WO2019198429A1 - Redispersible composition containing cellulose fibers and non-cellulose powder granules - Google Patents
Redispersible composition containing cellulose fibers and non-cellulose powder granules Download PDFInfo
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- WO2019198429A1 WO2019198429A1 PCT/JP2019/011052 JP2019011052W WO2019198429A1 WO 2019198429 A1 WO2019198429 A1 WO 2019198429A1 JP 2019011052 W JP2019011052 W JP 2019011052W WO 2019198429 A1 WO2019198429 A1 WO 2019198429A1
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- Prior art keywords
- cellulose
- mass
- powder
- composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 167
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- 150000001340 alkali metals Chemical class 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000832 lactitol Substances 0.000 description 1
- 235000010448 lactitol Nutrition 0.000 description 1
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 description 1
- 229960003451 lactitol Drugs 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229960002160 maltose Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
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- 229940127554 medical product Drugs 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 229940116317 potato starch Drugs 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a redispersible composition, an electrode coating composition using the same, and an electrode, and more particularly, a composition containing cellulose fibers and non-cellulose granules, and a polar solvent such as water
- the present invention relates to a composition excellent in redispersibility in water and an electrode coating composition from which an electrode excellent in conductivity can be obtained.
- Cellulose fiber is the basic skeletal material of all plants and is an abundant natural resource that exceeds 1 trillion tons on the earth. Now that environmental issues have begun to attract attention, it has attracted attention as a next-generation material because of its excellent characteristics. It is known that the main characteristics of cellulose fibers are that they are 5 times stronger than steel and have a low linear thermal expansion coefficient of 1/50 that of glass, despite being 1/5 lighter than steel. . Furthermore, since fine fibers having a size of about 4 to several hundreds of nanometers exhibit excellent water-based dispersibility and organic solvent dispersibility by surface chemical modification, it is not limited to foods, cosmetics, medical products or paints, but resins It is also expected to be used as a material reinforcement or emulsion stabilization aid.
- the aqueous suspension or dispersion of fine fibrous cellulose usually contains water several to several hundred times the mass of fine fibrous cellulose. Since solids obtained by drying fine fibrous cellulose dispersed in water (wet state) form hydrogen bonds between the fine cellulose fibers, even if water is added to the dried solids, Various properties such as solubility, dispersibility, sedimentation degree, and viscosity of (wet state) are not restored. For this reason, the dispersion
- Non-Patent Document 1 and Patent Document 1 disclose fine fibrous cellulose. And a composition containing non-cellulose granules (carbon nanotubes) and water.
- the blending ratio of the non-cellulose powder in the composition is small, and it is not redispersed in a polar solvent such as water. Accordingly, it is desirable to provide a composition that contains non-cellulose granules at a higher concentration and can be redispersed in a polar solvent such as water.
- Embodiment of this invention aims at providing the composition excellent in the redispersibility to polar solvents, such as water, in the composition containing a cellulose fiber and a non-cellulose granular material.
- the composition according to the first embodiment of the present invention comprises (A1) cellulose fibers having a short average number average width of 2 nm to 1000 nm, (B) non-cellulose granules, and (C) water. It is a composition containing at least, Comprising: Content of the said (B) non-cellulose granule is 14.0 mass% or more and 98.4 mass% or less with respect to the total mass of the said composition, Said (C ) The water content is 0.6% by mass or more and 72.0% by mass or less with respect to the total mass of the composition, and the content of the (A1) cellulose fiber and the (B) non-cellulose powder. Is a redispersible composition having a mass ratio (A1) / (B) to the content of 1.0 / 99.0 to 50.0 / 50.0.
- the composition according to the second embodiment of the present invention comprises (A1) cellulose fibers having a short width number average width of 2 nm to 1000 nm, (A2) carboxymethylcellulose salt, and (B) non-cellulose granules. And (C) a composition containing at least water, wherein the content of the non-cellulose powder (B) is 14.0% by mass or more and 98.4% by mass with respect to the total mass of the composition.
- the content of water (C) is 0.6% by mass or more and 72.0% by mass or less with respect to the total mass of the composition, and the content of the (A1) cellulose fiber and the above (A2)
- the mass ratio ((A1) + (A2)) / (B) of the total content of carboxymethylcellulose salt and the content of (B) non-cellulose powder is 1.0 / 99. 0 or more and 50.0 / 50.0 or less, redispersible It is a formed product.
- the redispersion according to the embodiment of the present invention is obtained by redispersing the composition in a polar solvent.
- the electrode coating composition according to the embodiment of the present invention uses the composition or the redispersion.
- the electrode which concerns on embodiment of this invention is produced using the said electrode coating material composition.
- composition according to the embodiment of the present invention contains non-cellulose powder at a high concentration and is excellent in redispersibility in a polar solvent such as water. Therefore, it is possible to improve the transportability by suppressing an increase in storage space and an increase in storage and transportation costs, and it is easy to apply to high-concentration usage applications.
- composition which concerns on this embodiment is (A1) a cellulose fiber, (B) the non-cellulose granular material, and (C) the redispersible composition (henceforth a granular material containing composition) containing water. Is).
- the composition may further contain (A2) a carboxymethylcellulose salt.
- A1 Cellulose fiber As the cellulose fiber, one having a short average number average width of 2 nm to 1000 nm is used. When the number average width of the shorter width is within this range, the function as a dispersant for the non-cellulose powder can be exhibited, and the effect of improving redispersibility can be enhanced.
- the number average width of the shorter width is preferably 200 nm or less, more preferably 100 nm or less, and still more preferably 50 nm or less.
- the number average width of the short side of the cellulose fiber is also referred to as the number average fiber diameter, and can be measured as follows. That is, an aqueous dispersion of cellulose fibers having a solid content of 0.05 to 0.1% by mass was prepared, and the aqueous dispersion was cast on a carbon film-coated grid that had been subjected to a hydrophilic treatment, so that transmission electron A sample for observation with a microscope (TEM) is used. In addition, when the fiber of a big fiber diameter is included, you may observe the scanning electron microscope (SEM) image of the surface cast on glass. Further, the observation sample may be negatively stained with, for example, a 2% by mass uranyl acetate aqueous solution.
- SEM scanning electron microscope
- observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times, or 50000 times depending on the size of the constituent fibers.
- an axis having an arbitrary vertical and horizontal image width is assumed in the obtained image, and the sample and observation conditions (magnification, etc.) are adjusted so that 20 or more fibers intersect the axis.
- draw two random axes in the vertical and horizontal directions per image and visually check the short width (fiber diameter) of the fibers that intersect the axis. I will read it.
- the cellulose fiber preferably has an aspect ratio of 7.5 or more and 250 or less.
- the aspect ratio is more preferably 10 or more, still more preferably 20 or more, more preferably 75 or less, and still more preferably 50 or less.
- the cellulose fiber has a type I crystal structure, and the crystallinity calculated by the Segal method using an X-ray diffractometer is preferably 70% or more and 95% or less.
- the crystallinity is 70% or more, the effect of improving redispersibility can be enhanced.
- the degree of crystallinity is more preferably 80% or more.
- the upper limit of the crystallinity is not particularly limited, but may be, for example, 95% or less or 92% or less.
- the crystallinity is cellulose I type crystallinity calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following equation.
- Cellulose type I crystallinity (%) [(I 22.6 -I 18.5 ) / I 22.6 ] ⁇ 100
- the I-type crystal structure is a crystal form of natural cellulose
- the cellulose I-type crystallinity means the ratio of the crystal region to the total cellulose.
- the cellulose fiber may have a hydroxyl group on the fiber surface chemically modified.
- a cellulose fiber having an anionic functional group is preferable from the viewpoint of maintaining an I-type crystal structure and enabling efficient defibration to a predetermined fiber diameter.
- the anionic functional group can be introduced by chemically modifying a part of the hydroxyl group of the glucose unit in the cellulose molecule.
- the anionic functional group is not particularly limited, and examples thereof include a carboxyl group, a functional group containing sulfur, and a functional group containing phosphorus.
- Preferable anionic functional groups include at least one selected from the group consisting of a carboxyl group, a phosphate group, a sulfonate group, and a sulfate group.
- the carboxyl group is not only an acid form (—COOH) but also a salt form, that is, a concept including a carboxylate group (—COOX, where X is a cation forming a salt with a carboxylic acid), Acid type and salt type may be mixed.
- the phosphoric acid group, the sulfonic acid group, and the sulfuric acid group are concepts including not only the acid type but also the salt type, and the acid type and the salt type may be mixed.
- the salt of the anionic functional group is not particularly limited, but alkali metal salts such as sodium salt, potassium salt and lithium salt, alkaline earth metal salts such as magnesium salt, calcium salt and barium salt, ammonium salt, phosphonium salt and the like Onium salts, primary amines, secondary amines, tertiary amines and other amine salts.
- alkali metal salts such as sodium salt, potassium salt and lithium salt
- alkaline earth metal salts such as magnesium salt, calcium salt and barium salt, ammonium salt, phosphonium salt and the like
- Onium salts primary amines, secondary amines, tertiary amines and other amine salts.
- the content of the anionic functional group in the cellulose fiber is not particularly limited, but is preferably 0.2 mmol / g or more, more preferably 0.5 mmol / g or more per dry mass of the cellulose fiber. It may be 0 mmol / g or more, 1.2 mmol / g or more, or 1.5 mmol / g or more. Moreover, it is preferable that it is 2.5 mmol / g or less, and 2.0 mmol / g or less may be sufficient.
- the content of the anionic functional group can be determined by measuring electrical conductivity.
- the cellulose fiber-containing slurry prepared to a concentration of about 0.05 to 1% by mass is neutralized with an aqueous sodium hydroxide solution, and neutralized.
- V (mL) of the aqueous sodium hydroxide solution consumed in the step and the molar concentration c (mol / L) of the aqueous sodium hydroxide solution, it can be obtained by the following equation.
- Anionic functional group amount (mmol / g) V ⁇ [c / mass of cellulose sample (g)]
- a cellulose fiber having an anionic functional group As an example of a cellulose fiber having an anionic functional group according to one embodiment, an oxidized cellulose fiber formed by oxidizing a hydroxyl group of a glucose unit constituting cellulose is illustrated in more detail, and an example of a production method Also explained.
- the hydroxyl group of 6th-position of a glucose unit is selectively oxidized. It can be confirmed, for example, by a 13 C-NMR chart that the oxidized cellulose fiber is one in which the hydroxyl group at the 6-position on the glucose unit is selectively oxidized.
- the oxidized cellulose fiber may have an aldehyde group or a ketone group together with the carboxyl group.
- Oxidized cellulose fiber uses natural cellulose fiber as a raw material, an oxidation reaction step (1) for obtaining a reaction product by oxidizing natural cellulose fiber by using a N-oxyl compound as an oxidation catalyst in water and acting a co-oxidant, impurities It can be obtained by a production method comprising a purification step (2) for obtaining a reaction product impregnated with water and a dispersion step (3) for dispersing the reaction product impregnated with water in a solvent.
- (1) Oxidation reaction step After the natural cellulose fiber and the N-oxyl compound are dispersed in water (dispersion medium), a cooxidant is added to start the reaction. During the reaction, a 0.5 M aqueous sodium hydroxide solution is added dropwise to maintain the pH at 10 to 11, and the reaction is regarded as complete when no change in pH is observed.
- the co-oxidant is not a substance that directly oxidizes a cellulose hydroxyl group but a substance that oxidizes an N-oxyl compound used as an oxidation catalyst.
- the above-mentioned natural cellulose fiber means a purified cellulose fiber isolated from a cellulose biosynthetic system such as a plant, animal or bacteria-producing gel. More specifically, softwood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, bacterial cellulose fiber (BC), cellulose fiber isolated from sea squirt And cellulose fibers isolated from seaweed. These may be used alone or in combination of two or more.
- a cellulose biosynthetic system such as a plant, animal or bacteria-producing gel. More specifically, softwood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, bacterial cellulose fiber (BC), cellulose fiber isolated from sea squirt And cellulose fibers isolated from seaweed.
- the dispersion medium of the natural cellulose fiber in the above reaction is water, and the concentration of the natural cellulose fiber in the reaction aqueous solution is arbitrary as long as the reagent (natural cellulose fiber) can be sufficiently diffused. Usually, it is about 5% or less with respect to the mass of the reaction aqueous solution, but the reaction concentration can be increased by using an apparatus having a strong mechanical stirring force.
- examples of the N-oxyl compound include compounds having a nitroxy radical generally used as an oxidation catalyst.
- the N-oxyl compound is preferably a water-soluble compound, and among them, piperidine nitroxyoxy radical is preferable, and 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) or 4-acetamido-TEMPO is particularly preferable.
- TEMPO 2,2,6,6-tetramethylpiperidinooxy radical
- a catalytic amount is sufficient for the addition of the N-oxyl compound, preferably 0.1 to 4 mmol / L, more preferably 0.2 to 2 mmol / L.
- co-oxidant examples include hypohalous acid or a salt thereof, halous acid or a salt thereof, perhalogen acid or a salt thereof, hydrogen peroxide, a perorganic acid, and the like. These may be used alone or in combination of two or more. Of these, alkali metal hypohalites such as sodium hypochlorite and sodium hypobromite are preferable. And when using the said sodium hypochlorite, it is preferable to advance reaction in presence of alkali metal bromides, such as sodium bromide, from the point of reaction rate. The addition amount of the alkali metal bromide is about 1 to 40 times mol, preferably about 10 to 20 times mol for the N-oxyl compound.
- the pH of the aqueous reaction solution is preferably maintained in the range of about 8-11.
- the temperature of the aqueous solution is arbitrary at about 4 to 40 ° C., but the reaction can be performed at room temperature (25 ° C.), and the temperature is not particularly required to be controlled.
- the degree of oxidation is controlled by the amount of co-oxidant added and the reaction time. Usually, the reaction time is about 5-120 minutes and is completed within 240 minutes at the most.
- the degree of hydrolysis of the cellulose molecules can be controlled to arbitrarily set the aspect ratio of the cellulose fiber.
- any apparatus can be used as long as it can achieve the above-described purpose, such as a method using centrifugal dehydration (for example, a continuous decanter).
- the aqueous dispersion of reactant fibers thus obtained may have a solid content (cellulose fiber) concentration in the range of approximately 10% to 50% by mass in the squeezed state.
- Dispersers used in the dispersion process include high-powered homomixers, high-pressure homogenizers, ultra-high-pressure homogenizers, ultrasonic dispersion processors, beaters, disk-type refiners, conical-type refiners, double-disk-type refiners, and grinders.
- the disperser include a screw mixer, paddle mixer, disper mixer, turbine mixer, disper, propeller mixer, kneader, blender, homogenizer, ultrasonic homogenizer, colloid mill, pebble mill, and bead mill grinder. There is no problem. Two or more types of dispersers may be used in combination.
- a cellulose fiber performs a reductive reaction after the said oxidation reaction.
- the oxidized cellulose fiber after the oxidation reaction is dispersed in purified water, the pH of the aqueous dispersion is adjusted to about 10, and the reduction reaction is performed with various reducing agents.
- the reducing agent it is possible to use a common one, preferably, LiBH 4, NaBH 3 CN, NaBH 4 , and the like.
- the amount of reducing agent may be in the range of 0.1 to 4% by weight, based on oxidized cellulose fibers.
- the reduction reaction is usually performed at room temperature or slightly higher than room temperature, usually for 10 minutes to 10 hours, preferably 30 minutes to 2 hours.
- the content of the cellulose fiber is preferably 0.3% by mass or more and 48.6% by mass or less based on the total mass of the granular material-containing composition.
- the dispersibility of (B) non-cellulose powder can be improved, and the redispersibility can be improved.
- the viscosity of a redispersion can be reduced because it is 48.6 mass% or less.
- the cellulose fiber content is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and preferably 45.0% by mass or less, more preferably 30.0% by mass or less. .
- (A2) Carboxymethylcellulose salt is a cellulose component that functions as a dispersant or dispersion stabilizer that disperses (B) non-cellulose granules together with the (A1) cellulose fiber, and a water-soluble carboxymethylcellulose salt is used.
- (A2) carboxymethylcellulose salt in combination with (A1) cellulose fiber, the conductivity in the case of using conductive powder as (B) non-cellulose powder can be improved.
- the powder-containing composition is used for an electrode coating composition, an electrode having excellent conductivity can be obtained.
- the salt of the carboxymethyl cellulose salt is preferably an alkali metal salt, and at least one selected from the group consisting of sodium salt, lithium salt, and potassium salt is particularly preferable. More preferred is carboxymethylcellulose sodium salt.
- the carboxymethylcellulose salt it is preferable to use a carboxymethylcellulose salt because it can provide more excellent conductivity when combined with the cellulose fiber.
- the viscosity of a 1% by mass aqueous solution of carboxymethyl cellulose salt is preferably 500 mPa ⁇ s or less, and more preferably 100 mPa ⁇ s or less.
- 10 mPa * s or more may be sufficient, for example.
- the viscosity of a 1% by mass aqueous solution of carboxymethyl cellulose salt is measured as follows. That is, carboxymethylcellulose salt (about 2.2 g) is placed in a 300 ml Erlenmeyer flask with a stopper and precisely weighed. The amount of water calculated by the calculation formula “sample (g) ⁇ (99 ⁇ water content (mass%))” is added thereto, left to stand for 12 hours, and further mixed for 5 minutes. Using the obtained solution, the viscosity at 25 ° C. is measured according to JIS Z8803 using a single cylindrical rotational viscometer.
- the content of the (A2) carboxymethyl cellulose salt is not particularly limited, but is preferably 0.1% by mass or more and 39% by mass or less, more preferably 1.% by mass with respect to the total mass of the granular material-containing composition. It is 5 mass% or more and 30 mass% or less.
- Non-cellulose powder granules As a non-cellulose granular material, various granular materials other than a cellulose are mentioned.
- Non-cellulose powder (hereinafter sometimes referred to simply as powder) is a powdery or granular substance, preferably a powdery substance consisting of fine particles having a particle diameter of 0.5 mm or less. .
- the average particle diameter of the non-cellulose powder is not particularly limited, and may be 100 ⁇ m or less, 30 ⁇ m or less, 5 nm to 5 ⁇ m, or 10 to 100 nm.
- the specific surface area of the non-cellulose powder by BET method may be 0.1 to 1400 m 2 / g, 1 to 300 m 2 / g, or 10 to 100 m 2 / g. But you can.
- grains of a non-cellulose granular material is not specifically limited, Any of spherical shape, plate shape, needle shape, etc. may be sufficient.
- the average particle diameter of the non-cellulose powder can be measured with a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., Microtrac UPA) and calculated as a median diameter on a volume basis.
- the specific surface area by the BET method can be measured by, for example, a gas adsorption method described in JIS Z8830: 2013.
- non-cellulose powder examples include inorganic particles and organic particles, and various functional particles can be used depending on the application.
- the inorganic particles are not particularly limited, and examples thereof include particles composed of metals, metal compounds, glass fibers, minerals, inorganic compounds, components produced by chemical synthesis, and the like. Specifically, carbon, zeolite, calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, zinc carbonate, aluminum silicate, diatomaceous earth, calcium silicate, silicic acid Examples of the particles include magnesium, silica, aluminum hydroxide, alumina, alumina hydrate, aluminosilicate, boehmite, pseudoboehmite, copper oxide, and iron oxide.
- Organic particles are not particularly limited, and examples thereof include particles made of resin, natural product-derived components, saccharides, components produced by chemical synthesis, and the like. Specifically, acrylic resin, polystyrene, silicone resin, fluorine resin, melamine resin, benzoguanamine resin, polycarbonate, polyamide, chitin, chitosan, dextrin, oligosaccharide, wheat starch, rice starch, corn starch, potato starch, dextrin, cyclohexane Examples thereof include particles of dextrin, lactose, glucose, sugar, reduced maltose, sorbitol, erythritol, xylitol, lactitol, mannitol, casein and the like.
- These inorganic particles and organic particles may be used alone or in combination of two or more.
- hydrophobic inorganic particles are inorganic particles that have substantially no hydrophilic group on the particle surface, and thus exhibit water repellency or oleophilicity. Originally hydrophilic inorganic particles, but the surface is treated with a water repellent. Inorganic particles exhibiting water repellency are also included.
- hydrophobic inorganic particles examples include carbon particles, some metal fine particles, and some natural clay minerals. Among these, carbon particles that are particles composed of carbon are preferably used. Examples of the carbon particles include carbon black such as furnace black, acetylene black, and ketjen black, as well as activated carbon, carbon nanotube, and carbon fiber. , Graphite, diamond, and the like. Any one of these may be used, or two or more may be used in combination.
- the water repellent is not particularly limited as long as it can introduce a hydrophobic group on the surface of the hydrophilic inorganic particles.
- the hydrophobic group include a group having a hydrocarbon group not having a polar group.
- water repellents include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and the like.
- the hydrophilic inorganic particles as the surface treatment target include metal oxides such as silica, alumina, titania and zirconia.
- a conductive powder As the non-cellulose powder, a conductive powder may be used.
- the conductive granular material include an electrode active material and / or a conductive aid described later.
- the content of the non-cellulose granular material is 14.0% by mass or more and 98.4% by mass or less with respect to the total mass of the granular material-containing composition.
- the content of the non-cellulose powder is preferably 25.0% by mass or more, more preferably 30.0% by mass or more, still more preferably 40.0% by mass or more, and 50.0% by mass. % Or more.
- 96.0 mass% or less may be sufficient, and 80.0 mass% or less may be sufficient.
- the granular material containing composition which concerns on this embodiment contains water. Content of water is 0.6 mass% or more and 72.0 mass% or less with respect to the total mass of a granular material containing composition.
- the higher concentration of the solid content of the powder-containing composition can ensure the concentration of (B) non-cellulose powder after re-dispersion. For example, when used in a paint, it is easier to produce a high-concentration paint. Become. Moreover, the change with time in long-term storage can be suppressed.
- the water content is preferably 0.6% by mass or more and 45.0% by mass or less, more preferably 30.0% by mass or less, with respect to the total mass of the granular material-containing composition. More preferably, it is 25.0 mass% or less, and may be 20.0 mass% or less. Moreover, it is preferable that it is 1.5 mass% or more, More preferably, it is 5.0 mass% or more, More preferably, it is 10.0 mass% or more.
- the water content in the present specification is such that the composition is heated at 140 ° C. using a heat drying moisture meter (MX-50 manufactured by A & D Co., Ltd.), and the weight change rate is 0.05% / It can be calculated by measuring the weight below the minute as an end point and comparing it with the weight before measurement.
- MX-50 manufactured by A & D Co., Ltd. a heat drying moisture meter
- the mass ratio of the content of (A1) cellulose fiber and the content of (B) non-cellulose granular material (that is, the component (A1 relative to the component (B)) ) (Mass ratio) (A1) / (B) is 1.0 / 99.0 or more and 50.0 / 50.0 or less.
- Mass ratio (A1) / (B) is 1.0 / 99.0 or more and 50.0 / 50.0 or less.
- the mass ratio (A1) / (B) is preferably 30.0 / 70.0 or less, more preferably 20.0 / 80.0 or less, and 2.0 / 98.0 or more. It is preferable that the ratio is 2.5 / 97.5 or more.
- the granular material-containing composition according to the second embodiment contains (A2) carboxymethylcellulose salt, and in that case, (A1) the content of cellulose fiber and (A2) the total content of carboxymethylcellulose salt, (B) Mass ratio with respect to the content of non-cellulose powder (that is, mass ratio of the total amount of component (A1) and component (A2) to component (B)) ((A1) + (A2)) / ( B) is 1.0 / 99.0 or more and 50.0 / 50.0 or less.
- the redispersibility of the powder-containing composition can be improved.
- an increase in viscosity of the redispersion can be suppressed, and for example, coating properties when used in a paint can be improved.
- the mass ratio ((A1) + (A2)) / (B) is preferably 30.0 / 70.0 or less, more preferably 20.0 / 80.0 or less, and 1.1 /98.9 or more, more preferably 2.0 / 98.0 or more, and further preferably 2.5 / 97.5 or more.
- mass ratio (A1) / (B) of content of (A1) cellulose fiber and content of (B) non-cellulose granular material is 1.0 / 99.0 or more and 50.0. /50.0 or less, more preferably 30.0 / 70.0 or less, still more preferably 20.0 / 80.0 or less, and 2.0 / 98.0 or more. More preferably, it is 2.5 / 97.5 or more.
- the mass ratio of the content of (A1) cellulose fiber and the content of (A2) carboxymethylcellulose salt (that is, the mass ratio of component (A1) to component (A2)) (A1) / ( A2) is preferably 20.0 / 80.0 or more and 99.0 / 1.0 or less.
- the mass ratio (A1) / (A2) is preferably 30.0 / 70.0 or more and 70.0 / 30.0 or less, more preferably 40.0 / 60.0 or more and 70.0 / 30. 0.0 or less.
- the manufacturing method of a granular material containing composition is not specifically limited.
- the (A1) cellulose fiber aqueous dispersion obtained as described above is mixed with (B) non-cellulose powder and, if necessary, additional water and other optional components, and dispersed. Can be prepared. Moreover, you may adjust the water content (namely, water content) of a granular material containing composition by drying after mixing and dispersion
- (A1) a cellulose fiber aqueous dispersion in which (A2) a carboxymethylcellulose salt is dissolved, (B) a non-cellulose powder, and, if necessary, additional Water and other optional components may be mixed and dispersed.
- the mixing / dispersing device used for the mixing / dispersing process is not particularly limited.
- a homodisper, a planetary mixer, a propeller mixer, a kneader, a homogenizer, an ultrasonic homogenizer, a colloid mill, a bead mill, a sand mill, a high-pressure homogenizer, or the like is used. be able to.
- the drying method is not particularly limited, and examples thereof include freeze drying, vacuum drying (for example, drying using a conical dryer), spray drying, blow drying, and heat drying (for example, drying using a drum dryer). .
- the water content of the resulting powder-containing composition can be adjusted within a predetermined range.
- the powder-containing composition includes a dispersion stabilizer, an organic solvent, and a surfactant as long as the effects of the present embodiment are not impaired.
- Other components such as may be contained.
- the dispersion stabilizer is added to further increase the dispersion stability, and is, for example, water-soluble such as methylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, polyvinyl alcohol, sodium polyacrylate, and polyethylene glycol. Examples include polymers.
- the organic solvent may be used as a dispersion medium in the above mixing / dispersing treatment. That is, the dispersion medium is basically water, but a water-miscible organic solvent may be used together with water, and in this case, the organic solvent may be included in the powder-containing composition.
- water-miscible organic solvents include alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, and t-butanol; polyhydric alcohols such as ethylene glycol and glycerin; ketones such as acetone; and tetrahydrofuran.
- Ethers such as ethyl acetate and methyl acetate
- amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone
- sulfoxides such as dimethyl sulfoxide.
- the particulate-containing composition according to the present embodiment is a redispersible composition that can be redispersed in a polar solvent such as water, and therefore, it is preferably used by being redispersed in a polar solvent such as water.
- a polar solvent such as water
- (A1) cellulose fibers and (B) non-cellulose powder are added to the polar solvent (this polar solvent was added during redispersion).
- (C) Polar solvent such as water (included in the powder-containing composition) is dispersed in addition to the polar solvent.
- redispersible means that (A1) cellulose fibers and (B) non-cellulose granules can be uniformly dispersed when redispersed in this way.
- redispersibility those of 3 or more can be said to be redispersible and excellent in redispersibility.
- the redispersion according to the present embodiment is obtained by redispersing the above-described powder-containing composition in a polar solvent, and can also be referred to as a redispersion liquid.
- the polar solvent for redispersion include water, a water-miscible organic solvent, and a mixture of water and a water-miscible organic solvent.
- the polar solvent is water or a mixture of water and a water-miscible organic solvent, in which case the water content is preferably 50% by mass or more, more preferably 70% by mass or more. is there. Specific examples of the water-miscible organic solvent are as described above.
- a dispersing device used for redispersion the same device as the mixing / dispersing device described in the above mixing / dispersing process can be used.
- the concentration in the redispersion is not particularly limited, and the concentration of the total solid content may be 0.5 to 20.0 mass% or 1.0 to 15.0 mass%.
- the granular material containing composition which is excellent in the redispersibility to polar solvents, such as water, contains non-cellulose granular material, such as a functional particle, in high concentration. Therefore, it is possible to improve transportability while suppressing an increase in storage space and an increase in storage and transportation costs.
