）の平均は、前記粒子を形成し易くすると共に、形成された粒子の膜強度を向上させる観点から、好ましくは１．０ｎｍ以上、より好ましくは１．５ｎｍ以上、更に好ましくは２．０ｎｍ以上、より更に好ましくは２．５ｎｍ以上であり、また、好ましくは１０００ｎｍ以下、より好ましくは５００ｎｍ以下、更に好ましくは２００ｎｍ以下、より更に好ましくは１００ｎｍ以下である。 The average of the diameter (thickness) of the cellulose nanofiber (A) used in one embodiment of the present invention is preferably 1. from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. 0 nm or more, more preferably 1.5 nm or more, still more preferably 2.0 nm or more, even more preferably 2.5 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less, and still more preferably 200 nm or less. More preferably, it is 100 nm or less.
　本発明の一態様で用いる、セルロースナノファイバー（Ａ）の繊維長の平均は、前記粒子を形成し易くすると共に、形成された粒子の膜強度を向上させる観点から、好ましくは０．０１μｍ以上、より好ましくは０．１μｍ以上、更に好ましくは０．２μｍ以上、より更に好ましくは０．３μｍ以上であり、また、好ましくは１０μｍ以下、より好ましくは７．０μｍ以下、更に好ましくは５．０μｍ以下、より更に好ましくは２．５μｍ以下である。 The average of the fiber length of the cellulose nanofiber (A) used in one embodiment of the present invention is preferably 0.01 μm or more from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. It is more preferably at least 0.1 μm, further preferably at least 0.2 μm, even more preferably at least 0.3 μm, and preferably at most 10 μm, more preferably at most 7.0 μm, even more preferably at most 5.0 μm, Even more preferably, it is 2.5 μm or less.
　本発明の一態様で用いる、セルロースナノファイバー（Ａ）の平均アスペクト比は、前記粒子を形成し易くすると共に、形成された粒子の膜強度を向上させる観点から、好ましくは５以上、より好ましくは１０以上、更に好ましくは１５以上であり、また、好ましくは１００００以下であり、より好ましくは５０００以下であり、更に好ましくは、３０００以下、より更に好ましくは１０００以下、特に好ましくは５００以下である。 The average aspect ratio of the cellulose nanofiber (A) used in one embodiment of the present invention is preferably 5 or more, more preferably 5 or more, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. It is 10 or more, more preferably 15 or more, and preferably 10,000 or less, more preferably 5,000 or less, further preferably 3,000 or less, still more preferably 1,000 or less, and particularly preferably 500 or less.
　なお、「アスペクト比」とは、対象であるセルロースナノファイバーの太さに対する長さの割合〔長さ／太さ〕であり、セルロースナノファイバーの「長さ」とは、当該セルロースナノファイバーの最も離れた２点間の距離を指す。
　また、対象となるセルロースナノファイバーの一部分が、他のセルロースナノファイバーと接触して「長さ」の認定が難しい場合には、対象のセルロースナノファイバーのうち、太さの測定が可能な部分のみの長さを測定し、当該部分のアスペクト比が上記範囲であればよい。
　セルロースナノファイバー（Ａ）の直径（太さ）及び繊維長は、透過型電子顕微鏡を用いて測定することができる。また、セルロースナノファイバー（Ａ）の直径（太さ）の平均及び繊維長の平均は、任意に選択した複数のセルロースナノファイバーの直径（太さ）及び繊維長を測定し、それぞれの平均値を算出することで得られる。セルロースナノファイバー（Ａ）の平均アスペクト比は、こうして得られた直径（太さ）の平均と繊維長の平均とを用いて算出することができる。セルロースナノファイバー（Ａ）の直径（太さ）、繊維長、これらの平均値、及び、平均アスペクト比は具体的には実施例に示す方法で算出することができる。 The “aspect ratio” is a ratio of the length to the thickness of the target cellulose nanofiber [length / thickness], and the “length” of the cellulose nanofiber is the most of the cellulose nanofiber. Refers to the distance between two distant points.
If a part of the target cellulose nanofiber is in contact with another cellulose nanofiber and it is difficult to determine the “length”, only the part of the target cellulose nanofiber whose thickness can be measured can be used. Is measured, and the aspect ratio of the portion may be within the above range.
The diameter (thickness) and fiber length of the cellulose nanofiber (A) can be measured using a transmission electron microscope. The average of the diameter (thickness) and the average of the fiber length of the cellulose nanofibers (A) are obtained by measuring the diameter (thickness) and the fiber length of a plurality of arbitrarily selected cellulose nanofibers, and calculating the average value of each. It is obtained by calculating. The average aspect ratio of the cellulose nanofiber (A) can be calculated using the thus obtained average of the diameter (thickness) and the average of the fiber length. The diameter (thickness), fiber length, average value, and average aspect ratio of the cellulose nanofiber (A) can be specifically calculated by the methods described in Examples.
　本発明の一態様の組成物において、セルロースナノファイバー（Ａ）の配合量は、当該組成物の全量（１００質量％）に対して、前記粒子を形成し易くすると共に、形成された粒子の膜強度を向上させる観点から、好ましくは０．７質量％以上、より好ましくは０．８質量％以上、更に好ましくは１．０質量％以上、より更に好ましくは１．２質量％以上であり、また、前記粒子を形成し易くするように、組成物の粘度を適切に調整する観点から、好ましくは１５質量％以下、より好ましくは１０質量％以下、更に好ましくは７質量％以下、より更に好ましくは５質量％以下、特に好ましくは３質量％以下である。 In the composition of one embodiment of the present invention, the blending amount of the cellulose nanofiber (A) facilitates the formation of the particles with respect to the total amount (100% by mass) of the composition, and a film of the formed particles. From the viewpoint of improving the strength, it is preferably at least 0.7% by mass, more preferably at least 0.8% by mass, still more preferably at least 1.0% by mass, even more preferably at least 1.2% by mass, and From the viewpoint of appropriately adjusting the viscosity of the composition so as to facilitate the formation of the particles, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less, and still more preferably It is at most 5% by mass, particularly preferably at most 3% by mass.
＜水（Ｂ）＞
　本発明の一態様の組成物において、水（Ｂ）は、そのほとんどが、前記粒子が備える外殻に吸着されているか、又は、前記粒子の外側に存在している。
　ただし、水（Ｂ）の一部が、前記粒子の内部で有機溶剤（Ｃ）と共に内包されていてもよい。 <Water (B)>
In the composition of one embodiment of the present invention, most of the water (B) is adsorbed on the outer shell of the particle, or is present outside the particle.
However, a part of the water (B) may be included together with the organic solvent (C) inside the particles.
　本発明の一態様の組成物において、適度な粘度を有する組成物を調製すると共に、前記粒子を形成し易くする観点から、水（Ｂ）の配合量は、当該組成物の全量（１００質量％）に対して、好ましくは１５質量％以上、より好ましくは３０質量％以上、更に好ましくは５０質量％以上、より更に好ましくは６０質量％以上であり、また、好ましくは９９質量％以下、より好ましくは９８．７質量％以下、更に好ましくは９８．５質量％以下である。 In the composition of one embodiment of the present invention, from the viewpoint of preparing a composition having an appropriate viscosity and facilitating the formation of the particles, the blending amount of water (B) is determined based on the total amount of the composition (100% by mass). ), Preferably 15% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and preferably 99% by mass or less, more preferably Is 98.7% by mass or less, more preferably 98.5% by mass or less.
　本発明の一態様の組成物において、適度な粘度を有する組成物を調製すると共に、前記粒子を形成し易くする観点から、セルロースナノファイバー（Ａ）１００質量部に対する、水（Ｂ）の配合割合は、好ましくは５００質量部以上、より好ましくは１０００質量部以上、更に好ましくは２０００質量部以上、より更に好ましくは３０００質量部以上であり、また、好ましくは２００００質量部以下、より好ましくは１５０００質量部以下、更に好ましくは１００００質量部以下である。 In the composition of one embodiment of the present invention, from the viewpoint of preparing a composition having an appropriate viscosity and facilitating the formation of the particles, the mixing ratio of water (B) to 100 parts by mass of the cellulose nanofiber (A) Is preferably 500 parts by mass or more, more preferably 1000 parts by mass or more, still more preferably 2000 parts by mass or more, still more preferably 3000 parts by mass or more, and preferably 20,000 parts by mass or less, more preferably 15,000 parts by mass. Parts by mass, more preferably 10,000 parts by mass or less.
