WO2020050155A1 - Composition - Google Patents

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Publication number
WO2020050155A1
WO2020050155A1 PCT/JP2019/034046 JP2019034046W WO2020050155A1 WO 2020050155 A1 WO2020050155 A1 WO 2020050155A1 JP 2019034046 W JP2019034046 W JP 2019034046W WO 2020050155 A1 WO2020050155 A1 WO 2020050155A1
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Prior art keywords
organic solvent
particles
composition
mass
less
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PCT/JP2019/034046
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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 JP2020541179A priority Critical patent/JPWO2020050155A1/ja
Publication of WO2020050155A1 publication Critical patent/WO2020050155A1/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 a property of gradually releasing the organic solvent to the outside with time (slow release) while taking in the organic solvent.
  • the formation of particles like capsules is required, and depending on the application, the property that the sustained release property can be stably maintained 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.
  • 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. Therefore, after a certain period of time, the organic solvent evaporates, and the remaining amount of the organic solvent in the composition becomes considerably small.
  • the present invention is a particle that incorporates an organic solvent, it is possible to stably maintain the sustained release property that is a property that can gradually release the organic solvent to the outside over time, and at a constant or higher pressure It is an object of the present invention to provide a composition containing particles capable of supplying an organic solvent to the outside when the outer shell is broken.
  • the present inventors have conducted various studies, cellulose nanofibers, water, and blended with an organic solvent, and a composition containing particles having an outer shell containing cellulose nanofibers, the composition of the particles, It has been found that the above problem can be solved by adjusting the average particle size and the standard deviation of the average particle size of the particles to a predetermined range.
  • the present invention has been completed based on this finding.
  • a composition comprising a cellulose nanofiber (A), water (B), and an organic solvent (C), An outer shell containing cellulose nanofiber (A), containing particles satisfying the following requirements (I) and (II); A composition in which at least a part of the organic solvent (C) is in a state of being incorporated in the particles.
  • Requirement (I) The average particle diameter of the particles is 1 to 60 ⁇ m.
  • -Requirement (II) The standard deviation of the average particle diameter of the particles is 20 ⁇ m or less.
  • 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 that incorporate an organic solvent, and can stably maintain a sustained release property that gradually releases the organic solvent to the outside over time, and can be constant or If the pressure is applied more than that, 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 with a digital microscope, (a) is a schematic plan view of the measurement sample in the middle of manufacture, (b) is the manufactured measurement sample FIG.
  • 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 particles contained in the composition of the present invention satisfy the following requirements (I) and (II).
  • Requirement (I) The average particle diameter of the particles is 1 to 60 ⁇ m.
  • -Requirement (II) The standard deviation of the average particle diameter of the particles is 20 ⁇ m or less. Since the particles satisfy the above requirements (I) and (II), the composition can stably maintain the sustained release property that gradually releases the organic solvent to the outside over time.
  • the average particle diameter of the particles is less than 1 ⁇ m, the particles are aggregated with each other in the composition, and the organic solvent is difficult to be released to the outside over time, and stable sustained release is difficult to be exhibited. There is fear. Further, when the average particle diameter of the particles is more than 60 ⁇ m, the particles are likely to settle in the composition, which may adversely affect the expression of stable sustained release.
  • the average particle size of the particles which is defined by the requirement (I), is 1 ⁇ m or more, preferably 5 ⁇ m or more, from the viewpoint of suppressing aggregation of the particles in the composition. It is preferably at least 7 ⁇ m, more preferably at least 10 ⁇ m, even more preferably at least 15 ⁇ m, and from the viewpoint of suppressing the floating of particles in the composition, is at most 60 ⁇ m, preferably at most 50 ⁇ m, more preferably at least 40 ⁇ m. Hereinafter, it is more preferably 35 ⁇ m or less, and still more preferably 30 ⁇ m or less.
