US20190177510A1 - Resin composition, filament and resin powder for three-dimensional printer, and shaped object and production process therefor - Google Patents

Resin composition, filament and resin powder for three-dimensional printer, and shaped object and production process therefor Download PDF

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US20190177510A1
US20190177510A1 US16/323,992 US201716323992A US2019177510A1 US 20190177510 A1 US20190177510 A1 US 20190177510A1 US 201716323992 A US201716323992 A US 201716323992A US 2019177510 A1 US2019177510 A1 US 2019177510A1
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resin
resin composition
shaped object
dimensional printer
filament
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US16/323,992
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Kousuke Inada
Masagoro Okada
Akira Takarada
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Otsuka Chemical Co Ltd
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Otsuka Chemical Co Ltd
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Assigned to OTSUKA CHEMICAL CO., LTD. reassignment OTSUKA CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INADA, KOUSUKE, OKADA, Masagoro, TAKARADA, AKIRA
Publication of US20190177510A1 publication Critical patent/US20190177510A1/en
Priority to US17/210,933 priority Critical patent/US20210206947A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present invention relates to resin compositions as shaping materials for three-dimensional printers, filaments and resin powders for three-dimensional printers, and shaped objects and production methods for the shaped objects.
  • a three-dimensional (3D) printer is technology for calculating the shapes of thin cross-sections from three-dimensional data input by a CAD or, the like and depositing layer upon layer of a material based on the calculation results to shape a 3D object and is also referred to as additive manufacturing technology.
  • the three-dimensional printer requires no mold assembly that should be used in injection molding, enables the shaping of complicated 3D structures that could not be molded by injection molding, and has therefore received attention as a high-mix low-volume manufacturing technology.
  • materials for the three-dimensional printer also referred as additive manufacturing materials
  • various materials have been developed according to the process or usage of the three-dimensional printer.
  • the major materials used include light curable resins, thermoplastic resins, metals, ceramics, and wax.
  • the three-dimensional printer technology is classified based on how to three-dimensionally shape an object from a material, into (1) binder jetting process, (2) directed energy deposition process, (3) material extrusion process, (4) material letting process, (5) powder bed fusion process, (6) sheet lamination process, (7) vat photopolymerization process, and others.
  • Three-dimensional printers adopting, among the above processes, the material extrusion process (also referred to as the fused deposition modeling process) are decreasing in price and therefore increasing in demand as those for home use and office use.
  • the powder bed fusion process is a process attracting much attention.
  • the fused deposition modeling process is a process for shaping an object by fluidizing a thermoplastic resin having the shape of a thread called a filament or other shapes with a heating device inside an extrusion head, then discharging the fluid resin through a nozzle onto a platform, and cooling the resin into a solid state while gradually depositing layer upon layer of it according to the cross-sectional shapes of a desired object to be shaped.
  • a thermoplastic resin not blended with any additive so-called neat resin
  • thermoplastic resin blended with a fibrous filler such as glass fibers or carbon fibers
  • Patent Literature 1 discloses that with the use of a thermoplastic resin blended with a nanofiller, such as carbon nanotubes, for a fused deposition modeling-based three-dimensional printer, a shaped object can be obtained which has a desired function that could not be achieved by a thermoplastic resin only.
  • the powder bed fusion process is a process for shaping an object by forming a thin layer of resin powder, melting it with an energy source, such as laser or electronic beam, according to the cross-sectional shape of a desired object to be shaped, solidifying it, depositing a new thin layer of resin powder on top of the solid, likewise melting it with the energy source, such as laser or electronic beam, according to the cross-sectional shape of the desired object to be shaped, solidifying it, and repeating these steps.
  • an energy source such as laser or electronic beam
  • Patent Literature 1 JP-A-2016-28887
  • Patent Literature 1 discloses no specific method for improving the resistance to delamination of a shaped object and the resistance to warpage and shrinkage of the shaped object. Also in the powder bed fusion process, since resin is deposited layer by layer, there arise problems of, like the fused deposition modeling process, delamination of a shaped object and warpage and shrinkage of the shaped object.
  • An object of the present invention is to provide a resin composition, a filament and resin powder for a three-dimensional printer, a shaped object, and a production method for the shaped object, all of which make it easy to produce a shaped object and can improve, in shaping using a three-dimension printer, the resistance to delamination of the shaped object and the resistance to warpage and shrinkage of the shaped object.
  • the present invention provides a resin composition, a filament and resin powder for a three-dimensional printer, a shaped object, and a method for producing the shaped object which are described below.
  • Aspect 2 The resin composition according to aspect 1, wherein the inorganic fibers have a Mohs hardness of 5 or less.
  • Aspect 3 The resin composition according to aspect 1 or 2, wherein the inorganic fibers are at least one selected from the group consisting of potassium titanate and wollastonite.
  • Aspect 4 The resin composition according to any one of aspects 1 to 3, wherein a content of the inorganic fibers is 1% by mass to 40% by mass in a total amount of 100% by mass of the resin composition.
  • Aspect 5 The resin composition according to any one of aspects 1 to 4, wherein the three-dimensional printer is based on a fused deposition modeling process or a powder bed fusion process.
  • a filament for a fused deposition modeling-based three-dimensional printer the filament being made of the resin composition according to any one of aspects 1 to 4.
  • a resin powder for a powder bed fusion-based three-dimensional printer the resin powder being made of the resin composition according to any one of aspects 1 to 4.
  • Aspect 8 A shaped object shaped from the resin composition according to any one of aspects 1 to 4 with a three-dimensional printer.
  • a method for producing a shaped object wherein a shaped object is produced with a three-dimensional printer using the resin composition according to any one of aspects 1 to 4.
  • a method for producing a shaped object wherein the filament according to aspect 6 is fed to a fused deposition modeling-based three-dimensional printer.
  • a method for producing a shaped object wherein the resin powder according to aspect 7 is fed to a powder bed fusion-based three-dimensional printer.
  • the present invention makes it easy to produce a shaped object and can improve, in shaping using a three-dimensional printer, the resistance to delamination of the shaped object and the resistance to warpage and shrinkage of the shaped object.
  • FIG. 1 is a photograph showing a shaped object produced using a resin composition according to Comparative Example 1.
  • FIG. 2 is a photograph showing a shaped object produced using a resin composition according to Example 2.
  • FIG. 3 is a side view showing the shape of a tensile specimen.
  • FIG. 4 is a cross-sectional view showing the shape of a bending specimen.
  • FIG. 5 is a schematic side view for illustrating the amount of warpage of flat-plate shaped objects made in Test Examples 1 to 11 and Comparative Test Examples 1 to 8.
  • FIG. 6 is a schematic side view for illustrating the amount of warpage of shaped objects of bending specimens made in Test Example 34 and Comparative Test Examples 23 to 24.
  • a resin composition according to the present invention contains: inorganic fibers (A) having an average fiber length of 1 ⁇ m to 300 ⁇ m and an average aspect ratio and a thermoplastic resin (B) and may further contain other additives (C) as necessary.
  • the inorganic fibers for se in the present invention are powder formed of fibrous particles, and have an average fiber length of 1 ⁇ m to 300 ⁇ m and an average aspect ratio of 3 to 200.
  • the average fiber length is preferably 1 ⁇ m to 200 ⁇ m, more preferably 3 ⁇ m to 100 ⁇ m, and still more preferably 5 ⁇ m to 50 ⁇ m.
  • the average aspect ratio is preferably 3 to 100, more preferably 5 to 50, and still more preferably 8 to 40.
  • the inorganic fibers for use in the present invention has, from the viewpoint of wear of an extrusion head, a Mohs hardness of preferably 5 or less, more preferably 1 to 5, and still more preferably 2 to 5.
  • a Mohs hardness preferably 5 or less, more preferably 1 to 5, and still more preferably 2 to 5.
  • examples of the type of the inorganic fibers include potassium titanate, wollastonite, aluminum borate, magnesium borate, xonotlite, zinc oxide, and basic magnesium sulfate.
  • Preferred among the above various types of inorganic fibers is, from the viewpoint of mechanical properties, at least one selected from the group consisting of potassium titanate and wollastonite.
  • the Mohs hardness is an index indicating the hardness of a substance, wherein when two different minerals are rubbed against each other, scratched one of them is a substance having a lower hardness.
  • potassium titanates can be widely used and examples include potassium tetratitanate, potassium hexatitanate, and potassium octatitanate.
  • the dimensions of potassium titanate so long as they are within the above-described dimensions of the inorganic fibers.
  • its average fiber diameter is 0.01 ⁇ m to 1 ⁇ m, preferably 0.05 ⁇ m to 0.8 ⁇ m, and more preferably 0.1 ⁇ m to 0.7 ⁇ m
  • its average fiber length is 1 ⁇ m to 50 ⁇ m, preferably 3 ⁇ m to 30 ⁇ m, and more preferably 10 ⁇ m to 20 ⁇ m
  • its average aspect ratio is 10 or more, preferably 10 to 100, and more preferably 15 to 35.
  • TISMO D average fiber length: 15 ⁇ m, average fiber diameter: 0.5 ⁇ m
  • TISMO N average fiber length: 15 ⁇ m, average fiber diameter: 0.5 ⁇ m
  • Wollastonite is inorganic fibers made of calcium metasilicate.
