WO2023013514A1 - セルロース含有樹脂組成物、３ｄプリンタ用フィラメント、及びセルロース含有樹脂組成物の製造方法 - Google Patents

セルロース含有樹脂組成物、３ｄプリンタ用フィラメント、及びセルロース含有樹脂組成物の製造方法 Download PDF

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WO2023013514A1
WO2023013514A1 PCT/JP2022/029071 JP2022029071W WO2023013514A1 WO 2023013514 A1 WO2023013514 A1 WO 2023013514A1 JP 2022029071 W JP2022029071 W JP 2022029071W WO 2023013514 A1 WO2023013514 A1 WO 2023013514A1
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cellulose
resin composition
polymer
containing resin
group
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PCT/JP2022/029071
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English (en)
French (fr)
Japanese (ja)
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憲治 青木
康太 井出
宏文 小倉
剛英 渡邉
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国立大学法人静岡大学
東洋レヂン株式会社
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Priority to JP2023540299A priority Critical patent/JPWO2023013514A1/ja
Publication of WO2023013514A1 publication Critical patent/WO2023013514A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters

Definitions

  • the present invention relates to a cellulose-containing resin composition, a 3D printer filament, and a method for producing a cellulose-containing resin composition.
  • the present invention relates to a cellulose-containing resin composition that can be used in a hot melt deposition method (FDM method) despite containing a crystalline resin, a filament for 3D printers, and a method for producing a cellulose-containing resin composition. .
  • FDM method hot melt deposition method
  • Cellulose and cellulose nanofibers are made from pulp, etc., and are obtained through mechanical fibrillation in water, so they exist in an aqueous dispersion or state containing a large amount of water.
  • CNF Cellulose and cellulose nanofibers
  • the cellulose or CNF is subjected to a normal heating and drying treatment, the cellulose or CNF becomes a firm aggregate due to the hydrogen bonding of the cellulose or CNF. Even if these aggregates are pulverized, the originally expected effects of cellulose and CNF are not exhibited. Therefore, various methods for extracting CNF capable of suppressing aggregation of cellulose and CNF and methods for dispersing cellulose in resin for the purpose of suppressing aggregation have been investigated.
  • modeling materials for 3D printers which are mainly composed of resin components consisting of (A) nanofibers, (B) dispersants, and (C) thermoplastic resins or photocurable resins, are known.
  • resin components consisting of (A) nanofibers, (B) dispersants, and (C) thermoplastic resins or photocurable resins.
  • Patent Document 1 See Patent Document 1, for example). According to the modeling material described in Patent Document 1, it is possible to obtain a three-dimensional model that has improved strength and elastic modulus, can reproduce surface conditions with fine patterns, has excellent surface smoothness, and is also excellent in transparency and dyeability. .
  • an object of the present invention is to provide a cellulose-containing resin composition, a filament for 3D printers, and a cellulose-containing resin that exhibit good molding properties in various types of 3D printers including the FDM method despite containing a crystalline resin.
  • An object of the present invention is to provide a method for producing a composition.
  • the present invention provides a cellulose-containing resin containing a crystalline resin and a cellulose composite comprising a hydroxyl group of cellulose and a non-polar polymer bonded via a reactive group capable of reacting with the hydroxyl group.
  • a composition is provided.
  • the present invention provides a 3D printer filament containing the cellulose-containing resin composition described above.
  • the present invention includes an aqueous emulsion of a cellulose having hydroxyl groups and containing moisture, and a polymer having a reactive group capable of reacting with the hydroxyl groups and having a nonpolar polymer molecular chain. a step of combining a hydroxyl group and a reactive group in an aqueous emulsion to obtain a cellulose composite; and a step of kneading the cellulose composite and a crystalline resin.
  • a manufacturing method is provided.
  • the present invention provides a cellulose-containing composite comprising a crystalline resin and a cellulose composite in which a non-polar polymer is bonded to the hydroxyl groups of cellulose via a reactive group capable of reacting with the hydroxyl groups.
  • a method for improving the formability of a 3D printer using a 3D printer filament constructed using a resin composition is provided.
  • the cellulose-containing resin composition the filament for 3D printer, and the method for producing the cellulose-containing resin composition according to the present invention, although it contains a crystalline resin, it is suitable for various types of 3D printers including the FDM type. It is possible to provide a cellulose-containing resin composition exhibiting moldability, a filament for 3D printers, and a method for producing a cellulose-containing resin composition.
  • an aqueous cellulose dispersion and maleic anhydride-modified polypropylene ( MAPP) emulsion was used to attempt to introduce MAPP into cellulose.
  • MAPP maleic anhydride-modified polypropylene
  • the inventors of the present invention have discovered that by simply adding a very small amount of a cellulose composite synthesized based on such findings to a thermoplastic resin, volumetric shrinkage can be greatly suppressed even if the thermoplastic resin is cooled after being heated and melted. .
  • the present invention is based on these findings and discoveries.
  • a cellulose composite according to an embodiment of the present invention is formed by binding a non-polar polymer to a hydroxyl group of cellulose via a reactive group.
  • the cellulose surface has a low molecular weight (for example, an organic compound having a weight average molecular weight of about 1,000 or less. 200) except for MA oligomers.)
  • a nonpolar polymer is bound to cellulose as a so-called "compatibility group" (conceptually , directly bonding a high molecular weight compatibilizer to cellulose). This eliminates the need to add a compatibilizer (dispersant) when dispersing the cellulose composite according to the present embodiment in a predetermined non-polar resin.
  • the cellulose composite is a polymer trapped in the cellulose composite (that is, a polymer containing the reactive group and the nonpolar polymer.
  • the molecular chain is the nonpolar polymer. and a polymer having a reactive group attached to the molecular chain.
  • the term “captured” means that the polymer is fixed to the cellulose composite to such an extent that the polymer does not easily detach from the cellulose composite, is entangled with the cellulose composite, or is at least one of the cellulose composite. It means at least one of coating the part. Since the cellulose composite contains a polymer trapped in the cellulose composite, the trapped polymer also exhibits the function as a compatibilizer while being trapped, so cellulose dispersion in a nonpolar resin becomes easier.
