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WO2024180960A1 - Composition de résine pour imprimantes 3d, objet fabriqué tridimensionnel et son procédé de production - Google Patents

Composition de résine pour imprimantes 3d, objet fabriqué tridimensionnel et son procédé de production Download PDF

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Publication number
WO2024180960A1
WO2024180960A1 PCT/JP2024/002359 JP2024002359W WO2024180960A1 WO 2024180960 A1 WO2024180960 A1 WO 2024180960A1 JP 2024002359 W JP2024002359 W JP 2024002359W WO 2024180960 A1 WO2024180960 A1 WO 2024180960A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
resin
particles
plate
printers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2024/002359
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English (en)
Japanese (ja)
Inventor
晃純 木村
敦理 内田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denka Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Denka Co Ltd filed Critical Denka Co Ltd
Priority to JP2025501388A priority Critical patent/JP7685125B2/ja
Priority to CN202480014634.4A priority patent/CN120752129A/zh
Publication of WO2024180960A1 publication Critical patent/WO2024180960A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a resin composition for 3D printers, a three-dimensional object, and a method for producing the same.
  • a 3D printer is a type of three-dimensional modeling machine that uses 3D data such as CAD and CG created on a computer as blueprints to produce three-dimensional objects made of plastic and other materials.
  • 3D printers are classified according to the deposition method they use; for example, binder jetting, fused deposition modeling, liquid vat photopolymerization, and powder sintering additive manufacturing (SLS (Selective Laser Sintering) or SLM (Selective Laser Melting)) are known.
  • SLS Selective Laser Sintering
  • SLM Selective Laser Melting
  • 3D printers use resin materials to create three-dimensional objects.
  • FDM fused deposition modeling
  • filaments of thermoplastic resin are used as materials, and the filaments are melted and extruded from the nozzle of the 3D printer, and laminated to form the desired shape.
  • Polylactic acid resin (PLA resin) and acrylonitrile-butadiene-styrene resin (ABS resin) are mainly used as filaments for FDM 3D printers.
  • ABS resin is easy to use to create three-dimensional objects with excellent heat resistance and has good post-processing properties, but it has the problem of warping during modeling. Therefore, a resin material for 3D printers has been proposed in which glass fiber is blended into ABS resin to reduce warping.
  • Patent Document 1 proposes using a styrene-based resin having a Tg of 50° C. or more and less than 100° C.
  • Patent Document 2 proposes a material for three-dimensional modeling in which a specific amount of filler (including talc) is blended with a thermoplastic resin and a thermoplastic elastomer.
  • a specific amount of filler including talc
  • Patent No. 7136131 International Publication No. 2021/060278
  • the present invention aims to provide a resin composition for 3D printers that reduces wear on the nozzles of 3D printers and achieves both suppressed warping and high-speed modeling, a method for manufacturing 3D objects using the composition, and 3D objects with minimal warping.
  • the present invention includes the following aspects.
  • the content of the plate-like particles (B) is 10 to 30% by mass relative to the total mass of the resin composition.
  • the present invention provides a resin composition for 3D printers that reduces wear on the nozzle of the 3D printer and achieves both suppressed warping and high-speed modeling, a method for manufacturing a 3D object using the resin composition, and a 3D object with minimal warping.
  • the resin composition for 3D printers according to the present embodiment is characterized in that it contains a rubber component-containing styrene-based resin (A) and plate-like particles (B) having a Mohs hardness of 3 or less and having a surface treated with a silane coupling agent (X), and the content of the plate-like particles (B) is 10 to 30% by mass relative to the total mass of the resin composition.
  • resin composition for 3D printers according to the present embodiment hereinafter, sometimes simply referred to as "resin composition” or "resin material"
  • warping refers to a phenomenon in which, when a three-dimensional object is produced using a 3D printer, at least a portion of the resin material (hereinafter sometimes referred to as "laminate") laminated on a substrate peels off from the substrate surface, resulting in a gap (floating) between the substrate and the laminate.
  • laminate the resin material laminated on a substrate peels off from the substrate surface, resulting in a gap (floating) between the substrate and the laminate.
  • problems occur, such as making it difficult to obtain a three-dimensional object of the desired shape, or the laminate coming into contact with the nozzle of the 3D printer, making further production impossible.
  • the resin composition according to this embodiment can suppress warping during production, thereby producing a three-dimensional object of the desired shape. It can also prevent problems during production caused by warping.