- the powder-containing composition according to the present embodiment can be applied to various coating compositions, and contains non-cellulose powder such as functional particles at a high concentration, the paint Even when it is added to the composition, a decrease in the solid concentration can be suppressed, and a high-concentration paint can be easily produced. Moreover, the effect which suppresses aggregation of the coating composition by the rapid change of a density
- concentration can also be anticipated.
- the powder-containing composition according to the present embodiment is excellent in redispersibility, for example, the paint composition under preparation after adjusting the powder-containing composition to an appropriate solid content concentration by redispersion in advance. It may be added to the product, or a coating composition may be prepared while adding and redispersing the powder-containing composition together with a polar solvent, and in any case, a coating composition having good coatability is prepared. Can be produced.
- the powder-containing composition according to the present embodiment is less likely to change with time even during long-term storage and is excellent in storage stability.
- the powder-containing composition can be handled as a powdery or solid solid material, and is particularly excellent in terms of transportability and fluidity. More preferable in terms.
- the water content is 10% by mass or more, even when solidified in a block shape depending on the drying conditions, it can be easily crushed with a small force, and thus it is more preferable in terms of handling.
- the granular material-containing composition according to this embodiment is excellent in redispersibility, it can be suitably used, for example, as a composition for paints and inks for various uses such as building materials, stationery, and electronic devices.
- Electrode coating composition and electrode The particulate-containing composition according to the present embodiment and the redispersion using the composition can be used for an electrode coating composition, and an electrode coating composition having a high solid content concentration can be easily produced. Moreover, electrodes, such as a device electrode, can be formed by apply
- the electrode coating composition contains an electrode active material (hereinafter sometimes simply referred to as an active material) and a conductive additive.
- an active material hereinafter sometimes simply referred to as an active material
- a conductive assistant is used as the (B) non-cellulose powder
- (A1) a powder-containing composition containing cellulose fibers and a conductive assistant is mixed with an active material and optional components to form an electrode coating composition.
- an active material is used as (B) non-cellulose powder
- (A1) a powder-containing composition containing cellulose fibers and an active material is mixed with a conductive additive and an optional component to form an electrode coating composition. May be produced.
- the active material and the conductive assistant are used as (B) non-cellulose powder, and (A1) the powder-containing composition containing the cellulose fiber, the active material and the conductive assistant is mixed together with optional components.
- An electrode coating composition may be prepared. At that time, a polar solvent may be added to the powder-containing composition in advance and redispersed, and then mixed with other components to prepare an electrode coating composition.
- the powder-containing composition may be An electrode coating composition may be prepared at the same time as adding and redispersing a polar solvent together with the other components.
- these granular material containing composition may contain the (A2) carboxymethylcellulose salt as an arbitrary component.
- the active material but is not particularly limited, as a positive electrode active material used in the positive electrode of a lithium secondary battery, for example, CuO, Cu 2 O, MnO 2, MoO 3, V 2 O 5, CrO 3, MoO 3, Metal oxides such as Fe 2 O 3 , Ni 2 O 3 and CoO 3 , complex oxides of lithium and transition metals such as Li x CoO 2 , Li x NiO 2 , Li x Mn 2 O 4 and LiFePO 4 (lithium) Composite oxide), metal chalcogenides such as TiS 2 , MoS 2 , and NbSe 3 , and conductive polymer compounds such as polyacene, polyparaphenylene, polypyrrole, and polyaniline.
- a positive electrode active material used in the positive electrode of a lithium secondary battery for example, CuO, Cu 2 O, MnO 2, MoO 3, V 2 O 5, CrO 3, MoO 3, Metal oxides such as Fe 2 O 3 , Ni 2 O 3 and CoO 3 , complex oxides of lithium and transition metal
- the negative electrode active material used for the negative electrode of the lithium secondary battery include carbon materials such as natural graphite, artificial graphite, non-graphitizable carbon, and graphitizable carbon, and metal materials such as metallic lithium, alloys, and tin compounds. , Lithium transition metal nitrides, crystalline metal oxides, amorphous metal oxides, silicon compounds, conductive polymers, and the like.
- Examples of the active material used for the electrode for the electric double layer capacitor include carbon allotropes such as activated carbon, polyacene, carbon whisker, and graphite.
- the active material As the active material, as the electrode active material used for the positive electrode of the lithium ion capacitor electrode, the carbon allotrope similar to the electrode for the electric double layer capacitor can be mentioned.
- the electrode active material used for the negative electrode of the lithium ion capacitor electrode include crystalline carbon materials such as graphite and non-graphitizable carbon, polyacene-based materials (PAS), and the like.
- Examples of the conductive assistant include carbon black (acetylene black, kettin black, etc.), natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon whisker, carbon fiber, metal (copper, nickel, (Aluminum, silver, gold, etc.) powder, metal fiber, conductive ceramic material and the like.
- the content of the active material is not particularly limited, but may be 60 to 97% by mass in 100% by mass of the total solid content. Further, the content of the conductive auxiliary agent may be 0.1 to 30% by mass with respect to the content of the active material.
- the amount of the (A1) cellulose fiber contained in the electrode coating composition by using the above-mentioned powder-containing composition is not particularly limited. For example, 0.05% in 100% by mass of the total solid content of the electrode coating composition. It may be up to 5.00% by mass.
- the amount of (A2) carboxymethylcellulose salt contained when using the powder-containing composition according to the second embodiment is not particularly limited. For example, the total solid content of the electrode coating composition is 100% by mass. It may be 0.02 to 5.00% by mass.
- the electrode coating composition according to the present embodiment includes, as optional components, for example, a binder (for example, a polymer compound having water solubility and / or water dispersibility), a thickener, and a dispersion stabilizer. You may mix
- the electrode according to the present embodiment is obtained by applying the electrode coating composition to a metal foil or a conductive substrate and drying it.
- a lithium secondary battery, a lithium ion capacitor, an electric double layer capacitor, etc. examples include a device electrode for an electricity storage device.
- the pH of the slurry was adjusted to 10 with a 24% NaOH aqueous solution.
- the slurry was reduced to 30 ° C. by adding 0.2 mmol / g of sodium borohydride to the cellulose fiber and reacting for 2 hours.
- 0.1N hydrochloric acid was added to adjust the pH to 2 or less, and then purification was repeated by filtration and washing with water. Pure water was added thereto so that the final concentration was 2% cellulose fiber and the balance was water. 24% sodium hydroxide aqueous solution was added here, and pH was adjusted to 7.
- the cellulose fiber A1-2 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
- Cellulose Fiber A1-3 (for Examples)
- the temperature of the reaction solution during the reaction was 40 ° C.
- the pH was 11
- the amount of sodium hypochlorite aqueous solution added was 4.0 mmol / g with respect to 1 g of the above pulp. Accordingly, cellulose fiber A1-3 was produced.
- Cellulose fiber A1-3 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
- Cellulose fiber A1-4 was produced according to the production of cellulose fiber A1-3, except that the amount of sodium hypochlorite aqueous solution added was 6.0 mmol / g with respect to 1 g of the above pulp.
- Cellulose fiber A1-4 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
- Cellulose fiber A1-5 is a cellulose nanofiber having a sulfonic acid group as an anionic functional group.
- a cellulose fiber dehydrated sheet was obtained in accordance with the method described in Production Example 1 of JP-A-2015-189698 (sheet after dehydration washing described in paragraphs 0080 to 0083). Distilled water was added to the obtained dehydrated sheet, the solid content was adjusted to 2.0% by stirring, and the fiber was processed three times at 100 MPa using a high-pressure homogenizer to produce cellulose fiber A1-6.
- the cellulose fiber A1-6 is a cellulose nanofiber having a phosphate group as an anionic functional group.
- the cellulose fibers A1-1 to A1-6, A′-1, and A′-2 obtained above were subjected to the following evaluation, and the results are shown in Table 1.
- Cellulose type I crystallinity The X-ray diffraction intensity of the cellulose fiber was measured by the X-ray diffraction method, and calculated from the measurement result by the following formula using the Segal method.
- Cellulose type I crystallinity (%) [(I 22.6 -I 18.5 ) / I 22.6 ] ⁇ 100
- the number average width of the cellulose fibers was observed using a transmission electron microscope (TEM) (JEM-1400, manufactured by JEOL Ltd.). That is, from the TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate after each cellulose fiber was cast on a hydrophilized carbon film-coated grid, The number average width of was calculated.
- TEM transmission electron microscope
- a cellulose aqueous dispersion 60 mL in which 0.25 g of cellulose fiber was dispersed in water was prepared, and the pH was adjusted to about 2.5 with a 0.1 M hydrochloric acid aqueous solution, and then a 0.05 M sodium hydroxide aqueous solution was dropped. Electrical conductivity measurements were made. The measurement was continued until the pH was 11. The amount of carboxyl groups was determined from the amount of consumed sodium hydroxide aqueous solution V (mL) in accordance with the following equation in the neutralization step of weak acid with a gradual change in electrical conductivity. Amount of carboxyl groups (mmol / g) V (mL) ⁇ [0.05 / cellulose fiber mass (g)]
- the amount of phosphate groups was measured according to the method described in JP-A-2015-189698. That is, a cellulose fiber-containing slurry containing a solid content of about 0.04 g in absolute dry mass was collected and diluted to about 50 g using ion-exchanged water. While stirring this solution using a magnetic stirrer, the change in the value of electrical conductivity when a 0.01 M sodium hydroxide aqueous solution was added was measured. The dropping amount of the 01M sodium hydroxide aqueous solution was defined as the dropping amount at the titration end point.
- V A dripping amount (mL) of 0.01 M sodium hydroxide aqueous solution
- W Solid content (g) contained in the fine cellulose fiber-containing slurry.
- the number average width of the shorter width was in the range of 2 to 1000 nm. Further, the aspect ratio was in the range of 7.5 to 250, and the crystallinity of the cellulose I-type crystal structure was 70% or more.
- the cellulose fiber A′-1 for comparative example does not have a cellulose I-type crystal structure and is in the form of fine particles, and the number average width and aspect ratio of the shorter width cannot be measured.
- the cellulose fiber A′-2 for the comparative example had a cellulose I-type crystal structure, the number average width of the shorter width was not less than the upper limit of the above range. In Table 1, “-” means not measured.
- Example 1 Both were added so that the mass ratio of the cellulose fiber A1-1 and the granular material B-1 was 2.6 / 97.4, and water was added so that the water content was 72%. The mixture was stirred at 40 rpm ⁇ 60 minutes with a mixer (Hibismix 2P-1 manufactured by PRIMIX Corporation). The obtained paste or clay-like composition was dried at 90 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
- a mixer Hibismix 2P-1 manufactured by PRIMIX Corporation
- Example 2 to 6 A powdery to solid state is obtained in the same manner as in Example 1 except that cellulose fibers A1-2, A1-3, A1-4, A1-5, A1-6 are used in place of the cellulose fibers A1-1. A powder-containing composition was prepared.
- Example 7 Both were added so that the mass ratio of the cellulose fiber A1-4 and the powder B-1 was 2.6 / 97.4, and water was added so that the water content was 72%, and the planetary A paste or clay-like granular material-containing composition was prepared by stirring at 40 rpm ⁇ 60 minutes with a mixer (Hibismix 2P-1 type manufactured by PRIMIX Corporation).
- Example 8 The powder-containing composition containing powder to solid was obtained by drying the powder-containing composition prepared in Example 4 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB).
- Example 9 A powder to solid powder-containing composition was obtained in the same manner as in Example 4 except that the mass ratio of cellulose fiber A1-4 to powder B-1 was changed as shown in Table 2. Was prepared.
- Example 11 Viscous solid powder-containing composition in the same manner as in Example 7, except that the contents of cellulose fiber A1-4, powder B-1, and water were changed as shown in Table 2. Was prepared.
- Example 12 The powder-containing composition prepared in Example 11 was dried at 80 ° C. for 8 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to prepare a viscous solid-like powder-containing composition.
- Example 13 A paste or clay-like powder-containing composition was prepared in the same manner as in Example 7 except that the cellulose fibers A1-4, the powder B-1 and the water content were changed as shown in Table 2. Prepared.
- Example 14 The powder-containing composition prepared in Example 13 was dried at 80 ° C. for 8 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a viscous solid-like powder-containing composition.
- Example 15 The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Example 14 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
- Examples 16 to 18, 20 to 21 The same procedure as in Example 4 except that the type of the powder was changed as shown in Table 2, and the mass ratio of the cellulose fibers A1-4 and the powder was changed as shown in Table 2. Thus, a powder to solid powder-containing composition was prepared.
- Example 19 Cellulose fiber A1-4 and powder B-5 so that the mass ratio of cellulose fiber A1-4 and powder B-5 is 50.0 / 50.0 and the water content is 90%. Then, the mixture was dispersed by irradiation with an ultrasonic homogenizer (VC-505, manufactured by Sonics) at an output of 40% for 10 minutes. Thereafter, the mixture was dried in a blow dryer (manufactured by ADVANTEC, DRM620DB) at 90 ° C. for 24 hours to obtain a powder-solid powder-containing composition.
- an ultrasonic homogenizer VC-505, manufactured by Sonics
- Example 22 Paste or clay-like powder by the same method as in Example 7 except that the type of the powder was changed as shown in Table 2, and the content of each component was changed as shown in Table 2. A product-containing composition was prepared.
- Example 23 The powder-containing composition containing powder to solid was obtained by drying the powder-containing composition prepared in Example 22 at 90 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB).
- Example 24 The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Example 23 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
- Example 3 A slurry-like granular material-containing composition was prepared in the same manner as in Example 4 except that the water content was changed as shown in Table 3.
- Example 6 The mass ratio of the cellulose fiber A1-4 to the granule B-1 was changed to 0.8 / 99.2, the water content was changed to 50%, and the other methods were the same as in Example 4. A composition was prepared. Thereafter, the prepared composition was dried at 90 ° C. for 24 hours and at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
- Example 7 The mass ratio of the cellulose fiber A1-4 to the granule B-1 was changed to 87.2 / 12.8, the water content was changed to 50%, and the other methods were the same as in Example 4. A composition was prepared. Thereafter, the prepared composition was dried at 90 ° C. for 24 hours and at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
- Comparative Example 8 The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Comparative Example 5 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
- Comparative Example 9 A slurry-like granular material-containing composition was prepared in the same manner as in Comparative Example 3, except that the water content was changed as shown in Table 3.
- the solid content concentration difference in the composition is 1% by mass or less 4: The solid content concentration difference in the composition is greater than 1% by mass and 2% by mass or less 3: Solid content in the composition The concentration difference is greater than 2% by mass and 3% by mass or less. 2: The solid content concentration difference in the composition is greater than 3% by mass and 5% by mass or less. 1: The solid content concentration difference in the composition is 5. Larger than mass%, but cannot be judged by visual inspection 0: Contents are separated to such an extent that they can be visually confirmed
- Results are as shown in Tables 2 and 3. All the examples showed sufficient redispersibility, and the shorter and thinner the cellulose fibers, the better the redispersibility. Moreover, since the viscosity increases at the time of redispersion as the cellulose fiber increases, it has been found that there is an optimum value for the ratio of the granular material to the cellulose fiber in consideration of the coating property.
- Comparative Example 1 since the cellulose fiber does not have a crystal structure and a large protective colloid is formed when redispersed, the redispersibility tends to be low.
- Comparative Example 2 the fiber width of the short side of the cellulose fiber was large and the fiber length was long, so the redispersibility was low due to the entanglement of the fibers.
- Comparative Example 3 because the water content was high, the contact between the cellulose fibers and the powder was insufficient, or the dispersion effect of the powder by the cellulose fibers was inferior and the redispersibility was low. It was. In addition, the storage stability was poor.
- Comparative Example 4 had little redispersibility because the cellulose fiber / powder particle ratio was small and the cellulose fiber content was small.
- Comparative Example 5 although the ratio of cellulose fiber / powder particles was large and the content of cellulose fiber was large, the redispersibility was good, but the viscosity at the time of redispersion was high and it was idle at the coating stage. As a result.
- Comparative Example 6 since the ratio of cellulose fiber / powder granules was small and the content of the pow- der granules was too much, there was almost no redispersibility.
- Comparative Example 7 had a large ratio of cellulose fibers / powder and a small content of the granules, so that excessive cellulose fibers were aggregated and redispersion was difficult.
- Comparative Example 8 since the ratio of cellulose fiber / particulate matter was large, the redispersibility was good, but the viscosity during redispersion was high, resulting in idleness in the coating stage.
- the powder-containing composition according to this embodiment exhibits good performance in terms of good redispersibility, coating property after redispersion, and storage stability.
- cellulose fiber, carboxymethylcellulose salt and powder used in Examples 25 to 28 and Comparative Example 11 are as follows.
- content of the cellulose fiber in Table 4 is a mass ratio as solid content.
- A1-2 2% by weight aqueous dispersion of cellulose fiber
- Carboxymethylcellulose salt Carboxymethylcellulose sodium salt (Sellogen PR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 1% by weight aqueous solution viscosity (25 ° C.): 35 mPa ⁇ S)
- B-1 Acetylene black (manufactured by Denka Co., Ltd., HS-100, BET surface area: 39 m 2 / g)
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Abstract
Provided is a composition which contains cellulose fibers and non-cellulose powder granules and has excellent redispersibility in a polar solvent such as water.
A composition according to an embodiment is a redispersible composition which contains at least (A1) cellulose fibers having a number average shorter-width of 2 to 1000 nm inclusive, (B) non-cellulose powder granules and (C) water, wherein the content of the non-cellulose powder granules (B) is 14.0 to 98.4% by mass inclusive relative to the whole mass of the composition, the content of the water (C) is 0.6 to 72.0% by mass inclusive relative to the whole mass of the composition, and the mass ratio of the content of the cellulose fibers (A1) to the content of the non-cellulose powder granules (B), i.e., (A1)/(B), is 1.0/99.0 to 50.0/50.0 inclusive.
Description
本発明は、再分散可能な組成物、これを用いた電極塗料組成物、および電極に関し、より詳細には、セルロース繊維と非セルロース粉粒物を含む組成物であって、水等の極性溶媒への再分散性に優れた組成物、および導電性に優れた電極が得られる電極塗料組成物に関するものである。
The present invention relates to a redispersible composition, an electrode coating composition using the same, and an electrode, and more particularly, a composition containing cellulose fibers and non-cellulose granules, and a polar solvent such as water The present invention relates to a composition excellent in redispersibility in water and an electrode coating composition from which an electrode excellent in conductivity can be obtained.
カーボンブラックやカーボンナノチューブなどの機能性粒子は、各種の電子情報素子、光機能素子、構造体材料、化粧品、薬品、セラミックスなどの素材として、近年ますます注目を集めている。機能性粒子のサイズとしては、ミクロンオーダー以上やサブミクロンのサイズのみならず、最近ではさらに粒子径の小さい100nm(0.1μm)以下のナノ粒子が各種開発されている。特に大きさが100nm以下のナノ粒子になると、その表面積や粒子間力により物理的・化学的性質が数100nmよりも大きい粒子に比べて大きく変化することから、各種材料への利用が増加しつつある。
In recent years, functional particles such as carbon black and carbon nanotubes have attracted more and more attention as materials for various electronic information devices, optical functional devices, structural materials, cosmetics, chemicals, and ceramics. As the size of the functional particle, not only the micron order or more and the submicron size, but recently, various nanoparticles having a smaller particle size of 100 nm (0.1 μm) or less have been developed. In particular, when the size of nanoparticles is 100 nm or less, the physical and chemical properties are greatly changed by the surface area and interparticle force as compared with particles larger than several hundred nm, so that the use for various materials is increasing. is there.
このような機能性粒子は非常に扱いづらいため、安全かつ簡便な使用方法が模索されている。その最適な利用法の一つとして、液体へ機能性粒子を分散させた「分散スラリー」が挙げられる。ただし、分散スラリーの作製にもいくつか問題点があり、特に注視すべきは均一な分散性である。一般的に、粉粒物はvan dar waals引力による粒子間相互作用と界面電気二重層の重なりによる静電相互作用の存在のため、液中分散制御が難しいとされている。また、上記のような機能性粒子は疎水性を有していることが多いことから、水中での均一分散は非常に困難である。このような粉粒物を水中に分散する手法のひとつとして、微細繊維状セルロースなどのセルロース繊維の利用が挙げられる。
Since such functional particles are very difficult to handle, a safe and simple usage method is being sought. One of the most suitable uses is “dispersed slurry” in which functional particles are dispersed in a liquid. However, there are some problems in the preparation of the dispersion slurry, and what should be particularly watched is uniform dispersibility. In general, it is considered difficult to control dispersion in a liquid because of the presence of interparticle interaction due to van dar Waals attraction and electrostatic interaction due to the overlap of the interfacial electric double layer. Moreover, since the functional particles as described above often have hydrophobicity, uniform dispersion in water is very difficult. One technique for dispersing such powder particles in water is to use cellulose fibers such as fine fibrous cellulose.
セルロース繊維は、全ての植物の基本骨格物質であり、地球上に一兆トンを超える豊富な天然資源である。環境問題が注目され始めた昨今、その優れた特徴から次世代材料として注目を集めている。セルロース繊維の主な特徴として、鋼鉄の1/5の軽さであるにも関わらず、鋼鉄の5倍以上の強度、ガラスの1/50の低線熱膨張係数を有することが知られている。さらに約4~数百nm程度の大きさの微細繊維になると優れた水系分散性を示し、表面化学修飾によって有機溶剤分散性も示すことから、食品、化粧品、医療品又は塗料に限らず、樹脂材料の強化や乳化安定化助剤としての利用も期待されている。
Cellulose fiber is the basic skeletal material of all plants and is an abundant natural resource that exceeds 1 trillion tons on the earth. Now that environmental issues have begun to attract attention, it has attracted attention as a next-generation material because of its excellent characteristics. It is known that the main characteristics of cellulose fibers are that they are 5 times stronger than steel and have a low linear thermal expansion coefficient of 1/50 that of glass, despite being 1/5 lighter than steel. . Furthermore, since fine fibers having a size of about 4 to several hundreds of nanometers exhibit excellent water-based dispersibility and organic solvent dispersibility by surface chemical modification, it is not limited to foods, cosmetics, medical products or paints, but resins It is also expected to be used as a material reinforcement or emulsion stabilization aid.
微細繊維状セルロースの水性懸濁液又は分散液は、通常、微細繊維状セルロースに対して数倍~数百倍の質量の水が含まれている。水に分散している状態(湿潤状態)の微細繊維状セルロースを乾燥させた固形物は、微細なセルロース繊維間に水素結合が形成されるため、この乾燥固形物に水を加えても乾燥前(湿潤状態)の溶解性、分散性、沈降度、及び粘度などの諸特性が復元しない。このため、微細繊維状セルロースを含む分散スラリーは、通常、水に分散している状態(湿潤状態)で製造され、乾燥させずに湿潤状態のままで各種ユーザーに運搬される。しかし、このような分散スラリーをそのままの状態で扱うことは、保存スペースの増大、保存及び輸送コストの増大、加えて高濃度使用用途に不向きといった問題点がある。
The aqueous suspension or dispersion of fine fibrous cellulose usually contains water several to several hundred times the mass of fine fibrous cellulose. Since solids obtained by drying fine fibrous cellulose dispersed in water (wet state) form hydrogen bonds between the fine cellulose fibers, even if water is added to the dried solids, Various properties such as solubility, dispersibility, sedimentation degree, and viscosity of (wet state) are not restored. For this reason, the dispersion | distribution slurry containing a fine fibrous cellulose is normally manufactured in the state disperse | distributed to water (wet state), and is conveyed to various users with the wet state, without drying. However, handling such a dispersed slurry as it is has problems such as an increase in storage space, an increase in storage and transportation costs, and in addition, it is unsuitable for high-concentration use.
従来、微細繊維状セルロースを分散剤として用いて、機能性粒子などの非セルロース粉粒物を水に分散させる技術が知られており、非特許文献1および特許文献1には、微細繊維状セルロースと非セルロース粉粒物(カーボンナノチューブ)と水を含有する組成物が記載されている。しかしながら、これらの文献に記載の技術では、組成物中における非セルロース粉粒物の配合比率が少なく、水等の極性溶媒に再分散されるものではない。従って、非セルロース粉粒物をより高濃度で含有し、水等の極性溶媒に再分散させることができる組成物を提供することが望まれる。
Conventionally, a technique of dispersing non-cellulose powder such as functional particles in water using fine fibrous cellulose as a dispersant is known. Non-Patent Document 1 and Patent Document 1 disclose fine fibrous cellulose. And a composition containing non-cellulose granules (carbon nanotubes) and water. However, in the techniques described in these documents, the blending ratio of the non-cellulose powder in the composition is small, and it is not redispersed in a polar solvent such as water. Accordingly, it is desirable to provide a composition that contains non-cellulose granules at a higher concentration and can be redispersed in a polar solvent such as water.
本発明の実施形態は、セルロース繊維と非セルロース粉粒物とを含有する組成物において、水等の極性溶媒への再分散性に優れた組成物を提供することを目的とする。
Embodiment of this invention aims at providing the composition excellent in the redispersibility to polar solvents, such as water, in the composition containing a cellulose fiber and a non-cellulose granular material.
本発明の第1の実施形態に係る組成物は、(A1)短幅の方の数平均幅が2nm以上1000nm以下のセルロース繊維と、(B)非セルロース粉粒物と、(C)水を少なくとも含有する組成物であって、前記(B)非セルロース粉粒物の含有量は、前記組成物の全質量に対して14.0質量%以上98.4質量%以下であり、前記(C)水の含有量は、前記組成物の全質量に対して0.6質量%以上72.0質量%以下であり、前記(A1)セルロース繊維の含有量と前記(B)非セルロース粉粒物の含有量との質量比率(A1)/(B)が1.0/99.0以上50.0/50.0以下である、再分散可能な組成物である。
The composition according to the first embodiment of the present invention comprises (A1) cellulose fibers having a short average number average width of 2 nm to 1000 nm, (B) non-cellulose granules, and (C) water. It is a composition containing at least, Comprising: Content of the said (B) non-cellulose granule is 14.0 mass% or more and 98.4 mass% or less with respect to the total mass of the said composition, Said (C ) The water content is 0.6% by mass or more and 72.0% by mass or less with respect to the total mass of the composition, and the content of the (A1) cellulose fiber and the (B) non-cellulose powder. Is a redispersible composition having a mass ratio (A1) / (B) to the content of 1.0 / 99.0 to 50.0 / 50.0.
本発明の第2の実施形態に係る組成物は、(A1)短幅の方の数平均幅が2nm以上1000nm以下のセルロース繊維と、(A2)カルボキシメチルセルロース塩と、(B)非セルロース粉粒物と、(C)水を少なくとも含有する組成物であって、前記(B)非セルロース粉粒物の含有量は、前記組成物の全質量に対して14.0質量%以上98.4質量%以下であり、前記(C)水の含有量は、前記組成物の全質量に対して0.6質量%以上72.0質量%以下であり、前記(A1)セルロース繊維の含有量と前記(A2)カルボキシメチルセルロース塩の含有量の合計量と、前記(B)非セルロース粉粒物の含有量との質量比率((A1)+(A2))/(B)が1.0/99.0以上50.0/50.0以下である、再分散可能な組成物である。
The composition according to the second embodiment of the present invention comprises (A1) cellulose fibers having a short width number average width of 2 nm to 1000 nm, (A2) carboxymethylcellulose salt, and (B) non-cellulose granules. And (C) a composition containing at least water, wherein the content of the non-cellulose powder (B) is 14.0% by mass or more and 98.4% by mass with respect to the total mass of the composition. The content of water (C) is 0.6% by mass or more and 72.0% by mass or less with respect to the total mass of the composition, and the content of the (A1) cellulose fiber and the above (A2) The mass ratio ((A1) + (A2)) / (B) of the total content of carboxymethylcellulose salt and the content of (B) non-cellulose powder is 1.0 / 99. 0 or more and 50.0 / 50.0 or less, redispersible It is a formed product.
本発明の実施形態に係る再分散体は、前記組成物を極性溶媒に再分散させたものである。本発明の実施形態に係る電極塗料組成物は、前記組成物または再分散体を用いたものである。本発明の実施形態に係る電極は、前記電極塗料組成物を用いて作製されたものである。
The redispersion according to the embodiment of the present invention is obtained by redispersing the composition in a polar solvent. The electrode coating composition according to the embodiment of the present invention uses the composition or the redispersion. The electrode which concerns on embodiment of this invention is produced using the said electrode coating material composition.
