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WO2024204368A1 - Matériau pour modélisation tridimensionnelle, corps moulé et son procédé de production - Google Patents

Matériau pour modélisation tridimensionnelle, corps moulé et son procédé de production Download PDF

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Publication number
WO2024204368A1
WO2024204368A1 PCT/JP2024/012279 JP2024012279W WO2024204368A1 WO 2024204368 A1 WO2024204368 A1 WO 2024204368A1 JP 2024012279 W JP2024012279 W JP 2024012279W WO 2024204368 A1 WO2024204368 A1 WO 2024204368A1
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Prior art keywords
resin powder
particle size
powder
resin
dimensional modeling
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English (en)
Japanese (ja)
Inventor
山末 奈央 吉田
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B33Y80/00—Products made by additive manufacturing

Definitions

  • the present invention relates to a material for three-dimensional modeling, and more specifically to a material for three-dimensional modeling that contains two types of resin powder with different resin compositions and particle sizes.
  • the present invention also relates to a molded body using this material for three-dimensional modeling, and a method for manufacturing the same.
  • 3D printers Today, three-dimensional printers (hereinafter sometimes referred to as "3D printers") that use various additive manufacturing methods (e.g., binder jetting, material extrusion, liquid vat photopolymerization, etc.) are available on the market.
  • 3D printer systems using the Powder Bed Fusion method such as the system manufactured by 3D Systems, Inc. of the United States, are used to heat and melt a thin layer (powder bed) of powder material such as resin to a temperature near the melting point of the resin powder using a heating means such as a high-power CO2 laser, and to build a three-dimensional object in layers based on a computer-aided design (CAD) model.
  • CAD computer-aided design
  • a laser used as a heating means scans a cross section in the XY direction on the surface of a powder bed formed based on 3D CAD data, and selectively melts the powder material.
  • a three-dimensional molded body can be obtained by repeatedly forming a powder bed and fusing it with a laser to form a laminate.
  • This system does not require the use of molds, can use a variety of resin powders as raw materials as long as they have a certain degree of heat resistance, and the resulting molded products are highly reliable, so it is a technology that has attracted attention in recent years.
  • thermoplastic resins are used as the material type of resin powder used in 3D printers.
  • polyamide resins such as nylon 12 and nylon 11 are widely used.
  • polyester resins such as polybutylene terephthalate, polyolefin resins such as polypropylene, and elastomer resins such as thermoplastic polyurethane have also been used.
  • 3D printers have been widely used for product prototyping. In recent years, the use of 3D printers for functional parts for practical use has also been considered. When considering practical applications, for example, when used as components for home appliances, building materials, aircraft, automotive materials, and the like, it is desirable for the molded articles obtained using three-dimensional modeling materials with a 3D printer to have high mechanical properties.
  • bodies produced by the process are prone to voids inside the bodies, and have poor mechanical properties.
  • Patent Document 1 discloses a method for obtaining a powder having excellent tensile elongation at break by specifying the ethylene molar ratio and melt flow rate of a polypropylene resin within specific ranges.
  • Patent Document 2 discloses a method for obtaining a powder having excellent strength in the layering direction of a molded body by melt-kneading talc as a filler into a polypropylene resin and specifying the mass ratio of silicon oxide to the total mass of the obtained resin powder within a specific range.
  • Patent Document 1 it is necessary to polymerize an ethylene-propylene copolymer having a specific composition, which is not preferable from the viewpoint of production and procurement of raw materials.
  • Patent Document 2 since talc which falls under the GHS classification is contained, there are concerns about safety during grinding. In none of the examples was any improvement in the impact resistance of the resulting molded article confirmed.
  • the present invention aims to provide a material for three-dimensional modeling that contains a resin composition and that uses existing resin powders and has excellent modeling properties in 3D printers and excellent impact resistance of the resulting molded bodies while maintaining safety during powder production.
  • the gist of the present invention is as follows:
  • a material for three-dimensional modeling comprising: a resin powder (A) having an average particle size (D50) of 30 ⁇ m or more and 250 ⁇ m or less as measured by a laser diffraction method; and a resin powder (B) having a resin composition different from that of the resin powder (A) and having an average particle size (D50) of 3% or more and 30% or less of the average particle size (D50) of the resin powder (A) as measured by a laser diffraction method.
  • a material for three-dimensional modeling characterized in that in a particle size distribution chart on a number basis obtained by image analysis using the method described below, it has multiple peaks between 5 ⁇ m and 250 ⁇ m and has at least one peak top in a region of 5 ⁇ m or more and smaller than 30 ⁇ m, and in a particle size distribution chart on a volume basis obtained by image analysis, it has a peak top in a region of 5 ⁇ m or more and smaller than 30 ⁇ m, the value of the volumetric peak top being 2.5 times or less than the value of at least one number-based peak top, and the volumetric average particle size (D50) is 30 ⁇ m or more.
  • Image analysis method 1 cc of resin powder is spread on a slide and observed under the following observation conditions, and particle size analysis is performed under the following particle size analysis conditions.
  • Observation conditions Measuring device: Horiba XploRA Plus Observation illumination: Transmitted light Objective lens: Olympus bright/dark field plan achromat MPLN 10 xBD Observation field: 15 x 11 mm area (17 x 15 field composite image)
  • Particle size analysis conditions Particle size analysis software: Particle Finder ver. 2
  • Particle size cutoff Equivalent circle diameter 4 ⁇ m or more Circularity cutoff: Circularity 0.6 or more Distribution criteria: Number distribution and volume distribution
  • [5] The material for three-dimensional modeling according to any one of [1] to [4], wherein the resin powder (A) has an average particle size (D50) of 35 ⁇ m or more, 40 ⁇ m or more, 45 ⁇ m or more, or 50 ⁇ m or more.
  • [6] The material for three-dimensional modeling according to any one of [1] to [5], wherein the resin powder (A) has an average particle size (D50) of 200 ⁇ m or less, 150 ⁇ m or less, or 120 ⁇ m or less.
  • [7] The material for three-dimensional modeling according to any one of [1] to [6], wherein the average particle size (D50) of the resin powder (B) is 5% or more or 10% or more of that of the resin powder (A).
  • [8] The material for three-dimensional modeling according to any one of [1] to [7], wherein the average particle size (D50) of the resin powder (B) is 25% or less or 20% or less of that of the resin powder (A).
  • [10] A material for three-dimensional modeling according to [4] or [9], in which the peak top of the resin powder (B) is 100 ⁇ m or less higher than the peak top of the resin powder (A).
  • [11] A material for three-dimensional modeling according to any one of [1] to [10], wherein the resin powder (A) is a powder of a polyolefin resin.
  • a three-dimensional modeling material according to any one of [1] to [12], wherein the resin powder (B) is a powder of at least one of polyethylene and a thermosetting elastomer.
  • [17] A material for three-dimensional modeling according to any one of [1] to [16], in which the content of the resin powder (B) is 1% by mass or more, 5% by mass or more, or 10% by mass or more relative to the total amount of the resin powder (A) and the resin powder (B).
  • [18] A material for three-dimensional printing according to any one of [1] to [17], in which the content of the resin powder (B) is less than 50% by mass, 45% by mass or less, or 40% by mass or less relative to the total amount of the resin powder (A) and the resin powder (B).
  • [20] A material for three-dimensional modeling according to any one of [1] to [19], which is a material for three-dimensional modeling using the Powder Bed Fusion method.
  • a method for producing a molded body comprising the step of forming a molded body in three dimensions by a powder bed fusion method using a material for three-dimensional modeling described in any one of [1] to [21].
  • the present invention it is possible to provide a material for three-dimensional modeling that uses existing resin powders and has excellent modeling properties in a 3D printer and excellent impact resistance of the resulting molded body while maintaining safety during powder production.
  • the present invention also provides a molded article produced by powder bed fusion using this material for three-dimensional modeling, and a method for producing the same.
  • 1 shows a particle size distribution based on number in Example 1.
  • 1 is a particle size distribution based on volume in Example 1.
  • 1 shows the particle size distribution based on the number of particles in Example 2.
  • 1 is a volume-based particle size distribution in Example 2.
  • 13 is a particle size distribution based on number in Example 3.
  • 1 is a particle size distribution based on volume in Example 3.
  • 13 is a particle size distribution based on number in Example 4.
  • 1 is a volume-based particle size distribution in Example 4.
  • 1 shows the particle size distribution based on number in Comparative Example 1.
  • 1 is a volume-based particle size distribution in Comparative Example 1.
  • 13 is a particle size distribution based on number in Comparative Example 2.
  • 1 is a volume-based particle size distribution in Comparative Example 2.
  • 13 is a particle size distribution based on number in Comparative Example 3.
  • 13 is a volume-based particle size distribution in Comparative Example 3.
  • present embodiment provides a detailed description of the form for carrying out the present invention (hereinafter referred to as the "present embodiment").
  • present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content.
  • present invention can be carried out in various modifications within the scope of its gist.
  • the material for three-dimensional modeling of the present invention is composed of a resin powder (A) (hereinafter, may be referred to as “resin powder (A) of the present invention”) and a resin powder (B) (hereinafter, may be referred to as “resin powder (B) of the present invention”).
  • the material for three-dimensional printing according to the first embodiment of the present invention is characterized in that the resin composition of resin powder (A) is different from the resin composition of resin powder (B), the average particle size (D50) of the resin powder (A) measured by a laser diffraction method is 30 ⁇ m or more and 250 ⁇ m or less, and the average particle size (D50) of the resin powder (B) measured by a laser diffraction method is 1 ⁇ m or more and less than 30 ⁇ m.
  • the average particle size (D50) of the resin powder (B) is preferably 3% to 30% of the average particle size (D50) of the resin powder (A).
  • the three-dimensional modeling material according to the second embodiment of the present invention is characterized in that the resin composition of the resin powder (A) is different from the resin composition of the resin powder (B), the average particle size (D50) of the resin powder (A) measured by a laser diffraction method is 30 ⁇ m or more and 250 ⁇ m or less, and the average particle size (D50) of the resin powder (B) measured by a laser diffraction method is 3% or more and 30% or less of the average particle size (D50) of the resin powder (A).
  • a material for three-dimensional modeling according to a third embodiment of the present invention is characterized in that in a particle size distribution chart on a number basis obtained by image analysis using the method described below, it has multiple peaks between 5 ⁇ m and 250 ⁇ m and has at least one number-based peak top in a region of 5 ⁇ m or more and smaller than 30 ⁇ m, and in a particle size distribution chart on a volume basis obtained by image analysis, it has a volume-based peak top in a region of 5 ⁇ m or more and smaller than 30 ⁇ m, the value of the volume-based peak top being 2.5 times or less than the value of at least one number-based peak top, and the volume-based average particle size (D50) is 30 ⁇ m or more.
  • Image analysis method 1 cc of resin powder is spread on a slide, and observation is performed under the following observation conditions, and particle size analysis is performed under the following particle size analysis conditions (observation conditions)
  • Measuring device Horiba XploRA Plus Observation illumination: Transmitted light
  • Objective lens Olympus bright/dark field plan achromat
  • MPLN 10 xBD Observation field 15 x 11 mm area (17 x 15 field composite image) (Particle size analysis conditions)
  • Particle size analysis software Particle Finder ver.
  • the resin composition of the resin powder (A) is different from the resin composition of the resin powder (B), and it is preferable that the peak top of the resin powder (B) is 100 ⁇ m or less higher than the peak top of the resin powder (A).
  • the three-dimensional modeling material according to the first embodiment of the present invention, the three-dimensional modeling material according to the second embodiment of the present invention, and the three-dimensional modeling material according to the third embodiment of the present invention are collectively referred to as the "three-dimensional modeling material of the present invention.”
  • the resin that is the material for the resin powder (A) may be referred to as "resin (a),” and the resin that is the material for the resin powder (B) may be referred to as "resin (b).”
  • the three-dimensional modeling material of the present invention is used in the Powder Bed Fusion method and contains at least the resin powder (A) and resin powder (B) of the present invention.
  • the three-dimensional modeling material of the present invention is preferably a material used to create three-dimensional objects (resin molded bodies) using a 3D printer, particularly using the Powder Bed Fusion method.
  • the shape of the material for three-dimensional modeling may be any shape that is applicable to various types of 3D printers, such as Powder Bed Fusion and Multi Jet Fusion.
  • the material for three-dimensional modeling of the present invention is preferably used for the Powder Bed Fusion method.
