WO2023286824A1 - 粉末組成物、粉末組成物を用いて粉末床溶融結合方式によって三次元造形物を製造する方法、および三次元造形物 - Google Patents
粉末組成物、粉末組成物を用いて粉末床溶融結合方式によって三次元造形物を製造する方法、および三次元造形物 Download PDFInfo
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- WO2023286824A1 WO2023286824A1 PCT/JP2022/027661 JP2022027661W WO2023286824A1 WO 2023286824 A1 WO2023286824 A1 WO 2023286824A1 JP 2022027661 W JP2022027661 W JP 2022027661W WO 2023286824 A1 WO2023286824 A1 WO 2023286824A1
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- powder composition
- polyamide
- reinforcing material
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- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
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- 239000010435 syenite Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- 238000011282 treatment Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Images
Classifications
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- 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
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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
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
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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
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a three-dimensional structure obtained by a powder bed fusion bonding method, a powder composition suitably used for obtaining the same, and a method of manufacturing a three-dimensional structure using the powder composition. .
- Known techniques for manufacturing three-dimensional objects include the material extrusion method, the powder bed fusion method, the liquid bath photopolymerization method, and the sheet lamination method.
- the powder bed fusion method after providing a layer of powder, the position corresponding to the cross section of the object is selectively melted, and these layers are adhered and laminated to form a three-dimensional model.
- methods for selectively melting the powder include selective laser sintering using a laser, selective absorption sintering using a melting aid, and selective suppression sintering in which areas not to be melted are masked.
- the powder bed fusion bonding method has the advantage that it is suitable for precision molding as compared with other molding methods and does not require support members during molding.
- the three-dimensional structure obtained by the above method can be used for mobility applications such as automobiles, aviation, and space, medical applications such as artificial limbs, braces, hearing aids, and catheters, sports applications, and sports applications. It is being considered for use in various fields such as electrical and electronic materials. Among these, mobility applications require high heat resistance and elastic modulus, so in many cases, resin materials containing reinforcing materials are used, and similar properties are required for 3D models.
- Patent Document 1 a three-dimensional model having a high elastic modulus compared to the case of polyamide powder alone by blending glass beads with irregular-shaped powder of polyamide 11 or polyamide 12. is disclosed.
- Patent Literature 2 discloses a three-dimensional molded article having a high elastic modulus and heat resistance by blending a polyamide powder with a predetermined glass fiber and a powdery fluidizing agent.
- JP 2008-266645 A Japanese Patent Publication No. 2020-536153
- the present invention has high fluidity by making a powder composition containing a specific polyamide powder and an inorganic reinforcing material, and maintains good fluidity even when used for recycling, and uses the powder composition for three-dimensional modeling. It is an object of the present invention to provide a shaped article that achieves both excellent surface smoothness and a high elastic modulus when applied to.
- the powder composition of the present invention is a powder composition containing a polyamide powder (A) and an inorganic reinforcing material (B), wherein the polyamide powder (A) has a D50 particle size of 1 ⁇ m or more and 100 ⁇ m or less, and a true sphere degree is 80 or more and 100 or less, the average major axis diameter of the inorganic reinforcing material (B) is 3 ⁇ m or more and 300 ⁇ m or less, and the average major axis diameter/average minor axis diameter is 1 or more and 15 or less, and the total of the powder composition It is characterized in that the inorganic reinforcing material (B) is contained in an amount of 5% by weight or more and 60% by weight or less based on the weight.
- the method of manufacturing a three-dimensional structure of the present invention is a method of manufacturing a three-dimensional structure by the powder bed fusion bonding method using the powder composition as described above.
- the three-dimensional structure of the present invention is a three-dimensional structure obtained by a powder bed fusion bonding method, has a surface roughness of 20 ⁇ m or less, an X-direction elastic modulus of 3500 MPa or more, and is observed by X-ray CT measurement. It is characterized in that the average spherical equivalent diameter of the pores is 1 ⁇ m or more and 100 ⁇ m or less.
- a powder composition containing a specific polyamide powder and an inorganic reinforcing material has high fluidity and can maintain good fluidity even when used for recycling, and the powder composition is three-dimensionally shaped.
- the powder composition is three-dimensionally shaped.
- FIG. 1 is a schematic diagram showing an example of a three-dimensional structure manufacturing apparatus according to the present invention
- FIG. 4 is a scanning electron micrograph of the powder composition obtained in Example 2.
- the elastic modulus of a three-dimensional model depends on the amount and shape of the reinforcing material contained in the raw material powder composition. Since the fluidity of the powder composition is lowered, the surface roughness of the shaped article is increased, and it is impossible to achieve both surface smoothness and elastic modulus. Furthermore, there was a problem that recycling use became difficult due to aggregation of the reinforcing material.
- the powder composition of the present invention contains a polyamide powder (A) and an inorganic reinforcing material (B), the D50 particle diameter of (A) is 1 ⁇ m or more and 100 ⁇ m or less, and the sphericity is 80 or more and 100 or less, The average major axis diameter of (B) is 3 ⁇ m or more and 300 ⁇ m or less, the average major axis diameter / average minor axis diameter is 1 or more and 15 or less, and the (B) is 5% by weight or more with respect to the total weight of the powder composition. It is characterized by containing 60% by weight or less.
- the powder composition in the present invention comprises polyamide powder composed of a polyamide having a structure containing amide groups.
- polyamides include polycaproamide (polyamide 6), polyundecamide (polyamide 11), polylauroamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polydecamethylene Bacamide (Polyamide 1010), Polydodecamethylene Sebacamide (Polyamide 1012), Polydodecamethylene Dodecamide (Polyamide 1212), Polyhexamethylene Sebacamide (Polyamide 610), Polyhexamethylene Dodecamide (Polyamide 612), Poly decamethylene adipamide (polyamide 106), polydodecamethylene adipamide (polyamide 126), polyhexamethylene terephthalamide (polyamide 6T), polydecamethylene terephthalamide (polyamide 10T), polydodecamethylene terephthalamide (polyamide 12), polycaproamide (polyamide 6), polyundec
- polycaproamide polyamide 6
- polyundecaamide polyamide 11
- polylauroamide polyamide 12
- polyhexamethylene adipamide polyamide 66
- Polydecamethylene Sebacamide Polyamide 1010
- Polydodecamethylene Sebacamide Polyamide 1012
- Polydodecamethylene Dodecamide Polyamide 1212
- Polyhexamethylene Sebacamide Polyamide 610
- Polyhexamethylene Dodecamide Polyamide 612
- polycaproamide polyamide 6
- polyundecaamide polyamide 11
- polylauroamide polyamide 12
- polyhexamethylene adipamide polyamide 66
- polycaproamide polyamide 6
- polyundecaamide polyamide 11
- polylauroamide polyamide 12
- polyhexamethylene adipamide polyamide 66
- polycaproamide polyamide 6
- polyundecaamide polyamide 11
- polylauroamide polyamide 12
- polyhexamethylene adipamide polyamide 66
- polycaproamide polyamide 6
- polyhexamethylene sebacamide polyamide 610
- polydecamethylene sebacamide polyamide 1010
- polydodecamethylene sebacamide polyamide 1012
- polycaproamide polyamide 6
- polyhexamethylene adipamide polyamide 66
- polyhexamethylene sebacamide polyamide 610
- the polyamide may be copolymerized as long as the effects of the present invention are not impaired.
- an elastomer component such as polyolefin or polyalkylene glycol that imparts flexibility, or a rigid aromatic component that improves heat resistance and strength can be appropriately selected.
- a copolymerization component that adjusts terminal groups may be used in order to reuse the polymer powder in the powder bed fusion bonding method.
- Such copolymerization components include monocarboxylic acids such as acetic acid, hexanoic acid, lauric acid and benzoic acid, and monoamines such as hexylamine, octylamine and aniline.
- the weight average molecular weight range of the polyamide is preferably 10,000 to 1,000,000.
- 200,000 or less are particularly preferred, and 100,000 or less are most preferred.
- the weight-average molecular weight of the polyamide constituting the polyamide powder refers to the value obtained by measuring the weight-average molecular weight by gel permeation chromatography using hexafluoroisopropanol as a solvent and converting it into polymethyl methacrylate.
- the polyamide powder composition of the present invention may contain other compounds as long as it does not impair the present invention.
- compounding agents include antioxidants, heat stabilizers, and the like, in order to suppress thermal deterioration due to heating during molding by the powder bed fusion bonding method.
- antioxidants and heat stabilizers include hindered phenols, hydroquinones, phosphites and substituted products thereof, phosphites and hypophosphites.
- pigments and dyes for coloring, plasticizers for adjusting viscosity, flow aids for improving fluidity, antistatic agents for functionalization, flame retardants and carbon black, silica, titanium dioxide, potassium titanate, Fillers such as glass fibers, glass beads, carbon fibers, and cellulose nanofibers can be used. These can be known substances, and may be present inside or outside the polyamide powder.
