CN116887973A - Method for producing three-dimensional molded article using resin powder, three-dimensional molded article, and resin powder - Google Patents
Method for producing three-dimensional molded article using resin powder, three-dimensional molded article, and resin powder Download PDFInfo
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- CN116887973A CN116887973A CN202280017187.9A CN202280017187A CN116887973A CN 116887973 A CN116887973 A CN 116887973A CN 202280017187 A CN202280017187 A CN 202280017187A CN 116887973 A CN116887973 A CN 116887973A
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- resin powder
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- molded article
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Abstract
The present invention provides a method for producing a three-dimensional molded article by a powder bed fusion method using a resin powder, wherein the resin powder comprises a resin powder (A) and a flow aid (B), the sphericity of the resin powder (A) is 80 to 100, the D80 particle diameter of the resin powder (A) is 60 [ mu ] m or less, the D20 particle diameter is 1 [ mu ] m or more, and the flow aid (B) is contained in an amount of more than 0.01 parts by mass and less than 5 parts by mass relative to 100 parts by mass of the resin powder (A), and the method is repeated in the order of the following steps (a) to (c): (a) Lowering a table for forming a groove of a three-dimensional modeling object by a range of 0.01mm or more and less than 0.10 mm; (b) Supplying resin powder to the groove for forming the three-dimensional modeling object, and laminating the resin powder; (c) The resin powder is selectively melt-sintered by applying heat energy thereto. In the three-dimensional molding, a molded article having a small surface roughness in the surface direction of the laminated resin powder and a small surface roughness in the height direction of the laminated resin powder can be obtained.
Description
Technical Field
The present invention relates to a method for producing a three-dimensional molded article using a resin powder or granule, a three-dimensional molded article obtained by the production method, and a resin powder or granule.
Background
As a technique for producing a three-dimensional shaped article (hereinafter, sometimes referred to as a shaped article), a powder bed fusion method is known. A molded article according to a powder bed fusion method is produced by sequentially repeating a thin layer forming step in which powder is spread into thin layers and a cross-sectional shape forming step in which the formed thin layers are selectively fused into a shape corresponding to the cross-sectional shape of a target molded article, thereby bonding resin powder particles. Here, as a method for selectively melting the powder, there are a selective laser sintering method using a laser, a selective absorption sintering method using a melting aid, a selective inhibition sintering method for masking a non-melted portion, and the like. By using this method, a molded article having a smooth surface can be obtained as compared with other molding methods. In addition, there are advantages in that a supporting member is not required. In recent years, there has been an increasing demand for molded articles having complicated shapes and contours which cannot be achieved by conventional processing methods, and it is therefore important to obtain molded articles having smooth surfaces without irregularities on the surfaces of the molded articles.
In order to solve such problems, patent document 1 discloses a method for producing a molded article having a smooth surface by using, as a resin powder, a polyamide powder containing a large amount of particles having a D50 particle diameter of 98 μm and an irregular shape and a hydrophobized silicic acid as a flow aid. Patent document 2 discloses a method for producing a molded article having a smooth surface by using a polyamide powder having a D50 particle diameter of 40 to 70 μm.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 4878102
Patent document 2: japanese patent application laid-open No. 2017-109492
Disclosure of Invention
Problems to be solved by the invention
However, in patent document 1, although a molded article having reduced surface defects can be produced by using a resin powder having excellent flowability, the shape of the polyamide powder is irregular, and it is insufficient to obtain a molded article having small surface roughness. In addition, patent document 2 discloses a polyamide powder excellent in sinterability, but contains coarse powder, and the height (lamination height) of the laminated resin powder particles during three-dimensional molding is as high as 0.15mm, and the like, and therefore there are problems in that the surface roughness in the height plane direction (hereinafter, X, Y direction in the plane direction of the laminated resin powder particles, which may be referred to as X direction or Y direction) and the surface roughness in the height direction (hereinafter, which may be referred to as Z direction) of the laminated resin powder particles become large, and the surface smoothness (quality) is deteriorated.
Accordingly, an object of the present invention is to provide a method for producing a molded article, in which the surface roughness in the X, Y direction among the surface directions of the laminated resin powder particles and the surface roughness in the Z direction, which is the height direction of the laminated resin powder particles, are small in three-dimensional molding.
Means for solving the problems
In order to solve the above problems, the present invention has the following configuration.
(1) A method for producing a three-dimensional molded article by powder bed fusion using a resin powder, characterized in that,
the resin powder particle comprises a resin powder (A) and a flow aid (B),
the sphericity of the resin powder (A) is 80-100, the D80 particle diameter of the resin powder (A) is 60 μm or less, the D20 particle diameter is 1 μm or more,
comprising more than 0.01 parts by mass and less than 5 parts by mass of the flow aid (B) per 100 parts by mass of the resin powder (A),
the method is repeated in the following steps (a) to (c):
(a) The table for forming the groove of the three-dimensional modeling object is lowered within the range of more than 0.01mm and less than 0.10mm,
(b) Supplying resin powder to the groove for forming the three-dimensional modeling object, laminating the resin powder,
(c) The resin powder is selectively melt-sintered by applying heat energy thereto.
(2) The method for producing a three-dimensional shaped article according to (1), wherein the D50 particle diameter of the resin powder (A) is 1 μm or more and 50 μm or less.
(3) The method for producing a three-dimensional shaped article according to (1) or (2), wherein the resin powder or granule contains 10 to 200 parts by mass of the inorganic reinforcing material (C) per 100 parts by mass of the resin powder (A).
(4) The method for producing a three-dimensional shaped object according to any one of (1) to (3), wherein the thermal energy is laser energy which is 0.2J/cm per unit area of the resin powder or granule 2 Above and below 2.0J/cm 2 。
(5) The method for producing a three-dimensional shaped article according to any one of (1) to (4), wherein the surface roughness of the shaped article in the surface direction of the laminated resin powder or granules is 20 μm or less and the surface roughness of the shaped article in the height direction of the laminated resin powder or granules is 20 μm or less.
(6) A three-dimensional molded article formed by a powder bed fusion method using resin powder, characterized in that the surface roughness of the molded article in the surface direction of the laminated resin powder is 20 [ mu ] m or less and the surface roughness of the molded article in the height direction of the laminated resin powder is 20 [ mu ] m or less.
(7) The three-dimensional object according to (6), wherein the average sphere equivalent diameter of the holes observed by X-ray CT measurement is 1 μm or more and 100 μm or less.
(8) A resin powder for producing a three-dimensional molded article by a powder bed fusion method, characterized in that the resin powder comprises a resin powder (A) having a sphericity of 80 to 100 inclusive, a resin powder (A) having a D80 particle diameter of 60 μm or less and a D20 particle diameter of 1 μm or more, and a flow aid (B) in an amount of more than 0.01 parts by mass and less than 5 parts by mass relative to 100 parts by mass of the resin powder (A).
(9) The resin powder or granule according to (8), wherein the D50 particle size of the resin powder (A) is 1 μm or more and 50 μm or less.
(10) The resin powder or granule according to (8) or (9), wherein the D50 particle size of the flow aid (B) is 20nm or more and 1 μm or less.
(11) The resin powder or granule according to any one of (8) to (10), wherein D50 particle diameter of the resin powder (A) is D50 (A), D50 particle diameter of the flow aid (B) is D50 (B), and D50 (A). Times.X/D50 (B) is more than 30 and less than 300 when the content of the flow aid (B) relative to 100 parts by mass of the resin powder (A) is X parts by mass.
(12) The resin powder or granule according to any one of (8) to (11), which contains 10 to 200 parts by mass of the inorganic reinforcing material (C) per 100 parts by mass of the resin powder (A).
Effects of the invention
According to the present invention, a molded article having a small surface roughness in the X, Y direction of the surface direction of the laminated resin powder and a small surface roughness in the Z direction, which is the height direction of the laminated resin powder, can be obtained in three-dimensional molding.
Drawings
Fig. 1 is a schematic view showing an example of a manufacturing apparatus for a three-dimensional shaped object according to the present invention.
Fig. 2 is a schematic view showing an example of a three-dimensional modeling object according to the present invention.
Fig. 3 is a scanning electron micrograph of the resin powder (polyamide powder) used in example 1 obtained in production example 1.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
In the case of manufacturing a three-dimensional molded article, since the molding speed is reduced by setting the lamination height of the resin powder particles to be low, the surface roughness in the Z direction cannot be made to be 20 μm or less because the stage of the groove is set to be lowered by 0.10mm or more.