  • the resin powder (A) and the resin powder (B) have different resin compositions, and the particle sizes of the resin powder (A) and the resin powder (B) are within a predetermined range, and the particle size of the resin powder (B) is smaller than the particle size of the resin powder (A).
  • the resin powder (B) exists between the particles of the resin powder (A) and is easily included in the model layer produced by melting and flowing the resin powder (A).
  • the three-dimensional modeling material according to the third embodiment of the present invention has multiple peaks between 5 ⁇ m and 250 ⁇ m, at least one number-based peak top in the region between 5 ⁇ m and 30 ⁇ m, and in a volume-based particle size distribution chart obtained by image analysis, has a volume-based peak top in the region between 5 ⁇ m and 30 ⁇ m, and the volume-based peak top value is 2.5 times or less than the value of at least one number-based peak top, and the volume-based average particle size (D50) is 30 ⁇ m or more.
  • D50 volume-based average particle size
  • the viscosity average molecular weight (Mv) of the resin powder (A) and the resin powder (B) is a value determined for the resin powder (A) and the resin powder (B) in accordance with the method specified in JIS K-736.
  • the specific viscosity ⁇ sp (dl/g) of a 0.05% decalin solution at 135°C is used in place of the intrinsic viscosity [ ⁇ ] (dl/g) in accordance with the method specified in ASTM D4020.
  • g) is the value calculated using
  • ⁇ Average particle size (D50)> The average particle size (D50) of the resin powder (A), the resin powder (B), and the powder of the material for three-dimensional modeling was measured on a volume basis using a particle size distribution measuring device that uses a laser diffraction method. The distribution is measured, and the particle size is determined as the particle size at 50% of the frequency distribution of the powder among the detected particle size distribution.
  • peaks and peak tops of particle size distribution chart based on number obtained by image analysis are determined by observing the powder spread on a slide glass using a particle size distribution meter with an analysis function (e.g., "XploRA PLUS" manufactured by HORIBA France SAS) equipped with particle size analysis software on a confocal laser Raman microscope, and creating a particle size distribution chart on a number basis using the circle equivalent diameters calculated from the area of the obtained particle images.
  • an analysis function e.g., "XploRA PLUS" manufactured by HORIBA France SAS
  • the melting points (Tm) of resin powder (A) and resin powder (B) are crystalline melting temperatures (melting points Tm) (°C) (reheating process) determined from thermograms measured using a differential scanning calorimeter in accordance with JIS K7121, in which the temperature is increased from room temperature to 200°C at a heating rate of 10°C/min, the temperature is maintained at that temperature for 1 minute, the temperature is decreased to 50°C at a heating rate of 10°C/min, and the temperature is increased again to 200°C at a heating rate of 10°C/min.
  • the glass transition temperatures (Tg) of the resin powder (A) and the resin powder (B) are values of glass transition temperatures determined from thermograms measured using a differential scanning calorimeter in accordance with JIS K7121, in which the temperature is increased from room temperature to 200° C. at a rate of 10° C./min, the temperature is maintained at that temperature for 1 minute, the temperature is decreased to 50° C. at a rate of 10° C./min, and the temperature is increased again to 200° C. at a rate of 10° C./min.
  • ⁇ Resin Composition> means that among the constituent units (monomer species of the resin raw material) constituting the resin, the constituent units that occupy the main component (constituent units that are contained in the resin at 50% by mass or more) are different. Therefore, for example, propylene-based copolymers that have different constituent units other than the propylene unit are considered to have the same resin composition.
  • the "different resin compositions" can be confirmed by micro-IR or micro-Raman spectroscopy.
  • the resin powders used in the three-dimensional modeling material of the present invention i.e., the resin powder (A) and the resin powder (B), particularly the resin powder (A), are preferably obtained using a thermoplastic resin.
  • the resin powder may contain other resins, additives, reinforcing materials, etc., other than the thermoplastic resin, to an extent that does not impair the effects of the present invention.
  • the resin powder may be a commercially available three-dimensional modeling material made of a thermoplastic resin.
  • the powdering means for producing the resin powder according to the present invention include melt granulation, in which a resin or a resin composition (hereinafter, these may be referred to as "resin material”) melted near the melting point is made into a fibrous form and then cut, and pulverization, in which the resin material is cut or destroyed by applying an impact or shear.
  • resin material a resin or a resin composition
  • pulverization in which the resin material is cut or destroyed by applying an impact or shear.
  • the resin powder according to the present invention does not contain fine powder of about 10 ⁇ m and has a certain particle size and particle size distribution, so that a powder of such a suitable shape can be obtained. Therefore, it is preferable to select a suitable powdering method.
  • a grinding means for example, a stamp mill, a ring mill, a stone mill, a mortar, a roller mill, a jet mill, a high-speed rotary mill, a hammer mill, a pin mill, a container-driven mill, a disk mill, a media stirring mill, etc. can be used.
  • classification methods include air classification, sieve classification, etc. If necessary, inorganic particles and reinforcing materials described below may be added to and mixed with the obtained powder.
  • the resin powder (A) of the present invention may be one type having the resin composition and physical properties shown below, or two or more types having different resin compositions or different physical properties may be mixed and used.
  • the resin (a) constituting the resin powder (A) used in the present invention is preferably a thermoplastic resin.
  • the thermoplastic resin may be any material that exhibits thermoplasticity due to the heat or light of the 3D printer device, and may be appropriately selected depending on the function to be imparted to the molded article to be formed.
  • thermoplastic resin of the resin powder (A) a commercially available thermoplastic resin material for three-dimensional modeling may be used.
  • the three-dimensional modeling material remaining after the model is produced by the Powder Bed Fusion method may be reused.
  • the three-dimensional modeling material of the present invention uses a combination of resin powder (A) and resin powder (B) described below, and can produce a molded body with excellent impact resistance and excellent modeling properties by using an existing resin powder for the Powder Bed Fusion method as the resin powder (A).
  • the resin powder (A) used in the present invention is not limited to the existing resin powder for the Powder Bed Fusion method.
