WO2019138588A1 - セルロースナノファイバー及びそれからなるシート状材料、並びにそれらの製造方法 - Google Patents

セルロースナノファイバー及びそれからなるシート状材料、並びにそれらの製造方法 Download PDF

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WO2019138588A1
WO2019138588A1 PCT/JP2018/009537 JP2018009537W WO2019138588A1 WO 2019138588 A1 WO2019138588 A1 WO 2019138588A1 JP 2018009537 W JP2018009537 W JP 2018009537W WO 2019138588 A1 WO2019138588 A1 WO 2019138588A1
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Prior art keywords
bamboo
sheet
cellulose nanofibers
treatment
suspension
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PCT/JP2018/009537
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English (en)
French (fr)
Japanese (ja)
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太郎 衣本
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国立大学法人大分大学
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Priority to CN201880061018.9A priority Critical patent/CN111133146A/zh
Priority to KR1020207007988A priority patent/KR20200088278A/ko
Priority to US16/649,108 priority patent/US20200224365A1/en
Priority to EP18900334.6A priority patent/EP3739118A4/en
Priority to JP2019564277A priority patent/JP7129710B2/ja
Publication of WO2019138588A1 publication Critical patent/WO2019138588A1/ja

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/06—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/007—Modification of pulp properties by mechanical or physical means
    • 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
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/02—Patterned paper

Definitions

  • the present invention relates to cellulose nanofibers, more specifically to cellulose nanofibers obtained from bamboo as a raw material, sheet-like materials comprising the same, and methods for producing them.
  • the invention also relates to the nanofibers obtained by said process, which also contain some amount of lignin, also known as "lignocellulose nanofibers”.
  • plant-based cellulose nanofibers have attracted attention in a wide range of fields such as plastic reinforcements, solar cells, and medicine, and in particular to sheet-like materials produced from them. It has increased.
  • softwood pulp has been mainly used as a raw material of cellulose nanofibers.
  • manufacture of cellulose nanofibers using bamboo as a raw material is also performed.
  • Patent Document 1 discloses a composite material obtained from bamboo-derived cellulose nanofibers and having high tensile strength and tensile modulus and excellent conductivity, and a method for producing the same.
  • Patent Document 2 describes a cellulose nanofiber having a diameter of about 50 nm and a method for producing the same, and bamboo is mentioned as a cellulose material together with various plant materials.
  • Patent Document 3 describes a method of producing fine fibrous cellulose, and as a cellulose raw material, bamboo is also mentioned together with various plant raw materials.
  • Methods of producing cellulose nanofibers include mechanical and chemical methods.
  • cellulose nanofibers are produced by mechanical loosening using softwood or bamboo as a raw material, the degree of crystallinity tends to be low.
  • Industrial products made of bamboo are provided, for example, by Chuetsu Pulp Industry Co., Ltd., and their manufacture is carried out by a mechanical solution method.
  • the known cellulose nanofibers have a purity of at most about 87%, a cellulose crystallinity of at most about 66%, and an aspect ratio of at most about 100. In order to obtain a higher performance sheet-like material, improvement of the properties of cellulose nanofibers is required.
  • An object of the present invention is to provide a cellulose nanofiber capable of providing a sheet material having higher performance, a method of producing the same, and a sheet material obtained from the cellulose nanofiber, in view of the above-mentioned current situation.
  • Another object of the present invention is to provide nanofibers which are obtained by the above-mentioned production method and which contain some amount of lignin and which are also known as "lignocellulose nanofibers".
  • cellulose nanofibers that use bamboo as a raw material instead of softwood pulp
  • the inventors have used both a relatively mild mechanical loosening method (using a mixer) and a multi-step chemical unraveling method.
  • the present inventors have found that cellulose nanofibers having a cellulose purity of 90% or more, a fiber diameter of about 10 to 20 nm, and a crystallinity of 70% or more can be obtained, thereby completing the present invention.
  • the bamboo-derived cellulose nanofiber according to the present invention is characterized by having a cellulose purity of 90% or more, a fiber diameter of 10 to 20 nm, and a crystallinity of 70% or more.
  • the bamboo-derived cellulose nanofiber according to the present invention can be obtained by a production method characterized by including the following steps (1) to (5).
