WO2015170613A1 - 複合体、複合体の製造方法、分散液、分散液の製造方法および光学材料 - Google Patents
複合体、複合体の製造方法、分散液、分散液の製造方法および光学材料 Download PDFInfo
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
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- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
- Y10S977/833—Thermal property of nanomaterial, e.g. thermally conducting/insulating or exhibiting peltier or seebeck effect
Definitions
- the present invention relates to a composite, a composite manufacturing method, a dispersion, a dispersion manufacturing method, and an optical material, and more particularly, to a composite of flat metal fine particles and fine cellulose.
- cellulose which is the main component of wood, is a natural polymer material that is accumulated in large quantities on the earth, and is expected as a key material for the transition to a resource recycling society.
- dozens or more of cellulose molecules are bundled to form fine fibers (microfibrils) having a high crystallinity and a fiber diameter on the order of nanometers.
- fine fibers microfibrils
- a large number of fine fibers form hydrogen bonds with each other to form cellulose fibers, which are plant supports.
- CNF fine cellulose fibers
- CNF cellulose nanofibers
- CNF obtained by this method has been reported to have a short axis diameter of 10 to 50 nm and a long axis diameter of 1 ⁇ m to 10 mm.
- This CNF is 1/5 lighter than steel, has a strength five times that of steel, and has a large non-surface area of 250 m 2 / g or more. For this reason, many examples of use as resin-reinforced nanofibers have already been reported. (For example, see Patent Documents 2 and 3)
- hydrophobic general-purpose resin and the hydrophilic CNF have low compatibility, and there is an essential problem that it is difficult to form a complete complex, and it has not yet been put into practical use.
- TEMPO 2,2,6,6-tetramethylpiperidinyl-1-oxy radical
- a method of selective oxidation has been reported (see, for example, Patent Document 4).
- the oxidation reaction (TEMPO oxidation reaction) using TEMPO as a catalyst can be an environmentally harmonious chemical reforming that proceeds in an aqueous system, normal temperature, and normal pressure.
- TEMPO oxidation reaction is applied to cellulose in wood, the reaction does not proceed inside the crystal, and only the alcoholic primary carbon possessed by the cellulose molecular chain on the crystal surface can be selectively converted into a carboxy group. .
- the cellulose single nanofiber (henceforth CSNF) disperse
- Wood-derived CSNF obtained from wood by a TEMPO oxidation reaction is a structure having a high aspect ratio with a minor axis diameter of around 3 nm and a major axis diameter of several tens to several ⁇ m. Therefore, it has been reported that the aqueous dispersion and the laminate have high transparency.
- CSNF for example, an application example in which a gas barrier film is formed by laminating on a transparent substrate and used as a plant-derived novel transparent packaging material has been reported (for example, see Patent Document 5). .
- CSNF has a very high hydrophilicity due to the introduction of a carboxy group, and in a warm and humid climate such as Japan, the problem that gas barrier properties deteriorate due to the inability to maintain a dense laminated structure of CSNF inside the gas barrier film. was there. For this reason, the prospect of practical use as a transparent packaging material is not standing at present.
- the size of the metal or metal oxide when reduced to the nanometer order, it may show physical and chemical properties different from the bulk state. This phenomenon is known as a so-called quantum size effect, and in metal nanoparticles, melting point drop and surface localized plasmon resonance can be mentioned.
- Metal nanoparticles are typically provided in a dispersion to maintain the quantum size effect.
- metal nanoparticles have an increased specific surface area, they tend to aggregate with each other in the dispersion, and there is a problem in dispersion stability. If the secondary particles are formed by aggregation, the quantum size effect is lost. Therefore, it is necessary to use various additives in order to prevent aggregation of metal nanoparticles.
- metal nanoparticles having an anisotropic shape have attracted attention.
- plate-shaped and rod-shaped metal nanoparticles exhibit optical, electronic, magnetic, chemical, and mechanical properties that are different from spherical nanoparticles, and are expected to be applied in various fields.
- metal nanoparticles having such an anisotropic shape have attracted attention as an attempt to use the quantum size effect at a high level.
- silver nanoparticles are expected to be particularly applied.
- spherical silver nanoparticles having a particle size of several nanometers to several tens of nanometers have a yellowish color due to absorption near a wavelength of 400 nm by surface localized plasmon resonance.
- anisotropically grown silver nanoparticles are not always yellowish, and, for example, plate-like silver nanoparticles are known to undergo red shift in absorption peak. At this time, it has been confirmed that the absorption peak shifts to the longer wavelength side as the aspect ratio (namely, particle diameter / particle thickness) of the plate-like silver nanoparticles increases.
- the plate-like silver nanoparticles can be used as an optical material that selectively absorbs light of an arbitrary wavelength. Further, if the absorption wavelength is controlled in the visible light region, plate-like silver nanoparticles exhibiting a vivid color tone such as red and blue in addition to yellow can be obtained, and use as a functional color material can be expected. Furthermore, depending on the aspect ratio of the plate-like silver nanoparticles, the absorption peak can be shifted to the near infrared region outside the visible light region, and in such a case, it can be applied as a near infrared absorbing material.
- near infrared refers to electromagnetic waves in a wavelength region (approximately 700 nm to 2500 nm) close to visible light among infrared rays.
- This near-infrared ray has a property close to visible light, and in particular, light in the wavelength region of 700 nm to 1200 nm contained in sunlight is known to be easily absorbed and converted into thermal energy.
- Such a near-infrared absorbing material is a functional material with high added value because it can shield heat rays. For example, it is possible to obtain a heat shielding effect by providing a layer containing a near-infrared absorbing material on a building or automobile window. That is, since a power saving effect due to an increase in cooling efficiency can be expected, it can also contribute to the improvement of the power shortage problem in summer.
- a number of synthesis methods have been proposed for tabular silver nanoparticles having interesting properties as optical materials.
- a synthesis method called a polyol method can be used as a method used for general purposes.
- the polyol method is a method in which ethylene glycol, which is a kind of polyol, is heated to 140 to 160 ° C. together with a metal salt under a polymer capping agent, and metal fine particles are synthesized by the reducing power of the generated glycolaldehyde.
- silver nanoparticles having various shapes can be obtained by inducing anisotropic growth of silver nanoparticles by selecting reducing conditions and an appropriate polymer capping agent.
- Patent Document 6 discloses a production example of plate-like silver nanoparticles using a polyol method.
- Patent Document 7 discloses a composite (metal nanoparticle-supported CSNF) in which metal nanoparticles are supported on CSNF as a composite of CSNF, which is a kind of micronized cellulose, and metal fine particles.
- Patent Document 7 discloses an example in which metal nanoparticle-supporting CSNF is used as a catalyst.
- JP 2010-216021 A JP 2006-240295 A JP 2008-007646 A JP 2008-001728 A International Publication No. 2013/042654 JP 2009-144188 A Republished WO2010 / 095574
- Patent Document 7 discloses a composite of finely divided cellulose and metal fine particles and its use. However, there is no disclosure or suggestion about the possibility of controlling the shape of the metal nanoparticles and the applicability to optical materials such as functional color materials and near-infrared absorbing materials.
- the present invention has been made in view of such circumstances, and it is an object of the present invention to provide a composite of flat metal fine particles and fine cellulose that can be applied to optical materials such as functional color materials and near-infrared absorbing materials.
- Another object of the present invention is to provide a method for producing a complex, which can provide the complex with a low environmental burden and can be provided by a simple method.
- this invention makes it a subject to provide the dispersion liquid which the said composite_body
- a dispersion containing anisotropic metal nanoparticles with high dispersion stability which is easy to manufacture, can be synthesized safely, and is a new environmentally friendly optical material that contains finely divided cellulose, which is a carbon neutral material. And providing a dispersion thereof.
- the inventors of the present application tried to create various organic-inorganic hybrids using finely divided cellulose, which is a carbon neutral material, and reduced metal in a finely divided cellulose dispersion under specific conditions. It has been found that by precipitation, a composite of flat metal fine particles and fine cellulose is obtained, and that the flat metal fine particles of the obtained composite and fine cellulose are in an indivisible state. . Further, by reducing and precipitating one or more kinds of metal containing silver in a dispersion of finely divided cellulose under a specific condition, the fine particles are refined with tabular fine particles made of at least one kind of metal containing silver or a compound thereof.
- the aspect ratio of the flat metal fine particle / refined cellulose composite can be controlled to an arbitrary size by controlling the conditions for the reduction precipitation reaction. Therefore, it was also found that the dispersion has a maximum absorbance at an arbitrary wavelength from 400 nm to 1500 nm, and can be used as a functional color material or a near-infrared absorbing material.
- the dispersion of the plate-like metal fine particles / micronized cellulose composite is extremely dispersed even when the particle size is 100 nm or more because aggregation and sedimentation are inhibited by steric hindrance or electrostatic repulsion between the micronized cellulose. Stability was good.
- the composite according to the first aspect of the present invention includes at least one or more types of metal or a compound thereof, and flat metal fine particles formed with the flat metal fine particles and at least one or more refined cellulose.
- Each of the micronized cellulose is at least partially taken into the flat metal fine particles, and the remaining part is exposed on the surface of the flat metal fine particles.
- the plate-like metal fine particles and the refined cellulose may be inseparable.
- the flat metal fine particles may be silver.
- the particle diameter of the flat metal fine particles may be twice or more the particle thickness of the flat metal fine particles.
- the fine cellulose may have a carboxy group on the crystal surface.
- the content of the carboxy group may be 0.1 mmol or more and 5.0 mmol or less per 1 g of cellulose.
- the crystal structure of the refined cellulose may be cellulose I type.
- the shape of the fine cellulose may be a fiber derived from a microfibril structure of natural cellulose.
- the fine cellulose may have a number average minor axis diameter of 1 nm or more and 100 nm or less, a number average major axis diameter of 50 nm or more, and a number average major axis diameter of 10 times or more the number average minor axis diameter.
- the refined cellulose dispersion is prepared by preparing refined cellulose and dispersing the refined cellulose in a solvent. And obtaining a mixed solution by mixing the finely divided cellulose dispersion and a solution containing metal ions, and reducing the metal ions in the mixed solution to grow flat metal particles. And composing the flat metal fine particles and the refined cellulose.
- the metal ion may be a silver ion.
- the fibrous refined cellulose may be prepared.
- a carboxy group may be introduced into the crystallized surface of the refined cellulose.
- an oxidation reaction using an N-oxyl compound may be used.
- the carboxy group When introducing the carboxy group, the carboxy group may be introduced so as to be 0.1 mmol or more and 5.0 mmol or less per 1 g of cellulose.
- the dispersion according to the third aspect of the present invention includes the composite according to the first aspect that is dispersed in water or an organic solvent.
- optical material according to the fourth aspect of the present invention includes the composite according to the first aspect.
