WO2020003901A1 - Composition pour imprimante 3d - Google Patents

Composition pour imprimante 3d Download PDF

Info

Publication number
WO2020003901A1
WO2020003901A1 PCT/JP2019/021893 JP2019021893W WO2020003901A1 WO 2020003901 A1 WO2020003901 A1 WO 2020003901A1 JP 2019021893 W JP2019021893 W JP 2019021893W WO 2020003901 A1 WO2020003901 A1 WO 2020003901A1
Authority
WO
WIPO (PCT)
Prior art keywords
dimensional printer
composition
organic binder
eva
thermoplastic resin
Prior art date
Application number
PCT/JP2019/021893
Other languages
English (en)
Japanese (ja)
Inventor
裕貴 井上
和田　誠
詠大 小笠原
望 林田
和幸 加藤
川北　晃司
Original Assignee
第一セラモ株式会社
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 第一セラモ株式会社 filed Critical 第一セラモ株式会社
Priority to JP2020527317A priority Critical patent/JP6849286B2/ja
Publication of WO2020003901A1 publication Critical patent/WO2020003901A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene

Definitions

  • the present invention relates to a composition suitable for use in a three-dimensional printer.
  • thermoplastic resin such as PLA (polylactic acid) or ABS (acrylonitrile-butadiene-styrene) are used as raw materials, and the molten resins are laminated one by one. It is general to obtain a three-dimensional structure made of a thermoplastic resin by cooling and solidifying.
  • Patent Document 1 a compound made by adding ceramics or metal powder to a thermoplastic resin
  • Patent Document 2 a three-dimensional printer having an extrusion device
  • Patent Document 1 After a molded article is manufactured using a compound containing inorganic powder as a raw material by using a three-dimensional printer of a hot-melt lamination method (FDM method), powder injection molding (PIM: Powder Injection Molding) is performed.
  • PIM Powder Injection Molding
  • Metal or ceramic products can be obtained by performing degreasing and sintering (sintering), which are generally performed in, so it is possible to solve the problem of expensive equipment and the problem of low laminating speed. It is.
  • the present invention provides a three-dimensional structure without causing cracks or stringing when using a three-dimensional printer of the FDM printer method to laminate-mold a composition containing an inorganic powder and an organic binder as a raw material.
  • An object of the present invention is to provide a composition for a three-dimensional printer that can be formed.
  • the present inventor has repeatedly studied to solve the above-described problems, and as a result, by mixing a specific organic binder with the inorganic powder in a specific ratio, the adhesiveness is high, and the stringiness (stringiness) is improved.
  • the present inventors have succeeded in developing a composition having a small composition and capable of forming a laminated structure excellent in strength and appearance even when used in a three-dimensional printer.
  • the composition (compound) for a three-dimensional printer of the present invention which can solve the above problems, (A) containing an inorganic powder and (B) an organic binder,
  • the organic binder (B) is (B1) a thermoplastic resin selected from an amorphous polymer and EVA, (B2) a thermoplastic resin selected from a crystalline polymer other than EVA, (B3) a wax, (B4) Being selected from the group consisting of lubricants, and (B5) other additives;
  • thermoplastic resin (B1) examples include acrylic resins such as polymethyl methacrylate (PMMA), polybutyl acrylate (Pn-BMA) and composite acrylic, atactic polystyrene (Atactic PS), polycarbonate (PC ), Amorphous polyolefins, and non-crystalline polymers selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), and ethylene-vinyl acetate copolymer (EVA).
  • acrylic resins such as polymethyl methacrylate (PMMA), polybutyl acrylate (Pn-BMA) and composite acrylic, atactic polystyrene (Atactic PS), polycarbonate (PC ), Amorphous polyolefins, and non-crystalline polymers selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), and ethylene-vinyl acetate copolymer (EVA).
  • PMMA polymethyl methacrylate
  • thermoplastic resin (B2) examples include polyethylene (PE), polypropylene (PP), polyacetal (POM), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polylactic acid (PLA). Is mentioned.
  • Preferred examples of the inorganic powder (A) include a metal oxide powder having an average particle diameter (D 50 ) of 0.1 to 1.0 ⁇ m.
  • Another preferred example of the inorganic powder (A) is a metal powder having an average particle diameter (D 50 ) of 1.0 to 10 ⁇ m.
  • the present invention is a method of manufacturing a product made of ceramics, cermet, or metal, and using the composition for a three-dimensional printer, forming a laminated structure by an FDM type three-dimensional printer, It is characterized by including a step of degreasing the laminated structure and a step of sintering.
  • the present invention is a method of manufacturing a product in which two or more selected from ceramics, cermets, and metals are joined, A laminated composite structure is formed by simultaneously laminating two or more types of the composition for a three-dimensional printer according to any one of claims 1 to 5 with a three-dimensional printer of a hot-melt lamination system including two or more extrusion devices. Performing a step of degreasing and sintering the laminated structure.