  • its average fiber diameter is 0.1 ⁇ m to 15 ⁇ m, preferably 1 ⁇ m to 10 ⁇ m, and more preferably 2 ⁇ m to 7 ⁇ m
  • its average fiber length is 3 ⁇ m to 180 ⁇ m, preferably 10 ⁇ m to 100 ⁇ m, and more preferably 20 ⁇ m to 40 ⁇ m
  • its average aspect ratio is 3 or more, preferably 3 to 30, and more preferably 5 to 15.
  • an example that can be used is “Bistal W” (average fiber length: 25 ⁇ m, average fiber diameter: 3 ⁇ m) manufactured by Otsuka Chemical Co., Ltd.
  • the above average fiber length and average fiber diameter can be measured by observation with a scanning electron microscope, and the average aspect ratio (average fiber length/average fiber diameter) can be calculated from the average fiber length and the average fiber diameter.
  • the average fiber length can be determined by adding all the fiber diameters and dividing the sum by the number of fibers, while the average fiber diameter can be determined by adding all the fiber diameters and dividing the sum by the number of fibers.
  • Fibrous particles as used in the present invention means particles having an L/B of 3 or more and an L/T of 3 or more where a length L represents the dimension of the longest side of, among cuboids (circumscribing cuboids) circumscribing the particle, a cuboid having the minimum volume, a breadth B represents the dimension of the second longest side of the cuboid and a thickness T represents the dimension of the shortest side of the cuboid.
  • the length L and the breadth B correspond to the fiber length and the fiber diameter, respectively.
  • Platy particles herein refer to particles having an L/B of below 3 and an L/T of 3 or more.
  • treated layers made of a surface treatment agent may be formed on the surfaces of inorganic fibers for use in the present invention.
  • the surface treatment agent include silane coupling agents and titanium coupling agents. Preferred among them are silane coupling agents and more preferred are aminosilane coupling agents, epoxysilane coupling agents, vinylsilane coupling agents, and alkylsilane coupling agents. These agents may be used alone or as a mixture of two or more.
  • aminosilane coupling agents include N-2-(aminoethyl)-3-aminopropylmethydimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminoproyrltrimethoxysilane.
  • epoxysilane coupling agents examples include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxpropyltrimethoxysilane diethoxy(3-(glycidyloxypropyl) methylsilane, triethoxy(3-glycidyloxypropyl)silane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
  • vinylsilane coupling agents examples include vinyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • alkylsilane coupling agents examples include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propylmethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoysilane, n-hexyltriethoxysilane, cyclphexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane
  • Known surface treatment methods can be used as the method for forming treated layers made of a surface treatment agent on the surfaces of the inorganic fibers and examples include: a wet method of dissolving the surface treatment agent solvent prompting hydrolysis (for example, water, an alcohol or a solvent of them) to prepare a solution and spraying the solution on the inorganic fibers; and an integral blend method of blending the inorganic fibers and the surface treatment agent with the resin composition.
  • the amount of surface treatment agent in treating the surfaces of the inorganic fibers according to the present invention with the surface treatment agent is not limited, but, in the case of the wet method, the solution of the surface treatment agent may be sprayed so that the amount of surface treatment agent reaches 0.1 parts by mass to 5 parts by mass and preferably 0.3 parts by mass to 2 parts by mass relative to 100 parts by mass inorganic fibers.
  • the treatment agent may be blended with the resin composition so that the amount of surface treatment agent reaches 0.1 parts by mass to 20 parts mass relative to 1 parts by mass of inorganic fibers. If the amount of surface treatment agent is within the above ranges, the adhesion of the inorganic fibers to the thermoplastic resin can increase to improve the dispersibility of the inorganic fibers.
  • thermoplastic resin for use in the resin composition according to the present invention so long as it can be used three-dimensional printers, but examples that can be cited include: polyolefin resins, such as polypropylene (PP) resin, polyethylene (PE) resin, cyclic polyolefin (CO,) resin, and cyclic olefin copolymer (COC) resin; styrene resins, such as polystyrene (PS) resin, syndiotactic polystyrene (SPS) resin, and acrylonitrile-butylene-styrene copolymer (ABS) resin; polyester resins, such as polylactic (PLA) resin, polyethylene terephthalate (PET) resin, and polybutylene terephthalate (PBT) resin; polyacetal (POM) resin; polycarbonate (PC) resin; aliphatic polyamide (PA) resins, such as polyamide 6 resin, polyamide 66
  • Preferred in the fused deposition modeling-based three-dimensional printer and the powder bed fusion-based three-dimensional printer is at least one selected from the group consisting of polyolefin resin, styrene resin, polyester resin, polyacetal (POM) resin, polycarbonate (PC) resin, aliphatic polyamide (PA) resin, semi-aromatic polyamide (PA) resin, polyphenylene sulfide (PPS) resin, polyether imide (PEI) resin, and polyether ether ketone (PEEK) resin.
  • thermoplastic resins selected from among the above thermoplastic resins, i.e., polymer alloys, or the like.
  • the resin composition according to the present invention may contain other additives without any loss of its preferred physical properties.
  • the other additives include inorganic fillers other than the above-mentioned inorganic fibers, a stabilizer, a nucleating agent, an antistat, an antioxidant, a weatherproofer, a metal deactivator, a ultraviolet ray absorber, a germ- and mildew-proofing agent, a deodorant, a conductive additive, a dispersant, a softener (plasticizer), a colorant, a flame retardant, a sound deadener, a neutralizer, an antiblocking agent, a flow modifier, a mold release agent, a lubricant, and an impact resistance improver.
  • the resin composition may contain at least one of these additives.
  • the resin composition according to the present invention can be produced mixing and heating (particularly, melt kneading) the above components, the inorganic fibers (A), the thermoplastic resin (B), and, as necessary, the other additives (C).
  • any known melt kneader for example, a biaxial extruder
  • the resin composition can be produced by: (1) a method of preliminarily mixing the components with a mixer (a tumbler, a Henschel mixer or the like), melt kneading the mixture with a melt kneader, and then pelletizing it with a pelletization device (such as a pelletizer); (2) a method of adjusting a master batch of desired components, mixing it with other components as necessary, and melt kneading the mixture into pellets with a melt kneader; (3) a method of feeding the components into a melt kneader to form pellets; or other methods.
  • a mixer a tumbler, a Henschel mixer or the like
  • a pelletization device such as a pelletizer
  • a method of adjusting a master batch of desired components mixing it with other components as necessary, and melt kneading the mixture into pellets with a melt kn
  • thermoplastic resin (B) can melt.
  • the cylinder temperature of a melt kneader for use in the melt kneading is controlled within this range.
  • the content of the inorganic fibers (A) in the resin composition according to the present invention is, in a total amount of 100% by mass of the resin composition, preferably 1% by mass to 40% by mass, more preferably 3% by mass to 30% by mass, and still more preferably 7% by mass to 25% by mass.
  • the content of the thermoplastic resin (B) in the resin composition according to the present invention is, in a total amount of 100% by mass of the resin composition, preferably 50% by mass to 99% by mass, more preferably 60% by mass to 97% by mass, and still more preferably 65% by mass to 93% by mass.
  • the content of the other additives is normally 10% by mass or less and preferably 5% by mass or less in a total amount of 100% by mass of the resin composition.
  • the resistance to delamination of a shaped object and the resistance to warpage and shrinkage of the shaped object in shaping using a three-dimensional printer can be improved.
  • the resin composition according to the present invention a shaping material for a three-dimensional printer.
  • the shaping material for a three-dimensional printer in the present invention refers to a material for use in applying it to a three-dimensional printer (also referred to as an additive manufacturing apparatus) to obtain a three-dimensional shaped object and is composed of the resin composition.
  • the shaping material for a three-dimensional printer according to the present invention can be used in any method so long as the method is to shape object by melting the shaping material by heat based on a design on a computer.
  • the shaping material can be suitably used in the fused deposition modeling process or the powder bed fusion process.
  • the fused deposition modeling process is a process for shaping a desired shaped object by fluidizing a thermoplastic resin having the shape of pellets, the shape of a thread called a filament or other shapes with a heating device inside an extrusion head, then discharging the fluid resin through a nozzle onto a platform, and cooling the resin into a solid state while gradually depositing layer upon layer of it.
  • the use of the resin composition according to the present invention as a shaping material enables shaping using a fused deposition modeling-based three-dimensional printer without clogging of the extrusion head or wear of the extrusion head that might occur with the use of a resin composition blended with a fibrous filler, such as glass fibers or carbon fibers.
  • the inorganic fibers (A) can not only improve the resistance to warpage and shrinkage of the shared object but also increase the interfacial strength between the layered resin portions, thus preventing delamination of the shaped object.
  • an example is a method including: an extrusion step of extruding the resin composition according to the present invention produced by the above-described method as molten strand through a die hole in a molder and guiding the molten strand into a cooling water bath to obtain a strand; a stretching step of hot stretching the strand to obtain a filament; and the step of rolling up the filament.
  • the shape of the filament No particular limitation is placed on the shape of the filament. Examples that can be cited as the cross-sectional shape thereof include circular, rectangular, flattened, ellipsoidal, cocoon-like, trefoil, and like non-circular shapes. Circular is preferred from the viewpoint of ease of handling.
  • the length of the filament No limitation is placed on the filament and it can be set at any value according to industrial production conditions or without interfering with the use for a fused deposition modeling-based three-dimensional printer.
  • No particular limitation is also placed on the diameter of the filament and, for example, it is 0.5 mm to 3 mm and particularly 1 mm to 2 mm. Note that the diameter of the filament refers to the maximum of diameters measured on cross-sections of the filament perpendicular to the direction of length of the filament.
