WO2020050150A1 - Structural object - Google Patents
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- WO2020050150A1 WO2020050150A1 PCT/JP2019/034041 JP2019034041W WO2020050150A1 WO 2020050150 A1 WO2020050150 A1 WO 2020050150A1 JP 2019034041 W JP2019034041 W JP 2019034041W WO 2020050150 A1 WO2020050150 A1 WO 2020050150A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
Definitions
- the present invention relates to a structure including cellulose nanofiber.
- CNF cellulose nanofibers
- Patent Document 1 a porous body made of CNF has been proposed (for example, see Patent Document 1).
- a method for producing a CNF porous body a method including a step of freeze-drying a water slurry in which CNF is uniformly dispersed at a low temperature is widely known.
- a porous body obtained by freeze-drying has a so-called open cell structure, and is expected to be used as an adsorbent, a heat insulating material, a sound absorbing material, and the like.
- the present invention provides a structure including a film containing cellulose nanofibers and a plurality of closed spaces formed by the film, in which a large proportion of the space exists, and in which unnecessary components are hardly mixed into a fluid held therein.
- the task is to provide
- the present inventors have conducted intensive studies in order to solve the above problems, and as a result, a structure including a plurality of closed spaces constituted by a membrane containing cellulose nanofibers, and having a surfactant content of a predetermined value or less.
- the present inventors have found that the above problem can be solved and completed the present invention. That is, the present invention provides the following [1] to [12].
- [1] A structure comprising a membrane containing cellulose nanofibers and a plurality of closed spaces constituted by the membrane, wherein the content of the surfactant is 10 parts by mass relative to 100 parts by mass of the cellulose nanofibers.
- the structure is less than one part.
- [2] The structure according to [1], wherein a set of adjacent closed spaces among the plurality of closed spaces shares at least one of the membranes.
- [3] The structure according to the above [1] or [2], wherein the average thickness of the film containing the cellulose nanofiber is 10 nm to 2000 nm.
- [4] The structure according to any one of the above [1] to [3], wherein the bulk density of the structure is 0.001 to 1.4 g / cm 3 .
- [5] The structure according to any one of [1] to [4], wherein the structure has a sheet shape.
- [6] The structure according to the above [5], wherein the thickness of the structure is 0.5 to 300 ⁇ m.
- the maximum length of the closed space in the thickness direction of the structure is a, and the maximum length of the closed space in the plane direction of the structure is b.
- the cellulose nanofiber is a plant-derived cellulose nanofiber.
- the present invention it is provided with a membrane containing cellulose nanofibers and a plurality of closed spaces composed of the membrane, the existence ratio of the space is large, and it is difficult for unnecessary components to be mixed into the fluid held therein.
- a structure can be provided.
- FIG. 1A is a partial cross-sectional view in the thickness direction of the sheet-like structure
- FIG. 1B is an enlarged view of a part of FIG. 1A
- FIG. 13 is a figure explaining the size of a closed space. It is a typical side view showing signs that a composition was applied on a support.
- 13 is an SEM image of a cross section in the thickness direction of the sheet-like structure manufactured in Example 6.
- the structure according to the embodiment of the present invention is a structure including a membrane including cellulose nanofibers (CNF) and a plurality of closed spaces constituted by the membrane, wherein the surfactant content is CNF100. Less than 10 parts by mass with respect to parts by mass.
- the term “occlusive space composed of a CNF-containing membrane” means a closed space in which the upper, lower, lateral, and other directions are all surrounded by the CNF-containing membrane.
- the film containing CNF is a dense film but has fine voids. Therefore, if the space surrounded by the film containing CNF does not lead to an opening having a size exceeding the above-mentioned minute gap, it corresponds to “an occluded space composed of a film containing CNF”.
- the shape of the structure is not particularly limited.
- the structure can be formed into an arbitrary shape by, for example, putting a composition described below in a mold and drying the composition.
- One preferred embodiment of the structure of the present invention is a sheet-like structure.
- the sheet-like structure can be easily mass-produced by applying the composition described below to a support and drying it, and can be used for a wide range of applications.
- a structure according to an embodiment of the present invention will be specifically described with reference to the drawings using a sheet-like structure as an example. 1 and 2 used in the following description are schematic views, and are exaggerated for easy understanding. The number and size of the closed space, the thickness of the structure, and the like are also schematically shown, and these are not limited by the drawings.
- FIG. 1A is a schematic partial cross-sectional view in the thickness direction of a sheet-like structure which is an embodiment of the structure of the present invention.
- a layer 31 provided on a support 40 and having a plurality of closed spaces 33 formed of a film 35 containing CNF forms a sheet-like structure.
- the sheet-like structure 50 with the support is constituted by the layer 31 which is the sheet-like structure and the support 40.
- the support 40 may be omitted. If the support 40 is not provided, the single sheet-shaped structure 31 is formed.
- the film 35 containing CNF formed by a manufacturing method described later is considered to be a mesh-like or fibrous dense film formed by arranging or tangling a plurality of CNFs. Therefore, for example, the sheet-like structure 31 or the sheet-like structure 50 with a support can be applied to a product that holds a fluid in the closed space 33 surrounded by the membrane 35 containing CNF. Such a product (hereinafter, sometimes referred to as a “fluid holding product”) can apply pressure to cleave the structure and supply the fluid to the outside when necessary. Further, since the film 35 containing CNF is a dense film of CNF, the film 35 has a certain strength without making the film thicker, and can form an occluded space capable of holding a fluid inside.
- a film containing CNF has a large number of minute voids, and can gradually transmit a fluid such as a gas or a liquid. Therefore, for example, the sheet-like structure 31 or the sheet-like structure 50 with a support can be used for a product in which a fluid is held in the closed space 33 and the fluid is gradually released to the outside through the membrane 35 containing CNF. Can be applied.
- the property of gradually releasing the fluid to the outside through the membrane is referred to as sustained release.
- the obtained porous body has a so-called open cell structure.
- a porous body having such an open-cell structure is not suitable for holding a fluid, and is difficult to apply to the above-mentioned product for holding a fluid or a product having a sustained release property.
- the structure does not contain a surfactant or has a low content of the surfactant, when the fluid is retained in the closed space, the surfactant is eluted into the fluid or the fluid is removed from the structure. It is possible to prevent the surfactant from being released together with the fluid when taken out. In addition, the presence of the surfactant destabilizes the physical properties of the structure, and for example, it is easy to prevent the structure from being deteriorated or the strength of the structure from being reduced. Therefore, the structure according to the embodiment of the present invention is suitable for a product for retaining a fluid or a product having a sustained release property as described above. A method for producing the above-mentioned structure having a plurality of closed spaces formed of a film containing CNF that does not contain a surfactant or has a low surfactant content will be described later.
- the upper limit of the content of the surfactant is less than 10 parts by mass, preferably less than 1 part by mass, more preferably less than 0.1 part by mass, and still more preferably less than 0.01 part by mass with respect to 100 parts by mass of CNF. Particularly preferably, it is less than 0.001 part by mass, and most preferably 0 part by mass.
- the surfactant is extracted with a solvent, and the chemical composition is identified by a high-performance liquid chromatograph mass spectrometer (LC-MS), a nuclear magnetic resonance apparatus (NMR), or the like. And a method of performing quantification. Further, as a means for identification, energy dispersive X-ray analysis (EDX) or infrared spectroscopy (IR) can be used. In the case of EDX, the composition may be directly observed and analyzed.
- EDX energy dispersive X-ray analysis
- IR infrared spectroscopy
- the structure may contain a polysaccharide other than CNF.
- a polysaccharide other than CNF in the above-mentioned fluid retaining product and the product having a sustained release property, unnecessary components are not mixed into the fluid discharged to the outside.
- the content is preferably less than 10 parts by mass, more preferably less than 1 part by mass, still more preferably less than 0.1 part by mass, even more preferably 0 part by mass relative to 100 parts by mass of the total amount of CNF. It is less than 0.01 parts by mass, particularly preferably 0 parts by mass.
- Polysaccharides can be identified and quantified by the same procedure as for surfactants.
- FIG. 1B is an enlarged view of a portion surrounded by a dashed line in FIG.
- a film 35a containing CNF is shared between a pair of adjacent closed spaces 33a and 33b.
- a set of adjacent closed spaces among a plurality of closed spaces forms at least one film, such as the sheet-like structure 31 or the sheet-like structure 50 with a support. Share.
- a boundary formed along the film containing CNF may be observed.
- the film containing CNF may include such a boundary. The boundary is presumed to reflect the difference in the existing state of CNF before forming the sheet-like structure, but the presence or absence of this boundary does not particularly affect the characteristics of the sheet-like structure.
- the size of the closed space is represented by the maximum Feret's diameter (the size of the closed space does not include the thickness of the membrane containing CNF).
- the average of the maximum Feret diameters of the plurality of closed spaces is preferably 1 ⁇ m to 60 ⁇ m.
- the lower limit of the average of the maximum Feret diameter of the plurality of closed spaces is more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more, and particularly preferably 20 ⁇ m or more.
- the average upper limit of the maximum Feret diameter of the plurality of closed spaces is more preferably 55 ⁇ m or less, further preferably 50 ⁇ m or less, still more preferably 45 ⁇ m or less, particularly preferably 40 ⁇ m or less, and most preferably 35 ⁇ m or less.
- the “maximum Feret diameter” of a certain figure means the maximum distance of the figure between two parallel lines.
- a figure corresponding to an occluded space is specified on a cut surface when a structure including a plurality of occluded spaces constituted by a membrane containing CNF is cut, and this figure is represented by two parallel lines.
- the maximum Feret diameter of the closed space is calculated by measuring the maximum distance between the blocks.
- the cut surface for calculating the maximum Feret diameter of the closed space may be appropriately selected so as to include as much closed space as possible so that the average of the maximum Feret diameter can be calculated.
- the maximum Feret diameter of the closed space is calculated in the cross section in the thickness direction of the body-shaped sheet-like structure 50.
- the maximum Feret diameter df of the closed space 33 matches the maximum opening width.
- the average of the maximum Feret diameters of the plurality of closed spaces is an average value of the maximum Feret diameters of the plurality of closed spaces at an arbitrary cut surface of the structure.
- an arbitrary 36 closed spaces are selected, each maximum Feret diameter is measured, and the average value thereof is referred to as “the average of the maximum Feret diameters of a plurality of closed spaces”. I do.
- the average of the maximum Feret diameters of the plurality of closed spaces in the cross section of the structure is in the above-described range, and the size of the closed space is small. For this reason, many films containing CNF exist inside the structure, and the strength of the structure can be increased. Therefore, it becomes easy to obtain a structure excellent in shape maintenance property against pressure or the like.
- the strength of the structure being increased, in cases where the structure is applied to the above-described fluid holding product or a product having a sustained release property, it is advantageous for holding the fluid in the closed space for a long time. work.
- the fluid can be individually held in many closed spaces, and the retention of the fluid can be improved, and the sustained release performance can be improved. Is released).
- the strength of the structure is increased by a plurality of closed spaces sharing the film, so that the film having self-holding properties without adding a binder component ( Self-standing film).
- This self-supporting film does not necessarily require a binder component, and for example, can increase the space for holding a fluid as compared with a case where a plurality of capsules having an internal space are connected with a binder.
- the size of the closed space in the structure can be adjusted, for example, by changing the size of particles having an outer shell containing CNF in the composition described below. Thereby, the maximum Feret diameter of the closed space can be adjusted, and the average of the maximum Feret diameters of the plurality of closed spaces can be set within the above numerical range.
- the shape of the closed space is arbitrary, but when the structure is manufactured using a manufacturing method described later, a pair of adjacent closed spaces form a film containing CNF as described above due to the manufacturing method.
- Each closed space has a polyhedral shape surrounded by a plurality of flat films so that a shared structure can be easily obtained. Therefore, at least one cut surface having a polygonal shape as shown in FIG. 1 can be formed in each closed space.
- the sheet-like structure 31 or the sheet-like structure 50 with a support in a cross section in the thickness direction, as shown in FIG.
- the maximum length in the thickness direction of the closed space of the structure (in other words, the distance from the lowest position to the highest position of the surface of the membrane including CNF on the closed space side) is a, and the closed space of the structure is Is the maximum length in the plane direction (in other words, the distance from one end to the other end in the plane direction of the surface of the membrane including CNF on the side of the closed space), b / a of the plurality of closed spaces. Is preferably greater than 1, more preferably greater than 1.5, and even more preferably greater than 2.
- the closed space generally has a shape extending in the planar direction of the structure, so that a large number of closed spaces can be provided without increasing the thickness of the structure. . Further, at the time of drying in the step (2-3) to be described later, a closed space extending in the planar direction is easily formed by the weight of the film containing CNF, so that the structure can be easily manufactured.
- the average of b / a of the plurality of closed spaces is preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of manufacturability and maintaining the strength of the structure. .
- the average thickness of the film containing CNF is preferably at least 10 nm, more preferably at least 50 nm, further preferably at least 75 nm, and preferably at most 2,000 nm, more preferably at most 1,750 nm, further preferably at most 1,500 nm, even more preferably Preferably it is 1250 nm or less.
- the average thickness of the film containing CNF can be determined by observing a cross section of each structure using a scanning electron microscope (SEM), arbitrarily selecting 36 occlusion spaces from the obtained enlarged image, and selecting the selected occlusion space.
- SEM scanning electron microscope
- One arbitrary side constituting the polygon corresponding to the space is specified, and the thickness dm (indicated by two triangular marks and a leader line in FIG. 1C) at the approximate center of the side is measured, It is obtained by calculating an average value.
- the thickness dm of the film containing CNF can be adjusted, for example, by changing the diameter (thickness) or fiber length of CNF. By increasing the diameter (thickness) of CNF or shortening the fiber length of CNF, the film containing CNF can be made thicker. Conversely, by decreasing the diameter (thickness) of CNF or increasing the fiber length of CNF, the film containing CNF can be made thinner.
- the bulk density of the structure is preferably 0.001 g / cm 3 or more, more preferably 0.005 g / cm 3 or more, more preferably 0.0075 g / cm 3 or higher, more preferably at 0.01 g / cm 3 or more And preferably 1.40 g / cm 3 or less, more preferably 1.20 g / cm 3 or less, still more preferably 0.920 g / cm 3 or less, still more preferably 0.800 g / cm 3 or less, and even more preferably 0.600 g / cm 3 or less, more preferably 0.500 g / cm 3 or less.
- the structure can be provided with a minimum necessary strength, for example, a strength that is not crushed when wound in a roll. Further, when the bulk density is 1.40 g / cm 3 or less, it becomes easy to hold many fluids in the closed space.
- the bulk density of a structure is calculated by dividing the mass of the structure by the volume of the entire structure including the closed space. In the case where a layer containing CNF is formed on a support as shown in FIG. 1, the thickness and the mass of the support may be measured in advance, and the calculation may be performed after subtracting these values.
- the bulk density of the structure can be adjusted, for example, by changing the diameter of a particle having a shell containing CNF in the composition.
- the diameter of the particles having an outer shell containing CNF in the composition can be adjusted by changing the type and blending ratio of the organic solvent or changing the stirring conditions.
- the thickness L of the structure excluding the support is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, and still more preferably. 3.5 ⁇ m or more, even more preferably 5.0 ⁇ m or more, particularly preferably 7.5 ⁇ m or more, and preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, further preferably 100 ⁇ m or less, even more preferably 75 ⁇ m or less, Particularly preferably, it is 50 ⁇ m or less.
- the thickness of the structure is 300 ⁇ m or less, it is possible to prevent the drying time from being prolonged or to cause poor drying.
- the variation in the shape and size of the closed space is suppressed, and It is easy to prevent problems such as deterioration.
- the thickness of the structure is 0.5 ⁇ m or more, it is easy to prevent the strength of the structure from becoming insufficient and the fluid that can be held in the closed space to decrease.
- the structure has a sheet shape or a band shape, there is no particular limitation on the area and the size in the longitudinal direction of the structure, and the structure can have any size as long as manufacturing facilities can be prepared.
- the maximum diameter of the structure is preferably 1 mm or more, more preferably 5 mm or more, It is more preferably at least 1 cm, further preferably at least 2.5 cm, particularly preferably at least 5 cm, and preferably at most 5 m, more preferably at most 3 m, still more preferably at most 1 m, even more preferably at most 50 cm, particularly preferably at most 50 cm. 10 cm or less.
- CNF Cellulose nanofiber
- the material, shape, and the like of CNF constituting the structure those described in CNF to be added to the composition described below apply as they are.
- polysaccharides other than CNF and other components excluding components such as organic solvents that are present in an enclosed space for the purpose of sustained release
- the structure has a support, such as a sheet-like structure 50 with a support.
- a support such as a sheet-like structure 50 with a support.
- the structure and the support may be integrated, or the structure may be separated from the support after the structure is formed. That is, the sheet-like structure may be formed on a temporarily used holder such as a release material.
- the surface of the support to which the composition is applied is subjected to an easy-adhesion treatment.
- the easy adhesion treatment for example, a corona discharge treatment, a plasma treatment, an ozone treatment, or the like can be used.
- an easy-adhesion layer can be provided using an acrylic resin, an ester resin, a urethane resin, or the like.
- a material having a release layer formed on the surface to which the composition is applied may be used, or a material in which the entire support is made of a material from which the structure is easily peeled may be used.
- the support is appropriately selected depending on the use of the sheet-like structure, and is, for example, a paper base such as high-quality paper, art paper, coated paper, or glassine paper; and a thermoplastic resin such as polyethylene is laminated on these paper bases.
- Laminated paper Laminated paper; metal foils such as aluminum foil, copper foil and iron foil; porous materials such as non-woven fabrics; polyolefin resins such as polyethylene resin and polypropylene resin; polyester resins such as polybutylene terephthalate resin and polyethylene terephthalate resin; acetate resins; A resin film or sheet containing at least one resin such as an ABS resin, a polystyrene resin, and a vinyl chloride resin;
- the support may be a single-layer film or sheet, or a multilayer film or sheet that is a laminate of two or more layers. Moreover, the resin film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as a vertical or horizontal direction.
- the resin film or sheet may contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent, and the like, in addition to the above-described resin.
- the thickness of the support is appropriately selected depending on the use of the sheet-like structure, but is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, further preferably 20 ⁇ m or more, and preferably 250 ⁇ m or less, more preferably Is 200 ⁇ m or less, more preferably 150 ⁇ m or less.
- a structure having a plurality of closed spaces composed of a film containing CNF can be manufactured by a manufacturing method having the following steps (1) and (2) as one embodiment.
- Step (1) a step of adding an organic solvent to an aqueous dispersion of CNF to prepare a composition.
- Step (2) a step of applying the composition on a support to form a coating film, and drying the coating film to form a sheet-like structure.
- the step (1) may be referred to as a “step of preparing a composition”, and the step (2) may be referred to as a “step of obtaining a structure”.
- the step (2) as described below, a step of supplying the composition to one surface of the support (step (2-1)) and a step of applying the composition to the support (step (2-2)) ) And drying the composition applied on the support (step (2-3)).
- FIG. 2 is a schematic diagram showing one step in the manufacturing process and showing a state in which the composition is applied on a support.
- the composition prepared in the step (1) contains particles having an outer shell containing CNF.
- the composition is applied on a support.
- the composition 30 includes particles 32 having an outer shell containing CNF, and a medium 34 mainly composed of water.
- the particles 32 contain a liquid mainly composed of an organic solvent, air, or both.
- step (2-3) the water and the organic solvent are removed by drying, and as shown in FIG. 1A, a layer in which a large number of closed spaces are formed by a CNF-containing film (ie, a sheet-like layer).
- a structure 31 is formed on the support 40.
- the sheet-like structure 31 or the sheet-like structure 50 with a support is applied to the above-described fluid holding product or a product having a sustained release property, the sheet-like structure is immersed in a specific liquid to close the closed space.
- the above-mentioned liquid can be sealed therein, or a specific kind of gas can be sealed in a closed space in a sheet-like structure under a specific gas atmosphere.
- these fluids may be included in the closed space during the manufacturing process of the sheet-like structure.
- a specific type of organic solvent for example, an organic solvent having a boiling point higher than the drying temperature
- the composition may be prepared in an atmosphere filled with a specific type of gas, so that the fluid is sealed in the closed space.
- Step (1) Step of Preparing Composition
- an organic solvent is further added, and the organic solvent is also uniformly dispersed, so that an interface between water and the organic solvent can be obtained without using a dispersant such as a surfactant.
- the process of forming particles having an outer shell containing CNF in the composition is not limited to this, but one is presumed to be due to the following mechanism.
- CNF is an insoluble material having amphipathic properties, it exists in an interface between water and an organic solvent used for emulsification, thereby creating an energy-stable state.
- CNF is insoluble and film-forming, it forms an irreversible independent phase as a result of localization at the interface.
- particles with a shell comprising CNF are formed in the composition.
- the total amount of the aqueous dispersion is 100 parts by mass.
- the amount of the organic solvent added 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, particularly preferably at least 5 parts by mass, and preferably at least 20 parts by mass. Parts or less, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, particularly preferably 7 parts by weight or less.
- the organic solvent may be supplied continuously, or the organic solvent may be supplied intermittently.
- the organic solvent is uniformly dispersed in the aqueous dispersion, and as a result, the particles having the outer shell containing CNF are excellent. Can be generated.
- step (1) it is preferable to add an organic solvent while stirring the aqueous dispersion using a stirrer equipped with a stirring blade such as a homodisper, a mixer, or a paddle blade.
- 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, more preferably 1000 rpm or more, from the viewpoint of suppressing the aggregation of CNF and reducing the variation in the shape and size of the formed particles. It is more preferably 1500 rpm or more, still more preferably 2000 rpm or more, and preferably 5000 rpm or less, more preferably 4500 rpm or less, still more preferably 4000 rpm or less, still more preferably 3500 rpm or less, and particularly preferably 3000 rpm or less.
- the stirring time is preferably 3 minutes or more, more preferably 5 minutes or more, and still more preferably 10 minutes or more, from the viewpoint of making the shape and size of the particles having the outer shell containing CNF uniform.
- the upper limit of the stirring time is preferably 180 minutes or less, more preferably 180 minutes or less, from the viewpoint of preventing the production time from becoming too long and avoiding variation in the shape and size of the particles having the outer shell containing CNF. It is 120 minutes or less, further preferably 60 minutes or less, even 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 temperature of the aqueous dispersion is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably 15 ° C., from the viewpoint of suppressing the aggregation of CNF and reducing the variation in the shape and size of the formed particles.
- the temperature is preferably 45 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 35 ° C. or lower.
- Step (1) is preferably performed at 80 kPa or more, more preferably 90 kPa or more, still more preferably 95 kPa or more, and is preferably performed at 120 kPa or less, more preferably 110 kPa or less, further preferably 105 kPa or less, and particularly preferably large.
- Perform under atmospheric pressure By preparing the composition under conditions close to atmospheric pressure, the composition can be prepared in a short time, and the production equipment can be simplified.
- Step (1) may be performed in an atmosphere of air or an inert gas. In an air atmosphere, the manufacturing equipment can be simplified, and in an inert gas atmosphere, deactivation of the composition and the like can be easily suppressed.
- the composition is prepared under an atmosphere of a specific type of gas so that the gas is sealed in the generated particles. You may. These temperature conditions, pressure conditions, and atmosphere conditions also apply to the step (2-1) and the step (2-2) described later.
- composition obtained in step (1) and constituent materials of the composition The composition prepared in the step (1) is obtained by blending CNF (A), water (B), and an organic solvent (C), and includes particles having an outer shell containing CNF (A). It contains.
- CNF (A), water (B), and organic solvent (C) may be collectively referred to as “components (A) to (C)”.
- components (A) to (C) In the above composition, at least a part of the organic solvent (C) is in a state of being taken in by the particles, specifically, in a state of being included in the particles, and forming an outer shell of the particles. It is preferable that the state is at least one of the state of being adsorbed by the CNF (A).
- the “state in which the organic solvent (C) is included in the particles” means that the particles form hollow particles from the outer shell containing CNF (A), and the organic solvent is contained in the hollow portion of the hollow particles.
- (C) means the state 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 CNF (A) constituting the outer shell of the particles is adsorbed on the organic solvent (C). It may be in the state where it is.
- the outer shell composed of CNF (A) adsorbs the organic solvent (C) means that the organic solvent (C) is contained in the network structure of the outer shell composed of CNF (A). Means exist.
- an organic solvent (C) that is not incorporated into the particles may be present.
- the average particle diameter of the particles having an outer shell containing CNF in the composition is set to an appropriate range.
- 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, still more preferably 7 ⁇ m or more, still more preferably 10 ⁇ m or more, and particularly preferably 15 ⁇ m or more.
- it is preferably 60 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably 40 ⁇ m or less, still more preferably 35 ⁇ m or less, particularly preferably 30 ⁇ m or less.
- the average particle diameter of the particles is 1 ⁇ m or more, aggregation of the particles is easily suppressed, and the closed space of the structure is easily prevented from becoming too small.
- the average particle diameter of the particles is 60 ⁇ m or less, the floating of the particles is easily suppressed.
- the standard deviation with respect to the average particle diameter of the particles contained in the composition of one embodiment of the present invention is such that the above-described fluid is held in a structure, and the fluid is externalized by cleavage of the structure when necessary.
- it is preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, further preferably 15 ⁇ m or less, further more preferably 12 ⁇ m or less, and usually 1 ⁇ m or more.
- the average particle diameter of the particles and the standard deviation with respect to the average particle diameter are calculated from an image obtained when the target composition is observed at a magnification of 500 to 1000 using a digital microscope. Can be calculated.
- the average value of the particle diameters (outer diameters) of the 36 particles arbitrarily selected among the particles shown in the image can be the above-mentioned “average particle diameter”.
- 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 viscosity of the composition used in one embodiment of the present invention at 23 ° C and a rotation speed of 50 rpm is preferably 500 mPa ⁇ s or more from the viewpoints of easy removal from a container, ease of stirring, and suppression of sedimentation. And more preferably 1000 mPa ⁇ s or more, further preferably 1200 mPa ⁇ s or more, preferably 20,000 mPa ⁇ s or less, more preferably 15000 mPa ⁇ s or less, and still more preferably 12000 mPa ⁇ s or less.
- the viscosity of the composition at the temperature at which the composition is applied to the support is within the above numerical range. It is preferable to select the material so that
- the TI value at 23 ° C (viscosity at 5 rpm / viscosity at 50 rpm) of the composition used in one embodiment of the present invention is storage stability, suppresses sedimentation when stored in a container, and From the viewpoint of easy removal from the container, etc., it is preferably 1.2 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 4 or more, and preferably 20 or less, more preferably It is 15 or less, more preferably 10 or less, even 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 used in one embodiment of the present invention is preferably 4 or more, more preferably 5 or more, and still more preferably 6 from the viewpoint that particles to be formed are stable and a dispersed state is easily maintained in the composition.
- the number is preferably 10 or less, more preferably 9 or less, and further preferably 8 or less.
- the composition used in one embodiment of the present invention may contain components other than the above components (A) to (C).
- the total content of CNF (A), water (B), and the organic solvent (C) is preferably 60% based on the total amount (100% by mass) of the composition. % By mass, more preferably 65% by mass or more, further preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 100% by mass or less.
- the active ingredient concentration of the composition used in one embodiment of the present invention is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and still more preferably, based on the total amount (100% by mass) of the composition. Is 1.0% by mass or more, even more preferably 1.5% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably Is 10% by mass or less.
- an "active ingredient” points out a component except water (B) and an organic solvent (C) among the components contained in a composition.
- the particles having an outer shell containing CNF (A) and incorporating the organic solvent (C) are used in the compounding amount of CNF (A), the compounding ratio of CNF (A) and the organic solvent (C), and the organic compound (C). It can be formed by appropriately adjusting the type of the solvent (C) and the like.
- the particles are obtained by blending an organic solvent (C) with an aqueous dispersion in which CNF (A) is dispersed in water (B).
- the composition is prepared to form.
- the composition is such that the particles are formed by blending an organic solvent (C), which is a non-aqueous solvent, with an aqueous dispersion in which CNF (A) is dispersed in water (B).
- an organic solvent (C) having a distance Ra of Hansen solubility parameter of 5.80 MPa 1/2 or less is mixed with an aqueous dispersion in which CNF (A) is dispersed in water (B).
- a composition is prepared to form the particles.
- the shape (diameter, fiber length, aspect ratio) of CNF (A), the amount of water (B) and the amount of organic solvent (C), the amount of water (B) and organic solvent (C) The composition can be prepared such that the particles can be easily formed by appropriately setting the amount ratio and the like.
- CNF Cellulose nanofiber
- Raw materials of CNF (A) used in one embodiment of the present invention include, for example, wood-based kraft pulp or sulfite pulp; powdered cellulose obtained by grinding kraft pulp or sulfite pulp with a high-pressure homogenizer or a mill; Cellulose such as microcrystalline cellulose powder purified by chemical treatment such as hydrolysis; bast fiber pulp such as mulberry, ganpi, mitsumata, etc .; System raw materials. Since plant-derived CNF has a high degree of crystallinity and a linear structure and a large aspect ratio, the strength of the outer shell can be increased, and it is easily available.
- 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 cellulosic raw material can be made into CNF by fibrillating into nanofibers.
- a method in which a dispersion liquid in which a cellulose-based material is dispersed in a dispersion medium such as water is prepared, and a shear force is applied to the cellulose-based material to obtain a dispersion containing CNF.
- a method of applying a shearing force to the cellulosic material after adding the cellulosic material to a dispersion medium such as water, using a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, an ultrasonic type or the like, The method of preparation is preferred.
- the pressure applied to the dispersion is preferably 50 MPa or more, more preferably 100 MPa or more, and further 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 CNF used in one embodiment of the present invention is preferably 1.0 nm or more, more preferably 1.0 nm or more, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles.
- the average fiber length of CNF used in one embodiment of the present invention is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. As described above, it is more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 7.0 ⁇ m or less, still more preferably 5.0 ⁇ m or less, and still more preferably 2.5 ⁇ m or less. It is.
- the average aspect ratio of CNF (A) used in one embodiment of the present invention is preferably 5 or more, more preferably 10 or more, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. It is still more preferably 15 or more, preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less, still more preferably 1,000 or less, and particularly preferably 500 or less.
- the “aspect ratio” is the ratio of the length to the thickness of the target CNF [length / thickness], and the “length” of the CNF is the distance between the two most distant points of the CNF. Refers to distance. If it is difficult to determine the “length” of a part of the target CNF due to contact with another CNF, measure the length of only the part of the target CNF whose thickness can be measured.
- the aspect ratio of the portion may be in the above range.
- the diameter (thickness) and fiber length of CNF (A) can be measured using a transmission electron microscope.
- the average of the diameter (thickness) and the average of the fiber length of CNF (A) are obtained by measuring the diameter (thickness) and the fiber length of arbitrarily selected plural CNFs and calculating the average value of each. can get.
- the average aspect ratio of CNF (A) can be calculated using the average of the diameter (thickness) and the average of the fiber length thus obtained.
- the diameter (thickness), fiber length, average value, and average aspect ratio of CNF (A) can be specifically calculated by the methods described in Examples.
- the numerical ranges of the fiber diameter, fiber length, and aspect ratio of the CNF described above are CNF before preparing the composition, CNF after preparing the composition, and a structure manufactured using the composition described below. The same holds true for any of the CNFs.
- the compounding amount of CNF (A) is such that the particles are easily formed and the film strength of the formed particles is based on the total amount (100% by mass) of the composition. From the viewpoint of improving the above, preferably 0.7% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, even more preferably 1.2% by mass or more, From the viewpoint of appropriately adjusting the viscosity of the composition so as to facilitate 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, even more preferably 5% by mass or less. % By mass or less, particularly preferably 3% by mass or less.
- Water (B) In the composition used in one embodiment of the present invention, most of the water (B) is adsorbed on the outer shell of the particle or exists 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 set to the total amount (100 mass) of the composition. %), 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, and preferably 99% by mass or less. It is preferably at most 98.7% by mass, more preferably at most 98.5% by mass.
- the mixing ratio of water (B) to 100 parts by mass of CNF (A) is as follows. , 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 also preferably at most 20,000 parts by mass, more preferably 15,000 parts by mass.
- the content is more preferably 10,000 parts by mass or less.
- an aqueous dispersion containing CNF and water can be used as an aqueous dispersion as it is by dispersing a cellulose-based material in water and then applying a shear force to the cellulose-based material. it can.
- a commercially available CNF aqueous dispersion can also be used.
- the pH of the aqueous dispersion is preferably 4 or more, more preferably 5 or more, from the viewpoint of suppressing aggregation of CNF (A) in the aqueous dispersion and reducing the variation in the shape and size of the formed particles. It is preferably 6 or more, more preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
- Organic solvent (C) As the organic solvent (C), from the viewpoint that it forms an independent phase with water when mixed with water, and can be temporarily emulsified by being added to water and stirring, it is insoluble in water. It is preferable to use a system solvent. By using a non-aqueous solvent, particles having an outer shell containing CNF can be generated without using a dispersant such as a surfactant.
- the organic solvent (C) has a distance Ra of the Hansen solubility parameter at 25 ° C. represented by the following formula (1) of 5.80 MPa 1/2 or less.
- ⁇ D is a dispersion component of the Hansen solubility parameter of the organic solvent
- ⁇ P is a polar component of the Hansen solubility parameter of the organic solvent
- ⁇ H indicates a hydrogen bonding component of the Hansen solubility parameter of the organic solvent.
- 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)".
- the present inventors have noticed that there is a difference in the ease of forming the particles depending on the type of the organic solvent (C) to be blended.
- the Hansen solubility parameters of the respective organic solvents are plotted in a three-dimensional space, the organic solvents used when the particles are formed are densely distributed in a certain area in the three-dimensional space. I understand. Therefore, when plotting the largest sphere (interaction sphere), the plot of the organic solvent in which the particles were formed was all included inside, and the plot of the organic solvent in which the particles were not formed was outside, The radius of the sphere was “5.80 MPa 1/2 ”.
- the distance Ra calculated from Expression (1) means the distance between the plot of the target organic solvent and the center of the sphere in the three-dimensional space of the Hansen solubility parameter. That is, if the distance Ra is equal to or less than the radius of the sphere, “5.80 MPa 1/2 ”, the plot of the target organic solvent is located inside the sphere, and the particles are easily formed. It can be determined that it is a solvent.
- the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is heptane, n-hexadecane, methyl ethyl ketone, and n-dodecane. As shown in Examples described later, when these organic solvents were used, the result that the particles were easily formed was obtained. In view of this result, it is presumed that even if the organic solvent (C) has a distance Ra of 5.80 MPa 1/2 or less, particles other than the organic solvents shown in Table 1 can be easily formed.
- ⁇ 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 organic solvent (C) may be used alone or as a mixed solvent using two or more kinds.
- 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 preferable that the determined distance Ra be 5.80 MPa 1/2 or less. Therefore, even if the organic solvent alone has a distance Ra of more than 5.80 MPa 1/2 , it is mixed with another organic solvent having a distance Ra of 5.80 MPa 1/2 or less at an appropriate volume ratio, and the distance Ra is adjusted.
- the use of the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is thought to facilitate the formation of the particles as compared with the case where another organic solvent is used. Whether or not it can be further changed depending on the blending amounts of CNF (A), water (B) and organic solvent (C), the shape of CNF (A), and the selection of the modifying group. Therefore, while using the organic solvent (C) having the distance Ra of 5.80 MPa 1/2 or less, the particles can be formed more easily by appropriately considering the items described in the item of each component in this specification. It is preferable to prepare it.
- 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 CNF (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 blending ratio of the organic solvent (C1) in the organic solvent (C) is preferably 20% by mass or more, more preferably 35% by mass or more based on the total amount (100% by mass) of the organic solvent (C). , More preferably 50% by mass or more, even more preferably 70% by mass or more.
- the amount of the organic solvent (C) is preferably 0.05% with respect to the total amount (100% by mass) of the composition.
- % By mass or more more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less.
- % By mass more preferably 45% by mass or less, still more preferably 42% by mass or less, further preferably 40% by mass or less, particularly preferably 38% by mass or less.
- the mixing ratio of the organic solvent (C) to 100 parts by mass of CNF (A) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 50 parts by mass or more, further preferably 75 parts by mass or more, further preferably 90 parts by mass or more, and preferably 6000 parts by mass or less, It is preferably at most 4,500 parts by mass, more preferably at most 4,000 parts by mass, even more preferably at most 3,500 parts by mass.
- the mixing ratio of water (B) to the organic solvent (C) [(B) / (C)] is expressed as a mass ratio.
- composition used in 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 and the like.
- the content of the surfactant is such that the content of the surfactant is less than 10 parts by mass relative to 100 parts by mass of CNF in the structure. It is.
- the surfactant may also be a penetrant and an irritant, especially for users with sensitive skin. Further, there is a concern that the composition containing a surfactant may affect the stability of physical properties of the composition.
- the content of the surfactant is preferably as small as possible. From the above viewpoint, in the composition used in one embodiment of the present invention, the content of the surfactant is preferably less than 10 parts by mass, more preferably less than 1 part by mass, based on 100 parts by mass of the total amount of CNF (A).
- the amount is less than 0.1 part by mass, still 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.
- a polysaccharide other than CNF (A) may be contained, but the thermal stability of the particles is improved, and the particles are easily formed.