  • Examples of the resin (a) in the resin powder (A) include polyacetal, polyacrylate, polyacrylic acid, polyamide, polyamideimide, polyacid anhydride, polyarylate, polyarylene ether, polyarylene sulfide, polybenzoxazole, polyester, polyetheretherketone, polyetherimide, polyetherketoneketone, polyetherketone, polyethersulfone, polyimide, polymethacrylate, polyolefin, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl ketone, polyvinyl fluoride, polyvinyl aromatic, polysulfone, polyarylene sulfone, polyarylate, polyary
  • ether ketone polylactic acid, polyglycolic acid, poly-3-hydroxybutyrate, polyhydroxyalkanoate, starch, cellulose ester, poly(phenylene ether), poly(methyl methacrylate), styrene-acrylonitrile copolymer resin, poly(ethylene oxide), epichlorohydrin polymer, polycarbonate homopolymer, polycarbonate copolymer, poly(ester carbonate), poly(ester-siloxane-carbonate), poly(carbonate-siloxane), vinyl polymer, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), polyvinyl chloride, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, and polyester-based thermoplastic elast
  • Resin (a) can be appropriately mixed with fillers such as carbon black, carbon fiber, glass fiber, talc, mica, nanoclay, and magnesium, as well as additives such as antioxidants, lubricants, and colorants.
  • fillers such as carbon black, carbon fiber, glass fiber, talc, mica, nanoclay, and magnesium
  • additives such as antioxidants, lubricants, and colorants.
  • polyolefin resins are preferred as resin (a).
  • Polyolefin resins are particularly useful for a wide variety of products, have good processability, and are recyclable.
  • the polyolefin resin used in the present invention is a polymer obtained by polymerization of a monomer having a polyolefin skeleton.
  • Polyolefin is a hydrocarbon resin having a carbon double bond.
  • the polyolefin resin is not particularly limited, and olefin homopolymers, block copolymers, random copolymers, etc. can be suitably used.
  • Specific examples include polypropylene; propylene copolymers obtained by copolymerizing propylene with ⁇ -olefins such as ethylene, 1-butene, 1-hexene, and 4-methyl-1-pentene; polyethylenes such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene; ethylene copolymers obtained by copolymerizing ethylene with ⁇ -olefins such as 1-butene, 1-hexene, and 4-methyl-1-pentene; poly(1-butene), poly(4-methyl-1-pentene), etc. These may be used alone or in combination of two or more types having different copolymer component compositions and physical properties.
  • propylene-based polymers are particularly preferred as polyolefin-based resins.
  • propylene-based copolymers obtained by copolymerizing propylene with ⁇ -olefins such as ethylene, 1-butene, 1-hexene, and 4-methyl-1-pentene are even more preferred, in order to suppress crystallization shrinkage during cooling and deformation such as warping of molded bodies during molding.
  • a propylene-based copolymer is a polypropylene-based resin that contains 50% by mass or more of propylene units in all monomer units.
  • propylene copolymers examples include products manufactured by Japan Polypropylene under the trade names “Novatec (registered trademark) PP,” “Wintech (registered trademark),” “Newcon (registered trademark),” and “Wellnex (registered trademark),” products manufactured by ExxonMobil Corporation under the trade name “Vistamax (registered trademark),” and products manufactured by The Dow Chemical Company under the trade name “Versify (registered trademark).” These products can be appropriately selected from the above product groups and used alone or in combination of two or more types.
  • the propylene copolymer may be a commercially available polypropylene resin 3D modeling material.
  • the 3D modeling material remaining after producing a molded body by the Powder Bed Fusion method may be reused.
  • the resin powder (A) of the present invention preferably has a melting point or glass transition temperature of 50 ° C. or higher, more preferably 100 ° C. or higher.
  • the resin powder (A) can be selected according to the thermal properties such as the melting point and crystallization temperature of the resin powder (B), but the melting point (Tm) measured by differential scanning calorimetry (DSC) is preferably similar to that of the resin powder (A) and the resin powder (B).
  • the difference between the melting point (Tm) of resin powder (A) and the melting point (Tm) of resin powder (B) is preferably 70°C or less, more preferably 40°C or less, and even more preferably 20°C or less.
  • the melting points (Tm) of resin powder (A) and resin powder (B) are close to each other, so that during Powder Bed Fusion modeling, both resins melt and the resins can be sufficiently bonded to each other, resulting in high interlayer adhesion in the modeled object, which is preferable.
  • the average particle size (D50) of the resin powder (A) of the present invention depends on, for example, the specifications of the system used to form a resin molded body by the Powder Bed Fusion method to which the three-dimensional modeling material of the present invention is applied, but from the viewpoint of applying the powder to a thickness within a predetermined range during modeling, it is usually 30 ⁇ m or more, preferably 35 ⁇ m or more, more preferably 40 ⁇ m or more, even more preferably 45 ⁇ m or more, and particularly preferably 50 ⁇ m or more, and is usually 250 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 120 ⁇ m or less.
  • the viscosity average molecular weight (Mv) of the resin powder (A) of the present invention is the viscosity average molecular weight (Mv) of the resin (a) and is preferably less than 500,000. If the viscosity average molecular weight (Mv) is 500,000 or more, the melt viscosity of the resin powder (A) becomes large, which is undesirable because it may impair the spreadability and moldability of the molding material during Powder Bed Fusion molding.
  • the lower limit of the viscosity average molecular weight (Mv) of the resin powder (A) is not particularly limited, but is preferably 10,000 or more.
  • the viscosity average molecular weight of the resin powder (A) is less than 10,000, the mechanical strength of the molded body obtained by the Powder Bed Fusion method may be insufficient, and it may not be possible to obtain one having sufficient mechanical strength.
  • the viscosity average molecular weight (Mv) of the resin powder (A), i.e., the resin (a) is preferably 500,000 or less, more preferably 450,000 or less, while the viscosity average molecular weight (Mv) of the resin (a) is more preferably 50,000 or more, even more preferably 100,000 or more.
  • the resin powder (B) of the present invention is obtained by using a thermoplastic resin or a thermosetting resin.
  • the resin powder (B) may contain other resins, additives, reinforcing materials, etc., other than the thermoplastic resin or the thermosetting resin, to the extent that the effect of the present invention is not impaired.
  • the resin powder (B) may be a commercially available three-dimensional modeling material made of a thermoplastic resin. When using a three-dimensional modeling material for the Powder Bed Fusion modeling method, the three-dimensional modeling material remaining after the molded body is produced by the Powder Bed Fusion method may be reused.
  • the resin powder (B) may be of one type, or may be a mixture of two or more types with different physical properties such as resin composition, viscosity average molecular weight (Mv), and average particle size (D50).
  • the resin (b) constituting the resin powder (B) of the present invention can be appropriately selected depending on the function to be imparted to the molded article to be shaped.
  • the resin powder (B) according to the first and second embodiments of the present invention must have a resin composition different from that of the resin powder (A) of the present invention, and it is particularly preferable to use a resin having different thermal properties and mechanical properties.
  • the resin powder (B) has a resin composition different from that of the resin powder (A), and it is particularly preferable to use a resin having different thermal properties and mechanical properties.
  • resin (b) may be any of those that can generally be used as an impact modifier for resins.
  • resins include polyethylene, polypropylene, polyolefin copolymers, acrylate copolymers, acrylic acid copolymers, vinyl acetate copolymers, styrene copolymers, styrene block copolymers, ionic ethylene copolymers in which some of the acid groups are neutralized with metal ions, core-shell impact modifiers, and mixtures thereof.
  • ultra-high molecular weight polyethylene which has excellent impact resistance.
  • thermosetting resin examples include thermosetting elastomers. Specific examples include silicone rubber, fluororubber, acrylic rubber, urethane rubber, polyamide rubber, polysulfide rubber, natural rubber, etc.
  • Resin (b) can be appropriately mixed with fillers such as carbon black, carbon fiber, glass fiber, talc, mica, nanoclay, and magnesium, as well as additives such as antioxidants, lubricants, and colorants.
  • fillers such as carbon black, carbon fiber, glass fiber, talc, mica, nanoclay, and magnesium
  • additives such as antioxidants, lubricants, and colorants.
  • the ultra-high molecular weight polyethylene preferably used as resin (b) of resin powder (B) of the present invention is an ultra-high molecular weight polyethylene having a viscosity average molecular weight (Mv) of 500,000 to 10,000,000.
  • Ultra-high molecular weight polyethylene having a viscosity average molecular weight (Mv) of 500,000 or more is a polyethylene resin having an extremely large molecular weight and a linear molecular structure with almost no branched chains, and is known to have an excellent effect of imparting impact resistance.
  • the viscosity average molecular weight (Mv) of the ultra-high molecular weight polyethylene is less than 500,000, the effect of the present invention, that is, the effect of imparting impact resistance to a molded body obtained by a 3D printer, may not be achieved.
  • the viscosity average molecular weight (Mv) of the ultra-high molecular weight polyethylene used in the present invention is preferably 1 million or more, more preferably 2 million or more.
  • the viscosity average molecular weight (Mv) of the ultra-high molecular weight polyethylene is 10 million or less, preferably 6 million or less, and more preferably 3 million or less.
  • the melting point (Tm) of the resin powder (B) such as ultra-high molecular weight polyethylene, i.e., the melting point (Tm) of the resin (b), is preferably 100 to 150°C, and more preferably 120 to 140°C, for reasons of superior effects of the present invention.
  • the melting point (Tm) of the resin powder (B) is preferably close to the melting point (Tm) of the resin powder (A).
  • the average particle size (D50) of the resin powder (A) in the first embodiment of the present invention depends on, for example, the specifications of the system used to form a resin molded body by the Powder Bed Fusion method to which the three-dimensional modeling material of the present invention is applied, but from the viewpoint of applying the powder to a thickness within a predetermined range during modeling, it is usually 30 ⁇ m or more, preferably 35 ⁇ m or more, more preferably 40 ⁇ m or more, even more preferably 45 ⁇ m or more, and particularly preferably 50 ⁇ m or more, and is usually 250 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 120 ⁇ m or less.
  • the average particle size (D50) of the resin powder (B) of the first embodiment of the present invention is smaller than 30 ⁇ m from the viewpoint of being present between the particles of the resin powder (A) and being easily included in the model layer produced by melting and flowing the resin powder (A).
  • the average particle size (D50) of the resin powder (B) is smaller than that of the resin powder (A) having an average particle size (D50) of 30 ⁇ m or more and 250 ⁇ m.
  • the average particle size (D50) of the resin powder (B) is less than 30 ⁇ m, this is preferable because it is smaller than the average particle size (D50) of the modeling materials for the Powder Bed Fusion method, which usually have an average particle size (D50) of 30 ⁇ m or more and 250 ⁇ m or less.
  • these modeling materials can be suitably used as the resin powder (A), and there is a tendency for the uneven distribution of coarse particles to be reduced and for the dispersion in the three-dimensional modeling material of the present invention to be good, and this is preferable because modeling properties are maintained when a molded body is modeled by the Powder Bed Fusion method.
  • the average particle size (D50) of the resin powder (B) is 30 ⁇ m or more, the resin powder (B) will not adhere to the surface of the resin powder (A) and will be present between the resin powders (A). In this case, in the molding process of a molded body by the Powder Bed Fusion method, the resin powder (B) present between the resin powders (A) will inhibit the melting of the resin powder (A), making the molded body prone to cracks and defects, which is not preferable. From this viewpoint, the average particle size (D50) of the resin powder (B) is preferably less than 30 ⁇ m, particularly preferably 20 ⁇ m or less.
  • the average particle size (D50) of the resin powder (B) is 1 ⁇ m or more, scattering or aggregation during handling as a material for three-dimensional modeling or modeling tends to be less likely to occur, which is preferable. From this perspective, the average particle size (D50) of the resin powder (B) is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the average particle size (D50) of the resin powder (B) is smaller than 10 ⁇ m, it will adhere to the surface of the resin powder (A), inhibiting the melting of the resin powder (A) and making the three-dimensional object more susceptible to cracks and defects, so it is preferable that the average particle size (D50) of the ultra-high molecular weight polyethylene is 10 ⁇ m or more.
  • the average particle size (D50) of the resin powder (B) in the present invention may be the average particle size of the particles before being made into a material for three-dimensional modeling, or may be the average particle size of the particles dispersed in the material for three-dimensional modeling by melt-kneading or the like.
  • the average particle size of the particles before being used as a material for three-dimensional modeling is the particle size (D50) at 50% of the frequency distribution of the powder in the particle size distribution detected by the laser diffraction method.
  • the average particle size may be measured by an electrical resistance method.
  • the average particle size may be obtained from 50 representative particles of the resin powder (B) enlarged by an optical microscope or the like. It has been confirmed that almost the same values are obtained regardless of the average particle size.
  • the ratio of the average particle size (D50) of the resin powder (B) to the average particle size (D50) of the resin powder (A) is preferably 3% or more and 30% or less.
  • the ratio is 3% or more, it is preferable because the generation of voids tends to be suppressed when mixing the resin powder (B) and the resin powder (A), and it is more preferable that it is 5% or more, and even more preferable that it is 10% or more.
  • the ratio when the ratio is 30% or less, the resin powder (B) tends to be well dispersed between the resin powder (A), and when forming a molded body by powder bed fusion, it is preferable because the moldability is maintained, and it is more preferable that it is 25% or less, and even more preferable that it is 20% or less.
  • the ratio exceeds 30%, the resin powder (B) does not adhere to the surface of the resin powder (A) and exists between the resin powders (A). In this case, in the molding process of a molded body by the Powder Bed Fusion method, the resin powder (B) existing between the resin powders (A) may inhibit the melting of the resin powder (A), and the molded body may be prone to cracks and defects.
  • the average particle size (D50) in the second embodiment of the present invention is usually 30 ⁇ m or more, preferably 35 ⁇ m or more, more preferably 40 ⁇ m or more, even more preferably 45 ⁇ m or more, and particularly preferably 50 ⁇ m or more, and is usually 250 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 120 ⁇ m or less.
  • the ratio of the average particle size (D50) of resin powder (B) to the average particle size (D50) of resin powder (A) is 3% or more and 30% or less, and this ratio is preferably 5% or more and more preferably 10% or more. On the other hand, this ratio is preferably 25% or less and more preferably 20% or less.
  • the average particle size (D50) of the resin powder (B) is preferably less than 30 ⁇ m, particularly preferably 20 ⁇ m or less, more preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
  • the material for three-dimensional printing has multiple peaks between 5 ⁇ m and 250 ⁇ m in a particle size distribution chart on a number basis obtained by image analysis, has a number-based peak in a region of 5 ⁇ m or more and smaller than 30 ⁇ m, has a volume-based peak top in a region of 5 ⁇ m or more and smaller than 30 ⁇ m in a particle size distribution chart on a volume basis obtained by image analysis, and the ratio of the number-based peak top and the volume-based peak top present in the region of 5 ⁇ m or more and smaller than 30 ⁇ m (volume-based peak top/number-based peak top) is 2.5 or less, and the average particle size on a volume basis (D50) is 30 ⁇ m or more.
  • the number-based peak top is preferably present between 5 ⁇ m and 30 ⁇ m, more preferably between 10 ⁇ m and 20 ⁇ m.
  • the volume-based peak top is preferably present between 5 ⁇ m and 30 ⁇ m, and more preferably between 10 ⁇ m and 20 ⁇ m. Furthermore, the ratio of the volumetric peak top to the numbertric peak top is 2.5 times or less, preferably 2.0 times or less, and more preferably 1.5 times or less. Also, it is usually 1.0 times or more. If the value of the volumetric peak top/numbertric peak top is equal to or less than the upper limit, the particle size of the resin particles derived from the peak is uniform, and the dispersibility in the material for three-dimensional modeling of the present invention is excellent.
  • the peak top on a number basis and the peak top on a volume basis satisfy the above conditions, other particles will be present between the particles when the material is used in the Powder Bed Fusion method, and small diameter particles will be more likely to be included in the model layer that is created by melting and flowing. In addition, there is little uneven distribution of coarse particles, which tends to result in good dispersion in the material for three-dimensional modeling of the present invention, and this is preferable because the modeling properties are maintained when a molded body is formed by the Powder Bed Fusion method.
  • the average particle size (D50) on a volume basis is 30 ⁇ m or more, preferably 35 ⁇ m or more, more preferably 40 ⁇ m or more, and is usually 120 ⁇ m or less.
  • the content of the resin powder (B) in the three-dimensional modeling material of the present invention may be selected to satisfy the sufficient impact resistance and moldability required for the obtained molded body, and specifically, from the viewpoint of imparting impact resistance, the content of the resin powder (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total amount of the resin powder (A) and the resin powder (B). In addition, from the viewpoint of moldability, the content of the resin powder (B) is preferably less than 50% by mass, more preferably 45% by mass or less, and even more preferably 40% by mass or less.
  • the content of the resin powder (B) is set to the above upper limit or less, it is preferable from the viewpoint of preventing the occurrence of a place where the molten resin does not flow in each layer in the three-dimensional modeling process, not reducing the interlayer adhesion, and maintaining the moldability and the mechanical properties of the obtained molded body.
  • the three-dimensional modeling material of the present invention may appropriately contain additives that are generally blended within a range that does not significantly impair the effects of the present invention.
  • the additives include inorganic particles such as silica, alumina, and kaolin, organic particles such as acrylic resin particles and melamine resin particles, pigments such as titanium oxide and carbon black, weather resistance stabilizers, heat resistance stabilizers, antistatic agents, electromagnetic wave absorbers, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, antiaging agents, antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and colorants, which are added for the purpose of improving and adjusting modeling properties, the stability of the three-dimensional model, and various physical properties of the three-dimensional model.
  • the amount of these additives contained is not particularly specified, but from the viewpoint of the stability of the resulting 3D modeling material and the 3D model formed therefrom, the total amount of additives is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.08 parts by mass or more, and particularly preferably 0.1 parts by mass or more, per 100 parts by mass of the 3D modeling material in total. Furthermore, from the viewpoint of suppressing a decrease in interlayer adhesion of the molded product to be modeled, the upper limit of the total amount of additives contained is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, and even more preferably 25 parts by mass or less.
  • the three-dimensional modeling material of the present invention may contain, in addition to the additives described above, a commonly used reinforcing material as appropriate, provided that the effect of the present invention is not significantly impaired.
  • the reinforcing material include inorganic fillers and inorganic fibers.
  • inorganic fillers include calcium carbonate, zinc carbonate, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, potassium titanate, glass balloons, glass flakes, glass powder, silicon carbide, silicon nitride, boron nitride, gypsum, calcined kaolin, zinc oxide, antimony trioxide, zeolite, hydrotalcite, wollastonite, silica, talc, mica, nanocloy, metal powders such as magnesium, alumina, graphite, carbon black, and carbon nanotubes.
  • Specific examples of inorganic fibers include cut glass fibers, milled glass fibers, glass fibers, gypsum whiskers, metal fibers, metal whiskers, ceramic whiskers, carbon fibers, and cellulose nanofibers.
  • the content of these reinforcing materials contained in the three-dimensional modeling material of the present invention is not particularly specified, but from the viewpoint of the strength of the molded body to be modeled, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the three-dimensional modeling material in total. Furthermore, from the viewpoint of suppressing a decrease in interlayer adhesion of the molded body to be modeled, the content of these reinforcing materials contained in the three-dimensional modeling material is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
  • the three-dimensional modeling material of the present invention can be produced by adding and mixing the resin powder (A) and resin powder (B) of the present invention and the other additives and reinforcing materials, etc., which are blended as necessary, in a predetermined ratio.
  • the method for producing the material for three-dimensional modeling of the present invention is not particularly limited as long as it contains each component.
  • the resin powder (A) and resin powder (B) of the present invention and other components such as additives and reinforcing materials that are blended as necessary can be pre-mixed using various mixers such as a tumbler or a Henschel mixer, and then melt-kneaded using a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, or the like to produce the material for three-dimensional modeling of the present invention.
  • various mixers such as a tumbler or a Henschel mixer, and then melt-kneaded using a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, or the like to produce the material for three-dimensional modeling of the present invention.
  • the three-dimensional modeling material of the present invention is preferably in the form of a powder containing the resin powder (A) and resin powder (B) of the present invention, and other additives, reinforcing materials, etc. that are blended as necessary, as a material for three-dimensional modeling by a Powder Bed Fusion method.
  • the average particle size (D50) of the powder for three-dimensional modeling of the present invention is preferably larger than the average particle size (D50) of the resin powder (B).
  • the average particle size (D50) of the powder for three-dimensional modeling of the present invention is preferably 3 to 30 times, and more preferably 5 to 20 times, the average particle size (D50) of the resin powder (B).
  • the average particle size (D50) depends on the specifications of the system used to form the molded body by the Powder Bed Fusion method, but from the viewpoint of applying the powder to a thickness within a predetermined range during modeling, it is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, even more preferably 40 ⁇ m or more, particularly preferably 50 ⁇ m or more, and most preferably 55 ⁇ m or more, and is preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, even more preferably 150 ⁇ m or less, and particularly preferably 120 ⁇ m or less.
  • the molded article of the present invention is made of the above-mentioned material for three-dimensional modeling of the present invention.
  • molding is preferably performed using a three-dimensional printer. The detailed manufacturing method is described below.
  • Method for producing molded body In the method for producing a molded article made of the three-dimensional modeling material of the present invention, the material for three-dimensional modeling of the present invention is used and molded with a three-dimensional printer to obtain a molded article.
  • molding methods using a three-dimensional printer include the Powder Bed Fusion method and the Multi Jet Fusion method. Among them, in the present invention, it is preferable to use the Powder Bed Fusion method in which the molding material is in powder form.
  • particles of a 3D modeling material spread on a stage are irradiated with a laser or electron beam to sinter or fuse the particles and form a layer in the vertical direction.
  • particles of the 3D modeling material are laid in contact with the layer formed above and irradiated with a laser or electron beam to form the next layer.
  • Tm melting point
  • the melting points (Tm) of the resin powder (A) and the resin powder (B) were measured by the following method. Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., product name "Pyris1 DSC", in accordance with JIS K7121, about 10 mg of a powder sample was heated from room temperature to 200°C at a heating rate of 10°C/min, held at that temperature for 1 minute, cooled to 50°C at a heating rate of 10°C/min, and then heated again to 200°C at a heating rate of 10°C/min. The crystal melting temperature (melting point: Tm) (°C) (reheating process) showing the maximum peak in the melting curve detected from the measured thermogram was determined. The measured values were rounded off to one decimal place.
  • a 0.3 g powder sample for 3D modeling was placed in a recess of a table having a size of 25 mm x 30 mm and a depth of 0.2 mm. A roller was then rolled on the table at a speed of approximately 64 mm/sec to level the powder in the recess. Based on the state of the powder filled in the recess, the dispersibility was evaluated according to the following criteria. A: The powder is evenly distributed. B: The powder is not uniformly dispersed or there is clumping of powder particles.
  • the test pieces prepared for evaluating the moldability were measured for Charpy impact strength in accordance with JIS K7111-1.
  • a Charpy impact test was carried out on this test piece at a measurement temperature of 25° C., with a hammer capacity of 4 J, and with the striking surface opposite to the notch portion, to measure the Charpy impact value.
  • the impact resistance of each test piece was calculated as a ratio to the Charpy impact value of Comparative Example 1, in which only the propylene-based copolymer powder was used as the molding material, and evaluated based on this ratio according to the following criteria.
  • AA The ratio of the Charpy impact value is 120% or more.
  • B The ratio of the Charpy impact value is 100% or less.
  • Example 1 As the resin powder (A), propylene-based copolymer powder (manufactured by Sinterit) (A-1) (Tm: 135 ° C., D50: 87 ⁇ m) of powder material for LisaPro 3D printers was used.
  • the resin powder (B) 10 parts by mass of ultra-high molecular weight polyethylene Mipelon (registered trademark) PM-200 (manufactured by Mitsui Chemicals, Inc.) (B-1) (Mv: 1.8 million, Tm: 137 ° C., D50: 10 ⁇ m) was added and dry blended, and 0.3 parts by mass of carbon powder (fine powder SGP-10, manufactured by SEC Carbon, average particle size 10 ⁇ m) as an electromagnetic wave absorber was added to 100 parts by mass of resin powder (B) to obtain a powder for three-dimensional modeling (D50: 79 ⁇ m). The obtained powder for three-dimensional modeling was used for the above-mentioned evaluation, and the results are shown in Table 1.
  • FIG. 1 shows a particle size distribution chart based on the number of particles obtained by image analysis of this powder for three-dimensional modeling
  • FIG. 2 shows a particle size distribution chart based on the volume of the powder.
  • Example 2 A powder for three-dimensional modeling (D50: 79 ⁇ m) was obtained in the same manner as in Example 1, except that silicone powder KMP-597 (Shin-Etsu Chemical Co., Ltd.) (B-2) (D50: 5 ⁇ m) was used instead of Mipelon (registered trademark) PM-200 (Mitsui Chemicals, Inc.) (B-1).
  • the obtained powder for three-dimensional modeling was used for the above-mentioned evaluation, and the results are shown in Table 1.
  • FIG. 3 shows a particle size distribution chart on a number basis obtained by image analysis of this powder for three-dimensional modeling
  • FIG. 4 shows a particle size distribution chart on a volume basis.
  • Example 3 A powder for three-dimensional modeling (D50: 70 ⁇ m) was obtained in the same manner as in Example 1, except that 20 parts by mass of Mipelon (registered trademark) PM-200 (manufactured by Mitsui Chemicals, Inc.) (B-1) was added to 80 parts by mass of a propylene-based copolymer powder (manufactured by Sinterit) (A-1).
  • the obtained powder for three-dimensional modeling was used for the above-mentioned evaluation, and the results are shown in Table 1.
  • FIG. 5 shows a particle size distribution chart on a number basis obtained by image analysis of this powder for three-dimensional modeling
  • FIG. 6 shows a particle size distribution chart on a volume basis.
  • Example 4 As the resin powder (A), a polyamide powder (manufactured by Sinterit) (A-2) (Tm: 185 ° C., D50: 38 ⁇ m) of powder material for LisaPro 3D printers was used, and as the resin powder (B), a vinylidene fluoride copolymer KynarFlex (registered trademark) 3121-50 (manufactured by Arkema) (B-3) (Tm: 165 ° C., D50: 10 ⁇ m) was used.
  • a powder for 3D modeling (D50: 34 ⁇ m) was obtained in the same manner as in Example 1. The obtained powder for three-dimensional modeling was used for the above-mentioned evaluation, and the results are shown in Table 1.
  • FIG. 7 shows a particle size distribution chart on a number basis obtained by image analysis of this powder for three-dimensional modeling
  • FIG. 8 shows a particle size distribution chart on a volume basis.
  • Example 2 A powder for three-dimensional modeling (D50: 81 ⁇ m) was obtained in the same manner as in Example 1, except that Mipelon (registered trademark) XM-220U (C-1) (Mv: 2 million, Tm: 136° C., D50: 30 ⁇ m) was used instead of Mipelon (registered trademark) PM-200 (manufactured by Mitsui Chemicals, Inc.) (B-1).
  • the obtained powder for three-dimensional modeling was used for the above-mentioned evaluation, and the results are shown in Table 1.
  • FIG. 11 shows a particle size distribution chart on a number basis obtained by image analysis of this powder for three-dimensional modeling
  • FIG. 12 shows a particle size distribution chart on a volume basis.
  • Example 3 A powder for three-dimensional modeling (D50: 80 ⁇ m) was produced in the same manner as in Example 1, except that a propylene copolymer powder (a powder of Wintech WFX4M manufactured by Japan Polypropylene Corporation, Tm: 127° C.)) (C-2) (D50: 18 ⁇ m) was used instead of Mipelon (registered trademark) PM-200 (manufactured by Mitsui Chemicals, Inc.) (B-1).
  • the obtained powder for three-dimensional modeling was used for the above-mentioned evaluation, and the results are shown in Table 1.
  • FIG. 13 shows a particle size distribution chart on a number basis obtained by image analysis of this powder for three-dimensional modeling
  • FIG. 14 shows a particle size distribution chart on a volume basis.
  • a three-dimensional modeling material containing two types of resin powder (A) and resin powder (B) with different resin compositions and particle sizes, in which the particle sizes or particle size distribution of resin powder (A) and resin powder (B) satisfy the specifications of the present invention, is found to have excellent modeling properties in a 3D printer and excellent impact resistance of the resulting molded body.
  • the three-dimensional modeling material of the present invention can provide a three-dimensional modeling material that has excellent impact resistance for molded objects produced by a 3D printer, while maintaining the modeling properties and safety of the powder material, even when using existing resin powders for the Powder Bed Fusion method. Therefore, the three-dimensional modeling material of the present invention can be used not only for prototypes, but also for practical applications such as components for home appliances, building materials, aircraft, and automotive materials.

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Abstract

L'invention concerne un matériau de modélisation tridimensionnelle qui contient une poudre de résine (A) ayant une taille de particule moyenne (D50) par un procédé de diffraction laser de 30 à 250 µm inclus et une poudre de résine (B) qui est une composition de résine différente de la poudre de résine (A) et a une taille de particule moyenne (D50) par un procédé de diffraction laser de 1 µm à moins de 30 µm.　L'invention concerne un matériau de modélisation tridimensionnelle qui contient une poudre de résine (A) ayant une taille de particule moyenne (D50) par un procédé de diffraction laser de 30 à 250 µm et une poudre de résine (B) qui est une composition de résine différente de la poudre de résine (A) et a une taille de particule moyenne (D50) par un procédé de diffraction laser de 3 à 30% inclus de la taille de particule moyenne (D50) de la poudre de résine (A).　L'invention concerne un matériau de modélisation tridimensionnelle qui contient une poudre de résine (A) qui a une pluralité de pics entre 5 µm et 250 µm dans un diagramme de distribution de taille de particule à base de nombre obtenu par analyse d'image et a un sommet de pic sur le côté de taille de particule le plus grand de la pluralité de pics et une poudre de résine (B) qui a un sommet de pic 20 µm ou moins au-dessous du sommet de pic de la poudre de résine (A).
PCT/JP2024/012279 2023-03-31 2024-03-27 Matériau pour modélisation tridimensionnelle, corps moulé et son procédé de production Pending WO2024204368A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018074353A1 (fr) * 2016-10-21 2018-04-26 東レ株式会社 Mélange de particules de résine de sulfure de polyarylène, et procédé de fabrication d'objet moulé en trois dimensions
JP2021146678A (ja) * 2020-03-23 2021-09-27 株式会社リコー 樹脂粉末、立体造形用樹脂粉末、立体造形物の製造方法、及び立体造形物の製造装置
JP7369326B2 (ja) * 2021-11-19 2023-10-25 ポリプラスチックス株式会社 ３ｄプリンター用粉末材料、三次元造形物及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018074353A1 (fr) * 2016-10-21 2018-04-26 東レ株式会社 Mélange de particules de résine de sulfure de polyarylène, et procédé de fabrication d'objet moulé en trois dimensions
JP2021146678A (ja) * 2020-03-23 2021-09-27 株式会社リコー 樹脂粉末、立体造形用樹脂粉末、立体造形物の製造方法、及び立体造形物の製造装置
JP7369326B2 (ja) * 2021-11-19 2023-10-25 ポリプラスチックス株式会社 ３ｄプリンター用粉末材料、三次元造形物及びその製造方法

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