本発明の実施形態に係る組成物であると、非セルロース粉粒物を高濃度で含有し、水等の極性溶媒への再分散性に優れる。そのため、保存スペースの増大や保存及び輸送コストの増大を抑えて運搬性を向上することができ、また、高濃度使用用途への適用が容易である。
The composition according to the embodiment of the present invention contains non-cellulose powder at a high concentration and is excellent in redispersibility in a polar solvent such as water. Therefore, it is possible to improve the transportability by suppressing an increase in storage space and an increase in storage and transportation costs, and it is easy to apply to high-concentration usage applications.
以下、本発明の好ましい実施形態について詳細に説明する。
Hereinafter, preferred embodiments of the present invention will be described in detail.
本実施形態に係る組成物は、(A1)セルロース繊維と、(B)非セルロース粉粒物と、(C)水を含有する再分散可能な組成物(以下、粉粒物含有組成物ということがある)である。該組成物は、さらに(A2)カルボキシメチルセルロース塩を含有してもよい。
The composition which concerns on this embodiment is (A1) a cellulose fiber, (B) the non-cellulose granular material, and (C) the redispersible composition (henceforth a granular material containing composition) containing water. Is). The composition may further contain (A2) a carboxymethylcellulose salt.
[(A1)セルロース繊維]
(A1)セルロース繊維としては、短幅の方の数平均幅が2nm以上1000nm以下であるものが用いられる。短幅の方の数平均幅がこの範囲内であることにより、非セルロース粉粒物に対する分散剤としての機能を発揮することができ、再分散性の向上効果を高めることができる。短幅の方の数平均幅は、好ましくは200nm以下、より好ましくは100nm以下、更に好ましくは50nm以下である。 [(A1) Cellulose fiber]
(A1) As the cellulose fiber, one having a short average number average width of 2 nm to 1000 nm is used. When the number average width of the shorter width is within this range, the function as a dispersant for the non-cellulose powder can be exhibited, and the effect of improving redispersibility can be enhanced. The number average width of the shorter width is preferably 200 nm or less, more preferably 100 nm or less, and still more preferably 50 nm or less.
(A1)セルロース繊維としては、短幅の方の数平均幅が2nm以上1000nm以下であるものが用いられる。短幅の方の数平均幅がこの範囲内であることにより、非セルロース粉粒物に対する分散剤としての機能を発揮することができ、再分散性の向上効果を高めることができる。短幅の方の数平均幅は、好ましくは200nm以下、より好ましくは100nm以下、更に好ましくは50nm以下である。 [(A1) Cellulose fiber]
(A1) As the cellulose fiber, one having a short average number average width of 2 nm to 1000 nm is used. When the number average width of the shorter width is within this range, the function as a dispersant for the non-cellulose powder can be exhibited, and the effect of improving redispersibility can be enhanced. The number average width of the shorter width is preferably 200 nm or less, more preferably 100 nm or less, and still more preferably 50 nm or less.
セルロース繊維の短幅の方の数平均幅は、数平均繊維径とも称され、次のようにして測定することができる。すなわち、固形分率で0.05~0.1質量%のセルロース繊維の水分散体を調製し、その水分散体を、親水化処理済みのカーボン膜被覆グリッド上にキャストして、透過型電子顕微鏡(TEM)の観察用試料とする。なお、大きな繊維径の繊維を含む場合には、ガラス上へキャストした表面の走査型電子顕微鏡(SEM)像を観察してもよい。また、観察用試料は、例えば2質量%ウラニルアセテート水溶液でネガティブ染色してもよい。そして、構成する繊維の大きさに応じて5000倍、10000倍あるいは50000倍のいずれかの倍率で電子顕微鏡画像による観察を行う。その際に、得られた画像内に縦横任意の画像幅の軸を想定し、その軸に対し、20本以上の繊維が交差するよう、試料および観察条件(倍率等)を調節する。そして、この条件を満たす観察画像を得た後、この画像に対し、1枚の画像当たり縦横2本ずつの無作為な軸を引き、軸に交錯する繊維の短幅(繊維径)を目視で読み取っていく。このようにして、最低3枚の重複しない表面部分の画像を、電子顕微鏡で撮影し、各々2つの軸に交錯する繊維の短幅の値を読み取る(したがって、最低20本×2×3=120本の短幅の情報が得られる)。このようにして得られた短幅の相加平均を数平均幅とする。
The number average width of the short side of the cellulose fiber is also referred to as the number average fiber diameter, and can be measured as follows. That is, an aqueous dispersion of cellulose fibers having a solid content of 0.05 to 0.1% by mass was prepared, and the aqueous dispersion was cast on a carbon film-coated grid that had been subjected to a hydrophilic treatment, so that transmission electron A sample for observation with a microscope (TEM) is used. In addition, when the fiber of a big fiber diameter is included, you may observe the scanning electron microscope (SEM) image of the surface cast on glass. Further, the observation sample may be negatively stained with, for example, a 2% by mass uranyl acetate aqueous solution. Then, observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times, or 50000 times depending on the size of the constituent fibers. At that time, an axis having an arbitrary vertical and horizontal image width is assumed in the obtained image, and the sample and observation conditions (magnification, etc.) are adjusted so that 20 or more fibers intersect the axis. Then, after obtaining an observation image that satisfies this condition, draw two random axes in the vertical and horizontal directions per image, and visually check the short width (fiber diameter) of the fibers that intersect the axis. I will read it. In this way, images of at least three non-overlapping surface portions are taken with an electron microscope and the short width values of the fibers intersecting with each of the two axes are read (thus, at least 20 × 2 × 3 = 120). Short information on the book is available). The short-width arithmetic average thus obtained is defined as the number-average width.
(A1)セルロース繊維は、アスペクト比が7.5以上250以下であることが好ましい。このようにアスペクト比が小さいものを用いることにより、再分散性の向上効果を高めることができ、また再分散体の粘度を低減することができる。アスペクト比は、より好ましくは10以上、更に好ましくは20以上であり、また、より好ましくは75以下、更に好ましくは50以下である。
(A1) The cellulose fiber preferably has an aspect ratio of 7.5 or more and 250 or less. Thus, by using a thing with a small aspect ratio, the improvement effect of redispersibility can be heightened, and the viscosity of a redispersion can be reduced. The aspect ratio is more preferably 10 or more, still more preferably 20 or more, more preferably 75 or less, and still more preferably 50 or less.
セルロース繊維のアスペクト比は、次のようにして測定することができる。すなわち、先に述べた方法に従い短幅の方の数平均幅を算出する。また、同様の観察画像からセルロース繊維の長幅の方の数平均幅(数平均繊維長)を算出する。詳細には、繊維の始点から終点までの長幅(繊維長)を最低10本目視で読み取る。なお、枝分かれしている繊維については、その繊維の最も長い部分の長さを長幅とする。このようにして得られた長幅の相加平均を算出し、長幅の数平均幅とする。これらの値を用いてアスペクト比を下記式に従い算出する。
アスペクト比=長幅の方の数平均幅(nm)/短幅の方の数平均幅(nm) The aspect ratio of the cellulose fiber can be measured as follows. That is, the number average width of the shorter width is calculated according to the method described above. Further, the number average width (number average fiber length) of the longer width of the cellulose fiber is calculated from the same observation image. Specifically, at least 10 long widths (fiber length) from the start point to the end point of the fiber are visually read. In addition, about the fiber which has branched, let the length of the longest part of the fiber be a long width. The arithmetic average of the long width obtained in this way is calculated and set as the number average width of the long width. Using these values, the aspect ratio is calculated according to the following formula.
Aspect ratio = number average width (nm) for longer width / number average width (nm) for shorter width
アスペクト比=長幅の方の数平均幅(nm)/短幅の方の数平均幅(nm) The aspect ratio of the cellulose fiber can be measured as follows. That is, the number average width of the shorter width is calculated according to the method described above. Further, the number average width (number average fiber length) of the longer width of the cellulose fiber is calculated from the same observation image. Specifically, at least 10 long widths (fiber length) from the start point to the end point of the fiber are visually read. In addition, about the fiber which has branched, let the length of the longest part of the fiber be a long width. The arithmetic average of the long width obtained in this way is calculated and set as the number average width of the long width. Using these values, the aspect ratio is calculated according to the following formula.
Aspect ratio = number average width (nm) for longer width / number average width (nm) for shorter width
(A1)セルロース繊維は、I型結晶構造を有し、X線回折装置を用いてSegal法で算出した結晶化度が70%以上95%以下であることが好ましい。結晶化度が70%以上であることにより、再分散性の向上効果を高めることができる。結晶化度は、より好ましくは80%以上である。結晶化度の上限は特に限定されないが、例えば、95%以下でもよく、92%以下でもよい。
(A1) The cellulose fiber has a type I crystal structure, and the crystallinity calculated by the Segal method using an X-ray diffractometer is preferably 70% or more and 95% or less. When the crystallinity is 70% or more, the effect of improving redispersibility can be enhanced. The degree of crystallinity is more preferably 80% or more. The upper limit of the crystallinity is not particularly limited, but may be, for example, 95% or less or 92% or less.
結晶化度は、X線回折法による回折強度値からSegal法により算出したセルロースI型結晶化度であり、次式により定義される。
セルロースI型結晶化度(%)=〔(I22.6-I18.5)/I22.6〕×100
式中、I22.6は、X線回折における格子面(002面)(回折角2θ=22.6°)の回折強度、I18.5は、アモルファス部(回折角2θ=18.5°)の回折強度を示す。なお、I型結晶構造は天然セルロースの結晶形のことであり、セルロースI型結晶化度とは、セルロース全体のうち結晶領域量の占める割合のことを意味する。 The crystallinity is cellulose I type crystallinity calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following equation.
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100
In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 is the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5 °). Indicates. Note that the I-type crystal structure is a crystal form of natural cellulose, and the cellulose I-type crystallinity means the ratio of the crystal region to the total cellulose.
セルロースI型結晶化度(%)=〔(I22.6-I18.5)/I22.6〕×100
式中、I22.6は、X線回折における格子面(002面)(回折角2θ=22.6°)の回折強度、I18.5は、アモルファス部(回折角2θ=18.5°)の回折強度を示す。なお、I型結晶構造は天然セルロースの結晶形のことであり、セルロースI型結晶化度とは、セルロース全体のうち結晶領域量の占める割合のことを意味する。 The crystallinity is cellulose I type crystallinity calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following equation.
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100
In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 is the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5 °). Indicates. Note that the I-type crystal structure is a crystal form of natural cellulose, and the cellulose I-type crystallinity means the ratio of the crystal region to the total cellulose.
(A1)セルロース繊維は、その繊維表面の水酸基が化学修飾されていてもよい。例えば、I型結晶構造を維持することができ、所定の繊維径まで効率良く解繊することができる観点から、アニオン性官能基を有するセルロース繊維であることが好ましい。アニオン性官能基は、セルロース分子中のグルコースユニットの水酸基の一部を化学修飾することにより導入することができる。
(A1) The cellulose fiber may have a hydroxyl group on the fiber surface chemically modified. For example, a cellulose fiber having an anionic functional group is preferable from the viewpoint of maintaining an I-type crystal structure and enabling efficient defibration to a predetermined fiber diameter. The anionic functional group can be introduced by chemically modifying a part of the hydroxyl group of the glucose unit in the cellulose molecule.
アニオン性官能基としては、特に限定されず、例えば、カルボキシル基、硫黄を含む官能基、リンを含む官能基などが挙げられる。好ましいアニオン性官能基としては、カルボキシル基、リン酸基、スルホン酸基、及び硫酸基からなる群から選択される少なくとも1種が挙げられる。なお、セルロースを構成するグルコースユニットと、アニオン性官能基との間に連結基を有していてもよい。
The anionic functional group is not particularly limited, and examples thereof include a carboxyl group, a functional group containing sulfur, and a functional group containing phosphorus. Preferable anionic functional groups include at least one selected from the group consisting of a carboxyl group, a phosphate group, a sulfonate group, and a sulfate group. In addition, you may have a coupling group between the glucose unit which comprises a cellulose, and an anionic functional group.
本明細書において、カルボキシル基は、酸型(-COOH)だけでなく、塩型、即ちカルボン酸塩基(-COOX、ここでXはカルボン酸と塩を形成する陽イオン)も含む概念であり、酸型と塩型が混在してもよい。リン酸基、スルホン酸基、及び硫酸基についても、同様に、酸型だけでなく、塩型も含む概念であり、酸型と塩型が混在してもよい。
In the present specification, the carboxyl group is not only an acid form (—COOH) but also a salt form, that is, a concept including a carboxylate group (—COOX, where X is a cation forming a salt with a carboxylic acid), Acid type and salt type may be mixed. Similarly, the phosphoric acid group, the sulfonic acid group, and the sulfuric acid group are concepts including not only the acid type but also the salt type, and the acid type and the salt type may be mixed.
アニオン性官能基の塩としては、特に限定されないが、ナトリウム塩、カリウム塩、リチウム塩等のアルカリ金属塩、マグネシウム塩、カルシウム塩、バリウム塩等のアルカリ土類金属塩、アンモニウム塩、ホスホニウム塩等のオニウム塩、1級アミン、2級アミン、3級アミン等のアミン塩等が挙げられる。
The salt of the anionic functional group is not particularly limited, but alkali metal salts such as sodium salt, potassium salt and lithium salt, alkaline earth metal salts such as magnesium salt, calcium salt and barium salt, ammonium salt, phosphonium salt and the like Onium salts, primary amines, secondary amines, tertiary amines and other amine salts.
セルロース繊維におけるアニオン性官能基の含有量は、特に限定されないが、セルロース繊維の乾燥質量あたり、0.2mmol/g以上であることが好ましく、より好ましくは0.5mmol/g以上であり、1.0mmol/g以上でもよく、1.2mmol/g以上でもよく、1.5mmol/g以上でもよい。また、2.5mmol/g以下であることが好ましく、2.0mmol/g以下でもよい。アニオン性官能基の含有量は、電気伝導度測定により求めることができ、例えば、0.05~1質量%程度の濃度に調製したセルロース繊維含有スラリーを水酸化ナトリウム水溶液により中和し、中和段階で消費された水酸化ナトリウム水溶液の量V(mL)と水酸化ナトリウム水溶液のモル濃度c(mol/L)を用いて次式により求めることができる。
アニオン性官能基量(mmol/g)=V×〔c/セルロース試料質量(g)〕 The content of the anionic functional group in the cellulose fiber is not particularly limited, but is preferably 0.2 mmol / g or more, more preferably 0.5 mmol / g or more per dry mass of the cellulose fiber. It may be 0 mmol / g or more, 1.2 mmol / g or more, or 1.5 mmol / g or more. Moreover, it is preferable that it is 2.5 mmol / g or less, and 2.0 mmol / g or less may be sufficient. The content of the anionic functional group can be determined by measuring electrical conductivity. For example, the cellulose fiber-containing slurry prepared to a concentration of about 0.05 to 1% by mass is neutralized with an aqueous sodium hydroxide solution, and neutralized. Using the amount V (mL) of the aqueous sodium hydroxide solution consumed in the step and the molar concentration c (mol / L) of the aqueous sodium hydroxide solution, it can be obtained by the following equation.
Anionic functional group amount (mmol / g) = V × [c / mass of cellulose sample (g)]
アニオン性官能基量(mmol/g)=V×〔c/セルロース試料質量(g)〕 The content of the anionic functional group in the cellulose fiber is not particularly limited, but is preferably 0.2 mmol / g or more, more preferably 0.5 mmol / g or more per dry mass of the cellulose fiber. It may be 0 mmol / g or more, 1.2 mmol / g or more, or 1.5 mmol / g or more. Moreover, it is preferable that it is 2.5 mmol / g or less, and 2.0 mmol / g or less may be sufficient. The content of the anionic functional group can be determined by measuring electrical conductivity. For example, the cellulose fiber-containing slurry prepared to a concentration of about 0.05 to 1% by mass is neutralized with an aqueous sodium hydroxide solution, and neutralized. Using the amount V (mL) of the aqueous sodium hydroxide solution consumed in the step and the molar concentration c (mol / L) of the aqueous sodium hydroxide solution, it can be obtained by the following equation.
Anionic functional group amount (mmol / g) = V × [c / mass of cellulose sample (g)]
一実施形態に係るアニオン性官能基を有するセルロース繊維の例として、セルロースを構成するグルコースユニットの水酸基を酸化してなる酸化セルロース繊維を例示して、より具体的に説明し、製造方法の例についても説明する。
As an example of a cellulose fiber having an anionic functional group according to one embodiment, an oxidized cellulose fiber formed by oxidizing a hydroxyl group of a glucose unit constituting cellulose is illustrated in more detail, and an example of a production method Also explained.
酸化セルロース繊維としては、特に限定されないが、グルコースユニットの6位の水酸基が選択的に酸化されたものであることが好ましい。酸化セルロース繊維がグルコースユニット上の6位の水酸基が選択的に酸化されたものであることは、例えば、13C-NMRチャートにより確認することができる。なお、酸化セルロース繊維は、カルボキシル基と共に、アルデヒド基又はケトン基を有していてもよい。
Although it does not specifically limit as an oxidized cellulose fiber, It is preferable that the hydroxyl group of 6th-position of a glucose unit is selectively oxidized. It can be confirmed, for example, by a 13 C-NMR chart that the oxidized cellulose fiber is one in which the hydroxyl group at the 6-position on the glucose unit is selectively oxidized. The oxidized cellulose fiber may have an aldehyde group or a ketone group together with the carboxyl group.
酸化セルロース繊維は、天然セルロース繊維を原料とし、水中においてN-オキシル化合物を酸化触媒とし、共酸化剤を作用させることにより天然セルロース繊維を酸化して反応物を得る酸化反応工程(1)、不純物を除去して水を含浸させた反応物を得る精製工程(2)、および水を含浸させた反応物を溶媒に分散させる分散工程(3)を含む製造方法により得ることができる。
Oxidized cellulose fiber uses natural cellulose fiber as a raw material, an oxidation reaction step (1) for obtaining a reaction product by oxidizing natural cellulose fiber by using a N-oxyl compound as an oxidation catalyst in water and acting a co-oxidant, impurities It can be obtained by a production method comprising a purification step (2) for obtaining a reaction product impregnated with water and a dispersion step (3) for dispersing the reaction product impregnated with water in a solvent.
(1)酸化反応工程
天然セルロース繊維とN-オキシル化合物とを水(分散媒体)に分散させた後、共酸化剤を添加して、反応を開始する。反応中は0.5Mの水酸化ナトリウム水溶液を滴下してpHを10~11に保ち、pHに変化が見られなくなった時点で反応終了と見なす。ここで、共酸化剤とは、直接的にセルロース水酸基を酸化する物質ではなく、酸化触媒として用いられるN-オキシル化合物を酸化する物質のことである。 (1) Oxidation reaction step After the natural cellulose fiber and the N-oxyl compound are dispersed in water (dispersion medium), a cooxidant is added to start the reaction. During the reaction, a 0.5 M aqueous sodium hydroxide solution is added dropwise to maintain the pH at 10 to 11, and the reaction is regarded as complete when no change in pH is observed. Here, the co-oxidant is not a substance that directly oxidizes a cellulose hydroxyl group but a substance that oxidizes an N-oxyl compound used as an oxidation catalyst.
天然セルロース繊維とN-オキシル化合物とを水(分散媒体)に分散させた後、共酸化剤を添加して、反応を開始する。反応中は0.5Mの水酸化ナトリウム水溶液を滴下してpHを10~11に保ち、pHに変化が見られなくなった時点で反応終了と見なす。ここで、共酸化剤とは、直接的にセルロース水酸基を酸化する物質ではなく、酸化触媒として用いられるN-オキシル化合物を酸化する物質のことである。 (1) Oxidation reaction step After the natural cellulose fiber and the N-oxyl compound are dispersed in water (dispersion medium), a cooxidant is added to start the reaction. During the reaction, a 0.5 M aqueous sodium hydroxide solution is added dropwise to maintain the pH at 10 to 11, and the reaction is regarded as complete when no change in pH is observed. Here, the co-oxidant is not a substance that directly oxidizes a cellulose hydroxyl group but a substance that oxidizes an N-oxyl compound used as an oxidation catalyst.
上記天然セルロース繊維は、植物、動物、バクテリア産生ゲル等のセルロースの生合成系から単離した精製セルロース繊維を意味する。より具体的には、針葉樹系パルプ、広葉樹系パルプ、コットンリンター,コットンリント等の綿系パルプ、麦わらパルプ,バガスパルプ等の非木材系パルプ、バクテリアセルロース繊維(BC)、ホヤから単離されるセルロース繊維、海草から単離されるセルロース繊維等を挙げることができる。これらは単独でもしくは二種以上併せて用いられる。
The above-mentioned natural cellulose fiber means a purified cellulose fiber isolated from a cellulose biosynthetic system such as a plant, animal or bacteria-producing gel. More specifically, softwood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, bacterial cellulose fiber (BC), cellulose fiber isolated from sea squirt And cellulose fibers isolated from seaweed. These may be used alone or in combination of two or more.
上記反応における天然セルロース繊維の分散媒体は水であり、反応水溶液中の天然セルロース繊維濃度は、試薬(天然セルロース繊維)の充分な拡散が可能な濃度であれば任意である。通常は、反応水溶液の質量に対して約5%以下であるが、機械的撹拌力の強い装置を使用することにより反応濃度を上げることができる。
The dispersion medium of the natural cellulose fiber in the above reaction is water, and the concentration of the natural cellulose fiber in the reaction aqueous solution is arbitrary as long as the reagent (natural cellulose fiber) can be sufficiently diffused. Usually, it is about 5% or less with respect to the mass of the reaction aqueous solution, but the reaction concentration can be increased by using an apparatus having a strong mechanical stirring force.
また、上記N-オキシル化合物としては、例えば、一般に酸化触媒として用いられるニトロキシラジカルを有する化合物が挙げられる。N-オキシル化合物は、水溶性の化合物が好ましく、なかでもピペリジンニトロキシオキシラジカルが好ましく、特に2,2,6,6-テトラメチルピペリジノオキシラジカル(TEMPO)または4-アセトアミド-TEMPOが好ましい。N-オキシル化合物の添加は、触媒量で充分であり、好ましくは0.1~4mmol/L、さらに好ましくは0.2~2mmol/Lの範囲で反応水溶液に添加する。
In addition, examples of the N-oxyl compound include compounds having a nitroxy radical generally used as an oxidation catalyst. The N-oxyl compound is preferably a water-soluble compound, and among them, piperidine nitroxyoxy radical is preferable, and 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) or 4-acetamido-TEMPO is particularly preferable. . A catalytic amount is sufficient for the addition of the N-oxyl compound, preferably 0.1 to 4 mmol / L, more preferably 0.2 to 2 mmol / L.
上記共酸化剤としては、例えば、次亜ハロゲン酸またはその塩、亜ハロゲン酸またはその塩、過ハロゲン酸またはその塩、過酸化水素、過有機酸等があげられる。これらは単独でもしくは二種以上併せて用いられる。なかでも、次亜塩素酸ナトリウム、次亜臭素酸ナトリウム等のアルカリ金属次亜ハロゲン酸塩が好ましい。そして、上記次亜塩素酸ナトリウムを使用する場合は、反応速度の点から、臭化ナトリウム等の臭化アルカリ金属の存在下で反応を進めることが好ましい。上記臭化アルカリ金属の添加量は、上記N-オキシル化合物に対して約1~40倍モル量、好ましくは約10~20倍モル量である。
Examples of the co-oxidant include hypohalous acid or a salt thereof, halous acid or a salt thereof, perhalogen acid or a salt thereof, hydrogen peroxide, a perorganic acid, and the like. These may be used alone or in combination of two or more. Of these, alkali metal hypohalites such as sodium hypochlorite and sodium hypobromite are preferable. And when using the said sodium hypochlorite, it is preferable to advance reaction in presence of alkali metal bromides, such as sodium bromide, from the point of reaction rate. The addition amount of the alkali metal bromide is about 1 to 40 times mol, preferably about 10 to 20 times mol for the N-oxyl compound.
上記反応水溶液のpHは約8~11の範囲で維持されることが好ましい。水溶液の温度は約4~40℃において任意であるが、反応は室温(25℃)で行うことが可能であり、特に温度の制御は必要としない。所望のカルボキシル基量等を得るためには、共酸化剤の添加量と反応時間により、酸化の程度を制御する。通常、反応時間は約5~120分、長くとも240分以内に完了する。また、共酸化剤の添加量と反応水溶液のpHを制御することにより、セルロース分子の加水分解の程度を制御しセルロース繊維のアスペクト比を任意に設定することもできる。
The pH of the aqueous reaction solution is preferably maintained in the range of about 8-11. The temperature of the aqueous solution is arbitrary at about 4 to 40 ° C., but the reaction can be performed at room temperature (25 ° C.), and the temperature is not particularly required to be controlled. In order to obtain a desired amount of carboxyl group and the like, the degree of oxidation is controlled by the amount of co-oxidant added and the reaction time. Usually, the reaction time is about 5-120 minutes and is completed within 240 minutes at the most. Moreover, by controlling the addition amount of the co-oxidant and the pH of the reaction aqueous solution, the degree of hydrolysis of the cellulose molecules can be controlled to arbitrarily set the aspect ratio of the cellulose fiber.
(2)精製工程
つぎに、未反応の共酸化剤(次亜塩素酸等)や、各種副生成物等を除く目的で精製を行う。反応物繊維は通常、この段階ではナノファイバー単位までばらばらに分散しているわけではないため、通常の精製法、すなわち水洗とろ過を繰り返すことで高純度(99質量%以上)の反応物繊維と水の分散体とする。 (2) Purification step Next, purification is performed for the purpose of removing unreacted co-oxidant (such as hypochlorous acid) and various by-products. At this stage, the reactant fibers are usually not dispersed evenly to the nanofiber unit. Therefore, by repeating the usual refining method, that is, water washing and filtration, the reactant fibers are highly purified (99% by mass or more). Use water dispersion.
つぎに、未反応の共酸化剤(次亜塩素酸等)や、各種副生成物等を除く目的で精製を行う。反応物繊維は通常、この段階ではナノファイバー単位までばらばらに分散しているわけではないため、通常の精製法、すなわち水洗とろ過を繰り返すことで高純度(99質量%以上)の反応物繊維と水の分散体とする。 (2) Purification step Next, purification is performed for the purpose of removing unreacted co-oxidant (such as hypochlorous acid) and various by-products. At this stage, the reactant fibers are usually not dispersed evenly to the nanofiber unit. Therefore, by repeating the usual refining method, that is, water washing and filtration, the reactant fibers are highly purified (99% by mass or more). Use water dispersion.
精製工程における精製方法は、遠心脱水を利用する方法(例えば、連続式デカンダー)のように、上述した目的を達成できる装置であればどのような装置を利用しても差し支えない。このようにして得られる反応物繊維の水分散体は、絞った状態で固形分(セルロース繊維)濃度としておよそ10質量%~50質量%の範囲としてもよい。
As the purification method in the purification step, any apparatus can be used as long as it can achieve the above-described purpose, such as a method using centrifugal dehydration (for example, a continuous decanter). The aqueous dispersion of reactant fibers thus obtained may have a solid content (cellulose fiber) concentration in the range of approximately 10% to 50% by mass in the squeezed state.
(3)分散工程(微細化処理工程)
上記精製工程にて得られる水を含浸した反応物(水分散体)を、分散媒体中に分散させ分散処理を行う。処理に伴って粘度が上昇し、微細化処理されたセルロース繊維の分散体を得ることができる。なお、セルロース繊維の微細化(解繊)に伴ってセルロース繊維の長さ方向の切断も同時に生じるため、微細化処理の程度(例えば、分散機の処理せん断力、処理圧力、処理回数、処理時間など)を制御することによって、任意にセルロース繊維のアスペクト比を設定することが可能である。 (3) Dispersion process (miniaturization process)
The reaction product (water dispersion) impregnated with water obtained in the purification step is dispersed in a dispersion medium and subjected to a dispersion treatment. With the treatment, the viscosity increases, and a dispersion of finely pulverized cellulose fibers can be obtained. In addition, since the lengthwise cutting of the cellulose fiber occurs simultaneously with the refinement (defibration) of the cellulose fiber, the degree of the refinement treatment (for example, the treatment shearing force of the disperser, the treatment pressure, the number of treatments, the treatment time) It is possible to arbitrarily set the aspect ratio of the cellulose fiber.