- the content of the polysaccharide is preferably as small as possible.
- the content of the polysaccharide other than CNF (A) is preferably less than 10 parts by mass, more preferably less than 10 parts by mass, based on 100 parts by mass of the total amount of CNF (A). Is less than 1 part by mass, more 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 (2) the composition is applied on a support to form a coating film, and the coating film is dried to form a sheet-like structure.
- the composition is preferably first placed on a support from the viewpoint of avoiding applying excessive stress to the particles having a shell containing CNF in the composition prepared in the step (1). (Step (2-1)), and then spread and spread the composition on the support uniformly (Step (2-2)). (Step (2-1): Step of Supplying Composition to One Side of Support)
- the step (2-1) for example, by tilting the container containing the composition to gradually move the composition from the container to the support under its own weight, the composition including the particles having the outer shell containing CNF Is supplied on a support. Further, the above composition may be supplied onto the support using a pump or the like.
- the temperature condition, pressure condition, and atmosphere condition in the step (2-1) may be set in the same manner as described in the step (1).
- the composition supplied on the support in the step (2-1) is applied on the support using a coating apparatus.
- the composition is applied to the support by moving the applicator relative to the support along a direction along the plane of the support (step (2-2)).
- the coating gap at the time of forming the coating film is such that a sufficient number of closed spaces composed of a film containing CNF are formed in a good shape, and it takes time for drying or heating at a relatively high temperature.
- some particles in the composition after application are preferably 30 ⁇ m or more, more preferably 100 ⁇ m or more, further preferably 150 ⁇ m or more, from the viewpoint of preventing breakage or disappearance. It is still more preferably 200 ⁇ m or more, preferably 1250 ⁇ m or less, more preferably 1000 ⁇ m or less, further preferably 750 ⁇ m or less, and still more preferably 500 ⁇ m or less.
- the method of applying the composition examples include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, gravure coating, and air knife coating. And a dip coating method. Among them, a knife coat method and a gravure coat method are preferable.
- the gap formed by the jig is preferably 1.5 times or more, more preferably 5 times or more, still more preferably 7.5 times or more, and still more preferably the diameter of the particle having the outer shell containing CNF. Is 9 times or more, preferably 62.5 times or less, more preferably 50 times or less, further preferably 37.5 times or less, and still more preferably 25 times or less.
- the composition is applied under an environment in which the temperature of the composition is preferably 45 ° C or lower, more preferably 40 ° C or lower, and further preferably 35 ° C or lower. I do.
- the temperature of the composition is preferably 45 ° C or lower, more preferably 40 ° C or lower, and further preferably 35 ° C or lower. I do.
- the viscosity of the composition from becoming too high to form a uniform coating layer or damaging particles having an outer shell containing CNF, it is preferably 5 ° C. or more, more preferably 10 ° C. or more.
- the coating is performed in an environment of not less than 15 ° C., more preferably not less than 15 ° C.
- the pressure condition and the atmosphere condition in the step (2-2) may be set in the same manner as described in the step (1).
- compositions to the support at the same time as applying the composition to the support using a coating apparatus such as a die coater (that is, simultaneously perform the step (2-1) and the step (2-2)).
- a coating apparatus such as a die coater
- Step (2-3) drying the composition applied on the support
- a layer having a plurality of closed spaces composed of a film containing CNF is formed by drying the layer of the composition applied on the support by heating or the like. Specifically, the layer of the composition applied on the support is dried by a heater or the like, and by evaporating water and an organic solvent from the composition, including those incorporated into the particles, A layer having a plurality of closed spaces formed of a film containing CNF is formed.
- the mechanism for forming the closed space composed of the membrane containing CNF is not necessarily limited to this, but is presumed as follows.
- the temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower. Dry below °C. By drying at 90 ° C. or higher, water and the organic solvent are promptly removed, and a closed space having a good shape is easily formed. By drying at 150 ° C. or less, it becomes easy to prevent the shape and size of the closed space from becoming uneven and the support from being deformed.
- the pressure condition and the atmosphere condition in the step (2-3) may be set in the same manner as described in the step (1).
- step (2-3) from the viewpoint of preventing water and the organic solvent from remaining without being removed and disturbing the shape of the closed space, it is preferably at least 10 seconds, more preferably at least 30 seconds, even more preferably. Is dried for 1 minute or more, more preferably 5 minutes or more, even more preferably 10 minutes or more, and preferably 2 hours or less, more preferably 1 hour or less, and even more preferably 30 minutes or less.
- a composition including particles having an outer shell containing CNF can be produced without using a dispersant such as a surfactant.
- the CNF content in the structure can be increased. Therefore, when the structure of the present embodiment is applied to the above-described fluid holding product or a product having a sustained release property, a large amount of fluid can be held inside the structure, and furthermore, discharged to the outside. It becomes easier to prevent unnecessary components from being mixed into the fluid.
- ⁇ Aqueous dispersion, pH of composition> Two-point calibration of pH 4.01 standard solution and pH 6.86 standard solution using a compact pH meter (product name “LAQUAtwin pH-22B” manufactured by HORIBA Advanced Techno Co., Ltd.) under an environment of 23 ° C. and 50% relative humidity. After the measurement, the sample was dropped and measured so as to cover the entire flat sensor.
- Example 1 Preparation of Composition 1
- aqueous dispersion (1) containing CNF was used.
- Aqueous dispersion (1) Product name "BiNFi-s AMa10002", manufactured by Sugino Machine Co., Ltd.
- An aqueous dispersion containing 2% by mass of mechanically treated CNF having an average diameter (thickness) of 76.8 nm, an average length of 1.4 ⁇ m, and an average aspect ratio of 18.2.
- the aqueous dispersion (1) contained 4900 parts by mass of water with respect to 100 parts by mass of CNF, and the pH of the aqueous dispersion (1) was 7.0.
- aqueous dispersion (1) 5000.0 parts by mass of the aqueous dispersion (1) (100.0 parts by mass of CNF) was charged into a container, and an ultra-high-speed multi-stirring system (manufactured by Primix Co., product name "Lab-Ruution (registered trademark)"; Using a homodisper (manufactured by the company, blade diameter: 35 mm), the aqueous dispersion at 23 ° C. was stirred at a rotation speed of 3000 rpm. After the start of stirring, n-dodecane was 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.
- composition 1 comprising particles with an outer shell containing CNF was prepared. No surfactant was used in preparing Composition 1.
- Sheet-like structure 1 Composition 1 is gently placed on a 50 ⁇ m-thick polyethylene terephthalate film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 ⁇ m) with easy adhesion. Then, Composition 1 was applied to the film using an applicator (coating gap: 254 ⁇ m (10 mil)). Furthermore, the sheet-like structure 1 was produced by heating and drying at 120 ° C. for 10 minutes. All steps from the preparation of the composition 1 to the application were performed in an air atmosphere at atmospheric pressure and 23 ° C. Thereafter, the sheet-shaped structure 1 was produced by heating and drying at 120 ° C. for 10 minutes.
- Examples 2 to 5 Composition containing particles having an outer shell containing CNF in the same procedure as in Example 1, except that the total amount of n-dodecane was changed to 500 parts by mass, 1000 parts by mass, 2000 parts by mass, and 3000 parts by mass, respectively. Products 2 to 5 were prepared. Then, sheet-like structures 2 to 5 were produced in the same procedure as in Example 1 except that compositions 2 to 5 were used instead of composition 1.
- Example 6 Composition 1 was applied to the easy-adhesion layer surface of the polyethylene terephthalate film in the same procedure as in Example 1 except that the coating gap of the applicator was changed to 762 ⁇ m (30 mil). Further, a sheet-like structure 6 was produced in the same procedure as in Example 5, except that the drying time was changed to 20 minutes.
- Example 7 to 9 An outer shell containing CNF in the same procedure as in Example 1 except that 100 parts by mass of methyl ethyl ketone (MEK), 100 parts by mass of heptane, and 100 parts by mass of n-hexadecane were used instead of 100 parts by mass of n-dodecane, respectively.
- Compositions 7 to 9 containing particles comprising were prepared. Then, sheet-like structures 7 to 9 were produced in the same procedure as in Example 1 except that compositions 7 to 9 were used instead of composition 1, respectively.
- MEK methyl ethyl ketone
- heptane 100 parts by mass of heptane
- n-hexadecane 100 parts by mass of n-hexadecane
- Example 10 Composition 10 containing particles having an outer shell containing CNF was prepared in the same manner as in Example 1, except that the total amount of n-dodecane was changed to 10 parts by mass. Then, a sheet-like structure 10 was produced in the same procedure as in Example 1, except that the composition 10 was used instead of the composition 1.
- Example 11 Preparation of Composition 11
- aqueous dispersion (2) containing CNF was used.
- -Aqueous dispersion (2) Product name "TEMPO oxidized CNF", manufactured by Nippon Paper Industries.
- 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.
- aqueous dispersion (2) 100.0 parts by mass of CNF
- CNF aqueous dispersion
- an ultra-high-speed multi-stirring system manufactured by Primix Co., product name "Lab-Ruution (registered trademark)"
- stirring blade Using a homodisper (manufactured by the company, blade diameter: 35 mm), the aqueous dispersion at 23 ° C. was stirred at a rotation speed of 3000 rpm. After the start of stirring, n-dodecane was added at a rate of 5 parts by mass every 10 seconds.
- composition 11 was prepared comprising particles with an outer shell comprising CNF.
- composition 11 is gently placed on a 50 ⁇ m-thick polyethylene terephthalate film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 ⁇ m) on an easily adhesive layer surface. Then, the composition 10 was applied to the above film using an applicator (coating gap: 254 ⁇ m (10 mil)), and further heated at 120 ° C. for 10 minutes and dried to produce a sheet-like structure 11. All steps from the preparation of the composition 11 to the application were performed in an air atmosphere at atmospheric pressure and 23 ° C. Then, the sheet-like structure 11 was produced by heating and drying at 120 ° C. for 10 minutes.
- Example 12 Composition 12 containing particles having an outer shell containing CNF was prepared in the same manner as in Example 11, except that the total amount of n-dodecane was changed to 3000 parts by mass. Then, a sheet-like structure 12 was produced in the same procedure as in Example 11, except that the composition 12 was used instead of the composition 11.
- Example 13 Composition 13 containing particles having an outer shell containing CNF was prepared in the same procedure as in Example 11, except that 200 parts by mass of n-hexadecane was used instead of 100 parts by mass of n-dodecane. Then, a sheet-like structure 13 was produced in the same procedure as in Example 11, except that the composition 13 was used instead of the composition 11.
- Composition C1 was prepared in the same manner as in Example 1, except that 100 parts by mass of n-dodecane was not added. The stirring time was set to 10 minutes as in Example 1. Then, a sheet-like structure C1 was produced in the same procedure as in Example 1 except that the composition C1 was used instead of the composition 1.
- compositions prepared in Examples and Comparative Examples were prepared in the same manner as in Example 1, except that 100 parts by mass of hexane, 100 parts by mass of dimethylsulfoxide (DMSO), 100 parts by mass of aniline, and 100 parts by mass of ethanol were used instead of 100 parts by mass of n-dodecane.
- Products C2-C5 were prepared.
- sheet-like structures C2 to C5 were produced in the same procedure as in Example 1 except that compositions C2 to C5 were used instead of composition 1, respectively.
- Table 2 summarizes each component and the like of the compositions prepared in Examples and Comparative Examples.
- compositions 1 to 13 and C1 to C5 and the sheet-like structures 1 to 13 and C1 to C5 were measured and evaluated according to the following procedures.
- Table 3 shows the results.
- FIG. 3 shows an example of an SEM image of a cross section of the sheet-like structure 6 in the thickness direction.
- ⁇ Maximum Feret diameter of closed space of structure and its average> By observing the cut surface of each sheet-like structure by SEM, arbitrarily selecting 36 closed spaces from the obtained SEM image, measuring each maximum Feret diameter, and calculating an average value thereof, The average of the maximum Feret diameter was used. ⁇ B / a> The cut surface of each sheet-like structure was observed by SEM, and 36 closed spaces were arbitrarily selected from the obtained SEM images. For each of them, the maximum length a in the thickness direction of the structure, The value of b / a was determined by measuring the maximum length b in the plane direction, and the average value was calculated to obtain the value of b / a.
- ⁇ Structure thickness and bulk density> The mass and thickness of the sheet-like structure with the support were measured by the following procedure. Using these, the bulk density of the sheet-like structure without a support was calculated. Mass: After cutting the sheet-like structure with the support into a size of 100 mm x 100 mm, the mass is measured, and the mass of the sheet-like structure without the support is reduced by reducing the known mass of the support. Calculated. Thickness: The thickness of the sheet-like structure without the support is measured by measuring the thickness of the entire sheet-like structure including the support using a constant-pressure film thickness meter, and reducing the known thickness of the base material. (Corresponding to the symbol L in FIG. 1A).
- FIG. 3 is an SEM image of a cross section in the thickness direction of the sheet-like structure 1 manufactured in Example 6. It is confirmed that all of the sheet-like structures 1 to 13 have a structure in which a pair of adjacent closed spaces share a membrane containing CNF, similarly to the closed space shown in the SEM image of FIG. did.
- the average of the maximum Feret diameter of the closed space was in the range of 1 to 60 ⁇ m, and a small-diameter closed space could be formed. Since the sheet-like structures 1 to 13 do not contain a surfactant, even when a fluid is held in the closed space, the fluid may be mixed with surface activity or the surfactant may be released to the outside together with the fluid. There is no fear. Further, there is no fear that the physical properties of the structure are destabilized by the presence of the surfactant.
- the thickness of the capsule outer shell varies, so that the size of the space in the particle also changes greatly, and in the finally obtained structure, the average of the maximum Feret diameter of the closed space, the film thickness of the film containing CNF, It is assumed that the thickness and the value of b / a are affected. This suggests that, since the capsule has a relatively small diameter, by adjusting the thickness of the outer shell of the capsule, there is a possibility that the porosity of the structure can be controlled to some extent. Further, as is clear from Example 1 and Examples 7 to 9, it is possible to change the size of the particles having the outer shell containing CNF contained in the composition by changing the type of the organic solvent. I understand.
- the sheet-like structure obtained by the manufacturing method of the present invention includes a plurality of closed spaces formed of a membrane containing CNF, has a large ratio of the space existing in the structure, and has a fluid holding inside the structure.
- a structure in which unnecessary components are hardly mixed can be obtained. Therefore, for example, the fluid is held inside the closed space, and when necessary, pressure is applied to cleave a part of the structure to supply the fluid to the outside, or to hold the fluid inside the closed space. It can be used as a sustained release structure that can release a fluid gradually.
- the structure can be used as a heat insulating material, an adsorbing material, a sound absorbing material, an insulating material, a base material for a flexible printed wiring board, a packaging material, and the like. Furthermore, when the structure is strongly pressed with a finger, the closed space is compressed and destroyed, and a pressing mark including a fingerprint remains on the surface of the structure, so that the structure can be used as a trace recording material.
- composition 31 Layer having a plurality of closed spaces (sheet-like structure) 32: Particles 33, 33a, 33b having an outer shell containing CNF: Occluded space 34: Medium mainly composed of water 35: Membrane containing CNF 35a: Membrane 40 shared by a pair of adjacent enclosed spaces 40: Support 40a: coating surface 50: sheet-like structure with a support a: maximum length of the closed space structure in the thickness direction b: maximum length of the closed space structure in the plane direction df: maximum ferrite of the closed space Diameter dm: thickness of membrane containing CNF L: thickness of layer having a plurality of closed spaces
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Abstract
A structural object which comprises cellulose-nanofiber-containing membranes and has a plurality of closed spaces formed by the membranes, the spaces being present in a high proportion. Any unnecessary ingredient is less apt to come into a fluid to be held inside the structural object. The structural object, which comprises cellulose-nanofiber-containing membranes and has a plurality of closed spaces formed by the membranes, has a surfactant content less than 10 parts by mass per 100 parts by mass of the cellulose nanofibers.
Description
本発明は、セルロースナノファイバーを含む構造体に関する。
The present invention relates to a structure including cellulose nanofiber.
セルロースナノファイバー(CNF)を様々な用途に用いることが試みられており、その一つとして、CNFからなる多孔質体が提案されている(例えば、特許文献1参照)。CNFの多孔質体の製造方法としては、CNFを均一に分散させた水スラリーを、低温で凍結乾燥する工程を含む方法が広く知られている。凍結乾燥によって得られる多孔質体は、いわゆる連続気泡構造を有しており、吸着剤、断熱材、吸音材等の用途が想定されている。
(4) Attempts have been made to use cellulose nanofibers (CNF) for various applications, and as one of them, a porous body made of CNF has been proposed (for example, see Patent Document 1). As a method for producing a CNF porous body, a method including a step of freeze-drying a water slurry in which CNF is uniformly dispersed at a low temperature is widely known. A porous body obtained by freeze-drying has a so-called open cell structure, and is expected to be used as an adsorbent, a heat insulating material, a sound absorbing material, and the like.
CNFの利用を促進し、その用途をさらに拡大するためには、従来の製造方法では得られなかった新たな構造を有する、CNFを含む構造体が求められている。例えば、構造体の内部に流体を保持させておき、必要になった場合に構造体の外側に流体を取り出す用途に適する構造体が求められている。このような用途に適する構造体には、構造体の内部にできるだけ多くの流体を保持できること、及び、内部に保持される流体に不要な成分が混入しないことが求められる。
In order to promote the use of CNF and further expand its use, there is a demand for a CNF-containing structure having a new structure that cannot be obtained by a conventional manufacturing method. For example, there is a demand for a structure suitable for use in which a fluid is held inside the structure and fluid is taken out of the structure when needed. A structure suitable for such an application is required to be able to hold as much fluid as possible inside the structure and not to mix unnecessary components into the fluid held inside.
本発明は、セルロースナノファイバーを含む膜とこの膜で構成された複数の閉塞空間とを備え、空間の存在割合が大きく、かつ、内部に保持される流体に不要な成分が混入しにくい構造体を提供することを課題とする。
The present invention provides a structure including a film containing cellulose nanofibers and a plurality of closed spaces formed by the film, in which a large proportion of the space exists, and in which unnecessary components are hardly mixed into a fluid held therein. The task is to provide
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、セルロースナノファイバーを含む膜から構成された複数の閉塞空間を備え、界面活性剤の含有量が所定値以下である構造体とすることで上記課題が解決できることを見出し、本発明を完成した。
すなわち、本発明は、以下の[1]~[12]を提供するものである。
[1]セルロースナノファイバーを含む膜と、該膜から構成された複数の閉塞空間とを備える構造体であって、界面活性剤の含有量が、前記セルロースナノファイバー100質量部に対して10質量部未満である、構造体。
[2]前記複数の閉塞空間のうち隣接する一組の閉塞空間は少なくとも一つの前記膜を共有している上記[1]に記載の構造体。
[3]前記セルロースナノファイバーを含む膜の平均厚さが、10nm~2000nmである上記[1]又は[2]に記載の構造体。
[4]前記構造体の嵩密度が、0.001~1.4g/cm3である上記[1]~[3]のいずれか一つに記載の構造体。
[5]前記構造体はシート形状を有する、上記[1]~[4]のいずれか一つに記載の構造体。
[6]前記構造体の厚さが0.5~300μmである上記[5]に記載の構造体。
[7]前記構造体の厚さ方向の断面において、前記閉塞空間の前記構造体の厚さ方向の最大長さをa、前記閉塞空間の前記構造体の平面方向の最大長さをbとするとき、前記複数の閉塞空間のb/aの平均が1より大きい、上記[5]又は[6]に記載の構造体。
[8]前記セルロースナノファイバーが植物由来のセルロースナノファイバーである上記[1]~[7]のいずれか一つに記載の構造体。
[9]前記セルロースナノファイバー以外の多糖類の含有量が、前記セルロースナノファイバーの100質量部に対して10質量部未満である、上記[1]~[8]のいずれか一つに記載の構造体。
[10]前記セルロースナノファイバーの直径(太さ)の平均が、1~1000nmである、上記[1]~[9]のいずれか一つに記載の構造体。
[11]前記セルロースナノファイバーの繊維長の平均が、0.01~10μmである、上記[1]~[10]のいずれか一つに記載の構造体。
[12]上記[1]~[11]のいずれか一つに記載の構造体が、支持体上に設けられている、支持体付き構造体。 The present inventors have conducted intensive studies in order to solve the above problems, and as a result, a structure including a plurality of closed spaces constituted by a membrane containing cellulose nanofibers, and having a surfactant content of a predetermined value or less. As a result, the present inventors have found that the above problem can be solved and completed the present invention.
That is, the present invention provides the following [1] to [12].
[1] A structure comprising a membrane containing cellulose nanofibers and a plurality of closed spaces constituted by the membrane, wherein the content of the surfactant is 10 parts by mass relative to 100 parts by mass of the cellulose nanofibers. The structure is less than one part.
[2] The structure according to [1], wherein a set of adjacent closed spaces among the plurality of closed spaces shares at least one of the membranes.
[3] The structure according to the above [1] or [2], wherein the average thickness of the film containing the cellulose nanofiber is 10 nm to 2000 nm.
[4] The structure according to any one of the above [1] to [3], wherein the bulk density of the structure is 0.001 to 1.4 g / cm 3 .
[5] The structure according to any one of [1] to [4], wherein the structure has a sheet shape.
[6] The structure according to the above [5], wherein the thickness of the structure is 0.5 to 300 μm.
[7] In the cross section in the thickness direction of the structure, the maximum length of the closed space in the thickness direction of the structure is a, and the maximum length of the closed space in the plane direction of the structure is b. The structure according to [5] or [6], wherein the average of b / a of the plurality of closed spaces is larger than 1.
[8] The structure according to any one of [1] to [7], wherein the cellulose nanofiber is a plant-derived cellulose nanofiber.
[9] The method according to any one of [1] to [8], wherein the content of the polysaccharide other than the cellulose nanofiber is less than 10 parts by mass with respect to 100 parts by mass of the cellulose nanofiber. Structure.
[10] The structure according to any one of [1] to [9], wherein the average of the diameter (thickness) of the cellulose nanofiber is 1 to 1000 nm.
[11] The structure according to any one of [1] to [10], wherein an average fiber length of the cellulose nanofiber is 0.01 to 10 μm.
[12] A structure with a support, wherein the structure according to any one of the above [1] to [11] is provided on a support.
すなわち、本発明は、以下の[1]~[12]を提供するものである。
[1]セルロースナノファイバーを含む膜と、該膜から構成された複数の閉塞空間とを備える構造体であって、界面活性剤の含有量が、前記セルロースナノファイバー100質量部に対して10質量部未満である、構造体。
[2]前記複数の閉塞空間のうち隣接する一組の閉塞空間は少なくとも一つの前記膜を共有している上記[1]に記載の構造体。
[3]前記セルロースナノファイバーを含む膜の平均厚さが、10nm~2000nmである上記[1]又は[2]に記載の構造体。
[4]前記構造体の嵩密度が、0.001~1.4g/cm3である上記[1]~[3]のいずれか一つに記載の構造体。
[5]前記構造体はシート形状を有する、上記[1]~[4]のいずれか一つに記載の構造体。
[6]前記構造体の厚さが0.5~300μmである上記[5]に記載の構造体。
[7]前記構造体の厚さ方向の断面において、前記閉塞空間の前記構造体の厚さ方向の最大長さをa、前記閉塞空間の前記構造体の平面方向の最大長さをbとするとき、前記複数の閉塞空間のb/aの平均が1より大きい、上記[5]又は[6]に記載の構造体。
[8]前記セルロースナノファイバーが植物由来のセルロースナノファイバーである上記[1]~[7]のいずれか一つに記載の構造体。
[9]前記セルロースナノファイバー以外の多糖類の含有量が、前記セルロースナノファイバーの100質量部に対して10質量部未満である、上記[1]~[8]のいずれか一つに記載の構造体。
[10]前記セルロースナノファイバーの直径(太さ)の平均が、1~1000nmである、上記[1]~[9]のいずれか一つに記載の構造体。
[11]前記セルロースナノファイバーの繊維長の平均が、0.01~10μmである、上記[1]~[10]のいずれか一つに記載の構造体。
[12]上記[1]~[11]のいずれか一つに記載の構造体が、支持体上に設けられている、支持体付き構造体。 The present inventors have conducted intensive studies in order to solve the above problems, and as a result, a structure including a plurality of closed spaces constituted by a membrane containing cellulose nanofibers, and having a surfactant content of a predetermined value or less. As a result, the present inventors have found that the above problem can be solved and completed the present invention.
That is, the present invention provides the following [1] to [12].
[1] A structure comprising a membrane containing cellulose nanofibers and a plurality of closed spaces constituted by the membrane, wherein the content of the surfactant is 10 parts by mass relative to 100 parts by mass of the cellulose nanofibers. The structure is less than one part.
[2] The structure according to [1], wherein a set of adjacent closed spaces among the plurality of closed spaces shares at least one of the membranes.
[3] The structure according to the above [1] or [2], wherein the average thickness of the film containing the cellulose nanofiber is 10 nm to 2000 nm.
[4] The structure according to any one of the above [1] to [3], wherein the bulk density of the structure is 0.001 to 1.4 g / cm 3 .
[5] The structure according to any one of [1] to [4], wherein the structure has a sheet shape.
[6] The structure according to the above [5], wherein the thickness of the structure is 0.5 to 300 μm.
[7] In the cross section in the thickness direction of the structure, the maximum length of the closed space in the thickness direction of the structure is a, and the maximum length of the closed space in the plane direction of the structure is b. The structure according to [5] or [6], wherein the average of b / a of the plurality of closed spaces is larger than 1.
[8] The structure according to any one of [1] to [7], wherein the cellulose nanofiber is a plant-derived cellulose nanofiber.
[9] The method according to any one of [1] to [8], wherein the content of the polysaccharide other than the cellulose nanofiber is less than 10 parts by mass with respect to 100 parts by mass of the cellulose nanofiber. Structure.
[10] The structure according to any one of [1] to [9], wherein the average of the diameter (thickness) of the cellulose nanofiber is 1 to 1000 nm.
[11] The structure according to any one of [1] to [10], wherein an average fiber length of the cellulose nanofiber is 0.01 to 10 μm.
[12] A structure with a support, wherein the structure according to any one of the above [1] to [11] is provided on a support.
本発明によれば、セルロースナノファイバーを含む膜とこの膜で構成された複数の閉塞空間とを備え、空間の存在割合が大きく、かつ、内部に保持される流体に不要な成分が混入しにくい構造体を提供することができる。
According to the present invention, it is provided with a membrane containing cellulose nanofibers and a plurality of closed spaces composed of the membrane, the existence ratio of the space is large, and it is difficult for unnecessary components to be mixed into the fluid held therein. A structure can be provided.
<構造体の構成>
本発明の実施形態に係る構造体は、セルロースナノファイバー(CNF)を含む膜と、該膜から構成された複数の閉塞空間とを備える構造体であって、界面活性剤の含有量が、CNF100質量部に対して10質量部未満である。
本明細書において、「CNFを含む膜から構成された閉塞空間」とは、上方、下方、側方等の全方位がCNFを含む膜によって囲まれた、閉じた空間を意味する。なお、後述するように、CNFを含む膜は緻密な膜であるが微細な空隙を有している。したがって、CNFを含む膜によって囲まれた空間が、上記微細空隙を超える大きさの開口に通じていなければ、「CNFを含む膜から構成された閉塞空間」に該当する。 <Structure of structure>
The structure according to the embodiment of the present invention is a structure including a membrane including cellulose nanofibers (CNF) and a plurality of closed spaces constituted by the membrane, wherein the surfactant content is CNF100. Less than 10 parts by mass with respect to parts by mass.
As used herein, the term “occlusive space composed of a CNF-containing membrane” means a closed space in which the upper, lower, lateral, and other directions are all surrounded by the CNF-containing membrane. As described later, the film containing CNF is a dense film but has fine voids. Therefore, if the space surrounded by the film containing CNF does not lead to an opening having a size exceeding the above-mentioned minute gap, it corresponds to “an occluded space composed of a film containing CNF”.
本発明の実施形態に係る構造体は、セルロースナノファイバー(CNF)を含む膜と、該膜から構成された複数の閉塞空間とを備える構造体であって、界面活性剤の含有量が、CNF100質量部に対して10質量部未満である。
本明細書において、「CNFを含む膜から構成された閉塞空間」とは、上方、下方、側方等の全方位がCNFを含む膜によって囲まれた、閉じた空間を意味する。なお、後述するように、CNFを含む膜は緻密な膜であるが微細な空隙を有している。したがって、CNFを含む膜によって囲まれた空間が、上記微細空隙を超える大きさの開口に通じていなければ、「CNFを含む膜から構成された閉塞空間」に該当する。 <Structure of structure>
The structure according to the embodiment of the present invention is a structure including a membrane including cellulose nanofibers (CNF) and a plurality of closed spaces constituted by the membrane, wherein the surfactant content is CNF100. Less than 10 parts by mass with respect to parts by mass.
As used herein, the term “occlusive space composed of a CNF-containing membrane” means a closed space in which the upper, lower, lateral, and other directions are all surrounded by the CNF-containing membrane. As described later, the film containing CNF is a dense film but has fine voids. Therefore, if the space surrounded by the film containing CNF does not lead to an opening having a size exceeding the above-mentioned minute gap, it corresponds to “an occluded space composed of a film containing CNF”.
上記構造体の形状は特に制限がなく、例えば、成形型に後述する組成物を入れて乾燥させる等の方法により、任意の形状とすることができる。本発明の構造体の好ましい一態様は、シート状構造体である。シート状構造体は、後述する組成物を、支持体に塗布して乾燥することにより容易に大量に製造でき、しかも幅広い用途に利用することができる。以下、シート状構造体を例にして、図を用いて具体的に本発明の実施形態に係る構造体を説明する。なお、以下の説明で用いる図1及び図2は模式図であり、理解を容易にするため誇張して図示されている。閉塞空間の数や大きさ、構造体の厚み等も模式的に示されており、これらは図面によって限定されるものではない。
The shape of the structure is not particularly limited. For example, the structure can be formed into an arbitrary shape by, for example, putting a composition described below in a mold and drying the composition. One preferred embodiment of the structure of the present invention is a sheet-like structure. The sheet-like structure can be easily mass-produced by applying the composition described below to a support and drying it, and can be used for a wide range of applications. Hereinafter, a structure according to an embodiment of the present invention will be specifically described with reference to the drawings using a sheet-like structure as an example. 1 and 2 used in the following description are schematic views, and are exaggerated for easy understanding. The number and size of the closed space, the thickness of the structure, and the like are also schematically shown, and these are not limited by the drawings.
図1(A)は、本発明の構造体の一実施態様であるシート状構造体の厚さ方向の模式的な部分断面図である。図1(A)に示すように、支持体40上に設けられた、CNFを含む膜35で構成される複数の閉塞空間33を有する層31がシート状構造体を構成する。そして、シート状構造体である層31と支持体40とで支持体付きのシート状構造体50が構成されている。なお、後述するように、支持体40はなくても構わない。支持体40がない場合は、単体のシート状構造体31となる。
後述する製造方法によって形成されるCNFを含む膜35は、複数のCNFが並んだり絡み合ったりすることで形成される網目状もしくは繊維状の緻密な膜であると考えられる。したがって、例えば、シート状構造体31や支持体付きのシート状構造体50を、CNFを含む膜35で囲まれた閉塞空間33内に流体を保持する製品に適用することができる。このような製品(以下、「流体保持用製品」ということがある)は、必要な場合に圧力を加えて構造体を開裂して流体を外部へ供給することができる。
また、CNFを含む膜35は、CNFの緻密な膜であるため、膜を厚くしなくても一定の強度を有しており、流体を内部に保持することができる閉塞空間を構成することができる。したがって、構造体内部に、例えばバインダー成分等の、CNFを含む膜以外の要素が必ずしも必要ではなくなり、構造体における空間の存在割合を高くすることができる。
さらに、CNFを含む膜は多数の微小な空隙を有しており、気体や液体などの流体を少しずつ透過させ得る。したがって、例えば、シート状構造体31や支持体付きのシート状構造体50は、閉塞空間33内に流体を保持させておき、CNFを含む膜35を通して外部に流体を徐々に放出する製品にも適用することができる。以下、膜を介して外部に流体を徐々に放出する性質を徐放性という。
なお、従来の凍結乾燥を用いた製造方法は工程が複雑であることに加えて、得られる多孔質体がいわゆる連続気泡構造を有している。このような連続気泡構造を有する多孔質体は、流体を保持するのに適しておらず、上記の流体保持用製品や徐放性を有する製品への適用が難しい。 FIG. 1A is a schematic partial cross-sectional view in the thickness direction of a sheet-like structure which is an embodiment of the structure of the present invention. As shown in FIG. 1A, alayer 31 provided on a support 40 and having a plurality of closed spaces 33 formed of a film 35 containing CNF forms a sheet-like structure. Then, the sheet-like structure 50 with the support is constituted by the layer 31 which is the sheet-like structure and the support 40. In addition, as described later, the support 40 may be omitted. If the support 40 is not provided, the single sheet-shaped structure 31 is formed.
Thefilm 35 containing CNF formed by a manufacturing method described later is considered to be a mesh-like or fibrous dense film formed by arranging or tangling a plurality of CNFs. Therefore, for example, the sheet-like structure 31 or the sheet-like structure 50 with a support can be applied to a product that holds a fluid in the closed space 33 surrounded by the membrane 35 containing CNF. Such a product (hereinafter, sometimes referred to as a “fluid holding product”) can apply pressure to cleave the structure and supply the fluid to the outside when necessary.
Further, since thefilm 35 containing CNF is a dense film of CNF, the film 35 has a certain strength without making the film thicker, and can form an occluded space capable of holding a fluid inside. it can. Therefore, elements other than the CNF-containing film, such as a binder component, are not necessarily required inside the structure, and the proportion of spaces in the structure can be increased.
Further, a film containing CNF has a large number of minute voids, and can gradually transmit a fluid such as a gas or a liquid. Therefore, for example, the sheet-like structure 31 or the sheet-like structure 50 with a support can be used for a product in which a fluid is held in the closed space 33 and the fluid is gradually released to the outside through the membrane 35 containing CNF. Can be applied. Hereinafter, the property of gradually releasing the fluid to the outside through the membrane is referred to as sustained release.
In addition, in the conventional manufacturing method using freeze-drying, in addition to the complicated process, the obtained porous body has a so-called open cell structure. A porous body having such an open-cell structure is not suitable for holding a fluid, and is difficult to apply to the above-mentioned product for holding a fluid or a product having a sustained release property.
後述する製造方法によって形成されるCNFを含む膜35は、複数のCNFが並んだり絡み合ったりすることで形成される網目状もしくは繊維状の緻密な膜であると考えられる。したがって、例えば、シート状構造体31や支持体付きのシート状構造体50を、CNFを含む膜35で囲まれた閉塞空間33内に流体を保持する製品に適用することができる。このような製品(以下、「流体保持用製品」ということがある)は、必要な場合に圧力を加えて構造体を開裂して流体を外部へ供給することができる。
また、CNFを含む膜35は、CNFの緻密な膜であるため、膜を厚くしなくても一定の強度を有しており、流体を内部に保持することができる閉塞空間を構成することができる。したがって、構造体内部に、例えばバインダー成分等の、CNFを含む膜以外の要素が必ずしも必要ではなくなり、構造体における空間の存在割合を高くすることができる。
さらに、CNFを含む膜は多数の微小な空隙を有しており、気体や液体などの流体を少しずつ透過させ得る。したがって、例えば、シート状構造体31や支持体付きのシート状構造体50は、閉塞空間33内に流体を保持させておき、CNFを含む膜35を通して外部に流体を徐々に放出する製品にも適用することができる。以下、膜を介して外部に流体を徐々に放出する性質を徐放性という。
なお、従来の凍結乾燥を用いた製造方法は工程が複雑であることに加えて、得られる多孔質体がいわゆる連続気泡構造を有している。このような連続気泡構造を有する多孔質体は、流体を保持するのに適しておらず、上記の流体保持用製品や徐放性を有する製品への適用が難しい。 FIG. 1A is a schematic partial cross-sectional view in the thickness direction of a sheet-like structure which is an embodiment of the structure of the present invention. As shown in FIG. 1A, a
The
Further, since the
Further, a film containing CNF has a large number of minute voids, and can gradually transmit a fluid such as a gas or a liquid. Therefore, for example, the sheet-
In addition, in the conventional manufacturing method using freeze-drying, in addition to the complicated process, the obtained porous body has a so-called open cell structure. A porous body having such an open-cell structure is not suitable for holding a fluid, and is difficult to apply to the above-mentioned product for holding a fluid or a product having a sustained release property.
上記構造体は、界面活性剤を含まないか又は界面活性剤の含有量が少ないため、閉塞空間内に流体を保持させた場合に、界面活性剤が流体に溶出したり、流体を構造体の外部へ取り出す際に界面活性剤が流体とともに放出されたりすることを防止できる。また、界面活性剤が存在することによって、構造体の物性が不安定化し、例えば、構造体が変質したり、構造体の強度が低下したりすることを防ぎやすくなる。したがって、本発明の実施形態に係る構造体は、上述したような、流体保持用製品や徐放性を有する製品に適している。なお、界面活性剤を含有しないか界面活性剤の含有量が少ない、CNFを含む膜から構成された複数の閉塞空間を有する上記構造体を製造する方法については後述する。
Since the structure does not contain a surfactant or has a low content of the surfactant, when the fluid is retained in the closed space, the surfactant is eluted into the fluid or the fluid is removed from the structure. It is possible to prevent the surfactant from being released together with the fluid when taken out. In addition, the presence of the surfactant destabilizes the physical properties of the structure, and for example, it is easy to prevent the structure from being deteriorated or the strength of the structure from being reduced. Therefore, the structure according to the embodiment of the present invention is suitable for a product for retaining a fluid or a product having a sustained release property as described above. A method for producing the above-mentioned structure having a plurality of closed spaces formed of a film containing CNF that does not contain a surfactant or has a low surfactant content will be described later.