  • the filament may be a composite filament in which the resin composition according to the present invention is combined with another or other resin components.
  • the cross-sectional structure of the composite filament that can be cited include a radially oriented structure, a side-by-side structure, a sea-island structure, and a core-in-sheath structure.
  • the powder bed fusion process is a process for shaping an object by depositing resin powder layer by layer, melting each layer into a particular cross-sectional shape, with an energy source, such as laser or electronic beam, and solidifying it. Since the resin composition according to the present invention is used as a shaping material, be assumed that, although the reason is not clear, the inorganic fibers (A) cannot only improve the resistance to warpage and shrinkage of the shaped object but also increase the interfacial strength between the layer resin portions, thus preventing delamination of the shaped object.
  • the method producing resin powder examples include: a method of producing resin powder by crushing the resin composition with a crusher or other means, then grinding the crushed product with a jet mill or other means, and then classifying the ground product (mechanical grinding method); a method of producing resin powder by dissolving the resin composition in a solvent and then cooling the solution (precipitation method; and a method of producing resin powder by melt mixing a resin A and a resin B incompatible with the in A and immersing the obtained molten mixture in a solvent poor for the resin A and good for the resin B, thus decomposing the molten mixture (melt-mixing method).
  • the particle diameter of the resin powder can be set at any value according to industrial production conditions or without interfering with the use for a three-dimensional printer, but the average particle diameter is preferably 10 ⁇ m to 150 ⁇ m and more preferably 30 ⁇ m to 80 ⁇ m.
  • the average particle diameter can be measured by the laser diffraction and scattering method and is a particle diameter at cumulative integrated value of 50% in a particle size distribution measured by the laser diffraction and scattering method (a volume-based 50% cumulative particle diameter), i.e., D 50 (a median diameter).
  • This volume-based 50% cumulative particle diameter (D 50 ) is a particle diameter at a cumulative value of 50% in a cumulative curve of a particle size distribution determined on a volume basis, the cumulative curve assuming the total volume of particles as 100%, where during accumulation the number of particles is counted from a smaller size side.
  • Examples of the shape of particles forming the powder include spherical and amorphous (amoeboid, boomerang-like, cross, konpeito-like, potato-like, and so on), but spherical is preferred from the viewpoint of interface strength.
  • the shapes of particles can be observed by scanning electron microscopy.
  • a shaped object according to the present invention is an object shaped from the resin composition according to the present invention with a three-dimensional printer.
  • a shaped object can be produced, for example, by performing shaping by feeding the filament into a fused deposition modeling-based three-dimensional printer.
  • a shaped object can be produced, for example, by performing shaping by feeding the powder into a powder bed fusion-based three-dimensional printer.
  • shaped object is produced by a three-dimensional printer using the resin composition according to the present invention.
  • a shaped object in using the resin composition according to the present invention in the form of a filament, can be produced, for example, feeding the filament into a fused deposition modeling-based three-dimensional printer.
  • a shaped object can be produced feeding the filament into a fused deposition modeling-based three-dimensional printer, fluidizing the filament with a heating device inside an extrusion head, then discharging the fluid through a nozzle onto a platform, and cooling it into a solid state while gradually depositing layer upon layer of it according to the cross-sectional shape of a desired object to be shaped.
  • a shaped object in using the resin composition according to the present invention in the form of powder, can be produced, for example, by feeding the powder into a powder bed fusion-based three-dimensional printer.
  • a shaped object can be produced by feeding the resin powder into powder bed fusion-based three-dimensional printer, forming on a vertically or electronic beam, according to the cross-sectional shape of a desired object to be shaped, solidifying it, depositing a new thin layer of the resin powder on top of the solid, likewise melting it with the energy source, such as laser or electronic beam, according to the cross-sectional shape of the desired object to be shaped, solidifying it, and repeating these steps.
  • the energy source such as laser or electronic beam
  • Potassium titanate (trade name: TISMO D102, manufactured Otsuka Chemical Co., Ltd., average fiber length: 15 ⁇ m, average fiber diameter: 0.5 ⁇ m, average aspect ratio: 30);
  • Wollastonite (trade name: Bistal W, manufactured by Otsuka Chemical Co., Ltd., average fiber length: 25 ⁇ m, average fiber diameter: 3 ⁇ m, average aspect ratio: 8)
  • Polyamide 12 resin (PA12 resin);
  • ABS resin Acrylonitrile-butylene-styrene copolymer resin
  • Cyclic olefin copolymer resin (COC resin);
  • PBT resin Polybutylene terephthalate resin
  • Carbon black (trade name: #3050, manufactured by Mitsubishi Chemical Corporation, average particle diameter: 50 nm, amorphous-shaped particles);
  • Glass beads (trade name: EGB 063Z manufactured by Potters-Ballotini Co., Ltd., average particle diameter: 25 ⁇ m spherical particles)
  • the obtained pellets were loaded into a filament extruder, thus obtaining a filament with a filament diameter of 1.7 mm.
  • the filament obtained in each of Examples 1 to 11 and Comparative Examples 1 to 8 was deposited into layers in a thickness direction by fused deposition modeling-based three-dimensional printer (manufactured by MUTOH INDUSTRIES, LTD., trade name: MF1100) under the associated printing conditions shown in Tables 3 and 4, thus producing a flat-plate shaped object 100 mm long, 2 mm wide, and 50 mm thick.
  • fused deposition modeling-based three-dimensional printer manufactured by MUTOH INDUSTRIES, LTD., trade name: MF1100
  • FIG. 1 shows a photograph of a shaped object (Comparative Test Example 1) produced using the resin composition according to Comparative Example 1
  • FIG. 2 shows a photograph of a shaped object (Test Example 2) produced using the resin composition according to Example 2.
  • the filament obtained in each of Examples 1 to 11 and Comparative Examples 1 to 8 was produced into a dumbbell tensile specimen having a shape shown in FIG. 3 by a fused deposition modeling-based three-dimensional printer (manufactured by MUTOH INDUSTRIES, LTD., trade name: MF 1100) under the associated printing conditions shown in Tables 5 and 6.
  • the filament obtained in each of Examples 1 to 11, Comparative Example 1, and Comparative Examples 4 to 8 was produced into a bending specimen having a shape shown in FIG. 4 by a fused deposition modeling-based three-dimensional printer (manufactured by MUTOH INDUSTRIES, LTD., trade name: MF1100) under the associated printing conditions shown in Tables 7 and 8.
  • a fused deposition modeling-based three-dimensional printer manufactured by MUTOH INDUSTRIES, LTD., trade name: MF1100
  • the flat-plate shaped objects produced under the conditions in Tables 3 and 4 were measured in terms of amount of warpage with a caliper.
  • the amount of warpage W is, as shown in FIG. 5 , a difference in height along a build-up direction during shaping between the middle and ends of the shaped object in a traveling direction during shaping.
  • the results are shown in Tables 3 and 4.
  • the flat-plate shaped objects produced under the conditions in Tables 3 and 4 were measured in terms of shrinkage.
  • the shrinkage was measured in the build-up direction and the traveling direction.
  • the shrinkage in the build-up direction is a shrinkage in the thickness b along the build-up direction during shaping shown in FIG. 5 .
  • the shrinkage in the traveling direction is a shrinkage in the length a along the traveling direction during shaping shown in FIG. 5 .
  • the results are shown in Tables 3 and 4.
  • Tables 3 and 4 show that Test Examples 1 to 11 in which inorganic fibers were blended with PA12 resin, PAMXD6 resin ABS resin, COC resin or PBT resin exhibited significantly low amounts of warpage and significantly low shrinkages both in the build-up direction and traveling direction as compared to Comparative Test Examples 1 to in which no inorganic fibers were blended with PA12 resin, PAMXD6 resin, ABS resin, COC resin or PBT resin. Furthermore, it is shown that their interface adhesions were significantly improved.
  • Tables 5 and 6 show that Test Examples 12 to 22 in which inorganic fibers were blended with the resin also exhibited high tensile strengths as compared to Comparative Test Examples 9 to 15 in which no inorganic fibers were blended with the resin.
  • Tables 7 and 8 show that Test Examples 23 to 33 in which inorganic fibers were blended with the resin also exhibited high flexural strengths and flexural moduli as compared to Comparative Test Examples 17 and 19 to 22 in which no inorganic fibers were blended with the resin.
  • the spherical resin powder obtained in each of Example 12 and Comparative Examples 9 to 10 was produced into a bending specimen having a shape shown in FIG. 4 by a powder bed fusion based three-dimensional printer (manufactured by ASPECT Inc., trade name: RaFaEl II 150-HT) under the associated printing conditions shown in Table 10.
  • the shaped objects of bending specimens produced under the conditions in Table 10 were measured in terms of amount of warpage with a non-contact roughness and shape measurement device (a one-shot 3D shape measuring microscope VR-3000 manufactured by Keyence Corporation).
  • the amount of warpage W is, as shown in FIG. 6 , a difference in height along a build-up direction during shaping between the middle and ends of the bending specimen.
  • the results are shown in Table 10.
  • the shaped objects of bending specimens produced under the conditions in Table 10 were measured in terms of shrinkage.
  • the shrinkage was measured in the build-up direction.
  • the shrinkage in the build-up direction is a shrinkage in the thickness of the bending specimen along the build-up direction during shaping.
  • Respective flexural strengths of the shaped objects of bending specimens produced under the conditions in Table 10 were divided by their respective packing densities and the obtained values were assumed as interface adhesions.