　なお、本発明の一態様の組成物は、セルロースナノファイバー（Ａ）及び水（Ｂ）を含む水分散液に、有機溶剤（Ｃ）を配合してなるものであることが好ましい。
　予め、前記水分散液を調製した後、有機溶剤（Ｃ）を配合することで、セルロースナノファイバー（Ａ）が有機溶剤（Ｃ）を取り込み易くなり、前記粒子が形成され易くなる。
　当該水分散液は、セルロースナノファイバー（Ａ）と水（Ｂ）との配合量比が上記範囲となるように、各成分を配合して調製することが好ましい。
　また、当該水分散液には、セルロースナノファイバー（Ａ）及び水（Ｂ）と共に、成分（Ａ）～（Ｃ）以外の他の成分を含有してもよい。 Note that the composition of one embodiment of the present invention is preferably formed by mixing an organic solvent (C) with an aqueous dispersion containing cellulose nanofibers (A) and water (B).
By preparing the aqueous dispersion in advance and blending the organic solvent (C), the cellulose nanofiber (A) can easily take in the organic solvent (C), and the particles can be easily formed.
It is preferable that the aqueous dispersion is prepared by blending the respective components such that the blending ratio of the cellulose nanofiber (A) and the water (B) is within the above range.
Further, the aqueous dispersion may contain components other than the components (A) to (C) together with the cellulose nanofiber (A) and the water (B).
＜有機溶剤（Ｃ）＞
　本発明で用いる有機溶剤（Ｃ）は、下記式（１）で表される、２５℃における、ハンセン溶解度パラメータの距離Ｒａが５．８０ＭＰａ１／２以下である有機溶剤である。
Figure JPOXMLDOC01-appb-M000003
（前記式中、δＤは、有機溶剤（Ｃ）のハンセン溶解度パラメータの分散成分、
　δＰは、有機溶剤（Ｃ）のハンセン溶解度パラメータの極性成分、
　δＨは、有機溶剤（Ｃ）のハンセン溶解度パラメータの水素結合成分を示す。） <Organic solvent (C)>
The organic solvent (C) used in the present invention is an organic solvent represented by the following formula (1) and having a distance Ra of the Hansen solubility parameter at 25 ° C. of 5.80 MPa 1/2 or less.
Figure JPOXMLDOC01-appb-M000003
(Wherein δD is a dispersion component of the Hansen solubility parameter of the organic solvent (C),
δP is the polar component of the Hansen solubility parameter of the organic solvent (C),
δH indicates the hydrogen bonding component of the Hansen solubility parameter of the organic solvent (C). )
　ハンセン溶解度パラメータは、ヒルデブランド（Ｈｉｌｄｅｂｒａｎｄ）によって導入された溶解度パラメータを、ハンセン（Ｈａｎｓｅｎ）が、δＤ（分散成分）、δＰ（極性成分）、δＨ（水素結合成分）の３成分に分割し、３次元空間に示したものである。
　なお、δＤ、δＰ、及びδＨの値は、有機溶剤ごとに固有の値であって、特定の計算から算出された値である。
　より具体的には、ハンセン溶解度パラメータの定義および計算方法は、「Ｈａｎｓｅｎ　Ｓｏｌｕｂｉｌｉｔｙ　Ｐａｒａｍｅｔｅｒｓ：　Ａ　Ｕｓｅｒｓ　Ｈａｎｄｂｏｏｋ（Ｃｈａｒｌｅｓ　Ｍ.　Ｈａｎｓｅｎ著、ＣＲＣプレス、２００７年）」に記載されたとおりである。 The Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components of Hansen, δD (dispersion component), δP (polar component), and δH (hydrogen bonding component). It is shown in a dimensional space.
Note that the values of δD, δP, and δH are values specific to each organic solvent, and are values calculated from specific calculations.
More specifically, the definition and calculation method of the Hansen solubility parameter are as described in "Hansen Solubility Parameters: A Users Handbook (by Charles M. Hansen, CRC Press, 2007)".
　また、本明細書において、δＤ、δＰ、及びδＨの値は、計算ソフト「Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03」（Steven Abbott,Charles M. Hansen,Hiroshi Yamamoto著）に含まれる、データベースの値を用いた。
　後述の実施例及び比較例で用いた、代表的な有機溶剤のδＤ、δＰ、及びδＨの値、並びに、上記式（１）から算出される距離Ｒａ（いずれも単位は「ＭＰａ１／２」）を表１に示す。 In the present specification, the values of δD, δP, and δH are calculated in a database included in calculation software “Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03” (Steven Abbott, Charles M. Hansen, Hiroshi Yamamoto). Was used.
The values of δD, δP, and δH of typical organic solvents used in Examples and Comparative Examples described later, and the distance Ra calculated from the above formula (1) (all units are “MPa 1/2 ”) ) Are shown in Table 1.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　なお、表１に示された以外の有機溶剤のδＤ、δＰ、及びδＨの値は、その有機溶剤の分子構造等から算出することができ、もしくは、表１に示すようなδＤ、δＰ、及びδＨの値が各種文献等により既知である有機溶剤との溶解性についての実験を行うことでも算出可能である。 The values of δD, δP, and δH of the organic solvent other than those shown in Table 1 can be calculated from the molecular structure of the organic solvent or the like, or δD, δP, and The value of δH can also be calculated by conducting an experiment on the solubility with an organic solvent known from various literatures.
　本発明者らは、配合する有機溶剤（Ｃ）の種類によって、前記粒子が形成される場合と、前記粒子が形成されない場合とがあることに着目した。
　そして、それぞれの有機溶剤のハンセン溶解度パラメータを３次元空間にプロットしたところ、当該３次元空間内において、前記粒子が形成される場合に用いた有機溶剤は、ある領域に密集して分布していることがわかった。
　そこで、前記粒子が形成された有機溶剤のプロットが全て内側に含まれ、前記粒子が形成されなかった有機溶剤のプロットが外側にくるような、最大の球を作図したところ、当該球の半径は「５．８０ＭＰａ１／２」となった。
　式（１）から算出される距離Ｒａは、ハンセン溶解度パラメータの３次元空間における、対象となる有機溶剤のプロットと、当該球の中心との距離を意味する。つまり、距離Ｒａが、当該球の半径である「５．８０ＭＰａ１／２」以下であれば、対象となる有機溶剤のプロットは、当該球の内側に位置しており、前記粒子を形成可能と判断し得る。
　一方で、距離Ｒａが５．８０ＭＰａ１／２超となる有機溶剤は、前記粒子を形成し難いと考えられる。 The present inventors have paid attention to the case where the particles are formed and the case where the particles are not formed, depending on the type of the organic solvent (C) to be blended.
When the Hansen solubility parameters of the respective organic solvents are plotted in a three-dimensional space, the organic solvents used when the particles are formed are densely distributed in a certain area in the three-dimensional space. I understand.
Therefore, when plotting the largest sphere such that the plot of the organic solvent in which the particles are formed is all included inside and the plot of the organic solvent in which the particles are not formed is outside, the radius of the sphere is "5.80 MPa 1/2 ".
The distance Ra calculated from Expression (1) means the distance between the plot of the target organic solvent and the center of the sphere in the three-dimensional space of the Hansen solubility parameter. That is, if the distance Ra is equal to or less than the radius of the sphere, “5.80 MPa 1/2 ”, the plot of the target organic solvent is located inside the sphere, and the particles can be formed. I can judge.
On the other hand, an organic solvent having a distance Ra of more than 5.80 MPa 1/2 is considered to be difficult to form the particles.
　実際に、距離Ｒａが５．８０ＭＰａ１／２以下の有機溶剤（Ｃ）は、表１に示すとおり、ヘプタン、ｎ－ヘキサデカン、トルエン、シクロヘキサノン、メチルエチルケトン、ｎ－ドデカンであるが、後述の実施例に示すとおり、これらの有機溶剤を用いた場合には、前記粒子が形成可能との結果が得られた。
　この結果に鑑みれば、表１に示す有機溶剤以外で、距離Ｒａが５．８０ＭＰａ１／２以下となる有機溶剤（Ｃ）であれば、前記粒子が形成できると推測される。 Actually, as shown in Table 1, the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is heptane, n-hexadecane, toluene, cyclohexanone, methyl ethyl ketone, or n-dodecane. As shown in Table 2, when these organic solvents were used, the result that the particles could be formed was obtained.
In view of this result, it is presumed that the particles can be formed with an organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less, other than the organic solvents shown in Table 1.