界面活性剤の含有量の上限は、CNF100質量部に対して、10質量部未満であり、好ましくは1質量部未満、より好ましくは0.1質量部未満、さらに好ましくは0.01質量部未満、特に好ましくは0.001質量部未満、最も好ましくは0質量部である。構造体における界面活性剤の含有量の測定方法としては、界面活性剤を溶媒により抽出し、高速液体クロマトグラフ質量分析計(LC-MS)や核磁気共鳴装置(NMR)等で化学組成の同定と定量を行う方法が挙げられる。また、同定の手段として、エネルギー分散型X線分析(EDX)や赤外分光法(IR)を用いることもできる。EDXの場合は、直接組成物を観測し、分析を行っても良い。
The upper limit of the content of the surfactant is less than 10 parts by mass, preferably less than 1 part by mass, more preferably less than 0.1 part by mass, and still more preferably less than 0.01 part by mass with respect to 100 parts by mass of CNF. Particularly preferably, it is less than 0.001 part by mass, and most preferably 0 part by mass. As a method of measuring the content of the surfactant in the structure, the surfactant is extracted with a solvent, and the chemical composition is identified by a high-performance liquid chromatograph mass spectrometer (LC-MS), a nuclear magnetic resonance apparatus (NMR), or the like. And a method of performing quantification. Further, as a means for identification, energy dispersive X-ray analysis (EDX) or infrared spectroscopy (IR) can be used. In the case of EDX, the composition may be directly observed and analyzed.
また、上記構造体において、CNF以外の多糖類を含有してもよいが、上述した流体保持用製品や徐放性を有する製品において、外部へ放出される流体に不要な成分が混入するのを防止する観点から、その含有量は、CNFの全量100質量部に対して、好ましくは10質量部未満、より好ましくは1質量部未満、さらに好ましくは0.1質量部未満、よりさらに好ましくは0.01質量部未満、特に好ましくは0質量部である。多糖類も界面活性剤と同様の手順で同定及び定量することができる。
The structure may contain a polysaccharide other than CNF. However, in the above-mentioned fluid retaining product and the product having a sustained release property, unnecessary components are not mixed into the fluid discharged to the outside. From the viewpoint of prevention, the content is preferably less than 10 parts by mass, more preferably less than 1 part by mass, still more preferably less than 0.1 part by mass, even more preferably 0 part by mass relative to 100 parts by mass of the total amount of CNF. It is less than 0.01 parts by mass, particularly preferably 0 parts by mass. Polysaccharides can be identified and quantified by the same procedure as for surfactants.
図1(B)は、図1(A)の一点鎖線で囲まれた部分の拡大図である。図1(B)に示すように、シート状構造体31や支持体付きのシート状構造体50においては、隣り合う一対の閉塞空間33a、33bの間で、CNFを含む膜35aが共有されている。本発明の構造体の好ましい一態様においては、シート状構造体31や支持体付きのシート状構造体50のように、複数の閉塞空間のうち隣り合う一組の閉塞空間が少なくとも一つの膜を共有する。
なお、CNFを含む膜の断面において、CNFを含む膜に沿うように形成された境界が観察されることがある。本実施形態のシート状構造体は、CNFを含む膜がこのような境界を含むものであっても構わない。上記境界は、シート状構造体になる前のCNFの存在状態の違いが反映されたものと推測されるが、この境界の有無はシート状構造体の特性に特に影響を与えない。 FIG. 1B is an enlarged view of a portion surrounded by a dashed line in FIG. As shown in FIG. 1B, in the sheet-like structure 31 and the sheet-like structure 50 with a support, a film 35a containing CNF is shared between a pair of adjacent closed spaces 33a and 33b. I have. In a preferred embodiment of the structure of the present invention, a set of adjacent closed spaces among a plurality of closed spaces forms at least one film, such as the sheet-like structure 31 or the sheet-like structure 50 with a support. Share.
Note that in a cross section of the film containing CNF, a boundary formed along the film containing CNF may be observed. In the sheet-like structure of the present embodiment, the film containing CNF may include such a boundary. The boundary is presumed to reflect the difference in the existing state of CNF before forming the sheet-like structure, but the presence or absence of this boundary does not particularly affect the characteristics of the sheet-like structure.
なお、CNFを含む膜の断面において、CNFを含む膜に沿うように形成された境界が観察されることがある。本実施形態のシート状構造体は、CNFを含む膜がこのような境界を含むものであっても構わない。上記境界は、シート状構造体になる前のCNFの存在状態の違いが反映されたものと推測されるが、この境界の有無はシート状構造体の特性に特に影響を与えない。 FIG. 1B is an enlarged view of a portion surrounded by a dashed line in FIG. As shown in FIG. 1B, in the sheet-
Note that in a cross section of the film containing CNF, a boundary formed along the film containing CNF may be observed. In the sheet-like structure of the present embodiment, the film containing CNF may include such a boundary. The boundary is presumed to reflect the difference in the existing state of CNF before forming the sheet-like structure, but the presence or absence of this boundary does not particularly affect the characteristics of the sheet-like structure.
[閉塞空間の最大フェレ径]
上記閉塞空間は様々な形状をとり得るため、本明細書においては、閉塞空間の大きさを最大フェレ径で表す(閉塞空間の大きさにはCNFを含む膜の厚みは含まれない)。本発明の実施形態に係る構造体においては、上記複数の閉塞空間の最大フェレ径の平均が1μm~60μmであることが好ましい。複数の閉塞空間の最大フェレ径の平均の下限は、より好ましくは5μm以上、さらに好ましくは10μm以上、さらにより好ましくは15μm以上、特に好ましくは20μm以上である。複数の閉塞空間の最大フェレ径の平均の上限は、より好ましくは55μm以下、さらに好ましくは50μm以下、さらにより好ましくは45μm以下、特に好ましくは40μm以下、最も好ましくは35μm以下である。
ここで、ある図形の「最大フェレ径」とは、2本の平行線で挟まれた当該図形の最大距離を意味する。本明細書においては、CNFを含む膜から構成された複数の閉塞空間を備える構造体を切断したときの切断面において、閉塞空間に対応する図形を特定し、この図形について2本の平行線で挟まれた最大距離を測定することで閉塞空間の最大フェレ径を算出する。
閉塞空間の最大フェレ径を算出するための切断面は、最大フェレ径の平均を算出できるように、できるだけ多くの閉塞空間が含まれるように適宜選べばよく、例えば、シート状構造体31や支持体付きのシート状構造体50では、図1(A)に示すように、その厚さ方向の断面において、閉塞空間の最大フェレ径を算出する。より具体的な例を挙げると、図1(A)の破線で囲まれた領域に存在している、シート状構造体31や支持体付きのシート状構造体50の平面に対して傾いた方向に最大の開口幅を有する閉塞空間33の場合、図1(C)に示すように、閉塞空間33の最大フェレ径dfはその最大開口幅に一致する。
本明細書において、「複数の閉塞空間の最大フェレ径の平均」は、構造体の任意の切断面における、複数の閉塞空間の最大フェレ径の平均値である。本明細書においては、構造体の上記断面において、任意の36個の閉塞空間を選んで各々の最大フェレ径を測定し、それらの平均値を「複数の閉塞空間の最大フェレ径の平均」とする。 [Maximum Feret diameter of closed space]
Since the closed space can take various shapes, in this specification, the size of the closed space is represented by the maximum Feret's diameter (the size of the closed space does not include the thickness of the membrane containing CNF). In the structure according to the embodiment of the present invention, the average of the maximum Feret diameters of the plurality of closed spaces is preferably 1 μm to 60 μm. The lower limit of the average of the maximum Feret diameter of the plurality of closed spaces is more preferably 5 μm or more, further preferably 10 μm or more, still more preferably 15 μm or more, and particularly preferably 20 μm or more. The average upper limit of the maximum Feret diameter of the plurality of closed spaces is more preferably 55 μm or less, further preferably 50 μm or less, still more preferably 45 μm or less, particularly preferably 40 μm or less, and most preferably 35 μm or less.
Here, the “maximum Feret diameter” of a certain figure means the maximum distance of the figure between two parallel lines. In the present specification, a figure corresponding to an occluded space is specified on a cut surface when a structure including a plurality of occluded spaces constituted by a membrane containing CNF is cut, and this figure is represented by two parallel lines. The maximum Feret diameter of the closed space is calculated by measuring the maximum distance between the blocks.
The cut surface for calculating the maximum Feret diameter of the closed space may be appropriately selected so as to include as much closed space as possible so that the average of the maximum Feret diameter can be calculated. As shown in FIG. 1A, the maximum Feret diameter of the closed space is calculated in the cross section in the thickness direction of the body-shaped sheet-like structure 50. To give a more specific example, a direction inclined with respect to the plane of the sheet-like structure 31 or the sheet-like structure 50 with a support, which exists in a region surrounded by a broken line in FIG. In the case of the closed space 33 having the largest opening width, as shown in FIG. 1 (C), the maximum Feret diameter df of the closed space 33 matches the maximum opening width.
In the present specification, “the average of the maximum Feret diameters of the plurality of closed spaces” is an average value of the maximum Feret diameters of the plurality of closed spaces at an arbitrary cut surface of the structure. In the present specification, in the above-mentioned cross section of the structure, an arbitrary 36 closed spaces are selected, each maximum Feret diameter is measured, and the average value thereof is referred to as “the average of the maximum Feret diameters of a plurality of closed spaces”. I do.
上記閉塞空間は様々な形状をとり得るため、本明細書においては、閉塞空間の大きさを最大フェレ径で表す(閉塞空間の大きさにはCNFを含む膜の厚みは含まれない)。本発明の実施形態に係る構造体においては、上記複数の閉塞空間の最大フェレ径の平均が1μm~60μmであることが好ましい。複数の閉塞空間の最大フェレ径の平均の下限は、より好ましくは5μm以上、さらに好ましくは10μm以上、さらにより好ましくは15μm以上、特に好ましくは20μm以上である。複数の閉塞空間の最大フェレ径の平均の上限は、より好ましくは55μm以下、さらに好ましくは50μm以下、さらにより好ましくは45μm以下、特に好ましくは40μm以下、最も好ましくは35μm以下である。
ここで、ある図形の「最大フェレ径」とは、2本の平行線で挟まれた当該図形の最大距離を意味する。本明細書においては、CNFを含む膜から構成された複数の閉塞空間を備える構造体を切断したときの切断面において、閉塞空間に対応する図形を特定し、この図形について2本の平行線で挟まれた最大距離を測定することで閉塞空間の最大フェレ径を算出する。
閉塞空間の最大フェレ径を算出するための切断面は、最大フェレ径の平均を算出できるように、できるだけ多くの閉塞空間が含まれるように適宜選べばよく、例えば、シート状構造体31や支持体付きのシート状構造体50では、図1(A)に示すように、その厚さ方向の断面において、閉塞空間の最大フェレ径を算出する。より具体的な例を挙げると、図1(A)の破線で囲まれた領域に存在している、シート状構造体31や支持体付きのシート状構造体50の平面に対して傾いた方向に最大の開口幅を有する閉塞空間33の場合、図1(C)に示すように、閉塞空間33の最大フェレ径dfはその最大開口幅に一致する。
本明細書において、「複数の閉塞空間の最大フェレ径の平均」は、構造体の任意の切断面における、複数の閉塞空間の最大フェレ径の平均値である。本明細書においては、構造体の上記断面において、任意の36個の閉塞空間を選んで各々の最大フェレ径を測定し、それらの平均値を「複数の閉塞空間の最大フェレ径の平均」とする。 [Maximum Feret diameter of closed space]
Since the closed space can take various shapes, in this specification, the size of the closed space is represented by the maximum Feret's diameter (the size of the closed space does not include the thickness of the membrane containing CNF). In the structure according to the embodiment of the present invention, the average of the maximum Feret diameters of the plurality of closed spaces is preferably 1 μm to 60 μm. The lower limit of the average of the maximum Feret diameter of the plurality of closed spaces is more preferably 5 μm or more, further preferably 10 μm or more, still more preferably 15 μm or more, and particularly preferably 20 μm or more. The average upper limit of the maximum Feret diameter of the plurality of closed spaces is more preferably 55 μm or less, further preferably 50 μm or less, still more preferably 45 μm or less, particularly preferably 40 μm or less, and most preferably 35 μm or less.
Here, the “maximum Feret diameter” of a certain figure means the maximum distance of the figure between two parallel lines. In the present specification, a figure corresponding to an occluded space is specified on a cut surface when a structure including a plurality of occluded spaces constituted by a membrane containing CNF is cut, and this figure is represented by two parallel lines. The maximum Feret diameter of the closed space is calculated by measuring the maximum distance between the blocks.
The cut surface for calculating the maximum Feret diameter of the closed space may be appropriately selected so as to include as much closed space as possible so that the average of the maximum Feret diameter can be calculated. As shown in FIG. 1A, the maximum Feret diameter of the closed space is calculated in the cross section in the thickness direction of the body-shaped sheet-
In the present specification, “the average of the maximum Feret diameters of the plurality of closed spaces” is an average value of the maximum Feret diameters of the plurality of closed spaces at an arbitrary cut surface of the structure. In the present specification, in the above-mentioned cross section of the structure, an arbitrary 36 closed spaces are selected, each maximum Feret diameter is measured, and the average value thereof is referred to as “the average of the maximum Feret diameters of a plurality of closed spaces”. I do.
本発明の実施形態に係る構造体は、当該構造体の断面における複数の閉塞空間の最大フェレ径の平均が上述した範囲にあり、閉塞空間の大きさが小さい。このため、CNFを含む膜が構造体の内部に多数存在することとなり、構造体の強度を高められる。したがって、加圧等に対する形状維持性に優れた構造体を得やすくなる。また、構造体の強度が高くなる結果、構造体を上記の流体保持用製品や徐放性を有する製品に適用する場合などにおいて、閉塞空間内に流体を長く保持することに対しても有利に働く。さらに、閉塞空間の大きさが小さいため、多くの閉塞空間内において個別に流体を保持することができ、流体の保持性を高められるとともに、徐放性能を向上させる(より長い時間をかけて流体を放出させる)ことができる。
さらに、図1(A)、(B)に示すように、複数の閉塞空間が膜を共有することにより、構造体の強度が増すので、バインダー成分を添加することなく自己保持性を有する膜(自立膜)を作製することができる。この自立膜はバインダー成分が必ずしも必要ではなくなり、例えば、内部空間を有する複数のカプセルをバインダーで結合したものに比べると、流体を保持する空間を大きくすることができる。 In the structure according to the embodiment of the present invention, the average of the maximum Feret diameters of the plurality of closed spaces in the cross section of the structure is in the above-described range, and the size of the closed space is small. For this reason, many films containing CNF exist inside the structure, and the strength of the structure can be increased. Therefore, it becomes easy to obtain a structure excellent in shape maintenance property against pressure or the like. In addition, as a result of the strength of the structure being increased, in cases where the structure is applied to the above-described fluid holding product or a product having a sustained release property, it is advantageous for holding the fluid in the closed space for a long time. work. Further, since the size of the closed space is small, the fluid can be individually held in many closed spaces, and the retention of the fluid can be improved, and the sustained release performance can be improved. Is released).
Further, as shown in FIGS. 1A and 1B, the strength of the structure is increased by a plurality of closed spaces sharing the film, so that the film having self-holding properties without adding a binder component ( Self-standing film). This self-supporting film does not necessarily require a binder component, and for example, can increase the space for holding a fluid as compared with a case where a plurality of capsules having an internal space are connected with a binder.
さらに、図1(A)、(B)に示すように、複数の閉塞空間が膜を共有することにより、構造体の強度が増すので、バインダー成分を添加することなく自己保持性を有する膜(自立膜)を作製することができる。この自立膜はバインダー成分が必ずしも必要ではなくなり、例えば、内部空間を有する複数のカプセルをバインダーで結合したものに比べると、流体を保持する空間を大きくすることができる。 In the structure according to the embodiment of the present invention, the average of the maximum Feret diameters of the plurality of closed spaces in the cross section of the structure is in the above-described range, and the size of the closed space is small. For this reason, many films containing CNF exist inside the structure, and the strength of the structure can be increased. Therefore, it becomes easy to obtain a structure excellent in shape maintenance property against pressure or the like. In addition, as a result of the strength of the structure being increased, in cases where the structure is applied to the above-described fluid holding product or a product having a sustained release property, it is advantageous for holding the fluid in the closed space for a long time. work. Further, since the size of the closed space is small, the fluid can be individually held in many closed spaces, and the retention of the fluid can be improved, and the sustained release performance can be improved. Is released).
Further, as shown in FIGS. 1A and 1B, the strength of the structure is increased by a plurality of closed spaces sharing the film, so that the film having self-holding properties without adding a binder component ( Self-standing film). This self-supporting film does not necessarily require a binder component, and for example, can increase the space for holding a fluid as compared with a case where a plurality of capsules having an internal space are connected with a binder.
構造体における閉塞空間の大きさは、例えば、後述する組成物中の、CNFを含む外殻を備える粒子の大きさを変えることによって調整することができる。これによって、閉塞空間の最大フェレ径を調整し、複数の閉塞空間の最大フェレ径の平均を上述した数値範囲内にすることができる。
大 き The size of the closed space in the structure can be adjusted, for example, by changing the size of particles having an outer shell containing CNF in the composition described below. Thereby, the maximum Feret diameter of the closed space can be adjusted, and the average of the maximum Feret diameters of the plurality of closed spaces can be set within the above numerical range.
[閉塞空間の形状]
上記閉塞空間の形状は任意であるが、後述する製造方法を用いて構造体を製造すると、その製造方法に由来して、上述したように隣り合う一組の閉塞空間同士がCNFを含む膜を共有する構造をとりやすくなるため、各閉塞空間は、複数の平坦な膜で囲まれた多面体形状を有している。したがって、各閉塞空間に対して、図1に示すような多角形状を示すような切断面を少なくとも一つ形成することができる。
また、本発明の構造体の好ましい一態様においては、シート状構造体31や支持体付きのシート状構造体50のように、その厚さ方向の断面において、図1(C)に示すように、構造体の閉塞空間の厚さ方向の最大長さ(換言すれば、CNFを含む膜の上記閉塞空間側の面の最下方位置から最上方位置までの距離)をa、構造体の閉塞空間の平面方向の最大長さ(換言すれば、CNFを含む膜の上記閉塞空間側の面の、平面方向における一端から他端までの距離)をbとするとき、複数の閉塞空間のb/aの平均が好ましくは1より大きく、より好ましくは1.5より大きく、さらに好ましくは2より大きい。複数の閉塞空間のb/aの平均が1より大きいと、総じて閉塞空間が構造体の平面方向に延びた形状となるため、構造体を厚くすることなく、多数の閉塞空間を設けることができる。また、後述する工程(2-3)における乾燥時に、CNFを含む膜の自重によって平面方向に延びた閉塞空間が形成されやすくなるため、構造体の製造も容易である。複数の閉塞空間のb/aの平均は、製造容易性及び構造体の強度維持等の観点から、好ましくは10以下、より好ましくは8以下、さらに好ましくは6以下、特に好ましくは5以下である。本明細書においては、構造体の上記断面において、任意の36個の閉塞空間を選んで各々のa及びbを測定してb/aを算出し、それらの平均値を「複数の閉塞空間のb/aの平均」とする。 [Shape of closed space]
The shape of the closed space is arbitrary, but when the structure is manufactured using a manufacturing method described later, a pair of adjacent closed spaces form a film containing CNF as described above due to the manufacturing method. Each closed space has a polyhedral shape surrounded by a plurality of flat films so that a shared structure can be easily obtained. Therefore, at least one cut surface having a polygonal shape as shown in FIG. 1 can be formed in each closed space.
In a preferred embodiment of the structure of the present invention, as in the sheet-like structure 31 or the sheet-like structure 50 with a support, in a cross section in the thickness direction, as shown in FIG. The maximum length in the thickness direction of the closed space of the structure (in other words, the distance from the lowest position to the highest position of the surface of the membrane including CNF on the closed space side) is a, and the closed space of the structure is Is the maximum length in the plane direction (in other words, the distance from one end to the other end in the plane direction of the surface of the membrane including CNF on the side of the closed space), b / a of the plurality of closed spaces. Is preferably greater than 1, more preferably greater than 1.5, and even more preferably greater than 2. If the average of b / a of the plurality of closed spaces is greater than 1, the closed space generally has a shape extending in the planar direction of the structure, so that a large number of closed spaces can be provided without increasing the thickness of the structure. . Further, at the time of drying in the step (2-3) to be described later, a closed space extending in the planar direction is easily formed by the weight of the film containing CNF, so that the structure can be easily manufactured. The average of b / a of the plurality of closed spaces is preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of manufacturability and maintaining the strength of the structure. . In the present specification, in the above-mentioned cross section of the structure, arbitrary 36 closed spaces are selected, each of a and b is measured, b / a is calculated, and the average value thereof is referred to as “a plurality of closed spaces. b / a average ”.
上記閉塞空間の形状は任意であるが、後述する製造方法を用いて構造体を製造すると、その製造方法に由来して、上述したように隣り合う一組の閉塞空間同士がCNFを含む膜を共有する構造をとりやすくなるため、各閉塞空間は、複数の平坦な膜で囲まれた多面体形状を有している。したがって、各閉塞空間に対して、図1に示すような多角形状を示すような切断面を少なくとも一つ形成することができる。
また、本発明の構造体の好ましい一態様においては、シート状構造体31や支持体付きのシート状構造体50のように、その厚さ方向の断面において、図1(C)に示すように、構造体の閉塞空間の厚さ方向の最大長さ(換言すれば、CNFを含む膜の上記閉塞空間側の面の最下方位置から最上方位置までの距離)をa、構造体の閉塞空間の平面方向の最大長さ(換言すれば、CNFを含む膜の上記閉塞空間側の面の、平面方向における一端から他端までの距離)をbとするとき、複数の閉塞空間のb/aの平均が好ましくは1より大きく、より好ましくは1.5より大きく、さらに好ましくは2より大きい。複数の閉塞空間のb/aの平均が1より大きいと、総じて閉塞空間が構造体の平面方向に延びた形状となるため、構造体を厚くすることなく、多数の閉塞空間を設けることができる。また、後述する工程(2-3)における乾燥時に、CNFを含む膜の自重によって平面方向に延びた閉塞空間が形成されやすくなるため、構造体の製造も容易である。複数の閉塞空間のb/aの平均は、製造容易性及び構造体の強度維持等の観点から、好ましくは10以下、より好ましくは8以下、さらに好ましくは6以下、特に好ましくは5以下である。本明細書においては、構造体の上記断面において、任意の36個の閉塞空間を選んで各々のa及びbを測定してb/aを算出し、それらの平均値を「複数の閉塞空間のb/aの平均」とする。 [Shape of closed space]
The shape of the closed space is arbitrary, but when the structure is manufactured using a manufacturing method described later, a pair of adjacent closed spaces form a film containing CNF as described above due to the manufacturing method. Each closed space has a polyhedral shape surrounded by a plurality of flat films so that a shared structure can be easily obtained. Therefore, at least one cut surface having a polygonal shape as shown in FIG. 1 can be formed in each closed space.
In a preferred embodiment of the structure of the present invention, as in the sheet-
[CNFを含む膜の平均厚さ]
CNFを含む膜の平均厚さは、好ましくは10nm以上、より好ましくは50nm以上、さらに好ましくは75nm以上であり、また、好ましくは2000nm以下、より好ましくは1750nm以下、さらに好ましくは1500nm以下、よりさらに好ましくは1250nm以下である。CNFを含む膜の平均厚さを2000nm以下とすることで、構造体を流体保持用製品に適用したときに、圧力を加えて構造体を開裂し流体を外部へ供給しやすくなる。また、構造体を徐放性を有する製品に適用したときに、閉塞空間内の流体を徐放させやすくなる。また、膜の平均厚さを10nm以上とすることで、構造体全体の強度を高くすることができ、閉塞空間内に流体を長く保持させやすくなる。
CNFを含む膜の平均厚さは、走査型電子顕微鏡(SEM)を用いて各構造体の断面を観察し、得られた拡大画像から36個の閉塞空間を任意に選択し、選択された閉塞空間に対応する多角形を構成する任意の辺を一つ特定し、その辺の略中央の厚さdm(図1(C)に2つの三角マークと引き出し線で示す)を測定し、それらの平均値を算出することにより求められる。
CNFを含む膜の厚さdmは、例えば、CNFの直径(太さ)や繊維長を異ならせることで調整できる。CNFの直径(太さ)を大きくしたり、CNFの繊維長を短くしたりすることで、CNFを含む膜を厚くすることができる。逆に、CNFの直径(太さ)を小さくしたり、CNFの繊維長を長くしたりすることで、CNFを含む膜を薄くすることができる。 [Average thickness of film containing CNF]
The average thickness of the film containing CNF is preferably at least 10 nm, more preferably at least 50 nm, further preferably at least 75 nm, and preferably at most 2,000 nm, more preferably at most 1,750 nm, further preferably at most 1,500 nm, even more preferably Preferably it is 1250 nm or less. By setting the average thickness of the film containing CNF to 2000 nm or less, when the structure is applied to a fluid holding product, it is easy to apply pressure to break the structure and supply the fluid to the outside. Further, when the structure is applied to a product having a sustained release property, the fluid in the closed space is easily released. Further, by setting the average thickness of the film to 10 nm or more, the strength of the whole structure can be increased, and the fluid can be easily held in the closed space for a long time.
The average thickness of the film containing CNF can be determined by observing a cross section of each structure using a scanning electron microscope (SEM), arbitrarily selecting 36 occlusion spaces from the obtained enlarged image, and selecting the selected occlusion space. One arbitrary side constituting the polygon corresponding to the space is specified, and the thickness dm (indicated by two triangular marks and a leader line in FIG. 1C) at the approximate center of the side is measured, It is obtained by calculating an average value.
The thickness dm of the film containing CNF can be adjusted, for example, by changing the diameter (thickness) or fiber length of CNF. By increasing the diameter (thickness) of CNF or shortening the fiber length of CNF, the film containing CNF can be made thicker. Conversely, by decreasing the diameter (thickness) of CNF or increasing the fiber length of CNF, the film containing CNF can be made thinner.
CNFを含む膜の平均厚さは、好ましくは10nm以上、より好ましくは50nm以上、さらに好ましくは75nm以上であり、また、好ましくは2000nm以下、より好ましくは1750nm以下、さらに好ましくは1500nm以下、よりさらに好ましくは1250nm以下である。CNFを含む膜の平均厚さを2000nm以下とすることで、構造体を流体保持用製品に適用したときに、圧力を加えて構造体を開裂し流体を外部へ供給しやすくなる。また、構造体を徐放性を有する製品に適用したときに、閉塞空間内の流体を徐放させやすくなる。また、膜の平均厚さを10nm以上とすることで、構造体全体の強度を高くすることができ、閉塞空間内に流体を長く保持させやすくなる。
CNFを含む膜の平均厚さは、走査型電子顕微鏡(SEM)を用いて各構造体の断面を観察し、得られた拡大画像から36個の閉塞空間を任意に選択し、選択された閉塞空間に対応する多角形を構成する任意の辺を一つ特定し、その辺の略中央の厚さdm(図1(C)に2つの三角マークと引き出し線で示す)を測定し、それらの平均値を算出することにより求められる。
CNFを含む膜の厚さdmは、例えば、CNFの直径(太さ)や繊維長を異ならせることで調整できる。CNFの直径(太さ)を大きくしたり、CNFの繊維長を短くしたりすることで、CNFを含む膜を厚くすることができる。逆に、CNFの直径(太さ)を小さくしたり、CNFの繊維長を長くしたりすることで、CNFを含む膜を薄くすることができる。 [Average thickness of film containing CNF]
The average thickness of the film containing CNF is preferably at least 10 nm, more preferably at least 50 nm, further preferably at least 75 nm, and preferably at most 2,000 nm, more preferably at most 1,750 nm, further preferably at most 1,500 nm, even more preferably Preferably it is 1250 nm or less. By setting the average thickness of the film containing CNF to 2000 nm or less, when the structure is applied to a fluid holding product, it is easy to apply pressure to break the structure and supply the fluid to the outside. Further, when the structure is applied to a product having a sustained release property, the fluid in the closed space is easily released. Further, by setting the average thickness of the film to 10 nm or more, the strength of the whole structure can be increased, and the fluid can be easily held in the closed space for a long time.
The average thickness of the film containing CNF can be determined by observing a cross section of each structure using a scanning electron microscope (SEM), arbitrarily selecting 36 occlusion spaces from the obtained enlarged image, and selecting the selected occlusion space. One arbitrary side constituting the polygon corresponding to the space is specified, and the thickness dm (indicated by two triangular marks and a leader line in FIG. 1C) at the approximate center of the side is measured, It is obtained by calculating an average value.
The thickness dm of the film containing CNF can be adjusted, for example, by changing the diameter (thickness) or fiber length of CNF. By increasing the diameter (thickness) of CNF or shortening the fiber length of CNF, the film containing CNF can be made thicker. Conversely, by decreasing the diameter (thickness) of CNF or increasing the fiber length of CNF, the film containing CNF can be made thinner.
[構造体の嵩密度]
構造体の嵩密度は、好ましくは0.001g/cm3以上、より好ましくは0.005g/cm3以上、さらに好ましくは0.0075g/cm3以上、さらに好ましくは0.01g/cm3以上であり、また、好ましくは1.40g/cm3以下、より好ましくは1.20g/cm3以下、さらに好ましくは0.920g/cm3以下、さらに好ましくは0.800g/cm3以下、さらに好ましくは0.600g/cm3以下、さらに好ましくは0.500g/cm3以下である。嵩密度が0.001g/cm3以上であれば構造体に必要最低限の強度を与えることができ、例えば、ロール状に巻いてもつぶれない程度の強度を与えることができる。また、嵩密度が1.40g/cm3以下であれば、多くの流体を閉塞空間内に保持しやすくなる。
本明細書において、構造体の嵩密度は、構造体の質量を、閉塞空間を含む構造体全体の体積で除すことにより算出される。図1のように、支持体上にCNFを含む層が形成されている場合は、予め支持体の厚さと質量を測定しておき、これを減じてから算出すればよい。
構造体の嵩密度は、例えば、組成物におけるCNFを含む外殻を備える粒子の直径を変化させることで調整することができる。つまり、組成物におけるCNFを含む外殻を備える粒子の直径が大きくなると嵩密度は小さくなり、CNFを含む外殻を備える粒子の直径が小さくなると、嵩密度は大きくなる。組成物におけるCNFを含む外殻を備える粒子の直径は、有機溶剤の種類と配合比率を変えたり、撹拌条件を変えたりすることで調整することができる。 [Bulk density of structure]
The bulk density of the structure is preferably 0.001 g / cm 3 or more, more preferably 0.005 g / cm 3 or more, more preferably 0.0075 g / cm 3 or higher, more preferably at 0.01 g / cm 3 or more And preferably 1.40 g / cm 3 or less, more preferably 1.20 g / cm 3 or less, still more preferably 0.920 g / cm 3 or less, still more preferably 0.800 g / cm 3 or less, and even more preferably 0.600 g / cm 3 or less, more preferably 0.500 g / cm 3 or less. When the bulk density is 0.001 g / cm 3 or more, the structure can be provided with a minimum necessary strength, for example, a strength that is not crushed when wound in a roll. Further, when the bulk density is 1.40 g / cm 3 or less, it becomes easy to hold many fluids in the closed space.
In this specification, the bulk density of a structure is calculated by dividing the mass of the structure by the volume of the entire structure including the closed space. In the case where a layer containing CNF is formed on a support as shown in FIG. 1, the thickness and the mass of the support may be measured in advance, and the calculation may be performed after subtracting these values.
The bulk density of the structure can be adjusted, for example, by changing the diameter of a particle having a shell containing CNF in the composition. That is, the larger the diameter of the particles having the outer shell containing CNF in the composition, the lower the bulk density becomes, and the smaller the diameter of the particles having the outer shell containing CNF becomes, the higher the bulk density becomes. The diameter of the particles having an outer shell containing CNF in the composition can be adjusted by changing the type and blending ratio of the organic solvent or changing the stirring conditions.
構造体の嵩密度は、好ましくは0.001g/cm3以上、より好ましくは0.005g/cm3以上、さらに好ましくは0.0075g/cm3以上、さらに好ましくは0.01g/cm3以上であり、また、好ましくは1.40g/cm3以下、より好ましくは1.20g/cm3以下、さらに好ましくは0.920g/cm3以下、さらに好ましくは0.800g/cm3以下、さらに好ましくは0.600g/cm3以下、さらに好ましくは0.500g/cm3以下である。嵩密度が0.001g/cm3以上であれば構造体に必要最低限の強度を与えることができ、例えば、ロール状に巻いてもつぶれない程度の強度を与えることができる。また、嵩密度が1.40g/cm3以下であれば、多くの流体を閉塞空間内に保持しやすくなる。
本明細書において、構造体の嵩密度は、構造体の質量を、閉塞空間を含む構造体全体の体積で除すことにより算出される。図1のように、支持体上にCNFを含む層が形成されている場合は、予め支持体の厚さと質量を測定しておき、これを減じてから算出すればよい。
構造体の嵩密度は、例えば、組成物におけるCNFを含む外殻を備える粒子の直径を変化させることで調整することができる。つまり、組成物におけるCNFを含む外殻を備える粒子の直径が大きくなると嵩密度は小さくなり、CNFを含む外殻を備える粒子の直径が小さくなると、嵩密度は大きくなる。組成物におけるCNFを含む外殻を備える粒子の直径は、有機溶剤の種類と配合比率を変えたり、撹拌条件を変えたりすることで調整することができる。 [Bulk density of structure]
The bulk density of the structure is preferably 0.001 g / cm 3 or more, more preferably 0.005 g / cm 3 or more, more preferably 0.0075 g / cm 3 or higher, more preferably at 0.01 g / cm 3 or more And preferably 1.40 g / cm 3 or less, more preferably 1.20 g / cm 3 or less, still more preferably 0.920 g / cm 3 or less, still more preferably 0.800 g / cm 3 or less, and even more preferably 0.600 g / cm 3 or less, more preferably 0.500 g / cm 3 or less. When the bulk density is 0.001 g / cm 3 or more, the structure can be provided with a minimum necessary strength, for example, a strength that is not crushed when wound in a roll. Further, when the bulk density is 1.40 g / cm 3 or less, it becomes easy to hold many fluids in the closed space.
In this specification, the bulk density of a structure is calculated by dividing the mass of the structure by the volume of the entire structure including the closed space. In the case where a layer containing CNF is formed on a support as shown in FIG. 1, the thickness and the mass of the support may be measured in advance, and the calculation may be performed after subtracting these values.
The bulk density of the structure can be adjusted, for example, by changing the diameter of a particle having a shell containing CNF in the composition. That is, the larger the diameter of the particles having the outer shell containing CNF in the composition, the lower the bulk density becomes, and the smaller the diameter of the particles having the outer shell containing CNF becomes, the higher the bulk density becomes. The diameter of the particles having an outer shell containing CNF in the composition can be adjusted by changing the type and blending ratio of the organic solvent or changing the stirring conditions.
[構造体の厚さ]
構造体がシート状や帯状である場合、支持体を除いた構造体の厚さL(図1(A)参照)は、好ましくは0.5μm以上、より好ましくは1.0μm以上、さらに好ましくは3.5μm以上、よりさらに好ましくは5.0μm以上、特に好ましくは7.5μm以上であり、また、好ましくは300μm以下、より好ましくは200μm以下、さらに好ましくは100μm以下、よりさらに好ましくは75μm以下、特に好ましくは50μm以下である。構造体の厚さが300μm以下であれば、乾燥時間が長くなったり、乾燥不良が発生したりするのを回避し、結果として、閉塞空間の形状や大きさにおけるばらつきを抑え、かつ、構造体が変質する等の問題を防ぎやすい。また、構造体の厚さが0.5μm以上であれば、構造体の強度が不足したり、閉塞空間内に保持できる流体が少なくなったりするのを防止しやすい。
構造体がシート状や帯状である場合、構造体の面積や長手方向の大きさに特に制限はなく、製造設備を用意できる範囲で任意の大きさとすることができる。なお、構造体がシート状や帯状以外の形状、例えば、塊状の形状を有する場合も、上述したのと同様の観点から、構造体の最大径を、好ましくは1mm以上、より好ましくは5mm以上、さらに好ましくは1cm以上、さらに好ましくは2.5cm以上、特に好ましくは5cm以上とし、また、好ましくは5m以下、より好ましくは3m以下、さらに好ましくは1m以下、よりさらに好ましくは50cm以下、特に好ましくは10cm以下とする。 [Structure thickness]
When the structure has a sheet shape or a band shape, the thickness L of the structure excluding the support (see FIG. 1A) is preferably 0.5 μm or more, more preferably 1.0 μm or more, and still more preferably. 3.5 μm or more, even more preferably 5.0 μm or more, particularly preferably 7.5 μm or more, and preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less, even more preferably 75 μm or less, Particularly preferably, it is 50 μm or less. When the thickness of the structure is 300 μm or less, it is possible to prevent the drying time from being prolonged or to cause poor drying. As a result, the variation in the shape and size of the closed space is suppressed, and It is easy to prevent problems such as deterioration. Further, when the thickness of the structure is 0.5 μm or more, it is easy to prevent the strength of the structure from becoming insufficient and the fluid that can be held in the closed space to decrease.
