[go: up one dir, main page]

WO2024171889A1 - Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau - Google Patents

Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau Download PDF

Info

Publication number
WO2024171889A1
WO2024171889A1 PCT/JP2024/003880 JP2024003880W WO2024171889A1 WO 2024171889 A1 WO2024171889 A1 WO 2024171889A1 JP 2024003880 W JP2024003880 W JP 2024003880W WO 2024171889 A1 WO2024171889 A1 WO 2024171889A1
Authority
WO
WIPO (PCT)
Prior art keywords
cnf
substrate
nonionic
powder composition
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2024/003880
Other languages
English (en)
Japanese (ja)
Inventor
翔 丸山
広徳 西山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kusumoto Chemicals Ltd
Original Assignee
Kusumoto Chemicals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kusumoto Chemicals Ltd filed Critical Kusumoto Chemicals Ltd
Priority to JP2025501074A priority Critical patent/JPWO2024171889A1/ja
Publication of WO2024171889A1 publication Critical patent/WO2024171889A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • 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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents

Definitions

  • the present invention relates to a powder composition, a method for producing the same, and a rheology control agent for aqueous coatings.
  • CNF Cellulose nanofiber
  • BNC bacterial nanocellulose
  • HPC hydroxypropyl cellulose
  • CMC carboxymethyl cellulose
  • CNF containing BNC composited with HPC or CMC is usually used in the form of an aqueous dispersion, with a low solids concentration of 1-3%. Therefore, when such CNF is blended into an aqueous resin composition, the amount of water brought into the aqueous resin exceeds the upper limit of the weight of water that can be blended into the aqueous resin composition, making it impossible to achieve the designed resin solids content, and in many cases, blending CNF altogether has to be abandoned. Furthermore, when the solids concentration of CNF is low, not only does the transportation cost per CNF solid increase, but there are also problems with storage, such as the susceptibility to mold growth due to the presence of moisture.
  • Patent Document 1 discloses bacterial nanocellulose composite powders obtained by adding hydroxyethyl cellulose or hydroxypropyl cellulose to bacterial nanocellulose composited with hydroxypropyl cellulose, bacterial nanocellulose composited with hydroxyethyl cellulose, and bacterial nanocellulose composited with carboxymethyl cellulose, and then drying the resulting mixture in a thermostatic chamber.
  • Patent Document 2 discloses a powder blend that contains bacterial cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, etc., and can be redispersed in an aqueous medium at 20°C by low shear mixing.
  • This powder blend is produced by adding a third component, such as carboxymethyl cellulose or hydroxyethyl cellulose, to an aqueous suspension of bacterial cellulose, and then drying and pulverizing the bacterial cellulose.
  • Patent Document 3 discloses a method for producing a dried product of dispersible bacterial nanocellulose, in which an organic solvent is added to an aqueous dispersion of bacterial nanocellulose, and then the water and organic solvent are removed from the dispersion to dry the bacterial nanocellulose. Drying methods include heat drying, ventilation drying, freeze drying, etc.
  • Patent Document 4 discloses a resin composition containing a thermoplastic resin, cellulose fibers, a water-soluble resin, and a modified olefin resin.
  • the examples in this document describe spray-drying a mixture containing mechanically defibrated cellulose nanofibers, an aqueous resin, and water, and then melt-kneading the dried mixture with a thermoplastic resin, etc.
  • Patent Document 5 discloses a resin composition having dried cellulose nanofibers, acid-modified polypropylene, and a polyolefin resin.
  • the examples in this document describe mixing mechanically defibrated cellulose nanofibers with oleic acid, spray drying the mixture, and then mixing it with a polyolefin resin.
  • Patent Documents 1 to 5 merely disclose dried CNF bodies that are redispersible in water, aqueous media that do not contain aqueous resins, or thermoplastic resins, or methods for producing such bodies, and do not disclose dried CNF bodies that are redispersible in aqueous resins or compositions that contain aqueous resins.
  • the present invention has been made in consideration of the above circumstances, and aims to provide a high solids content cellulose nanofiber-containing powder composition that has excellent redispersibility and pseudoplasticity-imparting effects in aqueous resins, a method for producing the same, and a rheology control agent for aqueous coatings that uses the cellulose nanofiber-containing powder composition.
  • the present invention is a cellulose nanofiber-containing powder composition containing composite nonionic CNF, which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose, and a substrate, wherein the substrate is at least one selected from the group consisting of sugars, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa ⁇ s or less at 25°C and 1000 s -1 , and when the total mass of the composite nonionic CNF and the substrate contained in the powder composition is taken as 100 mass%, the content of the composite nonionic CNF is 5 to 80 mass%, and the content of the substrate is 20 to 95 mass%.
  • composite nonionic CNF which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose
  • the substrate is at least one selected from the group consisting of sugars, sucrose fatty acid esters having
  • the composite nonionic CNF of the present invention may be bacterial nanocellulose.
  • the nonionic water-soluble polymer may be a polymer whose total light transmittance in a 2% aqueous solution is 80% or more.
  • the sugar may be a monosaccharide or a disaccharide.
  • the powder composition may be a powder obtained by spray-drying and granulating a dispersion containing the composite nonionic CNF and the substrate.
  • the powder composition may be used as a rheology control agent for water-based coatings.
  • the present invention also relates to a method for producing a cellulose nanofiber-containing powder composition containing composite nonionic CNF, which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose, and a substrate, the method including a spray-drying granulation step of forming a dispersion containing the composite nonionic CNF and the substrate into dry particles by spray drying, the substrate being at least one selected from the group consisting of sugars, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa ⁇ s or less at 25°C and 1000 s -1 , and the amount of the composite nonionic CNF in the dispersion is 5 to 80% by mass, and the amount of the substrate is 20 to 95% by mass, when the total mass of the composite nonionic CNF and the substrate is 100% by mass.
  • composite nonionic CNF which is a nonionic
  • the composite nonionic CNF is bacterial nanocellulose, and in the spray drying granulation process, water may be added to the composite nonionic CNF and the substrate to form the dispersion.
  • the nonionic water-soluble polymer may be a polymer whose total light transmittance in a 2% aqueous solution is 80% or more.
  • the sugar may be a monosaccharide or a disaccharide.
  • the present invention also relates to a rheology control agent for aqueous coatings, comprising composite nonionic CNF, which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose, and a substrate, wherein the substrate is at least one selected from the group consisting of sugars, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa ⁇ s or less at 25°C and 1000 s -1 , and wherein, when the total mass of the composite nonionic CNF and the substrate is taken as 100 mass%, the content of the composite nonionic CNF is 5 to 80 mass%, and the content of the substrate is 20 to 95 mass%.
  • composite nonionic CNF which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose
  • the substrate is at least one selected from the group consisting of sugars, suc
  • the present invention makes it possible to provide a high-solids dried CNF material that has excellent redispersibility in aqueous resins and the effect of imparting pseudoplasticity.
