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WO2020059859A1 - Boule de fibres cellulosiques et papier la contenant - Google Patents

Boule de fibres cellulosiques et papier la contenant Download PDF

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Publication number
WO2020059859A1
WO2020059859A1 PCT/JP2019/037037 JP2019037037W WO2020059859A1 WO 2020059859 A1 WO2020059859 A1 WO 2020059859A1 JP 2019037037 W JP2019037037 W JP 2019037037W WO 2020059859 A1 WO2020059859 A1 WO 2020059859A1
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Prior art keywords
cellulose fiber
cfb
pulp
cellulose
weight
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
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PCT/JP2019/037037
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English (en)
Japanese (ja)
Inventor
咲子 中田
雅人 高山
後藤　至誠
悠生 久永
田村　金也
遼 外岡
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Application filed by Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Priority to JP2020549142A priority Critical patent/JP7384813B2/ja
Publication of WO2020059859A1 publication Critical patent/WO2020059859A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres

Definitions

  • the present invention relates to a cellulose fiber ball and paper containing the same.
  • Cellulose fiber is a fiber mainly made of wood and is used in papermaking applications, but is expected to be applied in various fields other than papermaking due to its high functionality.
  • pulp used for papermaking is made of cellulose fiber, and is used after promoting fine fiberization (fibrillation) of the fiber surface by mechanical treatment such as beating.
  • Fibrils impart strength to a substrate by increasing the number of hydrogen bonding points in the substrate, such as paper.
  • Cellulose fiber having many hydroxyl groups has high affinity for water, so the fiber is easy to spread in water and has high water retention.On the other hand, handleability is not always necessary when preparing for transportation or reaction due to too good water retention. Not good.
  • cellulose nanofibers have attracted attention as a new material.
  • Cellulose nanofibers are roughly classified into those mechanically refined by the manufacturing method and those mechanically refined after chemical modification to improve the efficiency of the refinement and impart functionality. .
  • cellulose nanofibers made from chemically modified pulp obtained by introducing anionic or cationic substituents into pulp have been gathered, and various studies have been made.
  • chemically modified pulp has a very high hydrophilicity compared to ordinary pulp, and the more hydrophilic the amount of hydrophilic groups on the fiber surface increases as the size of the pulp increases, the more difficult it is to handle in hydrated conditions. was there.
  • Patent Literature 1 proposes a cellulose bead in which the surface of a cellulose bead is oxidized to impart functionality.
  • Patent Document 2 discloses a particulate cellulose composite in which a plurality of cellulose nanofibers are bound to each other and have an average circularity of 0.7 or more and less than 1.0 and containing at least one functional material. .
  • an object of the present invention is to provide a cellulose fiber ball that exists as a powder (powder) even at a relatively high water content.
  • a cellulose fiber ball satisfying the following (1) to (3) and formed by entanglement of fine cellulose fibers (1)
  • the average particle diameter (D50) by wet measurement using a laser diffraction type particle size analyzer is 50 ⁇ m to 2 mm.
  • the average aspect ratio (L / D) is 10 or less.
  • the angle of repose at a water content of 50% by weight is less than 58 °.
  • the cellulose fiber ball according to [1] wherein the fine cellulose fibers are chemically modified cellulose fibers.
  • the magnitude of the charge density when the pH of the suspension is acidic is a (meq./g), and the magnitude of the charge density when the pH is neutral to alkaline is b (meq./g).
  • [11] The method for producing a cellulose fiber ball according to any of [2] to [8], (A1) a step of chemically modifying the raw pulp; (A2) mechanically treating a mixture containing the chemically modified pulp obtained in the above step and water and having a solid content of 15% by weight or more to form a cellulose fiber ball; A manufacturing method including: [12] The production method according to [11], comprising a step of acid-treating the chemically modified pulp between the steps (A1) and (A2).
  • X to Y includes the end values X and Y.
  • Cellulose fiber ball is a substantially spherical (spherical or elliptical) material (aggregate) formed by entanglement of fine cellulose fibers like a pill (FIG. 1).
  • One cellulose fiber ball can be formed from one fine cellulose fiber, but is preferably formed from a plurality of fine cellulose fibers.
  • the cellulose fiber ball is also referred to as “CFB”.
  • the average particle diameter (D50) of CFB measured by a wet method using a laser diffraction type particle size analyzer is 50 ⁇ m to 2 mm.
  • microfibrillated cellulose fibers can be produced from CFB.
  • the average particle size exceeds the upper limit, it may be difficult to produce microfibrillated cellulose fibers. If the average particle diameter is less than the lower limit, handling may be difficult when CFB is isolated in the production process. From this viewpoint, the average particle diameter (D50) of CFB measured by a wet method is preferably 50 ⁇ m to 1.5 mm, and more preferably 50 ⁇ m to 1 mm.
  • the average particle size varies depending on pH and the like. Therefore, the average particle size and the aspect ratio described later in the present invention are measured using an acidic dispersion having a pH of 6 or less.
  • the aspect ratio (L / D) of CFB is 10 or less, preferably 8 or less.