  • the packing density value obtained by dividing the specific gravity of the shaped object of each bending specimen the density of an injection-molded piece (a piece of the same shape injection-molded using pellets having the same composition).
  • the flexural strength of the shaped object of each bending specimen obtained by the powder bed fusion process is the sum of interface strengths between powder particles. As the packing density decreases, the interface area correspondingly decreases and the flexural strength also correspondingly decreases.
  • the flexural strength was obtained by measuring each bending specimen produced under the conditions in Table 10 in terms of bending stress by a 60 mm-span three-point bending test with a tester Autograph AG-5000 (manufactured by Shimadzu Corporation). The specific gravity of each shaped object was measured in conformity to JIS Z8807.
  • the shaped objects of the bending specimens produced under the conditions in Table 10 were measured in terms of flexural strength by a 60 mm-span three-point bending test with a tester Autograph AG-5000 (manufactured by Shimadzu Corporation). The test results are shown in Table 10.

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Abstract

Provided is a resin composition, a filament and resin powder for a three-dimensional printer, a shaped object, and a production method for the shaped object, all of which make it easy to produce a shaped object and can improve, in shaping using a three-dimensional printer, the resistance to delamination of the shaped object and the resistance to warpage and shrinkage of the shaped object. A resin composition contains: inorganic fibers having an average fiber length of 1 μm to 300 μm and an average aspect ratio of 3 to 200; and a thermoplastic resin and serves as a shaping material for a three-dimensional printer.

Description

    TECHNICAL FIELD
  • The present invention relates to resin compositions as shaping materials for three-dimensional printers, filaments and resin powders for three-dimensional printers, and shaped objects and production methods for the shaped objects.
    • BACKGROUND ART
  • A three-dimensional (3D) printer is technology for calculating the shapes of thin cross-sections from three-dimensional data input by a CAD or, the like and depositing layer upon layer of a material based on the calculation results to shape a 3D object and is also referred to as additive manufacturing technology. The three-dimensional printer requires no mold assembly that should be used in injection molding, enables the shaping of complicated 3D structures that could not be molded by injection molding, and has therefore received attention as a high-mix low-volume manufacturing technology.
  • As materials for the three-dimensional printer (also referred as additive manufacturing materials), various materials have been developed according to the process or usage of the three-dimensional printer. The major materials used include light curable resins, thermoplastic resins, metals, ceramics, and wax.
  • The three-dimensional printer technology is classified based on how to three-dimensionally shape an object from a material, into (1) binder jetting process, (2) directed energy deposition process, (3) material extrusion process, (4) material letting process, (5) powder bed fusion process, (6) sheet lamination process, (7) vat photopolymerization process, and others. Three-dimensional printers adopting, among the above processes, the material extrusion process (also referred to as the fused deposition modeling process) are decreasing in price and therefore increasing in demand as those for home use and office use. Furthermore, in relation to three-dimensional printers adopting the powder bed fusion process, the development of a system achieving improvements in recyclability of powder materials has advanced. Therefore, the powder bed fusion process is a process attracting much attention.
  • The fused deposition modeling process is a process for shaping an object by fluidizing a thermoplastic resin having the shape of a thread called a filament or other shapes with a heating device inside an extrusion head, then discharging the fluid resin through a nozzle onto a platform, and cooling the resin into a solid state while gradually depositing layer upon layer of it according to the cross-sectional shapes of a desired object to be shaped. However, if the shaping is made using a thermoplastic resin not blended with any additive (so-called neat resin), there arise problems including delamination of a shaped object and warpage of the shaped object. Furthermore, if a thermoplastic resin blended with a fibrous filler, such as glass fibers or carbon fibers, is used, there arises a problem of difficulty of shaping due to clogging of the extrusion head, wear of the extrusion head, and so on.
  • Meanwhile, Patent Literature 1 discloses that with the use of a thermoplastic resin blended with a nanofiller, such as carbon nanotubes, for a fused deposition modeling-based three-dimensional printer, a shaped object can be obtained which has a desired function that could not be achieved by a thermoplastic resin only.
  • The powder bed fusion process is a process for shaping an object by forming a thin layer of resin powder, melting it with an energy source, such as laser or electronic beam, according to the cross-sectional shape of a desired object to be shaped, solidifying it, depositing a new thin layer of resin powder on top of the solid, likewise melting it with the energy source, such as laser or electronic beam, according to the cross-sectional shape of the desired object to be shaped, solidifying it, and repeating these steps.
    • CITATION LIST Patent Literature
  • Patent Literature 1: JP-A-2016-28887
    • SUMMARY OF INVENTION Technical Problem
  • However, it is known that uniform dispersion of a nanofiller in a thermoplastic resin as in Patent Literature 1 is not easy and that the melting viscosity of an obtained thermoplastic resin composition increases. Furthermore, Patent Literature 1 discloses no specific method for improving the resistance to delamination of a shaped object and the resistance to warpage and shrinkage of the shaped object. Also in the powder bed fusion process, since resin is deposited layer by layer, there arise problems of, like the fused deposition modeling process, delamination of a shaped object and warpage and shrinkage of the shaped object.
  • An object of the present invention is to provide a resin composition, a filament and resin powder for a three-dimensional printer, a shaped object, and a production method for the shaped object, all of which make it easy to produce a shaped object and can improve, in shaping using a three-dimension printer, the resistance to delamination of the shaped object and the resistance to warpage and shrinkage of the shaped object.
    • Solution to Problem
  • The present invention provides a resin composition, a filament and resin powder for a three-dimensional printer, a shaped object, and a method for producing the shaped object which are described below.
  • Aspect 1: A resin composition containing: inorganic fibers having an average fiber length of 1 μm to 300 μm and an average aspect ratio of 3 to 200; and a thermoplastic resin, the resin composition serving as a shaping material for a three-dimensional printer.
  • Aspect 2: The resin composition according to aspect 1, wherein the inorganic fibers have a Mohs hardness of 5 or less.
  • Aspect 3: The resin composition according to aspect 1 or 2, wherein the inorganic fibers are at least one selected from the group consisting of potassium titanate and wollastonite.
  • Aspect 4: The resin composition according to any one of aspects 1 to 3, wherein a content of the inorganic fibers is 1% by mass to 40% by mass in a total amount of 100% by mass of the resin composition.
  • Aspect 5: The resin composition according to any one of aspects 1 to 4, wherein the three-dimensional printer is based on a fused deposition modeling process or a powder bed fusion process.
  • Aspect 6: A filament for a fused deposition modeling-based three-dimensional printer, the filament being made of the resin composition according to any one of aspects 1 to 4.
  • Aspect 7: A resin powder for a powder bed fusion-based three-dimensional printer, the resin powder being made of the resin composition according to any one of aspects 1 to 4.
  • Aspect 8: A shaped object shaped from the resin composition according to any one of aspects 1 to 4 with a three-dimensional printer.
  • Aspect 9: A shaped object shaped from the filament according to aspect 6 with a fused deposition modeling-based three-dimensional printer.
  • Aspect 9: A shaped t shaped from the filament according to aspect 6 with a fused deposition modeling-based three-dimensional printer.
  • Aspect 10: A shaped object shaped from the resin powder according to aspect 7 with a powder bed fusion-based three-dimensional printer.
  • Aspect 11: A method for producing a shaped object, wherein a shaped object is produced with a three-dimensional printer using the resin composition according to any one of aspects 1 to 4.
  • Aspect 12: A method for producing a shaped object, wherein the filament according to aspect 6 is fed to a fused deposition modeling-based three-dimensional printer.
  • Aspect 13: A method for producing a shaped object, wherein the resin powder according to aspect 7 is fed to a powder bed fusion-based three-dimensional printer.
    • Advantageous Effects of Invention
  • The present invention makes it easy to produce a shaped object and can improve, in shaping using a three-dimensional printer, the resistance to delamination of the shaped object and the resistance to warpage and shrinkage of the shaped object.
    • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a photograph showing a shaped object produced using a resin composition according to Comparative Example 1.
  • FIG. 2 is a photograph showing a shaped object produced using a resin composition according to Example 2.
  • FIG. 3 is a side view showing the shape of a tensile specimen.
  • FIG. 4 is a cross-sectional view showing the shape of a bending specimen.
  • FIG. 5 is a schematic side view for illustrating the amount of warpage of flat-plate shaped objects made in Test Examples 1 to 11 and Comparative Test Examples 1 to 8.
  • FIG. 6 is a schematic side view for illustrating the amount of warpage of shaped objects of bending specimens made in Test Example 34 and Comparative Test Examples 23 to 24.
    •  DESCRIPTION OF EMBODIMENTS
  • Hereinafter, a description will be given of example of a preferred embodiment for working of the present invention. However, the following embodiment is simply illustrative. The present invention is not at all limited by the following embodiment.
    • <Resin Composition>
  • A resin composition according to the present invention contains: inorganic fibers (A) having an average fiber length of 1 μm to 300 μm and an average aspect ratio and a thermoplastic resin (B) and may further contain other additives (C) as necessary.
    • (Inorganic Fibers (A))
  • The inorganic fibers for se in the present invention are powder formed of fibrous particles, and have an average fiber length of 1 μm to 300 μm and an average aspect ratio of 3 to 200. The average fiber length is preferably 1 μm to 200 μm, more preferably 3 μm to 100 μm, and still more preferably 5 μm to 50 μm. The average aspect ratio is preferably 3 to 100, more preferably 5 to 50, and still more preferably 8 to 40. The use of the inorganic fibers having the above average fiber length and average aspect ratio makes it easy to produce a shaped object and can improve, in shaping using a three-dimensional printer, the resistance to delamination of the shaped object and the resistance to warpage and shrinkage of the shaped object.