上記精製工程にて得られる水を含浸した反応物(水分散体)を、分散媒体中に分散させ分散処理を行う。処理に伴って粘度が上昇し、微細化処理されたセルロース繊維の分散体を得ることができる。なお、セルロース繊維の微細化(解繊)に伴ってセルロース繊維の長さ方向の切断も同時に生じるため、微細化処理の程度(例えば、分散機の処理せん断力、処理圧力、処理回数、処理時間など)を制御することによって、任意にセルロース繊維のアスペクト比を設定することが可能である。 (3) Dispersion process (miniaturization process)
The reaction product (water dispersion) impregnated with water obtained in the purification step is dispersed in a dispersion medium and subjected to a dispersion treatment. With the treatment, the viscosity increases, and a dispersion of finely pulverized cellulose fibers can be obtained. In addition, since the lengthwise cutting of the cellulose fiber occurs simultaneously with the refinement (defibration) of the cellulose fiber, the degree of the refinement treatment (for example, the treatment shearing force of the disperser, the treatment pressure, the number of treatments, the treatment time) It is possible to arbitrarily set the aspect ratio of the cellulose fiber.
分散工程で使用する分散機としては、高速回転下でのホモミキサー、高圧ホモジナイザー、超高圧ホモジナイザー、超音波分散処理機、ビーター、ディスク型レファイナー、コニカル型レファイナー、ダブルディスク型レファイナー、グラインダー等の強力で叩解能力のある装置を使用することにより、より効率的かつ高度なダウンサイジングが可能となり、経済的に有利に含水潤滑剤組成物を得ることができる点で好ましい。なお、分散機としては、例えば、スクリュー型ミキサー、パドルミキサー、ディスパー型ミキサー、タービン型ミキサー、ディスパー、プロペラミキサー、ニーダー、ブレンダー、ホモジナイザー、超音波ホモジナイザー、コロイドミル、ペブルミル、ビーズミル粉砕機等を用いても差し支えない。また、2種類以上の分散機を組み合わせて用いてもよい。
Dispersers used in the dispersion process include high-powered homomixers, high-pressure homogenizers, ultra-high-pressure homogenizers, ultrasonic dispersion processors, beaters, disk-type refiners, conical-type refiners, double-disk-type refiners, and grinders. By using a device having a beating ability, it is preferable in that a more efficient and advanced downsizing is possible, and a hydrous lubricant composition can be obtained economically advantageously. Examples of the disperser include a screw mixer, paddle mixer, disper mixer, turbine mixer, disper, propeller mixer, kneader, blender, homogenizer, ultrasonic homogenizer, colloid mill, pebble mill, and bead mill grinder. There is no problem. Two or more types of dispersers may be used in combination.
なお、セルロース繊維は、上記酸化反応後に、さらに還元反応を行うことが好ましい。具体的には、酸化反応後の酸化セルロース繊維を精製水に分散し、水分散体のpHを約10に調整し、各種還元剤により還元反応を行う。還元剤としては、一般的なものを使用することが可能であるが、好ましくは、LiBH4、NaBH3CN、NaBH4等が挙げられる。還元剤の量は、酸化セルロース繊維を基準として、0.1~4質量%の範囲でもよい。還元反応は、室温または室温より若干高い温度で、通常、10分~10時間、好ましくは30分~2時間行う。
In addition, it is preferable that a cellulose fiber performs a reductive reaction after the said oxidation reaction. Specifically, the oxidized cellulose fiber after the oxidation reaction is dispersed in purified water, the pH of the aqueous dispersion is adjusted to about 10, and the reduction reaction is performed with various reducing agents. As the reducing agent, it is possible to use a common one, preferably, LiBH 4, NaBH 3 CN, NaBH 4 , and the like. The amount of reducing agent may be in the range of 0.1 to 4% by weight, based on oxidized cellulose fibers. The reduction reaction is usually performed at room temperature or slightly higher than room temperature, usually for 10 minutes to 10 hours, preferably 30 minutes to 2 hours.
(A1)セルロース繊維の含有量は、粉粒物含有組成物の全質量に対して0.3質量%以上48.6質量%以下であることが好ましい。0.3質量%以上であることにより、(B)非セルロース粉粒物の分散性を高めることができ、再分散性を向上することができる。また、48.6質量%以下であることにより、再分散体の粘度を低減することができる。セルロース繊維の含有量は、好ましくは1.0質量%以上、より好ましくは2.0質量%以上であり、また、45.0質量%以下が好ましく、より好ましくは30.0質量%以下である。
(A1) The content of the cellulose fiber is preferably 0.3% by mass or more and 48.6% by mass or less based on the total mass of the granular material-containing composition. By being 0.3 mass% or more, the dispersibility of (B) non-cellulose powder can be improved, and the redispersibility can be improved. Moreover, the viscosity of a redispersion can be reduced because it is 48.6 mass% or less. The cellulose fiber content is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and preferably 45.0% by mass or less, more preferably 30.0% by mass or less. .
[(A2)カルボキシメチルセルロース塩]
(A2)カルボキシメチルセルロース塩は、上記(A1)セルロース繊維とともに、(B)非セルロース粒状物を分散させる分散剤ないし分散安定剤として機能するセルロース成分であり、水溶性のカルボキシメチルセルロース塩が用いられる。(A2)カルボキシメチルセルロース塩を(A1)セルロース繊維と組み合わせて用いることにより、(B)非セルロース粉粒物として導電性粉粒物を用いた場合における導電性を向上させることができ、例として、粉粒物含有組成物を電極塗料組成物に用いた場合に、導電性に優れた電極を得ることができる。 [(A2) Carboxymethylcellulose salt]
(A2) Carboxymethylcellulose salt is a cellulose component that functions as a dispersant or dispersion stabilizer that disperses (B) non-cellulose granules together with the (A1) cellulose fiber, and a water-soluble carboxymethylcellulose salt is used. By using (A2) carboxymethylcellulose salt in combination with (A1) cellulose fiber, the conductivity in the case of using conductive powder as (B) non-cellulose powder can be improved. When the powder-containing composition is used for an electrode coating composition, an electrode having excellent conductivity can be obtained.
(A2)カルボキシメチルセルロース塩は、上記(A1)セルロース繊維とともに、(B)非セルロース粒状物を分散させる分散剤ないし分散安定剤として機能するセルロース成分であり、水溶性のカルボキシメチルセルロース塩が用いられる。(A2)カルボキシメチルセルロース塩を(A1)セルロース繊維と組み合わせて用いることにより、(B)非セルロース粉粒物として導電性粉粒物を用いた場合における導電性を向上させることができ、例として、粉粒物含有組成物を電極塗料組成物に用いた場合に、導電性に優れた電極を得ることができる。 [(A2) Carboxymethylcellulose salt]
(A2) Carboxymethylcellulose salt is a cellulose component that functions as a dispersant or dispersion stabilizer that disperses (B) non-cellulose granules together with the (A1) cellulose fiber, and a water-soluble carboxymethylcellulose salt is used. By using (A2) carboxymethylcellulose salt in combination with (A1) cellulose fiber, the conductivity in the case of using conductive powder as (B) non-cellulose powder can be improved. When the powder-containing composition is used for an electrode coating composition, an electrode having excellent conductivity can be obtained.
カルボキシメチルセルロース塩の塩としてはアルカリ金属塩が好ましく、中でもナトリウム塩、リチウム塩、及びカリウム塩からなる群から選択される少なくとも1種が好ましい。より好ましくはカルボキシメチルセルロースナトリウム塩である。
The salt of the carboxymethyl cellulose salt is preferably an alkali metal salt, and at least one selected from the group consisting of sodium salt, lithium salt, and potassium salt is particularly preferable. More preferred is carboxymethylcellulose sodium salt.
カルボキシメチルセルロース塩としては、粘度の低いものを用いることが、上記セルロース繊維と組み合わせたときに、より優れた導電性を付与することができることから好ましい。詳細には、カルボキシメチルセルロース塩の1質量%水溶液粘度が500mPa・s以下であることが好ましく、より好ましくは100mPa・s以下でもよい。1質量%水溶液粘度の下限としては、例えば10mPa・s以上でもよい。
As the carboxymethylcellulose salt, it is preferable to use a carboxymethylcellulose salt because it can provide more excellent conductivity when combined with the cellulose fiber. Specifically, the viscosity of a 1% by mass aqueous solution of carboxymethyl cellulose salt is preferably 500 mPa · s or less, and more preferably 100 mPa · s or less. As a minimum of 1 mass% aqueous solution viscosity, 10 mPa * s or more may be sufficient, for example.
ここで、カルボキシメチルセルロース塩の1質量%水溶液粘度は、次のようにして測定される。すなわち、カルボキシメチルセルロース塩(約2.2g)を共栓付き300ml三角フラスコに入れて精秤する。ここに、計算式「試料(g)×(99-水分量(質量%))」により算出される量の水を加えて12時間静置し、さらに5分間混合する。得られた溶液を用いて、単一円筒型回転粘度計を用いてJIS Z8803に準じて25℃における粘度を測定する。
Here, the viscosity of a 1% by mass aqueous solution of carboxymethyl cellulose salt is measured as follows. That is, carboxymethylcellulose salt (about 2.2 g) is placed in a 300 ml Erlenmeyer flask with a stopper and precisely weighed. The amount of water calculated by the calculation formula “sample (g) × (99−water content (mass%))” is added thereto, left to stand for 12 hours, and further mixed for 5 minutes. Using the obtained solution, the viscosity at 25 ° C. is measured according to JIS Z8803 using a single cylindrical rotational viscometer.
(A2)カルボキシメチルセルロース塩の含有量は、特に限定されないが、粉粒物含有組成物の全質量に対して、0.1質量%以上39質量%以下であることが好ましく、より好ましくは1.5質量%以上30質量%以下である。
The content of the (A2) carboxymethyl cellulose salt is not particularly limited, but is preferably 0.1% by mass or more and 39% by mass or less, more preferably 1.% by mass with respect to the total mass of the granular material-containing composition. It is 5 mass% or more and 30 mass% or less.
[(B)非セルロース粉粒物]
(B)非セルロース粉粒物としては、セルロース以外の様々な粉粒物が挙げられる。非セルロース粉粒物(以下、単に粉粒物ということがある。)は、粉状ないし粒状の物質であり、好ましくは粒子径が0.5mm以下の微細な粒子からなる粉状物質が用いられる。 [(B) Non-cellulose powder granules]
(B) As a non-cellulose granular material, various granular materials other than a cellulose are mentioned. Non-cellulose powder (hereinafter sometimes referred to simply as powder) is a powdery or granular substance, preferably a powdery substance consisting of fine particles having a particle diameter of 0.5 mm or less. .
(B)非セルロース粉粒物としては、セルロース以外の様々な粉粒物が挙げられる。非セルロース粉粒物(以下、単に粉粒物ということがある。)は、粉状ないし粒状の物質であり、好ましくは粒子径が0.5mm以下の微細な粒子からなる粉状物質が用いられる。 [(B) Non-cellulose powder granules]
(B) As a non-cellulose granular material, various granular materials other than a cellulose are mentioned. Non-cellulose powder (hereinafter sometimes referred to simply as powder) is a powdery or granular substance, preferably a powdery substance consisting of fine particles having a particle diameter of 0.5 mm or less. .
(B)非セルロース粉粒物の平均粒子径は、特に限定されず、100μm以下でもよく、30μm以下でもよく、5nm~5μmでもよく、10~100nmの粒子でもよい。粒子の大きさの指標として、(B)非セルロース粉粒物のBET法による比表面積は、0.1~1400m2/gでもよく、1~300m2/gでもよく、10~100m2/gでもよい。(B)非セルロース粉粒物の粒子の形状は、特に限定されず、球状、板状、針状等のいずれでもよい。
(B) The average particle diameter of the non-cellulose powder is not particularly limited, and may be 100 μm or less, 30 μm or less, 5 nm to 5 μm, or 10 to 100 nm. As an index of particle size, (B) the specific surface area of the non-cellulose powder by BET method may be 0.1 to 1400 m 2 / g, 1 to 300 m 2 / g, or 10 to 100 m 2 / g. But you can. (B) The shape of the particle | grains of a non-cellulose granular material is not specifically limited, Any of spherical shape, plate shape, needle shape, etc. may be sufficient.
非セルロース粉粒物の平均粒子径は、レーザー回折・散乱式粒度分布測定装置(日機装社製、マイクロトラックUPA)で測定し、体積基準でのメジアン径として算出することができる。
The average particle diameter of the non-cellulose powder can be measured with a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., Microtrac UPA) and calculated as a median diameter on a volume basis.
BET法による比表面積は、例えば、JIS Z8830:2013に記載のガス吸着法により測定することができる。
The specific surface area by the BET method can be measured by, for example, a gas adsorption method described in JIS Z8830: 2013.
(B)非セルロース粉粒物としては、例えば、無機粒子や有機粒子を挙げることができ、用途に応じた様々な機能性粒子を用いることができる。
(B) Examples of the non-cellulose powder include inorganic particles and organic particles, and various functional particles can be used depending on the application.
無機粒子(無機微粒子ともいう。)としては、特に限定されず、例えば、金属、金属化合物、ガラス繊維、鉱物、無機化合物、化学合成により製造された成分等からなる粒子が挙げられる。具体的には、カーボン、ゼオライト、炭酸カルシウム、炭酸マグネシウム、カオリン、タルク、硫酸カルシウム、硫酸バリウム、酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、ケイ酸アルミニウム、ケイソウ土、ケイ酸カルシウム、ケイ酸マグネシウム、シリカ、水酸化アルミニウム、アルミナ、アルミナ水和物、アルミノシリケート、ベーマイト、擬ベーマイト、酸化銅、酸化鉄などの粒子が挙げられる。
The inorganic particles (also referred to as inorganic fine particles) are not particularly limited, and examples thereof include particles composed of metals, metal compounds, glass fibers, minerals, inorganic compounds, components produced by chemical synthesis, and the like. Specifically, carbon, zeolite, calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, zinc carbonate, aluminum silicate, diatomaceous earth, calcium silicate, silicic acid Examples of the particles include magnesium, silica, aluminum hydroxide, alumina, alumina hydrate, aluminosilicate, boehmite, pseudoboehmite, copper oxide, and iron oxide.
有機粒子(有機微粒子ともいう。)としては、特に限定されず、例えば、樹脂、天然物由来成分、糖類、化学合成により製造された成分等からなる粒子が挙げられる。具体的には、アクリル樹脂、ポリスチレン、シリコーン樹脂、フッ素樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ポリカーボネート、ポリアミド、キチン、キトサン、デキストリン、オリゴ糖、コムギデンプン、コメデンプン、トウモロコシデンプン、バレイショデンプン、デキストリン、シクロデキストリン、乳糖、ブドウ糖、砂糖、還元麦芽糖、ソルビトール、エリスリトール、キシリトール、ラクチトール、マンニトール、カゼインなどの粒子が挙げられる。
Organic particles (also referred to as organic fine particles) are not particularly limited, and examples thereof include particles made of resin, natural product-derived components, saccharides, components produced by chemical synthesis, and the like. Specifically, acrylic resin, polystyrene, silicone resin, fluorine resin, melamine resin, benzoguanamine resin, polycarbonate, polyamide, chitin, chitosan, dextrin, oligosaccharide, wheat starch, rice starch, corn starch, potato starch, dextrin, cyclohexane Examples thereof include particles of dextrin, lactose, glucose, sugar, reduced maltose, sorbitol, erythritol, xylitol, lactitol, mannitol, casein and the like.
これらの無機粒子や有機粒子は、いずれか1種を用いても、2種以上組み合わせて用いてもよい。
These inorganic particles and organic particles may be used alone or in combination of two or more.
(B)非セルロース粉粒物としては無機粒子を用いることが好ましく、疎水性無機粒子を用いることがより好ましい。疎水性無機粒子は、粒子表面に親水基を実質的に持たず、そのため撥水性または親油性を示す無機粒子であり、本来は親水性無機粒子であるがその表面を撥水剤で処理することにより撥水性を示す無機粒子も含まれる。
(B) As the non-cellulose granular material, it is preferable to use inorganic particles, and it is more preferable to use hydrophobic inorganic particles. Hydrophobic inorganic particles are inorganic particles that have substantially no hydrophilic group on the particle surface, and thus exhibit water repellency or oleophilicity. Originally hydrophilic inorganic particles, but the surface is treated with a water repellent. Inorganic particles exhibiting water repellency are also included.
疎水性無機粒子としては、例えば、カーボン粒子、一部の金属微粒子、一部の天然の粘土鉱物などが挙げられる。これらの中でも、炭素から構成される粒子であるカーボン粒子を用いることが好ましく、カーボン粒子としては、例えば、ファーネスブラック、アセチレンブラック、ケッチェンブラック等のカーボンブラックの他、活性炭、カーボンナノチューブ、カーボンファイバー、黒鉛、ダイヤモンドなどが挙げられ、これらはいずれか1種用いても2種以上組み合わせて用いてもよい。
Examples of the hydrophobic inorganic particles include carbon particles, some metal fine particles, and some natural clay minerals. Among these, carbon particles that are particles composed of carbon are preferably used. Examples of the carbon particles include carbon black such as furnace black, acetylene black, and ketjen black, as well as activated carbon, carbon nanotube, and carbon fiber. , Graphite, diamond, and the like. Any one of these may be used, or two or more may be used in combination.
上記撥水剤としては、親水性無機粒子の表面に疎水基を導入できるものであれば特に限定されない。疎水基としては極性基を有さない炭化水素基を有する基等を挙げることができる。撥水剤の例としては、シランカップリング剤、シリル化剤、フッ化アルキル基を有するシランカップリング剤、有機チタネート系カップリング剤、アルミニウム系のカップリング剤、シリコーンオイル等を挙げることができる。表面処理対象としての親水性無機粒子としては、例えば、シリカ、アルミナ、チタニア、ジルコニアなどの金属酸化物などを挙げることができる。
The water repellent is not particularly limited as long as it can introduce a hydrophobic group on the surface of the hydrophilic inorganic particles. Examples of the hydrophobic group include a group having a hydrocarbon group not having a polar group. Examples of water repellents include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and the like. . Examples of the hydrophilic inorganic particles as the surface treatment target include metal oxides such as silica, alumina, titania and zirconia.
(B)非セルロース粉粒物としては、導電性粉粒物を用いてもよい。導電性粉粒物としては、後述する電極活物質及び/又は導電助剤が挙げられる。
(B) As the non-cellulose powder, a conductive powder may be used. Examples of the conductive granular material include an electrode active material and / or a conductive aid described later.
(B)非セルロース粉粒物の含有量は、粉粒物含有組成物の全質量に対して14.0質量%以上98.4質量%以下である。このように非セルロース粉粒物の含有量が高いことにより、再分散後における非セルロース粉粒物の濃度を確保することができる。非セルロース粉粒物の含有量は、25.0質量%以上であることが好ましく、より好ましくは30.0質量%以上であり、更に好ましくは40.0質量%以上であり、50.0質量%以上でもよい。また、96.0質量%以下でもよく、80.0質量%以下でもよい。
(B) The content of the non-cellulose granular material is 14.0% by mass or more and 98.4% by mass or less with respect to the total mass of the granular material-containing composition. Thus, when the content of the non-cellulose powder is high, the concentration of the non-cellulose powder after redispersion can be ensured. The content of the non-cellulose powder is preferably 25.0% by mass or more, more preferably 30.0% by mass or more, still more preferably 40.0% by mass or more, and 50.0% by mass. % Or more. Moreover, 96.0 mass% or less may be sufficient, and 80.0 mass% or less may be sufficient.
[(C)水]
本実施形態に係る粉粒物含有組成物は水を含有する。水の含有量は、粉粒物含有組成物の全質量に対して0.6質量%以上72.0質量%以下である。粉粒物含有組成物は、その固形分濃度が高いほど再分散後における(B)非セルロース粉粒物の濃度を確保することができ、例えば塗料に用いる場合に高濃度塗料の作製が容易となる。また、長期保存における経時変化を抑えることができる。 [(C) Water]
The granular material containing composition which concerns on this embodiment contains water. Content of water is 0.6 mass% or more and 72.0 mass% or less with respect to the total mass of a granular material containing composition. The higher concentration of the solid content of the powder-containing composition can ensure the concentration of (B) non-cellulose powder after re-dispersion. For example, when used in a paint, it is easier to produce a high-concentration paint. Become. Moreover, the change with time in long-term storage can be suppressed.
本実施形態に係る粉粒物含有組成物は水を含有する。水の含有量は、粉粒物含有組成物の全質量に対して0.6質量%以上72.0質量%以下である。粉粒物含有組成物は、その固形分濃度が高いほど再分散後における(B)非セルロース粉粒物の濃度を確保することができ、例えば塗料に用いる場合に高濃度塗料の作製が容易となる。また、長期保存における経時変化を抑えることができる。 [(C) Water]
The granular material containing composition which concerns on this embodiment contains water. Content of water is 0.6 mass% or more and 72.0 mass% or less with respect to the total mass of a granular material containing composition. The higher concentration of the solid content of the powder-containing composition can ensure the concentration of (B) non-cellulose powder after re-dispersion. For example, when used in a paint, it is easier to produce a high-concentration paint. Become. Moreover, the change with time in long-term storage can be suppressed.
水の含有量(含水量)は、粉粒物含有組成物の全質量に対して、0.6質量%以上45.0質量%以下であることが好ましく、より好ましくは30.0質量%以下、更に好ましくは25.0質量%以下であり、20.0質量%以下でもよい。また、1.5質量%以上であることが好ましく、より好ましくは5.0質量%以上、更に好ましくは10.0質量%以上である。
The water content (water content) is preferably 0.6% by mass or more and 45.0% by mass or less, more preferably 30.0% by mass or less, with respect to the total mass of the granular material-containing composition. More preferably, it is 25.0 mass% or less, and may be 20.0 mass% or less. Moreover, it is preferable that it is 1.5 mass% or more, More preferably, it is 5.0 mass% or more, More preferably, it is 10.0 mass% or more.
本願明細書における水の含有量は、加熱乾燥式水分計(株式会社エー・アンド・デイ製MX-50)を用いて、組成物を140℃で加熱し、重量変化速度が0.05%/分以下となった重量を終点として測定し、測定前の重量と比較することで算出することができる。
The water content in the present specification is such that the composition is heated at 140 ° C. using a heat drying moisture meter (MX-50 manufactured by A & D Co., Ltd.), and the weight change rate is 0.05% / It can be calculated by measuring the weight below the minute as an end point and comparing it with the weight before measurement.
[粉粒物含有組成物]
第1の実施形態に係る粉粒物含有組成物において、(A1)セルロース繊維の含有量と(B)非セルロース粉粒物の含有量との質量比率(即ち、成分(B)に対する成分(A1)の質量比)(A1)/(B)は1.0/99.0以上50.0/50.0以下である。このような範囲内に設定することにより、粉粒物含有組成物の再分散性を向上することができる。また、再分散体の粘度上昇を抑えることができ、例えば塗料に用いた場合の塗工性を向上することができる。該質量比率(A1)/(B)は、30.0/70.0以下であることが好ましく、より好ましくは20.0/80.0以下であり、また2.0/98.0以上であることが好ましく、より好ましくは2.5/97.5以上である。 [Powder-containing composition]
In the granular material-containing composition according to the first embodiment, the mass ratio of the content of (A1) cellulose fiber and the content of (B) non-cellulose granular material (that is, the component (A1 relative to the component (B)) ) (Mass ratio) (A1) / (B) is 1.0 / 99.0 or more and 50.0 / 50.0 or less. By setting it within such a range, the redispersibility of the powder-containing composition can be improved. In addition, an increase in viscosity of the redispersion can be suppressed, and for example, coating properties when used in a paint can be improved. The mass ratio (A1) / (B) is preferably 30.0 / 70.0 or less, more preferably 20.0 / 80.0 or less, and 2.0 / 98.0 or more. It is preferable that the ratio is 2.5 / 97.5 or more.
第1の実施形態に係る粉粒物含有組成物において、(A1)セルロース繊維の含有量と(B)非セルロース粉粒物の含有量との質量比率(即ち、成分(B)に対する成分(A1)の質量比)(A1)/(B)は1.0/99.0以上50.0/50.0以下である。このような範囲内に設定することにより、粉粒物含有組成物の再分散性を向上することができる。また、再分散体の粘度上昇を抑えることができ、例えば塗料に用いた場合の塗工性を向上することができる。該質量比率(A1)/(B)は、30.0/70.0以下であることが好ましく、より好ましくは20.0/80.0以下であり、また2.0/98.0以上であることが好ましく、より好ましくは2.5/97.5以上である。 [Powder-containing composition]
In the granular material-containing composition according to the first embodiment, the mass ratio of the content of (A1) cellulose fiber and the content of (B) non-cellulose granular material (that is, the component (A1 relative to the component (B)) ) (Mass ratio) (A1) / (B) is 1.0 / 99.0 or more and 50.0 / 50.0 or less. By setting it within such a range, the redispersibility of the powder-containing composition can be improved. In addition, an increase in viscosity of the redispersion can be suppressed, and for example, coating properties when used in a paint can be improved. The mass ratio (A1) / (B) is preferably 30.0 / 70.0 or less, more preferably 20.0 / 80.0 or less, and 2.0 / 98.0 or more. It is preferable that the ratio is 2.5 / 97.5 or more.
第2の実施形態に係る粒状物含有組成物は、(A2)カルボキシメチルセルロース塩を含有し、その場合、(A1)セルロース繊維の含有量と(A2)カルボキシメチルセルロース塩の含有量の合計量と、(B)非セルロース粉粒物の含有量との質量比率(即ち、成分(B)に対する成分(A1)及び成分(A2)の合計量の質量比)((A1)+(A2))/(B)は1.0/99.0以上50.0/50.0以下である。このような範囲内に設定することにより、粉粒物含有組成物の再分散性を向上することができる。また、再分散体の粘度上昇を抑えることができ、例えば塗料に用いた場合の塗工性を向上することができる。該質量比率((A1)+(A2))/(B)は、30.0/70.0以下であることが好ましく、より好ましくは20.0/80.0以下であり、また1.1/98.9以上であることが好ましく、より好ましくは2.0/98.0以上であり、更に好ましくは2.5/97.5以上である。
The granular material-containing composition according to the second embodiment contains (A2) carboxymethylcellulose salt, and in that case, (A1) the content of cellulose fiber and (A2) the total content of carboxymethylcellulose salt, (B) Mass ratio with respect to the content of non-cellulose powder (that is, mass ratio of the total amount of component (A1) and component (A2) to component (B)) ((A1) + (A2)) / ( B) is 1.0 / 99.0 or more and 50.0 / 50.0 or less. By setting it within such a range, the redispersibility of the powder-containing composition can be improved. In addition, an increase in viscosity of the redispersion can be suppressed, and for example, coating properties when used in a paint can be improved. The mass ratio ((A1) + (A2)) / (B) is preferably 30.0 / 70.0 or less, more preferably 20.0 / 80.0 or less, and 1.1 /98.9 or more, more preferably 2.0 / 98.0 or more, and further preferably 2.5 / 97.5 or more.
第2の実施形態において、(A1)セルロース繊維の含有量と(B)非セルロース粉粒物の含有量との質量比率(A1)/(B)は1.0/99.0以上50.0/50.0以下であることが好ましく、より好ましくは30.0/70.0以下、更に好ましくは20.0/80.0以下であり、また2.0/98.0以上であることが好ましく、より好ましくは2.5/97.5以上である。
In 2nd Embodiment, mass ratio (A1) / (B) of content of (A1) cellulose fiber and content of (B) non-cellulose granular material is 1.0 / 99.0 or more and 50.0. /50.0 or less, more preferably 30.0 / 70.0 or less, still more preferably 20.0 / 80.0 or less, and 2.0 / 98.0 or more. More preferably, it is 2.5 / 97.5 or more.
第2の実施形態において、(A1)セルロース繊維の含有量と(A2)カルボキシメチルセルロース塩の含有量との質量比率(即ち、成分(A2)に対する成分(A1)の質量比)(A1)/(A2)は、20.0/80.0以上99.0/1.0以下であることが好ましい。このような範囲内に設定することにより、粉粒物含有組成物の再分散性を向上させながら、導電性の向上効果を高めることができる。該質量比率(A1)/(A2)は、30.0/70.0以上70.0/30.0以下であることが好ましく、より好ましくは40.0/60.0以上70.0/30.0以下である。
In the second embodiment, the mass ratio of the content of (A1) cellulose fiber and the content of (A2) carboxymethylcellulose salt (that is, the mass ratio of component (A1) to component (A2)) (A1) / ( A2) is preferably 20.0 / 80.0 or more and 99.0 / 1.0 or less. By setting within such a range, the effect of improving conductivity can be enhanced while improving the redispersibility of the powder-containing composition. The mass ratio (A1) / (A2) is preferably 30.0 / 70.0 or more and 70.0 / 30.0 or less, more preferably 40.0 / 60.0 or more and 70.0 / 30. 0.0 or less.
