JP2021123521A - Method for producing a ceramic raw material compound, and method for producing ceramic article using the ceramic raw material compound obtained by the method - Google Patents
Method for producing a ceramic raw material compound, and method for producing ceramic article using the ceramic raw material compound obtained by the method Download PDFInfo
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- JP2021123521A JP2021123521A JP2020018535A JP2020018535A JP2021123521A JP 2021123521 A JP2021123521 A JP 2021123521A JP 2020018535 A JP2020018535 A JP 2020018535A JP 2020018535 A JP2020018535 A JP 2020018535A JP 2021123521 A JP2021123521 A JP 2021123521A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 122
- 239000002994 raw material Substances 0.000 title claims abstract description 110
- 150000001875 compounds Chemical class 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 98
- 239000000178 monomer Substances 0.000 claims abstract description 70
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 62
- 238000000465 moulding Methods 0.000 claims description 49
- 238000005245 sintering Methods 0.000 claims description 32
- 239000008187 granular material Substances 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 13
- 150000002894 organic compounds Chemical class 0.000 claims description 12
- 238000005238 degreasing Methods 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 5
- 238000004898 kneading Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 38
- 239000011230 binding agent Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 125000005641 methacryl group Chemical group 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000009694 cold isostatic pressing Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
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- 238000011899 heat drying method Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- MXBHZLBILICSRF-UHFFFAOYSA-N (4-methyl-3-oxopent-4-enyl) N-[2,3-dimethyl-7-[(4-methyl-3-oxopent-4-enoxy)carbonylamino]heptan-2-yl]carbamate Chemical compound C(C(=C)C)(=O)CCOC(=O)NC(C(CCCCNC(=O)OCCC(C(=C)C)=O)C)(C)C MXBHZLBILICSRF-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- RSHKWPIEJYAPCL-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(CC)COC1 RSHKWPIEJYAPCL-UHFFFAOYSA-N 0.000 description 1
- FIQBJLHOPOSODG-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]benzoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=CC=C1C(O)=O FIQBJLHOPOSODG-UHFFFAOYSA-N 0.000 description 1
- GWFCWZQFUSJPRE-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]cyclohexane-1-carboxylic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1CCCCC1C(O)=O GWFCWZQFUSJPRE-UHFFFAOYSA-N 0.000 description 1
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DWTKNKBWDQHROK-UHFFFAOYSA-N 3-[2-(2-methylprop-2-enoyloxy)ethyl]phthalic acid Chemical compound CC(=C)C(=O)OCCC1=CC=CC(C(O)=O)=C1C(O)=O DWTKNKBWDQHROK-UHFFFAOYSA-N 0.000 description 1
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 1
- CGRJJOYCFCCGPX-UHFFFAOYSA-N 3-ethyloxetane Chemical compound CCC1COC1 CGRJJOYCFCCGPX-UHFFFAOYSA-N 0.000 description 1
- ZEWLHMQYEZXSBH-UHFFFAOYSA-M 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoate Chemical compound CC(=C)C(=O)OCCOC(=O)CCC([O-])=O ZEWLHMQYEZXSBH-UHFFFAOYSA-M 0.000 description 1
- GOGCLLMDQOJKHB-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]phthalic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GOGCLLMDQOJKHB-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NCAVPEPBIJTYSO-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound C1OC1COCC1CO1.OCCCCOC(=O)C=C NCAVPEPBIJTYSO-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- SWHLOXLFJPTYTL-UHFFFAOYSA-N [2-methyl-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(COC(=O)C(C)=C)COC(=O)C(C)=C SWHLOXLFJPTYTL-UHFFFAOYSA-N 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910002113 barium 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
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000011351 dental ceramic Substances 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Dental Preparations (AREA)
Abstract
Description
本発明は、セラミック製歯科加工用ミルブランク等のセラミック製物品を製造する際に好適に使用されるセラミック原料コンパウンドの製造方法、及び当該方法で得られたセラミック原料コンパウンドを用いてセラミック物品を製造する方法に関する。 The present invention comprises a method for producing a ceramic raw material compound preferably used when producing a ceramic article such as a ceramic mill blank for dental processing, and a method for producing a ceramic article using the ceramic raw material compound obtained by the method. Regarding how to do it.