  • the composition for a three-dimensional printer of the present invention has high adhesion, when a laminated structure is formed by an FDM type three-dimensional printer, peeling between the laminated layers hardly occurs, and a laminated structure without cracks can be obtained. .
  • the stringiness is low, whisker-like burrs are not easily generated, and a laminated structure excellent in appearance can be obtained.
  • Examples of the inorganic powder (A) that can be used in the composition for a three-dimensional printer of the present invention include sinterable powders such as metal powder, ceramic powder, and cermet powder.
  • the metal powder include iron-based alloys such as pure iron, iron-nickel, iron-cobalt, iron-silicon, and stainless steel, tungsten, tungsten carbide, and cemented carbides (such as WC-Co-based alloys). , Aluminum alloy, copper, copper alloy, and the like.
  • the ceramic powder examples include oxides such as Al 2 O 3 , BeO, and ZrO 2 , carbides such as TiC, ZrC, and B 4 C, borides such as CrB and ZrB 2, and nitrides such as TiN and ZrN.
  • the cermet powder examples include Al 2 O 3 —Fe, TiC—Ni, TiC—Co, and B 4 C—Fe.
  • Particularly preferred examples of the inorganic powder (A) used in the present invention include metal oxide powders such as alumina (Al 2 O 3 ) and zirconia (ZrO 2 ), metal powders such as stainless steel, and carbide such as WC-Co. Alloy powder and the like.
  • the zirconia may be yttria partially stabilized zirconia.
  • metal oxide powder having an average particle diameter (D 50 ) of 0.1 to 1.0 ⁇ m, more preferably 0.1 to 0.8 ⁇ m is preferable.
  • the stainless steel powder preferably has an average particle diameter (D 50 ) of 1 to 15 ⁇ m, more preferably 5 to 10 ⁇ m.
  • the cemented carbide (WC-Co) powder preferably has an average particle diameter (D 50 ) of 0.1 to 50 ⁇ m, more preferably 1 to 3 ⁇ m.
  • the mass of (B) is less than 5 with respect to the mass of (A) of 100, the flow value is low and molding becomes difficult.
  • the mass of (B) exceeds 30, stringiness becomes large, and problems such as deformation during degreasing tend to occur.
  • the inorganic powder (A) is a metal powder (for example, stainless steel, cemented carbide, or the like)
  • the organic binder (B) used in the present invention includes a non-crystalline polymer and a thermoplastic resin (B1) selected from EVA.
  • a non-crystalline polymer and / or EVA as the thermoplastic resin, the adhesiveness can be improved.
  • thermoplastic resin (B1) examples include acrylic resins (for example, polymethyl methacrylate (PMMA), polybutyl acrylate (P-n-BMA) and composite acrylic), atactic polystyrene (Atactic PS), and polycarbonate. (PC), amorphous polyolefin, and an amorphous polymer selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), and an ethylene-vinyl acetate copolymer (EVA).
  • acrylic resins for example, polymethyl methacrylate (PMMA), polybutyl acrylate (P-n-BMA) and composite acrylic
  • atactic polystyrene Atactic PS
  • PC polycarbonate.
  • ABS acrylonitrile-butadiene-styrene
  • EVA ethylene-vinyl acetate copolymer
  • thermoplastic resin (B1) it is basically preferable to use a thermoplastic resin having a weight average molecular weight of 10,000 or more, preferably 20,000 or more, and particularly preferably 40,000 or more.
  • An amorphous polyolefin having a weight average molecular weight of 8000 or less (especially 5000 or less, for example, 2000 to 4000) may be used in combination.
  • the weight average molecular weight can be determined using gel permeation chromatography (GPC).
  • thermoplastic resins (B1) when the inorganic powder is a metal oxide powder, a combination of an acrylic resin and PS is used, and EVA and / or amorphous polyolefin are used in combination. It is particularly preferable to use acrylic resin, PS and EVA in combination.
  • the mass ratio of the acrylic resin to PS is preferably 20 to 100, more preferably 25 to 70, and particularly preferably 28 to 50, based on 100 of the acrylic resin.
  • EVA is used in addition to the acrylic resin and the PS
  • the mass ratio of the acrylic resin to the EVA is preferably 5 to 30, and more preferably 7 to 25 with respect to the acrylic resin 100. More preferred.
  • the inorganic powder is a metal powder
  • an acrylic resin and EVA in combination as the thermoplastic resin (B1)
  • PS and / or amorphous polyolefin in combination are preferable.
  • EVA is preferably used in an amount of 30 to 150, more preferably 50 to 120
  • an amorphous polyolefin is preferably used in an amount of 30 to 150, more preferably 50 to 120, and further optionally.
  • PS is used in an amount of 50 to 150, more preferably 70 to 120 (the numerical values are all parts by mass).