  • L / D is measured by an arbitrary microscope, for example, a fractionator manufactured by Valmet, a digital microscope (manufactured by Nikon), or a laser microscope (manufactured by Olympus) using a CFB in a dispersion (pH 6 or less) in which CFB is dispersed in water.
  • the long axis is determined as the axis indicating the maximum length in the longitudinal direction of the particle, and the short axis is determined as the axis orthogonal to the long axis and indicating the maximum length (width) in the direction.
  • the water content of CFB can be adjusted by a known drying method. In a high region where the water content exceeds 35% by weight, individual CFBs are hardly charged, and thus have a characteristic that they are hardly powdered. Therefore, in one embodiment, the upper limit of the water content is preferably 85% by weight or less, more preferably 80% by weight or less, further preferably 75% by weight or less, and the lower limit is preferably 40% by weight or more, more preferably It is at least 45% by weight. On the other hand, when the water content is low, the transport efficiency at the time of transport by air blowing, bagging, or the like is improved.
  • the upper limit of the water content is preferably 35% by weight or less, more preferably 30% by weight or less, and the lower limit may be 0% by weight, preferably 1% by weight or more, It is more preferably at least 2% by weight.
  • the water content is measured, for example, using a hot air circulation type constant temperature dryer (manufactured by Tokyo Glass Instruments Co., Ltd.) in accordance with JIS P # 8203.
  • the angle of repose of the CFB of the present invention is measured by the following method using a powder tester (PT-X type, manufactured by Hosokawa Micron Corporation). 1) A sample is dropped and deposited from a hole (diameter ⁇ 5 mm) of a metal funnel onto a horizontal plate having a predetermined area until the sample has a predetermined shape, thereby forming a conical specimen. 2) Measure the angle between the top and the bottom of the conical sample in the Peak @ Operation mode, and obtain the angle of repose.
  • the CFB of the present invention exhibits a repose angle of less than 58 ° at a water content of 50% by weight.
  • the lower limit of the angle of repose is not particularly limited, but is preferably 25.0 ° or more, more preferably 30.0 ° or more, and further preferably 35. 0 ° or more.
  • CFB has a disintegration property of being loosened by self-forming fine cellulose fibers (preferably, MFC described later).
  • CFB is disintegrated in water when the pH of the suspension is made neutral to alkaline after being made into a 2% by weight acidic aqueous suspension, and a dispersion liquid in which fine cellulose fibers are dispersed in water is produced.
  • the pH of the acidic aqueous suspension is preferably about 2 or more and less than 6.5. When the suspension is made neutral to alkaline, the pH is preferably 6.5 or more.
  • Fine cellulose fibers are fibers that collectively refer to cellulose nanofibers having an average fiber diameter of less than 500 nm (hereinafter also referred to as “CNF”) and microfibrillated cellulose having 500 nm or more (hereinafter also referred to as “MFC”).
  • CNF cellulose nanofibers having an average fiber diameter of less than 500 nm
  • MFC microfibrillated cellulose having 500 nm or more
  • the fine cellulose fibers obtained by disintegrating CFB are preferably chemically modified fine cellulose fibers, and more preferably anion-modified fine cellulose fibers.
  • the fine cellulose fibers obtained by disintegrating CFB are preferably MFC. Chemical denaturation, MFC, and CNF will be described later.
  • the ratio of fibers having a diameter of 0.6 mm or less is preferably 15% or more. If the ratio is less than 15%, the fineness of the fibers by beating is insufficient, and the function as fine cellulose is not sufficiently exhibited.
  • the upper limit of the ratio is not limited and is preferably 100% or less. Since the fiber length distribution cannot be measured by directly analyzing CFB, the fiber length distribution measured in this manner may be regarded as the fiber length distribution of the fine cellulose fibers constituting CFB.
  • ba is preferably 0.1 (meq./g) or more.
  • the fine cellulose is a chemically modified cellulose and the difference is within this range, the ratio of the dissociation type among the anionic groups of the chemically modified cellulose is sufficiently high and the terminals of the anionic group are dissociated and the celluloses are electrically connected to each other. CFB is likely to collapse due to repulsion.
  • the upper limit of ba is not limited, but is preferably 1 (meq./g) or less.
  • the charge density is the density of charge per predetermined amount of cellulose fiber.
  • the cation demand is measured by using a particle surface charge amount measuring device (manufactured by MUTEK, Particle Chargedetector PCD03) to calculate the anion charge density. Is measured.
  • CFB may contain other components other than the fine cellulose fiber.
  • Other components include various organic fibers such as chemical fibers, various inorganic pigments, various adhesive components such as starch and latex, various flocculants such as cationic, nonionic and anionic types, dyes, pigments, and fluorescent brighteners. , PH adjusters, defoamers, pitch control agents, slime control agents and the like. Since the CFB of the present invention has a feature that an adhesive or the like is not required in the forming process, the above-mentioned various additive components are added to impart necessary performance according to the use of the CFB. In one embodiment, these components are incorporated into the CFB, and in another embodiment, they are present, for example, by adhering to the surface of the CFB.
