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WO2015068818A1 - Procédé de fabrication de nanofibres de cellulose, pâte à papier pour la fabrication de nanofibres de cellulose, nanofibres de cellulose, composition de résine et article moulé - Google Patents

Procédé de fabrication de nanofibres de cellulose, pâte à papier pour la fabrication de nanofibres de cellulose, nanofibres de cellulose, composition de résine et article moulé Download PDF

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Publication number
WO2015068818A1
WO2015068818A1 PCT/JP2014/079626 JP2014079626W WO2015068818A1 WO 2015068818 A1 WO2015068818 A1 WO 2015068818A1 JP 2014079626 W JP2014079626 W JP 2014079626W WO 2015068818 A1 WO2015068818 A1 WO 2015068818A1
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WO
WIPO (PCT)
Prior art keywords
resin
pulp
cellulose
cellulose nanofibers
cellulose nanofiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/079626
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English (en)
Japanese (ja)
Inventor
啓信 瀧澤
崇人 生熊
哲哉 原田
伸治 佐藤
金野　晴男
健嗣 藤井
かおり 山邊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Original Assignee
DIC Corp
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2015545566A priority Critical patent/JP6016317B2/ja
Publication of WO2015068818A1 publication Critical patent/WO2015068818A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the present invention relates to a method for producing cellulose nanofibers, pulp for producing cellulose nanofibers, cellulose nanofibers, a resin composition, and a molded article.
  • Cellulose nanofibers developed in recent years are plant-derived natural raw material nanofillers, and have attracted attention as composite materials for resins having low specific gravity and high strength.
  • the cellulose nanofiber after defibration contains a lot of water (see Patent Document 1).
  • Patent Document 1 In order to compound this hydrous defibrated cellulose nanofiber into various resins, it is necessary to go through a step of dispersing the cellulose nanofiber in the resin after dehydration.
  • cellulose nanofibers when cellulose nanofibers are combined with a resin for dilution, a method for suppressing the increase in resin viscosity and improving handling and molding processability, and a high-strength resin composition and molding using cellulose nanofibers
  • the challenge is to provide a body.
  • the present inventors focused on the degree of cellulose polymerization of the raw material pulp when producing cellulose nanofibers.
  • cellulose nanofibers produced by controlling the degree of cellulose polymerization it is possible to significantly reduce the resin viscosity when cellulose nanofibers are combined with a resin for dilution, and handleability and moldability It was found that can be greatly improved.
  • the present invention is a method for producing cellulose nanofibers, comprising a step of preparing a pulp having a cellulose polymerization degree of 100 to 500, and a step of defibrating the pulp to form cellulose nanofibers. It provides the manufacturing method of a cellulose nanofiber characterized by including.
  • cellulose nanofibers when cellulose nanofibers are combined with a dilution resin, it is possible to suppress an increase in resin viscosity, and as a result, handling properties and moldability are improved. Therefore, a good cellulose nanofiber composite resin composition can be obtained by a simple method. Moreover, from the obtained resin composition, it becomes possible to obtain a high-strength molded article due to the effect of the cellulose nanofibers.
  • the cellulose nanofiber in the present invention is obtained by defibrating pulp having a cellulose polymerization degree of 100 to 500.
  • wood pulp and / or non-wood pulp can be suitably used as long as the degree of cellulose polymerization is 100 to 500.
  • Wood pulp includes mechanical pulp and chemical pulp, both of which can be preferably used. From the viewpoint of lignin content, chemical pulp having a low lignin content is preferred.
  • Chemical pulp includes sulfide pulp, kraft pulp, alkali pulp, and the like, and any of them can be suitably used.
  • non-wood pulp any of straw, bagasse, kenaf, bamboo, straw, firewood, flax, etc. can be used.
  • paper made from pulp can be used as the pulp of the present invention.
  • Waste paper such as newspapers, waste milk cartons, and copied papers can also be suitably used.
  • the cellulose polymerization degree of the pulp shown in the present invention can be obtained by the following method. That is, the pulp is dissolved in copper ethylenediamine, the viscosity is measured using a Canon-Fenske viscometer, the intrinsic viscosity count is obtained from the Schulz-Blaschke equation, and the degree of polymerization is calculated from the Mark-Houwink-Sakurada equation.
  • the pulp fiber length may be measured by a publicly known method.