When the structure has a sheet shape or a band shape, there is no particular limitation on the area and the size in the longitudinal direction of the structure, and the structure can have any size as long as manufacturing facilities can be prepared. In addition, when the structure has a shape other than the sheet shape or the band shape, for example, even when having a lump shape, from the same viewpoint as described above, the maximum diameter of the structure is preferably 1 mm or more, more preferably 5 mm or more, It is more preferably at least 1 cm, further preferably at least 2.5 cm, particularly preferably at least 5 cm, and preferably at most 5 m, more preferably at most 3 m, still more preferably at most 1 m, even more preferably at most 50 cm, particularly preferably at most 50 cm. 10 cm or less.
構造体がシート状や帯状である場合、支持体を除いた構造体の厚さL(図1(A)参照)は、好ましくは0.5μm以上、より好ましくは1.0μm以上、さらに好ましくは3.5μm以上、よりさらに好ましくは5.0μm以上、特に好ましくは7.5μm以上であり、また、好ましくは300μm以下、より好ましくは200μm以下、さらに好ましくは100μm以下、よりさらに好ましくは75μm以下、特に好ましくは50μm以下である。構造体の厚さが300μm以下であれば、乾燥時間が長くなったり、乾燥不良が発生したりするのを回避し、結果として、閉塞空間の形状や大きさにおけるばらつきを抑え、かつ、構造体が変質する等の問題を防ぎやすい。また、構造体の厚さが0.5μm以上であれば、構造体の強度が不足したり、閉塞空間内に保持できる流体が少なくなったりするのを防止しやすい。
構造体がシート状や帯状である場合、構造体の面積や長手方向の大きさに特に制限はなく、製造設備を用意できる範囲で任意の大きさとすることができる。なお、構造体がシート状や帯状以外の形状、例えば、塊状の形状を有する場合も、上述したのと同様の観点から、構造体の最大径を、好ましくは1mm以上、より好ましくは5mm以上、さらに好ましくは1cm以上、さらに好ましくは2.5cm以上、特に好ましくは5cm以上とし、また、好ましくは5m以下、より好ましくは3m以下、さらに好ましくは1m以下、よりさらに好ましくは50cm以下、特に好ましくは10cm以下とする。 [Structure thickness]
When the structure has a sheet shape or a band shape, the thickness L of the structure excluding the support (see FIG. 1A) is preferably 0.5 μm or more, more preferably 1.0 μm or more, and still more preferably. 3.5 μm or more, even more preferably 5.0 μm or more, particularly preferably 7.5 μm or more, and preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less, even more preferably 75 μm or less, Particularly preferably, it is 50 μm or less. When the thickness of the structure is 300 μm or less, it is possible to prevent the drying time from being prolonged or to cause poor drying. As a result, the variation in the shape and size of the closed space is suppressed, and It is easy to prevent problems such as deterioration. Further, when the thickness of the structure is 0.5 μm or more, it is easy to prevent the strength of the structure from becoming insufficient and the fluid that can be held in the closed space to decrease.
When the structure has a sheet shape or a band shape, there is no particular limitation on the area and the size in the longitudinal direction of the structure, and the structure can have any size as long as manufacturing facilities can be prepared. In addition, when the structure has a shape other than the sheet shape or the band shape, for example, even when having a lump shape, from the same viewpoint as described above, the maximum diameter of the structure is preferably 1 mm or more, more preferably 5 mm or more, It is more preferably at least 1 cm, further preferably at least 2.5 cm, particularly preferably at least 5 cm, and preferably at most 5 m, more preferably at most 3 m, still more preferably at most 1 m, even more preferably at most 50 cm, particularly preferably at most 50 cm. 10 cm or less.
[セルロースナノファイバー(CNF)、及び、その他の成分]
構造体を構成するCNFの材質や形状等は、後述する組成物に配合されるCNFで説明するものがそのまま当てはまる。また、構造体に含有し得る、CNF以外の多糖類やその他の成分(徐放を目的として閉塞空間内に存在させる有機溶媒等の成分を除く)についても、後述する組成物に配合される成分がそのまま当てはまる。したがって、ここではこれらについての詳しい説明を省略する。 [Cellulose nanofiber (CNF) and other components]
As for the material, shape, and the like of CNF constituting the structure, those described in CNF to be added to the composition described below apply as they are. In addition, polysaccharides other than CNF and other components (excluding components such as organic solvents that are present in an enclosed space for the purpose of sustained release) that can be contained in the structure are also included in the composition described below. Applies as is. Therefore, a detailed description thereof will be omitted here.
構造体を構成するCNFの材質や形状等は、後述する組成物に配合されるCNFで説明するものがそのまま当てはまる。また、構造体に含有し得る、CNF以外の多糖類やその他の成分(徐放を目的として閉塞空間内に存在させる有機溶媒等の成分を除く)についても、後述する組成物に配合される成分がそのまま当てはまる。したがって、ここではこれらについての詳しい説明を省略する。 [Cellulose nanofiber (CNF) and other components]
As for the material, shape, and the like of CNF constituting the structure, those described in CNF to be added to the composition described below apply as they are. In addition, polysaccharides other than CNF and other components (excluding components such as organic solvents that are present in an enclosed space for the purpose of sustained release) that can be contained in the structure are also included in the composition described below. Applies as is. Therefore, a detailed description thereof will be omitted here.
[支持体]
本発明の一態様においては、支持体付きのシート状構造体50のように、構造体が支持体を備えている。支持体を設ける場合、構造体と支持体とを一体のものとしてもよいし、構造体を形成した後に支持体から構造体を分離してもよい。つまり剥離材等の、一時的に使用する保持体上にシート状構造体を形成してもよい。
前者の場合は、好ましくは、支持体の、前記組成物が塗布される面に易接着処理を施しておく。易接着処理としては、例えば、コロナ放電処理、プラズマ処理、オゾン処理等を用いることができる。また、例えば、アクリル樹脂、エステル樹脂、ウレタン樹脂などを用いて易接着層を設けることもできる。後者の場合は、組成物を塗布する面に剥離層が形成されたものを用いてもよいし、支持体全体が、構造体を剥離しやすい材料から構成されているものを用いてもよい。
支持体は、シート状構造体の用途に応じて適宜選択され、例えば、上質紙、アート紙、コート紙、グラシン紙等の紙基材;これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙;アルミニウム箔や銅箔や鉄箔等の金属箔;不織布等の多孔質材料:ポリエチレン樹脂やポリプロピレン樹脂等のポリオレフィン樹脂、ポリブチレンテレフタレート樹脂やポリエチレンテレフタレート樹脂等のポリエステル樹脂、アセテート樹脂、ABS樹脂、ポリスチレン樹脂、塩化ビニル樹脂等の1種以上の樹脂を含む樹脂フィルム又はシート;等が挙げられる。
支持体は、単層フィルム又はシートであってもよく、2層以上の積層体である複層フィルム又はシートであってもよい。
また、樹脂フィルム又はシートは、未延伸でもよいし、縦又は横等の一軸方向あるいは二軸方向に延伸されていてもよい。
さらに、樹脂フィルム又はシートは、上述の樹脂のほかに、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、スリップ剤、アンチブロッキング剤、着色剤等が含有されていてもよい。
支持体の厚さは、シート状構造体の用途に応じて適宜選択されるが、好ましくは10μm以上、より好ましくは15μm以上、さらに好ましくは20μm以上であり、また、好ましくは250μm以下、より好ましくは200μm以下、さらに好ましくは150μm以下である。 [Support]
In one embodiment of the present invention, the structure has a support, such as a sheet-like structure 50 with a support. When a support is provided, the structure and the support may be integrated, or the structure may be separated from the support after the structure is formed. That is, the sheet-like structure may be formed on a temporarily used holder such as a release material.
In the former case, preferably, the surface of the support to which the composition is applied is subjected to an easy-adhesion treatment. As the easy adhesion treatment, for example, a corona discharge treatment, a plasma treatment, an ozone treatment, or the like can be used. Further, for example, an easy-adhesion layer can be provided using an acrylic resin, an ester resin, a urethane resin, or the like. In the latter case, a material having a release layer formed on the surface to which the composition is applied may be used, or a material in which the entire support is made of a material from which the structure is easily peeled may be used.
The support is appropriately selected depending on the use of the sheet-like structure, and is, for example, a paper base such as high-quality paper, art paper, coated paper, or glassine paper; and a thermoplastic resin such as polyethylene is laminated on these paper bases. Laminated paper; metal foils such as aluminum foil, copper foil and iron foil; porous materials such as non-woven fabrics; polyolefin resins such as polyethylene resin and polypropylene resin; polyester resins such as polybutylene terephthalate resin and polyethylene terephthalate resin; acetate resins; A resin film or sheet containing at least one resin such as an ABS resin, a polystyrene resin, and a vinyl chloride resin;
The support may be a single-layer film or sheet, or a multilayer film or sheet that is a laminate of two or more layers.
Moreover, the resin film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as a vertical or horizontal direction.
Further, the resin film or sheet may contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent, and the like, in addition to the above-described resin.
The thickness of the support is appropriately selected depending on the use of the sheet-like structure, but is preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm or more, and preferably 250 μm or less, more preferably Is 200 μm or less, more preferably 150 μm or less.
本発明の一態様においては、支持体付きのシート状構造体50のように、構造体が支持体を備えている。支持体を設ける場合、構造体と支持体とを一体のものとしてもよいし、構造体を形成した後に支持体から構造体を分離してもよい。つまり剥離材等の、一時的に使用する保持体上にシート状構造体を形成してもよい。
前者の場合は、好ましくは、支持体の、前記組成物が塗布される面に易接着処理を施しておく。易接着処理としては、例えば、コロナ放電処理、プラズマ処理、オゾン処理等を用いることができる。また、例えば、アクリル樹脂、エステル樹脂、ウレタン樹脂などを用いて易接着層を設けることもできる。後者の場合は、組成物を塗布する面に剥離層が形成されたものを用いてもよいし、支持体全体が、構造体を剥離しやすい材料から構成されているものを用いてもよい。
支持体は、シート状構造体の用途に応じて適宜選択され、例えば、上質紙、アート紙、コート紙、グラシン紙等の紙基材;これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙;アルミニウム箔や銅箔や鉄箔等の金属箔;不織布等の多孔質材料:ポリエチレン樹脂やポリプロピレン樹脂等のポリオレフィン樹脂、ポリブチレンテレフタレート樹脂やポリエチレンテレフタレート樹脂等のポリエステル樹脂、アセテート樹脂、ABS樹脂、ポリスチレン樹脂、塩化ビニル樹脂等の1種以上の樹脂を含む樹脂フィルム又はシート;等が挙げられる。
支持体は、単層フィルム又はシートであってもよく、2層以上の積層体である複層フィルム又はシートであってもよい。
また、樹脂フィルム又はシートは、未延伸でもよいし、縦又は横等の一軸方向あるいは二軸方向に延伸されていてもよい。
さらに、樹脂フィルム又はシートは、上述の樹脂のほかに、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、スリップ剤、アンチブロッキング剤、着色剤等が含有されていてもよい。
支持体の厚さは、シート状構造体の用途に応じて適宜選択されるが、好ましくは10μm以上、より好ましくは15μm以上、さらに好ましくは20μm以上であり、また、好ましくは250μm以下、より好ましくは200μm以下、さらに好ましくは150μm以下である。 [Support]
In one embodiment of the present invention, the structure has a support, such as a sheet-
In the former case, preferably, the surface of the support to which the composition is applied is subjected to an easy-adhesion treatment. As the easy adhesion treatment, for example, a corona discharge treatment, a plasma treatment, an ozone treatment, or the like can be used. Further, for example, an easy-adhesion layer can be provided using an acrylic resin, an ester resin, a urethane resin, or the like. In the latter case, a material having a release layer formed on the surface to which the composition is applied may be used, or a material in which the entire support is made of a material from which the structure is easily peeled may be used.
The support is appropriately selected depending on the use of the sheet-like structure, and is, for example, a paper base such as high-quality paper, art paper, coated paper, or glassine paper; and a thermoplastic resin such as polyethylene is laminated on these paper bases. Laminated paper; metal foils such as aluminum foil, copper foil and iron foil; porous materials such as non-woven fabrics; polyolefin resins such as polyethylene resin and polypropylene resin; polyester resins such as polybutylene terephthalate resin and polyethylene terephthalate resin; acetate resins; A resin film or sheet containing at least one resin such as an ABS resin, a polystyrene resin, and a vinyl chloride resin;
The support may be a single-layer film or sheet, or a multilayer film or sheet that is a laminate of two or more layers.
Moreover, the resin film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as a vertical or horizontal direction.
Further, the resin film or sheet may contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent, and the like, in addition to the above-described resin.
The thickness of the support is appropriately selected depending on the use of the sheet-like structure, but is preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm or more, and preferably 250 μm or less, more preferably Is 200 μm or less, more preferably 150 μm or less.
<構造体の製造方法>
CNFを含む膜から構成される複数の閉塞空間を有する構造体は、一態様として下記工程(1)~(2)を有する製造方法によって製造することができる。
・工程(1):CNFの水分散液に有機溶剤を添加して組成物を調製する工程。
・工程(2):前記組成物を支持体上に塗布して塗膜を形成し、当該塗膜を乾燥して、シート状構造体とする工程。 <Method of manufacturing structure>
A structure having a plurality of closed spaces composed of a film containing CNF can be manufactured by a manufacturing method having the following steps (1) and (2) as one embodiment.
Step (1): a step of adding an organic solvent to an aqueous dispersion of CNF to prepare a composition.
Step (2): a step of applying the composition on a support to form a coating film, and drying the coating film to form a sheet-like structure.
CNFを含む膜から構成される複数の閉塞空間を有する構造体は、一態様として下記工程(1)~(2)を有する製造方法によって製造することができる。
・工程(1):CNFの水分散液に有機溶剤を添加して組成物を調製する工程。
・工程(2):前記組成物を支持体上に塗布して塗膜を形成し、当該塗膜を乾燥して、シート状構造体とする工程。 <Method of manufacturing structure>
A structure having a plurality of closed spaces composed of a film containing CNF can be manufactured by a manufacturing method having the following steps (1) and (2) as one embodiment.
Step (1): a step of adding an organic solvent to an aqueous dispersion of CNF to prepare a composition.
Step (2): a step of applying the composition on a support to form a coating film, and drying the coating film to form a sheet-like structure.
以下、工程(1)を「組成物を準備する工程」、工程(2)を「構造体を得る工程」ということがある。工程(2)は、以下説明するように、支持体の一方の面に組成物を供給する工程(工程(2-1))、組成物を支持体に塗布する工程(工程(2-2))、支持体上に塗布された組成物を乾燥する工程(工程(2-3))を含む。
Hereinafter, the step (1) may be referred to as a “step of preparing a composition”, and the step (2) may be referred to as a “step of obtaining a structure”. In the step (2), as described below, a step of supplying the composition to one surface of the support (step (2-1)) and a step of applying the composition to the support (step (2-2)) ) And drying the composition applied on the support (step (2-3)).
図2は、製造工程中の一過程を示しており、組成物が支持体上に塗布された様子を示す模式図である。工程(1)で調製された組成物は、CNFを含む外殻を備える粒子を含んでおり、工程(2-1)~工程(2-2)において、この組成物が支持体上に塗布された時点では、図2に示すように、組成物30が、CNFを含む外殻を備える粒子32と、水を主体とする媒質34とを含んでいる。また、粒子32は、有機溶剤を主体とする液体もしくは空気、又はこれら両者を内部に含んでいる。この後、工程(2-3)において、水及び有機溶剤が乾燥により除去されて、図1(A)に示すように、CNFを含む膜による閉塞空間が多数形成された層(すなわち、シート状構造体)31が支持体40上に形成される。
なお、シート状構造体31や支持体付きのシート状構造体50を上述した流体保持用製品や徐放性を有する製品へ適用する場合、シート状構造体を特定の液体に浸漬して閉塞空間内に上記液体を封入したり、シート状構造体を特定の気体雰囲気下において特定種類の気体を閉塞空間内に封入したりすることができる。また、シート状構造体の製造工程中において、これらの流体が閉塞空間に含まれるようにしてもよい。例えば、工程(2-3)における乾燥後も閉塞空間33内に残るように、予め特定種類の有機溶剤(例えば、乾燥温度よりも高い沸点を有する有機溶剤)を組成物中に配合しておいてもよい。また、組成物の調製を特定種類の気体が満たされた雰囲気下で行うことで、閉塞空間内に流体を封入するようにしてもよい。 FIG. 2 is a schematic diagram showing one step in the manufacturing process and showing a state in which the composition is applied on a support. The composition prepared in the step (1) contains particles having an outer shell containing CNF. In the steps (2-1) to (2-2), the composition is applied on a support. At this point, as shown in FIG. 2, thecomposition 30 includes particles 32 having an outer shell containing CNF, and a medium 34 mainly composed of water. The particles 32 contain a liquid mainly composed of an organic solvent, air, or both. Thereafter, in step (2-3), the water and the organic solvent are removed by drying, and as shown in FIG. 1A, a layer in which a large number of closed spaces are formed by a CNF-containing film (ie, a sheet-like layer). A structure 31 is formed on the support 40.
When the sheet-like structure 31 or the sheet-like structure 50 with a support is applied to the above-described fluid holding product or a product having a sustained release property, the sheet-like structure is immersed in a specific liquid to close the closed space. The above-mentioned liquid can be sealed therein, or a specific kind of gas can be sealed in a closed space in a sheet-like structure under a specific gas atmosphere. Further, these fluids may be included in the closed space during the manufacturing process of the sheet-like structure. For example, a specific type of organic solvent (for example, an organic solvent having a boiling point higher than the drying temperature) is blended in the composition in advance so as to remain in the closed space 33 even after drying in the step (2-3). May be. The composition may be prepared in an atmosphere filled with a specific type of gas, so that the fluid is sealed in the closed space.
なお、シート状構造体31や支持体付きのシート状構造体50を上述した流体保持用製品や徐放性を有する製品へ適用する場合、シート状構造体を特定の液体に浸漬して閉塞空間内に上記液体を封入したり、シート状構造体を特定の気体雰囲気下において特定種類の気体を閉塞空間内に封入したりすることができる。また、シート状構造体の製造工程中において、これらの流体が閉塞空間に含まれるようにしてもよい。例えば、工程(2-3)における乾燥後も閉塞空間33内に残るように、予め特定種類の有機溶剤(例えば、乾燥温度よりも高い沸点を有する有機溶剤)を組成物中に配合しておいてもよい。また、組成物の調製を特定種類の気体が満たされた雰囲気下で行うことで、閉塞空間内に流体を封入するようにしてもよい。 FIG. 2 is a schematic diagram showing one step in the manufacturing process and showing a state in which the composition is applied on a support. The composition prepared in the step (1) contains particles having an outer shell containing CNF. In the steps (2-1) to (2-2), the composition is applied on a support. At this point, as shown in FIG. 2, the
When the sheet-
[工程(1):組成物を準備する工程]
工程(1)においては、水分散液を撹拌しながら、有機溶剤を少量ずつ水分散液に供給することが好ましい。
水中にCNFが均一に分散された状態で、さらに有機溶剤が添加され、この有機溶剤も均一に分散されることにより、界面活性剤などの分散剤を用いなくても、水と有機溶剤の界面にCNFが集まってCNFを含む外殻を備える粒子が形成される。組成物においてCNFを含む外殻を備える粒子が形成される過程は、これに限られるものではないが、一つには以下のようなメカニズムによるものと推測される。つまり、CNFは両親媒性を有する不溶材料であるため、乳化に用いられた水と有機溶剤との界面に存在することで、エネルギー的に安定な状態を作り出す。加えて、CNFは不溶性であり、造膜性があることから、界面への局在化の結果、不可逆的独立相を形成する。こうして、組成物中で、CNFを含む外殻を備える粒子が形成されるものと考えられる。
均一分散したCNFを含む水分散液に有機溶剤が添加された際に、CNFが界面に局在化して生成される粒子は比較的安定性が高いと考えられる。このため、生成されたカプセル同士の結合による大径カプセルへの変化は発生しにくく、上記有機溶剤が添加された水分散液を十分に撹拌することにより、小径でしかも均一な粒子になると考えられる。また、撹拌によって空気が水分散液に巻き込まれ、先に生成した安定な複数の粒子に囲まれて固定されることにより、この空気も安定して保持されることも考えられる(この固定された空気も乾燥後に気泡となると考えられる)。結果的に、組成物全体において、過度な刺激を与えたり、意図的に一定又はそれ以上の圧力を加えたりしない限り、数ヶ月以上消失せず安定して存在する粒子になると考えられる。 [Step (1): Step of Preparing Composition]
In the step (1), it is preferable to supply the organic solvent to the aqueous dispersion little by little while stirring the aqueous dispersion.
In a state where CNF is uniformly dispersed in water, an organic solvent is further added, and the organic solvent is also uniformly dispersed, so that an interface between water and the organic solvent can be obtained without using a dispersant such as a surfactant. Collects CNF to form particles having an outer shell containing CNF. The process of forming particles having an outer shell containing CNF in the composition is not limited to this, but one is presumed to be due to the following mechanism. That is, since CNF is an insoluble material having amphipathic properties, it exists in an interface between water and an organic solvent used for emulsification, thereby creating an energy-stable state. In addition, since CNF is insoluble and film-forming, it forms an irreversible independent phase as a result of localization at the interface. Thus, it is believed that particles with a shell comprising CNF are formed in the composition.
When an organic solvent is added to an aqueous dispersion containing uniformly dispersed CNF, particles generated by localization of CNF at the interface are considered to have relatively high stability. For this reason, it is unlikely that the generated capsules change into large-diameter capsules due to bonding between the capsules. By sufficiently stirring the aqueous dispersion to which the organic solvent has been added, small-sized and uniform particles are considered to be obtained. . It is also conceivable that air is stably retained by the air being entrained in the aqueous dispersion by stirring and being surrounded and fixed by the plurality of previously generated stable particles. It is considered that air also becomes bubbles after drying.) As a result, it is considered that the particles in the entire composition remain stable without disappearing for more than several months unless excessively stimulating or intentionally applying a constant or higher pressure.
工程(1)においては、水分散液を撹拌しながら、有機溶剤を少量ずつ水分散液に供給することが好ましい。
水中にCNFが均一に分散された状態で、さらに有機溶剤が添加され、この有機溶剤も均一に分散されることにより、界面活性剤などの分散剤を用いなくても、水と有機溶剤の界面にCNFが集まってCNFを含む外殻を備える粒子が形成される。組成物においてCNFを含む外殻を備える粒子が形成される過程は、これに限られるものではないが、一つには以下のようなメカニズムによるものと推測される。つまり、CNFは両親媒性を有する不溶材料であるため、乳化に用いられた水と有機溶剤との界面に存在することで、エネルギー的に安定な状態を作り出す。加えて、CNFは不溶性であり、造膜性があることから、界面への局在化の結果、不可逆的独立相を形成する。こうして、組成物中で、CNFを含む外殻を備える粒子が形成されるものと考えられる。
均一分散したCNFを含む水分散液に有機溶剤が添加された際に、CNFが界面に局在化して生成される粒子は比較的安定性が高いと考えられる。このため、生成されたカプセル同士の結合による大径カプセルへの変化は発生しにくく、上記有機溶剤が添加された水分散液を十分に撹拌することにより、小径でしかも均一な粒子になると考えられる。また、撹拌によって空気が水分散液に巻き込まれ、先に生成した安定な複数の粒子に囲まれて固定されることにより、この空気も安定して保持されることも考えられる(この固定された空気も乾燥後に気泡となると考えられる)。結果的に、組成物全体において、過度な刺激を与えたり、意図的に一定又はそれ以上の圧力を加えたりしない限り、数ヶ月以上消失せず安定して存在する粒子になると考えられる。 [Step (1): Step of Preparing Composition]
In the step (1), it is preferable to supply the organic solvent to the aqueous dispersion little by little while stirring the aqueous dispersion.
In a state where CNF is uniformly dispersed in water, an organic solvent is further added, and the organic solvent is also uniformly dispersed, so that an interface between water and the organic solvent can be obtained without using a dispersant such as a surfactant. Collects CNF to form particles having an outer shell containing CNF. The process of forming particles having an outer shell containing CNF in the composition is not limited to this, but one is presumed to be due to the following mechanism. That is, since CNF is an insoluble material having amphipathic properties, it exists in an interface between water and an organic solvent used for emulsification, thereby creating an energy-stable state. In addition, since CNF is insoluble and film-forming, it forms an irreversible independent phase as a result of localization at the interface. Thus, it is believed that particles with a shell comprising CNF are formed in the composition.
When an organic solvent is added to an aqueous dispersion containing uniformly dispersed CNF, particles generated by localization of CNF at the interface are considered to have relatively high stability. For this reason, it is unlikely that the generated capsules change into large-diameter capsules due to bonding between the capsules. By sufficiently stirring the aqueous dispersion to which the organic solvent has been added, small-sized and uniform particles are considered to be obtained. . It is also conceivable that air is stably retained by the air being entrained in the aqueous dispersion by stirring and being surrounded and fixed by the plurality of previously generated stable particles. It is considered that air also becomes bubbles after drying.) As a result, it is considered that the particles in the entire composition remain stable without disappearing for more than several months unless excessively stimulating or intentionally applying a constant or higher pressure.
工程(1)においては、CNFを含む外殻を備える粒子が形成されずに、有機溶剤が水と相分離してしまうことを防止する観点から、水分散液の全量100質量部に対して、10秒毎の有機溶剤の添加量が、好ましくは0.1質量部以上、より好ましくは1質量部以上、さらに好ましくは3質量部以上、特に好ましくは5質量部以上、また、好ましくは20質量部以下、より好ましくは15質量部以下、さらに好ましくは10質量部以下、特に好ましくは7質量部以下となるように有機溶剤を添加する。有機溶剤を連続的に供給してもよいし、有機溶剤を断続的に供給してもよい。いずれにしても、水分散液に限られた量の有機溶剤を添加しながら撹拌することで、有機溶剤が水分散液に均一に分散され、結果として、CNFを含む外殻を備える粒子を良好に生成することができる。
In the step (1), from the viewpoint of preventing the organic solvent from being phase-separated with water without forming particles having an outer shell containing CNF, the total amount of the aqueous dispersion is 100 parts by mass. The amount of the organic solvent added 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, particularly preferably at least 5 parts by mass, and preferably at least 20 parts by mass. Parts or less, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, particularly preferably 7 parts by weight or less. The organic solvent may be supplied continuously, or the organic solvent may be supplied intermittently. In any case, by stirring while adding a limited amount of the organic solvent to the aqueous dispersion, the organic solvent is uniformly dispersed in the aqueous dispersion, and as a result, the particles having the outer shell containing CNF are excellent. Can be generated.
工程(1)においては、ホモディスパー、ミキサー、パドル翼等の撹拌翼を取り付けた撹拌装置を用いて、水分散液を撹拌しながら、有機溶剤を添加することが好ましい。撹拌翼を水分散液に接触させて撹拌することにより、CNFを含む外殻を備える粒子を効率よく生成することができる。
In step (1), it is preferable to add an organic solvent while stirring the aqueous dispersion using a stirrer equipped with a stirring blade such as a homodisper, a mixer, or a paddle blade. By bringing the stirring blade into contact with the aqueous dispersion and stirring, particles having an outer shell containing CNF can be efficiently generated.
水分散液を撹拌する際の撹拌速度(回転数)は、CNFの凝集を抑え、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは500rpm以上、より好ましくは1000rpm以上、さらに好ましくは1500rpm以上、よりさらに好ましくは2000rpm以上であり、また、好ましくは5000rpm以下、より好ましくは4500rpm以下、さらに好ましくは4000rpm以下、よりさらに好ましくは3500rpm以下、特に好ましくは3000rpm以下である。
The stirring speed (rotation speed) when stirring the aqueous dispersion is preferably 500 rpm or more, more preferably 1000 rpm or more, from the viewpoint of suppressing the aggregation of CNF and reducing the variation in the shape and size of the formed particles. It is more preferably 1500 rpm or more, still more preferably 2000 rpm or more, and preferably 5000 rpm or less, more preferably 4500 rpm or less, still more preferably 4000 rpm or less, still more preferably 3500 rpm or less, and particularly preferably 3000 rpm or less.
撹拌時間は、CNFを含む外殻を備える粒子の形状や大きさを均一にする観点から、好ましくは3分以上、より好ましくは5分以上、さらに好ましくは10分以上とする。また、撹拌時間の上限は、製造時間が長くなり過ぎるのを防止し、CNFを含む外殻を備える粒子の形状や大きさがばらつくのを回避する観点から、好ましくは180分以下、より好ましくは120分以下、さらに好ましくは60分以下、よりさらに好ましくは40分以下、特に好ましくは20分以下である。なお、撹拌時間とは、有機溶剤(C)の添加から撹拌を終了するまでの時間を指す。有機溶剤(C)を十分に分散させるとともに粒子の形成を促進させるため、必要量の有機溶剤(C)の添加終了後も、有機溶剤(C)添加開始からの上記時間が経過するまで撹拌を継続することが望ましい。
The stirring time is preferably 3 minutes or more, more preferably 5 minutes or more, and still more preferably 10 minutes or more, from the viewpoint of making the shape and size of the particles having the outer shell containing CNF uniform. In addition, the upper limit of the stirring time is preferably 180 minutes or less, more preferably 180 minutes or less, from the viewpoint of preventing the production time from becoming too long and avoiding variation in the shape and size of the particles having the outer shell containing CNF. It is 120 minutes or less, further preferably 60 minutes or less, even more preferably 40 minutes or less, and particularly preferably 20 minutes or less. The stirring time refers to the time from the addition of the organic solvent (C) to the end of the stirring. In order to sufficiently disperse the organic solvent (C) and promote the formation of particles, after the addition of the required amount of the organic solvent (C) is completed, stirring is continued until the above-mentioned time from the start of the addition of the organic solvent (C) has elapsed. It is desirable to continue.
また、水分散液の温度は、CNFの凝集を抑え、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは5℃以上、より好ましくは10℃以上、さらに好ましくは15℃以上であり、また、添加した有機溶剤の揮発を抑制する観点から、好ましくは45℃以下、より好ましくは40℃以下、さらに好ましくは35℃以下である。
In addition, the temperature of the aqueous dispersion is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably 15 ° C., from the viewpoint of suppressing the aggregation of CNF and reducing the variation in the shape and size of the formed particles. From the viewpoint of suppressing volatilization of the added organic solvent, the temperature is preferably 45 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 35 ° C. or lower.
工程(1)は、好ましくは80kPa以上、より好ましくは90kPa以上、さらに好ましくは95kPa以上で行い、また、好ましくは120kPa以下、より好ましくは110kPa以下、さらに好ましくは105kPa以下で行い、特に好ましくは大気圧下で行う。大気圧に近い条件で組成物を調製することにより、短時間で組成物を調製することができ、製造設備も簡素なものにすることができる。また、工程(1)は、空気又は不活性ガスの雰囲気中で行えばよい。空気雰囲気中であれば、製造設備を簡素にすることができ、不活性ガス雰囲気中であれば、組成物の失活等を抑制しやすくなる。なお、シート状構造体を、上述した流体を徐放する製品に適用する場合、特定種類の気体の雰囲気下で組成物を調製して、生成される粒子内にこの気体が封入されるようにしてもよい。
これらの、温度条件、圧力条件、及び、雰囲気条件は、後述する工程(2-1)、工程(2-2)についても当てはまる。 Step (1) is preferably performed at 80 kPa or more, more preferably 90 kPa or more, still more preferably 95 kPa or more, and is preferably performed at 120 kPa or less, more preferably 110 kPa or less, further preferably 105 kPa or less, and particularly preferably large. Perform under atmospheric pressure. By preparing the composition under conditions close to atmospheric pressure, the composition can be prepared in a short time, and the production equipment can be simplified. Step (1) may be performed in an atmosphere of air or an inert gas. In an air atmosphere, the manufacturing equipment can be simplified, and in an inert gas atmosphere, deactivation of the composition and the like can be easily suppressed. When the sheet-like structure is applied to the above-mentioned product that releases the fluid slowly, the composition is prepared under an atmosphere of a specific type of gas so that the gas is sealed in the generated particles. You may.
These temperature conditions, pressure conditions, and atmosphere conditions also apply to the step (2-1) and the step (2-2) described later.
これらの、温度条件、圧力条件、及び、雰囲気条件は、後述する工程(2-1)、工程(2-2)についても当てはまる。 Step (1) is preferably performed at 80 kPa or more, more preferably 90 kPa or more, still more preferably 95 kPa or more, and is preferably performed at 120 kPa or less, more preferably 110 kPa or less, further preferably 105 kPa or less, and particularly preferably large. Perform under atmospheric pressure. By preparing the composition under conditions close to atmospheric pressure, the composition can be prepared in a short time, and the production equipment can be simplified. Step (1) may be performed in an atmosphere of air or an inert gas. In an air atmosphere, the manufacturing equipment can be simplified, and in an inert gas atmosphere, deactivation of the composition and the like can be easily suppressed. When the sheet-like structure is applied to the above-mentioned product that releases the fluid slowly, the composition is prepared under an atmosphere of a specific type of gas so that the gas is sealed in the generated particles. You may.
These temperature conditions, pressure conditions, and atmosphere conditions also apply to the step (2-1) and the step (2-2) described later.
[工程(1)で得られる組成物、及び、組成物の構成材料]
工程(1)によって調製される組成物は、CNF(A)、水(B)、及び、有機溶剤(C)を配合してなるものであって、CNF(A)を含む外殻を備える粒子を含有する。以下、CNF(A)、水(B)、及び、有機溶剤(C)をまとめて「成分(A)~(C)」と称することがある。
上記組成物において、有機溶剤(C)の少なくとも一部は、当該粒子に取り込まれた状態であり、具体的には、前記粒子に内包されている状態、及び、前記粒子の外殻を形成しているCNF(A)に吸着されている状態の少なくとも一方であることが好ましい。
ここで、「有機溶剤(C)が前記粒子に内包されている状態」とは、当該粒子が、CNF(A)を含む外殻から中空粒子を形成し、当該中空粒子の中空部分に有機溶剤(C)が取り込まれた状態を意味する。この際、中空粒子を構成する外殻によって、有機溶剤(C)は、中空粒子の外側から隔てられた状態となっている。
なお、本発明の一態様の組成物において、前記粒子は、有機溶剤(C)を内包しつつ、かつ、当該粒子の外殻を構成するCNF(A)が、有機溶剤(C)と吸着している状態であってもよい。本明細書において、「CNF(A)によって構成される外殻が有機溶剤(C)を吸着する」とは、CNF(A)によって構成される外殻の網目構造内に有機溶剤(C)が存在することを意味する。 [Composition obtained in step (1) and constituent materials of the composition]
The composition prepared in the step (1) is obtained by blending CNF (A), water (B), and an organic solvent (C), and includes particles having an outer shell containing CNF (A). It contains. Hereinafter, CNF (A), water (B), and organic solvent (C) may be collectively referred to as “components (A) to (C)”.
In the above composition, at least a part of the organic solvent (C) is in a state of being taken in by the particles, specifically, in a state of being included in the particles, and forming an outer shell of the particles. It is preferable that the state is at least one of the state of being adsorbed by the CNF (A).
Here, the “state in which the organic solvent (C) is included in the particles” means that the particles form hollow particles from the outer shell containing CNF (A), and the organic solvent is contained in the hollow portion of the hollow particles. (C) means the state 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.
Note that in the composition of one embodiment of the present invention, the particles contain the organic solvent (C), and the CNF (A) constituting the outer shell of the particles is adsorbed on the organic solvent (C). It may be in the state where it is. In this specification, "the outer shell composed of CNF (A) adsorbs the organic solvent (C)" means that the organic solvent (C) is contained in the network structure of the outer shell composed of CNF (A). Means exist.
