WO2016129613A1 - Matière à mouler - Google Patents

Matière à mouler Download PDF

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Publication number
WO2016129613A1
WO2016129613A1 PCT/JP2016/053884 JP2016053884W WO2016129613A1 WO 2016129613 A1 WO2016129613 A1 WO 2016129613A1 JP 2016053884 W JP2016053884 W JP 2016053884W WO 2016129613 A1 WO2016129613 A1 WO 2016129613A1
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WO
WIPO (PCT)
Prior art keywords
modeling material
fiber
modeling
fibers
fiber bundle
Prior art date
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PCT/JP2016/053884
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English (en)
Japanese (ja)
Inventor
雄俊 中谷
迫部　唯行
こゆ 田代
秀仁 安藤
Original Assignee
ユニチカ株式会社
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Publication of WO2016129613A1 publication Critical patent/WO2016129613A1/fr

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    • 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
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof

Definitions

  • the present invention relates to a modeling material, and more particularly to a modeling material that can be suitably used for a material extrusion molding apparatus such as a three-dimensional printer (hereinafter sometimes abbreviated as “3D printer”).
  • a material extrusion molding apparatus such as a three-dimensional printer (hereinafter sometimes abbreviated as “3D printer”).
  • 3D printers that create 3D objects based on design drawings on computers can easily make plastic parts, jigs, and products without using molds or melting equipment. For this reason, 3D printers are rapidly spreading mainly in companies.
  • a 3D printer using a hot melt lamination method (FDM) using a thermoplastic resin as a modeling material has been sold as a low-priced version and has begun to spread to individuals.
  • FDM hot melt lamination method
  • a linear resin molded product made of a thermoplastic resin having a diameter of several mm and continuous in the longitudinal direction is commercially available.
  • a high-precision modeling material an average diameter of 0.069 to 0.074 inches (about 1.75 to 1.88 mm), a length of 20 feet (about 6.1 m) or more, a diameter Has disclosed a modeling material (feed material) having a standard deviation of 0.0004 inches (0.01 mm) or less.
  • a thermoplastic resin constituting such a modeling material a thermoplastic resin such as ABS resin, polycarbonate, polyamide, polylactic acid is used.
  • the hot melt lamination method is also called a material extrusion method.
  • the modeling material constituted by the continuous linear resin molded product (monofilament-like product) as described above is hard and therefore has poor handleability.
  • the molding material formed of polylactic acid is particularly hard.
  • Such a hard linear modeling material is released from the state where it is wound around the bobbin or the like, and as soon as the winding tension is slightly relaxed, the wound state is released and is scattered from the bobbin. There is a case. This situation is called “crash”.
  • those that are not crystallized have a problem of being easily broken during use.
  • an object of the present invention is to provide a modeling material with good handleability.
  • the modeling material of the present invention is characterized in that it is formed of a long fiber bundling body configured by bundling a plurality of synthetic fibers.
  • the present invention since it is formed of a long fiber bundle formed by bundling a plurality of synthetic fibers, it is flexible, hard to break, and has good handleability.
  • a modeling material particularly suitable for a 3D printer can be provided.
  • the modeling material of the present invention is formed of a long fiber bundling body configured by bundling a plurality of synthetic fibers.
  • Synthetic fibers constituting the fiber bundle are not particularly limited.
  • polyester resins, polyamide resins, and polyolefin resins can be suitably used because of the ease of adjusting the single fiber fineness and mechanical properties and the high versatility.
  • polylactic acid is preferable because warpage is unlikely to occur, and poly-L lactic acid having a low D-form content is more preferable because it is less yellowish.
  • the D-form content is preferably less than 1.5 mol%.
  • the melting point of polylactic acid can be adjusted by adjusting the D-form content.
  • a fiber blended with a polymer blend or polymer alloy composed of two or more resins, or a composite fiber of two or more resins into a sea-island type, a core-sheath type, a side-by-side type, etc. can be used as a synthetic fiber. .
  • the modeling material of the present invention When the modeling material of the present invention is used for the melt lamination modeling method of a 3D printer, the modeling material needs to be meltable at the melting temperature of the modeling head in the 3D printer.
  • the resin melting point of the thermoplastic synthetic fiber constituting the modeling material is preferably 400 ° C. or less, more preferably 250 ° C. or less, and further preferably 200 ° C. or less.
  • the softening point can be considered the melting point.
  • the high molecular polymer used for synthetic fibers is amorphous and a clear peak cannot be obtained in a calorimetric analysis such as a differential scanning calorimeter (DSC), it can be melted by a melt flow rate or a capillary rheometer.
  • the flow start temperature in the viscosity analysis can be used as an alternative to the melting point.
  • the synthetic fiber constituting the fiber bundle can take the form of monofilament yarn, multifilament yarn, spun yarn and the like.
  • the diameter and cross-sectional shape are not limited.
  • the diameter and cross-sectional shape of the single yarn are not limited, and the number of filaments and the total fineness can be set to arbitrary values.
  • the diameter, cross-sectional shape, presence or absence of crimping, etc. of the short fiber material to be used is not limited, and the number of twists and yarn counts as well as the presence or absence of twisting are not limited.
  • the form of the synthetic fiber may be a form of only a continuous fiber or a form of a short fiber having a specific fiber length.
  • a continuous form in which mixed spun yarns obtained by mixing continuous fibers and short fibers are converged may be used.
  • Such spun yarn may be used as a bundle of thermoplastic synthetic fibers for obtaining braids or twisted yarns.
  • the form of the synthetic fiber may be a processed thread made of continuous fiber. Examples of the processed yarn include air entangled yarn, false twisted yarn, and BCF (Bulked Continuous Filament).
  • continuous fibers having different finenesses may be mixed.
  • continuous fibers having different finenesses it may be in the form of a composite yarn in which the periphery of a filament with a high fineness is braided with a multifilament yarn, or a composite yarn in which the periphery of a filament with a high fineness is wound with a multifilament yarn.
  • An example of the filament having a high fineness is a monofilament yarn. For example, by arranging the monofilament yarn at the center of the fiber bundle, the density at the center becomes uniform.
  • a monofilament yarn having a low-melting-point heat-bonding component on the fiber surface is a fiber bundling body arranged in the center part, and is excellent in close contact with the fibers arranged around the center part by heat treatment. Integrate and focus.
  • a composite fiber prepared by preparing a plurality of one or more types of synthetic fibers and combining them by means of drawing, twisting, blending, entanglement, etc. can be used as a synthetic fiber.
  • the spun yarn a plurality of types of short fiber materials can be combined by blending.
  • the fineness of the single fiber of the thermoplastic synthetic fiber can be appropriately set in consideration of the number of yarns when converging, the diameter of the modeling material, the density when converging, and the durability. For example, when the fineness of a single fiber is high, durability against friction and the like is high, but a gap between the fibers becomes large, and a void may be generated during modeling using a modeling material.
  • the cross-sectional shape of the single fiber can be appropriately set in consideration of handling properties, density at the time of focusing, and the like. Examples of the cross-sectional shape include a round shape, an oval shape, a polygonal shape (triangle, quadrangle, etc.), and a multi-leaf shape (cross shape, star shape, etc.). A combination of fibers having different cross-sectional shapes may be used.
  • the modeling material is formed by a fiber bundle formed of two types of resins having different melting points
  • a modeling material can be manufactured by heat-treating the fiber structure at a temperature TA (MX ⁇ TA ⁇ MY).
  • the melting temperature TB at the time of modeling is MX and MY ⁇ TB.
  • the fiber bundling body can be constituted by the composite-form fibers obtained by combining the two types of resins X and Y.
  • the composite form include a core-sheath composite form in which the resin X is arranged in the sheath and the resin Y is arranged in the core. It is also possible that a functional material described later is supported on the surface of the fiber bundle by melting and solidifying the low melting point resin X.
  • the fiber bundling body is formed by bundling a plurality of synthetic fibers into a single continuous thread form.
  • forms such as a twisted thread, a braid, a rope, a chain knitting, are mentioned.