　なお、本発明の組成物で用いる有機溶剤（Ｃ）は、単独で用いてもよく、２種以上を併用した混合溶剤としてもよい。
　有機溶剤（Ｃ）が混合溶剤の場合、混合溶剤の混合比（体積比）から、加重平均のハンセン溶解度パラメータの３成分（δＤ、δＰ、δＨ）の値を求め、上記式（１）から算出した距離Ｒａが５．８０ＭＰａ１／２以下となればよい。 The organic solvent (C) used in the composition of the present invention may be used alone or as a mixed solvent using two or more kinds.
When the organic solvent (C) is a mixed solvent, the values of the three components (δD, δP, δH) of the weighted average Hansen solubility parameter are determined from the mixing ratio (volume ratio) of the mixed solvent, and calculated from the above equation (1). It is sufficient that the determined distance Ra is equal to or less than 5.80 MPa 1/2 .
　例えば、有機溶剤（Ｃ）として、有機溶剤α及びβからなる混合溶剤を用いる場合、混合溶剤のハンセン溶解度パラメータの３成分δＤｍ、δＰｍ、δＨｍは、以下のように算出することができる。
　つまり、有機溶剤αのハンセン溶解度パラメータの３成分をδＤα、δＰα、δＨαとし、有機溶剤βのハンセン溶解度パラメータの３成分をδＤβ、δＰβ、δＨβとし、有機溶剤αの体積分率をｖα、有機溶剤βの体積分率をｖβとした場合、δＤｍ、δＰｍ、δＨｍは下記式から算出できる。
・δＤｍ＝（ｖα×δＤα＋ｖβ×δＤβ）／（ｖα＋ｖβ）
・δＰｍ＝（ｖα×δＰα＋ｖβ×δＰβ）／（ｖα＋ｖβ）
・δＨｍ＝（ｖα×δＨα＋ｖβ×δＨβ）／（ｖα＋ｖβ）
　そして、上記式から算出したδＤｍ、δＰｍ、δＨｍの値を用いて、前記式（１）から距離Ｒａを求めることができる。 For example, as the organic solvent (C), when using a mixed solvent composed of an organic solvent α and beta, 3-component [delta] D m Hansen parameter of the mixed solvent, [delta] P m, delta] H m can be calculated as follows .
That is, the three components of Hansen parameters of the organic solvent α δD α, δP α, and delta] H alpha, the three components of Hansen parameters of the organic solvents beta [delta] D beta, [delta] P beta, and delta] H beta, the volume of the organic solvent alpha the rate v alpha, if the volume fraction of organic solvents beta was v β, δD m, δP m , δH m can be calculated from the following equation.
· ΔD m = (v α × δD α + v β × δD β) / (v α + v β)
ΔP m = (v α × δP α + v β × δP β ) / (v α + v β )
ΔH m = (v α × δH α + v β × δH β ) / (v α + v β )
Then, using calculated from the equation [delta] D m, [delta] P m, the value of delta] H m, it is possible to determine the distance Ra from the equation (1).
　そのため、１種単独では距離Ｒａが５．８０ＭＰａ１／２超となる有機溶剤であっても、当該有機溶剤に、距離Ｒａが５．８０ＭＰａ１／２以下の有機溶剤等の他の有機溶剤と、適切な体積比で混合し、距離Ｒａを５．８０ＭＰａ１／２以下となるように調製した混合溶剤とすることで、前記粒子を形成し得る有機溶剤（Ｃ）とすることも可能である。
　例えば、１種単独では距離Ｒａが５．８０ＭＰａ１／２超となる有機溶剤を取り込んだ粒子を含む組成物を得たい場合には、距離Ｒａが５．８０ＭＰａ１／２以下の他の有機溶剤と混合して調製した、上記のような混合溶剤を用いることで、調製可能と考えられる。
　また、ハンセン溶解度パラメータは上述した３次元空間におけるベクトルで表現されるため、単独で距離Ｒａが５．８０ＭＰａ１／２超となる第１の有機溶剤と、単独で距離Ｒａが５．８０ＭＰａ１／２超となる第２の有機溶剤であって、上述した３次元空間における球の中心に対して第１の有機溶剤とは反対側に位置する第２の有機溶剤とを混合することによっても、距離Ｒａが５．８０ＭＰａ１／２以下となる混合溶剤を調製し得る。 Therefore, even in alone organic solvent distance Ra of 5.80MPa 1/2 greater, to the organic solvent, the distance Ra and the other organic solvents such as organic solvents 5.80MPa 1/2 or less An organic solvent (C) capable of forming the particles can be obtained by mixing the mixture at an appropriate volume ratio and preparing a mixed solvent prepared so that the distance Ra is 5.80 MPa 1/2 or less. .
For example, when it is desired to obtain a composition containing particles incorporating an organic solvent having a distance Ra of more than 5.80 MPa 1/2 by one type alone, another organic solvent having a distance Ra of 5.80 MPa 1/2 or less It is thought that it can be prepared by using the above-mentioned mixed solvent prepared by mixing with.
Further, since the Hansen solubility parameter represented by a vector in three-dimensional space as described above, the first organic solvent alone distance Ra of 5.80MPa 1/2 than alone distance Ra is 5.80MPa 1 / a second organic solvent comprising a 2 exceeds even by mixing a second organic solvent which is positioned on the opposite side of the first organic solvent with respect to the center of the sphere in the 3-dimensional space as described above, A mixed solvent having a distance Ra of 5.80 MPa 1/2 or less can be prepared.
　なお、本発明においては、距離Ｒａが５．８０ＭＰａ１／２以下となる有機溶剤（Ｃ）を用いることで、他の有機溶剤を用いる場合に比べて、前記粒子は形成し易くなるが、更に成分（Ａ）、（Ｂ）及び（Ｃ）の配合量の調整や、成分（Ａ）の形状、及び修飾基の選択を行うことによって、より粒子を形成し易くすることができると考えられる。
　そのため、本発明では、距離Ｒａが５．８０ＭＰａ１／２以下となる有機溶剤（Ｃ）を用いると共に、本明細書の各成分の項目に記載の事項を適宜考慮して、より容易に前記粒子を形成できるように調製することが好ましい。 In the present invention, by using the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less, the particles are more easily formed than in the case of using another organic solvent. It is considered that particles can be more easily formed by adjusting the amounts of the components (A), (B) and (C) and selecting the shape of the component (A) and the modifying group.
Therefore, in the present invention, the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is used, and the particles are more easily obtained by appropriately considering the items described in the item of each component in the present specification. Is preferably prepared so that
　本発明の一態様で用いる有機溶剤（Ｃ）は、炭素数２０未満の有機溶剤（Ｃ１）を含むことが好ましい。
　炭素数２０未満の有機溶剤（Ｃ１）は、セルロースナノファイバー（Ａ）に取り込まれ易く、前記粒子が形成され易い。
　つまり、炭素数が大きい有機溶剤は、有機溶剤の分子同士が集まり易く、また、粘度が高いため、真球に近い粒子の形成が行われ難くなる。その結果、このような有機溶剤は、セルロースナノファイバー（Ａ）に取り込まれずに、前記粒子の外側に残存する割合が多くなると考えられる。
　なお、有機溶剤（Ｃ１）の炭素数は、好ましくは２０未満、より好ましくは１～１８、更に好ましくは１～１６である。 The organic solvent (C) used in one embodiment of the present invention preferably contains an organic solvent (C1) having less than 20 carbon atoms.
The organic solvent (C1) having less than 20 carbon atoms is easily taken into the cellulose nanofiber (A), and the particles are easily formed.
That is, in an organic solvent having a large number of carbon atoms, molecules of the organic solvent are likely to collect with each other, and since the viscosity is high, it is difficult to form particles close to a true sphere. As a result, it is considered that such an organic solvent is not taken into the cellulose nanofiber (A), but remains at a higher rate outside the particles.
In addition, the carbon number of the organic solvent (C1) is preferably less than 20, more preferably 1 to 18, and still more preferably 1 to 16.
　上記観点から、有機溶剤（Ｃ）中の有機溶剤（Ｃ１）の配合割合は、有機溶剤（Ｃ）の全量（１００質量％）基準で、好ましくは２０質量％以上、より好ましくは３５質量％以上、更に好ましくは５０質量％以上、より更に好ましくは７０質量％以上である。 From the above viewpoint, the blending ratio of the organic solvent (C1) in the organic solvent (C) is preferably 20% by mass or more, more preferably 35% by mass or more based on the total amount (100% by mass) of the organic solvent (C). , More preferably 50% by mass or more, even more preferably 70% by mass or more.
