WO2015050126A1 - Nanocomposite and nanocomposite-manufacturing process - Google Patents
Nanocomposite and nanocomposite-manufacturing process Download PDFInfo
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- WO2015050126A1 WO2015050126A1 PCT/JP2014/076118 JP2014076118W WO2015050126A1 WO 2015050126 A1 WO2015050126 A1 WO 2015050126A1 JP 2014076118 W JP2014076118 W JP 2014076118W WO 2015050126 A1 WO2015050126 A1 WO 2015050126A1
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- inorganic compound
- polysaccharide
- fibrous
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- 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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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- 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
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- the present invention relates to a nanocomposite and a method for producing the nanocomposite.
- Cellulose is a natural and fibrous form of plants, for example, woody plants such as broad-leaved trees and conifers, and herbaceous plants such as bamboo and bamboo, some animals represented by sea squirts, and some represented by acetic acid bacteria. It is known that it is produced by fungi and the like.
- a cellulose fiber having a structure in which cellulose molecules are aggregated in a fibrous form is called a cellulose fiber.
- a cellulose fiber having a fiber width of 100 nm or less and an aspect ratio of 100 or more is generally called cellulose nanofiber (CNF), and has excellent properties such as light weight, high strength, and low thermal expansion coefficient.
- CNF cellulose nanofiber
- CNF does not exist as a single fiber except for CNF produced by some fungi represented by acetic acid bacteria. Most of CNF exists in the state which has the fiber width of the micro size tightly assembled by the interaction represented by the hydrogen bond between CNF. The fibers having the micro-sized fiber width also exist as higher order aggregates.
- the fiber aggregate wood is defibrated to a pulp state with a micro-sized fiber width by a pulping method represented by kraft cooking, which is one of chemical pulping methods.
- the paper is made from this.
- the fiber width of this pulp varies depending on the raw material, but it is 5-20 ⁇ m for bleached kraft pulp made from hardwood, 20-80 ⁇ m for bleached kraft pulp made from softwood, and 5-20 ⁇ m for bleached kraft pulp made from bamboo. Degree.
- the pulp having these micro-sized fiber widths is an aggregate of single fibers having a fibrous form in which CNF is firmly assembled by an interaction typified by hydrogen bonding, and by further defibrating.
- CNF which is a single fiber having a nano-sized fiber width, can be obtained.
- the TEMPO catalytic oxidation method which is one of the chemical preparation methods for CNF, uses a TEMPO catalyst to convert the hydroxyl group on the CNF surface of a CNF aggregate having a micro-sized fiber width represented by wood bleached kraft pulp to a carboxyl group. By converting it into Na salt, electrostatic repulsion between CNFs and osmotic pressure effect act in water, and nano dispersion of CNF is made possible by simple underwater fibrillation treatment.
- the underwater collision method which is one of the physical methods of preparing CNF, is the opposite collision of suspended water of CNF aggregates having a micro-sized fiber width represented by wood bleached kraft pulp under high pressure. Thus, only the interaction between CNFs is cleaved and nano-miniaturization is performed.
- FIG. 11 2), two opposing nozzles (FIG. 11: 4a, 4b), and as necessary.
- a heat exchanger (FIG. 11: 5) is provided, and fine particles dispersed in water are introduced into two nozzles and injected from opposite nozzles (FIG. 11: 4a, 4b) under high pressure to collide against each other in water.
- this method only water is used in addition to natural cellulose fibers, and only the interaction between the fibers is cleaved. It becomes possible to obtain a nano-miniaturized product in a minimized state.
- One of the methods for using CNF obtained by the above various preparation methods is to use it as a filler for composites using other compounds as a matrix. It has been reported that the characteristics of other compounds are greatly improved by mixing CNF as a filler with other compounds.
- An object of the present invention is to provide a nanocomposite that has not existed conventionally and a method for producing a nanocomposite having a completely different idea from the conventional one.
- the present inventor created a nanomaterial in an unprecedented form by simultaneously treating it in the suspension water mixed with bleached kraft pulp, which is one of the chemical pulps, and calcium carbonate, by the underwater collision method.
- the nanomaterial obtained in this way is a nanocomposite having a form in which spherical calcium carbonates are arranged in a bead shape with CNF as the axis, and CNF obtained by nano-refining only bleached kraft pulp by the underwater collision method and It cannot be obtained by mixing, which is a common complexing method with calcium carbonate.
- the nanocomposite of the present invention is characterized in that it has a form in which spherical inorganic compounds are linked in a bead-like state around a nano-sized fibrous polysaccharide.
- the nanocomposite of the present invention is attached in such a manner that an inorganic compound is complexed (forms a complex) on the surface of the nanosized fibrous polysaccharide, and the nanosized fibrous polysaccharide is covered with the inorganic compound. It is characterized by that.
- Nano refined fibrous polysaccharides can be made into cellulose nanofibers.
- the inorganic compound can be at least one selected from carbonates and sulfates of alkaline earth metals such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and magnesium sulfate.
- the method for producing a nanocomposite of the present invention comprises preparing suspension water of a fibrous polysaccharide and an inorganic compound, and combining the nanominiaturization of the fibrous polysaccharide with dissolution or decomposition of the inorganic compound in the suspension water.
- the nanocomposite of the said fibrous polysaccharide and the said inorganic compound is acquired by the process of characterized by the above-mentioned.
- a suspension water of a fibrous polysaccharide and an inorganic compound is prepared, and nano refinement of the fibrous polysaccharide in the suspension water and dissolution or decomposition of the inorganic compound are simultaneously performed. And obtaining a nanocomposite of the fibrous polysaccharide and the inorganic compound.
- the inorganic compound is dissolved or decomposed in one step or at the same time to obtain a nanocomposite of the fibrous polysaccharide and the inorganic compound.
- the nanocomposite obtained by the above-described method for producing a nanocomposite of the present invention is referred to as an on-site nanocomposite.
- the tank 1, the plunger 2, the chamber 3, the two nozzles 4 a and 4 b, and the heat exchanger 5 as necessary are configured as shown in FIG. 11.
- a device is used.
- Suspended water of fibrous polysaccharide and inorganic compound is sprayed from the nozzles 4a and 4b facing each other under high pressure to collide with each other.
- nano refinement of the fibrous polysaccharide and dissolution or decomposition of the inorganic compound can be performed in one step or simultaneously to obtain a nano-composite.
- Physical processing in general can be applied as nano refinement processing.
- This physical treatment includes a grinder method, a high-pressure homogenizer method, and an underwater collision method.
- Structural fibrous polysaccharides in particular pulp, can be used as the fibrous polysaccharide.
- pulp there can be used chemical pulp, mechanical pulp and waste paper made from woody plants such as hardwoods and conifers, and herbaceous plants such as bamboo and bamboo.
- the inorganic compound is at least one selected from carbonates and sulfates of alkaline earth metals such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and magnesium sulfate. It can be. In this case, when two or more are selected, a composite of nano-fine fibrous polysaccharide and two or more different inorganic compounds is obtained.
- the nanocomposite of the present invention has a form in which an inorganic compound such as spherical calcium carbonate is linked in a beaded manner around a nano-sized fibrous polysaccharide such as CNF, and compared with a general inorganic compound. In this case, it can be used as an inorganic compound in a completely different form.
- the nanocomposite of the present invention when compared with a nano-miniaturized fibrous polysaccharide such as general CNF, has a nano-miniaturized fibrous polysaccharide surface coated with an inorganic compound, thereby providing a reinforcing material such as a resin.
- the interaction that occurs at the interface of the nanocomposite surface and the resin as a matrix is different from that of general nano-sized fibrous polysaccharides. Therefore, it is expected to show a characteristic effect as a reinforcing material by improving the compatibility, and its application range is diverse.
- the nanocomposite suspension water of the present invention (a), and the composite suspension water (b) obtained by mixing the suspension water of CNF and the calcium carbonate suspension water, which are nano-miniaturized by the underwater collision of bleached kraft pulp An optical microscope image of the mixed suspension water (c) obtained by mixing the suspension water of the pulp and the suspension water of the calcium carbonate, both magnified 400 times.
- the composite suspension water (b) obtained by mixing the nanocomposite suspension water (a) of the present invention with the suspension solution of CNF nano-sized by the opposed collision of bleached kraft pulp and the suspension solution of calcium carbonate are optical microscope images observed at 100 times magnification. Explanatory drawing about the inorganic compound compounded with the manufacturing method of the nanocomposite of this invention.
- the nanocomposite of the present invention Transmission electron microscope observation was performed in order to examine the form of the nanocomposite of the present invention in more detail.
- spherical calcium carbonate particles having a diameter of about 50 nm are connected in a beaded state.
- the calcium carbonate before on-site nanocomposite shown in FIG. 2 has a width of 500-700 nm, a length of 2-3 ⁇ m, a completely different size, and a completely different spindle shape. It was.
- FIG. 1 Transmission electron microscope observation was performed in order to examine the form of the nanocomposite of the present invention in more detail.
- spherical calcium carbonate particles having a diameter of about 50 nm are connected in a beaded state.
- the calcium carbonate before on-site nanocomposite shown in FIG. 2 has a width of 500-700 nm, a length of 2-3 ⁇ m, a completely different size, and a completely different spindle shape. It was.
- FIG. 1 Transmission electron microscope observation was
- the nanocomposite suspension water of the present invention obtained by this on-site nanocomposite is compared with the calcium carbonate suspension water before the on-site nanocomposite shown in FIG. As shown in Fig. 2, the particle size of calcium carbonate is small. In addition, it can be seen that the particles are connected to form a more organized state.