  • the powder composition of the present invention is a CNF-containing powder composition that contains nonionic cellulose nanofibers (hereinafter referred to as "composite nonionic CNF") composited with hydroxypropyl cellulose (HPC) or carboxymethyl cellulose (CMC), and a substrate.
  • composite nonionic CNF nonionic cellulose nanofibers
  • HPC hydroxypropyl cellulose
  • CMC carboxymethyl cellulose
  • the powder composition of the present invention is a high solid content dried CNF product, which has high dispersibility in aqueous resins (excellent redispersibility) and exhibits a high pseudoplasticity-imparting effect.
  • solid content (CNF concentration) means the mass ratio of CNF in the powder composition when the mass of the entire powder composition is taken as 100% by mass.
  • high solid content means that the solid content is 5% by mass or more.
  • the solid content in the powder composition of the present invention is preferably 10% by mass or more.
  • the solid content of conventional aqueous dispersions of CNF is 1 to 3% by mass.
  • high dispersibility means that the particle size measured with a grind gauge having a maximum groove depth of 100 ⁇ m and a scale interval of 10 ⁇ m is 90 ⁇ m or less, and no poorly dispersed matter is found in visual observation of a dispersion in which the dried CNF (the powder composition of the present invention is also a type of dried CNF) is dispersed in an aqueous resin.
  • low dispersibility insufficient dispersibility of the powder composition of the present invention
  • a particle size of 30 ⁇ m or less is particularly suitable because of its high dispersibility. Poorly dispersed matter means undispersed particles or clumps of a size visible in a composition containing an aqueous resin.
  • the "particle size" in the present invention means the particle size measured using a grind gauge with a maximum groove depth of 100 ⁇ m, a scale interval of 10 ⁇ m, a groove width of 12 mm, and a groove length of 140 mm.
  • the point where noticeable spots begin to appear in the above dispersion sample is observed in accordance with JIS K5600-2-5:1999. Specifically, a point containing 5 or more particles per scale (a band with a width of 13 mm) along the groove is observed. Spots that appear sparsely before the point where noticeable spots begin to appear are ignored. The upper scale closest to the upper limit of the point containing 5 or more particles is taken as the particle size.
  • "pseudoplasticity” in the present invention refers to a property in which the viscosity is high before a force is applied to a target object such as a paint or the above-mentioned dispersion, and the viscosity decreases when a force is applied.
  • “high pseudoplasticity-imparting effect” means that the T.I. value (ratio of viscosity ⁇ 1 at 1 s -1 to viscosity ⁇ 100 at 100 s -1 : ⁇ 1 / ⁇ 100 ) is 2.0 or more.
  • the T.I. value is preferably 4.0 or more, and more preferably 9.0 or more . In these cases, it can be said that the pseudoplasticity-imparting effect is particularly high.
  • CNF Cellulose nanofibers
  • Examples of CNF include those extracted by mechanically defibrating wood-derived materials, those obtained by chemically modifying wood-derived materials (anion modification, etc.) and then mechanically defibrating them, and those synthesized by bacteria.
  • CNF has functions such as imparting pseudoplasticity, stabilizing pigment dispersion, and enhancing physical properties (coating strength, water resistance, etc.).
  • Nonionic CNF is used in the powder composition of the present invention.
  • anion-modified CNF maintains a fine fiber diameter due to the repulsive forces between ions when in an aqueous dispersion, but when the water is removed, the repulsive forces between the ions are lost, causing strong aggregation. Therefore, in the present invention, nonionic CNF is used to prevent strong aggregation of CNF.
  • BC Fibrous cellulose synthesized by bacteria
  • BC is obtained by culturing bacteria such as acetic acid bacteria
  • fibrous cellulose with a fiber diameter of 100 nm or less among BC is called bacterial nanocellulose (BNC) and is considered to be a type of CNF.
  • the fiber diameter of CNF can be measured, for example, by diluting a CNF dispersion with water so that the solid content (CNF concentration) is 0.05 mass%, and observing the freeze-dried fibers with a SEM.
  • the average fiber length of BNC is not particularly limited, but is about 10 to 20 ⁇ m.
  • BNC has a larger fiber diameter and fiber aspect ratio than wood-derived CNF, and is highly effective in strengthening the coating properties and imparting pseudoplasticity.
  • the CNF used as the composite nonionic CNF of the present invention is CNF composited with HPC or CMC (composite CNF).
  • CNF being "composited" with HPC or CMC means that the hydroxyl groups of HPC or CMC and the hydroxyl groups in the cellulose skeleton of CNF are bonded by hydrogen bonds or van der Waals forces, resulting in a structure in which HPC or CMC is intricately entangled with CNF.
  • the CNF being composited with HPC or CMC improves dispersibility in aqueous resin. Therefore, the CNF-containing powder composition of the present invention can suppress re-aggregation of CNF after dispersion in aqueous resin.
  • Examples of CNF composited with HPC or CMC include bacterial nanocellulose composited with HPC (HP-BNC) and bacterial nanocellulose composited with CMC (CM-BNC).
  • a method for obtaining HP-BNC or CM-BNC is to synthesize CNF using bacteria in a medium containing HPC or CMC (biological synthesis).
  • another method is to add HPC or CMC together with cellulose material when defibrating wood-derived materials or chemically treated materials using a device such as a high-pressure homogenizer (mechanical defibration treatment).
  • a high-pressure homogenizer mechanical defibration treatment
  • bacteria synthesize a single nano-sized fiber and move while discharging the synthesized fiber outside the bacterial body.
  • HPC or CMC can be directly and efficiently bound to one fiber of CNF.
  • the amount of HPC or CMC complexed with CNF increases, and HPC or CMC is less likely to detach from CNF.
  • the CNF defibrated by the mechanical fiberization process is compounded by physically bonding with the HPC and CMC that are charged at the same time, but since the CNFs are also in close proximity to each other during this process, there is a possibility that re-aggregation of the CNFs may occur. Therefore, compared to the biological synthesis method, the amount of HPC or CMC compounded with the CNF is smaller, and the HPC or CMC is more likely to detach from the CNF.
  • the CNF used in the present invention is HP-BNC or CM-BNC produced by biological synthesis.
  • the content of the composite nonionic CNF in the powder composition of the present invention is 5% by mass to 80% by mass, when the total mass of the composite nonionic CNF and the substrate contained in the powder composition is taken as 100% by mass.
  • the content of the composite nonionic CNF is within the range of 5% by mass to 80% by mass, when the powder composition of the present invention is added to an aqueous resin, the CNF can be dispersed in the aqueous resin, and a high pseudoplasticity-imparting effect can be exhibited.
  • the content of the composite nonionic CNF is less than 5% by mass, the amount of the substrate added to the composition containing the aqueous resin becomes too large, and the physical properties such as the water resistance of the coating film may be reduced.
  • the content of the composite nonionic CNF exceeds 80% by mass, the pseudoplasticity-imparting effect by the CNF cannot be exhibited.
  • the content of the composite nonionic CNF is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 50% by mass.
  • HPC, CMC The powder composition of the present invention contains either HPC, CMC, or both HPC and CMC in a composite state with CNF.
  • HPC and CMC interact with CNF through hydrogen bonds or van der Waals forces between the hydroxyl groups of HPC and CMC and the hydroxyl groups in the cellulose skeleton of CNF, and are adsorbed to CNF in a complex entangled state with CNF. This makes it possible to suppress the aggregation of CNF, and to exhibit high dispersibility in aqueous resins, and to have higher dispersibility in aqueous resins than CNF not composited with HPC or CMC.