  • The inorganic fibers for use in the present invention has, from the viewpoint of wear of an extrusion head, a Mohs hardness of preferably 5 or less, more preferably 1 to 5, and still more preferably 2 to 5. Examples of the type of the inorganic fibers include potassium titanate, wollastonite, aluminum borate, magnesium borate, xonotlite, zinc oxide, and basic magnesium sulfate. Preferred among the above various types of inorganic fibers is, from the viewpoint of mechanical properties, at least one selected from the group consisting of potassium titanate and wollastonite. The Mohs hardness is an index indicating the hardness of a substance, wherein when two different minerals are rubbed against each other, scratched one of them is a substance having a lower hardness.
  • Heretofore known potassium titanates can be widely used and examples include potassium tetratitanate, potassium hexatitanate, and potassium octatitanate. There is no particular limitation as to the dimensions of potassium titanate so long as they are within the above-described dimensions of the inorganic fibers. However, normally, its average fiber diameter is 0.01 μm to 1 μm, preferably 0.05 μm to 0.8 μm, and more preferably 0.1 μm to 0.7 μm, its average fiber length is 1 μm to 50 μm, preferably 3 μm to 30 μm, and more preferably 10 μm to 20 μm, and its average aspect ratio is 10 or more, preferably 10 to 100, and more preferably 15 to 35. In the present invention, even marketed products can be used and examples that can be used include “TISMO D” (average fiber length: 15 μm, average fiber diameter: 0.5 μm) and “TISMO N” (average fiber length: 15 μm, average fiber diameter: 0.5 μm) both manufactured by Otsuka Chemical Co., Ltd.
  • Wollastonite is inorganic fibers made of calcium metasilicate. There is no particular limitation as to the dimensions of wollastonite so long as they are within the above-described dimensions of the inorganic fibers. However, normally, its average fiber diameter is 0.1 μm to 15 μm, preferably 1 μm to 10 μm, and more preferably 2 μm to 7 μm, its average fiber length is 3 μm to 180 μm, preferably 10 μm to 100 μm, and more preferably 20 μm to 40 μm, and its average aspect ratio is 3 or more, preferably 3 to 30, and more preferably 5 to 15. In the present invention, even marketed products can be used and an example that can be used is “Bistal W” (average fiber length: 25 μm, average fiber diameter: 3 μm) manufactured by Otsuka Chemical Co., Ltd.
  • The above average fiber length and average fiber diameter can be measured by observation with a scanning electron microscope, and the average aspect ratio (average fiber length/average fiber diameter) can be calculated from the average fiber length and the average fiber diameter. For example, a plurality of inorganic fibers are shot with a scanning electron microscope, images of 300 inorganic fibers are arbitrarily selected from the observed images, and their fiber lengths and fiber diameters are measured. The average fiber length can be determined by adding all the fiber diameters and dividing the sum by the number of fibers, while the average fiber diameter can be determined by adding all the fiber diameters and dividing the sum by the number of fibers.
  • Fibrous particles as used in the present invention means particles having an L/B of 3 or more and an L/T of 3 or more where a length L represents the dimension of the longest side of, among cuboids (circumscribing cuboids) circumscribing the particle, a cuboid having the minimum volume, a breadth B represents the dimension of the second longest side of the cuboid and a thickness T represents the dimension of the shortest side of the cuboid. The length L and the breadth B correspond to the fiber length and the fiber diameter, respectively. Platy particles herein refer to particles having an L/B of below 3 and an L/T of 3 or more.
  • Regarding the inorganic fibers in order to increase the wettability with the thermoplastic resin and further improve physical properties, such as mechanical strength, of the obtained resin composition, treated layers made of a surface treatment agent may be formed on the surfaces of inorganic fibers for use in the present invention. Examples of the surface treatment agent include silane coupling agents and titanium coupling agents. Preferred among them are silane coupling agents and more preferred are aminosilane coupling agents, epoxysilane coupling agents, vinylsilane coupling agents, and alkylsilane coupling agents. These agents may be used alone or as a mixture of two or more.
  • Examples of the aminosilane coupling agents include N-2-(aminoethyl)-3-aminopropylmethydimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminoproyrltrimethoxysilane.
  • Examples of the epoxysilane coupling agents include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxpropyltrimethoxysilane diethoxy(3-(glycidyloxypropyl) methylsilane, triethoxy(3-glycidyloxypropyl)silane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
  • Examples of the vinylsilane coupling agents include vinyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • Examples of the alkylsilane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propylmethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoysilane, n-hexyltriethoxysilane, cyclphexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane
  • Known surface treatment methods can be used as the method for forming treated layers made of a surface treatment agent on the surfaces of the inorganic fibers and examples include: a wet method of dissolving the surface treatment agent solvent prompting hydrolysis (for example, water, an alcohol or a solvent of them) to prepare a solution and spraying the solution on the inorganic fibers; and an integral blend method of blending the inorganic fibers and the surface treatment agent with the resin composition.
  • No particular limitation is placed on the amount of surface treatment agent in treating the surfaces of the inorganic fibers according to the present invention with the surface treatment agent, but, in the case of the wet method, the solution of the surface treatment agent may be sprayed so that the amount of surface treatment agent reaches 0.1 parts by mass to 5 parts by mass and preferably 0.3 parts by mass to 2 parts by mass relative to 100 parts by mass inorganic fibers. On the other hand, in the case of the integral blend method, the treatment agent may be blended with the resin composition so that the amount of surface treatment agent reaches 0.1 parts by mass to 20 parts mass relative to 1 parts by mass of inorganic fibers. If the amount of surface treatment agent is within the above ranges, the adhesion of the inorganic fibers to the thermoplastic resin can increase to improve the dispersibility of the inorganic fibers.
    • (Thermoplastic Resin (B))
  • No particular limitation is placed on the type of the thermoplastic resin for use in the resin composition according to the present invention so long as it can be used three-dimensional printers, but examples that can be cited include: polyolefin resins, such as polypropylene (PP) resin, polyethylene (PE) resin, cyclic polyolefin (CO,) resin, and cyclic olefin copolymer (COC) resin; styrene resins, such as polystyrene (PS) resin, syndiotactic polystyrene (SPS) resin, and acrylonitrile-butylene-styrene copolymer (ABS) resin; polyester resins, such as polylactic (PLA) resin, polyethylene terephthalate (PET) resin, and polybutylene terephthalate (PBT) resin; polyacetal (POM) resin; polycarbonate (PC) resin; aliphatic polyamide (PA) resins, such as polyamide 6 resin, polyamide 66 resin, polyamide 11 resin, polyamide 12 resin, polyamide 46 resin, polyamide 6 resin-polyamide 66 resin copolymer (polyamide 6/66 resin) and polyamide 6 resin-polyamide 12 resin copolymer (polyamide 6/12 regin); semi-aromatic polyamide (PA) resins composed of a structural unit with an aromatic ring and structural unit free from aromatic ring, such as polyamide MXD6 resin, polyamide 6T resin, polyamide 9T resin, and polyamide 10T resin; polyphenylene sulfide (PPS) resin; polyether sulfone (PES) resin; liquid crystal polyester (LCP) resin; aromatic polyether ketone resins, such as polyether ketone (PEK) resin, polyether ether ketone (PEEK) resin, polyether ketone ketone (PEKK) resin, and polyether ether ketone ketone (PEEKK) resin; polyether imide (PEI) resin; polyamide-imide (PAI) resin; and thermoplastic polyimide (TPI) resin.
  • Preferred in the fused deposition modeling-based three-dimensional printer and the powder bed fusion-based three-dimensional printer is at least one selected from the group consisting of polyolefin resin, styrene resin, polyester resin, polyacetal (POM) resin, polycarbonate (PC) resin, aliphatic polyamide (PA) resin, semi-aromatic polyamide (PA) resin, polyphenylene sulfide (PPS) resin, polyether imide (PEI) resin, and polyether ether ketone (PEEK) resin.
  • Mixtures of at least two compatible thermoplastic resins selected from among the above thermoplastic resins, i.e., polymer alloys, or the like can also be used.
    • (Other Additives (C))
  • The resin composition according to the present invention may contain other additives without any loss of its preferred physical properties. Examples of the other additives include inorganic fillers other than the above-mentioned inorganic fibers, a stabilizer, a nucleating agent, an antistat, an antioxidant, a weatherproofer, a metal deactivator, a ultraviolet ray absorber, a germ- and mildew-proofing agent, a deodorant, a conductive additive, a dispersant, a softener (plasticizer), a colorant, a flame retardant, a sound deadener, a neutralizer, an antiblocking agent, a flow modifier, a mold release agent, a lubricant, and an impact resistance improver.
  • The resin composition may contain at least one of these additives.
    • (Method for Producing Resin Composition)
  • The resin composition according to the present invention can be produced mixing and heating (particularly, melt kneading) the above components, the inorganic fibers (A), the thermoplastic resin (B), and, as necessary, the other additives (C).
  • For melt kneading, any known melt kneader, for example, a biaxial extruder, can be used. Specifically, the resin composition can be produced by: (1) a method of preliminarily mixing the components with a mixer (a tumbler, a Henschel mixer or the like), melt kneading the mixture with a melt kneader, and then pelletizing it with a pelletization device (such as a pelletizer); (2) a method of adjusting a master batch of desired components, mixing it with other components as necessary, and melt kneading the mixture into pellets with a melt kneader; (3) a method of feeding the components into a melt kneader to form pellets; or other methods.
