WO2012043103A1 - Nanofibre cellulosique - Google Patents

Nanofibre cellulosique Download PDF

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Publication number
WO2012043103A1
WO2012043103A1 PCT/JP2011/069257 JP2011069257W WO2012043103A1 WO 2012043103 A1 WO2012043103 A1 WO 2012043103A1 JP 2011069257 W JP2011069257 W JP 2011069257W WO 2012043103 A1 WO2012043103 A1 WO 2012043103A1
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cellulose
raw material
cellulose nanofiber
oxidized
dispersion
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PCT/JP2011/069257
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English (en)
Japanese (ja)
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宮脇　正一
志穂 勝川
裕 阿部
知章 小柳
茶谷　明伸
武史 中山
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日本製紙株式会社
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • 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
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper

Definitions

  • the present invention relates to a cellulose nanofiber.
  • Cellulose nanofibers are fibers having a nano-level fiber diameter of about 1 to 100 nm obtained by oxidizing cellulose fibers in the presence of an N-oxyl compound or the like (for example, Patent Document 1: Japanese Patent Application Laid-Open No. 2008-1728). . In recent years, various studies have been conducted on cellulose nanofibers.
  • Patent Document 2 Japanese Patent Laid-Open No. 2009-298972
  • cellulose fibers are oxidized in the presence of 2,2,6,6, -tetramethyl-1-piperidine-N-oxyl (TEMPO), which is an N-oxyl compound. Thereafter, a method is described in which the product is treated with a mixer and further treated with cellulase. The film obtained from the cellulose nanofibers thus obtained is considered to have a high oxygen barrier property.
  • TEMPO 2,2,6,6, -tetramethyl-1-piperidine-N-oxyl
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2010-125814 describes a laminate including a first layer and a second layer containing cellulose nanofibers. When the crystallinity of the cellulose nanofiber is 50% or more, the oxygen barrier property of the laminate is improved.
  • materials such as a film made of cellulose nanofibers and a laminate including cellulose nanofibers are considered to have oxygen barrier properties.
  • conventional cellulose nanofibers have not obtained a film or laminate having a sufficient oxygen barrier property, and it has been desired to develop a cellulose nanofiber that can provide a film having a better oxygen barrier property.
  • paper with higher gloss such as inkjet recording paper
  • the inventors conducted preliminary studies on paper containing cellulose nanofibers and found that such paper may have high gloss. However, sufficient glossiness has not been obtained yet.
  • an object of the present invention is to provide a cellulose nanofiber that provides a film or laminate having excellent oxygen barrier properties, or paper having excellent gloss.
  • the inventors have focused on the crystallinity, the degree of polymerization, and the fiber diameter of cellulose nanofibers, found that these problems can be solved by cellulose nanofibers in a specific range, and completed the present invention. That is, the said subject is solved by the following this invention.
  • a paper coating material comprising a pigment and the cellulose nanofiber.
  • a barrier material obtained by applying the dispersion to a substrate.
  • cellulose nanofibers can be provided that give a film or laminate having excellent oxygen barrier properties, or paper having excellent gloss.
  • Cellulose nanofibers are cellulose single microfibrils having a diameter of 1 to 100 nm, which are obtained by defibrating cellulose-based raw materials.
  • Cellulose-based raw materials are kraft pulp or sulfite pulp derived from various woods, powdered cellulose obtained by pulverizing them with a high-pressure homogenizer or a mill, or microcrystalline cellulose powder obtained by purifying them by chemical treatment such as acid hydrolysis.
  • Cellulose-based materials include powdered cellulose and microcrystalline cellulose powder obtained from plants such as kenaf, hemp, rice, bagasse and bamboo. Among them, it is preferable to use bleached kraft pulp, bleached sulfite pulp, powdered cellulose, and microcrystalline cellulose powder as a cellulose-based raw material because cellulose nanofibers that give a dispersion having a relatively low viscosity can be obtained.
  • a dispersion is a liquid in which cellulose nanofibers are dispersed in a dispersion medium.
  • a dispersion in which the dispersion medium is water is also referred to as an aqueous dispersion in the present invention.