- the D50 particle size of the polyamide powder of the present invention is in the range of 1-100 ⁇ m. When the D50 particle size exceeds 100 ⁇ m, the particle size becomes equal to or larger than the stacking height of the powder layer at the time of molding, resulting in a rough surface. If the D50 particle size is less than 1 ⁇ m, the fine particles tend to adhere to a recoater or the like during modeling, making it impossible to raise the temperature of the modeling chamber to the required temperature.
- the upper limit of the D50 particle size of the polyamide powder is preferably 90 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 70 ⁇ m or less.
- the lower limit is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
- the D50 particle size of the polyamide powder is the particle size (D50 particle size) at which the cumulative frequency from the small particle size side of the particle size distribution measured with a laser diffraction particle size distribution meter is 50%.
- the particle size distribution of the polyamide powder is expressed by D90/D10, which is the ratio of D90 to D10 in particle size distribution, and is preferably less than 5.0.
- D90/D10 is more preferably less than 4.0, still more preferably less than 3.0, and particularly preferably less than 2.0.
- the lower limit is theoretically 1.0.
- D90/D10 which indicates the particle size distribution of the polyamide powder in the present invention, is the particle size (D90) at which the cumulative frequency from the small particle size side of the particle size distribution measured by the above-described laser diffraction particle size distribution meter is 90%. It is a value divided by the particle size (D10) at which the cumulative frequency from the small particle size side is 10%.
- the sphericity which indicates the sphericity of the polyamide powder of the present invention, is 80 or more and 100 or less. If the sphericity is less than 80, the fluidity is deteriorated and the surface of the model becomes rough.
- the sphericity is preferably 85 to 100, more preferably 90 to 100, still more preferably 93 to 100, particularly preferably 95 to 100, and extremely preferably 97 to 100.
- the sphericity of the polyamide powder of the present invention is determined by observing 30 particles at random from a photograph of a scanning electron microscope and using the minor axis and major axis of the particle according to the following formula.
- the surface smoothness and internal solidity of the polyamide powder of the present invention can be represented by the BET specific surface area determined by gas adsorption.
- the BET specific surface area is preferably 10 m 2 /g or less, more preferably 5 m 2 /g or less, still more preferably 3 m 2 /g or less, and particularly preferably 1 m 2 /g or less. and most preferably 0.5 m 2 /g or less.
- the lower limit is theoretically 0.05 m 2 /g when the particle diameter is 100 ⁇ m.
- the BET specific surface area is measured according to Japanese Industrial Standards (JIS) JIS R 1626 (1996) "Method for measuring specific surface area by gas adsorption BET method”.
- the solidity of the polyamide powder of the present invention can also be evaluated by the following formula showing the ratio of the theoretical surface area calculated from the BET specific surface area and the D50 particle size. The closer the above ratio is to 1, the more adsorption occurs only on the outermost surface of the particles, indicating that the particles are solid and have smooth surfaces.
- the surface area ratio in the following formula is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and most preferably 2 or less.
- the lower limit is theoretically 1.
- R ratio of surface area
- D D50 particle size
- ⁇ density of polyamide
- A BET specific surface area
- the polyamide monomers described in WO 2018/207728 previously disclosed by the present inventors are mixed in the presence of a polymer incompatible with polyamide, A technique of washing and drying the polyamide powder after polymerization at a temperature higher than the crystallization temperature of the polyamide can be used.
- the polyamide powder preferably used in the present invention contains less than 0.1% by mass of subcomponents used in the polyamide powder manufacturing process. Since such subcomponents cause deterioration of the fluidity and recyclability of the powder composition, it is more preferably less than 0.05% by mass, further preferably less than 0.01% by mass, and less than 0.007% by mass. is particularly preferred, less than 0.004% by weight is significantly preferred, and less than 0.001% by weight is most preferred.
- the content of such subcomponents can be analyzed by a known method, for example, after extraction from the polyamide powder with water or an organic solvent, after removing the solvent, by gel permeation chromatography using water as a solvent. can be quantified.
- the obtained polyamide powder may be additionally heat treated.
- the heat treatment method a known method can be used, and a normal pressure heat treatment using an oven or the like, a reduced pressure heat treatment using a vacuum dryer or the like, and a pressure heat treatment in which the mixture is heated with water in a pressure vessel such as an autoclave can be appropriately selected.
- a pressure vessel such as an autoclave
- the powder composition of the present invention is characterized by containing an inorganic reinforcing material composed of an inorganic compound.
- the inorganic reinforcing material may be dry-blended with the polyamide powder, or may be contained inside the polyamide powder. preferably.
- Such inorganic reinforcing materials include, for example, glass-based fillers such as glass fibers, glass beads, glass flakes, and foamed glass beads; nepheline syenite fine powder; calcined clays such as montmorillonite and bentonite; aluminum acid powder), silicic acid-containing compounds such as talc, diatomaceous earth, silica sand, crushed products of natural minerals such as pumice powder, pumice balloon, slate powder, mica powder, barium sulfate, lithopone, calcium sulfate, molybdenum disulfide , minerals such as graphite (graphite), silica (silicon dioxide) such as fused silica, crystalline silica, amorphous silica, alumina (aluminum oxide), alumina colloid (alumina sol), alumina such as alumina white, light calcium carbonate, heavy carbonate Calcium, micronized calcium carbonate, calcium carbonate such as special calcium carbonate filler
- Glass-based fillers, minerals, and carbon fibers are preferable because they are hard and have a large effect of improving strength, and glass-based fillers are more preferable because they have a narrow particle size distribution and a narrow fiber size distribution.
- These inorganic reinforcing materials can be used alone or in combination of two or more.
- Elements that constitute such inorganic reinforcing materials generally include sodium, potassium, magnesium, calcium, barium, titanium, iron, aluminum, zinc, boron, aluminum, silicon, oxygen, etc., and have high rigidity and heat resistance. It preferably contains silicon and aluminum, and more preferably contains silicon, aluminum, magnesium, and calcium because it can contribute to improvement. Specific examples of inorganic reinforcing materials containing silicon and aluminum include mica, kaolin clay, montmorillonite, glass-based fillers, etc. Specific examples of inorganic reinforcing materials containing silicon, aluminum, magnesium, and calcium include A glass-type filler etc. are mentioned.
- the constituent elements of the inorganic reinforcing material can be determined from the spectral data of the inorganic reinforcing material detected by an energy dispersive X-ray spectrometer.
- glass-based fillers preferably used in the present invention include glass fibers, glass beads, glass flakes, foamed glass beads, etc., and the point that it is possible to express a high elastic modulus in a three-dimensional modeled object. and glass fibers, glass beads, or mixtures thereof are more preferred. Among these, glass fiber or a mixture of glass fiber and glass beads is particularly preferable in terms of suppressing warping of the model. Furthermore, glass fiber is extremely preferable in that the shaped article has high strength. The glass fiber may have a circular cross section or a flat cross section. Further, glass beads are remarkably preferable in that the strength anisotropy of the molded article is small.
- a surface-treated inorganic reinforcing material for the purpose of improving the adhesion between the inorganic reinforcing material and the polyamide powder.
- examples of such surface treatments include silane coupling agents such as aminosilane, epoxysilane, and acrylsilane. These surface treatment agents may be immobilized on the surface of the inorganic reinforcing material by a coupling reaction, or may cover the surface of the inorganic reinforcing material. In view of being difficult to be reformed by heat or the like, those immobilized by a coupling reaction are preferable.
- the average major axis diameter of the inorganic reinforcing material of the present invention is in the range of 3-300 ⁇ m. If the average major axis diameter exceeds 300 ⁇ m, unevenness of the inorganic reinforcing material appears on the modeled surface, which impairs the surface smoothness, which is not preferable. If the average major axis diameter is less than 3 ⁇ m, it will not be possible to contribute to the improvement of the elastic modulus, which is not preferable.
- the upper limit of the average major axis diameter of the inorganic reinforcing material is preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, even more preferably 150 ⁇ m or less, particularly preferably 120 ⁇ m or less, significantly preferably 100 ⁇ m or less, and most preferably 90 ⁇ m or less.
- the lower limit is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more, particularly preferably 20 ⁇ m or more, and significantly preferably 30 ⁇ m or more.
- the shape of the inorganic reinforcing material of the present invention is represented by the average major axis diameter/average minor axis diameter, which is the ratio of the average major axis diameter to the average minor axis diameter, and is 1 or more and 15 or less. If the average major axis diameter/average minor axis diameter exceeds 15, the orientation in the X direction in the modeled article described later becomes conspicuous, and the strength anisotropy with respect to the Z direction increases, which is not preferable. Therefore, the average major axis diameter/average minor axis diameter is preferably 13 or less, more preferably 12 or less, and even more preferably 10 or less. Moreover, the lower limit is theoretically 1.