粉粒物含有組成物の製造方法は、特に限定されない。例えば、上記のようにして得られた(A1)セルロース繊維の水分散体に、(B)非セルロース粉粒物、及び、必要に応じて追加の水、その他の任意成分を混合し、分散することにより調製することができる。また、混合・分散後に乾燥することにより、粉粒物含有組成物の含水量(即ち、水の含有量)を調整してもよい。第2の実施形態の場合、例えば、(A1)セルロース繊維の水分散体に(A2)カルボキシメチルセルロース塩を溶解させたものに、(B)非セルロース粉粒物、及び、必要に応じて追加の水、その他の任意成分を混合し、分散させてもよい。
The manufacturing method of a granular material containing composition is not specifically limited. For example, the (A1) cellulose fiber aqueous dispersion obtained as described above is mixed with (B) non-cellulose powder and, if necessary, additional water and other optional components, and dispersed. Can be prepared. Moreover, you may adjust the water content (namely, water content) of a granular material containing composition by drying after mixing and dispersion | distribution. In the case of the second embodiment, for example, (A1) a cellulose fiber aqueous dispersion in which (A2) a carboxymethylcellulose salt is dissolved, (B) a non-cellulose powder, and, if necessary, additional Water and other optional components may be mixed and dispersed.
混合・分散処理に用いる混合・分散装置としては、特に限定されず、例えば、ホモディスパー、プラネタリーミキサー、プロペラミキサー、ニーダー、ホモジナイザー、超音波ホモジナイザー、コロイドミル、ビーズミル、サンドミル、高圧ホモジナイザー等を用いることができる。
The mixing / dispersing device used for the mixing / dispersing process is not particularly limited. For example, a homodisper, a planetary mixer, a propeller mixer, a kneader, a homogenizer, an ultrasonic homogenizer, a colloid mill, a bead mill, a sand mill, a high-pressure homogenizer, or the like is used. be able to.
乾燥方法としては、特に限定されず、例えば、凍結乾燥、真空乾燥(例えば、コニカルドライヤーを用いた乾燥)、噴霧乾燥、送風乾燥、加熱乾燥(例えば、ドラムドライヤーを用いた乾燥)などが挙げられる。乾燥温度及び乾燥時間などの乾燥条件により、得られる粉粒物含有組成物の含水量を所定範囲内に調整することができる。
The drying method is not particularly limited, and examples thereof include freeze drying, vacuum drying (for example, drying using a conical dryer), spray drying, blow drying, and heat drying (for example, drying using a drum dryer). . Depending on drying conditions such as the drying temperature and drying time, the water content of the resulting powder-containing composition can be adjusted within a predetermined range.
粉粒物含有組成物には、上記成分(A1)、(A2)、(B)及び(C)の他、本実施形態の効果を阻害しない範囲において、分散安定剤、有機溶媒、界面活性剤などの他の成分を含有してもよい。
In addition to the components (A1), (A2), (B), and (C), the powder-containing composition includes a dispersion stabilizer, an organic solvent, and a surfactant as long as the effects of the present embodiment are not impaired. Other components such as may be contained.
分散安定剤は、分散安定性を更に高めるために添加されるものであり、例えば、メチルセルロース、ヒロドキシエチルセルロース、ポリビニルピロリドン、カルボキシビニルポリマー、ポリビニルアルコール、ポリアクリル酸ナトリウム、ポリエチレングリコールなどの水溶性高分子が挙げられる。
The dispersion stabilizer is added to further increase the dispersion stability, and is, for example, water-soluble such as methylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, polyvinyl alcohol, sodium polyacrylate, and polyethylene glycol. Examples include polymers.
有機溶媒は、上記の混合・分散処理における分散媒として用いられるものでもよい。すなわち、分散媒は基本的には水であるが、水とともに水混和性の有機溶媒を用いてもよく、その場合、該有機溶媒が粉粒物含有組成物に含まれてもよい。かかる水混和性有機溶媒としては、例えば、メタノール、エタノール、1-プロパノール、イソプロピルアルコール、t-ブタノールなどのアルコール類; エチレングリコール、グリセリンなどの多価アルコール類; アセトンなどのケトン類; テトラヒドロフランなどのエーテル類;酢酸エチル、酢酸メチルなどのエステル類; N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドンなどのアミド類; ジメチルスルホキシドなどのスルホキシド類などが挙げられる。これらはいずれか一種用いても、2種以上組み合わせて用いてもよい。
The organic solvent may be used as a dispersion medium in the above mixing / dispersing treatment. That is, the dispersion medium is basically water, but a water-miscible organic solvent may be used together with water, and in this case, the organic solvent may be included in the powder-containing composition. Examples of such water-miscible organic solvents include alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, and t-butanol; polyhydric alcohols such as ethylene glycol and glycerin; ketones such as acetone; and tetrahydrofuran. Ethers; esters such as ethyl acetate and methyl acetate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; and sulfoxides such as dimethyl sulfoxide. These may be used alone or in combination of two or more.
本実施形態に係る粉粒物含有組成物は、水などの極性溶媒に再分散可能な再分散性組成物であり、そのため、水などの極性溶媒に再分散させて用いられることが好ましい。再分散とは、粉粒物含有組成物に水等の極性溶媒を加えて、(A1)セルロース繊維と(B)非セルロース粉粒物を極性溶媒(この極性溶媒には、再分散に際して加えた極性溶媒だけでなく、粉粒物含有組成物に含まれていた(C)水などの極性溶媒も含まれる。)中に分散させることである。また、再分散可能とは、このように再分散させたときに、(A1)セルロース繊維と(B)非セルロース粉粒物を均一に分散させることができることをいい、例えば、後述する実施例における再分散性の評価で3以上のものは再分散可能であり、かつ再分散性に優れるといえる。
The particulate-containing composition according to the present embodiment is a redispersible composition that can be redispersed in a polar solvent such as water, and therefore, it is preferably used by being redispersed in a polar solvent such as water. In redispersion, a polar solvent such as water is added to the powder-containing composition, and (A1) cellulose fibers and (B) non-cellulose powder are added to the polar solvent (this polar solvent was added during redispersion). (C) Polar solvent such as water (included in the powder-containing composition) is dispersed in addition to the polar solvent. In addition, redispersible means that (A1) cellulose fibers and (B) non-cellulose granules can be uniformly dispersed when redispersed in this way. In the evaluation of redispersibility, those of 3 or more can be said to be redispersible and excellent in redispersibility.
[再分散体]
本実施形態に係る再分散体は、上記粉粒物含有組成物を極性溶媒に再分散させたものであり、再分散液ということもできる。再分散させる際の極性溶媒としては、水、水混和性有機溶媒、水と水混和性有機溶媒との混合物を挙げることができる。好ましくは、極性溶媒は、水、又は、水と水混和性有機溶媒との混合物であり、その場合、水の含有量は50質量%以上であることが好ましく、より好ましくは70質量%以上である。水混和性有機溶媒の具体例としては、上記の通りである。再分散させる際に用いる分散装置としては、上記の混合・分散処理で記載した混合・分散装置と同様のものを用いることができる。 [Redispersion]
The redispersion according to the present embodiment is obtained by redispersing the above-described powder-containing composition in a polar solvent, and can also be referred to as a redispersion liquid. Examples of the polar solvent for redispersion include water, a water-miscible organic solvent, and a mixture of water and a water-miscible organic solvent. Preferably, the polar solvent is water or a mixture of water and a water-miscible organic solvent, in which case the water content is preferably 50% by mass or more, more preferably 70% by mass or more. is there. Specific examples of the water-miscible organic solvent are as described above. As a dispersing device used for redispersion, the same device as the mixing / dispersing device described in the above mixing / dispersing process can be used.
本実施形態に係る再分散体は、上記粉粒物含有組成物を極性溶媒に再分散させたものであり、再分散液ということもできる。再分散させる際の極性溶媒としては、水、水混和性有機溶媒、水と水混和性有機溶媒との混合物を挙げることができる。好ましくは、極性溶媒は、水、又は、水と水混和性有機溶媒との混合物であり、その場合、水の含有量は50質量%以上であることが好ましく、より好ましくは70質量%以上である。水混和性有機溶媒の具体例としては、上記の通りである。再分散させる際に用いる分散装置としては、上記の混合・分散処理で記載した混合・分散装置と同様のものを用いることができる。 [Redispersion]
The redispersion according to the present embodiment is obtained by redispersing the above-described powder-containing composition in a polar solvent, and can also be referred to as a redispersion liquid. Examples of the polar solvent for redispersion include water, a water-miscible organic solvent, and a mixture of water and a water-miscible organic solvent. Preferably, the polar solvent is water or a mixture of water and a water-miscible organic solvent, in which case the water content is preferably 50% by mass or more, more preferably 70% by mass or more. is there. Specific examples of the water-miscible organic solvent are as described above. As a dispersing device used for redispersion, the same device as the mixing / dispersing device described in the above mixing / dispersing process can be used.
再分散体における濃度は特に限定されず、全固形分の濃度が0.5~20.0質量%でもよく、1.0~15.0質量%でもよい。
The concentration in the redispersion is not particularly limited, and the concentration of the total solid content may be 0.5 to 20.0 mass% or 1.0 to 15.0 mass%.
[作用効果]
本実施形態によれば、機能性粒子などの非セルロース粉粒物を高濃度で含有し、かつ、水等の極性溶媒への再分散性に優れる粉粒物含有組成物が得られる。そのため、保存スペースの増大や保存及び輸送コストの増大を抑えて運搬性を向上することができる。 [Function and effect]
According to this embodiment, the granular material containing composition which is excellent in the redispersibility to polar solvents, such as water, contains non-cellulose granular material, such as a functional particle, in high concentration. Therefore, it is possible to improve transportability while suppressing an increase in storage space and an increase in storage and transportation costs.
本実施形態によれば、機能性粒子などの非セルロース粉粒物を高濃度で含有し、かつ、水等の極性溶媒への再分散性に優れる粉粒物含有組成物が得られる。そのため、保存スペースの増大や保存及び輸送コストの増大を抑えて運搬性を向上することができる。 [Function and effect]
According to this embodiment, the granular material containing composition which is excellent in the redispersibility to polar solvents, such as water, contains non-cellulose granular material, such as a functional particle, in high concentration. Therefore, it is possible to improve transportability while suppressing an increase in storage space and an increase in storage and transportation costs.
また、本実施形態に係る粉粒物含有組成物は、様々な塗料組成物への応用が可能であり、その際、機能性粒子などの非セルロース粉粒物を高濃度で含むことから、塗料組成物に添加する場合にも固形分濃度の低下を抑えることができ、高濃度塗料の作製を簡便に行うことができる。また、濃度の急激な変化による塗料組成物の凝集を抑制する効果も期待できる。本実施形態に係る粉粒物含有組成物は、再分散性に優れているので、例えば、粉粒物含有組成物を再分散により予め適切な固形分濃度に調整した上で作製中の塗料組成物に添加してもよく、あるいは粉粒物含有組成物を極性溶媒とともに加えて再分散させながら塗料組成物を作製してもよく、いずれにしても良好な塗工性を有する塗料組成物を作製することができる。
In addition, since the powder-containing composition according to the present embodiment can be applied to various coating compositions, and contains non-cellulose powder such as functional particles at a high concentration, the paint Even when it is added to the composition, a decrease in the solid concentration can be suppressed, and a high-concentration paint can be easily produced. Moreover, the effect which suppresses aggregation of the coating composition by the rapid change of a density | concentration can also be anticipated. Since the powder-containing composition according to the present embodiment is excellent in redispersibility, for example, the paint composition under preparation after adjusting the powder-containing composition to an appropriate solid content concentration by redispersion in advance. It may be added to the product, or a coating composition may be prepared while adding and redispersing the powder-containing composition together with a polar solvent, and in any case, a coating composition having good coatability is prepared. Can be produced.
本実施形態に係る粉粒物含有組成物であると、更に、長期間の保存でも経時変化が起こりにくく、保存安定性に優れる。また、含水量が30質量%以下の場合、粉粒体含有組成物は粉体状ないし固形状の固体材料として扱うことができ、運搬性、流動性の面で特に優れているため、取り扱いの点でさらに好ましい。また、含水量が10質量%以上の場合、乾燥条件によってブロック状に固形化した場合でも小さな力で容易に粉体に解砕することができるため、取り扱いの面でより好ましい。
The powder-containing composition according to the present embodiment is less likely to change with time even during long-term storage and is excellent in storage stability. In addition, when the water content is 30% by mass or less, the powder-containing composition can be handled as a powdery or solid solid material, and is particularly excellent in terms of transportability and fluidity. More preferable in terms. Further, when the water content is 10% by mass or more, even when solidified in a block shape depending on the drying conditions, it can be easily crushed with a small force, and thus it is more preferable in terms of handling.
本実施形態に係る粉粒物含有組成物は、再分散性に優れているため、例えば、建材、文房具、電子デバイスなどの各種用途の塗料やインクの組成物として好適に使用することができる。
Since the granular material-containing composition according to this embodiment is excellent in redispersibility, it can be suitably used, for example, as a composition for paints and inks for various uses such as building materials, stationery, and electronic devices.
[電極塗料組成物および電極]
本実施形態に係る粉粒物含有組成物及びそれを用いた再分散体は、電極塗料組成物に用いることができ、固形分濃度の高い電極塗料組成物を簡便に作製することができる。また、該電極塗料組成物を金属箔や導電性基板に塗布し乾燥することにより、デバイス電極などの電極を形成することができる。また、粉粒物含有組成物に(A1)セルロース繊維とともに(A2)カルボキシメチルセルロース塩を用いた場合、電極の導電性を向上することができる。 [Electrode coating composition and electrode]
The particulate-containing composition according to the present embodiment and the redispersion using the composition can be used for an electrode coating composition, and an electrode coating composition having a high solid content concentration can be easily produced. Moreover, electrodes, such as a device electrode, can be formed by apply | coating this electrode coating composition to a metal foil or an electroconductive board | substrate, and drying. Moreover, when (A2) carboxymethylcellulose salt is used with (A1) cellulose fiber for a granular material containing composition, the electroconductivity of an electrode can be improved.
本実施形態に係る粉粒物含有組成物及びそれを用いた再分散体は、電極塗料組成物に用いることができ、固形分濃度の高い電極塗料組成物を簡便に作製することができる。また、該電極塗料組成物を金属箔や導電性基板に塗布し乾燥することにより、デバイス電極などの電極を形成することができる。また、粉粒物含有組成物に(A1)セルロース繊維とともに(A2)カルボキシメチルセルロース塩を用いた場合、電極の導電性を向上することができる。 [Electrode coating composition and electrode]
The particulate-containing composition according to the present embodiment and the redispersion using the composition can be used for an electrode coating composition, and an electrode coating composition having a high solid content concentration can be easily produced. Moreover, electrodes, such as a device electrode, can be formed by apply | coating this electrode coating composition to a metal foil or an electroconductive board | substrate, and drying. Moreover, when (A2) carboxymethylcellulose salt is used with (A1) cellulose fiber for a granular material containing composition, the electroconductivity of an electrode can be improved.
電極塗料組成物は、電極活物質(以下、単に活物質ということがある。)と、導電助剤とを含有する。そのうち、導電助剤を上記(B)非セルロース粉粒物として用いて、(A1)セルロース繊維と導電助剤を含む粉粒物含有組成物を、活物質及び任意成分とともに混合して電極塗料組成物を作製してもよい。あるいはまた、活物質を(B)非セルロース粉粒物として用いて、(A1)セルロース繊維と活物質を含む粉粒物含有組成物を、導電助剤及び任意成分とともに混合して電極塗料組成物を作製してもよい。あるいはまた、活物質と導電助剤を(B)非セルロース粉粒物として用いて、(A1)セルロース繊維と活物質と導電助剤を含む粉粒物含有組成物を、任意成分とともに混合して電極塗料組成物を作製してもよい。その際、粉粒物含有組成物に予め極性溶媒を添加して再分散させてから他の成分と混合して電極塗料組成物を作製してもよく、あるいはまた、粉粒物含有組成物に上記他の成分とともに極性溶媒を添加して再分散させると同時に電極塗料組成物を作製してもよい。なお、これらの粉粒物含有組成物は、任意成分としての(A2)カルボキシメチルセルロース塩を含んでもよい。
The electrode coating composition contains an electrode active material (hereinafter sometimes simply referred to as an active material) and a conductive additive. Among them, a conductive assistant is used as the (B) non-cellulose powder, and (A1) a powder-containing composition containing cellulose fibers and a conductive assistant is mixed with an active material and optional components to form an electrode coating composition. You may make things. Alternatively, an active material is used as (B) non-cellulose powder, and (A1) a powder-containing composition containing cellulose fibers and an active material is mixed with a conductive additive and an optional component to form an electrode coating composition. May be produced. Alternatively, the active material and the conductive assistant are used as (B) non-cellulose powder, and (A1) the powder-containing composition containing the cellulose fiber, the active material and the conductive assistant is mixed together with optional components. An electrode coating composition may be prepared. At that time, a polar solvent may be added to the powder-containing composition in advance and redispersed, and then mixed with other components to prepare an electrode coating composition. Alternatively, the powder-containing composition may be An electrode coating composition may be prepared at the same time as adding and redispersing a polar solvent together with the other components. In addition, these granular material containing composition may contain the (A2) carboxymethylcellulose salt as an arbitrary component.
活物質としては、特に限定さないが、リチウム二次電池の正極に使用する正極活物質として、例えば、CuO、Cu2O、MnO2、MoO3、V2O5、CrO3、MoO3、Fe2O3、Ni2O3、CoO3等の金属酸化物、LixCoO2、LixNiO2、LixMn2O4、LiFePO4等のリチウムと遷移金属との複合酸化物(リチウム複合酸化物)や、TiS2、MoS2、NbSe3等の金属カルコゲン化物、ポリアセン、ポリパラフェニレン、ポリピロール、ポリアニリン等の導電性高分子化合物等が挙げられる。また、リチウム複合酸化物に、少量のフッ素、ホウ素、アルミニウム、クロム、ジルコニウム、モリブデン、鉄などの元素をドーブしたものや、リチウム複合酸化物の粒子表面を、炭素、MgO、Al2O3、SiO2等で表面処理したものも使用できる。また、リチウム二次電池の負極に使用する負極活物質としては、例えば、天然黒鉛、人造黒鉛、難黒鉛化炭素、易黒鉛化炭素などの炭素材料、金属リチウムや合金、スズ化合物などの金属材料、リチウム遷移金属窒化物、結晶性金属酸化物、非晶質金属酸化物、ケイ素化合物、導電性ポリマー等が挙げられる。
As the active material, but is not particularly limited, as a positive electrode active material used in the positive electrode of a lithium secondary battery, for example, CuO, Cu 2 O, MnO 2, MoO 3, V 2 O 5, CrO 3, MoO 3, Metal oxides such as Fe 2 O 3 , Ni 2 O 3 and CoO 3 , complex oxides of lithium and transition metals such as Li x CoO 2 , Li x NiO 2 , Li x Mn 2 O 4 and LiFePO 4 (lithium) Composite oxide), metal chalcogenides such as TiS 2 , MoS 2 , and NbSe 3 , and conductive polymer compounds such as polyacene, polyparaphenylene, polypyrrole, and polyaniline. Further, a lithium composite oxide doped with a small amount of elements such as fluorine, boron, aluminum, chromium, zirconium, molybdenum, iron, etc., or the lithium composite oxide particle surface is made of carbon, MgO, Al 2 O 3 , What was surface-treated with SiO 2 or the like can also be used. Examples of the negative electrode active material used for the negative electrode of the lithium secondary battery include carbon materials such as natural graphite, artificial graphite, non-graphitizable carbon, and graphitizable carbon, and metal materials such as metallic lithium, alloys, and tin compounds. , Lithium transition metal nitrides, crystalline metal oxides, amorphous metal oxides, silicon compounds, conductive polymers, and the like.
活物質として、電気二重層キャパシタ用電極に用いる電極活物質としては、例えば、活性炭、ポリアセン、カーボンウイスカー及びグラファイト等の炭素の同素体が挙げられる。
Examples of the active material used for the electrode for the electric double layer capacitor include carbon allotropes such as activated carbon, polyacene, carbon whisker, and graphite.
活物質として、リチウムイオンキャパシタ用電極の正極に用いる電極活物質としては、電気二重層キャパシタ用電極と同様の、炭素の同素体が挙げられる。また、リチウムイオンキャパシタ用電極の負極に用いる電極活物質としては、例えば、黒鉛、難黒鉛化炭素等の結晶性炭素材料、ポリアセン系物質(PAS)等を挙げることができる。
As the active material, as the electrode active material used for the positive electrode of the lithium ion capacitor electrode, the carbon allotrope similar to the electrode for the electric double layer capacitor can be mentioned. Examples of the electrode active material used for the negative electrode of the lithium ion capacitor electrode include crystalline carbon materials such as graphite and non-graphitizable carbon, polyacene-based materials (PAS), and the like.
導電助剤としては、例えば、カーボンブラック(アセチレンブラックやケッチンブラック等)、天然黒鉛(鱗状黒鉛、鱗片状黒鉛、土状黒鉛など)、人造黒鉛、カーボンウイスカー、炭素繊維、金属(銅、ニッケル、アルミニウム、銀、金等)粉末、金属繊維、導電性セラミックス材料等が挙げられる。
Examples of the conductive assistant include carbon black (acetylene black, kettin black, etc.), natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon whisker, carbon fiber, metal (copper, nickel, (Aluminum, silver, gold, etc.) powder, metal fiber, conductive ceramic material and the like.
本実施形態に係る電極塗料組成物において、活物質の含有量は、特に制限されないが、全固形分100質量%中60~97質量%でもよい。また、導電助剤の含有量は、活物質の含有量に対して0.1~30質量%でもよい。また、上記粉粒物含有組成物を用いることで電極塗料組成物に含まれる(A1)セルロース繊維の量は特に限定されず、例えば、電極塗料組成物の全固形分100質量%中0.05~5.00質量%でもよい。また、上記第2の実施形態に係る粉粒物含有組成物を用いた場合に含まれる(A2)カルボキシメチルセルロース塩の量も特に限定されず、例えば、電極塗料組成物の全固形分100質量%中0.02~5.00質量%でもよい。
In the electrode coating composition according to this embodiment, the content of the active material is not particularly limited, but may be 60 to 97% by mass in 100% by mass of the total solid content. Further, the content of the conductive auxiliary agent may be 0.1 to 30% by mass with respect to the content of the active material. Moreover, the amount of the (A1) cellulose fiber contained in the electrode coating composition by using the above-mentioned powder-containing composition is not particularly limited. For example, 0.05% in 100% by mass of the total solid content of the electrode coating composition. It may be up to 5.00% by mass. In addition, the amount of (A2) carboxymethylcellulose salt contained when using the powder-containing composition according to the second embodiment is not particularly limited. For example, the total solid content of the electrode coating composition is 100% by mass. It may be 0.02 to 5.00% by mass.
本実施形態に係る電極塗料組成物には、上記の他、任意成分として、例えば、結着剤(例えば、水溶性及び/又は水分散性を有する高分子化合物)、増粘剤、分散安定剤などの公知の添加剤を配合してもよい。
In addition to the above, the electrode coating composition according to the present embodiment includes, as optional components, for example, a binder (for example, a polymer compound having water solubility and / or water dispersibility), a thickener, and a dispersion stabilizer. You may mix | blend well-known additives, such as.
本実施形態に係る電極は、該電極塗料組成物を金属箔や導電性基板に塗布し乾燥することにより得られるものであり、例えば、リチウム二次電池、リチウムイオンキャパシタ、電気二重層キャパシタ等の蓄電デバイスのためのデバイス電極が挙げられる。
The electrode according to the present embodiment is obtained by applying the electrode coating composition to a metal foil or a conductive substrate and drying it. For example, a lithium secondary battery, a lithium ion capacitor, an electric double layer capacitor, etc. Examples include a device electrode for an electricity storage device.
以下、実施例により更に詳細に説明するが、本発明はこれらに限定されない。なお、以下、「%」とあるのは、特に限定しない限り質量基準を意味する。
Hereinafter, although an Example demonstrates in detail, this invention is not limited to these. In the following, “%” means mass basis unless otherwise specified.
[セルロース繊維A1-1(実施例用)の製造]
針葉樹漂白クラフトパルプ(NBKP)50gを水4950gに分散させ、パルプ濃度1質量%の分散液を調整した。この分散液をグラインダー(増幸産業(株)製、セレンディピターMKCA6-3)で5回処理し、セルロース繊維A1―1を得た。セルロース繊維A1-1は化学修飾されていない、即ち無置換のセルロースナノファイバーである。 [Production of Cellulose Fiber A1-1 (for Examples)]
50 g of softwood bleached kraft pulp (NBKP) was dispersed in 4950 g of water to prepare a dispersion having a pulp concentration of 1% by mass. This dispersion was treated five times with a grinder (manufactured by Masuko Sangyo Co., Ltd., Serendipeater MKCA6-3) to obtain cellulose fiber A1-1. Cellulose fiber A1-1 is not chemically modified, that is, is an unsubstituted cellulose nanofiber.
針葉樹漂白クラフトパルプ(NBKP)50gを水4950gに分散させ、パルプ濃度1質量%の分散液を調整した。この分散液をグラインダー(増幸産業(株)製、セレンディピターMKCA6-3)で5回処理し、セルロース繊維A1―1を得た。セルロース繊維A1-1は化学修飾されていない、即ち無置換のセルロースナノファイバーである。 [Production of Cellulose Fiber A1-1 (for Examples)]
50 g of softwood bleached kraft pulp (NBKP) was dispersed in 4950 g of water to prepare a dispersion having a pulp concentration of 1% by mass. This dispersion was treated five times with a grinder (manufactured by Masuko Sangyo Co., Ltd., Serendipeater MKCA6-3) to obtain cellulose fiber A1-1. Cellulose fiber A1-1 is not chemically modified, that is, is an unsubstituted cellulose nanofiber.
[セルロース繊維A1-2(実施例用)の製造]
針葉樹パルプ2gに、水150ml、臭化ナトリウム0.25g、TEMPO0.025gを加え、充分撹拌して分散させた後、13%次亜塩素酸ナトリウム水溶液(共酸化剤)を、上記パルプ1.0gに対して次亜塩素酸ナトリウム量が6.5mmol/gとなるように加え、反応を開始した。反応中は温度を10℃に保持した。反応の進行に伴いpHが低下するため、pHを10~11に保持するように0.5N水酸化ナトリウム水溶液を滴下しながら、pHの変化が見られなくなるまで反応させた(反応時間:120分)。反応終了後、0.1N塩酸を添加してpHを2以下に調整した後、ろ過と水洗を繰り返して精製した。これに純水を加えて固形分濃度2%に調整した。 [Production of Cellulose Fiber A1-2 (for Examples)]
After adding 150 ml of water, 0.25 g of sodium bromide, and 0.025 g of TEMPO to 2 g of softwood pulp, and thoroughly stirring and dispersing, 13% sodium hypochlorite aqueous solution (co-oxidant) was added to 1.0 g of the above pulp. Was added so that the amount of sodium hypochlorite was 6.5 mmol / g, and the reaction was started. The temperature was kept at 10 ° C. during the reaction. Since the pH decreased with the progress of the reaction, the reaction was continued until no change in pH was observed while dropping a 0.5N aqueous sodium hydroxide solution so that the pH was maintained at 10 to 11 (reaction time: 120 minutes). ). After completion of the reaction, 0.1N hydrochloric acid was added to adjust the pH to 2 or less, and then purification was repeated by filtration and washing with water. Pure water was added thereto to adjust the solid content concentration to 2%.