工程(1)によって調製される組成物は、CNF(A)、水(B)、及び、有機溶剤(C)を配合してなるものであって、CNF(A)を含む外殻を備える粒子を含有する。以下、CNF(A)、水(B)、及び、有機溶剤(C)をまとめて「成分(A)~(C)」と称することがある。
上記組成物において、有機溶剤(C)の少なくとも一部は、当該粒子に取り込まれた状態であり、具体的には、前記粒子に内包されている状態、及び、前記粒子の外殻を形成しているCNF(A)に吸着されている状態の少なくとも一方であることが好ましい。
ここで、「有機溶剤(C)が前記粒子に内包されている状態」とは、当該粒子が、CNF(A)を含む外殻から中空粒子を形成し、当該中空粒子の中空部分に有機溶剤(C)が取り込まれた状態を意味する。この際、中空粒子を構成する外殻によって、有機溶剤(C)は、中空粒子の外側から隔てられた状態となっている。
なお、本発明の一態様の組成物において、前記粒子は、有機溶剤(C)を内包しつつ、かつ、当該粒子の外殻を構成するCNF(A)が、有機溶剤(C)と吸着している状態であってもよい。本明細書において、「CNF(A)によって構成される外殻が有機溶剤(C)を吸着する」とは、CNF(A)によって構成される外殻の網目構造内に有機溶剤(C)が存在することを意味する。 [Composition obtained in step (1) and constituent materials of the composition]
The composition prepared in the step (1) is obtained by blending CNF (A), water (B), and an organic solvent (C), and includes particles having an outer shell containing CNF (A). It contains. Hereinafter, CNF (A), water (B), and organic solvent (C) may be collectively referred to as “components (A) to (C)”.
In the above composition, at least a part of the organic solvent (C) is in a state of being taken in by the particles, specifically, in a state of being included in the particles, and forming an outer shell of the particles. It is preferable that the state is at least one of the state of being adsorbed by the CNF (A).
Here, the “state in which the organic solvent (C) is included in the particles” means that the particles form hollow particles from the outer shell containing CNF (A), and the organic solvent is contained in the hollow portion of the hollow particles. (C) means the state 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.
Note that in the composition of one embodiment of the present invention, the particles contain the organic solvent (C), and the CNF (A) constituting the outer shell of the particles is adsorbed on the organic solvent (C). It may be in the state where it is. In this specification, "the outer shell composed of CNF (A) adsorbs the organic solvent (C)" means that the organic solvent (C) is contained in the network structure of the outer shell composed of CNF (A). Means exist.
本発明の一態様の組成物において、前記粒子に取り込まれない有機溶剤(C)が存在していてもよい。
有機 In the composition of one embodiment of the present invention, an organic solvent (C) that is not incorporated into the particles may be present.
(組成物中のCNFを含む外殻を備える粒子の平均粒子径)
構造体の閉塞空間の最大フェレ径の平均が上述した数値範囲になるようにするためには、組成物における、CNFを含む外殻を備える粒子の平均粒子径を適切な範囲に設定することが好ましい。
本発明の一態様の組成物に含まれる、前記粒子の平均粒子径は、好ましくは1μm以上、より好ましくは5μm以上、さらに好ましくは7μm以上、よりさらに好ましくは10μm以上、特に好ましくは15μm以上であり、また、好ましくは60μm以下、より好ましくは50μm以下、さらに好ましくは40μm以下、よりさらに好ましくは35μm以下、特に好ましくは30μm以下である。
前記粒子の平均粒子径が1μm以上であれば、粒子同士の凝集を抑制しやすくなり、また、構造体の閉塞空間が小さくなりすぎるのを防止しやすくなる。
また、前記粒子の平均粒子径が60μm以下であれば、粒子の浮上を抑制しやすくなる。 (Average particle diameter of particles having an outer shell containing CNF in the composition)
In order for the average of the maximum Feret diameter of the closed space of the structure to be in the above-mentioned numerical range, the average particle diameter of the particles having the outer shell containing CNF in the composition is set to an appropriate range. preferable.
The average particle diameter of the particles contained in the composition of one embodiment of the present invention is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 7 μm or more, still more preferably 10 μm or more, and particularly preferably 15 μm or more. In addition, it is preferably 60 μm or less, more preferably 50 μm or less, further preferably 40 μm or less, still more preferably 35 μm or less, particularly preferably 30 μm or less.
When the average particle diameter of the particles is 1 μm or more, aggregation of the particles is easily suppressed, and the closed space of the structure is easily prevented from becoming too small.
When the average particle diameter of the particles is 60 μm or less, the floating of the particles is easily suppressed.
構造体の閉塞空間の最大フェレ径の平均が上述した数値範囲になるようにするためには、組成物における、CNFを含む外殻を備える粒子の平均粒子径を適切な範囲に設定することが好ましい。
本発明の一態様の組成物に含まれる、前記粒子の平均粒子径は、好ましくは1μm以上、より好ましくは5μm以上、さらに好ましくは7μm以上、よりさらに好ましくは10μm以上、特に好ましくは15μm以上であり、また、好ましくは60μm以下、より好ましくは50μm以下、さらに好ましくは40μm以下、よりさらに好ましくは35μm以下、特に好ましくは30μm以下である。
前記粒子の平均粒子径が1μm以上であれば、粒子同士の凝集を抑制しやすくなり、また、構造体の閉塞空間が小さくなりすぎるのを防止しやすくなる。
また、前記粒子の平均粒子径が60μm以下であれば、粒子の浮上を抑制しやすくなる。 (Average particle diameter of particles having an outer shell containing CNF in the composition)
In order for the average of the maximum Feret diameter of the closed space of the structure to be in the above-mentioned numerical range, the average particle diameter of the particles having the outer shell containing CNF in the composition is set to an appropriate range. preferable.
The average particle diameter of the particles contained in the composition of one embodiment of the present invention is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 7 μm or more, still more preferably 10 μm or more, and particularly preferably 15 μm or more. In addition, it is preferably 60 μm or less, more preferably 50 μm or less, further preferably 40 μm or less, still more preferably 35 μm or less, particularly preferably 30 μm or less.
When the average particle diameter of the particles is 1 μm or more, aggregation of the particles is easily suppressed, and the closed space of the structure is easily prevented from becoming too small.
When the average particle diameter of the particles is 60 μm or less, the floating of the particles is easily suppressed.
また、本発明の一態様の組成物に含まれる、前記粒子の平均粒子径に対する標準偏差は、上述した流体を構造体内に保持させておき、必要な場合に構造体の開裂によって流体を外部に供給する用途において、流体の放出量を安定させる観点から、好ましくは20μm以下、より好ましくは18μm以下、さらに好ましくは15μm以下、よりさらに好ましくは12μm以下であり、また、通常1μm以上である。
なお、本明細書において、前記粒子の平均粒子径、及び平均粒子径に対する標準偏差は、対象となる組成物を、デジタル顕微鏡を用いて倍率500~1000倍にて観察した際に取得した画像から算出することができる。
つまり、当該画像に写し出された前記粒子のうち、任意に選択した36個の粒子の粒径(外径)の平均値を上記の「平均粒子径」とすることができる。また、36個の各粒子の粒径の値から、「平均粒子径に対する標準偏差」も算出することができる。上記標準偏差は母集団の標準偏差であり、上記計算においては、36個の粒径の値の全てを対象として標準偏差を算出する。 In addition, the standard deviation with respect to the average particle diameter of the particles contained in the composition of one embodiment of the present invention is such that the above-described fluid is held in a structure, and the fluid is externalized by cleavage of the structure when necessary. In the supply application, from the viewpoint of stabilizing the release amount of the fluid, it is preferably 20 μm or less, more preferably 18 μm or less, further preferably 15 μm or less, further more preferably 12 μm or less, and usually 1 μm or more.
In the present specification, the average particle diameter of the particles and the standard deviation with respect to the average particle diameter are calculated from an image obtained when the target composition is observed at a magnification of 500 to 1000 using a digital microscope. Can be calculated.
In other words, the average value of the particle diameters (outer diameters) of the 36 particles arbitrarily selected among the particles shown in the image can be the above-mentioned “average particle diameter”. In addition, the “standard deviation with respect to the average particle size” can be calculated from the value of the particle size of each of the 36 particles. The standard deviation is the standard deviation of the population. In the above calculation, the standard deviation is calculated for all 36 particle size values.
なお、本明細書において、前記粒子の平均粒子径、及び平均粒子径に対する標準偏差は、対象となる組成物を、デジタル顕微鏡を用いて倍率500~1000倍にて観察した際に取得した画像から算出することができる。
つまり、当該画像に写し出された前記粒子のうち、任意に選択した36個の粒子の粒径(外径)の平均値を上記の「平均粒子径」とすることができる。また、36個の各粒子の粒径の値から、「平均粒子径に対する標準偏差」も算出することができる。上記標準偏差は母集団の標準偏差であり、上記計算においては、36個の粒径の値の全てを対象として標準偏差を算出する。 In addition, the standard deviation with respect to the average particle diameter of the particles contained in the composition of one embodiment of the present invention is such that the above-described fluid is held in a structure, and the fluid is externalized by cleavage of the structure when necessary. In the supply application, from the viewpoint of stabilizing the release amount of the fluid, it is preferably 20 μm or less, more preferably 18 μm or less, further preferably 15 μm or less, further more preferably 12 μm or less, and usually 1 μm or more.
In the present specification, the average particle diameter of the particles and the standard deviation with respect to the average particle diameter are calculated from an image obtained when the target composition is observed at a magnification of 500 to 1000 using a digital microscope. Can be calculated.
In other words, the average value of the particle diameters (outer diameters) of the 36 particles arbitrarily selected among the particles shown in the image can be the above-mentioned “average particle diameter”. In addition, the “standard deviation with respect to the average particle size” can be calculated from the value of the particle size of each of the 36 particles. The standard deviation is the standard deviation of the population. In the above calculation, the standard deviation is calculated for all 36 particle size values.
本発明の一態様に用いる組成物の23℃、回転数50rpmにおける粘度は、容器からの取り出しの容易性、撹拌の容易性、及び、沈降の抑制性等の観点から、好ましくは500mPa・s以上、より好ましくは1000mPa・s以上、さらに好ましくは1200mPa・s以上であり、また、好ましくは20000mPa・s以下、より好ましくは15000mPa・s以下、さらに好ましくは12000mPa・s以下である。
なお、後述する工程(2-2)において、組成物を支持体に良好に塗布できるようにするために、組成物を支持体に塗布する際の温度において、組成物の粘度が上記数値範囲となるように材料を選択することが好ましい。 The viscosity of the composition used in one embodiment of the present invention at 23 ° C and a rotation speed of 50 rpm is preferably 500 mPa · s or more from the viewpoints of easy removal from a container, ease of stirring, and suppression of sedimentation. And more preferably 1000 mPa · s or more, further preferably 1200 mPa · s or more, preferably 20,000 mPa · s or less, more preferably 15000 mPa · s or less, and still more preferably 12000 mPa · s or less.
In order to be able to apply the composition to the support favorably in the step (2-2) described later, the viscosity of the composition at the temperature at which the composition is applied to the support is within the above numerical range. It is preferable to select the material so that
なお、後述する工程(2-2)において、組成物を支持体に良好に塗布できるようにするために、組成物を支持体に塗布する際の温度において、組成物の粘度が上記数値範囲となるように材料を選択することが好ましい。 The viscosity of the composition used in one embodiment of the present invention at 23 ° C and a rotation speed of 50 rpm is preferably 500 mPa · s or more from the viewpoints of easy removal from a container, ease of stirring, and suppression of sedimentation. And more preferably 1000 mPa · s or more, further preferably 1200 mPa · s or more, preferably 20,000 mPa · s or less, more preferably 15000 mPa · s or less, and still more preferably 12000 mPa · s or less.
In order to be able to apply the composition to the support favorably in the step (2-2) described later, the viscosity of the composition at the temperature at which the composition is applied to the support is within the above numerical range. It is preferable to select the material so that
また、本発明の一態様で用いる組成物の23℃でのTI値(回転数5rpmにおける粘度/回転数50rpmにおける粘度)は、貯蔵安定性、容器中に保存するときの沈降の抑制性、及び、容器からの取り出し容易性等の観点から、好ましくは1.2以上、より好ましくは2以上、さらに好ましくは3以上、よりさらに好ましくは4以上であり、また、好ましくは20以下、より好ましくは15以下、さらに好ましくは10以下、よりさらに好ましくは8以下である。
また、本明細書において、組成物の粘度は、JIS Z 8803:2011に準拠して、B型粘度計を用いて測定した値を意味する。 The TI value at 23 ° C (viscosity at 5 rpm / viscosity at 50 rpm) of the composition used in one embodiment of the present invention is storage stability, suppresses sedimentation when stored in a container, and From the viewpoint of easy removal from the container, etc., it is preferably 1.2 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 4 or more, and preferably 20 or less, more preferably It is 15 or less, more preferably 10 or less, even more preferably 8 or less.
In this specification, the viscosity of the composition means a value measured using a B-type viscometer according to JIS Z 8803: 2011.
また、本明細書において、組成物の粘度は、JIS Z 8803:2011に準拠して、B型粘度計を用いて測定した値を意味する。 The TI value at 23 ° C (viscosity at 5 rpm / viscosity at 50 rpm) of the composition used in one embodiment of the present invention is storage stability, suppresses sedimentation when stored in a container, and From the viewpoint of easy removal from the container, etc., it is preferably 1.2 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 4 or more, and preferably 20 or less, more preferably It is 15 or less, more preferably 10 or less, even more preferably 8 or less.
In this specification, the viscosity of the composition means a value measured using a B-type viscometer according to JIS Z 8803: 2011.
本発明の一態様で用いる組成物のpHは、形成される粒子が安定し、組成物中で分散状態を維持し易いという観点から、好ましくは4以上、より好ましくは5以上、さらに好ましくは6以上であり、好ましくは10以下、より好ましくは9以下、さらに好ましくは8以下である。
The pH of the composition used in one embodiment of the present invention is preferably 4 or more, more preferably 5 or more, and still more preferably 6 from the viewpoint that particles to be formed are stable and a dispersed state is easily maintained in the composition. The number is preferably 10 or less, more preferably 9 or less, and further preferably 8 or less.
本発明の一態様で用いる組成物は、上記成分(A)~(C)以外の成分を含有してもよい。
ただし、本発明の一態様の組成物において、CNF(A)、水(B)及び有機溶剤(C)の合計含有量は、前記組成物の全量(100質量%)に対して、好ましくは60質量%以上、より好ましくは65質量%以上、さらに好ましくは70質量%以上、よりさらに好ましくは80質量%以上であり、また、好ましくは100質量%以下である。 The composition used in one embodiment of the present invention may contain components other than the above components (A) to (C).
However, in the composition of one embodiment of the present invention, the total content of CNF (A), water (B), and the organic solvent (C) is preferably 60% based on the total amount (100% by mass) of the composition. % By mass, more preferably 65% by mass or more, further preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 100% by mass or less.
ただし、本発明の一態様の組成物において、CNF(A)、水(B)及び有機溶剤(C)の合計含有量は、前記組成物の全量(100質量%)に対して、好ましくは60質量%以上、より好ましくは65質量%以上、さらに好ましくは70質量%以上、よりさらに好ましくは80質量%以上であり、また、好ましくは100質量%以下である。 The composition used in one embodiment of the present invention may contain components other than the above components (A) to (C).
However, in the composition of one embodiment of the present invention, the total content of CNF (A), water (B), and the organic solvent (C) is preferably 60% based on the total amount (100% by mass) of the composition. % By mass, more preferably 65% by mass or more, further preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 100% by mass or less.
本発明の一態様で用いる組成物の有効成分濃度は、前記組成物の全量(100質量%)に対して、好ましくは0.5質量%以上、より好ましくは0.7質量%以上、さらに好ましくは1.0質量%以上、よりさらにより好ましくは1.5質量%以上であり、また、好ましくは50質量%以下、より好ましくは20質量%以下、さらに好ましくは15質量%以下、よりさらに好ましくは10質量%以下である。
なお、本明細書において、「有効成分」とは、組成物に含まれる成分のうち、水(B)及び有機溶剤(C)を除いた成分を指す。 The active ingredient concentration of the composition used in one embodiment of the present invention is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and still more preferably, based on the total amount (100% by mass) of the composition. Is 1.0% by mass or more, even more preferably 1.5% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably Is 10% by mass or less.
In addition, in this specification, an "active ingredient" points out a component except water (B) and an organic solvent (C) among the components contained in a composition.
なお、本明細書において、「有効成分」とは、組成物に含まれる成分のうち、水(B)及び有機溶剤(C)を除いた成分を指す。 The active ingredient concentration of the composition used in one embodiment of the present invention is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and still more preferably, based on the total amount (100% by mass) of the composition. Is 1.0% by mass or more, even more preferably 1.5% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably Is 10% by mass or less.
In addition, in this specification, an "active ingredient" points out a component except water (B) and an organic solvent (C) among the components contained in a composition.
CNF(A)を含む外殻を備え、有機溶剤(C)を取り込んだ粒子は、配合するCNF(A)の配合量、CNF(A)と有機溶剤(C)との配合量比、及び有機溶剤(C)の種類等を適宜調製することで、形成させ得る。
The particles having an outer shell containing CNF (A) and incorporating the organic solvent (C) are used in the compounding amount of CNF (A), the compounding ratio of CNF (A) and the organic solvent (C), and the organic compound (C). It can be formed by appropriately adjusting the type of the solvent (C) and the like.
なお、本発明の一態様で用いる組成物においては、後述のとおり、CNF(A)を水(B)に分散させた水分散液に、有機溶剤(C)を配合することで、前記粒子を形成するように組成物を調製している。より好ましい態様においては、CNF(A)を水(B)に分散させた水分散液に、非水溶系溶媒である有機溶剤(C)を配合することで、前記粒子を形成するように組成物を調製する。さらに好ましい態様においては、CNF(A)を水(B)に分散させた水分散液に、ハンセン溶解度パラメータの距離Raが5.80MPa1/2以下となる有機溶剤(C)を配合することで、前記粒子を形成するように組成物を調製する。
また、上記以外にも、CNF(A)の形状(直径、繊維長、アスペクト比)、水(B)及び有機溶剤(C)の配合量、水(B)と有機溶剤(C)との配合量比等を適宜設定することによっても、前記粒子を形成し易くなるように組成物を調製することができる。 In the composition used in one embodiment of the present invention, as described below, the particles are obtained by blending an organic solvent (C) with an aqueous dispersion in which CNF (A) is dispersed in water (B). The composition is prepared to form. In a more preferred embodiment, the composition is such that the particles are formed by blending an organic solvent (C), which is a non-aqueous solvent, with an aqueous dispersion in which CNF (A) is dispersed in water (B). Is prepared. In a more preferred embodiment, an organic solvent (C) having a distance Ra of Hansen solubility parameter of 5.80 MPa 1/2 or less is mixed with an aqueous dispersion in which CNF (A) is dispersed in water (B). A composition is prepared to form the particles.
In addition to the above, the shape (diameter, fiber length, aspect ratio) of CNF (A), the amount of water (B) and the amount of organic solvent (C), the amount of water (B) and organic solvent (C) The composition can be prepared such that the particles can be easily formed by appropriately setting the amount ratio and the like.
また、上記以外にも、CNF(A)の形状(直径、繊維長、アスペクト比)、水(B)及び有機溶剤(C)の配合量、水(B)と有機溶剤(C)との配合量比等を適宜設定することによっても、前記粒子を形成し易くなるように組成物を調製することができる。 In the composition used in one embodiment of the present invention, as described below, the particles are obtained by blending an organic solvent (C) with an aqueous dispersion in which CNF (A) is dispersed in water (B). The composition is prepared to form. In a more preferred embodiment, the composition is such that the particles are formed by blending an organic solvent (C), which is a non-aqueous solvent, with an aqueous dispersion in which CNF (A) is dispersed in water (B). Is prepared. In a more preferred embodiment, an organic solvent (C) having a distance Ra of Hansen solubility parameter of 5.80 MPa 1/2 or less is mixed with an aqueous dispersion in which CNF (A) is dispersed in water (B). A composition is prepared to form the particles.
In addition to the above, the shape (diameter, fiber length, aspect ratio) of CNF (A), the amount of water (B) and the amount of organic solvent (C), the amount of water (B) and organic solvent (C) The composition can be prepared such that the particles can be easily formed by appropriately setting the amount ratio and the like.
(セルロースナノファイバー(CNF)(A))
本発明の一態様で用いるCNF(A)の原料としては、例えば、木材由来のクラフトパルプ又はサルファイトパルプ;クラフトパルプ又はサルファイトパルプを高圧ホモジナイザーやミル等で粉砕した粉末セルロース;粉末セルロースを酸加水分解などの化学処理により精製した微結晶セルロース粉末;コウゾ、雁皮、三椏等の靭皮繊維パルプ;コットンパルプ、ケナフ、麻、イネ、バカス、竹等の植物由来のセルロース系原料;等のセルロース系原料が挙げられる。植物由来のCNFは、結晶化度が高く直鎖構造を有しアスペクト比が大きいため、外殻の強度を高くでき、しかも入手しやすい。 (Cellulose nanofiber (CNF) (A))
Raw materials of CNF (A) used in one embodiment of the present invention include, for example, wood-based kraft pulp or sulfite pulp; powdered cellulose obtained by grinding kraft pulp or sulfite pulp with a high-pressure homogenizer or a mill; Cellulose such as microcrystalline cellulose powder purified by chemical treatment such as hydrolysis; bast fiber pulp such as mulberry, ganpi, mitsumata, etc .; System raw materials. Since plant-derived CNF has a high degree of crystallinity and a linear structure and a large aspect ratio, the strength of the outer shell can be increased, and it is easily available.
本発明の一態様で用いるCNF(A)の原料としては、例えば、木材由来のクラフトパルプ又はサルファイトパルプ;クラフトパルプ又はサルファイトパルプを高圧ホモジナイザーやミル等で粉砕した粉末セルロース;粉末セルロースを酸加水分解などの化学処理により精製した微結晶セルロース粉末;コウゾ、雁皮、三椏等の靭皮繊維パルプ;コットンパルプ、ケナフ、麻、イネ、バカス、竹等の植物由来のセルロース系原料;等のセルロース系原料が挙げられる。植物由来のCNFは、結晶化度が高く直鎖構造を有しアスペクト比が大きいため、外殻の強度を高くでき、しかも入手しやすい。 (Cellulose nanofiber (CNF) (A))
Raw materials of CNF (A) used in one embodiment of the present invention include, for example, wood-based kraft pulp or sulfite pulp; powdered cellulose obtained by grinding kraft pulp or sulfite pulp with a high-pressure homogenizer or a mill; Cellulose such as microcrystalline cellulose powder purified by chemical treatment such as hydrolysis; bast fiber pulp such as mulberry, ganpi, mitsumata, etc .; System raw materials. Since plant-derived CNF has a high degree of crystallinity and a linear structure and a large aspect ratio, the strength of the outer shell can be increased, and it is easily available.
なお、これらの原料中に、リグニンが多く残留してしまうと、当該原料の酸化反応を阻害する恐れがあるため、これらの原料に対して、リグニンの除去を施した、セルロース系原料が好ましい。
また、上述のセルロース系原料を高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式などの分散装置、湿式の高圧または超高圧ホモジナイザー等で微細化したものを使用することもできる。 If a large amount of lignin remains in these raw materials, the oxidation reaction of the raw materials may be hindered. Therefore, a cellulose-based raw material obtained by removing lignin from these raw materials is preferable.
Further, the above-mentioned cellulose-based raw material may be used as finely divided by a high-speed rotation type, colloid mill type, high pressure type, roll mill type, ultrasonic type or other dispersing device, wet type high pressure or ultra high pressure homogenizer, or the like.
また、上述のセルロース系原料を高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式などの分散装置、湿式の高圧または超高圧ホモジナイザー等で微細化したものを使用することもできる。 If a large amount of lignin remains in these raw materials, the oxidation reaction of the raw materials may be hindered. Therefore, a cellulose-based raw material obtained by removing lignin from these raw materials is preferable.
Further, the above-mentioned cellulose-based raw material may be used as finely divided by a high-speed rotation type, colloid mill type, high pressure type, roll mill type, ultrasonic type or other dispersing device, wet type high pressure or ultra high pressure homogenizer, or the like.
また、これらのセルロース系原料は、化学修飾及び/又は物理修飾して機能性を高めたものであってもよい。ここで、化学修飾としては、アセチル化、カルボキシ化、カルボキシナトリウム化、エステル化、シアノエチル化、アセタール化、エーテル化、アリール化、アルキル化、アクリロイル化、イソシアネート化等によって官能基を付加させること、及び、シリケートやチタネート等の無機物を化学反応やゾルゲル法等によって複合化や被覆化させること等が挙げられる。
また、物理修飾としては、金属やセラミック原料を、真空蒸着、イオンプレーティング、スパッタリング等の物理蒸着法(PVD法)、化学蒸着法(CVD法)、無電解メッキや電解メッキ等のメッキ法等によって表面被覆させることが挙げられる。
なお、これらの変性処理は、セルロース系原料を解繊時もしくは解繊する前後のいずれに行ってもよい。 In addition, these cellulosic raw materials may be those having improved functionality by chemical modification and / or physical modification. Here, the chemical modification includes acetylation, carboxylation, carboxysodiumation, esterification, cyanoethylation, acetalization, etherification, arylation, alkylation, acryloylation, addition of a functional group by isocyanation, etc. And a method in which an inorganic substance such as silicate or titanate is compounded or coated by a chemical reaction, a sol-gel method, or the like.
In addition, as the physical modification, a metal or ceramic raw material is subjected to a physical vapor deposition method (PVD method) such as vacuum deposition, ion plating, and sputtering, a chemical vapor deposition method (CVD method), and a plating method such as electroless plating and electrolytic plating. Surface coating.
These modification treatments may be performed either at the time of defibrating the cellulose-based material or before or after defibrating.
また、物理修飾としては、金属やセラミック原料を、真空蒸着、イオンプレーティング、スパッタリング等の物理蒸着法(PVD法)、化学蒸着法(CVD法)、無電解メッキや電解メッキ等のメッキ法等によって表面被覆させることが挙げられる。
なお、これらの変性処理は、セルロース系原料を解繊時もしくは解繊する前後のいずれに行ってもよい。 In addition, these cellulosic raw materials may be those having improved functionality by chemical modification and / or physical modification. Here, the chemical modification includes acetylation, carboxylation, carboxysodiumation, esterification, cyanoethylation, acetalization, etherification, arylation, alkylation, acryloylation, addition of a functional group by isocyanation, etc. And a method in which an inorganic substance such as silicate or titanate is compounded or coated by a chemical reaction, a sol-gel method, or the like.
In addition, as the physical modification, a metal or ceramic raw material is subjected to a physical vapor deposition method (PVD method) such as vacuum deposition, ion plating, and sputtering, a chemical vapor deposition method (CVD method), and a plating method such as electroless plating and electrolytic plating. Surface coating.
These modification treatments may be performed either at the time of defibrating the cellulose-based material or before or after defibrating.
上述のセルロース系原料は、解繊してナノファイバー化することで、CNFとすることができる。
具体的な方法としては、セルロース系原料が水等の分散媒に分散している分散液を調製した後、セルロース系原料にせん断力を印加することで、CNFを含む分散液とする方法が挙げられる。
セルロース系原料にせん断力を印加する方法としては、水等の分散媒にセルロース系原料を添加した後、高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式等の装置を用いて調製する方法が好ましい。
この際、分散液にかかる圧力は、好ましくは50MPa以上、より好ましくは100MPa以上、さらに好ましくは140MPa以上である。
このような高圧下で、セルロース系原料に強力なせん断力を印加する観点から、湿式の高圧又は超高圧ホモジナイザーを用いることが好ましい。 The above-mentioned cellulosic raw material can be made into CNF by fibrillating into nanofibers.
As a specific method, a method in which a dispersion liquid in which a cellulose-based material is dispersed in a dispersion medium such as water is prepared, and a shear force is applied to the cellulose-based material to obtain a dispersion containing CNF. Can be
As a method of applying a shearing force to the cellulosic material, after adding the cellulosic material to a dispersion medium such as water, using a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, an ultrasonic type or the like, The method of preparation is preferred.
At this time, the pressure applied to the dispersion is preferably 50 MPa or more, more preferably 100 MPa or more, and further 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.
具体的な方法としては、セルロース系原料が水等の分散媒に分散している分散液を調製した後、セルロース系原料にせん断力を印加することで、CNFを含む分散液とする方法が挙げられる。
セルロース系原料にせん断力を印加する方法としては、水等の分散媒にセルロース系原料を添加した後、高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式等の装置を用いて調製する方法が好ましい。
この際、分散液にかかる圧力は、好ましくは50MPa以上、より好ましくは100MPa以上、さらに好ましくは140MPa以上である。
このような高圧下で、セルロース系原料に強力なせん断力を印加する観点から、湿式の高圧又は超高圧ホモジナイザーを用いることが好ましい。 The above-mentioned cellulosic raw material can be made into CNF by fibrillating into nanofibers.
As a specific method, a method in which a dispersion liquid in which a cellulose-based material is dispersed in a dispersion medium such as water is prepared, and a shear force is applied to the cellulose-based material to obtain a dispersion containing CNF. Can be
As a method of applying a shearing force to the cellulosic material, after adding the cellulosic material to a dispersion medium such as water, using a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, an ultrasonic type or the like, The method of preparation is preferred.
At this time, the pressure applied to the dispersion is preferably 50 MPa or more, more preferably 100 MPa or more, and further preferably 140 MPa or more.
From the viewpoint of applying a strong shearing force to the cellulosic material under such a high pressure, it is preferable to use a wet high-pressure or ultra-high-pressure homogenizer.
本発明の一態様で用いるCNFの直径(太さ)の平均は、前記粒子を形成し易くするとともに、形成された粒子の膜強度を向上させる観点から、好ましくは1.0nm以上、より好ましくは1.5nm以上、さらに好ましくは2.0nm以上、よりさらに好ましくは2.5nm以上であり、また、好ましくは1000nm以下、より好ましくは500nm以下、さらに好ましくは200nm以下、よりさらに好ましくは100nm以下である。
The average of the diameter (thickness) of CNF used in one embodiment of the present invention is preferably 1.0 nm or more, more preferably 1.0 nm or more, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. 1.5 nm or more, 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, still more preferably 200 nm or less, even more preferably 100 nm or less. is there.
本発明の一態様で用いるCNFの繊維長の平均は、前記粒子を形成し易くすると共に、形成された粒子の膜強度を向上させる観点から、好ましくは0.01μm以上、より好ましくは0.1μm以上、さらに好ましくは0.2μm以上、よりさらに好ましくは0.3μm以上であり、好ましくは10μm以下、より好ましくは7.0μm以下、さらに好ましくは5.0μm以下、よりさらに好ましくは2.5μm以下である。
The average fiber length of CNF used in one embodiment of the present invention is preferably 0.01 μm or more, more preferably 0.1 μm, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. As described above, it is more preferably 0.2 μm or more, still more preferably 0.3 μm or more, preferably 10 μm or less, more preferably 7.0 μm or less, still more preferably 5.0 μm or less, and still more preferably 2.5 μm or less. It is.
本発明の一態様で用いるCNF(A)の平均アスペクト比は、前記粒子を形成し易くするとともに、形成された粒子の膜強度を向上させる観点から、好ましくは5以上、より好ましくは10以上、さらに好ましくは15以上であり、また、好ましくは10000以下であり、より好ましくは5000以下であり、さらに好ましくは3000以下、よりさらに好ましくは1000以下、特に好ましくは500以下である。
The average aspect ratio of CNF (A) used in one embodiment of the present invention is preferably 5 or more, more preferably 10 or more, from the viewpoint of facilitating the formation of the particles and improving the film strength of the formed particles. It is still more preferably 15 or more, preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less, still more preferably 1,000 or less, and particularly preferably 500 or less.
なお、「アスペクト比」とは、対象であるCNFの太さに対する長さの割合〔長さ/太さ〕であり、CNFの「長さ」とは、当該CNFの最も離れた2点間の距離を指す。
また、対象となるCNFの一部分が、他のCNFと接触して「長さ」の認定が難しい場合には、対象のCNFのうち、太さの測定が可能な部分のみの長さを測定し、当該部分のアスペクト比が上記範囲であればよい。
CNF(A)の直径(太さ)及び繊維長は、透過型電子顕微鏡を用いて測定することができる。また、CNF(A)の直径(太さ)の平均及び繊維長の平均は、任意に選択した複数のCNFの直径(太さ)及び繊維長を測定し、それぞれの平均値を算出することで得られる。CNF(A)の平均アスペクト比は、こうして得られた直径(太さ)の平均と繊維長の平均とを用いて算出することができる。CNF(A)の直径(太さ)、繊維長、これらの平均値、及び、平均アスペクト比は具体的には実施例に示す方法で算出することができる。 The “aspect ratio” is the ratio of the length to the thickness of the target CNF [length / thickness], and the “length” of the CNF is the distance between the two most distant points of the CNF. Refers to distance.
If it is difficult to determine the “length” of a part of the target CNF due to contact with another CNF, measure the length of only the part of the target CNF whose thickness can be measured. The aspect ratio of the portion may be in the above range.
The diameter (thickness) and fiber length of CNF (A) can be measured using a transmission electron microscope. Further, the average of the diameter (thickness) and the average of the fiber length of CNF (A) are obtained by measuring the diameter (thickness) and the fiber length of arbitrarily selected plural CNFs and calculating the average value of each. can get. The average aspect ratio of CNF (A) can be calculated using the average of the diameter (thickness) and the average of the fiber length thus obtained. The diameter (thickness), fiber length, average value, and average aspect ratio of CNF (A) can be specifically calculated by the methods described in Examples.
また、対象となるCNFの一部分が、他のCNFと接触して「長さ」の認定が難しい場合には、対象のCNFのうち、太さの測定が可能な部分のみの長さを測定し、当該部分のアスペクト比が上記範囲であればよい。
CNF(A)の直径(太さ)及び繊維長は、透過型電子顕微鏡を用いて測定することができる。また、CNF(A)の直径(太さ)の平均及び繊維長の平均は、任意に選択した複数のCNFの直径(太さ)及び繊維長を測定し、それぞれの平均値を算出することで得られる。CNF(A)の平均アスペクト比は、こうして得られた直径(太さ)の平均と繊維長の平均とを用いて算出することができる。CNF(A)の直径(太さ)、繊維長、これらの平均値、及び、平均アスペクト比は具体的には実施例に示す方法で算出することができる。 The “aspect ratio” is the ratio of the length to the thickness of the target CNF [length / thickness], and the “length” of the CNF is the distance between the two most distant points of the CNF. Refers to distance.
If it is difficult to determine the “length” of a part of the target CNF due to contact with another CNF, measure the length of only the part of the target CNF whose thickness can be measured. The aspect ratio of the portion may be in the above range.
The diameter (thickness) and fiber length of CNF (A) can be measured using a transmission electron microscope. Further, the average of the diameter (thickness) and the average of the fiber length of CNF (A) are obtained by measuring the diameter (thickness) and the fiber length of arbitrarily selected plural CNFs and calculating the average value of each. can get. The average aspect ratio of CNF (A) can be calculated using the average of the diameter (thickness) and the average of the fiber length thus obtained. The diameter (thickness), fiber length, average value, and average aspect ratio of CNF (A) can be specifically calculated by the methods described in Examples.
なお、本実施形態の製造方法では、組成物を調製する際に、CNFに対して過度のストレスが加わらないため、配合前のCNFの繊維径や繊維長は、シート状構造体においてもほぼそのまま維持される。したがって、上述したCNFの繊維径、繊維長、アスペクト比についての数値範囲は、組成物を調製する前のCNF、組成物調製後のCNF、及び、後述する組成物を用いて作製された構造体におけるCNFのいずれについてもそのまま当てはまる。
In the production method of the present embodiment, when the composition is prepared, excessive stress is not applied to CNF. Therefore, the fiber diameter and fiber length of CNF before blending are almost unchanged in the sheet-like structure. Will be maintained. Accordingly, the numerical ranges of the fiber diameter, fiber length, and aspect ratio of the CNF described above are CNF before preparing the composition, CNF after preparing the composition, and a structure manufactured using the composition described below. The same holds true for any of the CNFs.
(組成物中のCNFの含有量)
本発明の一態様で用いる組成物において、CNF(A)の配合量は、当該組成物の全量(100質量%)に対して、前記粒子を形成し易くするとともに、形成された粒子の膜強度を向上させる観点から、好ましくは0.7質量%以上、より好ましくは0.8質量%以上、さらに好ましくは1.0質量%以上、よりさらに好ましくは1.2質量%以上であり、また、前記粒子を形成し易くするように、組成物の粘度を適切に調製する観点から、好ましくは15質量%以下、より好ましくは10質量%以下、さらに好ましくは7質量%以下、よりさらに好ましくは5質量%以下、特に好ましくは3質量%以下である。 (Content of CNF in composition)
In the composition used in one embodiment of the present invention, the compounding amount of CNF (A) is such that the particles are easily formed and the film strength of the formed particles is based on the total amount (100% by mass) of the composition. From the viewpoint of improving the above, preferably 0.7% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, even more preferably 1.2% by mass or more, From the viewpoint of appropriately adjusting the viscosity of the composition so as to facilitate 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, even more preferably 5% by mass or less. % By mass or less, particularly preferably 3% by mass or less.
本発明の一態様で用いる組成物において、CNF(A)の配合量は、当該組成物の全量(100質量%)に対して、前記粒子を形成し易くするとともに、形成された粒子の膜強度を向上させる観点から、好ましくは0.7質量%以上、より好ましくは0.8質量%以上、さらに好ましくは1.0質量%以上、よりさらに好ましくは1.2質量%以上であり、また、前記粒子を形成し易くするように、組成物の粘度を適切に調製する観点から、好ましくは15質量%以下、より好ましくは10質量%以下、さらに好ましくは7質量%以下、よりさらに好ましくは5質量%以下、特に好ましくは3質量%以下である。 (Content of CNF in composition)
In the composition used in one embodiment of the present invention, the compounding amount of CNF (A) is such that the particles are easily formed and the film strength of the formed particles is based on the total amount (100% by mass) of the composition. From the viewpoint of improving the above, preferably 0.7% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, even more preferably 1.2% by mass or more, From the viewpoint of appropriately adjusting the viscosity of the composition so as to facilitate 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, even more preferably 5% by mass or less. % By mass or less, particularly preferably 3% by mass or less.