  • laminate refers to a three-dimensional object in the middle of production.
  • the resin composition according to the present embodiment can achieve high-speed modeling properties in addition to suppressing warping.
  • high-speed modeling properties refers to the ability to model a three-dimensional object at a modeling speed of, for example, 80 to 150 mm/s. Resin materials with poor high-speed modeling properties will be discharged unevenly at the above-mentioned modeling speed, or holes will appear in the appearance of the obtained three-dimensional object. With the resin composition according to the present embodiment, a three-dimensional object with excellent appearance can be modeled even at high speed.
  • the resin composition "for 3D printers" in the present disclosure means that it can be used as a filament when forming a three-dimensional object with a 3D printer.
  • the resin composition according to the present embodiment contains a rubber component-containing styrene-based resin (A) (hereinafter referred to as "resin (A)").
  • resin (A) a rubber component-containing styrene-based resin
  • the "rubber component-containing styrene-based resin” refers to a resin obtained by copolymerizing or blending a rubber component with a styrene-based resin.
  • styrene-based resin refers to a polymer mainly composed of a compound having a styrene skeleton.
  • mainly composed of a compound having a styrene skeleton refers to a ratio of the compound having a styrene skeleton to the total amount (100% by mass) of raw material monomers exceeding 50% by mass. The ratio may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more.
  • Examples of compounds having a styrene skeleton include styrene, ⁇ -methylstyrene, paramethylstyrene, vinyltoluene, and vinylxylene, with styrene being preferred.
  • the styrene-based resin may be a copolymer obtained by copolymerizing the above-mentioned compound having a styrene skeleton with other monomers.
  • copolymers include acrylonitrile-styrene copolymer (AS resin), maleic anhydride-styrene copolymer (maleic anhydride modified polystyrene resin), etc.
  • the rubber component may be a conjugated diene rubber or a non-diene rubber.
  • conjugated diene rubber include conjugated diene hydrocarbons such as butadiene, isoprene, and 1,3-pentadiene.
  • non-diene rubber include silicone rubber, ethylene-propylene rubber, acrylic rubber, and urethane rubber.
  • styrene-based resins containing such conjugated diene rubber or non-diene rubber include high impact polystyrene (HIPS); acrylonitrile-butadiene-styrene copolymer (ABS resin); AXS resins such as acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), and acrylonitrile-(ethylene-propylene-diene rubber)-styrene copolymer (AES resin); and methyl methacrylate-butadiene-styrene copolymer (MBS resin).
  • HIPS high impact polystyrene
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • AXS resins such as acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile
  • the resin (A) preferably contains a conjugated diene rubber as a rubber component.
  • the resin (A) may contain at least one resin selected from HIPS and ABS resin.
  • the resin (A) is an ABS resin.
  • the mass average molecular weight (Mw) of the resin (A) is preferably 110,000 to 150,000. Also, from the viewpoint of easily obtaining a three-dimensional model with good impact resistance and heat resistance, the Mw may be 140,000 to 170,000. Note that two or more types of ABS resins with different Mw may be mixed to achieve both the fluidity, heat resistance, and impact resistance. When two or more types of ABS resins are mixed and used, it is preferable to adjust the average Mw of the mixture to be in the above-mentioned range (for example, 110,000 to 170,000).
  • ABS resin when one type of ABS resin is used, it is particularly preferable to use an ABS resin with a Mw of 130,000 to 150,000 from the viewpoint of the above-mentioned fluidity, heat resistance, and impact resistance.
  • Mw of the resin (A) refers to a value measured using GPC, solvent: THF, measurement temperature: 40°C, and standard substance: polystyrene conversion.
  • ABS resin When resin (A) contains an ABS resin, the ABS resin preferably has a butadiene content of 12 to 22% by mass, more preferably 16 to 20% by mass, relative to the total mass of the ABS resin. Furthermore, as described above, resin (A) may be a mixture of two or more types of ABS resins.
  • the ABS resin preferably has an MFR (220°C, 10 kg load) of 10 to 30 g/10 min, more preferably 15 to 30 g/10 min, and even more preferably 20 to 30 g/10 min.
  • MFR 220°C, 10 kg load
  • the blending ratio of each ABS resin may be adjusted so that the MFR (220°C, 10 kg load) of the ABS resin mixture is 10 to 30 g/10 min.