  • the synthetic fibers and / or fiber bundles may be heat-set by dry heat or steam.
  • a part of the fiber bundle is formed by heat setting at a temperature not lower than the melting point of the low melting point synthetic fiber and not higher than the melting point of the high melting point synthetic fiber as described above.
  • the heat setting may be performed simultaneously with the coating and impregnation processing of the resin portion described later, or may be performed before or after the processing of the resin portion.
  • Examples of the method for bundling a plurality of synthetic fibers include a method of twisting, a method of making a string, a method of heat bonding by heat treatment, a method of entanglement, and a method of mixing fibers. More specifically, a method of twisting and focusing a plurality of synthetic fibers, forming a braid by making a string using two or more bundles of a plurality of synthetic fibers aligned and twisted.
  • a method of bundling a method of bundling a plurality of synthetic fibers by heat treating them to melt or soften a part of the thermoplastic resin constituting the synthetic fibers and thermally bonding the fibers together, a plurality of And a method in which these synthetic fibers are bundled by entanglement, or a combination of these twists, string making, thermal bonding, and entanglement.
  • two or more single-twisted fiber bundles are twisted in a direction opposite to the single-twist and converged, and so-called various twists are applied to make it difficult to unwind. It is also preferable to heat-treat after twisting and fix the form by heat fixing or heat bonding.
  • the twist direction of the fiber bundle that has been twisted before the various twists that is, the direction of the lower twist is the same direction. That is, a fiber bundle twisted in the same direction is selected. What is necessary is just to adjust suitably the number of times of under twist according to the fineness. A preferred range is 50 to 1000 times / m.
  • the number of twists can be appropriately determined according to the thickness and number of fiber bundles used.
  • either flat punching, square punching or round punching may be applied.
  • a continuous linear material generally used as a feed material to a hot melt lamination type 3D printer a braided cord by round punching is preferable because many of the continuous linear materials have a circular cross section.
  • round punching in order to obtain a more perfect circle shape, it is preferable to use four or more strikes, more preferably eight or more strikes, and further preferably 16 or more strikes.
  • a form in which a core thread is arranged at the center part in the radial direction of the braid and a plurality of threads are arranged as side threads around the core thread as a center is preferable. This is because the density of the central portion is increased in the cross section of the resulting modeling material, and voids are less likely to occur.
  • the braid can be adjusted in the texture and the density of fibers can be improved by heat treatment.
  • a low-melting point thermoplastic synthetic fiber is mixed as the bundling thermoplastic synthetic fiber, and after bundling or twisting, the low melting point It is preferable that heat treatment is performed at a temperature at which the thermoplastic synthetic fiber melts to cause the low-melting thermoplastic synthetic fiber to function as an adhesive so that the constituent fibers are thermally bonded to each other, thereby improving convergence.
  • the modeling material of the present invention may have a configuration in which at least a part of the plurality of thermoplastic synthetic fibers constituting the fiber bundle includes a functional additive.
  • the functional additive is added to a modeling material that is a material for imparting a desired function to a modeled object manufactured by the modeling material.
  • a modeling material that is a material for imparting a desired function to a modeled object manufactured by the modeling material.
  • antioxidants for example, antioxidants, weathering agents, antistatic agents, dispersants, lubricants, flame retardants, colorants, antibacterial agents, thermal conductive additives, conductive soot additives, perfumes, water-soluble additives, smoothing agents, plasticizers , X-ray opaquers, fillers, impact resistance improvers, crystal accelerators, compatibilizers and the like.
  • examples of the antioxidant include phenol-based, organic phosphite-based, organic phosphorus-based and thioether-based compounds such as eggplant.
  • weathering agents examples include hindered amines, benzophenones, benzotriazoles, and benzoates.
  • antistatic agent examples include nonionic, cationic and anionic agents.
  • dispersing agent examples include bisamide-based, wax-based and organometallic salt-based ones.
  • lubricants examples include amides, waxes, organometallic salts, and esters.
  • Examples of the flame retardant include bromine-containing organic, phosphoric acid, antimony trioxide, magnesium hydroxide, ammonium phosphate, and red phosphorus.
  • colorant examples include pigments such as carbon black, titanium oxide, perylene, quinacridone, and phthalocyanine, and dyes such as azo, indigo, quinone, xanthene, and pyridone benzodifuranone.
  • dyes such as azo, indigo, quinone, xanthene, and pyridone benzodifuranone.
  • examples include quinoline-based, pyridinone-based, organometallic-based fluorescent / phosphorescent pigments, and vanadium oxide, polydiacetylene-based, viologen-based chromic pigments, and the like.
  • antibacterial agent examples include silver, copper, silver-zeolite, photocatalytic titanium oxide, organic nitrogen sulfur compound, isothiazolone, carboxylic acid, and organometallic.
  • heat conductive additive examples include metals, carbons, ceramics, and silicate minerals.
  • Examples of the conductive additive include metals, carbons, ceramics, and conductive polymers.
  • fragrances include natural fragrances, synthetic fragrances, and compounds that generate fragrances. More specifically, there are animal flavors such as vegetable essential oils and musks, and synthetic flavors such as limonene and nerolidol.
  • water-soluble additives examples include polyvinyl alcohol, starch and acrylic acid.
  • Examples of the smoothing agent include silicones, fluorines, and waxes.
  • plasticizer examples include phthalic acid, adipic acid, phosphoric acid, and wax.
  • X-ray opaquers examples include barium sulfate, lead-based, tungsten-based and the like.
  • fillers examples include metal-based, carbon-based, glass-based, and cellulose-based materials.
  • impact resistance improvers include various polymers, elastomers, and core-shell impact resistance improvers.
  • crystallization accelerator examples include metal oxide, silicate, fatty acid ester, organic sulfonate, phosphate metal salt, glycerin, and polyalkylene glycol.
  • compatibilizer examples include ethylene vinyl alcohol, styrene, ester and amide.
  • thermoplastic synthetic fiber constituting the modeling material.
  • the containing method include a method of blending in a step of producing a thermoplastic polymer composition that is a material for synthetic fibers by appropriately combining one or more of the above-described additives.
  • additives can be blended by melt kneading using a known kneading apparatus such as a single or twin screw extruder, a Banbury mixer, a kneader, or a mixing roll.
  • a so-called master batch having a high concentration may be prepared using an additive, and this may be diluted and used.
  • an additive to the fiber by immersing or exhausting the additive in a single synthetic fiber or a bundle of synthetic fibers in a later step.
  • the additive is, for example, a dye
  • it can be supported on the surface and inside of the synthetic fiber by a known method such as vat dyeing or washer dyeing.
  • auxiliary agents such as carriers, leveling agents, and pH adjusting agents can be used as necessary, and a refining step, a soaping step, and a fixing step can be added.
  • the content of the functional additive may be an amount that can exhibit a desired function, and can be appropriately set according to the type of the additive.
  • all the synthetic fibers may contain a functional additive. Or only some synthetic fibers may contain a specific functional additive. Furthermore, a plurality of synthetic fibers may contain different additives, and a plurality of synthetic fibers containing different additives may be converged to form a modeling material containing a plurality of types of additives.
  • the amount of the functional additive contained in the modeling material can be easily adjusted to a desired amount by appropriately combining the synthetic fiber containing the additive and the synthetic fiber not containing the additive.
  • a modeling material capable of imparting various functions can be obtained. According to this modeling material, it is possible to easily obtain a modeled object that can exhibit various functions.
  • Fluorescent materials and phosphorescent materials can be mentioned as functional additives.
  • the fluorescent material and the phosphorescent material include known materials. Specifically, examples thereof include fluorescent whitening agents, labels, organic materials and inorganic materials used as light emitting elements for various displays, and nanomaterials such as quantum dots and carbon nanotubes.
  • examples of low molecular weight organic materials include fluoresceins, rhodamines, coumarins, pyrenes, and cyanines.
  • the polymer include poly (1,4-phenylenevinylene) s, polythiophenines, and polyfluorenes.
  • inorganic materials include aluminates, silicates, halophosphones, oxynitrides and the like.