  • the contents of HPC and CMC in the composite CNF used in the powder composition of the present invention are not particularly limited and can be appropriately set.
  • BNC is used as the nonionic CNF
  • the contents of HPC and CMC are 10 parts by mass to 35 parts by mass, and high dispersibility in the aqueous resin is obtained. If the contents of HPC and CMC are less than 10 parts by mass, re-aggregation of CNF cannot be prevented, and aggregates are generated when added to the aqueous resin.
  • the contents of HPC and CMC in the composite CNF can be determined as follows.
  • the composite CNF is freeze-dried, tetrabutylphosphonium hydride is added to dissolve it, and then water is added to precipitate only cellulose.
  • the precipitate is filtered and dried, and the mass of the dried material (corresponding to the cellulose in the composite CNF) is subtracted from the dry mass of the composite CNF to obtain the content of HPC and CMC in the composite CNF.
  • the substrate according to the present invention is at least one selected from the group consisting of saccharides, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa ⁇ s or less at 25° C. and 1000 s ⁇ 1.
  • the substrate is present between the fibers of the composite CNF (when described as “composite CNF”, it is not limited to nonionic CNF), thereby suppressing aggregation of the composite CNFs during the process of producing the CNF-containing powder composition of the present invention.
  • the substrate disperses or dissolves quickly, so that the composite CNFs can be dispersed in the aqueous resin without agglomeration.
  • This allows the composite CNFs to have excellent dispersibility in aqueous resins while exhibiting the pseudoplasticity-imparting effect and coating property-enhancing properties of the composite CNFs.
  • the preferred characteristics of the above substrate are: (I) it is solid at 40°C, (II) it is nonionic, (III) it has high affinity with the composite CNF, (IV) it has a relatively low molecular weight, and (V) it has high water solubility.
  • the substrate must be solid at 40°C in order for the CNF-containing powder composition of the present invention to be in a solid form. If a substrate that is liquid at 40°C is used, it may not be possible to sufficiently suppress the aggregation of CNF during the drying process. For this reason, it is preferable that the substrate of the present invention is solid at 40°C.
  • a nonionic substance is used as the substrate.
  • a powdered composition cannot be obtained by mixing the composite nonionic CNF with the substrate to prepare a CNF dispersion and drying the dispersion.
  • an amphoteric substrate is not suitable because it reduces the dispersibility of CNF in aqueous resins. Therefore, in the present invention, a nonionic substrate is used.
  • the substrate must have a high affinity with the composite CNF. If the affinity with the composite CNF is low, the aggregation of the composite CNF cannot be suppressed.
  • a substrate that can hydrogen bond with cellulose or has a structure similar to cellulose is preferable.
  • the compound selected as the substrate has a low molecular weight and high water solubility. If the substrate has a high molecular weight or low water solubility, the dispersibility of the CNF-containing powder composition in the aqueous resin decreases.
  • the substrate having the above characteristics is at least one selected from the group consisting of saccharides, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa ⁇ s or less at 25° C. and 1000 s ⁇ 1 .
  • the saccharides that can be used as the substrate of the present invention are preferably monosaccharides or disaccharides.
  • monosaccharides include glucose, galactose, fructose, etc.
  • disaccharides include sucrose, lactulose, lactose, maltose, cellobiose, trehalose, etc.
  • the sucrose fatty acid ester usable as the substrate of the present invention has an HLB of 11 or more. If the HLB is less than 11, the sucrose fatty acid ester cannot be dissolved or dispersed in water, and the sucrose fatty acid ester cannot be adsorbed around the CNF, so that the effect of containing the substrate, i.e., the effect of preventing aggregation of composite CNF, cannot be obtained. On the other hand, there is no particular problem even if the HLB is large, and the maximum HLB of the sucrose fatty acid ester usable as the substrate is 19. Incidentally, commercially available sucrose fatty acid esters generally have an HLB of about 16 at most.
  • the HLB in this invention is a value determined experimentally using a standard sample. Specifically, first, multiple emulsions are prepared by changing the blending ratio of two types of emulsifiers with different HLBs (the HLBs of the two types of emulsifiers are known). As a result, multiple standard samples are obtained in which the average HLB calculated from the blending ratio changes stepwise. Next, an aqueous solution of sucrose fatty acid ester is prepared, and the HLB of the one that has the closest appearance among the multiple standard samples can be estimated as the HLB of the sucrose fatty acid ester by visual inspection. In this invention, this estimated HLB value is taken as the HLB value of the sucrose fatty acid ester.
  • sucrose fatty acid esters include, for example, fatty acids having 12 to 18 carbon atoms.
  • sucrose fatty acid esters that can be used as substrates include, for example, sucrose laurate, sucrose myristate, sucrose palmitate, and sucrose stearate.
  • water-soluble polymer in the context of the water-soluble polymer of the present invention means that a 2% aqueous solution of the polymer has a total light transmittance of 80% or more.
  • the total light transmittance can be measured by placing a 2% aqueous solution of the water-soluble polymer in a cell with an optical path length of 1 cm in accordance with JIS K7361-1:1997 using an NDH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the water-soluble polymer of the present invention includes not only those generally called polymers, but also those called oligomers. Specifically, the water-soluble polymer of the present invention includes polymers or copolymers with three or more repeating units.
  • water-soluble polymers examples include vinyl polymers containing vinylpyrrolidone or vinyl alcohol as structural units (e.g., polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), copolymers containing vinylpyrrolidone and vinyl alcohol as structural units, etc.), polyacrylamide, starch, dextrin, HPC, HEC, methylhydroxypropylcellulose, methylhydroxyethylcellulose, methylcellulose, polyethylene glycol (PEG), polyoxyethylene alkyl ether, polymers having a PEG skeleton or hydroxyl groups (e.g., nonionic polymers consisting of a combination of unsaturated polymerizable monomers having a PEG skeleton or hydroxyl groups, including (meth)acrylic polymers and vinyl ester polymers).
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • copolymers containing vinylpyrrolidone and vinyl alcohol as structural units, etc. examples include polyacrylamide, star
  • nonionic polymers consisting of a combination of unsaturated polymerizable monomers having a PEG skeleton or hydroxyl groups include copolymers of monomers such as PEG (meth)acrylate, alkyl PEG (meth)acrylate, and hydroxyalkyl (meth)acrylate with other nonionic polymerizable monomers (alkyl (meth)acrylate, alkyl vinyl ester, etc.).
  • PEG (meth)acrylate alkyl PEG (meth)acrylate
  • hydroxyalkyl (meth)acrylate with other nonionic polymerizable monomers
  • alkyl (meth)acrylate, alkyl vinyl ester, etc. water-soluble polymers
  • PVP, dextrin, HPC, and PEG are particularly suitable because they have good stability in aqueous resins.
  • the viscosity of a 2% aqueous solution of the water-soluble polymer of the present invention is set to 5 mPa ⁇ s or less because if the viscosity at high shear rates (high shear rates) is high, the handleability of compositions such as water-based paints containing the water-soluble polymer as a substrate deteriorates, or the cohesive force of the substrate becomes so strong that the powder composition of the present invention cannot be dispersed in aqueous resin, resulting in the loss of the pseudoplasticity-imparting effect of CNF and the property-enhancing performance.