　また、本発明の一態様の組成物において、前記粒子を形成し易くする観点から、有機溶剤（Ｃ）の２５℃における粘度は、好ましくは０．１ｍＰａ・ｓ以上、より好ましくは０．１５ｍＰａ・ｓ以上、更に好ましくは０．２ｍＰａ・ｓ以上、より更に好ましくは０．２５ｍＰａ・ｓ以上であり、また、好ましくは３０ｍＰａ・ｓ以下、より好ましくは１０ｍＰａ・ｓ以下、更に好ましくは６．０ｍＰａ・ｓ以下、より更に好ましくは２．８ｍＰａ・ｓ以下である。 In the composition of one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the viscosity of the organic solvent (C) at 25 ° C is preferably 0.1 mPa · s or more, more preferably 0.15 mPa · s. s or more, more preferably 0.2 mPa · s or more, even more preferably 0.25 mPa · s or more, and preferably 30 mPa · s or less, more preferably 10 mPa · s or less, and still more preferably 6.0 mPa · s or less. s or less, more preferably 2.8 mPa · s or less.
　本発明の一態様の組成物において、前記粒子を形成し易くする観点から、有機溶剤（Ｃ）の配合量は、当該組成物の全量（１００質量％）に対して、好ましくは０．０５質量％以上、より好ましくは０．１質量％以上、更に好ましくは０．５質量％以上、より更に好ましくは０．８質量％以上であり、また、好ましくは８０質量％以下、より好ましくは６０質量％以下、より好ましくは４５質量％以下、更に好ましくは４２質量％以下、更に好ましくは４０質量％以下、更に好ましくは３８質量％以下である。 In the composition of one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the amount of the organic solvent (C) is preferably 0.05% by mass based on the total amount (100% by mass) of the composition. % Or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass. %, More preferably 45% by mass or less, further preferably 42% by mass or less, further preferably 40% by mass or less, and still more preferably 38% by mass or less.
　本発明の一態様の組成物において、前記粒子を形成し易くする観点から、セルロースナノファイバー（Ａ）１００質量部に対する、有機溶剤（Ｃ）の配合割合は、好ましくは１質量部以上、より好ましくは５質量部以上、更に好ましくは１０質量部、より更に好ましくは５０質量部以上、特に好ましくは７５質量部以上、最も好ましくは９０質量部以上であり、また、好ましくは６０００質量部以下、より好ましくは４５００質量部以下、更に好ましくは４０００質量部以下、より更に好ましくは３５００質量部以下である。 In the composition of one embodiment of the present invention, the blending ratio of the organic solvent (C) to 100 parts by mass of the cellulose nanofiber (A) is preferably 1 part by mass or more, and more preferably from the viewpoint of facilitating the formation of the particles. Is at least 5 parts by mass, more preferably at least 10 parts by mass, even more preferably at least 50 parts by mass, particularly preferably at least 75 parts by mass, most preferably at least 90 parts by mass, and also preferably at most 6000 parts by mass. It is preferably at most 4,500 parts by mass, more preferably at most 4,000 parts by mass, even more preferably at most 3,500 parts by mass.
　本発明の一態様の組成物において、前記粒子を形成し易くする観点から、水（Ｂ）と有機溶剤（Ｃ）との配合量比〔（Ｂ）／（Ｃ）〕は、質量比で、好ましくは０．１以上、より好ましくは０．５以上、更に好ましくは１．０以上、より更に好ましくは１．５以上であり、また、好ましくは１０００以下、より好ましくは７００以下、更に好ましくは５００以下、より更に好ましくは３００以下、特に好ましくは１００以下である。 In the composition of one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the blending ratio [(B) / (C)] of water (B) and the organic solvent (C) is expressed by mass ratio, It is preferably at least 0.1, more preferably at least 0.5, further preferably at least 1.0, even more preferably at least 1.5, and preferably at most 1,000, more preferably at most 700, still more preferably It is at most 500, more preferably at most 300, particularly preferably at most 100.
＜成分（Ａ）～（Ｃ）以外の他の成分＞
　本発明の一態様の組成物において、本発明の効果を損なわない範囲で、成分（Ａ）～（Ｃ）以外の他の成分を含有してもよい。
　このような他の成分としては、前記組成物の用途に応じて適宜選択されるが、例えば、着色剤、酸化防止剤、ｐＨ調整剤、甘味料、香料、防腐剤、紫外線吸収剤、重合禁止剤、防菌剤、殺虫剤、消泡剤、気泡剤、凝集剤、増粘剤、可塑剤、改質剤、防炎剤、難燃剤等が挙げられる。 <Other components other than components (A) to (C)>
The composition of one embodiment of the present invention may contain components other than the components (A) to (C) as long as the effects of the present invention are not impaired.
Such other components are appropriately selected according to the use of the composition, and include, for example, a colorant, an antioxidant, a pH adjuster, a sweetener, a flavor, a preservative, an ultraviolet absorber, and a polymerization inhibitor. Agents, fungicides, insecticides, defoamers, foaming agents, flocculants, thickeners, plasticizers, modifiers, flame retardants, flame retardants and the like.
　本発明の一態様の組成物において、界面活性剤を含有してもよい。
　ただし、界面活性剤を含む組成物を人体に触れる用途に使用する場合、特に、敏感肌の使用者にとって、当該界面活性剤は浸透剤及び刺激的な刺激物ともなる。また、界面活性剤を含む組成物は、当該組成物の物性の安定性に影響を与える懸念もある。
　そのため、本発明一態様の組成物において、界面活性剤の含有量は少ないほど好ましい。
　上記観点から、本発明の一態様の組成物において、界面活性剤の含有量は、セルロースナノファイバー（Ａ）の全量１００質量部に対して、好ましくは１０質量部未満、より好ましくは１質量部未満、更に好ましくは０．１質量部未満、より更に好ましくは０．０１質量部未満、特に好ましくは０．００１質量部未満、最も好ましくは０質量部である。 In the composition of one embodiment of the present invention, a surfactant may be contained.
However, when the composition containing a surfactant is used for the purpose of touching the human body, the surfactant also becomes a penetrant and an irritating irritant, especially for users with sensitive skin. Further, there is a concern that the composition containing a surfactant may affect the stability of physical properties of the composition.
Therefore, in the composition of one embodiment of the present invention, the content of the surfactant is preferably as small as possible.
From the above viewpoint, in the composition of one embodiment of the present invention, the content of the surfactant is preferably less than 10 parts by mass, more preferably 1 part by mass, based on 100 parts by mass of the total amount of the cellulose nanofiber (A). Less than 0.1 part by mass, more preferably less than 0.01 part by mass, particularly preferably less than 0.001 part by mass, and most preferably 0 part by mass.
　また、本発明の一態様の組成物において、セルロースナノファイバー（Ａ）以外の多糖類を含有してもよいが、前記粒子の熱的安定性を向上させると共に、粒子を形成し易くする観点から、当該多糖類の含有量は少ないほど好ましい。
　上記観点から、本発明の一態様の組成物において、セルロースナノファイバー（Ａ）以外の多糖類の含有量は、セルロースナノファイバー（Ａ）の全量１００質量部に対して、好ましくは１０質量部未満、より好ましくは１質量部未満、更に好ましくは０．１質量部未満、より更に好ましくは０．０１質量部未満、特に好ましくは０質量部である。 Further, the composition of one embodiment of the present invention may contain a polysaccharide other than the cellulose nanofiber (A), but from the viewpoint of improving the thermal stability of the particles and facilitating the formation of the particles. The smaller the content of the polysaccharide, the better.
From the above viewpoint, in the composition of one embodiment of the present invention, the content of the polysaccharide other than the cellulose nanofibers (A) is preferably less than 10 parts by mass relative to 100 parts by mass of the total amount of the cellulose nanofibers (A). , More preferably less than 1 part by mass, further preferably less than 0.1 part by mass, still more preferably less than 0.01 part by mass, particularly preferably 0 part by mass.
〔組成物の製造方法〕
　本発明の組成物の製造方法としては、特に制限はないが、前記粒子を形成し易くする観点から、下記工程（１）～（２）を有する方法が好ましい。
・工程（１）：セルロースナノファイバー（Ａ）及び水（Ｂ）を含む水分散液を調製する工程。
・工程（２）：工程（１）で得た水分散液に、有機溶剤（Ｃ）を添加する工程。
　なお、工程（１）及び（２）で用いる、成分（Ａ）～（Ｃ）の詳細は、上述のとおりである。 (Production method of the composition)
The method for producing the composition of the present invention is not particularly limited, but a method having the following steps (1) and (2) is preferable from the viewpoint of facilitating the formation of the particles.