- bleached kraft pulp is not nano-miniaturized.
- the fiber width exists in a large state.
- Calcium carbonate also has a large particle size, exists in a mixed state rather than in a composite state, and is completely different from the nanocomposite obtained by the on-site nanocomposite of the present invention.
- the off-site complex is a loose complex in which CNF and calcium carbonate obtained by nano-refining bleached kraft pulp in advance by an underwater facing collision method are aggregated due to surface adsorption and the like. It is presumed that it was easily dissociated and dispersed by being weakened by the addition of.
- the nanocomposite of the present invention does not disperse with the addition of a dispersant, and CNF and calcium carbonate are not aggregated due to surface adsorption, etc., but both are complexed by an interaction different from surface adsorption, etc. It is presumed that it did not disperse because it changed to a strong composite.
- the inorganic compound to be complexed with CNF is decomposed or dissolved by an underwater collision, and then aggregated or recrystallized after being decomposed or dissolved.
- compounds with stable structure, or compounds that can be decomposed or dissolved by underwater collision but do not aggregate or crystallize after decomposition or dissolution cannot be obtained.
- calcium carbonate As compounds having both of these characteristics, that is, decomposition or dissolution by underwater collision, and aggregation or recrystallization after decomposition or dissolution, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, magnesium sulfate, etc. There are alkaline earth metal carbonates and sulfates. Calcium carbonate is particularly desirable. A mixture of these compounds can also be used.
- CNF preparation process In general compounding of CNF having a nano-sized fiber width and another compound, three steps of “CNF preparation process”, “decomposition or dissolution process of other compound”, and “compounding process” are required.
- these three treatments can be performed in one step, and the nanocomposite can be produced by a simplified procedure, so that the production method is excellent in terms of production cost. It can be said.
- inorganic compound particles such as spherical calcium carbonate having a diameter of about 50 nm are arranged in a beaded manner using a nano-sized fibrous polysaccharide such as CNF as a scaffold. Linked in a state. As shown in FIG. 8, it can be used as a nano-sized fibrous polysaccharide whose surface is coated with an inorganic compound or as an inorganic compound connected in a bead shape in a spherical state.
- CNF nano-sized fibrous polysaccharide
- CNF has excellent properties such as light weight, high strength, and low thermal expansion coefficient. It can be used for compounding with a resin using
- CNF having a hydrophilic surface has low compatibility with a hydrophobic resin and does not disperse neatly due to agglomeration of CNFs, reducing the effect as a reinforcing material. .
- the CNF surface is coated with an inorganic compound such as calcium carbonate, the interfacial interaction with the resin is different from that of ordinary CNF, and it is reinforced by improving compatibility and dispersibility. The improvement of the function as a material can be expected.
- the nanocomposite of the present invention is regarded as “inorganic compounds such as calcium carbonate connected in a spherical shape in a rosary shape”, the inorganic compound such as normal calcium carbonate, or calcium carbonate that is simply nano-miniaturized, etc. Since the form is different from that of the inorganic compound, a new function can be expected by simply replacing the inorganic compound in the product using the conventional inorganic compound.
- the nanocomposite of the example of the present invention was manufactured by carrying out the method of manufacturing the nanocomposite of the present invention as follows. After adding 10 wt% of calcium carbonate in water suspension to the wet suspension of kraft pulp in a wet state with a concentration of 0.10 wt% with respect to the weight of the dry kraft pulp in the dry state, uniformly stirred with an agitator, and bleached kraft A pulp-calcium carbonate mixed suspension was prepared. The mixed suspension water is put into the tank (FIG. 11: 1) shown in FIG. 11, and the pressure is increased by the plunger (FIG. 11: 2) so that the injection pressure in the chamber (FIG. 11: 3) becomes 180 MPa.
- the concentration of the bleached kraft pulp in the bleached kraft pulp-calcium carbonate mixed water suspension is not particularly limited as long as it does not cause problems such as clogging in the flow path in the underwater collision method.
- the amount of calcium carbonate added is not particularly limited, and is usually 1 wt.% To 200 wt.%, Preferably 5 wt.% To 50 wt.%, Based on the weight of the dry kraft pulp.
- a sheet of on-site complex was prepared as follows (see FIG. 9). After adding 10 wt% of calcium carbonate in a water suspension state to bleached kraft pulp derived from hardwood in a dry kraft pulp suspension water derived from wet hardwood with a concentration of 0.10 wt%, uniformly stirred with an agitator, Bleached kraft pulp-calcium carbonate mixed suspension water derived from hardwood was prepared. The mixed suspension was subjected to an underwater collision under the conditions of an ejection pressure of 180 MPa and a treatment frequency of 90 Pass to obtain an on-site complex using bleached kraft pulp derived from hardwood.
- a wet sheet was prepared by suction filtration of 70 ml of the on-site complex suspension water made from the bleached kraft pulp derived from the hardwood, and dried in a dryer set at 130 ° C. for 24 hours.
- An on-site composite dry sheet was prepared from bleached kraft pulp derived from hardwood.
- Comparative Example 1 As Comparative Example 1, an uncomplexed CNF sheet of only CNF obtained by nano-refining bleached kraft pulp by underwater facing collision was prepared as follows (see FIG. 9). A bleached kraft pulp suspension water derived from wet hardwood with a concentration of 0.10 wt% was subjected to an underwater collision under the conditions of an ejection pressure of 180 MPa and a processing frequency of 90 Pass to obtain CNF using bleached kraft pulp derived from hardwood as a raw material. A wet sheet was prepared by suction filtration of 70 ml of CNF suspension water made from the obtained hardwood-derived bleached kraft pulp, and dried in a dryer set at 130 ° C. for 24 hours. A dry sheet of CNF was prepared using as a raw material.
- Comparative Example 2 As Comparative Example 2, an off-site composite sheet was prepared as follows (see FIG. 9). First, CNF made from bleached kraft pulp derived from broad-leaved trees was subjected to an underwater collision with a 0.10 wt% wet hardwood-derived bleached kraft pulp suspension water under a jet pressure of 180 MPa and a treatment count of 90 Pass. Obtained. Next, after adding 10 wt% of calcium carbonate in a water suspension state to the CNF suspension water made from the obtained hardwood-derived bleached kraft pulp as a raw material, with respect to the hardwood-derived bleached kraft pulp, a household mixer was mixed vigorously for 3 minutes to obtain an off-site complex of CNF derived from hardwood bleached kraft pulp and calcium carbonate.
- each dry sheet was prepared by the same method in each case except that the raw material was bamboo-derived bleached kraft pulp instead of hardwood-derived bleached kraft pulp. did. Since unrefined bamboo-derived bleached kraft pulp contains a large amount of tissue parenchyma contained in bamboo, the pulp fibers and tissue parenchymal cells are separated by repeated filtration through the mesh, and bamboo-derived bleached kraft pulp The pulp in a state where tissue parenchymal cells were almost removed was used as a raw material for the dry sheet.
- Example 2 and Comparative Examples 1 and 2 of the present invention mechanical properties were compared by a tensile test, and the difference in functionality was verified.
- Test pieces each having a width of 7 mm and a length of 25-30 mm were cut out from the central portions of the sheets of Example 2 and Comparative Examples 1 and 2, respectively, and conditioned for 3 days or more under an environmental condition of 23 ° C. and 50% RH. Later, it was subjected to a tensile test.
- the tensile test was performed using a desktop material testing machine (STA-1225: manufactured by Orientec Co., Ltd.) under the conditions of a measurement length of 20 mm and a tensile speed of 2 mm / min.
- test piece cut out in the same manner was conditioned for 3 days or more under an environmental condition of 23 ° C. and 50% RH, it was dried in a dryer set at 130 ° C. for 24 hours, allowed to cool in a desiccator, and then quickly The sample was subjected to a tensile test.
- the tensile test was performed using a desktop material testing machine (STA-1225: manufactured by Orientec Co., Ltd.) under the conditions of a measurement length of 20 mm and a tensile speed of 2 mm / min.
- Table 1 shows the mechanical strengths obtained from the tensile tests of the sheets of Example 2 and Comparative Examples 1 and 2.
- the tensile test result (1) shows a stress-strain curve obtained by a tensile test of each sheet conditioned under the environmental conditions of 23 ° C. and 50% RH.
- the tensile test result (2) shows a stress-strain curve obtained by a tensile test of each sheet dried in a dryer at 130 ° C. for 24 hours.
- the Example 2 sheet of the present invention exhibited an intermediate behavior between the Comparative Example 1 sheet and the Comparative Example 2 sheet.
- the mechanical strength of “paper added with a filler such as calcium carbonate” is lower than that of “pulp-only paper”. This is due to the fact that the interaction between pulp fibers is lowered by being inhibited by the added “filler”. Due to the same phenomenon, it is considered that the mechanical strength of the Example 2 sheet and the Comparative Example 2 sheet also decreased in this test result compared to the Comparative Example 1 sheet.
- the degree of decrease in mechanical strength was different between the Example 1 sheet and the Comparative Example 2 sheet, and the Example 2 sheet showed higher mechanical strength than the Comparative Example 2 sheet.
- the nanocomposite of the present invention exhibits different properties from the composite obtained by general mixing even when the network structure is formed by sheet formation.
- the complex obtained by general mixing is considered that CNF and calcium carbonate are complexed only by physical interaction such as adsorption.
- calcium carbonate decomposed or dissolved by underwater collision is agglomerated or recrystallized with CNF as a scaffold, and thus CNF is complexed in a state covered with calcium carbonate.