  • the viscosity of a 2% aqueous solution of the water-soluble polymer is preferably 2 mPa ⁇ s or less.
  • the lower limit of the viscosity of a 2% aqueous solution of the water-soluble polymer is not particularly limited, but from the viewpoint of the stability of the dispersion, it is preferably 0.1 mPa ⁇ s or more.
  • the viscosity of a 2% aqueous solution of a water-soluble polymer is a value measured at 25 °C using a rheometer with a shear rate of 1000 s and a geometry (cone-plate) of 60 mm diameter and an angle of 1° between the generatrix and the circular surface of the cone.
  • the content of the substrate in the powder composition of the present invention is 20% by mass to 95% by mass, when the total mass of the composite nonionic CNF and the substrate contained in the powder composition is taken as 100% by mass.
  • the content of the substrate is within the range of 20% by mass to 95% by mass, when the powder composition of the present invention is added to an aqueous resin, the CNF can be dispersed in the aqueous resin, and a high pseudoplasticity-imparting effect can be exhibited.
  • the content of the substrate is less than 20% by mass, the pseudoplasticity-imparting effect of the CNF cannot be exhibited.
  • the content of the substrate is more than 95% by mass, the amount of the substrate added to the composition containing the aqueous resin becomes too large, and the physical properties such as the water resistance of the coating film may be reduced.
  • the content of the substrate is preferably 50% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.
  • the content of the substrate can also be calculated from the heating residue of the supernatant after dispersing the CNF-containing powder composition in water to dissolve the substrate and centrifuging the dispersion.
  • the CNF-containing powder composition of the present invention is suitable for use as a rheology control agent for aqueous coatings. That is, the CNF-containing powder composition of the present invention has high dispersibility in aqueous resins and a high pseudoplasticity-imparting effect, as described above, and is therefore particularly suitable as a rheology control agent for aqueous coatings.
  • the powder composition according to the present invention is a powder obtained by spray-drying and granulating a dispersion containing the above-mentioned composite nonionic CNF and a substrate.
  • the method for producing the CNF-containing powder composition according to the present invention will be described in detail below.
  • the method for producing the powder composition according to the present invention includes a spray-drying granulation process in which a dispersion containing the above-mentioned composite nonionic CNF and substrate is spray-dried to form dry particles.
  • the composite nonionic CNF can be produced as exemplified below, or can be purchased commercially.
  • the method for producing the composite nonionic CNF of the present invention is not particularly limited, but as an example, the production method in the case where the nonionic CNF is BNC is described below.
  • bacterial cellulose hereinafter, sometimes referred to as "BC" producing bacteria is cultured with aeration and stirring in a medium to which HPC or CMC has been added, and the bacterial components are removed from the obtained culture solution to purify BNC, thereby obtaining a composite nonionic CNF derived from bacteria.
  • the CNF obtained by bacteria in this way has a larger fiber diameter and fiber aspect ratio than those obtained by mechanically defibrating wood materials, etc., and is preferable because it has a high performance in strengthening the physical properties of the coating film and a high effect of imparting pseudoplasticity.
  • the amount of HPC or CMC added to the medium may be appropriately set according to the desired amount of HPC or CMC bound to the composite nonionic CNF.
  • the final concentration of the first substrate in the medium may be set to 0.5 to 5.0% (w/v).
  • BC producing bacteria known bacteria capable of producing BC can be used, for example, Gluconacetobacter xylinus ATCC53582 strain, Gluconacetobacter hansenii ATCC23769 strain, Gluconacetobacter xylinus ATCC700178 (BPR2001) strain, Gluconacetobacter swingsii BPR3001E strain, Acetobacter xylinum JCM10150 strain, Enterobacter sp. CJF-002 strain, Gluconacetobacter intermedius SIID9587 strain (accession number NITE BP-01495), etc.
  • the culture conditions for the BC-producing bacteria can be the known culture conditions used for culturing the above-mentioned bacteria, and examples of the culture conditions include an aeration rate of 1 to 10 L/min, a rotation speed of 100 to 800 rpm, a temperature of 20 to 40°C, and a culture period of 1 to 7 days.
  • the culture medium can be a known culture medium used for culturing the above-mentioned bacteria, such as Hestrin-Schramm standard medium (HS medium).
  • HP-BNC commercially available HP-BNC or CM-BNC may be used.
  • HP-BNC or CM-BNC include Fibnano (registered trademark) HP-NFBC and Fibnano (registered trademark) CM-NFBC (both manufactured by Kusano Sakuko Co., Ltd.).
  • the method of preparing the dispersion is not particularly limited, and the substrate may be directly dispersed in the composite nonionic CNF, or the composite nonionic CNF and the substrate may be dispersed by adding water.
  • the nonionic CNF is BNC
  • the substrate is mixed with the BNC composited with HPC or CMC, or water is further added to the mixture to prepare a dispersion.
  • the substrate in the range of blending amounts described below is added to water, stirred with a disperser or the like to dissolve, and then the BNC composited with HPC or CMC (HP-BNC or CM-BNC in the present invention) is added and stirred with a disperser or the like to prepare the dispersion.
  • the stirring method in preparing the dispersion is not limited to a disperser, and any method may be used as long as the composite nonionic CNF and the substrate can be sufficiently dispersed in water.
  • the amount of the composite nonionic CNF when the total mass of the composite nonionic CNF and the substrate is 100 mass%, the amount of the composite nonionic CNF is 5 mass% to 80 mass%.
  • the amount of the composite nonionic CNF when the composition obtained by the manufacturing method of the powder composition of the present invention is added to an aqueous resin, the CNF can be dispersed in the aqueous resin and a high pseudoplasticity-imparting effect can be exhibited.
  • the amount of the composite nonionic CNF is less than 5 mass%, the amount of the substrate added to the composition containing the aqueous resin becomes too large, and the physical properties such as the water resistance of the coating film may decrease.
  • the amount of the composite nonionic CNF when the amount of the composite nonionic CNF is more than 80 mass%, the pseudoplasticity-imparting effect of the CNF cannot be exhibited.
  • the amount of composite nonionic CNF when the total mass of the composite nonionic CNF and the substrate is taken as 100 mass%, is preferably 5 mass% to 50 mass%, and more preferably 10 mass% to 50 mass%.
  • the amount of composite nonionic CNF to be blended relative to the total mass of the dispersion is not particularly limited, but considering the production efficiency in the spray drying process and the atomization properties of the dispersion, 0.3% to 3.0% by mass is preferable, and 0.3% to 1.0% by mass is more preferable. If the amount of composite nonionic CNF to be blended relative to the total mass of the dispersion is less than 0.3% by mass, this is undesirable because it reduces production efficiency, such as lengthening the drying time per weight of the obtained CNF powder and reducing the yield.
  • the amounts of HPC and CMC in the dispersion are determined by the final concentrations of HPC and CMC added to the medium, as described above.
  • the amount of the substrate is 20 mass% to 95 mass%.