  • the standard deviation of the average particle diameter of the particles is more than 20 ⁇ m, the difference in the amount of the organic solvent taken in for each particle is large, and the amount of the organic solvent released over time varies. In addition, it is difficult to achieve stable sustained release. Furthermore, when the outer shell of the particles is broken by applying a certain or more pressure, there is a possibility that the amount of the organic solvent incorporated in the particles to the outside may be different.
  • the standard deviation with respect to the average particle diameter of the particles defined by the above requirement (II) is 20 ⁇ m or less, preferably 18 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably, from the above viewpoint. Is 12 ⁇ m or less, and is usually 1 ⁇ m or more.
  • the average particle diameter of the particles defined by the above requirement (I) and the standard deviation with respect to the average particle diameter defined by the above requirement (II) are obtained by using a digital microscope for the target composition. It can be calculated from the image obtained when observed at a magnification of 500 to 1000 times.
  • 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.
  • the particles having the outer shell containing the cellulose nanofiber (A), taking in the organic solvent (C), and satisfying the above requirements (I) and (II) are the particles (diameter, fiber) of the blended cellulose nanofiber (A). Length, aspect ratio), the compounding amounts of each of the components (A) to (C), the compounding ratio of the cellulose nanofiber (A) and the organic solvent (C), and the mixing amount of water (B) and the organic solvent (C). By appropriately adjusting the compounding ratio, the type of the organic solvent (C), and the like, formation can be facilitated.
  • the details of each component will be described focusing on a specific method for forming the particles satisfying the requirements (I) and (II).
  • ⁇ 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 facilitates the formation of the particles satisfying the requirements (I) and (II), and the film strength of the formed particles. From the viewpoint of improving, it is preferably at least 1.0 nm, more preferably at least 1.5 nm, further preferably at least 2.0 nm, still more preferably at least 2.5 nm, and also preferably at most 1,000 nm, It is preferably at most 500 nm, more preferably at most 200 nm, even more preferably at most 100 nm.
  • the average fiber length of the cellulose nanofibers (A) used in one embodiment of the present invention facilitates the formation of the particles satisfying the requirements (I) and (II), and improves the film strength of the formed particles. From the viewpoint, it is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, still more preferably 0.2 ⁇ m or more, even more preferably 0.3 ⁇ m, and preferably 10 ⁇ m or less, more preferably 7.0 ⁇ m or less. , More preferably 5.0 ⁇ m or less, even more preferably 2.5 ⁇ m or less.
  • the average aspect ratio of the cellulose nanofiber (A) used in one embodiment of the present invention facilitates formation of the particles satisfying the requirements (I) and (II), and improves the film strength of the formed particles. Therefore, it is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less, and still more preferably 1,000 or less. Or less, 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) is such that the particles satisfying the requirements (I) and (II) are formed with respect to the total amount (100% by mass) of the composition.
  • the viewpoint of facilitating and improving the film strength of the formed particles preferably 0.7% by mass or more, more preferably 0.8% by mass or more, still more preferably 1.0% by mass or more, further more preferably 1.2% by mass or more, and preferably from 15% by mass or less, from the viewpoint of appropriately adjusting the viscosity of the composition so that the particles satisfying the requirements (I) and (II) are easily formed. It is more preferably at most 10% by mass, further preferably at most 7% by mass, still more preferably 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 amount of the water (B) is as follows: , 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, even more preferably 60% by mass or more; , Preferably 99% by mass or less, more preferably 98.7% by mass or less, still more preferably 98.5% by mass or less.
  • the composition of one embodiment of the present invention from the viewpoint of preparing a composition having an appropriate viscosity and easily forming the particles satisfying the requirements (I) and (II), 100 mass% of the cellulose nanofiber (A) is used.
  • the mixing ratio of water (B) to the parts is preferably at least 500 parts by mass, more preferably at least 1,000 parts by mass, still more preferably at least 2,000 parts by mass, even more preferably at least 3,000 parts by mass, and preferably at least 3,000 parts by mass. It is at most 20,000 parts by mass, more preferably at most 15,000 parts by mass, further preferably at most 10,000 parts by mass.