  • the measurement may be performed using an optical microscope or a fiber analyzer fiber tester (manufactured by Lorentzen & Wettre).
  • the pulp for producing cellulose nanofibers in the present invention has a cellulose polymerization degree of 100 to 500. By adopting this degree of polymerization, it is possible to lower the viscosity when the obtained cellulose nanofiber is diluted into a resin.
  • the cellulose polymerization degree of the pulp is more preferably 150 to 500. When the degree of cellulose polymerization exceeds 500, there is a possibility that the fluidity of the resin composited with the cellulose nanofibers to be obtained is reduced, or that bubbles are easily involved and defoaming becomes difficult. If the degree of cellulose polymerization is less than 100, the toughness inherent to the obtained cellulose nanofiber is impaired, and the intended function as a nanofiller may not be obtained.
  • the pulp having a cellulose polymerization degree of 100 to 500 as defined in the present invention can be prepared by depolymerizing the pulp as a raw material.
  • the method for the depolymerization treatment is not particularly limited, and can be selected as necessary. However, it is preferred to prepare by acid hydrolysis treatment.
  • a desired pulp can be obtained by performing a depolymerization process by alkali hydrolysis, enzymatic decomposition, blasting process, vibration ball mill process, or the like.
  • the fiber length of the pulp is preferably 10 to 1000 ⁇ m.
  • the fiber length is preferable because the viscosity of the obtained cellulose nanofiber is further reduced.
  • the fiber length of the pulp is more preferably 10 to 850 ⁇ m, still more preferably 10 to 500 ⁇ m, and particularly preferably 10 to 350 ⁇ m.
  • the fiber length may be prepared by any method.
  • the pulp of the target fiber length can be obtained by finely pulverizing and / or classifying by mechanical pulverization.
  • an apparatus used in the mechanical treatment for example, an impact mill such as a hammer mill or a pin mill, a medium mill such as a ball mill or a tower mill, a cutting mill, or an airflow mill may be used alone or in combination.
  • the cellulose nanofiber in the present invention can be produced by mechanically applying a shearing force to the raw material pulp.
  • the medium used for shearing may be an aqueous solvent or a resin medium.
  • a resin-based medium is preferable from the viewpoint that when the obtained cellulose nanofibers are combined with another dilution resin, it is not necessary to remove water or an organic solvent. That is, a defibrating resin (defining resin) can be used more preferably if necessary.
  • the type of defibrating resin can be selected as necessary. Specific examples include polyester resins and acrylic resins described later.
  • the means for applying the shearing force can be arbitrarily selected.
  • a known kneader such as a bead mill, an ultrasonic homogenizer, an extruder such as a single screw extruder or a twin screw extruder, a Banbury mixer, a grinder, a pressure kneader, or a two-roller. Etc. can be used.
  • a pressure kneader is preferably used from the viewpoint of obtaining a stable shear force even in a high-viscosity resin.
  • a general refining method such as a refiner, a high-pressure homogenizer, a medium stirring mill, a stone mortar, a grinder, a twin screw extruder, or the like can be preferably used.
  • a general refining method such as a refiner, a high-pressure homogenizer, a medium stirring mill, a stone mortar, a grinder, a twin screw extruder, or the like can be preferably used.
  • a general refining method such as a refiner, a high-pressure homogenizer, a medium stirring mill, a stone mortar, a grinder, a twin screw extruder, or the like can be preferably used.
  • the raw material pulp is refined to produce cellulose nanofibers.
  • the pulp and the defibrating medium may be mixed to form a composition and then put into the above apparatus or the like for defibration, or each may be put into the apparatus and then defibrated. good.
  • the cellulose nanofiber may mean a nanofiller
  • the cellulose nanofibers obtained by defibration are preferably, for example, 100 nm to 1000000 nm in the major axis direction.
  • the length in the minor axis direction is preferably 5 nm to 1000 nm, for example. These lengths can be obtained, for example, by measuring with a scanning electron microscope.
  • the defibrating resin used for defibrating can be selected as necessary.
  • the polyester resin described below is preferably used.
  • Examples of the defibrating resin that can be used in the present invention include polyester resins.
  • the polyester resin of the present invention includes one or more polyols represented by the following general formula (1), one or more polycarboxylic acids represented by the following general formula (2), and It is preferable that it is polyester obtained by making this react.