  • the amount of the substrate is within the range of 20 mass% to 95 mass%, when the composition obtained by the manufacturing method of the powder composition of the present invention is added to an aqueous resin, the CNF can be dispersed in the aqueous resin and a high pseudoplasticity-imparting effect can be exhibited.
  • the amount of the substrate is less than 20 mass%, the pseudoplasticity-imparting effect of the CNF cannot be exhibited.
  • the amount of the substrate is more than 95 mass%, the amount of the substrate added to the composition containing the aqueous resin becomes too large, and the physical properties such as the water resistance of the coating film may be reduced.
  • the amount of the substrate is preferably 50 mass% to 95 mass%, and more preferably 50 mass% to 90 mass%.
  • the spray drying method is not particularly limited, and a known method can be used.
  • a spray dryer is used to spray and dry the dispersion containing the nonionic CNF under conditions of a spray pressure of 0.2 to 0.6 MPa, a hot air temperature of 100 to 250°C, and a liquid delivery rate of 0.1 to 30 kg/h.
  • the particle size of the CNF-containing powder composition thus obtained is about 5 ⁇ m to 20 ⁇ m in median diameter (D50).
  • the CNF-containing powder composition produced by spray drying preferably has a circularity of 0.9 or more.
  • the circularity is a value obtained by dividing the circle-equivalent perimeter calculated from the average particle size of the primary particles of the obtained powder by the average particle perimeter estimated by image analysis or the like.
  • the spray dryer a commercially available one can be used.
  • the CNF-containing powder composition of the present invention obtained by the above-mentioned manufacturing method is a high-solids dried CNF product that has excellent redispersibility in aqueous resins and the effect of imparting pseudoplasticity.
  • Aqueous resin composition The CNF-containing powder composition of the present invention described above has excellent redispersibility in aqueous resins. Therefore, an aqueous resin composition in which the CNF-containing powder composition of the present invention is dispersed in an aqueous resin has a high T.I. value due to the effect of CNF imparting high pseudoplasticity.
  • the aqueous resin composition of the present invention contains the above-mentioned CNF-containing powder composition and an aqueous resin as essential components, and contains other components as optional components.
  • the aqueous resin usable in the aqueous resin composition of the present invention is a resin component dispersed in a medium mainly composed of water, and examples of the resin component include acrylic resins, acrylic silicone resins, alkyd resins, polyester resins, urethane resins, epoxy resins, silicone resins, and fluororesins.
  • the form of the aqueous resin is divided into water-soluble, colloidal dispersion, and emulsion depending on the dispersion form, and any form is applicable.
  • These resins may be, for example, heat-curable, ultraviolet-curable, electron beam-curable, oxidation-curable, photocation-curable, peroxide-curable, and curable with a chemical reaction in the presence or absence of a catalyst, or may be a resin with a high glass transition point that does not involve a chemical reaction and becomes a coating only when the dilution medium evaporates.
  • the curing agent include amino resins, melamine resins, isocyanate compounds, blocked isocyanate compounds, and epoxy compounds.
  • the aqueous resin composition of the present invention may contain other substances, for example, other additives such as pigments, dehydrating agents (e.g., silane coupling agents), adhesion improvers, surfactants, curing catalysts, film-forming assistants, driers, anti-staining agents, sensitizers, antioxidants, light stabilizers, ultraviolet absorbers, water-resistant agents, preservatives and antifungal agents, defoamers, leveling agents, dispersants, flame retardants, antistatic agents, release agents, deodorizers, pH adjusters, and fragrances, so long as the properties of the aqueous resin composition and the objects of the present invention are not impaired.
  • dehydrating agents e.g., silane coupling agents
  • adhesion improvers e.g., surfactants, curing catalysts, film-forming assistants, driers
  • anti-staining agents sensitizers, antioxidants, light stabilizers, ultraviolet absorbers, water-resistant agents, preservative
  • the aqueous resin composition of the present invention can be suitably used as an aqueous coating material such as an aqueous paint containing a general color pigment or an extender pigment, or an aqueous coating material such as an aqueous ink.
  • the aqueous resin composition of the present invention can be manufactured according to the known manufacturing method of aqueous paints, aqueous coating materials, etc.
  • the above-mentioned CNF-containing powder composition (rheology control agent for aqueous coatings) and components other than the pigment are mixed with stirring in a medium mainly composed of water such as ion-exchanged water, and then the pH is adjusted as necessary to prepare a clear paint.
  • the aqueous resin composition can be manufactured by adding the CNF-containing powder composition (rheology control agent for aqueous coatings) and the pigment to this clear paint and dispersing them in the clear paint.
  • a solid medium component is necessary between the cellulose fibers to prevent aggregation during the drying process.
  • a material with high affinity for water should be selected as this medium component. If a medium with poor diffusibility in aqueous resin, such as a high molecular weight substrate, is selected as the medium, adding a large amount can result in the generation of poorly dispersed materials and the disappearance of the viscous characteristics of CNF (the effect of imparting high pseudoplasticity).
  • Examples of such disappearance of viscous characteristics include unnecessary thickening of high shear viscosity (viscosity at high shear rate) due to the thickening properties of polysaccharides. For this reason, a low molecular weight substrate is suitable as a medium to prevent aggregation during the drying process.
  • the present invention by using a nonionic low molecular weight substrate as a substrate in addition to the composite nonionic CNF, it is possible to form a powder in which the substrate is adsorbed onto cellulose fibers to which HPC or CMC is adsorbed.
  • the substrate portion is immediately dissolved or dispersed, providing a state in which the CNF composited with HPC or CMC is dispersed. Therefore, even when a powder composition with a high CNF content is used, it is possible to obtain excellent dispersibility in aqueous resins and a high pseudoplasticity-imparting effect.
  • the preferred embodiment of the present invention provides the following effects:
  • the fiber diameter of BNC is larger and the aspect ratio is larger than that of CNF obtained by mechanically defibrating wood materials (mechanically defibrated CNF), and therefore it can exert a higher pseudoplasticity-imparting effect than mechanically defibrated CNF.
  • BNC composited with HPC or CMC such as HP-BNC and CM-BNC
  • HPC or CMC adsorbed on the surface of the CNF which prevents re-agglomeration in the water-soluble resin, and therefore the CNF-containing powder composition of the present invention exhibits excellent effects derived from CNF in aqueous resins (pseudoplasticity-imparting effect, coating property enhancing effect).
  • freeze-drying is a drying method that is less likely to cause volumetric shrinkage of the dispersion during drying, and the substrate dries without being able to be adsorbed around the CNF.
  • a cellulose nanofiber-containing powder composition comprising a composite nonionic CNF, which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose, and a substrate, the substrate is at least one selected from the group consisting of saccharides, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa s or less at 25° C.
  • a composite nonionic CNF which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose
  • the substrate is at least one selected from the group consisting of saccharides, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa s or less at 25° C.