(水(B))
本発明の一態様で用いる組成物において、水(B)は、そのほとんどが、前記粒子が備える外殻に吸着されているか、又は、前記粒子の外側に存在している。
ただし、水(B)の一部が、前記粒子の内部で有機溶剤(C)とともに内包されていてもよい。 (Water (B))
In the composition used in one embodiment of the present invention, most of the water (B) is adsorbed on the outer shell of the particle or exists outside the particle.
However, a part of the water (B) may be included together with the organic solvent (C) inside the particles.
本発明の一態様で用いる組成物において、水(B)は、そのほとんどが、前記粒子が備える外殻に吸着されているか、又は、前記粒子の外側に存在している。
ただし、水(B)の一部が、前記粒子の内部で有機溶剤(C)とともに内包されていてもよい。 (Water (B))
In the composition used in one embodiment of the present invention, most of the water (B) is adsorbed on the outer shell of the particle or exists outside the particle.
However, a part of the water (B) may be included together with the organic solvent (C) inside the particles.
本発明の一態様で用いる組成物において、適度な粘度を有する組成物に調製するとともに、前記粒子を形成し易くする観点から、水(B)の配合量は、当該組成物の全量(100質量%)に対して、好ましくは15質量%以上、より好ましくは30質量%以上、さらに好ましくは50質量%以上、よりさらに好ましくは60質量%以上であり、また、好ましくは99質量%以下、より好ましくは98.7質量%以下、さらに好ましくは98.5質量%以下である。
In the composition used in one embodiment of the present invention, from the viewpoint of preparing the composition having an appropriate viscosity and facilitating the formation of the particles, the blending amount of water (B) is set to the total amount (100 mass) of the composition. %), 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, and preferably 99% by mass or less. It is preferably at most 98.7% by mass, more preferably at most 98.5% by mass.
本発明の一態様で用いる組成物において、適度な粘度を有する組成物に調製するとともに、前記粒子を形成し易くする観点から、CNF(A)100質量部に対する、水(B)の配合割合は、好ましくは500質量部以上、より好ましくは1000質量部以上、さらに好ましくは2000質量部以上、よりさらに好ましくは3000質量部以上であり、また、好ましくは20000質量部以下、より好ましくは15000質量部以下、さらに好ましくは10000質量部以下である。
In the composition used in one embodiment of the present invention, from the viewpoint of preparing a composition having an appropriate viscosity and facilitating the formation of the particles, the mixing ratio of water (B) to 100 parts by mass of CNF (A) is as follows. , 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 also preferably at most 20,000 parts by mass, more preferably 15,000 parts by mass. The content is more preferably 10,000 parts by mass or less.
(水分散液)
CNF及び水を含む水分散液は、上述したように、セルロース系原料を水に分散させた後、セルロース系原料にせん断力を印加することで得られる分散液をそのまま水分散液として用いることができる。CNFの水分散液として市販されているものを用いることもできる。
水分散液のpHは、水分散液中でCNF(A)の凝集を抑え、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは4以上、より好ましくは5以上、さらに好ましくは6以上であり、また、好ましくは10以下、より好ましくは9以下、さらに好ましくは8以下である。 (Water dispersion)
As described above, an aqueous dispersion containing CNF and water can be used as an aqueous dispersion as it is by dispersing a cellulose-based material in water and then applying a shear force to the cellulose-based material. it can. A commercially available CNF aqueous dispersion can also be used.
The pH of the aqueous dispersion is preferably 4 or more, more preferably 5 or more, from the viewpoint of suppressing aggregation of CNF (A) in the aqueous dispersion and reducing the variation in the shape and size of the formed particles. It is preferably 6 or more, more preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
CNF及び水を含む水分散液は、上述したように、セルロース系原料を水に分散させた後、セルロース系原料にせん断力を印加することで得られる分散液をそのまま水分散液として用いることができる。CNFの水分散液として市販されているものを用いることもできる。
水分散液のpHは、水分散液中でCNF(A)の凝集を抑え、形成される粒子の形状及び大きさのばらつきを小さくする観点から、好ましくは4以上、より好ましくは5以上、さらに好ましくは6以上であり、また、好ましくは10以下、より好ましくは9以下、さらに好ましくは8以下である。 (Water dispersion)
As described above, an aqueous dispersion containing CNF and water can be used as an aqueous dispersion as it is by dispersing a cellulose-based material in water and then applying a shear force to the cellulose-based material. it can. A commercially available CNF aqueous dispersion can also be used.
The pH of the aqueous dispersion is preferably 4 or more, more preferably 5 or more, from the viewpoint of suppressing aggregation of CNF (A) in the aqueous dispersion and reducing the variation in the shape and size of the formed particles. It is preferably 6 or more, more preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
(有機溶剤(C))
有機溶剤(C)としては、水と混ぜた際に水に対して独立した相を形成し、かつ、水に添加して撹拌することで一時的に乳化状態をとり得るという観点から、非水溶系溶媒を用いることが好ましい。非水溶系溶媒を用いることで、界面活性剤等の分散剤を用いることなく、CNFを含む外殻を備える粒子を生成させることができる。 (Organic solvent (C))
As the organic solvent (C), from the viewpoint that it forms an independent phase with water when mixed with water, and can be temporarily emulsified by being added to water and stirring, it is insoluble in water. It is preferable to use a system solvent. By using a non-aqueous solvent, particles having an outer shell containing CNF can be generated without using a dispersant such as a surfactant.
有機溶剤(C)としては、水と混ぜた際に水に対して独立した相を形成し、かつ、水に添加して撹拌することで一時的に乳化状態をとり得るという観点から、非水溶系溶媒を用いることが好ましい。非水溶系溶媒を用いることで、界面活性剤等の分散剤を用いることなく、CNFを含む外殻を備える粒子を生成させることができる。 (Organic solvent (C))
As the organic solvent (C), from the viewpoint that it forms an independent phase with water when mixed with water, and can be temporarily emulsified by being added to water and stirring, it is insoluble in water. It is preferable to use a system solvent. By using a non-aqueous solvent, particles having an outer shell containing CNF can be generated without using a dispersant such as a surfactant.
有機溶剤(C)は、より好ましくは、下記式(1)で表される、25℃における、ハンセン溶解度パラメータの距離Raが5.80MPa1/2以下である。
(前記式中、δDは、前記有機溶剤のハンセン溶解度パラメータの分散成分、
δPは、前記有機溶剤のハンセン溶解度パラメータの極性成分、
δHは、前記有機溶剤のハンセン溶解度パラメータの水素結合成分を示す。) More preferably, the organic solvent (C) has a distance Ra of the Hansen solubility parameter at 25 ° C. represented by the following formula (1) of 5.80 MPa 1/2 or less.
(Wherein δD is a dispersion component of the Hansen solubility parameter of the organic solvent,
δP is a polar component of the Hansen solubility parameter of the organic solvent,
δH indicates a hydrogen bonding component of the Hansen solubility parameter of the organic solvent. )
(前記式中、δDは、前記有機溶剤のハンセン溶解度パラメータの分散成分、
δPは、前記有機溶剤のハンセン溶解度パラメータの極性成分、
δHは、前記有機溶剤のハンセン溶解度パラメータの水素結合成分を示す。) More preferably, the organic solvent (C) has a distance Ra of the Hansen solubility parameter at 25 ° C. represented by the following formula (1) of 5.80 MPa 1/2 or less.
(Wherein δD is a dispersion component of the Hansen solubility parameter of the organic solvent,
δP is a polar component of the Hansen solubility parameter of the organic solvent,
δH indicates a hydrogen bonding component of the Hansen solubility parameter of the organic solvent. )
ハンセン溶解度パラメータは、ヒルデブランド(Hildebrand)によって導入された溶解度パラメータを、ハンセン(Hansen)が、δD(分散成分)、δP(極性成分)、δH(水素結合成分)の3成分に分割し、3次元空間に示したものである。
なお、δD、δP、及びδHの値は、有機溶剤ごとに固有の値であって、特定の計算から算出された値である。
より具体的には、ハンセン溶解度パラメータの定義および計算方法は、「Hansen Solubility Parameters: A Users Handbook(Charles M. Hansen著、CRCプレス、2007年)」に記載されたとおりである。
また、本明細書において、δD、δP、及びδHの値は、計算ソフト「Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03」(Steven Abbott,Charles M. Hansen,Hiroshi Yamamoto著)に含まれる、データベースの値を用いた。 The Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components of Hansen, δD (dispersion component), δP (polar component), and δH (hydrogen bonding component). It is shown in a dimensional space.
Note that the values of δD, δP, and δH are values specific to each organic solvent, and are values calculated from specific calculations.
More specifically, the definition and calculation method of the Hansen solubility parameter are as described in "Hansen Solubility Parameters: A Users Handbook (by Charles M. Hansen, CRC Press, 2007)".
In the present specification, the values of δD, δP, and δH are calculated in a database included in calculation software “Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03” (Steven Abbott, Charles M. Hansen, Hiroshi Yamamoto). Was used.
なお、δD、δP、及びδHの値は、有機溶剤ごとに固有の値であって、特定の計算から算出された値である。
より具体的には、ハンセン溶解度パラメータの定義および計算方法は、「Hansen Solubility Parameters: A Users Handbook(Charles M. Hansen著、CRCプレス、2007年)」に記載されたとおりである。
また、本明細書において、δD、δP、及びδHの値は、計算ソフト「Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03」(Steven Abbott,Charles M. Hansen,Hiroshi Yamamoto著)に含まれる、データベースの値を用いた。 The Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components of Hansen, δD (dispersion component), δP (polar component), and δH (hydrogen bonding component). It is shown in a dimensional space.
Note that the values of δD, δP, and δH are values specific to each organic solvent, and are values calculated from specific calculations.
More specifically, the definition and calculation method of the Hansen solubility parameter are as described in "Hansen Solubility Parameters: A Users Handbook (by Charles M. Hansen, CRC Press, 2007)".
In the present specification, the values of δD, δP, and δH are calculated in a database included in calculation software “Hansen Solubility Parameters in Practice (HSPiP) Version4.1.03” (Steven Abbott, Charles M. Hansen, Hiroshi Yamamoto). Was used.
本発明者らは、配合する有機溶剤(C)の種類によって、前記粒子の形成されやすさに違いがあることに着目した。
そして、それぞれの有機溶剤のハンセン溶解度パラメータを3次元空間にプロットしたところ、当該3次元空間内において、前記粒子が形成される場合に用いた有機溶剤は、ある領域に密集して分布していることがわかった。
そこで、前記粒子が形成された有機溶剤のプロットが全て内側に含まれ、前記粒子が形成されなかった有機溶剤のプロットが外側にくるような、最大の球(相互作用球)を作図したところ、当該球の半径は「5.80MPa1/2」となった。
式(1)から算出される距離Raは、ハンセン溶解度パラメータの3次元空間における、対象となる有機溶剤のプロットと、当該球の中心との距離を意味する。つまり、距離Raが、当該球の半径である「5.80MPa1/2」以下であれば、対象となる有機溶剤のプロットは、当該球の内側に位置しており、前記粒子を形成しやすい溶剤であると判断し得る。 The present inventors have noticed that there is a difference in the ease of forming the particles depending on the type of the organic solvent (C) to be blended.
When the Hansen solubility parameters of the respective organic solvents are plotted in a three-dimensional space, the organic solvents used when the particles are formed are densely distributed in a certain area in the three-dimensional space. I understand.
Therefore, when plotting the largest sphere (interaction sphere), the plot of the organic solvent in which the particles were formed was all included inside, and the plot of the organic solvent in which the particles were not formed was outside, The radius of the sphere was “5.80 MPa 1/2 ”.
The distance Ra calculated from Expression (1) means the distance between the plot of the target organic solvent and the center of the sphere in the three-dimensional space of the Hansen solubility parameter. That is, if the distance Ra is equal to or less than the radius of the sphere, “5.80 MPa 1/2 ”, the plot of the target organic solvent is located inside the sphere, and the particles are easily formed. It can be determined that it is a solvent.
そして、それぞれの有機溶剤のハンセン溶解度パラメータを3次元空間にプロットしたところ、当該3次元空間内において、前記粒子が形成される場合に用いた有機溶剤は、ある領域に密集して分布していることがわかった。
そこで、前記粒子が形成された有機溶剤のプロットが全て内側に含まれ、前記粒子が形成されなかった有機溶剤のプロットが外側にくるような、最大の球(相互作用球)を作図したところ、当該球の半径は「5.80MPa1/2」となった。
式(1)から算出される距離Raは、ハンセン溶解度パラメータの3次元空間における、対象となる有機溶剤のプロットと、当該球の中心との距離を意味する。つまり、距離Raが、当該球の半径である「5.80MPa1/2」以下であれば、対象となる有機溶剤のプロットは、当該球の内側に位置しており、前記粒子を形成しやすい溶剤であると判断し得る。 The present inventors have noticed that there is a difference in the ease of forming the particles depending on the type of the organic solvent (C) to be blended.
When the Hansen solubility parameters of the respective organic solvents are plotted in a three-dimensional space, the organic solvents used when the particles are formed are densely distributed in a certain area in the three-dimensional space. I understand.
Therefore, when plotting the largest sphere (interaction sphere), the plot of the organic solvent in which the particles were formed was all included inside, and the plot of the organic solvent in which the particles were not formed was outside, The radius of the sphere was “5.80 MPa 1/2 ”.
The distance Ra calculated from Expression (1) means the distance between the plot of the target organic solvent and the center of the sphere in the three-dimensional space of the Hansen solubility parameter. That is, if the distance Ra is equal to or less than the radius of the sphere, “5.80 MPa 1/2 ”, the plot of the target organic solvent is located inside the sphere, and the particles are easily formed. It can be determined that it is a solvent.
後述の実施例及び比較例で用いた、代表的な有機溶剤のδD、δP、及びδHの値、並びに、上記式(1)から算出される距離Ra(いずれも単位は「MPa1/2」)を表1に示す。
The values of δD, δP, and δH of typical organic solvents used in Examples and Comparative Examples described later, and the distance Ra calculated from the above formula (1) (all units are “MPa 1/2 ”) ) Are shown in Table 1.
表1に示すように、距離Raが5.80MPa1/2以下の有機溶剤(C)は、ヘプタン、n-ヘキサデカン、メチルエチルケトン、n-ドデカンである。後述の実施例に示すとおり、これらの有機溶剤を用いた場合には、前記粒子が形成しやすいとの結果が得られた。
この結果に鑑みれば、表1に示す有機溶剤以外であっても、距離Raが5.80MPa1/2以下となる有機溶剤(C)であれば、前記粒子が形成しやすくなると推測される。
なお、表1に示された以外の有機溶剤のδD、δP、及びδHの値は、その有機溶剤の分子構造等から算出することができ、もしくは、表1に示すようなδD、δP、及びδHの値が各種文献等により既知である有機溶剤との溶解性についての実験を行うことでも算出可能である。 As shown in Table 1, the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is heptane, n-hexadecane, methyl ethyl ketone, and n-dodecane. As shown in Examples described later, when these organic solvents were used, the result that the particles were easily formed was obtained.
In view of this result, it is presumed that even if the organic solvent (C) has a distance Ra of 5.80 MPa 1/2 or less, particles other than the organic solvents shown in Table 1 can be easily formed.
The values of δD, δP, and δH of the organic solvent other than those shown in Table 1 can be calculated from the molecular structure of the organic solvent or the like, or δD, δP, and The value of δH can also be calculated by conducting an experiment on the solubility with an organic solvent known from various literatures.
この結果に鑑みれば、表1に示す有機溶剤以外であっても、距離Raが5.80MPa1/2以下となる有機溶剤(C)であれば、前記粒子が形成しやすくなると推測される。
なお、表1に示された以外の有機溶剤のδD、δP、及びδHの値は、その有機溶剤の分子構造等から算出することができ、もしくは、表1に示すようなδD、δP、及びδHの値が各種文献等により既知である有機溶剤との溶解性についての実験を行うことでも算出可能である。 As shown in Table 1, the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is heptane, n-hexadecane, methyl ethyl ketone, and n-dodecane. As shown in Examples described later, when these organic solvents were used, the result that the particles were easily formed was obtained.
In view of this result, it is presumed that even if the organic solvent (C) has a distance Ra of 5.80 MPa 1/2 or less, particles other than the organic solvents shown in Table 1 can be easily formed.
The values of δD, δP, and δH of the organic solvent other than those shown in Table 1 can be calculated from the molecular structure of the organic solvent or the like, or δD, δP, and The value of δH can also be calculated by conducting an experiment on the solubility with an organic solvent known from various literatures.
有機溶剤(C)は、単独で用いてもよく、2種以上を併用した混合溶剤としてもよい。
有機溶剤(C)が混合溶剤の場合、混合溶剤の混合比(体積比)から、加重平均のハンセン溶解度パラメータの3成分(δD、δP、δH)の値を求め、上記式(1)から算出した距離Raが5.80MPa1/2以下となることが好ましい。
そのため、単体では距離Raが5.80MPa1/2超となる有機溶剤であっても、距離Raが5.80MPa1/2以下の他の有機溶剤と、適切な体積比で混合し、距離Raを5.80MPa1/2以下となるように調製した混合溶剤とすることで、前記粒子の形成しやすい有機溶剤(C)とすることも可能である。
つまり、単体では距離Raが5.80MPa1/2超となる有機溶剤を取り込んだ粒子を含む組成物を得たい場合には、上記のような混合溶媒を用いることで、調製しやすくなると考えられる。 The organic solvent (C) may be used alone or as a mixed solvent using two or more kinds.
When the organic solvent (C) is a mixed solvent, the values of the three components (δD, δP, δH) of the weighted average Hansen solubility parameter are determined from the mixing ratio (volume ratio) of the mixed solvent, and calculated from the above equation (1). It is preferable that the determined distance Ra be 5.80 MPa 1/2 or less.
Therefore, even if the organic solvent alone has a distance Ra of more than 5.80 MPa 1/2 , it is mixed with another organic solvent having a distance Ra of 5.80 MPa 1/2 or less at an appropriate volume ratio, and the distance Ra is adjusted. Is adjusted to be 5.80 MPa 1/2 or less, whereby the organic solvent (C) in which the particles are easily formed can be obtained.
That is, when it is desired to obtain a composition containing particles incorporating an organic solvent having a distance Ra of more than 5.80 MPa 1/2 in a simple substance, the use of the above-mentioned mixed solvent is considered to facilitate preparation. .
有機溶剤(C)が混合溶剤の場合、混合溶剤の混合比(体積比)から、加重平均のハンセン溶解度パラメータの3成分(δD、δP、δH)の値を求め、上記式(1)から算出した距離Raが5.80MPa1/2以下となることが好ましい。
そのため、単体では距離Raが5.80MPa1/2超となる有機溶剤であっても、距離Raが5.80MPa1/2以下の他の有機溶剤と、適切な体積比で混合し、距離Raを5.80MPa1/2以下となるように調製した混合溶剤とすることで、前記粒子の形成しやすい有機溶剤(C)とすることも可能である。
つまり、単体では距離Raが5.80MPa1/2超となる有機溶剤を取り込んだ粒子を含む組成物を得たい場合には、上記のような混合溶媒を用いることで、調製しやすくなると考えられる。 The organic solvent (C) may be used alone or as a mixed solvent using two or more kinds.
When the organic solvent (C) is a mixed solvent, the values of the three components (δD, δP, δH) of the weighted average Hansen solubility parameter are determined from the mixing ratio (volume ratio) of the mixed solvent, and calculated from the above equation (1). It is preferable that the determined distance Ra be 5.80 MPa 1/2 or less.
Therefore, even if the organic solvent alone has a distance Ra of more than 5.80 MPa 1/2 , it is mixed with another organic solvent having a distance Ra of 5.80 MPa 1/2 or less at an appropriate volume ratio, and the distance Ra is adjusted. Is adjusted to be 5.80 MPa 1/2 or less, whereby the organic solvent (C) in which the particles are easily formed can be obtained.
That is, when it is desired to obtain a composition containing particles incorporating an organic solvent having a distance Ra of more than 5.80 MPa 1/2 in a simple substance, the use of the above-mentioned mixed solvent is considered to facilitate preparation. .
なお、距離Raが5.80MPa1/2以下となる有機溶剤(C)を用いることで、他の有機溶剤を用いる場合に比べて、前記粒子は形成しやすいものと考えられるが、粒子が形成し得るか否かは、さらに、CNF(A)、水(B)及び有機溶剤(C)の配合量や、CNF(A)の形状、及び修飾基の選択によっても変化する。
そのため、距離Raが5.80MPa1/2以下となる有機溶剤(C)を用いるとともに、本明細書の各成分の項目に記載の事項を適宜考慮して、より容易に前記粒子を形成できるように調製することが好ましい。 The use of the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is thought to facilitate the formation of the particles as compared with the case where another organic solvent is used. Whether or not it can be further changed depending on the blending amounts of CNF (A), water (B) and organic solvent (C), the shape of CNF (A), and the selection of the modifying group.
Therefore, while using the organic solvent (C) having the distance Ra of 5.80 MPa 1/2 or less, the particles can be formed more easily by appropriately considering the items described in the item of each component in this specification. It is preferable to prepare it.
そのため、距離Raが5.80MPa1/2以下となる有機溶剤(C)を用いるとともに、本明細書の各成分の項目に記載の事項を適宜考慮して、より容易に前記粒子を形成できるように調製することが好ましい。 The use of the organic solvent (C) having a distance Ra of 5.80 MPa 1/2 or less is thought to facilitate the formation of the particles as compared with the case where another organic solvent is used. Whether or not it can be further changed depending on the blending amounts of CNF (A), water (B) and organic solvent (C), the shape of CNF (A), and the selection of the modifying group.
Therefore, while using the organic solvent (C) having the distance Ra of 5.80 MPa 1/2 or less, the particles can be formed more easily by appropriately considering the items described in the item of each component in this specification. It is preferable to prepare it.
本発明の一態様で用いる有機溶剤(C)は、炭素数20未満の有機溶剤(C1)を含むことが好ましい。
炭素数20未満の有機溶剤(C1)は、CNF(A)に取り込まれ易く、前記粒子が形成され易い。
つまり、炭素数が大きい有機溶剤は、有機溶剤の分子同士が集まり易く、また、粘度が高いため、真球に近い粒子の形成が行われ難くなる。その結果、このような有機溶剤は、セルロースナノファイバー(A)に取り込まれずに、前記粒子の外側に残存する割合が多くなると考えられる。 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 CNF (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.
炭素数20未満の有機溶剤(C1)は、CNF(A)に取り込まれ易く、前記粒子が形成され易い。
つまり、炭素数が大きい有機溶剤は、有機溶剤の分子同士が集まり易く、また、粘度が高いため、真球に近い粒子の形成が行われ難くなる。その結果、このような有機溶剤は、セルロースナノファイバー(A)に取り込まれずに、前記粒子の外側に残存する割合が多くなると考えられる。 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 CNF (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.
上記観点から、有機溶剤(C)中の有機溶剤(C1)の配合割合は、有機溶剤(C)の全量(100質量%)基準で、好ましくは20質量%以上、より好ましくは35質量%以上、さらに好ましくは50質量%以上、よりさらに好ましくは70質量%以上である。
From the above viewpoint, the blending ratio of the organic solvent (C1) in the organic solvent (C) is preferably 20% by mass or more, more preferably 35% by mass or more based on the total amount (100% by mass) of the organic solvent (C). , More preferably 50% by mass or more, even more preferably 70% by mass or more.
本発明の一態様で用いる組成物において、前記粒子を形成し易くする観点から、有機溶剤(C)の配合量は、当該組成物の全量(100質量%)に対して、好ましくは0.05質量%以上、より好ましくは0.1質量%以上、さらに好ましくは0.5質量%以上、よりさらに好ましくは0.8質量%以上であり、また、好ましくは80質量%以下、より好ましくは60質量%以下、さらに好ましくは45質量%以下、よりさらに好ましくは42質量%以下、さらに好ましくは40質量%以下、特に好ましくは38質量%以下である。
In the composition used in one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the amount of the organic solvent (C) is preferably 0.05% with respect to the total amount (100% by mass) of the composition. % By mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less. % By mass, more preferably 45% by mass or less, still more preferably 42% by mass or less, further preferably 40% by mass or less, particularly preferably 38% by mass or less.
(組成物中の有機溶剤の含有量)
本発明の一態様で用いる組成物において、前記粒子を形成し易くする観点から、CNF(A)100質量部に対する、有機溶剤(C)の配合割合は、好ましくは1質量部以上、より好ましくは5質量部以上、さらに好ましくは10質量部以上、よりさらに好ましくは50質量部以上、さらに好ましくは75質量部以上、さらに好ましくは90質量部以上であり、また、好ましくは6000質量部以下、より好ましくは4500質量部以下、さらに好ましくは4000質量部以下、よりさらに好ましくは3500質量部以下である。 (Content of organic solvent in composition)
In the composition used in one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the mixing ratio of the organic solvent (C) to 100 parts by mass of CNF (A) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 50 parts by mass or more, further preferably 75 parts by mass or more, further preferably 90 parts by mass or more, and preferably 6000 parts by mass or less, It is preferably at most 4,500 parts by mass, more preferably at most 4,000 parts by mass, even more preferably at most 3,500 parts by mass.
本発明の一態様で用いる組成物において、前記粒子を形成し易くする観点から、CNF(A)100質量部に対する、有機溶剤(C)の配合割合は、好ましくは1質量部以上、より好ましくは5質量部以上、さらに好ましくは10質量部以上、よりさらに好ましくは50質量部以上、さらに好ましくは75質量部以上、さらに好ましくは90質量部以上であり、また、好ましくは6000質量部以下、より好ましくは4500質量部以下、さらに好ましくは4000質量部以下、よりさらに好ましくは3500質量部以下である。 (Content of organic solvent in composition)
In the composition used in one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the mixing ratio of the organic solvent (C) to 100 parts by mass of CNF (A) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 50 parts by mass or more, further preferably 75 parts by mass or more, further preferably 90 parts by mass or more, and preferably 6000 parts by mass or less, It is preferably at most 4,500 parts by mass, more preferably at most 4,000 parts by mass, even more preferably at most 3,500 parts by mass.
(水と有機溶剤の割合)
本発明の一態様で用いる組成物において、前記粒子を形成し易くする観点から、水(B)と有機溶剤(C)との配合量比〔(B)/(C)〕は、質量比で、好ましくは0.1以上、より好ましくは0.5以上、さらに好ましくは1.0以上、よりさらに好ましくは1.5以上であり、また、好ましくは1000以下、より好ましくは700以下、さらに好ましくは500以下、よりさらに好ましくは300以下、特に好ましくは100以下である。 (Ratio of water and organic solvent)
In the composition used in one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the mixing ratio of water (B) to the organic solvent (C) [(B) / (C)] is expressed as a mass ratio. , Preferably 0.1 or more, more preferably 0.5 or more, further preferably 1.0 or more, even more preferably 1.5 or more, and preferably 1000 or less, more preferably 700 or less, and still more preferably Is 500 or less, more preferably 300 or less, particularly preferably 100 or less.
本発明の一態様で用いる組成物において、前記粒子を形成し易くする観点から、水(B)と有機溶剤(C)との配合量比〔(B)/(C)〕は、質量比で、好ましくは0.1以上、より好ましくは0.5以上、さらに好ましくは1.0以上、よりさらに好ましくは1.5以上であり、また、好ましくは1000以下、より好ましくは700以下、さらに好ましくは500以下、よりさらに好ましくは300以下、特に好ましくは100以下である。 (Ratio of water and organic solvent)
In the composition used in one embodiment of the present invention, from the viewpoint of facilitating the formation of the particles, the mixing ratio of water (B) to the organic solvent (C) [(B) / (C)] is expressed as a mass ratio. , Preferably 0.1 or more, more preferably 0.5 or more, further preferably 1.0 or more, even more preferably 1.5 or more, and preferably 1000 or less, more preferably 700 or less, and still more preferably Is 500 or less, more preferably 300 or less, particularly preferably 100 or less.
(他の成分)
本発明の一態様で用いる組成物において、本発明の効果を損なわない範囲で、成分(A)~(C)以外の他の成分を含有してもよい。
このような他の成分としては、前記組成物の用途に応じて適宜選択されるが、例えば、着色剤、酸化防止剤、pH調整剤、甘味料等が挙げられる。 (Other ingredients)
The composition used in 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 and the like.
本発明の一態様で用いる組成物において、本発明の効果を損なわない範囲で、成分(A)~(C)以外の他の成分を含有してもよい。
このような他の成分としては、前記組成物の用途に応じて適宜選択されるが、例えば、着色剤、酸化防止剤、pH調整剤、甘味料等が挙げられる。 (Other ingredients)
The composition used in 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 and the like.
本発明の実施形態に係る構造体を作製するのに用いる組成物において、界面活性剤の含有量は、構造体において、CNF100質量部に対する界面活性剤の含有量が10質量部未満となる含有量である。
界面活性剤を含む組成物を人体に触れる用途に使用する場合、特に、敏感肌の使用者にとって、当該界面活性剤は浸透剤及び刺激的な刺激物ともなる。また、界面活性剤を含む組成物は、当該組成物の物性の安定性に影響を与える懸念もある。さらに、構造体を上述した流体保持用製品や流体を徐放する製品に適用する場合、構造体の開裂によって放出される流体や膜を通じて放出される流体に界面活性剤が混入する恐れや、界面活性剤が構造体の物性の安定性に影響を与え、流体の保持性が損なわれたりするおそれがある。
そのため、本発明一態様の組成物において、界面活性剤の含有量は少ないほど好ましい。
上記観点から、本発明の一態様で用いる組成物において、界面活性剤の含有量は、CNF(A)の全量100質量部に対して、好ましくは10質量部未満、より好ましくは1質量部未満、さらに好ましくは0.1質量部未満、よりさらに好ましくは0.01質量部未満、特に好ましくは0.001質量部未満、最も好ましくは0質量部である。組成物における界面活性剤の含有量をこのように調整することで、構造体における界面活性剤の含有量を上述した範囲内とすることができる。 In the composition used for producing the structure according to the embodiment of the present invention, the content of the surfactant is such that the content of the surfactant is less than 10 parts by mass relative to 100 parts by mass of CNF in the structure. It is.
When a composition containing a surfactant is used for touching the human body, the surfactant may also be a penetrant and an irritant, especially for users with sensitive skin. Further, there is a concern that the composition containing a surfactant may affect the stability of physical properties of the composition. Further, when the structure is applied to the above-described fluid holding product or a product that releases the fluid slowly, a surfactant may be mixed into a fluid released by cleavage of the structure or a fluid released through a membrane, The activator may affect the stability of the physical properties of the structure and impair the fluid retention.
Therefore, in the composition of one embodiment of the present invention, the content of the surfactant is preferably as small as possible.
From the above viewpoint, in the composition used in one embodiment of the present invention, the content of the surfactant is preferably less than 10 parts by mass, more preferably less than 1 part by mass, based on 100 parts by mass of the total amount of CNF (A). More preferably, the amount is less than 0.1 part by mass, still 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. By adjusting the content of the surfactant in the composition in this manner, the content of the surfactant in the structure can be set within the above-described range.
界面活性剤を含む組成物を人体に触れる用途に使用する場合、特に、敏感肌の使用者にとって、当該界面活性剤は浸透剤及び刺激的な刺激物ともなる。また、界面活性剤を含む組成物は、当該組成物の物性の安定性に影響を与える懸念もある。さらに、構造体を上述した流体保持用製品や流体を徐放する製品に適用する場合、構造体の開裂によって放出される流体や膜を通じて放出される流体に界面活性剤が混入する恐れや、界面活性剤が構造体の物性の安定性に影響を与え、流体の保持性が損なわれたりするおそれがある。
そのため、本発明一態様の組成物において、界面活性剤の含有量は少ないほど好ましい。
上記観点から、本発明の一態様で用いる組成物において、界面活性剤の含有量は、CNF(A)の全量100質量部に対して、好ましくは10質量部未満、より好ましくは1質量部未満、さらに好ましくは0.1質量部未満、よりさらに好ましくは0.01質量部未満、特に好ましくは0.001質量部未満、最も好ましくは0質量部である。組成物における界面活性剤の含有量をこのように調整することで、構造体における界面活性剤の含有量を上述した範囲内とすることができる。 In the composition used for producing the structure according to the embodiment of the present invention, the content of the surfactant is such that the content of the surfactant is less than 10 parts by mass relative to 100 parts by mass of CNF in the structure. It is.
When a composition containing a surfactant is used for touching the human body, the surfactant may also be a penetrant and an irritant, especially for users with sensitive skin. Further, there is a concern that the composition containing a surfactant may affect the stability of physical properties of the composition. Further, when the structure is applied to the above-described fluid holding product or a product that releases the fluid slowly, a surfactant may be mixed into a fluid released by cleavage of the structure or a fluid released through a membrane, The activator may affect the stability of the physical properties of the structure and impair the fluid retention.
Therefore, in the composition of one embodiment of the present invention, the content of the surfactant is preferably as small as possible.
From the above viewpoint, in the composition used in one embodiment of the present invention, the content of the surfactant is preferably less than 10 parts by mass, more preferably less than 1 part by mass, based on 100 parts by mass of the total amount of CNF (A). More preferably, the amount is less than 0.1 part by mass, still 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. By adjusting the content of the surfactant in the composition in this manner, the content of the surfactant in the structure can be set within the above-described range.
また、本発明の一態様で用いる組成物において、CNF(A)以外の多糖類を含有してもよいが、前記粒子の熱的安定性を向上させること、及び、前記粒子を形成し易くする観点から、当該多糖類の含有量は少ないほど好ましい。
上記観点から、本発明の一態様で用いる組成物において、CNF(A)以外の多糖類の含有量は、CNF(A)の全量100質量部に対して、好ましくは10質量部未満、より好ましくは1質量部未満、さらに好ましくは0.1質量部未満、よりさらに好ましくは0.01質量部未満、特に好ましくは0質量部である。組成物における、CNF(A)以外の多糖類の含有量をこのように調整することで、構造体における、CNF(A)以外の多糖類の含有量を上述した範囲内とすることができる。 In the composition used in one embodiment of the present invention, a polysaccharide other than CNF (A) may be contained, but the thermal stability of the particles is improved, and the particles are easily formed. From the viewpoint, the content of the polysaccharide is preferably as small as possible.
From the above viewpoint, in the composition used in one embodiment of the present invention, the content of the polysaccharide other than CNF (A) is preferably less than 10 parts by mass, more preferably less than 10 parts by mass, based on 100 parts by mass of the total amount of CNF (A). Is less than 1 part by mass, more preferably less than 0.1 part by mass, still more preferably less than 0.01 part by mass, particularly preferably 0 part by mass. By adjusting the content of the polysaccharide other than CNF (A) in the composition in this way, the content of the polysaccharide other than CNF (A) in the structure can be within the above-described range.
上記観点から、本発明の一態様で用いる組成物において、CNF(A)以外の多糖類の含有量は、CNF(A)の全量100質量部に対して、好ましくは10質量部未満、より好ましくは1質量部未満、さらに好ましくは0.1質量部未満、よりさらに好ましくは0.01質量部未満、特に好ましくは0質量部である。組成物における、CNF(A)以外の多糖類の含有量をこのように調整することで、構造体における、CNF(A)以外の多糖類の含有量を上述した範囲内とすることができる。 In the composition used in one embodiment of the present invention, a polysaccharide other than CNF (A) may be contained, but the thermal stability of the particles is improved, and the particles are easily formed. From the viewpoint, the content of the polysaccharide is preferably as small as possible.
From the above viewpoint, in the composition used in one embodiment of the present invention, the content of the polysaccharide other than CNF (A) is preferably less than 10 parts by mass, more preferably less than 10 parts by mass, based on 100 parts by mass of the total amount of CNF (A). Is less than 1 part by mass, more preferably less than 0.1 part by mass, still more preferably less than 0.01 part by mass, particularly preferably 0 part by mass. By adjusting the content of the polysaccharide other than CNF (A) in the composition in this way, the content of the polysaccharide other than CNF (A) in the structure can be within the above-described range.
[工程(2)]
工程(2)においては、組成物を支持体上に塗布して塗膜を形成し、当該塗膜を乾燥してシート状構造体とする。工程(2)においては、工程(1)で調製した組成物中の、CNFを含む外殻を備える粒子に過度なストレスがかかるのを回避する観点から、好ましくは、まず組成物を支持体上に供給し(工程(2-1))、次に支持体上の組成物を均一に押し広げて塗布する(工程(2-2))。
(工程(2-1):支持体の一方の面に組成物を供給する工程)
工程(2-1)においては、例えば、組成物の入った容器を傾けて組成物を自重で容器から支持体へと徐々に移動させることにより、CNFを含む外殻を備える粒子を含む組成物を支持体上に供給する。また、ポンプ等を用いて上記組成物を支持体上に供給しても良い。
工程(2-1)における、温度条件、圧力条件、及び、雰囲気条件は、工程(1)で説明したのと同様に設定すればよい。 [Step (2)]
In the step (2), the composition is applied on a support to form a coating film, and the coating film is dried to form a sheet-like structure. In the step (2), the composition is preferably first placed on a support from the viewpoint of avoiding applying excessive stress to the particles having a shell containing CNF in the composition prepared in the step (1). (Step (2-1)), and then spread and spread the composition on the support uniformly (Step (2-2)).