  • CFB CFB can be handled as a dispersion liquid containing a dispersion medium, or can be handled as a powder after removing the dispersion medium, so that it has an advantage of being excellent in handling properties and convenient for transportation.
  • a functional CFB can be obtained by adding and manufacturing components for imparting various functions.
  • CFB is a raw material for fine cellulose fibers such as MFC or CNF.
  • CFB dispersions and powders are commonly used in various fields where additives are used, for thickeners, gelling agents, sizing agents, food additives, excipients, paint additives, adhesives.
  • the field includes foods, beverages, cosmetics, pharmaceuticals, papermaking, various chemical supplies, paints, sprays, pesticides, civil engineering, architecture, electronic materials, flame retardants, household goods, adhesives, cleaning agents, fragrances, and lubricating compositions. Objects and the like.
  • the CFB of the present invention can be used as a powder containing CFB by mixing with other particles (for example, non-cellulose fiber aggregates and the like).
  • the content of the other particles in the powder is preferably 10% by weight or less, more preferably 8% by weight or less, and further preferably 5% by weight or less.
  • the lower limit is not limited, but is preferably more than 0% by weight, more preferably 0.5% by weight or more.
  • the fine cellulose fiber refers to a fiber that collectively refers to cellulose nanofibers (CNF) having an average fiber diameter of less than 500 nm and microfibrillated cellulose (MFC) having an average fiber diameter of 500 nm or more.
  • the average fiber diameter is a length-weighted average fiber diameter, and can be measured by observing fine cellulose fibers using, for example, a fractionator manufactured by Valmet, an optical microscope, an electron microscope, or an atomic force microscope (AFM).
  • MFC and CNF differ in the method of measuring the average fiber diameter. Therefore, first, the average fiber diameter of the obtained fine cellulose fibers is subjected to image analysis using a fiber tester manufactured by ABB Co., Ltd.
  • the average fiber diameter is determined by measuring with the above-mentioned fractionator.
  • the average fiber diameter can be measured using AFM.
  • the lower limit of the average fiber diameter of the MFC is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and the upper limit is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the average fiber length of the MFC is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 50 ⁇ m or more.
  • the upper limit is preferably 2.0 mm or less, and more preferably about 1.5 mm or less. In the present invention, the average fiber length is a length-weighted average fiber length.
  • the average fiber diameter of CNF is preferably 100 nm or less, more preferably 50 nm or less.
  • the lower limit is preferably at least 1 nm, more preferably at least 2 nm.
  • the average fiber length of CNF is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the average fiber length of CNF is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the lower limit of the average fiber length is about 0.1 ⁇ m or more.
  • the aspect ratio of the CNF of the present invention is preferably 50 or more.
  • Aspect ratio average fiber length / average fiber diameter
  • the degree of mechanical treatment differs between MFC and cellulose fiber as a raw material.
  • the degree of mechanical treatment can be confirmed by directly observing the fibers.
  • it is generally not easy to quantify the degree of mechanical treatment it is also possible to quantify the degree of change in freeness or water retention or the amount of change in surface area (for example, BET) after mechanical treatment.
  • BET surface area
  • the degree of mechanical treatment can be specified according to the above definition because the degree of freeness of pulp before mechanical treatment is used as a reference, regardless of the degree of chemical modification.
  • the fibrillation ratio of the chemically modified MFC obtained in this manner is preferably 1.0% or more, more preferably 2.5% or more, and more preferably 3.5. % Is more preferable.
  • the fibrillation rate varies depending on the type of pulp, but within the above range, it is considered that the mechanical treatment has been sufficiently performed.
  • the degree of the mechanical treatment can be evaluated not only by the above-mentioned index but also by the absorbance and viscosity characteristics (for example, the relationship between rotation speed and viscosity) of the slurry.
  • CFB is manufactured by a method including the following steps.
  • A2) a step of mechanically treating a mixture containing the chemically modified pulp obtained in the above step and water and having a solid content of 15% by weight or more to form CFB.
  • Step (A1) [Raw pulp]
  • the raw pulp is chemically modified to obtain a chemically modified pulp.
  • raw material pulp softwood unbleached kraft pulp (NUKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), hardwood bleached kraft pulp (LBKP), softwood unbleached sulfite pulp (NUSP), softwood Bleached sulphite pulp (NBSP), hardwood unbleached sulphite pulp (LUSP), hardwood bleached sulphite pulp (LBSP), thermomechanical pulp (TMP), chemishermomechanical pulp (CTMP), pressurized wood pulp (PGW), Refiner groundwood pulp (RGP), alkaline hydrogen peroxide mechanical pulp (APMP), alkaline hydrogen peroxide thermomechanical pulp (APTMP), pulp derived from herbs such as linter, jute, hemp, kozo, mitsumata, kenaf, etc. Pulp from bamboo, recycled pulp,
  • Chemical modification is the introduction of a functional group into the pulp. Chemical modification may be cation modification or anion modification, but is preferably anion modification. That is, the chemically modified pulp preferably has an anionic group.