  • the cellulose nanofiber dispersion is useful as a raw material for membranes and the like, and a dispersion having a relatively low viscosity is excellent in film-forming properties.
  • the cellulose nanofiber of the present invention has a crystallinity of 70% or more. Since cellulose nanofibers have an amorphous part and a crystalline part, the crystallinity is the ratio of the crystalline part in the whole cellulose nanofiber. In the present invention, the crystallinity is measured by X-ray diffraction.
  • the crystallinity of the cellulose nanofiber is high, a film having a dense structure can be formed, so that a film having a high oxygen barrier property can be obtained.
  • the crystallinity of the cellulose nanofiber is 70% or more, preferably 80% or more, and more preferably 85% or more.
  • the upper limit of crystallinity is preferably 95% or less, and more preferably 90% or less.
  • the crystallinity is obtained by using a cellulose-based raw material having a high crystallinity, or treating wood pulp or microcrystalline cellulose obtained by acid hydrolysis with an oxidizing agent such as ozone, ultraviolet rays, or cellulase, or dry pulverizing. Can be adjusted.
  • an oxidizing agent such as ozone, ultraviolet rays, or cellulase, or dry pulverizing.
  • the degree of polymerization by a viscosity method using a copper ethylenediamine solution of the cellulose nanofiber of the present invention is 160 or less.
  • the degree of polymerization is the number of linkages of “two molecules of ⁇ -glucose” which is the minimum constitutional unit of cellulose.
  • the degree of polymerization is determined by the viscosity method using the following copper ethylenediamine solution.
  • c is the cellulose nanofiber concentration (g / dL)
  • A is a value determined by the type of the solution 1.
  • A is 0.28.
  • K and a are values determined by the type of polymer. In the case of cellulose, K is 5.7 ⁇ 10 ⁇ 3 and a is 1.
  • the viscometer is preferably a capillary viscometer, examples of which include a Canon-Fenske viscometer.
  • the viscosity average degree of polymerization of cellulose nanofiber affects the viscosity of the dispersion.
  • the degree of polymerization is high, the entanglement between fibers increases and the viscosity of the dispersion increases.
  • the viscosity of the dispersion liquid is high, the fluidity is not sufficient when the base material is applied or impregnated, and the density of the fibers is uneven in the film made of cellulose nanofibers. Since the oxygen barrier property is lowered at a portion where the fiber concentration is low, the oxygen barrier property of the resulting film or laminate is also lowered. In addition, when the fiber concentration is uneven, the smoothness of the film surface is lowered, so that the glossiness when paper containing cellulose nanofibers is also lowered.
  • the polymerization degree of the cellulose nanofiber of the present invention is 160 or less, preferably 140 or less, and more preferably 110 or less.
  • the degree of polymerization of cellulose nanofibers is too low, the strength of the resulting film and the like may be reduced. For this reason, 80 or more are preferable and, as for the minimum of the polymerization degree of a cellulose nanofiber, 100 or more are more preferable.
  • the degree of polymerization can be adjusted by using a cellulose-based raw material having a desired degree of polymerization, or by a lower viscosity process described later.
  • the fiber diameter of the cellulose nanofiber of this invention is 50 nm or less. Since the fiber diameter is related to the denseness of the film when it is made into a film and the smoothness of the surface, it affects the oxygen barrier properties and the glossiness when made into paper.
  • the upper limit of the fiber diameter may be 50 nm, but 40 nm or less is preferable and 30 nm or less is more preferable in order to improve the oxygen barrier property when the film is formed.
  • the lower limit is preferably 2 nm, and more preferably 10 nm.
  • the fiber diameter can be determined from an electron microscope image or an atomic force microscope image of cellulose nanofiber. As will be described later, the fiber diameter can be adjusted mainly by the atomization step in cellulose nanofiber production.
  • the primary hydroxyl group at the 6-position in the pyranose ring of cellulose is oxidized to a carboxyl group or a salt thereof.
  • a pyranose ring is a six-membered ring carbohydrate consisting of five carbons and one oxygen.
  • the 6-position primary hydroxyl group is an OH group bonded to a 6-membered ring via a methylene group.