If the lamination height at the time of three-dimensional molding is not set to a value exceeding the maximum particle size contained in the resin powder, a molded article having a poor surface roughness in the X-direction and the Y-direction is formed. In addition, when the particle size of the resin powder is small, the contact resistance between the resin powders is large, and thus the fluidity is insufficient, and the resin powder cannot be applied to three-dimensional molding. However, even when the particle size of the resin powder or granule is small, it is surprising that fluidity suitable for three-dimensional molding can be ensured when certain conditions are satisfied, and a molded article having a small surface roughness in the X, Y direction among the surface directions of the laminated resin powder or granule and a small surface roughness in the Z direction, which is the height direction of the laminated resin powder or granule, can be provided in three-dimensional molding.
That is, the method for producing a three-dimensional molded article according to the present invention is a method for producing a three-dimensional molded article by a powder bed fusion method using a resin powder,
the resin powder particle comprises a resin powder (A) and a flow aid (B),
the sphericity of the resin powder (A) is 80-100, the D80 particle diameter of the resin powder (A) is 60 μm or less, the D20 particle diameter is 1 μm or more,
Comprising more than 0.01 parts by mass and less than 5 parts by mass of the flow aid (B) per 100 parts by mass of the resin powder (A),
the method is repeated in the following steps (a) to (c):
(a) The table for forming the groove of the three-dimensional modeling object is lowered within the range of more than 0.01mm and less than 0.10mm,
(b) Supplying resin powder to the groove for forming the three-dimensional modeling object, laminating the resin powder,
(c) The resin powder is selectively melt-sintered by applying heat energy thereto.
Hereinafter, each step of the method for producing a three-dimensional shaped object will be described with reference to fig. 1.
In the step (a), the table 2 of the tank 1 for forming the molded article is lowered in a range of 0.01mm or more and less than 0.10 mm. By setting the range to this, a space capable of being filled with the resin powder or granular material P is formed.
In the step (b), the table 4 of the tank 3 (hereinafter, sometimes referred to as a supply tank) in which the molded resin powder particles P of the supply tank 1 are previously filled is raised to a height at which a sufficient amount of the resin powder particles P is supplied, the amount of the resin powder particles P being sufficient to fill a predetermined lamination height formed in the tank 1. Then, the applicator 5 is moved from the left end of the supply tank 3 to the right end of the tank 1, and the resin powder particles P are stacked in the tank 1. The direction parallel to the movement of the applicator 5 is the X direction, and the direction perpendicular to the movement direction of the applicator 5 on the powder surface of the resin powder or granule P is the Y direction. Reference numeral 7 denotes a coordinate system in the X direction, Y direction, and Z direction. Reference numeral 8 denotes the surface direction of the laminated resin powder and 9 denotes the height direction of the laminated resin powder.
In the step (c), heat energy 6 capable of melting is applied to the resin powder particles P filled in the tank 1 at the predetermined lamination height in the step (b), and the resin powder particles are selectively melt-sintered according to the molding data.
By repeating the steps (a) to (c), a three-dimensional shaped object 10 (also shown in fig. 2) is obtained. In fig. 2, reference numeral 11 denotes a molded object surface in the surface direction of the laminated resin powder and granules, and reference numeral 12 denotes a molded object surface in the height direction of the laminated resin powder and granules.
The lamination height in the present invention is 0.01mm or more and less than 0.10mm. When the thickness is less than 0.01mm, irregularities are formed on the laminated surface, and a molded article having a large surface roughness in the X-direction and the Y-direction is formed. When the thickness is 0.10mm or more, a lamellar step is generated in the lamination height direction of the resin powder and granular material, and a molded article having a large surface roughness in the Z direction is formed. In view of expanding the allowable range of the maximum particle size contained in the resin powder, it is preferably 0.02mm or more, more preferably 0.03mm or more, and still more preferably 0.04mm or more. From the viewpoint of being able to reduce the surface roughness in the Z direction, it is preferably less than 0.09mm, more preferably less than 0.08mm, further preferably less than 0.07mm, particularly preferably less than 0.06mm.
In the step (b), the height of the elevation of the table 4 for feeding the tank is preferably 0.03mm or more, more preferably 0.04mm or more, still more preferably 0.05mm or more, and particularly preferably 0.06mm or more, in order to be able to feed a sufficient amount of the resin powder or granules for filling the space formed in the tank 1 in the step (a). In addition, if an excessive amount of the resin powder is supplied, the resin powder prepared in the tank 3 is excessively consumed, and from this point of view, it is preferably 0.15mm or less, more preferably 0.13mm or less, still more preferably 0.11mm or less, and particularly preferably 0.10mm or less.
The speed at which the applicator 5 is moved in the step (b) is preferably a speed at which the powder surface of the resin powder can be formed uniformly in the tank 1. The upper limit of the speed is preferably 1.00m/s or less, more preferably 0.70m/s or less, still more preferably 0.50m/s or less, and particularly preferably 0.30m/s or less. Since the molding speed decreases when the moving speed of the coater is low, the lower limit is preferably 0.01m/s or more, more preferably 0.02m/s or more, still more preferably 0.03m/s or more, and particularly preferably 0.05m/s or more, in relation to the production efficiency of the three-dimensional molded article.
As a method for performing the selective melt sintering in the step (c), for example, a selective laser sintering method in which a laser beam is irradiated to a shape corresponding to the cross-sectional shape of the molded article to bond the resin powder particles is given. Further, a printing step of printing an energy absorption accelerator or an energy absorption inhibitor into a shape corresponding to the cross-sectional shape of the object, a selective absorption (or inhibition) sintering method of bonding resin powder using electromagnetic radiation, and the like are also included.
The laser used in the selective laser sintering method is not particularly limited as long as the quality of the resin powder or molded article is not impaired. Examples thereof include carbon dioxide laser, YAG laser, excimer laser, he-Cd laser, and semiconductor-excited solid laser. Among them, carbon dioxide laser is preferable in terms of simplicity of operation and easiness of control.
In the present invention, in the step (c), meltable heat energy is applied to the resin powder or granule filled in the tank 1 at the predetermined lamination height in the step (b). In the present invention, for example, the energy applied to the resin powder by the laser can be evaluated by the laser energy Ea per unit area. Ea is calculated from the laser output power, the laser scanning speed, and the laser scanning interval by the following equation.
Ea＝Q/(vw)
Q in the formula: laser output power, v: laser scanning speed, w: represents the laser scanning interval, ea: representing the laser energy per unit area.
When Ea is small, the resin powder tends to be insufficiently sintered, and the strength of the molded article may be lowered. Therefore, it is preferably 0.2J/cm 2 The above is more preferably 0.3J/cm 2 The above is more preferably 0.4J/cm 2 The above is particularly preferably 0.5J/cm 2 The above. On the other hand, in the case where the value of Ea is excessively large, laser energy is given to an amount equal to or larger than the lamination height, and the molded article may expand downward. Therefore, it is preferably less than 2.0J/cm 2 More preferably less than 1.8J/cm 2 More preferably less than 1.6J/cm 2 Particularly preferably less than 1.5J/cm 2 。
The electromagnetic radiation used for the selective absorption (suppression) of sintering may be any electromagnetic radiation as long as it does not impair the quality of the resin powder or granular material or molded article, but is preferably infrared radiation because it is relatively inexpensive and can obtain energy suitable for molding. Furthermore, electromagnetic radiation may or may not be coherent.
The energy absorption enhancer is a substance that absorbs electromagnetic radiation. Examples of such a substance include carbon black, carbon fiber, copper hydroxyphosphate, near infrared ray absorbing dye, near infrared ray absorbing pigment, metal nanoparticle, polythiophene, poly (p-phenylene sulfide), polyaniline, poly (pyrrole), polyacetylene, poly (p-phenylene), poly (styrene sulfonate), poly (3, 4-ethylenedioxythiophene) -poly (styrene phosphonate) p-diethylaminobenzaldehyde diphenyl hydrazone, and a conjugated polymer formed by a combination of these, and these may be used alone or in combination of two or more.
The energy absorption inhibitor is a substance which is not likely to absorb electromagnetic radiation. Examples of such a substance include a substance reflecting electromagnetic radiation such as titanium, a heat-insulating powder such as mica powder or ceramic powder, water, etc., and these may be used alone or in combination of two or more.
These selective absorbents or selective inhibitors may be used either alone or in combination.
In the step of printing the selective absorber or selective inhibitor into a shape corresponding to the cross-sectional shape of the target molded article, a known method such as ink jet can be used. In this case, the selective absorber and the selective inhibitor may be used as they are, or may be dispersed or dissolved in a solvent.
Next, the resin powder and the resin powder particle used in the present invention will be described in detail.
The D50 particle diameter of the resin powder (A) in the present invention is preferably in the range of 1 μm to 50. Mu.m. If the D50 particle diameter exceeds 50 μm, the maximum particle size in the resin powder becomes equal to or larger than the lamination height, and thus the lamination height in molding cannot be reduced, and a molded article having a small surface roughness in the Z direction cannot be obtained, which is not preferable. When the D50 particle diameter is less than 1. Mu.m, the resin powder (A) is fine, and therefore, the resin powder tends to adhere to a coater during molding, and the molding chamber cannot be raised to a desired temperature, which is not preferable. The upper limit of the D50 particle diameter of the resin powder is more preferably 45 μm or less, still more preferably 40 μm or less, particularly preferably 35 μm or less. The lower limit is more preferably 3 μm or more, still more preferably 5 μm or more, particularly preferably 10 μm or more.
The D50 particle diameter of the resin powder (a) can be measured by a laser diffraction particle diameter distribution meter. The D50 particle diameter means a particle diameter at which the cumulative frequency of the particle diameter distribution obtained by the measurement from the small particle diameter side reaches 50%.
In the present invention, the D80 particle diameter of the resin powder (A) is 60 μm or less. When the D80 particle diameter is 60 μm or less, the particles having a particle size of not less than the lamination height are reduced, and the irregularities in the X, Y direction of the molded article are reduced, so that a molded article having a small surface roughness can be obtained. The D80 particle diameter is preferably 55 μm or less, more preferably 50 μm or less, further preferably 48 μm or less, particularly preferably 46 μm or less, and particularly preferably 45 μm or less. The lower limit is theoretically equal to or greater than the D50 particle size.
The D80 particle diameter of the resin powder (A) in the present invention can be measured by the aforementioned laser diffraction particle diameter distribution meter. D80 particle diameter means a particle diameter at which the cumulative frequency of the particle diameter distribution obtained by the measurement from the small particle diameter side reaches 80%.
In the present invention, the D20 particle diameter of the resin powder (A) is 1 μm or more. When the D20 particle diameter is less than 1 μm, the powder tends to be caught in the applicator during lamination, and a speckle pattern is generated due to falling of the powder from the applicator, which is not preferable. The D20 particle diameter is preferably 2 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, particularly preferably 7 μm or more, and particularly preferably 10 μm or more. The upper limit is theoretically equal to or less than the D50 particle size.
The D20 particle diameter of the resin powder (a) in the present invention can be measured by the aforementioned laser diffraction particle diameter distribution meter. D20 particle diameter means a particle diameter at which the cumulative frequency of the particle diameter distribution obtained by the measurement from the small particle diameter side reaches 20%.
The sphericity in the present invention means the sphericity of the resin powder (a) and is 80 to 100. When the sphericity is less than 80, fluidity is deteriorated and the surface of the molded article becomes rough. The sphericity is preferably 85 or more and 100 or less, more preferably 90 or more and 100 or less, still more preferably 93 or more and 100 or less, particularly preferably 95 or more and 100 or less, and particularly preferably 97 or more and 100 or less.
The sphericity of the present invention is an average value of the ratio of the short diameter to the long diameter obtained by randomly observing 30 particles from a photograph of a scanning electron microscope.
The surface smoothness and internal solidity of the resin powder (a) of the present invention can be expressed by BET specific surface area by gas adsorption. If the surface of the resin powder is smooth and the interior is solid, the surface area thereof is reduced, the fluidity is improved, and the surface of the molded article is smoothed, which is preferable. Here, the smoother the surface, the smaller the BET specific surface area. Specifically, it is preferably 10m 2 Preferably less than or equal to/g, more preferably 5m 2 Preferably 3m or less per gram 2 Preferably 1m or less per gram 2 Preferably less than or equal to/g, most preferably 0.5m 2 And/g or less. In addition, the lower limit of the particle diameter of 100 μm is theoretically 0.05m 2 /g。
The BET specific surface area can be measured according to the japanese industrial standard (JIS standard) JIS R1626 (1996) 'method for measuring specific surface area by the gas adsorption BET method'.
In the present invention, the theoretical specific surface area when the resin powder is entirely spherical can be expressed by the ratio of the surface area of the single sphere calculated from the D50 particle diameter of the resin powder to the product of the volume and the density of the single sphere calculated from the D50 particle diameter of the resin powder, i.e., the weight of the single sphere. The solidity of the resin powder (a) can also be evaluated by the ratio of the BET specific surface area to the theoretical specific surface area calculated from the D50 particle size. The closer the above ratio is to 1, the adsorption occurs only on the outermost surface of the particles, and thus the particles are smooth and solid in surface. Preferably 5 or less, more preferably 4 or less, further preferably 3 or less, and most preferably 2 or less. The lower limit is theoretically 1.
The resin powder of the present invention exhibits high fluidity. Any known measurement method may be used for the index. Specifically, a repose angle is exemplified, and the angle is preferably 40 degrees or less. More preferably 37 degrees or less, still more preferably 35 degrees or less, and particularly preferably 33 degrees or less. The lower limit is 20 degrees or more.
The polymer constituting the resin powder in the present invention is a polymer suitable for producing a three-dimensional shaped article by powder bed fusion, and preferably comprises polyethylene, polypropylene, polyester, polyamide, polyphenylene sulfide, polyether ether ketone, polyether imide, polyamide imide, polyether sulfone, polytetrafluoroethylene or a mixture thereof. From the viewpoint of excellent heat resistance of the obtained three-dimensional molded article, polyesters, polyamides, polyphenylene sulfide, polyether ether ketone, polyether imide, polyamide imide, polyether sulfone, and polytetrafluoroethylene are more preferable, and from the viewpoint of clear difference between melting point and crystallization temperature and excellent moldability and reproducibility, polyesters, polyamides, polyphenylene sulfide, polyether ether ketone, and polytetrafluoroethylene are more preferable, and from the viewpoint of excellent moldability when using a general-purpose molding machine, polyesters and polyamides are particularly preferable, and from the viewpoint of excellent mechanical properties such as toughness and strength of the obtained molded article, polyamides are particularly preferable.
The polyamide in the present invention is obtained by polycondensation of a 3-or more-membered ring lactam, a polymerizable aminocarboxylic acid, a dibasic acid and a diamine or a salt thereof, or a mixture thereof. Specific examples of such polyamides include polycaprolactam (polyamide 6), polyundecamide (polyamide 11), polylaurolactam (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sebacamide (polyamide 1010), polydodecyl adipamide (polyamide 1012), polydodecyl adipamide (polyamide 1212), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene adipamide (polyamide 612), polyhexamethylene adipamide (polyamide 106), polyhexamethylene adipamide (polyamide 126), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene terephthalamide (polyamide 10T), polyhexamethylene terephthalamide (polyamide 12T), polycaprolactam/polyhexamethylene adipamide copolymer (polyamide 6/66), polycaprolactam/polylaurolactam copolymer (6/12), and the like. Among them, polycaprolactam (polyamide 6), polyundecamide (polyamide 11), polylaurolactam (polyamide 12), polyhexamethylene adipamide (polyamide 66), polydecanediamine (polyamide 1010), polydecanediamine (polyamide 1012), polydecanediamine (polyamide 1212), polyhexamethylene sebacamide (polyamide 610), and polydecanediamine (polyamide 612) are preferable from the viewpoint of easy control into a spherical shape. In addition, from the viewpoint of thermal characteristics suitable for molding, polycaprolactam (polyamide 6), polyundecamide (polyamide 11), polylaurolactam (polyamide 12), polyhexamethylene adipamide (polyamide 66), polydecanediamine (polyamide 1010), and polydecanediamine (polyamide 1012) are particularly preferable. Among them, polycaprolactam (polyamide 6) and polyhexamethylene adipamide (polyamide 66) are particularly preferable from the viewpoint of heat resistance at the time of molding.
The polyester of the present invention is obtained by polycondensation of a lactone or lactide having 3 or more rings, a polymerizable hydroxycarboxylic acid, a dibasic acid and a polyhydric alcohol or a salt thereof, or a mixture thereof. Specific examples of such polyesters include polycaprolactone, polylactic acid, polyglycolic acid, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethanol terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, and copolymers thereof. Among them, polylactic acid, polyglycolic acid, polybutylene terephthalate, polybutylene succinate, polybutylene adipate and copolymers thereof are preferable in terms of having thermal characteristics suitable for molding. In addition, polylactic acid and polybutylene succinate are particularly preferable because they are excellent in biodegradability.
The polyamide and the polyester may be copolymerized within a range that does not impair the effects of the present invention. As the copolymerizable component, an elastomer component such as polyolefin and polyalkylene glycol which imparts flexibility, a rigid aromatic component which improves heat resistance and strength, and the like can be appropriately selected. In addition, as described later, in order to reuse the resin powder by the powder bed fusion method, a copolymerization component for adjusting the terminal group may be used. Examples of the copolymerization component include monocarboxylic acids such as acetic acid, caproic acid, lauric acid and benzoic acid, and monoamines such as hexylamine, octylamine and aniline.
The resin powder of the present invention can be produced by a known method, for example, a liquid-in-dry method in which a polymer is dissolved in an organic solvent to form an O/W emulsion by adding water, and then the organic solvent is dried under reduced pressure to remove the emulsion, a method in which a polymer and polyvinyl alcohol are dissolved in an organic solvent to form an emulsion, and then the emulsion is brought into contact with water as a poor solvent for the polymer, or a method in which a monomer of polyamide is polymerized at a temperature higher than the crystallization temperature of polyamide in the presence of a polymer incompatible with polyamide, as described in the previously published international publication No. WO2018/207728 by the present inventors, and then the resin powder is washed and dried. Among them, the method described in international publication No. WO2018/207728 is preferable in that the content of the subcomponents used in the resin powder production process and the like can be reduced by cleaning the resin powder, and the resin powder excellent in moldability can be obtained.
In the production of the resin powder of the present invention, the purification step for separating the resin powder preferably includes a step of removing coarse particles and fine particles so that the D80 particle size is 60 μm or less and the D20 particle size is 1 μm or more. The coarse particles and fine particles may be removed by either wet classification or dry classification, but wet classification is preferred in view of being able to classify the particles with high accuracy by monodispersing them.
As a wet classification method preferably used for removing coarse particles in the present invention, a known method may be used, and examples thereof include a wet classification method using a sieve, a liquid cyclone separation method using a sedimentation velocity difference, a decantation method, and the like, and a wet classification method is preferable in view of the capability of efficiently removing coarse particles.
As a wet classification method preferably used for removing fine particles in the present invention, a known method may be used, and examples thereof include wet classification method, liquid cyclone separation method using a difference in sedimentation velocity, decantation method, and the like, and liquid cyclone separation method and decantation method are preferable in view of being able to selectively remove only fine particles.
The content of the subcomponents used in the resin powder production process and the like is preferably less than 0.1% by mass. Such subcomponents cause a decrease in the flowability and recyclability of the powder composition, and therefore, are more preferably less than 0.05 mass%, still more preferably less than 0.01 mass%, particularly preferably less than 0.007 mass%, significantly preferably less than 0.004 mass%, and most preferably less than 0.001 mass%. The content of such a subcomponent may be analyzed by a known method, for example, by extracting a resin powder with water or an organic solvent, removing the solvent, and then quantifying the water as a solvent by gel permeation chromatography.
The heat treatment may be additionally performed on the obtained resin powder within a range that does not impair the effects of the present invention. As a method of the heat treatment, a known method can be used, and an atmospheric heat treatment using an oven or the like, a vacuum heat treatment using a vacuum dryer or the like, and a pressurized heat treatment in which water is heated together in a pressure vessel such as an autoclave or the like can be appropriately selected. The molecular weight, crystallinity, and melting point of the resin powder can be controlled within desired ranges by performing the heat treatment.
In the resin powder of the present invention, other compounds may be added within a range that does not impair the effects of the present invention. Examples of the other compound include an antioxidant, a heat stabilizer, and the like for suppressing thermal degradation due to heating at the time of molding in the powder bed fusion system. Examples of the antioxidant and the heat stabilizer include hindered phenols, hydroquinones, phosphites, and their substitutes, phosphites, hypophosphites, and the like. Examples of the filler include pigments for coloring, dyes, plasticizers for adjusting viscosity, flow aids for improving fluidity, antistatic agents for imparting functions, flame retardants, carbon black, silica, titanium dioxide, glass fibers, glass beads, and carbon fibers. These may be used as known materials, or may be present inside or outside the resin powder.
The resin powder of the present invention is characterized by containing a flow aid (B). In the present invention, the flow aid (B) refers to a substance that suppresses aggregation of the resin powder due to adhesion of the resin particles to each other. By containing the flow aid (B), the fluidity of the resin powder can be improved, and the filling property of the resin powder can be improved when a molded article is produced. As a result, defects, which are major factors affecting mechanical properties, are reduced, and the strength of the molded article obtained tends to be further improved.
Examples of the flow aid include silica (silica) such as fused silica, crystalline silica, and amorphous silica, alumina (alumina), alumina colloid (alumina sol), alumina such as alumina white, light calcium carbonate, heavy calcium carbonate, micronized calcium carbonate, calcium carbonate such as a special calcium carbonate filler, calcined clay such as nepheline syenite micropowder, montmorillonite, bentonite, clay (aluminum silicate powder) such as silane modified clay, silicic acid-containing compounds such as talc, diatomaceous earth, silica sand, pulverized natural minerals such as pumice powder, pumice ball, slate powder, mica powder, glass fillers such as barium sulfate, lithopone, calcium sulfate, molybdenum disulfide, graphite, glass fibers, glass beads, glass flakes, and foaming glass beads, fly ash balls, volcanic glass hollow bodies, synthetic inorganic hollow bodies, single crystal potassium titanate, carbon fibers, carbon nanotubes, carbon hollow balls, graphene, anthracite powder, artificial cryolite, titanium oxide, magnesium oxide, basic magnesium carbonate, white, potassium titanate, calcium sulfate, mica, calcium sulfide, molybdenum sulfide, boron sulfide, silicon carbide fibers, and bituminous coal. Further preferred are silica, alumina, calcium carbonate powder, glass filler and titanium oxide. Silica is particularly preferred in view of its hardness and improved strength and fluidity.
As a commercial product of the silica, there is a silica, examples of the silica powder include fumed silica "AEROSIL" manufactured by the company of a large scale of japan, dry silica "leon" manufactured by the company of a large scale of japan, and sol-gel silica powder X-24 manufactured by the company of the chemical industry of the signal industry.
The D50 particle diameter of the flow aid (B) is preferably 20nm to 1 μm. The upper limit of the D50 particle diameter of the flow aid (B) is preferably 1 μm or less in view of suppressing aggregation of the resin powder in a smaller amount when the particle diameter is small and the surface area is large. More preferably 500nm or less, still more preferably 400nm or less, particularly preferably 300nm or less, and particularly preferably 250nm or less. The lower limit is preferably 20nm or more in view of preventing the filling property and the density reduction of the molded article when the surface area is too large. More preferably 30nm or more, still more preferably 50nm or more, particularly preferably 100nm or more. If the average particle diameter of the flow aid (B) is within the above range, the flow aid (B) tends to be uniformly dispersed in the resin powder while improving the fluidity of the resin powder.
The D50 particle diameter of the flow aid (B) in the present invention is a value obtained by setting the total volume of particles obtained by analyzing scattered light of laser light by a dynamic light scattering method to 100% and obtaining a cumulative curve, and the cumulative curve from the small particle diameter side reaches 50%.
The amount of the flow aid (B) to be blended is more than 0.01 parts by mass and less than 5 parts by mass relative to 100 parts by mass of the resin powder (A). The upper limit of the blending amount is preferably less than 4 parts by mass, more preferably less than 3 parts by mass, further preferably less than 2 parts by mass, particularly preferably less than 1 part by mass. The lower limit of the amount is preferably more than 0.02 parts by mass, more preferably more than 0.03 parts by mass, still more preferably more than 0.05 parts by mass, and particularly preferably more than 0.1 parts by mass. When the amount of the flow aid (B) is 0.01 parts by mass or less, fluidity becomes insufficient, and the surface roughness of the molded article obtained is deteriorated, and defects and voids at the end of the molded article are caused. In addition, the filling property during molding is lowered, voids which become defects are easily generated in terms of mechanical properties, and the strength of the molded article obtained is lowered. When the amount of the flow aid is 5 parts by mass or more, the surface of the resin powder is coated with the flow aid, which may cause inhibition of sintering, resulting in a decrease in the strength of the molded article.
In the present invention, the blending amount of the flow aid (B) with respect to the resin powder (a) may be selected in a preferred range depending on the particle size of the resin powder and the particle size of the flow aid. When the D50 particle diameter of the resin powder (a) is set to D50 (a), the D50 particle diameter of the flow aid (B) is set to D50 (B), and the content of the flow aid (B) relative to 100 parts by mass of the resin powder (a) is set to X parts by mass, the D50 (a) ×x/D50 (B) is preferably more than 30 and less than 300. D50 When (A). Times.X/D50 (B) is 30 or less, the flow aid is not preferable because the aggregation of the resin powders cannot be sufficiently suppressed and the fluidity is lowered. The lower limit thereof is more preferably more than 35, still more preferably more than 40, particularly preferably more than 50. D50 When (A). Times.X/D50 (B) is 300 or more, the flow aid is not preferable because it completely coats the resin powder and inhibits sintering. The upper limit is more preferably less than 250, still more preferably less than 200, particularly preferably less than 150, and particularly preferably less than 100.
In the powder bed fusion method, a molded article is produced from a part of the resin powder used, and a large amount of resin powder remains. In view of cost, it is important to reuse the resin powder or granule. For this reason, it is important that the properties of the resin powder are not changed in the step of heating and molding. Examples of such a method include a method of adding a stabilizer such as an antioxidant to the inside of the pellets to suppress thermal degradation, a method of reducing the terminal group of polyamide to suppress molecular weight change during molding, and the like. The terminal groups of the polyamide are carboxyl groups and amino groups, and it is preferable to reduce the amino groups in view of high reactivity during molding and heating. As a method for reducing these, for example, a method is used in which, when a polyamide is polymerized, a monofunctional end-capping material such as a monocarboxylic acid such as acetic acid, caproic acid, lauric acid, or benzoic acid, or a monoamine such as hexylamine, octylamine, or aniline is used. By properly using such adjustment, both moldability and reuse tend to be achieved.
The resin powder or granule of the present invention may contain an inorganic reinforcing material (C) composed of an inorganic compound, in order to improve the dimensional accuracy of the molded article. In the case of containing an inorganic reinforcing material, the volume change accompanied by fusion can be suppressed. The inorganic reinforcing material may be dry-blended with the resin powder (a) or may be contained in the resin powder (a), and dry-blending is preferably performed in view of controlling the resin powder (a) to a spherical shape and improving fluidity.
Examples of the inorganic reinforcing material (C) include glass fillers such as glass fibers, glass beads, glass flakes, and foam glass beads, calcined clay such as nepheline syenite fine powder, montmorillonite, and bentonite, clay (aluminum silicate powder) such as silane modified clay, crushed natural minerals such as talc, diatomaceous earth, silica sand, and the like, silicic acid-containing compounds such as pumice powder, pumice pellets, slate powder, and mica powder, minerals such as barium sulfate, lithopone, calcium sulfate, molybdenum disulfide, and graphite, fused silica, crystalline silica, and silica (silica) such as amorphous silica, alumina (alumina), alumina colloid (alumina sol), alumina such as alumina white, light calcium carbonate, heavy calcium carbonate, calcium carbonate such as micronized calcium carbonate, special calcium carbonate filler, fly ash balls, hollow volcanic glass, synthetic inorganic hollow bodies, single crystal potassium titanate, potassium titanate fibers, carbon nanotubes, carbon hollow spheres, fullerene, anthracite, cellulose nanofibers, artificial cryolite, titanium oxide, magnesium oxide, basic magnesium carbonate, white mica, calcium silicate, calcium sulfate, calcium sulfide, boron sulfide, and the like. From the viewpoint of the hardness and the great strength-improving effect, glass fillers, minerals and carbon fibers are preferable, and from the viewpoint of the particle size distribution and the narrow fiber diameter distribution, glass fillers are more preferable. These inorganic reinforcing materials may be used either individually or in combination of two or more.
Examples of the glass filler preferably used in the present invention include glass fibers, glass beads, glass flakes, and foam glass beads, and glass fibers and glass beads are particularly preferred in view of the ability to exhibit a high elastic modulus in a three-dimensional molded article. Among them, glass fibers are significantly preferred from the viewpoint of achieving high strength of the molded article, and the glass fibers may have a circular or flat cross section. In addition, glass beads are significantly preferred in view of the small strength anisotropy of the molded article.
In order to improve the adhesion between the inorganic reinforcing material and the resin powder, a surface-treated inorganic reinforcing material may be used within a range that does not impair the effect of the present invention. Examples of such surface treatments include silane coupling agents such as aminosilanes, epoxysilanes, and acrylic silanes. These surface treating agents may be immobilized on the surface of the inorganic reinforcing material by a coupling reaction or coated on the surface of the inorganic reinforcing material, and are preferably immobilized by a coupling reaction in view of recycling of the powder used for three-dimensional molding and being less likely to cause quality change by heat or the like.
The average long diameter of the inorganic reinforcing material of the present invention is preferably in the range of 3 to 100. Mu.m. When the average major diameter exceeds 100. Mu.m, irregularities of the inorganic reinforcing material appear on the molding surface, and the surface smoothness is impaired, which is not preferable. If the average major axis is less than 3. Mu.m, the elastic modulus cannot be improved, which is not preferable. The upper limit of the average major axis of the inorganic reinforcing material is preferably 80 μm or less, more preferably 70 μm or less, further preferably 60 μm or less, particularly preferably 50 μm or less. The lower limit is preferably 5 μm or more, more preferably 8 μm or more, and still more preferably 10 μm or more.
The shape of the inorganic reinforcing material of the present invention is 1 to 15 inclusive, expressed as average long diameter/average short diameter, which is the ratio of average long diameter to average short diameter. If the average major axis/average minor axis exceeds 15, the orientation in the X direction in the molded article becomes remarkable, and the strength anisotropy with respect to the Z direction becomes large, which is not preferable. Therefore, the average major axis/average minor axis is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. The lower limit is theoretically 1. Among them, from the viewpoint of increasing the strength, it is particularly preferably 2 or more and 8 or less, and it is significantly preferably 3 or more and 8 or less. From the viewpoint of reducing the anisotropy, it is particularly preferably 1 to 5, and significantly preferably 1 to 3.
In the present invention, the average long diameter and the average short diameter of the inorganic reinforcing material mean a number average value obtained by randomly observing the long diameter and the short diameter of 100 fibers or particles from a photograph obtained by photographing the inorganic reinforcing material with a scanning electron microscope. The long diameter is the diameter at which the interval between parallel lines is maximum when an image of a particle is sandwiched by 2 parallel lines, and the short diameter is the diameter at which the interval between parallel lines is minimum when the image is sandwiched by 2 parallel lines in a direction orthogonal to the long diameter. When the average long diameter and the average short diameter of the inorganic reinforcing material are measured, the long diameter and the short diameter can be measured by selecting the inorganic reinforcing material from a scanning electron micrograph of the powder composition as shown in fig. 2.
The amount of the inorganic reinforcing material to be blended is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the resin powder (a). The upper limit of the amount of the resin powder is more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 75 parts by mass or less, from the viewpoint of obtaining a molded article excellent in surface smoothness without deteriorating the fluidity of the resin powder. The lower limit of the blending amount is more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more, from the viewpoint of improving the elastic modulus and strength of the molded article.
The molded article of the present invention has a surface roughness of 20 [ mu ] m or less in the X, Y direction which is the surface direction of the laminated resin powder particles. The smaller the surface roughness is, the more excellent the adhesion of the joint between the molded articles is, and therefore the surface roughness of the molded articles in the X, Y direction is preferably 18 μm or less, more preferably 15 μm or less, still more preferably 12 μm or less, and particularly preferably 10 μm or less.
The surface roughness of the molded article of the present invention in the Z direction, which is the height direction of the laminated resin powder particles, means the surface roughness in the direction perpendicular to the X, Y direction. The surface roughness of the molded article of the present invention in the Z direction is 20 μm or less, preferably 18 μm or less, more preferably 15 μm or less, still more preferably 12 μm or less, and particularly preferably 10 μm or less. Since the surface roughness in the Z direction depends on the lamination height at the time of molding, the lower limit of the surface roughness in the Z direction is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more.
The surface roughness of the molded article is a value obtained by observing the surface of the molded article with an optical microscope, three-dimensionally imaging the irregularities on the surface of the molded article in the automatic synthesis mode, obtaining a height profile of a cross section over a length of 1mm or more, and calculating the surface roughness Ra (arithmetic average roughness) by arithmetic average.
In addition, in three-dimensional molding, a molded article is formed from a powder-filled state by melt sintering at normal pressure, and therefore, it is generally accompanied by a density change due to shrinkage. Therefore, in order to obtain the three-dimensional modeling object size with high accuracy with respect to the desired modeling data, it is preferable to have a proper hole inside. The proportion and shape of the holes present in the three-dimensional shaped object of the present invention can be observed by X-ray CT.
The three-dimensional modeling object of the present invention is photographed by X-ray CT, and the ratio of the portion observed as the hole to the volume of the entire modeling object can be expressed as a porosity. The porosity of the three-dimensional molded article of the present invention as measured by X-ray CT is preferably 0.1% by volume or more and 5.0% by volume or less. When the lower limit of the porosity is too small, the problem arises that the entire molded article shrinks with respect to the molding data, and therefore, the porosity is more preferably 0.2% by volume or more, still more preferably 0.3% by volume or more, and particularly preferably 0.5% by volume or more. In addition, when the number of holes is large, the upper limit thereof is more preferably 4.0% by volume or less, still more preferably 3.0% by volume or less, and particularly preferably 2.0% by volume or less, which causes a decrease in strength.
The three-dimensional object of the present invention is photographed using X-ray CT, and the size of each individual hole observed as a hole can be expressed as a sphere equivalent diameter. The average sphere equivalent diameter of the holes observed by X-ray CT measurement of the three-dimensional shaped object of the present invention is preferably 1 μm or more and 100 μm or less. In the case of melt molding without using a three-dimensional molding process, the average sphere equivalent diameter of the holes is usually designed to be smaller than 1 μm, and in the case of intentional formation of holes such as foam molding, the average sphere equivalent diameter of the holes is usually larger than 100 μm, and therefore the average sphere equivalent diameter is 1 μm or more and 100 μm or less, which is a characteristic of a three-dimensional molded article. As described above, since a certain amount of voids are generated in three-dimensional molding under normal pressure, the lower limit thereof is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more, because of the problem of shrinkage of the molded article as a whole. The upper limit is preferably 80 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less, because large holes become defects and reduce the strength of the molded article.
Further, since the three-dimensional shaped article is obtained by crystallization by a process of normal pressure and low temperature reduction compared with the usual melt molding, the state of crystallization is different from the usual melt molding, but it is difficult to express it as a characteristic of the article, and therefore, the production method is limited by a method of obtaining it by three-dimensional molding, preferably a powder bed fusion method. It is known that a molded article having a smooth surface can be obtained by a mold structure in the case of usual melt molding, but in the case of three-dimensional molding in which complicated shape molding is possible, a molded article having a smooth surface cannot be obtained, which is made possible by the present invention for the first time.
The three-dimensional molded article of the present invention can have a small surface roughness in the X-direction, Y-direction, and Z-direction. In addition, the adhesion of the joint between the molded articles is excellent, and good slidability and adhesion can be obtained in a structure having a male and a female such as a screw. In addition, with respect to piping and the like, leakage at the joint portion can be reduced due to good adhesion.
Examples
The present invention will be described below based on examples.
(1) D80 particle diameter, D50 particle diameter and D20 particle diameter of the resin powder
To a measuring apparatus (Microtrac MT3300 EXII) of laser diffraction particle size distribution instrument manufactured by diurnal corporation, a dispersion liquid in which about 100mg of a resin powder particle is dispersed in about 5mL of deionized water was added until a concentration capable of measurement was reached, and after ultrasonic dispersion was performed in the measuring apparatus at 30W for 60 seconds, a particle diameter in which the cumulative frequency of the particle size distribution measured for 10 seconds from the small particle diameter side reached 80% was defined as the D80 particle diameter of the resin powder, a particle diameter in which the cumulative frequency reached 50% was defined as the D50 particle diameter of the resin powder, and a particle diameter in which the cumulative frequency reached 20% was defined as the D20 particle diameter of the resin powder. The refractive index at the time of measurement was 1.52, and the refractive index of the medium (deionized water) was 1.333.
(2) Sphericity of resin powder
The sphericity of the resin powder was calculated as an average value of the ratio of the short diameter to the long diameter by randomly observing 30 particles from a photograph of a scanning electron microscope (manufactured by Japanese electron Co., ltd., scanning electron microscope: JSM-6301 NF).
(3) Solidity of resin powder based on ratio of BET specific surface area to theoretical specific surface area
According to the "method for measuring specific surface area by gas adsorption BET method" of JISR1626 (JIS standard (1996)), about 0.2g of a resin powder was put into a glass cell using BELSORP-max manufactured by Japanese Seopen, and deaerated under reduced pressure at 80℃for about 5 hours, and then krypton gas adsorption isotherm at liquid nitrogen temperature was measured and calculated by the BET method.
Further, the theoretical specific surface area of the resin powder was calculated from the ratio of the surface area of the single sphere calculated from the D50 particle diameter of the resin powder to the product of the volume and the density of the single sphere calculated from the D50 particle diameter of the resin powder, i.e., the weight of the single sphere. The solidity of the resin powder was evaluated by calculating the ratio of the BET specific surface area to the theoretical specific surface area.
(4) Crystallization temperature and melting point of resin powder
Using a differential scanning calorimeter (DSCQ 20) manufactured by TA clamping company, the temperature was raised from 30 ℃ to a temperature 30 ℃ higher than the endothermic peak indicating the melting point of the resin at a rate of 20 ℃/min under a nitrogen atmosphere, and then the temperature was kept for 1 minute, and the peak of the exothermic peak occurring when the temperature was cooled to 30 ℃ at a rate of 20 ℃/min was used as the crystallization temperature. After cooling, the temperature was further raised at 20℃per minute, and the endothermic peak at this time was taken as the melting point. The amount of the resin powder required for measurement was about 8mg.
(5) Content of subcomponents of the resin powder
400g of water was added to 200g of the resin powder, and the mixture was left at 80℃for 1 hour to extract the subcomponents. The weight of the extract was determined by comparing the extract sample with a standard curve made of subcomponents using gel permeation chromatography. The content (mass%) of the subcomponents of the resin powder was calculated by dividing the weight of the subcomponents by the weight of the resin powder.
The device comprises: LC-10A series manufactured by Shimadzu corporation
Column: TSKgelG3000PWXL manufactured by TSKgelG corporation
Mobile phase: 100mmol/L sodium chloride aqueous solution
Flow rate: 0.8ml/min
Temperature: 40 DEG C
And (3) detection: differential refractometer.
(6) Average long diameter and average short diameter of inorganic reinforcing material
The inorganic reinforcing material was observed by a scanning electron microscope (JSM-6301 NF) manufactured by japan electronics corporation, and the average value of the long diameter and the short diameter of 100 inorganic reinforcing materials randomly selected from the photograph thereof was taken as the average long diameter and the average short diameter.
(7) Evaluation of flowability of resin powder
100g of the resin powder was dropped from the hopper onto the flat plate using a multifunctional tester MT-1 manufactured by setar corporation, and the angle and repose angle between the inclined surface of the volume mountain and the plate were measured. When the angle of repose was 40 degrees or less, the fluidity was evaluated as "good", and when it exceeded 40 degrees, it was evaluated as "poor".
(8) Surface roughness of molded article
For the surface roughness of a three-dimensional molded article produced using a resin powder or granule, a test piece having a width of 20mm, a length of 20mm and a thickness of 10mm was produced using a powder bed fusion 3D printer (RaFaEl II 150C-HT, manufactured by the company corporation), an optical microscope (VHX-5000) manufactured by the company doku, and an objective lens using VH-ZST (ZS-20) were used, and the surface of the molded article was observed at a magnification of 200 times. By using software (system version 1.04) attached to the apparatus, the surface roughness Ra (center line average surface roughness) was calculated by arithmetic average after three-dimensionally imaging the irregularities on the surface of the molded object in the automatic synthesis mode and obtaining the height profile of the cross section over a length of 1mm or more. The smaller the surface roughness Ra, the more excellent the smoothness (quality) of the surface.
(9) Flexural Strength of molded article
The flexural strength of a three-dimensional molded article produced using a resin powder was measured using a powder bed fusion 3D printer (RaFaEl II 150C-HT, manufactured by Kyoku Co., ltd.) to produce a test piece having a width of 10mm, a length of 80mm, and a thickness of 4mm, and using a Tensiron universal tester (TENSIRON TRG-1250, manufactured by A & D). The bending strength was measured by measuring a 3-point bending test in accordance with JIS K7171 (2008) under conditions of a fulcrum spacing of 64mm and a test speed of 2 mm/min. The measurement temperature was set at room temperature (23 ℃), the number of measurements was set at n=5, and the average value was obtained.
(10) Joint adhesion between molded articles
For adhesion of joints between molded articles of three-dimensional molded articles made of resin powder particles, a pipe shape was molded using a powder bed fusion 3D printer (RaFaEl II 150C-HT, corporation), 2 pipes were joined, and water leakage from the joints was evaluated when water was passed. The adhesion was considered good when there was no water leakage, and the adhesion was considered poor when there was water leakage.
Production example 1 (Polyamide 12 powder preferably used in the present invention)
Into a 3L autoclave equipped with a spiral belt type stirring blade, 300g of aminododecanoic acid (Fusiformis and Wako pure chemical industries, ltd.) as a monomer of polyamide and polyethylene glycol (Fusiformis) as a polymer incompatible with polyamide were addedPrepared by Miao and Wako pure chemical industries, ltd., primary polyethylene glycol 20,000, weight average molecular weight 18,600) 700g, and water 1000g, were formed into a uniform solution, and then sealed and replaced with nitrogen gas. Then, the stirring speed was set at 60rpm, and the temperature was raised to 210 ℃. At this time, the pressure of the system reached 10kg/cm 2 After that, the pressure was controlled by slightly releasing water vapor so as to maintain the pressure at 10kg/cm 2 . After the temperature reached 210℃at 0.2kg/cm 2 The pressure was released at a rate of minutes. Then, the polymerization was completed by maintaining the temperature for 1 hour while flowing nitrogen gas, and when the polyethylene glycol was kept in a molten state, the mixture of the resin powder and the polyethylene glycol was discharged into a 2000g water bath to obtain a slurry. After the slurry was sufficiently homogenized by stirring, filtration was performed, 2000g of water was added to the filtrate, and washing was performed at 80 ℃. The washed slurry was first settled by decantation, and the supernatant was removed, thereby removing fine particles that were not gravity-settled in the polyethylene glycol aqueous solution. Then, 2000g of water was added to conduct repulping, and the slurry from which aggregates were removed by passing through a sieve having a mesh size of 100. Mu.m, was further removed by passing through a sieve having a mesh size of 63. Mu.m. The filtrate separated by the filtration was dried at 80℃for 12 hours to prepare 240g of polyamide 12 powder. To 100 parts by mass of the polyamide 12 powder, 0.3 part by mass of trimethylsilylated amorphous silica (X-24-9500, manufactured by Xinyue chemical Co., ltd.) having an average particle diameter of 170nm was added as a flow aid. The obtained resin powder had a D80 particle diameter of 44. Mu.m, a D50 particle diameter of 32. Mu.m, a D20 particle diameter of 22. Mu.m, a sphericity of 97, a content of subcomponents of 0.0005 mass%, and a repose angle of 30 degrees. BET specific surface area of 0.23m 2 The ratio of BET specific surface area to theoretical specific surface area was 1.3.
Production example 2 (Polyamide 6 powder 1 preferably used in the present invention)
A resin powder for three-dimensional molding was produced in the same manner as in production example 1, except that 0.5 parts by mass of trimethylsilylated amorphous silica was added to 100 parts by mass of the polyamide 6 powder obtained by changing aminododecanoic acid to epsilon-caprolactam as a monomer of polyamide. D80 of the obtained resin powderThe particle size was 29. Mu.m, the D50 particle size was 21. Mu.m, the D20 particle size was 17. Mu.m, the sphericity was 96, the content of subcomponents was 0.0006 mass%, and the repose angle was 31 degrees. BET specific surface area of 0.41m 2 The ratio of BET specific surface area to theoretical specific surface area was 1.6.
Production example 3 (Polyamide 6 powder 2 preferably used in the present invention)
A resin powder or granule for three-dimensional molding was produced in the same manner as in production example 2, except that the stirring speed of the stirring blade provided in the autoclave was changed to 45rpm, and 0.1 part by mass of trimethylsilylated amorphous silica was added to 100 parts by mass of the obtained polyamide 6 powder. The obtained resin powder had a D80 particle diameter of 56. Mu.m, a D50 particle diameter of 43. Mu.m, a D20 particle diameter of 30. Mu.m, a sphericity of 94, a content of subcomponents of 0.0004 mass%, and a repose angle of 36 degrees. BET specific surface area of 0.19m 2 The ratio of BET specific surface area to theoretical specific surface area was 1.5.
Production example 4 (polybutylene terephthalate powder preferably used in the present invention)
A1000 ml pressure-resistant glass autoclave was charged with 33.25g of polybutylene terephthalate (Butthe コ N (registered trademark) 1401X 06), 299.25g of N-methyl-2-pyrrolidone, and 17.5g of polyvinyl alcohol (polyvinyl alcohol having a weight average molecular weight of 29,000, PVA-1500, manufactured by Wako pure chemical industries, ltd.) in which the sodium acetate content was reduced to 0.05% by mass by washing with methanol, and after nitrogen substitution, the mixture was heated to 180℃and stirred for 4 hours until the polymer was dissolved. Then, 350g of ion exchange water as a poor solvent was added dropwise via a liquid feed pump at a rate of 2.92 g/min. After the completion of the addition of all water, the resultant suspension was cooled with stirring, filtered, re-slurried and washed with 700g of ion-exchanged water, and the filtered matter was dried under vacuum at 80℃for 10 hours to obtain 28.3g of polybutylene terephthalate powder. 0.5 part by mass of trimethylsilylated amorphous silica having an average particle diameter of 170nm was added as a flow aid to 100 parts by mass of the polybutylene terephthalate powder. The obtained resin powder had a D80 particle diameter of 24 μm, a D50 particle diameter of 16 μm, a D20 particle diameter of 11 μm and a sphericity of 89, the content of the subcomponent was 0.02 mass%, and the angle of repose was 39 degrees. BET specific surface area of 0.78m 2 The ratio of BET specific surface area to theoretical specific surface area was 2.7.
Production example 5 (Polyamide 12 powder having a larger particle diameter as a comparative example)
A resin powder for three-dimensional molding was produced in the same manner as in production example 1, except that the stirring speed of the stirring blade attached to the autoclave was changed to 25rpm, and coarse particles were removed without using a sieve having a mesh size of 63 μm. The obtained resin powder had a D80 particle diameter of 91. Mu.m, a D50 particle diameter of 72. Mu.m, a D20 particle diameter of 52. Mu.m, a sphericity of 97, a content of subcomponents of 0.0004 mass%, and a repose angle of 29 degrees. BET specific surface area of 0.12m 2 The ratio of BET specific surface area to theoretical specific surface area was 1.5.
Production example 6 (Polyamide 12 powder having a small particle size as a comparative example)
A resin powder for three-dimensional molding was produced in the same manner as in production example 1, except that the stirring speed of the stirring blade attached to the autoclave was changed to 150rpm, and the fine particles were not removed by decantation, to prepare a polyamide 12 powder, and 1.0 part by mass of trimethylsilylated amorphous silica was added to 100 parts by mass of the polyamide 12 powder obtained. The obtained resin powder had a D80 particle diameter of 7. Mu.m, a D50 particle diameter of 4. Mu.m, a D20 particle diameter of 0.8. Mu.m, a sphericity of 96 and a repose angle of 39 degrees. BET specific surface area of 2.0m 2 The ratio of BET specific surface area to theoretical specific surface area was 1.4.
Production example 7 (resin powder containing no flow aid as comparative example)
A resin powder and particle for three-dimensional molding was produced in the same manner as in production example 1, except that trimethylsilylated amorphous silica was not added to 100 parts by mass of the polyamide 12 powder. The obtained resin powder had a D80 particle diameter of 44. Mu.m, a D50 particle diameter of 32. Mu.m, a D20 particle diameter of 22. Mu.m, a sphericity of 97 and a repose angle of 46 degrees. BET specific surface area of 0.23m 2 The ratio of BET specific surface area to theoretical specific surface area was 1.3.
Production example 8 (Polyamide 12 powder having a small sphericity as a comparative example)
Polyamide 12 ("VESTAMID" (registered trademark) L1600) 400g, ethanol 2.2L were heated to a temperature of 140℃in a 3L autoclave, and dissolved. 0.2L of ethanol was distilled therefrom, cooled to 117℃and kept at that temperature for 9 hours, then cooled to 45℃and the resulting slurry was filtered and dried at 90℃to prepare a polyamide 12 powder. To 100 parts by mass of the obtained polyamide 12 powder, 0.1 part by mass of hydrophobated silicic acid ("AEROSIL" (registered trademark) R972) was added to prepare a resin powder for three-dimensional molding. The obtained resin powder had a D80 particle diameter of 75. Mu.m, a D50 particle diameter of 56. Mu.m, a D20 particle diameter of 13. Mu.m, a sphericity of 67, a content of subcomponents of 1.54 mass%, and a repose angle of 32 degrees. BET specific surface area of 0.87m 2 The ratio of BET specific surface area to theoretical specific surface area in per gram was 8.4.
Production example 9 (resin powder particle 1 containing an inorganic reinforcing material preferably used in the present invention)
67 parts by mass of glass beads GB731A (manufactured by polyethylene, 27 μm in average major diameter and 26 μm in average minor diameter by Pop) and 0.3 part by mass of trimethylsilylated amorphous silica were added to 100 parts by mass of the polyamide 6 powder obtained in production example 2, and dry-blended to prepare a resin powder for three-dimensional molding containing an inorganic reinforcing material.
Production example 10 (resin powder particle 2 containing inorganic reinforcing material preferably used in the present invention)
43 parts by mass of EPG70M-01N (manufactured by Nitro Kabushiki Kaisha, average major diameter 73 μm, average minor diameter 10 μm) and 0.3 part by mass of trimethylsilylated amorphous silica were added to 100 parts by mass of the polyamide 6 powder obtained in production example 3, and dry-blended to prepare a resin powder for three-dimensional molding containing an inorganic reinforcing material.
Example 1
A stereolithography product was produced by using 1.5kg of the resin powder obtained in production example 1 (scanning electron micrograph shown in FIG. 3) and using a Selager powder bed fusion device (RaFaEl II 150C-HT) from Kabushiki Kaisha. Set conditions to use 60WCO 2 Laser, laminated heightThe degree was set to 0.05mm, the laser scanning interval was set to 0.1mm, the laser scanning speed was set to 5.00m/s, and the laser output power was set to 5W. At this time, the laser energy Ea per unit area was 1.0J/cm 2 . With respect to the temperature setting, the component bed temperature was set to the melting point-15℃and the supply tank temperature was set to the crystallization temperature-5 ℃. The properties of the resin powder and the molded article obtained are shown in Table 1.
Example 2
A three-dimensional molded article was produced in the same manner as in example 1, except that the setting conditions for three-dimensional molding were changed to a lamination height of 0.07mm and a laser output of 7W. The properties of the resin powder and the molded article obtained are shown in Table 1.
Example 3
A three-dimensional molded article was produced in the same manner as in example 1, except that the resin powder obtained in production example 2 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Example 4
A three-dimensional molded article was produced in the same manner as in example 2, except that the resin powder obtained in production example 3 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Example 5
A three-dimensional molded article was produced in the same manner as in example 1, except that the resin powder obtained in production example 4 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Comparative example 1
A three-dimensional molded article was produced in the same manner as in example 1, except that the setting conditions for three-dimensional molding were changed to a lamination height of 0.10mm and a laser output of 10W. The properties of the resin powder and the molded article obtained are shown in Table 1.
Comparative example 2
A three-dimensional molded article was produced in the same manner as in example 1, except that the resin powder obtained in production example 5 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Comparative example 3
A three-dimensional molded article was produced in the same manner as in comparative example 2, except that the setting conditions for three-dimensional molding were changed to a lamination height of 0.10mm and a laser output of 10W. The properties of the resin powder and the molded article obtained are shown in Table 1.
Comparative example 4
A three-dimensional molded article was produced in the same manner as in example 1, except that the resin powder obtained in production example 6 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Comparative example 5
A three-dimensional molded article was produced in the same manner as in example 1, except that the resin powder obtained in production example 7 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Comparative example 6
A three-dimensional molded article was produced in the same manner as in example 1, except that the resin powder obtained in production example 8 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Example 6
A three-dimensional molded article was produced in the same manner as in example 1, except that the resin powder obtained in production example 9 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Example 7
A three-dimensional molded article was produced in the same manner as in example 2, except that the resin powder obtained in production example 10 was used. The properties of the resin powder and the molded article obtained are shown in Table 1.
Industrial applicability
The present invention can provide a method for producing a molded article having a small surface roughness in the X, Y direction and a small surface roughness in the Z direction, which are the height directions of the laminated resin powder and granules, in three-dimensional molding. Further, the molded article obtained by the above-described production method is excellent in adhesion at the joint portion between the molded articles, and therefore can be preferably used for the production of precision parts or the production of three-dimensional molded articles in which a load is applied to the joint portion.
Symbol description
1 grooves for forming shaped articles
2 table for forming grooves of molded articles
3 filling a supply tank for supplying resin powder
4 Table for filling in advance grooves for supplying resin powder
5. Coating device
6. Thermal energy
7X, Y, Z coordinate System
8 the surface direction of the laminated resin powder
9 height direction of laminated resin powder
10 three-dimensional modeling object
11 layering the surface of the molded article in the surface direction of the resin powder
12 layering the surface of the molded article in the height direction of the resin powder
P resin powder
Claims (12)
1. A method for producing a three-dimensional molded article by powder bed fusion using a resin powder, characterized in that,
the resin powder particle comprises a resin powder (A) and a flow aid (B),
the sphericity of the resin powder (A) is 80-100, the D80 particle diameter of the resin powder (A) is 60 μm or less, the D20 particle diameter is 1 μm or more,
comprising more than 0.01 parts by mass and less than 5 parts by mass of the flow aid (B) per 100 parts by mass of the resin powder (A),
the method is repeated in the following steps (a) to (c):
(a) The table for forming the groove of the three-dimensional modeling object is lowered in the range of more than 0.01mm and less than 0.10mm,
(b) Supplying resin powder to the groove for forming the three-dimensional modeling object, laminating the resin powder,
(c) The resin powder is selectively melt-sintered by applying heat energy thereto.
2. The method of producing a three-dimensional shaped article according to claim 1, wherein the D50 particle diameter of the resin powder (A) is 1 μm or more and 50 μm or less.
3. The method of producing a three-dimensional shaped article according to claim 1 or 2, wherein the resin powder or granule contains not less than 10 parts by mass and not more than 200 parts by mass of the inorganic reinforcing material (C) per 100 parts by mass of the resin powder (a).
4. The method for producing a three-dimensional shaped article according to any one of claims 1 to 3, wherein the thermal energy is laser energy, and the laser energy applied to the resin powder or granular material per unit area is 0.2J/cm 2 Above and below 2.0J/cm 2 。
5. The method for producing a three-dimensional shaped article according to any one of claims 1 to 4, wherein the surface roughness of the shaped article in the surface direction of the laminated resin powder or granules is 20 μm or less and the surface roughness of the shaped article in the height direction of the laminated resin powder or granules is 20 μm or less.
6. A three-dimensional molded article formed by a powder bed fusion method using resin powder, characterized in that the surface roughness of the molded article in the surface direction of the laminated resin powder is 20 [ mu ] m or less and the surface roughness of the molded article in the height direction of the laminated resin powder is 20 [ mu ] m or less.
7. The three-dimensional object according to claim 6, wherein the average sphere equivalent diameter of the holes observed by X-ray CT measurement is 1 μm or more and 100 μm or less.
8. A resin powder for producing a three-dimensional molded article by a powder bed fusion method, characterized in that the resin powder comprises a resin powder (A) having a sphericity of 80 to 100 inclusive, a resin powder (A) having a D80 particle diameter of 60 μm or less and a D20 particle diameter of 1 μm or more, and a flow aid (B) in an amount of more than 0.01 parts by mass and less than 5 parts by mass relative to 100 parts by mass of the resin powder (A).
9. A resin powder or granule according to claim 8, wherein the D50 particle diameter of the resin powder (A) is 1 μm or more and 50 μm or less.
10. The resin powder or granule according to claim 8 or 9, wherein the D50 particle size of the flow aid (B) is 20nm or more and 1 μm or less.
11. The resin powder or granule according to any one of claims 8 to 10, wherein D50 particle diameter of the resin powder (a) is D50 (a), D50 particle diameter of the flow aid (B) is D50 (B), and D50 (a) ×x/D50 (B) is greater than 30 and less than 300 when the content of the flow aid (B) relative to 100 parts by mass of the resin powder (a) is X parts by mass.
12. The resin powder or granule according to any one of claims 8 to 11, which contains 10 to 200 parts by mass of the inorganic reinforcing material (C) per 100 parts by mass of the resin powder (a).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-028424 | 2021-02-25 | ||
| JP2021171167 | 2021-10-19 | ||
| JP2021-171167 | 2021-10-19 | ||
| PCT/JP2022/007369 WO2022181634A1 (en) | 2021-02-25 | 2022-02-22 | Method for manufacturing three-dimensionally shaped article using resin granular material, three-dimensionally shaped article, and resin granular material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116887973A true CN116887973A (en) | 2023-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280017187.9A Pending CN116887973A (en) | 2021-02-25 | 2022-02-22 | Method for producing three-dimensional molded article using resin powder, three-dimensional molded article, and resin powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116887973A (en) |
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2022
- 2022-02-22 CN CN202280017187.9A patent/CN116887973A/en active Pending
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