- the interaction between the complexes at the cross-linking points in the formed network is different, and the characteristics are different from those of the complex obtained by general mixing. It was also found that the same tendency was shown regardless of the type of bleached kraft pulp as the raw material and the water content in the network structure.
- the specific form of the nanocomposite of the present invention is that even when a network structure such as sheet formation is formed, the interaction between the composites in a network different from the composite obtained by general mixing is different. As a result, it is expected to exhibit characteristics and physical properties different from those of composites obtained by general mixing in other applications.
Abstract
The present invention addresses the problem of providing a novel nanocomposite and a nanocomposite-manufacturing process based on an idea which is entirely different from that of a conventional process. This nanocomposite contains spherical inorganic compound particles which each have a diameter of about 50nm and which are linked in a beaded state. This nanocomposite -manufacturing process comprises: preparing a dispersion of a fibrous polysaccharide and an inorganic compound; conducting the nanofibrillation of the fibrous polysaccharide and the dissolution or disintegration of the inorganic compound either simultaneously or in one step in the dispersion; and thus obtaining a nanocomposite which comprises the nanofibrillated fibrous polysaccharide and the inorganic compound.
Description
本発明はナノ複合体及びナノ複合体の製造法に関する。
The present invention relates to a nanocomposite and a method for producing the nanocomposite.
セルロースは、天然で繊維形態として、植物、例えば、広葉樹や針葉樹などの木本植物、及び竹や葦などの草本植物、ホヤに代表される一部の動物、および酢酸菌に代表される一部の菌類等によって産生されることが知られている。このセルロース分子が繊維状に集合した構造を有するものをセルロースファイバーと呼ぶ。特に繊維幅が１００ｎｍ以下でアスペクト比が１００以上のセルロースファイバーは一般的にセルロースナノファイバー（ＣＮＦ）と呼ばれ、軽量、高強度、低熱膨張率等の優れた性質を有する。
Cellulose is a natural and fibrous form of plants, for example, woody plants such as broad-leaved trees and conifers, and herbaceous plants such as bamboo and bamboo, some animals represented by sea squirts, and some represented by acetic acid bacteria. It is known that it is produced by fungi and the like. A cellulose fiber having a structure in which cellulose molecules are aggregated in a fibrous form is called a cellulose fiber. In particular, a cellulose fiber having a fiber width of 100 nm or less and an aspect ratio of 100 or more is generally called cellulose nanofiber (CNF), and has excellent properties such as light weight, high strength, and low thermal expansion coefficient.
Cellulose is a natural and fibrous form of plants, for example, woody plants such as broad-leaved trees and conifers, and herbaceous plants such as bamboo and bamboo, some animals represented by sea squirts, and some represented by acetic acid bacteria. It is known that it is produced by fungi and the like. A cellulose fiber having a structure in which cellulose molecules are aggregated in a fibrous form is called a cellulose fiber. In particular, a cellulose fiber having a fiber width of 100 nm or less and an aspect ratio of 100 or more is generally called cellulose nanofiber (CNF), and has excellent properties such as light weight, high strength, and low thermal expansion coefficient.
天然においてＣＮＦは、酢酸菌に代表される一部の菌類等によって産生されたＣＮＦを除くと、単繊維として存在しない。ＣＮＦの殆どはＣＮＦ間の水素結合に代表される相互作用によって強固に集合したマイクロサイズの繊維幅を有した状態で存在する。そのマイクロサイズの繊維幅を有した繊維もさらに高次の集合体として存在する。
In nature, CNF does not exist as a single fiber except for CNF produced by some fungi represented by acetic acid bacteria. Most of CNF exists in the state which has the fiber width of the micro size tightly assembled by the interaction represented by the hydrogen bond between CNF. The fibers having the micro-sized fiber width also exist as higher order aggregates.
製紙の過程では、これらの繊維集合体である木材を化学パルプ化法の一つであるクラフト蒸解法に代表されるパルプ化法によって、マイクロサイズの繊維幅を有するパルプの状態にまで解繊し、これを原料に紙を製造している。このパルプの繊維幅は、原料によって異なるが、広葉樹を原料とした晒クラフトパルプで５－２０μｍ、針葉樹を原料とした晒クラフトパルプで２０－８０μｍ、竹を原料とした晒クラフトパルプで５－２０μｍ程度である。
In the papermaking process, the fiber aggregate wood is defibrated to a pulp state with a micro-sized fiber width by a pulping method represented by kraft cooking, which is one of chemical pulping methods. The paper is made from this. The fiber width of this pulp varies depending on the raw material, but it is 5-20 μm for bleached kraft pulp made from hardwood, 20-80 μm for bleached kraft pulp made from softwood, and 5-20 μm for bleached kraft pulp made from bamboo. Degree.
前述のとおりこれらマイクロサイズの繊維幅を有するパルプは、ＣＮＦが水素結合に代表される相互作用によって強固に集合した繊維状の形態を有する単繊維の集合体であり、さらに解繊を進めることによってナノサイズの繊維幅を有する単繊維であるＣＮＦを得ることができる。
As described above, the pulp having these micro-sized fiber widths is an aggregate of single fibers having a fibrous form in which CNF is firmly assembled by an interaction typified by hydrogen bonding, and by further defibrating. CNF, which is a single fiber having a nano-sized fiber width, can be obtained.
ＣＮＦの調製方法は多々報告されているが、酸加水分解法やＴＥＭＰＯ触媒酸化法といった化学的方法と、グラインダー法や高圧ホモジナイザー法、水中対向衝突法といった物理的方法の２種類に大別される。
Many methods for preparing CNF have been reported, but they are roughly classified into two types: chemical methods such as acid hydrolysis and TEMPO catalytic oxidation, and physical methods such as grinder method, high-pressure homogenizer method, and underwater facing collision method. .
ＣＮＦの化学的調製方法の一つであるＴＥＭＰＯ触媒酸化法は、木材の晒クラフトパルプに代表されるマイクロサイズの繊維幅を有するＣＮＦ集合体のＣＮＦ表面の水酸基を、ＴＥＭＰＯ触媒を用いてカルボキシル基に変換してＮａ塩にすることによって、水中でＣＮＦ間の静電反発と浸透圧効果が作用し、簡単な水中解繊処理でＣＮＦのナノ分散を可能にする。
The TEMPO catalytic oxidation method, which is one of the chemical preparation methods for CNF, uses a TEMPO catalyst to convert the hydroxyl group on the CNF surface of a CNF aggregate having a micro-sized fiber width represented by wood bleached kraft pulp to a carboxyl group. By converting it into Na salt, electrostatic repulsion between CNFs and osmotic pressure effect act in water, and nano dispersion of CNF is made possible by simple underwater fibrillation treatment.
ＣＮＦの調製方法のうち物理的方法の一つである水中対向衝突法は、木材の晒クラフトパルプに代表されるマイクロサイズの繊維幅を有するＣＮＦ集合体の懸濁水を高圧下で対向衝突させることによって、ＣＮＦ間の相互作用のみを解裂させてナノ微細化を行う。
The underwater collision method, which is one of the physical methods of preparing CNF, is the opposite collision of suspended water of CNF aggregates having a micro-sized fiber width represented by wood bleached kraft pulp under high pressure. Thus, only the interaction between CNFs is cleaved and nano-miniaturization is performed.
この水中対向衝突法は特許文献１にも開示されているように、水に懸濁した天然セルロース繊維をチャンバー（図１１：３）内で相対する二つのノズル（図１１：４ａ，４ｂ）に導入され、これらのノズルから一点に向かって噴射、衝突させる手法である（図１１）。この手法によれば、天然微結晶セルロース繊維(例えば、フナセル)の懸濁水を対向衝突させ、その表面をナノフィブリル化させて引き剥がし、キャリアーである水との親和性を向上させることによって、最終的には溶解に近い状態に至らせることが可能となる。図１１に示される装置は液体循環型となっており、タンク（図１１：１）、プランジャー（図１１：２）、対向する二つのノズル（図１１：４ａ，４ｂ）、必要に応じて熱交換器（図１１：５）を備え、水中に分散させた微粒子を二つのノズルに導入し高圧下で合い対するノズル（図１１：４ａ，４ｂ）から噴射して水中で対向衝突させる。この手法では天然セルロース繊維の他には水しか使用せず、繊維間の相互作用のみを解裂させることによってナノ微細化を行うためセルロース分子の構造変化がなく、解裂に伴う重合度低下を最小限にした状態でナノ微細化品を得ることが可能となる。
In this underwater facing collision method, as disclosed in
以上の各種調製方法によって得られるＣＮＦの利用方法のひとつとして、他化合物をマトリックスとした複合体のフィラーとしての利用が挙げられる。ＣＮＦをフィラーとして他化合物と混合することで、他化合物の特性を大きく向上させることが報告されている。
One of the methods for using CNF obtained by the above various preparation methods is to use it as a filler for composites using other compounds as a matrix. It has been reported that the characteristics of other compounds are greatly improved by mixing CNF as a filler with other compounds.