  • ABS resin 1 with an MFR (220°C, 10 kg load) of 30 to 45 g/10 min and ABS resin 2 with an MFR (220°C, 10 kg load) of 10 to 15 g/10 min may be combined in a ratio of ABS resin 1:ABS resin 2 of 3 to 7:7 to 3.
  • the proportion of ABS resin in resin (A) is preferably 50% by mass or more, and more preferably 80% by mass or more, relative to the total mass of resin (A).
  • Resin (A) may also contain only ABS resin. In other words, the proportion of resin (A) in resin (A) may be 50 to 100% by mass, or 80 to 100% by mass.
  • the proportion of resin (A) in the resin composition can be adjusted as desired within the range of 70 to 90% by mass relative to the total mass of the resin composition.
  • the proportion of resin (A) in the resin composition may be 70 to 85% by mass, 73 to 83% by mass, or 73 to 80% by mass relative to the total mass of the resin composition.
  • the resin composition according to this embodiment contains 10 to 30% by mass of plate-like particles (B) having a Mohs hardness of 3 or less and having a surface treated with a silane coupling agent (X) relative to the total mass of the resin composition.
  • the term "plate-like particles” refers to particles that are thin and have an aspect ratio of 1.0 or more. Therefore, the plate-like particles may include particles other than spherical particles, such as those expressed as scaly particles, rod-like particles, or needle-like (fibrous) particles. In a preferred embodiment, the plate-like particles include scaly particles such as talc, clay (kaolin, bentonite), and mica. Whether the particles in the resin composition are plate-like particles can be determined, for example, by observing the particles (100 or more) contained in the resin composition according to this embodiment with an electron microscope such as SEM, and determining whether the particles are thin and have an aspect ratio of 1.0 or more by more than 50% by number. In one embodiment, the aspect ratio of the plate-like particles (B) may be 10-90, 10-80, or 20-70.
  • the "Mohs hardness scale” is a hardness index expressed on a 10-point scale, and is a value obtained by rubbing the material being measured against a corresponding standard material and evaluating its hardness relative to the standard material based on whether or not it is scratched.
  • the standard materials are, in order from softest (Mohs hardness 1) to hardest (Mohs hardness 10), 1: talc, 2: gypsum, 3: calcite, 4: fluorite, 5: apatite, 6: feldspar, 7: quartz, 8: topaz, 9: corundum, and 10: diamond.
  • the Mohs hardness is measured by preparing two smooth plates with known Mohs hardness, placing the foreign object to be measured between the two plates, and rubbing the two plates together to check for the presence or absence of scratches on the plate surface.
  • the particles constituting the plate-like particles (B) according to this embodiment are not particularly limited as long as they are inorganic particles having a Mohs hardness of 3 or less, and examples thereof include at least one selected from the group consisting of diatomaceous earth, bentonite, boron nitride, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, calcium carbonate, talc, kaolin, clay, and mica. Of these, from the viewpoint of water absorption of the particles and warpage suppression effect, it is preferable that the raw material particles include at least one plate-like particle selected from talc and mica. That is, in a preferred embodiment, the plate-like particles (B) include at least one plate-like particle selected from talc and mica, the surface of which has been treated with a silane coupling agent (X).
  • X silane coupling agent
  • the average particle size (D50) of the plate-like particles (B) is preferably 1 to 50 ⁇ m, more preferably 5 to 40 ⁇ m, and even more preferably 10 to 35 ⁇ m.
  • the average particle size (D50) of B) may be 1 to 10 ⁇ m, 7 to 30 ⁇ m, 10 to 50 ⁇ m, 20 to 50 ⁇ m, or 20 to 35 ⁇ m. If the average particle size (D50) is within the above range, the decrease in MFR during mixing is small, so it is easy to adjust the filament to achieve a high MFR required for a 3D printer filament. Since the increase in elastic modulus during mixing is small, filaments do not break during production, and productivity is likely to be good.
  • the average particle size (D50) of the plate-like particles (B) is evaluated by a laser diffraction scattering method. This refers to the volume-based cumulative diameter (D50) measured.
  • volume-based cumulative diameter (D50) refers to a particle diameter at which the cumulative value is 50% in a volume-based cumulative particle size distribution measured by a laser diffraction scattering method.
  • the cumulative particle size distribution is It is expressed as a distribution curve with the particle diameter ( ⁇ m) on the horizontal axis and the cumulative value (%) on the vertical axis.
  • the plate-like particle (B) has its surface treated with a silane coupling agent (X).
  • the surface is treated with a silane coupling agent (X) means that at least a part of the surface of the plate-like particle (B) is coated with a silane coupling agent (X).
  • silane coupling agent (X) for example, a silane coupling agent containing a functional group such as a vinyl group, an amino group, a styryl group, an epoxy group, a mercapto group, etc. in the structure can be used alone or in combination of two or more kinds.
  • silane coupling agents containing a vinyl group in the structure examples include vinyltrimethoxysilane, vinyltriethoxysilane, etc. These may be used alone or in combination of two or more types.
  • Silane coupling agents containing an amino group in the structure include, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxylane, N-2-(aminoethyl)-3-aminopropylmethyltrimethoxylane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane. These may be used alone or in combination of two or more.
  • silane coupling agents containing an epoxy group in the structure examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. These may be used alone or in combination of two or more types.
  • silane coupling agent that contains a styryl group in its structure (a styryl-based silane coupling agent) is p-styryltrimethoxysilane.
  • silane coupling agents containing a mercapto group in the structure examples include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. These may be used alone or in combination of two or more types.
  • the silane coupling agent (X) is preferably a silane coupling agent containing an amino group or an epoxy group, and more preferably contains a silane coupling agent containing an epoxy group (epoxy-based silane coupling agent).
  • the silane coupling agent (X) contains 3-glycidoxypropyltrimethoxysilane. It is presumed that the inclusion of plate-like particles (B) having a Mohs hardness of 3 or less and having a surface treated with such a silane coupling agent (X) makes it easier to develop adhesion derived from the functional group in the silane coupling agent (X), preferably the epoxy group, and makes it easier to suppress warping. It is also presumed that the reaction between the carbonyl group derived from the oxidation of the resin (A) and the functional group in the silane coupling agent (X) (preferably the amino group or epoxy group) makes it easier to suppress thermal shrinkage.
  • the ratio of the silane coupling agent (X) in the plate-like particle (B) is preferably 0.1 to 3 mass%, more preferably 0.1 to 2 mass%, more preferably 0.5 to 1.5 mass%, and even more preferably 0.5 to 1 mass%, based on the total mass of the raw material particles.
  • the method of treating the surface of the raw material particles with the silane coupling agent (X) is not particularly limited, and a general method can be adopted, such as dissolving the silane coupling agent in an organic solvent such as ethanol, spraying it on the raw material particles, and heating while stirring. Whether the surfaces of the plate-like particles (B) in the resin composition have been treated with a silane coupling agent can be determined, for example, by measuring the particles dispersed in the resin with TEM-EDX and detecting the Si element.
  • the ratio of the plate-like particles (B) to the total mass of the resin composition can be adjusted arbitrarily within the range of 10 to 30 mass%. If the ratio of the plate-like particles (B) is 10 to 30 mass%, it is possible to achieve both high-speed modeling properties and warpage suppression while suppressing nozzle wear. From the viewpoint of making it easier to adjust the MFR (220°C, 10 kg load) of the resin composition described below to 30 g/10 min or less and making it easier to obtain a resin composition with better high-speed modeling properties, the ratio of the plate-like particles (B) may be 11 to 27 mass% or 15 to 25 mass%.
  • the resin composition according to this embodiment can contain components (other components) other than the above-mentioned resin (A) and plate-like particles (B) within the range that does not impair the effects of the present invention.
  • other components include thermoplastic resins other than the resin (A) (e.g., PLA resin, PC resin, etc.); inorganic particles other than the plate-like particles (B); polymer fillers; additives such as ultraviolet absorbers, stabilizers, antioxidants, plasticizers, colorants, tinting agents, flame retardants, antistatic agents, fluorescent brighteners, matting agents, and impact strength improvers. These may be used alone or in combination of two or more.
  • the resin composition may be blended in an amount of 2 mass% or less based on the total mass of the resin composition.
  • the MFR (220 ° C., 10 kg load) of the resin composition is preferably 30 g / 10 min or less, more preferably 6 g / 10 min or more and less than 30 g / 10 min, and even more preferably 8 to 28 g / 10 min.
  • the MFR (220 ° C., 10 kg load) of the resin composition may be in the range of 10 to 30 g / 10 min.
  • the MFR (220 ° C., 10 kg load) of the resin composition can be measured, for example, according to JIS K7210-1 A method using a product name "Melt Indexer G-02" manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • the method for producing the resin composition according to the present embodiment is not particularly limited as long as it has the effect of the present invention, and for example, a method in which the resin (A), the plate-like particles (B), and other components as necessary are mixed in a twin-screw kneader or the like, and then extruded into a desired shape to obtain a resin composition can be mentioned.
  • the kneader is preferably equipped with a strand spooler, a gear pump, etc. for producing filaments. Since the resin composition according to the present embodiment contains the specific surface-treated plate-like particles (B), it has good mixability with the resin (A).
  • mixing can be performed under the conditions of a set temperature of 200 to 220°C, a discharge rate of 30 to 40 kg/hr, and a rotation speed of 250 to 350 rpm.
  • the method for producing a resin composition may include preparing plate-like particles (B). That is, the method may include surface-treating raw material particles with the above-mentioned silane coupling agent (X) to obtain plate-like particles (B), and mixing resin (A) and plate-like particles (B) and extruding them into a desired shape to obtain a resin composition.
  • preparing plate-like particles (B) That is, the method may include surface-treating raw material particles with the above-mentioned silane coupling agent (X) to obtain plate-like particles (B), and mixing resin (A) and plate-like particles (B) and extruding them into a desired shape to obtain a resin composition.
  • the method for producing a three-dimensional object according to the present embodiment is a method for producing a three-dimensional object, which includes a resin composition according to the present embodiment as a raw material resin, the resin composition comprising a rubber component-containing styrene-based resin (A) and plate-like particles (B) having a Mohs hardness of 3 or less and having a surface treated with a silane coupling agent (X), the content of the plate-like particles (B) being 10 to 30 mass% relative to the total mass of the resin composition.
  • the raw material resin is composed only of the resin composition according to the present embodiment.
  • the manufacturing method according to the present embodiment includes melting the resin composition and extruding the melted resin composition from a nozzle to form a three-dimensional object.
  • the manufacturing method according to the present embodiment is preferably a method for manufacturing a three-dimensional object using an FDM 3D printer.
  • a filament-shaped resin composition is used.
  • FDM 3D printers generally have a heatable substrate (modeling table), an extrusion head (nozzle), a heating melter, a filament guide, a filament installation, and other raw material supply sections. Some FDM 3D printers have an integrated nozzle and heating melter.
  • the nozzle is installed in a gantry structure, allowing it to move freely on the XY plane of the substrate.
  • the substrate is a platform for constructing the desired three-dimensional object or support material. There are no particular limitations on the substrate configuration, but a configuration that allows it to be heated and kept warm is preferable from the viewpoint of making it easier to improve the adhesion and dimensional stability of the laminate.
  • at least one of the nozzle and the substrate is movable in the Z-axis direction perpendicular to the XY plane.
  • a filament made of the resin composition of this embodiment is unwound from a raw material supply section and fed into a nozzle by a pair of opposing rollers or gears. It is then heated and melted in the nozzle, and the molten filament is extruded from the tip of the nozzle.
  • the nozzle moves its position while supplying and stacking the molten filament onto a substrate to form a three-dimensional object. After this process is completed, the stacked object can be removed from the substrate, and the desired three-dimensional object can be obtained by peeling off supporting materials, etc., or cutting off excess portions as necessary.
  • One example of a method for supplying a filament to a nozzle is to unwind and supply the filament. It is preferable that the filament is stored in a cartridge wound into a bobbin, from the standpoint of stable unwinding, protection from environmental factors such as moisture, and prevention of twisting and kinking.
  • a preferred method for feeding the filament to the nozzle while unwinding it is to engage the filament with a driving roll such as a nip roll or gear roll, and feed it to the nozzle while pulling it up. From the viewpoint of stabilizing the filament feed by more firmly gripping the filament through the engagement between the filament and the driving roll, a fine uneven shape may be transferred to the surface of the filament.
  • the nozzle temperature is preferably set to 220 to 260°C, more preferably 240 to 260°C, to melt the filaments made of the resin composition.
  • the substrate temperature is preferably set to 110°C or less, more preferably 100°C or less.
  • the modeling speed can be set high.
  • the modeling speed may be 80 to 150 mm/s, or 90 to 120 mm/s.
  • the printing atmosphere temperature inside the 3D printer is preferably room temperature to 50°C, and more preferably 30 to 40°C.
  • the three-dimensional object according to this embodiment is formed using the resin composition described above. That is, the three-dimensional object according to this embodiment contains the resin composition described above. In a preferred embodiment, the three-dimensional object is composed only of the resin composition of this embodiment. Such a three-dimensional object has little warping and a good appearance. Therefore, the three-dimensional object according to this embodiment can be suitably used for applications such as stationery; toys; covers for electronic devices such as smartphones; parts such as grips; school teaching materials, home appliances, repair parts for office automation equipment, various parts for automobiles, motorcycles, bicycles, etc.; building materials; plastic shaping molds, etc.
  • the maximum value of the gap (floating amount) between the bottom surface of the three-dimensional object and the horizontal plate is preferably less than 1 mm, and more preferably 0.3 mm or less.
  • the floating amount can be calculated from the maximum value of the gap distance between the horizontal plate and the three-dimensional object at the point where the bottom of the three-dimensional object is separated from the horizontal plate and floating away from the horizontal plate while the three-dimensional object is placed on the horizontal plate.
  • a method for using the resin composition according to this embodiment as a resin raw material (filament) for a 3D printer includes, for example, obtaining a resin composition by the above-described method for producing a resin composition, supplying the resin composition to a 3D printer, and extruding the resin composition from a nozzle while melting it to form a three-dimensional object.
  • a resin composition for 3D printers A rubber component-containing styrene-based resin (A), and plate-like particles (B) having a Mohs hardness of 3 or less and having a surface treated with a silane coupling agent (X), The content of the plate-like particles (B) is 10 to 30% by mass relative to the total mass of the resin composition.
  • [6] The resin composition for 3D printers according to any one of [1] to [5], wherein the MFR of the resin composition at 220 ° C. and a load of 10 kg is 10 to 30 g / 10 min or less.
  • a method for producing a three-dimensional object comprising: melting a resin composition for a 3D printer according to any one of [1] to [7]; and extruding the molten resin composition from a nozzle to form a three-dimensional object.
  • a three-dimensional object comprising the resin composition for 3D printers according to any one of [1] to [7].
  • resin (A) The following was used as resin (A).
  • Resin (A) Resin (A-1): ABS resin (manufactured by Denka Co., Ltd., product name "GR3000", MFR (220°C, 10 kg load): 14g/10min).
  • Resin (A-2) ABS resin (manufactured by Denka Co., Ltd., product name "QF”, MFR (220°C, 10 kg load): 44g/10min).
  • the MFR of the resin (A) is a value measured at 220° C. under a load of 10 kg.
  • the amount of silane coupling agent (X) added means the ratio to the total mass of the raw material particles.
  • Plate-like particles (B'-3) mica (Mohs hardness: 3, manufactured by Yamaguchi Mica Co., Ltd., product name "A-21S”, average particle size (D50): 23 ⁇ m).
  • Plate-like particles (B'-4) Alumina (Mohs hardness: 8, manufactured by Kinsei Matec Co., Ltd., product name "Seraph (registered trademark) (product number 10030)", average particle size (D50): 10 ⁇ m).
  • the average particle size of the glass fibers of the plate-like particles (B'-5) was determined by measuring the major axis of 100 particles at a magnification of 40 times using an SEM (manufactured by Hitachi High-Technologies, product name "TM-1000") and averaging the results.
  • Example 1 A twin-screw kneader (manufactured by Thermo Fisher Scientific, product name “Process 11”) was equipped with a monofilament-making strand spooler and a gear pump, and 80 parts by mass of resin (A-1) and 20 parts by mass of plate-like particles (B-1) were mixed and mixed at 220 ° C., and then extruded to produce a filament made of a resin composition for 3D printers having a diameter of 1.75 mm.
  • A-1 resin
  • B-1 plate-like particles
  • the MFR (220 ° C., 10 kg load) of the obtained filament was measured according to JIS K7210-1 A method using a product name "Melt Indexer G-02" manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • a three-dimensional object was formed using the obtained filament, and the warpage, high-speed formability, and nozzle wear resistance were evaluated under the following conditions. The results are shown in Table 2.
  • the obtained sample plate was placed on a horizontal glass plate, and the maximum value of the gap distance at the contact surface between the sample plate and the glass plate was measured with a curved ruler (if the maximum value of the gap distance is 1 mm or less, it was measured with a high-precision contact digital sensor GT2 (manufactured by Keyence Corporation)), and if the maximum value was less than 1 mm (A rating or higher in the evaluation criteria below), it was considered to have passed.
  • Evaluation Criteria S: There is no gap between the sample plate and the glass plate (the gap distance is 0 mm).
  • A The gap distance (maximum value) between the sample plate and the glass plate is more than 0 mm and less than 1 mm.
  • B The gap distance (maximum value) between the sample plate and the glass plate is 1 mm or more and less than 3 mm.
  • C The gap distance (maximum value) between the sample plate and the glass plate is 3 mm or more.
  • Example 2 to 9 and Comparative Examples 1 to 7 Filaments were produced under the same conditions as in Example 1, except that the resin composition was as shown in Table 1.
  • the MFR (220°C, 10 kg load) of the filaments in each example was measured under the same conditions as in Example 1.
  • warping, high-speed modeling ability, and nozzle abrasion resistance were evaluated under the same conditions as in Example 1. The results are shown in Table 2.
  • the resin composition satisfying the configuration of this embodiment is used as a filament for a 3D printer, it is possible to suppress the wear of the nozzle, suppress warping, and achieve both high-speed modeling.
  • the resin composition of Comparative Example 1 in which the amount of plate-like particles (B) is less than 10 parts by mass, had a large warp in the obtained three-dimensional object.
  • the resin composition of Comparative Example 2 in which the amount of plate-like particles (B) is more than 30 parts by mass, had poor high-speed modeling properties.
  • the resin composition according to this embodiment has industrial applicability as a filament for producing three-dimensional objects using a 3D printer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une composition de résine pour imprimantes 3D qui réduit au minimum l'usure d'une buse d'une imprimante 3D et présente à la fois une inhibition de gauchissement et des propriétés de fabrication à grande vitesse; un procédé de production d'un objet fabriqué tridimensionnel à l'aide de la composition de résine; et un objet fabriqué 3D présentant peu de gauchissement.　La composition de résine pour imprimantes 3D comprend : une résine de styrène (A) contenant un composant caoutchouc; et des particules lamellaires (B) ayant une dureté Mohs d'au plus 3 et ayant des surfaces traitées avec un agent de couplage silane (X). La teneur en particules lamellaires (B) est de 10 à 30% en masse par rapport à la masse totale de la composition de résine. Le procédé de production d'un objet fabriqué tridimensionnel comprend : la fusion de la composition de résine pour des imprimantes 3D; et l'extrusion de la composition de résine fondue à travers une buse pour former un objet fabriqué tridimensionnel. L'objet fabriqué tridimensionnel contient la composition de résine pour imprimantes 3D.
PCT/JP2024/002359 2023-02-27 2024-01-26 Composition de résine pour imprimantes 3d, objet fabriqué tridimensionnel et son procédé de production Ceased WO2024180960A1 (fr)

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CN202480014634.4A CN120752129A (zh) 2023-02-27 2024-01-26 3d打印机用树脂组合物、三维造型物及其制造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025143189A1 (fr) * 2023-12-27 2025-07-03 デンカ株式会社 Article issue de la fabrication additive et procédé de production d'un article issu de la fabrication additive

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017209969A (ja) * 2016-05-27 2017-11-30 株式会社リコー 立体造形用材料、立体造形物の製造方法、及び立体造形物製造装置
JP2018131497A (ja) * 2017-02-14 2018-08-23 東京インキ株式会社 立体造形装置用樹脂成形材料および立体造形装置用フィラメント
WO2019146474A1 (fr) * 2018-01-29 2019-08-01 コニカミノルタ株式会社 Composition de résine pour moulage 3d, et article moulé en 3d ainsi que procédé de fabrication de celui-ci
JP2023500431A (ja) * 2019-11-08 2023-01-06 ジャビル インク 積層造形のための組成物

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Publication number Priority date Publication date Assignee Title
JP2017209969A (ja) * 2016-05-27 2017-11-30 株式会社リコー 立体造形用材料、立体造形物の製造方法、及び立体造形物製造装置
JP2018131497A (ja) * 2017-02-14 2018-08-23 東京インキ株式会社 立体造形装置用樹脂成形材料および立体造形装置用フィラメント
WO2019146474A1 (fr) * 2018-01-29 2019-08-01 コニカミノルタ株式会社 Composition de résine pour moulage 3d, et article moulé en 3d ainsi que procédé de fabrication de celui-ci
JP2023500431A (ja) * 2019-11-08 2023-01-06 ジャビル インク 積層造形のための組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025143189A1 (fr) * 2023-12-27 2025-07-03 デンカ株式会社 Article issue de la fabrication additive et procédé de production d'un article issu de la fabrication additive

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