  • the anionic group include an acid group such as a carboxyl group, a carboxyl group-containing group, a phosphate group, a phosphate group-containing group, and a sulfate group.
  • the carboxyl group-containing group include -COOH group, -R-COOH (R is an alkylene group having 1 to 3 carbon atoms), -OR-COOH (R is an alkylene group having 1 to 3 carbon atoms) Is mentioned.
  • the phosphate group-containing group examples include a polyphosphate group, a phosphite group, a phosphonic acid group, a polyphosphonic acid group, and the like. These acid groups may be introduced in a salt form (for example, a carboxylate group (—COOM, M is a metal atom)) depending on reaction conditions.
  • the chemical modification is particularly preferably oxidation or etherification.
  • the oxidation can be carried out as known.
  • the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized to generate a group selected from the group consisting of an aldehyde group, a carboxyl group, and a carboxylate group.
  • an ozone oxidation method may be used.
  • this oxidation reaction at least the hydroxyl groups at the 2- and 6-positions of the glucopyranose ring constituting cellulose are oxidized, and the cellulose chain is decomposed.
  • the amount of carboxyl groups in the oxidized cellulose thus measured is preferably 0.1 mmol / g or more, more preferably 0.3 mmol / g or more, and further preferably 0.5 mmol / g, based on the absolute dry weight. It is more preferably 0.8 mmol / g or more.
  • the upper limit of the amount is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, and even more preferably 2.0 mmol / g or less.
  • the amount is preferably 0.1 to 3.0 mmol / g, more preferably 0.3 to 2.5 mmol / g, still more preferably 0.5 to 2.5 mmol / g, and 0.8 to 2.0 mmol / g. / G is even more preferred.
  • the method for producing CFB of the present invention may include a step (A1 ′) of acid-treating the chemically modified pulp obtained in the above step.
  • a step (A1 ′) of acid-treating the chemically modified pulp obtained in the above step When the terminal of the anionic group of the chemically modified pulp is dissociated, that is, in the case of dissociation type, the hydrophilicity of the pulp becomes high, and it becomes difficult to increase the concentration of the pulp when subjected to the step (A2). There is. For this reason, it is preferable to provide a step (A1 ′) of performing an acid treatment between the step (A1) and the step (A2).
  • the acid used in this step is not limited, but an inorganic acid such as hydrochloric acid, sulfuric acid and phosphoric acid, and an organic acid such as acetic acid are preferable.
  • the treatment method is not limited, the treatment can be performed by dispersing the chemically modified pulp in a dispersion medium such as water and adding an acid to the dispersion.
  • the pH of the dispersion is preferably adjusted to 2 to 6, more preferably 4 to 5.
  • the solid content of the dispersion is preferably 0.5 to 10% by weight.
  • the acid-treated chemically modified pulp has an anionic group of an acid type instead of an isolated type. For example, when the functional group is a carboxyl group, the carboxyl group of the acid-treated chemically modified pulp is -COOH instead of -COOM (M is a metal ion).
  • Step (A2) the chemically modified pulp is subjected to a mechanical treatment.
  • the mechanical treatment refers to a treatment for imparting a mechanical shear force to the fibers to fibrillate or refine the fibers, and includes beating, defibrating, dispersing, kneading, and the like. Refining means reducing the fiber length, fiber width, etc., and fibrillating means increasing the fluffing of the fibers.
  • the mechanical treatment is preferably performed under acidic conditions (preferably pH 5 or less) in order to maintain the acid form.
  • the mechanical treatment is carried out using a mixture of a chemically modified pulp and a dispersion medium, and the mixture has a solid content of 15% by weight or more.
  • the solid content concentration is the concentration of the solid content in the mixture subjected to the mechanical treatment, and is usually the concentration of the chemically modified pulp.
  • the dispersion medium is not limited as long as the CFB of the present invention can be formed, and an organic solvent or water can be used, but water is preferable. If the concentration is less than 15% by weight, CFB may not be formed due to insufficient shear force applied to the pulp.
  • the mechanical treatment in this step is preferably beating.
  • the apparatus used for the treatment is not particularly limited, and examples thereof include a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, an ultrasonic type and the like, and a high-pressure or ultra-high pressure homogenizer, a refiner, a beater, PFI Mills, kneaders, dispersers, high-speed disintegrators, top-finers, and the like, in which a pulp fiber acts with a metal or a knife around a rotation axis, or a pulp fiber by friction can be used.
  • the mechanical treatment is performed one or more times, but the number is appropriately adjusted in order to achieve a desired CFB particle diameter. Further, as described later, MFC and CNF can be produced using CFB as a raw material. At this time, the number of treatments is adjusted to achieve a desired fibrillation rate.
  • CFB can be formed more efficiently by using an acid-treated chemically modified pulp.
  • This mechanism is not limited, but is presumed as follows. Beating of the chemically modified pulp is usually performed using a mixture of the pulp and water.