  • the term "molecular chain” refers to a polymer, an oligomer molecule, or a polymer composed of structural units that are linearly or branchedly connected between terminal groups, branch points, or boundary structural units unique to polymers. Or refers to a configuration including all or part of a block.
  • a cellulose-containing resin composition according to an embodiment of the present invention comprises a crystalline resin and a cellulose composite in which a non-polar polymer is bonded to hydroxyl groups of cellulose via reactive groups capable of reacting with hydroxyl groups.
  • composed of A filament for a 3D printer is produced by filamentizing the cellulose-containing resin composition according to the present embodiment.
  • the content of cellulose in the cellulose-containing resin composition is adjusted to a concentration within a range in which aggregation of cellulose can be suppressed in the cellulose-containing resin composition and a network structure of cellulose is formed.
  • a cellulose composite is a composite formed by binding a nonpolar polymer to cellulose via a predetermined bond formed by reacting a predetermined reactive group with a hydroxyl group of cellulose.
  • the cellulose composite can be obtained in powder form.
  • cellulose cellulose fibers, cellulose nanofibers (CNF), and/or microfibrillated cellulose (MFC) can be used.
  • cellulose fiber Various cellulose fibers can be used as long as the cellulose fibers have hydroxyl groups on the surface.
  • Cellulose fibers include plant-derived cellulose fibers, animal-derived cellulose fibers (e.g., cellulose fibers isolated from sea squirts, seaweed, etc.), microorganism-derived cellulose fibers (e.g., cellulose fibers produced by acetic acid bacteria, etc.), and the like.
  • One or more cellulose fibers can be selected and used from among them. From the viewpoints of practicality, price, and/or availability, it is preferable to use plant-derived cellulose fibers as the cellulose fibers.
  • raw materials for plant-derived cellulose fibers include plant fibers such as pulp obtained from natural plant raw materials such as wood, bamboo, hemp, jute, kenaf, cotton, beets, agricultural waste, and cloth.
  • waste papers such as waste newspapers, waste cardboards, waste magazines, waste copy papers, etc.
  • wood include cedar, cypress, eucalyptus, and acacia.
  • Pulp or fibrillated cellulose obtained by fibrillating pulp can also be used as a raw material for cellulose fibers.
  • the raw materials for the cellulose fiber can be used singly or in combination of two or more.
  • plant fibers When using plant-derived raw materials (that is, plant fibers) as raw materials for cellulose fibers, it is preferable to remove lignin in the plant fibers. That is, plant fibers have a structure in which lignin and hemicellulose are filled between cellulose fibers, and hemicellulose and/or lignin cover a part or all of the bundles of cellulose microfibrils. It has a structure in which cellulose microfibrils and/or bundles of cellulose microfibrils are covered with hemicellulose, and the hemicellulose is further covered with lignin. As a result, the plant fibers are formed in a state in which the cellulose fibers are strongly bonded together by lignin. Therefore, from the viewpoint of suppressing aggregation of cellulose fibers in plant fibers, it is preferable to remove lignin in plant fibers.
  • the amount of lignin in the raw material may be adjusted by subjecting the cellulose fiber raw material to treatments such as delignification and bleaching, if necessary.
  • the lignin content in the cellulose fiber raw material is not particularly limited, but from the viewpoint of suppressing aggregation of cellulose fibers, the lignin content in the plant fiber-containing material is about 40% by mass or less, and 10% by mass. About mass % or less is preferable. Also, the lower limit of lignin is not particularly limited, and the closer to 0% by mass, the better. In addition, lignin content can be measured by the Klason method.
  • the average fiber length of cellulose fibers is not particularly limited. However, the longer the average fiber length of the cellulose fibers, the more the effect of improving the properties can be expected. Incidentally, for example, when CNF obtained by chemical fibrillation (for example, TEMPO-oxidized CNF) is used as the cellulose fiber, the aspect ratio of this CNF is about 1,000 (that is, the width of the cellulose fiber is 3 nm to 5 nm. , fiber length is about 3 ⁇ m).
  • CNF obtained by chemical fibrillation for example, TEMPO-oxidized CNF
  • CNF Cellulose nanofibers
  • cellulose nanofiber Cellulose nanofibers
  • Various CNFs can be used as the CNFs according to the present embodiment as long as they have hydroxyl groups on the surface.
  • CNF can be prepared by defibrating a raw material of cellulose fibers (for example, pulp or the like).
  • a raw material of cellulose fibers for example, pulp or the like.
  • the fibrillation method first, an aqueous suspension or slurry of cellulose fibers is prepared, and the prepared aqueous suspension or slurry is processed using a refiner, a high-pressure homogenizer, a grinder, a kneader (extruder), a bead mill, or the like.
  • CNF can be prepared by defibrating the cellulose fibers by mechanical grinding or the like.
  • the average value of the CNF fiber diameter may be 4 nm or more and about 200 nm or less, may be about 150 nm or less, may be about 100 nm or less, or may be about 50 nm or less.
  • the average value of the fiber length of CNF may be about 3 ⁇ m or more, may be about 5 ⁇ m or more, may be about 100 ⁇ m or less, or may be about 500 ⁇ m or less.
  • the average value of the fiber diameter and the average value of the fiber length of the CNF are, for example, a predetermined number or more (for example, 50 or more) of CNF observed in a predetermined field of view of an electron microscope. It may be a calculated average value.
  • the specific surface area of CNF is preferably 70 m 2 /g or more, more preferably 100 m 2 /g or more, preferably about 300 m 2 /g or less, more preferably about 250 m 2 /g or less, and about 200 m 2 /g or less. is more preferable, and about 150 m 2 /g or less is most preferable.
  • the specific surface area of carboxymethyl cellulose (CMC, chemically treated CNF), which is CNF is about 300 m 2 /g. The specific surface area can be measured by the BET method.
  • Microfibrillated cellulose is a fiber with a larger average fiber diameter than CNF. Microfibrillated cellulose (MFC) is obtained by defibrating a material containing cellulose fibers (for example, the raw material for the cellulose fibers described above). Various types of MFC can be used as the MFC according to the present embodiment as long as it has hydroxyl groups on its surface.
  • MFC can be prepared by beating or fibrillating raw materials of cellulose fibers (for example, pulp).