ＴＥＭＰＯ触媒酸化法や酸加水分解法等の化学的処理や、特許文献１に示した水中対向衝突法やグラインダー法、高圧ホモジナイザー法といった物理的処理によって得られたＣＮＦを用いた複合化は数多く報告されている。しかし、その大半はマトリックスである樹脂にCNFを配合して複合体を得ることによって強度向上を図る手法であり、フィラーとしての機能性が注視されている。マトリックス中での分散性を向上させるため、繊維表面の化学修飾や分散剤添加等も試みられている。さらに、前もってナノ微細化したＣＮＦの懸濁水と他の化合物の懸濁水とを、単に混合することにより得られるCNFと他の化合物の複合体が、知られている。しかしながら、この複合体は、緩やかな複合体であり、そのため、例えば、分散剤の添加により容易に分解され、その機能が損なわれるという欠点がある。
There have been many reports of compounding using CNF obtained by chemical treatment such as TEMPO catalytic oxidation method and acid hydrolysis method, and physical treatment such as underwater facing collision method, grinder method, and high-pressure homogenizer method disclosed in
本発明は、従来存在しなかったナノ複合体及び従来とは全く異なる発想のナノ複合体の製造法を提供することを目的とする。
An object of the present invention is to provide a nanocomposite that has not existed conventionally and a method for producing a nanocomposite having a completely different idea from the conventional one.
本発明者は化学パルプの一つである晒クラフトパルプと炭酸カルシウムとを混合した懸濁水の状態で、水中対向衝突法にて同時に処理することによって、今までに無い形態のナノ材料を創成し得ることを知見した。これによって得られたナノ材料はＣＮＦを軸に球形の炭酸カルシウムが数珠状に連なった形態を有したナノ複合体であり、晒クラフトパルプのみを水中対向衝突法によってナノ微細化して得られるＣＮＦと炭酸カルシウムとの一般的な複合化方法である混合では得られない。
The present inventor created a nanomaterial in an unprecedented form by simultaneously treating it in the suspension water mixed with bleached kraft pulp, which is one of the chemical pulps, and calcium carbonate, by the underwater collision method. I found out that The nanomaterial obtained in this way is a nanocomposite having a form in which spherical calcium carbonates are arranged in a bead shape with CNF as the axis, and CNF obtained by nano-refining only bleached kraft pulp by the underwater collision method and It cannot be obtained by mixing, which is a common complexing method with calcium carbonate.
すなわち本発明のナノ複合体は、ナノ微細化した繊維状多糖を軸にして球形の無機化合物が数珠状に連なった状態で連結した形態を有することを特徴とする。
また本発明のナノ複合体は、ナノ微細化した繊維状多糖表面に無機化合物が複合化(複合体を形成)する態様で付着し、ナノ微細化した繊維状多糖が無機化合物に覆われていることを特徴とする。
That is, the nanocomposite of the present invention is characterized in that it has a form in which spherical inorganic compounds are linked in a bead-like state around a nano-sized fibrous polysaccharide.
In addition, the nanocomposite of the present invention is attached in such a manner that an inorganic compound is complexed (forms a complex) on the surface of the nanosized fibrous polysaccharide, and the nanosized fibrous polysaccharide is covered with the inorganic compound. It is characterized by that.
ナノ微細化した繊維状多糖をセルロースナノファイバーとすることができる。また無機化合物が炭酸カルシウム、炭酸マグネシウム、硫酸カルシウム、硫酸バリウム、硫酸マグネシウム等のアルカリ土類金属の炭酸塩や硫酸塩のうちから選ばれた少なくとも１とすることができる。
Nano refined fibrous polysaccharides can be made into cellulose nanofibers. The inorganic compound can be at least one selected from carbonates and sulfates of alkaline earth metals such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and magnesium sulfate.
また本発明のナノ複合体の製造法は、繊維状多糖と無機化合物との懸濁水を調製し、その懸濁水内において前記繊維状多糖のナノ微細化と前記無機化合物の溶解若しくは分解とを一の工程で行い前記繊維状多糖と前記無機化合物とのナノ複合体を取得することを特徴とする。
In addition, the method for producing a nanocomposite of the present invention comprises preparing suspension water of a fibrous polysaccharide and an inorganic compound, and combining the nanominiaturization of the fibrous polysaccharide with dissolution or decomposition of the inorganic compound in the suspension water. The nanocomposite of the said fibrous polysaccharide and the said inorganic compound is acquired by the process of characterized by the above-mentioned.
さらに本発明のナノ複合体の製造法は、繊維状多糖と無機化合物との懸濁水を調製し、その懸濁水中の前記繊維状多糖のナノ微細化と前記無機化合物の溶解若しくは分解とを同時に行い、前記繊維状多糖と前記無機化合物とのナノ複合体を取得することを特徴とする。
Furthermore, in the method for producing a nanocomposite of the present invention, a suspension water of a fibrous polysaccharide and an inorganic compound is prepared, and nano refinement of the fibrous polysaccharide in the suspension water and dissolution or decomposition of the inorganic compound are simultaneously performed. And obtaining a nanocomposite of the fibrous polysaccharide and the inorganic compound.
このように本発明のナノ複合体の製造法では、セルロースに代表される繊維状多糖と炭酸カルシウムに代表される無機化合物とが混合した懸濁水中に分散させた繊維状多糖のナノ微細化と無機化合物の溶解若しくは分解を、一の工程で若しくは同時に行いナノ微細化させて前記繊維状多糖と前記無機化合物とのナノ複合体を取得する。
As described above, in the method for producing the nanocomposite of the present invention, the nano-refining of the fibrous polysaccharide dispersed in the suspension water in which the fibrous polysaccharide typified by cellulose and the inorganic compound typified by calcium carbonate are mixed, and The inorganic compound is dissolved or decomposed in one step or at the same time to obtain a nanocomposite of the fibrous polysaccharide and the inorganic compound.
以上の本発明のナノ複合体の製造法によって得られるナノ複合体を本明細書においてはｏｎ－ｓｉｔｅナノ複合体とする。
In the present specification, the nanocomposite obtained by the above-described method for producing a nanocomposite of the present invention is referred to as an on-site nanocomposite.
具体的には例えばナノ化処理がＡＣＣ法である場合、図１１に示されるタンク１，プランジャ２、チャンバー３、二つの合い対するノズル４ａ，４ｂ、必要に応じて熱交換器５によって構成される装置が用いられる。繊維状多糖と無機化合物の懸濁水を高圧下で合い対するノズル４ａ，４ｂから噴射し、対向衝突させる。それによって前記繊維状多糖のナノ微細化と前記無機化合物の溶解若しくは分解とを一の工程で若しくは同時に行い、ナノ化複合体を得ることが可能となる。
Specifically, for example, when the nano-treatment is the ACC method, the
なお晒クラフトパルプを前もって水中対向衝突法によってナノ微細化したＣＮＦなどの、前もってナノ微細化した繊維状多糖の懸濁水と炭酸カルシウムなどの無機化合物の懸濁水とを混合することによって得られる、すなわち一般的な複合化方法によって得られる複合体を本明細書ではｏｆｆ－ｓｉｔｅ複合体とする。
In addition, it is obtained by mixing the suspension water of the fibrous polysaccharide and the suspension of inorganic compounds such as calcium carbonate, such as CNF that has been nano-miniaturized by bleaching kraft pulp in advance by an underwater facing collision method, that is, In this specification, a complex obtained by a general complexing method is referred to as an off-site complex.
ナノ微細化処理として物理的処理一般を適用することが可能である。この物理的処理にはグラインダー法や高圧ホモジナイザー法、水中対向衝突法が含まれる。
Physical processing in general can be applied as nano refinement processing. This physical treatment includes a grinder method, a high-pressure homogenizer method, and an underwater collision method.
繊維状多糖として構造繊維状多糖類、特にはパルプを用いることができる。パルプとしては、広葉樹や針葉樹といった木本植物、竹や葦といった草本植物を原料とした化学パルプ、機械パルプ及び古紙を用いることができる。
Structural fibrous polysaccharides, in particular pulp, can be used as the fibrous polysaccharide. As the pulp, there can be used chemical pulp, mechanical pulp and waste paper made from woody plants such as hardwoods and conifers, and herbaceous plants such as bamboo and bamboo.
以上の本発明のナノ複合体の製造法では、無機化合物が炭酸カルシウム、炭酸マグネシウム、硫酸カルシウム、硫酸バリウム、硫酸マグネシウム等のアルカリ土類金属の炭酸塩や硫酸塩のうちから選ばれた少なくとも１とすることができる。その場合に、２以上を選択した場合には、ナノ微細化した繊維状多糖と２以上の異なる無機化合物との複合体が得られる。
In the above-described method for producing a nanocomposite of the present invention, the inorganic compound is at least one selected from carbonates and sulfates of alkaline earth metals such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and magnesium sulfate. It can be. In this case, when two or more are selected, a composite of nano-fine fibrous polysaccharide and two or more different inorganic compounds is obtained.
本発明のナノ複合体は、球形の炭酸カルシウムなどの無機化合物がCNFなどのナノ微細化した繊維状多糖を軸に数珠状に連なった形態を有しており、一般的な無機化合物と比較した場合、全く異なる形態の無機化合物としての利用が考えられる。また一般的なCNFなどのナノ微細化した繊維状多糖と比較した場合、本発明のナノ複合体はナノ微細化した繊維状多糖表面を無機化合物が被覆していることによって、樹脂等の補強材として用いる際にはナノ複合体表面とマトリックスである樹脂等の界面に生じる相互作用が一般的なナノ微細化した繊維状多糖とは異なる。そのため、相溶性の向上によって補強材として特徴的な効果を示すことが期待され、その応用範囲は多岐に渡る。
The nanocomposite of the present invention has a form in which an inorganic compound such as spherical calcium carbonate is linked in a beaded manner around a nano-sized fibrous polysaccharide such as CNF, and compared with a general inorganic compound. In this case, it can be used as an inorganic compound in a completely different form. In addition, when compared with a nano-miniaturized fibrous polysaccharide such as general CNF, the nanocomposite of the present invention has a nano-miniaturized fibrous polysaccharide surface coated with an inorganic compound, thereby providing a reinforcing material such as a resin. When it is used as, the interaction that occurs at the interface of the nanocomposite surface and the resin as a matrix is different from that of general nano-sized fibrous polysaccharides. Therefore, it is expected to show a characteristic effect as a reinforcing material by improving the compatibility, and its application range is diverse.