  • the acrylic resin As particularly preferred examples of the acrylic resin, as described in JP-A-2000-303103, An ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer; Dispersing a solution comprising a (meth) acrylate monomer alone or a mixture of a (meth) acrylate monomer and a styrene monomer and a polymerization initiator in an aqueous medium containing a dispersant.
  • a composite acrylic resin obtained by suspension polymerization is exemplified.
  • the acrylic resin a polymer of (meth) acrylic acid ester, which is an ester of (meth) acrylic acid having 1 to 8 carbon atoms, can be used.
  • a (meth) acrylate monomer examples include, for example, n-alkyl (meth) acrylate having 1 to 8 carbon atoms in the alkyl group, isopropyl (meth) acrylate, isobutyl (meth) acrylate, Examples include t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate.
  • n-alkyl (meth) acrylates having 1 to 4 carbon atoms in the alkyl group such as n-butyl (meth) acrylate, isopropyl (meth) acrylate, and isobutyl (meth) acrylate are particularly preferable. Or two or more of them may be used in combination.
  • ⁇ PS having a weight average molecular weight of about 100,000 to 300,000, and more preferably about 150,000 to 250,000.
  • EVA it is more preferable to use one having a low crystallinity (for example, one having a crystallinity of 25% or less). Since the crystallinity of EVA correlates with vinyl acetate (VA) content, preferred EVA is, for example, a vinyl acetate content (mass percentage: JIS K 7192: 1999) of 20% to 50%, more preferably 25% to 40%. EVA. Further, those having a weight average molecular weight of about 30,000 to 120,000 are preferably used, and those having a weight average molecular weight of about 50,000 to 100,000 are more preferably used.
  • amorphous polyolefin those having a weight average molecular weight of about 1,000 to 8,000, more preferably about 2,000 to 4,000 can be used.
  • the organic binder (B) used in the present invention may optionally contain a thermoplastic resin (B2) selected from crystalline polymers (excluding EVA; the same applies hereinafter).
  • a thermoplastic resin selected from crystalline polymers (excluding EVA; the same applies hereinafter).
  • crystalline polymer for example, a crystalline polymer having a weight average molecular weight of 10,000 or more, preferably 20,000 or more, particularly preferably 40,000 or more can be used.
  • thermoplastic resin (B2) examples include polyethylene (PE), polypropylene (PP), polyacetal (POM), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polylactic acid (PLA). Is mentioned. In particular, PP and POM are preferred.
  • those having a weight average molecular weight of about 10,000 to 70,000 are preferably used, and those having a weight average molecular weight of about 20,000 to 50,000 are more preferable.
  • those having a weight average molecular weight of about 100,000 to 400,000 are preferably used, and those having a weight average molecular weight of about 200,000 to 300,000 are more preferably used.
  • the use of the crystalline polymer makes it easier to suppress the problem at the time of degreasing, but when the proportion of the crystalline polymer (B2) is larger than that of the thermoplastic resin (B1) selected from the non-crystalline polymer and EVA.
  • (B2) is preferably smaller than (B1).
  • the inorganic powder (A) is a metal powder (for example, stainless steel, cemented carbide, or the like)
  • the thermoplastic resin (B1 and B2) preferably has a softening point of 65 ° C. or higher, more preferably 70 ° C. or higher.
  • the softening point (Vicat softening temperature) can be measured by JIS K7206 B50 method. Further, the melting point of the thermoplastic resin (B1 and B2) is preferably 170 ° C. or less.
  • thermoplastic resins (B1 and B2) it is more preferable to use a plurality of resins having different rheological properties in combination as the thermoplastic resins (B1 and B2).
  • a thermoplastic resin eg, PP, PS, POM, etc.
  • a flow value at 180 ° C. 0.002 to 0.08 ml / sec, more preferably 0.003 to 0.07 ml / sec
  • Thermoplastic resin having a flow value at 180 ° C.
  • a resin having too high a fluidity can be determined using a flow tester (for example, a constant-test-force extruded capillary rheometer sold by Shimadzu Corporation) as shown in the Examples section.
  • the organic binder (B) used in the present invention contains a wax (B3).
  • a wax either a synthetic wax or a natural wax can be used, and specific examples thereof include paraffin wax, microcrystalline wax, polyethylene wax, beeswax, carnauba wax, montan wax, and polyalkylene glycol. Particularly preferred waxes include paraffin wax and microcrystalline wax.
  • the organic binder (B) used in the present invention may optionally contain a lubricant (B4).
  • a lubricant include fatty acids and derivatives of fatty acids such as esters, amides, and metal salts.
  • Preferred lubricants include higher fatty acids and derivatives thereof.
  • Particularly preferred lubricants include stearic acid and esters thereof (for example, Sorbitan monostearate).
  • (B4) / (B) is preferably 0.01 to 0.18, more preferably 0.02 to 0.16, and more preferably 0.03 to 0.16. It is particularly preferred that it is 0.10.15.