Step (1): a step of preparing an aqueous dispersion containing the cellulose nanofiber (A) and water (B).
Step (2): a step of adding an organic solvent (C) to the aqueous dispersion obtained in Step (1).
The details of the components (A) to (C) used in the steps (1) and (2) are as described above.
＜工程（１）＞
　工程（１）は、セルロースナノファイバー（Ａ）及び水（Ｂ）を含む水分散液を調製する工程である。
　本工程において、市販の水分散液を用いる場合には、当該工程は省略してもよく、また、市販の水分散液に、セルロースナノファイバー（Ａ）又は水（Ｂ）を加え、所望の配合量とした水分散液に調製してもよい。 <Step (1)>
Step (1) is a step of preparing an aqueous dispersion containing cellulose nanofibers (A) and water (B).
In the case where a commercially available aqueous dispersion is used in this step, the step may be omitted. In addition, the cellulose nanofiber (A) or water (B) is added to the commercially available aqueous dispersion, and a desired blending is performed. It may be prepared in a volume of aqueous dispersion.
　また、成分（Ａ）～（Ｃ）以外の他の成分を配合する場合には、工程（１）の水分散液の調製の際に配合してもよく、工程（１）と工程（２）との間に配合してもよく、工程（２）の際に配合してもよく、工程（２）の後に配合してもよい。 When components other than the components (A) to (C) are blended, they may be blended in the preparation of the aqueous dispersion in the step (1), and the steps (1) and (2) May be added during the step (2), may be added during the step (2), or may be added after the step (2).
　工程（１）で得られた水分散液のｐＨは、水分散液中でセルロースナノファイバー（Ａ）の凝集を抑え、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは４以上、より好ましくは５以上、更に好ましくは６以上であり、また、好ましくは１０以下、より好ましくは９以下、更に好ましくは８以下である。 The pH of the aqueous dispersion obtained in the step (1) is preferably from the viewpoint of suppressing aggregation of the cellulose nanofibers (A) in the aqueous dispersion and reducing variations in the shape and size of the formed particles. It is 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
＜工程（２）＞
　工程（２）は、工程（１）で得た水分散液に、有機溶剤（Ｃ）を添加する工程である。
　本工程において、ホモディスパー、ミキサー、パドル翼等の撹拌翼を取り付けた撹拌装置を用いて、水分散液を撹拌しながら、有機溶剤（Ｃ）を添加することが好ましい。 <Step (2)>
Step (2) is a step of adding an organic solvent (C) to the aqueous dispersion obtained in step (1).
In this step, it is preferable to add the organic solvent (C) while stirring the aqueous dispersion using a stirrer equipped with a stirring blade such as a homodisper, a mixer, or a paddle blade.
　水分散液を撹拌する際の撹拌速度（回転数）は、セルロースナノファイバー（Ａ）の凝集を抑え、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは５００ｒｐｍ以上、より好ましくは１０００ｒｐｍ以上、更に好ましくは１５００ｒｐｍ以上、より更に好ましくは２０００ｒｐｍ以上であり、また、好ましくは５０００ｒｐｍ以下、より好ましくは４５００ｒｐｍ以下、より好ましくは４０００ｒｐｍ以下、更に好ましくは３５００ｒｐｍ以下、より更に好ましくは３０００ｒｐｍ以下である。 The stirring speed (rotation speed) when stirring the aqueous dispersion is preferably 500 rpm or more, from the viewpoint of suppressing aggregation of the cellulose nanofibers (A) and reducing variations in the shape and size of the formed particles. It is preferably at least 1,000 rpm, more preferably at least 1500 rpm, even more preferably at least 2,000 rpm, and preferably at most 5,000 rpm, more preferably at most 4,500 rpm, more preferably at most 4,000 rpm, further preferably at most 3,500 rpm, even more preferably at 3,000 rpm. It is as follows.
　また、水分散液の温度は、セルロースナノファイバー（Ａ）の凝集を抑え、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは５℃以上、より好ましくは１０℃以上、更に好ましくは１５℃以上であり、また、添加した有機溶剤（Ｃ）の揮発を抑制する観点から、好ましくは４５℃以下、より好ましくは４０℃以下、更に好ましくは３５℃以下である。 In addition, the temperature of the aqueous dispersion is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of suppressing aggregation of the cellulose nanofibers (A) and reducing the variation in the shape and size of the formed particles. It is more preferably at least 15 ° C, and from the viewpoint of suppressing the volatilization of the added organic solvent (C), preferably at most 45 ° C, more preferably at most 40 ° C, even more preferably at most 35 ° C.
　有機溶剤（Ｃ）の添加方法としては、形成される粒子の形状及び大きさのばらつきを小さくする観点から、一定時間ごとに一定量ずつ添加する方法が好ましい。
　具体的には、水分散液の全量１００質量部に対する、１０秒ごとの有機溶剤（Ｃ）の添加量は、好ましくは０．１質量部以上、より好ましくは１質量部以上、更に好ましくは３質量部以上、より更に好ましくは５質量部以上であり、また、好ましくは２０質量部以下、より好ましくは１５質量部以下、更に好ましくは１０質量部以下、より更に好ましくは７質量部以下である。 As a method of adding the organic solvent (C), a method of adding the organic solvent (C) in a constant amount at regular time intervals is preferable from the viewpoint of reducing the variation in the shape and size of the formed particles.
Specifically, the addition amount of the organic solvent (C) every 10 seconds is preferably at least 0.1 part by mass, more preferably at least 1 part by mass, further preferably at least 3 parts by mass based on 100 parts by mass of the total amount of the aqueous dispersion. It is at least 5 parts by mass, more preferably at least 5 parts by mass, and preferably at most 20 parts by mass, more preferably at most 15 parts by mass, further preferably at most 10 parts by mass, even more preferably at most 7 parts by mass. .
　有機溶剤（Ｃ）の添加開始からの撹拌時間は、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは３分以上、より好ましくは５分以上、更に好ましくは１０分以上であり、また、好ましくは１８０分以下、より好ましくは１２０分以下、更に好ましくは６０分以下、より更に好ましくは４０分以下、特に好ましくは２０分以下である。なお、撹拌時間とは、有機溶剤（Ｃ）の添加から撹拌を終了するまでの時間を指す。有機溶剤（Ｃ）を十分に分散させるとともに粒子の形成を促進させるため、必要量の有機溶剤（Ｃ）の添加終了後も、有機溶剤（Ｃ）添加開始からの上記時間が経過するまで撹拌を継続することが望ましい。 The stirring time from the start of the addition of the organic solvent (C) is preferably 3 minutes or more, more preferably 5 minutes or more, and still more preferably 10 minutes or more, from the viewpoint of reducing the variation in the shape and size of the formed particles. In addition, the time is preferably 180 minutes or less, more preferably 120 minutes or less, further preferably 60 minutes or less, still more preferably 40 minutes or less, and particularly preferably 20 minutes or less. The stirring time refers to the time from the addition of the organic solvent (C) to the end of the stirring. In order to sufficiently disperse the organic solvent (C) and promote the formation of particles, after the addition of the required amount of the organic solvent (C) is completed, stirring is continued until the above-mentioned time from the start of the addition of the organic solvent (C) has elapsed. It is desirable to continue.
＜組成物の用途＞
　本発明の組成物に含まれる粒子は、有機溶剤を内包する粒子であって、経時的に有機溶剤を少しずつ外部へ放出することができる性質である徐放性を有すると共に、一定又はそれ以上の圧力をかけると外殻が破れて有機溶剤を外部へ供給することができる。
　このような特性を有する粒子を含む組成物は、農業、食品、化粧品、薬剤等の分野において使用し得る。
　具体的には、加圧に応じて供給される液体香料、温度に応じて供給される液体香料、温度に応じて舌の上で味が変化する食材、温度に応じて徐放される冷却材、感圧型接着剤、ドラックデリバリーシステム等が挙げられる。
　より具体的には、上記各用途における有効成分（香料、栄養分、機能性物質、薬剤等）を適当な有機溶剤に混合したものを、上述したセルロースナノファイバーを含む外殻からなる中空粒子に取り込ませた組成物を調製して、それぞれの用途に用いることができる。 <Use of composition>
The particles contained in the composition of the present invention are particles containing an organic solvent, and have a sustained release property that is capable of gradually releasing the organic solvent to the outside over time, and at least a certain amount or more. When the pressure is applied, the outer shell is broken and the organic solvent can be supplied to the outside.
A composition containing particles having such properties can be used in the fields of agriculture, food, cosmetics, medicine, and the like.
Specifically, a liquid fragrance supplied according to the pressure, a liquid fragrance supplied according to the temperature, a foodstuff whose taste changes on the tongue according to the temperature, a coolant gradually released according to the temperature , A pressure-sensitive adhesive, a drug delivery system, and the like.
More specifically, a mixture of the active ingredients (flavors, nutrients, functional substances, drugs, etc.) for each of the above uses in an appropriate organic solvent is incorporated into the hollow particles formed of the outer shell containing the cellulose nanofibers described above. The composition can be prepared and used for each application.
　本発明について、以下の実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、下記物性値の測定法は、以下のとおりである。 The present invention will be described specifically with reference to the following examples, but the present invention is not limited to the following examples. The methods for measuring the following physical properties are as follows.
（１）セルロースナノファイバーの直径（太さ）の平均、長さの平均、平均アスペクト比
　透過型電子顕微鏡（カールツァイス社製、製品名「ＬＥＯ９１２」）を用いて、任意に選択した１０本のセルロースナノファイバーの直径（太さ）及び長さを測定し、１０本の平均値を、対象となるセルロースナノファイバーの「直径（太さ）の平均」及び「長さの平均」とした。また、「長さの平均／直径（太さ）の平均」を平均アスペクト比とした。
（２）水分散液、組成物のｐＨ
　２３℃、相対湿度５０％の環境下、コンパクトｐＨメータ（株式会社堀場アドバンスドテクノ製、製品名「ＬＡＱＵＡｔｗｉｎ　ｐＨ－２２Ｂ」）を用いて、ｐＨ４．０１標準液とｐＨ６．８６標準液の2点校正を行った後、平面センサ全体を覆うように試料を滴下して測定した。
（３）有機溶剤の粘度
　ＪＩＳ　Ｚ　８８０３：２０１１に準拠して、Ｂ型粘度計を用いて、２３℃、回転数５ｒｐｍにて測定した。
（４）組成物の粘度、ＴＩ値
　ＪＩＳ　Ｚ　８８０３：２０１１に準拠して、Ｂ型粘度計を用いて、２３℃、回転数５ｒｐｍ及び５０ｒｐｍにおける組成物の粘度を測定した。また、〔回転数５ｒｐｍにおける粘度〕／〔回転数５０ｒｐｍにおける粘度〕の比をＴＩ値とした。 (1) Average of diameter (thickness), average of length, average aspect ratio of cellulose nanofiber 10 randomly selected 10 pieces using a transmission electron microscope (manufactured by Carl Zeiss, product name "LEO912") The diameter (thickness) and length of the cellulose nanofiber were measured, and the average value of the ten fibers was defined as the “average diameter (thickness)” and “average length” of the target cellulose nanofiber. The “average length / average diameter (thickness)” was defined as the average aspect ratio.
(2) Aqueous dispersion, pH of composition
Two-point calibration of pH 4.01 standard solution and pH 6.86 standard solution using a compact pH meter (product name "LAQUAtwin pH-22B" manufactured by Horiba Advanced Techno Co., Ltd.) in an environment of 23 ° C. and 50% relative humidity. After the measurement, the sample was dropped and measured so as to cover the entire flat sensor.
(3) Viscosity of Organic Solvent It was measured at 23 ° C. and 5 rpm using a B-type viscometer in accordance with JIS Z 8803: 2011.
(4) Viscosity and TI value of composition According to JIS Z 8803: 2011, the viscosity of the composition was measured using a B-type viscometer at 23 ° C, rotation speed of 5 rpm and 50 rpm. The ratio of [viscosity at 5 rpm] / [viscosity at 50 rpm] was defined as the TI value.
実施例１～１３、比較例１～５
　組成物の調製に際し、下記の市販品のセルロースナノファイバーを含む水分散液（１）又は（２）を使用した。
・水分散液（１）：製品名「ＢｉＮＦｉ－ｓ　ＡＭａ　１０００２」、株式会社スギノマシン製。直径（太さ）の平均＝７６．８ｎｍ、長さの平均＝１．４μｍ、平均アスペクト比＝１８．２である、機械処理型のセルロースナノファイバーを２質量％含む水分散液。
　水分散液（１）は、セルロースナノファイバー１００質量部に対して、水を４９００質量部含有するものであり、水分散液（１）のｐＨ＝７．０であった。
・水分散液（２）：製品名「ＴＥＭＰＯ酸化ＣＮＦ」、日本製紙株式会社製。直径（太さ）の平均＝３．８ｎｍ、長さの平均＝０．７μｍ、平均アスペクト比＝１８４である、化学処理型のセルロースナノファイバーを１質量％含む水分散液。
　水分散液（２）は、セルロースナノファイバー１００質量部に対して、水を９９００質量部含有するものであり、水分散液（２）のｐＨ＝７．０であった。 Examples 1 to 13 and Comparative Examples 1 to 5
In preparing the composition, an aqueous dispersion (1) or (2) containing the following commercially available cellulose nanofiber was used.
Aqueous dispersion (1): Product name "BiNFi-s AMa 10002", manufactured by Sugino Machine Co., Ltd. An aqueous dispersion containing 2% by mass of mechanically processed cellulose nanofibers having an average diameter (thickness) of 76.8 nm, an average length of 1.4 μm, and an average aspect ratio of 18.2.
The aqueous dispersion (1) contained 4900 parts by mass of water with respect to 100 parts by mass of the cellulose nanofiber, and the pH of the aqueous dispersion (1) was 7.0.
-Aqueous dispersion (2): Product name "TEMPO oxidized CNF", manufactured by Nippon Paper Industries. An aqueous dispersion containing 1% by mass of chemically treated cellulose nanofibers having an average diameter (thickness) of 3.8 nm, an average length of 0.7 μm, and an average aspect ratio of 184.
The aqueous dispersion (2) contained 9900 parts by mass of water with respect to 100 parts by mass of the cellulose nanofibers, and the pH of the aqueous dispersion (2) was 7.0.
　上記水分散液（１）又は（２）に、表２に示す種類の有機溶剤を、水分散液（１）又は（２）中のセルロースナノファイバー１００質量部に対して表２に示す配合量となるように添加した。
　具体的には、超高速マルチ撹拌システム（プライミクス株式会社製、製品名「ラボ・リューション（登録商標）」、撹拌羽：ホモディスパー（同社製、羽の直径３５ｍｍ））を用いて、２３℃の水分散液を、回転数３０００ｒｐｍで撹拌した。撹拌開始後、表２に記載の有機溶剤を、水分散液（１）又は（２）の全量１００質量部に対して、１０秒毎に５質量部の速さで添加した。有機溶剤を添加後も撹拌を続け、撹拌開始から１０分後に撹拌を終了し、組成物を調製した。 The amount of the organic solvent shown in Table 2 is added to the aqueous dispersion (1) or (2) with respect to 100 parts by mass of the cellulose nanofiber in the aqueous dispersion (1) or (2). Was added so that
Specifically, at 23 ° C. using an ultra-high-speed multi-stirring system (manufactured by Primix Corporation, product name “Lab-Ruution (registered trademark)”, stirring blade: homodisper (manufactured by the company, blade diameter 35 mm)). Was stirred at 3000 rpm. After the start of stirring, the organic solvents shown in Table 2 were added at a rate of 5 parts by mass every 10 seconds to 100 parts by mass of the total amount of the aqueous dispersion (1) or (2). Stirring was continued after the addition of the organic solvent, and the stirring was stopped 10 minutes after the start of stirring to prepare a composition.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実施例及び比較例で調製した組成物について、粘性（５ｒｐｍ及び５０ｒｐｍにおける粘度、ＴＩ値）を測定及び算出すると共に、下記の評価及び測定を行った。これらの結果を表３に示す。 粘性 The compositions prepared in Examples and Comparative Examples were measured and calculated for viscosity (viscosity at 5 rpm and 50 rpm, TI value), and evaluated and measured as follows. Table 3 shows the results.
（１）組成物中の固形分率の測定
　上底面の直径７．２ｃｍ、下底面の直径６．８ｃｍ、高さ８ｃｍの円錐台形のコップを用いて、コップの上底面に、一辺１０ｃｍの正方形に切断したテトロンメッシュ（＃２００メッシュ）を載せて、クリップでコップの淵とテトロンメッシュを固定し、測定用容器を作製した。
　実施例及び比較例で調製した組成物１０ｇを、この測定用容器のテトロンメッシュ上に薄く広げるように塗布し１分間静置した。そして、測定用容器内に落下した組成物中の液体の質量ｗ［ｇ］を測定し、下記式から、組成物中の固形分率を算出した。
・固形分率［質量％］＝１００－（ｗ［ｇ］／１０［ｇ］×１００） (1) Measurement of solid content ratio in composition Using a truncated conical cup having a diameter of 7.2 cm on the upper bottom, a diameter of 6.8 cm on the lower bottom, and a height of 8 cm, a square with a side of 10 cm on the upper bottom of the cup The tetron mesh (# 200 mesh) cut into pieces was placed, and the edge of the cup and the tetron mesh were fixed with a clip to prepare a measuring container.
10 g of the compositions prepared in Examples and Comparative Examples were spread thinly on the tetron mesh of this measuring container, and allowed to stand for 1 minute. Then, the mass w [g] of the liquid in the composition dropped into the measuring container was measured, and the solid content in the composition was calculated from the following equation.
・ Solid content [mass%] = 100− (w [g] / 10 [g] × 100)
（２）粒子の存在の有無の観察
　図３（ａ）に示す平面模式図のように、スライドガラス１１の表面上に、各厚さ１２５μｍの２枚の帯状のポリエチレンテレフタレート（ＰＥＴ）フィルム２１、２２を、水平方向に５ｃｍ離れるように平行に設置し、２枚のＰＥＴフィルム２１、２２で挟まれた隙間３０を設け、隙間３０に、調製した組成物を約０．０６ｍｌ滴下した。
　そして、図３（ｂ）に示す正面模式図のように、別のスライドガラス１２を、２枚のＰＥＴフィルム２１、２２と、隙間３０に満たした組成物４０とを覆うように積層し、測定サンプル１００を作製した。
　上記測定サンプルを用いて、デジタル顕微鏡（キーエンス社製、製品名「ＶＨＸ－５０００」）を用いて、倍率５００倍にて、組成物を観察した際のデジタル画像を取得した。そして、当該デジタル画像から、セルロースナノファイバーを含む外殻を備える粒子の存在を確認し、以下の基準で評価した。
・Ａ：前記粒子の存在が確認できた。
・Ｆ：前記粒子の存在が確認できなかった。
　なお、以下の（３）～（５）の評価は、前記粒子が確認できた組成物についてのみ行った。 (2) Observation of Presence or Absence of Particles As shown in the schematic plan view of FIG. 3A, two strip-shaped polyethylene terephthalate (PET) films 21 each having a thickness of 125 μm are formed on the surface of the slide glass 11. 22 were placed in parallel with each other at a distance of 5 cm in the horizontal direction, a gap 30 sandwiched between two PET films 21 and 22 was provided, and about 0.06 ml of the prepared composition was dropped into the gap 30.
Then, as shown in the schematic front view of FIG. 3B, another slide glass 12 is laminated so as to cover the two PET films 21 and 22 and the composition 40 filling the gap 30, and the measurement is performed. Sample 100 was produced.
Using the above measurement sample, a digital image was obtained when the composition was observed at a magnification of 500 times using a digital microscope (manufactured by KEYENCE CORPORATION, product name "VHX-5000"). Then, the presence of particles having an outer shell containing cellulose nanofibers was confirmed from the digital image, and evaluated based on the following criteria.
A: The presence of the particles was confirmed.
F: The presence of the particles could not be confirmed.
In addition, the following evaluations (3) to (5) were performed only for the composition in which the particles were confirmed.
（３）粒子の平均粒子径、及び、粒子の平均粒子径に対する標準偏差の算出
　上記（２）で得たデジタル画像から、任意に選択した３６個の粒子の粒径（粒子を構成する外殻の外径）を測定し、粒子の平均粒子径、及び、粒子の平均粒子径に対する標準偏差を算出した。 (3) Calculation of the average particle diameter of the particles and the standard deviation with respect to the average particle diameter of the particles From the digital image obtained in the above (2), the particle diameters of the arbitrarily selected 36 particles (the outer shell constituting the particles) Was measured, and the average particle diameter of the particles and the standard deviation with respect to the average particle diameter of the particles were calculated.
（４）粒子に有機溶剤が取り込まれているか否かの確認
　２３℃、５０％ＲＨ（相対湿度）の環境下で、調製した組成物をガラス板の表面に着滴し、組成物の表面をガラス棒で叩いた際に、粒子が割れて有機溶剤が放出されるか否かの様子を、デジタル顕微鏡（キーエンス社製、製品名「ＶＨＸ－５０００」）を用いて、倍率５００倍で観察しながら確認し、下記基準で評価した。
・Ａ：粒子が割れて有機溶剤が放出される様子が確認された。
・Ｆ：粒子に変化は起こらず、有機溶剤が放出される様子は確認できなかった。 (4) Confirmation of whether or not an organic solvent is incorporated in the particles In an environment of 23 ° C. and 50% RH (relative humidity), the prepared composition is dropped on the surface of a glass plate, and the surface of the composition is cleaned. Using a digital microscope (manufactured by KEYENCE CORPORATION, product name "VHX-5000"), the state of whether or not the particles were broken and the organic solvent was released when hit with a glass rod was observed at a magnification of 500 times. While checking, the evaluation was made according to the following criteria.
A: It was confirmed that the particles were cracked and the organic solvent was released.
-F: No change occurred in the particles, and no appearance of the organic solvent could be confirmed.
（５）粒子の徐放性の確認
　直径４．２ｃｍの円柱状のガラス製の透明容器に、調製した組成物を１００ｇ入れたものを試験サンプルとした。また、測定対象となる組成物１００ｇ中に含まれる質量の有機溶剤を、上記の同じ種類の透明容器に入れたものを比較サンプルとした。
　そして、試験サンプル及び比較サンプルを、蓋をしていない状態で、２３℃で、相対湿度５０％とし、連続作動させたドラフト内で、６時間静置した。
　静置後にドラフトから取り出した試験サンプル及び比較サンプルの臭いを、５人の評価者が確認した。そして、表３には「比較サンプルに比べて試験サンプルの方が臭いがする」と判断した評価者の数を記載した。当該評価者の数が多いほど、高い確度で粒子が徐放性を有しているといえる。 (5) Confirmation of sustained release properties of particles A test sample was prepared by putting 100 g of the prepared composition in a cylindrical transparent glass container having a diameter of 4.2 cm. A comparative sample was prepared by putting an organic solvent having a mass contained in 100 g of the composition to be measured in the same type of transparent container as described above.
Then, the test sample and the comparative sample were left uncovered at 23 ° C. and a relative humidity of 50%, and allowed to stand in a continuously operated draft for 6 hours.
Five evaluators confirmed the odor of the test sample and the comparative sample taken out of the draft after standing still. Table 3 shows the number of evaluators who judged that the test sample smelled better than the comparative sample. It can be said that the larger the number of the evaluators, the higher the accuracy of the particles in the sustained release.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　図１は、実施例７の組成物をデジタル顕微鏡で観察した際に取得した画像であり、粒子が存在していることが分かる。実施例１～６及び８～１３の組成物においても、同様の粒子の存在が確認された。そして、これらの粒子が徐放性を有することも確認された。
　なお、実施例７の組成物のｐＨは７．０であった。 FIG. 1 is an image obtained when the composition of Example 7 was observed with a digital microscope, and it can be seen that particles were present. In the compositions of Examples 1 to 6 and 8 to 13, the presence of similar particles was confirmed. And it was also confirmed that these particles have a sustained release property.
The composition of Example 7 had a pH of 7.0.
　また、実施例７及び１０で調製した組成物をそれぞれ、支持材であるＰＥＴフィルム（東洋紡株式会社製コスモシャイン（登録商標）、品番「Ａ４１００」、厚さ：５０μｍ）の易接着層面上に塗布し、１２０℃で１０分間乾燥して、厚さ５０μｍの塗膜を形成し、当該塗膜の断面を走査型電子顕微鏡（ＳＥＭ）（株式会社日立製作所製　Ｓ－４７００）で観察した際の画像を取得した。そして、画像に写し出された前記粒子のうち、任意に選択した３６個の粒子の外殻の厚さをそれぞれ測定し、これらの平均値を、上記の「外殻の厚さの平均」として算出した。
　その結果、組成物中の前記粒子の外殻の厚さの平均は、実施例７で「１２０２ｎｍ」であり、実施例１０で「９３ｎｍ」であった。 Each of the compositions prepared in Examples 7 and 10 was applied onto the surface of an easily adhesive layer of a PET film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 μm) as a support material. And dried at 120 ° C. for 10 minutes to form a coating film having a thickness of 50 μm, and an image obtained by observing a cross section of the coating film with a scanning electron microscope (SEM) (S-4700 manufactured by Hitachi, Ltd.) I got Then, among the particles projected on the image, the thicknesses of the outer shells of 36 particles arbitrarily selected are measured, and the average value thereof is calculated as the above-mentioned “average of outer shell thickness”. did.