針葉樹パルプ2gに、水150ml、臭化ナトリウム0.25g、TEMPO0.025gを加え、充分撹拌して分散させた後、13%次亜塩素酸ナトリウム水溶液(共酸化剤)を、上記パルプ1.0gに対して次亜塩素酸ナトリウム量が6.5mmol/gとなるように加え、反応を開始した。反応中は温度を10℃に保持した。反応の進行に伴いpHが低下するため、pHを10~11に保持するように0.5N水酸化ナトリウム水溶液を滴下しながら、pHの変化が見られなくなるまで反応させた(反応時間:120分)。反応終了後、0.1N塩酸を添加してpHを2以下に調整した後、ろ過と水洗を繰り返して精製した。これに純水を加えて固形分濃度2%に調整した。 [Production of Cellulose Fiber A1-2 (for Examples)]
After adding 150 ml of water, 0.25 g of sodium bromide, and 0.025 g of TEMPO to 2 g of softwood pulp, and thoroughly stirring and dispersing, 13% sodium hypochlorite aqueous solution (co-oxidant) was added to 1.0 g of the above pulp. Was added so that the amount of sodium hypochlorite was 6.5 mmol / g, and the reaction was started. The temperature was kept at 10 ° C. during the reaction. Since the pH decreased with the progress of the reaction, the reaction was continued until no change in pH was observed while dropping a 0.5N aqueous sodium hydroxide solution so that the pH was maintained at 10 to 11 (reaction time: 120 minutes). ). After completion of the reaction, 0.1N hydrochloric acid was added to adjust the pH to 2 or less, and then purification was repeated by filtration and washing with water. Pure water was added thereto to adjust the solid content concentration to 2%.
その後、24%NaOH水溶液にてスラリーのpHを10に調整した。スラリーの温度を30℃として水素化ホウ素ナトリウムをセルロース繊維に対して0.2mmol/g加え、2時間反応させることで還元処理した。反応後、0.1N塩酸を添加してpHを2以下に調整した後、ろ過と水洗を繰り返して精製した。これに純水を加え、終濃度がセルロース繊維2%、残分が水となるように調製した。ここに24%水酸化ナトリウム水溶液を添加し、pHを7に調整した。これを高圧ホモジナイザー(三和エンジニアリング製、H11)を用いて圧力100MPaで3回処理することにより、セルロース繊維A1-2を得た。セルロース繊維A1-2は、アニオン性官能基としてカルボキシル基を有するセルロースナノファイバーである。
Thereafter, the pH of the slurry was adjusted to 10 with a 24% NaOH aqueous solution. The slurry was reduced to 30 ° C. by adding 0.2 mmol / g of sodium borohydride to the cellulose fiber and reacting for 2 hours. After the reaction, 0.1N hydrochloric acid was added to adjust the pH to 2 or less, and then purification was repeated by filtration and washing with water. Pure water was added thereto so that the final concentration was 2% cellulose fiber and the balance was water. 24% sodium hydroxide aqueous solution was added here, and pH was adjusted to 7. This was treated three times at a pressure of 100 MPa using a high pressure homogenizer (manufactured by Sanwa Engineering Co., Ltd., H11) to obtain cellulose fiber A1-2. The cellulose fiber A1-2 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
[セルロース繊維A1-3(実施例用)の製造]
反応中の反応液の温度を40℃、pHを11とし、次亜塩素酸ナトリウム水溶液の添加量を上記パルプ1gに対して4.0mmol/gとした以外は、セルロース繊維A1-2の製造に準じてセルロース繊維A1-3を製造した。セルロース繊維A1-3は、アニオン性官能基としてカルボキシル基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-3 (for Examples)]
For the production of cellulose fiber A1-2, except that the temperature of the reaction solution during the reaction was 40 ° C., the pH was 11, and the amount of sodium hypochlorite aqueous solution added was 4.0 mmol / g with respect to 1 g of the above pulp. Accordingly, cellulose fiber A1-3 was produced. Cellulose fiber A1-3 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
反応中の反応液の温度を40℃、pHを11とし、次亜塩素酸ナトリウム水溶液の添加量を上記パルプ1gに対して4.0mmol/gとした以外は、セルロース繊維A1-2の製造に準じてセルロース繊維A1-3を製造した。セルロース繊維A1-3は、アニオン性官能基としてカルボキシル基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-3 (for Examples)]
For the production of cellulose fiber A1-2, except that the temperature of the reaction solution during the reaction was 40 ° C., the pH was 11, and the amount of sodium hypochlorite aqueous solution added was 4.0 mmol / g with respect to 1 g of the above pulp. Accordingly, cellulose fiber A1-3 was produced. Cellulose fiber A1-3 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
[セルロース繊維A1-4(実施例用)の製造]
次亜塩素酸ナトリウム水溶液の添加量を上記パルプ1gに対して6.0mmol/gとした以外は、セルロース繊維A1-3の製造に準じてセルロース繊維A1-4を製造した。セルロース繊維A1-4は、アニオン性官能基としてカルボキシル基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-4 (for Examples)]
Cellulose fiber A1-4 was produced according to the production of cellulose fiber A1-3, except that the amount of sodium hypochlorite aqueous solution added was 6.0 mmol / g with respect to 1 g of the above pulp. Cellulose fiber A1-4 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
次亜塩素酸ナトリウム水溶液の添加量を上記パルプ1gに対して6.0mmol/gとした以外は、セルロース繊維A1-3の製造に準じてセルロース繊維A1-4を製造した。セルロース繊維A1-4は、アニオン性官能基としてカルボキシル基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-4 (for Examples)]
Cellulose fiber A1-4 was produced according to the production of cellulose fiber A1-3, except that the amount of sodium hypochlorite aqueous solution added was 6.0 mmol / g with respect to 1 g of the above pulp. Cellulose fiber A1-4 is a cellulose nanofiber having a carboxyl group as an anionic functional group.
[セルロース繊維A1-5(実施例用)の製造]
平均粒子径が45μmの微小結晶セルロース(日本製紙株式会社製「KC-フロックW-50」)10gをガラス製セパラブルフラスコ内で200mLの蒸留水に懸濁させた。このセパラブルフラスコを氷浴中に置き、撹拌しながら系中の温度を40℃以下に維持しながら、最終濃度が48%となるまで濃硫酸を徐々に加えた。次いで、この懸濁液を60℃の水浴に移して30分間撹拌を継続した後、粗製物を取り出し、8000rpmで10分間遠心分離を行った。この遠心分離操作により余剰の硫酸を除去し、残留物を蒸留水に再懸濁させ、遠心分離後、再び蒸留水を添加する操作を繰り返して洗浄と再懸濁を5回繰り返した。この操作で得られた残留物を蒸留水に懸濁させ、pHを8に調整した後、固形分が5%となるように調整した。その後、得られたセルロース懸濁液を高圧ホモジナイザーを用いて圧力140MPaで3回処理してセルロース繊維A1-5を製造した。セルロース繊維A1-5は、アニオン性官能基としてスルホン酸基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-5 (for Examples)]
10 g of microcrystalline cellulose having an average particle size of 45 μm (“KC-Flock W-50” manufactured by Nippon Paper Industries Co., Ltd.) was suspended in 200 mL of distilled water in a glass separable flask. The separable flask was placed in an ice bath, and concentrated sulfuric acid was gradually added until the final concentration reached 48% while maintaining the temperature in the system at 40 ° C. or lower while stirring. Next, this suspension was transferred to a 60 ° C. water bath and stirring was continued for 30 minutes, and then the crude product was taken out and centrifuged at 8000 rpm for 10 minutes. Excess sulfuric acid was removed by this centrifugation operation, the residue was resuspended in distilled water, the operation of adding distilled water again after centrifugation was repeated, and washing and resuspension were repeated 5 times. The residue obtained by this operation was suspended in distilled water, the pH was adjusted to 8, and the solid content was adjusted to 5%. Thereafter, the obtained cellulose suspension was treated three times at a pressure of 140 MPa using a high-pressure homogenizer to produce cellulose fibers A1-5. Cellulose fiber A1-5 is a cellulose nanofiber having a sulfonic acid group as an anionic functional group.
平均粒子径が45μmの微小結晶セルロース(日本製紙株式会社製「KC-フロックW-50」)10gをガラス製セパラブルフラスコ内で200mLの蒸留水に懸濁させた。このセパラブルフラスコを氷浴中に置き、撹拌しながら系中の温度を40℃以下に維持しながら、最終濃度が48%となるまで濃硫酸を徐々に加えた。次いで、この懸濁液を60℃の水浴に移して30分間撹拌を継続した後、粗製物を取り出し、8000rpmで10分間遠心分離を行った。この遠心分離操作により余剰の硫酸を除去し、残留物を蒸留水に再懸濁させ、遠心分離後、再び蒸留水を添加する操作を繰り返して洗浄と再懸濁を5回繰り返した。この操作で得られた残留物を蒸留水に懸濁させ、pHを8に調整した後、固形分が5%となるように調整した。その後、得られたセルロース懸濁液を高圧ホモジナイザーを用いて圧力140MPaで3回処理してセルロース繊維A1-5を製造した。セルロース繊維A1-5は、アニオン性官能基としてスルホン酸基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-5 (for Examples)]
10 g of microcrystalline cellulose having an average particle size of 45 μm (“KC-Flock W-50” manufactured by Nippon Paper Industries Co., Ltd.) was suspended in 200 mL of distilled water in a glass separable flask. The separable flask was placed in an ice bath, and concentrated sulfuric acid was gradually added until the final concentration reached 48% while maintaining the temperature in the system at 40 ° C. or lower while stirring. Next, this suspension was transferred to a 60 ° C. water bath and stirring was continued for 30 minutes, and then the crude product was taken out and centrifuged at 8000 rpm for 10 minutes. Excess sulfuric acid was removed by this centrifugation operation, the residue was resuspended in distilled water, the operation of adding distilled water again after centrifugation was repeated, and washing and resuspension were repeated 5 times. The residue obtained by this operation was suspended in distilled water, the pH was adjusted to 8, and the solid content was adjusted to 5%. Thereafter, the obtained cellulose suspension was treated three times at a pressure of 140 MPa using a high-pressure homogenizer to produce cellulose fibers A1-5. Cellulose fiber A1-5 is a cellulose nanofiber having a sulfonic acid group as an anionic functional group.
[セルロース繊維A1-6(実施例用)の製造]
特開2015-189698号公報の製造例1に記載の方法に準じ、セルロース繊維の脱水シートを得た(段落0080~0083に記載の脱水洗浄後のシート)。得られた脱水シートに蒸留水を添加、撹拌して固形分を2.0%に調整し、高圧ホモジナイザーを用いて100MPaで3回処理することにより、セルロース繊維A1-6を製造した。セルロース繊維A1-6は、アニオン性官能基としてリン酸基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-6 (for Examples)]
A cellulose fiber dehydrated sheet was obtained in accordance with the method described in Production Example 1 of JP-A-2015-189698 (sheet after dehydration washing described in paragraphs 0080 to 0083). Distilled water was added to the obtained dehydrated sheet, the solid content was adjusted to 2.0% by stirring, and the fiber was processed three times at 100 MPa using a high-pressure homogenizer to produce cellulose fiber A1-6. The cellulose fiber A1-6 is a cellulose nanofiber having a phosphate group as an anionic functional group.
特開2015-189698号公報の製造例1に記載の方法に準じ、セルロース繊維の脱水シートを得た(段落0080~0083に記載の脱水洗浄後のシート)。得られた脱水シートに蒸留水を添加、撹拌して固形分を2.0%に調整し、高圧ホモジナイザーを用いて100MPaで3回処理することにより、セルロース繊維A1-6を製造した。セルロース繊維A1-6は、アニオン性官能基としてリン酸基を有するセルロースナノファイバーである。 [Production of Cellulose Fiber A1-6 (for Examples)]
A cellulose fiber dehydrated sheet was obtained in accordance with the method described in Production Example 1 of JP-A-2015-189698 (sheet after dehydration washing described in paragraphs 0080 to 0083). Distilled water was added to the obtained dehydrated sheet, the solid content was adjusted to 2.0% by stirring, and the fiber was processed three times at 100 MPa using a high-pressure homogenizer to produce cellulose fiber A1-6. The cellulose fiber A1-6 is a cellulose nanofiber having a phosphate group as an anionic functional group.
[セルロース繊維A’-1(比較例用)の製造]
原料の針葉樹パルプに替えて再生セルロースを使用するとともに、次亜塩素酸ナトリウム水溶液の添加量を、再生セルロース1.0gに対して27.0mmol/gとした以外は、セルロース繊維A1-2の製造に準じて、セルロースA’-1を製造した。 [Production of Cellulose Fiber A′-1 (for Comparative Example)]
Manufacture of cellulose fiber A1-2, except that regenerated cellulose is used in place of the raw conifer pulp and the amount of sodium hypochlorite aqueous solution added is 27.0 mmol / g with respect to 1.0 g of regenerated cellulose. Cellulose A′-1 was produced according to the above.
原料の針葉樹パルプに替えて再生セルロースを使用するとともに、次亜塩素酸ナトリウム水溶液の添加量を、再生セルロース1.0gに対して27.0mmol/gとした以外は、セルロース繊維A1-2の製造に準じて、セルロースA’-1を製造した。 [Production of Cellulose Fiber A′-1 (for Comparative Example)]
Manufacture of cellulose fiber A1-2, except that regenerated cellulose is used in place of the raw conifer pulp and the amount of sodium hypochlorite aqueous solution added is 27.0 mmol / g with respect to 1.0 g of regenerated cellulose. Cellulose A′-1 was produced according to the above.
[セルロース繊維A’-2(比較例用)の製造]
針葉樹漂白クラフトパルプ(NBKP)50gを水4950gに分散させ、パルプ濃度1%の分散液を調整した。この分散液をグラインダー(増幸産業(株)製、セレンディピターMKCA6-3)で1回処理し、セルロース繊維A’-2を得た。 [Production of Cellulose Fiber A′-2 (for Comparative Example)]
50 g of softwood bleached kraft pulp (NBKP) was dispersed in 4950 g of water to prepare a dispersion having a pulp concentration of 1%. This dispersion was treated once with a grinder (manufactured by Masuko Sangyo Co., Ltd., Serendipeater MKCA6-3) to obtain cellulose fiber A′-2.
針葉樹漂白クラフトパルプ(NBKP)50gを水4950gに分散させ、パルプ濃度1%の分散液を調整した。この分散液をグラインダー(増幸産業(株)製、セレンディピターMKCA6-3)で1回処理し、セルロース繊維A’-2を得た。 [Production of Cellulose Fiber A′-2 (for Comparative Example)]
50 g of softwood bleached kraft pulp (NBKP) was dispersed in 4950 g of water to prepare a dispersion having a pulp concentration of 1%. This dispersion was treated once with a grinder (manufactured by Masuko Sangyo Co., Ltd., Serendipeater MKCA6-3) to obtain cellulose fiber A′-2.
上記で得られたセルロース繊維A1-1~A1-6、およびA’-1、A’-2について、下記の評価に供し、その結果を表1に記載した。
The cellulose fibers A1-1 to A1-6, A′-1, and A′-2 obtained above were subjected to the following evaluation, and the results are shown in Table 1.
[セルロースI型結晶化度]
セルロース繊維のX線回折強度をX線回折法にて測定し、その測定結果からSegal法を用いて下記式により算出した。
セルロースI型結晶化度(%)=〔(I22.6-I18.5)/I22.6〕×100
式中、I22.6は、X線回折における格子面(002面)(回折角2θ=22.6°)の回折強度、I18.5は、アモルファス部(回折角2θ=18.5°)の回折強度を示す。 サンプルのX線回折強度の測定は、株式会社リガク製の「RINT2200」を用いて以下の条件にて実施した。
X線源:Cu/Kα-radiation
管電圧:40Kv
管電流:30mA
測定範囲:回折角2θ=5~35°
X線のスキャンスピード:10°/min [Cellulose type I crystallinity]
The X-ray diffraction intensity of the cellulose fiber was measured by the X-ray diffraction method, and calculated from the measurement result by the following formula using the Segal method.
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100
In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 is the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5 °). Indicates. The measurement of the X-ray diffraction intensity of the sample was performed under the following conditions using “RINT2200” manufactured by Rigaku Corporation.
X-ray source: Cu / Kα-radiation
Tube voltage: 40Kv
Tube current: 30 mA
Measurement range: Diffraction angle 2θ = 5-35 °
X-ray scanning speed: 10 ° / min
セルロース繊維のX線回折強度をX線回折法にて測定し、その測定結果からSegal法を用いて下記式により算出した。
セルロースI型結晶化度(%)=〔(I22.6-I18.5)/I22.6〕×100
式中、I22.6は、X線回折における格子面(002面)(回折角2θ=22.6°)の回折強度、I18.5は、アモルファス部(回折角2θ=18.5°)の回折強度を示す。 サンプルのX線回折強度の測定は、株式会社リガク製の「RINT2200」を用いて以下の条件にて実施した。
X線源:Cu/Kα-radiation
管電圧:40Kv
管電流:30mA
測定範囲:回折角2θ=5~35°
X線のスキャンスピード:10°/min [Cellulose type I crystallinity]
The X-ray diffraction intensity of the cellulose fiber was measured by the X-ray diffraction method, and calculated from the measurement result by the following formula using the Segal method.
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100
In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 is the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5 °). Indicates. The measurement of the X-ray diffraction intensity of the sample was performed under the following conditions using “RINT2200” manufactured by Rigaku Corporation.
X-ray source: Cu / Kα-radiation
Tube voltage: 40Kv
Tube current: 30 mA
Measurement range: Diffraction angle 2θ = 5-35 °
X-ray scanning speed: 10 ° / min
[短幅の方の数平均幅]
セルロース繊維の数平均幅を、透過型電子顕微鏡(TEM)(日本電子社製、JEM-1400)を用いて観察した。すなわち、各セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャストした後、2%ウラニルアセテートでネガティブ染色したTEM像(倍率:10000倍)から、先に述べた方法に従い、短幅の方の数平均幅を算出した。 [Number average width of shorter width]
The number average width of the cellulose fibers was observed using a transmission electron microscope (TEM) (JEM-1400, manufactured by JEOL Ltd.). That is, from the TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate after each cellulose fiber was cast on a hydrophilized carbon film-coated grid, The number average width of was calculated.
セルロース繊維の数平均幅を、透過型電子顕微鏡(TEM)(日本電子社製、JEM-1400)を用いて観察した。すなわち、各セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャストした後、2%ウラニルアセテートでネガティブ染色したTEM像(倍率:10000倍)から、先に述べた方法に従い、短幅の方の数平均幅を算出した。 [Number average width of shorter width]
The number average width of the cellulose fibers was observed using a transmission electron microscope (TEM) (JEM-1400, manufactured by JEOL Ltd.). That is, from the TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate after each cellulose fiber was cast on a hydrophilized carbon film-coated grid, The number average width of was calculated.
[アスペクト比]
セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャストした後、2%ウラニルアセテートでネガティブ染色したTEM像(倍率:5000倍あるいは10000倍)から、セルロース繊維の短幅の方の数平均幅、長幅の方の数平均幅を観察した。すなわち、各先に述べた方法に従い、短幅の方の数平均幅、および長幅の方の数平均幅を算出し、これらの値を用いてアスペクト比を下記の式に従い算出した。
アスペクト比=長幅の方の数平均幅(nm)/短幅の方の数平均幅(nm) [aspect ratio]
From the TEM image (magnification: 5000 times or 10,000 times) of the cellulose fiber cast negatively with 2% uranyl acetate after casting the cellulose fiber on the hydrophilized carbon film-coated grid, the number average width of the short side of the cellulose fiber The number average width of the longer width was observed. That is, according to each method described above, the number average width of the shorter width and the number average width of the longer width were calculated, and the aspect ratio was calculated according to the following formula using these values.
Aspect ratio = number average width (nm) for longer width / number average width (nm) for shorter width
セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャストした後、2%ウラニルアセテートでネガティブ染色したTEM像(倍率:5000倍あるいは10000倍)から、セルロース繊維の短幅の方の数平均幅、長幅の方の数平均幅を観察した。すなわち、各先に述べた方法に従い、短幅の方の数平均幅、および長幅の方の数平均幅を算出し、これらの値を用いてアスペクト比を下記の式に従い算出した。
アスペクト比=長幅の方の数平均幅(nm)/短幅の方の数平均幅(nm) [aspect ratio]
From the TEM image (magnification: 5000 times or 10,000 times) of the cellulose fiber cast negatively with 2% uranyl acetate after casting the cellulose fiber on the hydrophilized carbon film-coated grid, the number average width of the short side of the cellulose fiber The number average width of the longer width was observed. That is, according to each method described above, the number average width of the shorter width and the number average width of the longer width were calculated, and the aspect ratio was calculated according to the following formula using these values.
Aspect ratio = number average width (nm) for longer width / number average width (nm) for shorter width
[アニオン性官能基量]
作製したセルロース繊維について、アニオン性官能基量として、セルロース繊維A1-5についてはスルホン酸基量、A1-6についてはリン酸基量、それ以外のセルロース繊維についてはカルボキシル基量を下記に示す方法で算出した。 [Anionic functional group content]
For the produced cellulose fibers, the amount of anionic functional group, the amount of sulfonic acid groups for cellulose fibers A1-5, the amount of phosphoric acid groups for A1-6, and the amount of carboxyl groups for other cellulose fibers are shown below. Calculated with
作製したセルロース繊維について、アニオン性官能基量として、セルロース繊維A1-5についてはスルホン酸基量、A1-6についてはリン酸基量、それ以外のセルロース繊維についてはカルボキシル基量を下記に示す方法で算出した。 [Anionic functional group content]
For the produced cellulose fibers, the amount of anionic functional group, the amount of sulfonic acid groups for cellulose fibers A1-5, the amount of phosphoric acid groups for A1-6, and the amount of carboxyl groups for other cellulose fibers are shown below. Calculated with
[カルボキシル基量]
セルロース繊維0.25gを水に分散させたセルロース水分散体60mLを調製し、0.1Mの塩酸水溶液によってpHを約2.5とした後、0.05Mの水酸化ナトリウム水溶液を滴下して、電気伝導度測定を行った。測定はpHが11になるまで続けた。電気伝導度の変化が緩やかな弱酸の中和段階において、消費された水酸化ナトリウム水溶液の量V(mL)から、下記の式に従いカルボキシル基量を求めた。
カルボキシル基量(mmol/g)=V(mL)×〔0.05/セルロース繊維質量(g)〕 [Amount of carboxyl group]
A cellulose aqueous dispersion 60 mL in which 0.25 g of cellulose fiber was dispersed in water was prepared, and the pH was adjusted to about 2.5 with a 0.1 M hydrochloric acid aqueous solution, and then a 0.05 M sodium hydroxide aqueous solution was dropped. Electrical conductivity measurements were made. The measurement was continued until the pH was 11. The amount of carboxyl groups was determined from the amount of consumed sodium hydroxide aqueous solution V (mL) in accordance with the following equation in the neutralization step of weak acid with a gradual change in electrical conductivity.
Amount of carboxyl groups (mmol / g) = V (mL) × [0.05 / cellulose fiber mass (g)]
セルロース繊維0.25gを水に分散させたセルロース水分散体60mLを調製し、0.1Mの塩酸水溶液によってpHを約2.5とした後、0.05Mの水酸化ナトリウム水溶液を滴下して、電気伝導度測定を行った。測定はpHが11になるまで続けた。電気伝導度の変化が緩やかな弱酸の中和段階において、消費された水酸化ナトリウム水溶液の量V(mL)から、下記の式に従いカルボキシル基量を求めた。
カルボキシル基量(mmol/g)=V(mL)×〔0.05/セルロース繊維質量(g)〕 [Amount of carboxyl group]
A cellulose aqueous dispersion 60 mL in which 0.25 g of cellulose fiber was dispersed in water was prepared, and the pH was adjusted to about 2.5 with a 0.1 M hydrochloric acid aqueous solution, and then a 0.05 M sodium hydroxide aqueous solution was dropped. Electrical conductivity measurements were made. The measurement was continued until the pH was 11. The amount of carboxyl groups was determined from the amount of consumed sodium hydroxide aqueous solution V (mL) in accordance with the following equation in the neutralization step of weak acid with a gradual change in electrical conductivity.
Amount of carboxyl groups (mmol / g) = V (mL) × [0.05 / cellulose fiber mass (g)]
[スルホン酸基量]
スルホン酸基量は非特許文献(I.Kalashnikova et al.Biomacromolecules 2012,13,267‐275)を参考に測定した。つまり、セルロース繊維0.05gを水に分散させたセルロース水分散体50mLを調製し、0.05Mの水酸化ナトリウム水溶液を滴下して電気伝導度測定を行った。消費された水酸化ナトリウム水溶液の量V(mL)から、下記の式に従いスルホン酸基量を求めた。
スルホン酸基量(mmol/g)=V(mL)×〔0.05/セルロース繊維質量(g)〕 [Amount of sulfonic acid group]
The amount of sulfonic acid group was measured with reference to non-patent literature (I. Kalashnikova et al. Biomacromolecules 2012, 13, 267-275). That is, 50 mL of a cellulose aqueous dispersion in which 0.05 g of cellulose fiber was dispersed in water was prepared, and 0.05 M sodium hydroxide aqueous solution was dropped to conduct electrical conductivity measurement. From the amount of consumed sodium hydroxide aqueous solution V (mL), the amount of sulfonic acid group was determined according to the following formula.
Amount of sulfonic acid group (mmol / g) = V (mL) × [0.05 / cellulose fiber mass (g)]
スルホン酸基量は非特許文献(I.Kalashnikova et al.Biomacromolecules 2012,13,267‐275)を参考に測定した。つまり、セルロース繊維0.05gを水に分散させたセルロース水分散体50mLを調製し、0.05Mの水酸化ナトリウム水溶液を滴下して電気伝導度測定を行った。消費された水酸化ナトリウム水溶液の量V(mL)から、下記の式に従いスルホン酸基量を求めた。
スルホン酸基量(mmol/g)=V(mL)×〔0.05/セルロース繊維質量(g)〕 [Amount of sulfonic acid group]
The amount of sulfonic acid group was measured with reference to non-patent literature (I. Kalashnikova et al. Biomacromolecules 2012, 13, 267-275). That is, 50 mL of a cellulose aqueous dispersion in which 0.05 g of cellulose fiber was dispersed in water was prepared, and 0.05 M sodium hydroxide aqueous solution was dropped to conduct electrical conductivity measurement. From the amount of consumed sodium hydroxide aqueous solution V (mL), the amount of sulfonic acid group was determined according to the following formula.
Amount of sulfonic acid group (mmol / g) = V (mL) × [0.05 / cellulose fiber mass (g)]
[リン酸基量]
リン酸基量は特開2015-189698号公報に記載の手法に従い測定した。つまり、セルロース繊維を絶乾質量で0.04g程度の固形分を含む微細セルロース繊維含有スラリーを分取し、イオン交換水を用いて50g程度に希釈した。この溶液を、マグネチックスターラーを用いて撹拌しながら、0.01Mの水酸化ナトリウム水溶液を加えていったときの電気伝導度の値の変化を測定し、その値が極小となる時の0.01M水酸化ナトリウム水溶液の滴下量を滴定終点における滴下量とした。この時、セルロース表面のリン酸基量XはX(mmol/g)=0.01(mol/L)×V(mL)/W(g)で表される。ここで、V:0.01M水酸化ナトリウム水溶液の滴下量(mL)、W:微細セルロース繊維含有スラリーが含む固形分(g)である。 [Amount of phosphate group]
The amount of phosphate groups was measured according to the method described in JP-A-2015-189698. That is, a cellulose fiber-containing slurry containing a solid content of about 0.04 g in absolute dry mass was collected and diluted to about 50 g using ion-exchanged water. While stirring this solution using a magnetic stirrer, the change in the value of electrical conductivity when a 0.01 M sodium hydroxide aqueous solution was added was measured. The dropping amount of the 01M sodium hydroxide aqueous solution was defined as the dropping amount at the titration end point. At this time, the phosphate group amount X on the cellulose surface is represented by X (mmol / g) = 0.01 (mol / L) × V (mL) / W (g). Here, V: A dripping amount (mL) of 0.01 M sodium hydroxide aqueous solution, W: Solid content (g) contained in the fine cellulose fiber-containing slurry.