  • the organic binder (B) used in the present invention may optionally contain other additives (B5) which do not correspond to (B1) to (B4).
  • additives include, for example, plasticizers and antioxidants.
  • the plasticizer include, for example, phthalic acid esters (eg, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl terephthalate), adipic acid esters (eg, di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate) ), Trimellitates (tri-2-ethylhexyl trimellitate, triisodecyl trimellitate, etc.), citrates (tributyl acetyl citrate), diisononyl 1,2-cyclohexanedicarboxylate, 4-cyclohexene-1, Examples thereof include bis (2-ethylhexyl) 2-
  • antioxidants include, for example, a phenolic antioxidant.
  • additives other than the plasticizer and the antioxidant that correspond to (B5) include additives such
  • (B5) / (B) is preferably 0.03 to 0.30, more preferably 0.05 to 0.25, and more preferably 0.07 to 0.25. It is particularly preferable that it is 0.15.
  • (B5) / (B) is preferably 0.01 to 0.20, and more preferably 0.02 to 0.15.
  • the molecular weight (or weight average molecular weight) is preferably 2,000 or less, more preferably 1,000 or less.
  • (B3) to (B5) having a heating loss starting point of 150 ° C. or less.
  • the starting point of the heating loss can be determined by a thermogravimetric method defined in JIS K7120.
  • the method for producing a composition for a three-dimensional printer of the present invention is prepared by melt-kneading an inorganic powder (A) and an organic binder (B).
  • a pressurized kneader is an example of a preferred embodiment.
  • Various types of kneaders such as a batch type such as a double-arm kneader type kneader and a Banbury type kneader, and a continuous type such as a single-screw or twin-screw extruder can be used.
  • the shape of the composition for a three-dimensional printer of the present invention is not particularly limited, but an example of a preferable form includes a pellet-like form used in PIM. Although it is not particularly limited, an example of a preferable embodiment is one in which the extruded melt after kneading is pelletized by a hot-cut type pelletizer in which the melt is cut into pellets in the air by a rotary cutter.
  • the present invention provides a three-dimensional printer using an FDM type three-dimensional printer to form a laminated structure using the composition for a three-dimensional printer (composition highly filled with inorganic powder), and performs degreasing and sintering.
  • a method for manufacturing a product made of ceramics, cermet, or metal is provided.
  • Examples of the FDM three-dimensional printer include a cylinder, a screw, a gear pump, an extrusion device having a nozzle, and a nozzle of the extrusion device as disclosed in Patent Document 2 (WO2015 / 129733). Controlling the discharge of resin from the nozzle in the extruding device and the table device located opposite to the extruding device and / or the extruding device and / or the table device in the X-axis, Y-axis, and Z-axis directions with respect to a reference plane; A three-dimensional printer equipped with a control device for controlling the movement of the camera can be used.
  • a three-dimensional printer including a plurality of the extrusion devices can be used to form a structure in which two or more of the three-dimensional printer compositions are laminated and combined.
  • the laminated structure is formed, for example, by forming two or more types of three-dimensional printer compositions containing the different metal powders into a laminated structure having a predetermined structure, degreased, and sintered, thereby forming two or more types.
  • a sintered body in which the inorganic materials are joined can be obtained.
  • the conditions for degreasing and sintering may be the same as those for degreasing and sintering of PIM, and can be set as appropriate according to the type of inorganic powder contained in the composition.
  • the inorganic powder is zirconia (such as yttria-stabilized zirconia) or alumina
  • the temperature is raised to about 450 to 550 ° C. at a rate of 5 to 20 ° C./h to perform degreasing, and then the rate of temperature rise is 40 to 60.
  • the sintering can be performed by increasing the temperature to 1300 to 1600 ° C. at a rate of ° C./h.
  • degreasing is performed by raising the temperature to about 450 to 550 ° C. at a rate of 5 to 20 ° C./h in an inert gas atmosphere, and then performing a temperature increase of 1300 to 40 ° C./h at a rate of 40 to 60 ° C./h.
  • the temperature can be raised to 1400 ° C. for sintering.
  • the following substances were used as other additives.
  • the flow value was measured by using a flow tester "CFD-500D” manufactured by Shimadzu Corporation, setting a 1 mm diameter x 1 mm length die, applying a load of 0.98 MPa, and flowing at 180 ° C per unit time. It was determined by measuring the amount (ml / sec). In the case where the fluidity was too high at 180 ° C. to measure an accurate value, the set temperature was changed to 140 ° C. and the flow value was obtained.