  • the acid group such as a carboxyl group
  • a dissociated form such as a salt form (Na salt)
  • it easily swells with water and easily forms a gel.
  • a gel Becomes difficult. Therefore, it is necessary to perform the beating treatment under the condition where the pulp concentration is low.
  • the fibrillation proceeds by the beating process, but it is difficult to form CFB in which a plurality of fibers are entangled.
  • the acid group is not a dissociated type but an acid type, the dispersion liquid does not easily gel, so that the solid content concentration can be increased.
  • the solid content of the mixture is at least 15% by weight, preferably at least 17% by weight, more preferably at least 19% by weight, even more preferably at least 21% by weight. If the solid content is excessively high, the processing efficiency is reduced. Therefore, the upper limit of the solid content is preferably 70% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less.
  • One or more kinds of chemically modified pulp may be used. For example, a chemically modified pulp having a carboxyl group and a chemically modified pulp having a carboxymethyl group may be used in combination.
  • the ratio of the chemically modified pulp to the solid content of the mixture is preferably 30% by weight or more, more preferably 45% by weight or more, and further preferably 50% by weight or more. Components other than the chemically modified pulp in the solid content will be described later.
  • the solid concentration at the start of the mechanical treatment is referred to as the solid concentration in the treatment.
  • Manufacturing method of MFC MFC can be manufactured from CFB. Specifically, the method preferably includes the following steps. (B1) Step of preparing CFB. (B2) a step of treating CFB with an alkali;
  • Step (B1) This step can be performed as described above.
  • Step (B2) CFB is subjected to alkali treatment.
  • the treatment By the treatment, the aggregate formed by entanglement of the chemically modified cellulose fibers is loosened to obtain MFC.
  • the method of the treatment is not limited, the treatment can be performed by dispersing the chemically modified pulp in a dispersion medium such as water and adding an alkali to the dispersion.
  • the pH of the dispersion after the addition of the alkali is preferably adjusted to 6.5 to 14, more preferably 7 to 9.
  • the solid content of the dispersion is preferably 0.5 to 10% by weight.
  • an additional treatment may be performed in addition to the steps B1 and B2 as long as the MFC can be manufactured.
  • an additional mechanical treatment can be performed after the step B2.
  • the additional mechanical processing specifically, the aforementioned mechanical processing can be performed.
  • the mechanism by which the MFC is obtained by this process is not limited, but is presumed as follows.
  • the acid groups of the chemically modified cellulose fibers constituting the CFB are converted into a dissociated type such as a Na salt by an alkali.
  • the acid groups of the chemically modified cellulose fibers are ionized, and repulsion between negative charges occurs. Therefore, it is considered that the fibers are loosened and MFC is formed.
  • the alkali used in this step preferably contains monovalent metal ions from this viewpoint. Examples of the alkali include KOH, NaOH and the like.
  • Method for Producing Cellulose Nanofiber CNF can be produced by subjecting MFC obtained as described above to mechanical treatment. Specifically, the method preferably includes the following steps. (C1) Step of preparing CFB. (C2) A step of obtaining MFC by treating CFB with alkali. (C3) A step of subjecting the MFC to a mechanical treatment.
  • Step (C1), (C2) These steps can be performed as described above.
  • the mechanical treatment here refers to a treatment in which a strong shearing force is applied to the MFC to make it nano-sized to form CNF, and specifically, it is preferably a fibrillation treatment.
  • the apparatus used for the treatment is not limited, and examples thereof include an apparatus of a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, an ultrasonic type, and a type in which pulp fibers are defibrated by cavitation, water flow or water pressure.
  • a device using cavitation or a high-pressure or ultra-high pressure homogenizer is preferable, and a wet high-pressure or ultra-high pressure homogenizer is more preferable.
  • the shear rate is preferably 1000 sec -1 or more. This makes it possible to uniformly form nanofibers with a small aggregate structure.
  • the pressure applied to the chemically modified cellulose is preferably 50 MPa or more, more preferably 100 MPa or more, and further preferably 140 MPa or more.
  • the mechanical treatment here is usually performed using a dispersion in which the MFC is dispersed in a dispersion medium.
  • the dispersion medium is preferably an aqueous dispersion medium such as water.
  • preliminary processing may be performed as necessary.
  • the pretreatment includes, for example, mixing, stirring, and emulsification, and may be performed using a known device (for example, a high-speed shear mixer).
  • the lower limit of the solid content concentration of the MFC in the dispersion is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.3% by weight or more. At this concentration, the amount of liquid to the raw material becomes an appropriate amount, and efficient fibrillation can be performed.
  • the upper limit of the concentration is usually 10% by weight or less, preferably 6% by weight or less. With this concentration, the fluidity of the dispersion can be maintained.
  • the MFC and CNF thus obtained have substituents introduced by chemical denaturation, their functionality and functionality are higher than that of non-chemically denatured fine cellulose fibers which are only micronized by mechanical fibrillation. Excellent in various properties such as water retention. For this reason, the MFC and CNF can be widely used for applications requiring water retention.