  • No particular limitation is placed on the processing temperature during melt kneading so long as it is within a temperature range in which the thermoplastic resin (B) can melt. Normally, the cylinder temperature of a melt kneader for use in the melt kneading is controlled within this range.
  • The content of the inorganic fibers (A) in the resin composition according to the present invention is, in a total amount of 100% by mass of the resin composition, preferably 1% by mass to 40% by mass, more preferably 3% by mass to 30% by mass, and still more preferably 7% by mass to 25% by mass.
  • The content of the thermoplastic resin (B) in the resin composition according to the present invention is, in a total amount of 100% by mass of the resin composition, preferably 50% by mass to 99% by mass, more preferably 60% by mass to 97% by mass, and still more preferably 65% by mass to 93% by mass.
  • No particular limitation is placed on the content of other additives (C) which are additives except for the above-described essential components and allowed to be used the present invention, without any loss of the preferred physical properties of the resin composition. The content of the other additives is normally 10% by mass or less and preferably 5% by mass or less in a total amount of 100% by mass of the resin composition.
  • By controlling the components of the resin composition according to the present invention within the above ranges, the resistance to delamination of a shaped object and the resistance to warpage and shrinkage of the shaped object in shaping using a three-dimensional printer can be improved.
  • In this manner, the resin composition according to the present invention exerting desired effects is produced.
    • <Shaping Material for Three-Dimensional Printer>
  • The resin composition according to the present invention a shaping material for a three-dimensional printer. The shaping material for a three-dimensional printer in the present invention refers to a material for use in applying it to a three-dimensional printer (also referred to as an additive manufacturing apparatus) to obtain a three-dimensional shaped object and is composed of the resin composition.
  • The shaping material for a three-dimensional printer according to the present invention can be used in any method so long as the method is to shape object by melting the shaping material by heat based on a design on a computer. For example, the shaping material can be suitably used in the fused deposition modeling process or the powder bed fusion process.
  • The fused deposition modeling process is a process for shaping a desired shaped object by fluidizing a thermoplastic resin having the shape of pellets, the shape of a thread called a filament or other shapes with a heating device inside an extrusion head, then discharging the fluid resin through a nozzle onto a platform, and cooling the resin into a solid state while gradually depositing layer upon layer of it. The use of the resin composition according to the present invention as a shaping material enables shaping using a fused deposition modeling-based three-dimensional printer without clogging of the extrusion head or wear of the extrusion head that might occur with the use of a resin composition blended with a fibrous filler, such as glass fibers or carbon fibers. For example, even through a thin nozzle having a head diameter of 0.5 mm or less, shaping can be achieved without the occurrence of the clogging of the extrusion head or wear of the extrusion head. In addition, it can be assumed that, although the reason is not clear, the inorganic fibers (A) can not only improve the resistance to warpage and shrinkage of the shared object but also increase the interfacial strength between the layered resin portions, thus preventing delamination of the shaped object.
  • No particular limitation is placed on the method for producing filament and an example is a method including: an extrusion step of extruding the resin composition according to the present invention produced by the above-described method as molten strand through a die hole in a molder and guiding the molten strand into a cooling water bath to obtain a strand; a stretching step of hot stretching the strand to obtain a filament; and the step of rolling up the filament.
  • No particular limitation is placed on the shape of the filament. Examples that can be cited as the cross-sectional shape thereof include circular, rectangular, flattened, ellipsoidal, cocoon-like, trefoil, and like non-circular shapes. Circular is preferred from the viewpoint of ease of handling. No limitation is placed on the length of the filament and it can be set at any value according to industrial production conditions or without interfering with the use for a fused deposition modeling-based three-dimensional printer. No particular limitation is also placed on the diameter of the filament and, for example, it is 0.5 mm to 3 mm and particularly 1 mm to 2 mm. Note that the diameter of the filament refers to the maximum of diameters measured on cross-sections of the filament perpendicular to the direction of length of the filament.
  • The filament may be a composite filament in which the resin composition according to the present invention is combined with another or other resin components. Examples of the cross-sectional structure of the composite filament that can be cited include a radially oriented structure, a side-by-side structure, a sea-island structure, and a core-in-sheath structure.
  • The powder bed fusion process is a process for shaping an object by depositing resin powder layer by layer, melting each layer into a particular cross-sectional shape, with an energy source, such as laser or electronic beam, and solidifying it. Since the resin composition according to the present invention is used as a shaping material, be assumed that, although the reason is not clear, the inorganic fibers (A) cannot only improve the resistance to warpage and shrinkage of the shaped object but also increase the interfacial strength between the layer resin portions, thus preventing delamination of the shaped object.
  • No particular limitation is placed on the method producing resin powder and examples include: a method of producing resin powder by crushing the resin composition with a crusher or other means, then grinding the crushed product with a jet mill or other means, and then classifying the ground product (mechanical grinding method); a method of producing resin powder by dissolving the resin composition in a solvent and then cooling the solution (precipitation method; and a method of producing resin powder by melt mixing a resin A and a resin B incompatible with the in A and immersing the obtained molten mixture in a solvent poor for the resin A and good for the resin B, thus decomposing the molten mixture (melt-mixing method). No limitation is placed on the particle diameter of the resin powder and it can be set at any value according to industrial production conditions or without interfering with the use for a three-dimensional printer, but the average particle diameter is preferably 10 μm to 150 μm and more preferably 30 μm to 80 μm.
  • The average particle diameter can be measured by the laser diffraction and scattering method and is a particle diameter at cumulative integrated value of 50% in a particle size distribution measured by the laser diffraction and scattering method (a volume-based 50% cumulative particle diameter), i.e., D50 (a median diameter). This volume-based 50% cumulative particle diameter (D50) is a particle diameter at a cumulative value of 50% in a cumulative curve of a particle size distribution determined on a volume basis, the cumulative curve assuming the total volume of particles as 100%, where during accumulation the number of particles is counted from a smaller size side.
  • Examples of the shape of particles forming the powder include spherical and amorphous (amoeboid, boomerang-like, cross, konpeito-like, potato-like, and so on), but spherical is preferred from the viewpoint of interface strength. The shapes of particles can be observed by scanning electron microscopy.
    • <Shaped Object and Production Method Therefor>
  • A shaped object according to the present invention is an object shaped from the resin composition according to the present invention with a three-dimensional printer. In using the resin composition according to the present invention in the form of a filament, a shaped object can be produced, for example, by performing shaping by feeding the filament into a fused deposition modeling-based three-dimensional printer. In using the resin composition according to the present invention in the form of powder, a shaped object can be produced, for example, by performing shaping by feeding the powder into a powder bed fusion-based three-dimensional printer.
  • In a method for producing a shaped object according to the present invention, shaped object is produced by a three-dimensional printer using the resin composition according to the present invention.
  • In using the resin composition according to the present invention in the form of a filament, a shaped object can be produced, for example, feeding the filament into a fused deposition modeling-based three-dimensional printer. Specifically, a shaped object can be produced feeding the filament into a fused deposition modeling-based three-dimensional printer, fluidizing the filament with a heating device inside an extrusion head, then discharging the fluid through a nozzle onto a platform, and cooling it into a solid state while gradually depositing layer upon layer of it according to the cross-sectional shape of a desired object to be shaped.
  • In using the resin composition according to the present invention in the form of powder, a shaped object can be produced, for example, by feeding the powder into a powder bed fusion-based three-dimensional printer. Specifically, a shaped object can be produced by feeding the resin powder into powder bed fusion-based three-dimensional printer, forming on a vertically or electronic beam, according to the cross-sectional shape of a desired object to be shaped, solidifying it, depositing a new thin layer of the resin powder on top of the solid, likewise melting it with the energy source, such as laser or electronic beam, according to the cross-sectional shape of the desired object to be shaped, solidifying it, and repeating these steps.
    • EXAMPLES
  • Hereinafter, a specific description will be given of the present invention with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. Details of raw materials used in Examples and Comparative Examples are as described below. The average fiber diameter and the average aspect ratio were measured using a field-emission scanning electron microscope (SEM, S-4800 manufactured by Hitachi High-Technologies Corporation), the shapes of particles were confirmed by the SEM, the average particle diameter was measured using, with the exception of carbon black, a laser diffraction particle size distribution measurement device (SALD-2100 manufactured by Shimadzu Corporation), and the average particle diameter of carbon black was measured using the SEM.
    • (Inorganic Fibers))
  • Potassium titanate (trade name: TISMO D102, manufactured Otsuka Chemical Co., Ltd., average fiber length: 15 μm, average fiber diameter: 0.5 μm, average aspect ratio: 30); and
  • Wollastonite (trade name: Bistal W, manufactured by Otsuka Chemical Co., Ltd., average fiber length: 25 μm, average fiber diameter: 3 μm, average aspect ratio: 8)
    • (Thermoplastic Resin)
  • Polyamide 12 resin (PA12 resin);
  • Polyamide MXD6 resin (PAMXD6 resin)
  • Acrylonitrile-butylene-styrene copolymer resin (ABS resin);
  • Cyclic olefin copolymer resin (COC resin);
  • Polybutylene terephthalate resin (PBT resin); and
  • Polyphenylene sulfide resin PPS resin)
    • (Other Additives)
  • Carbon black (trade name: #3050, manufactured by Mitsubishi Chemical Corporation, average particle diameter: 50 nm, amorphous-shaped particles);
  • Talc (average particle diameter: 8 μm, platy particles); and
  • Glass beads (trade name: EGB 063Z manufactured by Potters-Ballotini Co., Ltd., average particle diameter: 25 μm spherical particles)
    • <Production of Resin Composition and Filament> (Examples 1 to 11 and Comparative Examples 1 to 8)
  • Materials were melt-kneaded in each composition ratio shown in Tables 1 and 2 using a biaxial extruder to produce pellets The cylinder temperature of the biaxial extruder was 190° C. to 230° C. in Examples 1 to 4 and Comparative Examples 1 to 4, 230° C. to 270° C. in Examples 5 and 6 and Comparative Example 5, 200° C. to 230° C. in Examples 7 and 8 and Comparative Example 6, 210° C. to 240° C. in Example 9 and Comparative Example 7, and 200° C. to 250° C. in Examples 10 and 11 and Comparative Example 8.