  • thermoplastic resin / acrylic resin selected from an amorphous polymer and EVA (copolymer of n-butyl methacrylate and methyl methacrylate, weight average molecular weight 50,000, flow rate at 180 ° C.
  • Thermoplastic resin / PP selected from crystalline polymers excluding EVA (weight average molecular weight 240,000, flow rate at 180 ° C 0.051 ml / sec, melting point 163 ° C) -POM (weight average molecular weight 50,000, flow rate at 180 ° C 0.003 ml / sec, melting point 165 ° C)
  • DOP dioctyl phthalate
  • Mw 394 Bis (2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate
  • Mw 394 1,2-cyclohexanedicarboxylic acid diisononyl ester
  • Phenolic antioxidant (1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane) (molecular weight: 545, melting point: 183 to 185 ° C.)
  • composition for three-dimensional printer The above (A) and (B1) to (B5) were blended in the proportions shown in the table, and were melt-kneaded at 170 ° C. using a pressurized kneader manufactured by Nippon Spindle Manufacturing Co., Ltd. (former Moriyama Seisakusho). .
  • the pellets having a diameter of 3 mm and a length of 3 mm were produced from the obtained melt using a pelletizer type plunger extruder manufactured by Toshin Co., Ltd.
  • the presence or absence of a gap between the layers of the obtained molded article was visually confirmed, and the laminated structure was placed sideways on two fulcrums arranged at an interval of 10 mm (that is, the width). 20 mm x 5 mm deep x 5 mm high) was placed and judged by the easiness of cracking when a load of 5 N was applied.
  • the molded object was manufactured by laminating molten raw materials in the height direction. When a load is applied with the object placed sideways, breakage is likely to occur between layers if the adhesion between the layers is poor.
  • the criteria are as follows.
  • sintering was performed in the atmosphere at a heating rate of 50 ° C./h at a temperature of 1450 ° C. for zirconia and 1600 ° C. for alumina to obtain a sintered body.
  • the stainless steel was degreased by raising the temperature to about 500 ° C. at a rate of 10 ° C./h in a nitrogen gas atmosphere, and deformation or cracks and blisters were confirmed in the same manner as described above. Thereafter, the temperature was raised to 1350 ° C. at a rate of 50 ° C./h to obtain a sintered body.
  • WC-Co was also degreased in a nitrogen gas atmosphere at a heating rate of about 10 ° C./h to about 500 ° C.
  • Tables 1 and 2 summarize the compositions and test results of the composition (pellet) for the three-dimensional printer.
  • the mass of (B) is in the range of 5 to 30 with respect to the mass 100 of (A), and (B1) / (B1 + B2) is in the range of 0.5 to 1.0, Examples 1 to 5 (inorganic powders) in which (B3) / (B) is in the range of 0.07 to 0.4 and (B4) / (B) is in the range of 0 to 0.18.
  • Example 6 using alumina powder as inorganic powder
  • Example 7 using stainless steel powder as inorganic powder
  • Example 8 using cemented carbide powder as inorganic powder
  • a molded article having high adhesion, low stringiness, and excellent appearance was able to be produced.
  • pellets of the first component and the second component having a diameter of 3 mm and a length of 3 mm were manufactured from the obtained melt using a pelletizer type plunger extruder manufactured by Toshin Co., Ltd.
  • pellets of the first component and the second component were produced in the same manner.
  • CERA # P3 manufactured by S. Lab Co., Ltd., molding range X150 mm ⁇ Y150 mm ⁇ Z150 mm, screw diameter ⁇ 20 mm
  • the two components were formed by lamination under the following conditions.
  • the molding speed was 100 to 2000 mm / min
  • the molding temperature was 150 to 190 ° C.
  • the nozzle diameter was 1.0 mm.
  • the distance between each laminated structure (modeled object) was 30 mm.
  • the laminated structure has no gap between the layers, and has the laminated structure laid sideways on two fulcrums arranged at an interval of 10 mm (that is, a width of 20 mm ⁇ a depth of 5 mm ⁇ a height of 5 mm). ) And no breakage occurred between the layers when a load of 5 N was applied.
  • the stainless steel was degreased by raising the temperature to about 500 ° C. at a rate of 10 ° C./h in a nitrogen gas atmosphere, and deformation or cracks and blisters were confirmed in the same manner as described above. Thereafter, the temperature was raised to 1350 ° C. at a rate of 50 ° C./h to obtain a sintered body.
  • WC-Co was also degreased in a nitrogen gas atmosphere at a heating rate of about 10 ° C./h to about 500 ° C. in the same manner as stainless steel, and deformation or cracks and blisters were confirmed in the same manner as described above. Thereafter, the temperature was raised to 1390 ° C. at a rate of 50 ° C./h to obtain a sintered body.
  • composition and the method of the present invention it is possible to efficiently produce a ceramic product, a metal product, and the like having excellent appearance and strength using an FDM three-dimensional printer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Powder Metallurgy (AREA)
  • Press-Shaping Or Shaping Using Conveyers (AREA)
  • Producing Shaped Articles From Materials (AREA)