  • a powder composition wherein the content of the composite nonionic CNF is 5 to 80 mass%, and the content of the substrate is 20 to 95 mass%, when the total mass of the composite nonionic CNF and the substrate contained in the powder composition is 100 mass%.
  • the powder composition according to any one of (1) to (4), wherein the content of the substrate is 50 to 95 mass %.
  • nonionic water-soluble polymer is a vinyl polymer containing vinylpyrrolidone or vinyl alcohol as a constituent unit, polyacrylamide, starch, dextrin, hydroxypropyl cellulose (in this case, the hydroxypropyl cellulose complexed with the nonionic cellulose nanofiber does not fall under the substrate), hydroxyethyl cellulose, methylhydroxypropyl cellulose, methylhydroxyethyl cellulose, methyl cellulose, polyethylene glycol (PEG), polyoxyethylene alkyl ether, a polymer having a PEG skeleton or a hydroxyl group.
  • the nonionic water-soluble polymer is a vinyl polymer containing vinylpyrrolidone or vinyl alcohol as a constituent unit, polyacrylamide, starch, dextrin, hydroxypropyl cellulose (in this case, the hydroxypropyl cellulose complexed with the nonionic cellulose nanofiber does not fall under the substrate), hydroxyethyl cellulose, methylhydroxypropyl cellulose
  • the saccharide is a monosaccharide or a disaccharide.
  • a method for producing a cellulose nanofiber-containing powder composition containing a composite nonionic CNF, which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose, and a substrate comprising: A spray-drying granulation step is included in which a dispersion containing the composite nonionic CNF and the substrate is spray-dried to form dry particles, the substrate is at least one selected from the group consisting of saccharides, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa s or less at 25° C.
  • a method for producing a powder composition wherein, in the dispersion, when the total mass of the composite nonionic CNF and the substrate is 100 mass%, the blending amount of the composite nonionic CNF is 5 to 80 mass%, and the blending amount of the substrate is 20 to 95 mass%.
  • the composite nonionic CNF is bacterial nanocellulose
  • nonionic water-soluble polymer is a vinyl polymer containing vinylpyrrolidone or vinyl alcohol as a constituent unit, polyacrylamide, starch, dextrin, hydroxypropyl cellulose (in this case, the hydroxypropyl cellulose complexed with the nonionic cellulose nanofiber does not fall under the substrate), hydroxyethyl cellulose, methylhydroxypropyl cellulose, methylhydroxyethyl cellulose, methyl cellulose, polyethylene glycol (PEG), polyoxyethylene alkyl ether, a polymer having a PEG skeleton or a hydroxyl group.
  • the nonionic water-soluble polymer is a vinyl polymer containing vinylpyrrolidone or vinyl alcohol as a constituent unit, polyacrylamide, starch, dextrin, hydroxypropyl cellulose (in this case, the hydroxypropyl cellulose complexed with the nonionic cellulose nanofiber does not fall under the substrate), hydroxyethyl cellulose, methylhydroxypropyl cellulose
  • a method for producing a nanofiber composition comprising the steps of: (a) providing a nanofiber composition comprising: a composite nonionic CNF, which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose; and a substrate; the substrate is at least one selected from the group consisting of saccharides, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa s or less at 25° C.
  • a composite nonionic CNF which is a nonionic cellulose nanofiber composited with hydroxypropyl cellulose or carboxymethyl cellulose
  • the substrate is at least one selected from the group consisting of saccharides, sucrose fatty acid esters having an HLB of 11 or more, and nonionic water-soluble polymers having a 2% aqueous solution viscosity of 5 mPa s or less at 25° C.
  • a rheology control agent for aqueous coating in which the content of the composite nonionic CNF is 5 to 80 mass % and the content of the substrate is 20 to 95 mass % when the total mass of the composite nonionic CNF and the substrate is 100 mass %.
  • nonionic water-soluble polymer is a vinyl polymer containing vinylpyrrolidone or vinyl alcohol as a constituent unit, polyacrylamide, starch, dextrin, hydroxypropyl cellulose (in this case, the hydroxypropyl cellulose complexed with the nonionic cellulose nanofiber does not fall under the category of the substrate), hydroxyethyl cellulose, methylhydroxypropyl cellulose, methylhydroxyethyl cellulose, methyl cellulose, polyethylene glycol (PEG), polyoxyethylene alkyl ether, a polymer having a PEG skeleton or a hydroxyl group.
  • PEG polyethylene glycol
  • PEG polyoxyethylene alkyl ether
  • dispersion for drying granulation A dispersion of CNF to be subjected to the drying granulation process (hereinafter referred to as "dispersion for drying granulation") was prepared as follows.
  • Fibnano (registered trademark) HP-NFBC and Fibnano (registered trademark) CM-NFBC were used as bacterial nanocellulose (BNC) dispersions (dispersions in which HP-BNC or CM-BNC is dispersed in water), and either of these was added to the aqueous solution of the substrate and stirred with a disperser to prepare a dispersion for dry granulation containing nonionic CNF (composite nonionic CNF) and substrate complexed with HPC or CMC.
  • BNC bacterial nanocellulose
  • Fibnano (registered trademark) HP-NFBC has a content of HP-BNC of 1%
  • Fibnano (registered trademark) CM-NFBC has a content of CM-BNC of 1%.
  • the amount of BNC dispersion added was adjusted so that the content of HP-BNC or CM-BNC in the dry granulation dispersion was 0.3%.
  • the amount of substrate added was adjusted so that the blending ratio was as shown in Table 2 relative to the amount of HP-BNC or CM-BNC added as adjusted above.
  • HP-NFBC Fibnano (registered trademark) HP-NFBC was used as the HP-BNC dispersion, and HP-NFBC was added to water so that the content of HP-BNC in the dispersion for dry granulation was 0.3%, and the mixture was stirred with a disperser to prepare a dispersion for dry granulation.
  • BC bacterial cellulose not composited with HPC or CMC
  • HS medium Hetrithrin-Schramm standard medium
  • BC was produced by aeration and agitation culture for 3 days under the conditions of aeration amount of 7 to 10 L/min, rotation speed of 200 to 500 rpm, and temperature of 30°C.
  • Sample No. C-4 was used to prepare a BC dispersion (water dispersion of BC) produced in the same manner as above, and a predetermined amount of the substrate listed in Table 1 was added to water and stirred with a disperser to prepare an aqueous solution in which the substrate was dissolved in water.
  • the BC dispersion was then added to the aqueous solution of the substrate and stirred with a disperser to prepare a dispersion for dry granulation containing nonionic CNF (BC) and the substrate.
  • BC dispersion added was adjusted so that the content of BC in the dispersion for dry granulation was 0.3%.
  • Fibnano (registered trademark) HP-NFBC was used as the HP-BNC dispersion, and a predetermined amount of substrate was added to this HP-NFBC dispersion and stirred with a disperser to prepare a dispersion for dry granulation.
  • the amount of substrate added was adjusted so as to obtain the blending ratio shown in Table 2 relative to the content of HP-BNC adjusted as described above.
  • Fibnano (registered trademark) HP-NFBC was used as the HP-BNC dispersion, and the same amount of tert-butanol (t-BuOH) as the HP-BNC dispersion was added. After stirring, the mixture was centrifuged, and the supernatant was discarded. The same amount of t-BuOH was then added. This operation was repeated five times to prepare a dispersion for dry granulation in which water was replaced with t-BuOH.
  • Example No. C-21 Dissolving pulp (manufactured by Marubeni Corporation) was adjusted to 2% in water and stirred with a disperser. The obtained aqueous dispersion was subjected to a micronization process using a high-pressure homogenizer to prepare a mechanically defibrated CNF dispersion containing 2% mechanically defibrated CNF. Next, PVP K90 was added to water and stirred with a disperser to dissolve. The obtained mechanically defibrated CNF dispersion was added to an aqueous solution in which PVP K90 was dissolved, and stirred with a disperser to prepare a dispersion for dry granulation.