以下、本発明のナノ複合体の一実施の形態につき説明する。
本発明のナノ複合体の形態をより詳細に検討するため透過型電子顕微鏡観察を行った。
図１に示す本発明のナノ複合体は直径５０ｎｍ程度の球形の炭酸カルシウム粒子が数珠状に連なった状態で連結している。これに対して図２に示すｏｎ－ｓｉｔｅナノ複合化前の炭酸カルシウムは、幅５００－７００ｎｍ、長さ２－３μｍであり大きさが全く異なり、形状も紡錘状の全く異なる形態を有していた。図３に示したように、水中対向衝突処理によって炭酸カルシウムが分解もしくは溶解したところに、同時にナノ微細化された晒クラフトパルプからなるＣＮＦが存在することによって、ＣＮＦを足場に分解もしくは溶解された炭酸カルシウムが凝集もしくは再結晶することで、特異的な形態を有する本発明のナノ複合体が生成されたと推測される。この結果から本発明のｏｎ－ｓｉｔｅナノ複合化によって得られる物質は混合物ではなく複合体であり、またその大きさからナノ複合体であると言える。
Hereinafter, one embodiment of the nanocomposite of the present invention will be described.
Transmission electron microscope observation was performed in order to examine the form of the nanocomposite of the present invention in more detail.
In the nanocomposite of the present invention shown in FIG. 1, spherical calcium carbonate particles having a diameter of about 50 nm are connected in a beaded state. On the other hand, the calcium carbonate before on-site nanocomposite shown in FIG. 2 has a width of 500-700 nm, a length of 2-3 μm, a completely different size, and a completely different spindle shape. It was. As shown in FIG. 3, when calcium carbonate was decomposed or dissolved by the underwater collision process, CNF made of bleached kraft pulp that was nano-sized at the same time was decomposed or dissolved into the scaffold. It is presumed that the nanocomposite of the present invention having a specific form was generated by aggregation or recrystallization of calcium carbonate. From this result, it can be said that the substance obtained by the on-site nanocomposite of the present invention is not a mixture but a composite, and it is a nanocomposite because of its size.
以下、本発明のナノ複合体を得る一手法である本発明のナノ複合体の製造法の一実施の形態について詳細に説明する。
図３に示されるように本発明のナノ複合体の製造法では、晒クラフトパルプのナノ微細化と炭酸カルシウムの分解もしくは溶解を同じ装置内で同時に行う。これによって、分解もしくは溶解された炭酸カルシウムが晒クラフトパルプのナノ微細化によって創製されたＣＮＦを足場にして凝集もしくは結晶成長する。その結果、今までに無い形態のＣＮＦと炭酸カルシウムのナノ複合体が創製される。
Hereinafter, an embodiment of the method for producing a nanocomposite of the present invention, which is one method for obtaining the nanocomposite of the present invention, will be described in detail.
As shown in FIG. 3, in the method for producing a nanocomposite of the present invention, nano-miniaturization of bleached kraft pulp and decomposition or dissolution of calcium carbonate are simultaneously performed in the same apparatus. As a result, the decomposed or dissolved calcium carbonate aggregates or grows crystals using the CNF created by nano-miniaturization of bleached kraft pulp as a scaffold. As a result, a nanocomposite of CNF and calcium carbonate in an unprecedented form is created.
このｏｎ－ｓｉｔｅナノ複合化によって得られた本発明のナノ複合体懸濁水は、図４（ａ）に示されるｏｎ－ｓｉｔｅナノ複合化前の炭酸カルシウム懸濁水と比べると、図４（ｂ）に示されるように、炭酸カルシウムの粒子径が小さい。また、粒子が連結していることによって、よりまとまった状態をとっていることが伺える。
The nanocomposite suspension water of the present invention obtained by this on-site nanocomposite is compared with the calcium carbonate suspension water before the on-site nanocomposite shown in FIG. As shown in Fig. 2, the particle size of calcium carbonate is small. In addition, it can be seen that the particles are connected to form a more organized state.
図５（ｂ）に示すｏｆｆ－ｓｉｔｅ複合体懸濁水ではＣＮＦによって炭酸カルシウム粒子が凝集していることは伺える。しかし、図５（ａ）に示す本発明のｏｎ－ｓｉｔｅナノ複合化によって得られたナノ複合体懸濁水と比べ、炭酸カルシウムの粒子径が大きく本発明のｏｎ－ｓｉｔｅナノ複合化によって得られたナノ複合体とは全く状態が異なる。
In the off-site complex suspension water shown in FIG. 5B, it can be seen that the calcium carbonate particles are aggregated by CNF. However, compared with the nanocomposite suspension water obtained by the on-site nanocomposite of the present invention shown in FIG. 5 (a), the particle diameter of calcium carbonate is large and obtained by the on-site nanocomposite of the present invention. The state is completely different from nanocomposites.
一方、ナノ微細化されてない晒クラフトパルプと炭酸カルシウムの一般的な複合化方法である混合によって得られた混合懸濁水（図５：ｃ）では、晒クラフトパルプはナノ微細化されていないため繊維幅が大きな状態で存在する。また炭酸カルシウムも大きな粒子径のままであり、複合化というよりは混在した状態で存在し、本発明のｏｎ－ｓｉｔｅナノ複合化によって得られたナノ複合体とは全く状態が異なる。
On the other hand, in the mixed suspension water obtained by mixing, which is a general compounding method of bleached kraft pulp and calcium carbonate that have not been nano-miniaturized (FIG. 5c), bleached kraft pulp is not nano-miniaturized. The fiber width exists in a large state. Calcium carbonate also has a large particle size, exists in a mixed state rather than in a composite state, and is completely different from the nanocomposite obtained by the on-site nanocomposite of the present invention.
図５（ａ）に示した本発明のｏｎ－ｓｉｔｅナノ複合化によって得られたナノ複合体懸濁水と、図５（ｂ）に示したｏｆｆ－ｓｉｔｅ複合体懸濁水とは炭酸カルシウムの粒子径こそ異なるもののその凝集形態は光学顕微鏡観察においては類似している。そこでそれぞれの懸濁水に分散剤を加え、分散剤添加後の挙動について比較を行った。これを図６に示す。図６においては図６（ａ）と図６（ｂ）それぞれにおいて上側の図が分散剤添加前を示し、下側の図が分散剤添加後を示す。
The nanocomposite suspension water obtained by the on-site nanocomposite of the present invention shown in FIG. 5 (a) and the off-site composite suspension water shown in FIG. Although different, their aggregated forms are similar in optical microscopy. Therefore, a dispersant was added to each suspension water, and the behavior after adding the dispersant was compared. This is shown in FIG. In FIG. 6, in each of FIGS. 6A and 6B, the upper diagram shows before the dispersant addition, and the lower diagram shows after the dispersant addition.
ｏｆｆ－ｓｉｔｅ複合体懸濁水に分散剤を添加したところ、図６（ｂ）に示すように凝集体が容易に解離して分散した。一方、本発明のｏｎ－ｓｉｔｅナノ複合化によって得られたナノ複合体懸濁水では、図６（ａ）に示すように分散剤を添加しても個々には分散せず一定の大きさの凝集状態を維持した。すなわち本発明のｏｎ－ｓｉｔｅナノ複合化によって得られたナノ複合体分散水は分散剤の添加によって、ｏｆｆ－ｓｉｔｅ複合体懸濁水とは明らかに異なる挙動を示し、全く異なる形態を有することが確認された。
When a dispersant was added to the off-site complex suspension water, the aggregates were easily dissociated and dispersed as shown in FIG. 6 (b). On the other hand, in the nanocomposite suspension water obtained by the on-site nanocomposite of the present invention, as shown in FIG. The state was maintained. That is, it was confirmed that the nanocomposite dispersed water obtained by the on-site nanocomposite of the present invention showed a completely different form from the off-site complex suspended water by the addition of a dispersant. It was done.
このことからｏｆｆ－ｓｉｔｅ複合体は、晒クラフトパルプを予め水中対向衝突法によってナノ微細化したＣＮＦと炭酸カルシウムが表面の吸着作用等によって凝集した緩やかな複合体であり、その相互作用が分散剤の添加によって弱まることで容易に解離して分散したと推測される。一方、本発明のナノ複合体は分散剤の添加では分散せず、ＣＮＦと炭酸カルシウムが表面の吸着作用等で凝集しているのではなく、両者が表面吸着等とは異なる相互作用によって複合化した強固な複合体に変化しているため分散しなかったと推測される。
Therefore, the off-site complex is a loose complex in which CNF and calcium carbonate obtained by nano-refining bleached kraft pulp in advance by an underwater facing collision method are aggregated due to surface adsorption and the like. It is presumed that it was easily dissociated and dispersed by being weakened by the addition of. On the other hand, the nanocomposite of the present invention does not disperse with the addition of a dispersant, and CNF and calcium carbonate are not aggregated due to surface adsorption, etc., but both are complexed by an interaction different from surface adsorption, etc. It is presumed that it did not disperse because it changed to a strong composite.