- the dispersion according to the fifth aspect of the present invention includes a composite of flat metal fine particles made of one or more kinds of metals or their compounds and fine cellulose.
- each of the micronized cellulose may be taken into the flat metal fine particles, and the rest may be exposed on the surface of the flat metal fine particles.
- the plate-like metal fine particles and the refined cellulose may be inseparable.
- the flat metal fine particles may contain at least silver.
- the particle diameter of the flat metal fine particles may be twice or more the particle thickness of the flat metal fine particles.
- a carboxy group may be introduced on the crystal surface of the fine cellulose.
- the carboxy group of the fine cellulose may be introduced by an oxidation reaction using an N-oxyl compound.
- the amount of carboxy groups introduced into the fine cellulose may be 0.1 mmol / g or more and 5.0 mmol / g or less based on the dry weight of cellulose.
- the crystal structure of the refined cellulose may be cellulose I type.
- the shape of the refined cellulose may be a fibrous form derived from a microfibril structure of natural cellulose.
- the number average minor axis diameter of the micronized cellulose may be 1 nm or more and 100 nm or less, the number average major axis diameter may be 50 nm or more, and the number average major axis diameter may be 10 times or more the number average minor axis diameter.
- the method for producing the dispersion liquid according to the fifth aspect of the sixth aspect of the present invention is obtained by dispersing finely divided cellulose fibers in a solvent to obtain a finely divided cellulose dispersion liquid. And a metal ion-containing solution are mixed to obtain a mixed solution, and the metal ions in the mixed solution are reduced to obtain a composite of the plate-like metal fine particles and the fine cellulose.
- the metal ion may be a silver ion.
- a carboxy group may be introduced into the crystallized surface of the refined cellulose.
- an oxidation reaction using an N-oxyl compound may be used.
- the carboxy group When introducing the carboxy group, the carboxy group may be introduced so as to be 0.1 mmol / g or more and 5.0 mmol / g or less based on the dry weight of cellulose.
- the composite according to the above aspect of the present invention has a configuration in which at least a part or all of the refined cellulose is taken into the flat metal fine particles, and the rest is exposed on the surface of the flat metal fine particles. . Therefore, it is a composite of novel flat metal fine particles and refined cellulose, which can be applied to optical materials such as functional color materials and near-infrared absorbing materials.
- the method for producing a composite according to the above aspect of the present invention includes a step of growing plate-like metal fine particles by reducing metal ions in a mixed solution and combining the plate-like metal fine particles and fine cellulose. ing. Therefore, the above-mentioned complex has a low environmental load and can be provided easily.
- the complex is dispersed in water or an organic solvent, and aggregation is inhibited by steric hindrance or electrostatic repulsion between finely divided celluloses, and the dispersion stability is excellent.
- optical material according to the above aspect of the present invention is useful as a functional color material or a near-infrared absorbing material because it contains the composite having the maximum absorbance at an arbitrary wavelength of 400 nm to 1500 nm.
- complex of the flat metal fine particle and fine cellulose which have not been reported until now will be obtained. Since the dispersion selectively absorbs light having an arbitrary wavelength from visible light to near infrared light, it can be used as a novel optical material molding composition. In addition, since finely divided cellulose is bonded to the plate-like metal fine particles contained in the dispersion, it is possible to maintain a good dispersion state for a long time.
- FIG. 3B is a schematic diagram of the SEM image of FIG. 3A. It is a figure (SEM image) which shows the result of having observed the composite_body
- FIG. 5A is a STEM image showing an observation result of the composite obtained in Example 2 with a scanning transmission electron microscope (STEM).
- FIG. 5C. 4 is a STEM image showing the observation result of the composite obtained in Example 3 with a scanning transmission electron microscope (STEM).
- FIG. 5E is a diagram showing spectral transmission spectra of composites of flat metal fine particles and CSNF produced in Examples 1 to 4 and Comparative Examples 1 and 2.
- STEM scanning transmission electron microscope
- FIG. 7A is a schematic diagram of FIG. 7A.
- FIG. 8A is an element mapping image (photograph) by SEM-EDX of a composite of flat metal fine particles and CSNF produced in Example 1.
- FIG. It is the TEM image of the composite_body
- FIG. 1 is a perspective view schematically showing a configuration of a complex (complex included in a dispersion) 1 according to an embodiment of the present invention.
- the composite 1 includes a plate-like metal fine particle and a fine particle in which plate-like metal fine particles (plate-like metal fine particles) 2 and at least one or more refined cellulose 3 are compounded. It is a composite with chlorinated cellulose.
- the composite 1 at least a part (a part) or the whole of each micronized cellulose 3 is taken into the flat metal fine particles 2, and the remainder is composited so as to be exposed on the surface of the flat metal fine particles 2. Yes.
- each refined cellulose 3 includes a portion 3 a taken in the flat metal fine particles 2, and a portion 3 b exposed on the surface of the flat metal fine particles 2. It consists of And by the presence of this taken-in part 3a, the flat metal fine particle 2 and each refined cellulose 3 are inseparable. That is, in the flat metal fine particles 2 and the refined cellulose 3, at least a part (that is, the portion 3 a) of the refined cellulose 3 is taken into the flat metal fine particles 2. Thereby, it is in an inseparable state, when at least one part couple
- “at least a part of the refined cellulose 3 (that is, the portion 3 a) is taken into the flat metal fine particles 2” means that the metal fine particle unit is in the growth stage of the flat metal fine particles 2. It is synonymous with the state in which fine cellulose is sandwiched along the grain boundary.
- the “inseparable” state means that it cannot be separated into the flat metal fine particles 2 and the fine cellulose 3 by a physical method such as a centrifuge. .
- metal species constituting the flat metal fine particles 2 silver is preferable, but not particularly limited thereto. Specifically, a plurality of metal species may be used as the metal species, and metal species other than silver are not particularly limited. Examples of metal species other than silver include platinum group elements such as platinum, palladium, ruthenium, iridium, rhodium, and osmium. Other metal species include metals such as gold, iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, and aluminum, metal salts, metal complexes and their alloys, oxides, and double oxides. Etc.
- platinum group elements such as platinum, palladium, ruthenium, iridium, rhodium, and osmium.
- Other metal species include metals such as gold, iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, and aluminum, metal salts, metal
- the “flat plate” is a plate-like particle having a shape such as a triangle, a hexagon, or a pentagon, and has an average aspect ratio (particle diameter / particle thickness) obtained by dividing the particle diameter by the particle thickness. It means a particle that is 2.0 or more.
- the particle size of the flat metal fine particles 2 is preferably 20 to 500 nm, and more preferably 20 to 400 nm.
- the thickness of the tabular metal fine particles 2 is preferably 5 to 100 nm, more preferably 8 to 50 nm.
- the average aspect ratio (particle diameter / particle thickness) is preferably 2.0 or more, more preferably 2.0 to 100, still more preferably 2.0 to 50.
- specific examples of the method for measuring the particle diameter and thickness of the flat metal fine particles and the method for calculating the aspect ratio include the following methods.
- (1) Measuring method of particle diameter The dispersion containing the composite is cast on a copper grid with a support film for TEM observation and air-dried, and then observed with a transmission electron microscope. The diameter when the tabular silver nanoparticles in the obtained image are approximated by a circle is calculated as the particle diameter in the plane direction.
- Thickness measurement method A dispersion containing the composite is cast on a PET film, air-dried and fixed with an embedding resin, and a resin lump is cut in a cross-sectional direction with a microtome and observed with a transmission electron microscope. I do.
- the thickness of the tabular silver nanoparticles in the obtained image is calculated as the particle diameter in the plane direction.
- the fine cellulose 3 preferably has a fiber shape derived from a microfibril structure.
- the number average minor axis diameter is 1 nm or more and 100 nm or less
- the number average major axis diameter is 50 nm or more
- the number average major axis diameter is 10 times or more of the number average minor axis diameter.
- the crystal structure of the refined cellulose 3 is cellulose I type.
- the refined cellulose 3 has a carboxy group on the crystal surface, and the content of the carboxy group is preferably 0.1 mmol or more and 5.0 mmol or less per 1 g of cellulose.
- the composite 1 is a composite of the flat metal fine particles 2 made of one or more kinds of metals or their compounds and the refined cellulose fibers 3. Further, in the composite 1, the flat metal fine particles 2 and the refined cellulose fibers 3 are physically bonded and in an inseparable state. Furthermore, the composite 1 is a carbon neutral organic-inorganic hybrid material.
- a method for producing the composite 1 includes producing a metal crystal by reducing and precipitating a metal in a dispersion containing refined cellulose and metal ions, and growing the metal crystal with anisotropy, This is a method of obtaining a composite of flat metal fine particles and fine cellulose.
- refined cellulose is prepared (first step). Subsequently, the fine cellulose is dispersed in a solvent to obtain a fine cellulose dispersion (second step). Subsequently, the finely divided cellulose dispersion and a solution containing metal ions are mixed to obtain a mixed solution (third step). Further, the metal ions in the mixed solution are reduced to grow the flat metal fine particles, and the flat metal fine particles and the refined cellulose are combined (fourth step). Below, each process is demonstrated in detail.
- complex of this embodiment is prepared.
- This 1st process includes the process of preparing fibrous refined cellulose, and the process of introduce
- the refined cellulose used in the method for producing a composite according to the present embodiment is not particularly limited as long as at least one side of its structure is on the order of nanometers.
- micronized cellulose takes the shape of a fiber derived from a microfibril structure. Therefore, as the refined cellulose used in the production method of the present embodiment, the refined cellulose shown below is preferable. That is, the shape of the fine cellulose is preferably a fiber shape such as a fiber shape derived from a microfibril structure.
- the fibrous finely divided cellulose may have a number average minor axis diameter of 1 nm or more and 100 nm or less, preferably 2 nm or more and 50 nm or less.
- the number average minor axis diameter is less than 1 nm, a highly crystalline rigid refined cellulose fiber structure cannot be obtained, and anisotropic growth of metal fine particles cannot be sufficiently promoted.
- the thickness exceeds 100 nm, the size becomes too large with respect to the metal fine particles, and therefore, it cannot have a shape of a composite of flat metal fine particles and fine cellulose.
- the number average major axis diameter is not particularly limited, but is preferably 10 times or more of the number average minor axis diameter.
- the number average major axis diameter may be not less than 50 nm and not less than 10 times the number average minor axis diameter. If the number average major axis diameter is less than 10 times the number average minor axis diameter, anisotropic growth of metal fine particles cannot be promoted sufficiently, which is not preferable.
- the number average minor axis diameter of the fine cellulose fiber is obtained by measuring the minor axis diameter (minimum diameter) of 100 fibers by observation with a transmission electron microscope and observation with an atomic force microscope, and calculating the average value.