(Step (2-1): Step of Supplying Composition to One Side of Support)
In the step (2-1), for example, by tilting the container containing the composition to gradually move the composition from the container to the support under its own weight, the composition including the particles having the outer shell containing CNF Is supplied on a support. Further, the above composition may be supplied onto the support using a pump or the like.
The temperature condition, pressure condition, and atmosphere condition in the step (2-1) may be set in the same manner as described in the step (1).
工程(2)においては、組成物を支持体上に塗布して塗膜を形成し、当該塗膜を乾燥してシート状構造体とする。工程(2)においては、工程(1)で調製した組成物中の、CNFを含む外殻を備える粒子に過度なストレスがかかるのを回避する観点から、好ましくは、まず組成物を支持体上に供給し(工程(2-1))、次に支持体上の組成物を均一に押し広げて塗布する(工程(2-2))。
(工程(2-1):支持体の一方の面に組成物を供給する工程)
工程(2-1)においては、例えば、組成物の入った容器を傾けて組成物を自重で容器から支持体へと徐々に移動させることにより、CNFを含む外殻を備える粒子を含む組成物を支持体上に供給する。また、ポンプ等を用いて上記組成物を支持体上に供給しても良い。
工程(2-1)における、温度条件、圧力条件、及び、雰囲気条件は、工程(1)で説明したのと同様に設定すればよい。 [Step (2)]
In the step (2), the composition is applied on a support to form a coating film, and the coating film is dried to form a sheet-like structure. In the step (2), the composition is preferably first placed on a support from the viewpoint of avoiding applying excessive stress to the particles having a shell containing CNF in the composition prepared in the step (1). (Step (2-1)), and then spread and spread the composition on the support uniformly (Step (2-2)).
(Step (2-1): Step of Supplying Composition to One Side of Support)
In the step (2-1), for example, by tilting the container containing the composition to gradually move the composition from the container to the support under its own weight, the composition including the particles having the outer shell containing CNF Is supplied on a support. Further, the above composition may be supplied onto the support using a pump or the like.
The temperature condition, pressure condition, and atmosphere condition in the step (2-1) may be set in the same manner as described in the step (1).
(工程(2-2):組成物を支持体に塗布する工程(工程(2-2)))
工程(2-2)においては、工程(2-1)で支持体上に供給された組成物を、塗布装置を用いて支持体上に塗布する。一態様においては、アプリケーターを支持体の平面に沿う方向に沿って、支持体に対して相対移動させ、組成物を支持体に塗布する(工程(2-2))。
ここで、塗膜を形成する際のコーティングギャップは、CNFを含む膜で構成される閉塞空間を良好な形状で十分な数だけ形成するとともに、乾燥に時間を要したり比較的高温での加熱が必要になったりする結果、塗布後の組成物における一部の粒子が、壊れたり消失したりするのを防止する観点から、好ましくは30μm以上、より好ましくは100μm以上、さらに好ましくは150μm以上、よりさらに好ましくは200μm以上であり、また、好ましくは1250μm以下、より好ましくは1000μm以下、さらに好ましくは750μm以下、よりさらに好ましくは500μm以下とする。 (Step (2-2): Step of Applying Composition to Support (Step (2-2)))
In the step (2-2), the composition supplied on the support in the step (2-1) is applied on the support using a coating apparatus. In one embodiment, the composition is applied to the support by moving the applicator relative to the support along a direction along the plane of the support (step (2-2)).
Here, the coating gap at the time of forming the coating film is such that a sufficient number of closed spaces composed of a film containing CNF are formed in a good shape, and it takes time for drying or heating at a relatively high temperature. As a result, some particles in the composition after application are preferably 30 μm or more, more preferably 100 μm or more, further preferably 150 μm or more, from the viewpoint of preventing breakage or disappearance. It is still more preferably 200 μm or more, preferably 1250 μm or less, more preferably 1000 μm or less, further preferably 750 μm or less, and still more preferably 500 μm or less.
工程(2-2)においては、工程(2-1)で支持体上に供給された組成物を、塗布装置を用いて支持体上に塗布する。一態様においては、アプリケーターを支持体の平面に沿う方向に沿って、支持体に対して相対移動させ、組成物を支持体に塗布する(工程(2-2))。
ここで、塗膜を形成する際のコーティングギャップは、CNFを含む膜で構成される閉塞空間を良好な形状で十分な数だけ形成するとともに、乾燥に時間を要したり比較的高温での加熱が必要になったりする結果、塗布後の組成物における一部の粒子が、壊れたり消失したりするのを防止する観点から、好ましくは30μm以上、より好ましくは100μm以上、さらに好ましくは150μm以上、よりさらに好ましくは200μm以上であり、また、好ましくは1250μm以下、より好ましくは1000μm以下、さらに好ましくは750μm以下、よりさらに好ましくは500μm以下とする。 (Step (2-2): Step of Applying Composition to Support (Step (2-2)))
In the step (2-2), the composition supplied on the support in the step (2-1) is applied on the support using a coating apparatus. In one embodiment, the composition is applied to the support by moving the applicator relative to the support along a direction along the plane of the support (step (2-2)).
Here, the coating gap at the time of forming the coating film is such that a sufficient number of closed spaces composed of a film containing CNF are formed in a good shape, and it takes time for drying or heating at a relatively high temperature. As a result, some particles in the composition after application are preferably 30 μm or more, more preferably 100 μm or more, further preferably 150 μm or more, from the viewpoint of preventing breakage or disappearance. It is still more preferably 200 μm or more, preferably 1250 μm or less, more preferably 1000 μm or less, further preferably 750 μm or less, and still more preferably 500 μm or less.
組成物の塗布方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ロールナイフコート法、ブレードコート法、ダイコート法、グラビアコート法、エアーナイフコート法、ディップコート法等が挙げられる。中でも、ナイフコート法、グラビアコート法が好ましい。
工程(2-2)においては、組成物中の、CNFを含む外殻を備える粒子が塗布によって壊れることを回避する観点から、上記粒子の直径よりも大きいギャップを形成し得る治具を用いることが好ましい。この場合、治具が形成するギャップを、CNFを含む外殻を備える粒子の直径の、好ましくは1.5倍以上、より好ましくは5倍以上、さらに好ましくは7.5倍以上、さらにより好ましくは9倍以上であり、好ましくは62.5倍以下、より好ましくは50倍以下、さらに好ましくは37.5倍以下、さらにより好ましくは25倍以下とする。 Examples of the method of applying the composition include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, gravure coating, and air knife coating. And a dip coating method. Among them, a knife coat method and a gravure coat method are preferable.
In the step (2-2), using a jig capable of forming a gap larger than the diameter of the particles having the outer shell containing CNF in the composition from the viewpoint of avoiding the particles having the outer shell containing CNF from being broken by coating. Is preferred. In this case, the gap formed by the jig is preferably 1.5 times or more, more preferably 5 times or more, still more preferably 7.5 times or more, and still more preferably the diameter of the particle having the outer shell containing CNF. Is 9 times or more, preferably 62.5 times or less, more preferably 50 times or less, further preferably 37.5 times or less, and still more preferably 25 times or less.
工程(2-2)においては、組成物中の、CNFを含む外殻を備える粒子が塗布によって壊れることを回避する観点から、上記粒子の直径よりも大きいギャップを形成し得る治具を用いることが好ましい。この場合、治具が形成するギャップを、CNFを含む外殻を備える粒子の直径の、好ましくは1.5倍以上、より好ましくは5倍以上、さらに好ましくは7.5倍以上、さらにより好ましくは9倍以上であり、好ましくは62.5倍以下、より好ましくは50倍以下、さらに好ましくは37.5倍以下、さらにより好ましくは25倍以下とする。 Examples of the method of applying the composition include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, gravure coating, and air knife coating. And a dip coating method. Among them, a knife coat method and a gravure coat method are preferable.
In the step (2-2), using a jig capable of forming a gap larger than the diameter of the particles having the outer shell containing CNF in the composition from the viewpoint of avoiding the particles having the outer shell containing CNF from being broken by coating. Is preferred. In this case, the gap formed by the jig is preferably 1.5 times or more, more preferably 5 times or more, still more preferably 7.5 times or more, and still more preferably the diameter of the particle having the outer shell containing CNF. Is 9 times or more, preferably 62.5 times or less, more preferably 50 times or less, further preferably 37.5 times or less, and still more preferably 25 times or less.
工程(2-2)においては、有機溶剤の揮発を防止する観点から、組成物の温度が、好ましくは45℃以下、より好ましくは40℃以下、さらに好ましくは35℃以下となる環境下で塗布を行う。また、組成物の粘性が高くなりすぎて塗布層が均一に形成できなくなったり、CNFを含む外殻を備える粒子が損傷したりするのを防ぐ観点から、好ましくは5℃以上、より好ましくは10℃以上、さらに好ましくは15℃以上となる環境下で塗布を行う。
工程(2-2)における、圧力条件、及び、雰囲気条件は、工程(1)で説明したのと同様に設定すればよい。 In the step (2-2), from the viewpoint of preventing volatilization of the organic solvent, the composition is applied under an environment in which the temperature of the composition is preferably 45 ° C or lower, more preferably 40 ° C or lower, and further preferably 35 ° C or lower. I do. In addition, from the viewpoint of preventing the viscosity of the composition from becoming too high to form a uniform coating layer or damaging particles having an outer shell containing CNF, it is preferably 5 ° C. or more, more preferably 10 ° C. or more. The coating is performed in an environment of not less than 15 ° C., more preferably not less than 15 ° C.
The pressure condition and the atmosphere condition in the step (2-2) may be set in the same manner as described in the step (1).
工程(2-2)における、圧力条件、及び、雰囲気条件は、工程(1)で説明したのと同様に設定すればよい。 In the step (2-2), from the viewpoint of preventing volatilization of the organic solvent, the composition is applied under an environment in which the temperature of the composition is preferably 45 ° C or lower, more preferably 40 ° C or lower, and further preferably 35 ° C or lower. I do. In addition, from the viewpoint of preventing the viscosity of the composition from becoming too high to form a uniform coating layer or damaging particles having an outer shell containing CNF, it is preferably 5 ° C. or more, more preferably 10 ° C. or more. The coating is performed in an environment of not less than 15 ° C., more preferably not less than 15 ° C.
The pressure condition and the atmosphere condition in the step (2-2) may be set in the same manner as described in the step (1).
なお、ダイコーターのような塗布装置を用いて、組成物を支持体に供給すると同時に塗布を行う(つまり、工程(2-1)と工程(2-2)を同時に行う)ことも可能であるが、この場合は、組成物中の、CNFを含む外殻を備える粒子に過度なストレスが加わらないように、射出条件等を調整することが好ましい。
Note that it is also possible to apply the composition to the support at the same time as applying the composition to the support using a coating apparatus such as a die coater (that is, simultaneously perform the step (2-1) and the step (2-2)). However, in this case, it is preferable to adjust the injection conditions and the like so that excessive stress is not applied to particles having an outer shell containing CNF in the composition.
(工程(2-3):支持体上に塗布された組成物を乾燥する工程)
工程(2-3)においては、支持体上に塗布された組成物の層を加熱等により乾燥することにより、CNFを含む膜で構成された複数の閉塞空間を備える層を形成する。具体的には、支持体上に塗布された組成物の層を、ヒーター等によって乾燥し、粒子の内部に取り込まれているものも含めて、組成物から水や有機溶剤を蒸発させることにより、CNFを含む膜で構成された複数の閉塞空間を備える層を形成する。
工程(2-3)においてCNFを含む膜で構成される閉塞空間が形成される機構は、必ずしもこれに限られるものではないが、次のように推測される。つまり、組成物の層から水と有機溶剤が揮発する過程において、隣接する粒子同士で粒子の一部が固着したり、一部の粒子がより安定な位置へ移動したりして、粒子間の隙間が徐々になくなり、その一方、有機溶剤と水との界面に集まったCNFが安定に存在するため、CNFを含む膜が破壊されることなく、最終的に密な閉塞空間が形成されるものと推測される。 (Step (2-3): drying the composition applied on the support)
In the step (2-3), a layer having a plurality of closed spaces composed of a film containing CNF is formed by drying the layer of the composition applied on the support by heating or the like. Specifically, the layer of the composition applied on the support is dried by a heater or the like, and by evaporating water and an organic solvent from the composition, including those incorporated into the particles, A layer having a plurality of closed spaces formed of a film containing CNF is formed.
In the step (2-3), the mechanism for forming the closed space composed of the membrane containing CNF is not necessarily limited to this, but is presumed as follows. In other words, in the process of evaporating water and the organic solvent from the layer of the composition, some of the particles are fixed between adjacent particles, or some of the particles move to a more stable position, and between the particles. The gap gradually disappears, while the CNF gathered at the interface between the organic solvent and water is stably present, so that the CNF-containing film is not destroyed and a tightly closed space is finally formed. It is presumed.
工程(2-3)においては、支持体上に塗布された組成物の層を加熱等により乾燥することにより、CNFを含む膜で構成された複数の閉塞空間を備える層を形成する。具体的には、支持体上に塗布された組成物の層を、ヒーター等によって乾燥し、粒子の内部に取り込まれているものも含めて、組成物から水や有機溶剤を蒸発させることにより、CNFを含む膜で構成された複数の閉塞空間を備える層を形成する。
工程(2-3)においてCNFを含む膜で構成される閉塞空間が形成される機構は、必ずしもこれに限られるものではないが、次のように推測される。つまり、組成物の層から水と有機溶剤が揮発する過程において、隣接する粒子同士で粒子の一部が固着したり、一部の粒子がより安定な位置へ移動したりして、粒子間の隙間が徐々になくなり、その一方、有機溶剤と水との界面に集まったCNFが安定に存在するため、CNFを含む膜が破壊されることなく、最終的に密な閉塞空間が形成されるものと推測される。 (Step (2-3): drying the composition applied on the support)
In the step (2-3), a layer having a plurality of closed spaces composed of a film containing CNF is formed by drying the layer of the composition applied on the support by heating or the like. Specifically, the layer of the composition applied on the support is dried by a heater or the like, and by evaporating water and an organic solvent from the composition, including those incorporated into the particles, A layer having a plurality of closed spaces formed of a film containing CNF is formed.
In the step (2-3), the mechanism for forming the closed space composed of the membrane containing CNF is not necessarily limited to this, but is presumed as follows. In other words, in the process of evaporating water and the organic solvent from the layer of the composition, some of the particles are fixed between adjacent particles, or some of the particles move to a more stable position, and between the particles. The gap gradually disappears, while the CNF gathered at the interface between the organic solvent and water is stably present, so that the CNF-containing film is not destroyed and a tightly closed space is finally formed. It is presumed.
工程(2-3)においては、好ましくは90℃以上、より好ましくは100℃以上、さらに好ましくは110℃以上であり、また、好ましくは150℃以下、より好ましくは140℃以下、さらに好ましくは130℃以下で乾燥を行う。90℃以上で乾燥することにより、水と有機溶剤が速やかに除去され、良好な形状の閉塞空間を形成しやすくなる。150℃以下で乾燥することにより、閉塞空間の形状や大きさが不均一になったり、支持体が変形したりするのを防止しやすくなる。
工程(2-3)における、圧力条件、及び、雰囲気条件は、工程(1)で説明したのと同様に設定すればよい。 In the step (2-3), the temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower. Dry below ℃. By drying at 90 ° C. or higher, water and the organic solvent are promptly removed, and a closed space having a good shape is easily formed. By drying at 150 ° C. or less, it becomes easy to prevent the shape and size of the closed space from becoming uneven and the support from being deformed.
The pressure condition and the atmosphere condition in the step (2-3) may be set in the same manner as described in the step (1).
工程(2-3)における、圧力条件、及び、雰囲気条件は、工程(1)で説明したのと同様に設定すればよい。 In the step (2-3), the temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower. Dry below ℃. By drying at 90 ° C. or higher, water and the organic solvent are promptly removed, and a closed space having a good shape is easily formed. By drying at 150 ° C. or less, it becomes easy to prevent the shape and size of the closed space from becoming uneven and the support from being deformed.
The pressure condition and the atmosphere condition in the step (2-3) may be set in the same manner as described in the step (1).
工程(2-3)においては、水と有機溶剤が除去されずに残存して、閉塞空間の形状が崩れるのを防止する観点から、好ましくは10秒以上、より好ましくは30秒以上、さらに好ましくは1分以上、よりさらに好ましくは5分以上、よりさらに好ましくは10分以上、また、好ましくは2時間以下、より好ましくは1時間以下、さらに好ましくは30分以下の時間をかけて乾燥する。
In the step (2-3), from the viewpoint of preventing water and the organic solvent from remaining without being removed and disturbing the shape of the closed space, it is preferably at least 10 seconds, more preferably at least 30 seconds, even more preferably. Is dried for 1 minute or more, more preferably 5 minutes or more, even more preferably 10 minutes or more, and preferably 2 hours or less, more preferably 1 hour or less, and even more preferably 30 minutes or less.
上述した製造方法によって上記構造体を作製すると、界面活性剤などの分散剤を用いずとも、CNFを含む外殻を備える粒子を含む組成物を生成することができ、この組成物を用いることで、構造体におけるCNF含有率を高くすることができる。したがって、本実施形態の構造体を、上述した流体保持用製品や徐放性を有する製品に適用した場合に、多くの流体を構造体内部に保持することができ、しかも、外部へ放出される流体に、不要な成分が混入するのを防ぎやすくなる。
When the above structure is produced by the above-described production method, a composition including particles having an outer shell containing CNF can be produced without using a dispersant such as a surfactant. In addition, the CNF content in the structure can be increased. Therefore, when the structure of the present embodiment is applied to the above-described fluid holding product or a product having a sustained release property, a large amount of fluid can be held inside the structure, and furthermore, discharged to the outside. It becomes easier to prevent unnecessary components from being mixed into the fluid.
本発明について、以下の実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、以下の製造例及び実施例における物性値は、以下の方法により測定した値である。
The present invention will be described specifically with reference to the following examples, but the present invention is not limited to the following examples. The physical properties in the following Production Examples and Examples are values measured by the following methods.
<CNFの直径(太さ)の平均、長さの平均、平均アスペクト比>
透過型電子顕微鏡(カールツァイス社製、製品名「LEO912」)を用いて、任意に選択した10本のCNFの直径(太さ)及び長さを測定し、10本の平均値を、対象となるCNFの「直径(太さ)の平均」及び「長さの平均」とした。また、「長さの平均/直径(太さ)の平均」を平均アスペクト比とした。
<水分散液、組成物のpH>
23℃、相対湿度50%の環境下、コンパクトpHメータ(株式会社堀場アドバンスドテクノ製、製品名「LAQUAtwin pH-22B」)を用いて、pH4.01標準液とpH6.86標準液の2点校正を行った後、平面センサ全体を覆うように試料を滴下して測定した。 <Average of CNF diameter (thickness), average of length, average aspect ratio>
Using a transmission electron microscope (manufactured by Carl Zeiss, product name "LEO912"), the diameter (thickness) and length of 10 CNFs arbitrarily selected are measured, and the average value of the 10 CNFs is taken as an object. The "average of diameter (thickness)" and "average of length" of the resulting CNF. The “average length / average diameter (thickness)” was defined as the average aspect ratio.
<Aqueous dispersion, pH of composition>
Two-point calibration of pH 4.01 standard solution and pH 6.86 standard solution using a compact pH meter (product name “LAQUAtwin pH-22B” manufactured by HORIBA Advanced Techno Co., Ltd.) under an environment of 23 ° C. and 50% relative humidity. After the measurement, the sample was dropped and measured so as to cover the entire flat sensor.
透過型電子顕微鏡(カールツァイス社製、製品名「LEO912」)を用いて、任意に選択した10本のCNFの直径(太さ)及び長さを測定し、10本の平均値を、対象となるCNFの「直径(太さ)の平均」及び「長さの平均」とした。また、「長さの平均/直径(太さ)の平均」を平均アスペクト比とした。
<水分散液、組成物のpH>
23℃、相対湿度50%の環境下、コンパクトpHメータ(株式会社堀場アドバンスドテクノ製、製品名「LAQUAtwin pH-22B」)を用いて、pH4.01標準液とpH6.86標準液の2点校正を行った後、平面センサ全体を覆うように試料を滴下して測定した。 <Average of CNF diameter (thickness), average of length, average aspect ratio>
Using a transmission electron microscope (manufactured by Carl Zeiss, product name "LEO912"), the diameter (thickness) and length of 10 CNFs arbitrarily selected are measured, and the average value of the 10 CNFs is taken as an object. The "average of diameter (thickness)" and "average of length" of the resulting CNF. The “average length / average diameter (thickness)” was defined as the average aspect ratio.
<Aqueous dispersion, pH of composition>
Two-point calibration of pH 4.01 standard solution and pH 6.86 standard solution using a compact pH meter (product name “LAQUAtwin pH-22B” manufactured by HORIBA Advanced Techno Co., Ltd.) under an environment of 23 ° C. and 50% relative humidity. After the measurement, the sample was dropped and measured so as to cover the entire flat sensor.
(実施例1)
1.組成物1の調製
組成物1の調製に際し、下記の市販品のCNFを含む水分散液(1)を使用した。
・水分散液(1)製品名「BiNFi-s AMa10002」、株式会社スギノマシン製。直径(太さ)の平均=76.8nm、長さの平均=1.4μm、平均アスペクト比=18.2である、機械処理型のCNFを2質量%含む水分散液。
水分散液(1)は、CNF100質量部に対して、水を4900質量部含有するものであり、水分散液(1)のpH=7.0であった。
水分散液(1)5000.0質量部(CNF100.0質量部)を容器に投入し、超高速マルチ攪拌システム(プライミクス社製、製品名「ラボ・リューション(登録商標)」、撹拌羽:ホモディスパー(同社製、羽の直径35mm))を用いて、23℃の水分散液を、回転数3000rpmで撹拌した。撹拌開始後、n-ドデカンを、水分散液の全量100質量部に対して、10秒毎に5質量部の速さで添加した。上記水分散液5000.0質量部(CNF100.0質量部)に対して、n-ドデカンが100質量部となるまでn-ドデカンの添加を続け、撹拌開始から10分経過後に撹拌を終了し、CNFを含む外殻を備える粒子を含む組成物1を調製した。組成物1を調製する際に界面活性剤は使用しなかった。 (Example 1)
1. Preparation of Composition 1 In preparing Composition 1, the following aqueous dispersion (1) containing CNF was used.
Aqueous dispersion (1) Product name "BiNFi-s AMa10002", manufactured by Sugino Machine Co., Ltd. An aqueous dispersion containing 2% by mass of mechanically treated CNF having an average diameter (thickness) of 76.8 nm, an average length of 1.4 μm, and an average aspect ratio of 18.2.
The aqueous dispersion (1) contained 4900 parts by mass of water with respect to 100 parts by mass of CNF, and the pH of the aqueous dispersion (1) was 7.0.
5000.0 parts by mass of the aqueous dispersion (1) (100.0 parts by mass of CNF) was charged into a container, and an ultra-high-speed multi-stirring system (manufactured by Primix Co., product name "Lab-Ruution (registered trademark)"; Using a homodisper (manufactured by the company, blade diameter: 35 mm), the aqueous dispersion at 23 ° C. was stirred at a rotation speed of 3000 rpm. After the start of stirring, n-dodecane was 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. With respect to 5000.0 parts by mass of the aqueous dispersion (100.0 parts by mass of CNF), the addition of n-dodecane was continued until the amount of n-dodecane became 100 parts by mass, and the stirring was terminated 10 minutes after the start of stirring, Composition 1 comprising particles with an outer shell containing CNF was prepared. No surfactant was used in preparing Composition 1.
1.組成物1の調製
組成物1の調製に際し、下記の市販品のCNFを含む水分散液(1)を使用した。
・水分散液(1)製品名「BiNFi-s AMa10002」、株式会社スギノマシン製。直径(太さ)の平均=76.8nm、長さの平均=1.4μm、平均アスペクト比=18.2である、機械処理型のCNFを2質量%含む水分散液。
水分散液(1)は、CNF100質量部に対して、水を4900質量部含有するものであり、水分散液(1)のpH=7.0であった。
水分散液(1)5000.0質量部(CNF100.0質量部)を容器に投入し、超高速マルチ攪拌システム(プライミクス社製、製品名「ラボ・リューション(登録商標)」、撹拌羽:ホモディスパー(同社製、羽の直径35mm))を用いて、23℃の水分散液を、回転数3000rpmで撹拌した。撹拌開始後、n-ドデカンを、水分散液の全量100質量部に対して、10秒毎に5質量部の速さで添加した。上記水分散液5000.0質量部(CNF100.0質量部)に対して、n-ドデカンが100質量部となるまでn-ドデカンの添加を続け、撹拌開始から10分経過後に撹拌を終了し、CNFを含む外殻を備える粒子を含む組成物1を調製した。組成物1を調製する際に界面活性剤は使用しなかった。 (Example 1)
1. Preparation of Composition 1 In preparing Composition 1, the following aqueous dispersion (1) containing CNF was used.
Aqueous dispersion (1) Product name "BiNFi-s AMa10002", manufactured by Sugino Machine Co., Ltd. An aqueous dispersion containing 2% by mass of mechanically treated CNF having an average diameter (thickness) of 76.8 nm, an average length of 1.4 μm, and an average aspect ratio of 18.2.
The aqueous dispersion (1) contained 4900 parts by mass of water with respect to 100 parts by mass of CNF, and the pH of the aqueous dispersion (1) was 7.0.
5000.0 parts by mass of the aqueous dispersion (1) (100.0 parts by mass of CNF) was charged into a container, and an ultra-high-speed multi-stirring system (manufactured by Primix Co., product name "Lab-Ruution (registered trademark)"; Using a homodisper (manufactured by the company, blade diameter: 35 mm), the aqueous dispersion at 23 ° C. was stirred at a rotation speed of 3000 rpm. After the start of stirring, n-dodecane was 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. With respect to 5000.0 parts by mass of the aqueous dispersion (100.0 parts by mass of CNF), the addition of n-dodecane was continued until the amount of n-dodecane became 100 parts by mass, and the stirring was terminated 10 minutes after the start of stirring, Composition 1 comprising particles with an outer shell containing CNF was prepared. No surfactant was used in preparing Composition 1.
2.シート状構造体1の作製
組成物1を、厚さ50μmのポリエチレンテレフタレートフィルム(東洋紡株式会社製コスモシャイン(登録商標)、品番「A4100」、厚さ:50μm)の易接着層面に静かに載置し、アプリケーター(コーティングギャップ:254μm(10mil))を用いて組成物1を上記フィルムに塗布した。さらに、120℃で10分間加熱して乾燥することにより、シート状構造体1を作製した。
組成物1の調製から塗布までの工程は、全て、空気雰囲気中で、大気圧下、23℃の条件で行った。この後、120℃で10分間加熱して乾燥することにより、シート状構造体1を作製した。 2. Preparation of sheet-like structure 1 Composition 1 is gently placed on a 50 μm-thick polyethylene terephthalate film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 μm) with easy adhesion. Then, Composition 1 was applied to the film using an applicator (coating gap: 254 μm (10 mil)). Furthermore, the sheet-like structure 1 was produced by heating and drying at 120 ° C. for 10 minutes.
All steps from the preparation of the composition 1 to the application were performed in an air atmosphere at atmospheric pressure and 23 ° C. Thereafter, the sheet-shaped structure 1 was produced by heating and drying at 120 ° C. for 10 minutes.
組成物1を、厚さ50μmのポリエチレンテレフタレートフィルム(東洋紡株式会社製コスモシャイン(登録商標)、品番「A4100」、厚さ:50μm)の易接着層面に静かに載置し、アプリケーター(コーティングギャップ:254μm(10mil))を用いて組成物1を上記フィルムに塗布した。さらに、120℃で10分間加熱して乾燥することにより、シート状構造体1を作製した。
組成物1の調製から塗布までの工程は、全て、空気雰囲気中で、大気圧下、23℃の条件で行った。この後、120℃で10分間加熱して乾燥することにより、シート状構造体1を作製した。 2. Preparation of sheet-like structure 1 Composition 1 is gently placed on a 50 μm-thick polyethylene terephthalate film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 μm) with easy adhesion. Then, Composition 1 was applied to the film using an applicator (coating gap: 254 μm (10 mil)). Furthermore, the sheet-like structure 1 was produced by heating and drying at 120 ° C. for 10 minutes.
All steps from the preparation of the composition 1 to the application were performed in an air atmosphere at atmospheric pressure and 23 ° C. Thereafter, the sheet-shaped structure 1 was produced by heating and drying at 120 ° C. for 10 minutes.
(実施例2~5)
n-ドデカンの総添加量を、それぞれ、500質量部、1000質量部、2000質量部、3000質量部に変えた以外は、実施例1と同じ手順でCNFを含む外殻を備える粒子を含む組成物2~5を調製した。そして、それぞれ、組成物1に代えて組成物2~5を用いた以外は実施例1と同じ手順でシート状構造体2~5を作製した。 (Examples 2 to 5)
Composition containing particles having an outer shell containing CNF in the same procedure as in Example 1, except that the total amount of n-dodecane was changed to 500 parts by mass, 1000 parts by mass, 2000 parts by mass, and 3000 parts by mass, respectively. Products 2 to 5 were prepared. Then, sheet-like structures 2 to 5 were produced in the same procedure as in Example 1 except that compositions 2 to 5 were used instead of composition 1.
n-ドデカンの総添加量を、それぞれ、500質量部、1000質量部、2000質量部、3000質量部に変えた以外は、実施例1と同じ手順でCNFを含む外殻を備える粒子を含む組成物2~5を調製した。そして、それぞれ、組成物1に代えて組成物2~5を用いた以外は実施例1と同じ手順でシート状構造体2~5を作製した。 (Examples 2 to 5)
Composition containing particles having an outer shell containing CNF in the same procedure as in Example 1, except that the total amount of n-dodecane was changed to 500 parts by mass, 1000 parts by mass, 2000 parts by mass, and 3000 parts by mass, respectively. Products 2 to 5 were prepared. Then, sheet-like structures 2 to 5 were produced in the same procedure as in Example 1 except that compositions 2 to 5 were used instead of composition 1.
(実施例6)
アプリケーターのコーティングギャップを762μm(30mil)に変更した以外は実施例1と同じ手順で、組成物1を上記ポリエチレンテレフタレートフィルムの易接着層面に塗布した。さらに、乾燥時間を20分に変更した以外は実施例5と同じ手順で、シート状構造体6を作製した。 (Example 6)
Composition 1 was applied to the easy-adhesion layer surface of the polyethylene terephthalate film in the same procedure as in Example 1 except that the coating gap of the applicator was changed to 762 μm (30 mil). Further, a sheet-like structure 6 was produced in the same procedure as in Example 5, except that the drying time was changed to 20 minutes.
アプリケーターのコーティングギャップを762μm(30mil)に変更した以外は実施例1と同じ手順で、組成物1を上記ポリエチレンテレフタレートフィルムの易接着層面に塗布した。さらに、乾燥時間を20分に変更した以外は実施例5と同じ手順で、シート状構造体6を作製した。 (Example 6)
Composition 1 was applied to the easy-adhesion layer surface of the polyethylene terephthalate film in the same procedure as in Example 1 except that the coating gap of the applicator was changed to 762 μm (30 mil). Further, a sheet-like structure 6 was produced in the same procedure as in Example 5, except that the drying time was changed to 20 minutes.
(実施例7~9)
n-ドデカン100質量部に代えて、それぞれ、メチルエチルケトン(MEK)100質量部、ヘプタン100質量部、n-ヘキサデカン100質量部を用いた以外は、実施例1と同様の手順でCNFを含む外殻を備える粒子を含む組成物7~9を調製した。そして、それぞれ、組成物1に代えて組成物7~9を用いた以外は、実施例1と同じ手順でシート状構造体7~9を作製した。 (Examples 7 to 9)
An outer shell containing CNF in the same procedure as in Example 1 except that 100 parts by mass of methyl ethyl ketone (MEK), 100 parts by mass of heptane, and 100 parts by mass of n-hexadecane were used instead of 100 parts by mass of n-dodecane, respectively. Compositions 7 to 9 containing particles comprising were prepared. Then, sheet-like structures 7 to 9 were produced in the same procedure as in Example 1 except that compositions 7 to 9 were used instead of composition 1, respectively.
n-ドデカン100質量部に代えて、それぞれ、メチルエチルケトン(MEK)100質量部、ヘプタン100質量部、n-ヘキサデカン100質量部を用いた以外は、実施例1と同様の手順でCNFを含む外殻を備える粒子を含む組成物7~9を調製した。そして、それぞれ、組成物1に代えて組成物7~9を用いた以外は、実施例1と同じ手順でシート状構造体7~9を作製した。 (Examples 7 to 9)
An outer shell containing CNF in the same procedure as in Example 1 except that 100 parts by mass of methyl ethyl ketone (MEK), 100 parts by mass of heptane, and 100 parts by mass of n-hexadecane were used instead of 100 parts by mass of n-dodecane, respectively. Compositions 7 to 9 containing particles comprising were prepared. Then, sheet-like structures 7 to 9 were produced in the same procedure as in Example 1 except that compositions 7 to 9 were used instead of composition 1, respectively.
(実施例10)
n-ドデカンの添加総量を10質量部に変えた以外は、実施例1と同様の手順でCNFを含む外殻を備える粒子を含む組成物10を調製した。そして、組成物1に代えて組成物10を用いた以外は、実施例1と同じ手順でシート状構造体10を作製した。 (Example 10)
Composition 10 containing particles having an outer shell containing CNF was prepared in the same manner as in Example 1, except that the total amount of n-dodecane was changed to 10 parts by mass. Then, a sheet-like structure 10 was produced in the same procedure as in Example 1, except that the composition 10 was used instead of the composition 1.
n-ドデカンの添加総量を10質量部に変えた以外は、実施例1と同様の手順でCNFを含む外殻を備える粒子を含む組成物10を調製した。そして、組成物1に代えて組成物10を用いた以外は、実施例1と同じ手順でシート状構造体10を作製した。 (Example 10)
Composition 10 containing particles having an outer shell containing CNF was prepared in the same manner as in Example 1, except that the total amount of n-dodecane was changed to 10 parts by mass. Then, a sheet-like structure 10 was produced in the same procedure as in Example 1, except that the composition 10 was used instead of the composition 1.
(実施例11)
1.組成物11の調製
組成物11の調製に際し、下記の市販品のCNFを含む水分散液(2)を使用した。
・水分散液(2):製品名「TEMPO酸化CNF」、日本製紙株式会社製。直径(太さ)の平均=3.8nm、長さの平均=0.7μm、平均アスペクト比=184である、化学処理型のセルロースナノファイバーを1質量%含む水分散液。
水分散液(2)は、セルロースナノファイバー100質量部に対して、水を9900質量部含有するものであり、水分散液(2)のpH=7.0であった。
水分散液(2)5000.0質量部(CNF100.0質量部)を容器に投入し、超高速マルチ攪拌システム(プライミクス社製、製品名「ラボ・リューション(登録商標)」、撹拌羽:ホモディスパー(同社製、羽の直径35mm))を用いて、23℃の水分散液を、回転数3000rpmで撹拌した。撹拌開始後、n-ドデカンを10秒毎に5質量部の速さで添加した。上記水分散液5000.0質量部(CNF100.0質量部)に対して、n-ドデカンが100質量部となるまでn-ドデカンの添加を続け、撹拌開始から10分経過後に撹拌を終了し、CNFを含む外殻を備える粒子を含む組成物11を調製した。 (Example 11)
1. Preparation of Composition 11 In preparing Composition 11, the following aqueous dispersion (2) containing CNF was used.
-Aqueous dispersion (2): Product name "TEMPO oxidized CNF", manufactured by Nippon Paper Industries. An aqueous dispersion containing 1% by mass of chemically treated cellulose nanofibers having an average diameter (thickness) of 3.8 nm, an average length of 0.7 μm, and an average aspect ratio of 184.
The aqueous dispersion (2) contained 9900 parts by mass of water with respect to 100 parts by mass of the cellulose nanofibers, and the pH of the aqueous dispersion (2) was 7.0.
5000.0 parts by mass of the aqueous dispersion (2) (100.0 parts by mass of CNF) is charged into a container, and an ultra-high-speed multi-stirring system (manufactured by Primix Co., product name "Lab-Ruution (registered trademark)", stirring blade: Using a homodisper (manufactured by the company, blade diameter: 35 mm), the aqueous dispersion at 23 ° C. was stirred at a rotation speed of 3000 rpm. After the start of stirring, n-dodecane was added at a rate of 5 parts by mass every 10 seconds. With respect to 5000.0 parts by mass of the aqueous dispersion (100.0 parts by mass of CNF), the addition of n-dodecane was continued until the amount of n-dodecane became 100 parts by mass, and the stirring was terminated 10 minutes after the start of stirring, Composition 11 was prepared comprising particles with an outer shell comprising CNF.