図７に示すように、本発明のｏｎ－ｓｉｔｅナノ複合化においては、ＣＮＦと複合化する無機化合物が水中対向衝突によって分解もしくは溶解し、かつ分解もしくは溶解したのちに凝集もしくは再結晶する。水中対向衝突によって分解もしくは溶解することが難しい非常に硬い化合物や安定構造を有する化合物、または水中対向衝突によって分解もしくは溶解することが可能でも分解もしくは溶解したのちに凝集もしくは結晶化しないような化合物では、本発明のナノ複合体は得られない。この両方の特徴、すなわち水中対向衝突によって分解もしくは溶解し、分解もしくは溶解したのちに凝集もしくは再結晶するような特徴を有する化合物として、炭酸カルシウムや炭酸マグネシウム、硫酸カルシウム、硫酸バリウム、硫酸マグネシウム等のアルカリ土類金属の炭酸塩や硫酸塩がある。特に炭酸カルシウムが望ましい。それらの化合物を混合して用いることもできる。
As shown in FIG. 7, in the on-site nanocomposite of the present invention, the inorganic compound to be complexed with CNF is decomposed or dissolved by an underwater collision, and then aggregated or recrystallized after being decomposed or dissolved. For very hard compounds that are difficult to decompose or dissolve by underwater collision, compounds with stable structure, or compounds that can be decomposed or dissolved by underwater collision but do not aggregate or crystallize after decomposition or dissolution The nanocomposite of the present invention cannot be obtained. As compounds having both of these characteristics, that is, decomposition or dissolution by underwater collision, and aggregation or recrystallization after decomposition or dissolution, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, magnesium sulfate, etc. There are alkaline earth metal carbonates and sulfates. Calcium carbonate is particularly desirable. A mixture of these compounds can also be used.
ナノサイズの繊維幅を持つＣＮＦと他化合物の一般的な複合化においては、「ＣＮＦの調製処理」「他化合物の分解又は溶解処理」「複合化処理」の３つの工程が必要である。
本発明のナノ複合体の製造法ではこれら３つの処理を一工程で行うことが可能であり、簡素化された手順でナノ複合体の製造が可能であるため製造コストの面でも優れた製造法といえる。
In general compounding of CNF having a nano-sized fiber width and another compound, three steps of “CNF preparation process”, “decomposition or dissolution process of other compound”, and “compounding process” are required.
In the method for producing a nanocomposite of the present invention, these three treatments can be performed in one step, and the nanocomposite can be produced by a simplified procedure, so that the production method is excellent in terms of production cost. It can be said.
本発明のｏｎ－ｓｉｔｅナノ複合化によって得られたナノ複合体は、CNFなどのナノ微細化した繊維状多糖を足場に直径５０ｎｍ程度の球形の炭酸カルシウムなどの無機化合物粒子が数珠状に連なった状態で連結している。図８に示すように表面を無機化合物で被覆したナノ微細化した繊維状多糖としても、また球形の状態で数珠状に連なった無機化合物としても利用できる。
In the nanocomposite obtained by the on-site nanocomposite of the present invention, inorganic compound particles such as spherical calcium carbonate having a diameter of about 50 nm are arranged in a beaded manner using a nano-sized fibrous polysaccharide such as CNF as a scaffold. Linked in a state. As shown in FIG. 8, it can be used as a nano-sized fibrous polysaccharide whose surface is coated with an inorganic compound or as an inorganic compound connected in a bead shape in a spherical state.
本発明のナノ複合体を「表面を炭酸カルシウムなどの無機化合物で被覆したCNFなどのナノ微細化した繊維状多糖」として捉えた場合、ＣＮＦの軽量、高強度、低熱膨張率等の優れた性質を利用した樹脂との複合化に利用することができる。通常のＣＮＦを樹脂の補強材として利用すると、親水性表面を有するＣＮＦは疎水性の樹脂とは相溶性が低いうえＣＮＦ同士の凝集によってきれいに分散せず、補強材としての効果は低減してしまう。しかし本発明のナノ複合体の場合、ＣＮＦ表面を炭酸カルシウムなどの無機化合物が被覆しているため樹脂との界面相互作用が通常のＣＮＦとは異なり、相溶性の向上や分散性の向上によって補強材としての機能の向上が期待できる。
When the nanocomposite of the present invention is regarded as "a nano-sized fibrous polysaccharide such as CNF whose surface is coated with an inorganic compound such as calcium carbonate", CNF has excellent properties such as light weight, high strength, and low thermal expansion coefficient. It can be used for compounding with a resin using When normal CNF is used as a resin reinforcing material, CNF having a hydrophilic surface has low compatibility with a hydrophobic resin and does not disperse neatly due to agglomeration of CNFs, reducing the effect as a reinforcing material. . However, in the case of the nanocomposite of the present invention, since the CNF surface is coated with an inorganic compound such as calcium carbonate, the interfacial interaction with the resin is different from that of ordinary CNF, and it is reinforced by improving compatibility and dispersibility. The improvement of the function as a material can be expected.
また、本発明のナノ複合体を「球形の状態で数珠状に連なった炭酸カルシウムなどの無機化合物」として捉えた場合、通常の炭酸カルシウムなどの無機化合物や単にナノ微細化しただけの炭酸カルシウムなどの無機化合物とは形態が異なるため、従来の無機化合物を利用している製品中の無機化合物と置き換えるだけで新たな機能の発現が期待できる。
In addition, when the nanocomposite of the present invention is regarded as “inorganic compounds such as calcium carbonate connected in a spherical shape in a rosary shape”, the inorganic compound such as normal calcium carbonate, or calcium carbonate that is simply nano-miniaturized, etc. Since the form is different from that of the inorganic compound, a new function can be expected by simply replacing the inorganic compound in the product using the conventional inorganic compound.
以下、本発明を実施例によってさらに具体的に説明する。
実施例１
Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
以下のように本発明のナノ複合体の製造法を実施して本発明の実施例のナノ複合体を製造した。
濃度０．１０ｗｔ％の湿潤状態の晒クラフトパルプ水懸濁液に水懸濁液状態の炭酸カルシウムを絶乾状態の晒クラフトパルプの重量に対し10wt%添加したのちアジテーターで均一攪拌し、晒クラフトパルプ－炭酸カルシウム混合懸濁水を調製した。この混合懸濁水を図１１に示すタンク（図１１：１）に投入し、チャンバー（図１１：３）内での噴射圧力が１８０ＭＰａになるようにプランジャー（図１１：２）で昇圧して水中対向衝突させ、熱交換器（図１１：５）によって冷却した後、タンク（図１１：１）へ戻した。試料懸濁水のこの一連の流れ（タンク→プランジャー→チャンバー→熱交換器）を循環させながら90回繰り返した。なお、この循環サイクルの反復数を、処理回数(パス)とする。
また、炭酸カルシウムを絶乾状態の晒クラフトパルプの重量に対してそれぞれ50wt%、130wt%の添加量で添加したこと以外は上記と同様にしてナノ複合体の懸濁水を調製したところ、炭酸カルシウム添加量の増加に伴い得られたナノ複合体懸濁水は白濁し、ナノ複合体に関しては、透過型電子顕微鏡観察によって観察し、図２に示す「未処理の炭酸カルシウム」と似た形態を有するものが増加した。
The nanocomposite of the example of the present invention was manufactured by carrying out the method of manufacturing the nanocomposite of the present invention as follows.
After adding 10 wt% of calcium carbonate in water suspension to the wet suspension of kraft pulp in a wet state with a concentration of 0.10 wt% with respect to the weight of the dry kraft pulp in the dry state, uniformly stirred with an agitator, and bleached kraft A pulp-calcium carbonate mixed suspension was prepared. The mixed suspension water is put into the tank (FIG. 11: 1) shown in FIG. 11, and the pressure is increased by the plunger (FIG. 11: 2) so that the injection pressure in the chamber (FIG. 11: 3) becomes 180 MPa. After opposing collision in water and cooling by a heat exchanger (FIG. 11: 5), it was returned to the tank (FIG. 11: 1). This sequence of sample suspension water (tank → plunger → chamber → heat exchanger) was repeated 90 times while circulating. The number of repetitions of this circulation cycle is the number of processing (pass).
In addition, the suspension water of the nanocomposite was prepared in the same manner as above except that calcium carbonate was added at an addition amount of 50 wt% and 130 wt% with respect to the weight of the bleached kraft pulp in an absolutely dry state. The nanocomposite suspension water obtained with the increase in the amount added becomes cloudy, and the nanocomposite is observed through a transmission electron microscope and has a form similar to “untreated calcium carbonate” shown in FIG. Things have increased.
以上の結果、図４（ｂ）、図５（ａ）、図６（ａ）、図１に示すナノ複合体を得た。
晒クラフトパルプ－炭酸カルシウム混合水懸濁液内の晒クラフトパルプの濃度は、水中対向衝突法における流路内で詰まりなどの問題が生じない濃度であればよく、特段の制限はない。また炭酸カルシウムの添加量にも特段の制限はなく、通常、絶乾状態の晒クラフトパルプの重量に対して1wt.%－200wt.％、好ましくは5wt.％－50wt.％である。
実施例２
As a result, the nanocomposites shown in FIGS. 4B, 5A, 6A, and 1 were obtained.
The concentration of the bleached kraft pulp in the bleached kraft pulp-calcium carbonate mixed water suspension is not particularly limited as long as it does not cause problems such as clogging in the flow path in the underwater collision method. The amount of calcium carbonate added is not particularly limited, and is usually 1 wt.% To 200 wt.%, Preferably 5 wt.% To 50 wt.%, Based on the weight of the dry kraft pulp.