- the number average major axis diameter of the refined cellulose fiber is obtained by measuring the major axis diameter (maximum diameter) of 100 fibers by observation with a transmission electron microscope and observation with an atomic force microscope, and calculating the average value thereof. Desired.
- the type and crystal structure of cellulose that can be used as a raw material for the refined cellulose fiber are not particularly limited.
- a raw material comprising cellulose I-type crystals for example, in addition to wood-based natural cellulose, non-wood-based natural cellulose such as cotton linter, bamboo, hemp, bagasse, kenaf, bacterial cellulose, squirt cellulose, and valonia cellulose Can be used.
- crystallization, and a cupra fiber can also be used. From the viewpoint of easy material procurement, it is preferable to use wood-based natural cellulose as a raw material.
- the method for refining cellulose is not particularly limited, but dilute acid hydrolysis treatment, enzyme treatment, or the like may be used in addition to the above-described mechanical treatment by a grinder, chemical treatment by TEMPO oxidation treatment, or the like.
- Bacterial cellulose can also be used as finely divided cellulose fibers.
- finely regenerated cellulose fibers obtained by dissolving various natural celluloses in various cellulose solvents and then performing electrospinning may be used.
- the fiber width is large, the transparency of the dispersion and the molded body using the same is lowered, and the use is limited when it is handled as an optical material such as a functional color material or a near-infrared absorbing material and a composition for forming the same. There is a risk of being.
- the short axis diameter of CSNF is reduced. Since it is as fine as about 3 nm and carbon nanotubes, it is possible to achieve high transparency of the dispersion and a molded body using the dispersion. In that case, for example, it can be suitably used as an optical member such as a near-infrared absorbing film.
- CSNF produced by TEMPO oxidation achieves anisotropic growth of metal fine particles more uniformly and with better reproducibility than CNF.
- the minor axis diameter is uniform at about 3 nm, it has carboxy groups that interact with metal ions, and these carboxy groups are fixed on the CSNF crystal surface at regular intervals. It is inferred that the structure is a cause. That is, both CNF and CSNF can be used as the refined cellulose fiber in the production method of the present embodiment.
- the refined cellulose used in the present embodiment is preferably a refined cellulose fiber having a carboxy group introduced on the crystal surface, and wood is used in terms of price and supply.
- CSNF obtained by TEMPO oxidation is more preferable.
- the wood-derived CSNF used in the present embodiment can be obtained through a step of oxidizing wood-derived cellulose and a step of finely pulverizing and dispersing it.
- transduced into CSNF 0.1 mmol / g or more and 5.0 mmol / g or less are preferable, and 0.5 mmol / g or more and 2.0 mmol / g or less are more preferable.
- the amount of carboxy group is less than 0.1 mmol / g, electrostatic repulsion does not work between cellulose microfibrils. Therefore, it is difficult to make cellulose finely dispersed uniformly.
- the wood-based natural cellulose is not particularly limited, and materials generally used for producing cellulose nanofibers such as softwood pulp, hardwood pulp, and waste paper pulp can be used. In view of ease of refining and refinement, softwood pulp or hardwood pulp is preferred.
- the method for introducing a carboxy group into the fiber surface of cellulose derived from wood is not particularly limited. Specifically, for example, carboxymethylation may be performed by reacting cellulose with monochloroacetic acid or sodium monochloroacetate in a high-concentration alkaline aqueous solution. Further, a carboxy group may be introduced by directly reacting a carboxylic anhydride compound such as maleic acid or phthalic acid gasified in an autoclave with cellulose. Furthermore, co-oxidation is performed in the presence of N-oxyl compounds such as TEMPO, which has high selectivity to the oxidation of alcoholic primary carbon while maintaining the crystal structure of cellulose as much as possible under relatively mild conditions in water. A technique using an agent may be used. TEMPO oxidation is more preferable from the viewpoint of selectivity of a carboxy group introduction site and environmental load.
- TEMPO N-oxyl compounds
- N-oxyl compound TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy radical), 2,2,6,6-tetramethyl-4-hydroxypiperidine-1 -Oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-ethoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamido-2,2 , 6,6-tetramethylpiperidine-N-oxyl, and the like.
- TEMPO is preferable.
- the amount of the N-oxyl compound used is not particularly limited, and may be an amount as a catalyst. Usually, it is about 0.01 to 5.0% by mass with respect to the solid content of wood-based natural cellulose to be oxidized.
- Examples of the oxidation method using an N-oxyl compound include a method in which wood-based natural cellulose is dispersed in water and oxidized in the presence of an N-oxyl compound. At this time, it is preferable to use a co-oxidant together with the N-oxyl compound.
- the N-oxyl compound is sequentially oxidized by a co-oxidant to produce an oxoammonium salt, and cellulose is oxidized by the oxoammonium salt. According to such oxidation treatment, the oxidation reaction proceeds smoothly even under mild conditions, and the introduction efficiency of the carboxy group is improved. When the oxidation treatment is performed under mild conditions, it is easy to maintain the crystal structure of cellulose.
- co-oxidant it is possible to promote an oxidation reaction such as halogen, hypohalous acid, halous acid or perhalogen acid, or a salt thereof, halogen oxide, nitrogen oxide, or peroxide.
- Any oxidizing agent can be used.
- Sodium hypochlorite is preferred because of its availability and reactivity.
- the amount of the co-oxidant used is not particularly limited, and may be an amount that can promote the oxidation reaction. Usually, it is about 1 to 200% by mass relative to the solid content of wood-based natural cellulose to be oxidized.
- At least one compound selected from the group consisting of bromide and iodide may be used in combination with the N-oxyl compound and the co-oxidant.
- an oxidation reaction can be advanced smoothly and the introduction efficiency of a carboxy group can be improved.
- sodium bromide or lithium bromide is preferable, and sodium bromide is more preferable from the viewpoint of cost and stability.
- the amount of the compound used is not particularly limited, and may be an amount that can promote the oxidation reaction. Usually, it is about 1 to 50% by mass relative to the solid content of wood-based natural cellulose to be oxidized.
- the reaction temperature of the oxidation reaction is preferably 4 ° C. or higher and 80 ° C. or lower, and more preferably 10 ° C. or higher and 70 ° C. or lower. If it is lower than 4 ° C., the reactivity of the reagent is lowered and the reaction time is prolonged. If the temperature exceeds 80 ° C., the side reaction is promoted, the sample is reduced in molecular weight, the highly crystalline rigidly refined cellulose fiber structure is collapsed, and the anisotropic growth of the metal fine particles cannot be sufficiently promoted.
- reaction time of the oxidation treatment can be appropriately set in consideration of the reaction temperature, the desired amount of carboxy group, etc., and is not particularly limited, but is usually about 10 minutes to 5 hours.
- the pH of the reaction system during the oxidation reaction is preferably 9 or more and 11 or less.
- the pH is 9 or more, the reaction can be efficiently carried out. If the pH exceeds 11, side reactions may progress and the decomposition of the sample may be accelerated.
- the pH of the reaction system is preferably maintained at 9 or more and 11 or less during the oxidation treatment. Examples of a method for maintaining the pH of the reaction system at 9 or more and 11 or less include a method of adding an alkaline aqueous solution in accordance with a decrease in pH.
- alkaline aqueous solutions examples include sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia aqueous solution, tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution, and benzyltrimethylammonium hydroxide aqueous solution.
- organic alkalis A sodium hydroxide aqueous solution is preferable from the viewpoint of cost.
- the oxidation reaction with the N-oxyl compound can be stopped by adding alcohol to the reaction system.
- the pH of the reaction system is preferably maintained within the above range.
- alcohol to be added low molecular weight alcohols such as methanol, ethanol and propanol are preferable in order to quickly terminate the reaction, and ethanol is particularly preferable from the viewpoint of safety of by-products generated by the reaction.
- the reaction solution after the oxidation treatment may be directly subjected to a refinement process, but in order to remove a catalyst such as an N-oxyl compound, impurities, etc., the oxidized cellulose contained in the reaction solution is recovered and washed with a washing solution. It is preferable. Oxidized cellulose can be collected by a known method such as filtration using a glass filter or a nylon mesh having a 20 ⁇ m pore size. As a cleaning liquid used for cleaning oxidized cellulose, pure water is preferable.
- the fine cellulose prepared in the first step is dispersed in a solvent to obtain a fine cellulose dispersion.
- an aqueous medium is added to cellulose and suspended (cellulose dispersion step).
- the aqueous medium include those described above, and water is particularly preferable.
- the pH of the suspension may be adjusted in order to increase the dispersibility of cellulose and the produced CSNF.
- the alkaline aqueous solution used for pH adjustment include the same alkaline aqueous solution as mentioned in the description of the oxidation step.
- the suspension is physically defibrated to refine the cellulose.
- Physical fibrillation treatment includes high-pressure homogenizer, ultra-high pressure homogenizer, ball mill, roll mill, cutter mill, planetary mill, jet mill, attritor, grinder, juicer mixer, homomixer, ultrasonic homogenizer, nanogenizer, underwater collision, etc. These mechanical treatments can be mentioned.
- a physical defibrating process on, for example, TEMPO oxidized cellulose, the cellulose in the suspension is refined. Thereby, a dispersion of CSNF having a carboxy group on the fiber surface can be obtained.
- the number average minor axis diameter and number average major axis diameter of CSNF contained in the obtained CSNF dispersion can be adjusted by the time and number of times of physical fibrillation treatment at this time.
- a CSNF dispersion into which a carboxy group has been introduced is obtained.
- the obtained dispersion can be used as a reaction field for reducing and precipitating metal fine particles as it is or by diluting, concentrating and the like.
- Flat silver nanoparticles can absorb light of any wavelength ranging from visible light to near infrared light by shape control, and can easily impart desired optical properties according to the use of various compositions. .
- silver itself has antibacterial properties against many bacterial species but is inert to the human body, a composition having good storage stability and safety can be obtained.
- metal species to be combined with wood-derived CSNF a plurality of metal species may be used, and metal species other than silver are not particularly limited.
- platinum group elements such as platinum, palladium, ruthenium, iridium, rhodium and osmium
- the corrosion resistance of CSNF can also be improved.
- the stability of the silver nanoparticles may be improved by coating the surrounding silver nanoparticles with a metal noble than silver or a metal oxide such as silica.
- a method for producing a composite by depositing metal fine particles in a wood-derived CSNF dispersion is not particularly limited, but is a solution of metal or alloy including silver, oxide, double oxide, etc. (metal ion-containing solution) ) And the CSNF dispersion are mixed (mixing step) and can be easily deposited by adding a reducing agent (reducing step).
- a reducing agent reducing step
- the type of the aqueous solution containing silver ions used for the reduction is not particularly limited, but a silver nitrate aqueous solution is preferable from the viewpoint of availability and ease of handling.