  • a step of producing bamboo fiber by subjecting bamboo to alkali treatment and mechanical treatment (2) Step of delignifying the obtained bamboo fiber (3) mechanically unraveling bamboo fiber subjected to delignification treatment Process (4) Process of removing hemicellulose from unfolded bamboo fiber (5) Process of removing metal component from bamboo fiber after hemicellulose removal
  • the sheet-like material comprising bamboo-derived cellulose nanofibers according to the present invention is characterized by exhibiting a tensile strength of 7 to 200 N at a basis weight of 10 to 210 g / cm 2 . It is also characterized in that it exhibits a tensile strength of 7 to 200 N for a density of 0.3 to 1.1 g / cm 3 .
  • the sheet-like material comprising bamboo-derived cellulose nanofibers according to the present invention can be obtained by the production method of sheet-forming bamboo-derived cellulose nanofibers according to the present invention.
  • Sheeting can be performed by a method of removing the dispersion medium from the suspension of cellulose nanofibers. Natural drying, hot pressing, or lyophilization can be mentioned as an example of the method of removing the dispersion medium.
  • the dispersion medium water and an organic solvent can be used, and an alcohol can be mentioned as an example of the organic solvent.
  • cellulose nanofibers In the case of hot pressing, preferably (A) preparing a suspension of bamboo-derived cellulose nanofibers dispersed in water; (B) removing water from the suspension to recover the residue; (C) subjecting the recovered residue to hot pressing to obtain a sheet-like material,
  • the cellulose nanofibers can be sheeted by
  • the cellulose nanofibers may be recovered from the suspension (a), and another suspension obtained by dispersing the recovered cellulose nanofibers in alcohol may be hot-pressed to obtain a sheet-like material.
  • cellulose nanofibers preferably (A) preparing a suspension of cellulose nanofibers dispersed in alcohol, (B) spreading the suspension on a substrate to form a film; (C) subjecting the film-like suspension to a freeze-drying treatment to obtain a sheet-like material,
  • the cellulose nanofibers can be sheeted by
  • the lignocellulosic nanofibers derived from bamboo according to the present invention have a lignin content of about 1 to 2 wt%, and the delignification treatment in the step (2) of the method for producing cellulose nanofibers derived from bamboo described above is It is obtained by stopping when lignin content is obtained.
  • bamboo-derived lignocellulose nanofibers according to the present invention are more useful composite materials than composite materials using high purity cellulose nanofibers whose lignin content is further reduced by mixing with a resin (for example, automobile It can be expected that it can be used as a composite material for applications and home appliances.
  • bamboo-derived cellulose nanofibers As the raw material. According to the present invention, by using a combination of a relatively mild mechanical unwinding method (using a mixer) and a multi-step chemical unwinding method, cellulose nanofiber production exhibiting improved properties over the prior art can do.
  • the method for producing bamboo-derived cellulose nanofibers according to the present invention includes the following steps (1) to (5).
  • a step of producing bamboo fiber by subjecting bamboo to alkali treatment and mechanical treatment (2) Step of delignifying the obtained bamboo fiber (3) mechanically unraveling bamboo fiber subjected to delignification treatment Process (4) Process of removing hemicellulose from unfolded bamboo fiber (5) Process of removing metal component from bamboo fiber after hemicellulose removal
  • bamboo fibers are produced from bamboo using alkali treatment and mechanical treatment.
  • the bamboo material used in the present invention is not particularly limited, and for example, a plant containing so-called bamboo fibers such as jinso bamboo, bamboo bamboo, black bamboo, bamboo bamboo and the like can be used.
  • inner and outer shells of bamboo In order to improve the effect of the alkali treatment and the purity of the obtained fiber, it is preferable to remove the inner and outer shells of bamboo in advance. More preferably, in order to make the diameter of the produced fiber uniform, inner and outer skin removal is performed such that only the portion where the fiber bundle of bamboo material used is uniform remains.
  • the bamboo material be loosened by pressure rolling (squeezing treatment) with, for example, a pinch roll having a peripheral speed difference in advance, prior to the subsequent treatment with an aqueous alkaline solution.
  • pressure rolling squeeze treatment
  • a pinch roll having a peripheral speed difference in advance
  • This makes it possible to increase the penetration rate of the alkaline aqueous solution and to make the penetration uniform, thereby enhancing the separation and removal efficiency of lignin and hemicellulose in the subsequent alkali treatment.
  • the bamboo material when the bamboo material is dried during the treatment using an alkaline aqueous solution, the treatment effect is reduced, so the bamboo material may be stored in a liquid without being dried until the start of the treatment, or it may be stored frozen or refrigerated Is preferred. More preferably, in order to suppress the growth of various bacteria, it is immersed in an effective liquid such as an aqueous solution of hydrogen peroxide, perchloric acid, sulfuric acid and the like, and kept refrigerated. It is most preferable to use hydrogen peroxide in terms of safety and waste.
  • the bamboo material to which the alkali treatment is applied is appropriately cut and used according to the volume of the treatment container.
  • a bamboo material cut into chips of about 1 to 10 cm in length.
  • the alkali treatment can be performed, for example, by immersing bamboo in an aqueous alkaline solution such as sodium hydroxide, sodium hydrogencarbonate or potassium hydroxide.
  • an aqueous solution of sodium hydroxide is used, the concentration of the aqueous solution is preferably 0.01 to 1.00 M, more preferably 0.10 to 1.00 M, and still more preferably 0.10 to 0.50 M, from the viewpoint of efficiency.
  • the treatment temperature is preferably 30 to 200 ° C., more preferably 50 to 150 ° C., and still more preferably 100 to 150 ° C.
  • the processing pressure is preferably 101 to 500 kPa, and preferably 101 to 200 kPa.
  • the treatment time is preferably 1 to 3 hours, more preferably 3 hours.
  • the alkali-treated bamboo pieces are removed from the aqueous alkali solution and washed with water. Washing with water continues until the water after washing becomes neutral.
  • the pieces of bamboo are then processed mechanically in order to obtain bamboo fibres.
  • This process can be performed using a common mixer and stirring bamboo pieces with water at room temperature.
  • the type of mixer used is not particularly limited as long as bamboo pieces can be disassembled into fibers. Further, the processing conditions may be appropriately set so as to obtain a predetermined processing effect. After treatment, it is dried to obtain bamboo fiber.
  • the delignification treatment step (2) can be carried out by bringing the bamboo fiber obtained in the step (1) into contact with the delignification treatment solution.
  • the delignification treatment solution a solution of peracetic acid, chlorous acid, sodium sulfite, sulfuric acid, ozone, enzymes, microorganisms (bacteria) and the like can be used.
  • bamboo fibers are dispersed in a delignification treatment solution and allowed to stand, and then separated from the treatment solution, followed by washing and drying to obtain a bamboo fiber subjected to delignification treatment.
  • the delignification treatment solution can be carried out, for example, at a temperature of about room temperature to about 220 ° C., preferably about 60 to 100 ° C.
  • the standing time is preferably 1 to 8 hours, more preferably 1 to 6 hours, and still more preferably 3 to 6 hours.
  • the bamboo-derived lignocellulose nanofibers according to the present invention having a lignin content of about 1 to 2 wt% have the lignin content of the bamboo fibers in the delignification treatment solution in this delignification treatment step (2) It is obtained by stopping when the amount is obtained.
  • the standing here may be, for example, about 0.5 to 2 hours, or about 0.5 to 1.5 hours when left at 80 ° C. using peracetic acid as described above. Except for the standing time in step (2), the bamboo-derived lignocellulose nanofibers of the present invention can be produced by the same method as the production of bamboo-derived cellulose nanofibers of the present invention.
  • the mechanical loosening step (3) of the delignified bamboo fiber can be performed by stirring the bamboo fiber with water with a mixer.
  • the type of mixer is not particularly limited as long as unwinding by stirring is performed without any problem.
  • the amount of water is preferably about 10 to 1000 times, more preferably about 100 to 500 times, and still more preferably about 100 to 150 times the mass of bamboo fiber.
  • the stirring treatment is preferably performed at a temperature of about 5 to 60 ° C., and more preferably about 5 to 40 ° C.
  • the operating conditions of the mixer may be set appropriately so as to obtain a predetermined unwinding effect.
  • the step (4) of removing hemicellulose from the unfolded bamboo fiber can be carried out by alkali treatment of the unfolded bamboo fiber.
  • the alkali treatment can be carried out by immersing the unfolded bamboo fiber in an aqueous alkali solution.
  • an aqueous alkali solution an aqueous solution of potassium hydroxide can be used, and in addition, an aqueous sodium hydroxide solution or the like can also be used.
  • an aqueous solution of about 0.5 to 5.0 M, preferably about 1.0 to 2.0 M of KOH aqueous solution is used in an amount of about 50 to 500 ml, preferably 200 It can be used up to about 500 ml.
  • the immersion can be performed at about 20 to 100 ° C.
  • the immersion time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and still more preferably 1 to 8 hours.
  • the step (5) of removing metal components from bamboo fiber after hemicellulose removal can be carried out by acid treatment of bamboo fiber from which hemicellulose has been removed.
  • the acid treatment can be carried out by bringing bamboo fiber into contact with an acid solution and shaking for a predetermined time.
  • an aqueous solution of hydrochloric acid, perchloric acid, sulfuric acid, nitric acid or the like can be used.
  • the concentration of the solution is preferably about 0.001 to 1.0 M, more preferably 0.01 to 1.0 M, and still more preferably 0.01 to 0.1 M.
  • the contact time is preferably 1 to 24 hours, more preferably 3 to 24 hours, still more preferably 1 to 12 hours.
  • This treatment can be carried out at room temperature (about 20 to 30 ° C.).
  • the amount of lignin in bamboo fiber can be measured, for example, by the sulfuric acid method (Japanese Wood Research Society, Wood Science Experiment Manual, pp. 96-97, Bun-ei-do (2010)) (see Examples described later).
  • the hemicellulose content of bamboo fiber can be measured based on the mass of bamboo fiber before and after hemicellulose removal (see Examples described later).
  • the characteristics of bamboo-derived cellulose nanofibers produced by the method of the present invention are that the cellulose purity is 90% or more, the fiber diameter is 10 to 20 nm, and the crystallinity is 70% or more.
  • the cellulose purity and crystallinity of the cellulose nanofibers of the present invention are much higher than those of conventional cellulose nanofibers (about 87% at the maximum) and crystallinity (about 66% at the maximum).
  • the sheet-like material according to the present invention can be obtained by forming the bamboo-derived cellulose nanofibers according to the present invention into a sheet. Sheeting can be performed, for example, using a hot press or using lyophilization. It is also possible to use natural drying.
  • Sheeting by hot pressing can be preferably performed using a suspension obtained by stirring a liquid to be treated to which cellulose nanofibers after removal of metal components are added to water. Water remaining in the dispersion medium is removed from the suspension, and the recovered residue is processed with a hot press into a sheet without drying, and a sheet-like material comprising cellulose nanofibers according to the present invention can be obtained.
  • the residue obtained by removing the water from the suspension may be re-dispersed in a dispersion medium of an alcohol such as ethanol.
  • a dispersion medium such as ethanol
  • the dispersion medium is water
  • aggregation of the fibers is observed in the obtained sheet-like material
  • disintegration of the fibers occurs by alcohol solvation between the cellulose molecules. Is recognized.
  • Sheeting by lyophilization can be preferably performed using a suspension containing an organic solvent (for example, alcohol) as a dispersion medium.
  • the suspension can be spread on a predetermined substrate to form a film, frozen, and subjected to a freeze-drying treatment to obtain a sheet-like material comprising cellulose nanofibers according to the present invention.
  • the dispersion medium is alcohol, ethanol, butanol or the like can be used.
  • the organic solvent other than alcohol ketones (eg, acetone), aromatic compounds (eg, toluene), carboxylic acids (eg, acetic acid), amines (eg, N, N-dimethylformamide), acetonitrile and the like can be used.
  • Coagulation of the fibers is suppressed by sublimation of the dispersion medium (such as alcohol) by lyophilization.
  • the dispersion medium such as alcohol
  • only one type for example, ethanol
  • a mixture of two or more types may be used, or two or more types may be sequentially used (for example, after temporarily recovering bamboo fiber from a suspension of ethanol) , Making a sheet-like material from a suspension in which it is redispersed in butanol). The latter case is advantageous in suppressing aggregation of the cellulose nanofibers.