Example 2
ｏｎ－ｓｉｔｅ複合体のシートを次のようにして調製した（図９参照）。
濃度０．１０ｗｔ％の湿潤状態の広葉樹由来の晒クラフトパルプ懸濁水に水懸濁液状態の炭酸カルシウムを絶乾重量で広葉樹由来の晒クラフトパルプに対し１０ｗｔ％添加したのちアジテーターで均一攪拌し、広葉樹由来の晒クラフトパルプ－炭酸カルシウム混合懸濁水を調製した。この混合懸濁水を噴出圧力１８０ＭＰａ、処理回数９０Ｐａｓｓの条件で水中対向衝突を行い、広葉樹由来の晒クラフトパルプを原料にしたｏｎ－ｓｉｔｅ複合体を得た。
A sheet of on-site complex was prepared as follows (see FIG. 9).
After adding 10 wt% of calcium carbonate in a water suspension state to bleached kraft pulp derived from hardwood in a dry kraft pulp suspension water derived from wet hardwood with a concentration of 0.10 wt%, uniformly stirred with an agitator, Bleached kraft pulp-calcium carbonate mixed suspension water derived from hardwood was prepared. The mixed suspension was subjected to an underwater collision under the conditions of an ejection pressure of 180 MPa and a treatment frequency of 90 Pass to obtain an on-site complex using bleached kraft pulp derived from hardwood.
その後、得られた広葉樹由来の晒クラフトパルプを原料にしたｏｎ－ｓｉｔｅ複合体懸濁水７０ｍｌを吸引濾過することによってウェット状のシートを作成し、１３０℃に設定した乾燥機内で２４時間乾燥させ、広葉樹由来の晒クラフトパルプを原料としたｏｎ－ｓｉｔｅ複合体のドライシートを調製した。
Then, a wet sheet was prepared by suction filtration of 70 ml of the on-site complex suspension water made from the bleached kraft pulp derived from the hardwood, and dried in a dryer set at 130 ° C. for 24 hours. An on-site composite dry sheet was prepared from bleached kraft pulp derived from hardwood.
比較例１ 比較例１として晒クラフトパルプを水中対向衝突によってナノ微細化して得られたＣＮＦのみの複合化させていないＣＮＦシートを次のようにして調製した（図９参照）。
濃度０．１０ｗｔ％の湿潤状態の広葉樹由来の晒クラフトパルプ懸濁水を噴出圧力１８０ＭＰａ、処理回数９０Ｐａｓｓの条件で水中対向衝突を行い、広葉樹由来の晒クラフトパルプを原料にしたＣＮＦを得た。得られた広葉樹由来の晒クラフトパルプを原料にしたＣＮＦ懸濁水７０ｍｌを吸引濾過することによってウェット状のシートを作成し、１３０℃に設定した乾燥機内で２４時間乾燥させ、広葉樹由来の晒クラフトパルプを原料としたＣＮＦのドライシートを調製した。
Comparative Example 1 As Comparative Example 1, an uncomplexed CNF sheet of only CNF obtained by nano-refining bleached kraft pulp by underwater facing collision was prepared as follows (see FIG. 9).
A bleached kraft pulp suspension water derived from wet hardwood with a concentration of 0.10 wt% was subjected to an underwater collision under the conditions of an ejection pressure of 180 MPa and a processing frequency of 90 Pass to obtain CNF using bleached kraft pulp derived from hardwood as a raw material. A wet sheet was prepared by suction filtration of 70 ml of CNF suspension water made from the obtained hardwood-derived bleached kraft pulp, and dried in a dryer set at 130 ° C. for 24 hours. A dry sheet of CNF was prepared using as a raw material.
比較例２ 比較例２として、ｏｆｆ－ｓｉｔｅ複合体シートを次のようにして調製した（図９参照）。
まず、濃度０．１０ｗｔ％の湿潤状態の広葉樹由来の晒クラフトパルプ懸濁水を用いて噴出圧力１８０ＭＰａ、処理回数９０Ｐａｓｓの条件で水中対向衝突を行い、広葉樹由来の晒クラフトパルプを原料にしたＣＮＦを得た。次に、得られた広葉樹由来の晒クラフトパルプを原料にしたＣＮＦ懸濁水に水懸濁液状態の炭酸カルシウムを絶乾重量で広葉樹由来の晒クラフトパルプに対し１０ｗｔ％添加したのち、家庭用ミキサーを用いて３分間激しく攪拌することによって広葉樹の晒クラフトパルプ由来のＣＮＦと炭酸カルシウムのｏｆｆ－ｓｉｔｅ複合体を得た。
Comparative Example 2 As Comparative Example 2, an off-site composite sheet was prepared as follows (see FIG. 9).
First, CNF made from bleached kraft pulp derived from broad-leaved trees was subjected to an underwater collision with a 0.10 wt% wet hardwood-derived bleached kraft pulp suspension water under a jet pressure of 180 MPa and a treatment count of 90 Pass. Obtained. Next, after adding 10 wt% of calcium carbonate in a water suspension state to the CNF suspension water made from the obtained hardwood-derived bleached kraft pulp as a raw material, with respect to the hardwood-derived bleached kraft pulp, a household mixer Was mixed vigorously for 3 minutes to obtain an off-site complex of CNF derived from hardwood bleached kraft pulp and calcium carbonate.
その後、得られたｏｆｆ－ｓｉｔｅ複合体懸濁水７０ｍｌを吸引濾過することによってウェット状のシートを作成し、１３０℃に設定した乾燥機内で２４時間乾燥させ、広葉樹由来の晒クラフトパルプを原料としたｏｆｆ－ｓｉｔｅ複合体のドライシートを調製した。
Thereafter, 70 ml of the obtained off-site complex suspension water was subjected to suction filtration to prepare a wet sheet, which was dried in a dryer set at 130 ° C. for 24 hours, and a hardwood-derived bleached kraft pulp was used as a raw material. A dry sheet of off-site complex was prepared.
以上の実施例２、比較例１，２の各場合において、広葉樹由来の晒クラフトパルプの代わりに竹由来の晒クラフトパルプを原料とする以外は各場合において同様の手法によって、各ドライシートを調製した。
なお、未精製の竹由来の晒クラフトパルプには竹材に含まれる組織柔細胞が多く混在するため、メッシュによる濾過を繰り返すことによってパルプ繊維と組織柔細胞の分離を行い、竹由来の晒クラフトパルプを精製し、ドライシートの原料として組織柔細胞をほぼ除去した状態のパルプを使用した。
In each case of Example 2 and Comparative Examples 1 and 2 described above, each dry sheet was prepared by the same method in each case except that the raw material was bamboo-derived bleached kraft pulp instead of hardwood-derived bleached kraft pulp. did.
Since unrefined bamboo-derived bleached kraft pulp contains a large amount of tissue parenchyma contained in bamboo, the pulp fibers and tissue parenchymal cells are separated by repeated filtration through the mesh, and bamboo-derived bleached kraft pulp The pulp in a state where tissue parenchymal cells were almost removed was used as a raw material for the dry sheet.
以上の本発明の実施例２、比較例１、２のシートを用いて引張試験によって力学的特性の比較を行い、その機能性の差異を検証した。
実施例２、比較例１、２のシートの中央部からそれぞれ幅７ｍｍ、長さ２５－３０ｍｍの大きさの試験片を切り出し、２３℃、５０％ＲＨの環境条件下で３日以上調湿したのち引張試験に供した。引張試験は卓上型材料試験機（ＳＴＡ－１２２５：（株）オリエンテック製）を使用し、測定長２０ｍｍ、引張速度２ｍｍ／ｍｉｎの条件で行った。
Using the sheets of Example 2 and Comparative Examples 1 and 2 of the present invention described above, mechanical properties were compared by a tensile test, and the difference in functionality was verified.
Test pieces each having a width of 7 mm and a length of 25-30 mm were cut out from the central portions of the sheets of Example 2 and Comparative Examples 1 and 2, respectively, and conditioned for 3 days or more under an environmental condition of 23 ° C. and 50% RH. Later, it was subjected to a tensile test. The tensile test was performed using a desktop material testing machine (STA-1225: manufactured by Orientec Co., Ltd.) under the conditions of a measurement length of 20 mm and a tensile speed of 2 mm / min.
また、同様にして切り出した試験片を２３℃、５０％ＲＨの環境条件下で３日以上調湿したのち、１３０℃に設定した乾燥機内で２４時間乾燥させ、デシケーター内で放冷後、速やかに引張試験に供した。引張試験は卓上型材料試験機（ＳＴＡ－１２２５：（株）オリエンテック製）を使用し、測定長２０ｍｍ、引張速度２ｍｍ／ｍｉｎの条件で行った。
In addition, after the test piece cut out in the same manner was conditioned for 3 days or more under an environmental condition of 23 ° C. and 50% RH, it was dried in a dryer set at 130 ° C. for 24 hours, allowed to cool in a desiccator, and then quickly The sample was subjected to a tensile test. The tensile test was performed using a desktop material testing machine (STA-1225: manufactured by Orientec Co., Ltd.) under the conditions of a measurement length of 20 mm and a tensile speed of 2 mm / min.
表１は実施例２、比較例１、２のシートそれぞれの引張試験から得られた力学的強度を示す。
Table 1 shows the mechanical strengths obtained from the tensile tests of the sheets of Example 2 and Comparative Examples 1 and 2.