  • A- (OH) m (1) [Wherein, A represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, an aromatic group which may have a substituent, or a heterocyclic aromatic group. m represents an integer of 2 to 4. ]
  • B- (COOH) n (2) [Wherein, B represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group which may have a substituent, or a heterocyclic aromatic group. n represents an integer of 2 to 4. ]
  • Examples of the polyol represented by the general formula (1) include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, pentyl glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1 , 12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, -Butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2 Ethyl-1
  • Examples of the polycarboxylic acid represented by the general formula (2) include unsaturated dibasic acid and anhydride thereof, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid and these Furthermore, there may be mentioned ⁇ , ⁇ -unsaturated dibasic acids such as halogenated maleic anhydride and aconitic acid, and ⁇ , ⁇ -unsaturated dibasic acids such as dihydromuconic acid.
  • saturated dibasic acids and anhydrides thereof include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydro Examples include phthalic anhydride, halogenated phthalic anhydride, and esters thereof.
  • monohydric alcohol monovalent carboxylic acid, and hydroxycarboxylic acid may be further used to such an extent that the characteristics are not substantially impaired.
  • monohydric alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, 3-butanol, n-amyl alcohol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n -Octanol, 2-ethylhexanol, isooctanol, n-nonanol, isononanol, n-decanol, isodecanol, isoundecanol, lauryl alcohol, cetyl alcohol, decyl alcohol, undecyl alcohol, tridecyl alcohol, benzyl alcohol stearyl alcohol,
  • Examples of monovalent carboxylic acids include benzoic acid, heptanoic acid, nonanoic acid, caprylic acid, nonanoic acid, capric acid, undecylic acid, lauric acid, and the like, and one or more of these may be used.
  • Examples of hydroxycarboxylic acids include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyiso Examples include caproic acid and p-hydroxybenzoic acid, and one or more of these may be used.
  • polyester resin in the present invention a modified polyester resin obtained by modifying a polyester may be used.
  • modified polyester resin include urethane-modified polyester, acrylic-modified polyester, epoxy-modified polyester, and silicone-modified polyester.
  • polyester resin in the present invention may be linear, or a multi-branched polyester may be used.
  • the polyester resin in the present invention preferably has an ester group concentration of 6.0 mmol / g or more. More preferably, it is 6.0 to 30 mmol / g, still more preferably 6.0 to 20 mmol / g, and particularly preferably 6.0 to 14 mmol / g. It is also preferable that the ester group concentration is 6.0 mmol / g or more and the acid value is 10 KOHmg / g or more. The acid value is more preferably 10 to 300 KOH mg / g, still more preferably 10 to 200 KOH mg / g, and particularly preferably 10 to 100 KOH mg / g.
  • the ester group concentration is 6.0 mmol / g or more and the hydroxyl value is 10 KOHmg / g or more. More preferably, the hydroxyl value is 10 to 1000 KOH mg / g, more preferably 10 to 800 KOH mg / g, and particularly preferably 10 to 500 KOH mg / g. Further, the polyester resin in the present invention is particularly preferable when the ester group concentration is 6.0 mmol / g or more, the acid value is 10 KOHmg / g or more, and the hydroxyl value is 10 KOHmg / g or more.
  • the polyester resins may be used alone or in combination.
  • the pulp is refined into nanofibers by the refinement method of the present invention.
  • the micronization method of the present invention as described above, it is possible to miniaturize to 100 nm to 1000000 nm in the major axis direction and 5 nm to 1000 nm in the minor axis direction, for example.
  • the ratio between the defibrated resin and the pulp can be arbitrarily changed.
  • the effect of strengthening the resin is more enhanced when the pulp ratio in the defibrated resin is higher to some extent.
  • the ratio of the pulp in the composition containing pulp and defibrating resin is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 40% by mass to 60% by mass.
  • the cellulose nanofibers obtained by refining the pulp in the defibrating resin may be used as a master batch (resin composition) containing the defibrated resin and the cellulose nanofiber without undergoing a purification step.
  • the master batch can be further combined with a dilution resin and used as a combined composite resin composition.
  • the master batch itself may be used as the resin composition of the present invention without using a dilution resin, and a molded article may be directly produced.
  • the cellulose nanofiber of the present invention is preferable because it is easy to mold because the viscosity of the master batch is low when it is masterbatched.