1.組成物11の調製
組成物11の調製に際し、下記の市販品のCNFを含む水分散液(2)を使用した。
・水分散液(2):製品名「TEMPO酸化CNF」、日本製紙株式会社製。直径(太さ)の平均=3.8nm、長さの平均=0.7μm、平均アスペクト比=184である、化学処理型のセルロースナノファイバーを1質量%含む水分散液。
水分散液(2)は、セルロースナノファイバー100質量部に対して、水を9900質量部含有するものであり、水分散液(2)のpH=7.0であった。
水分散液(2)5000.0質量部(CNF100.0質量部)を容器に投入し、超高速マルチ攪拌システム(プライミクス社製、製品名「ラボ・リューション(登録商標)」、撹拌羽:ホモディスパー(同社製、羽の直径35mm))を用いて、23℃の水分散液を、回転数3000rpmで撹拌した。撹拌開始後、n-ドデカンを10秒毎に5質量部の速さで添加した。上記水分散液5000.0質量部(CNF100.0質量部)に対して、n-ドデカンが100質量部となるまでn-ドデカンの添加を続け、撹拌開始から10分経過後に撹拌を終了し、CNFを含む外殻を備える粒子を含む組成物11を調製した。 (Example 11)
1. Preparation of Composition 11 In preparing Composition 11, the following aqueous dispersion (2) containing CNF was used.
-Aqueous dispersion (2): Product name "TEMPO oxidized CNF", manufactured by Nippon Paper Industries. An aqueous dispersion containing 1% by mass of chemically treated cellulose nanofibers having an average diameter (thickness) of 3.8 nm, an average length of 0.7 μm, and an average aspect ratio of 184.
The aqueous dispersion (2) contained 9900 parts by mass of water with respect to 100 parts by mass of the cellulose nanofibers, and the pH of the aqueous dispersion (2) was 7.0.
5000.0 parts by mass of the aqueous dispersion (2) (100.0 parts by mass of CNF) is charged into a container, and an ultra-high-speed multi-stirring system (manufactured by Primix Co., product name "Lab-Ruution (registered trademark)", stirring blade: Using a homodisper (manufactured by the company, blade diameter: 35 mm), the aqueous dispersion at 23 ° C. was stirred at a rotation speed of 3000 rpm. After the start of stirring, n-dodecane was added at a rate of 5 parts by mass every 10 seconds. With respect to 5000.0 parts by mass of the aqueous dispersion (100.0 parts by mass of CNF), the addition of n-dodecane was continued until the amount of n-dodecane became 100 parts by mass, and the stirring was terminated 10 minutes after the start of stirring, Composition 11 was prepared comprising particles with an outer shell comprising CNF.
2.シート状構造体11の作製
組成物11を、厚さ50μmのポリエチレンテレフタレートフィルム(東洋紡株式会社製コスモシャイン(登録商標)、品番「A4100」、厚さ:50μm)の易接着層面に静かに載置し、アプリケーター(コーティングギャップ:254μm(10mil))を用いて組成物10を上記フィルムに塗布し、さらに、120℃で10分間加熱して乾燥することにより、シート状構造体11を作製した。
組成物11の調製から塗布までの工程は、全て、空気雰囲気中で、大気圧下、23℃の条件で行った。この後、120℃で10分間加熱して乾燥することにより、シート状構造体11を作製した。 2. Preparation of sheet-like structure 11 The composition 11 is gently placed on a 50 μm-thick polyethylene terephthalate film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 μm) on an easily adhesive layer surface. Then, the composition 10 was applied to the above film using an applicator (coating gap: 254 μm (10 mil)), and further heated at 120 ° C. for 10 minutes and dried to produce a sheet-like structure 11.
All steps from the preparation of the composition 11 to the application were performed in an air atmosphere at atmospheric pressure and 23 ° C. Then, the sheet-like structure 11 was produced by heating and drying at 120 ° C. for 10 minutes.
組成物11を、厚さ50μmのポリエチレンテレフタレートフィルム(東洋紡株式会社製コスモシャイン(登録商標)、品番「A4100」、厚さ:50μm)の易接着層面に静かに載置し、アプリケーター(コーティングギャップ:254μm(10mil))を用いて組成物10を上記フィルムに塗布し、さらに、120℃で10分間加熱して乾燥することにより、シート状構造体11を作製した。
組成物11の調製から塗布までの工程は、全て、空気雰囲気中で、大気圧下、23℃の条件で行った。この後、120℃で10分間加熱して乾燥することにより、シート状構造体11を作製した。 2. Preparation of sheet-like structure 11 The composition 11 is gently placed on a 50 μm-thick polyethylene terephthalate film (Cosmoshine (registered trademark) manufactured by Toyobo Co., Ltd., product number “A4100”, thickness: 50 μm) on an easily adhesive layer surface. Then, the composition 10 was applied to the above film using an applicator (coating gap: 254 μm (10 mil)), and further heated at 120 ° C. for 10 minutes and dried to produce a sheet-like structure 11.
All steps from the preparation of the composition 11 to the application were performed in an air atmosphere at atmospheric pressure and 23 ° C. Then, the sheet-like structure 11 was produced by heating and drying at 120 ° C. for 10 minutes.
(実施例12)
n-ドデカンの総添加量を3000質量部に変えた以外は、実施例11と同じ手順でCNFを含む外殻を備える粒子を含む組成物12を調製した。そして、組成物11に代えて組成物12を用いた以外は実施例11と同じ手順でシート状構造体12を作製した。 (Example 12)
Composition 12 containing particles having an outer shell containing CNF was prepared in the same manner as in Example 11, except that the total amount of n-dodecane was changed to 3000 parts by mass. Then, a sheet-like structure 12 was produced in the same procedure as in Example 11, except that the composition 12 was used instead of the composition 11.
n-ドデカンの総添加量を3000質量部に変えた以外は、実施例11と同じ手順でCNFを含む外殻を備える粒子を含む組成物12を調製した。そして、組成物11に代えて組成物12を用いた以外は実施例11と同じ手順でシート状構造体12を作製した。 (Example 12)
Composition 12 containing particles having an outer shell containing CNF was prepared in the same manner as in Example 11, except that the total amount of n-dodecane was changed to 3000 parts by mass. Then, a sheet-like structure 12 was produced in the same procedure as in Example 11, except that the composition 12 was used instead of the composition 11.
(実施例13)
n-ドデカン100質量部に代えて、n-ヘキサデカン200質量部を用いた以外は、実施例11と同様の手順でCNFを含む外殻を備える粒子を含む組成物13を調製した。そして、組成物11に代えて組成物13を用いた以外は、実施例11と同じ手順でシート状構造体13を作製した。 (Example 13)
Composition 13 containing particles having an outer shell containing CNF was prepared in the same procedure as in Example 11, except that 200 parts by mass of n-hexadecane was used instead of 100 parts by mass of n-dodecane. Then, a sheet-like structure 13 was produced in the same procedure as in Example 11, except that the composition 13 was used instead of the composition 11.
n-ドデカン100質量部に代えて、n-ヘキサデカン200質量部を用いた以外は、実施例11と同様の手順でCNFを含む外殻を備える粒子を含む組成物13を調製した。そして、組成物11に代えて組成物13を用いた以外は、実施例11と同じ手順でシート状構造体13を作製した。 (Example 13)
Composition 13 containing particles having an outer shell containing CNF was prepared in the same procedure as in Example 11, except that 200 parts by mass of n-hexadecane was used instead of 100 parts by mass of n-dodecane. Then, a sheet-like structure 13 was produced in the same procedure as in Example 11, except that the composition 13 was used instead of the composition 11.
(比較例1)
n-ドデカン100質量部を添加しなかったこと以外は実施例1と同様の手順で組成物C1を調製した。撹拌時間は実施例1と同様に10分間とした。そして、組成物1に代えて、組成物C1を用いた以外は実施例1と同様の手順でシート状構造体C1を作製した。 (Comparative Example 1)
Composition C1 was prepared in the same manner as in Example 1, except that 100 parts by mass of n-dodecane was not added. The stirring time was set to 10 minutes as in Example 1. Then, a sheet-like structure C1 was produced in the same procedure as in Example 1 except that the composition C1 was used instead of the composition 1.
n-ドデカン100質量部を添加しなかったこと以外は実施例1と同様の手順で組成物C1を調製した。撹拌時間は実施例1と同様に10分間とした。そして、組成物1に代えて、組成物C1を用いた以外は実施例1と同様の手順でシート状構造体C1を作製した。 (Comparative Example 1)
Composition C1 was prepared in the same manner as in Example 1, except that 100 parts by mass of n-dodecane was not added. The stirring time was set to 10 minutes as in Example 1. Then, a sheet-like structure C1 was produced in the same procedure as in Example 1 except that the composition C1 was used instead of the composition 1.
(比較例2~5)
n-ドデカン100質量部に代えて、それぞれ、ヘキサン100質量部、ジメチルスルホキシド(DMSO)100質量部、アニリン100質量部、エタノール100質量部を用いた以外は、実施例1と同様の手順で組成物C2~C5を調製した。そして、それぞれ、組成物1に代えて、組成物C2~C5を用いた以外は、実施例1と同様の手順でシート状構造体C2~C5を作製した。
実施例及び比較例で調製した組成物の各成分等を表2にまとめた。 (Comparative Examples 2 to 5)
A composition was prepared in the same manner as in Example 1, except that 100 parts by mass of hexane, 100 parts by mass of dimethylsulfoxide (DMSO), 100 parts by mass of aniline, and 100 parts by mass of ethanol were used instead of 100 parts by mass of n-dodecane. Products C2-C5 were prepared. Then, sheet-like structures C2 to C5 were produced in the same procedure as in Example 1 except that compositions C2 to C5 were used instead of composition 1, respectively.
Table 2 summarizes each component and the like of the compositions prepared in Examples and Comparative Examples.
n-ドデカン100質量部に代えて、それぞれ、ヘキサン100質量部、ジメチルスルホキシド(DMSO)100質量部、アニリン100質量部、エタノール100質量部を用いた以外は、実施例1と同様の手順で組成物C2~C5を調製した。そして、それぞれ、組成物1に代えて、組成物C2~C5を用いた以外は、実施例1と同様の手順でシート状構造体C2~C5を作製した。
実施例及び比較例で調製した組成物の各成分等を表2にまとめた。 (Comparative Examples 2 to 5)
A composition was prepared in the same manner as in Example 1, except that 100 parts by mass of hexane, 100 parts by mass of dimethylsulfoxide (DMSO), 100 parts by mass of aniline, and 100 parts by mass of ethanol were used instead of 100 parts by mass of n-dodecane. Products C2-C5 were prepared. Then, sheet-like structures C2 to C5 were produced in the same procedure as in Example 1 except that compositions C2 to C5 were used instead of composition 1, respectively.
Table 2 summarizes each component and the like of the compositions prepared in Examples and Comparative Examples.
組成物1~13、C1~C5、及び、シート状構造体1~13、C1~C5について、以下の手順で測定及び評価を行った。結果を表3に示す。
The compositions 1 to 13 and C1 to C5 and the sheet-like structures 1 to 13 and C1 to C5 were measured and evaluated according to the following procedures. Table 3 shows the results.
<閉塞空間の有無>
各シート状構造体を厚さ方向に切断した。そして、各々の切断面を、SEMによって観察し、中空の閉塞空間が形成されているか否かを確認した。図3に、シート状構造体6の厚さ方向の断面のSEM画像の一例を示す。 <Occluded space>
Each sheet-like structure was cut in the thickness direction. And each cut surface was observed by SEM, and it was confirmed whether the hollow closed space was formed. FIG. 3 shows an example of an SEM image of a cross section of the sheet-like structure 6 in the thickness direction.
各シート状構造体を厚さ方向に切断した。そして、各々の切断面を、SEMによって観察し、中空の閉塞空間が形成されているか否かを確認した。図3に、シート状構造体6の厚さ方向の断面のSEM画像の一例を示す。 <Occluded space>
Each sheet-like structure was cut in the thickness direction. And each cut surface was observed by SEM, and it was confirmed whether the hollow closed space was formed. FIG. 3 shows an example of an SEM image of a cross section of the sheet-like structure 6 in the thickness direction.
<CNFを含む膜の平均厚さ>
走査型電子顕微鏡(SEM)(日立製作所社製S-4700型)を用いて、各シート状構造体の上記切断面を観察し、得られた拡大画像から36個の閉塞空間を任意に選択し、それぞれを構成する任意の辺を一つ特定し、その辺の略中央の厚さを測定した。それらの平均値を算出することにより、複数の閉塞空間の、CNFを含む膜の厚さの平均とした。 <Average thickness of film containing CNF>
Using a scanning electron microscope (SEM) (S-4700 manufactured by Hitachi, Ltd.), the cut surface of each sheet-like structure was observed, and 36 closed spaces were arbitrarily selected from the obtained enlarged images. Then, one arbitrary side constituting each was specified, and the thickness at the approximate center of the side was measured. By calculating the average value, the average of the thicknesses of the CNF-containing films in the plurality of closed spaces was obtained.
走査型電子顕微鏡(SEM)(日立製作所社製S-4700型)を用いて、各シート状構造体の上記切断面を観察し、得られた拡大画像から36個の閉塞空間を任意に選択し、それぞれを構成する任意の辺を一つ特定し、その辺の略中央の厚さを測定した。それらの平均値を算出することにより、複数の閉塞空間の、CNFを含む膜の厚さの平均とした。 <Average thickness of film containing CNF>
Using a scanning electron microscope (SEM) (S-4700 manufactured by Hitachi, Ltd.), the cut surface of each sheet-like structure was observed, and 36 closed spaces were arbitrarily selected from the obtained enlarged images. Then, one arbitrary side constituting each was specified, and the thickness at the approximate center of the side was measured. By calculating the average value, the average of the thicknesses of the CNF-containing films in the plurality of closed spaces was obtained.
<構造体の閉塞空間の最大フェレ径とその平均>
各シート状構造体の上記切断面をSEM観察し、得られたSEM画像から36個の閉塞空間を任意に選択し、それぞれの最大フェレ径を測定し、それらの平均値を算出することにより、最大フェレ径の平均とした。
<b/a>
各シート状構造体の上記切断面をSEM観察し、得られたSEM画像から36個の閉塞空間を任意に選択し、各々について、構造体の厚さ方向の最大長さaと、構造体の平面方向の最大長さbとを測定してb/aの値を求め、それらの平均値を算出することにより、b/aの値とした。 <Maximum Feret diameter of closed space of structure and its average>
By observing the cut surface of each sheet-like structure by SEM, arbitrarily selecting 36 closed spaces from the obtained SEM image, measuring each maximum Feret diameter, and calculating an average value thereof, The average of the maximum Feret diameter was used.
<B / a>
The cut surface of each sheet-like structure was observed by SEM, and 36 closed spaces were arbitrarily selected from the obtained SEM images. For each of them, the maximum length a in the thickness direction of the structure, The value of b / a was determined by measuring the maximum length b in the plane direction, and the average value was calculated to obtain the value of b / a.
各シート状構造体の上記切断面をSEM観察し、得られたSEM画像から36個の閉塞空間を任意に選択し、それぞれの最大フェレ径を測定し、それらの平均値を算出することにより、最大フェレ径の平均とした。
<b/a>
各シート状構造体の上記切断面をSEM観察し、得られたSEM画像から36個の閉塞空間を任意に選択し、各々について、構造体の厚さ方向の最大長さaと、構造体の平面方向の最大長さbとを測定してb/aの値を求め、それらの平均値を算出することにより、b/aの値とした。 <Maximum Feret diameter of closed space of structure and its average>
By observing the cut surface of each sheet-like structure by SEM, arbitrarily selecting 36 closed spaces from the obtained SEM image, measuring each maximum Feret diameter, and calculating an average value thereof, The average of the maximum Feret diameter was used.
<B / a>
The cut surface of each sheet-like structure was observed by SEM, and 36 closed spaces were arbitrarily selected from the obtained SEM images. For each of them, the maximum length a in the thickness direction of the structure, The value of b / a was determined by measuring the maximum length b in the plane direction, and the average value was calculated to obtain the value of b / a.
<構造体の厚さと嵩密度>
以下の手順で、支持体付きのシート状構造体の質量と厚さを測定した。そして、これらを用いて、支持体無しのシート状構造体の嵩密度を算出した。
質量:支持体付きのシート状構造体を100mm×100mmの大きさに切断した後、質量を測定し、既知である支持体の質量を減じることで、支持体無しのシート状構造体の質量を算出した。
厚さ:定圧膜厚計を用いて、支持体を含むシート状構造体全体の厚さを測定し、既知である基材の厚さを減じることで、支持体無しのシート状構造体の厚さ(図1(A)の符号Lに相当)を算出した。 <Structure thickness and bulk density>
The mass and thickness of the sheet-like structure with the support were measured by the following procedure. Using these, the bulk density of the sheet-like structure without a support was calculated.
Mass: After cutting the sheet-like structure with the support into a size of 100 mm x 100 mm, the mass is measured, and the mass of the sheet-like structure without the support is reduced by reducing the known mass of the support. Calculated.
Thickness: The thickness of the sheet-like structure without the support is measured by measuring the thickness of the entire sheet-like structure including the support using a constant-pressure film thickness meter, and reducing the known thickness of the base material. (Corresponding to the symbol L in FIG. 1A).
以下の手順で、支持体付きのシート状構造体の質量と厚さを測定した。そして、これらを用いて、支持体無しのシート状構造体の嵩密度を算出した。
質量:支持体付きのシート状構造体を100mm×100mmの大きさに切断した後、質量を測定し、既知である支持体の質量を減じることで、支持体無しのシート状構造体の質量を算出した。
厚さ:定圧膜厚計を用いて、支持体を含むシート状構造体全体の厚さを測定し、既知である基材の厚さを減じることで、支持体無しのシート状構造体の厚さ(図1(A)の符号Lに相当)を算出した。 <Structure thickness and bulk density>
The mass and thickness of the sheet-like structure with the support were measured by the following procedure. Using these, the bulk density of the sheet-like structure without a support was calculated.
Mass: After cutting the sheet-like structure with the support into a size of 100 mm x 100 mm, the mass is measured, and the mass of the sheet-like structure without the support is reduced by reducing the known mass of the support. Calculated.
Thickness: The thickness of the sheet-like structure without the support is measured by measuring the thickness of the entire sheet-like structure including the support using a constant-pressure film thickness meter, and reducing the known thickness of the base material. (Corresponding to the symbol L in FIG. 1A).
<界面活性剤の有無>
シートの作製に用いた原料、及び、作製したシートについて、溶媒を用いた抽出を行い、それらの抽出物のIR分析を行った。その結果、いずれのサンプルからも、新たなピークは観測されず、界面活性剤が含まれていないことを確認した。 <Presence or absence of surfactant>
The raw materials used for the production of the sheet and the produced sheet were subjected to extraction using a solvent, and IR analysis of these extracts was performed. As a result, no new peak was observed from any of the samples, and it was confirmed that no surfactant was contained.
シートの作製に用いた原料、及び、作製したシートについて、溶媒を用いた抽出を行い、それらの抽出物のIR分析を行った。その結果、いずれのサンプルからも、新たなピークは観測されず、界面活性剤が含まれていないことを確認した。 <Presence or absence of surfactant>
The raw materials used for the production of the sheet and the produced sheet were subjected to extraction using a solvent, and IR analysis of these extracts was performed. As a result, no new peak was observed from any of the samples, and it was confirmed that no surfactant was contained.
表3から明らかなように、実施例1~13においては、界面活性剤等の分散剤を用いることなく、組成物中にCNFを含む外殻を備える粒子を生じさせることができた。また、実施例1~13においては、組成物を支持体に塗布し乾燥することで、CNFを含む膜から構成される多数の閉塞空間を備え、自己保持性を有するシート状構造体を得ることができた。図3は、実施例6で作製されたシート状構造体1の厚さ方向の断面のSEM画像である。シート状構造体1~13の全てが、図3のSEM画像に示された閉塞空間と同様に、隣り合う一組の閉塞空間がCNFを含む膜を共有する構造を有していることを確認した。実施例1~13のシート状構造体においては、閉塞空間の最大フェレ径の平均が、1~60μmの範囲にあり、小径の閉塞空間を形成することができた。シート状構造体1~13は界面活性剤を含んでいないため、閉塞空間内部に流体を保持した場合でも、この流体に界面活性が混入したり、流体とともに界面活性剤が外部に放出されたりする恐れがない。また、界面活性剤の存在によって、構造体の物性が不安定化する恐れもない。
明 ら か As is clear from Table 3, in Examples 1 to 13, particles having an outer shell containing CNF could be produced in the composition without using a dispersant such as a surfactant. In Examples 1 to 13, the composition was applied to a support and dried to obtain a self-holding sheet-like structure having a large number of closed spaces composed of a CNF-containing film. Was completed. FIG. 3 is an SEM image of a cross section in the thickness direction of the sheet-like structure 1 manufactured in Example 6. It is confirmed that all of the sheet-like structures 1 to 13 have a structure in which a pair of adjacent closed spaces share a membrane containing CNF, similarly to the closed space shown in the SEM image of FIG. did. In the sheet-like structures of Examples 1 to 13, the average of the maximum Feret diameter of the closed space was in the range of 1 to 60 μm, and a small-diameter closed space could be formed. Since the sheet-like structures 1 to 13 do not contain a surfactant, even when a fluid is held in the closed space, the fluid may be mixed with surface activity or the surfactant may be released to the outside together with the fluid. There is no fear. Further, there is no fear that the physical properties of the structure are destabilized by the presence of the surfactant.
実施例1~5、9から明らかなように、有機溶剤の使用量を調整することで、閉塞空間の最大フェレ径の平均、CNFを含む膜の厚さ、構造体の厚さ、b/aの値、及び、構造体の嵩密度を変化させ得ることが判る。また、シート状構造体におけるCNFを含む膜の厚さが小さくなるほど、シート状構造体は厚くなり、かつ、シート状構造体の嵩密度は小さくなることが判る。組成物に含まれる、CNFを含む外殻を備える粒子の大きさが比較的小さい場合、カプセルの内部空間の容積当たりの、カプセル外殻の厚さの影響が、大径カプセルにおけるそれよりも大きいため、カプセル外殻の膜厚が様々であることによって、粒子内の空間の大きさもより大きく変化し、最終的に得られる構造体における、閉塞空間の最大フェレ径の平均、CNFを含む膜の厚さ、b/aの値に影響を与えるものと推測される。このことは、カプセルが比較的小径であるが故に、カプセルの外殻の厚さを調整することによって、構造体になったときの空間率をある程度制御し得る可能性を示唆している。
また、実施例1及び実施例7~9から明らかなように、有機溶剤の種類を変更することによっても、組成物に含まれる、CNFを含む外殻を備える粒子の大きさを変化させ得ることが判る。 As is clear from Examples 1 to 5 and 9, by adjusting the amount of the organic solvent used, the average of the maximum Feret diameter of the closed space, the thickness of the film containing CNF, the thickness of the structure, and b / a And the bulk density of the structure can be changed. Further, it can be seen that the smaller the thickness of the film containing CNF in the sheet-like structure, the thicker the sheet-like structure and the lower the bulk density of the sheet-like structure. If the size of the particles comprising the CNF-containing shell included in the composition is relatively small, the effect of the thickness of the capsule shell per volume of the internal space of the capsule is larger than that in the large-diameter capsule. Therefore, the thickness of the capsule outer shell varies, so that the size of the space in the particle also changes greatly, and in the finally obtained structure, the average of the maximum Feret diameter of the closed space, the film thickness of the film containing CNF, It is assumed that the thickness and the value of b / a are affected. This suggests that, since the capsule has a relatively small diameter, by adjusting the thickness of the outer shell of the capsule, there is a possibility that the porosity of the structure can be controlled to some extent.
Further, as is clear from Example 1 and Examples 7 to 9, it is possible to change the size of the particles having the outer shell containing CNF contained in the composition by changing the type of the organic solvent. I understand.
また、実施例1及び実施例7~9から明らかなように、有機溶剤の種類を変更することによっても、組成物に含まれる、CNFを含む外殻を備える粒子の大きさを変化させ得ることが判る。 As is clear from Examples 1 to 5 and 9, by adjusting the amount of the organic solvent used, the average of the maximum Feret diameter of the closed space, the thickness of the film containing CNF, the thickness of the structure, and b / a And the bulk density of the structure can be changed. Further, it can be seen that the smaller the thickness of the film containing CNF in the sheet-like structure, the thicker the sheet-like structure and the lower the bulk density of the sheet-like structure. If the size of the particles comprising the CNF-containing shell included in the composition is relatively small, the effect of the thickness of the capsule shell per volume of the internal space of the capsule is larger than that in the large-diameter capsule. Therefore, the thickness of the capsule outer shell varies, so that the size of the space in the particle also changes greatly, and in the finally obtained structure, the average of the maximum Feret diameter of the closed space, the film thickness of the film containing CNF, It is assumed that the thickness and the value of b / a are affected. This suggests that, since the capsule has a relatively small diameter, by adjusting the thickness of the outer shell of the capsule, there is a possibility that the porosity of the structure can be controlled to some extent.
Further, as is clear from Example 1 and Examples 7 to 9, it is possible to change the size of the particles having the outer shell containing CNF contained in the composition by changing the type of the organic solvent. I understand.
さらに、実施例5、6から明らかなように、組成物を塗布する際にアプリケーターのギャップを変更して塗布された組成物の厚みを変えることで、閉塞空間の最大フェレ径の平均、及び、CNFを含む膜の厚さをほとんど変えることなく、構造体の厚さを大きく変えられることが判る。
さらに、実施例11~13から明らかなように、CNFの種類を変更した場合でも、上述したのと同様の傾向を示すことが判る(つまり、有機溶媒の種類や添加量を変えることによって、閉塞空間の最大フェレ径の平均、CNFを含む膜の厚さ、構造体の厚さ、b/aの値、及び、構造体の嵩密度を変化させ得る)。 Further, as is clear from Examples 5 and 6, by changing the thickness of the applied composition by changing the gap of the applicator when applying the composition, the average of the maximum Feret diameter of the closed space, and It can be seen that the thickness of the structure can be changed significantly without changing the thickness of the film containing CNF.
Further, as is apparent from Examples 11 to 13, even when the type of CNF is changed, the same tendency as described above is exhibited (that is, when the type and the amount of the organic solvent are changed, the clogging is prevented). The average of the maximum Feret diameter of the space, the thickness of the film containing CNF, the thickness of the structure, the value of b / a, and the bulk density of the structure can be changed).
さらに、実施例11~13から明らかなように、CNFの種類を変更した場合でも、上述したのと同様の傾向を示すことが判る(つまり、有機溶媒の種類や添加量を変えることによって、閉塞空間の最大フェレ径の平均、CNFを含む膜の厚さ、構造体の厚さ、b/aの値、及び、構造体の嵩密度を変化させ得る)。 Further, as is clear from Examples 5 and 6, by changing the thickness of the applied composition by changing the gap of the applicator when applying the composition, the average of the maximum Feret diameter of the closed space, and It can be seen that the thickness of the structure can be changed significantly without changing the thickness of the film containing CNF.
Further, as is apparent from Examples 11 to 13, even when the type of CNF is changed, the same tendency as described above is exhibited (that is, when the type and the amount of the organic solvent are changed, the clogging is prevented). The average of the maximum Feret diameter of the space, the thickness of the film containing CNF, the thickness of the structure, the value of b / a, and the bulk density of the structure can be changed).
一方、比較例1~5では、組成物中に、CNFを含む外殻を備える粒子を生成することができず、結果として、構造体にCNFを含む膜から構成される閉塞空間を生じさせることができなかった。
On the other hand, in Comparative Examples 1 to 5, particles having an outer shell containing CNF could not be produced in the composition, and as a result, an occluded space composed of a film containing CNF was generated in the structure. Could not.
本発明の製造方法によって得られるシート状構造体は、CNFを含む膜から構成される閉塞空間を複数備え、構造体に存在する空間の割合が大きく、しかも構造体の内部に保持される流体に不要な成分が混入しにくい構造体とすることができる。したがって、例えば、閉塞空間の内部に流体を保持させておき、必要になった場合に圧力を加えて構造体の一部を開裂し流体を外部へ供給する構造体や、閉塞空間内に保持した流体を徐々に放出し得る徐放性の構造体として使用することができる。また、断熱材、吸着材、吸音材、絶縁材料、フレキシブルプリント配線基板用の基材、包装材料等として使用できる。さらに、構造体を指で強く押したときに閉塞空間が圧縮破壊されて、構造体表面に指紋を含む押圧痕が残るので、痕跡記録材として使用することもできる。
The sheet-like structure obtained by the manufacturing method of the present invention includes a plurality of closed spaces formed of a membrane containing CNF, has a large ratio of the space existing in the structure, and has a fluid holding inside the structure. A structure in which unnecessary components are hardly mixed can be obtained. Therefore, for example, the fluid is held inside the closed space, and when necessary, pressure is applied to cleave a part of the structure to supply the fluid to the outside, or to hold the fluid inside the closed space. It can be used as a sustained release structure that can release a fluid gradually. Further, it can be used as a heat insulating material, an adsorbing material, a sound absorbing material, an insulating material, a base material for a flexible printed wiring board, a packaging material, and the like. Furthermore, when the structure is strongly pressed with a finger, the closed space is compressed and destroyed, and a pressing mark including a fingerprint remains on the surface of the structure, so that the structure can be used as a trace recording material.
30:組成物
31:複数の閉塞空間を有する層(シート状構造体)
32:CNFを含む外殻を備える粒子
33、33a、33b:閉塞空間
34:水を主体とする媒質
35:CNFを含む膜
35a:隣り合う一組の閉塞空間で共有される膜
40:支持体
40a:塗布面
50:支持体付きのシート状構造体
a:閉塞空間の構造体の厚さ方向の最大長さ
b:閉塞空間の構造体の平面方向の最大長さ
df:閉塞空間の最大フェレ径
dm:CNFを含む膜の厚さ
L:複数の閉塞空間を有する層の厚さ 30: Composition 31: Layer having a plurality of closed spaces (sheet-like structure)
32: Particles 33, 33a, 33b having an outer shell containing CNF: Occluded space 34: Medium mainly composed of water 35: Membrane containing CNF 35a: Membrane 40 shared by a pair of adjacent enclosed spaces 40: Support 40a: coating surface 50: sheet-like structure with a support a: maximum length of the closed space structure in the thickness direction b: maximum length of the closed space structure in the plane direction df: maximum ferrite of the closed space Diameter dm: thickness of membrane containing CNF L: thickness of layer having a plurality of closed spaces
31:複数の閉塞空間を有する層(シート状構造体)
32:CNFを含む外殻を備える粒子
33、33a、33b:閉塞空間
34:水を主体とする媒質
35:CNFを含む膜
35a:隣り合う一組の閉塞空間で共有される膜
40:支持体
40a:塗布面
50:支持体付きのシート状構造体
a:閉塞空間の構造体の厚さ方向の最大長さ
b:閉塞空間の構造体の平面方向の最大長さ
df:閉塞空間の最大フェレ径
dm:CNFを含む膜の厚さ
L:複数の閉塞空間を有する層の厚さ 30: Composition 31: Layer having a plurality of closed spaces (sheet-like structure)
32:
Claims (12)
- セルロースナノファイバーを含む膜と、該膜から構成された複数の閉塞空間とを備える構造体であって、界面活性剤の含有量が、前記セルロースナノファイバー100質量部に対して10質量部未満である、構造体。 A film comprising a cellulose nanofiber and a plurality of closed spaces formed from the film, wherein the content of the surfactant is less than 10 parts by mass with respect to 100 parts by mass of the cellulose nanofiber. There is a structure.
- 前記複数の閉塞空間のうち隣接する一組の閉塞空間は少なくとも一つの前記膜を共有している請求項1に記載の構造体。 The structure according to claim 1, wherein an adjacent set of the closed spaces among the plurality of closed spaces shares at least one of the membranes.
- 前記セルロースナノファイバーを含む膜の平均厚さが、10nm~2000nmである請求項1又は2に記載の構造体。 The structure according to claim 1, wherein the average thickness of the film containing the cellulose nanofiber is 10 nm to 2000 nm.
- 前記構造体の嵩密度が、0.001~1.4g/cm3である請求項1~3のいずれか1項に記載の構造体。 The structure according to any one of claims 1 to 3, wherein the bulk density of the structure is 0.001 to 1.4 g / cm 3 .
- 前記構造体はシート形状を有する、請求項1~4のいずれか1項に記載の構造体。 The structure according to any one of claims 1 to 4, wherein the structure has a sheet shape.
- 前記構造体の厚さが0.5~300μmである請求項5に記載の構造体。 構造 The structure according to claim 5, wherein the thickness of the structure is 0.5 to 300 μm.
- 前記構造体の厚さ方向の断面において、前記閉塞空間の前記構造体の厚さ方向の最大長さをa、前記閉塞空間の前記構造体の平面方向の最大長さをbとするとき、前記複数の閉塞空間のb/aの平均が1より大きい、請求項5又は6に記載の構造体。 In the cross section in the thickness direction of the structure, the maximum length of the closed space in the thickness direction of the structure is a, and the maximum length of the closed space in the planar direction of the structure is b, The structure according to claim 5, wherein the average of b / a of the plurality of closed spaces is greater than 1.
- 前記セルロースナノファイバーが植物由来のセルロースナノファイバーである請求項1~7のいずれか1項に記載の構造体。 The structure according to any one of claims 1 to 7, wherein the cellulose nanofiber is a plant-derived cellulose nanofiber.
- 前記セルロースナノファイバー以外の多糖類の含有量が、前記セルロースナノファイバー100質量部に対して10質量部未満である、請求項1~8のいずれか1項に記載の構造体。 The structure according to any one of claims 1 to 8, wherein the content of the polysaccharide other than the cellulose nanofiber is less than 10 parts by mass relative to 100 parts by mass of the cellulose nanofiber.
- 前記セルロースナノファイバーの直径(太さ)の平均が、1~1000nmである、請求項1~9のいずれか1項に記載の構造体。 The structure according to any one of claims 1 to 9, wherein the average of the diameter (thickness) of the cellulose nanofiber is 1 to 1000 nm.
- 前記セルロースナノファイバーの繊維長の平均が、0.01~10μmである、請求項1~10のいずれか1項に記載の構造体。 The structure according to any one of claims 1 to 10, wherein an average fiber length of the cellulose nanofiber is 0.01 to 10 μm.
- 請求項1~11のいずれか1項に記載の構造体が、支持体上に設けられている、支持体付き構造体。
A structure with a support, wherein the structure according to any one of claims 1 to 11 is provided on a support.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013054899A1 (en) * | 2011-10-13 | 2013-04-18 | 特種東海製紙株式会社 | Microporous membrane and manufacturing method therefor |
JP2013253137A (en) * | 2012-06-05 | 2013-12-19 | Hokuetsu Kishu Paper Co Ltd | Porous cellulose body and method for producing the same |
US20150368441A1 (en) * | 2014-06-24 | 2015-12-24 | Api Intellectual Property Holdings, Llc | Oleophilic and hydrophobic nanocellulose materials |
JP2016196534A (en) * | 2015-04-02 | 2016-11-24 | 北越紀州製紙株式会社 | Manufacturing method of cellulose porous body |
JP2017036461A (en) * | 2016-11-10 | 2017-02-16 | 北越紀州製紙株式会社 | Cellulose porous body and manufacturing method therefor |
WO2017111016A1 (en) * | 2015-12-25 | 2017-06-29 | 日本製紙株式会社 | Method for producing cellulose nanofiber dry solid |
JP2017533321A (en) * | 2014-10-30 | 2017-11-09 | セルテック・アクチボラゲットCellutech Ab | CNF porous solid material |
JP2017535641A (en) * | 2014-10-30 | 2017-11-30 | セルテック・アクチボラゲットCellutech Ab | CNF porous solid material having an anionic surfactant |
-
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- 2019-08-30 JP JP2020541174A patent/JP7385577B2/en active Active
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013054899A1 (en) * | 2011-10-13 | 2013-04-18 | 特種東海製紙株式会社 | Microporous membrane and manufacturing method therefor |
JP2013253137A (en) * | 2012-06-05 | 2013-12-19 | Hokuetsu Kishu Paper Co Ltd | Porous cellulose body and method for producing the same |
US20150368441A1 (en) * | 2014-06-24 | 2015-12-24 | Api Intellectual Property Holdings, Llc | Oleophilic and hydrophobic nanocellulose materials |
JP2017533321A (en) * | 2014-10-30 | 2017-11-09 | セルテック・アクチボラゲットCellutech Ab | CNF porous solid material |
JP2017535641A (en) * | 2014-10-30 | 2017-11-30 | セルテック・アクチボラゲットCellutech Ab | CNF porous solid material having an anionic surfactant |
JP2016196534A (en) * | 2015-04-02 | 2016-11-24 | 北越紀州製紙株式会社 | Manufacturing method of cellulose porous body |
WO2017111016A1 (en) * | 2015-12-25 | 2017-06-29 | 日本製紙株式会社 | Method for producing cellulose nanofiber dry solid |
JP2017036461A (en) * | 2016-11-10 | 2017-02-16 | 北越紀州製紙株式会社 | Cellulose porous body and manufacturing method therefor |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2020050151A1 (en) * | 2018-09-03 | 2021-08-26 | リンテック株式会社 | Manufacturing method of sheet-like structure |
JP7296971B2 (en) | 2018-09-03 | 2023-06-23 | リンテック株式会社 | Method for manufacturing sheet-like structure |
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