WO2020050153A1 - Composition - Google Patents

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Publication number
WO2020050153A1
WO2020050153A1 PCT/JP2019/034044 JP2019034044W WO2020050153A1 WO 2020050153 A1 WO2020050153 A1 WO 2020050153A1 JP 2019034044 W JP2019034044 W JP 2019034044W WO 2020050153 A1 WO2020050153 A1 WO 2020050153A1
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Prior art keywords
organic solvent
composition
particles
mass
less
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PCT/JP2019/034044
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English (en)
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 JP2020541177A priority Critical patent/JPWO2020050153A1/ja
Publication of WO2020050153A1 publication Critical patent/WO2020050153A1/fr

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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.
  • a composition containing such particles usually supplies the organic solvent to the outside by suppressing the release of the organic solvent to the outside, but 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 that can gradually release the organic solvent to the outside over time, and the outer shell when a certain or more pressure is applied It is an object of the present invention to provide a composition containing particles that can be broken to supply an organic solvent to the outside.
  • the present inventors have made various studies, cellulose nanofiber, water, and, in a composition comprising an organic solvent, the compounding ratio of the organic solvent and the cellulose nanofiber is in a predetermined range. It has been found that a composition containing particles having an outer shell containing cellulose nanofibers can be obtained by such preparation. The present invention has been completed based on this finding.
  • a composition comprising a cellulose nanofiber (A), water (B), and an organic solvent (C),
  • the compounding ratio of the organic solvent (C) and the cellulose nanofiber (A) [(C) / (A)] is 0.05 to 45 by mass ratio, Containing particles having an outer shell containing cellulose nanofibers (A),
  • the average fiber length of the cellulose nanofiber (A) is 0.01 to 10 ⁇ m.
  • the particles contained in the composition of the present invention are particles incorporating 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. When the pressure is 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. 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 in which the organic solvent (C) is taken inside and the water (B) is held in 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 from an image acquired 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.
  • the particles having the 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 organic solvent (C) By appropriately adjusting the compounding ratio, the type of the organic solvent (C), and the like, it is possible to facilitate the formation.
  • the blending ratio [(C) / (A)] of the organic solvent (C) and the cellulose nanofiber (A) is adjusted to be 0.05 to 45 in mass ratio.
  • the particles are easily formed. That is, if the compounding ratio [(C) / (A)] is less than 0.05, the amount of the organic solvent (C) incorporated into the cellulose nanofiber (A) is too small, and thus the particles formed are The number is small and the sustained release of the whole composition tends to be insufficient. If the compounding ratio [(C) / (A)] is more than 45, the amount of the organic solvent (C) is too large relative to the cellulose nanofiber (A). It becomes difficult to stir the aqueous dispersion of the cellulose nanofibers (A) thus formed, and it becomes difficult to form the particles. As a result, the sustained release of the whole composition tends to be insufficient.
  • the blending ratio [(C) / (A)] of the organic solvent (C) and the cellulose nanofiber (A) is 0.05 or more in terms of mass ratio. Is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 0.75 or more, even more preferably 0.9 part by mass or more, and 45 or less, and preferably 45 or less. It is 40 or less, more preferably 35 or less.
  • ⁇ 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 10000 or less, more preferably 5,000 or less, further preferably 3,000 or less, still more preferably 1,000, 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).
  • Organic solvent (C) used in one embodiment of the present invention can be appropriately selected depending on the use of the composition.
  • the organic solvent (C) used in one embodiment of the present invention can be appropriately selected depending on the use of the composition.
  • 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) 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 mixing ratio of the organic solvent (C1) in the organic solvent (C) is preferably 20% by mass or more, more preferably 35% by mass, based on the total amount (100% by mass) of the organic solvent (C).
  • the content is more preferably 50% by mass or more, and even more preferably 70% by mass or more.
  • the organic solvents (C1) one or more organic solvents (C2) selected from heptane, n-hexadecane, toluene, cyclohexanone, methyl ethyl ketone, and n-dodecane are preferred.
  • the particles can be more easily formed.
  • the mixing ratio of the organic solvent (C2) in the organic solvent (C) is preferably 20% by mass or more based on the total amount (100% by mass) of the organic solvent (C). It is more preferably at least 35% by mass, further preferably at least 50% by mass, even more preferably at least 70% by mass.
  • 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 [(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 to the total amount of 100 parts by mass of the aqueous dispersion is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and still more preferably. 3 parts by mass or more, more preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, even more preferably 7 parts by mass or less. is there.
  • 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 1 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 1 were added at a rate of 5 parts by mass every 10 seconds to 100 parts by mass 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 2 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 2 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 on the surface of an easy-adhesion layer of a PET film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 ⁇ m) as a support. 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 the 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

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  • Dispersion Chemistry (AREA)
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Abstract

L'invention concerne une composition obtenue par combinaison de: (A) nanofibres de cellulose, (B) eau, et (C) solvant organique, cette composition contenant des particules dans lesquelles un solvant organique est incorporé, ces particules permettant présentant une caractéristique de libération prolongée pour évacuer peu à peu vers l'extérieur le solvant organique, tout en permettant de libérer ce solvant lorsqu'une pression supérieure à une pression spécifique est appliquée, par rupture de l'enveloppe extérieure desdites particules. Le rapport entre la quantité de solvant organique (C) et de nanofibres de cellulose (A), [(C) / (A)], en terme de rapport massique, est de 0,05 à 45, et les particules comportent une enveloppe externe contenant les nanofibres de cellulose. Au moins une partie du solvant organique (C) est incorporée aux particules.
PCT/JP2019/034044 2018-09-03 2019-08-30 Composition WO2020050153A1 (fr)

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JP2015057277A (ja) * 2013-08-12 2015-03-26 日本合成化学工業株式会社 マイクロカプセル、および固体物質内包型マイクロカプセルならびにその製法
WO2015059179A1 (fr) * 2013-10-24 2015-04-30 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Capsule, à savoir nanocapsule, microcapsule ou macrocapsule, ayant une très faible perméabilité à l'oxygène
JP2017043750A (ja) * 2015-11-25 2017-03-02 第一工業製薬株式会社 セルロースエステル水性分散体
WO2017126566A1 (fr) * 2016-01-20 2017-07-27 日本製紙株式会社 Composition de résine de polyuréthane et son procédé de production
WO2017138574A1 (fr) * 2016-02-08 2017-08-17 日本製紙株式会社 Dispersion de nanofibres de cellulose carboxyméthylée modifiée et son procédé de fabrication
JP2018076495A (ja) * 2016-10-28 2018-05-17 日本製紙株式会社 分散樹脂組成物及びその用途
JP2018104502A (ja) * 2016-12-22 2018-07-05 日本製紙株式会社 エステル化セルロースナノファイバー分散液の製造方法

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JP6363340B2 (ja) * 2013-11-19 2018-07-25 中越パルプ工業株式会社 ナノ微細化した繊維状多糖を含むエマルション、材料及びそれらの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015057277A (ja) * 2013-08-12 2015-03-26 日本合成化学工業株式会社 マイクロカプセル、および固体物質内包型マイクロカプセルならびにその製法
WO2015059179A1 (fr) * 2013-10-24 2015-04-30 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Capsule, à savoir nanocapsule, microcapsule ou macrocapsule, ayant une très faible perméabilité à l'oxygène
JP2017043750A (ja) * 2015-11-25 2017-03-02 第一工業製薬株式会社 セルロースエステル水性分散体
WO2017126566A1 (fr) * 2016-01-20 2017-07-27 日本製紙株式会社 Composition de résine de polyuréthane et son procédé de production
WO2017138574A1 (fr) * 2016-02-08 2017-08-17 日本製紙株式会社 Dispersion de nanofibres de cellulose carboxyméthylée modifiée et son procédé de fabrication
JP2018076495A (ja) * 2016-10-28 2018-05-17 日本製紙株式会社 分散樹脂組成物及びその用途
JP2018104502A (ja) * 2016-12-22 2018-07-05 日本製紙株式会社 エステル化セルロースナノファイバー分散液の製造方法

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