  • 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) After preparing the aqueous dispersion in advance, by blending the organic solvent (C), the cellulose nanofiber (A) can easily take in the organic solvent (C) and satisfy the requirements (I) and (II). Particles are 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.
  • organic solvent (C) it is preferable to use 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 a typical organic solvent used in Examples described later, and the distance Ra calculated from the above formula (1) (all units are “MPa 1/2 ”) are shown. It is shown in FIG.
  • ⁇ 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 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 are easily formed. Can be determined.
  • 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 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 satisfying the requirements (I) and (II) 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.
  • 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 satisfying the requirements (I) and (II) can be more easily formed.
  • the blending ratio of the organic solvent (C2) in the organic solvent (C) is determined based on the total amount of the organic solvent (C) (100% by mass). On a basis, it is preferably 20% by mass or more, more preferably 35% by mass or more, further preferably 50% by mass or more, and still more preferably 70% by mass or more.
  • the viscosity of the organic solvent (C) at 25 ° C is preferably 0.1 mPa ⁇ from the viewpoint of facilitating the formation of the particles satisfying the requirements (I) and (II). s or more, more preferably 0.15 mPa ⁇ s or more, still 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. s or less, more preferably 6.0 mPa ⁇ s or less, even more preferably 2.8 mPa ⁇ s or less.
  • the compounding amount of the organic solvent (C) is set to the total amount of the composition (100% by mass). Is preferably 0.05% by mass 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 It is 80% by mass or less, more preferably 60% by mass or less, 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 compounding ratio of the organic solvent (C) to the cellulose nanofiber (A) [(C ) / (A)] is preferably at least 0.01, more preferably at least 0.05, more preferably at least 0.1, further preferably at least 0.5, further preferably at least 0.75, by mass ratio. And still more preferably 0.9 parts by mass or more, and preferably 60 or less, more preferably 45 or less, more preferably 40 or less, and still more preferably 35 or less.
  • the mixing ratio of water (B) to the organic solvent (C) [(B) / (C)] is preferably not less than 0.1, more preferably not less than 0.5, still more preferably not less than 1.0, still more preferably not less than 1.5, and preferably not more than 1000 in terms of mass ratio. , More preferably 700 or less, still more preferably 500 or less, even more preferably 300 or less, and particularly preferably 100 or less.
  • 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.
  • 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 suppresses the aggregation of the cellulose nanofibers (A), reduces the variation in the shape and size of the formed particles, and satisfies the requirements (I) and (II).
  • the temperature of the aqueous dispersion suppresses the aggregation of the cellulose nanofiber (A), reduces the variation in the shape and size of the formed particles, and facilitates the formation of particles satisfying the requirements (I) and (II).
  • it is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably 15 ° C. or higher, and from the viewpoint of suppressing the volatilization of the added organic solvent (C), preferably 45 ° C. or lower.
  • it is 40 ° C. or lower, more preferably 35 ° C. or lower.
  • 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, from the viewpoint of easily forming particles satisfying the requirements (I) and (II). Minutes or more, 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 can stably maintain a sustained release property, which is a property capable of gradually releasing the organic solvent to the outside over time.
  • a sustained release property which is a property capable of gradually releasing the organic solvent to the outside over time.
  • 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 the 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. Even after 6 hours, it can be said that the larger the number of the evaluators, the more stable the sustained release of the particles.
  • 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 the sustained release properties of these particles were stably maintained.
  • 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

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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 d'obtenir et de maintenir de façon équilibrée une capacité 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 ou égale à une pression spécifique est appliquée, par rupture de l'enveloppe extérieure desdites particules, cette enveloppe externe contenant les nanofibres de cellulose (A). Plus spécifiquement, cette composition contient des particules satisfaisant les conditions (I) et (II) suivantes, au moins une partie du solvant organique (C) étant incorporée aux particules. Condition (I): le diamètre particulaire moyen des particules est de 1 à 6 μm. Condition (II): l'écart type du diamètre particulaire moyen des particules est inférieur ou égal à 20 μm.
PCT/JP2019/034046 2018-09-03 2019-08-30 Composition WO2020050155A1 (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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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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