  • the master batch in the present invention contains cellulose nanofibers obtained by defibrating defibrated resin and pulp as essential components.
  • cellulose nanofibers obtained by defibrating defibrated resin and pulp as essential components.
  • Various resins, additives, organic and inorganic fillers, etc. can be added to the master batch as long as the effects of the present invention are not impaired.
  • an aqueous solvent can be used for defibration.
  • pulp and water or an aqueous solvent may be mixed to form a composition, and defibration work may be performed using this composition.
  • the aqueous solvent can be selected as necessary.
  • the aqueous solvent that can be used in the present invention means water or an aqueous solvent such as alcohols. Specific examples include water, ethanol, methanol, propanol, butanol, and acetone. It is also possible to select and use alcohols listed as materials for polyester resins as necessary. Combinations can be selected as necessary, and one kind may be used, or two or more kinds may be mixed and used.
  • the defibrating method used in the present invention is not particularly limited as long as the cellulose polymerization degree of the pulp to be used is 100 to 500, and can be arbitrarily selected. General methods and conditions used in this field can be preferably used.
  • the pulp may be added to a defibrated resin at room temperature and mixed to form a mixture, and then kneaded using a kneader or the like.
  • melt kneading may be performed while applying heat to the mixture as necessary.
  • the defibrated resin may be kneaded, melted by applying heat, or melt-kneaded first, and then pulp may be added thereto and kneaded.
  • the pulp when the pulp is defibrated in water or an aqueous solvent, the pulp can be defibrated by adding the pulp to water or an aqueous solvent and dispersing using a disperser such as a homogenizer. Conditions and the like may be selected as necessary. In the present invention, if necessary, after defibration, washing or solvent replacement using water or an aqueous solvent, and / or lyophilization treatment or separation may be performed.
  • a disperser such as a homogenizer
  • the cellulose nanofiber obtained by this invention or the masterbatch containing a cellulose nanofiber can be mixed with the resin for dilution as a resin reinforcing agent, and can improve the intensity
  • the dilution resin may be a homopolymer or a copolymer, and any of a thermoplastic resin and a thermosetting resin can be used. Moreover, one type may be used and a plurality of types of resins may be used in combination.
  • the monomer may be referred to as a dilution resin for convenience, and after mixing the master batch and the monomer, the monomer may be polymerized or the following resin may be formed.
  • the types of the defibrating resin and the dilution resin may be the same or different.
  • the ratio of the defibrating resin and the dilution resin can be arbitrarily selected.
  • the ratio of the aqueous solvent containing cellulose nanofibers and the dilution resin can be arbitrarily selected.
  • Thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin.
  • thermoplastic resins Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, Polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone Resins, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyether ether ketone resin, polyketone resin, liquid crystal polyester resins, fluorine resins, syndiotactic polystyrene resin, cyclic polyolefin resin.
  • thermoplastic resins can be used alone or in combination of two or more.
  • thermosetting resin is a resin having characteristics that can be changed into substantially insoluble and infusible when cured by heat by means of heating or radiation or a catalyst.
  • Specific examples include phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, xylene.
  • resins and thermosetting polyimide resins examples. These thermosetting resins can be used alone or in combination of two or more.
  • thermosetting resin when the main component of the resin of the present invention is a thermoplastic resin, a small amount of a thermosetting resin is added within a range that does not impair the properties of the thermoplastic resin, or conversely, when the main component is a thermosetting resin. It is also possible to add a small amount of thermoplastic resin as long as the properties of the thermosetting resin are not impaired.
  • the ratio of the master batch and the dilution resin in the resin composition can be arbitrarily selected as long as the effects of the present invention are not impaired.
  • the amount of cellulose nanofibers in the resin composition containing the master batch and the dilution resin is preferably 0.5% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass. More preferably, it is 0.5 to 10% by mass, and particularly preferably 0.5 to 3% by mass.
  • the ratio of the aqueous solvent containing cellulose nanofibers and the dilution resin can be arbitrarily selected as long as the effects of the present invention are not impaired.
  • the resin composition may contain conventionally known various additives depending on the application.
  • hydrolysis inhibitors, colorants, flame retardants, antioxidants, polymerization initiators, polymerization inhibitors, UV absorbers, antistatic agents, lubricants, curing agents, mold release agents, antifoaming agents, leveling agents, light A stabilizer (for example, hindered amine etc.), antioxidant, an inorganic filler, an organic filler etc. can be mention
  • melt molding method It does not specifically limit about the method of shape
  • an extrusion molding method is generally used, but a flat press is also possible.
  • a profile extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, and the like can be used. If a film-like product or the like is produced, a melt molding method or a solution casting method can be used in addition to the melt extrusion method.
  • melt molding method examples include inflation film molding, cast molding, extrusion lamination molding, calender molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding.
  • resin hardened cured with an active energy ray
  • a molded object can be manufactured using the various hardening methods using an active energy ray.
  • the resin composition in the present invention can be suitably used for various uses such as molding materials, coating materials, coating materials, and adhesives. Examples include, but are not limited to, use for automobile parts, aircraft parts, electronic and electrical parts, building materials, containers and packaging members, daily necessities, sports and leisure goods, and the like.
  • the acid value, hydroxyl value, and ester group concentration were defined by the following methods.
  • Measurement method of acid value In a 500 ml beaker, 33 g of reagent-grade potassium hydroxide was weighed, and 150 ml of ion exchange water was gradually added and cooled (KOH solution). Half of this amount of industrial methanol was placed in a 5 liter container, and the KOH solution was gradually transferred to the container while mixing with methanol. Further, industrial methanol was gradually added to make a total volume of 5 liters (0.1 mol potassium hydroxide alcohol solution).
  • the terminal hydroxyl value was determined from the area ratio of each peak derived from the terminal structure and the ester bond in the 13C-NMR spectrum.
  • JNM-LA300 manufactured by JEOL Ltd. was used as a measuring device.
  • 10 mg of Cr (acac) 3 as a relaxation reagent was added to a 10 wt% deuterated chloroform solution of the sample, and 13C-NMR quantitative measurement was performed by gate decoupling method. Integration was performed 4000 times.
  • ester group concentration was determined by the following calculation formula (5).
  • Ester group concentration (mmol / g) Amount of ester group produced (mol) / [Amount of monomer charged (weight) ⁇ Amount of water produced (weight)] ⁇ 1000 (5)
  • the pulp fiber length was measured using a fiber tester (manufactured by Lorentzen & Wettre).
  • the pulp fiber length refers to the length-weighted average fiber length of the pulp.
  • Example 1 (Manufacture of cellulose nanofibers using defibrating resin (polyester resin)) (Example 1) Production of master batch 1 400 parts by mass of polyester resin 1 and cellulose powder product (pulp) “KC Flock W-400G (cellulose polymerization degree 154, average fiber length of 50 ⁇ m or less) manufactured by Nippon Paper Industries Co., Ltd. (Fiber tester measurement limit value or less) “600 parts by mass were prepared. Each material was put into a pressure kneader (DS1-5GHH-H) manufactured by Moriyama Seisakusho and pressurized at 60 rpm for 480 minutes using this kneader. The mixture was kneaded and the pulp was refined to obtain a master batch 1.
  • a pressure kneader DS1-5GHH-H
  • the obtained master batch 1 was dispersed in acetone so as to be 1% by mass, and dropped onto glass to be dried.
  • a photograph was taken at a magnification of 10,000 using a scanning electron microscope S-3400 manufactured by High Technology, cellulose fiber of pulp , It was confirmed that a miniaturized up to several tens of nanometers in diameter.
  • the cellulose content of the master batch 1 is 60%.
  • Example 2 Production of master batch 2 An apparatus and method similar to those of the manufacturing method of Example 1 were used except that the materials and amounts were changed. Specifically, 500 parts by mass of polyester resin 1 and 500 parts by mass of cellulose powder product (pulp) “KC Flock W-100G (cellulose polymerization degree 264, average fiber length 216 ⁇ m)” manufactured by Nippon Paper Industries Co., Ltd. are prepared. did. Using a pressure kneader (DS1-5GHH-H) manufactured by Moriyama Seisakusho, the mixture of the above materials was subjected to pressure kneading at 60 rpm for 480 minutes to carry out a pulp refining treatment to obtain a master batch 2. When the obtained master batch 2 was measured by the method using a scanning electron microscope described in Example 1, it was confirmed that the cellulose fiber of the pulp was refined to a diameter of several tens of nanometers. The master batch 2 has a cellulose content of 50%.
  • Example 3 Manufacture of masterbatch 3 Except having changed material and quantity, the apparatus and method similar to the manufacturing method of Example 1 were used. Specifically, 500 parts by mass of polyester resin 1 and 500 parts by mass of cellulose powder W-50S (pulp) (cellulose polymerization degree 420, average fiber length 347 ⁇ m) manufactured by Nippon Paper Industries Co., Ltd. were prepared. Using a pressure kneader (DS1-5GHH-H), the mixture of the above materials was subjected to pressure kneading at 60 rpm for 480 minutes to carry out pulp refinement to obtain master batch 3. Master batch 3 obtained was obtained. Was measured by the method using a scanning electron microscope described in Example 1. As a result, it was confirmed that the cellulose fibers of the pulp were refined to a diameter of several tens of nanometers. 50%.
  • a pressure kneader DS1-5GHH-H
  • Comparative example 1 Production of comparative master batch 1
  • a comparative experiment was performed using the same apparatus as the manufacturing method of Example 1. Specifically, 600 parts by mass of polyester resin 1 and 400 parts by mass of a cellulose powder product “KC Flock W-50GK (cellulose polymerization degree 549, average fiber length 302 ⁇ m)” manufactured by Nippon Paper Industries Co., Ltd. were prepared. Using a pressure kneader (DS1-5GHH-H) manufactured by Moriyama Seisakusho, the mixture of the above materials was subjected to pressure kneading at 60 rpm for 480 minutes to carry out a pulp refining treatment, whereby Comparative Master Batch 1 was obtained. When the obtained comparative master batch 1 was measured by the method using a scanning electron microscope described in Example 1, it was confirmed that the cellulose fiber of the pulp was refined to a diameter of several tens of nanometers. The cellulose content of the comparative master batch is 40%.
  • Example 4 100 parts by weight of epoxy resin EPICLON 850 manufactured by DIC Corporation, 90 parts by weight of methylated tetrahydrophthalic anhydride (Me-THPA), and the master batch 1 obtained in Example 1 were obtained from cellulose nanofibers.
  • a homomixer manufactured by Primix Co., Ltd.
  • the mixture was dispersed and stirred with a homomixer to obtain a composition, and the viscosity was measured.
  • the stirring conditions were stirring for 20 minutes and the stirring speed was 12000 rpm.
  • the viscosity was measured using an R / S-CPS type rotational viscometer manufactured by BROOKFIELD, using a cone spindle RC3-50-2 at a measurement temperature of 25 ° C.
  • Example 5 In Example 4, the viscosity was measured in the same manner except that the weight part of the cellulose nanofiber was changed to 3 parts by weight.
  • Example 6 In Example 4, the viscosity was measured in the same manner except that master batch 1 was changed to master batch 2 (cellulose nanofiber content 1%).
  • Example 7 In Example 4, the viscosity was measured in the same manner except that the master batch 1 was changed to the master batch 3 (cellulose nanofiber content 1%).
  • Example 2 In Example 4, the viscosity was measured in the same manner except that the master batch 1 was changed to the comparative master batch 1 (cellulose nanofiber content 1%).
  • Example 3 (Comparative Example 3) In Example 5, the viscosity was measured in the same manner except that the master batch 1 was changed to the comparative master batch 1 and the weight part of the cellulose nanofiber was further changed to 3 parts by weight.
  • Example 4 Measurement of resin viscosity without adding cellulose nanofibers.
  • the viscosity was measured in the same manner except that Master Batch 1 was not mixed (cellulose nanofiber content: 0%).
  • Example 8 Manufacture of resin molded body to which master batch 1 obtained in Example 1 was added and measurement of fracture toughness value
  • a test piece (molded body) was prepared from the master batch 1 obtained in Example 1 using the molding method shown below, and the fracture toughness value was measured. [Molding method] Hereinafter, a method for forming the test plate will be described.
  • 4.5 parts by weight of master batch 1 obtained in Example 1 was added to 77.8 parts by weight of epoxy resin EPICLON 850 manufactured by DIC Corporation, and dispersed and stirred with a homomixer (manufactured by Primix).
  • Example 5 Manufacture of the resin molding which added the comparison masterbatch 1 obtained by the comparative example 1, and measurement of a fracture toughness value In Example 8, the masterbatch 1 was changed into the comparison masterbatch 1 (cellulose nanofiber In the same manner except that the content was 3%, an attempt was made to produce a molded plate. However, since the resin viscosity is high, it was not possible to uniformly disperse, and it was not possible to pour into a mold and perform molding.