  • One kind of fluorescent material or phosphorescent material may be used, or two or more kinds thereof may be used in combination, or one or more of each of fluorescent material and phosphorescent material may be used.
  • the excitation wavelength of light emission and the light emission wavelength may be overlapping or different.
  • the content of the fluorescent material or phosphorescent material in the fiber is preferably 0.1 to 20% by mass, although it depends on the light emitting property of the material.
  • thermoplastic resin constituting the fiber Since the thermoplastic resin constituting the fiber is highly transparent, the luminous efficiency can be increased when a fluorescent material or a phosphorescent material is included in the resin. When some of the fibers contain a fluorescent material or a phosphorescent material, other fibers that do not contain these materials are also highly transparent, so that these light emitting functions can be exhibited effectively. .
  • the thermoplastic resin constituting the fiber is preferably hydrophobic. The hydrophobic resin does not easily absorb moisture, and therefore does not absorb moisture at the time of manufacturing or storing the modeling material, or at the time of manufacturing or after the manufacturing of the modeled object obtained using the modeling material. Therefore, the fluorescent material or phosphorescent material contained in the resin constituting the fiber does not deteriorate in function due to moisture absorption, and the performance can be effectively exhibited over a long period of time.
  • Fluorescent materials and phosphorescent materials often deteriorate in function under the influence of ultraviolet rays, humidity, and moisture. If the function deteriorates, it becomes difficult to maintain the light emission characteristics over the long term. For this reason, fibers containing fluorescent material or phosphorescent material are arranged in the center of the fiber bundling body to form a light emitting region, and fibers not containing fluorescent material or phosphorescent material are arranged and focused so as to cover the periphery. A configuration in which the fibers containing the fluorescent material or the phosphorescent material are not easily exposed on the surface of the fiber bundle is preferable.
  • a configuration in which a fiber bundle containing a fluorescent material or a phosphorescent material is arranged on the core yarn, and a fiber not containing the fluorescent material or the phosphorescent material is arranged on the side yarn, and a braided string is preferable.
  • the fiber constituting the fiber bundle is a core-sheath composite fiber, a resin containing a fluorescent material or phosphorescent material is arranged in the core component, and another resin not containing the fluorescent material or phosphorescent material is a sheath component
  • a configuration arranged in the above is also preferable.
  • a fiber containing a fluorescent material or a phosphorescent material and a fiber not containing this are melted or softened by heating, but are unlikely to be mixed and have a cross-sectional structure in which the outer periphery of the light emitting region is covered by a non-light emitting region While maintaining, predetermined modeling is performed.
  • the thermoplastic resin containing the fluorescent material or phosphorescent material is not exposed to the outer surface, and therefore the fluorescent material or phosphorescent material is exposed to the outside air. In other words, these materials are covered with a thermoplastic resin that does not contain these materials.
  • the light emitting function can be exhibited for a long time and effectively. Therefore, the shaped object to be obtained can be used in applications where it comes into contact with water or in places with high humidity. More specifically, the present invention can be applied to outdoor use, vase, cup, use around a washstand, and use around a bathtub, and in that case, the light emitting function can be exhibited over a long period of time.
  • thermoplastic resin As long as a positive stirring mechanism is not provided in the nozzle head of the modeling device or a low-viscosity thermoplastic resin is used so that the resins are mixed in the nozzle head, the modeling material does not cause mixing as described above. A shaped article can be obtained while maintaining the cross-sectional structure. Therefore, it is preferable to appropriately select the viscosity and design temperature of each thermoplastic resin so that the two regions in the nozzle head are not mixed by melting.
  • the modeling material described above protects the fluorescent material and the phosphorescent material by covering the light emitting region containing the fluorescent material or phosphorescent material which is the functional agent with the non-light emitting region not containing the fluorescent material or phosphorescent material.
  • the function is prevented from deteriorating and the light emitting function is maintained for a long time.
  • This action can be applied not only to the case where the functional agent is a fluorescent material or a phosphorescent material, but also to other functional agents whose function is deteriorated due to moisture absorption or the like.
  • the modeling material can be in the form of a composite in which the above-described fiber bundle is coated and impregnated with the resin portion.
  • This resin part is mainly composed of a thermoplastic resin, and is impregnated and / or coated on a fiber base material (fiber bundle itself or synthetic fibers constituting the fiber bundle) by a wet or dry method.
  • the material constituting the plastic resin part can be selected from various resins depending on the adhesiveness and workability with the synthetic fiber as the base material, or the properties of the obtained composite or molded product.
  • polyolefin resin acrylic resin, vinyl acetate resin, polyester resin, polyamide resin, vinyl chloride resin, vinylidene chloride resin, polytetrafluoroethylene resin, silicone resin, polyurethane resin, etc. are suitable. It is. It is also possible to use a mixture of a plurality of types of resins depending on the required performance. If necessary, other components may be added to the resin. Fillers, plasticizers, flame retardants, colorants, lubricants, weathering agents, antibacterial agents, antioxidants, heat-resistant agents, etc. You may add suitably in the range which does not impair an effect.
  • the fiber base material is impregnated and / or coated by a method such as dipping or padding.
  • a method such as dipping or padding.
  • the above resin can be melted by heat and impregnated and / or coated by extrusion molding or pultrusion molding through a pore together with a fiber base material.
  • the synthetic fiber constituting the fiber bundle may be subjected to a surface treatment such as grafting or plasma processing with an electron beam or radiation in order to enhance adhesion with the resin part. Furthermore, in the fiber manufacturing process and / or the post-process, an appropriate fiber oil or coating agent may be applied or impregnated from the viewpoint of adhesiveness.
  • the composite obtained by the above method is formed by linearly forming a long fiber bundle by covering and / or impregnating a resin part, and for a 3D printer using a hot melt lamination method It can be used as a modeling material. That is, a resin molded product can be obtained by melting and molding this modeling material at a temperature equal to or higher than the melting point of the synthetic fiber constituting the fiber bundle and the thermoplastic resin constituting the resin portion.
  • the composite as the modeling material is flexible because it is composed of a long fiber bundle formed by bundling a plurality of synthetic fibers, and the resin bundle is coated on the fiber bundle.
  • the fiber bundle since the fiber bundle is integrated, it has an appropriate rigidity and durability, that is, it has both flexibility, rigidity and durability. Therefore, the composite can be particularly preferably used as a modeling material for a 3D printer. That is, since it has appropriate flexibility, it is easy to handle.
  • the feeding in order to have appropriate rigidity and durability, even if feeding is performed by a knurling type feeding device inside the 3D printer, the feeding can be satisfactorily performed, and the surface is damaged by the knurling of the feeding device. It has the advantage that there is nothing.
  • the modeling material can be one in which a functional material is supported on a fiber bundle.
  • the functional material can contain the aforementioned functional additives.
  • the functional additive include a conductive additive, a heat conductive additive, an antioxidant, a weathering agent, an antistatic agent, a dispersant, a lubricant, a flame retardant, a colorant, a fluorescent agent, and a phosphorescent agent. It is done. Short fiber-like organic fiber cocoons, inorganic fibers, and natural fibers are also included.
  • the functional material preferably contains a thermoplastic binder in addition to the above functional additive in order to obtain an adhesive force with the fiber bundle.
  • “Supporting” means a state in which the functional material is not present inside the polymer constituting the fiber bundle by kneading or the like, but is integrally present on the outer surface by adhesion or the like.
  • the functional material is a conductive material including a conductive additive and a thermoplastic binder, it is difficult to achieve both the mechanical properties and the conductive performance of the synthetic fiber by the method of kneading the conductive additive, There are limitations on the type and amount of conductive additive that can be used.
  • the mechanical properties as a modeling material for the melt lamination type 3D printer can be adjusted by the synthetic fiber, and the conductivity of the obtained molded product is the structure of the conductive material or The amount of the conductive material can be adjusted, and the type and amount of the conductive material can be selected widely.
  • the conductive additive can be selected from carbon-based, metal-based, ceramic-based and conductive polymers.
  • carbon-based materials include conductive carbon black such as ketjen black, carbon fiber, and carbon nanotube (CNT).