リン酸基量は特開2015-189698号公報に記載の手法に従い測定した。つまり、セルロース繊維を絶乾質量で0.04g程度の固形分を含む微細セルロース繊維含有スラリーを分取し、イオン交換水を用いて50g程度に希釈した。この溶液を、マグネチックスターラーを用いて撹拌しながら、0.01Mの水酸化ナトリウム水溶液を加えていったときの電気伝導度の値の変化を測定し、その値が極小となる時の0.01M水酸化ナトリウム水溶液の滴下量を滴定終点における滴下量とした。この時、セルロース表面のリン酸基量XはX(mmol/g)=0.01(mol/L)×V(mL)/W(g)で表される。ここで、V:0.01M水酸化ナトリウム水溶液の滴下量(mL)、W:微細セルロース繊維含有スラリーが含む固形分(g)である。 [Amount of phosphate group]
The amount of phosphate groups was measured according to the method described in JP-A-2015-189698. That is, a cellulose fiber-containing slurry containing a solid content of about 0.04 g in absolute dry mass was collected and diluted to about 50 g using ion-exchanged water. While stirring this solution using a magnetic stirrer, the change in the value of electrical conductivity when a 0.01 M sodium hydroxide aqueous solution was added was measured. The dropping amount of the 01M sodium hydroxide aqueous solution was defined as the dropping amount at the titration end point. At this time, the phosphate group amount X on the cellulose surface is represented by X (mmol / g) = 0.01 (mol / L) × V (mL) / W (g). Here, V: A dripping amount (mL) of 0.01 M sodium hydroxide aqueous solution, W: Solid content (g) contained in the fine cellulose fiber-containing slurry.
表1に示すように、実施例用のセルロース繊維A1-1~A1-6は、短幅の方の数平均幅が2~1000nmの範囲内であった。また、アスペクト比が7.5~250の範囲内であり、更に、セルロースI型結晶構造の結晶化度が70%以上であった。これに対し、比較例用のセルロース繊維A’-1はセルロースI型結晶構造を持たず、微粒子状をなしており、短幅の方の数平均幅とアスペクト比は測定不可であった。また、比較例用のセルロース繊維A’-2は、セルロースI型結晶構造は有していたが、短幅の方の数平均幅が上記範囲の上限以上であった。なお、表1中「-」は測定していないことを意味する。
As shown in Table 1, in the cellulose fibers A1-1 to A1-6 for Examples, the number average width of the shorter width was in the range of 2 to 1000 nm. Further, the aspect ratio was in the range of 7.5 to 250, and the crystallinity of the cellulose I-type crystal structure was 70% or more. On the other hand, the cellulose fiber A′-1 for comparative example does not have a cellulose I-type crystal structure and is in the form of fine particles, and the number average width and aspect ratio of the shorter width cannot be measured. Further, although the cellulose fiber A′-2 for the comparative example had a cellulose I-type crystal structure, the number average width of the shorter width was not less than the upper limit of the above range. In Table 1, “-” means not measured.
セルロース繊維A1-2~A1-4に関し、セルロース表面上のグルコースユニットのC6位の水酸基のみが選択的にカルボキシル基に酸化されているかどうかについて、13C-NMRチャートで確認した結果、酸化前のセルロースの13C‐NMRチャートで確認できるグルコース単位の1級水酸基のC6位に相当する62ppmのピークが、酸化反応後は消失し、代わりに178ppmにカルボキシル基に由来するピークが現れていた。このことから、セルロース繊維A1-2~A1-4は、いずれもグルコース単位のC6位水酸基のみがカルボキシル基等に酸化されていることが確認された。
Regarding the cellulose fibers A1-2 to A1-4, whether or not only the hydroxyl group at the C6 position of the glucose unit on the cellulose surface was selectively oxidized to a carboxyl group was confirmed by a 13 C-NMR chart. A 62 ppm peak corresponding to the C6 position of the primary hydroxyl group of the glucose unit, which can be confirmed by a 13 C-NMR chart of cellulose, disappeared after the oxidation reaction, and instead a peak derived from a carboxyl group appeared at 178 ppm. From this, it was confirmed that in each of the cellulose fibers A1-2 to A1-4, only the C6 hydroxyl group of the glucose unit was oxidized to a carboxyl group or the like.
[実施例1]
セルロース繊維A1-1と粉粒物B-1との質量比率が2.6/97.4となるように両者を加え、かつ水の含有割合が72%となるように水を加え、プラネタリーミキサー(プライミクス株式会社製 ハイビスミックス2P-1型)で40rpm×60分間攪拌した。得られたペースト又は粘土状の組成物を90℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 1]
Both were added so that the mass ratio of the cellulose fiber A1-1 and the granular material B-1 was 2.6 / 97.4, and water was added so that the water content was 72%. The mixture was stirred at 40 rpm × 60 minutes with a mixer (Hibismix 2P-1 manufactured by PRIMIX Corporation). The obtained paste or clay-like composition was dried at 90 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
セルロース繊維A1-1と粉粒物B-1との質量比率が2.6/97.4となるように両者を加え、かつ水の含有割合が72%となるように水を加え、プラネタリーミキサー(プライミクス株式会社製 ハイビスミックス2P-1型)で40rpm×60分間攪拌した。得られたペースト又は粘土状の組成物を90℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 1]
Both were added so that the mass ratio of the cellulose fiber A1-1 and the granular material B-1 was 2.6 / 97.4, and water was added so that the water content was 72%. The mixture was stirred at 40 rpm × 60 minutes with a mixer (Hibismix 2P-1 manufactured by PRIMIX Corporation). The obtained paste or clay-like composition was dried at 90 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
[実施例2~6]
セルロース繊維A1-1に代えて、セルロース繊維A1-2、A1-3、A1-4、A1-5、A1-6を用いた以外は、実施例1と同様の手法で粉体~固形状の粉粒物含有組成物を調製した。 [Examples 2 to 6]
A powdery to solid state is obtained in the same manner as in Example 1 except that cellulose fibers A1-2, A1-3, A1-4, A1-5, A1-6 are used in place of the cellulose fibers A1-1. A powder-containing composition was prepared.
セルロース繊維A1-1に代えて、セルロース繊維A1-2、A1-3、A1-4、A1-5、A1-6を用いた以外は、実施例1と同様の手法で粉体~固形状の粉粒物含有組成物を調製した。 [Examples 2 to 6]
A powdery to solid state is obtained in the same manner as in Example 1 except that cellulose fibers A1-2, A1-3, A1-4, A1-5, A1-6 are used in place of the cellulose fibers A1-1. A powder-containing composition was prepared.
[実施例7]
セルロース繊維A1-4と粉粒物B-1との質量比率が2.6/97.4となるように両者を加え、かつ水の含有割合が72%となるように水を加え、プラネタリーミキサー(プライミクス株式会社製 ハイビスミックス2P-1型)で40rpm×60分間攪拌することで、ペースト又は粘土状の粉粒物含有組成物を調製した。 [Example 7]
Both were added so that the mass ratio of the cellulose fiber A1-4 and the powder B-1 was 2.6 / 97.4, and water was added so that the water content was 72%, and the planetary A paste or clay-like granular material-containing composition was prepared by stirring at 40 rpm × 60 minutes with a mixer (Hibismix 2P-1 type manufactured by PRIMIX Corporation).
セルロース繊維A1-4と粉粒物B-1との質量比率が2.6/97.4となるように両者を加え、かつ水の含有割合が72%となるように水を加え、プラネタリーミキサー(プライミクス株式会社製 ハイビスミックス2P-1型)で40rpm×60分間攪拌することで、ペースト又は粘土状の粉粒物含有組成物を調製した。 [Example 7]
Both were added so that the mass ratio of the cellulose fiber A1-4 and the powder B-1 was 2.6 / 97.4, and water was added so that the water content was 72%, and the planetary A paste or clay-like granular material-containing composition was prepared by stirring at 40 rpm × 60 minutes with a mixer (Hibismix 2P-1 type manufactured by PRIMIX Corporation).
[実施例8]
実施例4で調製した粉粒物含有組成物を100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 8]
The powder-containing composition containing powder to solid was obtained by drying the powder-containing composition prepared in Example 4 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB).
実施例4で調製した粉粒物含有組成物を100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 8]
The powder-containing composition containing powder to solid was obtained by drying the powder-containing composition prepared in Example 4 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB).
[実施例9、10]
セルロース繊維A1-4と粉粒物B-1との質量比率を表2に記載の通りに変更した以外は、実施例4と同様の手法により、粉体~固形状の粉粒物含有組成物を調製した。
[実施例11]
セルロース繊維A1-4と粉粒物B-1と水の含有量を表2に記載の通りに変更した以外は、実施例7と同様の手法により、粘稠固体状の粉粒物含有組成物を調製した。 [Examples 9 and 10]
A powder to solid powder-containing composition was obtained in the same manner as in Example 4 except that the mass ratio of cellulose fiber A1-4 to powder B-1 was changed as shown in Table 2. Was prepared.
[Example 11]
Viscous solid powder-containing composition in the same manner as in Example 7, except that the contents of cellulose fiber A1-4, powder B-1, and water were changed as shown in Table 2. Was prepared.
セルロース繊維A1-4と粉粒物B-1との質量比率を表2に記載の通りに変更した以外は、実施例4と同様の手法により、粉体~固形状の粉粒物含有組成物を調製した。
[実施例11]
セルロース繊維A1-4と粉粒物B-1と水の含有量を表2に記載の通りに変更した以外は、実施例7と同様の手法により、粘稠固体状の粉粒物含有組成物を調製した。 [Examples 9 and 10]
A powder to solid powder-containing composition was obtained in the same manner as in Example 4 except that the mass ratio of cellulose fiber A1-4 to powder B-1 was changed as shown in Table 2. Was prepared.
[Example 11]
Viscous solid powder-containing composition in the same manner as in Example 7, except that the contents of cellulose fiber A1-4, powder B-1, and water were changed as shown in Table 2. Was prepared.
[実施例12]
実施例11で調製した粉粒物含有組成物を80℃で8時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粘稠固体状の粉粒物含有組成物を調製した。 [Example 12]
The powder-containing composition prepared in Example 11 was dried at 80 ° C. for 8 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to prepare a viscous solid-like powder-containing composition.
実施例11で調製した粉粒物含有組成物を80℃で8時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粘稠固体状の粉粒物含有組成物を調製した。 [Example 12]
The powder-containing composition prepared in Example 11 was dried at 80 ° C. for 8 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to prepare a viscous solid-like powder-containing composition.
[実施例13]
セルロース繊維A1-4と粉粒物B-1と水の含有量を表2に記載の通りに変更した以外は、実施例7と同様の手法によりペースト又は粘土状の粉粒物含有組成物を調製した。 [Example 13]
A paste or clay-like powder-containing composition was prepared in the same manner as in Example 7 except that the cellulose fibers A1-4, the powder B-1 and the water content were changed as shown in Table 2. Prepared.
セルロース繊維A1-4と粉粒物B-1と水の含有量を表2に記載の通りに変更した以外は、実施例7と同様の手法によりペースト又は粘土状の粉粒物含有組成物を調製した。 [Example 13]
A paste or clay-like powder-containing composition was prepared in the same manner as in Example 7 except that the cellulose fibers A1-4, the powder B-1 and the water content were changed as shown in Table 2. Prepared.
[実施例14]
実施例13で調製した粉粒物含有組成物を80℃で8時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粘稠固体状の粉粒物含有組成物を得た。 [Example 14]
The powder-containing composition prepared in Example 13 was dried at 80 ° C. for 8 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a viscous solid-like powder-containing composition.
実施例13で調製した粉粒物含有組成物を80℃で8時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粘稠固体状の粉粒物含有組成物を得た。 [Example 14]
The powder-containing composition prepared in Example 13 was dried at 80 ° C. for 8 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a viscous solid-like powder-containing composition.
[実施例15]
実施例14で調製した粉粒物含有組成物をさらに100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 15]
The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Example 14 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
実施例14で調製した粉粒物含有組成物をさらに100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 15]
The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Example 14 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
[実施例16~18,20~21]
粉粒物の種類を表2に記載の通りに変更し、さらにセルロース繊維A1-4と粉粒物との質量比率を表2に記載の通りに変更した以外は、実施例4と同様の手法により粉体~固形状の粉粒物含有組成物を調製した。 [Examples 16 to 18, 20 to 21]
The same procedure as in Example 4 except that the type of the powder was changed as shown in Table 2, and the mass ratio of the cellulose fibers A1-4 and the powder was changed as shown in Table 2. Thus, a powder to solid powder-containing composition was prepared.
粉粒物の種類を表2に記載の通りに変更し、さらにセルロース繊維A1-4と粉粒物との質量比率を表2に記載の通りに変更した以外は、実施例4と同様の手法により粉体~固形状の粉粒物含有組成物を調製した。 [Examples 16 to 18, 20 to 21]
The same procedure as in Example 4 except that the type of the powder was changed as shown in Table 2, and the mass ratio of the cellulose fibers A1-4 and the powder was changed as shown in Table 2. Thus, a powder to solid powder-containing composition was prepared.
[実施例19]
セルロース繊維A1-4と粉粒物B-5との質量比率を50.0/50.0とし、水の含有量が90%となるように、セルロース繊維A1-4、粉粒物B-5および水を加え、超音波ホモジナイザー(ソニックス社製、VC-505)で出力40%にて10分間照射して混合分散させた。その後、90℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 19]
Cellulose fiber A1-4 and powder B-5 so that the mass ratio of cellulose fiber A1-4 and powder B-5 is 50.0 / 50.0 and the water content is 90%. Then, the mixture was dispersed by irradiation with an ultrasonic homogenizer (VC-505, manufactured by Sonics) at an output of 40% for 10 minutes. Thereafter, the mixture was dried in a blow dryer (manufactured by ADVANTEC, DRM620DB) at 90 ° C. for 24 hours to obtain a powder-solid powder-containing composition.
セルロース繊維A1-4と粉粒物B-5との質量比率を50.0/50.0とし、水の含有量が90%となるように、セルロース繊維A1-4、粉粒物B-5および水を加え、超音波ホモジナイザー(ソニックス社製、VC-505)で出力40%にて10分間照射して混合分散させた。その後、90℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 19]
Cellulose fiber A1-4 and powder B-5 so that the mass ratio of cellulose fiber A1-4 and powder B-5 is 50.0 / 50.0 and the water content is 90%. Then, the mixture was dispersed by irradiation with an ultrasonic homogenizer (VC-505, manufactured by Sonics) at an output of 40% for 10 minutes. Thereafter, the mixture was dried in a blow dryer (manufactured by ADVANTEC, DRM620DB) at 90 ° C. for 24 hours to obtain a powder-solid powder-containing composition.
[実施例22]
粉粒物の種類を表2に記載の通りに変更し、さらに各成分の含有量を表2に記載の通りに変更した以外は、実施例7と同様の手法によりペースト又は粘土状の粉粒物含有組成物を調製した。 [Example 22]
Paste or clay-like powder by the same method as in Example 7 except that the type of the powder was changed as shown in Table 2, and the content of each component was changed as shown in Table 2. A product-containing composition was prepared.
粉粒物の種類を表2に記載の通りに変更し、さらに各成分の含有量を表2に記載の通りに変更した以外は、実施例7と同様の手法によりペースト又は粘土状の粉粒物含有組成物を調製した。 [Example 22]
Paste or clay-like powder by the same method as in Example 7 except that the type of the powder was changed as shown in Table 2, and the content of each component was changed as shown in Table 2. A product-containing composition was prepared.
[実施例23]
実施例22で調製した粉粒物含有組成物を90℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 23]
The powder-containing composition containing powder to solid was obtained by drying the powder-containing composition prepared in Example 22 at 90 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB).
実施例22で調製した粉粒物含有組成物を90℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 23]
The powder-containing composition containing powder to solid was obtained by drying the powder-containing composition prepared in Example 22 at 90 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB).
[実施例24]
実施例23で調製した粉粒物含有組成物をさらに100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 24]
The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Example 23 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
実施例23で調製した粉粒物含有組成物をさらに100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Example 24]
The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Example 23 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
[比較例1、2]
セルロース繊維A1-1に代えて、セルロース繊維A’-1、A’-2を用いた以外は、実施例1と同様の手法で粉体~固形状の粉粒物含有組成物を調製した。 [Comparative Examples 1 and 2]
A powder to solid powder-containing composition was prepared in the same manner as in Example 1 except that cellulose fibers A′-1 and A′-2 were used in place of cellulose fiber A1-1.
セルロース繊維A1-1に代えて、セルロース繊維A’-1、A’-2を用いた以外は、実施例1と同様の手法で粉体~固形状の粉粒物含有組成物を調製した。 [Comparative Examples 1 and 2]
A powder to solid powder-containing composition was prepared in the same manner as in Example 1 except that cellulose fibers A′-1 and A′-2 were used in place of cellulose fiber A1-1.
[比較例3]
水の含有量を表3に記載の通りに変更した以外は、実施例4と同様の手法でスラリー状の粉粒物含有組成物を調製した。 [Comparative Example 3]
A slurry-like granular material-containing composition was prepared in the same manner as in Example 4 except that the water content was changed as shown in Table 3.
水の含有量を表3に記載の通りに変更した以外は、実施例4と同様の手法でスラリー状の粉粒物含有組成物を調製した。 [Comparative Example 3]
A slurry-like granular material-containing composition was prepared in the same manner as in Example 4 except that the water content was changed as shown in Table 3.
[比較例4、5]
セルロース繊維A1-4と粉粒物B-1との質量比率を表3に記載の通りに変更した以外は、実施例1と同様の手法で粉体~固形の粉粒物含有組成物を調製した。 [Comparative Examples 4 and 5]
A powder-solid powder-containing composition was prepared in the same manner as in Example 1 except that the mass ratio of the cellulose fiber A1-4 to the powder B-1 was changed as shown in Table 3. did.
セルロース繊維A1-4と粉粒物B-1との質量比率を表3に記載の通りに変更した以外は、実施例1と同様の手法で粉体~固形の粉粒物含有組成物を調製した。 [Comparative Examples 4 and 5]
A powder-solid powder-containing composition was prepared in the same manner as in Example 1 except that the mass ratio of the cellulose fiber A1-4 to the powder B-1 was changed as shown in Table 3. did.
[比較例6]
セルロース繊維A1-4と粉粒物B-1との質量比率を0.8/99.2とし、水の含有量が50%となるように変更し、その他は実施例4と同様の手法で組成物を調製した。その後、調製した組成物を90℃で24時間、100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Comparative Example 6]
The mass ratio of the cellulose fiber A1-4 to the granule B-1 was changed to 0.8 / 99.2, the water content was changed to 50%, and the other methods were the same as in Example 4. A composition was prepared. Thereafter, the prepared composition was dried at 90 ° C. for 24 hours and at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
セルロース繊維A1-4と粉粒物B-1との質量比率を0.8/99.2とし、水の含有量が50%となるように変更し、その他は実施例4と同様の手法で組成物を調製した。その後、調製した組成物を90℃で24時間、100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Comparative Example 6]
The mass ratio of the cellulose fiber A1-4 to the granule B-1 was changed to 0.8 / 99.2, the water content was changed to 50%, and the other methods were the same as in Example 4. A composition was prepared. Thereafter, the prepared composition was dried at 90 ° C. for 24 hours and at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
[比較例7]
セルロース繊維A1-4と粉粒物B-1との質量比率を87.2/12.8とし、水の含有量が50%となるように変更し、その他は実施例4と同様の手法で組成物を調製した。その後、調製した組成物を90℃で24時間、100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Comparative Example 7]
The mass ratio of the cellulose fiber A1-4 to the granule B-1 was changed to 87.2 / 12.8, the water content was changed to 50%, and the other methods were the same as in Example 4. A composition was prepared. Thereafter, the prepared composition was dried at 90 ° C. for 24 hours and at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
セルロース繊維A1-4と粉粒物B-1との質量比率を87.2/12.8とし、水の含有量が50%となるように変更し、その他は実施例4と同様の手法で組成物を調製した。その後、調製した組成物を90℃で24時間、100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Comparative Example 7]
The mass ratio of the cellulose fiber A1-4 to the granule B-1 was changed to 87.2 / 12.8, the water content was changed to 50%, and the other methods were the same as in Example 4. A composition was prepared. Thereafter, the prepared composition was dried at 90 ° C. for 24 hours and at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB) to obtain a powder-solid powder-containing composition.
[比較例8]
比較例5で調製した粉粒物含有組成物をさらに100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Comparative Example 8]
The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Comparative Example 5 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
比較例5で調製した粉粒物含有組成物をさらに100℃で24時間、送風乾燥機中(ADVANTEC製、DRM620DB)で乾燥させることにより粉体~固形状の粉粒物含有組成物を得た。 [Comparative Example 8]
The powder-containing composition containing powder to solid was obtained by further drying the powder-containing composition prepared in Comparative Example 5 at 100 ° C. for 24 hours in an air dryer (manufactured by ADVANTEC, DRM620DB). .
[比較例9]
水の含有量を表3に記載の通りに変更した以外は、比較例3と同様の手法でスラリー状の粉粒物含有組成物を調製した。 [Comparative Example 9]
A slurry-like granular material-containing composition was prepared in the same manner as in Comparative Example 3, except that the water content was changed as shown in Table 3.
水の含有量を表3に記載の通りに変更した以外は、比較例3と同様の手法でスラリー状の粉粒物含有組成物を調製した。 [Comparative Example 9]
A slurry-like granular material-containing composition was prepared in the same manner as in Comparative Example 3, except that the water content was changed as shown in Table 3.
[比較例10]
セルロース繊維A1-4と粉粒物B-1との質量比率を80.0/20.0とし、水の含有量が42%となるように変更し、その他は実施例4と同様の手法で粘稠固体状の組成物を調製した。 [Comparative Example 10]
The mass ratio between the cellulose fibers A1-4 and the granular material B-1 was changed to 80.0 / 20.0, and the water content was changed to 42%. A viscous solid composition was prepared.
セルロース繊維A1-4と粉粒物B-1との質量比率を80.0/20.0とし、水の含有量が42%となるように変更し、その他は実施例4と同様の手法で粘稠固体状の組成物を調製した。 [Comparative Example 10]
The mass ratio between the cellulose fibers A1-4 and the granular material B-1 was changed to 80.0 / 20.0, and the water content was changed to 42%. A viscous solid composition was prepared.
上記の実施例及び比較例で使用したセルロース繊維及び粉粒物の詳細は以下の通りである。なお、表2及び表3におけるセルロース繊維の含有量は固形分としての質量比率である。
(セルロース繊維)
・A1-1:セルロース繊維A1-1の1質量%水分散体
・A1-2:セルロース繊維A1-2の2質量%水分散体
・A1-3:セルロース繊維A1-3の2質量%水分散体
・A1-4:セルロース繊維A1-4の2質量%水分散体
・A1-5:セルロース繊維A1-5の5質量%水分散体
・A1-6:セルロース繊維A1-6の2質量%水分散体
・A’-1:セルロース繊維A’-1の2質量%水分散体
・A’-2:セルロース繊維A’-2の1質量%水分散体
(粉粒物)
・B-1:アセチレンブラック(デンカ株式会社製、HS-100、BET表面積:39m2/g)
・B-2:ケッチェンブラック(ライオン株式会社製、EC600JD、BET表面積:1270m2/g)
・B-3:カーボンブラック(イメリス社製、Super-P、BET表面積:60m2/g)
・B-4:活性炭(関東化学株式会社製、平均粒子径:20μm)
・B-5:多層カーボンナノチューブ(シグマアルドリッチ製、BET表面積:220m2/g)
・B-6:TiO2(日本アエロジル製、AEROXIDE TiO2 P25、BET表面積:50m2/g)
・B-7:シリコン粒子(エルケム社製、Silgrain e-Si、平均粒子径:3μm)
・B-8:カーボンファイバー(昭和電工製、VGCF-H、BET表面積:13m2/g) The details of the cellulose fiber and powder used in the above Examples and Comparative Examples are as follows. In addition, content of the cellulose fiber in Table 2 and Table 3 is a mass ratio as solid content.
(Cellulose fiber)
A1-1: 1% by weight aqueous dispersion of cellulose fiber A1-1 A1-2: 2% by weight aqueous dispersion of cellulose fiber A1-2 A1-3: 2% by weight aqueous dispersion of cellulose fiber A1-3 Body A1-4: 2% by weight aqueous dispersion of cellulose fiber A1-4 A1-5: 5% by weight aqueous dispersion of cellulose fiber A1-5 A1-6: 2% by weight water of cellulose fiber A1-6 Dispersion A′-1: 2% by weight aqueous dispersion of cellulose fiber A′-1 A′-2: 1% by weight aqueous dispersion of cellulose fiber A′-2 (powder)
B-1: Acetylene black (manufactured by Denka Co., Ltd., HS-100, BET surface area: 39 m 2 / g)
B-2: Ketjen Black (Lion Corporation, EC600JD, BET surface area: 1270 m 2 / g)
B-3: Carbon black (Imeris Super-P, BET surface area: 60 m 2 / g)
B-4: Activated carbon (manufactured by Kanto Chemical Co., Inc., average particle size: 20 μm)
B-5: Multi-walled carbon nanotube (manufactured by Sigma-Aldrich, BET surface area: 220 m 2 / g)
B-6: TiO 2 (manufactured by Nippon Aerosil, AEROXIDE TiO 2 P25, BET surface area: 50 m 2 / g)
B-7: Silicon particles (manufactured by Elchem, Silgrain e-Si, average particle size: 3 μm)
B-8: Carbon fiber (made by Showa Denko, VGCF-H, BET surface area: 13 m 2 / g)
(セルロース繊維)
・A1-1:セルロース繊維A1-1の1質量%水分散体
・A1-2:セルロース繊維A1-2の2質量%水分散体
・A1-3:セルロース繊維A1-3の2質量%水分散体
・A1-4:セルロース繊維A1-4の2質量%水分散体
・A1-5:セルロース繊維A1-5の5質量%水分散体
・A1-6:セルロース繊維A1-6の2質量%水分散体
・A’-1:セルロース繊維A’-1の2質量%水分散体
・A’-2:セルロース繊維A’-2の1質量%水分散体
(粉粒物)
・B-1:アセチレンブラック(デンカ株式会社製、HS-100、BET表面積:39m2/g)
・B-2:ケッチェンブラック(ライオン株式会社製、EC600JD、BET表面積:1270m2/g)
・B-3:カーボンブラック(イメリス社製、Super-P、BET表面積:60m2/g)
・B-4:活性炭(関東化学株式会社製、平均粒子径:20μm)
・B-5:多層カーボンナノチューブ(シグマアルドリッチ製、BET表面積:220m2/g)
・B-6:TiO2(日本アエロジル製、AEROXIDE TiO2 P25、BET表面積:50m2/g)
・B-7:シリコン粒子(エルケム社製、Silgrain e-Si、平均粒子径:3μm)
・B-8:カーボンファイバー(昭和電工製、VGCF-H、BET表面積:13m2/g) The details of the cellulose fiber and powder used in the above Examples and Comparative Examples are as follows. In addition, content of the cellulose fiber in Table 2 and Table 3 is a mass ratio as solid content.
(Cellulose fiber)
A1-1: 1% by weight aqueous dispersion of cellulose fiber A1-1 A1-2: 2% by weight aqueous dispersion of cellulose fiber A1-2 A1-3: 2% by weight aqueous dispersion of cellulose fiber A1-3 Body A1-4: 2% by weight aqueous dispersion of cellulose fiber A1-4 A1-5: 5% by weight aqueous dispersion of cellulose fiber A1-5 A1-6: 2% by weight water of cellulose fiber A1-6 Dispersion A′-1: 2% by weight aqueous dispersion of cellulose fiber A′-1 A′-2: 1% by weight aqueous dispersion of cellulose fiber A′-2 (powder)
B-1: Acetylene black (manufactured by Denka Co., Ltd., HS-100, BET surface area: 39 m 2 / g)
B-2: Ketjen Black (Lion Corporation, EC600JD, BET surface area: 1270 m 2 / g)
B-3: Carbon black (Imeris Super-P, BET surface area: 60 m 2 / g)
B-4: Activated carbon (manufactured by Kanto Chemical Co., Inc., average particle size: 20 μm)
B-5: Multi-walled carbon nanotube (manufactured by Sigma-Aldrich, BET surface area: 220 m 2 / g)
B-6: TiO 2 (manufactured by Nippon Aerosil, AEROXIDE TiO 2 P25, BET surface area: 50 m 2 / g)
B-7: Silicon particles (manufactured by Elchem, Silgrain e-Si, average particle size: 3 μm)
B-8: Carbon fiber (made by Showa Denko, VGCF-H, BET surface area: 13 m 2 / g)
粉粒物含有組成物の含水量の測定方法は、以下の通りである。5g以上の粉粒物含有組成物Xgを、加熱乾燥式水分計(株式会社エー・アンド・デイ製MX-50)の試料皿にのせ、サンプルを140℃で加熱し、重量変化速度が0.05%/分以下となった重量Yを測定し、下式により含水量を算出する。
組成物の含水量(%)=〔(X-Y)/X〕×100 The measuring method of the water content of the powder-containing composition is as follows. 5 g or more of the powder-containing composition Xg is placed on a sample pan of a heat-drying moisture meter (MX-50 manufactured by A & D Co., Ltd.), the sample is heated at 140 ° C., and the weight change rate is 0.00. The weight Y, which is equal to or less than 05% / min, is measured, and the water content is calculated by the following formula.
Water content of composition (%) = [(XY) / X] × 100
組成物の含水量(%)=〔(X-Y)/X〕×100 The measuring method of the water content of the powder-containing composition is as follows. 5 g or more of the powder-containing composition Xg is placed on a sample pan of a heat-drying moisture meter (MX-50 manufactured by A & D Co., Ltd.), the sample is heated at 140 ° C., and the weight change rate is 0.00. The weight Y, which is equal to or less than 05% / min, is measured, and the water content is calculated by the following formula.
Water content of composition (%) = [(XY) / X] × 100
[粉粒物含有組成物の評価]
上記により得られた実施例1~24、および比較例1~10の粉粒物含有組成物について、下記の基準に従って各特性の評価を行なった。その結果を下記表2,3に示した。 [Evaluation of Composition Containing Powder Particles]
The characteristics of the powder-containing compositions of Examples 1 to 24 and Comparative Examples 1 to 10 obtained as described above were evaluated according to the following criteria. The results are shown in Tables 2 and 3 below.
上記により得られた実施例1~24、および比較例1~10の粉粒物含有組成物について、下記の基準に従って各特性の評価を行なった。その結果を下記表2,3に示した。 [Evaluation of Composition Containing Powder Particles]
The characteristics of the powder-containing compositions of Examples 1 to 24 and Comparative Examples 1 to 10 obtained as described above were evaluated according to the following criteria. The results are shown in Tables 2 and 3 below.
[粉粒物含有組成物の再分散性]
調製した粉粒物含有組成物を一部取り、全固形分が1.0質量%になるよう水を加え、ホモディスパー(プライミクス株式会社製、2.5型)で1,600rpm×15分間撹拌することによって、粉粒物含有組成物の再分散体を調製した。得られた再分散体を用いてプレパラートを作製し、光学顕微鏡(倍率200倍)で観察することにより、粉粒物含有組成物の再分散性を以下の6段階で評価し、3以上を合格とした。
5:凝集物が見られない
4:1画像中に1~7個の凝集物が見られる
3:1画像中に8~15個の凝集物が見られる
2:1画像中に16~25個の凝集物が見られる
1:1画像中に26個以上の凝集物が見られる
0:1画像中に納まらないほどの大きい凝集物が見られる [Re-dispersibility of powder-containing composition]
Part of the prepared powder-containing composition is taken, water is added so that the total solid content is 1.0% by mass, and the mixture is stirred at 1,600 rpm × 15 minutes with a homodisper (Primics Co., Ltd., 2.5 type) Thus, a redispersion of the powder-containing composition was prepared. Using the obtained redispersed material, a preparation was prepared and observed with an optical microscope (200 times magnification), thereby evaluating the redispersibility of the powder-containing composition in the following 6 stages, and passing 3 or more. It was.
5: Aggregates are not observed 4: 1-7 aggregates are observed in the 1: 1 image 8-15 aggregates are observed in the 3: 1 image 2: 16-25 are observed in the 2: 1 image Agglomerates of 26 or more are observed in the 1: 1 image. Aggregates that are too large to fit in the 0: 1 image are observed.
調製した粉粒物含有組成物を一部取り、全固形分が1.0質量%になるよう水を加え、ホモディスパー(プライミクス株式会社製、2.5型)で1,600rpm×15分間撹拌することによって、粉粒物含有組成物の再分散体を調製した。得られた再分散体を用いてプレパラートを作製し、光学顕微鏡(倍率200倍)で観察することにより、粉粒物含有組成物の再分散性を以下の6段階で評価し、3以上を合格とした。
5:凝集物が見られない
4:1画像中に1~7個の凝集物が見られる
3:1画像中に8~15個の凝集物が見られる
2:1画像中に16~25個の凝集物が見られる
1:1画像中に26個以上の凝集物が見られる
0:1画像中に納まらないほどの大きい凝集物が見られる [Re-dispersibility of powder-containing composition]
Part of the prepared powder-containing composition is taken, water is added so that the total solid content is 1.0% by mass, and the mixture is stirred at 1,600 rpm × 15 minutes with a homodisper (Primics Co., Ltd., 2.5 type) Thus, a redispersion of the powder-containing composition was prepared. Using the obtained redispersed material, a preparation was prepared and observed with an optical microscope (200 times magnification), thereby evaluating the redispersibility of the powder-containing composition in the following 6 stages, and passing 3 or more. It was.
5: Aggregates are not observed 4: 1-7 aggregates are observed in the 1: 1 image 8-15 aggregates are observed in the 3: 1 image 2: 16-25 are observed in the 2: 1 image Agglomerates of 26 or more are observed in the 1: 1 image. Aggregates that are too large to fit in the 0: 1 image are observed.
[粉粒物含有組成物再分散体の塗工性]
調製した粉粒物含有組成物を一部取り、全固形分が13.0質量%になるよう水を加え、ホモディスパー(プライミクス株式会社製)で1,600rpm×15分間撹拌することによって、粉粒物含有組成物の再分散体を調製した。得られた再分散体を、アルミ箔上にベーカー式フィルムアプリケーター((株)安田精機製作所製 No.510)と卓上コーター(三井電気精機(株)製 TC-3型)を用いて塗工した。塗工速度は10mm/秒、塗工厚みは50μm。その際の塗布状態を目視で観察し、以下の5段階で評価し、3以上を合格とした。
5:スジやムラ、凝集物がなく、均一な塗工が可能である
4:部分的にスジやムラ、凝集物などはみられるが、8割方均一な塗工が可能である
3:塗工面積の50%以上の部分にスジやムラ、凝集物に加え、気泡などが確認される
2:塗工面積の80%以上の部分にスジやムラ、凝集物に加え、気泡などが確認され、均一な塗工が難しい
1:塗料がアプリケーター上で転がり、塗工することができない [Coating properties of powder-containing composition redispersion]
Part of the prepared granular material-containing composition is taken, water is added so that the total solid content is 13.0% by mass, and the mixture is stirred with a homodisper (Primics Co., Ltd.) at 1,600 rpm × 15 minutes, A redispersion of the granule-containing composition was prepared. The obtained redispersion was coated on an aluminum foil using a baker-type film applicator (No. 510 manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and a tabletop coater (TC-3 model manufactured by Mitsui Electric Seiki Co., Ltd.). . The coating speed is 10 mm / second, and the coating thickness is 50 μm. The coating state at that time was visually observed, evaluated in the following five stages, and 3 or more were determined to be acceptable.
5: There is no streak, unevenness, and aggregate, and uniform coating is possible 4: Although streaks, unevenness, and aggregates are partially seen, 80% uniform coating is possible 3: Coating In addition to streaks, unevenness and aggregates in the area of 50% or more of the area, air bubbles etc. are confirmed 2: In addition to the stripes, unevenness and aggregates in the area of 80% or more of the coating area, air bubbles etc. are confirmed, Uniform coating is difficult 1: The paint rolls on the applicator and cannot be applied
調製した粉粒物含有組成物を一部取り、全固形分が13.0質量%になるよう水を加え、ホモディスパー(プライミクス株式会社製)で1,600rpm×15分間撹拌することによって、粉粒物含有組成物の再分散体を調製した。得られた再分散体を、アルミ箔上にベーカー式フィルムアプリケーター((株)安田精機製作所製 No.510)と卓上コーター(三井電気精機(株)製 TC-3型)を用いて塗工した。塗工速度は10mm/秒、塗工厚みは50μm。その際の塗布状態を目視で観察し、以下の5段階で評価し、3以上を合格とした。
5:スジやムラ、凝集物がなく、均一な塗工が可能である
4:部分的にスジやムラ、凝集物などはみられるが、8割方均一な塗工が可能である
3:塗工面積の50%以上の部分にスジやムラ、凝集物に加え、気泡などが確認される
2:塗工面積の80%以上の部分にスジやムラ、凝集物に加え、気泡などが確認され、均一な塗工が難しい
1:塗料がアプリケーター上で転がり、塗工することができない [Coating properties of powder-containing composition redispersion]
Part of the prepared granular material-containing composition is taken, water is added so that the total solid content is 13.0% by mass, and the mixture is stirred with a homodisper (Primics Co., Ltd.) at 1,600 rpm × 15 minutes, A redispersion of the granule-containing composition was prepared. The obtained redispersion was coated on an aluminum foil using a baker-type film applicator (No. 510 manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and a tabletop coater (TC-3 model manufactured by Mitsui Electric Seiki Co., Ltd.). . The coating speed is 10 mm / second, and the coating thickness is 50 μm. The coating state at that time was visually observed, evaluated in the following five stages, and 3 or more were determined to be acceptable.
5: There is no streak, unevenness, and aggregate, and uniform coating is possible 4: Although streaks, unevenness, and aggregates are partially seen, 80% uniform coating is possible 3: Coating In addition to streaks, unevenness and aggregates in the area of 50% or more of the area, air bubbles etc. are confirmed 2: In addition to the stripes, unevenness and aggregates in the area of 80% or more of the coating area, air bubbles etc. are confirmed, Uniform coating is difficult 1: The paint rolls on the applicator and cannot be applied
[粉粒物含有組成物の保存安定性]
調製した粉粒物含有組成物の保存安定性を評価するため、経時変化評価を行った。50mLの密閉容器の50体積%を粉粒物含有組成物で満たしたサンプルを準備し、1ヶ月間室温下で放置後、粉粒物含有組成物を容器上部と下部から各2g採取し、水分/揮発分測定装置((株)アクタック製 マーク3)にて粉粒物含有組成物の揮発分測定を行い、固形分濃度の差を以下の6段階で評価し、2以上を合格とした。
5:組成物中における固形分の濃度差が1質量%以下である
4:組成物中における固形分の濃度差が1質量%より大きく2質量%以下である
3:組成物中における固形分の濃度差が2質量%より大きく3質量%以下である
2:組成物中における固形分の濃度差が3質量%より大きく5質量%以下である
1:組成物中における固形分の濃度差が5質量%より大きいが、目視では判断できない
0:目視で確認できる程度に内容物が分離している [Storage stability of powder-containing composition]
In order to evaluate the storage stability of the prepared granule-containing composition, change with time was evaluated. Prepare a sample in which 50% by volume of a 50 mL airtight container is filled with the powder-containing composition. After leaving at room temperature for 1 month, 2 g each of the powder-containing composition is collected from the upper and lower parts of the container, / The volatile matter content of the powder-containing composition was measured with a volatile matter measuring apparatus (Mark 3 manufactured by Actac Co., Ltd.), and the difference in solid content concentration was evaluated in the following 6 stages, with 2 or more being acceptable.
5: The solid content concentration difference in the composition is 1% by mass or less 4: The solid content concentration difference in the composition is greater than 1% by mass and 2% by mass or less 3: Solid content in the composition The concentration difference is greater than 2% by mass and 3% by mass or less. 2: The solid content concentration difference in the composition is greater than 3% by mass and 5% by mass or less. 1: The solid content concentration difference in the composition is 5. Larger than mass%, but cannot be judged by visual inspection 0: Contents are separated to such an extent that they can be visually confirmed
調製した粉粒物含有組成物の保存安定性を評価するため、経時変化評価を行った。50mLの密閉容器の50体積%を粉粒物含有組成物で満たしたサンプルを準備し、1ヶ月間室温下で放置後、粉粒物含有組成物を容器上部と下部から各2g採取し、水分/揮発分測定装置((株)アクタック製 マーク3)にて粉粒物含有組成物の揮発分測定を行い、固形分濃度の差を以下の6段階で評価し、2以上を合格とした。
5:組成物中における固形分の濃度差が1質量%以下である
4:組成物中における固形分の濃度差が1質量%より大きく2質量%以下である
3:組成物中における固形分の濃度差が2質量%より大きく3質量%以下である
2:組成物中における固形分の濃度差が3質量%より大きく5質量%以下である
1:組成物中における固形分の濃度差が5質量%より大きいが、目視では判断できない
0:目視で確認できる程度に内容物が分離している [Storage stability of powder-containing composition]
In order to evaluate the storage stability of the prepared granule-containing composition, change with time was evaluated. Prepare a sample in which 50% by volume of a 50 mL airtight container is filled with the powder-containing composition. After leaving at room temperature for 1 month, 2 g each of the powder-containing composition is collected from the upper and lower parts of the container, / The volatile matter content of the powder-containing composition was measured with a volatile matter measuring apparatus (Mark 3 manufactured by Actac Co., Ltd.), and the difference in solid content concentration was evaluated in the following 6 stages, with 2 or more being acceptable.
5: The solid content concentration difference in the composition is 1% by mass or less 4: The solid content concentration difference in the composition is greater than 1% by mass and 2% by mass or less 3: Solid content in the composition The concentration difference is greater than 2% by mass and 3% by mass or less. 2: The solid content concentration difference in the composition is greater than 3% by mass and 5% by mass or less. 1: The solid content concentration difference in the composition is 5. Larger than mass%, but cannot be judged by visual inspection 0: Contents are separated to such an extent that they can be visually confirmed
結果は表2,3に示す通りである。実施例についてはいずれも十分な再分散性を示しており、セルロース繊維が短く、細いほど良好な再分散性を示した。また、セルロース繊維が増えるほど再分散時に増粘するため、塗工性を考慮すると粉粒物とセルロース繊維の割合にも最適値があると判明した。
Results are as shown in Tables 2 and 3. All the examples showed sufficient redispersibility, and the shorter and thinner the cellulose fibers, the better the redispersibility. Moreover, since the viscosity increases at the time of redispersion as the cellulose fiber increases, it has been found that there is an optimum value for the ratio of the granular material to the cellulose fiber in consideration of the coating property.
比較例1に関しては、結晶構造を有していないセルロース繊維であり、再分散させると大きな保護コロイドを生成することから、再分散性は低い傾向にあった。比較例2に関しては、セルロース繊維の短幅の方の繊維幅が大きく、繊維長が長いため繊維同士の絡まりから再分散性は低い結果であった。比較例3に関しては、含水量が多いことから、セルロース繊維と粉粒物との接触が不十分となったためか、セルロース繊維による粉粒物の分散効果に劣り、再分散性が低い結果であった。また、保存安定性にも劣っていた。
Regarding Comparative Example 1, since the cellulose fiber does not have a crystal structure and a large protective colloid is formed when redispersed, the redispersibility tends to be low. Regarding Comparative Example 2, the fiber width of the short side of the cellulose fiber was large and the fiber length was long, so the redispersibility was low due to the entanglement of the fibers. Regarding Comparative Example 3, because the water content was high, the contact between the cellulose fibers and the powder was insufficient, or the dispersion effect of the powder by the cellulose fibers was inferior and the redispersibility was low. It was. In addition, the storage stability was poor.
比較例4に関しては、セルロース繊維/粉粒物の比が小さく、セルロース繊維の含有量が少ないために、再分散性はほとんど有していなかった。比較例5に関しては、セルロース繊維/粉粒物の比が大きく、セルロース繊維の含有量が多いために、再分散性は良好であったものの、再分散時の粘度が高く、塗工段階で空回りする結果となった。比較例6に関しては、セルロース繊維/粉粒物の比が小さく、また粉粒物の含有量が多すぎたため、再分散性はほとんど有していなかった。
Comparative Example 4 had little redispersibility because the cellulose fiber / powder particle ratio was small and the cellulose fiber content was small. Regarding Comparative Example 5, although the ratio of cellulose fiber / powder particles was large and the content of cellulose fiber was large, the redispersibility was good, but the viscosity at the time of redispersion was high and it was idle at the coating stage. As a result. Regarding Comparative Example 6, since the ratio of cellulose fiber / powder granules was small and the content of the pow- der granules was too much, there was almost no redispersibility.
比較例7に関しては、セルロース繊維/粉粒物の比が大きく、粉粒物の含有量が少ないために、過剰のセルロース繊維同士が凝集し、再分散が難しい結果であった。比較例8に関しては、セルロース繊維/粉粒物の比が大きいため、再分散性は良好であったものの、再分散時の粘度が高く、塗工段階で空回りする結果となった。
Comparative Example 7 had a large ratio of cellulose fibers / powder and a small content of the granules, so that excessive cellulose fibers were aggregated and redispersion was difficult. Regarding Comparative Example 8, since the ratio of cellulose fiber / particulate matter was large, the redispersibility was good, but the viscosity during redispersion was high, resulting in idleness in the coating stage.
表2,3の結果より、本実施形態に係る粉粒物含有組成物は良好な再分散性と再分散後塗工性、保存安定性の点で良好な性能を示すことがわかる。
From the results shown in Tables 2 and 3, it can be seen that the powder-containing composition according to this embodiment exhibits good performance in terms of good redispersibility, coating property after redispersion, and storage stability.
[実施例25~28,比較例11]
(A1)セルロース繊維、(A2)カルボキシメチルセルロース塩、(B)粉粒物、および(C)水の含有量を表4に記載の通りに変更した以外は、実施例8と同様の手法により、粉体~固形状の粉粒物含有組成物を得た。 [Examples 25 to 28, Comparative Example 11]
(A1) Cellulose fiber, (A2) Carboxymethylcellulose salt, (B) Granules, and (C) Except for changing the water content as described in Table 4, by the same method as in Example 8, A powder to solid powder-containing composition was obtained.
(A1)セルロース繊維、(A2)カルボキシメチルセルロース塩、(B)粉粒物、および(C)水の含有量を表4に記載の通りに変更した以外は、実施例8と同様の手法により、粉体~固形状の粉粒物含有組成物を得た。 [Examples 25 to 28, Comparative Example 11]
(A1) Cellulose fiber, (A2) Carboxymethylcellulose salt, (B) Granules, and (C) Except for changing the water content as described in Table 4, by the same method as in Example 8, A powder to solid powder-containing composition was obtained.
実施例25~28及び比較例11で使用したセルロース繊維、カルボキシメチルセルロース塩及び粉粒物の詳細は以下の通りである。なお、表4におけるセルロース繊維の含有量は固形分としての質量比率である。
・A1-2:セルロース繊維A1-2の2質量%水分散体
・カルボキシメチルセルロース塩:カルボキシメチルセルロースナトリウム塩(第一工業製薬(株)製、セロゲンPR、1質量%水溶液粘度(25℃):35mPa・s)
・B-1:アセチレンブラック(デンカ株式会社製、HS-100、BET表面積:39m2/g) Details of the cellulose fiber, carboxymethylcellulose salt and powder used in Examples 25 to 28 and Comparative Example 11 are as follows. In addition, content of the cellulose fiber in Table 4 is a mass ratio as solid content.
A1-2: 2% by weight aqueous dispersion of cellulose fiber A1-2 Carboxymethylcellulose salt: Carboxymethylcellulose sodium salt (Sellogen PR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 1% by weight aqueous solution viscosity (25 ° C.): 35 mPa・ S)
B-1: Acetylene black (manufactured by Denka Co., Ltd., HS-100, BET surface area: 39 m 2 / g)
・A1-2:セルロース繊維A1-2の2質量%水分散体
・カルボキシメチルセルロース塩:カルボキシメチルセルロースナトリウム塩(第一工業製薬(株)製、セロゲンPR、1質量%水溶液粘度(25℃):35mPa・s)
・B-1:アセチレンブラック(デンカ株式会社製、HS-100、BET表面積:39m2/g) Details of the cellulose fiber, carboxymethylcellulose salt and powder used in Examples 25 to 28 and Comparative Example 11 are as follows. In addition, content of the cellulose fiber in Table 4 is a mass ratio as solid content.
A1-2: 2% by weight aqueous dispersion of cellulose fiber A1-2 Carboxymethylcellulose salt: Carboxymethylcellulose sodium salt (Sellogen PR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 1% by weight aqueous solution viscosity (25 ° C.): 35 mPa・ S)
B-1: Acetylene black (manufactured by Denka Co., Ltd., HS-100, BET surface area: 39 m 2 / g)
上記により得られた実施例25~28及び比較例11の粉粒物含有組成物について、再分散性、塗工性、保存安定性及び導電性の評価を行なった。その結果を下記表4に示した。再分散性、塗工性及び保存安定性の評価方法は上記の通りであり、導電性の評価方法は以下の通りである。
The powder-containing compositions of Examples 25 to 28 and Comparative Example 11 obtained as described above were evaluated for redispersibility, coatability, storage stability, and conductivity. The results are shown in Table 4 below. The evaluation method of redispersibility, coating property, and storage stability is as described above, and the evaluation method of conductivity is as follows.
[粉粒物含有組成物の導電性]
作製した粉粒物含有組成物を一部取り、乳鉢で十分に粉砕した後、直径12mmのペレット作製のプレス用金型に0.3gの粉粒物含有組成物を挿入し、圧縮装置(理研精機株式会社製、SMP-3,S1-100)で40MPa×30秒間圧縮することによって、粉粒物含有組成物のペレットを調製した。得られたペレットについて、抵抗率計(株式会社三菱化学アナリテック製、ロレスタGP)を用いて導電率を測定し、比較例11の値を100とした指数で表示した。指数が大きいほど導電性が高いことを示す。 [Conductivity of powder-containing composition]
A part of the produced granular material-containing composition is taken and sufficiently pulverized in a mortar. Then, 0.3 g of the granular material-containing composition is inserted into a pressing mold for producing a pellet having a diameter of 12 mm, and a compression device (RIKEN The pellets of the composition containing a granular material were prepared by compressing with 40 MPa × 30 seconds using SMP-3, S1-100) manufactured by Seiki Co., Ltd. About the obtained pellet, the electrical conductivity was measured using the resistivity meter (Mitsubishi Chemical Analytech make, Loresta GP), and it displayed with the index | exponent which set the value of the comparative example 11 to 100. It shows that electroconductivity is so high that an index | exponent is large.
作製した粉粒物含有組成物を一部取り、乳鉢で十分に粉砕した後、直径12mmのペレット作製のプレス用金型に0.3gの粉粒物含有組成物を挿入し、圧縮装置(理研精機株式会社製、SMP-3,S1-100)で40MPa×30秒間圧縮することによって、粉粒物含有組成物のペレットを調製した。得られたペレットについて、抵抗率計(株式会社三菱化学アナリテック製、ロレスタGP)を用いて導電率を測定し、比較例11の値を100とした指数で表示した。指数が大きいほど導電性が高いことを示す。 [Conductivity of powder-containing composition]
A part of the produced granular material-containing composition is taken and sufficiently pulverized in a mortar. Then, 0.3 g of the granular material-containing composition is inserted into a pressing mold for producing a pellet having a diameter of 12 mm, and a compression device (RIKEN The pellets of the composition containing a granular material were prepared by compressing with 40 MPa × 30 seconds using SMP-3, S1-100) manufactured by Seiki Co., Ltd. About the obtained pellet, the electrical conductivity was measured using the resistivity meter (Mitsubishi Chemical Analytech make, Loresta GP), and it displayed with the index | exponent which set the value of the comparative example 11 to 100. It shows that electroconductivity is so high that an index | exponent is large.
結果は表4に示す通りであり、セルロース繊維とともにカルボキシメチルセルロース塩を併用することで導電性を向上できることが分かる。
The results are as shown in Table 4. It can be seen that the conductivity can be improved by using carboxymethyl cellulose salt together with the cellulose fiber.
以上、本発明のいくつかの実施形態を説明したが、これら実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその省略、置き換え、変更などは、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。
Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and their omissions, replacements, changes, and the like are included in the inventions described in the claims and their equivalents as well as included in the scope and gist of the invention.
Claims (10)
- (A1)短幅の方の数平均幅が2nm以上1000nm以下のセルロース繊維と、(B)非セルロース粉粒物と、(C)水を少なくとも含有する組成物であって、前記(B)非セルロース粉粒物の含有量は、前記組成物の全質量に対して14.0質量%以上98.4質量%以下であり、 前記(C)水の含有量は、前記組成物の全質量に対して0.6質量%以上72.0質量%以下であり、 前記(A1)セルロース繊維の含有量と前記(B)非セルロース粉粒物の含有量との質量比率(A1)/(B)が1.0/99.0以上50.0/50.0以下であることを特徴とする再分散可能な組成物。 (A1) A composition containing at least a cellulose fiber having a number average width of 2 nm or more and 1000 nm or less, (B) a non-cellulose granule, and (C) water, wherein the (B) The content of the cellulose granule is 14.0% by mass or more and 98.4% by mass or less with respect to the total mass of the composition, and the content of the water (C) is the total mass of the composition. It is 0.6 mass% or more and 72.0 mass% or less with respect to the mass ratio (A1) / (B) of the content of the (A1) cellulose fiber and the content of the (B) non-cellulose powder. Is 1.0 / 99.0 or more and 50.0 / 50.0 or less.
- (A1)短幅の方の数平均幅が2nm以上1000nm以下のセルロース繊維と、(A2)カルボキシメチルセルロース塩と、(B)非セルロース粉粒物と、(C)水を少なくとも含有する組成物であって、
前記(B)非セルロース粉粒物の含有量は、前記組成物の全質量に対して14.0質量%以上98.4質量%以下であり、 前記(C)水の含有量は、前記組成物の全質量に対して0.6質量%以上72.0質量%以下であり、前記(A1)セルロース繊維の含有量と前記(A2)カルボキシメチルセルロース塩の含有量の合計量と、前記(B)非セルロース粉粒物の含有量との質量比率((A1)+(A2))/(B)が1.0/99.0以上50.0/50.0以下である ことを特徴とする再分散可能な組成物。 (A1) a composition containing at least a cellulose fiber having a number average width of 2 nm to 1000 nm, (A2) carboxymethylcellulose salt, (B) non-cellulose granules, and (C) water. There,
The content of the (B) non-cellulose granular material is 14.0% by mass or more and 98.4% by mass or less with respect to the total mass of the composition, and the content of the (C) water is the composition. 0.6 mass% or more and 72.0 mass% or less with respect to the total mass of the product, the total content of the content of the (A1) cellulose fiber and the content of the (A2) carboxymethylcellulose salt, and the (B ) The mass ratio ((A1) + (A2)) / (B) to the content of non-cellulose powder is 1.0 / 99.0 or more and 50.0 / 50.0 or less. Redispersible composition. - 前記(A1)セルロース繊維の含有量と前記(A2)カルボキシメチルセルロース塩の含有量との質量比率(A1)/(A2)が20.0/80.0以上99.0/1.0以下である、請求項2に記載の組成物。 The mass ratio (A1) / (A2) between the content of the (A1) cellulose fiber and the content of the (A2) carboxymethylcellulose salt is 20.0 / 80.0 or more and 99.0 / 1.0 or less. The composition according to claim 2.
- 前記(A2)カルボキシメチルセルロース塩の1質量%水溶液粘度(25℃)が500mPa・s以下である、請求項2または3に記載の組成物 The composition according to claim 2 or 3, wherein the (A2) carboxymethylcellulose salt has a 1 mass% aqueous solution viscosity (25 ° C) of 500 mPa · s or less.
- 前記(B)非セルロース粉粒物の含有量は、前記組成物の全質量に対して25.0質量%以上98.4質量%以下であり、
前記(C)水の含有量は、前記組成物の全質量に対して0.6質量%以上45.0質量%以下である、請求項1ないし4のいずれか1項に記載の組成物。 The content of the (B) non-cellulose granule is 25.0 mass% or more and 98.4 mass% or less with respect to the total mass of the composition,
5. The composition according to claim 1, wherein a content of the (C) water is 0.6% by mass or more and 45.0% by mass or less with respect to a total mass of the composition. - 前記(A1)セルロース繊維はアスペクト比が7.5以上250以下である、請求項1ないし5のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 5, wherein the (A1) cellulose fiber has an aspect ratio of 7.5 or more and 250 or less.
- 前記(B)非セルロース粉粒物が炭素から構成される粒子である、請求項1ないし6のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 6, wherein the (B) non-cellulose powder is a particle composed of carbon.
- 請求項1ないし7のいずれか1項に記載の組成物を極性溶媒に再分散させた再分散体。 A redispersed product obtained by redispersing the composition according to any one of claims 1 to 7 in a polar solvent.
- 請求項1ないし7のいずれか1項に記載の組成物または請求項8に記載の再分散体を用いた電極塗料組成物。 An electrode coating composition using the composition according to any one of claims 1 to 7 or the redispersion according to claim 8.
- 請求項9に記載の電極塗料組成物を用いて作製された電極。 An electrode produced using the electrode coating composition according to claim 9.
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