- the reducing agent used There is no particular limitation on the reducing agent used.
- ascorbic acid, citric acid, hydroquinone, sodium borohydride, sodium cyanoborohydride, dimethylamine borane, hydrazine and the like are used.
- Ascorbic acid, citric acid, and sodium borohydride are preferable from the viewpoint of safety and price.
- the solvent used for the dispersion of CSNF derived from wood contains 50% or more of water, and a solvent other than water is preferably a hydrophilic solvent.
- a solvent other than water is preferably a hydrophilic solvent.
- the hydrophilic solvent is not particularly limited, but alcohols such as methanol, ethanol and isopropanol; cyclic ethers such as tetrahydrofuran are preferred.
- the pH of the suspension may be adjusted in order to increase the dispersibility of cellulose and the produced CSNF. Examples of the alkaline aqueous solution used for pH adjustment include the same alkaline aqueous solution as described above.
- the concentration of the CSNF dispersion used for the preparation is not particularly limited, but is preferably 0.1% or more and less than 20%. If it is less than 0.1%, the composition for forming a molded body is excessive in solvent and the effect of controlling the particle size of the metal nanoparticles is insufficient, and if it is 20% or more, the viscosity is rapidly increased due to the entanglement between the finely divided cellulose fibers. And uniform stirring becomes difficult.
- the metal ion concentration of the solution containing metal ions to be used is not limited, but it is preferably prepared so that the amount of metal ions in the dispersion is less than the amount of carboxy groups present on the CSNF surface.
- CSNF aggregates if the amount of metal ions in the dispersion exceeds the amount of carboxy groups present on the CSNF surface.
- the three conditions of the CSNF concentration, the metal ion concentration, and the reducing agent concentration determine the aspect ratio of the precipitated flat metal fine particles. That is, by setting the three conditions to appropriate values, it is possible to appropriately produce a dispersion having an absorption peak at the target wavelength.
- the dispersion may contain spherical metal fine particles with a diameter of several nanometers as a by-product in addition to the flat metal fine particles / refined cellulose composite, but the spherical metal fine particles can be removed by a centrifuge. It is. Spherical fine particles of several nm containing at least silver absorb light at a wavelength of around 400 nm and exhibit a yellowish taste. However, if the spherical fine particles are removed, only the wavelength derived from the resonance peak of the plate-like metal fine particles / micronized cellulose composite is obtained. An absorbing dispersion can be obtained.
- the aspect ratio of the flat metal fine particle / fine cellulose cellulose composite is increased (for example, the particle diameter of the composite is more than twice the particle thickness), it should be used as a near-infrared absorbing material with high visible light transmittance. Is possible.
- the CSNF concentration, the metal ion concentration and the reducing agent concentration and the aspect ratio of the obtained tabular metal fine particle / CSNF composite there are many unclear points about the theoretical mechanism, but the plate metal fine particle / CSNF composite
- the specific method for producing the composition for molding an optical material that can also be used for an infrared absorbing material or the like is described in detail in Examples.
- the amount of silver used in the reduction precipitation treatment is 0.0005 mmol or more and 0.4 mmol or less with respect to 1 g of CSNF. It is preferably in the range, more preferably in the range of 0.001 mmol to 0.2 mmol, and particularly preferably in the range of 0.002 mmol to 0.1 mmol.
- the dispersion may contain other components than the components used for preparing the plate-like fine metal particles / CSNF composite and its preparation, as long as the effects of the present invention are not impaired.
- the other components are not particularly limited, and can be appropriately selected from known additives according to the use of the dispersion.
- organometallic compounds such as alkoxysilanes or hydrolysates thereof, inorganic layered compounds, inorganic needle minerals, antifoaming agents, inorganic particles, organic particles, lubricants, antioxidants, antistatic agents, Examples thereof include an ultraviolet absorber, a stabilizer, magnetic powder, an alignment accelerator, a plasticizer, and a crosslinking agent.
- the dispersion thus obtained is a dispersion containing a composite of at least one kind of metal containing silver or a fine particle of a compound thereof and a finely divided cellulose fiber.
- the dispersion has very good dispersion stability, and even when the contained particle size is 100 nm or more, the particles do not settle, and have a maximum absorbance at an arbitrary wavelength from 400 nm to 1500 nm.
- Industrial application is possible as a coating liquid for forming various optical members including an infrared absorbing material.
- a solution containing metal ions (metal ion-containing solution) is prepared by dissolving a metal or alloy, metal oxide, metal double oxide, or the like in a solvent such as water.
- a mixed solution of the refined cellulose dispersion and the metal ion-containing solution is obtained by adding the prepared metal ion-containing solution little by little while stirring the refined cellulose dispersion.
- tabular silver nanoparticles can absorb light of any wavelength ranging from visible light to near-infrared light by shape control, and easily impart desired optical characteristics according to the use of various compositions. be able to.
- silver itself since silver itself has antibacterial properties against many bacterial species but is inert to the human body, a composition having good storage stability and safety can be obtained.
- silver is preferable as the metal species to be combined with wood-derived CSNF, but is not particularly limited thereto.
- a plurality of metal species may be used as the metal species to be combined, and the metal species other than silver is not particularly limited.
- metals such as gold, iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, and aluminum, metal salts, metal complexes and alloys thereof, or oxides, double oxides, etc. Is mentioned.
- the corrosion resistance of CSNF can also be improved.
- the stability of the silver nanoparticles may be improved by coating the surrounding silver nanoparticles with a metal noble than silver or a metal oxide such as silica.
- the method for producing a composite by depositing metal fine particles in a wood-derived CSNF dispersion is not particularly limited. Precipitation can be easily carried out by adding a reducing agent in a mixed state of the above-described metal or alloy such as silver, a solution of oxide, double oxide and the CSNF dispersion.
- the type of aqueous solution containing silver ions used for the reduction is not particularly limited, but an aqueous silver nitrate solution is preferable from the viewpoint of availability and ease of handling.
- the reducing agent to be used is not particularly limited.
- As the silver reducing agent for example, ascorbic acid, citric acid, hydroquinone, sodium borohydride, sodium cyanoborohydride, dimethylamine borane, hydrazine and the like are used. Ascorbic acid, citric acid, and sodium borohydride are preferable from the viewpoint of safety and price.
- the amount of silver used in the reduction precipitation treatment is 0.0005 mmol or more to 0.1 g of CSNF. It is preferably in the range of 4 mmol or less, more preferably in the range of 0.001 mmol or more and 0.2 mmol or less, and particularly preferably in the range of 0.002 mmol or more and 0.1 mmol or less.
- FIG. 2 is a schematic diagram for explaining a part of the steps of the method for producing a composite body which is an embodiment to which the present invention is applied.
- the metal deposition starts from the carboxy group provided in the micronized cellulose 3 by the addition of the reducing agent in the mixed solution.
- the deposited metal forms primary particles (metal nanoparticles) 2a (see the left figure in FIG. 2).
- these primary particles 2 a aggregate to form flat metal fine particles (that is, flat metal fine particles) 2.
- a part 3a of CSNF (fine cellulose fiber) 3 is incorporated into the metal fine particles 2 and is compounded with the remaining part 3b exposed (see the right figure in FIG. 2).
- the composite 1 of the flat metal fine particles 2 and the refined cellulose 3 of the present embodiment can be obtained.
- the concentration of the CSNF dispersion is not particularly limited in the second step described above, but is preferably 0.1% or more and less than 20%.
- the concentration for forming a molded body becomes excessive in solvent.
- the viscosity rapidly increases due to the entanglement between the finely divided cellulose fibers, and uniform stirring becomes difficult.
- the concentration of metal ions in the solution containing metal ions is not particularly limited, but it is preferable to prepare so that the amount of metal ions in the dispersion is less than the amount of carboxy groups present on the CSNF surface. . This is because CSNF aggregates if the amount of metal ions in the dispersion exceeds the amount of carboxy groups present on the CSNF surface.
- the concentration of the reducing agent in the mixed solution is not particularly limited, but is preferably adjusted to be equal to or higher than the metal ion concentration. This is because unreduced metal ions remain in the mixed solution when the reducing agent concentration in the mixed solution is equal to or lower than the metal ion concentration.
- the three conditions of the CSNF concentration, the metal ion concentration, and the reducing agent concentration determine the aspect ratio of the precipitated flat metal fine particles. That is, by setting these three conditions to appropriate values, it is possible to appropriately produce a composite of flat metal fine particles having an absorption peak at a target wavelength and fine cellulose.
- the aspect ratio of the flat metal fine particles increases, and when the metal ion concentration increases, the aspect ratio decreases.
- the relationship between the CSNF concentration, the metal ion concentration, the reducing agent concentration, and the aspect ratio of the composite of the obtained flat metal fine particles and CSNF is theoretical.
- the mechanism is unclear.
- the specific method for producing an optical material that can be used for a composite of flat metal fine particles and CSNF, a near-infrared absorbing material, and the like is described in detail in the examples.
- a dispersion of the composite can be obtained by dispersing the composite of the flat metal fine particles and the fine cellulose in the present embodiment in water or an organic solvent.
- an organic solvent what was mentioned above can be used and it is preferable to use alcohols, such as methanol, ethanol, and IPA.
- arbitrary addition components such as aqueous alkali solution used for pH adjustment, may be included.
- reaction liquid after the fourth step in the above-described method for producing a composite according to this embodiment can be used as a dispersion as it is.
- dispersion of the composite of the present embodiment composite dispersion
- aggregation is inhibited by steric hindrance and electrostatic repulsion between micronized cellulose, so that the composite in the dispersion medium is difficult to settle and dispersion stability. Excellent.
- the near-infrared absorbing material Since the composite of the plate-like fine metal particles and fine cellulose of this embodiment and the composite dispersion described above have a maximum absorbance at an arbitrary wavelength in the wavelength range of 400 nm to 1500 nm, the near-infrared absorbing material is first used. It can be used as various optical members.
- spherical metal fine particles having a diameter of about several nm may be included as a by-product.
- these spherical metal fine particles can be separated by a centrifuge.
- spherical fine particles having a diameter of several nanometers containing at least silver have a yellowish color to absorb light having a wavelength of around 400 nm.
- centrifugation or the like by removing these spherical fine particles by the above-mentioned centrifugation or the like, it can be used as a novel optical material that absorbs only the wavelength derived from the resonance peak of the complex of flat metal fine particles and fine cellulose. Is possible.
- the composite of the flat metal fine particles and the fine cellulose of the present embodiment having a large aspect ratio can be used as a near-infrared absorbing material having a high visible light transmittance.
- the composite 1 of the present embodiment at least a part (3a) of each of the refined celluloses 3 is taken into the flat metal fine particles 2 and the remaining part (3b) is a flat metal.