  • Natural cellulose is a nanofiber when it is biosynthesized, but it is not a nanofiber because hydrogen bonds are mainly formed on the surface of the nanofiber when they converge to form large units.
  • the primary hydroxyl group at the C6 position of the pyranose ring is selectively oxidized, and this oxidation reaction remains on the surface of the microfibril.
  • Carboxyl groups are introduced at a high concentration. Since the carboxyl groups are negatively charged, they repel each other, and when dispersed in water, the aggregation of microfibrils is hindered, resulting in cellulose nanofibers.
  • the carboxyl group may form a salt with an alkali metal or the like.
  • the amount of the carboxyl group and its salt (hereinafter collectively referred to as “carboxyl group and the like”) is preferably 1.10 mmol / g or more based on the dry mass of the cellulose nanofiber. Since the carboxyl group or the like is a polar group, when the amount is large, the cellulose nanofibers are more likely to be firmly adhered to each other when formed into a film or a laminate, thereby improving the oxygen barrier property. Furthermore, since the cellulose nanofibers are firmly adhered to each other to form a smooth film, the gloss when made into paper is also improved.
  • the lower limit of this amount is more preferably 1.20 mmol / g or more, and further preferably 1.40 mmol / g or more.
  • the upper limit of the amount of carboxyl groups and the like is preferably 1.70 mmol / g or less, and more preferably 1.60 mmol / g or less.
  • the amount of carboxyl groups and the like is measured from the change in electrical conductivity as follows. An aqueous dispersion of about 0.5% by mass cellulose nanofibers is prepared, 0.1M hydrochloric acid aqueous solution is added to adjust the pH to 2.5, and 0.05N sodium hydroxide aqueous solution is dropped to measure the electrical conductivity. The measurement is continued until the pH is 11.
  • FIG. 1 shows changes in electrical conductivity when the electrical conductivity of an aqueous dispersion of an oxidized cellulose-based raw material is measured.
  • the conductivity rapidly decreases due to neutralization of protons from hydrochloric acid.
  • the weak acid carboxyl group
  • the decrease in conductivity becomes gradual.
  • the conductivity begins to increase with the addition of sodium hydroxide, as shown in the curve section (C).
  • the amount (a) (that is, the amount of sodium hydroxide consumed in the neutralization step of the weak acid) is determined, and the carboxyl group amount is calculated using the following formula.
  • Amount of carboxyl group [mmol / g oxidized cellulose raw material] a [ml] ⁇ 0.05 / mass of oxidized cellulose raw material [g]
  • the amount of carboxyl groups and the like in cellulose nanofibers can be mainly adjusted by the oxidation step in cellulose nanofiber production.
  • the oxidation process will be described in detail later.
  • the cellulose nanofiber of the present invention is oxidized in the presence of a compound selected from the group consisting of (A) N-oxyl compound and (B) bromide, iodide and a mixture thereof. It is manufactured by a method including an oxidation step of oxidizing a cellulose raw material using an agent to prepare an oxidized cellulose raw material, and a atomization step of wet oxidation atomization treatment of the oxidized cellulose raw material into nanofibers It is preferable.
  • N-oxyl compound refers to a compound capable of generating a nitroxy radical.
  • Examples of the N-oxyl compound used in the present invention include substances represented by the following general formula (Formula 1).
  • R 1 to R 4 are the same or different alkyl groups having about 1 to 4 carbon atoms.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical
  • 4-hydroxy-2,2,6,6-tetra A compound that generates a methyl-1-piperidine-N-oxy radical (hereinafter referred to as 4-hydroxy TEMPO) is preferable.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical
  • 4-hydroxy TEMPO derivatives are most preferred from the viewpoint of activity.
  • Preferred examples thereof include derivatives obtained by etherifying the hydroxyl group of 4-hydroxy TEMPO with an alcohol having a linear or branched carbon chain having 4 or less carbon atoms, and derivatives obtained by esterifying with a carboxylic acid or a sulfonic acid. included.
  • 4-hydroxy TEMPO derivative examples include compounds of the following formulas 2 to 4.