Abstract

Le problème à résoudre par la présente invention est de fournir une composition pour une imprimante 3D de telle sorte que, lors de la formation d'un modèle (corps de structure en couches) avec une imprimante 3D de laminage par thermofusion à l'aide d'une composition contenant une poudre inorganique en tant que matière première, le modèle est obtenu avec des fissures inter-couches et un cordage minimes. L'invention est une composition pour une imprimante 3D comprenant (A) une poudre inorganique et (B) un liant organique, la composition pour une imprimante 3D étant caractérisée en ce que : le liant organique (B) est choisi dans le groupe constitué de (B1) résines thermoplastiques choisies parmi des polymères non cristallins et des CAV/E, (B2) des résines thermoplastiques choisies parmi des polymères cristallins à l'exclusion de des CAV/E, (B3) des cires, (B4) des lubrifiants, et (B5) d'autres additifs ; (A)/(B) = 100/5 à 100/30 ; (B1)/(B1 + B2) = 0,5 à 1,0 ; (B3)/(B) = 0,07 à 0,4 ; et (B4)/(B) = 0 à 0,18.
PCT/JP2019/021893 2018-06-29 2019-06-01 Composition pour imprimante 3d WO2020003901A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020527317A JP6849286B2 (ja) 2018-06-29 2019-06-01 ３次元プリンタ用組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-124994 2018-06-29
JP2018124994 2018-06-29

Publications (1)

Publication Number Publication Date
WO2020003901A1 true WO2020003901A1 (fr) 2020-01-02

Family

ID=68985007

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/021893 WO2020003901A1 (fr) 2018-06-29 2019-06-01 Composition pour imprimante 3d

Country Status (2)

Country Link
JP (1) JP6849286B2 (fr)
WO (1) WO2020003901A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020015848A (ja) * 2018-07-26 2020-01-30 第一セラモ株式会社 ３次元プリンタ用組成物及び、当該組成物を用いた大型積層造形物の製造方法
CN111906308A (zh) * 2020-08-10 2020-11-10 广东中发摩丹科技有限公司 铍铝合金航空航天构件的粉末增塑增材制造烧结成形方法
US20220033664A1 (en) * 2020-07-31 2022-02-03 Seiko Epson Corporation Molding composition and method for manufacturing three-dimensional shaped object
WO2022092780A1 (fr) * 2020-10-27 2022-05-05 코오롱플라스틱 주식회사 Composition de filament d'imprimante 3d contenant une poudre métallique, et filament l'utilisant
CN115043654A (zh) * 2021-03-08 2022-09-13 比亚迪股份有限公司 一种电子烟雾化芯用多孔陶瓷基体组合物、多孔陶瓷基体及其制备方法、电子烟雾化芯
JP7376736B1 (ja) 2023-02-01 2023-11-08 第一セラモ株式会社 ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、多孔質焼結体、焼結体の製造方法、および多孔質焼結体の製造方法
JP7399340B1 (ja) 2023-06-16 2023-12-15 第一セラモ株式会社 ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、及び焼結体の製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113878113B (zh) * 2021-08-30 2023-05-02 广东省科学院新材料研究所 一种陶瓷-不锈钢复合材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH036302A (ja) * 1989-06-02 1991-01-11 Japan Steel Works Ltd:The 粉末成形用バインダー及び金属粉末またはセラミック粉末からなる焼結品の製造方法
JP2000303103A (ja) * 1999-04-19 2000-10-31 Dai Ichi Kogyo Seiyaku Co Ltd 金属粉末射出成形用組成物
JP2005205805A (ja) * 2004-01-23 2005-08-04 Daiichi Seramo Kk 粉末射出成形用組成物、及びその焼結体
JP2005255802A (ja) * 2004-03-10 2005-09-22 Daiichi Seramo Kk 粉末射出成形用組成物
JP2006213585A (ja) * 2005-02-07 2006-08-17 Daiichi Seramo Kk 粉末射出成形用組成物
WO2015129733A1 (fr) * 2014-02-25 2015-09-03 精一 柚山 Imprimante 3d

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH036302A (ja) * 1989-06-02 1991-01-11 Japan Steel Works Ltd:The 粉末成形用バインダー及び金属粉末またはセラミック粉末からなる焼結品の製造方法
JP2000303103A (ja) * 1999-04-19 2000-10-31 Dai Ichi Kogyo Seiyaku Co Ltd 金属粉末射出成形用組成物
JP2005205805A (ja) * 2004-01-23 2005-08-04 Daiichi Seramo Kk 粉末射出成形用組成物、及びその焼結体
JP2005255802A (ja) * 2004-03-10 2005-09-22 Daiichi Seramo Kk 粉末射出成形用組成物
JP2006213585A (ja) * 2005-02-07 2006-08-17 Daiichi Seramo Kk 粉末射出成形用組成物
WO2015129733A1 (fr) * 2014-02-25 2015-09-03 精一 柚山 Imprimante 3d

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020015848A (ja) * 2018-07-26 2020-01-30 第一セラモ株式会社 ３次元プリンタ用組成物及び、当該組成物を用いた大型積層造形物の製造方法
JP7123682B2 (ja) 2018-07-26 2022-08-23 第一セラモ株式会社 ３次元プリンタ用組成物及び、当該組成物を用いた大型積層造形物の製造方法
US20220033664A1 (en) * 2020-07-31 2022-02-03 Seiko Epson Corporation Molding composition and method for manufacturing three-dimensional shaped object
CN114082940A (zh) * 2020-07-31 2022-02-25 精工爱普生株式会社 成型用组合物以及三维造型物的制造方法
CN114082940B (zh) * 2020-07-31 2024-05-03 精工爱普生株式会社 成型用组合物以及三维造型物的制造方法
CN111906308A (zh) * 2020-08-10 2020-11-10 广东中发摩丹科技有限公司 铍铝合金航空航天构件的粉末增塑增材制造烧结成形方法
WO2022092780A1 (fr) * 2020-10-27 2022-05-05 코오롱플라스틱 주식회사 Composition de filament d'imprimante 3d contenant une poudre métallique, et filament l'utilisant
KR20220056292A (ko) * 2020-10-27 2022-05-06 코오롱플라스틱 주식회사 3d 프린터용 금속 분말 함유 조성물 및 이를 이용한 필라멘트
KR102415965B1 (ko) * 2020-10-27 2022-07-01 코오롱플라스틱 주식회사 3d 프린터용 금속 분말 함유 조성물 및 이를 이용한 필라멘트
CN115043654A (zh) * 2021-03-08 2022-09-13 比亚迪股份有限公司 一种电子烟雾化芯用多孔陶瓷基体组合物、多孔陶瓷基体及其制备方法、电子烟雾化芯
JP7376736B1 (ja) 2023-02-01 2023-11-08 第一セラモ株式会社 ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、多孔質焼結体、焼結体の製造方法、および多孔質焼結体の製造方法
JP7399340B1 (ja) 2023-06-16 2023-12-15 第一セラモ株式会社 ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、及び焼結体の製造方法

Also Published As

Publication number Publication date
JPWO2020003901A1 (ja) 2021-03-11
JP6849286B2 (ja) 2021-03-24

Similar Documents

Publication Publication Date Title
JP6849286B2 (ja) ３次元プリンタ用組成物
JP7123682B2 (ja) ３次元プリンタ用組成物及び、当該組成物を用いた大型積層造形物の製造方法
US11135830B2 (en) Sinterable feedstock for use in 3D printing devices
JP2019188744A (ja) ３次元プリンタ用組成物
US11633786B2 (en) Feedstock for an additive manufacturing method, additive manufacturing method using the same, and article obtained therefrom
JP5439194B2 (ja) 有機バインダの製造方法および有機バインダ
JP2022153896A (ja) 中子用樹脂組成物および焼結体の製造方法
JP2022153895A (ja) サポート材用樹脂組成物および焼結体の製造方法
KR101875703B1 (ko) 3d 프린터용 필라멘트 조성물
CN114082940B (zh) 成型用组合物以及三维造型物的制造方法
JP2014129573A (ja) 射出成形用組成物
JP7376736B1 (ja) ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、多孔質焼結体、焼結体の製造方法、および多孔質焼結体の製造方法
JP3911596B2 (ja) 粉末射出成形用組成物
KR101626878B1 (ko) 금속사출 성형용 바인더 조성물
JP7399340B1 (ja) ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、及び焼結体の製造方法
JP7496927B1 (ja) ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、及び焼結体の製造方法
TWI580746B (zh) 射出成型用結合劑
JP2006328099A (ja) 射出成形用組成物
JPH02204355A (ja) 焼結性混合物の製造方法
JP2003095728A (ja) 射出成形用組成物
JP2517762B2 (ja) 金属粉末射出成形用組成物
JP2006328435A (ja) 射出成形用組成物
JP2006257485A (ja) 射出成形用組成物
JPH11278915A (ja) セラミック射出成形用組成物
JP2004216663A (ja) 射出成形用組成物の調整方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19824607

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020527317

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19824607

Country of ref document: EP

Kind code of ref document: A1