  • Example 6 Manufacture of the resin molding which did not add a cellulose nanofiber, and measurement of a fracture toughness value In Example 8, it is the same except not having mixed the masterbatch 1 (cellulose nanofiber content rate 0%). Thus, the fracture toughness value was calculated.
  • the obtained cellulose nanofiber was measured by the method using a scanning electron microscope described in Example 1, it was confirmed that the cellulose fiber of the pulp was refined to a diameter of several tens of nanometers.
  • the obtained cellulose nanofibers were subjected to solvent substitution with t-butanol and then recovered by freeze-drying to obtain water-defined cellulose nanofibers 1.
  • Example 7 Production of Comparative Water-Defibrated Cellulose Nanofiber 1
  • the raw material pulp was changed from “KC Flock W-400G” to “KC Flock W-50GK (pulp viscosity 8.2, cellulose polymerization degree 549, average fiber length).
  • Aqueous defibration was carried out in the same manner except that it was changed to “302 ⁇ m)”.
  • the obtained cellulose nanofiber was measured by the method using a scanning electron microscope described in Example 1, it was confirmed that the cellulose fiber of the pulp was refined to a diameter of several tens of nanometers. Thereafter, freeze-drying treatment was performed to recover the cellulose nanofibers, and a comparative water-defibrated cellulose nanofiber 1 was obtained.
  • Example 10 Measurement of resin viscosity obtained by adding the water-defined cellulose nanofiber 1 obtained in Example 9 to a resin so as to have a cellulose concentration of 0.1%. 100 parts by weight of epoxy resin EPICLON 850 manufactured by DIC Co., Ltd. 0.1 parts by weight of the water-defined cellulose nanofiber 1 obtained in Example 9 was added (content ratio of cellulose nanofiber in the obtained composition was 0) 0.1%), and this was dispersed and stirred with a Hoover Muller manufactured by Toyo Seiki Seisakusho Co., Ltd., and the viscosity of the obtained resin composition was measured. The viscosity was measured using an R / S-CPS type rotational viscometer manufactured by BROOKFIELD, using a cone spindle RC3-50-2 at a measurement temperature of 25 ° C.
  • Comparative example 8 The measurement of the resin viscosity added to resin so that it might become a 0.1-% cellulose density
  • FIG. 10 the same operation was performed except that the water-defibrated cellulose nanofiber 1 was changed to the comparative water-defibrated cellulose nanofiber 1 (cellulose nanofiber content 0.1%) obtained in Comparative Example 7, and the viscosity was changed. I tried to measure. However, the dispersibility to resin was bad and it was not able to disperse
  • Comparative Example 2 using Comparative Master Batch 1 of Comparative Example 1 showed a considerably higher viscosity than Examples 4-6. Further, in Comparative Example 3 used so that the amount of cellulose was tripled, the viscosity was so large that the viscosity measurement itself could not be carried out. In Comparative Example 4 not containing the master batch, the viscosity value was low. However, from the results of Comparative Example 6 below, it was expected that Comparative Example 4 would have poor fracture toughness. In Example 8, Comparative Example 5 and Comparative Example 6, the fracture toughness value of the composite resin composition was measured and compared. Example 8 in which the degree of cellulose polymerization was within the scope of the present invention showed excellent fracture toughness values.
  • Comparative Example 5 in which the degree of cellulose polymerization was outside the range of the present invention, the viscosity was too high to be measured.
  • Comparative Example 6 containing no cellulose nanofibers was inferior in fracture toughness value compared to Example 8.
  • the resin composition of Example 10 using water-defined cellulose nanofibers 1 having a cellulose polymerization degree within the range of the present invention showed a slightly high resin viscosity.
  • the composite resin composition of Comparative Example 8 using the comparative hydrolyzed cellulose nanofiber 1 having a cellulose polymerization degree outside the range of the present invention showed a very high resin viscosity.
  • the present invention provides a method for producing cellulose nanofiber, a pulp for producing cellulose nanofiber, a cellulose nanofiber, a resin composition, and a molded article.
  • cellulose nanofibers when cellulose nanofibers are combined with a dilution resin, the increase in resin viscosity can be suppressed, and handling and molding processability can be improved.

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Abstract

　L'invention concerne un procédé de fabrication de nanofibres de cellulose caractérisé par fibrillation de pâte à papier ayant un degré de polymérisation de cellulose de 100 à 500 afin d'obtenir des nanofibres de cellulose.
PCT/JP2014/079626 2013-11-08 2014-11-07 Procédé de fabrication de nanofibres de cellulose, pâte à papier pour la fabrication de nanofibres de cellulose, nanofibres de cellulose, composition de résine et article moulé Ceased WO2015068818A1 (fr)

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JPWO2017078048A1 (ja) * 2015-11-02 2018-01-11 日本製紙株式会社 セルロースナノファイバーの製造方法
WO2018199191A1 (fr) * 2017-04-27 2018-11-01 日本製紙株式会社 Mélange-maître, composition de caoutchouc et procédé de production des deux
WO2018221663A1 (fr) * 2017-06-01 2018-12-06 日本電気株式会社 Résine à base de cellulose, matériau de moulage, corps moulé et procédé de fabrication d'une résine à base de cellulose
JP2019038980A (ja) * 2017-08-29 2019-03-14 王子ホールディングス株式会社 繊維状セルロース含有組成物及び塗料
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EP3771773A1 (fr) * 2019-08-02 2021-02-03 Hosiden Corporation Procédé de fabrication d'un comprimé de nanofibres de cellulose
WO2021107146A1 (fr) * 2019-11-29 2021-06-03 王子ホールディングス株式会社 Cellulose fibreuse, dispersion de cellulose fibreuse et feuille
WO2022102703A1 (fr) 2020-11-13 2022-05-19 東亞合成株式会社 Procédé de fabrication d'une composition contenant de la nanocellulose

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JP2016222745A (ja) * 2015-05-26 2016-12-28 大阪瓦斯株式会社 混練組成物及びその製造方法並びに複合体
JPWO2017078048A1 (ja) * 2015-11-02 2018-01-11 日本製紙株式会社 セルロースナノファイバーの製造方法
JP2018090949A (ja) * 2015-11-02 2018-06-14 日本製紙株式会社 セルロースナノファイバーの製造方法
JP6473550B1 (ja) * 2017-04-27 2019-02-20 日本製紙株式会社 マスターバッチ、ゴム組成物及びそれらの製造方法
WO2018199191A1 (fr) * 2017-04-27 2018-11-01 日本製紙株式会社 Mélange-maître, composition de caoutchouc et procédé de production des deux
JPWO2018221663A1 (ja) * 2017-06-01 2020-04-02 日本電気株式会社 セルロース系樹脂、成形用材料、成形体及びセルロース系樹脂の製造方法
WO2018221663A1 (fr) * 2017-06-01 2018-12-06 日本電気株式会社 Résine à base de cellulose, matériau de moulage, corps moulé et procédé de fabrication d'une résine à base de cellulose
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JP2019038980A (ja) * 2017-08-29 2019-03-14 王子ホールディングス株式会社 繊維状セルロース含有組成物及び塗料
JP2020026460A (ja) * 2018-08-09 2020-02-20 大王製紙株式会社 繊維状セルロース及びその製造方法、並びに繊維状セルロース複合樹脂及びその製造方法
JP7220534B2 (ja) 2018-08-09 2023-02-10 大王製紙株式会社 繊維状セルロースの製造方法、及び繊維状セルロース複合樹脂の製造方法
EP3771773A1 (fr) * 2019-08-02 2021-02-03 Hosiden Corporation Procédé de fabrication d'un comprimé de nanofibres de cellulose
US11525216B2 (en) 2019-08-02 2022-12-13 Hosiden Corporation Method of manufacturing cellulose nanofiber compact
WO2021107146A1 (fr) * 2019-11-29 2021-06-03 王子ホールディングス株式会社 Cellulose fibreuse, dispersion de cellulose fibreuse et feuille
JPWO2021107146A1 (fr) * 2019-11-29 2021-06-03
JP7593329B2 (ja) 2019-11-29 2024-12-03 王子ホールディングス株式会社 繊維状セルロース、繊維状セルロース分散液及びシート
WO2022102703A1 (fr) 2020-11-13 2022-05-19 東亞合成株式会社 Procédé de fabrication d'une composition contenant de la nanocellulose

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