また図１０において引張試験結果（１）は、２３℃、５０％ＲＨの環境条件下で調湿した各シートの引張試験によって得られた応力―ひずみ曲線を示す。一方、引張試験結果（２）は１３０℃乾燥機内で２４時間乾燥させた各シートの引張試験によって得られた応力－ひずみ曲線を示す。
In FIG. 10, the tensile test result (1) shows a stress-strain curve obtained by a tensile test of each sheet conditioned under the environmental conditions of 23 ° C. and 50% RH. On the other hand, the tensile test result (2) shows a stress-strain curve obtained by a tensile test of each sheet dried in a dryer at 130 ° C. for 24 hours.
図１０、表１に示されるように本発明の実施例２シートは、比較例１シートと比較例２シートとの中間的な挙動を示した。一般的な紙の場合、「パルプのみの紙」に比べ「炭酸カルシウム等の填料を加えた紙」の力学的強度は低下する。これはパルプ繊維間の相互作用が添加された「填料」によって阻害されることで低下することに起因する。これと同様の現象によって、本試験結果においても比較例１シートに比べ、実施例２シートや比較例２シートの力学的強度が低下したと考えられる。しかし力学的強度の低下程度は実施例１シートと比較例２シートで異なり、実施例２シートは比較例２シートに比べ高い力学的強度を示した。
As shown in FIG. 10 and Table 1, the Example 2 sheet of the present invention exhibited an intermediate behavior between the Comparative Example 1 sheet and the Comparative Example 2 sheet. In the case of general paper, the mechanical strength of “paper added with a filler such as calcium carbonate” is lower than that of “pulp-only paper”. This is due to the fact that the interaction between pulp fibers is lowered by being inhibited by the added “filler”. Due to the same phenomenon, it is considered that the mechanical strength of the Example 2 sheet and the Comparative Example 2 sheet also decreased in this test result compared to the Comparative Example 1 sheet. However, the degree of decrease in mechanical strength was different between the Example 1 sheet and the Comparative Example 2 sheet, and the Example 2 sheet showed higher mechanical strength than the Comparative Example 2 sheet.
またこの傾向は、原料であるパルプが広葉樹由来の晒クラフトパルプであるシートだけでなく草本類である竹由来の晒クラフトパルプのシートにおいても認められた。さらには、引張試験時の測定環境条件が異なる場合においても同様の挙動を示した。すなわち２３℃、５０％ＲＨの環境条件下で調湿することによってシートの含水率を約５－７％にした場合（図１０：引張試験結果（１））、および１３０℃に設定した乾燥機内で乾燥させることによってシートの含水率をほぼ０％にした場合（図１０：引張試験結果（２））の両条件下において同様の挙動を示した
Moreover, this tendency was recognized not only in the sheet | seat in which the pulp which is a raw material is a bleached kraft pulp derived from hardwood, but also in the sheet | seat of the bleached kraft pulp derived from bamboo which is herbaceous. Furthermore, the same behavior was exhibited even when the measurement environment conditions during the tensile test were different. That is, when the moisture content of the sheet is adjusted to about 5-7% by adjusting the humidity at 23 ° C. and 50% RH (FIG. 10: Tensile test result (1)), and in the dryer set to 130 ° C. When the moisture content of the sheet was reduced to almost 0% by drying with (Fig. 10: Tensile test result (2)), the same behavior was exhibited.
これらの結果から、本発明のナノ複合体はシート化によってネットワーク構造を形成させた場合においても一般的な混合によって得られる複合体とは異なる特性を示すことが明らかになった。一般的な混合によって得られる複合体はＣＮＦと炭酸カルシウムが吸着等の物理的相互作用のみで複合化していると考えられる。しかし、本発明のナノ複合体では水中対向衝突によって分解もしくは溶解した炭酸カルシウムがＣＮＦを足場に凝集もしくは再結晶することによってＣＮＦが炭酸カルシウムに被覆されたような状態で複合化している。そのため、形成されたネットワークにおける架橋点での複合体間の相互作用が異なり一般的な混合によって得られる複合体とは異なる特性を示したと考えられる。
また原料である晒クラフトパルプの種類やネットワーク構造内の水分含量によらず同様の傾向を示すことも明らかになった。
From these results, it was revealed that the nanocomposite of the present invention exhibits different properties from the composite obtained by general mixing even when the network structure is formed by sheet formation. The complex obtained by general mixing is considered that CNF and calcium carbonate are complexed only by physical interaction such as adsorption. However, in the nanocomposite of the present invention, calcium carbonate decomposed or dissolved by underwater collision is agglomerated or recrystallized with CNF as a scaffold, and thus CNF is complexed in a state covered with calcium carbonate. For this reason, it is considered that the interaction between the complexes at the cross-linking points in the formed network is different, and the characteristics are different from those of the complex obtained by general mixing.
It was also found that the same tendency was shown regardless of the type of bleached kraft pulp as the raw material and the water content in the network structure.
以上のことから、本発明のナノ複合体の特異的な形態は、シート化といったネットワーク構造を形成させた場合においても一般的な混合によって得られる複合体と異なるネットワークにおける複合体間の相互作用が生じることから、他用途においても一般的な混合によって得られる複合体とは異なる特性や物性を示すことが期待される。
From the above, the specific form of the nanocomposite of the present invention is that even when a network structure such as sheet formation is formed, the interaction between the composites in a network different from the composite obtained by general mixing is different. As a result, it is expected to exhibit characteristics and physical properties different from those of composites obtained by general mixing in other applications.
Claims (11)
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ナノ微細化した繊維状多糖を軸にして球形の無機化合物が数珠状に連なった状態で連結した形態を有することを特徴とするナノ複合体。
A nanocomposite characterized in that it has a form in which spherical inorganic compounds are linked in a bead-like shape with nano-sized fibrous polysaccharides as axes.
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ナノ微細化した繊維状多糖と無機化合物とを含むナノ複合体であり、前記ナノ微細化した繊維状多糖表面に前記無機化合物が複合化する態様で付着し、前記ナノ微細化した繊維状多糖が前記無機化合物に覆われていることを特徴とするナノ複合体。
A nano-composite comprising a nano-fine fibrous polysaccharide and an inorganic compound, the nano-fine fiber polysaccharide is attached to the nano-fine fiber polysaccharide surface in a form of complexing, and the nano-fine fiber polysaccharide is A nanocomposite which is covered with the inorganic compound.
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前記ナノ微細化した繊維状多糖がセルロースナノファイバーである請求項１又は請求項２に記載したナノ複合体。
The nanocomposite according to claim 1 or 2, wherein the nano-sized fibrous polysaccharide is a cellulose nanofiber.
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前記無機化合物がアルカリ土類金属の炭酸塩及び硫酸塩のうちから選ばれた少なくとも１である請求項１～請求項３のいずれか一に記載したナノ複合体。
The nanocomposite according to any one of claims 1 to 3, wherein the inorganic compound is at least one selected from carbonates and sulfates of alkaline earth metals.
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前記無機化合物が炭酸カルシウム、炭酸マグネシウム、硫酸カルシウム、硫酸バリウム、硫酸マグネシウムのうちから選ばれた少なくとも１である請求項１～請求項３のいずれか一に記載したナノ複合体。
The nanocomposite according to any one of claims 1 to 3, wherein the inorganic compound is at least one selected from calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and magnesium sulfate.
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繊維状多糖と無機化合物の懸濁水を調製し、その懸濁水内において前記繊維状多糖のナノ微細化と前記無機化合物の溶解若しくは分解とを一の工程で行い前記繊維状多糖と前記無機化合物とのナノ複合体を取得することを特徴とするナノ複合体の製造法。
A suspension water of a fibrous polysaccharide and an inorganic compound is prepared, and in the suspension water, nano-miniaturization of the fibrous polysaccharide and dissolution or decomposition of the inorganic compound are performed in one step, and the fibrous polysaccharide and the inorganic compound A method for producing a nanocomposite comprising obtaining a nanocomposite of the above.
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繊維状多糖と無機化合物の懸濁水を調製し、その懸濁水中の前記繊維状多糖のナノ微細化と前記無機化合物の溶解若しくは分解とを同時に行い、前記繊維状多糖と前記無機化合物とのナノ複合体を取得することを特徴とするナノ複合体の製造法。
A suspension of a fibrous polysaccharide and an inorganic compound is prepared, and nano refinement of the fibrous polysaccharide and dissolution or decomposition of the inorganic compound are simultaneously performed in the suspension water. The manufacturing method of the nanocomposite characterized by acquiring a composite_body | complex.
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前記ナノ微細化処理が物理的処理である請求項６又は請求項７に記載のナノ複合体の製造法。
The method for producing a nanocomposite according to claim 6 or 7, wherein the nano-miniaturization treatment is a physical treatment.
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前記物理的処理が水中対向衝突である請求項８に記載のナノ複合体の製造法。
The method for producing a nanocomposite according to claim 8, wherein the physical treatment is an underwater collision.
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前記繊維状多糖がパルプである請求項６～請求項９のいずれか一に記載のナノ複合体の製造法。
The method for producing a nanocomposite according to any one of claims 6 to 9, wherein the fibrous polysaccharide is pulp.
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前記パルプが、広葉樹や針葉樹といった木本植物、竹や葦といった草本植物を原料とした化学パルプ、機械パルプ及び古紙である請求項１０に記載のナノ複合体の製造法。
The method for producing a nanocomposite according to claim 10, wherein the pulp is a chemical pulp, a mechanical pulp, and a waste paper made from woody plants such as hardwoods and conifers, and herbaceous plants such as bamboo and bamboo.
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| US11186952B2 (en) | 2017-02-14 | 2021-11-30 | Nippon Paper Industries Co., Ltd. | Composition which contains composite fibers composed of inorganic particles and fibers |
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