As a result, the average of the outer shell thickness of the particles in the composition was “1202 nm” in Example 7 and “93 nm” in Example 10.
　一方、図２は、比較例３の組成物をデジタル顕微鏡で観察した際に取得した画像であるが、粒子の存在は確認できなかった。また、比較例１、２、４及び５の組成物においても同様に粒子の存在は確認できなかった。 On the other hand, FIG. 2 is an image obtained when the composition of Comparative Example 3 was observed with a digital microscope, but the presence of particles could not be confirmed. Similarly, in the compositions of Comparative Examples 1, 2, 4, and 5, the presence of particles could not be confirmed.

Claims (12)

  1. 　セルロースナノファイバー（Ａ）、水（Ｂ）、及び、下記式（１）で表される、２５℃における、ハンセン溶解度パラメータの距離Ｒａが５．８０ＭＰａ１／２以下である有機溶剤（Ｃ）を配合してなる組成物であって、
    　セルロースナノファイバー（Ａ）を含む外殻を備える粒子を含有し、
    　有機溶剤（Ｃ）の少なくとも一部が、前記粒子に取り込まれている状態である、組成物。
    Figure JPOXMLDOC01-appb-M000001
    （前記式中、δＤは、有機溶剤（Ｃ）のハンセン溶解度パラメータの分散成分、
    　δＰは、有機溶剤（Ｃ）のハンセン溶解度パラメータの極性成分、
    　δＨは、有機溶剤（Ｃ）のハンセン溶解度パラメータの水素結合成分を示す。）     Cellulose nanofiber (A), water (B), and organic solvent (C) represented by the following formula (1) and having a Hansen solubility parameter distance Ra at 25 ° C. of 5.80 MPa 1/2 or less. A composition comprising:
    Containing particles having an outer shell containing cellulose nanofibers (A),
    A composition in which at least a part of the organic solvent (C) is in a state of being incorporated in the particles.
    Figure JPOXMLDOC01-appb-M000001
    (Wherein δD is a dispersion component of the Hansen solubility parameter of the organic solvent (C),
    δP is the polar component of the Hansen solubility parameter of the organic solvent (C),
    δH indicates the hydrogen bonding component of the Hansen solubility parameter of the organic solvent (C). )
  2. 　有機溶剤（Ｃ）の少なくとも一部が、前記粒子に内包されている状態、及び、前記粒子の外殻を形成しているセルロースナノファイバー（Ａ）に吸着されている状態の少なくとも一方である、請求項１に記載の組成物。 At least one of a state in which at least a part of the organic solvent (C) is included in the particles and a state in which the organic solvent (C) is adsorbed on the cellulose nanofibers (A) forming the outer shell of the particles. The composition according to claim 1.
  3. 　前記組成物中の固形分率が、当該組成物の全量に対して、８０～１００質量％である、請求項１又は２に記載の組成物。 The composition according to claim 1, wherein the solid content in the composition is from 80 to 100% by mass based on the total amount of the composition.
  4. 　前記組成物の２３℃、５０ｒｐｍにおける粘度が、５００～２００００ｍＰａ・ｓである、請求項１～３のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 3, wherein the composition has a viscosity at 23 ° C and 50 rpm of 500 to 20,000 mPa · s.
  5. 　前記組成物の２３℃でのＴＩ値（回転数５ｒｐｍにおける粘度／回転数５０ｒｐｍにおける粘度）が、１．２～２０である、請求項１～４のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the composition has a TI value at 23 ° C (viscosity at a rotation speed of 5 rpm / viscosity at a rotation speed of 50 rpm) of 1.2 to 20.
  6. 　セルロースナノファイバー（Ａ）の直径（太さ）の平均が、１～１０００ｎｍである、請求項１～５のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 5, wherein the average of the diameter (thickness) of the cellulose nanofiber (A) is 1 to 1000 nm.
  7. 　セルロースナノファイバー（Ａ）の繊維長の平均が、０．０１～１０μｍである、請求項１～６のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 6, wherein the average of the fiber length of the cellulose nanofiber (A) is 0.01 to 10 µm.
  8. 　有機溶剤（Ｃ）の配合量が、前記組成物の全量に対して、０．０５～８０質量％である、請求項１～７のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the amount of the organic solvent (C) is 0.05 to 80% by mass relative to the total amount of the composition.
  9. 　水（Ｂ）と有機溶剤（Ｃ）との配合量比〔（Ｂ）／（Ｃ）〕が、質量比で、０．１～１０００である、請求項１～８のいずれか一項に記載の組成物。 9. The method according to claim 1, wherein the compounding ratio [(B) / (C)] of the water (B) and the organic solvent (C) is 0.1 to 1000 in terms of mass ratio. Composition.
  10. 　有機溶剤（Ｃ）が、炭素数２０未満の有機溶剤（Ｃ１）を含む、請求項１～９のいずれか一項に記載の組成物。 (10) The composition according to any one of (1) to (9), wherein the organic solvent (C) contains an organic solvent (C1) having less than 20 carbon atoms.
  11. 　界面活性剤の含有量が、セルロースナノファイバー（Ａ）の全量１００質量部に対して、１０質量部未満である、請求項１～１０のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 10, wherein the content of the surfactant is less than 10 parts by mass based on 100 parts by mass of the total amount of the cellulose nanofiber (A).
  12. 　セルロースナノファイバー（Ａ）以外の多糖類の含有量が、セルロースナノファイバー（Ａ）の全量１００質量部に対して、１０質量部未満である、請求項１～１１のいずれか一項に記載の組成物。 12. The method according to claim 1, wherein the content of the polysaccharide other than the cellulose nanofiber (A) is less than 10 parts by mass based on 100 parts by mass of the total amount of the cellulose nanofiber (A). Composition.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015057277A (en) * 2013-08-12 2015-03-26 日本合成化学工業株式会社 Microcapsule, solid material-including microcapsule, and manufacturing method thereof
WO2015059179A1 (en) * 2013-10-24 2015-04-30 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Capsule, namely nanocapsule, microcapsule or macrocapsule, having a very low oxygen permeability
JP2017043750A (en) * 2015-11-25 2017-03-02 第一工業製薬株式会社 Cellulose ester aqueous dispersion
WO2017126566A1 (en) * 2016-01-20 2017-07-27 日本製紙株式会社 Polyurethane resin composition and process for producing same
WO2017138574A1 (en) * 2016-02-08 2017-08-17 日本製紙株式会社 Modified carboxymethylated cellulose nanofiber dispersion and method for manufacturing same
JP2018076495A (en) * 2016-10-28 2018-05-17 日本製紙株式会社 Dispersion resin composition and the use thereof
JP2018104502A (en) * 2016-12-22 2018-07-05 日本製紙株式会社 Manufacturing method of esterified cellulose nanofiber dispersion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6363340B2 (en) * 2013-11-19 2018-07-25 中越パルプ工業株式会社 Emulsions containing nano-sized fibrous polysaccharides, materials and methods for producing them

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015057277A (en) * 2013-08-12 2015-03-26 日本合成化学工業株式会社 Microcapsule, solid material-including microcapsule, and manufacturing method thereof
WO2015059179A1 (en) * 2013-10-24 2015-04-30 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Capsule, namely nanocapsule, microcapsule or macrocapsule, having a very low oxygen permeability
JP2017043750A (en) * 2015-11-25 2017-03-02 第一工業製薬株式会社 Cellulose ester aqueous dispersion
WO2017126566A1 (en) * 2016-01-20 2017-07-27 日本製紙株式会社 Polyurethane resin composition and process for producing same
WO2017138574A1 (en) * 2016-02-08 2017-08-17 日本製紙株式会社 Modified carboxymethylated cellulose nanofiber dispersion and method for manufacturing same
JP2018076495A (en) * 2016-10-28 2018-05-17 日本製紙株式会社 Dispersion resin composition and the use thereof
JP2018104502A (en) * 2016-12-22 2018-07-05 日本製紙株式会社 Manufacturing method of esterified cellulose nanofiber dispersion

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