  • R is a linear or branched carbon chain having 4 or less carbon atoms.
  • a radical of an N-oxyl compound represented by the following formula 5, that is, an azaadamantane type nitroxy radical is preferable because it can produce uniform cellulose nanofibers in a short time.
  • R 5 is the same or different and represents hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms.
  • the amount of the N-oxyl compound is not particularly limited as long as it is a catalyst amount that can convert the cellulose-based raw material into nanofibers.
  • the amount of the N-oxyl compound is, for example, about 0.01 to 10 mmol, preferably 0.01 to 1 mmol, and more preferably about 0.05 to 5 mmol with respect to 1 g of an absolutely dry cellulosic raw material.
  • Bromide and iodide is a compound containing bromine, and examples thereof include alkali metal bromide that can be dissociated and ionized in water.
  • An iodide is a compound containing iodine, and examples thereof include alkali metal iodide.
  • the amount of bromide or iodide used can be selected as long as the oxidation reaction can be promoted.
  • the total amount of bromide and iodide is, for example, about 0.1 to 100 mmol, preferably about 0.1 to 10 mmol, and more preferably about 0.5 to 5 mmol, with respect to 1 g of cellulosic raw material.
  • Oxidizing agent As the oxidizing agent, a known oxidizing agent such as halogen, hypohalous acid, halous acid, perhalogen acid or a salt thereof, halogen oxide, or peroxide can be used. From the viewpoint of production cost, sodium hypochlorite, which is currently most widely used in industrial processes and has low environmental impact, is particularly preferred.
  • the amount of the oxidizing agent used can be selected within a range that can promote the oxidation reaction. The amount thereof is, for example, about 0.5 to 500 mmol, preferably 0.5 to 50 mmol, and more preferably about 2.5 to 25 mmol with respect to 1 g of cellulosic raw material.
  • Cellulose-based material The cellulose-based material is as described above.
  • the reaction temperature may be a room temperature of about 15 to 30 ° C.
  • a carboxyl group is generated in the cellulose, so that the pH of the reaction solution is reduced.
  • an alkaline solution such as an aqueous sodium hydroxide solution is added to maintain the pH of the reaction solution at about 9 to 12, preferably about 10 to 11.
  • the reaction medium is preferably water because it is easy to handle and hardly causes side reactions.
  • a cellulose nanofiber is manufactured from the oxidized cellulose raw material obtained at the said process.
  • the wet atomization treatment refers to a treatment for reducing the size of the oxidized cellulose-based raw material performed in a dispersion medium such as water. That is, the oxidized cellulose raw material is defibrated by this wet atomization treatment to form nanofibers.
  • a mixing / stirring or emulsifying / dispersing device such as a high-speed shear mixer or a high-pressure homogenizer can be used alone or in combination of two or more.
  • the manufacturing method of the cellulose nanofiber of this invention may have a viscosity reduction process after the said oxidation process.
  • the viscosity reducing step is a step of reducing the viscosity of a dispersion containing cellulose, that is, a step of reducing the molecular weight of cellulose.
  • the cellulose nanofiber is shortened by this process.
  • the low viscosity process can be applied to the oxidized cellulose raw material obtained in the oxidation process or the cellulose nanofibers obtained in the micronization process.
  • the viscosity reduction step is performed by irradiating the oxidized cellulose-based material or cellulose nanofiber with ultraviolet light, or reacting the oxidized cellulose-based material or cellulose nanofiber with a cellulose-degrading enzyme, ie, cellulase.
  • the reaction medium is preferably water for the reasons described above.
  • the oxidized cellulose raw material obtained in the oxidation step is not defibrated, the viscosity of the dispersion of the oxidized cellulose raw material is not so high. Therefore, when this dispersion is irradiated with ultraviolet rays, the oxidized cellulose-based raw material can be reduced in molecular weight efficiently and uniformly. In addition, when cellulase is added to the dispersion for reaction, an efficient and uniform reaction can be performed.
  • the dispersion obtained in the micronization step is a cellulose nanofiber dispersion obtained by defibrating an oxidized cellulose raw material. Since a considerable number of fibers having nano-level fiber diameters exist in the dispersion, the interaction between the fibers becomes remarkable.
  • the cellulose nanofiber dispersion has a higher viscosity than the dispersion of the oxidized cellulose raw material. Therefore, even when the cellulose nanofiber dispersion is subjected to a viscosity reduction step, the above efficient reaction may not occur.
  • UV light is preferably 100 to 400 nm, more preferably 100 to 300 nm.
  • ultraviolet rays having a wavelength of 135 to 260 nm are preferable because they can directly act on cellulose and hemicellulose to cut the main chain, thereby reducing the molecular weight, that is, shortening the fiber.
  • ultraviolet light sources examples include xenon short arc lamps, ultra high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, deuterium lamps, metal halide lamps, and the like. In this step, one or more of these can be used in any combination. In particular, it is preferable to use a combination of a plurality of light sources having different wavelength characteristics because ultraviolet rays having different wavelengths can be simultaneously irradiated, so that the number of cut sites in the cellulose chain and hemicellulose chain increases and shortening of the fiber is promoted.
  • a hard glass container can be used in this step.
  • ultraviolet rays having a wavelength longer than 300 nm it is preferable to use a container made of quartz glass that transmits ultraviolet rays more.
  • the concentration of the oxidized cellulose-based raw material dispersion is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. Further, from the viewpoint of improving the flowability of the cellulosic raw material and increasing the reaction efficiency, the concentration is preferably 12% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
  • the dispersion medium is preferably water from the viewpoint of handleability.
  • the temperature of the dispersion of the oxidized cellulose raw material is preferably 20 ° C. or higher from the viewpoint of the efficiency of the photooxidation reaction. On the other hand, if the temperature is too high, the quality may be deteriorated and the pressure in the reaction vessel may be increased. Therefore, the temperature is preferably 95 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 50 ° C. or lower.
  • the pH of the dispersion of the oxidized cellulose raw material is not particularly limited, but in view of simplification of the process, a neutral region, for example, about pH 6.0 to 8.0 is preferable.
  • the amount of ultraviolet rays received by the oxidized cellulose raw material can be adjusted by adjusting the irradiation time, the amount of energy of the light source, the concentration of the oxidized cellulose raw material in the dispersion, and the like.
  • auxiliary agents such as oxygen, ozone, or peroxides (hydrogen peroxide, peracetic acid, sodium percarbonate, sodium perborate, etc.) Is preferable.
  • UV irradiation can be repeated multiple times.
  • ultraviolet rays of 100 to 400 nm, preferably 135 to 260 nm can be irradiated 1 to 10 times, preferably about 2 to 5 times, and about 0.5 to 3 hours per time.
  • Cellulase is an enzyme having an activity to cleave ⁇ -1,4-glycoside bond of cellulose.
  • Known cellulases can be used in this step, but examples include cellulases derived from cellulase-producing filamentous fungi, bacteria, actinomycetes, basidiomycetes, and cellulases produced by genetic engineering such as genetic recombination and cell fusion. It is. These can be used alone or in combination of two or more. Commercially available cellulase can also be used.
  • Examples include Novozyme 476 manufactured by Novozymes Japan, Cellulase AP3 manufactured by Amano Enzyme, Cellulase Onozuka RS manufactured by Yakult Pharmaceutical Co., Ltd., Optimase CX40L manufactured by Genencor Kyowa Co., Ltd. GEDO-TCL, manufactured by Nagase ChemteX Corporation, Cellulase XL-522, manufactured by Nagase ChemteX, Inc.
  • the addition amount of cellulase (dry solid content of cellulase aqueous solution) is preferably 0.001% by mass or more and 0.01% by mass or more with respect to the absolutely dry cellulosic raw material from the viewpoint of reaction efficiency. More preferred is 0.05% by mass or more.
  • the amount of cellulase added is preferably 10% by mass or less, more preferably 5% by mass, and even more preferably 2% by mass or less.
  • the pH of the oxidized cellulose-based raw material dispersion is preferably 4 to 10, more preferably 5 to 9, and further preferably 6 to 8.