  • the MFC and CNF are used in various fields where additives are generally used as in CFB, such as thickeners, gelling agents, sizing agents, food additives, excipients, paint additives, and adhesives.
  • the field includes foods, beverages, cosmetics, pharmaceuticals, papermaking, various chemical supplies, paints, sprays, pesticides, civil engineering, architecture, electronic materials, flame retardants, household goods, adhesives, cleaning agents, fragrances, and lubricating compositions. Objects and the like.
  • Paper The paper of the present invention contains the CFB.
  • CFB may be added to paper internally or externally.
  • the paper contains CFB in the base paper layer, and in the case of external addition, the paper has a CFB-containing layer (preferably a coating layer) on the base paper layer.
  • These papers are suitable as printing paper, information paper, industrial paper, household paper, packaging materials, and the like.
  • the content of CFB in the base paper layer is preferably 0.01 to 20% by weight. Further, the content of CFB in the coating layer is preferably 0.01 to 20% by weight.
  • Paper Production Method It is preferable that the paper into which CFB is added is produced through the following steps.
  • (D1) A step of preparing a slurry containing CFB and pulp.
  • (D2) a step of paper-making the slurry.
  • CFB is prepared as described above.
  • the same pulp as the “raw material pulp” described above can be used.
  • this step can be carried out by mixing a previously prepared pulp slurry with a mixture of CFB and water. Mixing can be performed as known.
  • a slurry can be prepared by mixing both using a known mixer or the like.
  • the concentration of CFB in the slurry is preferably 0.01 to 20% by weight based on the total solid content of pulp and CFB.
  • the upper limit exceeds this value, the dispersion of CFB becomes insufficient, and undispersed substances may be generated in the dispersion, or the viscosity of the dispersion may be too high, and the handleability may be reduced.
  • the upper limit of the concentration is more preferably 10% by weight or less, and the lower limit is preferably 0.1% by weight or more.
  • the B-type viscosity (25 ° C., 60 rpm) of the slurry may be within a range that can be transferred by a pipe or a pump used in a normal papermaking process, and is preferably 600 mPa ⁇ s or less, more preferably 200 mPa ⁇ s or less. Fillers and additives usually used for papermaking can be added to the slurry.
  • Step D2 the slurry is made into paper to obtain paper.
  • Papermaking can be performed as known, for example, using a known paper machine such as a long net wet paper machine, a twin wire paper machine, a Yankee paper machine, a round paper machine, a short net combination machine, and the like. .
  • the paper may be made by hand.
  • CFB usually exists in the base paper layer in a substantially spherical state.
  • the manufacturing method may include a coating step of providing a known clear coating layer or a pigment coating layer on the base paper, or may include a step of surface-treating the paper. These methods can be performed as known. Further, a coating liquid containing CFB can be applied onto the base paper as described later.
  • the paper to which CFB is externally added is preferably manufactured through the following steps.
  • Step E1 This step can be performed as known.
  • the coating liquid containing CFB can be prepared by dispersing CFB in a dispersion medium such as water.
  • the coating liquid may include a binder component, a pigment, and the like.
  • the concentration of CFB in the coating liquid is not limited as long as it can be applied, but is preferably, for example, 0.01 to 20% by weight in the solid content.
  • a coating machine a two-roll size press coater, a gate roll coater, a blade metaling coater, a rod metaling coater, a curtain coater, or the like can be used.
  • base paper may be impregnated with the coating liquid.
  • Example A1 ⁇ Preparation of chemically modified pulp> 5.00 g (absolutely dry) of bleached unbeaten kraft pulp derived from softwood (whiteness 85%, manufactured by Nippon Paper Industries Co., Ltd.) is mixed with 39 mg of TEMPO (manufactured by Sigma Aldrich) (0.05 mmol per 1 g of absolutely dry cellulose). 514 mg of sodium bromide (1.0 mmol per 1 g of absolutely dried cellulose) was added to 500 mL of an aqueous solution, and the mixture was stirred until the pulp was uniformly dispersed.
  • TEMPO manufactured by Sigma Aldrich
  • FIG. 3 shows a photograph of the fiber that has not been beaten.
  • the average particle diameter (D50) of the CFB measured by a wet method using a laser diffraction type particle size analyzer (manufactured by Malvern Panalytical) was 588 ⁇ m.
  • the magnitude of the charge density measured by the method described later was 0.098 meq / g.
  • CFB ⁇ PH adjustment from neutral to alkali>
  • CFB was suspended in water to form a 2% by weight aqueous suspension (pH 4.5) using ion-exchanged water, and then the pH of the suspension was adjusted to 7.5.
  • a dispersion in which the fibers were dispersed in water was obtained.
  • MFC was observed as shown in FIG.
  • the height (longitudinal dimension) of the photograph shown in FIG. 3 corresponds to the actual size of 5.8 mm
  • the width (horizontal dimension) corresponds to the actual size of 7.8 mm.
  • the average fiber length and average fiber diameter of this MFC were measured using a fractionator, and were found to be 0.33 mm and 16.1 ⁇ m.