  • metal-based material include single metal such as silver, copper, and zinc, or compound particles and fibrous materials.
  • ceramic system include materials such as silicon carbide and alumina.
  • the conductive polymer include polythiophene compounds, polyaniline compounds, and polypyrrole compounds. The above conductive additives can be used singly or in a plurality of types depending on the usage and required performance of the shaped article.
  • the thermoplastic binder functions as a matrix for the conductive material and plays a role of bonding the fiber bundle and the conductive material.
  • the thermoplastic binder is composed of a thermoplastic resin material, but can be selected from various resins depending on the adhesiveness and workability with the synthetic fibers that make up the fiber bundle and the properties of the resulting composite and molded product. It is. For example, polyolefin resins, acrylic resins, vinyl acetate resins, polyester resins, polyamide resins, vinyl chloride resins, polytetrafluoroethylene resins, silicone resins, polyurethane resins and the like can be suitably used. Depending on the required performance, it is possible to mix a plurality of types of resins to form a thermoplastic binder.
  • the compounding ratio of the conductive additive and the thermoplastic binder in the conductive material is not particularly limited, and the mass ratio of the conductive material to the fiber bundle is not particularly limited, either of which can be freely set depending on the application and required performance. .
  • other components may be added to the conductive material, such as fillers, plasticizers, flame retardants, colorants, lubricants, weathering agents, antibacterial agents, antioxidants, heat resistant agents, short fiber fillers, A fragrance, a water-soluble material, a smoothing agent, an X-ray impermeable agent, an impact resistance improver, a compatibilizing agent, a viscosity modifier, and the like may be appropriately added within a range not impairing the effects of the present invention. These components may be the same as those described above.
  • the specific resistance value of the conductive material is preferably 10 7 ⁇ ⁇ cm or less.
  • the method for supporting the conductive material on the fiber bundle is not particularly limited, and commonly used processing means can be applied. For example, a technique of immersing and drying a fiber bundle in a dispersion containing a conductive additive and a thermoplastic binder, a technique of coating the dispersion, and the like can be given. If necessary, the amount of the conductive material supported can be increased by repeating the method for supporting the conductive material. In addition to the treatment of supporting the conductive material on the fiber bundle, it is also possible to form the fiber bundle using synthetic fibers carrying the conductive material. Depending on the purpose, another synthetic fiber or a binder may be further coated on the outer layer of the composite obtained by supporting the conductive material on the fiber bundle. By doing so, a protective film against external force such as friction can be configured.
  • a synthetic fiber subjected to bulk processing or crimping processing can be suitably used in order to structurally improve the adhesive force and carrying amount with the conductive material.
  • Such a composite can be used as a modeling material for a 3D printer of the hot melt lamination method.
  • a conductive resin molded product By melting and molding at a temperature equal to or higher than the melting point of the synthetic fiber and the thermoplastic binder, a conductive resin molded product can be obtained. Obtainable.
  • the method of mixing modeling materials include a method of supplying materials simultaneously or sequentially to one feeder of a hot melt lamination type 3D printer, and a method of supplying materials separately to a plurality of feeders. This composite is also applicable to 3D pens.
  • the discharge speed from the nozzle head of the 3D printer when a known monofilament as the modeling material is used is usually specified.
  • the fiber form of the modeling material is compared with the case of using a monofilament. Therefore, it is necessary to change the discharge speed accordingly.
  • K 2500 ⁇ ⁇ ⁇ ⁇ ⁇ R 2 ⁇ cos ⁇ ⁇ (A ⁇ F) (1) here, ⁇ : Specific gravity of resin constituting the synthetic fiber ⁇ : Circumferential ratio A: Total fineness (dtex) of the synthetic fiber used for the fiber bundle ⁇ : Angle (degrees) formed by the fiber axis of the synthetic fiber with respect to the longitudinal direction of the fiber bundle F: Overfeed rate when the fiber bundle is heat-treated R: Cross-sectional diameter of the modeling material (mm) It is.
  • the angle ⁇ formed by the fiber axis of the synthetic fiber with respect to the longitudinal direction of the modeling material can mean, for example, the twist angle when the synthetic fiber is twisted.
  • the synthetic fiber means a synthetic fiber used when the fiber bundle is finally formed.
  • this synthetic fiber is a single piece of the original synthetic fiber, or a plurality of the original synthetic fibers are bundled and aligned, combined by means such as twisting and entanglement
  • the angle formed by the fiber axis of the synthetic fiber with respect to the longitudinal direction of the fiber bundle is defined as ⁇ .
  • the fiber bundling body is a braid composed of a plurality of synthetic fibers (a braid angle of 20 degrees), and a plurality of synthetic fibers based on the synthetic fiber are twisted together (a twist angle of 10 degrees).
  • a braid angle of 20 degrees a braid angle of 20 degrees
  • a plurality of synthetic fibers based on the synthetic fiber are twisted together (a twist angle of 10 degrees).
  • the angle ⁇ used in the equation (1) is 20 degrees.
  • the overfeed rate F takes this into consideration. For this reason, the overfeed rate F is usually a value larger than 1. On the other hand, when the fiber is stretched during the heat treatment, underfeed may occur. In this case, the overfeed rate F is a value smaller than 1.
  • the formula (1) is transformed into the following formula (2).
  • the subscript 1-n means the number of the synthetic fiber.
  • K 2500 ⁇ ⁇ ⁇ R 2 ⁇ F ⁇ ⁇ (A 1 ⁇ ⁇ 1 ⁇ cos ⁇ 1 ) + (A 2 ⁇ ⁇ 2 ⁇ cos ⁇ 2 ) +... + (A n ⁇ ⁇ n ⁇ cos ⁇ n ) ⁇ ...
  • ⁇ n Specific gravity of the resin constituting the synthetic fiber n
  • An Total fineness (dtex) of the synthetic fiber n used in the fiber bundle
  • ⁇ n angle (degree) formed by the fiber axis of the synthetic fiber n with respect to the longitudinal direction of the fiber bundle It is.
  • the modeling material is a fiber bundling body constituted by a plurality of types of synthetic fibers having different materials or different single fiber finenesses
  • the case where the modeling material is a fiber bundling body constituted by monofilament yarns and multifilament yarns Apply Equation (2).
  • the modeling material currently formed with the converging body can be used appropriately.
  • the physical properties of the fibers were tested according to JIS-L-1013 of Japanese Industrial Standard.
  • 1 kg was wound around a bobbin having a diameter of 100 mm and evaluated.
  • a cube having a modeling temperature of 230 ° C., a stacking pitch of 0.1 mm, a density of 100% and a side of 3 cm was prepared using a SCOEVO C170 type 3D printer manufactured by Abee Corporation. The appearance was visually confirmed.
  • Example 1 A polylactic acid chip (manufactured by Nature Works LLC (6201D): D body content: 1.4%) is melt-spun with an extruder-type spinning machine, stretched, and has a strength of 4.0 cN / dtex and an elongation of A multifilament made of polylactic acid fibers of 30%, 1900 dtex / 210 filaments was obtained. The multifilament made of the polylactic acid fiber was stringed with a 16 round stringing machine, and then heat-set at 100 ° C. for 2 minutes to obtain the modeling material of Example 1.
  • Example 2 A polylactic acid chip (manufactured by Nature Works LLC (6400D): D-form content 1.9%) is melt-spun with an extruder-type spinning machine and stretched to have a strength of 5.6 cN / dtex and an elongation of A multifilament made of polylactic acid fibers of 27%, 1900 dtex / 210 filaments was obtained. A multifilament made of the polylactic acid fiber was stringed with a 16 round stringing machine, and then heat-set at 100 ° C. for 2 minutes to obtain a modeling material of Example 2.
  • Example 3 A polylactic acid chip (manufactured by Nature Works LLC (6201D): D body content: 1.4%) is melt-spun with an extruder-type spinning machine, stretched, and has a strength of 4.0 cN / dtex and an elongation of A multifilament made of polylactic acid fibers of 30%, 1900 dtex / 210 filaments was obtained.