  • The obtained pellets were loaded into a filament extruder, thus obtaining a filament with a filament diameter of 1.7 mm.
  • TABLE 1
    Comp. Comp. Comp. Comp.
    Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 1 Ex. 2 Ex. 3 Ex. 4
    Inorganic fibers potassium titanate % by mass 5 10 20
    wollastonite % by mass 10
    Thermoplastic resin PA12 resin % by mass 95 90 80 90 100 99 95 90
    Other additives carbon black % by mass 1 5
    talc % by mass 10
  • TABLE 2
    Comp. Comp. Comp. Comp.
    Ex. 5 Ex. 6 Ex. 5 Ex. 7 Ex. 8 Ex. 6 Ex. 9 Ex. 7 Ex. 10 Ex. 11 Ex. 8
    Inorganic fibers potassium titanate % by mass 10 20 10 20 10 10 20
    Thermoplastic resin PAMXDS resin % by mass 90 80 100
    ABS resin % by mass 90 80 100
    COC resin % by mass 90 100
    PBT resin % by mass 90 80 100
    • <Production of Three-Dimensional Shaped Object Based on Fused Deposition Modeling Process> (Test Examples 1 to 11 and Comparative Test Examples 1 to 8)
  • The filament obtained in each of Examples 1 to 11 and Comparative Examples 1 to 8 was deposited into layers in a thickness direction by fused deposition modeling-based three-dimensional printer (manufactured by MUTOH INDUSTRIES, LTD., trade name: MF1100) under the associated printing conditions shown in Tables 3 and 4, thus producing a flat-plate shaped object 100 mm long, 2 mm wide, and 50 mm thick.
  • FIG. 1 shows a photograph of a shaped object (Comparative Test Example 1) produced using the resin composition according to Comparative Example 1, and FIG. 2 shows a photograph of a shaped object (Test Example 2) produced using the resin composition according to Example 2.
    • (Test Examples 12 to 22 and Comparative Test Examples 9 to 16)
  • The filament obtained in each of Examples 1 to 11 and Comparative Examples 1 to 8 was produced into a dumbbell tensile specimen having a shape shown in FIG. 3 by a fused deposition modeling-based three-dimensional printer (manufactured by MUTOH INDUSTRIES, LTD., trade name: MF 1100) under the associated printing conditions shown in Tables 5 and 6.
    • (Test Examples 23 to 33 and Comparative Test Examples 17 to 22)
  • The filament obtained in each of Examples 1 to 11, Comparative Example 1, and Comparative Examples 4 to 8 was produced into a bending specimen having a shape shown in FIG. 4 by a fused deposition modeling-based three-dimensional printer (manufactured by MUTOH INDUSTRIES, LTD., trade name: MF1100) under the associated printing conditions shown in Tables 7 and 8.
    • <Evaluation> (1) Amount of Warpage
  • The flat-plate shaped objects produced under the conditions in Tables 3 and 4 were measured in terms of amount of warpage with a caliper. The amount of warpage W is, as shown in FIG. 5, a difference in height along a build-up direction during shaping between the middle and ends of the shaped object in a traveling direction during shaping. The results are shown in Tables 3 and 4.
    • (2) Shrinkage
  • The flat-plate shaped objects produced under the conditions in Tables 3 and 4 were measured in terms of shrinkage. The shrinkage was measured in the build-up direction and the traveling direction. The shrinkage in the build-up direction is a shrinkage in the thickness b along the build-up direction during shaping shown in FIG. 5. The shrinkage in the traveling direction is a shrinkage in the length a along the traveling direction during shaping shown in FIG. 5. The results are shown in Tables 3 and 4.
    • (3) Interface Adhesion
  • The flat-plate shaped objects produced under the conditions in Tables 3 and 4 were cut along the build-up direction into 10 mm-wide strips, the obtained strips were measured in terms of bending stress by a 30 mm-span three-point bending test with a tester Autograph AG-5000 (manufactured Shimadzu Corporation), and the measured values were assumed as interface adhesions. The results are shown in Tables 3 and 4.
    • (4) Tensile Strength
  • Dumbbell tensile specimens produced under the conditions in Tables 5 and 6 were measured in terms of tensile strength with a tester Autograph AG-1 (manufactured by Shimadzu Corporation). The results are shown in Tables 5 and 6.
    • (5) Flexural Strength and Flexural Modulus
  • Bending specimens produced under the conditions in Tables 7 and 8 were measured in terms of flexural strength and flexural modulus by a 60 mm-span three-point bending test with a tester Autograph AG-5000 (manufactured by Shimadzu Corporation). The test results are shown in Tables 7 and 8.
  • TABLE 3
    Comp. Comp. Comp. Comp.
    Test Test Test Test Test Test Test Test
    Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 1 Ex. 2 Ex. 3 Ex. 4
    Materials used Ex. 1 Ex. 2 Ex. 3 Ex. 4 Comp. Comp. Comp. Comp.
    Ex. 1 Ex. 2 Ex. 3 Ex. 4
    Shaping nozzle temperature (° C.) 250 250 250 250 210 250 250 250
    conditions heated bed temperature (° C.) 30 30 30 30 30 30 30 30
    layer height (mm) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    head feed speed (mm/sec) 30 30 30 30 30 30 30 30
    Properties amount of warpage (mm) 1.2 0.4 0.3 2.0 3.1 3.0 3.0 1.9
    shrinkage in build-up direction (%) 0.32 0.18 0.02 0.08 0.64 0.61 0.54 0.43
    shrinkage in traveling direction (%) 1.2 0.72 0.56 1.1 5.3 5.1 4.9 2.3
    interface adhesion (MPa) 59 68 60 58 50 48 47 44
  • TABLE 4
    Comp. Comp. Comp. Comp.
    Test Test Test Test Test Test Test Test Test Test Test
    Ex. 5 Ex. 6 Ex. 5 Ex. 7 Ex. 8 Ex. 6 Ex. 9 Ex. 7 Ex. 10 Ex. 11 Ex. 8
    Materials used Ex. 5 Ex. 6 Comp. Ex. 7 Ex. 8 Comp. Ex. 9 Comp. Ex. 10 Ex. 11 Comp.
    Ex. 5 Ex. 6 Ex. 7 Ex. 8
    Shaping nozzle temperature (° C.) 250 250 250 230 230 230 230 220 265 265 265
    conditions heated bed temperature (° C.) 30 30 30 80 80 80 85 85 30 30 30
    layer height (mm) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    head diameter (mm) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    head feed speed (mm/sec) 30 30 30 30 30 30 30 30 30 30 30
    Properties amount of warpage (mm) 0.5 0.3 2.9 0.8 0.5 1.5 0.1 0.8 1.5 0.9 3.8
    shrinkage in build-up 0.21 0.09 0.58 0.18 0.15 0.88 0.6 1.0 0.58 0.23 1.1
    direction (%)
    shrinkage in traveling 0.79 0.84 4.8 0.10 0.08 0.28 0.04 0.25 1.42 0.96 6.21
    direction (%)
    interface adhesion (MPa) 75 77 81 41 42 35 25 19 82 88 52
  • Tables 3 and 4 show that Test Examples 1 to 11 in which inorganic fibers were blended with PA12 resin, PAMXD6 resin ABS resin, COC resin or PBT resin exhibited significantly low amounts of warpage and significantly low shrinkages both in the build-up direction and traveling direction as compared to Comparative Test Examples 1 to in which no inorganic fibers were blended with PA12 resin, PAMXD6 resin, ABS resin, COC resin or PBT resin. Furthermore, it is shown that their interface adhesions were significantly improved.
  • As is obvious from comparison of Comparative Test Example 1 with Comparative Test Examples 2 to 4, the addition of an inorganic additive, such as carbon black or talc, into a thermoplastic resin generally decreases the interface adhesion. However, for example, comparison of Test Examples 1 to 4 with Comparative Test Example 1 shows that the addition of the inorganic fibers according to the present invention into a thermoplastic resin offered an unforeseen effect of increased interface adhesion.
  • TABLE 5
    Comp. Comp. Comp. Comp.
    Test Test Test Test Test Test Test Test
    Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 9 Ex. 10 Ex. 11 Ex. 12
    Materials used Ex. 1 Ex. 2 Ex. 3 Ex. 4 Comp. Comp. Comp. Comp.
    Ex. 1 Ex. 2 Ex. 3 Ex. 4
    Shaping nozzle temperature (° C.) 250 250 250 250 210 250 250 250
    conditions heated bed temperature (° C.) 30 30 30 30 30 30 30 30
    layer height (mm) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
    head diameter (mm) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    head feed speed (mm/sec) 30 30 30 30 30 30 30 30
    Properties tensile strength (MPa) 60 64 74 60 57 52 43 50
  • TABLE 6
    Comp. Comp. Comp. Comp.