  • the amount of mechanically defibrated CNF dispersion was adjusted so that the mechanically defibrated CNF content in the dispersion for dry granulation was 0.3%.
  • the amount of substrate added was adjusted to the amount of mechanically defibrated CNF added as above to obtain the blending ratio shown in Table 2.
  • Example No. C-1 For Sample No. C-1, the preparation of a dispersion for drying granulation and the subsequent drying granulation process were not carried out, and PVP K15 (reagent powder) was added directly to the aqueous resin in the test example described below.
  • PVP K15 reagent powder
  • the dried granulation dispersion was dried in a thermostatic bath at 80°C for 8 hours, and then crushed using an ultracentrifugal grinder, Retsch ZM200 (manufactured by Verder Scientific Co., Ltd.), with a screen hole diameter of 0.5 mm and a rotor rotation speed of 18,000 rpm, and the powder that passed through a 300 mesh was collected.
  • Retsch ZM200 manufactured by Verder Scientific Co., Ltd.
  • the obtained t-BuOH-substituted HP-BNC dispersion was frozen at -40°C and dried under vacuum at 20°C.
  • the obtained dried body was pulverized in a mortar.
  • compositions of the CNF-containing powder composition samples E-1 to 22 and C-1 to 21 obtained in the above manner are shown in Table 2.
  • Test Example 1 Effect of CNF content on effect
  • the effect of the solid content of the CNF-containing powder composition i.e., the CNF content in the CNF-containing powder composition
  • the effect of imparting pseudoplasticity was evaluated.
  • aqueous resin composition Preparation of aqueous resin composition
  • three types of aqueous resins were used: Burnock (registered trademark) WD-551 (isocyanate-cured acrylic dispersion manufactured by DIC Corporation), Burnock WE-304 (isocyanate-cured acrylic emulsion manufactured by DIC Corporation), and Polysol (registered trademark) AP-3900 (acrylic silicone emulsion manufactured by Resonac Corporation).
  • the CNF-containing powder compositions of Samples No. E-1 to E-10 and C-1 to C-4 were added to each of these three types of aqueous resins in the formulations shown in Tables 3 to 5.
  • the mixture of the CNF-containing powder composition and the aqueous resin was mixed while stirring at 1000 rpm using a disper for 10 minutes to disperse the CNF in the aqueous resin, thereby producing the aqueous resin compositions of Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-4.
  • These aqueous resin compositions were degassed using a planetary centrifugal mixer, and the presence or absence of poorly dispersed matter was confirmed visually.
  • the amount (parts) x of the CNF-containing powder composition in Tables 3 to 5 is the amount of the CNF-containing powder composition when HP-BNC or CM-BNC is added to the aqueous resin composition (resin liquid containing the CNF-containing powder composition and aqueous resin) so that the amount is 0.3%.
  • the powder composition contains only the substrate (when sample No. C-1 is used)
  • the powder composition is added so that the amount of the substrate in the aqueous resin composition is 3%.
  • the CNF-containing powder composition contains only composite CNF (BNC)
  • the CNF-containing powder composition is added so that the amount of the composite CNF in the aqueous resin composition is 0.3%.
  • the particle size of the aqueous resin composition obtained as described above was measured using a grind gauge with a maximum groove depth of 100 ⁇ m, a scale interval of 10 ⁇ m, a groove width of 12 mm, and a groove length of 140 mm.
  • the point where noticeable spots began to appear in the above dispersion sample was observed according to JIS K5600-2-5:1999. Specifically, the point containing 5 or more particles in one scale (a band with a width of 13 mm) along the groove was observed. Spots that appeared sparsely before the point where noticeable spots began to appear were ignored.
  • the upper scale closest to the upper limit of the point containing 5 or more particles was taken as the particle size.
  • the resin dispersibility was evaluated according to the following criteria. When at least one of the three types of aqueous resins was rated C, it was determined that the effects of the present invention were not achieved.
  • T.I. is 9.0 or more
  • B T.I. is 4.0 or more and less than 9.0
  • C T.I. is 2.0 or more and less than 4.0
  • D T.I. is less than 2.0
  • Test Example 2 Effect of substrate type on effect
  • Test Example 2 the influence of the type of substrate on the dispersibility in the aqueous resin and the effect of imparting pseudoplasticity was evaluated.
  • aqueous resin compositions of Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-11 obtained as described above were evaluated for dispersibility in aqueous resin (hereinafter, may be simply referred to as "resin dispersibility") and pseudoplasticity-imparting effect by the same method as in Test Example 1. If the presence of poorly dispersed matter was confirmed when the CNF-containing powder composition was dispersed in the aqueous resin, the resin dispersibility was determined to be extremely low, and viscosity measurement was not performed. Therefore, in this case, the T.I. value could not be calculated, and the pseudoplasticity-imparting effect was not evaluated.
  • Comparative Examples 2-7 and 2-10 in which the substrate was anionic
  • Comparative Examples 2-1 to 2-6 and 2-10 in which the 2% aqueous solution viscosity of the substrate exceeded 5.0 mPa ⁇ s, resulted in low resin dispersibility (rating C).
  • Comparative Examples 2-1 to 2-6, 2-9 and 2-10 the presence of poorly dispersed matter was confirmed when the CNF-containing composition was dispersed in the aqueous resin, so it was determined that the resin dispersibility was extremely low and viscosity measurements were discontinued. Therefore, the pseudoplasticity imparting effect was not evaluated.
  • C-11 the CNF-containing powder composition used in Comparative Example 2-7, did not become a powder when spray-dried. However, a film-like dried body was obtained, and when it was dispersed in an aqueous resin, the presence of poorly dispersed matter was confirmed, and viscosity measurements were discontinued.
  • C-12 and C-15 the CNF-containing powder compositions used in Comparative Examples 2-8 and 2-11, did not become a powder when spray-dried, and no film-like dried body was obtained, so all evaluation tests were discontinued.
  • Test Example 3 Other Comparative Examples
  • a comparative example not listed in Test Examples 1 and 2 was investigated.
  • the amount (parts) y of the CNF-containing powder composition listed in Tables 11 to 13 is the amount of the CNF-containing powder composition when the amount of HP-BNC or BC is added to the aqueous resin composition (resin liquid containing the CNF-containing powder composition and the aqueous resin) so that the amount is 0.3%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne : une composition de poudre contenant des nanofibres de cellulose (CNF) à haute teneur en solides qui a un excellent effet de redispersibilité et de pseudoplasticité par rapport à des résines aqueuses ; un procédé de production de la composition ; et un agent de contrôle de rhéologie pour un revêtement à base d'eau.　Cette composition de poudre contenant des CNF contient un substrat et des CNF non ioniques composites qui sont des CNF non ioniques qui sont composées avec de l'hydroxypropylcellulose ou de la carboxyméthylcellulose. Le substrat est au moins l'un choisi dans le groupe constitué par les sucres, les esters d'acide gras de saccharose ayant un HLB de 11 ou plus, et des polymères hydrosolubles non ioniques ayant, lorsqu'ils sont transformés en une solution aqueuse à 2 %, une viscosité de 5 mPa·s ou moins à 25 °C et 1 000 s-1. Lorsque la masse totale du substrat et des CNF non ioniques composites contenus dans la composition de poudre est définie comme étant 100 % en masse, la quantité contenue des CNF non ioniques composites est de 5 à 80 % en masse et la quantité contenue du substrat est de 20 à 95 % en masse.
PCT/JP2024/003880 2023-02-15 2024-02-06 Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau Ceased WO2024171889A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2025501074A JPWO2024171889A1 (fr) 2023-02-15 2024-02-06

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023022039 2023-02-15
JP2023-022039 2023-02-15

Publications (1)

Publication Number Publication Date
WO2024171889A1 true WO2024171889A1 (fr) 2024-08-22

Family

ID=92421761

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/003880 Ceased WO2024171889A1 (fr) 2023-02-15 2024-02-06 Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau

Country Status (3)

Country Link
JP (1) JPWO2024171889A1 (fr)
TW (1) TW202440770A (fr)
WO (1) WO2024171889A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016210958A (ja) * 2014-11-28 2016-12-15 キヤノン株式会社 粉末、熱可塑性組成物、および立体物の製造方法
WO2018038055A1 (fr) * 2016-08-23 2018-03-01 草野作工株式会社 Procédé de fabrication d'un produit sec de cellulose bactérienne dispersible et procédé de production d'une dispersion de cellulose bactérienne
WO2018143150A1 (fr) * 2017-02-03 2018-08-09 株式会社片山化学工業研究所 Procédé de fabrication de nanofibres de cellulose sèche
JP2020132826A (ja) * 2019-02-25 2020-08-31 Ｆｏｎｔｅｃ Ｒ＆Ｄ株式会社 加水分解バクテリアセルロース繊維並びにそれを含む分散液、粉体及び成形品
JP2021126054A (ja) * 2020-02-12 2021-09-02 伊那食品工業株式会社 バクテリアセルロース複合化粉末およびその製造方法
JP2022517739A (ja) * 2018-12-28 2022-03-10 ユニベルズィダード ドゥ ミンホ バクテリアセルロースの配合物、方法および使用法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016210958A (ja) * 2014-11-28 2016-12-15 キヤノン株式会社 粉末、熱可塑性組成物、および立体物の製造方法
WO2018038055A1 (fr) * 2016-08-23 2018-03-01 草野作工株式会社 Procédé de fabrication d'un produit sec de cellulose bactérienne dispersible et procédé de production d'une dispersion de cellulose bactérienne
WO2018143150A1 (fr) * 2017-02-03 2018-08-09 株式会社片山化学工業研究所 Procédé de fabrication de nanofibres de cellulose sèche
JP2022517739A (ja) * 2018-12-28 2022-03-10 ユニベルズィダード ドゥ ミンホ バクテリアセルロースの配合物、方法および使用法
JP2020132826A (ja) * 2019-02-25 2020-08-31 Ｆｏｎｔｅｃ Ｒ＆Ｄ株式会社 加水分解バクテリアセルロース繊維並びにそれを含む分散液、粉体及び成形品
JP2021126054A (ja) * 2020-02-12 2021-09-02 伊那食品工業株式会社 バクテリアセルロース複合化粉末およびその製造方法

Also Published As

Publication number Publication date
TW202440770A (zh) 2024-10-16
JPWO2024171889A1 (fr) 2024-08-22

Similar Documents

Publication Publication Date Title
JP6727522B2 (ja) 多糖類懸濁液、その調製方法、及びその使用
JP6173222B2 (ja) 改良された分散特性を有する水溶性ポリマー粉末配合物
CN113272377B (zh) 细菌纤维素配制品、方法及其用途
CN104684935B (zh) 用于水性丙烯酸漆和涂料组合物的防裂剂
EP2949624A1 (fr) Dispersion de nanotubes de carbone, procédé de fabrication de cette dispersion, composition de nanotubes de carbone, et procédé de fabrication de cette composition
CN102099412A (zh) 无羧甲基纤维素组分的含细菌纤维素配方
CA2640616C (fr) Procede de production d'ethers de cellulose dispersibles dans l'eau froide et leurs utilisations
Martins et al. Dry Bacterial Cellulose and Carboxymethyl Cellulose formulations with interfacial-active performance: processing conditions and redispersion
JP2015522095A (ja) 分散性が改善した水溶性高分子粉末
JPWO2018038055A1 (ja) 分散性バクテリアセルロース乾燥物の製造方法およびバクテリアセルロース分散液の製造方法
CN106687537B (zh) 书写工具用水性墨组合物
JP2016069617A (ja) 水性インク組成物およびそれを用いた筆記具
WO2021111730A1 (fr) Particules de cellulose et leur procédé de production
JP2024051046A (ja) バクテリアセルロース複合化粉末およびその製造方法
CN102442797A (zh) 用于水解硬化组合物的具有调节的颗粒形态的多糖衍生物
WO2001005838A1 (fr) Sechage de cellulose bacterienne reticulee sans co-agents
WO2024171889A1 (fr) Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau
EP3924390A1 (fr) Microparticules nanoredispersibles de nanocristaux de cellulose séchés et leur procédé de production
JPH04504867A (ja) 流動性易溶解性乾燥接着剤粉末、その製造方法およびその使用
JP3328024B2 (ja) 水に容易に分散する複合体
JP2020002504A (ja) バクテリアセルロースと樹脂との複合糸およびその製造方法
US7473391B2 (en) Methods for making molding material, molded body, and sintered body
JP7772408B1 (ja) セルロースナノファイバーのスラリーおよびその粉体
EP4365227A1 (fr) Procédé de production d'une composition de polysaccharide mélangé à des nanofibres de polysaccharide
EP1343853A1 (fr) Compositions de liant particulaire a tendance faible a la pulverulence, sa production et son utilisation---------------

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24756738

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2025501074

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025501074

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE