JP2014188871A - Composite material powder and method of producing molding - Google Patents
Composite material powder and method of producing molding Download PDFInfo
- Publication number
- JP2014188871A JP2014188871A JP2013067250A JP2013067250A JP2014188871A JP 2014188871 A JP2014188871 A JP 2014188871A JP 2013067250 A JP2013067250 A JP 2013067250A JP 2013067250 A JP2013067250 A JP 2013067250A JP 2014188871 A JP2014188871 A JP 2014188871A
- Authority
- JP
- Japan
- Prior art keywords
- average particle
- polyamide
- particle size
- spherical
- aggregate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000000465 moulding Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 title description 24
- 239000002245 particle Substances 0.000 claims abstract description 67
- 229920000571 Nylon 11 Polymers 0.000 claims abstract description 39
- 230000005484 gravity Effects 0.000 claims abstract description 10
- 238000000110 selective laser sintering Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 238000000149 argon plasma sintering Methods 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229920000299 Nylon 12 Polymers 0.000 description 10
- 238000005452 bending Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- -1 diisopropoxyaluminum ethyl acetoacetate Chemical compound 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004959 Rilsan Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HIQAWCBKWSQMRQ-UHFFFAOYSA-N 16-methylheptadecanoic acid;2-methylprop-2-enoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O HIQAWCBKWSQMRQ-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- VGNMBOBKLDHWRC-UHFFFAOYSA-N 2-methyl-n,n-bis(3-trimethoxysilylpropyl)prop-2-enamide Chemical compound CO[Si](OC)(OC)CCCN(C(=O)C(C)=C)CCC[Si](OC)(OC)OC VGNMBOBKLDHWRC-UHFFFAOYSA-N 0.000 description 1
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 1
- CMCTWNKBDTVMGR-UHFFFAOYSA-K C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-] Chemical compound C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-] CMCTWNKBDTVMGR-UHFFFAOYSA-K 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N N-undecane Natural products CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241001483078 Phyto Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- DYHSMQWCZLNWGO-UHFFFAOYSA-N di(propan-2-yloxy)alumane Chemical compound CC(C)O[AlH]OC(C)C DYHSMQWCZLNWGO-UHFFFAOYSA-N 0.000 description 1
- MQVULIBSPNZEFI-UHFFFAOYSA-M di(propan-2-yloxy)alumanylium;2-methylprop-2-enoate Chemical compound CC(=C)C([O-])=O.CC(C)O[Al+]OC(C)C MQVULIBSPNZEFI-UHFFFAOYSA-M 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- XEJNLUBEFCNORG-UHFFFAOYSA-N ditridecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCC XEJNLUBEFCNORG-UHFFFAOYSA-N 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- RMBYJMVHGICGMN-UHFFFAOYSA-N n',n'-bis(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCN(CCN)CCC[Si](OC)(OC)OC RMBYJMVHGICGMN-UHFFFAOYSA-N 0.000 description 1
- AEXNXFCTHRXVMT-UHFFFAOYSA-N n',n'-bis[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCN(CCN)CCC[Si](C)(OC)OC AEXNXFCTHRXVMT-UHFFFAOYSA-N 0.000 description 1
- AIRYAPRCQFBWIL-UHFFFAOYSA-N n,n-bis[3-[dimethoxy(methyl)silyl]propyl]-2-methylprop-2-enamide Chemical compound CO[Si](C)(OC)CCCN(C(=O)C(C)=C)CCC[Si](C)(OC)OC AIRYAPRCQFBWIL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- JTBKFHQUYVNHSR-UHFFFAOYSA-N propan-2-yloxyalumane Chemical compound CC(C)O[AlH2] JTBKFHQUYVNHSR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、複合材料粉末、及び、複合材料粉末を選択的にレーザー焼結することにより成形体を製造する方法に関する。 The present invention relates to a composite material powder and a method for producing a molded body by selectively laser sintering the composite material powder.
選択的レーザー焼結法（ＳＬＳ法：Ｓｅｌｅｃｔｉｖｅ Ｌａｓｅｒ Ｓｉｎｔｅｒｉｎｇ法）は、積層造形法の一つであり、最終目的物の成形体に関する、一定間隔の断面形状の３Ｄデータを予め作成し、この３Ｄデータに基づいて、選択的レーザー焼結用の粉末材料を敷き詰め、レーザーを走査照射して加熱することにより該粉末材料を焼結するという操作を、前記一定間隔ごとに行うことで成形体を製造する方法である。 The selective laser sintering method (SLS method: Selective Laser Sintering method) is one of the additive manufacturing methods, and 3D data of a cross-sectional shape at a constant interval is created in advance for the molded object of the final object. Based on the above, the powder material for selective laser sintering is spread, and the powder material is sintered by scanning and irradiating the laser, and the molded material is manufactured by performing the operation at regular intervals. Is the method.
選択的レーザー焼結用の粉末材料には、一般的に、ポリアミド１２の樹脂粉末が用いられている。ポリアミド１２を用いた場合、ポリアミド１１を用いた場合に比べて、熱収縮が生じにくいため、所望の寸法を有する成形体が得られやすく、成形性が良い。ところが、粉末材料としてポリアミド１２の樹脂粉末を単独で用いた場合、得られる成形体は、弾性率が低いため、外力によって変形しやすい、という問題があった。
この問題を解決するため、ポリアミド１２に、特定の球状骨材を組み合わせた複合材料粉末が提案されている（特許文献１参照）。この複合材料粉末によれば、ポリアミド１２の樹脂粉末を単独で用いた場合に比べて、得られる成形体の弾性率が高まり、強度が向上する。加えて、ポリアミド１２と球状骨材とが分離しにくいため、ＳＬＳ法においてリサイクルが可能であり、成形性も向上する。
Generally, resin powder of polyamide 12 is used as a powder material for selective laser sintering. When polyamide 12 is used, heat shrinkage is less likely to occur than when polyamide 11 is used, and thus a molded body having a desired dimension can be easily obtained and the moldability is good. However, when the polyamide 12 resin powder is used alone as the powder material, the resulting molded article has a problem of being easily deformed by an external force because of its low elastic modulus.
In order to solve this problem, a composite material powder in which a specific spherical aggregate is combined with polyamide 12 has been proposed (see Patent Document 1). According to this composite material powder, the elastic modulus of the obtained molded body is increased and the strength is improved as compared with the case where the resin powder of polyamide 12 is used alone. In addition, since the polyamide 12 and the spherical aggregate are difficult to separate, they can be recycled by the SLS method and the moldability is improved.
しかしながら、特許文献１に記載の複合材料粉末を用いて製造される成形体は、引張破壊ひずみ、曲げ強さが不充分であり、強度の点で未だ問題がある。
本発明は、上記事情に鑑みてなされたものであり、成形性（熱収縮の生じにくさ）及びリサイクル性を維持しつつ、成形体の強度を向上できる選択的レーザー焼結用の複合材料粉末を提供することを課題とする。
However, the molded body produced using the composite material powder described in Patent Document 1 has insufficient tensile fracture strain and bending strength, and still has problems in terms of strength.
The present invention has been made in view of the above circumstances, and is a composite material powder for selective laser sintering that can improve the strength of a molded product while maintaining moldability (hardness of heat shrinkage) and recyclability. It is an issue to provide.
本発明者らは、樹脂粉末のなかでポリアミド１１を選択し、特定の骨材と組み合わせることで、ＳＬＳ法により製造される成形体の強度が格段に向上することを見出し、本発明を完成するに至った。 The present inventors have found that the strength of a molded article produced by the SLS method is remarkably improved by selecting polyamide 11 among resin powders and combining with a specific aggregate, thereby completing the present invention. It came to.
本発明の第一の態様は、ＳＬＳ法に使用する複合材料粉末において、真比重０．８〜２．０、平均粒径１０〜１５０μｍの融点を持たない球状骨材と、平均粒径が３０〜１５０μｍのポリアミド１１と、を含有し、下式で定義される粒径差が±２５％の範囲内であることを特徴とする複合材料粉末である。
粒径差（％）＝｛（球状骨材の平均粒径−ポリアミド１１の平均粒径）／ポリアミド１１の平均粒径｝×１００
The first aspect of the present invention is a composite powder used in the SLS method, a spherical aggregate having a true specific gravity of 0.8 to 2.0 and an average particle size of 10 to 150 μm and no melting point, and an average particle size of 30. And a polyamide 11 having a particle size of ˜150 μm, and having a particle size difference defined by the following formula within a range of ± 25%.
Particle size difference (%) = {(average particle size of spherical aggregate−average particle size of polyamide 11) / average particle size of polyamide 11} × 100
本発明の複合材料粉末においては、前記球状骨材の球形度が０．７〜１．０であり、かつ、該球状骨材の含有量が１０〜８０質量％であることが好ましい。
また、本発明の複合材料粉末においては、前記球状骨材が、球状熱硬化性樹脂硬化物及び球状カーボンからなる群より選ばれる少なくとも一種を含有することが好ましい。
また、本発明の複合材料粉末においては、前記ポリアミド１１の球形度が０．６〜１．０であることが好ましい。
In the composite material powder of the present invention, it is preferable that the sphericity of the spherical aggregate is 0.7 to 1.0 and the content of the spherical aggregate is 10 to 80% by mass.
Moreover, in the composite material powder of the present invention, it is preferable that the spherical aggregate contains at least one selected from the group consisting of a spherical thermosetting resin cured product and spherical carbon.
Moreover, in the composite material powder of the present invention, the sphericity of the polyamide 11 is preferably 0.6 to 1.0.
本発明の第二の態様は、前記第一の態様の複合材料粉末を選択的にレーザー焼結することにより成形体を製造することを特徴とする成形体の製造方法である。 According to a second aspect of the present invention, there is provided a method for producing a molded article, wherein the molded article is produced by selectively laser sintering the composite material powder of the first aspect.
本発明によれば、成形性（熱収縮の生じにくさ）及びリサイクル性を維持しつつ、成形体の強度を向上できる選択的レーザー焼結用の複合材料粉末を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the composite material powder for selective laser sintering which can improve the intensity | strength of a molded object can be provided, maintaining moldability (it is hard to produce heat shrink) and recyclability.
＜複合材料粉末＞
本発明の複合材料粉末は、ＳＬＳ法に使用する材料であり、特定の球状骨材と、特定のポリアミド１１と、を含有する。
<Composite material powder>
The composite material powder of the present invention is a material used for the SLS method, and contains a specific spherical aggregate and a specific polyamide 11.
（球状骨材）
本発明における球状骨材は、融点を持たない、すなわち、加熱されても溶けない粒子状の材料である。
球状骨材の真比重は、０．８〜２．０であり、好ましくは１．０〜１．５であり、ナイロンより高融点を持つガラス粉末、セラミック粉末又は金属粉末の真比重に比べて小さく、ポリアミド１１の比重１．０３〜１．０５（ポリアミド樹脂（福本修編）日刊工業新聞社，第４７頁）に近い。このため、リサイクルの際、球状骨材とポリアミド１１との分離が生じにくく、両者を均一に混合した状態で回収できることから、ＳＬＳ法においてリサイクルが可能であり、これに伴って生産コストの低減化も図れる。
(Spherical aggregate)
The spherical aggregate in the present invention is a particulate material that does not have a melting point, that is, does not melt even when heated.
The true specific gravity of the spherical aggregate is 0.8 to 2.0, preferably 1.0 to 1.5, compared to the true specific gravity of glass powder, ceramic powder or metal powder having a higher melting point than nylon. It is small and close to the specific gravity of polyamide 11 of 1.03 to 1.05 (polyamide resin (Fukumoto Osamu), Nikkan Kogyo Shimbun, page 47). For this reason, it is difficult to separate the spherical aggregate from the polyamide 11 during recycling, and both can be collected in a uniformly mixed state, and therefore can be recycled in the SLS method, and the production cost is reduced accordingly. Can also be planned.
本発明において「平均粒径」とは、レーザー回折散乱法により測定される体積平均粒径を意味する。
球状骨材の平均粒径は、１０〜１５０μｍであり、好ましくは２０〜８０μｍであり、より好ましくは４０〜６０μｍである。
球状骨材の平均粒径が下限値未満では、積層の際に複合材料粉末を敷きにくく、該平均粒径が上限値を超えると、微細な形状の成形体が得られにくい。
In the present invention, the “average particle diameter” means a volume average particle diameter measured by a laser diffraction scattering method.
The average particle diameter of the spherical aggregate is 10 to 150 μm, preferably 20 to 80 μm, and more preferably 40 to 60 μm.
When the average particle size of the spherical aggregate is less than the lower limit value, it is difficult to spread the composite material powder during lamination, and when the average particle size exceeds the upper limit value, it is difficult to obtain a compact shaped product.
本発明において「球形度」とは、（粒子の投影面積に等しい円の直径）／（粒子の投影像に外接する最小円の直径）で決定される指数である。この指数が１．０に近いほど、真球体に近い粒子であることを意味する。
球状骨材の球形度は、０．７〜１．０であることが好ましく、より好ましくは０．８〜１．０であり、さらに好ましくは０．９５〜１．０である。
球状骨材の球形度が好ましい下限値未満では、積層の際に複合材料粉末を均一に敷くことが難しく、成形不良を起こす場合がある。球状骨材の球形度が好ましい下限値以上であると、成形体における部位ごとの強度のばらつきがより少なくなる。
In the present invention, “sphericity” is an index determined by (the diameter of a circle equal to the projected area of the particle) / (the diameter of the smallest circle circumscribing the projected image of the particle). The closer this index is to 1.0, the closer to a true sphere.
The sphericity of the spherical aggregate is preferably 0.7 to 1.0, more preferably 0.8 to 1.0, and still more preferably 0.95 to 1.0.
If the sphericity of the spherical aggregate is less than the preferred lower limit, it is difficult to uniformly spread the composite material powder during lamination, which may cause molding failure. When the sphericity of the spherical aggregate is equal to or more than the preferable lower limit value, the variation in strength of each part in the molded body is further reduced.
球状骨材としては、球状熱硬化性樹脂硬化物、球状カーボン等が挙げられる。
球状熱硬化性樹脂硬化物としては、たとえばフェノール樹脂の球状硬化物を用いることができる。フェノール樹脂の球状硬化物は、フェノール類とアルデヒド類とを、水性媒体中で、縮合反応触媒及び乳化分散剤の存在下、高温高圧の条件で縮合反応させることにより得ることができる。具体的には、完全硬化型球状フェノール樹脂が挙げられ、より具体的には、群栄化学工業株式会社製のＨＦシリーズが好ましい。
球状カーボンとしては、たとえば前記球状熱硬化性樹脂硬化物を、温度４００〜１０００℃、窒素雰囲気下で炭化することにより得ることができる。具体的には、群栄化学工業株式会社製のＧＣシリーズが好ましい。
Examples of the spherical aggregate include a spherical thermosetting resin cured product and spherical carbon.
As the spherical thermosetting resin cured product, for example, a spherical cured product of a phenol resin can be used. A spherical cured product of a phenol resin can be obtained by subjecting phenols and aldehydes to a condensation reaction in an aqueous medium in the presence of a condensation reaction catalyst and an emulsifying dispersant under high temperature and high pressure conditions. Specifically, a fully curable spherical phenol resin is mentioned, and more specifically, HF series manufactured by Gunei Chemical Industry Co., Ltd. is preferable.
The spherical carbon can be obtained, for example, by carbonizing the spherical thermosetting resin cured product at a temperature of 400 to 1000 ° C. in a nitrogen atmosphere. Specifically, GC series manufactured by Gunei Chemical Industry Co., Ltd. is preferable.
球状骨材は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
なかでも、球状骨材としては、球状熱硬化性樹脂硬化物及び球状カーボンからなる群より選ばれる少なくとも一種を含有するものが好ましく、球状カーボンを含有するものがより好ましい。
本発明の複合材料粉末中、球状骨材の含有量は、１０〜８０質量％であることが好ましく、より好ましくは２０〜６０質量％である。球状骨材の含有量が好ましい下限値未満では、得られる成形体の収縮率が大きいため、良好な成形性が得られにくく、該含有量が好ましい上限値を超えると、成形不良を生じやすい。
One kind of spherical aggregate may be used alone, or two or more kinds may be used in combination.
Especially, as a spherical aggregate, what contains at least 1 type chosen from the group which consists of spherical thermosetting resin hardened | cured material and spherical carbon is preferable, and what contains spherical carbon is more preferable.
In the composite material powder of the present invention, the content of the spherical aggregate is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass. When the content of the spherical aggregate is less than the preferred lower limit, the resulting molded article has a high shrinkage rate, and therefore, it is difficult to obtain good moldability. When the content exceeds the preferred upper limit, molding defects tend to occur.
球状骨材として球状カーボンを用いる場合、その配合量を変えることにより、成形体の体積固有抵抗率を調節することが可能である。
たとえば、複合材料粉末中、球状カーボンの含有量が３５質量％以上５５質量％未満の場合、得られる成形体の体積固有抵抗率を１０６〜１０１０Ω・ｃｍの範囲に容易に調節でき、該成形体は静電気防止効果を有する。
複合材料粉末中、球状カーボンの含有量が５５〜８０質量％の場合、得られる成形体の体積固有抵抗率を１０１Ω・ｃｍ以上１０６Ω・ｃｍ未満の範囲に容易に調節でき、該成形体は、電気電子分野の包装用部品やＯＡ機器用部品に応用可能である。
When spherical carbon is used as the spherical aggregate, it is possible to adjust the volume resistivity of the molded body by changing the blending amount.
For example, in the composite material powder, when the content of spherical carbon is 35% by mass or more and less than 55% by mass, the volume resistivity of the obtained molded body can be easily adjusted to a range of 10 6 to 10 10 Ω · cm, The molded body has an antistatic effect.
When the content of spherical carbon in the composite material powder is 55 to 80% by mass, the volume resistivity of the obtained molded body can be easily adjusted to a range of 10 1 Ω · cm to less than 10 6 Ω · cm, The molded body can be applied to packaging parts and OA equipment parts in the electrical and electronic field.
尚、球状骨材は、カップリング剤等によって表面処理が施されたものを用いてもよい。球状骨材に対して表面処理を施すことで、成形時に球状骨材とポリアミド１１との接着性を向上させることができる。
かかるカップリング剤としては、シランカップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤などが挙げられる。
シランカップリング剤としては、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ，Ｎ−ビス［３−（トリメトキシシリル）プロピル］アミン、Ｎ，Ｎ−ビス［３−（トリメトキシシリル）プロピル］エチレンジアミン、Ｎ，Ｎ−ビス［３−（トリメトキシシリル）プロピル］メタクリルアミド、Ｎ−グリシジル−Ｎ，Ｎ−ビス［３−（トリメトキシシリル）プロピル］アミン、γ−アミノプロピルテトラエトキシジシロオキサン、Ｎ，Ｎ−ビス［３−（メチルジメトキシシリル）プロピル］アミン、Ｎ，Ｎ−ビス［３−（メチルジメトキシシリル）プロピル］エチレンジアミン、Ｎ，Ｎ−ビス［３−（メチルジメトキシシリル）プロピル］メタクリルアミド、Ｎ−グリシジル−Ｎ，Ｎ−ビス［３−（メチルジメトキシシリル）プロピル］アミン等が挙げられる。
チタネート系カップリング剤としては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２、２−ジアリルオキシメチル−１−ブチル）ビス（ジトリデシル）ホスファイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート等が挙げられる。
アルミニウム系カップリング剤としては、アセトアルコキシアルミニウムジイソプロピレート、ジイソプロポキシアルミニウムエチルアセトアセテート、ジイソプロポキシアルミニウムアルキルアセトアセテート、イソプロポキシアルミニウムアルキルアセトアセテートモノ（ジオクチルホスフェート）、ジイソプロポキシアルミニウムモノメタクリレート、アルミニウム−２−エチルヘキサノエートオキサイドトリマー、アルミニウムステアレートオキサイドトリマー、アルキルアセトアセテートアルミニウムオキサイドトリマー等が挙げられる。
カップリング剤は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
Note that the spherical aggregate may be subjected to surface treatment with a coupling agent or the like. By subjecting the spherical aggregate to surface treatment, the adhesion between the spherical aggregate and the polyamide 11 can be improved during molding.
Examples of such coupling agents include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like.
Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, N, N-bis [3- (tri Methoxysilyl) propyl] amine, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide, N-glycidyl-N, N- Bis [3- (trimethoxysilyl) propyl] amine, γ-aminopropyltetraethoxydisilooxane, N, N-bis [3- (methyldimethoxysilyl) propyl] amine, N, N-bis [3- (methyl Dimethoxysilyl) propyl] ethylenediamine, N, N-bis [3- (methyldimethoxysilyl) Propyl] methacrylamide, N- glycidyl -N, N- bis [3- (methyldimethoxysilyl) propyl] amine.
The titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphate). Phyto) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like.
Aluminum coupling agents include acetoalkoxyaluminum diisopropylate, diisopropoxyaluminum ethyl acetoacetate, diisopropoxyaluminum alkyl acetoacetate, isopropoxyaluminum alkyl acetoacetate mono (dioctyl phosphate), diisopropoxyaluminum monomethacrylate, Examples thereof include aluminum-2-ethylhexanoate oxide trimer, aluminum stearate oxide trimer, and alkyl acetoacetate aluminum oxide trimer.
A coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.
（ポリアミド１１）
ポリアミド１１は、ウンデカンラクタムを開環重縮合したポリアミド、いわゆるナイロン１１である。
ポリアミド１１の平均粒径は、３０〜１５０μｍであり、好ましくは４０〜１００μｍであり、より好ましくは４５〜６０μｍである。
ポリアミド１１の平均粒径が下限値未満では、積層の際に複合材料粉末を敷きにくく、該平均粒径が上限値を超えると、微細な形状の成形体が得られにくい。
(Polyamide 11)
The polyamide 11 is a polyamide obtained by ring-opening polycondensation of undecane lactam, so-called nylon 11.
The average particle diameter of the polyamide 11 is 30 to 150 μm, preferably 40 to 100 μm, and more preferably 45 to 60 μm.
When the average particle size of the polyamide 11 is less than the lower limit value, it is difficult to spread the composite material powder at the time of lamination, and when the average particle size exceeds the upper limit value, it is difficult to obtain a compact shaped product.
ポリアミド１１の球形度は、０．６〜１．０であることが好ましく、より好ましくは０．７〜１．０であり、さらに好ましくは０．７５〜１．０である。
ポリアミド１１の球形度が好ましい下限値未満では、積層の際に複合材料粉末を均一に敷くことが難しく、成形不良を起こす場合がある。
The sphericity of the polyamide 11 is preferably 0.6 to 1.0, more preferably 0.7 to 1.0, and still more preferably 0.75 to 1.0.
When the sphericity of the polyamide 11 is less than the preferred lower limit, it is difficult to uniformly spread the composite material powder during lamination, which may cause molding failure.
ポリアミド１１は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
本発明の複合材料粉末中、ポリアミド１１の含有量は、２０〜９０質量％であることが好ましく、より好ましくは４０〜８０質量％である。ポリアミド１１の含有量が好ましい下限値未満では、得られる成形体の引張破壊ひずみ、曲げ強さで表される強度が向上しにくく、該含有量が好ましい上限値を超えると、成形不良を生じやすい。
本発明の複合材料粉末においては、ポリアミド１１を採用することで、ポリアミド１２を用いる場合に比べて、理由は定かではないが、成形性を良好に維持したまま、成形体の強度が向上する。
Polyamide 11 may be used alone or in combination of two or more.
In the composite material powder of the present invention, the content of polyamide 11 is preferably 20 to 90% by mass, and more preferably 40 to 80% by mass. If the content of polyamide 11 is less than the preferred lower limit, the strength represented by the tensile fracture strain and bending strength of the resulting molded product is difficult to improve, and if the content exceeds the preferred upper limit, molding defects tend to occur. .
In the composite material powder of the present invention, the use of polyamide 11 improves the strength of the molded body while maintaining good moldability, although the reason is not clear as compared with the case of using polyamide 12.
本発明の複合材料粉末においては、球状骨材とポリアミド１１との粒径差が、下式で定義される粒径差で±２５％の範囲内であり、好ましくは±２０％の範囲内である。
粒径差（％）＝｛（球状骨材の平均粒径−ポリアミド１１の平均粒径）／ポリアミド１１の平均粒径｝×１００
該粒径差が±２５％の範囲内であることにより、得られる成形体の引張破壊ひずみ、曲げ強さで表される強度が向上する。
In the composite material powder of the present invention, the particle size difference between the spherical aggregate and the polyamide 11 is within a range of ± 25%, preferably within a range of ± 20%, as a particle size difference defined by the following formula. is there.
Particle size difference (%) = {(average particle size of spherical aggregate−average particle size of polyamide 11) / average particle size of polyamide 11} × 100
When the particle size difference is within a range of ± 25%, the strength represented by the tensile fracture strain and the bending strength of the obtained molded body is improved.
また、本発明の複合材料粉末において、球状骨材とポリアミド１１との混合比率は、球状骨材／ポリアミド１１で表される質量比で１０／９０〜８０／２０であることが好ましく、より好ましくは３０／７０〜６０／４０であり、さらに好ましくは４０／６０〜５０／５０である。
該質量比が好ましい下限値以上である（球状骨材の割合が好ましい下限値以上である）と、得られる成形体の収縮率が低下し、成形性がより向上する。該質量比が好ましい上限値以下である（ポリアミド１１の割合が好ましい下限値以上である）と、得られる成形体の引張破壊ひずみで表される強度がより向上する。
Moreover, in the composite material powder of the present invention, the mixing ratio of the spherical aggregate and the polyamide 11 is preferably 10/90 to 80/20 in terms of mass ratio represented by the spherical aggregate / polyamide 11 and more preferably. Is 30 / 70-60 / 40, more preferably 40 / 60-50 / 50.
When the mass ratio is not less than the preferred lower limit (the ratio of the spherical aggregate is not less than the preferred lower limit), the shrinkage rate of the obtained molded article is reduced, and the moldability is further improved. When the mass ratio is less than or equal to the preferred upper limit (the ratio of polyamide 11 is greater than or equal to the preferred lower limit), the strength represented by the tensile fracture strain of the obtained molded body is further improved.
本発明の複合材料粉末は、さらに、任意成分として帯電防止剤、滑剤などを含有してもよい。帯電防止剤、滑剤を添加することで、複合材料粉末の流動性が向上し、成形しやすくなる。帯電防止剤、滑剤として具体的には、界面活性剤、シリコーン樹脂、金属石鹸などが挙げられる。
本発明の複合材料粉末中、任意成分の含有量は、０．０５〜０．１質量％が好ましい。
The composite material powder of the present invention may further contain an antistatic agent, a lubricant and the like as optional components. By adding an antistatic agent and a lubricant, the fluidity of the composite material powder is improved and molding becomes easier. Specific examples of the antistatic agent and the lubricant include a surfactant, a silicone resin, and a metal soap.
In the composite material powder of the present invention, the content of optional components is preferably 0.05 to 0.1% by mass.
＜成形体の製造方法＞
本発明の成形体の製造方法は、上述した本発明の複合材料粉末を選択的にレーザー焼結することにより成形体を製造する方法であり、常法により実施できる。
かかる製造方法においては、成形の際、熱収縮が生じにくいため、所望の寸法を有する成形体が容易に得られる。具体的には、収縮率が２．５％以下の成形体が容易に得られる。
また、かかる製造方法により、従来に比して引張破壊ひずみ及び曲げ強さの高い成形体を製造できる。具体的には、引張破壊ひずみが５〜９％の成形体が容易に得られ、曲げ強さが６０〜８０ＭＰａの成形体が容易に得られる。
本発明において「引張破壊ひずみ」は、ＪＩＳ Ｋ ７１６１及びＪＩＳ Ｋ ７１６２に準拠した方法により測定される値を示す。
本発明において「曲げ強さ」は、ＪＩＳ Ｋ ７１７１に準拠した方法により測定される値を示す。
<Method for producing molded body>
The method for producing a molded article of the present invention is a method for producing a molded article by selectively laser sintering the above-mentioned composite material powder of the present invention, and can be carried out by a conventional method.
In such a manufacturing method, since heat shrinkage hardly occurs during molding, a molded body having a desired dimension can be easily obtained. Specifically, a molded article having a shrinkage rate of 2.5% or less can be easily obtained.
Moreover, by this manufacturing method, it is possible to manufacture a molded body having a higher tensile fracture strain and bending strength than conventional ones. Specifically, a molded body having a tensile fracture strain of 5 to 9% can be easily obtained, and a molded body having a bending strength of 60 to 80 MPa can be easily obtained.
In the present invention, “tensile fracture strain” indicates a value measured by a method based on JIS K 7161 and JIS K 7162.
In the present invention, “bending strength” indicates a value measured by a method according to JIS K 7171.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。
本実施例で使用した原料を以下に示す。
（骨材）
・球状カーボン（１）：群栄化学工業株式会社製、商品名「ＧＣ−０５０」、平均粒径５０μｍ。
・球状カーボン（２）：群栄化学工業株式会社製、商品名「ＧＣ−０５０」、平均粒径４５μｍ。
・球状カーボン（３）：群栄化学工業株式会社製、商品名「ＧＣ−０５０」、平均粒径５９μｍ。
・球状カーボン（４）：群栄化学工業株式会社製、商品名「ＧＣ−０７５」、平均粒径７２μｍ。
・球状カーボン（５）：群栄化学工業株式会社製、商品名「ＧＣ−０１０」、平均粒径９μｍ。
・球状熱硬化性樹脂硬化物：群栄化学工業株式会社製、商品名「ＨＦ−０５０」、平均粒径６０μｍ。
・ガラスビーズ：ポッターズ・バロティーニ株式会社製、ガラスビーズ、平均粒径５０μｍ。
・中空ガラスビーズ：ポッターズ・バロティーニ株式会社製、商品名「Ｑ―ＣＥＬ」、平均粒径４５μｍ。
（樹脂粉末）
・ポリアミド１１（１）：アルケマ株式会社製、商品名「ＲＩＬＳＡＮ ＩＮＶＥＮＴ ＮＡＴＵＲＡＬ」、平均粒径５０μｍ。
・ポリアミド１１（２）：アルケマ株式会社製、商品名「ＲＩＬＳＡＮ ＩＮＶＥＮＴ ＮＡＴＵＲＡＬ」、平均粒径４５μｍ。
・ポリアミド１２：ＥＯＳ社製、商品名「ＰＡ２２００」、平均粒径５０μｍ。
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
The raw materials used in this example are shown below.
(aggregate)
Spherical carbon (1): Gunei Chemical Industry Co., Ltd., trade name “GC-050”, average particle size 50 μm.
Spherical carbon (2): Gunei Chemical Industry Co., Ltd., trade name “GC-050”, average particle size 45 μm.
Spherical carbon (3): manufactured by Gunei Chemical Industry Co., Ltd., trade name “GC-050”, average particle size 59 μm.
Spherical carbon (4): manufactured by Gunei Chemical Industry Co., Ltd., trade name “GC-075”, average particle size 72 μm.
Spherical carbon (5): Gunei Chemical Industry Co., Ltd., trade name “GC-010”, average particle size 9 μm.
Spherical thermosetting resin cured product: manufactured by Gunei Chemical Industry Co., Ltd., trade name “HF-050”, average particle size 60 μm.
Glass beads: manufactured by Potters Barotini Co., Ltd., glass beads, average particle size 50 μm.
Hollow glass beads: Potters Barotini Co., Ltd., trade name “Q-CEL”, average particle size 45 μm.
(Resin powder)
Polyamide 11 (1): manufactured by Arkema Co., Ltd., trade name “RILSAN INVENT NATURAL”, average particle size 50 μm.
Polyamide 11 (2): manufactured by Arkema Co., Ltd., trade name “RILSAN INVENT NATURAL”, average particle size 45 μm.
Polyamide 12: manufactured by EOS, trade name “PA2200”, average particle size 50 μm.
各例の複合材料粉末に用いた骨材及び樹脂粉末について、種類、物性（真比重、平均粒径、球形度）、複合材料粉末中の含有量をそれぞれ表１に示した。
骨材についての真比重、骨材及び樹脂粉末についての平均粒径と球形度は、それぞれ以下のようにして求めた。
Table 1 shows the type, physical properties (true specific gravity, average particle diameter, sphericity), and content in the composite powder for the aggregate and resin powder used in the composite material powder of each example.
The true specific gravity of the aggregate and the average particle diameter and sphericity of the aggregate and resin powder were determined as follows.
［真比重］
骨材についての真比重は、ＪＩＳ Ｒ ７２２２に準拠した方法により測定した。
[True specific gravity]
The true specific gravity of the aggregate was measured by a method based on JIS R7222.
［平均粒径］
骨材及び樹脂粉末についての平均粒径（μｍ）は、日機装株式会社製の粒度分析計９３２０−Ｘ−１００により測定した。
また、骨材の平均粒径について、樹脂粉末の平均粒径との差を割合で表示した。具体的には、下式で定義される粒径差（％）を算出した。一例として実施例２［球状カーボン（２）の平均粒径が４５μｍ、ポリアミド１１の平均粒径が５０μｍ］の場合、以下のようにして算出される。
粒径差（％）
＝｛（骨材の平均粒径−樹脂粉末の平均粒径）／樹脂粉末の平均粒径｝×１００
＝｛（４５−５０）／５０｝×１００
＝−１０
[Average particle size]
The average particle size (μm) of the aggregate and the resin powder was measured with a particle size analyzer 9320-X-100 manufactured by Nikkiso Co., Ltd.
In addition, the average particle size of the aggregate was expressed as a percentage of the difference from the average particle size of the resin powder. Specifically, the particle size difference (%) defined by the following formula was calculated. As an example, in the case of Example 2 [the average particle diameter of the spherical carbon (2) is 45 μm and the average particle diameter of the polyamide 11 is 50 μm], it is calculated as follows.
Particle size difference (%)
= {(Average particle size of aggregate-average particle size of resin powder) / average particle size of resin powder} × 100
= {(45-50) / 50} × 100
= -10
［球形度］
骨材及び樹脂粉末についての球形度は、（粒子の投影面積に等しい円の直径）／（粒子の投影像に外接する最小円の直径）で求めた指数であり、この指数が１．０に近いほど、真球体に近い粒子であることを意味する。
[Sphericality]
The sphericity of the aggregate and the resin powder is an index obtained by (the diameter of a circle equal to the projected area of the particle) / (the diameter of the smallest circle circumscribing the projected image of the particle). The closer it is, the closer the particle is to a true sphere.
＜選択的レーザー焼結用の粉末材料の製造：実施例１〜６、比較例１〜７＞
表１に示すように骨材と樹脂粉末とを組み合わせて、各例の粉末材料（試料）をそれぞれ以下のようにして製造した。
<Manufacture of powder material for selective laser sintering: Examples 1-6, Comparative Examples 1-7>
As shown in Table 1, aggregates and resin powders were combined to produce powder materials (samples) of each example as follows.
（実施例１）
それぞれ所定量の球状カーボン（１）とポリアミド１１とを、スクリュー型ミキサーで５分間混合することにより試料を得た。
Example 1
A sample was obtained by mixing a predetermined amount of spherical carbon (1) and polyamide 11 with a screw mixer for 5 minutes.
（実施例２、３）
骨材を球状カーボン（２）、球状カーボン（３）にそれぞれ変更した以外は、実施例１と同様にして試料を得た。
(Examples 2 and 3)
A sample was obtained in the same manner as in Example 1 except that the aggregate was changed to spherical carbon (2) and spherical carbon (3), respectively.
（実施例４）
樹脂粉末をポリアミド（２）に変更した以外は、実施例１と同様にして試料を得た。
Example 4
A sample was obtained in the same manner as in Example 1 except that the resin powder was changed to polyamide (2).
（実施例５）
骨材の含有量を４０質量％、樹脂粉末の含有量を６０質量％に変更した以外は、実施例１と同様にして試料を得た。
(Example 5)
A sample was obtained in the same manner as in Example 1 except that the aggregate content was changed to 40% by mass and the resin powder content was changed to 60% by mass.
（実施例６）
骨材を球状熱硬化性樹脂硬化物に変更した以外は、実施例１と同様にして試料を得た。
(Example 6)
A sample was obtained in the same manner as in Example 1 except that the aggregate was changed to a spherical thermosetting resin cured product.
（比較例１、２）
骨材を球状カーボン（５）、球状カーボン（４）にそれぞれ変更した以外は、実施例１と同様にして試料を得た。
(Comparative Examples 1 and 2)
A sample was obtained in the same manner as in Example 1 except that the aggregate was changed to spherical carbon (5) and spherical carbon (4), respectively.
（比較例３）
樹脂粉末をポリアミド１２に変更した以外は、実施例１と同様にして試料を得た。
(Comparative Example 3)
A sample was obtained in the same manner as in Example 1 except that the resin powder was changed to polyamide 12.
（比較例４）
骨材を用いず、樹脂粉末としてポリアミド１２を用い、これを試料とした。
(Comparative Example 4)
An aggregate was not used, but polyamide 12 was used as a resin powder, and this was used as a sample.
（比較例５）
骨材を用いず、樹脂粉末としてポリアミド１１を用い、これを試料とした。
(Comparative Example 5)
An aggregate was not used, but polyamide 11 was used as a resin powder, and this was used as a sample.
（比較例６）
骨材をガラスビーズに変更した以外は、実施例１と同様にして試料を得た。
(Comparative Example 6)
A sample was obtained in the same manner as in Example 1 except that the aggregate was changed to glass beads.
（比較例７）
骨材を中空ガラスビーズに変更した以外は、実施例１と同様にして試料を得た。
(Comparative Example 7)
A sample was obtained in the same manner as in Example 1 except that the aggregate was changed to hollow glass beads.
＜成形体の製造＞
（実施例７〜１２、比較例８〜１３）
粉末積層造形機（ＥＯＳ社製、製品名：ＥＯＳＩＮＴ Ｐ３８０）を用いて、各例の試料をそれぞれ選択的にレーザー焼結することにより成形体（試験片）を得た。
（比較例１４）
比較例１４で用いた比較例７の試料は、リサイクルの際、衝撃が加わることで、骨材と樹脂粉末とが分離し、不均一な混合物となった。ＳＬＳ法において、この比較例７の試料がリサイクルされた場合、均質な成形体を製造できないため、比較例１４は成形不可とした。
<Manufacture of molded body>
(Examples 7-12, Comparative Examples 8-13)
Using a powder additive manufacturing machine (manufactured by EOS, product name: EOSINT P380), a sample (test piece) was obtained by selectively laser sintering the sample of each example.
(Comparative Example 14)
When the sample of Comparative Example 7 used in Comparative Example 14 was subjected to an impact during recycling, the aggregate and the resin powder separated, resulting in a non-uniform mixture. In the SLS method, when the sample of Comparative Example 7 was recycled, a homogeneous molded body could not be produced.
＜評価＞
リサイクル性についての評価、成形性についての評価、及び、成形体の強度についての評価をそれぞれ行った。これらの結果を表２に示した。
<Evaluation>
Evaluation on recyclability, evaluation on formability, and evaluation on strength of the molded body were performed. These results are shown in Table 2.
［リサイクル性についての評価］
リサイクル性の評価は、以下に示す手順（１）〜（３）により行った。
手順（１）：骨材と樹脂粉末とをスクリュー型ミキサーで５分間混合した後、静電気除去のため、室温２３℃、相対湿度５０％以下で８時間放置する（得られた混合物を試料とする）。
手順（２）：８時間放置の後、試料を、目開き１５０μｍの篩にかける。
手順（３）：篩を通過した試料について、倍率２００倍のマイクロスコープを用い、観察領域を１ｍｍ×１ｍｍとしてランダムに１０ヶ所、該領域の分散状態（骨材と樹脂粉末との均一性）を目視で観察する。観察の結果、骨材と樹脂粉末とが混ざり合っていることが確認された領域を、骨材と樹脂粉末とが分散している領域と判定した。これに対して、骨材と樹脂粉末とが偏在していることが確認された領域を、骨材と樹脂粉末とは分散していない領域と判定した。
そして、該混合物における骨材と樹脂粉末との均一性を、下記評価基準に基づいて２段階で評価した。
（評価基準）
○：骨材と樹脂粉末とが分散している領域が、１０ヶ所中９ヶ所以上で確認された。
×：骨材と樹脂粉末とが分散している領域が、１０ヶ所中８ヶ所以下であった。
骨材と樹脂粉末とが混ざりやすい（分離しにくい）ほど、ＳＬＳ法においてその粉末材料をリサイクルしやすいこと、加えて、リサイクルした際にも、均質な成形体を製造できることを意味する。
[Evaluation of recyclability]
Evaluation of recyclability was performed by the following procedures (1) to (3).
Procedure (1): Aggregate and resin powder are mixed for 5 minutes with a screw-type mixer and then left for 8 hours at room temperature of 23 ° C. and relative humidity of 50% or less to remove static electricity (use the resulting mixture as a sample) ).
Procedure (2): After standing for 8 hours, the sample is passed through a sieve having an opening of 150 μm.
Procedure (3): For the sample that passed through the sieve, using a microscope with a magnification of 200 times, the observation area was 1 mm × 1 mm, and 10 locations were randomly distributed (the uniformity between the aggregate and the resin powder). Observe visually. As a result of observation, a region where the aggregate and the resin powder were confirmed to be mixed was determined as a region where the aggregate and the resin powder were dispersed. On the other hand, the region in which the aggregate and the resin powder were confirmed to be unevenly distributed was determined as the region in which the aggregate and the resin powder were not dispersed.
And the uniformity of the aggregate and resin powder in this mixture was evaluated in two steps based on the following evaluation criteria.
(Evaluation criteria)
○: The region where the aggregate and the resin powder were dispersed was confirmed at 9 or more of 10 locations.
X: The area | region where the aggregate and the resin powder are disperse | distributing was 8 or less places in 10 places.
It means that the more easily the aggregate and the resin powder are mixed (harder to separate), the easier it is to recycle the powder material in the SLS method, and in addition, it is possible to produce a homogeneous molded body even when recycled.
［成形性についての評価］
各例の試料を用いてＳＬＳ法により成形する際の、熱収縮の生じにくさを指標とし、成形性を評価した。
尚、比較例１４では、成形不可であったことから、熱収縮の生じにくさの評価を行っていない。
[Evaluation of formability]
The moldability was evaluated using as an index the difficulty of thermal shrinkage when molding by the SLS method using the sample of each example.
In Comparative Example 14, since the molding was impossible, the evaluation of the difficulty of heat shrinkage was not performed.
・熱収縮の生じにくさ
熱収縮の生じにくさの評価は、ＳＬＳ法により成形する際の成形体（試験片）の収縮率を測定することにより行った。
試験片の収縮率は、以下のようにして測定した。
粉末積層造形機（ＥＯＳ社製、製品名：ＥＯＳＩＮＴ Ｐ３８０）を用い、最終的に得られる直方体状の試験片のサイズが、該試験片の縦の長さをｘ（ｍｍ）とした際、縦ｘ（ｍｍ）×横１０（ｍｍ）×高さ４（ｍｍ）［ｘ＝２０，５０，１００，１５０，２００］となる各設定条件で、粉末材料（試料）を選択的にレーザー焼結することにより試験片を得た。
得られた試験片の縦の長さを実測し、下式より縦方向の収縮率を算出した。
縦方向の収縮率（％）＝｛（ｘ−実測値）／ｘ｝×１００
ｘ＝２０，５０，１００，１５０，２００の場合ごとに算出した、縦方向の収縮率を平均した値を「収縮率（％）」として表２に示した。この「収縮率（％）」が２．５％以下であれば、成形の際に熱収縮が生じにくく、所望の寸法を有する成形体が得られやすいことを意味する。
-Hardness of heat shrinkage Evaluation of the difficulty of heat shrinkage was performed by measuring the shrinkage rate of a molded body (test piece) when molded by the SLS method.
The shrinkage rate of the test piece was measured as follows.
Using a powder additive manufacturing machine (manufactured by EOS, product name: EOSINT P380), the size of the finally obtained rectangular parallelepiped test piece is vertical when the vertical length of the test piece is x (mm). A powder material (sample) is selectively laser-sintered under each setting condition of x (mm) × width 10 (mm) × height 4 (mm) [x = 20, 50, 100, 150, 200]. A test piece was obtained.
The vertical length of the obtained test piece was measured, and the vertical shrinkage was calculated from the following formula.
Vertical shrinkage (%) = {(x−actual measurement value) / x} × 100
Table 2 shows the average value of the shrinkage ratio in the vertical direction calculated for each case of x = 20, 50, 100, 150, and 200 as “shrinkage ratio (%)”. If this “shrinkage rate (%)” is 2.5% or less, it means that heat shrinkage hardly occurs during molding, and a molded body having a desired dimension can be easily obtained.
［成形体の強度についての評価］
各例の成形体（試験片）について、引張破壊ひずみ、曲げ強さをそれぞれ測定することにより、成形体の強度を評価した。
尚、比較例１４では、成形不可であったことから、成形体の強度についての評価を行っていない。
[Evaluation of strength of molded body]
About the molded object (test piece) of each example, the strength of the molded object was evaluated by measuring the tensile fracture strain and the bending strength, respectively.
In Comparative Example 14, since the molding was impossible, the strength of the molded body was not evaluated.
・引張破壊ひずみ
試験片の引張破壊ひずみは、ＪＩＳ Ｋ ７１６１及びＪＩＳ Ｋ ７１６２に準拠した方法により測定した。この引張破壊ひずみが５％以上であれば、充分な強度を有すると言える。
-Tensile fracture strain The tensile fracture strain of the test piece was measured by a method based on JIS K 7161 and JIS K 7162. If this tensile fracture strain is 5% or more, it can be said that it has sufficient strength.
・曲げ強さ
試験片の曲げ強さは、ＪＩＳ Ｋ ７１７１に準拠した方法により測定した。この曲げ強さが６０ＭＰａ以上であれば、充分な強度を有すると言える。
-Bending strength The bending strength of the test piece was measured by the method based on JISK7171. If this bending strength is 60 MPa or more, it can be said that it has sufficient strength.
表２に示す結果から、本発明を適用した実施例１〜６の複合材料粉末を、ＳＬＳ法に用いることで、成形性（熱収縮の生じにくさ）及びリサイクル性を維持しつつ、強度が向上した成形体を製造できることが分かる。 From the results shown in Table 2, the composite material powders of Examples 1 to 6 to which the present invention is applied are used for the SLS method, so that the moldability (hardness of heat shrinkage) and the recyclability are maintained and the strength is increased. It can be seen that an improved molded body can be produced.
Claims (5)
真比重０．８〜２．０、平均粒径１０〜１５０μｍの融点を持たない球状骨材と、
平均粒径が３０〜１５０μｍのポリアミド１１と、
を含有し、
下式で定義される粒径差が±２５％の範囲内であることを特徴とする複合材料粉末。
粒径差（％）＝｛（球状骨材の平均粒径−ポリアミド１１の平均粒径）／ポリアミド１１の平均粒径｝×１００ In composite powders used for selective laser sintering,
A spherical aggregate not having a melting point with a true specific gravity of 0.8 to 2.0 and an average particle size of 10 to 150 μm;
Polyamide 11 having an average particle size of 30 to 150 μm;
Containing
A composite powder characterized by having a particle size difference defined by the following formula within a range of ± 25%.
Particle size difference (%) = {(average particle size of spherical aggregate−average particle size of polyamide 11) / average particle size of polyamide 11} × 100
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013067250A JP6057806B2 (en) | 2013-03-27 | 2013-03-27 | COMPOSITE MATERIAL POWDER AND METHOD FOR PRODUCING MOLDED ARTICLE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013067250A JP6057806B2 (en) | 2013-03-27 | 2013-03-27 | COMPOSITE MATERIAL POWDER AND METHOD FOR PRODUCING MOLDED ARTICLE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014188871A true JP2014188871A (en) | 2014-10-06 |
| JP6057806B2 JP6057806B2 (en) | 2017-01-11 |
Family
ID=51835658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013067250A Active JP6057806B2 (en) | 2013-03-27 | 2013-03-27 | COMPOSITE MATERIAL POWDER AND METHOD FOR PRODUCING MOLDED ARTICLE |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6057806B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016102229A (en) * | 2014-11-27 | 2016-06-02 | 山陽特殊製鋼株式会社 | Metal powder for molding |
| EP3272501A1 (en) * | 2016-07-20 | 2018-01-24 | Xerox Corporation | Method of selective laser sintering |
| JP2018144354A (en) * | 2017-03-06 | 2018-09-20 | セイコーエプソン株式会社 | Paste, and method for manufacturing three-dimensional shaped article |
| JP2018149800A (en) * | 2017-03-14 | 2018-09-27 | 株式会社リコー | Resin powder for stereoscopic shaping and device for manufacturing stereoscopic shaping object |
| US10649355B2 (en) | 2016-07-20 | 2020-05-12 | Xerox Corporation | Method of making a polymer composite |
| CN114349988A (en) * | 2021-12-29 | 2022-04-15 | 湖南华曙高科技股份有限公司 | High polymer powder material for selective laser sintering and preparation method thereof |
| CN114350144A (en) * | 2021-12-29 | 2022-04-15 | 湖南华曙高科技股份有限公司 | High-molecular powder material for selective laser sintering and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007537064A (en) * | 2004-05-14 | 2007-12-20 | デグサ ゲーエムベーハー | POLYMER POWDER HAVING POLYAMIDE, USE IN FORMING METHOD, AND MOLDED BODY MADE FROM THE POLYMER POWDER |
| JP2009013395A (en) * | 2007-06-07 | 2009-01-22 | Gun Ei Chem Ind Co Ltd | Composite material powder for selective laser sintering |
-
2013
- 2013-03-27 JP JP2013067250A patent/JP6057806B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007537064A (en) * | 2004-05-14 | 2007-12-20 | デグサ ゲーエムベーハー | POLYMER POWDER HAVING POLYAMIDE, USE IN FORMING METHOD, AND MOLDED BODY MADE FROM THE POLYMER POWDER |
| JP2009013395A (en) * | 2007-06-07 | 2009-01-22 | Gun Ei Chem Ind Co Ltd | Composite material powder for selective laser sintering |
Non-Patent Citations (1)
| Title |
|---|
| JPN6016032716; 水鳥正路、萩原茂示、川添邦太朗、福田義民: 'カーボンブラックの真比重' 工業化学雑誌 第６６巻第１２号（１９６３）, 20110902, １７５７-１７５９ * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102266772B1 (en) | 2014-11-27 | 2021-06-18 | 산요오도꾸슈세이꼬 가부시키가이샤 | Metal Powder for Modeling |
| KR102266771B1 (en) | 2014-11-27 | 2021-06-18 | 산요오도꾸슈세이꼬 가부시키가이샤 | Metal Powder for Modeling |
| WO2016084832A1 (en) * | 2014-11-27 | 2016-06-02 | 山陽特殊製鋼株式会社 | Metal powder for modeling |
| KR20180115366A (en) * | 2014-11-27 | 2018-10-22 | 산요오도꾸슈세이꼬 가부시키가이샤 | Metal Powder for Modeling |
| KR20180115365A (en) * | 2014-11-27 | 2018-10-22 | 산요오도꾸슈세이꼬 가부시키가이샤 | Metal Powder for Modeling |
| JP2016102229A (en) * | 2014-11-27 | 2016-06-02 | 山陽特殊製鋼株式会社 | Metal powder for molding |
| KR20170048438A (en) * | 2014-11-27 | 2017-05-08 | 산요오도꾸슈세이꼬 가부시키가이샤 | Metal Powder for Modeling |
| CN106794515A (en) * | 2014-11-27 | 2017-05-31 | 山阳特殊制钢株式会社 | Appearance metal dust |
| US10315409B2 (en) | 2016-07-20 | 2019-06-11 | Xerox Corporation | Method of selective laser sintering |
| US10649355B2 (en) | 2016-07-20 | 2020-05-12 | Xerox Corporation | Method of making a polymer composite |
| EP3272501A1 (en) * | 2016-07-20 | 2018-01-24 | Xerox Corporation | Method of selective laser sintering |
| JP2018144354A (en) * | 2017-03-06 | 2018-09-20 | セイコーエプソン株式会社 | Paste, and method for manufacturing three-dimensional shaped article |
| JP7351363B2 (en) | 2017-03-14 | 2023-09-27 | 株式会社リコー | Resin powder for three-dimensional modeling and method for producing three-dimensional objects |
| JP7043865B2 (en) | 2017-03-14 | 2022-03-30 | 株式会社リコー | Equipment for manufacturing resin powder for 3D modeling and 3D modeling |
| JP2022075764A (en) * | 2017-03-14 | 2022-05-18 | 株式会社リコー | Resin powder for three-dimensional modeling, and manufacturing method of three-dimensional modeling product |
| JP2018149800A (en) * | 2017-03-14 | 2018-09-27 | 株式会社リコー | Resin powder for stereoscopic shaping and device for manufacturing stereoscopic shaping object |
| CN114349988A (en) * | 2021-12-29 | 2022-04-15 | 湖南华曙高科技股份有限公司 | High polymer powder material for selective laser sintering and preparation method thereof |
| CN114350144A (en) * | 2021-12-29 | 2022-04-15 | 湖南华曙高科技股份有限公司 | High-molecular powder material for selective laser sintering and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6057806B2 (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6057806B2 (en) | COMPOSITE MATERIAL POWDER AND METHOD FOR PRODUCING MOLDED ARTICLE | |
| JP5214313B2 (en) | Composite powder for selective laser sintering | |
| US10328491B2 (en) | Surface modified particulate and sintered or injection molded products | |
| EP3419399A1 (en) | Heat conductive sheet | |
| CN104086983B (en) | Graphene/nylon composite materials and its preparation method and application | |
| Çantı et al. | Effects of micro particle reinforcement on mechanical properties of 3D printed parts | |
| KR102574040B1 (en) | Synthetic modified thermoplastic polymer composite with cellulose nanomaterial | |
| EP3620283B1 (en) | Resin powder, as well as method of and device for manufacturing a solid freeform object using said powder | |
| CN107109070A (en) | The manufacture method of moulding material, products formed and products formed | |
| DE212013000158U1 (en) | Composite materials for use in injection molding processes | |
| Siqueiros et al. | In situ wire drawing of phosphate glass in polymer matrices for material extrusion 3D printing | |
| US10510471B2 (en) | Composition for bonded magnets, bonded magnet and integrally molded component | |
| JP2015108126A (en) | Method for recycling fluororesin | |
| Gonzalez-Gutierrez et al. | Time-dependent properties of multimodal polyoxymethylene based binder for powder injection molding | |
| EP3882300A1 (en) | Resin powder and resin powder for producing three-dimensional object, and three-dimensional object producing method and three-dimensional object producing apparatus | |
| JP2006070233A (en) | Mixed type of non-melt processable fluororesins | |
| KR100825092B1 (en) | A preparation method of graphite solid | |
| JP2011068125A (en) | Heat-resistant molding and method for producing the same | |
| KR20160063537A (en) | Expanded graphite, method for preparing the same and thermal conductive resin composition comprising the same | |
| Ong et al. | Electrically conductive polyamide 11 nanocomposites for selective laser sintering: properties characterization | |
| WO2024048376A1 (en) | Boron nitride particle, boron nitride particle production method, and resin composition | |
| JP7393714B1 (en) | Flat cross-section glass fibers, glass fiber reinforced resin compositions and glass fiber reinforced resin molded products | |
| JP5179956B2 (en) | Method for producing polyimide powder | |
| EP4317292A1 (en) | Molded product and processed article | |
| Hammiche et al. | Correlation between composites behavior and the manufacturing process used |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20151210 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160819 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160830 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161027 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20161122 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161206 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6057806 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |