JP6699824B2 - Modeling powder - Google Patents
Modeling powder Download PDFInfo
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- JP6699824B2 JP6699824B2 JP2016007442A JP2016007442A JP6699824B2 JP 6699824 B2 JP6699824 B2 JP 6699824B2 JP 2016007442 A JP2016007442 A JP 2016007442A JP 2016007442 A JP2016007442 A JP 2016007442A JP 6699824 B2 JP6699824 B2 JP 6699824B2
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- 239000000843 powder Substances 0.000 title claims description 233
- 239000002245 particle Substances 0.000 claims description 75
- 239000011230 binding agent Substances 0.000 claims description 71
- 229920001169 thermoplastic Polymers 0.000 claims description 65
- 239000004416 thermosoftening plastic Substances 0.000 claims description 65
- 238000009826 distribution Methods 0.000 claims description 59
- 239000002994 raw material Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000000919 ceramic Substances 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 17
- 230000004927 fusion Effects 0.000 claims description 15
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- -1 fatty acid ester Chemical class 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 10
- 239000011246 composite particle Substances 0.000 claims description 8
- 239000012169 petroleum derived wax Substances 0.000 claims description 7
- 235000019381 petroleum wax Nutrition 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 30
- 239000011362 coarse particle Substances 0.000 description 25
- 239000007787 solid Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 235000021355 Stearic acid Nutrition 0.000 description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 15
- 239000008117 stearic acid Substances 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 13
- 239000007921 spray Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000007493 shaping process Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 235000019271 petrolatum Nutrition 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 239000011361 granulated particle Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 4
- 235000019809 paraffin wax Nutrition 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004200 microcrystalline wax Substances 0.000 description 3
- 235000019808 microcrystalline wax Nutrition 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229940066842 petrolatum Drugs 0.000 description 2
- 150000004671 saturated fatty acids Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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- 238000010079 rubber tapping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
本発明は、粉末床溶融結合法に使用される造形用粉末に関する。 The present invention relates to a shaping powder used in a powder bed fusion bonding method.
近年、複雑な形状を有するセラミックス部材、モデル品、或いは少量多品種のセラミックス部材の製造方法として、粉末床溶融結合法が注目されている。粉末床溶融結合法とは、原料として粉末を用いた粉末床溶融結合法であり、造形用粉末を厚さ数十〜数百μｍの粉末層を形成させる粉末層形成工程と、こうして形成された粉末層に対して三次元造形物の断面形状にレーザーや電子ビーム等を照射することで選択的に加熱し、溶融固化または焼結させる断面形状形成行程と、を繰り返して積層することにより、三次元造形物を作製する方法である。 In recent years, a powder bed fusion bonding method has been attracting attention as a method for producing a ceramic member having a complicated shape, a model product, or a small amount of a large variety of ceramic members. The powder bed fusion bonding method is a powder bed fusion bonding method using powder as a raw material, and a powder layer forming step of forming a powder layer having a thickness of several tens to several hundreds of μm for forming powder, and thus formed. By selectively laminating the cross-sectional shape of the three-dimensional structure on the powder layer with a laser, an electron beam, or the like, and melting and solidifying or sintering the cross-sectional shape forming step, by repeatedly stacking, This is a method of producing an original shaped article.
しかし、セラミックスや金属は、樹脂に比べて融点が高いことから、これら材料自身を溶融固化または焼結により造形物を作製することは困難である。また、セラミックスや一部の金属については、塑性変形し難く、熱応力が大きいため、溶融固化または焼結することができても、造形物に割れやクラック等が生じ易くなり、良好な造形物を得ることは困難である。このため、これらのセラミックスや金属の粉末積層造形においては、まずはバインダーを含んだ原料粉末を積層し、バインダーをレーザー等で固化することにより成形体を作製した後、焼結を行うことが行われている。 However, since ceramics and metals have higher melting points than resins, it is difficult to produce a shaped article by melting and solidifying or sintering these materials themselves. In addition, ceramics and some metals are difficult to plastically deform and have a large thermal stress, so even if they can be melted and solidified or sintered, cracks and cracks are likely to occur in the molded object, and a good molded object Is hard to get. Therefore, in these ceramics and metal powder laminating processes, first, raw material powders containing a binder are laminated, and a binder is solidified with a laser or the like to prepare a molded body, and then sintering is performed. ing.
例えば、特許文献１には、熱可塑性樹脂を含む、平均粒子径が1〜１００μｍの球状の粉末床溶融結合法に使用される微小球体であって、微小球体の表面の一部又は全部が凝集防止粒子で被覆されていることで、滑り性もしくは流動性に優れ、かつ高い充填率が達成可能な粉末床溶融結合法に適した微小球体について記載されている。 For example, Patent Document 1 discloses a microsphere containing a thermoplastic resin and having an average particle diameter of 1 to 100 μm, which is used in a powder bed fusion bonding method, in which a part or all of the surface of the microsphere aggregates. It describes a microsphere suitable for a powder bed melt-bonding method, which is excellent in slipperiness or fluidity and can achieve a high packing rate by being coated with the prevention particles.
また、特許文献２には、合成樹脂粉末３０〜９０重量％と無機充填剤１０〜７０重量％からなる材料を粉末層に展開し、レーザー光を照射して照射部位を溶融、固化させる。材料の粉末層展開とレーザー光照射による溶融固化を繰り返し行うことで三次元的モデルを作製することが記載されている。 Further, in Patent Document 2, a material composed of 30 to 90% by weight of synthetic resin powder and 10 to 70% by weight of an inorganic filler is spread on a powder layer, and a laser beam is irradiated to melt and solidify the irradiated portion. It is described that a three-dimensional model is prepared by repeatedly performing powder layer development of a material and melting and solidifying by laser light irradiation.
さらに、特許文献３には、金属又はセラミックスの無機材料１００重量部に対し、ポリアミド又はポリエステルの樹脂粉末１５重量部以下に調製し得られた粉末を粉末層に展開し、所望のパターンでレーザー光を照射することで粉末層内の樹脂粉末を溶着して粉末層の造形物を形成し、この造形物形成工程を複数回繰り返して造形物を形成し、脱脂および焼結工程を経て焼結体を得ることが記載されている。 Further, in Patent Document 3, a powder obtained by preparing a resin powder of polyamide or polyester in an amount of 15 parts by weight or less with respect to 100 parts by weight of an inorganic material of metal or ceramics is spread on a powder layer, and laser light is formed in a desired pattern. The resin powder in the powder layer is welded to form a molded article of the powder layer by irradiating with, and the molded article is formed by repeating this molded object forming step a plurality of times, and the sintered body is subjected to degreasing and sintering steps. Is described.
しかし、上記の従来のセラミックスや金属の粉末を原料とする粉末床溶融結合法では、粉末層に対してレーザー等で加熱した場合、急激な温度変化により造形物に反りやクラックが生じるという問題があった。この問題を解決するため、レーザー等を照射する前に粉末層を融点付近まで予熱しておくことが行われていた。しかしながら、粉末層を予熱するためには装置内部全体を加熱する必要があるため、多くの時間とエネルギーを必要とするため、生産速度の低下やコスト増を招くという不具合を生じることになる。
本発明は、上記従来の実情に鑑みてなされたものであって、セラミックスを原料とする粉末床溶融結合法において、粉末層を予熱することなく造形物を作成することが可能な造形用粉末を提供することを課題とする。
However, in the powder bed fusion bonding method using the above-mentioned conventional ceramics or metal powder as a raw material, when the powder layer is heated by a laser or the like, there is a problem that a warp or a crack is generated in the molded article due to a rapid temperature change. there were. In order to solve this problem, the powder layer has been preheated to near the melting point before being irradiated with a laser or the like. However, in order to preheat the powder layer, it is necessary to heat the entire inside of the apparatus, which requires a lot of time and energy, which causes a problem that the production rate is lowered and the cost is increased.
The present invention has been made in view of the above conventional circumstances, in a powder bed fusion bonding method using ceramics as a raw material, a molding powder capable of forming a molded article without preheating the powder layer, The challenge is to provide.
本発明の造形用粉末は、粉末床溶融結合法に使用される造形用粉末であって、セラミックス及び／又は金属と、熱可塑性バインダーとを含む原料粉末からなり、前記熱可塑性バインダーは石油ワックス、脂肪酸、脂肪酸エステル、脂肪酸アミド、及びポリビニルアセタールからなる群より選ばれた少なくとも１種類を含み、前記熱可塑性バインダーの融点又はガラス転移点が２０℃以上１３０℃以下の範囲にあることを特徴とする。 The modeling powder of the present invention is a modeling powder used in a powder bed melt-bonding method, and is made of a raw material powder containing ceramics and/or a metal and a thermoplastic binder, and the thermoplastic binder is petroleum wax, At least one selected from the group consisting of fatty acids, fatty acid esters, fatty acid amides, and polyvinyl acetals is included, and the melting point or glass transition point of the thermoplastic binder is in the range of 20°C to 130°C. ..
本発明の造形用粉末では、熱可塑性バインダーとして融点又はガラス転移点が２０℃以上１３０℃以下という低い温度のものを使用する。このため、粉末床溶融結合法における粉末層にレーザー等を照射してバインダーを溶融する場合に、それほど急激な温度変化は起こらず、造形物に反りやクラックが生じるおそれが少ない。このため、粉末層をレーザー等を照射する前に予熱しておく必要がなく、多くの時間とエネルギーを必要とすることもないことから、ひいては、生産速度の向上と製造コストの低廉化を実現できる。
また、発明者らは、こうした低融点あるいは低ガラス転移点の熱可塑性バインダーとして、石油ワックス、脂肪酸、脂肪酸エステル、及び脂肪酸アミドを用いれば、変形やクラックのない造形物を提供できることを確認している。ここで、石油ワックスとは、常温でろう状固体の炭化水素類であり、日本工業規格 (JIS K2235)により定義されている石油ワックスをいい、パラフィンワックス、マイクロクリスタリンワックス、及びペトロラタムの3種がある。
In the powder for modeling of the present invention, a thermoplastic binder having a low melting point or glass transition point of 20°C or higher and 130°C or lower is used. For this reason, when the powder layer in the powder bed fusion bonding method is irradiated with a laser or the like to melt the binder, a drastic temperature change does not occur, and there is little risk of warping or cracks in the modeled object. For this reason, it is not necessary to preheat the powder layer before irradiating it with a laser or the like, and it does not require a lot of time and energy, which results in improvement of production speed and reduction of manufacturing cost. it can.
Further, the inventors have confirmed that if petroleum wax, a fatty acid, a fatty acid ester, and a fatty acid amide are used as the thermoplastic binder having such a low melting point or a low glass transition point, it is possible to provide a shaped article without deformation or cracks. There is. Here, the petroleum wax is a hydrocarbon that is a waxy solid at room temperature, and refers to a petroleum wax defined by Japanese Industrial Standards (JIS K2235), and three types are paraffin wax, microcrystalline wax, and petrolatum. is there.
本発明における原料となるセラミックス及び／又は金属としては、金属酸化物、金属非酸化物、及び金属の少なくとも１種類を用いることができる。 As the ceramic and/or metal used as the raw material in the present invention, at least one kind of metal oxide, metal non-oxide, and metal can be used.
また、粉末床溶融結合法では、粉末層を形成する粉末層形成工程において、ブレードやローラー等のリコータにより造形用粉末を粉末収納領域から造形領域に移動させて、粉末層を造形領域の全面に一定の層厚で形成させる必要がある。このため、造形用粉末の良好な流動性が要求される。
しかしながら、造形用粉末の流動性があまり高くなると、粉末層形成工程におけるリコータにより造形用粉末を粉末収納領域から造形領域に移動させる際に、形成された断面形状の造形物が造形用粉末とともにリコータの移動方向に滑り易くなるという問題が生じる。
以上の理由から、発明者らは、粉末床溶融結合法に用いられる造形用粉末は、単に優れた流動性を有すればよいというのではなく、最適な粉末流動性の範囲が存在することを見出した。すなわち、流動性を評価するＨａｕｓｎｅｒ比(タップ密度/かさ密度の比)の値が１．１０以上１．４０以下であることが好ましい。なお、ここでタップ密度とは、ＪＩＳ−Ｋ５１０１に準じ、タップ回数は２００回とした場合の値をいう。
Further, in the powder bed fusion bonding method, in the powder layer forming step of forming the powder layer, the shaping powder is moved from the powder storage area to the shaping area by a recoater such as a blade or a roller, and the powder layer is formed on the entire surface of the shaping area. It is necessary to form it with a constant layer thickness. Therefore, good flowability of the molding powder is required.
However, if the fluidity of the modeling powder becomes too high, when the modeling powder is moved from the powder storage area to the modeling area by the recoater in the powder layer forming step, the molded article having the cross-sectional shape formed together with the modeling powder is recoated. There is a problem that it becomes slippery in the moving direction of the.
For the above reasons, the inventors have found that the molding powder used in the powder bed melt-bonding method does not simply have to have excellent fluidity, but that the optimum powder fluidity range exists. I found it. That is, it is preferable that the value of Hausner ratio (ratio of tap density/bulk density) for evaluating fluidity is 1.10 or more and 1.40 or less. Here, the tap density means a value when the number of taps is 200 according to JIS-K5101.
また、本発明の造形用粉末では、１０μｍ以上５００μｍ以下の範囲に単一もしくは複数の粒度分布ピークを有しているものを用いることができる。１０μｍ未満では粉末の流動性が低下するため粉末層の形成が困難となるおそれがある。また５００μｍを超えると造形物の強度が低く、ハンドリングが困難となるおそれがある。 Further, as the modeling powder of the present invention, one having a single or plural particle size distribution peaks in the range of 10 μm or more and 500 μm or less can be used. If it is less than 10 μm, the fluidity of the powder is lowered, and it may be difficult to form a powder layer. On the other hand, when it exceeds 500 μm, the strength of the shaped article is low and handling may be difficult.
さらに、本発明の造形用粉末では、熱可塑性バインダーの体積をセラミックス及び／又は金属の表面積で除した値が０.０３μｍ以上３．００μｍ以下であることが好ましい。０.０３μｍ未満では熱可塑性バインダーの含有量が少なくなり、造形物の機械的強度が低下する恐れがある。また３．００μｍを超えると熱可塑性バインダー含有量が多くなり、溶融時に変形等を起こしやすくなる。 Further, in the modeling powder of the present invention, the value obtained by dividing the volume of the thermoplastic binder by the surface area of the ceramic and/or metal is preferably 0.03 μm or more and 3.00 μm or less. If it is less than 0.03 μm, the content of the thermoplastic binder is reduced, and the mechanical strength of the molded article may be reduced. On the other hand, when it exceeds 3.00 μm, the content of the thermoplastic binder increases, and deformation or the like is likely to occur during melting.
また、本発明の造形用粉末では、セラミックス及び／又は金属からなる粉末と、熱可塑性バインダーからなる原料粉末と、が合体して単一の複合粒子を形成しているものを用いることができる。この場合において、セラミックス及び／又は金属からなる原料粉末の粒度分布ピークは１０μｍ以上４００μｍ以下に存在しており、前記複合粒子の粒度分布ピークは１０μｍ以上５００μｍ以下に存在していることが好ましい。また、セラミックス及び／又は金属からなる原料粉末の粒度分布ピークは０．１μｍ以上１０μｍ未満に存在しており、前記複合粒子の粒度分布ピークは１０μｍ以上５００μｍ以下に存在していることが好ましい。
さらには、
粒度分布ピークが０．１μｍ以上１０μｍ未満に存在する第１の原料粉末と、粒度分布ピークが１０μｍ以上４００μｍ以下に存在する第２の原料粉末と、熱可塑性バインダーと、を含有しており、
前記複合粒子の粒度分布ピークが１０μｍ以上５００μｍ以下に存在することも好ましい。
Further, as the modeling powder of the present invention, it is possible to use a powder in which a powder made of ceramics and/or a metal and a raw material powder made of a thermoplastic binder are united to form a single composite particle. In this case, it is preferable that the particle size distribution peak of the raw material powder made of ceramics and/or metal exists in the range of 10 μm to 400 μm, and the particle size distribution peak of the composite particles exists in the range of 10 μm to 500 μm. Further, it is preferable that the particle size distribution peak of the raw material powder made of ceramics and/or metal is present at 0.1 μm or more and less than 10 μm, and the particle size distribution peak of the composite particles is present at 10 μm or more and 500 μm or less.
Moreover,
It contains a first raw material powder having a particle size distribution peak of 0.1 μm or more and less than 10 μm, a second raw material powder having a particle size distribution peak of 10 μm or more and 400 μm or less, and a thermoplastic binder,
It is also preferable that the particle size distribution peak of the composite particles exists in the range of 10 μm to 500 μm.
本発明の造形用粉末において、セラミックス及び／又は金属からなる原料粉末と、熱可塑性バインダーからなる原料粉末と、が合体することなくそれぞれ別の粒子として存在していてもよい。この場合において、セラミックス及び／又は金属からなる原料粉末の粒度分布ピークは１０μｍ以上４００μｍ以下に存在していることが好ましい。 In the modeling powder of the present invention, the raw material powder made of ceramics and/or metal and the raw material powder made of a thermoplastic binder may exist as separate particles without being combined. In this case, it is preferable that the particle size distribution peak of the raw material powder made of ceramics and/or metal exists in the range of 10 μm to 400 μm.
本発明の造形用粉末を用いれば、粉末床溶融結合法によって造形物を製造する際、粉末層を予熱しなくても造形物を作成することができる。 When the modeling powder of the present invention is used, the modeled article can be prepared without preheating the powder layer when the modeled article is manufactured by the powder bed fusion bonding method.
以下、本発明を具体化した実施形態について説明する。
本発明の造形用粉末の原料となるセラミックスとしては、特に限定はなく、例えば、金属酸化物、金属窒化物、金属炭化物、複合酸化物等が挙げられる。これらは、単独でもよいし、二種以上を併用してもよい。また、本発明の造形用粉末の原料となる金属としてはシリコン、アルミニウム、鉄、ステンレス、チタン、タングステン等が挙げられる。
Embodiments embodying the present invention will be described below.
There is no particular limitation on the ceramics as a raw material of the modeling powder of the present invention, and examples thereof include metal oxides, metal nitrides, metal carbides, and complex oxides. These may be used alone or in combination of two or more. In addition, examples of the metal that is a raw material of the modeling powder of the present invention include silicon, aluminum, iron, stainless steel, titanium, and tungsten.
金属酸化物としては特に限定されないが、例えば、酸化アルミニウム、酸化マグネシウム、酸化ケイ素、酸化カルシウム、酸化チタン、酸化バナジウム、酸化クロム、酸化マンガン、酸化鉄、酸化コバルト、酸化銅、酸化亜鉛、酸化イットリウム、酸化ジルコニウム、酸化ニオブ、酸化モリブデン、酸化タンタル、酸化タングステン、アパタイトなどが挙げられる。
また、金属窒化物としては特に限定されないが、例えば、窒化アルミニウム、窒化ケイ素、窒化ホウ素、窒化チタン、窒化バナジウム、窒化クロム、窒化ジルコニウム、窒化ニオブ、窒化タンタルなどが挙げられる。
さらに、金属炭化物としては特に限定されないが、例えば、炭化ケイ素、炭化チタン、炭化バナジウム、炭化ジルコニウム、炭化ニオブ、炭化モリブデン、炭化タンタル、炭化タングステンなどが挙げられ、
また、複合酸化物としては特に限定されないが、例えば、コージェライト、ムライト、サイアロン、チタン酸バリウム、チタン酸ストロンチウムなどが挙げられる。
The metal oxide is not particularly limited, for example, aluminum oxide, magnesium oxide, silicon oxide, calcium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, copper oxide, zinc oxide, yttrium oxide. , Zirconium oxide, niobium oxide, molybdenum oxide, tantalum oxide, tungsten oxide, and apatite.
The metal nitride is not particularly limited, but examples thereof include aluminum nitride, silicon nitride, boron nitride, titanium nitride, vanadium nitride, chromium nitride, zirconium nitride, niobium nitride, and tantalum nitride.
Furthermore, the metal carbide is not particularly limited, and examples thereof include silicon carbide, titanium carbide, vanadium carbide, zirconium carbide, niobium carbide, molybdenum carbide, tantalum carbide, and tungsten carbide.
The composite oxide is not particularly limited, and examples thereof include cordierite, mullite, sialon, barium titanate, and strontium titanate.
本発明の造形粉末においてセラミックスとともに添加されるバインダーとしては、加熱によって溶融あるいは軟化するものであって、融点あるいはガラス転移点が２０℃以上１３０℃以下であるものであれば、融点を有する結晶性の有機化合物やガラス転移点を有する非結晶性の有機化合物等を用いることができる。融点あるいはガラス転移点が２０℃以上１３０℃以下であるものであれば、粉末層形成工程において形成された粉末層に対し、レーザーや電子ビーム等を照射することによって、容易に溶解、固化して造形物を形成することができるため、予熱を行う必要がない。 The binder to be added together with the ceramics in the shaping powder of the present invention is one that is melted or softened by heating and has a melting point or a glass transition point of 20° C. or higher and 130° C. or lower, and has a melting point. The organic compounds described above, non-crystalline organic compounds having a glass transition point, and the like can be used. If the melting point or glass transition point is 20° C. or higher and 130° C. or lower, the powder layer formed in the powder layer forming step is easily dissolved and solidified by irradiating it with a laser or an electron beam. Since a shaped object can be formed, it is not necessary to perform preheating.
熱可塑性バインダーは、結晶質であるか、非晶質であるかを問わず、石油ワックス、脂肪酸、脂肪酸エステル、及び脂肪酸アミドからなる群より選ばれた少なくとも１種類を用いることができる。
石油ワックスとしては、日本工業規格 (JIS K2235) によって規定されている、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタムのいずれも用いることができる。好適には炭素鎖が直鎖構造を持った飽和脂肪族炭化水素で、かつ炭素原子数が１８以上３５以下のものが好ましく、炭素原子数が２０以上３０以下のものはさらに好ましい。
また、脂肪酸としては、炭素鎖の形状（鎖状及び環状のいずれでもよく、分枝があってもよい）及び環状炭素原子数、炭素鎖の結合状態（飽和もしくは不飽和）によって特に限定されるものではないが、好適には炭素鎖が直鎖構造を持った飽和脂肪酸で、かつ炭素原子数が１０以上２５以下のものが好ましく、１５以上２０以下のものがさらに好ましい。
さらに、脂肪酸エステルとしては、脂肪酸とアルコールの炭素鎖の形状、炭素原子数、炭素鎖の結合状態（飽和もしくは不飽和）によって特に限定されるものではないが、好適には炭素鎖が直鎖構造をもった飽和脂肪酸エステルで、かつ炭素原子数が、１０以上２５以下のものが好ましく、１５以上２０以下のものはさらに好ましい。
また、脂肪酸アミドとしては、脂肪酸の炭素鎖の形状、炭素原子数、炭素鎖の結合状態（飽和もしくは不飽和）によって特に限定されるものではないが、好適には炭素鎖が直鎖構造を持った飽和脂肪酸アミドであり、かつ炭素原子数が、１０以上２５以下のものが好ましく、１５以上２０以下のものがさらに好ましい。
さらに、ポリビニルアセタールとしては、例えばポリビニルブチラールが挙げられる。ポリビニルブチラールとしては、分子量が１．０×１０４以上２０.０×１０４以下であることが好ましく、さらに好ましいのは１．５×１０４以上１０.０×１０４以下である。
Regardless of whether the thermoplastic binder is crystalline or amorphous, at least one selected from the group consisting of petroleum wax, fatty acid, fatty acid ester, and fatty acid amide can be used.
As the petroleum wax, any of paraffin wax, microcrystalline wax and petrolatum defined by Japanese Industrial Standards (JIS K2235) can be used. Preferable are saturated aliphatic hydrocarbons having a straight-chain carbon chain and having 18 to 35 carbon atoms, and more preferably 20 to 30 carbon atoms.
Further, the fatty acid is particularly limited depending on the shape of the carbon chain (whether it is chain-shaped or cyclic, may be branched), the number of cyclic carbon atoms, and the bonding state (saturated or unsaturated) of the carbon chain. Although not limited to these, it is preferably a saturated fatty acid having a straight chain carbon chain and having 10 or more and 25 or less carbon atoms, and more preferably 15 or more and 20 or less.
Further, the fatty acid ester is not particularly limited by the shape of the carbon chain of the fatty acid and alcohol, the number of carbon atoms, and the bond state (saturated or unsaturated) of the carbon chain, but preferably the carbon chain has a linear structure. A saturated fatty acid ester having a number of carbon atoms of 10 or more and 25 or less is preferable, and a fatty acid ester of 15 or more and 20 or less is more preferable.
The fatty acid amide is not particularly limited depending on the shape of the carbon chain of the fatty acid, the number of carbon atoms, and the bond state (saturated or unsaturated) of the carbon chain, but preferably the carbon chain has a linear structure. It is preferably a saturated fatty acid amide and has 10 or more and 25 or less carbon atoms, and more preferably 15 or more and 20 or less.
Furthermore, examples of the polyvinyl acetal include polyvinyl butyral. The polyvinyl butyral preferably has a molecular weight of 1.0×10 4 or more and 20.0×10 4 or less, and more preferably 1.5×10 4 or more and 10.0×10 4 or less.
また、熱可塑性バインダーの融点又はガラス転移点は、２０℃未満ではハンドリング時に熱可塑性バインダーの融解が容易に始まるために用いることができず、１３０℃を超えると造形前に予熱を必要とするため、２０℃以上１３０℃以下の範囲にあることが必要である。好ましくは３０℃以上１２０℃以下であり、さらに好ましいのは４０℃以上１１０℃以下である。また、熱可塑性バインダーは２種類以上を混合して用いてもよく、結晶質の熱可塑性バインダーと非晶質の熱可塑性バインダーとを混合して用いてもよい。 If the melting point or glass transition point of the thermoplastic binder is less than 20°C, it cannot be used because the melting of the thermoplastic binder easily starts during handling, and if it exceeds 130°C, preheating is required before shaping. It is necessary to be in the range of 20°C or higher and 130°C or lower. It is preferably 30°C or higher and 120°C or lower, and more preferably 40°C or higher and 110°C or lower. Two or more kinds of thermoplastic binders may be mixed and used, or a crystalline thermoplastic binder and an amorphous thermoplastic binder may be mixed and used.
本発明の造形用粉末のＨａｕｓｎｅｒ比は１．１０以上１．４０以下であることが好ましく、１．１０以上１．３０以下であることがさらに好ましく、１．１１以上１．２０以下であることが最も好ましい。Ｈａｕｓｎｅｒ比が１．１０未満であると造形用粉末の流動性が高くなりすぎて、粉末層形成時に造形物のすべりが生じやすくなる。また、Ｈａｕｓｎｅｒ比が１．４０を超えると造形用粉末の流動性が悪くなり、やはり粉末層形成時の層の乱れが生じやすくなる。Ｈａｕｓｎｅｒ比とは、造形用粉末の静かさ密度とタップ密度の値を、下記の式（１）を用いて計算した値をいう。ここで、静かさ密度とは、造形用粉末を静かに容器に入れたときの粉末の密度であり、ＪＩＳ−Ｒ１６２８に準じて測定した値をいう。また、タップ密度とは、造形用粉末を容器に入れた後，容器にタップによる衝撃を加え，体積変化がなくなったときの粉末の密度を指し、ＪＩＳ−Ｋ５１０１に準じて、タップ回数は２００回とした場合の値をいう。
また、本発明の造形用粉末は、単一もしくは複数の粒度分布ピークが１０μｍ以上５００μｍ以下の範囲にあることが好ましく、さらに好ましいのは２０μｍ以上３００μｍ以下であり、最も好ましいのは３０μｍ以上１００μｍ以下である。造形用粉末の粒度分布ピークが１０μｍ以上であれば流動性に優れ、粉末層形成における精度が向上する。また、造形用粉末の粒度分布ピークが５００μｍ以下であれば、作製した造形物の強度に優れたものとなる。なお、造形用粉末の粒度分布は、測定方法が特に限定されるものではないが、例えば、乾式のレーザー回折・散乱式粒度分布計や写真撮影と画像解析による分布測定により測定することができる。 Further, the modeling powder of the present invention preferably has a single or a plurality of particle size distribution peaks in the range of 10 μm or more and 500 μm or less, more preferably 20 μm or more and 300 μm or less, and most preferably 30 μm or more and 100 μm or less. Is. If the particle size distribution peak of the modeling powder is 10 μm or more, the fluidity is excellent and the accuracy in forming the powder layer is improved. Further, when the particle size distribution peak of the modeling powder is 500 μm or less, the strength of the fabricated model is excellent. The particle size distribution of the modeling powder is not particularly limited in the measuring method, but can be measured by, for example, a dry laser diffraction/scattering particle size distribution meter or distribution measurement by photography and image analysis.
また、熱可塑性バインダーの体積をセラミックス及び/又は金属の原料粉末の表面積で除した値は、０.０３μｍ以上３．００μｍ以下が好ましく、さらに好ましいのは０．０４μｍ以上１．００μｍ以下である。熱可塑性バインダーの体積を原料粉末の表面積で除した値が０．０３μｍ未満では、加熱による造形用粉末の固化体の強度が小さくなる。また、３．００μｍを超える場合、熱可塑性バインダーの含有量が多すぎて加熱時の熱可塑性バインダー溶融により造形物の寸法精度が低下するおそれがある。なお、原料粉末の表面積は、測定方法が特に限定されるものではないが、例えば、ガス吸着法を用いた表面積分析装置により比表面積を測定したのち、式（２）を用いて計算することができる。
（製造方法）
造形用粉末は、セラミックス及び／又は金属の原料粉末と熱可塑性バインダーとを混合することによって製造することができる。混合方法としては、乾式法（原料粉末と熱可塑性バインダーを乾式で混合する方法）及び湿式法（原料粉末と熱可塑性バインダーを湿式溶媒中に分散し、あるいは、溶解した熱可塑性バインダーを原料粉末と混ぜた後に、溶媒を取り除き、熱可塑性バインダーを原料粉末の粒子表面に固定化させる方法で混合する方法）のいずれの方法も用いることができる。乾式混合の方法ではボールミルやＶ型混合機を用いた混合方法などが挙げられ、湿式混合ではバインダーを分散させた溶液と原料粉末と混ぜ合わせた後に、加熱噴霧・乾燥させるスプレードライ法や、溶媒に溶かしたバインダーを加熱減圧下で溶媒を取り除き混合させる方法などが挙げられる。なお、湿式法で混合した場合においいて、溶媒中に分散した熱可塑性バインダーを用いた場合、原料粉末と混合後に溶媒を熱可塑性バインダーの融点よりも低い温度で取り除くことで熱可塑性バインダーが分散粒子状態で原料粉末の粒子表面に吸着され、分散した熱可塑性バインダーの融点よりも高い温度で溶媒を取り除く、もしくは溶媒に溶解した熱可塑性バインダーを用いた場合、熱可塑性バインダーが原料粉末の粒子表面に膜状に吸着される。
(Production method)
The modeling powder can be manufactured by mixing the raw material powder of ceramics and/or metal with a thermoplastic binder. As a mixing method, a dry method (a method of mixing the raw material powder and the thermoplastic binder in a dry method) and a wet method (dispersing the raw material powder and the thermoplastic binder in a wet solvent or dissolving the thermoplastic binder into the raw material powder After the mixing, the solvent is removed, and the thermoplastic binder is immobilized on the particle surfaces of the raw material powders). Examples of the dry mixing method include a mixing method using a ball mill and a V-type mixer. In the wet mixing, a solution in which a binder is dispersed and a raw material powder are mixed and then spray-dried by heating and spraying, or a solvent. Examples of the method include a method of removing the solvent and mixing the binder dissolved in the solvent under heating and reduced pressure. In the case of mixing by a wet method, when a thermoplastic binder dispersed in a solvent is used, the thermoplastic binder is dispersed particles by removing the solvent at a temperature lower than the melting point of the thermoplastic binder after mixing with the raw material powder. Adsorbed on the particle surface of the raw material powder in the state, the solvent is removed at a temperature higher than the melting point of the dispersed thermoplastic binder, or when a thermoplastic binder dissolved in the solvent is used, the thermoplastic binder is on the particle surface of the raw material powder. Adsorbed in the form of a film.
（使用方法）
本発明の造形用粉末を用いて粉末床溶融結合法を実施する場合、粉末層形成の方法としては、ブレード等を移動させて粉末を粉末層に展開する方法や、回転するローラーを移動させて粉末を粉末層に展開する方法、逆回転のローラーを移動させて粉末を粉末層に展開する方法などが挙げられる。
また、本発明の造形用粉末に対してレーザー光としては、例えばＣＯ２レーザー、ファイバーレーザー、ＹＡＧレーザー、エキシマレーザー、Ｈｅ−Ｃｄレーザー、半導体励起固体レーザーなどを挙げることができる。この中で、ＣＯ２レーザーは、簡易に制御でき、特に好適に用いることができる。これらのレーザーは、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることができる。
さらに、本発明の造形用粉末を造形する際に、レーザー照射時の雰囲気としては、例えばヘリウム、窒素、アルゴンなどのガス中、あるいは大気中においても実施できる。雰囲気を不活性ガスとすることで、造形用粉末の酸化や腐食を防止するとともに、レーザー光照射による造形物の過熱による変形を防止することができる。
(how to use)
When carrying out the powder bed fusion bonding method using the molding powder of the present invention, as a method for forming the powder layer, a method of moving the blade or the like to develop the powder into the powder layer, or a rotating roller is moved. Examples thereof include a method of spreading the powder in the powder layer and a method of moving the reversely rotating roller to spread the powder in the powder layer.
Further, examples of the laser light for the modeling powder of the present invention include CO 2 laser, fiber laser, YAG laser, excimer laser, He-Cd laser, and semiconductor-excited solid-state laser. Among these, the CO 2 laser can be easily controlled and can be used particularly preferably. These lasers can be used alone or in combination of two or more.
Furthermore, when shaping the shaping powder of the present invention, the atmosphere during laser irradiation can be carried out in a gas such as helium, nitrogen, or argon, or in the atmosphere. By making the atmosphere an inert gas, it is possible to prevent oxidation and corrosion of the modeling powder and prevent deformation of the modeled article due to overheating due to laser light irradiation.
[実施例１]
アルミナ粗粒粉(粒度分布ピーク４１μｍ)１００重量部に対してステアリン酸粗粒粉(粒度分布ピーク１２５μｍ)１５重量部を温エタノール（５０℃）に溶解させ、アルミナ粗粒粉と混合した。加熱減圧下でエタノールを取り除き、粉砕した。１００μｍのふるいを通して粗大な粒子を取り除き、実施例１の造形用粉末を得た。
[Example 1]
15 parts by weight of stearic acid coarse powder (particle size distribution peak 125 μm) was dissolved in 100 parts by weight of alumina coarse powder (particle size distribution peak 41 μm) in warm ethanol (50° C.) and mixed with alumina coarse powder. The ethanol was removed under heating and reduced pressure, and the mixture was crushed. Coarse particles were removed through a 100 μm sieve to obtain a molding powder of Example 1.
[実施例２]
アルミナ粗粒粉(粒度分布ピーク４１μｍ)１００重量部に対してステアリン酸エマルジョン（固形成分３０重量％、溶媒：水）中の固形成分が２０重量部になるよう、アルミナ粗粒粉とステアリン酸エマルジョンを混合した。混合水溶液を室温で乾燥させ粉砕した。１００μｍのふるいを通して粗大な粒子を取り除き、実施例２の造形用粉末を得た。
[Example 2]
Alumina coarse powder and stearic acid emulsion so that the solid component in the stearic acid emulsion (solid content 30% by weight, solvent: water) is 20 parts by weight with respect to 100 parts by weight of alumina coarse powder (particle size distribution peak 41 μm). Were mixed. The mixed aqueous solution was dried at room temperature and ground. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 2.
[実施例３〜実施例１１]
アルミナ粗粒粉(粒度分布ピーク３１μｍ)１００重量部に対してステアリン酸粗粒粉(粒度分布ピーク５５μｍ)粉末１５重量部をＶ型混合機（ＶＭ−２：筒井理化学器機株式会社製）にて混合した。２５０μｍのふるいを通して粗大な粒子を取り除き、実施例３の造形用粉末を得た。
また、実施例４では熱可塑性バインダーとしてポリビニルブチラール粗粒粉(粒度分布ピーク５５μｍ)を用い、実施例５ではベヘニル酸エステル粗粒粉（粒度分布ピーク７６μｍ）を用い、その他の条件は実施例３と同様にして造形用粉末を得た。
さらに、実施例６シリコン粗粒粉(粒度分布ピーク２３μｍ)、実施例７ではシリカ粗粒粉(粒度分布ピーク４６μｍ)、実施例８ではムライト粗粒粉(粒度分布ピーク１５μｍ)、実施例９ではジルコニア粗粒粉(粒度分布ピーク２８μｍ)、実施例１０では炭化ケイ素粗粒粉(粒度分布ピーク２６μｍ)、実施例１１では炭化ケイ素粗粒粉(粒度分布ピーク４３μｍ)、を用い、その他の条件は実施例３と同様にして造形用粉末を得た。
[Examples 3 to 11]
15 parts by weight of coarse powder of stearic acid (particle size distribution peak: 55 μm) was added to 100 parts by weight of coarse alumina powder (particle size distribution peak: 31 μm) with a V-type mixer (VM-2: Tsutsui Rikagiki Co., Ltd.). Mixed. Coarse particles were removed through a 250 μm sieve to obtain a molding powder of Example 3.
In Example 4, polyvinyl butyral coarse particles (particle size distribution peak 55 μm) was used as the thermoplastic binder, and in Example 5, behenyl ester coarse particles (particle size distribution peak 76 μm) were used. Other conditions were those of Example 3 A molding powder was obtained in the same manner as in.
Further, Example 6 silicon coarse powder (particle size distribution peak 23 μm), Example 7 silica coarse powder (particle size distribution peak 46 μm), Example 8 mullite coarse powder (particle size distribution peak 15 μm), Example 9 Zirconia coarse particles (particle size distribution peak 28 μm), silicon carbide coarse particles (particle size distribution peak 26 μm) in Example 10, silicon carbide coarse particles (particle size distribution peak 43 μm) in Example 11, and other conditions were used. A molding powder was obtained in the same manner as in Example 3.
［実施例１２〜実施例１５］
アルミナ微粒粉(粒度分布ピーク０．５μｍ)１００重量部に対して分散剤（Ａ６１１４、東亜合成株式会社製）1重量部、水２５重量部を加え、各種熱可塑性バインダーの水系エマルジョン（実施例１２ではマイクロクリスタリンワックスのエマルジョン、実施例１３ではステアリン酸のエマルジョン、実施例１４ではパラフィンワックスのエマルジョン、実施１５ではステアリン酸アミドのエマルジョン）をアルミナ微粒粉１００重量部に対して熱可塑性バインダー固形成分が２０重量部になるように混合した。混合水溶液をスプレードライ装置（スプレードライヤＡＤＬ３１１Ｓ：ヤマト科学株式会社製）にて造粒粒子径が約３０μｍになるように調製して造粒した。１００μｍのふるいを通して粗大な粒子を取り除き、実施例１２〜実施例１５の造形用粉末を得た。
[Examples 12 to 15]
To 100 parts by weight of fine alumina powder (particle size distribution peak: 0.5 μm), 1 part by weight of a dispersant (A6114, manufactured by Toagosei Co., Ltd.) and 25 parts by weight of water were added, and an aqueous emulsion of various thermoplastic binders (Example 12). Microcrystalline wax emulsion, stearic acid emulsion in Example 13, paraffin wax emulsion in Example 14, stearic acid amide emulsion in Example 15), and the thermoplastic binder solid component was added to 100 parts by weight of alumina fine powder. It mixed so that it might become 20 weight part. The mixed aqueous solution was prepared with a spray dryer (Spray dryer ADL311S: manufactured by Yamato Scientific Co., Ltd.) so as to have a granulated particle diameter of about 30 μm and granulated. Coarse particles were removed through a 100 μm sieve to obtain the modeling powders of Examples 12 to 15.
［実施例１６］
アルミナ微粒粉(粒度分布ピーク０．５μｍ)１００重量部に対してステアリン酸エマルジョン（固形成分３０重量％、溶媒：水）の固形成分が２０重量部になるように混合した。混合水溶液を室温で乾燥させ、１００μｍのふるいを通して粗大な粒子を取り除き、実施例１６の造形用粉末を得た。
[Example 16]
A solid component of a stearic acid emulsion (solid component 30% by weight, solvent: water) was mixed in an amount of 20 parts by weight with respect to 100 parts by weight of fine alumina powder (particle size distribution peak: 0.5 μm). The mixed aqueous solution was dried at room temperature, and coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 16.
［実施例１７］
アルミナ粗粒粉(粒度分布ピーク１２μｍ)７０重量部とアルミナ微粒粉(粒度分布ピーク０．５μｍ) ３０重量部を混合し、混合したアルミナ原料粉末１００重量部に対して分散剤（Ａ６１１４、東亜合成株式会社製）1重量部、水２５重量部を加え、ステアリン酸エマルジョン(固形成分３０重量％、溶媒：水)の固形成分が２０重量部になるように混合した。混合水溶液をスプレードライ装置（スプレードライヤＡＤＬ３１１Ｓ：ヤマト科学株式会社製）にて造粒粒子径が約３０μｍになるように調製して造粒した。１００μｍのふるいを通して粗大な粒子を取り除き、実施例１７の造形用粉末を得た。
[Example 17]
70 parts by weight of coarse alumina powder (particle size distribution peak 12 μm) and 30 parts by weight of fine alumina powder (particle size distribution peak 0.5 μm) were mixed, and a dispersant (A6114, Toa Gosei) was added to 100 parts by weight of the mixed alumina raw material powder. 1 part by weight and 25 parts by weight of water were added and mixed so that the solid component of the stearic acid emulsion (solid component 30% by weight, solvent: water) was 20 parts by weight. The mixed aqueous solution was prepared with a spray dryer (Spray dryer ADL311S: manufactured by Yamato Scientific Co., Ltd.) so as to have a granulated particle diameter of about 30 μm and granulated. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 17.
［実施例１８］
アルミナ粗粒粉(粒度分布ピーク３１μｍ) ８０重量部とアルミナ微粒粉(粒度分布ピーク０．５μｍ) ２０重量部を混合し、混合したアルミナ原料粉末１００重量部に対してステアリン酸エマルジョン(固形成分３０重量％、溶媒：水)の固形成分が２０重量部になるように混合した。混合水溶液を室温で乾燥させ粉砕後、１００μｍのふるいを通して粗大な粒子を取り除き、実施例１８の造形用粉末を得た。
[Example 18]
80 parts by weight of coarse alumina powder (particle size distribution peak 31 μm) and 20 parts by weight of fine alumina powder (particle size distribution peak 0.5 μm) were mixed, and stearic acid emulsion (solid component 30 The solid components (wt%, solvent: water) were mixed so as to be 20 parts by weight. After the mixed aqueous solution was dried at room temperature and pulverized, coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 18.
［実施例１９］
アルミナ微粒粉(粒度分布ピーク０．５μｍ)１００重量部に対して分散剤（Ａ６１１４、東亜合成株式会社製）1重量部、水３０重量部を加え、ステアリン酸エマルジョン（固形成分３０重量％、溶媒：水）をアルミナ微粒粉１００重量部に対して熱可塑性バインダー固形成分が３０重量部になるように混合した。混合水溶液をスプレードライ装置（スプレードライヤＡＤＬ３１１Ｓ：ヤマト科学株式会社製）にて造粒した。１００μｍのふるいを通して粗大な粒子を取り除き、造粒粉を作製した。作製した造粒粉１００重量部に対して、アルミナ粗粒粉(粒度分布ピーク３１μｍ)を２０重量部に配合して、Ｖ型混合機（ＶＭ−２：筒井理化学器機株式会社製）にて混合した。１００μｍのふるいを通して粗大な粒子を取り除き、実施例１９の造形用粉末を得た。
[Example 19]
1 part by weight of a dispersant (A6114, manufactured by Toagosei Co., Ltd.) and 30 parts by weight of water were added to 100 parts by weight of fine alumina powder (particle size distribution peak: 0.5 μm), and a stearic acid emulsion (solid component 30% by weight, solvent) was added. : Water) was mixed such that the solid component of the thermoplastic binder was 30 parts by weight with respect to 100 parts by weight of the alumina fine powder. The mixed aqueous solution was granulated by a spray dryer (Spray dryer ADL311S: manufactured by Yamato Scientific Co., Ltd.). Coarse particles were removed through a 100 μm sieve to prepare granulated powder. 20 parts by weight of coarse alumina powder (particle size distribution peak 31 μm) was mixed with 100 parts by weight of the produced granulated powder, and mixed with a V-type mixer (VM-2: Tsutsui Rikagiki Co., Ltd.). did. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 19.
[実施例２０]
アルミナ微粒粉(粒度分布ピーク０．５μｍ)１００重量部に対してステアリン酸粗粒粉(粒度分布ピーク１２５μｍ)を２０重量部加え混合した。２５０μｍのふるいを通して粗大な粒子を取り除き、実施例２０の造形用粉末を得た。
[Example 20]
20 parts by weight of coarse stearic acid powder (particle size distribution peak 125 μm) was added to 100 parts by weight of alumina fine particle powder (particle size distribution peak 0.5 μm) and mixed. Coarse particles were removed through a 250 μm sieve to obtain a modeling powder of Example 20.
[実施例２１]
アルミナ微粒粉(昭和電工株式会社製、粒度分布ピーク０．５μｍ)１００重量部に対してステアリン酸（純度９５％）２０重量部を温エタノール（５０℃）に溶かし、アルミナ微粒粉と混合した。加熱減圧下でエタノールを除き、粉砕。１００μｍのふるいを通して粗大な粒子を取り除き、実施例２１の造形用粉末を得た。
[Example 21]
20 parts by weight of stearic acid (purity 95%) was dissolved in 100 parts by weight of alumina fine powder (Showa Denko KK, particle size distribution peak: 0.5 μm) in warm ethanol (50° C.) and mixed with alumina fine powder. Remove ethanol under heating and reduced pressure and crush. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 21.
[実施例２２]
アルミナ微粒粉(粒度分布ピーク０．５μｍ)１００重量部に対して分散剤（Ａ６１１４、東亜合成株式会社製）1重量部、水２５重量部を加え、ステアリン酸エマルジョン（固形成分３０重量％、溶媒：水）をアルミナ微粒粉１００重量部に対して熱可塑性バインダー固形成分が２０重量部になるように混合した。混合水溶液をスプレードライ装置（スプレードライヤＡＤＬ３１１Ｓ：ヤマト科学株式会社製）にて造粒粒子径が約４０μｍになるように調製して造粒した。１００μｍのふるいを通して粗大な粒子を取り除き、実施例２２の造形用粉末を得た。
[Example 22]
To 100 parts by weight of fine alumina powder (particle size distribution peak: 0.5 μm), 1 part by weight of a dispersant (A6114, manufactured by Toagosei Co., Ltd.) and 25 parts by weight of water were added, and a stearic acid emulsion (solid content 30% by weight, solvent) : Water) was mixed such that the solid component of the thermoplastic binder was 20 parts by weight with respect to 100 parts by weight of the fine alumina powder. The mixed aqueous solution was prepared with a spray dryer (Spray dryer ADL311S: manufactured by Yamato Scientific Co., Ltd.) so as to have a granulated particle diameter of about 40 μm and granulated. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 22.
[実施例２３]
アルミナ微粒粉(昭和電工株式会社製、粒度分布ピーク０．５μｍ)１００重量部に対して分散剤（Ａ６１１４、東亜合成株式会社製）1重量部、水２５重量部を加え、ステアリン酸をアルミナ微粒粉１００重量部に対して熱可塑性バインダー固形成分が１０重量部になるように混合した。混合水溶液をスプレードライ装置（スプレードライヤＡＤＬ３１１Ｓ：ヤマト科学株式会社製）にて、造粒粒子径が約３０μｍになるように調製して造粒した。１００μｍのふるいを通して粗大な粒子を取り除き、実施例２３の造形用粉末を得た。
[Example 23]
1 part by weight of a dispersant (A6114, manufactured by Toagosei Co., Ltd.) and 25 parts by weight of water were added to 100 parts by weight of alumina fine powder (Showa Denko KK, particle size distribution peak 0.5 μm), and stearic acid was added as alumina fine particles. The thermoplastic binder solid component was mixed in an amount of 10 parts by weight with respect to 100 parts by weight of the powder. The mixed aqueous solution was prepared and granulated by a spray dryer (Spray dryer ADL311S: manufactured by Yamato Scientific Co., Ltd.) so that the granulated particle diameter was about 30 μm. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Example 23.
[実施例２４]
熱可塑性バインダーとしてパラフィンワックスを用い、その他の条件は実施例２３と同様にして実施例２４の造形用粉末を得た。
[Example 24]
Paraffin wax was used as the thermoplastic binder, and the other conditions were the same as in Example 23 to obtain a modeling powder of Example 24.
[実施例２５]
アルミナ微粒粉(粒度分布ピーク０．５μｍ) ３０重量部とアルミナ粗粒粉(粒度分布ピーク１２μｍ)７０重量部を混合し、混合したアルミナ原料粉末１００重量部に対してステアリン酸エマルジョン(固形成分３０重量％、溶媒：水)固形成分が１４重量部になるように混合した。混合水溶液をスプレードライ装置（スプレードライヤＡＤＬ３１１Ｓ、ヤマト科学株式会社製）にて、造粒粒子径が約３０μｍになるように調製して造粒した。造粒粉を１００μｍのふるいを通して、粗大な粒子を取り除き、実施例２５の造形用粉末を得た。
[Example 25]
30 parts by weight of fine alumina powder (particle size distribution peak 0.5 μm) and 70 parts by weight of coarse alumina powder (particle size peak 12 μm) were mixed, and 100 parts by weight of the mixed alumina raw material powder was mixed with a stearic acid emulsion (solid component 30 (Wt%, solvent: water) The solid components were mixed so as to be 14 parts by weight. The mixed aqueous solution was prepared and granulated with a spray dryer (Spray dryer ADL311S, manufactured by Yamato Scientific Co., Ltd.) so that the granulated particle diameter was about 30 μm. The granulated powder was passed through a 100 μm sieve to remove coarse particles, and a molding powder of Example 25 was obtained.
[実施例２６]
アルミナ粗粒粉（粒度分布ピーク３１μｍ）１００重量部に対して、実施例４で作製した造粒粉（アルミナ微粒粉/ステアリン酸）５０重量部をＶ型混合機（ＶＭ−２：筒井理化学器機株式会社製）にて混合した。１００μｍのふるいを通し、粗大な粒子を取り除き、実施例２６の造形用粉末を得た。
[Example 26]
50 parts by weight of the granulated powder (alumina fine particles/stearic acid) produced in Example 4 was added to 100 parts by weight of coarse alumina powder (particle size distribution peak 31 μm) in a V-type mixer (VM-2: Tsutsui Rikagikiki). (Made by KK). Coarse particles were removed through a 100 μm sieve to obtain a powder for modeling in Example 26.
［比較例１］
アルミナ粗粒粉(粒度分布ピーク３１μｍ) １００重量部に対してナイロン樹脂粗粒粉(粒度分布ピーク５０μｍ)１０重量部をＶ型混合機（ＶＭ−２：筒井理化学器機株式会社製）にて混合した。１００μｍのふるいを通して粗大な粒子を取り除き、比較例１の造形用粉末を得た。
[Comparative Example 1]
Alumina coarse particles (particle size distribution peak 31 μm) 100 parts by weight Nylon resin coarse particles (particle size distribution peak 50 μm) 10 parts by weight are mixed by a V-type mixer (VM-2: Tsutsui Rikagiki Co., Ltd.). did. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Comparative Example 1.
[比較例２]
アルミナ粗粒粉(粒度分布ピーク３１μｍ) １００重量部に対してポリプロピレン樹脂微粒粉(粒度分布ピーク７μｍ)１０重量部をＶ型混合機（ＶＭ−２：筒井理化学器機株式会社製）にて混合した。１００μｍのふるいを通して粗大な粒子を取り除き、比較例２の造形用粉末を得た。
[Comparative Example 2]
10 parts by weight of polypropylene resin fine particles (particle size distribution peak 7 μm) were mixed with 100 parts by weight of alumina coarse particle powder (particle size distribution peak 31 μm) by a V-type mixer (VM-2: Tsutsui Rikagiki Co., Ltd.). .. Coarse particles were removed through a 100 μm sieve to obtain a modeling powder of Comparative Example 2.
以上のようにして得られた実施例１〜２６及び比較例１、２の造形用粉末を、粉末床溶融結合装置（Ｒａｆａｅｌ３００：株式会社アスペクト製）を用いて予熱を行わず、レーザー出力１０Ｗで造形物を作製した。 The shaping powders of Examples 1 to 26 and Comparative Examples 1 and 2 obtained as described above were not preheated using a powder bed fusion bonding apparatus (Rafael 300: manufactured by Aspect Co., Ltd.), and laser output was 10 W. A shaped article was produced.
＜評 価＞
以上のようにして調製した実施例１〜２６及び比較例１、２の造形用粉末、及びそれによって製造された造形物について、以下の測定を行った。結果を表１及び表２に示す。
［熱可塑性バインダー含有量の測定］
熱分析装置（ＴＧ８１２０：リガク株式会社製）を用いて、大気下で１０００℃まで加熱し熱可塑性バインダーを燃焼させ、重量減少から熱可塑性バインダー含有量（ｇ）、残留重量から原料粉末含有量（ｇ）を計算した。
［熱可塑性バインダー融点の測定］
熱分析装置（ＴＧ８１２０：リガク株式会社製）を用いて、ＤＴＡ曲線をから判断した。
［熱可塑性バインダーガラス転移点の測定］
熱分析装置（ＳＤＴ Ｑ６００：ティ・エイ・インストルメンツ・ジャパン株式会社製）を用いて、ＤＳＣ曲線から判断した
［Ｈａｕｓｎｅｒ比の測定］
粉末の静かさ密度とタップ密度を測定し、前述した式（１）を用いて計算した。
[粒度分布の測定］
乾式のレーザー回折・散乱式粒度分析計（ＭＴ３０００、マイクロトラックベル社製）により測定した。
[原料粉末の表面積]
比表面積を表面積分析装置（ＡＵＴＯＳＯＲＢ-３：ユアサアイオニクス株式会社製）を用いて測定し、前述した式（２）を用いて計算した。
[熱可塑性バインダーの体積]
造形粉末中の熱可塑性バインダーの重量と熱可塑性バインダーの密度から、前述した式（３）を用いて体積を計算した。
［造形物の作製］
粉末床溶融結合装置（Ｒａｆａｅｌ３００、光源：ＣＯ２のレーザー、株式会社アスペクト製）を用い、大気下、予熱無しで造形物（３ｍｍ×５ｍｍ×７０ｍｍ）を作製した。
<Evaluation>
The following measurements were performed on the modeling powders of Examples 1 to 26 and Comparative Examples 1 and 2 prepared as described above, and the molded articles manufactured thereby. The results are shown in Tables 1 and 2.
[Measurement of Thermoplastic Binder Content]
Using a thermal analyzer (TG8120: manufactured by Rigaku Co., Ltd.), the thermoplastic binder is burned by heating to 1000° C. in the atmosphere, the thermoplastic binder content (g) is calculated from the weight loss, and the raw material powder content (g) from the residual weight ( g) was calculated.
[Measurement of melting point of thermoplastic binder]
Using a thermal analyzer (TG8120: manufactured by Rigaku Corporation), the DTA curve was determined.
[Measurement of glass transition point of thermoplastic binder]
A thermal analyzer (SDT Q600: manufactured by TA Instruments Japan Co., Ltd.) was used to judge from the DSC curve [measurement of Hausner ratio].
The quietness density and tap density of the powder were measured and calculated using equation (1) above.
[Measurement of particle size distribution]
It was measured by a dry laser diffraction/scattering particle size analyzer (MT3000, manufactured by Microtrac Bell).
[Surface area of raw material powder]
The specific surface area was measured using a surface area analyzer (AUTOSORB-3: manufactured by Yuasa Ionics Co., Ltd.) and calculated using the above-mentioned formula (2).
[Volume of thermoplastic binder]
From the weight of the thermoplastic binder in the modeling powder and the density of the thermoplastic binder, the volume was calculated using the above formula (3).
[Preparation of modeled object]
Using a powder bed fusion bonder (Rafael 300, light source: CO 2 laser, manufactured by Aspect Co., Ltd.), a modeled object (3 mm×5 mm×70 mm) was produced in the atmosphere without preheating.
表１に示すように、融点（非晶質ではガラス転移点）が低い熱可塑性バインダーを用いた実施例１〜１１では、粉末層形成の工程を１回又は複数回行えば、予熱すること無しに、粉末床溶融結合法により造形物の作製が可能であった。一方、高融点の熱可塑性バインダーを用いた比較例１及び比較例２では、粉末層の予熱を行わず造形を行うと、造形物に反りやクラックが生じ、正常な造形物を作成することができなかった。 As shown in Table 1, in Examples 1 to 11 using the thermoplastic binder having a low melting point (glass transition point in the case of amorphous), preheating is not performed if the step of forming the powder layer is performed once or plural times. In addition, it was possible to produce a molded article by the powder bed fusion bonding method. On the other hand, in Comparative Example 1 and Comparative Example 2 using the high melting point thermoplastic binder, when modeling is performed without preheating the powder layer, the modeled product is warped or cracked, and a normal modeled product can be created. could not.
表２に示すように、実施例１２〜２６の造形用粉末を用いた場合、粉末層の予熱を行わなくても、造形物を作製することが可能であった。ただし、Ｈａｕｓｎｅｒ比が１．４０を超える実施例２０及び実施例２１では、造形用粉末を粉末層に敷く際に、粉末層上に亀裂や引きずりが生じ、造形物の内外部に欠陥が生じた。また、Ｈａｕｓｎｅｒ比が１．１０未満である実施例２２では、造形中に造形物のすべりが起きて、造形物中に積層のズレが生じた。以上のことから、造形用の粉末の流動性は、Ｈａｕｓｎｅｒ比が１．１０以上１．４０以下であることが好ましいことが分かった。
また、熱可塑性バインダーの体積を前記セラミックス及び／又は金属の表面積で除した値が０.０３μｍ以下である実施例２３〜２６では、造形物が脆く、壊れやすかった。
As shown in Table 2, when the modeling powders of Examples 12 to 26 were used, it was possible to fabricate a modeled object without preheating the powder layer. However, in Examples 20 and 21 in which the Hausner ratio exceeds 1.40, when the modeling powder was laid on the powder layer, cracks and drag were generated on the powder layer, and defects were generated inside and outside the molded article. .. Further, in Example 22 in which the Hausner ratio was less than 1.10, slippage of the shaped product occurred during shaping, and a displacement of stacking occurred in the shaped product. From the above, it was found that the Hausner ratio of the powder for modeling is preferably 1.10 or more and 1.40 or less.
Further, in Examples 23 to 26 in which the value obtained by dividing the volume of the thermoplastic binder by the surface area of the ceramics and/or the metal was 0.03 μm or less, the shaped objects were brittle and were easily broken.
＜造形用粉末の構造＞
実施例の造形用粉末を走査型電子顕微鏡で観察した結果、得られた模式図を図１に示す。以下に図１中の文言の意味を以下に示す。
・粗粒粉：粒度分布ピークが１０μｍ以上４００μｍ以下の範囲にある原料粉末。
・微粒粉：粒度分布ピークが０．１μｍ以上１０μｍ未満の範囲にある原料粉末。
・粉末粒子状：乾式混合で作製した造形用粉末であり、原料粉末と熱可塑性バインダーの粒子が別粒子状態であることを示す。
・膜状：湿式混合で作製した造形用粉末であり、原料粉末と熱可塑性バインダーが造形用粉末粒子に含まれ、熱可塑性バインダーが溶融固化した状態を示す。
・分散粒子状：湿式混合で作製した造形用粉末であり、原料粉末と熱可塑性バインダーが造形用粉末粒子に含まれ、エマルジョン化した熱可塑性バインダー粒子が原料粉末表面に吸着もしくは一部溶解した状態を示す。
<Structure of modeling powder>
As a result of observing the modeling powder of the example with a scanning electron microscope, a schematic diagram obtained is shown in FIG. The meanings of the words in FIG. 1 are shown below.
Coarse-grained powder: Raw material powder having a particle size distribution peak in the range of 10 μm to 400 μm.
-Fine particle powder: Raw material powder having a particle size distribution peak in the range of 0.1 µm or more and less than 10 µm.
-Powder particle form: It is a powder for modeling produced by dry mixing, and shows that the raw material powder and the particles of the thermoplastic binder are in different particle states.
Membrane: A modeling powder produced by wet mixing, in which the raw material powder and the thermoplastic binder are included in the modeling powder particles, and the thermoplastic binder is melted and solidified.
・Dispersed particles: A powder for modeling produced by wet mixing, in which the raw material powder and the thermoplastic binder are included in the powder particles for modeling, and the emulsified thermoplastic binder particles are adsorbed or partially dissolved on the surface of the raw material powder. Indicates.
この発明は上記発明の実施の態様及び実施例の説明に何ら限定されるものではない。特許請求の範囲を逸脱せず、当業者が容易に想到できる範囲で種々の変形態様もこの発明に含まれる。 The present invention is not limited to the description of the embodiments and examples of the invention. Various modifications are also included in the present invention within the scope that can be easily conceived by those skilled in the art without departing from the scope of the claims.
Claims (9)
セラミックス及び／又は金属と、熱可塑性バインダーとを含む原料粉末からなり、
前記熱可塑性バインダーは石油ワックス、脂肪酸、脂肪酸エステル、脂肪酸アミド、及びポリビニルアセタールからなる群より選ばれた少なくとも１種類を含み、
前記熱可塑性バインダーの融点又はガラス転移点が２０℃以上１３０℃以下の範囲にあり、
Ｈａｕｓｎｅｒ比(タップ密度/かさ密度)が１．１０以上１．４０以下であり、
前記熱可塑性バインダーの体積を前記セラミックス及び／又は金属の表面積で除した値が０．０４μｍ以上１．００μｍ以下であることを特徴とする造形用粉末。 A molding powder used in a powder bed fusion bonding method,
A raw material powder containing ceramics and/or metal and a thermoplastic binder,
The thermoplastic binder contains at least one selected from the group consisting of petroleum wax, fatty acid, fatty acid ester, fatty acid amide, and polyvinyl acetal,
The melting point or glass transition point of the thermoplastic binder is in the range of 20° C. or higher and 130° C. or lower,
Hausner ratio (tap density/bulk density) is 1.10 or more and 1.40 or less,
A molding powder, wherein a value obtained by dividing the volume of the thermoplastic binder by the surface area of the ceramic and/or metal is 0.04 μm or more and 1.00 μm or less.
粒度分布ピークが１０μｍ以上４００μｍ以下に存在する第２の原料粉末と、
熱可塑性バインダーと、を含有しており、
前記複合粒子の粒度分布ピークが１０μｍ以上５００μｍ以下に存在していることを特徴とする請求項４に記載の造形用粉末。 A first raw material powder having a particle size distribution peak of 0.1 μm or more and less than 10 μm;
A second raw material powder having a particle size distribution peak of 10 μm or more and 400 μm or less;
Contains a thermoplastic binder,
The powder for modeling according to claim 4 , wherein the particle size distribution peak of the composite particles exists in a range of 10 μm to 500 μm.
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