  • a multifilament made of the polylactic acid fiber is S-twisted at 120 times / m in a ring twisting machine, and then two twisted yarns are similarly twisted at a Z-twisting 100 times / m, and then 100 ° C. 2 Heat setting was performed in minutes, and the modeling material of Example 3 was obtained.
  • Example 4 A polylactic acid chip (manufactured by Nature Works LLC (6201D)) was melt-spun with an extruder-type spinning machine and stretched to have a strength of 4.0 cN / dtex, an elongation of 30%, and a dry heat shrinkage of 15 %, 800 dtex / 96 filament, single phase multifilament (A) made of polylactic acid fiber was obtained.
  • a polylactic acid chip for the core manufactured by Nature Works LLC (6201D): D-form content 1.4%, melting point 170 ° C.
  • a polylactic acid chip for the sheath (Nature Works LLC) (6302D): D body content: 9.9%, melting point: 130 ° C.)
  • melt-spun at a core-sheath mass ratio of 1: 1 melt-spun at a core-sheath mass ratio of 1: 1, and stretched to have a strength of 3.0 cN / dtex and an elongation of 35%.
  • a single-phase multifilament (A) made of polylactic acid fiber and a core-sheath multifilament (B) made of polylactic acid binder fiber are S-twisted at a rate of 120 times / m in a ring twisting machine, and 16 Stringing was carried out with this round punching machine, and then heat setting was performed at 140 ° C. for 2 minutes to obtain a modeling material of Example 4.
  • Comparative Example 1 Using a polylactic acid chip (manufactured by Nature Works LLC (6201D)), melt spinning with an extruder-type spinning machine and drawing, the strength is 3.5 cN / dtex, the elongation is 28%, 30000 dtex (diameter of about 1) .75 mm) of polylactic acid monofilament.
  • the handling properties of the modeling materials of Examples 1 to 4 were all flexible and could be wound up neatly on a bobbin.
  • the handling property of the modeling material of Comparative Example 1 was hard and difficult to wind around the bobbin, and when the winding force was weakened, a crash occurred.
  • the molding materials of Examples 1 to 4 can be applied to a 3D printer using a hot melt lamination method to obtain a good three-dimensional molded product, and are more flexible and easier to handle than the monofilament of Comparative Example 1. Was confirmed to be good.
  • Example 5 Using a polylactic acid chip (manufactured by Nature Works LLC (6201D)), melt spinning with an extruder-type spinning machine and drawing were performed to obtain colorless multifilaments of polylactic acid fibers of 560 dtex / 96 filaments.
  • a polylactic acid chip manufactured by Nature Works LLC (6201D)
  • the resulting fiber bundles in which 5 multifilaments were aligned were further bundled together and bundled by twisting them with an S twist of 150 times / m (S-150) using a ring twisting machine.
  • the bundled twisted yarn was heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 5 having a wire diameter of 1.75 mm.
  • the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 6 The fiber bundle obtained by aligning the five multifilaments used in Example 5 was twisted using a ring twisting machine at a Z twist of 60 times / m (Z-60). Seven pieces of the obtained twisted yarn (Z-60) were bundled and subjected to top twisting at 150 times S / m (S-150) using a ring twisting machine to obtain various twisted yarns. The various plied yarns were heat-treated at 165 ° C. for 1 minute to obtain the modeling material of Example 6 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 7 Compared to Example 6, the difference was that the number of preliminary twists was Z twist 180 times / m (Z-180). Other than that was carried out similarly to Example 6, and obtained the modeling material of Example 7 of wire diameter 1.75mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 8 Compared to Example 6, the difference was that the number of times of lower twist was Z twist 300 times / m (Z-300). Other than that was carried out similarly to Example 6, and obtained the modeling material of Example 8 with a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 9 Using a polylactic acid chip (manufactured by Nature Works LLC (6201D)), melt spinning was performed with an extruder-type spinning machine, and drawing was performed to obtain a filament. The obtained filaments were mechanically crimped and cut to obtain colorless staple fibers made of polylactic acid having a single yarn fineness of 1.7 dtex and a fiber length of 51 mm. Spinning was performed using this staple fiber to obtain a 20th spun yarn.
  • a polylactic acid chip manufactured by Nature Works LLC (6201D)
  • melt spinning was performed with an extruder-type spinning machine, and drawing was performed to obtain a filament.
  • the obtained filaments were mechanically crimped and cut to obtain colorless staple fibers made of polylactic acid having a single yarn fineness of 1.7 dtex and a fiber length of 51 mm. Spinning was performed using this staple fiber to obtain a 20th spun yarn.
  • Eight of the obtained spun yarns were twisted using a ring twisting machine at a Z twist of 60 times / m (Z-60) to form a twisted yarn, and eight of the obtained twisted yarns (Z-60) were bundled to form a ring.
  • S-twist was 150 times / m (S-150), and an upper twist was applied to obtain various twisted yarns.
  • the various plied yarns were heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 9 having a wire diameter of 1.75 mm.
  • the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 10 Ten spun yarns used in Example 9 were subjected to Z twist 60 times / m (Z-60) with a ring twisting machine to form a spun yarn.
  • Example 5 four multifilaments used in Example 5 were subjected to a Z twist 60 times / m (Z-60) with a ring twisting machine to form a multifilament twisted yarn.
  • Example 11 Two spun yarns used in Example 9 and three multifilaments used in Example 5 were bundled, and a twisted yarn was obtained by applying a lower twist at a Z twist of 60 times / m (Z-60) with a ring twisting machine. It was. Seven pieces of the obtained twisted yarn (Z-60) were bundled and subjected to top twisting at 150 times S / m (S-150) using a ring twisting machine to obtain various twisted yarns. The various plied yarns were heat-treated at 165 ° C. for 1 minute to obtain the modeling material of Example 11 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 12 Five multifilaments used in Example 5 were conducted to an air jet nozzle, and the filaments were entangled with compressed air of 8 MPa to obtain an air entangled yarn. Six of the obtained air entangled yarns were bundled and converged by twisting with an S twist of 150 times / m (S-150) using a ring twisting machine. The bundled twisted yarn was heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 12 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • the obtained fiber bundle in which five multifilaments were aligned was subjected to a lower twist at a Z twist of 60 times / m (Z-60) using a ring twister to obtain a twisted yarn.
  • Seven pieces of the obtained twisted yarn (Z-60) were bundled and subjected to top twisting at 150 times S / m (S-150) using a ring twisting machine to obtain various twisted yarns.
  • the various plied yarns were heat-treated at 150 ° C. for 1 minute to obtain the modeling material of Example 13 having a wire diameter of 1.75 mm.
  • the constituent fibers were melted and fixed by thermal bonding by heat treatment.
  • Example 14 Two multifilaments used in Example 5 and three core-sheath composite multifilaments used in Example 13 were bundled and subjected to a lower twist at a Z twist of 60 times / m (Z-60) by a ring twisting machine. A twisted yarn was obtained. Seven pieces of the obtained twisted yarn (Z-60) were bundled and subjected to top twisting at 150 times S / m (S-150) using a ring twisting machine to obtain various twisted yarns. The various plied yarns were heat-treated at 150 ° C. for 1 minute to obtain the modeling material of Example 14 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were thermally bonded by heat treatment and partially melted and fixed.
  • Example 15 Using an extruder-type spinning machine from which a core-sheath composite fiber is obtained, a polylactic acid chip for the core (Nature Works LLC (6201D): melting point 170 ° C.) and a polylactic acid chip for the sheath (Nature Works LLC) (6302D): melting point 130 ° C.) was melt-spun and drawn to obtain a core-sheath composite filament.
  • a polylactic acid chip for the core (Nature Works LLC (6201D): melting point 170 ° C.) and a polylactic acid chip for the sheath (Nature Works LLC) (6302D): melting point 130 ° C.) was melt-spun and drawn to obtain a core-sheath composite filament.
  • the fiber bundle obtained by aligning the four spun yarns obtained was twisted using a ring twisting machine at a Z twist of 60 times / m (Z-60). 8 pieces of the obtained twisted yarn (Z-60) were bundled and subjected to top twisting at 150 times / m (S-150) using a ring twisting machine to obtain various twisted yarns.
  • the various plied yarns were heat-treated at 150 ° C. for 1 minute to obtain the modeling material of Example 15 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were melted and fixed by thermal bonding by heat treatment.
  • Example 16 Two spun yarns composed of the core-sheath composite staple fiber used in Example 15 and two multifilaments used in Example 5 were bundled and Z-twisted 60 times / m (Z-60) using a ring twisting machine. ) To give a twisted yarn. 8 pieces of the obtained twisted yarn (Z-60) were bundled and subjected to top twisting at 150 times / m (S-150) using a ring twisting machine to obtain various twisted yarns. The various plied yarns were heat-treated at 150 ° C. for 1 minute to obtain the modeling material of Example 16 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were thermally bonded by heat treatment and partially melted and fixed.
  • Example 17 Using a 16 round stringing machine, a fiber bundle in which 20 multifilaments used in Example 5 are arranged is arranged on the core thread, and the multifilaments are arranged one by one as side threads. I got a braid. The obtained braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 17 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 18 Using an 8-round stringing machine, a fiber bundle in which 20 multifilaments used in Example 5 are arranged is arranged on the core yarn, and a fiber bundle in which two multifilaments are arranged as side threads is arranged. A braid was obtained from the braid. The obtained braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 18 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 19 Compared to Example 17, it was different that the following twisted yarns were used as the core yarn. Other than that was carried out similarly to Example 17, and obtained the modeling material of Example 19. FIG. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Various twisted yarns were obtained as follows. That is, three multifilaments used in Example 5 were bundled and twisted using a ring twisting machine at a Z twist of 200 times / m (Z-200). Six twisted yarns (Z-200) thus obtained were bundled and subjected to top twisting at 120 times / m (S-120) S twist using a ring twisting machine to obtain various twisted yarns.
  • Example 20 Compared to Example 17, the following monofilament yarn was used as the core yarn. Otherwise in the same manner as in Example 17, the modeling material of Example 20 was obtained. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Monofilament yarn was obtained as follows. That is, using a polylactic acid chip (manufactured by Nature Works LLC (6201D)), melt spinning was performed with an extruder-type spinning machine, and drawing was performed to obtain a monofilament yarn made of 13,000 dtex13 / 1 filament polylactic acid.
  • a polylactic acid chip manufactured by Nature Works LLC (6201D)
  • Example 21 Compared to Example 17, the following core-sheath composite monofilament yarn was used as the core yarn. Otherwise in the same manner as in Example 17, the modeling material of Example 21 was obtained. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • the core-sheath composite monofilament yarn was obtained as follows. That is, using an extruder-type spinning machine capable of obtaining a core-sheath composite fiber, a polylactic acid chip for the core (Nature Works LLC (6201D): melting point 170 ° C.) and a polylactic acid chip for the sheath ( Nature Works LLC (6302D): melting point 130 ° C.) was melt-spun and drawn to obtain a core-sheath composite monofilament yarn composed of two types of polylactic acid of 13000 dtex / 1 filament.
  • Example 22 Using a 16 round stringing machine, a fiber bundle in which 18 spun yarns used in Example 9 are arranged is arranged on the core yarn, and the spun yarns are arranged one by one as side yarns. I got a braid. The obtained braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 22 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 23 Using a 16 round stringing machine, place 16 bundles of the following air entangled yarns on the core yarn, and place the following air entangled yarns on the side yarns one by one. Got. The obtained braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 23 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • the air entangled yarn was obtained as follows. That is, one multifilament used in Example 5 was conducted to an air jet nozzle, and the filaments were entangled with compressed air of 8 MPa to obtain an air entangled yarn.
  • Example 24 instead of the multifilament used in Example 17, the core-sheath composite multifilament used in Example 13 was used. And the process temperature at the time of heat-processing the obtained braid was 150 degreeC. Otherwise in the same manner as in Example 17, the modeling material of Example 24 was obtained. In the obtained modeling material, the constituent fibers were thermally bonded by heat treatment and melted and fixed.
  • Example 25 Using a 16 round stringing machine, a fiber bundle in which 18 spun yarns used in Example 15 are aligned is arranged on the core yarn, and the spun yarns are arranged one by one as side yarns. I got a braid. The obtained braid was heat-treated at 150 ° C. for 1 minute to obtain a modeling material of Example 25 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were thermally bonded by heat treatment and melted and fixed.
  • Example 26 Using an 8-round stringing machine, a fiber bundle in which 20 multifilaments used in Example 5 are arranged is arranged on the core yarn, and two spun yarns used in Example 15 are used as side yarns. A bundle was arranged and a braid was obtained from the cord. The obtained braid was heat-treated at 150 ° C. for 1 minute to obtain a modeling material of Example 26 having a wire diameter of 1.75 mm. The obtained modeling material had the constituent fibers thermally bonded to each other on the surface thereof and melted and fixed.
  • Example 27 Using an 8-round stringing machine, a fiber bundle in which 18 spun yarns used in Example 15 are aligned is arranged on the core yarn, and two multifilaments used in Example 5 are aligned as side yarns. A bundle was arranged and a braid was obtained from the cord. The obtained braid was heat-treated at 150 ° C. for 1 minute to obtain a modeling material of Example 27 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were solidified by heat shrinkage and melt softening due to heat treatment.
  • Example 28 Using an 8-round stringing machine, a fiber bundle in which 10 multifilaments used in Example 5 and 9 spun yarns used in Example 15 are aligned is arranged on the core yarn, and the multifilament is used as a side yarn. A fiber bundle in which one filament and one spun yarn were aligned was arranged, and a braid was obtained from the cord. The obtained braid was heat-treated at 150 ° C. for 1 minute to obtain the modeling material of Example 28 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were partially melt-fixed by thermal bonding.
  • Example 29 A master chip was produced by mixing 10% by mass of carbon black and 1% by mass of copper iodide with a polylactic acid chip (manufactured by Nature Works LLC (6201D): D-form content: 1.4%). 4 parts by mass of the master chip and 96 parts by mass of the polylactic acid chip (6201D) are mixed, melt-spun using an extruder-type spinning machine, and stretched to have a strength of 4.0 cN / dtex and an elongation of 30. %, 1900 dtex / 210 filaments of multi-filament made of original polylactic acid fiber. The multifilament made of the polylactic acid fiber was stringed with a 16 round stringing machine, and then heat-set at 100 ° C. for 2 minutes to obtain a modeling material of Example 29.
  • a polylactic acid chip manufactured by Nature Works LLC (6201D): D-form content: 1.4%. 4 parts by mass of the master chip and 96 parts by mass of the polylactic acid chip (6201D) are mixed,
  • Example 30 A polylactic acid chip (manufactured by Nature Works LLC (6201D)) was melt-spun with an extruder-type spinning machine and stretched to have a strength of 4.0 cN / dtex, an elongation of 30%, and 1900 dtex / 210 filament. A colorless multifilament made of polylactic acid fiber was obtained.
  • Example 29 The eight colorless multifilaments made of the polylactic acid fiber and the eight multifilaments made of the original polylactic acid fiber used in Example 29 were made with a 16 round punching machine, and then 100 ° C. 2 Heat setting was performed in minutes, and the modeling material of Example 30 was obtained.
  • Example 31 Twelve colorless multifilaments made of polylactic acid used in Example 30 and four multifilaments made of original polylactic acid fiber used in Example 29 were made by a 16 round stringing machine, Thereafter, heat setting was performed at 100 ° C. for 2 minutes to obtain a modeling material of Example 31.
  • Example 30 the hue was thinner than that in Example 29, and in Example 31, the hue was considerably thinner than that in Examples 29 and 30. That is, as the combination of multifilaments constituting the modeling material, the amount of the colorant contained as the modeling material could be adjusted by appropriately adjusting the number of colored multifilaments. Therefore, it was possible to easily provide a three-dimensional structure having light and shade.
  • Example 32 Using a polylactic acid chip (manufactured by Nature Works LLC (6201D)), melt spinning was performed with an extruder-type spinning machine and drawing to obtain colorless multifilaments composed of polylactic acid fibers of 560 dtex / 96 filaments.
  • the above-mentioned polylactic acid chip (6201D) and carbon black as a colorant (functional additive) were melt-kneaded with a twin-screw extruder to obtain a kneaded chip.
  • the compounding amount of carbon black was 0.5% by mass in the kneading chip.
  • This kneaded chip was melt-spun with an extruder-type spinning machine and drawn to obtain a monofilament containing a colorant of 560 dtex / 1 filament.
  • the obtained fiber bundle obtained by arranging three multifilaments and two monofilaments was subjected to a lower twist at a Z twist of 60 times / m (Z-60) using a ring twister to obtain a twisted yarn.
  • Seven pieces of the obtained twisted yarn were bundled, and using a ring twisting machine, an upper twist was applied at an S twist of 150 times / m (S-150) to obtain various twisted yarns.
  • the various plied yarns were heat-treated at 165 ° C. for 1 minute to obtain the modeling material of Example 32 having a wire diameter of 1.75 mm.
  • the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 33 Compared to Example 32, the following monofilament fiber was used as the monofilament fiber containing the functional additive. Otherwise in the same manner as in Example 32, the modeling material of Example 33 was obtained. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • the fiber containing the functional additive was obtained as follows. That is, the polylactic acid chip (6201D) used in Example 32 and silver-zeolite as an antibacterial agent were melt-kneaded with a twin-screw extruder to obtain a kneaded chip. The compounding amount of silver-zeolite was 5% by mass in the kneading chip. This kneaded chip was melt-spun with an extruder-type spinning machine and drawn to obtain a monofilament containing an antibacterial agent of 560 dtex / 1 filament.
  • Example 34 Compared to Example 32, the following fibers were used as fibers containing functional additives. Otherwise in the same manner as in Example 32, the modeling material of Example 34 was obtained. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • the fiber containing the functional additive was obtained as follows. That is, the polylactic acid chip (6201D) used in Example 32 and conductive carbon black as a conductive additive were melt-kneaded with a twin-screw extruder to obtain a kneaded chip. The compounding amount of the conductive carbon black was 10% by mass in the kneading chip. This kneaded chip was melt-spun with an extruder-type spinning machine and drawn to obtain a monofilament containing a conductive additive of 560 dtex / 1 filament.
  • Example 35 Compared to Example 32, the following fibers were used as the fibers containing the functional additive. Otherwise in the same manner as in Example 32, the modeling material of Example 35 was obtained. In the obtained modeling material, the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • the fiber containing the functional additive was obtained as follows. That is, the polylactic acid chip (6201D) used in Example 32 and barium sulfate as an X-ray impermeable agent were melt-kneaded with a twin-screw extruder to obtain a kneaded chip. The compounding quantity of barium sulfate was 10 mass% in the kneading chip. This kneaded chip was melt-spun with an extruder-type spinning machine and drawn to obtain a monofilament containing an X-ray impermeable agent of 560 dtex / 1 filament.
  • Example 36 The polylactic acid chip (6201D) used in Example 32 was melt-spun with an extruder-type spinning machine and drawn to obtain a filament. The obtained filaments were subjected to mechanical crimping and then cut to obtain colorless staple fibers having a single yarn fineness of 1.7 dtex and a fiber length of 51 mm. This staple fiber was spun to obtain 20th colorless spun yarn.
  • a part of the obtained colorless spun yarn was dyed with a disperse dye using a pressurized high-temperature dyeing machine to obtain a dyed yarn dyed pink.
  • the above-described colorless spun yarn bundle of 8 fibers was subjected to a lower twist at a Z twist of 60 times / m (Z-60) using a ring twister to obtain a colorless twisted yarn.
  • a fiber bundle obtained by arranging eight dyed yarns was subjected to a lower twist at a Z twist of 60 times / m (Z-60) using a ring twisting machine to obtain a dyed twisted yarn.
  • Seven colorless twisted yarns and one dyed twisted yarn were bundled and subjected to S twist at 150 times / m (S-150) using a ring twister to obtain various twisted yarns.
  • the various plied yarns were heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 36 having a wire diameter of 1.75 mm. In the obtained modeling material, the constituent fibers were melted and fixed by thermal bonding by heat treatment.
  • Example 37 Using the polylactic acid chip (6201D) used in Example 32, 6% by mass of phosphorescent material (fluorescent yellow-green phosphorescent pigment composed of aluminates (SrAl 2 O 4 : Eu, Dy)) is contained.
  • a phosphorescent polylactic acid chip and a polylactic acid chip containing no phosphorescent material were prepared. Melt spinning was performed with an extruder spinning machine using a composite spinneret with phosphorescent polylactic acid as a core component and polylactic acid not containing a phosphorescent material as a sheath component. The obtained yarn was stretched to obtain a phosphorescent core-sheath multifilament of 560 dtex / 48 filament having a core-sheath composite cross section. In this phosphorescent core-sheath multifilament, the volume ratio of the core part to the sheath part was 1: 1, and the concentration of the phosphorescent pigment was 3% by mass. The sheath part completely covered the core part
  • the obtained bundle of three luminous core-sheath multifilaments and two multifilaments used in Example 32 were aligned at a Z twist of 60 times / m (Z-60) using a ring twisting machine.
  • a twisted yarn was obtained by applying a lower twist. Seven pieces of the obtained twisted yarn were bundled, and using a ring twisting machine, an upper twist was applied at an S twist of 150 times / m (S-150) to obtain various twisted yarns.
  • the obtained plied yarns were heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 37 having a wire diameter of 1.75 mm. The concentration of the phosphorescent pigment in the modeling material was 1.8% by mass.
  • the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 38 A light-storing polylactic acid chip containing 3% by mass of the light-storing pigment used in Example 37 was prepared in the polylactic acid chip (6201D) used in Example 32. Using this phosphorescent polylactic acid chip, melt spinning was performed with an extruder-type spinning machine and drawn to obtain a phosphorescent multifilament of 560 dtex / 48 filaments.
  • a fiber bundle in which 20 luminous multifilaments are aligned is arranged on the core yarn, and the multifilaments used in Example 32 are arranged one by one as side yarns.
  • a braid was obtained from the string.
  • the obtained braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material of Example 38 having a wire diameter of 1.75 mm.
  • the concentration of the phosphorescent pigment in the modeling material was 1.6% by mass.
  • the constituent fibers were solidified by softening and shrinkage during heat treatment.
  • Example 39 Polylactic acid (melting point: 170 ° C., D-form content: 1.4 mol%) was melt-spun to obtain a polyester fiber of 560 dtex / 96 filaments. A braided string having a diameter of 1.75 mm was produced as a fiber bundling body using eight polyester fibers that had been drawn together and eight corners.
  • a treatment liquid containing 15% by mass of a urethane resin having a flow start temperature of 170 ° C. as a binder component was used, and the above-mentioned fiber bundle was immersed in this treatment liquid to hold the dispersion. Then, after adjusting the amount of dispersion held by squeezing with a mangle, the dispersion is introduced into a pin tenter type heat treatment apparatus, dried at 130 ° C. for 2 minutes, and a resin layer is formed on the surface of the polyester fiber, thereby forming a model. Obtained material. The mass ratio of the resin layer in the fiber bundle was 7.5% by mass.
  • Example 40 An aqueous dispersion of carbon nanotubes (CNT) (containing 2.3% by mass of multi-walled CNT as CNT and 15% by mass of urethane resin having a softening point of 150 ° C. as a binder component) was used as the treatment liquid.
  • CNT carbon nanotubes
  • the same fiber bundle as in Example 39 is immersed in this treatment liquid to hold the dispersion liquid, and the amount of the dispersion liquid is adjusted by squeezing with a mangle, and then introduced into a pin tenter type heat treatment apparatus. Dry for a minute.
  • a conductive material containing CNTs was supported on the surface of the polyester fiber to obtain a modeling material. In this modeling material, the ratio of the conductive material to the fiber bundle was 8.5% by mass.
  • the resistance value ( ⁇ ) of the obtained modeling material was measured using a tester, and the specific resistivity was calculated from this resistance value, the cross-sectional area of the specimen, and the distance between the electrodes, the value was approximately 10 2. It was ⁇ ⁇ cm.
  • Example 41 A silver dispersion (containing 20% by mass of silver and 2% by mass of vinyl chloride binder) was used as the treatment liquid.
  • the same fiber bundle as in Example 39 is immersed in this treatment liquid to hold the dispersion liquid, and the amount of the dispersion liquid is adjusted by squeezing with a mangle, and then introduced into a pin tenter type heat treatment apparatus. Dry for a minute.
  • modeling material was obtained by making silver carry on the surface of a polylactic acid fiber. In this modeling material, the ratio of the silver carrying layer in the fiber bundle was 8.5% by mass.
  • Example 42 As the treatment liquid, a water-based paint of conductive polymer (containing PEDOT (poly3,4-ethylenedioxythiophene) / PSS (polystyrene sulfonic acid)) was used.
  • the same fiber bundle as in Example 39 is immersed in this treatment liquid to hold the dispersion liquid, and the amount of the dispersion liquid held is adjusted by squeezing with a mangle, and then introduced into a pin tenter type heat treatment apparatus. Dry for a minute.
  • modeling material was obtained by carrying a conductive polymer on the surface of polylactic acid fiber. In this modeling material, the ratio of the conductive polymer in the fiber bundle was 1% by mass.
  • Example 43 An aqueous dispersion of a weathering agent (containing 7% by mass of a benzotrial compound and 7% by mass of a urethane resin having a softening point of 150 ° C.) was used as the treatment liquid.
  • the same fiber bundle as in Example 39 is immersed in this treatment liquid to hold the dispersion liquid, and the amount of the dispersion liquid is adjusted by squeezing with a mangle, and then introduced into a pin tenter type heat treatment apparatus. Dry for a minute.
  • the modeling material was obtained by carrying a weathering agent on the surface of the polylactic acid fiber. In this modeling material, the ratio of the weathering agent-containing resin layer in the fiber bundle was 6% by mass.
  • Example 44 As the treatment liquid, an aqueous dispersion of an antibacterial agent (containing 7% by mass of a silver-zeolite antibacterial agent and 7% by mass of a urethane resin having a softening point of 150 ° C.) was used. The same fiber bundle as in Example 39 is immersed in this treatment liquid to hold the dispersion liquid, and the amount of the dispersion liquid is adjusted by squeezing with a mangle, and then introduced into a pin tenter type heat treatment apparatus. Dry for a minute. Thereby, the modeling material was obtained by carrying
  • Comparative Example 2 A modeling material manufactured by ProtoPasta (trade name “Conductive PLA” made of PLA resin with conductive carbon) was used. If it was bent by hand, it would break easily, making it difficult to use with a three-dimensional printer.
  • Comparative Example 3 The plied yarns using a total of 35 560 dtex 96 filament polylactic acid multifilaments (melting point: 170 ° C.) were heat-treated at 165 ° C. for 1 minute. Thereby, the modeling material equivalent to the Example of this invention with a wire diameter of 1.75 mm was obtained.
  • K 1 that does not match Formula (1).
  • Example 46 A fiber bundle in which 20 polylactic acid multifilaments used in Comparative Example 3 were aligned was arranged on the core yarn, and the same multifilament was arranged one by one on the side yarn to obtain 16 round braided braids.
  • the braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material having a wire diameter of 1.75 mm.
  • the variables of this modeling material were as follows. In the following, subscript 1 corresponds to the core yarn, and subscript 2 corresponds to the side yarn.
  • Example 47 Various twisted yarns using a total of 18 polylactic acid multifilaments used in Comparative Example 3 were arranged for the core yarn, and the same multifilaments were arranged one by one for the side yarns to obtain 16 round braided braids.
  • the braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material having a wire diameter of 1.75 mm.
  • the variables of this modeling material were as follows. In the following, subscript 1 corresponds to the core yarn, and subscript 2 corresponds to the side yarn.
  • Example 48 Various twisted yarns using a total of 18 polyfilament multifilaments used in Comparative Example 3 and 9 560 dtex 96 filaments isophthalic acid copolyester multifilaments (melting point 160 ° C.). And 16 round punched braids were obtained in which the polylactic acid multifilaments were arranged one by one on the side threads. The braid was heat-treated at 165 ° C. for 1 minute to obtain a modeling material having a wire diameter of 1.75 mm.
  • the variables of this modeling material were as follows. In the following, subscript 1 corresponds to the core yarn, and subscript 2 corresponds to the side yarn.
  • the discharge coefficient K of this modeling material was determined from the formula (2) and was 1.28.

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  • Manufacturing & Machinery (AREA)
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  • Mechanical Engineering (AREA)
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Abstract

La présente invention concerne une matière à mouler constituée de faisceaux de longues fibres formés par mise en faisceau d'une pluralité de fibres synthétiques. Ladite matière à mouler est ainsi souple, résistante à la flexion, facile à manipuler et convient particulièrement à des imprimantes 3D de stratification de matière thermofusible.
PCT/JP2016/053884 2015-02-10 2016-02-10 Matière à mouler WO2016129613A1 (fr)

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JP2018127740A (ja) * 2017-02-10 2018-08-16 信越化学工業株式会社 蛍光体含有熱可塑性樹脂フィラメント、その製造方法、及び波長変換部材の製造方法
WO2018151074A1 (fr) * 2017-02-15 2018-08-23 学校法人日本大学 Appareil d'impression tridimensionnel
WO2019013195A1 (fr) * 2017-07-11 2019-01-17 株式会社ナノマテックス Système de fabrication, bobine en résine et procédé de fabrication
WO2019245845A1 (fr) * 2018-06-22 2019-12-26 3D Systems, Inc. Matériaux de construction et matériaux de support pour impression 3d comprenant un phosphore
JP2020111867A (ja) * 2020-03-13 2020-07-27 信越化学工業株式会社 蛍光体含有熱可塑性樹脂フィラメント
CN111531881A (zh) * 2020-04-03 2020-08-14 湖南大学 一种多方式多材料3d打印设备
JP2021123026A (ja) * 2020-02-05 2021-08-30 株式会社神戸製鋼所 ストランド及び造形物

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US11117312B2 (en) 2016-01-22 2021-09-14 Mitsubishi Gas Chemical Company, Inc. Method for manufacturing a three-dimensional structure
WO2017126476A1 (fr) * 2016-01-22 2017-07-27 三菱瓦斯化学株式会社 Procédé de production de structures tridimensionnelles et filament pour imprimantes 3d
JP2017128072A (ja) * 2016-01-22 2017-07-27 国立大学法人岐阜大学 立体構造物の製造方法および３ｄプリンタ用フィラメント
JP2018127740A (ja) * 2017-02-10 2018-08-16 信越化学工業株式会社 蛍光体含有熱可塑性樹脂フィラメント、その製造方法、及び波長変換部材の製造方法
WO2018151074A1 (fr) * 2017-02-15 2018-08-23 学校法人日本大学 Appareil d'impression tridimensionnel
JPWO2018151074A1 (ja) * 2017-02-15 2019-12-12 学校法人日本大学 ３次元プリンティング装置
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JP7093857B2 (ja) 2018-06-22 2022-06-30 スリーディー システムズ インコーポレーテッド 蛍燐光体を含む３ｄプリント用の造形材料およびサポート材料
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JP2021123026A (ja) * 2020-02-05 2021-08-30 株式会社神戸製鋼所 ストランド及び造形物
JP7451200B2 (ja) 2020-02-05 2024-03-18 株式会社神戸製鋼所 ストランド
JP2020111867A (ja) * 2020-03-13 2020-07-27 信越化学工業株式会社 蛍光体含有熱可塑性樹脂フィラメント
CN111531881A (zh) * 2020-04-03 2020-08-14 湖南大学 一种多方式多材料3d打印设备

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