  • the temperature of the oxidized cellulose raw material dispersion is preferably 40 to 70 ° C, more preferably 45 to 65 ° C, and further preferably 50 to 60 ° C.
  • the reaction time is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and further preferably 2 to 6 hours.
  • the cellulose nanofiber of the present invention can be used as a dispersion.
  • the dispersion is a liquid in which the cellulose nanofibers of the present invention are dispersed in a dispersion medium.
  • the dispersion medium is a medium, and in the present invention, water is preferable from the viewpoint of handleability and the like.
  • the dispersion is useful as a raw material for the cellulose nanofiber film or as a coating material applied on a substrate.
  • the concentration of the dispersion is preferably from 0.1 to 10% by mass, more preferably from 1 to 3% by mass, and even more preferably from 1.5 to 2.5% by mass, from the viewpoint of the strength of the resulting film.
  • the viscosity of the dispersion is preferably 500 to 2000 mPa ⁇ s at 2% by mass from the viewpoint of workability during film formation. Viscosity was measured at 25 ° C. using a B-type viscometer. 64.
  • the dispersion may be prepared arbitrarily, but an oxidized cellulose raw material is prepared by the production method described above, and then a dispersion medium of a desired concentration is added by adding a dispersion medium such as water and stirring with an ultrahigh pressure homogenizer or the like. It is preferable to obtain
  • the cellulose nanofiber of this invention is useful as a raw material of a barrier material.
  • the barrier material is a material having an oxygen barrier property obtained by applying the cellulose nanofiber dispersion on a substrate.
  • the substrate examples include a polymer film such as PET.
  • PET is used in containers such as beverages, further improvement in oxygen barrier properties is required. Therefore, the laminated body which apply
  • the cellulose nanofiber dispersion of the present invention when applied onto a porous substrate such as a non-woven cloth or a porous membrane made of chemical fibers, the substrate is impregnated with the dispersion, and the pores are impregnated. A material filled with the cellulose nanofibers of the present invention is obtained. Such a material is also an excellent barrier material.
  • the oxygen permeability of the barrier material is preferably 0.60 (ml / m 2 ⁇ 24 h ⁇ atm) or less, and more preferably 0.30 (ml / m 2 ⁇ 24 h ⁇ atm) or less.
  • a barrier material containing cellulose nanofibers obtained through ultraviolet treatment is particularly preferable. Since the cellulose nanofibers thus obtained have a large amount of polar groups as described above, the adhesion between the cellulose nanofibers in the membrane is strong and a very dense membrane is obtained. Furthermore, the adhesion between the substrate and the cellulose nanofibers is also excellent. Therefore, the oxygen barrier property of the barrier material containing cellulose nanofibers obtained through the ultraviolet treatment is extremely high.
  • the cellulose nanofiber of the present invention is useful as a papermaking coating material, that is, a papermaking coating solution.
  • the papermaking coating liquid is a liquid for application to a paper substrate, and usually contains a binder and a pigment.
  • the paper substrate is a base paper obtained by making a paper stock containing pulp, or a paper having a known coating layer on the base paper. From the viewpoint of the strength of the obtained paper, the concentration of cellulose nanofibers in the solid content of the papermaking coating material is preferably 0.02 to 0.5% by mass, more preferably 0.05 to 0.3% by mass.
  • the solid content of the papermaking coating material is a solid component obtained by drying the coating material.
  • the composition of the papermaking coating solution is usually 5 to 20 parts by mass of binder with respect to 100 parts by mass of pigments such as calcium carbonate and kaolin.
  • the cellulose nanofiber of the present invention is preferably used as a binder in combination with a known adhesive such as latex.
  • the cellulose nanofiber of the present invention in the binder is preferably 0.5 to 5% by mass, more preferably 0.7 to 3% by mass.
  • the papermaking coating solution contains various auxiliary agents blended in a normal coating solution, such as a dispersant, a thickener, a water retention agent, a defoaming agent, a water resistance agent, and a colorant, if necessary. You may go out.
  • the paper formed by applying the coating liquid comprising cellulose nanofibers of the present invention is filled with cellulose nanofibers in the pores of the paper base material, and on the paper base material, a dense layer of cellulose nanofibers ( Film) is formed. Therefore, such paper has excellent oxygen barrier properties. Furthermore, the paper obtained in this way is also excellent in gloss.
  • the reason for the excellent glossiness is that the pores of the paper substrate are blocked and a dense layer (film) of cellulose nanofibers is formed on the paper substrate, which improves the smoothness of the paper surface. Conceivable.
  • the glossiness of the paper is preferably 48% or more, more preferably 50% or more, as measured by JIS-Z 8741. Such paper is suitable for uses that require gloss, such as inkjet recording paper.
  • the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
  • the value indicating the coating amount indicates the solid content mass after drying unless otherwise specified.
  • a 0.5N aqueous sodium hydroxide solution was successively added to adjust the pH to 10.
  • the product was filtered through a glass filter and washed thoroughly with water to obtain oxidized pulp.
  • the ultraviolet-treated oxidized pulp aqueous dispersion was treated 10 times with an ultra-high pressure homogenizer (treatment pressure 140 MPa) and subjected to wet atomization to obtain a transparent gel-like aqueous dispersion, that is, a cellulose nanofiber aqueous dispersion.
  • the fiber diameter, polymerization degree, crystallization degree, crystallization degree, crystal size, and carboxyl group amount of the cellulose nanofibers thus obtained were measured by the following methods. The results are shown in Table 1.
  • ⁇ Fiber diameter> Water was further added to the cellulose nanofiber aqueous dispersion to prepare a diluted dispersion in which the concentration of cellulose nanofiber was 0.001% by mass.
  • the diluted dispersion was thinly spread on a mica sample stage, heated and dried at 50 ° C. to prepare an observation sample, and the cross-sectional height of the shape image observed with an atomic force microscope (AFM) was measured.
  • AFM atomic force microscope
  • Crystal size 0.9 ⁇ 0.15418 / (B ⁇ cos ⁇ )
  • the transparency was determined as the transmittance of 660 nm light in the cellulose nanofiber aqueous dispersion. The measurement was performed using a UV-VIS spectrophotometer UV-265FS (manufactured by Shimadzu Corporation).
  • the cellulase-treated oxidized pulp slurry was boiled to deactivate the cellulase, and then treated 10 times with an ultra-high pressure homogenizer (treatment pressure 140 MPa).
  • treatment pressure 140 MPa treatment pressure 140 MPa
  • cellulose nanofibers having a degree of polymerization of 160 or less can be obtained when wet atomization is performed using an ultra-high pressure homogenizer after the viscosity reduction step. Is clear. It is also clear that the cellulose nanofiber aqueous dispersions obtained in Production Examples 1 and 2 have extremely high transparency. The cellulose nanofibers obtained in Production Examples 1 and 2 have a polymerization degree of 160 or less, and the fiber length is considered to be about the wavelength of visible light or shorter. Therefore, since the cellulose nanofiber aqueous dispersion obtained in Production Examples 1 and 2 does not scatter visible light, it is presumed that the transparency is high.
  • Comparative production example 5 is a method according to the example of patent document 2 (paragraphs 0060 to 0064 of patent document 2 specification). In Comparative Production Example 5, since the viscosity of the oxidized cellulose-based raw material aqueous dispersion increased by the mixer treatment, it was considered that the subsequent reaction with cellulase did not proceed sufficiently and the degree of polymerization increased.
  • ⁇ Oxygen permeability (differential pressure method)> A gas permeability measuring device (K-315N-03, manufactured by Tsukubarika Seiki Co., Ltd.) was used for the measurement. The measurement conditions were 0% relative humidity (% RH) at standard temperature and standard pressure (STP).
  • the barrier material containing the cellulose nanofiber of the present invention has a low oxygen permeability and an excellent oxygen barrier property.
  • the barrier material of Example 1 has an extremely low oxygen permeability of 0.34 (ml / m 2 ⁇ 24 hr ⁇ atm). This is because the cellulose nanofibers used in Example 1 have been subjected to a low viscosity process by ultraviolet irradiation, and as described above, there are many polar groups in the molecule, which strongly bond the fibers. This is probably because a dense film is formed.
  • the barrier material of Comparative Example 3 has considerably higher oxygen permeability than the barrier material of Example 2. This is because the cellulose nanofibers used in Comparative Example 3 have a degree of polymerization greater than 160, that is, long cellulose nanofibers are entangled with each other, and a portion having a low fiber concentration is formed in the film. It is guessed.
  • Example 3 To 100% by mass of hardwood bleached kraft pulp (freezing degree 400 ml), 0.5% by mass of cationized starch, 0.05% by mass of alkyl ketene dimer, 2% by mass of sulfate band, and 12% by mass of calcium carbonate were added. Furthermore, 0.3 parts of an ester compound of polyhydric alcohol and fatty acid (product name: KB-115, manufactured by Kao Co., Ltd.) as a densification chemical is added to a total of 100 parts by mass of these materials. Got.
  • an ester compound of polyhydric alcohol and fatty acid product name: KB-115, manufactured by Kao Co., Ltd.
  • an on-top twin-wire paper machine is used to form a web, dry it by performing a three-stage wet press, and then apply a 10% by weight aqueous oxidized starch solution again with a two-roll size press coater. This was dried to obtain a base paper having a basis weight of 80 g / m 2 .
  • Kaolin A product name: Capim DG, manufactured by IMERYS 80 parts by mass, gel method silica A (product name: NIPGEL AY-200, manufactured by Tosoh Silica Co., Ltd.), 20 parts by mass, SB latex as a binder (glass transition temperature 15 ° C 9.90 parts by mass, and further, the cellulose nanofiber aqueous dispersion obtained in Production Example 1 as a binder was blended so that the cellulose nanofibers were 0.10 parts by mass, and then sodium hydroxide 0.2 A coating liquid having a solid content of 50% was obtained by mixing 0.25 part by mass of polyacrylic acid soda as a dispersing agent and diluting water.
  • This coating solution was applied on both sides of the base paper using a blade coater so that the coating amount per side was 13 g / m 2 .
  • the coated paper is dried until the moisture content in the paper reaches 5% by mass, subjected to supercalender treatment so that the glossiness of white paper at a light incident angle of 75 degrees according to JIS-Z 8741 is 60%, and ink jet recording. A medium was obtained.
  • the obtained inkjet recording medium was evaluated for the glossiness of blank paper as follows. The results are shown in Table 3.
  • Example 5 An inkjet recording medium was obtained in the same manner as in Example 3 except that the blending amount of cellulose nanofiber was 0.25 parts and the blending amount of SB latex (glass transition temperature 15 ° C.) was 9.75 parts. The results are shown in Table 3.
  • the ink jet recording medium containing the cellulose nanofiber of the present invention has excellent glossiness.
  • the reason for this is considered to be that, as described above, a film having extremely high surface smoothness was formed on the paper substrate by the cellulose nanofiber of the present invention.
  • the inkjet recording medium of Comparative Example 5 is considered to have low glossiness because long cellulose nanofibers are entangled with each other and a film with low surface smoothness is formed on the paper substrate.

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Abstract

La présente invention concerne une nanofibre cellulosique qui permet la production d'une pellicule présentant d'excellentes propriétés barrières vis-à-vis de l'oxygène, etc. La nanofibre cellulosique présente une cristallinité d'au moins 70 %, un indice de polymérisation de 160 ou moins comme déterminé par une méthode utilisant la viscosité avec une solution d'éthylènediamine-cuivre et un diamètre de fibre de 50 nm ou moins. Il est préféré que la nanofibre cellulosique soit produite par un procédé comprenant les étapes suivantes : oxydation d'une matière brute cellulosique par un agent oxydant en présence d'un N-oxyle, etc. ; diminution de la viscosité de la matière brute cellulosique oxydée ; et soumission de la matière brute cellulosique oxydée à un traitement de microparticulation en mode humide pour produire la nanofibre.
PCT/JP2011/069257 2010-09-28 2011-08-26 Nanofibre cellulosique WO2012043103A1 (fr)

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