  • the magnitude of the charge density measured by the method described later was 0.522 meq / g. Table 1 shows the results.
  • Example A1 An attempt was made to produce CFB in the same manner as in Example A1 except that the solid content concentration (pulp concentration) in the refiner treatment was 4% by weight and the treatment time was 7 minutes, but no CFB was produced.
  • the CCD camera photograph of the product and the average fiber length are shown in FIG.
  • the low-concentration mechanical treatment in the 14-inch laboratory refiner was circulated by connecting the tank and the refiner with a pipe, so the degree of treatment was adjusted by the treatment time.
  • Example A2 A mixture of the chemically modified pulp and water obtained in Example A1 was prepared, the pH was adjusted to 7.5, and dehydration and refiner treatment were attempted. However, dehydration could not be performed until the solid content concentration was increased. The beating process could not be performed.
  • the charge density was measured as follows using a particle surface charge amount measuring device (MUTEK, Particle Charge Detector PCD03) and an automatic titrator ([Model Titrino702] Mutek). 1) A sample and ion-exchanged water were mixed to prepare a solution having a sample concentration of 0.01% by weight. 2) 10 mL of the solution was titrated with a cationic polyelectrolyte (Polydimethyl diallyl ammonium chloride, 1 / 1000N) solution, and the consumption to the zero charge point was measured. 3) The charge density (cation required amount) was determined according to the following equation.
  • Example A5 Production of CNF using CFB
  • the CFB obtained in Example 1 was suspended in water to prepare a suspension having a CFB concentration of 1% by weight.
  • An aqueous sodium hydroxide solution was added to the suspension, the pH of the suspension was adjusted from 4.5 to 7.5, and the carboxyl group of CFB was converted to a dissociated type. Thereafter, the suspension was subjected to one-pass treatment with an ultra-high pressure homogenizer to produce CNF.
  • the physical properties of CNF are shown in Table 2, and the AFM observation image is shown in FIG.
  • Example 2 As shown in FIG. 4, it was confirmed that CNF could be produced. Further, as shown in Table 2, the CNF dispersion obtained in Example 2 was a highly transparent gel. The transparency was measured as follows.
  • Example A6 Measurement of L / D Using a nanosearch microscope LEXT OLS4500 (manufactured by Olympus, magnification: 107 times), the slurry after beating obtained in Example 1 was observed. Eleven CFBs are randomly selected from the image, L (the length of the long axis of the CFB) and D (the length of the short axis of the CFB) are visually determined, and the respective lengths are determined using image analysis software. It was measured. In the table, the CFB is described as FB1 to FB11. In addition, four fibers that did not form CFB were randomly selected, and L (fiber length) and D (fiber diameter) were measured. Table 3 shows the results.
  • Example B1 ⁇ Preparation of chemically modified pulp> 5.00 g (absolutely dry) of bleached unbeaten kraft pulp derived from softwood (whiteness 85%, manufactured by Nippon Paper Industries Co., Ltd.) is mixed with 39 mg of TEMPO (manufactured by Sigma Aldrich) (0.05 mmol per 1 g of absolutely dry cellulose). 514 mg of sodium bromide (1.0 mmol per 1 g of absolutely dried cellulose) was added to 500 mL of an aqueous solution, and the mixture was stirred until the pulp was uniformly dispersed.
  • TEMPO manufactured by Sigma Aldrich
  • the average particle size (D50) of the CFB was 200 ⁇ m as determined by wet measurement using a laser diffraction type particle sizer (Malvern, PA).
  • the aspect ratio of the CFB was 1-4.
  • the moisture content of CFB was measured using a hot air circulation type constant temperature dryer (manufactured by Tokyo Glass Instruments Co., Ltd.) according to JIS P # 8203.
  • the water content was 51.9% by weight.
  • a sample is dropped and deposited from a hole (diameter ⁇ 5 mm) of a metal funnel onto a horizontal plate having a constant area until a uniform shape is obtained, and a conical specimen is formed. Was formed. The value of the angle between the top and the bottom of the conical sample was measured in the Peak @ Operation mode, and the angle of repose was determined.
  • Example B2 CFB was obtained and evaluated in the same manner as in Example B1, except that the same chemically modified pulp as in Example A1 was used and the concentration of the treated pulp in the refiner was 25% by weight.
  • Example B3 The CFB obtained in Example B1 was dried by air drying and evaluated.
  • Example B4 The CFB obtained in Example B2 was air-dried and evaluated. Table 5 shows the results.
  • the CFB of the present invention can be handled as a powder while having a high water content.
  • the angle of repose becomes smaller as the particle size becomes smaller and the water content becomes smaller. Therefore, it is clear that the CFB obtained in Examples B1 and B2 exhibits a repose angle of less than 58 ° at a water content of 50% by weight.
  • the cellulose powder of the comparative example has a smaller particle size than the CFB obtained in the present invention, so that the angle of repose should be easy to measure. However, in the region where the water content is 35% or more, the cellulose powder may pass through the powder tester. I could not measure the angle of repose.
  • the CFB obtained by the present invention can measure the angle of repose even in a state where the particle size is large and the water content is high.