    Test Test Test Test Test Test Test Test Test Test Test
    Ex. 16 Ex. 17 Ex. 13 Ex. 18 Ex. 19 Ex. 14 Ex. 20 Ex. 15 Ex. 21 Ex. 22 Ex. 16
    Materials used Ex. 5 Ex. 6 Comp. Ex. 7 Ex. 8 Comp. Ex. 9 Comp. Ex. 10 Ex. 11 Comp.
    Ex. 5 Ex. 6 Ex. 7 Ex. 9
    Shaping nozzle temperature (° C.) 250 250 250 230 230 230 230 220 265 265 265
    conditions heated bed temperature (° C.) 30 30 30 80 80 80 85 85 30 30 30
    layer height (mm) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.5 0.5 0.5
    head diameter (mm) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    head feed speed (mm/sec) 30 30 30 30 30 30 30 30 30 30 30
    Properties tensile strength (MPa) 90 107 72 46 50 39 53 48 54 65 46
  • Tables 5 and 6 show that Test Examples 12 to 22 in which inorganic fibers were blended with the resin also exhibited high tensile strengths as compared to Comparative Test Examples 9 to 15 in which no inorganic fibers were blended with the resin.
  • TABLE 7
    Comp. Comp.
    Test Test Test Test Test Test
    Ex. 23 Ex. 24 Ex. 25 Ex. 26 Ex. 17 Ex. 18
    Materials used Ex. 1 Ex. 2 Ex. 3 Ex. 4 Comp. Comp.
    Ex. 1 Ex. 4
    Shaping nozzle temperature (° C.) 250 250 250 250 210 250
    conditions heated bed temperature (° C.) 30 30 30 30 30 30
    layer height (mm) 0.2 0.2 0.2 0.2 0.2 0.2
    head diameter (mm) 0.5 0.5 0.5 0.5 0.5 0.5
    head feed speed (mm/sec) 30 30 30 30 30 30
    Properties flexural strength (MPa) 52 58 73 54 48 54
    flexural modulus (GPa) 1.7 2.1 3.2 1.8 1.3 2.4
  • TABLE 8
    Comp. Comp. Comp. Comp.
    Test Test Test Test Test Test Test Test Test Test Test
    Ex. 27 Ex. 28 Ex. 19 Ex. 29 Ex. 30 Ex. 20 Ex. 31 Ex. 21 Ex. 32 Ex. 33 Ex. 22
    Materials used Ex. 5 Ex. 6 Comp. Ex. 7 Ex. 8 Comp. Ex. 9 Comp. Ex. 10 Ex. 11 Comp.
    Ex. 5 Ex. 6 Ex. 7 Ex. 8
    Shaping nozzle temperature (° C.) 250 250 250 230 230 230 230 220 265 265 265
    conditions heated bed temperature (° C.) 30 30 30 80 80 80 85 85 30 30 30
    layer height (mm) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.5 0.5 0.5
    head diameter (mm) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    head feed speed (mm/sec) 30 30 30 30 30 30 30 30 30 30 30
    Properties flexural strength (MPa) 132 187 114 72 72 51 83 80 82 115 69
    flexural modulus (GPa) 4.6 6.8 2.6 3.8 5.9 1.7 4.3 2.1 3.7 5.8 2.1
  • Tables 7 and 8 show that Test Examples 23 to 33 in which inorganic fibers were blended with the resin also exhibited high flexural strengths and flexural moduli as compared to Comparative Test Examples 17 and 19 to 22 in which no inorganic fibers were blended with the resin. Comparative Test Example 18 in which platy particles were blended with the resin exhibited high flexural strength and flexural modulus but was shown from Tables 3 and 5 not to have increased the shrinkages, interface adhesion, and tensile strength.
    • <Production of Resin Composition and Resin Powder> (Example 12 and Comparative Examples 9 to 10)
  • Materials were melt-kneaded in each composition ratio shown in Table 9 using a biaxial extruder to produce pellets. The cylinder temperature of the biaxial extruder was 270° C. to 300° C. The obtained pellets and polyethylene oxide were melt-mixed at 280° C. to 300° C. and the resultant mixture was immersed in water to dissolve polyethylene oxide in water, thus obtaining spherical resin powder. The average particle diameter of the spherical resin powder was measured with a laser diffraction particle size distribution measurement device (SALD-2100 manufactured Shimadzu Corporation). The average particle diameters of Example 12, Comparative Example 9, and Comparative Example 10 were 70 μm, 50 μm, and 50 μm respectively.
  • TABLE 9
    Ex. Comp. Comp.
    12 Ex. 9 Ex. 10
    Inorganic fibers potassium titanate % by mass 20
    Thermoplastic resin PPS resin % by mass 80 100 50
    Other additives glass beads % by mass 50
    • <Production of Three-Dimensional Shaped Object Based on Powder Bed Fusion Process (Test Examples 34 and Comparative Test Examples 23 to 24)
  • The spherical resin powder obtained in each of Example 12 and Comparative Examples 9 to 10 was produced into a bending specimen having a shape shown in FIG. 4 by a powder bed fusion based three-dimensional printer (manufactured by ASPECT Inc., trade name: RaFaEl II 150-HT) under the associated printing conditions shown in Table 10.
    • <Evaluation> (1) Amount of Warpage
  • The shaped objects of bending specimens produced under the conditions in Table 10 were measured in terms of amount of warpage with a non-contact roughness and shape measurement device (a one-shot 3D shape measuring microscope VR-3000 manufactured by Keyence Corporation). The amount of warpage W is, as shown in FIG. 6, a difference in height along a build-up direction during shaping between the middle and ends of the bending specimen. The results are shown in Table 10.
    • (2) Shrinkage
  • The shaped objects of bending specimens produced under the conditions in Table 10 were measured in terms of shrinkage. The shrinkage was measured in the build-up direction. The shrinkage in the build-up direction is a shrinkage in the thickness of the bending specimen along the build-up direction during shaping.
    • (3) Interface Adhesion
  • Respective flexural strengths of the shaped objects of bending specimens produced under the conditions in Table 10 were divided by their respective packing densities and the obtained values were assumed as interface adhesions. The packing density value obtained by dividing the specific gravity of the shaped object of each bending specimen the density of an injection-molded piece (a piece of the same shape injection-molded using pellets having the same composition). The flexural strength of the shaped object of each bending specimen obtained by the powder bed fusion process is the sum of interface strengths between powder particles. As the packing density decreases, the interface area correspondingly decreases and the flexural strength also correspondingly decreases.
  • The flexural strength was obtained by measuring each bending specimen produced under the conditions in Table 10 in terms of bending stress by a 60 mm-span three-point bending test with a tester Autograph AG-5000 (manufactured by Shimadzu Corporation). The specific gravity of each shaped object was measured in conformity to JIS Z8807.
    • (4) Flexural Strength
  • The shaped objects of the bending specimens produced under the conditions in Table 10 were measured in terms of flexural strength by a 60 mm-span three-point bending test with a tester Autograph AG-5000 (manufactured by Shimadzu Corporation). The test results are shown in Table 10.
  • TABLE 10
    Comp. Test Comp. Test
    Test Ex. 23 Ex. 24
    Ex. 34 Comp. Comp.
    Materials used Ex. 12 Ex. 9 Ex. 10
    Shaping laser power (W) 11 11 11
    conditions feed temperature (° C.) 240 240 240
    part temperature (° C.) 250 250 250
    layer height (mm) 0.1 0.1 0.1
    Properties amount of warpage (mm) 2.1 3.9 3.2
    shrinkage (%) 0.9 1.5 1.1
    interface adhesion (MPa) 97 84 48
    flexural strength (MPa) 92 80 46

Claims (13)

1. A resin composition containing; inorganic fibers having an average fiber length of 1 μm to 300 μm and an average aspect ratio of 3 to 200; and a thermoplastic resin, the resin composition serving as a shaping material for a three-dimensional printer.
2. The resin composition according to claim wherein the inorganic fibers have a Mohs hardness of 5 or less.
3. The resin composition according to claim 1, wherein the inorganic fibers are at least one selected from the group consisting of potassium titanate and wollastonite.
4. The resin composition according to claim 1, wherein a content of the inorganic fibers is 1% by mass to 40% by mass in a total amount of 100% by mass of the resin composition.
5. The resin composition according to claim 1, wherein the three-dimensional printer is based on a fused deposition modeling process or a powder bed fusion process.
6. A filament for a fused deposition modeling-based three-dimensional printer, the filament being made of the resin composition according to claim 1.
7. A resin powder for a powder bed fusion-based three-dimensional printer, the resin powder being made of the resin composition according to claim 1.
8. A shaped object shaped from the resin composition according to claim 1 with a three-dimensional printer.
9. A shaped object shaped from the filament according to claim 6 with a fused deposition modeling-based three-dimensional printer.
10. A shaped object shaped from the resin powder according to claim 7 with a powder bed fusion-based three-dimensional printer.
11. A method for producing a shaped object, wherein a shaped object is produced with a three-dimensional printer using the resin composition according to claim 1.
12. A method for producing a shaped object, wherein the filament according to claim 6 is fed to a fused deposition modeling-based three-dimensional printer.
13. A method for producing a shaped object, wherein the resin powder according to claim 7 is fed to a powder bed fusion-based three-dimensional printer.
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