  • the average value of the MFC fiber diameter may be, for example, about 0.3 ⁇ m or more, about 1 ⁇ m or more, about 5 ⁇ m or more, about 8 ⁇ m or more, or about 50 ⁇ m or less. may be about 40 ⁇ m or less, and may be about 30 ⁇ m or less.
  • the average value of the fiber length of MFC may be about 500 ⁇ m or more, may be about 700 ⁇ m or more, may be about 800 ⁇ m or more, may be about 3 mm or less, and may be 2 mm or less. It may be to some extent.
  • the average value of the fiber diameter and the average value of the fiber length of MFC are, for example, the fiber diameter and fiber length of a predetermined number or more (for example, 50 or more) of MFC observed in a predetermined field of view of an electron microscope or an optical microscope. It may be an average value calculated by measurement.
  • a polymer according to the present embodiment (that is, a polymer consisting of a predetermined molecular chain having a reactive group) has a reactive group capable of reacting with a hydroxyl group, and the molecular chain is substantially nonpolar or hydrophobic. It is a polymer. This reactive group reacts with the hydroxyl group of cellulose to form a predetermined bond, thereby bonding the molecular chain of the polymer to the cellulose.
  • the polymer only needs to have a reactive group in its molecular chain, and the chain length of the reactive group need not be controlled.
  • other structural units may be partly contained in the molecular chain as long as they do not inhibit the reaction between the reactive group and the hydroxyl group.
  • the non-polar macromolecules of the molecular chain may have other groups different from the reactive groups.
  • the reactive groups that react with the hydroxyl groups of cellulose may be at least a part of the reactive groups in the polymer, and it is not necessary that all the reactive groups and the hydroxyl groups of cellulose form bonds. .
  • Reactive groups include at least one group selected from the group consisting of succinic anhydride groups, carbonyl groups (eg, methoxycarbonyl groups), and carboxyl groups. Therefore, the bond formed by the reaction between the hydroxyl group of cellulose and the reactive group is an ester bond. Also, the bond formed by reacting with a hydroxyl group may be an amide bond, an ether bond, or a urethane bond.
  • non-polar polymer is a polymer substance that does not have a permanent dipole. is also a non-polar polymer. Examples of nonpolar polymers include polyethylene resins, polypropylene resins, tetrafluoroethylene resins, and the like.
  • the non-polar polymer that is the molecular chain includes substantially non-polar or hydrophobic olefin resins.
  • Olefin resins include polypropylene, polyethylene, ethylene/vinyl acetate copolymer resin, vinyl chloride resin, styrene resin, (meth)acrylic resin, vinyl ether resin, polyamide resin, polycarbonate resin, polysulfone resin, polyester resin, Examples include polyvinyl acetal resins, polyvinylidene chloride resins, polyurethane resins, and the like.
  • the reactive group may be a methoxycarbonyl group or the like contained in the molecular chain.
  • the nonpolar polymer in the present embodiment refers to the molecular structure of the portion containing a methoxycarbonyl group or the like (in this case, the molecular chain is a structure in which the molecular chain itself contains a reactive group In this case, if the molecular chain portion excluding the reactive group is non-polar, it is considered to be a non-polar polymer).
  • another reactive group (a reactive group different from the methoxycarbonyl group) may be separately introduced into the ethylene/vinyl acetate copolymer resin, (meth)acrylic resin, or the like by graft polymerization or the like.
  • nonpolar polymer at least one polymer selected from the group consisting of polypropylene, ethylene-vinyl acetate copolymer resin, and acrylic resin from the viewpoint of availability, low specific gravity, versatility, and/or processability.
  • a non-polar polymer is preferred.
  • polypropylene is more preferred.
  • These olefinic resins may contain other copolymerizable units. Moreover, these olefinic resins can be used singly or in combination of two or more.
  • Examples of the polymer comprising the above molecular chain and reactive group include various polymers in which the above molecular chain and the above reactive group are combined. Examples thereof include polypropylene, ethylene/vinyl acetate copolymer resin, and acrylic resin having at least one reactive group among the above reactive groups.
  • a polymer in which a reactive group is bonded to a molecular chain like a pendant group is more preferable, and for example, a graft copolymer is preferable.
  • maleic anhydride-modified polypropylene which has a maleic anhydride group as a reactive group and a polypropylene molecular chain, is used from the viewpoint of activating the movement of the reactive group with respect to the molecular chain. Most preferably used.
  • the weight-average molecular weight of the polymer containing a reactive group and a nonpolar polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 15,000 or more, and 200,000 or less. is preferred, 150,000 or less is more preferred, and 100,000 or less is even more preferred.
  • the weight average molecular weight can be calculated using high temperature gel permeation chromatography (high temperature GPC) and converted to polystyrene, and then converted to polypropylene using the Q factor.
  • graft rate For example, when maleic anhydride is grafted onto polypropylene to obtain MAPP, polymer radicals are generated on the polypropylene chain in the grafting reaction, and maleic anhydride is grafted onto these polymer radicals.
  • a molecular scission reaction of polypropylene chains occurs as a competing reaction of the graft reaction. Since the molecular scission reaction is superior to the graft reaction, the graft ratio and the molecular weight are in a trade-off relationship, such that the molecular weight of MAPP obtained decreases as the graft ratio increases.
  • the graft ratio is low (that is, when the graft copolymer has a high molecular weight and the MA concentration is low), emulsification of the polymer is difficult, and when the graft ratio is high, the molecular weight of the graft copolymer increases. extremely low.
  • the molecular weight of the graft copolymer is low, the graft copolymer trapped in the cellulose composite is also low molecular weight, so the properties of the cellulose composite itself (for example, strength, etc.) may decrease.
  • the graft ratio is preferably 0.2% or more, more preferably 1.0%, from the viewpoint of facilitating the formation of an emulsion of the polymer.
  • the above is more preferable.
  • the graft ratio is preferably 4.0% or less, more preferably 3.0% or less, from the viewpoint of suppressing deterioration in the properties of the cellulose composite/resin composition due to a decrease in the molecular weight of the polymer.
  • melting point The melting point of the above polymer depends on the melting point of the non-polar polymer used for the molecular chain. For example, when a polypropylene-based polymer is used for the molecular chain, the melting point of the polymer is about 80° C. or higher and 175° C. or lower.
  • the macromolecules trapped in the cellulose composite are the same as the macromolecules described above.
  • the non-polar polymer bound to the hydroxyl group of cellulose through the reactive group that is, the polymer having the non-polar polymer with this reactive group, and the captured polymer are the same. is a polymer of
  • the extracted insoluble component contains the cellulose composite
  • the extracted soluble component contains the polymer. If so, the macromolecules are said to be "entrapped" in the cellulose composite.
  • the cellulose composite is Soxhlet-extracted to separate the extractable insoluble components from the extractable soluble components.
  • FT-IR measurement, 1 H-NMR measurement and/or 13 C-NMR measurement are performed for each of the extracted insoluble component and the extracted soluble component.
  • a composite formed by binding MAPP to CNF is taken as an example of a cellulose composite.
  • CNF itself is insoluble in xylene, while MAPP itself is soluble.
  • xylene is used as an organic solvent for the Soxhlet extraction, an extraction-insoluble component and an extraction-soluble component are obtained.
  • the amount (wt%) of the extracted insoluble component is greater than the amount (wt%) of CNF used for the synthesis of the cellulose composite, and the presence of an ester bond is confirmed by NMR measurement , indicating that MAPP was bound to CNF via an ester bond.
  • a peak based on the polypropylene (PP) skeleton was observed by 13 C-NMR measurement of the extractable soluble component, and a peak based on the MA skeleton was observed by FT -IR measurement and 1 H-NMR measurement.
  • a peak based on the cellulose skeleton was observed by H-NMR measurement, and a carbonyl peak based on the MA skeleton was observed by FT-IR measurement of the extracted insoluble component and 13 C-NMR measurement, and cellulose skeleton was observed by 13 C-NMR measurement. is observed, it can be assumed that the macromolecules are trapped in the cellulose composite.
  • a cellulose composite/resin composition according to the present embodiment is a composition obtained by dispersing a cellulose composite in a predetermined non-polar resin. Since the cellulose composite is a state in which a nonpolar polymer is bound to cellulose, it can be substantially uniformly dispersed in a nonpolar resin. Also, when there is a polymer trapped in the cellulose composite, the cellulose composite can be more easily dispersed in the non-polar resin.
  • resins can be used as the resin in the cellulose composite/resin composition.
  • resins include thermoplastic resins, thermosetting resins, and/or photocurable resins.
  • a nonpolar or hydrophobic resin is preferably used as the resin in the cellulose composite/resin composition.
  • thermoplastic resins include styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, olefin resins (e.g., aliphatic polyolefin resins, cyclic olefin-based resins), polyamide-based resins, polyphenylene ether-based resins, thermoplastic polyimide-based resins, polyacetal-based resins, polysulfone-based resins, and amorphous fluorine-based resins.
  • styrene resins acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, olefin resins (e.g., aliphatic polyolefin resins, cyclic olefin-based resins), polyamide-based resins, polyphenylene ether-based resins, thermoplastic polyimide-based resins
  • thermosetting resins examples include epoxy resins, acrylic resins, oxetane resins, phenol resins, urea resins, polyimide resins, melamine resins, unsaturated polyester resins, silicon resins, polyurethane resins, allyl ester resins, and diallyl phthalate resins. be done.
  • photocurable resins examples include epoxy resins, acrylic resins, and oxetane resins.
  • thermoplastic resin such as an olefin resin (polypropylene, etc.) from the viewpoint that it can be applied to various industries and is relatively easy to mold.
  • a cellulose-containing resin composition is a composition containing a crystalline resin and the cellulose composite according to the present embodiment.
  • Olefin resins include polypropylene, polyethylene, polymethylpentene, ethylene/vinyl acetate copolymer resin, vinyl chloride resin, styrene resin, (meth)acrylic resin, vinyl ether resin, polyamide resin, polycarbonate resin, polysulfone resin, Examples include polyester resins, polyvinyl acetal resins, polyvinylidene chloride resins, polyurethane resins, and the like.
  • the crystalline resin may be used alone or in combination of two or more of these resins.
  • polypropylene as the crystalline resin from the viewpoints of good resin properties, availability, and the like.
  • the crystalline resin means a resin having a melting peak when measured according to ISO 3146 (method for measuring plastic transition temperature, JIS K7121).
  • the concentration of cellulose (cellulose, CNF, and/or MFC) in the cellulose-containing resin composition is within a range where aggregation of cellulose can be suppressed in the cellulose-containing resin composition and a network structure of cellulose is formed. preferably adjusted. Further, the cellulose concentration achieves a predetermined laminate height when, for example, a 3D printer filament formed using a cellulose-containing resin composition is used in a material extrusion deposition type (FDM method) 3D printer. It is also preferable that the concentration be adjusted to a possible value. For example, the concentration of cellulose in the cellulose-containing resin composition must exceed 0 wt%, preferably 3 wt% or less, more preferably 2.6 wt% or less, and even more preferably 1.5 wt% or less.
  • ⁇ Other additives The cellulose composite, the cellulose composite/resin composition, and/or the cellulose-containing resin composition according to the present embodiment, the physical properties of the cellulose composite, the cellulose composite/resin composition, and/or the cellulose-containing resin composition, etc. Extenders, plasticizers, moisture absorbers, physical property modifiers, reinforcing agents, coloring agents, flame retardants, antioxidants, anti-aging agents, conductive agents, antistatic agents, UV absorbers , UV dispersants, solvents, fragrances, deodorants, pigments, dyes, fillers, diluents, talc, and other additives may be added.
  • the cellulose-containing resin composition according to this embodiment can be used for various purposes. Specifically, it can be used for various products such as automobile parts, home appliances, housing/building materials, and packaging materials. Further, since the cellulose-containing resin composition according to the present embodiment does not easily shrink in volume even if it is cooled after being melted by heat, filaments for 3D printers, especially filaments for 3D printers of material extrusion deposition type (FDM method) 3D printers is useful as
  • the method for producing a cellulose composite generally includes the following steps. That is, the method for producing a cellulose composite comprises a mixing step of mixing cellulose having a hydroxyl group and a polymer having a reactive group to prepare a mixture, and a heating step of heating the mixture. Moreover, the method for producing a cellulose composite can further include a drying step of drying the cellulose composite obtained after the heating step. The heating step can be performed after the mixing step, or the mixing step and the heating step can be performed at the same time (the mixing step can be performed while heating).
  • cellulose having hydroxyl groups that is, a predetermined amount of cellulose fibers, cellulose nanofibers (CNF), and/or microfibrillated cellulose (MFC), and a predetermined amount of polymers (that is, reactive groups capable of reacting with hydroxyl groups) and the molecular chain is a non-polar polymer) are mixed to prepare a mixture.
  • the mixing method is not particularly limited, and manual mixing, mixing using a stirrer or mixer, or the like can be appropriately selected.
  • CNF aqueous dispersion an aqueous dispersion of CNF (hereinafter referred to as "CNF aqueous dispersion").
  • CNF aqueous dispersion the various CNFs described above can be used.
  • cellulose fibers previously hydrophobized by chemical treatment. However, when the cellulose fibers are hydrophobized in advance by chemical treatment, the number of steps such as refining accompanying the chemical treatment is increased, resulting in an increase in cost and labor.
  • MFC microfibrillated cellulose
  • the amount of water contained in cellulose fibers varies depending on the manufacturing method of cellulose fibers.
  • methods for producing cellulose fibers include mechanical fibrillation in which cellulose is fibrillated to a fiber width of several tens to 200 nm using a grinder or ultrahigh-pressure water, TEMPO oxidation, phosphoric acid esterification, etc., to achieve a fiber width of 10 nm.
  • TEMPO oxidation oxidation
  • phosphoric acid esterification etc.
  • the solid content concentration of cellulose fibers is usually about 2 wt% or more and 10 wt% or less (note that at about 10 wt%, the shape of cellulose fibers is becomes sherbet-like).
  • the solid content concentration of the cellulose fibers is about 0.5 wt% or more and 2 wt% or less (2 wt% is the upper limit of the solid content concentration that maintains the gel state).
  • the solid content concentration of the CNF water dispersion is preferably a concentration at which the viscosity becomes a level that allows stirring without temperature unevenness when mixed with a polymer emulsion.
  • the solid content concentration of the CNF aqueous dispersion is 0.5 wt% or more, preferably 2 wt% or more, may be 5 wt% or more, and 15 wt% or less, from the viewpoint of facilitating mixing with the polymer. and preferably 10 wt % or less.
  • the viscosity of the CNF aqueous dispersion for example, using a Brookfield viscometer, a representative value of the viscosity when measured at 25 ° C.
  • 60 rpm is 700 mPa s or more, and 3,000 mPa s or more. may be 6,000 mPa ⁇ s or more, may be 40,000 mPa ⁇ s or more, and is 130,000 mPa ⁇ s or less, preferably 110,000 mPa ⁇ s or less.
  • polymer used for mixing As the polymer used in the mixing step, it is preferable to use a polymer aqueous emulsion in which polymer fine particles are dispersed in water.
  • a polymer aqueous emulsion As the polymer constituting the polymer aqueous emulsion, the various polymers described above can be used.
  • a system (emulsion) in which polymer microparticles (dispersoids) are stably dispersed in water (dispersion medium) is called “latex.”
  • latex a system in which polymer microparticles (dispersoids) are stably dispersed in water
  • the proportion of solids in the polymer aqueous emulsion is 5 wt% or more, preferably 10 wt% or more, more preferably 15 wt% or more, still more preferably 20 wt% or more, and 25 wt% or more. There may be.
  • the proportion of solids in the aqueous polymer emulsion is 45 wt % or less, preferably 30 wt % or less, from the viewpoint of facilitating preparation of the emulsion.
  • emulsions can be used as the polymer water-based emulsion.
  • a maleic anhydride-modified polypropylene (MAPP) emulsion it is preferable to use a maleic anhydride-modified polypropylene (MAPP) emulsion, an ethylene-vinyl acetate copolymer (EVA) emulsion, and an acrylic emulsion of an acrylic resin.
  • MAPP maleic anhydride-modified polypropylene
  • EVA ethylene-vinyl acetate copolymer
  • acrylic emulsion of an acrylic resin acrylic resin.
  • the MAPP emulsion is most preferable because the reactive groups are suspended from the molecular chain, so that the reactive groups can easily approach the hydroxyl groups of the cellulose, and the collision frequency of the reactive groups with the hydroxyl groups can be improved.
  • aqueous dispersion of cellulose and the aqueous polymer emulsion By mixing the aqueous dispersion of cellulose and the aqueous polymer emulsion, mixing at the molecular level can be facilitated at a low temperature or in a state in which thermal deterioration is less than in the case of mixing solids.
  • the mixing ratio of cellulose and polymer can be defined by the solid content ratio of cellulose and polymer. That is, the solid content ratio of cellulose (cellulose fiber, CNF, or MFC) in the mixture is 3 wt% or more, may be 5 wt% or more, preferably 10 wt% or more, and may be 20 wt% or more, From the viewpoint of suppressing aggregation of cellulose (typically CNF) and appropriately forming a complex with a polymer, the content is 50 wt% or less, preferably 40 wt% or less.
  • the solid content ratio of the polymer in the mixture may be a ratio equal to or higher than the solid content ratio of cellulose, preferably a higher ratio, for example, 10 wt% or more, may be 15 wt% or more, or 25 wt%. or more, or 45 wt % or more.
  • the ratio of the solid content ratio of cellulose to the solid content ratio of the polymer in the mixture that is, the solid content ratio of cellulose: the solid content of the polymer
  • the cellulose (moisture-containing cellulose Fiber, CNF aqueous dispersion, or MFC) and polymer (water-based emulsion of polymer) are weighed and mixed.
  • the heating step the mixture obtained in the mixing step is controlled to a predetermined temperature or less and heated for a predetermined time.
  • This heating step causes the hydroxyl groups of the cellulose to react with the reactive groups of the polymer to form predetermined bonds, through which the polymer is bound to the cellulose.
  • the reactive group is at least one reactive group selected from the group consisting of a succinic anhydride group, a carbonyl group, and a carboxyl group
  • the bond formed by the hydroxyl group of cellulose and the reactive group is an ester It is a bond. That is, in this case, the esterification reaction proceeds in the heating step.
  • the reaction temperature in the heating step is 50°C or higher, preferably 70°C or higher, and may be 80°C or higher, from the viewpoint of enabling formation of a predetermined bond (eg, an ester bond).
  • the reaction temperature is 200° C. or lower, preferably 160° C. or lower, and may be 145° C. or lower in order to suppress thermal deterioration of cellulose.
  • the heating step preferably heats the mixture under reduced pressure.
  • the pressure during heating may be less than normal pressure.
  • the pressure in the heating step may be approximately 0.09 MPa or less. Heating under reduced pressure helps remove water from the system.
  • a cellulose composite powder is obtained.
  • the reaction product obtained after the heating step may be filtered under reduced pressure (reduced pressure filtration step). That is, the reaction product according to this embodiment can be subjected to dehydration treatment. By going through the vacuum filtration step, it is possible to apply a more powerful dehydration treatment to the reaction product.
  • a device such as a planetary stirring type heating and reduced pressure drying device can be used.
  • the heating process is a process of heating and reacting the mixture in a pot of a normal pressure open system, followed by a process of primary dehydration treatment with a centrifuge, a filter press, etc. It may include a step of drying under reduced pressure using (secondary dehydration treatment step). From the viewpoint of the amount of cellulose composite powder to be obtained and/or production costs, the heating step is preferably a step in which the primary dehydration treatment step and the secondary dehydration treatment step are combined.
  • this cellulose composite contains macromolecules trapped in the cellulose composite.
  • cellulose water-containing cellulose fiber, CNF aqueous dispersion, or MFC
  • an aqueous emulsion of a polymer not only a cellulose composite is formed, but also a non-polar polymer bound to the cellulose is highly It is presumed that the molecules are easily entangled and the macromolecules are easily trapped in the cellulose composite.
  • a drying process dries the water
  • the drying step is a step of drying the cellulose composite with warm air.
  • the temperature of the warm air is, for example, about 80° C.
  • the drying time is about 8 hours.
  • the temperature and the drying time are not limited to these, as long as the thermal deterioration of the cellulose contained in the cellulose composite can be suppressed.
  • the cellulose composite/resin composition can be prepared through a kneading step of kneading the cellulose composite obtained above with a predetermined nonpolar resin at a predetermined temperature for a predetermined time. After the kneading step, a curing step for curing the obtained cellulose composite/resin composition may be further carried out.
  • the kneading step is a step of kneading the cellulose composite and a predetermined nonpolar resin under a predetermined temperature environment, and the kneading method is not particularly limited, and the kneading may be performed in one step or in a plurality of times. It can also be divided into steps.
  • the kneading step can be carried out using, for example, a kneader, a twin-screw kneader, and/or an injection molding machine, which is a device for kneading the charged materials by rotating blades in a container.
  • the cellulose composite used in the kneading step may be in the form of powder, or may be in the form of pellets from the viewpoint of ease of handling during compounding.
  • the shape of the non-polar resin is not particularly limited, and may be in the form of pellets or powder.
  • the cellulose (CNF) content of the cellulose composite is preferably 5 wt% or more, more preferably 10 wt% or more, still more preferably 15 wt% or more, still more preferably 20 wt% or more, preferably 40 wt% or less, and 35 wt%. The following are more preferable, and 30 wt% or less is even more preferable.
  • the cellulose (CNF) content in the cellulose composite/resin composition is preferably 2 wt% or more, more preferably 3 wt% or more, and preferably 15 wt% or less, from the viewpoint of ensuring mechanical properties and raw material costs. 10 wt% or less is more preferable, and 5 wt% or less is considered to be even more preferable.
  • the heating temperature during kneading is a temperature higher than or equal to the temperature at which the resin melts, from the viewpoint of melting the resin and dispersing the cellulose composite in the melted resin (that is, adding the cellulose composite to the resin melt). It is preferable to control the temperature below the temperature at which the cellulose contained in the cellulose composite is less likely to be thermally degraded.
  • the temperature is 175 ° C. or higher. It is preferable to control the heating temperature, and it is preferable to control the heating temperature to 190° C. or 220° C. or less.
  • the kneading step for example, it is preferable to first melt the resin using a twin-screw extruder or the like, add the cellulose composite to the melted resin, and knead.
  • heat amount of heat
  • the cellulose composite can be reduced, and thermal deterioration of the cellulose contained in the cellulose composite can be suppressed.
  • the cellulose composite is substantially uniformly dispersed in the resin.
  • This dispersed state can be confirmed by, for example, an infrared imaging method, a three-dimensional TEM, or the like.
  • the cellulose-containing resin composition according to this embodiment can be produced through a step of kneading the cellulose composite and the crystalline resin obtained above.
  • This kneading step may be the same as the kneading step described above.
  • a mixture obtained by mixing a crystalline resin, a cellulose composite, and/or other additives (such as talc) at a predetermined mixing ratio for example, various shapes such as powder, paste, and pellets can be used.
  • a kneading device for example, various shapes such as powder, paste, and pellets can be used.
  • the cellulose-containing resin composition is extruded from a predetermined die in the form of filaments to produce filaments for 3D printers having a predetermined diameter.
  • the crystalline resin contains the cellulose composite according to this embodiment.
  • a non-polar polymer is bonded to the hydroxyl group of cellulose through a reactive group.
  • the cellulose composite can be substantially uniformly dispersed in the resin without the presence of the cellulose. Therefore, in the cellulose-containing resin composition according to the present embodiment, for example, since cellulose fibers, CNF, and / or MFC are uniformly dispersed in olefin resins such as polyethylene and polypropylene, raw material costs and manufacturing facility costs can be reduced and a high-performance structural material can be manufactured.
  • the cellulose composite uses a cellulose aqueous dispersion and a polymer aqueous emulsion, the cellulose composite can be prepared while suppressing thermal deterioration of cellulose.
  • the cellulose-containing resin composition can exhibit properties that incorporate the inherent properties of cellulose.
  • the cellulose composite can be prepared in a state in which the polymer used for preparing the cellulose composite is captured.
  • the cellulose-containing resin composition produced using the cellulose composite according to the present embodiment is added to the resin, the cellulose is more easily dispersed in the resin.
  • the cellulose-containing resin composition according to the present embodiment contains a predetermined amount of cellulose in the crystalline resin, and the cellulose is substantially uniformly dispersed in the crystalline resin to form a network without aggregation. Therefore, volumetric shrinkage can be greatly reduced even when the material is cooled after thermal melting. Thereby, the cellulose-containing resin composition according to the present embodiment can be utilized as a high-performance 3D printer filament.
  • the 3D printer filament comprising the cellulose-containing resin composition according to the present embodiment contains a predetermined amount of cellulose in the crystalline resin (eg, polypropylene), and is , good formability (that is, properties that can suppress the occurrence of cracks and cracks in the model because shrinkage after cooling after hot melting can be suppressed, and properties that have good workability after cooling after hot melting, etc.) and dimensional stability.
  • a predetermined amount of cellulose in the crystalline resin eg, polypropylene
  • good formability that is, properties that can suppress the occurrence of cracks and cracks in the model because shrinkage after cooling after hot melting can be suppressed, and properties that have good workability after cooling after hot melting, etc.
  • Cellmapp25 has a CNF content of 25 wt%) powder was prepared. Subsequently, the obtained powder of Cellmapp 25 according to Synthesis Example 1 was dried using a warm air dryer. Drying conditions were set at 80° C. for 8 hours. Cellmapp50 according to Synthesis Example 2 was also prepared in the same manner.
  • the unit of the compounding amount of each compounding substance is "wt%". Further, the details of the compounded substances are as follows. ⁇ Cellulose nanofiber (CNF) slurry (BiNFi-s WFo-10010: solid content 10 wt%, manufactured by Sugino Machine Co., Ltd.) ⁇ MAPP emulsion (aqueous emulsion of maleic anhydride-modified polypropylene (MAPP): prepared with water to a solid content of 25 wt%.)
  • CNF Cellulose nanofiber
  • BiNFi-s WFo-10010 solid content 10 wt%, manufactured by Sugino Machine Co., Ltd.
  • MAPP emulsion aqueous emulsion of maleic anhydride-modified polypropylene (MAPP): prepared with water to a solid content of 25 wt%.
  • the blending amount of CNF slurry is represented by the amount of CNF contained in the CNF slurry
  • the blending amount of MAPP emulsion is represented by the amount of MAPP contained in the MAPP emulsion.
  • kneading For kneading, a twin-screw extruder (KZW20TW, manufactured by Technobell Co., Ltd.) was used. Further, the kneading conditions are as follows. ⁇ Screw rotation speed: 200 rpm - Kneading temperature: Set the temperature of zone 1 to 130°C, the temperature of zone 2 to 160°C, and the temperature of the head to 180°C.
  • PP powder PP powder for dilution (PP powder obtained by freeze-pulverizing homotype Prime Polypro J107G (MFR: 30, manufactured by Prime Polymer Co., Ltd.))
  • the coefficient of variation CV is obtained by taking 16,384 pixels as a plurality of clusters (window size), obtaining the standard deviation (SD) and the average value (Avg.) in the cluster, and averaging the standard deviations Calculated by dividing by the value. Therefore, the smaller the standard deviation, the smaller the CV value. That is, when the window size is small, the small CV value indicates that the presence of cellulose is uniform.
  • Synthesis Example 3 (cellulose composite containing Cellmapp25) and Synthesis Example 4 (cellulose composite containing Cellmapp50) both have CV values as low as 0.0 to less than 0.4, and CNF is good. shown to be dispersed. In addition, the CV value of Synthesis Example 3 was lower than that of Synthesis Example 4, indicating that the dispersibility was more excellent.
  • Example 4 Each compounded substance was kneaded at the compounding ratio shown in Table 4 to prepare a resin for filaments for 3D printers, and then the resin was formed into filaments.
  • filaments for 3D printers were produced as follows. First, Laboplastomill ⁇ (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used as a kneading device. Mixed pellets of the compounded substances dry-blended at the compounding ratio shown in Table 4 were put into a kneading device. The kneading temperature was set to 173° C. for barrel 1, 175° C. for barrel 2, and 178° C. for the die. to prepare filaments for 3D printers (diameter: 1.75 mm ⁇ 0.1 mm) according to Comparative Example 1 and Examples 1 to 6.
  • a box-shaped structure (size: length 39 mm x width 33 mm x height 18 mm) was prototyped.
  • a 3D printer (MF-2500EP, manufactured by MUTOH INDUSTRIES CO., LTD.) was used for modeling the structure, and the temperature during modeling was set to 200° C. for the nozzle and 100° C. or 110° C. for the heater bed.
  • the nozzle operation was set at a packing density of 40% and a speed of 20 to 25 mm/s. That is, the box shape was formed by forming a flat bottom portion as the first layer and forming wall portions one by one around the bottom portion in the direction perpendicular to the bottom surface. It should be noted that the box-shaped model to be modeled is completed by stacking 59 layers.
  • the ease of modeling is determined by the height of the wall that can be modeled (that is, the first layer to the x layer and x is the number of layers that can be formed.). Specifically, the layer thickness of the first layer was set to 0.4 mm, and the layer thickness of each layer after the second layer was set to 0.3 mm in the setting at the time of modeling of the 3D printer. . Then, evaluation was performed by calculating the height of the wall from the number of layers that could be laminated by the 3D printer and the set layer thickness. It can be determined that the higher the height of the wall, the easier it is to form.
  • one of the important evaluation indices for ease of modeling is the stable formation of the first layer. If the first layer is warped or the like, the contact area with the heater bed becomes smaller, and the resistance of the resin against the heater bed becomes smaller. This is because it becomes impossible to form a model up to
  • Table 5 shows the molding results when the heater bed temperature is 110°C
  • Table 6 shows the molding results when the heater bed temperature is 100°C.
  • Example 1 it was also shown that the first layer can be shaped without warping if the height is equal to or less than the height of each wall. In other words, even when the temperature of the heater bed of the 3D printer is lower than 110° C., it was shown that warping of the first layer can be suppressed in Examples 1 to 6. In particular, in Example 1, it was shown that the inhibitory effect was remarkable.
  • the amount of CNF-15MB added was varied. That is, the CNF concentrations in the resins for filaments for 3D printers according to Example 1, and Examples 4, 5, and 6 were 1.3 wt%, 0.7 wt%, and 1.9 wt% in this order. , 2.5 wt %. Then, as shown in Table 6, when the 3D printer filament according to Example 4 was used, up to 39 layers could be modeled, and when the 3D printer filament according to Example 5 was used, up to 8 layers could be modeled. Further, when the 3D printer filament according to Example 6 was used, up to nine layers could be modeled. Therefore, it was shown that the number of layers that can be laminated can be controlled by adjusting the CNF concentration in the resin.
  • talc is contained in the resin.
  • Talc is added for the purpose of suppressing heat shrinkage when the filament melts and solidifies during modeling with a 3D printer.
  • Table 6 when the temperature of the heater bed was 100 ° C., the number of layers was up to 4 when the 3D printer filament according to Comparative Example 1 was used, while Example 3 containing no talc When such a filament for a 3D printer was used, the number of layers was 16 layers. From this result, it was shown that CNF suppresses thermal shrinkage during modeling.
  • the cellulose-containing resin composition (PP-based 3D filament composition) according to the example greatly improved the moldability of a modeled object by a 3D printer by blending CNF.
  • this improvement effect can be realized only by blending about 1 wt% of CNF with respect to the resin, so that a significant reduction in raw material costs can be realized.
  • Example using microfibrillated cellulose A composite of MFC and PP was prepared using microfibrillated cellulose (MFC).
  • MFC Microfibrillated cellulose
  • MFC Microfibrillated Cellulose
  • PP Composite a mixture obtained by mixing each compounding substance at the compounding ratio shown in Table 7 was kneaded. The mixture obtained after kneading was pulled out as a strand, cooled in a water bath, and pelletized. For kneading, a twin-screw extruder (KZW20TW, manufactured by Technobell Co., Ltd.) was used. Further, the kneading conditions are as follows. As a result, two types of MFC/PP composites (MFC-30MB(h) and MFC-30MB(b)) were obtained. ⁇ Screw rotation speed: 200 rpm - Kneading temperature: Set the temperature of zone 1 to 130°C, the temperature of zone 2 to 160°C, and the temperature of the head to 180°C.
  • ⁇ PP is a homo type (PP (homo)) prime polypro J107G (MFR: 30, manufactured by Prime Polymer Co., Ltd.) and a block type (PP (block)) prime polypro J707G (MFR: 30, manufactured by Prime Polymer Co., Ltd.). Two types were used.
  • ⁇ MAPP Kayabrid 002PP (graft rate: 2%, manufactured by Kayaku Noorion Co., Ltd.)
  • filaments for 3D printers were produced as follows. First, Laboplastomill ⁇ (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used as a kneading device. Mixed pellets of compounded substances dry-blended at the compounding ratio shown in Table 8 were put into a kneading device. The kneading temperature was set to 173° C. for barrel 1, 175° C. for barrel 2, and 178° C. for the die. 3D printer filaments (diameter: 1.75 mm ⁇ 0.1 mm) according to Examples 7 to 12 and Comparative Example 2 were produced.
  • a box-shaped structure (size: length 39 mm x width 33 mm x height 18 mm) was prototyped.
  • a 3D printer (MF-2500EP, manufactured by MUTOH INDUSTRIES CO., LTD.) was used for modeling the structure, and the nozzle temperature was 200° C. and the heater bed was 110° C. during modeling.
  • the nozzle operation was set at a packing density of 40% and a speed of 20 to 25 mm/s. That is, the box shape was formed by forming a flat bottom portion as the first layer and forming wall portions one by one around the bottom portion in the direction perpendicular to the bottom surface. It should be noted that the box-shaped model to be modeled is completed by stacking 59 layers.
  • the ease of modeling is determined by the height of the wall that can be modeled (that is, the first layer to the x layer and x is the number of layers that can be formed.). Specifically, the layer thickness of the first layer was set to 0.4 mm, and the layer thickness of each layer after the second layer was set to 0.3 mm in the setting at the time of modeling of the 3D printer. . Then, evaluation was performed by calculating the height of the wall from the number of layers that could be laminated by the 3D printer and the set layer thickness. It can be determined that the higher the height of the wall, the easier it is to form.
  • one of the important evaluation indices for ease of modeling is the stable formation of the first layer. If the first layer is warped or the like, the contact area with the heater bed becomes smaller, and the resistance of the resin against the heater bed becomes smaller. This is because it becomes impossible to form a model up to Table 9 shows the molding results when the heater bed temperature is 110°C.
  • MFC microfibrillated cellulose
  • CNF cellulose nanofibers

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JP2012229350A (ja) * 2011-04-27 2012-11-22 Kyoto Univ 樹脂組成物
JP2017141323A (ja) * 2016-02-08 2017-08-17 大日精化工業株式会社 易分散性セルロース組成物、易分散性セルロース組成物の製造方法、セルロース分散樹脂組成物及びセルロース分散樹脂組成物の製造方法
JP2017170881A (ja) * 2016-03-18 2017-09-28 スターライト工業株式会社 ３ｄプリンタ用造形材料、その製造方法、および三次元造形物
JP2021503394A (ja) * 2017-11-16 2021-02-12 ユニバーシティー オブ メイン システム ボード オブ トラスティーズ ３ｄ印刷のための改善されたフィラメント
WO2021075224A1 (ja) * 2019-10-17 2021-04-22 国立大学法人静岡大学 セルロース複合体の製造方法、セルロース複合体／樹脂組成物の製造方法、セルロース複合体、及びセルロース複合体／樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012229350A (ja) * 2011-04-27 2012-11-22 Kyoto Univ 樹脂組成物
JP2017141323A (ja) * 2016-02-08 2017-08-17 大日精化工業株式会社 易分散性セルロース組成物、易分散性セルロース組成物の製造方法、セルロース分散樹脂組成物及びセルロース分散樹脂組成物の製造方法
JP2017170881A (ja) * 2016-03-18 2017-09-28 スターライト工業株式会社 ３ｄプリンタ用造形材料、その製造方法、および三次元造形物
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WO2021075224A1 (ja) * 2019-10-17 2021-04-22 国立大学法人静岡大学 セルロース複合体の製造方法、セルロース複合体／樹脂組成物の製造方法、セルロース複合体、及びセルロース複合体／樹脂組成物

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