  • the angle of repose cannot be measured when the conventional powder has a high water content. Therefore, it is clear that the CFB of the present invention has different physical properties from the conventional powder.
  • Decay angle The impact was applied three times to the horizontal plate on which the specimen for which the angle of repose was determined was placed to collapse the conical specimen, and the angle was determined in the same manner as the angle of repose, and the angle was determined as the collapse angle. Difference angle: The difference between the angle of repose and the angle of collapse was defined as the difference angle.
  • Loose bulk density Using a powder tester, a container of a fixed volume was filled with a specimen by natural fall and weighed to determine the density.
  • Solidified bulk density Using a powder tester, the sample was packed most closely while tapping into a container of a fixed volume, and then weighed to determine the density.
  • Example C1 Production of paper using CFB Sulfuric acid band, cationized starch, CFB, PAM, and retention agent obtained in Example B1 were added to deinked waste paper pulp (manufactured by Nippon Paper Industries) in this order. Then, water was further added to prepare a pulp slurry. The amount was as follows. Deinked waste paper pulp: 96 parts by weight CFB: 4 parts by weight Sulfuric acid band: 0.9% by weight based on the total amount of deinked waste paper pulp and CFB (pulp raw material) Cationized starch: 0.3% by weight based on pulp raw material PAM: 0.06% by weight based on pulp raw material Retention agent: 200 ppm based on pulp raw material
  • Example C2 A handsheet was manufactured and evaluated in the same manner as in Example C1, except that the CFB obtained in Example B2 was used.
  • Example C1 A handsheet was manufactured and evaluated in the same manner as in Example C1 except that CFB was not used. Table 7 shows the results.
  • ⁇ Paper obtained by the production method of the present invention has excellent air resistance, tensile strength, tensile stiffness, and breaking length.

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Abstract

L'invention concerne une boule de fibres cellulosiques, formée par enchevêtrement de fines fibres cellulosiques les unes avec les autres, satisfaisant aux conditions (1)-(3) ci-dessous. (1) Le diamètre moyen des particules (D50) obtenu par une mesure humide à l'aide d'un granulomètre à diffraction laser va de 50 µm à 2 mm. (2) Le rapport d'aspect moyen (L/D) est inférieur ou égal à 10. (3) L'angle de repos pour une teneur en eau de 50 % en poids est inférieur à 58°.
PCT/JP2019/037037 2018-09-20 2019-09-20 Boule de fibres cellulosiques et papier la contenant Ceased WO2020059859A1 (fr)

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WO2023095421A1 (fr) * 2021-11-29 2023-06-01 大王製紙株式会社 Particules de cellulose et dispersion de particules de cellulose
WO2024202688A1 (fr) * 2023-03-29 2024-10-03 日本製紙株式会社 Poudre contenant des nanofibres de cellulose modifiée par des anions
WO2024202689A1 (fr) * 2023-03-29 2024-10-03 日本製紙株式会社 Poudre contenant des nanofibres de cellulose modifiée anionique
WO2024253027A1 (fr) * 2023-06-06 2024-12-12 第一工業製薬株式会社 Feuille de fibres et son procédé de fabrication

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JP7554770B2 (ja) * 2019-12-03 2024-09-20 日本製紙株式会社 変性セルロースマイクロフィブリルの製造方法
JP7574553B2 (ja) * 2020-06-30 2024-10-29 日本製紙株式会社 化学変性ミクロフィブリルセルロース繊維の製造方法
JP7690729B2 (ja) * 2020-10-30 2025-06-11 日本製紙株式会社 化学変性ミクロフィブリルセルロース繊維及びその製造方法
JP7655728B2 (ja) * 2021-01-20 2025-04-02 日本製紙株式会社 化学変性ミクロフィブリルセルロース繊維の製造方法
JP2025088036A (ja) * 2023-11-30 2025-06-11 第一工業製薬株式会社 難燃性材料及び難燃性シート

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WO2023095422A1 (fr) * 2021-11-29 2023-06-01 大王製紙株式会社 Particules de cellulose et dispersion de particules de cellulose
WO2023095421A1 (fr) * 2021-11-29 2023-06-01 大王製紙株式会社 Particules de cellulose et dispersion de particules de cellulose
JP2023079481A (ja) * 2021-11-29 2023-06-08 大王製紙株式会社 セルロース粒子及びセルロース粒子分散液
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JP7461920B2 (ja) 2021-11-29 2024-04-04 大王製紙株式会社 セルロース粒子及びセルロース粒子分散液
WO2024202688A1 (fr) * 2023-03-29 2024-10-03 日本製紙株式会社 Poudre contenant des nanofibres de cellulose modifiée par des anions
WO2024202689A1 (fr) * 2023-03-29 2024-10-03 日本製紙株式会社 Poudre contenant des nanofibres de cellulose modifiée anionique
WO2024253027A1 (fr) * 2023-06-06 2024-12-12 第一工業製薬株式会社 Feuille de fibres et son procédé de fabrication

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