- the average major axis diameter and average minor axis diameter of the inorganic reinforcing material are the major axis diameters of 100 fibers or particles randomly selected from a photograph obtained by imaging the inorganic reinforcing material with a scanning electron microscope. and the numerical average value observed for the minor axis diameter.
- the major axis diameter is the diameter at which the distance between the parallel lines when the image of the particle is sandwiched between two parallel lines is the maximum. This is the diameter that minimizes the distance between parallel lines when sandwiched between lines.
- the inorganic reinforcing material is selected from the scanning electron micrograph of the powder composition as shown in FIG. 2 and the major axis diameter and minor axis diameter are measured.
- the blending amount of such inorganic reinforcing material is 5% by weight or more and 60% by weight or less with respect to the total weight of the powder composition.
- the upper limit of the compounding amount is preferably 55% by weight or less, more preferably 50% by weight or less.
- the lower limit of the blending amount is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably 20% by weight or more. If the content of the inorganic reinforcing material is 5% by weight or more, it is possible to improve the elastic modulus and strength of a modeled product obtained by three-dimensionally modeling the powder composition. Further, when the amount of the inorganic reinforcing material is 60% by weight or less, the flowability of the powder composition does not deteriorate, and there is a tendency to obtain a shaped article having excellent surface smoothness.
- the powder composition of the present invention preferably contains a fluidity aid in terms of improving fluidity.
- a fluidity aid refers to a substance that suppresses aggregation of powder due to adhesion between powders.
- the fluidity of the powder composition can be improved, that is, the repose angle, which is an index of fluidity described later, can be improved to a desired range, and defects that cause deterioration of mechanical properties can be reduced. , there is a tendency that the appearance of the resulting shaped article can be further improved.
- Such flow aids include, for example, silica (silicon dioxide) such as fused silica, crystalline silica, and amorphous silica, alumina (aluminum oxide), alumina colloid (alumina sol), alumina such as alumina white, light calcium carbonate, and heavy calcium carbonate. , finely divided calcium carbonate, calcium carbonate such as special calcium carbonate-based fillers, titanium oxide, magnesium oxide, basic magnesium carbonate, potassium titanate fiber, boron fiber, silicon carbide fiber, and the like. More preferred are silica, alumina, calcium carbonate powder, and titanium oxide. Silica is particularly preferable because it is hard and can contribute to improvement in strength and fluidity.
- silica Commercial products of such silica include the fumed silica "AEROSIL” (registered trademark) series manufactured by Nippon Aerosil Co., Ltd., the dry silica “Reolosil” (registered trademark) series manufactured by Tokuyama Co., Ltd., and the sol-gel silica powder X manufactured by Shin-Etsu Chemical Co., Ltd. -24 series and the like.
- AEROSIL registered trademark
- Reolosil registered trademark
- sol-gel silica powder X manufactured by Shin-Etsu Chemical Co., Ltd. -24 series and the like.
- the D50 particle size of such flow aid is preferably 20 nm or more and 3000 nm or less.
- the upper limit of the D50 particle size of the flow aid is more preferably 2000 nm, more preferably 1000 nm, particularly preferably 500 nm, extremely preferably 300 nm and most preferably 200 nm.
- the lower limit is more preferably 30 nm, more preferably 50 nm, particularly preferably 100 nm, extremely preferably 120 nm, most preferably 140 nm.
- the D50 particle size of the flow aid in the present invention is obtained by determining the cumulative curve with the total volume of fine particles obtained by analyzing the scattered light of the laser by the dynamic light scattering method as 100%, and calculating the cumulative curve from the small particle size side. is the particle diameter (D50) at which the is 50%.
- the blending amount of such flow aid is preferably 0.01% by weight or more and 2.0% by weight or less with respect to the total weight of the powder composition.
- the upper limit of the content is more preferably 1.5% by weight or less, more preferably 1.0% by weight or less, particularly preferably 0.8% by weight or less, and significantly preferably 0.7% by weight or less.
- the lower limit of the compounding amount is more preferably 0.02% by weight or more, further preferably 0.03% by weight or more, and particularly preferably 0.04% by weight or more. If the blending amount of the flow aid is 0.01% by weight or more, the fluidity of the powder composition is further improved, and the filling property when molded is increased, so voids that are defects in mechanical properties are less likely to occur.
- the resulting shaped article tends to exhibit high strength.
- the amount of the flow aid is 2.0% by weight or less, there is no inhibition of sintering due to the coating of the surface of the polyamide powder with the flow aid, and there is a tendency to obtain a molded object with high strength. It is in.
- the powder composition of the present invention is preferably a powder mixture obtained by dry blending the aforementioned polyamide powder with an inorganic reinforcing material and, if necessary, a flow aid and other additives. It can be anything. If excessive shearing force is applied during blending, the inorganic reinforcing material may be damaged. Therefore, it is preferable to select a mixing method that does not apply excessive shearing force.
- a powder composition containing an inorganic reinforcing material may be prepared by powdering a polyamide resin kneaded with an inorganic reinforcing material.
- the powder composition of the present invention exhibits high fluidity.
- Any known measurement method can be used as the indicator.
- a specific example is the angle of repose, which is preferably 60 degrees or less. It is more preferably 50 degrees or less, still more preferably 40 degrees or less, and particularly preferably 35 degrees or less. The lower limit is usually 30 degrees or more. Due to its high fluidity, the powder composition of the present invention is suitable for producing a three-dimensional structure by the powder bed fusion bonding method.
- the filling properties of the powder composition of the present invention are, as a rough filling rate, the true density T (A) of the polyamide powder (A), the true density T (B) of the inorganic reinforcing material (B), and the inorganic reinforcing material (B)
- T (A) the true density of the polyamide powder
- T (B) the true density of the inorganic reinforcing material
- B the inorganic reinforcing material
- the coarse filling rate of the powder composition of the present invention is preferably 0.40 or more and 0.70 or less.
- the coarse filling rate is less than 0.40, the voids between the powders are large, and when applied to three-dimensional modeling, melting and sintering do not proceed sufficiently, and voids are generated in the modeled object, and the modeled object may be damaged. It is not preferable because it becomes difficult to obtain. If the coarse packing rate is more than 0.70, the powder is excessively densely packed and is constrained to impair fluidity, which is not preferable.
- the lower limit of the coarse filling rate is more preferably 0.41 or more, still more preferably 0.42 or more, and particularly preferably 0.43 or more.
- the upper limit is more preferably 0.65 or less, more preferably 0.62 or less, and particularly preferably 0.60 or less.
- the bulk density of the powder composition indicates the mass per unit volume when the powder is filled in a container.
- the bulk density is obtained by measuring the powder composition according to Japanese Industrial Standards (JIS) JIS K 7365 (1999) "Method for Determining Apparent Density of Materials Pourable from a Specified Funnel".
- the true density T (A) of the polyamide powder (A) and the true density T (B) of the inorganic reinforcing material (B) can use literature values, for example, polyamide 6 is 1.1 g / cm 3 , 1.0 g/cm 3 for polyamide 12, 1.1 g/cm 3 for polyamide 1010, 1.1 g/cm 3 for polyamide 66, 1.0 g/cm 3 for polyamide 11, 2.6 g/cm 3 for glass fiber 3 , 2.5 g/cm 3 for glass beads, and 1.8 g/cm 3 for carbon fibers.
- a method for increasing the coarse filling rate a method using an inorganic reinforcing material with excellent filling properties and a short fiber length, a method using a flow aid having a particle size of 100 nm to 300 nm with an appropriate dispersing force, a method using a true sphere
- a method using a polyamide powder having a high degree of 80 or more a method using a high melting point polyamide powder having many amide bonds, or a combination thereof.
- the powder composition of the present invention is a material useful for manufacturing three-dimensional objects by the powder bed fusion method. A method for manufacturing a three-dimensional structure will be described below with reference to FIG.
- the stage 2 of the bath 1 that forms the modeled object is lowered.
- a stage 4 of a tank 3 filled in advance with a powder composition P to be supplied to the tank 1 for forming a model (hereinafter sometimes referred to as a supply tank) is formed in the tank 1.
- a sufficient amount of the powder composition P to fill the stack height of is raised by a height that can be supplied.
- the recoater 5 is moved from the left end of the supply tank 3 to the right end of the tank 1 to stack the powder composition P in the tank 1 .
- the direction parallel to the movement of the recoater 5 is the X direction
- the direction perpendicular to the movement direction of the recoater 5 on the powder surface of the powder composition P is the Y direction.
- Reference numeral 7 indicates a coordinate system representing the X, Y and Z directions.
- Reference numeral 8 indicates the plane direction in which the powder composition is laminated
- reference numeral 9 indicates the height direction in which the powder composition is laminated.
- the powder composition P filled in the tank 1 for a predetermined stacking height in the step (b) is given heat energy 6 capable of being melted, and selectively melted and sintered according to the modeling data.
- the three-dimensional structure 10 is obtained by repeating the above steps (a) to (c).
- a method of selectively melting and sintering in the step (c) for example, a selective laser sintering method in which the powder composition is bonded by irradiating a laser to a shape corresponding to the cross-sectional shape of the modeled object. be done.
- a printing process of printing an energy absorption accelerator or an energy absorption inhibitor in a shape corresponding to the cross-sectional shape of a molding object, and a selective absorption (or suppression) sintering method of bonding resin powder using electromagnetic radiation. is also mentioned.
- the laser beam used in the selective laser sintering method is not particularly limited as long as it does not impair the quality of the powder composition or the modeled object.
- a carbon dioxide laser, a YAG laser, an excimer laser, a He--Cd laser, a semiconductor excitation solid-state laser, and the like can be used.
- the carbon dioxide laser is preferred because it is easy to operate and easy to control.
- Any electromagnetic radiation used for selective absorption (suppression) sintering may be used as long as it does not impair the quality of the powder composition or the shaped article. Infrared is preferred because it provides more energy. Also, the electromagnetic radiation may or may not be coherent.
- An energy absorption accelerator is a substance that absorbs electromagnetic radiation.
- Such materials include carbon black, carbon fiber, copper hydroxyphosphate, near-infrared absorbing dyes, near-infrared absorbing pigments, metal nanoparticles, polythiophenes, poly(p-phenylene sulfide), polyaniline, poly(pyrrole), Polyacetylene, poly(p-phenylenevinylene), polyparaphenylene, poly(styrenesulfonate), poly(3,4-ethylenedioxythiophene)-poly(styrenephosphonate) p-diethylaminobenzaldehyde diphenylhydrazone, or combinations thereof Conjugated polymers and the like can be exemplified, and these may be used singly or in combination.
- An energy absorption inhibitor is a substance that does not easily absorb electromagnetic radiation.
- examples of such substances include substances that reflect electromagnetic radiation such as titanium, heat insulating powders such as mica powder and ceramic powder, and water. These substances may be used singly or in combination.
- a known technique such as inkjet can be used in the step of printing the selective absorber or selective suppressor in a shape corresponding to the cross-sectional shape of the object to be molded.
- the selective absorbent and selective inhibitor may be used as they are, or may be used after being dispersed or dissolved in a solvent.
- the three-dimensional model of the present invention can be obtained by shaping the powder composition of the present invention by the powder bed fusion bonding method.
- the three-dimensional structure of the present invention will be described below.
- the surface roughness of the three-dimensional structure of the present invention is 20 ⁇ m or less.
- the lower limit is not particularly limited, and a small one is preferable, but the lower limit is usually 1 ⁇ m.
- the surface roughness of the modeled object is determined by observing the surface of the modeled object with an optical microscope, creating a three-dimensional image of the irregularities on the surface of the modeled object in automatic synthesis mode, and then obtaining a cross-sectional height profile over a length of 1 mm or more. and the surface roughness Ra is calculated by arithmetic mean.
- the X-direction elastic modulus of the three-dimensional structure of the present invention is 3500 MPa or more.
- the upper limit is not particularly limited, but generally, if the elastic modulus becomes too large, it tends to be brittle and the strength tends to be low. .
- the X-direction elastic modulus is the bending test piece that is formed with the longest side facing the X direction in the three-dimensional modeling. It is a flexural modulus measured according to ".
- the X-direction bending strength of the three-dimensional structure of the present invention is preferably 65 MPa or more.
- the strength anisotropy of the three-dimensional structure of the present invention can be evaluated by Z-direction bending strength/X-direction bending strength.
- the bending strength in the X direction and the bending strength in the Z direction are measured in accordance with Japanese Industrial Standards (JIS) JIS K7171 (2016) "Plastics - How to determine bending properties" with the above-mentioned X direction facing the longest side. It is the value of the maximum bending stress measured for each of the shaped bending test piece and the bending test piece shaped with the longest side in the Z direction.
- JIS Japanese Industrial Standards
- the deflection temperature under load of the three-dimensional structure of the present invention is preferably 150°C or higher. The higher the deflection temperature under load, the more difficult it is for the modeled article to deform in a high-temperature environment.
- the deflection temperature under load is a value measured under a load of 0.45 MPa in accordance with Japanese Industrial Standards (JIS) JIS K7191-1 (2015) "Plastics - Determination of deflection temperature under load”.
- the powder-filled state is melted and sintered under normal pressure to create a modeled object, so it usually involves a change in density due to shrinkage. Therefore, in order to obtain the dimensions of the three-dimensional modeled object with high accuracy with respect to desired modeling data, it is preferable to have an appropriate number of holes inside.
- the ratio and shape of the pores present in the three-dimensional structure of the present invention can be observed by X-ray CT.
- the three-dimensional structure of the present invention is imaged by X-ray CT, and the ratio of the portions observed as voids to the volume of the entire structure can be expressed as the porosity.
- the porosity observed by X-ray CT measurement of the three-dimensional structure of the present invention is preferably 0.1% by volume or more and 10% by volume or less.
- the lower limit of the porosity is more preferably 0.2% by volume or more, more preferably 0.3% by volume or more, further preferably 0.5%, because if the lower limit of the porosity is too small, the entire model shrinks against the modeling data. Volume % or more is particularly preferred.
- the upper limit thereof is more preferably 5.0% by volume or less, still more preferably 4.0% by volume or less, and particularly preferably 3.0% by volume or less, because a large number of pores cause a decrease in strength.
- the size of each independent hole observed as a hole by imaging the three-dimensional structure of the present invention by X-ray CT can be expressed as a sphere-equivalent diameter.
- the three-dimensional structure of the present invention is characterized in that the average spherical equivalent diameter of pores observed by X-ray CT measurement is 1 ⁇ m or more and 100 ⁇ m or less.
- the average spherical equivalent diameter of the pores is usually designed to be less than 1 ⁇ m. Since the average equivalent spherical diameter of the pores is more than 100 ⁇ m, it is a feature of the three-dimensional structure that the average equivalent spherical diameter is 1 ⁇ m or more and 100 ⁇ m or less.
- the lower limit is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
- the upper limit is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 50 ⁇ m or less, because large pores become a defect and cause a reduction in the strength of the molded product.
- three-dimensional molded objects are obtained by crystallization under normal pressure and in a process of lowering the temperature at a lower speed than in ordinary melt molding, so the crystal state is different from ordinary melt molding.
- the manufacturing method which is obtained by three-dimensional modeling, preferably by the powder bed fusion bonding method. It is well known that in the case of ordinary melt molding, it is possible to obtain a molded product with a smooth surface and a molded product with a large elastic modulus depending on the structure of the mold. In shaping, it is impossible to obtain a molded product with a smooth surface and a large elastic modulus, which has been made possible for the first time by the present invention.
- the three-dimensional structure of the present invention achieves both surface smoothness and a high elastic modulus, exhibits excellent adhesion at joints between structures, and exhibits good airtightness.
- the three-dimensional structure obtained using the powder composition of the present invention is suitable for automobile parts requiring high heat resistance and elastic modulus, especially automobile engine peripheral parts, automobile underhood parts, automobile gear parts, automobile interior parts, and automobiles. It can be effectively used for exterior parts, intake/exhaust system parts, engine cooling water system parts, and automotive electrical parts, and can obtain a three-dimensional molded object with an optimally designed complex shape.
- D50 particle size of polyamide powder A dispersion prepared by previously dispersing about 100 mg of polyamide powder in about 5 mL of deionized water was measured using a laser diffraction particle size distribution measuring device (Microtrac MT3300EXII) manufactured by Nikkiso Co., Ltd. After adding until the concentration becomes possible and performing ultrasonic dispersion for 60 seconds at 30 W in a measuring device, the cumulative frequency from the small particle size side of the particle size distribution measured at a measurement time of 10 seconds is 50%. The particle size was defined as the D50 particle size.
- the refractive index at the time of measurement was 1.52, and the refractive index of the medium (deionized water) was 1.333.
- JIS Japanese Industrial Standards
- JISR1626 (1996) "Method for measuring specific surface area by gas adsorption BET method", using BELSORP-max manufactured by Bell Japan, about 0.2 g of polyamide powder in a glass cell After degassing under reduced pressure at 80° C. for about 5 hours, the krypton gas adsorption isotherm at liquid nitrogen temperature was measured and calculated by the BET method.
- the inorganic reinforcing material is accelerated with a scanning electron microscope (Regulus 8220) manufactured by Hitachi High-Technologies Corporation and an energy dispersive X-ray analyzer manufactured by BRUKER (“XFlash” (registered trademark) 5060 FlatQUAD). The image was taken under the conditions of a voltage of 5 kV and a measurement time of 180 seconds. From the obtained spectral data, the 1.49 keV peak is attributed to the aluminum element and the 1.74 keV peak to the silicon element, and when a peak of 1 cps/eV or more is detected, it is considered to contain the element Judged.
- D50 Particle Size of Flow Aid A sample obtained by dispersing the flow aid in deionized water or ethanol at a concentration of 0.1% by weight was measured with a zeta potential/particle size analyzer (ELSZ- Measured by the dynamic light scattering method in 2), the particle size at which the cumulative frequency from the small particle size side of the particle size distribution is 50% was defined as the D50 particle size.
- the bulk density of the powder composition is measured according to Japanese Industrial Standards (JIS) JIS Z 7365 ( 1999). It was dropped, the volume was read, and the weight of the powder composition was divided by the volume.
- JIS Japanese Industrial Standards
- the true density T (B) of the inorganic reinforcing material (B) the content X (B) of the inorganic reinforcing material (B)
- the bulk density D of the powder composition Then, the rough filling rate D/ ⁇ T(A) ⁇ (100 ⁇ X(B))/100+T(B) ⁇ X(B)/100 ⁇ was calculated.
- the true density is 1.1 g/cm 3 for polyamide 6, 1.0 g/cm 3 for polyamide 12, 1.1 g/cm 3 for polyamide 1010, 1.1 g/cm 3 for polyamide 66, and 1.1 g/cm 3 for polyamide 11. 0 g/cm 3 , 2.6 g/cm 3 for glass fibers, 2.5 g/cm 3 for glass beads, and 1.8 g/cm 3 for carbon fibers.
- Deflection temperature under load of the modeled object was measured using a 3D printer (RaFaElII 150C-HT) manufactured by Aspect Co., Ltd. with a width of 10 mm, a length of 80 mm, and a thickness of 4 mm.
- MIX ratio of recycled modeling Collect the used powder remaining in the modeling room after modeling using a powder bed fusion method 3D printer (RaFaElII 150C-HT) manufactured by Aspect Co., Ltd. After mixing with the used powder, three-dimensional modeling was performed again. When the surface roughness, flexural modulus, and flexural strength of the modeled product obtained here changed by 10% or less compared to the case where the modeled product was made only with virgin powder, it was marked as " ⁇ " for recycled modeling. . The mixing ratio of the used powder when the recycled modeling was "O" was defined as the MIX ratio.
- the pressure of the system reached 10 kg/cm 2
- the pressure was controlled while slightly releasing the steam so as to maintain the pressure at 10 kg/cm 2 .
- the pressure was released at a rate of 0.2 kg/cm 2 ⁇ min.
- the temperature was maintained for 1 hour while flowing nitrogen to complete the polymerization, and the mixture of polyamide powder and polyethylene glycol was discharged into a 2000 g water bath while the polyethylene glycol was kept in a molten state to obtain a slurry. After sufficiently homogenizing the slurry by stirring, it was filtered, and 2,000 g of water was added to the filter cake and washed at 80°C.
- Polyamide 12 powder was prepared in the same manner as in Production Example 1, except that aminododecanoic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the polyamide monomer and the polymerization temperature was changed to 210°C.
- the obtained polyamide powder had a D50 particle size of 55 ⁇ m and a sphericity of 97.
- Polyamide 11 powder was prepared in the same manner as in Production Example 1, except that aminoundecanoic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the polyamide monomer and the polymerization temperature was changed to 210°C.
- the obtained polyamide powder had a D50 particle size of 51 ⁇ m and a sphericity of 92.
- Example 1 1050 g of polyamide 6 powder of Production Example 1 as polyamide powder (A) and glass fiber EPG40M-10A (manufactured by Nippon Electric Glass Co., Ltd., average major axis diameter 43 ⁇ m, average minor axis diameter 10 ⁇ m) as inorganic reinforcing material (B) 450 g Mixed. Furthermore, 4.5 g of trimethylsilylated amorphous silica X-24-9500 (manufactured by Shin-Etsu Chemical Co., Ltd., D50 particle size: 170 nm) was added as a flow aid (C) to prepare a powder composition.
- a three-dimensional model was produced using a powder bed fusion bonding apparatus (RaFaElII 150C-HT) manufactured by Aspect Co., Ltd.
- the setting conditions were 60 WCO 2 laser, lamination height of 0.1 mm, laser scanning interval of 0.1 mm, laser scanning speed of 5 m/s, and laser output of 12 W.
- Temperature settings were such that the part bed temperature was ⁇ 15° C. below the melting point, and the supply tank temperature was ⁇ 5° C. from the crystallization temperature.
- the three-dimensional structure obtained had a good appearance, with a surface roughness of 9 ⁇ m, an X-direction elastic modulus of 5600 MPa, an X-direction bending strength of 151 MPa, a Z-direction bending strength of 115 MPa, a deflection temperature under load of 217° C., and a void in X-ray CT.
- the ratio was 1.2% by volume, and the sphere-equivalent diameter of the pores was 34 ⁇ m.
- the MIX ratio was 70%. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 2 A three-dimensional model was produced in the same manner as in Example 1 except that 750 g of the polyamide 12 powder of Production Example 2 was used as the polyamide powder (A) and 750 g of the glass fiber EPG40M-10A was used as the inorganic reinforcing material (B). and recycling properties were evaluated. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 3 1200 g of polyamide powder (A), glass fiber EPG70M-01N (manufactured by Nippon Electric Glass Co., Ltd., average major axis diameter 73 ⁇ m, average minor axis diameter 10 ⁇ m) as inorganic reinforcing material (B) 300 g, flow aid (C) A three-dimensional structure was produced in the same manner as in Example 1, except that the composition was changed to 3.0 g, and the recycling characteristics were evaluated. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 4 900 g of polyamide powder (A), glass fiber EPH80M-10A (manufactured by Nippon Electric Glass Co., Ltd., average major axis diameter 88 ⁇ m, average minor axis diameter 11 ⁇ m) as inorganic reinforcing material (B) 600 g, flow aid (C) A three-dimensional structure was produced in the same manner as in Example 1, except that the composition was changed to 7.5 g, and the recycling characteristics were evaluated. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 5 900 g of polyamide powder (A), 120 g of glass fiber EPG40M-10A as an inorganic reinforcing material (B) and 480 g of glass beads GB731A (manufactured by Potters Barrotini, average major axis diameter 27 ⁇ m, average minor axis diameter 26 ⁇ m).
- a three-dimensional structure was produced in the same manner as in Example 1, except that the composition of the auxiliary agent (C) was changed to 1.5 g, and the recycling characteristics were evaluated.
- Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 6 1050 g of polyamide powder (A), 450 g of glass fiber EPG70M-01N as inorganic reinforcing material (B), and 4.5 g of fumed silica "AEROSIL (registered trademark)" R972 as flow aid (C).
- a three-dimensional structure was produced in the same manner as in Example 1, except that it was used, and the recycling characteristics were evaluated.
- Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 7 A three-dimensional structure was produced in the same manner as in Example 5, except that the polyamide powder (A) was changed to the polyamide 1010 powder of Production Example 3, and the recycling characteristics were evaluated. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 8 900 g of polyamide 66 powder of Production Example 4 as polyamide powder (A), 600 g of glass beads GB731 (manufactured by Potters Barrotini, average major axis diameter 31 ⁇ m, average minor axis diameter 31 ⁇ m) as inorganic reinforcing material (B), flow A three-dimensional structure was produced in the same manner as in Example 1, except that the amount of the auxiliary agent (C) was changed to 0.75 g, and the recycling characteristics were evaluated. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 9 Example 6 except that 750 g of the polyamide 6 powder of Production Example 1 was used as the polyamide powder (A), 750 g of the glass beads GB731A was used as the inorganic reinforcing material (B), and the amount of the flow aid (C) was changed to 1.5 g.
- a three-dimensional model was produced in the same manner as above, and the recycling characteristics were evaluated. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 10 A three-dimensional structure was produced in the same manner as in Example 6 except that the polyamide 6 powder of Production Example 1 was used as the polyamide powder (A) and the flow aid (C) was not blended, and the recycling characteristics were evaluated. .
- Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 11 A three-dimensional model was produced and recycled in the same manner as in Example 9 except that 1050 g of the polyamide 11 powder of Production Example 5 was used as the polyamide powder (A) and 450 g of the glass beads GB731 were used as the inorganic reinforcing material (B). properties were evaluated. Table 1 shows the characteristics of the obtained shaped article and the MIX ratio, which is the recycling characteristics.
- Example 12 A three-dimensional model was produced and recycled in the same manner as in Example 9 except that 900 g of the polyamide 12 powder of Production Example 6 was used as the polyamide powder (A) and 600 g of the glass beads GB731 were used as the inorganic reinforcing material (B). properties were evaluated. Table 1 shows the characteristics of the obtained shaped article and the MIX ratio, which is the recycling characteristics.
- Example 13 1125 g of polyamide powder (A), 375 g of carbon fiber Panex 35 (manufactured by Zoltek, average major axis diameter 80 ⁇ m, average minor axis diameter 7 ⁇ m) as inorganic reinforcing material (B), and 4.5 g of flow aid (C).
- a three-dimensional structure was produced in the same manner as in Example 1, except that the composition was changed, and the recycling characteristics were evaluated. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 1 Same as Example 1, except that 1500 g of the polyamide 1010 powder of Production Example 3 was used as the polyamide powder (A), the inorganic reinforcing material (B) was not blended, and the blending amount of the flow aid (C) was changed to 1.5 g. A three-dimensional structure was produced by the method of and the recycling characteristics were evaluated. The resulting shaped article was found to have a large amount of warpage. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 3 A three-dimensional model was produced and recycled in the same manner as in Example 9 except that the pulverized polyamide 6 powder of Comparative Example 2 was used as the polyamide powder (A) and the glass beads GB731 were used as the inorganic reinforcing material (B). properties were evaluated.
- the resulting molded product had a surface roughness of 31 ⁇ m and was insufficient in surface smoothness.
- Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 4 A three-dimensional structure was produced in the same manner as in Example 9, except that the blending composition was changed to 1450 g of the polyamide powder (A) and 45 g of the inorganic reinforcing material (B), and the recycling characteristics were evaluated.
- the resulting model had an X-direction elastic modulus of 3200 MPa, which was insufficient.
- Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- Example 5 As an inorganic reinforcing material (B), chopped strand T-275H (manufactured by Nippon Electric Glass Co., Ltd., average major axis diameter 3000 ⁇ m, average minor axis diameter 10 ⁇ m) was crushed with a pestle in a mortar to give an average major axis diameter of 420 ⁇ m. A three-dimensional structure was produced in the same manner as in Example 5, except that it was used. When this powder was repeatedly used for recycling, the glass fibers aggregated and did not flow, and could not be used for molding. Table 1 shows the powders used, the properties of the resulting shaped article, and the MIX ratio, which is a recycling property.
- GF in the reinforcing material types in Table 1 indicates glass fiber
- GB indicates glass beads
- CF indicates carbon fiber
- the molded article obtained using the powder composition of the present invention has excellent surface smoothness and high elastic modulus, and the powder used for molding can be recycled at a high rate, so it can be used for three-dimensional applications such as industrial applications. It can be effectively used as a powder raw material for a modeled object. In particular, since it has a high elastic modulus of 3500 MPa or more, it can be used as a structural member.
- vat 2 forming object 2 stage of vat forming object 3 feed vat 4 pre-filled with powder composition to be fed stage 5 vat pre-filled with powder composition to be fed recoater 6 thermal energy 7 X , Y, Z coordinate system 8 Surface direction for stacking the powder composition 9 Height direction for stacking the powder composition 10 Three-dimensional model P Powder composition
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Abstract
Description
すなわち、本発明の粉末組成物は、ポリアミド粉末(A)と無機強化材(B)を含む粉末組成物であって、前記ポリアミド粉末(A)のD50粒子径が1μm以上100μm以下、かつ真球度が80以上100以下であり、前記無機強化材(B)の平均長軸径が3μm以上300μm以下、かつ平均長軸径/平均短軸径が1以上15以下であり、粉末組成物の総重量に対して前記無機強化材(B)が5重量%以上60重量%以下含まれることを特徴とするものである。
従来、三次元造形物の弾性率は原料である粉末組成物に含まれる強化材の配合量や形状に依存し、高い弾性率の造形物が得られる組成とするためには多量の強化材を配合する必要があり、粉末組成物の流動性は低下するため、造形物の表面粗度は増大し、表面平滑性と弾性率を両立することはできなかった。さらには強化材の凝集などによってリサイクル使用が困難となる課題があった。
本発明における粉末組成物は、アミド基を含む構造のポリアミドから構成されるポリアミド粉末を含む。かかるポリアミドの具体的な例としては、ポリカプロアミド(ポリアミド6)、ポリウンデカアミド(ポリアミド11)、ポリラウロアミド(ポリアミド12)、ポリヘキサメチレンアジパミド(ポリアミド66)、ポリデカメチレンセバカミド(ポリアミド1010)、ポリドデカメチレンセバカミド(ポリアミド1012)、ポリドデカメチレンドデカミド(ポリアミド1212)、ポリヘキサメチレンセバカミド(ポリアミド610)、ポリヘキサメチレンドデカミド(ポリアミド612)、ポリデカメチレンアジパミド(ポリアミド106)、ポリドデカメチレンアジパミド(ポリアミド126)、ポリヘキサメチレンテレフタルアミド(ポリアミド6T)、ポリデカメチレンテレフタルアミド(ポリアミド10T)、ポリドデカメチレンテレフタルアミド(ポリアミド12T)、ポリカプロアミド/ポリヘキサメチレンアジパミド共重合体(ポリアミド6/66)、ポリカプロアミド/ポリラウロアミド共重合体(ポリアミド6/12)などが挙げられる。中でも、真球形状に制御し易い点から好ましくは、ポリカプロアミド(ポリアミド6)、ポリウンデカアミド(ポリアミド11)、ポリラウロアミド(ポリアミド12)、ポリヘキサメチレンアジパミド(ポリアミド66)、ポリデカメチレンセバカミド(ポリアミド1010)、ポリドデカメチレンセバカミド(ポリアミド1012)、ポリドデカメチレンドデカミド(ポリアミド1212)、ポリヘキサメチレンセバカミド(ポリアミド610)、ポリヘキサメチレンドデカミド(ポリアミド612)などが挙げられる。また、造形に適した熱特性である点から、ポリカプロアミド(ポリアミド6)、ポリウンデカアミド(ポリアミド11)、ポリラウロアミド(ポリアミド12)、ポリヘキサメチレンアジパミド(ポリアミド66)、ポリヘキサメチレンセバカミド(ポリアミド610)、ポリデカメチレンセバカミド(ポリアミド1010)、ポリドデカメチレンセバカミド(ポリアミド1012)が特に好ましい。この中でも、造形時の耐熱性の点では、ポリカプロアミド(ポリアミド6)、ポリヘキサメチレンアジパミド(ポリアミド66)、ポリヘキサメチレンセバカミド(ポリアミド610)が著しく好ましい。
日機装株式会社製レーザー回折式粒径分布計測定装置(マイクロトラックMT3300EXII)に、予め100mg程度のポリアミド粉末を5mL程度の脱イオン水で分散させた分散液を測定可能濃度になるまで添加し、測定装置内で30Wにて60秒間の超音波分散を行った後、測定時間10秒で測定される粒径分布の小粒径側からの累積度数が50%となる粒径をD50粒子径とした。なお測定時の屈折率は1.52、媒体(脱イオン水)の屈折率は1.333を用いた。
ポリアミド粉末の真球度は、日本電子株式会社製走査型電子顕微鏡(JSM-6301NF)写真から無作為に30個の粒子を観察し、その短径と長径から下記数式に従い算出した。
日本工業規格(JIS規格)JISR1626(1996)「気体吸着BET法による比表面積の測定方法」に従い、日本ベル製BELSORP-maxを用いて、ポリアミド粉末約0.2gをガラスセルに入れ、80℃で約5時間減圧脱気した後に、液体窒素温度におけるクリプトンガス吸着等温線を測定し、BET法により算出した。
無機強化材を日本電子株式会社製走査型電子顕微鏡(JSM-6301NF)で観察し、その写真から無作為に選んだ100個の無機強化材の長径および短径の平均値を平均長軸径、平均短軸径とした。
無機強化材を株式会社日立ハイテクノロジーズ製走査型電子顕微鏡(Regulus8220)及びBRUKER社製エネルギー分散型X線分析装置(“XFlash”(登録商標)5060FlatQUAD)にて加速電圧5kV、測定時間180秒の条件で撮像した。得られたスペクトルデータから、1.49keVのピークをアルミニウム元素、1.74keVのピークをケイ素元素と帰属し、1cps/eV以上のピークが検出されている場合に当該元素を含有しているものと判定した。
流動助剤を脱イオン水またはエタノール中に0.1重量%の濃度で分散させたサンプルを、大塚電子株式会社製ゼータ電位・粒径測定装置(ELSZ-2)の動的光散乱法にて測定し、粒径分布の小粒径側からの累積度数が50%となる粒径をD50粒子径とした。
粉末組成物の嵩密度は、日本工業規格(JIS規格)JIS Z 7365(1999)に従い、50gのポリマー粉末をロートから100cm3のメスシリンダーに落下させ、体積を読み取り、粉末組成物の重量を当該体積で除した値とした。ポリアミド粉末(A)の真密度T(A)、無機強化材(B)の真密度T(B)、無機強化材(B)の含有量X(B)、粉末組成物の嵩密度Dとしたとき、粗充填率D/{T(A)×(100-X(B))/100+T(B)×X(B)/100}を算出した。なお真密度は、ポリアミド6は1.1g/cm3、ポリアミド12は1.0g/cm3、ポリアミド1010は1.1g/cm3、ポリアミド66は1.1g/cm3、ポリアミド11は1.0g/cm3、ガラス繊維は2.6g/cm3、ガラスビーズは2.5g/cm3、炭素繊維は1.8g/cm3の数値を用いた。
得られた三次元造形物に、1mm以上の欠損部や斑点がないものを「◎」、1mm以上の欠損部はないが一部斑点があるものを「〇」、1mm以上の欠損部があるものを「△」とした。ランク「◎」、「〇」を合格とした。
得られた試験片を水平な場所に、上に凸な状態で静置し、水平面と試験片の隙間に精密テーパーゲージを挿入し、隙間の高さを計測し、試験片長さ10cm当たりに換算した値を反り量として算出して、以下の基準で反り量を評価した。
〇:反り量が0.1mm/10cm以下。
△:反り量が0.1mm/10cmより大きく、0.3mm/10cm以下。
×:反り量が0.3mm/10cmより大きい。
ランク「〇」、「△」を合格とした。
株式会社キーエンス製光学顕微鏡(VHX-5000)、対物レンズはVH-ZST(ZS-20)を使用し、倍率200倍で造形物の表面を観察した。装置に付属のソフトウェア(システムバージョン1.04)を用い自動合成モードで造形物表面の凹凸を三次元画像化したのち、1mm以上長さにわたって断面の高さプロファイルを取得し、算術平均によって表面粗度Raを計算した。表面粗度Raが小さいほど、表面の平滑性に優れることを示している。
三次元造形物の曲げ弾性率、曲げ強度は、株式会社アスペクト製粉末床溶融結合方式3Dプリンター(RaFaElII 150C-HT)を使用して幅10mm、長さ80mm、厚さ4mmの試験片を、80mmの長さ方向がX方向、またはZ方向となるように作製し、エー・アンド・デイ社製テンシロン万能試験機(TENSIRON TRG-1250)を用いてX方向、およびZ方向の曲げ弾性率、曲げ強度をそれぞれ測定した。JIS K7171(2016)に従い、支点間距離64mm、試験速度2mm/分の条件で3点曲げ試験を測定して曲げ弾性率を求めた。また曲げ強度は最大曲げ応力とした。測定温度は室温(23℃)、測定数はn=5とし、その平均値を求めた。
三次元造形物の荷重たわみ温度は株式会社アスペクト製粉末床溶融結合方式3Dプリンター(RaFaElII 150C-HT)を使用して幅10mm、長さ80mm、厚さ4mmの試験片を、80mmの長さ方向がX方向となるように作製し、株式会社安田精機製作所製ヒートディストーションテスター(No.148)を用い、JIS K7191-1(2015)に従い、0.45MPaの荷重にて測定した。測定数はn=3とし、その平均値を求めた。
ZEISS社製X線CT装置(Xradia 510 Versa)を使用し、分解能5μm、視野5mm、電圧80kV、電力7Wにて三次元透過画像観察を行った。観察画像の空孔部をラベリング処理し、各独立した空孔を球とした場合のその直径である球相当径を算出し、その平均値を空孔の平均球相当径として求めた。また前述のラベリング処理した空孔部の体積に対し、観察画像中の造形物に当たる部分で、空孔部を埋めた全体積で除した値に100をかけ、空孔率として求めた。
株式会社アスペクト製粉末床溶融結合方式3Dプリンター(RaFaElII 150C-HT)を使用して造形した後の造形室に残った使用済粉末を回収し、一定の比率で未使用粉末と混合後、再度三次元造形を行った。ここで得られた造形物の表面粗度、曲げ弾性率、曲げ強度が、未使用粉末のみで造形した場合と比較して、変化が10%以下となったとき、リサイクル造形「〇」とした。リサイクル造形が「〇」となったときの使用済粉末の混合割合をMIX比とした。
3Lのヘリカルリボン型の撹拌翼が付属したオートクレーブに、ポリアミドの単量体としてε-カプロラクタム(富士フィルム和光純薬株式会社製)300g、ポリアミドとは非相溶のポリマーとしてポリエチレングリコール(富士フィルム和光純薬株式会社製1級ポリエチレングリコール20,000、重量平均分子量18,600)700g、水1000gを加え均一な溶液を形成後に密封し、窒素で置換した。その後、撹拌速度を40rpmに設定し、温度を210℃まで昇温させた。この際、系の圧力が10kg/cm2に達した後、圧が10kg/cm2を維持するよう水蒸気を微放圧させながら制御した。温度が210℃に達した後に、0.2kg/cm2・分の速度で放圧させた。その後、窒素を流しながら1時間温度を維持し重合を完了させ、ポリアミド粉末とポリエチレングリコールの混合物から、ポリエチレングリコールが溶融状態を維持したまま、2000gの水浴に吐出しスラリーを得た。スラリーを撹拌により十分に均質化させた後に、ろ過を行い、ろ上物に水2000gを加え、80℃で洗浄を行った。その後100μmの篩を通過させた凝集物を除いたスラリー液を、再度ろ過して単離したろ上物を80℃で12時間乾燥させ、ポリアミド6粉末を170g作製した。得られたポリアミド粉末のD50粒子径は51μm、D90/D10は2.5、真球度は95、BET比表面積は0.16m2/gでR=1.3であった。
ポリアミドの単量体としてε-カプロラクタムをアミノドデカン酸(富士フィルム和光純薬株式会社製)、重合温度を210℃に変更した以外は製造例1と同様の方法でポリアミド12粉末を作製した。得られたポリアミド粉末のD50粒子径は55μm、真球度は97であった。
ポリアミドの単量体としてε-カプロラクタムをセバシン酸162g(東京化成工業株式会社製)、ジアミノデカン138g(東京化成工業株式会社製)、重合温度を210℃に変更した以外は製造例1と同様の方法でポリアミド1010粉末を作製した。得られたポリアミド粉末のD50粒子径は49μm、真球度は93であった。
ポリアミドの単量体としてε-カプロラクタムをアジピン酸170g(東京化成工業株式会社製)、ヘキサメチレンジアミン50%水溶液260g(東京化成工業株式会社製)、重合温度を230℃に変更した以外は製造例1と同様の方法でポリアミド66粉末を作製した。得られたポリアミド粉末のD50粒子径は49μm、真球度は91であった。
ポリアミドの単量体としてε-カプロラクタムをアミノウンデカン酸(富士フィルム和光純薬株式会社製)、重合温度を210℃に変更した以外は製造例1と同様の方法でポリアミド11粉末を作製した。得られたポリアミド粉末のD50粒子径は51μm、真球度は92であった。
ポリアミドの単量体としてε-カプロラクタムをω-ラウリンラクタム600g(東京化成工業株式会社製)、ポリエチレングリコールを400g、水80gとし、初期昇温温度を280℃に変更した以外は製造例1と同様の方法でポリアミド12粉末を作製した。得られたポリアミド粉末のD50粒子径は53μm、真球度は91であった。
ポリアミド粉末(A)として製造例1のポリアミド6粉末1050gと、無機強化材(B)としてガラス繊維EPG40M-10A(日本電気硝子株式会社製、平均長軸径43μm、平均短軸径10μm)450gを混合した。さらに流動助剤(C)としてトリメチルシリル化非晶質シリカX-24-9500(信越化学工業株式会社製、D50粒子径170nm)を4.5g添加し、粉末組成物とした。本粉末組成物1.5kgを用いて、株式会社アスペクト製粉末床溶融結合装置(RaFaElII 150C-HT)を使用し、立体造形物の製造を行った。設定条件は、60WCO2レーザーを使用し、積層高さ0.1mm、レーザー走査間隔を0.1mm、レーザー走査速度を5m/s、レーザー出力を12Wとした。温度設定は、部品床温度を融点より-15℃、供給槽温度を結晶化温度-5℃とした。得られた三次元造形物の外観は良好で、表面粗度は9μm、X方向弾性率は5600MPa、X方向曲げ強度151MPa、Z方向曲げ強度115MPa、荷重たわみ温度217℃、X線CTにおける空孔率1.2体積%、空孔の球相当径34μmであった。さらに、使用済粉末を回収し、未使用粉末と混合してリサイクル造形のMIX比について評価したところ、MIX比は70%であった。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例2のポリアミド12粉末を750g、無機強化材(B)としてガラス繊維EPG40M-10Aを750gに変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)を1200g、無機強化材(B)としてガラス繊維EPG70M-01N(日本電気硝子株式会社製、平均長軸径73μm、平均短軸径10μm)を300g、流動助剤(C)を3.0gに配合組成を変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)を900g、無機強化材(B)としてガラス繊維EPH80M-10A(日本電気硝子株式会社製、平均長軸径88μm、平均短軸径11μm)を600g、流動助剤(C)を7.5gに配合組成を変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)を900g、無機強化材(B)としてガラス繊維EPG40M-10Aを120gとガラスビーズGB731A(ポッターズバロティーニ社製、平均長軸径27μm、平均短軸径26μm)を480g、流動助剤(C)を1.5gに配合組成を変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)を1050g、無機強化材(B)としてガラス繊維EPG70M-01Nを450g、流動助剤(C)としてフュームドシリカ“AEROSIL(登録商標)”R972を4.5gに配合組成を変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例3のポリアミド1010粉末に変更した以外は実施例5と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例4のポリアミド66粉末を900g、無機強化材(B)としてガラスビーズGB731(ポッターズバロティーニ社製、平均長軸径31μm、平均短軸径31μm)を600g、流動助剤(C)の配合量を0.75gに変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例1のポリアミド6粉末を750g、無機強化材(B)としてガラスビーズGB731Aを750g、流動助剤(C)の配合量を1.5gに変更した以外は実施例6と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例1のポリアミド6粉末とし、流動助剤(C)を配合しなかったこと以外は実施例6と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例5のポリアミド11粉末を1050g、無機強化材(B)としてガラスビーズGB731を450gに変更した以外は実施例9と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例6のポリアミド12粉末を900g、無機強化材(B)としてガラスビーズGB731を600gに変更した以外は実施例9と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)を1125g、無機強化材(B)として炭素繊維Panex35(Zoltek社製、平均長軸径80μm、平均短軸径7μm)を375g、流動助剤(C)を4.5gに配合組成を変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)として製造例3のポリアミド1010粉末を1500g、無機強化材(B)は配合せず、流動助剤(C)の配合量を1.5gに変更した以外は実施例1と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。得られた造形物は反りが大きく見られた。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
東レ株式会社製ポリアミド“アミラン(登録商標)”CM1007をジェットミル(ホソカワミクロン製100AFG)で120分間粉砕し、D50粒子径50μm、真球度60の粉砕ポリアミド6粉末を得た。ポリアミド粉末(A)をこの粉砕ポリアミド6粉末に変更した以外は実施例6と同様の方法で三次元造形物を作製、およびリサイクル特性を評価しようとした。しかし、使用した粉末組成物は流動性が悪く、また造形時に焼結が阻害され、造形物を得ることができなかった。
ポリアミド粉末(A)として比較例2の粉砕ポリアミド6粉末を使用し、無機強化材(B)としてガラスビーズGB731に変更した以外は実施例9と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。得られた造形物は表面粗度31μmで表面平滑性が不十分であった。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
ポリアミド粉末(A)を1450g、無機強化材(B)を45gに配合組成を変更した以外は実施例9と同様の方法で三次元造形物を作製、およびリサイクル特性を評価した。得られた造形物はX方向弾性率3200MPaで弾性率が不十分であった。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
無機強化材(B)としてチョップドストランドT-275H(日本電気硝子株式会社製、平均長軸径3000μm、平均短軸径10μm)を乳鉢中で乳棒によって破砕し、平均長軸径420μmとしたものを使用した以外は実施例5と同様の方法で三次元造形物を作製した。この粉末を繰り返しリサイクルに使用したところ、ガラス繊維が凝集して流動せず、造形に使用できなかった。使用した粉末、得られた造形物の特性、およびリサイクル特性であるMIX比を表1に示す。
2 造形物を形成する槽のステージ
3 供給する粉末組成物を事前に充填する供給槽
4 供給する粉末組成物を事前に充填する槽のステージ
5 リコーター
6 熱エネルギー
7 X、Y、Z座標系
8 粉末組成物を積層する面方向
9 粉末組成物を積層する高さ方向
10 三次元造形物
P 粉末組成物
Claims (12)
- ポリアミド粉末(A)と無機強化材(B)を含む粉末組成物であって、前記ポリアミド粉末(A)のD50粒子径が1μm以上100μm以下、かつ真球度が80以上100以下であり、前記無機強化材(B)の平均長軸径が3μm以上300μm以下、かつ平均長軸径/平均短軸径が1以上15以下であり、粉末組成物の総重量に対して前記無機強化材(B)が5重量%以上60重量%以下含まれることを特徴とする粉末組成物。
- 前記粉末組成物が、流動助剤(C)を、粉末組成物の総重量に対して0.01重量%以上2.0重量%以下含む、請求項1に記載の粉末組成物。
- 前記流動助剤(C)のD50粒子径が、10nm以上3000nm以下である、請求項2に記載の粉末組成物。
- 前記ポリアミド粉末(A)の真密度T(A)、無機強化材(B)の真密度T(B)、無機強化材(B)の含有量X(B)、粉末組成物の嵩密度Dとしたとき、粗充填率D/{T(A)×(100-X(B))/100+T(B)×X(B)/100}が0.40以上0.70以下である、請求項1~3のいずれかに記載の粉末組成物。
- 前記無機強化材(B)の構成元素にケイ素およびアルミニウムを含む、請求項1~4のいずれかに記載の粉末組成物。
- 前記無機強化材(B)の平均長軸径が10μm以上100μm以下である、請求項1~5のいずれかに記載の粉末組成物。
- 前記無機強化材(B)がガラス繊維またはガラスビーズである、請求項1~6のいずれかに記載の粉末組成物。
- 前記流動助剤(C)がシリカである、請求項2~7のいずれかに記載の粉末組成物。
- 請求項1~8のいずれかに記載の粉末組成物を用いて粉末床溶融結合方式によって三次元造形物を製造する方法。
- 得られる三次元造形物の表面粗度が20μm以下、X方向弾性率が3500MPa以上である、請求項9に記載の三次元造形物を製造する方法。
- 粉末床溶融結合方式によって得られる三次元造形物であって、表面粗度が20μm以下、X方向弾性率が3500MPa以上、かつX線CT測定によって観測される空孔の平均球相当径が1μm以上100μm以下である三次元造形物。
- X線CT測定によって観測される空孔が0.1体積%以上10体積%以下である、請求項11に記載の三次元造形物。
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JP2008266645A (ja) | 2007-04-20 | 2008-11-06 | Evonik Degussa Gmbh | 複合粉末、成形法における該粉末の使用および該粉末から製造される成形体 |
JP2018196983A (ja) * | 2016-07-22 | 2018-12-13 | 株式会社リコー | 立体造形用樹脂粉末、立体造形物の製造装置、及び立体造形物の製造方法 |
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JP2021053887A (ja) * | 2019-09-30 | 2021-04-08 | 東レ株式会社 | 粉末床溶融結合方式による3dプリンター用樹脂粉粒体およびその製造方法、および樹脂粉粒体を用いた三次元造形物の製造方法 |
WO2021090768A1 (ja) * | 2019-11-05 | 2021-05-14 | 東レ株式会社 | 3次元造形物を製造するためのポリマー粉末、ポリマー粉末を用いて粉末床溶融結合方式によって3次元造形物を製造する方法、および3次元造形物 |
JP2022015603A (ja) * | 2020-07-09 | 2022-01-21 | ダイキン工業株式会社 | 三次元造形物 |
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JP2008266645A (ja) | 2007-04-20 | 2008-11-06 | Evonik Degussa Gmbh | 複合粉末、成形法における該粉末の使用および該粉末から製造される成形体 |
JP2018196983A (ja) * | 2016-07-22 | 2018-12-13 | 株式会社リコー | 立体造形用樹脂粉末、立体造形物の製造装置、及び立体造形物の製造方法 |
JP2020536153A (ja) | 2017-10-04 | 2020-12-10 | アルケマ フランス | 熱可塑性粉末組成物及びそのような組成物の3d印刷により製造された強化三次元物体 |
JP2021053887A (ja) * | 2019-09-30 | 2021-04-08 | 東レ株式会社 | 粉末床溶融結合方式による3dプリンター用樹脂粉粒体およびその製造方法、および樹脂粉粒体を用いた三次元造形物の製造方法 |
WO2021090768A1 (ja) * | 2019-11-05 | 2021-05-14 | 東レ株式会社 | 3次元造形物を製造するためのポリマー粉末、ポリマー粉末を用いて粉末床溶融結合方式によって3次元造形物を製造する方法、および3次元造形物 |
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