- the structure is exposed on the surface of the fine particles 2. Therefore, the composite 1 of the flat metal fine particles 2 and the refined cellulose 3 having applicability to an optical material such as a functional color material or a near-infrared absorbing material can be provided.
- the method for producing a composite of the present embodiment there is a step of reducing the metal ions in the mixed solution to grow the flat metal fine particles and combining the flat metal fine particles and the fine cellulose. Therefore, the above-mentioned complex can be easily provided with a low environmental load.
- dispersion of the composite of this embodiment aggregation is inhibited by steric hindrance or electrostatic repulsion between the refined celluloses, so that the composite in the dispersion medium is less likely to settle and has excellent dispersion stability.
- a dispersion can be provided.
- the composite dispersion can also be used as an optical material.
- the optical material of the present embodiment includes a composite having a maximum absorbance at an arbitrary wavelength from 400 nm to 1500 nm, and thus is useful as a functional color material or a near-infrared absorbing material.
- Example 1> (TEMPO oxidation of wood cellulose) 70 g of softwood kraft pulp was suspended in 3500 g of distilled water, and a solution of 0.7 g of TEMPO and 7 g of sodium bromide dissolved in 350 g of distilled water was added and cooled to 20 ° C. 450 g of sodium hypochlorite aqueous solution having a concentration of 2 mol / L and a density of 1.15 g / mL was added dropwise thereto to initiate an oxidation reaction. The temperature in the system was always kept at 20 ° C., and the decrease in pH during the reaction was kept at pH 10 by adding a 0.5N aqueous sodium hydroxide solution.
- Oxidized pulp and re-oxidized pulp obtained by the TEMPO oxidation were weighed in an amount of 0.1 g by solid content, dispersed in water at a concentration of 1%, and hydrochloric acid was added to adjust the pH to 2.5. Thereafter, the amount of carboxy groups (mmol / g) was determined by conductivity titration using a 0.5 M aqueous sodium hydroxide solution. The result was 1.6 mmol / g.
- a silver nitrate aqueous solution was prepared by dissolving 50 mg of silver nitrate in 10 mL of distilled water.
- FIG. 3A shows a schematic diagram of the SEM image obtained in FIG. 3A.
- a dispersion containing a complex of purified flat metal fine particles and refined cellulose was cast on a PET film, and observed from the cross-sectional direction using a transmission electron microscope (manufactured by JEOL Ltd., “JEM2100F”).
- JEM2100F transmission electron microscope
- the result observed from the cross-sectional direction with a transmission electron microscope (TEM) is shown in FIG.
- the thickness of the flat metal fine particles was calculated from the obtained TEM image.
- a dispersion containing a complex of refined planar metal fine particles and refined cellulose was cast on a silicon wafer plate, followed by SEM observation without vapor deposition, followed by elemental mapping by energy dispersive X-ray analysis. . The result is shown in FIG.
- FIGS. 5A and 5B are an enlarged view of FIG. 5A.
- the diameter when the tabular silver nanoparticles in the obtained image were approximated by a circle was calculated as the particle diameter in the plane direction.
- Example 2 a dispersion containing a tabular silver / refined cellulose composite was produced under the same conditions as in Example 1 except that the addition amount of the aqueous silver nitrate solution was 1.0 mL.
- the obtained tabular silver / micronized cellulose composite was observed with an electron microscope and measured with a spectral absorption spectrum in the same manner as in Example 1. The results are shown in Table 1, FIG. 5C, FIG. 5D, and FIG. 5D is an enlarged view of FIG. 5C.
- Example 3 a dispersion containing a tabular silver / fine cellulose composite was produced under the same conditions as in Example 1 except that the addition amount of the aqueous silver nitrate solution was 0.5 mL.
- the obtained tabular silver / micronized cellulose composite was observed with an electron microscope and measured with a spectral absorption spectrum in the same manner as in Example 1. The results are shown in Table 1 and FIGS. 5E, 5F, and 6.
- FIG. 5F is an enlarged view of FIG. 5E.
- Example 4 In Example 1, except that the CSNF concentration was 1.5%, the addition amount of the aqueous silver nitrate solution was 3 mL, and the addition amount of the aqueous sodium borohydride solution was 3 mL, tabular silver / fine particles were obtained under the same conditions as in Example 1. A cellulose cellulose composite was prepared. The obtained tabular silver / micronized cellulose composite was observed with an electron microscope and measured with a spectral absorption spectrum in the same manner as in Example 1. The results are shown in Table 1 and FIG.
- Example 1 ⁇ Comparative Example 1>
- an experiment was performed under the same conditions as in Example 1 except that an aqueous polyvinyl alcohol (PVA) solution having a concentration of 1% was used instead of the CSNF aqueous dispersion having a concentration of 1%.
- PVA polyvinyl alcohol
- Example 2 ⁇ Comparative example 2>
- an experiment was performed under the same conditions as in Example 1 except that an aqueous solution of sodium polyacrylate (PAANA) having a concentration of 1% was used in place of the CSNF aqueous dispersion having a concentration of 1%. Then, electron microscope observation and spectral absorption spectrum measurement of the obtained composition were performed in the same manner as in Example 1. The results are shown in Table 1 and FIG.
- the shape of the plate-like silver viewed from the cross-sectional direction is a rectangle, and the length in the minor axis direction is about 10 nm. Therefore, the plate-like silver is about 10 nm thick. Turned out to be particles. The thickness was about 10 nm in any of the samples of Examples 1 to 4, indicating that only the size parallel to the plane can be selectively controlled only by the difference in the amount of silver nitrate aqueous solution added. .
- the composite of silver and refined cellulose contained in the dispersions obtained in Examples 1 to 4 is a composite in which tabular silver fine particles and CSNF are completely bonded. It has been shown that it is a new environmentally friendly optical material using carbon neutral materials.
- the diameter when the tabular silver nanoparticles in the images shown in FIGS. 5A to 5F were approximated by a circle was calculated as the particle diameter in the plane direction, and the particle diameter in the plane direction was compared for each example.
- FIG. 6 is a diagram showing spectral transmission spectra of composites of flat metal fine particles and CSNF produced in Examples 1 to 4 and Comparative Examples 1 and 2.
- Table 1 and FIG. 6 from the measurement result of the spectral transmission spectrum, the absorption peak of the dispersion obtained in Example 1 is 758 nm, Example 2 is 832 nm, Example 3 is 966 nm, and Example 4 is 724 nm. It was confirmed that. That is, it is confirmed that the composite of flat silver fine particles and refined cellulose has an absorption peak wavelength that shifts to a longer wavelength region as the aspect ratio (particle diameter / particle thickness) increases. It was confirmed that it was available as
- Example 4 the absorption peak of Example 4 was 724 nm, which was about the same as that of Example 1, but the transmittance was lower than that of Example 1. This is because the concentration of the complex contained in the dispersion increased due to the increase in the CSNF concentration and the charged amount of the aqueous silver nitrate solution during the production.
- FIG. 7A shows the result of further STEM imaging of the composite of tabular silver and fine cellulose obtained in Example 3
- FIG. 8A shows the result of SEM imaging of the enlargement.
- FIG. 7A shows an enlarged STEM image of the composite obtained in Example 3 with a scanning transmission electron microscope (STEM)
- FIG. 7B is a schematic diagram of the STEM image of FIG. 7A.
- FIG. 8A has shown the SEM image observed by expanding with the scanning electron microscope (SEM) of the composite_body
- FIG. 8B is a schematic diagram of the SEM image of FIG. 8A. .
- the fibrous trace which seems to be originated from CSNF caught in the silver crystal part was able to be observed.
- the silver crystal portion is denoted by reference numeral 22, and the fibrous trace that appears to be derived from CSNF is denoted by reference numeral 23 a.
- FIG. 8A fibrous traces that were thought to be derived from CSNF exposed from the silver crystal portion could be observed.
- the silver crystal portion is denoted by reference numeral 22, and the fibrous trace that appears to be derived from CSNF is denoted by reference numeral 23 b.
- the dispersion containing the tabular silver fine particles / micronized cellulose composite prepared in Examples 1 to 4 can remove spherical silver nanoparticles by centrifugation, it is visible while maintaining the absorbance in the near infrared region. It was also confirmed that the light transmittance in the light region can be increased.
- Comparative Examples 1 and 2 only spherical silver fine particles were confirmed by electron microscope observation, and only an absorption peak around 420 nm derived from the resonance peak of the spherical silver fine particles was detected in the spectral transmission spectrum (see Table 1). reference). That is, in this reaction, CSNF was shown to be an essential material as a shape control material that promotes anisotropic growth of metal fine particles and controls the shape. The detailed mechanism for this is unknown. However, since PAANA Na used in Comparative Example 2 does not function as a shape control material even though it contains a lot of carboxy groups like CSNF, the structure of carboxy groups regularly fixed and arranged at high density on the crystal surface of CSNF. It may be a factor that induces anisotropic growth of silver fine particles.
- Example 5 In Example 1, an experiment was performed under the same conditions as in Example 1 except that a 20 mM chloroauric acid aqueous solution was used instead of the silver nitrate aqueous solution, and the resulting composition was observed under an electron microscope as in Example 1. Went in the way.
- Example 6 In Example 1, an experiment was performed under the same conditions as in Example 1 except that a 15 mM chloroplatinic acid aqueous solution was used instead of the silver nitrate aqueous solution, and the obtained composition was observed under an electron microscope as in Example 1. Went in the way.
- Example 5 flat gold fine particles (flat gold fine particles) having a particle diameter of about 50 to 100 nm, A complex with chlorinated cellulose was observed.
- Example 6 a complex of flat platinum fine particles (flat platinum fine particles) having a particle diameter of about 40 to 80 nm and fine cellulose was observed.
- Example 3 a dispersion containing tabular silver nanoparticles was prepared. That is, 15 mL of an ethylene glycol solution of 800 mM polyvinylpyrrolidone (PVP) (K30, mass average molecular weight 40000) was added to 15 mL of an ethylene glycol solution of 50 mM silver nitrate (manufactured by Kanto Chemical Co., Inc.). When this reaction solution was stirred with a hot stirrer at 130 ° C. for 1 hour, the color of the reaction solution changed from colorless to blue.
- PVP polyvinylpyrrolidone
- the present invention when used, a dispersion containing flat metal fine particles / refined cellulose composite that has not been reported so far can be obtained. Since the dispersion selectively absorbs light having an arbitrary wavelength from visible light to near infrared light, it can be used as a novel optical material molding composition. In addition, since finely divided cellulose is bonded to the plate-like metal fine particles contained in the dispersion, it is possible to maintain a good dispersion state for a long time.
- a complex of flat metal fine particles and fine cellulose by a low environmental load and simple process using a biomass material a dispersion containing a complex of flat metal fine particles and fine cellulose, and It is possible to provide a novel optical material that can be used as a manufacturing method thereof, a functional color material, and a near-infrared absorbing material.
- a composite of flat metal fine particles and fine cellulose is a novel carbon-neutral organic-inorganic hybrid material that has not been reported so far.
- a dispersion containing a composite of flat metal fine particles and finely divided cellulose is a composition for forming a new optical material that can be applied to near-infrared absorbing materials and heat shielding materials. Application as a coating liquid is possible.
- special optical materials, security materials, optical sensors, dye-sensitized solar cells, antibacterial medical members, antibacterial additives for personal care products, etc. are also considered as new optical material applications.
- a ripple effect is expected.
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Abstract
Description
本願は、2014年5月9日に日本に出願された特願2014-097635号、及び2014年5月15日に日本に出願された特願2014-101632号に基づき優先権を主張し、その内容をここに援用する。
更にまた、本発明は、機能性色材や近赤外線吸収材料として利用可能な光学材料を提供することを課題とする。
本発明の第1態様に係る複合体は、少なくとも1種類以上の金属又はそれらの化合物で形成される平板状金属微粒子と、前記平板状金属微粒子と複合化され、少なくとも一つ以上の微細化セルロースと、を備え、前記微細化セルロースのそれぞれは、少なくとも一部が前記平板状金属微粒子に取り込まれるとともに、残部が前記平板状金属微粒子の表面に露出する。
なお、以下の説明で用いる図面は、特徴をわかりやすくするために、便宜上特徴となる部分を拡大して示している場合があり、各構成要素の寸法比率などが実際と同じであるとは限らない。
先ず、本発明の一実施形態に係る複合体及び分散液に含まれる複合体について説明する。
図1は、本発明の一実施形態に係る複合体(分散液に含まれる複合体)1の構成を模式的に示す斜視図である。図1に示すように、複合体1は、平板状の金属微粒子(平板状金属微粒子)2と、少なくとも一つ以上の微細化されたセルロース3とが複合化された、平板状金属微粒子と微細化セルロースとの複合体である。複合体1では、それぞれの微細化セルロース3について少なくとも一部(一部分)又は全部が平板状金属微粒子2に取り込まれており、残部が平板状金属微粒子2の表面に露出するように複合化されている。
平板状金属微粒子2の粒子径は、20~500nmが好ましく、20~400nmがより好ましい。
平板状金属微粒子2の粒子厚みは、5~100nmが好ましく、8~50nmがより好ましい。
平均アスペクト比(粒子径/粒子厚み)は、2.0以上が好ましく、2.0~100がより好ましく、2.0~50が更に好ましい。
(1)粒子径の測定法
複合体を含む分散液をTEM観察用支持膜付き銅グリッド上にキャストして風乾したのち、透過型電子顕微鏡観察を行う。得られた画像中の平板状銀ナノ粒子を、円で近似した際の径を平面方向の粒子径として算出する。
(2)厚みの測定法
複合体を含む分散液をPETフィルム上にキャストして風乾し包埋樹脂で固定して得られた樹脂の塊をミクロトームで断面方向に切削し、透過型電子顕微鏡観察を行う。得られた画像中の平板状銀ナノ粒子の厚みを平面方向の粒子径として算出する。
(3)アスペクト比の算出方法
上述のようにして求めた粒子径をaとし、粒子厚みをbとした際に、粒子径aを粒子厚みbで割った値を、アスペクト比=a/bとして算出する。
なお、上述した測定方法および算出方法は一例であり、特にこれらに限定されない。
次に、上述した実施形態に係る複合体1の製造方法について説明する。複合体1の製造方法は、微細化されたセルロースと金属イオンとを含む分散液中で、金属を還元析出させて金属結晶を生成するとともに、異方性をもってこの金属結晶を成長させることにより、平板状金属微粒子と微細化セルロースとの複合体を得る方法である。
先ず、第1工程では、本実施形態の複合体を構成する微細化セルロースを調製する。この第1工程は、繊維状の微細化セルロースを調製する工程と、微細化セルロースの結晶表面にカルボキシ基を導入する工程と、を含んでいる。
本実施形態に係る複合体の製造方法に用いる微細化セルロースは、その構造の少なくとも一辺がナノメートルオーダーであればよく、その調製方法については特に限定されない。通常、微細化セルロースは、ミクロフィブリル構造由来の繊維形状を取る。そのため、本実施形態の製造方法に用いる微細化セルロースとしては、以下に示す微細化セルロースが好ましい。すなわち、微細化セルロースの形状としては、例えばミクロフィブリル構造由来の繊維形状などの繊維状であることが好ましい。また、繊維状の微細化セルロースは、短軸径において数平均短軸径が1nm以上100nm以下であればよく、好ましくは2nm以上50nm以下であればよい。ここで、数平均短軸径が1nm未満では高結晶性の剛直な微細化セルロース繊維構造をとることが出来ず、金属微粒子の異方成長を十分に促進することができない。一方、100nmを超えると、金属微粒子に対してサイズが大きくなり過ぎるため、平板状金属微粒子と微細化セルロースとの複合体の形状を有することができない。
また、数平均長軸径においては特に制限はないが、好ましくは数平均短軸径の10倍以上であればよい。より好ましくは、数平均長軸径が50nm以上であってかつ数平均短軸径の10倍以上であればよい。数平均長軸径が数平均短軸径の10倍未満であると、金属微粒子の異方成長を十分に促進することができないために好ましくない。
一方、微細化セルロース繊維の数平均長軸径は、透過型電子顕微鏡観察および原子間力顕微鏡観察により100本の繊維の長軸径(最大径)を測定し、その平均値を算出することで求められる。
木材系天然セルロースとしては、特に限定されず、針葉樹パルプや広葉樹パルプ、古紙パルプ、など、一般的にセルロースナノファイバーの製造に用いられる材料を用いることができる。精製および微細化のしやすさから、針葉樹パルプまたは広葉樹パルプが好ましい。
次に、第2工程では、上記第1工程で調製した微細化セルロースを溶媒中に分散させて微細化セルロース分散液を得る。
平板状銀ナノ粒子は形状制御により可視光線から近赤外光線にわたる任意の波長光を吸収することが可能であり、各種組成物の用途に合わせて所望の光学特性を容易に付与することができる。また、銀そのものが多菌種に対し抗菌性を有しながらも人体に対し不活性であることから、保存性、安全性の良好な組成物を得ることができる。木材由来のCSNFと複合化する金属種としては複数の金属種を用いても良く、銀以外の金属種としては特に限定しないが、例えば白金やパラジウム、ルテニウム、イリジウム、ロジウム、オスミウムの白金族元素の他、金、鉄、鉛、銅、クロム、コバルト、ニッケル、マンガン、バナジウム、モリブデン、ガリウム、アルミニウムなどの金属、金属塩、金属錯体およびこれらの合金、または酸化物、複酸化物等が挙げられる。また、銀と複合体を形成することで抗菌性を付与できることから、CSNFの耐腐食性も改善することができる。複数の金属種を用いる場合、析出した銀ナノ粒子の周りを銀より貴な金属あるいはシリカ等の金属酸化物などで被覆して、銀ナノ粒子の安定性を向上させても良い。木材由来のCSNF分散液中に金属微粒子を析出させ複合体を製造する方法としては、特に限定しないが、銀をはじめとする金属または合金、酸化物、複酸化物等の溶液(金属イオン含有溶液)とCSNF分散液とを混合(混合工程)した状態で、還元剤を添加すれば容易に析出させることができる(還元工程)。銀の場合、還元を行う際に用いる銀イオンを含む水溶液の種類には特に制限は無いが、入手の容易さと取り扱い易さの点から硝酸銀水溶液であることが好ましい。用いる還元剤に関しても特に限定しない。例えばアスコルビン酸、クエン酸、ヒドロキノン、水素化ホウ素ナトリウム、シアノ水素化ホウ素ナトリウム、ジメチルアミンボラン、ヒドラジン等が用いられる。安全性や価格の面からアスコルビン酸、クエン酸、水素化ホウ素ナトリウムが好ましい。
次に、第3工程では、上述の第2工程で得られた微細化セルロース分散液と、金属イオンを含有する溶液と、を混合して混合溶液を得る。
具体的には、先ず、金属または合金、金属酸化物、金属複酸化物などを水などの溶媒に溶解させて、金属イオンを含有する溶液(金属イオン含有溶液)を調製する。次に、微細化セルロース分散液を攪拌しながら、調製した金属イオン含有溶液を少しずつ添加することにより、微細化セルロース分散液と金属イオン含有溶液との混合溶液を得る。
次に、第4工程では、上述の第3工程で得られた混合溶液中の金属イオンを還元して平板状金属微粒子を成長させるとともに、平板状金属微粒子と微細化セルロースとを複合化する。
本実施形態の製造方法の第4工程では、先ず、混合溶液中への還元剤の添加により、微細化セルロース3に設けたカルボキシ基を起点に金属の析出が開始する。そして、析出した金属は一次粒子(金属ナノ粒子)2aを形成する(図2中の左図を参照)。さらに反応が進むと、これらの一次粒子2a同士が凝集して、平板状の金属微粒子(すなわち、平板状金属微粒子)2を形成する。この際、CSNF(微細化セルロースの繊維)3の一部3aが金属微粒子2に取り込まれるとともに残部3bが露出した状態で複合化する(図2中の右図を参照)。
以上の工程により、本実施形態の平板状金属微粒子2と微細化セルロース3との複合体1を得ることができる。
本実施形態の平板状金属微粒子と微細化セルロースとの複合体を、水または有機溶媒に分散させることによって、複合体の分散液とすることができる。ここで、有機溶媒としては、上述したものを用いることができ、メタノール、エタノール、IPAなどのアルコール類を用いることが好ましい。また、pH調整に用いられるアルカリ水溶液等の、任意の添加成分を含んでいてもよい。
本実施形態の平板状金属微粒子と微細化セルロースとの複合体、および上述した複合体分散液は、波長400nmから1500nmにおける任意の波長に吸光度の最大値を有することから、近赤外線吸収材料を初めとした様々な光学部材として用いることができる。
(木材セルロースのTEMPO酸化)
針葉樹クラフトパルプ70gを蒸留水3500gに懸濁し、蒸留水350gにTEMPOを0.7g、臭化ナトリウムを7g溶解させた溶液を加え、20℃まで冷却した。ここに2mol/L、密度1.15g/mLの次亜塩素酸ナトリウム水溶液450gを滴下により添加し、酸化反応を開始した。系内の温度は常に20℃に保ち、反応中のpHの低下は0.5Nの水酸化ナトリウム水溶液を添加することでpH10に保ち続けた。セルロースの重量に対して、水酸化ナトリウムの添加量の合計が3.50mmol/gに達した時点で、約100mLのエタノールを添加し反応を停止させた。その後、ガラスフィルターを用いて蒸留水によるろ過洗浄を繰り返し、酸化パルプを得た。
上記TEMPO酸化で得た酸化パルプおよび再酸化パルプを固形分重量で0.1g量りとり、1%濃度で水に分散させ、塩酸を加えてpHを2.5とした。その後0.5M水酸化ナトリウム水溶液を用いた電導度滴定法により、カルボキシ基量(mmol/g)を求めた。結果は1.6mmol/gであった。
上記TEMPO酸化で得た酸化パルプ1gを99gの蒸留水に分散させ、ジューサーミキサーで30分間微細化処理し、CSNF濃度1%のCSNF水分散液を得た。このCSNF水分散液に含まれるCSNFの数平均短軸径は4nm、数平均長軸径は1110nmであった。また、レオメーターを用いて定常粘弾性測定を行ったところ、このCSNF分散液はチキソトロピック性を示した。
硝酸銀50mgを蒸留水10mLに溶解させ、硝酸銀水溶液を調製した。
水素化ホウ素ナトリウム50mgを蒸留水10mLに溶解させ、水素化ホウ素ナトリウム水溶液を調製した。
上述した1%CSNF水分散液50gを温度一定(15℃)に保ち攪拌しながら、硝酸銀水溶液2.0mLを添加した。5分攪拌を続けたのち、水素化ホウ素ナトリウム水溶液を2mL添加し、さらに30分ほど攪拌を続けることによって分散液中に平板状金属微粒子と微細化セルロースとの複合体を作製した。
得られた分散液中の平板状金属微粒子と微細化セルロースとの複合体を、高速冷却遠心機を用い、75,600g(30分×5セット)の条件で精製・分画した。精製済みの平板状金属微粒子を含む分散液をシリコンウェハ板上にキャストし、白金蒸着処理を施した後、走査型電子顕微鏡(日立ハイテク社製、「S-4800」)を用いて垂直方向から観察した。得られた複合体の走査型電子顕微鏡(SEM)による観察結果を図3Aに示す。また、図3Bには図3Aで得られたSEM画像の模式図を示す。平板状金属微粒子とCSNFとの同時観察を行うことで、CSNFと平板状金属微粒子との間の相互結合状態を確認した。
平板状金属微粒子と微細化セルロースとの複合体の水分散液を石英セルに入れ、分光光度計(島津製作所社製、「UV-3600」)を用いて分光スペクトルの測定を行った。
結果を表1および図6に示す。
実施例1において、硝酸銀水溶液の添加量を1.0mLとした以外は、実施例1と同様の条件で平板状銀/微細化セルロース複合体含む分散液を作製した。そして、得られた平板状銀/微細化セルロース複合体の電子顕微鏡観察および分光吸収スペクトル測定を実施例1と同様の方法で行った。結果を表1、図5C、図5D、及び図6に示す。なお、図5Dは、図5Cの拡大図である。
実施例1において、硝酸銀水溶液の添加量を0.5mLとした以外は、実施例1と同様の条件で平板状銀/微細化セルロース複合体を含む分散液を作製した。そして、得られた平板状銀/微細化セルロース複合体の電子顕微鏡観察および分光吸収スペクトル測定を実施例1と同様の方法で行った。結果を表1および図5E、図5F、及び図6に示す。なお、図5Fは、図5Eの拡大図である。
実施例1において、CSNFの濃度を1.5%、硝酸銀水溶液の添加量を3mL、水素化ホウ素ナトリウム水溶液の添加量を3mLとした以外は、実施例1と同様の条件で平板状銀/微細化セルロース複合体を作製した。そして、得られた平板状銀/微細化セルロース複合体の電子顕微鏡観察および分光吸収スペクトル測定を実施例1と同様の方法で行った。結果を表1および図6に示す。
実施例1において、濃度1%のCSNF水分散液の代わりに濃度1%のポリビニルアルコール(PVA)水溶液を用いたこと以外は、実施例1と同様の条件で実験を行った。そして、得られた組成物の電子顕微鏡観察および分光吸収スペクトル測定を実施例1と同様の方法で行った。結果を表1および図6に示す。
実施例1において、濃度1%のCSNF水分散液の代わりに濃度1%のポリアクリル酸ナトリウム(PAANa)水溶液を用いたこと以外は、実施例1と同様の条件で実験を行った。そして、得られた組成物の電子顕微鏡観察および分光吸収スペクトル測定を実施例1と同様の方法で行った。結果を表1および図6に示す。
表1及び図6に示すように、分光透過スペクトルの測定結果から、実施例1で得られた分散液の吸収ピークは758nm、実施例2は832nm、実施例3は966nm、実施例4は724nmであることが確認された。すなわち、平板状銀微粒子と微細化セルロースとの複合体は、アスペクト比(粒子径/粒子厚み)が大きくなればなるほど吸収ピーク波長が長波長領域へとシフトすることが確認され、近赤外線吸収材料として利用可能であることが確かめられた。
図8Aに示すように、銀結晶部分から露出したCSNF由来と思われる繊維状の形跡を観察することができた。また、図8Bに示す模式図では、銀結晶部分には符号22を付しており、CSNF由来と思われる繊維状の形跡には符号23bを付している。
実施例1において、硝酸銀水溶液の代わりに20mM塩化金酸水溶液を用いたこと以外は、実施例1と同様の条件で実験を行い、得られた組成物の電子顕微鏡観察を実施例1と同様の方法で行った。
実施例1において、硝酸銀水溶液の代わりに15mM塩化白金酸水溶液を用いたこと以外は、実施例1と同様の条件で実験を行い、得られた組成物の電子顕微鏡観察を実施例1と同様の方法で行った。
特許文献6に記載の実施例3に従い、平板状銀ナノ粒子を含む分散液を作製した。
すなわち、50mMの硝酸銀(関東化学株式会社製)のエチレングリコール溶液15mLに、800mMのポリビニルピロリドン(PVP)(K30、質量平均分子量40000)のエチレングリコール溶液15mLを添加した。この反応液をホットスターラーで、130℃にて1時間加熱して攪拌したところ、反応液の色が無色から青色に変化した。この反応液を冷却した後、水で5倍希釈し、遠心分離(10500rpm×30分)により精製することにより、平板状銀ナノ粒子分散液を作製した。
得られた分散液に対し、得られた組成物の電子顕微鏡観察を実施例1と同様の方法(図5A~5Fを参照)で行った。その結果、平面方向の粒子径として、100~150nm程度の粒子径を有する平板状銀ナノ粒子が多く観察された。
実施例1~4および比較例3で得られた精製済み分散液を4℃冷蔵庫内で1ヶ月保存した後、沈殿物の有無を目視で確認した。結果を表2に示す。
2・・・平板状金属微粒子(平板状銀微粒子)
3・・・微細化セルロース(CSNF)
3a・・・平板状金属微粒子に取り込まれている部分
3b・・・平板状金属微粒子の表面に露出している部分
Claims (34)
- 少なくとも1種類以上の金属又はそれらの化合物で形成される平板状金属微粒子と、
前記平板状金属微粒子と複合化され、少なくとも一つ以上の微細化セルロースと、を備える複合体であって、
前記微細化セルロースのそれぞれは、少なくとも一部が前記平板状金属微粒子に取り込まれるとともに、残部が前記平板状金属微粒子の表面に露出する複合体。 - 前記平板状金属微粒子と前記微細化セルロースとが不可分である請求項1に記載の複合体。
- 前記平板状金属微粒子が、銀である請求項1又は2に記載の複合体。
- 前記平板状金属微粒子の粒子径が、前記平板状金属微粒子の粒子厚みの2倍以上である請求項1乃至3のいずれか一項に記載の複合体。
- 前記微細化セルロースが、結晶表面にカルボキシ基を有する請求項1乃至4のいずれか一項に記載の複合体。
- 前記カルボキシ基の含有量が、セルロース1g当たり0.1mmol以上5.0mmol以下である請求項5に記載の複合体。
- 前記微細化セルロースの結晶構造が、セルロースI型である請求項1乃至6のいずれか一項に記載の複合体。
- 前記微細化セルロースの形状が、天然セルロースのミクロフィブリル構造由来の繊維状である請求項1乃至7のいずれか一項に記載の複合体。
- 前記微細化セルロースは、数平均短軸径が1nm以上100nm以下、数平均長軸径が50nm以上であり、かつ数平均長軸径が数平均短軸径の10倍以上である請求項1乃至8のいずれか一項に記載の複合体。
- 平板状金属微粒子と微細化セルロースとの複合体を製造する方法であって、
微細化セルロースを調製し、
前記微細化セルロースを溶媒中に分散させることで微細化セルロース分散液を得て、
前記微細化セルロース分散液と、金属イオンを含有する溶液と、を混合することで混合溶液を得て、
前記混合溶液中の前記金属イオンを還元して平板状金属微粒子を成長させるとともに、前記平板状金属微粒子と前記微細化セルロースとを複合化することを含む複合体の製造方法。 - 前記金属イオンが、銀イオンである請求項10に記載の複合体の製造方法。
- 前記微細化セルロースを調製する際に、繊維状の前記微細化セルロースを調製する請求項10又は11に記載の複合体の製造方法。
- 前記微細化セルロースを調製する際に、前記微細化セルロースの結晶表面にカルボキシ基を導入する請求項10乃至12のいずれか一項に記載の複合体の製造方法。
- 前記カルボキシ基を導入する際に、N-オキシル化合物を用いた酸化反応を用いる請求項13に記載の複合体の製造方法。
- 前記カルボキシ基を導入する際に、セルロース1g当たり0.1mmol以上5.0mmol以下となるように前記カルボキシ基を導入する請求項13又は14に記載の複合体の製造方法。
- 水または有機溶媒中に分散する請求項1に記載の複合体を含む、分散液。
- 請求項1に記載の複合体を含む、光学材料。
- 1種類以上の金属またはそれらの化合物からなる平板状金属微粒子と、微細化セルロースとの複合体を含む、分散液。
- 前記複合体において、前記微細化セルロースのそれぞれは、少なくとも一部が前記平板状金属微粒子に取り込まれるとともに、残部が前記平板状金属微粒子の表面に露出する請求項18に記載の分散液。
- 前記平板状金属微粒子と前記微細化セルロースとが不可分であることを特徴とする請求項18又は19に記載の分散液。
- 前記平板状金属微粒子が少なくとも銀を含む、請求項18乃至20のいずれか一項に記載の分散液。
- 前記平板状金属微粒子の粒子径が、前記平板状金属微粒子の粒子厚みの2倍以上である、請求項18乃至21のいずれか一項に記載の分散液。
- 前記微細化セルロースの結晶表面にカルボキシ基が導入されている、請求項18乃至22のいずれか一項に記載の分散液。
- 前記微細化セルロースのカルボキシ基が、N-オキシル化合物を用いた酸化反応により導入されている、請求項23に記載の分散液。
- 前記微細化セルロースに導入されているカルボキシ基量がセルロースの乾燥重量を基準として0.1mmol/g以上5.0mmol/g以下である、請求項23又は24に記載の分散液。
- 前記微細化セルロースの結晶構造がセルロースI型である、請求項18乃至25のいずれか一項に記載の分散液。
- 前記微細化セルロースの形状が天然セルロースのミクロフィブリル構造由来の繊維状である、請求項18乃至26のいずれか一項に記載の分散液。
- 前記微細化セルロースの数平均短軸径が1nm以上100nm以下、数平均長軸径が50nm以上であり、かつ数平均長軸径が数平均短軸径の10倍以上である、請求項27に記載の分散液。
- 波長400nm以上1500nm以下の領域に吸光度の最大値を有する、請求項18乃至28のいずれか一項に記載の分散液。
- 請求項18乃至29のいずれか一項に記載の分散液を製造する方法であって、
微細化されたセルロース繊維を溶媒中に分散させて微細化セルロース分散液を得て、
前記微細化セルロース分散液と金属イオン含有溶液とを混合することで混合溶液を得て、
前記混合溶液中の金属イオンを還元して前記平板状金属微粒子と前記微細化セルロースとの複合体を得ること、を含む、分散液の製造方法。 - 前記金属イオンが、銀イオンである請求項30に記載の分散液の製造方法。
- 前記微細化セルロースを調製する際に、前記微細化セルロースの結晶表面にカルボキシ基を導入する請求項30又は31に記載の分散液の製造方法。
- 前記カルボキシ基を導入する際に、N-オキシル化合物を用いた酸化反応を用いる請求項32に記載の分散液の製造方法。
- 前記カルボキシ基を導入する際に、セルロースの乾燥重量を基準として0.1mmol/g以上5.0mmol/g以下となるように前記カルボキシ基を導入する請求項32又は33に記載の分散液の製造方法。
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015218421A (ja) * | 2014-05-21 | 2015-12-07 | 凸版印刷株式会社 | 多孔質体とその製造方法、ならびに遮熱フィルム |
WO2016125498A1 (ja) * | 2015-02-04 | 2016-08-11 | 日本ゼオン株式会社 | 消臭剤およびその製造方法 |
JP2018095705A (ja) * | 2016-12-09 | 2018-06-21 | トヨタ自動車株式会社 | 装飾被膜 |
WO2018181480A1 (ja) | 2017-03-29 | 2018-10-04 | 古河電気工業株式会社 | 一体形成体、並びに該一体形成体を有する複合材、電気接点用端子及びプリント配線板 |
JP2018193551A (ja) * | 2017-05-12 | 2018-12-06 | 凸版印刷株式会社 | 樹脂成形体、及びその製造方法、並びに樹脂組成物 |
JP2019002004A (ja) * | 2017-06-16 | 2019-01-10 | 凸版印刷株式会社 | 光熱変換材料、光熱変換組成物、および光熱変換成形体 |
JP2019099687A (ja) * | 2017-12-01 | 2019-06-24 | 凸版印刷株式会社 | 樹脂組成物および樹脂組成物の製造方法 |
JP2022548274A (ja) * | 2020-05-29 | 2022-11-17 | エルジー・ケム・リミテッド | フィブリル化繊維およびその製造方法 |
JP2022178056A (ja) * | 2021-05-19 | 2022-12-02 | 株式会社豊田中央研究所 | 分散液、形成物の製造方法、分散液の使用方法及び分散液の製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016208331A1 (ja) * | 2015-06-22 | 2016-12-29 | 富士フイルム株式会社 | 熱線遮蔽材、及びこれを用いる建築部材、ケージ部材並びに側面壁 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005105376A (ja) * | 2003-09-30 | 2005-04-21 | Sumitomo Osaka Cement Co Ltd | 銀微粒子及びその製造方法 |
WO2006082962A1 (ja) * | 2005-02-07 | 2006-08-10 | Shinano Kenshi Kabushiki Kaisha | 複合粒子の製造方法 |
JP2014055323A (ja) * | 2012-09-12 | 2014-03-27 | Toppan Printing Co Ltd | 金属/セルロース複合化微細繊維、その製造方法、ならびに金属/セルロース複合化微細繊維を含む透明導電膜 |
JP2014070158A (ja) * | 2012-09-28 | 2014-04-21 | Toppan Printing Co Ltd | 抗菌性微細セルロース、その製造方法ならびに抗菌性コーティング剤 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4540945B2 (ja) * | 2003-06-26 | 2010-09-08 | 住友大阪セメント株式会社 | 金属薄膜形成用塗料と金属薄膜及びその製造方法 |
JP5283050B2 (ja) | 2005-02-07 | 2013-09-04 | 国立大学法人京都大学 | 繊維強化複合材料 |
JP4998981B2 (ja) | 2006-06-20 | 2012-08-15 | 国立大学法人 東京大学 | 微細セルロース繊維 |
JP4919264B2 (ja) | 2006-06-29 | 2012-04-18 | 国立大学法人京都大学 | 繊維樹脂複合材料 |
JP2009144188A (ja) | 2007-12-12 | 2009-07-02 | Fujifilm Corp | 平板状金属粒子及びその製造方法、並びに平板状金属粒子含有組成物、及び赤外線吸収材料 |
EP2222883B1 (en) * | 2007-12-19 | 2012-07-04 | Universität Potsdam | Synthesis of au, pd, pt or ag nano- or microcrystals via reduction of metal salts by cellulose in the ionic liquid 1-butyl-3-methyl imidazolium chloride |
JP2010202856A (ja) * | 2009-02-06 | 2010-09-16 | Kao Corp | セルロース繊維の懸濁液とその製造方法 |
JP5566368B2 (ja) * | 2009-02-18 | 2014-08-06 | 日本製紙株式会社 | セルロースナノファイバーおよび金属ナノ粒子を含む複合体、ならびにその製造方法 |
JP5500842B2 (ja) | 2009-03-13 | 2014-05-21 | 国立大学法人京都大学 | セルロースナノファイバーの製造方法 |
JP5570305B2 (ja) * | 2009-11-06 | 2014-08-13 | 富士フイルム株式会社 | 熱線遮蔽材 |
JP5688950B2 (ja) * | 2010-11-15 | 2015-03-25 | 富士フイルム株式会社 | 熱線遮蔽材 |
CN103842452B (zh) | 2011-09-22 | 2017-05-31 | 凸版印刷株式会社 | 膜形成用组合物、层叠体、膜、片材基体、包装材料、膜形成用组合物的制造方法以及纤维素分散液的制造方法 |
-
2015
- 2015-04-24 JP JP2016517870A patent/JP6690531B2/ja active Active
- 2015-04-24 WO PCT/JP2015/062517 patent/WO2015170613A1/ja active Application Filing
- 2015-04-24 EP EP15789071.6A patent/EP3141323B1/en active Active
-
2016
- 2016-11-07 US US15/345,028 patent/US9987686B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005105376A (ja) * | 2003-09-30 | 2005-04-21 | Sumitomo Osaka Cement Co Ltd | 銀微粒子及びその製造方法 |
WO2006082962A1 (ja) * | 2005-02-07 | 2006-08-10 | Shinano Kenshi Kabushiki Kaisha | 複合粒子の製造方法 |
JP2014055323A (ja) * | 2012-09-12 | 2014-03-27 | Toppan Printing Co Ltd | 金属/セルロース複合化微細繊維、その製造方法、ならびに金属/セルロース複合化微細繊維を含む透明導電膜 |
JP2014070158A (ja) * | 2012-09-28 | 2014-04-21 | Toppan Printing Co Ltd | 抗菌性微細セルロース、その製造方法ならびに抗菌性コーティング剤 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3141323A4 * |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015218421A (ja) * | 2014-05-21 | 2015-12-07 | 凸版印刷株式会社 | 多孔質体とその製造方法、ならびに遮熱フィルム |
WO2016125498A1 (ja) * | 2015-02-04 | 2016-08-11 | 日本ゼオン株式会社 | 消臭剤およびその製造方法 |
JPWO2016125498A1 (ja) * | 2015-02-04 | 2017-11-16 | 日本ゼオン株式会社 | 消臭剤およびその製造方法 |
JP2018095705A (ja) * | 2016-12-09 | 2018-06-21 | トヨタ自動車株式会社 | 装飾被膜 |
US11361876B2 (en) | 2017-03-29 | 2022-06-14 | Furukawa Electric Co., Ltd. | Integrally formed product, and composite material, terminal for electrical contact and printed wiring board including the integrally formed product |
WO2018181480A1 (ja) | 2017-03-29 | 2018-10-04 | 古河電気工業株式会社 | 一体形成体、並びに該一体形成体を有する複合材、電気接点用端子及びプリント配線板 |
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JP7143628B2 (ja) | 2017-05-12 | 2022-09-29 | 凸版印刷株式会社 | 樹脂成形体、及びその製造方法 |
JP2019002004A (ja) * | 2017-06-16 | 2019-01-10 | 凸版印刷株式会社 | 光熱変換材料、光熱変換組成物、および光熱変換成形体 |
JP7259218B2 (ja) | 2017-06-16 | 2023-04-18 | 凸版印刷株式会社 | 光熱変換材料、光熱変換組成物、および光熱変換成形体 |
JP2019099687A (ja) * | 2017-12-01 | 2019-06-24 | 凸版印刷株式会社 | 樹脂組成物および樹脂組成物の製造方法 |
JP7167433B2 (ja) | 2017-12-01 | 2022-11-09 | 凸版印刷株式会社 | 樹脂組成物および樹脂組成物の製造方法 |
JP2022548274A (ja) * | 2020-05-29 | 2022-11-17 | エルジー・ケム・リミテッド | フィブリル化繊維およびその製造方法 |
JP7378595B2 (ja) | 2020-05-29 | 2023-11-13 | エルジー・ケム・リミテッド | フィブリル化繊維およびその製造方法 |
JP2022178056A (ja) * | 2021-05-19 | 2022-12-02 | 株式会社豊田中央研究所 | 分散液、形成物の製造方法、分散液の使用方法及び分散液の製造方法 |
JP7439791B2 (ja) | 2021-05-19 | 2024-02-28 | 株式会社豊田中央研究所 | 分散液、形成物の製造方法、分散液の使用方法及び分散液の製造方法 |
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US20170072472A1 (en) | 2017-03-16 |
EP3141323A1 (en) | 2017-03-15 |
JPWO2015170613A1 (ja) | 2017-04-20 |
JP6690531B2 (ja) | 2020-04-28 |
EP3141323B1 (en) | 2022-02-09 |
EP3141323A4 (en) | 2018-01-10 |
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