  • stirring to obtain the suspension can be carried out, for example, using a common mixer or by means of ultrasound.
  • the content of cellulose nanofibers in the suspension may generally be 0.1 to 10 wt%, more preferably 0.1 to 2.0 wt%, and still more preferably 0.1 to 1.0 wt%.
  • the stirring conditions are not particularly limited as long as a suspension in which the cellulose nanofibers are sufficiently dispersed can be obtained. Any treatment such as filtration can be used to remove the dispersion medium water or alcohol.
  • the dispersion medium may be water or an organic solvent such as alcohol. In some cases, the removal of the dispersion medium can be promoted by ventilation or the like.
  • the sheet-like material produced from the bamboo-derived cellulose nanofiber according to the present invention exhibits improved strength when measured under the same conditions as compared to the sheet-like material produced from conventional cellulose nanofibers.
  • Cellulose for example, when comparing the tensile strength for the basis weight of 200 g / m 2 (mass per sheet material 1 m 2), tensile strength of the sheet material according to the present invention whereas about 200 N, were obtained from Daicel Finechem Corporation
  • the tensile strengths of the sheet material produced from the fiber FD100G and the commercial paper obtained from Mondi (ISO 9707-obtained paper) are about 100 N and 145 N, respectively.
  • the sheet-like material made of bamboo-derived cellulose nanofibers according to the present invention exhibiting such high tensile strength can be expected to be used in the fields of reinforcement, acoustics, medicine, food, packaging materials, transportation and the like.
  • the temperature of the water bath (EYELA, SB-350) is 80
  • the vessel was set in a low-temperature water bath (EYELA, NCB-1200) set at o C, and allowed to stand for 1, 3, 6 or 8 hours while refluxing. Thereafter, it was allowed to cool, and suction filtration was performed using a plastic filter (ADVANTEC, KP-47H and KP-47S). The residue was washed with ultrapure water until neutral and then dried for 12 hours with a drier maintained at 60 ° C. to obtain a delignified bamboo fiber.
  • the content of lignin and the extraction ratio with respect to the treatment time with peracetic acid are shown in Table 1, and the graph is shown in FIG.
  • bamboo fibers (containing about 1 wt% residual lignin) obtained after about 1 hour of treatment
  • the process can be continued according to the procedure described below.
  • hemicellulose According to the reference, ⁇ -cellulose and ⁇ -cellulose and hemicellulose are classified as hemicellulose, and others are classified as ⁇ -cellulose (Japan Wood Research Society, Wood Science Experiment Manual, pp. 95, Bungeidou Press (2010) )reference). In the present invention, according to that, hemicellulose was measured using a method for quantifying ⁇ -cellulose (see Japan Wood Research Society, Wood Science Experiment Manual, pp 96-97, Bun-ei-do (2010)). Thus, the hemicellulose here also includes beta and gamma cellulose.
  • the hemicellulose content and extraction rate of bamboo fiber after peracetic acid treatment are shown in Table 2, and the graph is shown in FIG.
  • the peracetic acid treatment did not significantly reduce the hemicellulose content. In addition, there was no significant difference depending on the processing time.
  • the concentration of KOH aqueous solution is fixed at 1.18 M, and the amount of solution is changed to 100 or 200 mL. 4 and the relationship between the solution amount and the hemicellulose content and extraction rate is shown in FIG. From these results, it was found that in this example, the largest amount of hemicellulose was extracted when 200 mL of 1.18 M KOH aqueous solution was used for 5 g of bamboo fiber.
  • ⁇ -cellulose content in the product treated under the most appropriate conditions is around 93%.
  • 200 mL of the washing solution obtained in the above 5 is added to 10 mL of a 30% aqueous acetic acid solution, heated to 80 ° C., and kept warm for 9 hours I left it.
  • the obtained precipitate was collected by a filter paper which was weighed in advance, and the mass increase after drying was taken as the ⁇ -cellulose content (The Japan Wood Research Society, Wood Science Experiment Manual, pp 96, Bun Eido Press (2010) reference).
  • FIGS. 6 (a) to 10 (a) FE-SEM image
  • FIGS. 6 (b) to 10 (b) fiber distribution map
  • the fiber diameter was 15.9 nm on average after 8 hours. Generally, since the diameter of cellulose nanofibers contained in wood and the like is several nm, the diameter is slightly larger than that. The reason for this is that it is essential for the observation material to be completely dried in the observation by FE-SEM, which may be due to the association by the hydrogen bond between the cellulose molecules at the time of the drying.
  • FIG. 11 (a) FE-SEM image
  • FIG. 11 (b) fiber distribution map
  • FT-IR Fourier transform infrared spectrometer
  • the bamboo fiber (bamboo fiber from which lignin was removed) obtained from the above 2 was brought into contact with a hydrochloric acid aqueous solution to remove the metal component.
  • a hydrochloric acid aqueous solution In a plastic sample tube, 1 g of bamboo fiber and 50 mL of a 0.01 M hydrochloric acid aqueous solution were placed. From the sample tube, the solution was immediately removed leaving bamboo fiber to obtain a "pre-treatment" solution. After adding 50 mL of a new hydrochloric acid aqueous solution to the sample tube and continuing shaking for 24 hours, the solution was taken out immediately, leaving bamboo fibers, to obtain a “post-treatment” solution.
  • bamboo is mainly rich in silica (silicon oxide), calcium, potassium, magnesium and sodium as an inorganic substance.
  • the bamboo fiber according to the present invention analyzed here was confirmed to contain potassium and zinc, but other than these, it was a very small amount close to 0%. According to the present invention, it was revealed that metals can be removed by immersing them in hydrochloric acid for 24 hours, and the content can be reduced to about 0.06% with respect to the mass of the obtained cellulose nanofibers.
  • the prepared sheet is ultrasonically dispersed in 1-butanol, dropped onto a grid for TEM (Sek 150, STEM 150 Cu grid), dried in a dryer at 100 ° C., and then the sheet form is transmitted. Observation was performed with an electron microscope (TEM (JEOL, JEM-2100).
  • FIG. 13 (a) A TEM image of a cellulose nanofiber sheet prepared by hot pressing using water as a dispersion medium is shown in FIG. 13 (a), an appearance photograph and an FE-SEM image are shown in FIG. 13 (b). Those of the sheets are shown in FIGS. 14 (a) and 14 (b).
  • the dispersion medium When the dispersion medium is water, it is confirmed that fibers are aggregated, which is considered to be due to strong hydrogen bonding between cellulose molecules. When the dispersion medium was changed to ethanol, it was confirmed that the fibers were slightly dispersed, which is considered to be because ethanol entered between cellulose molecules and was disintegrated by solvation.
  • FIG. 15 (a) The TEM image of the cellulose nanofiber sheet produced by lyophilization is shown in FIG. 15 (a), the appearance photograph and the FE-SEM image are shown in FIG. 15 (b).
  • the sheet Figs. 13 (a) and (b) and Figs. 14 (a) and 14 (b)
  • the XRD patterns of three samples of cellulose nanofiber sheet obtained from three samples are shown in FIGS.
  • the crystallinity of cellulose calculated from these peak intensities is shown in Table 14. The degree of crystallinity was 71 to 77% regardless of the dispersion medium.
  • the BET surface area of the obtained cellulose nanofiber sheet was measured by using a nitrogen gas adsorption / desorption device (AUTOSARB-3, manufactured by Yuasa Ionics Co., Ltd.).
  • An adsorption / desorption isotherm was obtained by adsorbing nitrogen (purity 99.9%) at 77 K to the sheet in the cell and measuring the adsorption amount and the pressure in the cell.
  • the BET surface area was calculated by analyzing the obtained adsorption and desorption isotherm by the BET method.
  • the sample was deaerated by applying a vacuum at 200 ° C. for 24 hours before measurement.
  • the measured gas adsorption / desorption isotherm is shown in FIG. 19, and its BET surface area is shown in Table 15.
  • FIG. 20 sheet produced by hot press using dispersion medium as water
  • FIG. 21 sheet produced by hot press using dispersion medium as ethanol
  • FIG. Sheet the pore size distribution of the sheet is shown in FIG. 20 (sheet produced by hot press using dispersion medium as water), FIG. 21 (sheet produced by hot press using dispersion medium as ethanol), and FIG. Sheet).
  • the dispersion medium was water, and the tensile strength of a cellulose nanofiber sheet produced using a hot press was measured. Cut the prepared sheet into a strip 1.5 cm wide and 2.5 cm long, grasp the top and bottom about 5 mm, and use a bench-type precision universal testing machine (SHIMADZU, AGS-J) at a tension speed of 1 mm / min. Measurements were taken. In addition, as a comparison, a sheet formed by using a hot press from cellulose nanofibers for food (Celish (trademark)) manufactured by Daicel Finechem Co., Ltd. and a commercially available paper manufactured by Mondi (ISO 9707 acquired paper, residual amount of low lignin) are the same. It measured.
  • the bamboo-derived cellulose nanofiber sheet according to the present invention showed the largest strength. This is thought to be because the bamboo-derived cellulose nanofibers according to the present invention are thinner than other fibers, so the amount of fibers per mass is large and the points at which hydrogen bonds between fibers are increased, thereby increasing the strength.
  • an FE-SEM image and a fiber diameter distribution obtained from a sheet of bamboo-derived cellulose nanofiber according to the present invention and a sheet made of Celish (trademark), which is similarly a cellulose nanofiber (FIG. 28) (a) and (b)) it can be confirmed that the fiber of the former is thinner.

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PCT/JP2018/009537 2018-01-10 2018-03-12 セルロースナノファイバー及びそれからなるシート状材料、並びにそれらの製造方法 WO2019138588A1 (ja)

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CN201880061018.9A CN111133146A (zh) 2018-01-10 2018-03-12 纤维素纳米纤维及由其形成的片状材料、以及它们的制造方法
KR1020207007988A KR20200088278A (ko) 2018-01-10 2018-03-12 셀룰로오스 나노화이버 및 그것으로 구성된 시트상 재료, 및 그들의 제조 방법
US16/649,108 US20200224365A1 (en) 2018-01-10 2018-03-12 Cellulose nanofiber, sheet-like material obtained therefrom, and method for producing cellulose nanofiber and sheet-like material
EP18900334.6A EP3739118A4 (en) 2018-01-10 2018-03-12 CELLULOSIC NANOFIBER, LEAF-SHAPED MATERIAL PRODUCED THEREOF, AND METHOD FOR MANUFACTURING CELLULOSIC NANOFIBER AND LEAF-SHAPED MATERIAL
JP2019564277A JP7129710B2 (ja) 2018-01-10 2018-03-12 セルロースナノファイバー及びそれからなるシート状材料、並びにそれらの製造方法

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EP4139254A4 (en) * 2020-04-21 2024-03-27 Univ Maryland EVAPORATION DEVICES WITH DELIGNIFIED PLANT MATERIALS AND SYSTEMS AND METHODS FOR THE PRODUCTION AND USE THEREOF

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EP3954813A4 (en) * 2019-04-10 2022-11-30 Rinnovation Co., Ltd. PAPER YARN, PAPER CLOTH AND CLOTH-LIKE PRODUCT
CN112982028B (zh) * 2021-03-15 2022-06-07 浙江理工大学 一种可生物降解疏水防油纸的制备方法
CN115142263B (zh) * 2021-03-30 2023-07-04 赣南师范大学 阳离子竹纤维素纳米纤维及其制备方法
WO2023235269A1 (en) * 2022-05-31 2023-12-07 University Of Washington Producing nanofibers, microfibers, and lignin from lignocellulosic biomass
KR102535872B1 (ko) * 2023-01-18 2023-05-26 하민우 보온 성능이 우수한 기능성 시트 제조방법

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Publication number Priority date Publication date Assignee Title
EP4139254A4 (en) * 2020-04-21 2024-03-27 Univ Maryland EVAPORATION DEVICES WITH DELIGNIFIED PLANT MATERIALS AND SYSTEMS AND METHODS FOR THE PRODUCTION AND USE THEREOF
WO2023162263A1 (ja) * 2022-02-28 2023-08-31 株式会社ダイセル 多糖類ナノシート及びその製造方法

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CN111133146A (zh) 2020-05-08
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KR20200088278A (ko) 2020-07-22
US20200224365A1 (en) 2020-07-16
JPWO2019138588A1 (ja) 2020-11-19
EP3739118A1 (en) 2020-11-18

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