セラミック物品の製造は一般的に、セラミック無機粉体と有機バインダーを含む組成物（複合物：コンパウンド）を調製し、これを目的とする形状に成形してから有機バインダーを除去し、更に焼結することによって製造されている。有機バインダーとしては、ポリビニルアルコールやエチレン樹脂、パラフィンなどのワックスといった有機樹脂を用いるのが一般的である。 In the production of ceramic articles, generally, a composition (composite: compound) containing a ceramic inorganic powder and an organic binder is prepared, molded into a desired shape, the organic binder is removed, and the mixture is further sintered. Manufactured by As the organic binder, an organic resin such as polyvinyl alcohol, ethylene resin, or wax such as paraffin is generally used.
例えば、特許文献１には、「有機バインダーとジルコニアを含有する成形体とアルカリ水溶液とを接触するアルカリ処理工程、及び、成形体を焼結する焼結工程、を有することを特徴とするジルコニア焼結体の製造方法」に関する発明が記載されており、具体的には、ジルコニア粉末とオレフィン樹脂系有機バインダーとを１７０℃で混練してコンパウンドを得、得られたコンパウンドを射出成形して成形体を得た後に、これをアルカリ水溶液で処理してから大気中、４５０℃で脱脂し、更に大気中１５００℃で２時間焼結してジルコニア焼結体を得たことが記載されている。また、特許文献２には、「焼結可能な金属またはセラミックスからなる無機系微粉末と有機系バインダー樹脂とを混練してコンパウンドを作製する工程と、次いで、このコンパウンドを射出成形して成形体を形成する工程と、次いで、得られた成形体をアルカリ性水溶液中に保持し、選択的にバインダー樹脂を加水分解除去して、脱脂体を得る工程と、次いで、この脱脂体を焼結し、粉末焼結体を得る工程とを有することを特徴とする粉末焼結体の製造方法」に関する発明が記載されている。 For example, Patent Document 1 includes a zirconia baking step of contacting a molded product containing an organic binder and zirconia with an alkaline aqueous solution, and a sintering step of sintering the molded product. An invention relating to "a method for producing a body" is described. Specifically, a zirconia powder and an olefin resin-based organic binder are kneaded at 170 ° C. to obtain a compound, and the obtained compound is injection-molded to form a molded product. It is described that this was treated with an alkaline aqueous solution, degreased in the air at 450 ° C., and further sintered in the air at 1500 ° C. for 2 hours to obtain a zirconia sintered body. Further, Patent Document 2 describes "a step of kneading an inorganic fine powder made of a sinterable metal or ceramics and an organic binder resin to prepare a compound, and then injection molding the compound to form a molded product. And then, the obtained molded article was held in an alkaline aqueous solution, and the binder resin was selectively hydrolyzed and removed to obtain a defatted body, and then the defatted body was sintered. An invention relating to "a method for producing a powder sintered body, which comprises a step of obtaining a powder sintered body" is described.
一方、デジタル技術の進歩により、所謂３Ｄプリンターなどを用いた光造形技術により得られた成形体を焼結することによりセラミックス物品を得る方法も知られている。たとえば特許文献３には、歯科材料形成用のジルコニア成形体の製造方法であって、ジルコニア粒子、重合性単量体及び光重合開始剤を含む組成物を用いて光造形する工程を有し、ジルコニア粒子の平均一次粒子径が３０ｎｍ以下であり、ジルコニア粒子の単分散度が５０％以上である、製造方法が記載されている。ここで、光造形とは上記組成物に光を照射することにより局所的に層を硬化させて成形体を一層ずつ順次形成していく技術であり、目的とする対象物（人工歯等）の３次元形状に対応した３次元ＣＡＤデータに基づく一層毎のスライスデータに従って光を照射することで、所望の形状を有する成形体を得ることができるとされている。なお、特許文献３の具体例では、上記組成物として、水にジルコニア微粒子が分散した水系ジルコニアスラリーに有機溶媒を添加してから共沸により水を除去することにより、分散媒を水から有機溶媒に置換した有機系スラリーとしてから重合性単量体と混合するといった煩雑な方法で得られたものが使用され、更に光造形後も長時間（５日間）乾燥した後に４００℃に加熱して仮焼体を得、更にそれを１０５０℃で焼結することによりセラミックス物品（人工歯）を得ている。 On the other hand, with the progress of digital technology, a method of obtaining a ceramic article by sintering a molded product obtained by a stereolithography technique using a so-called 3D printer or the like is also known. For example, Patent Document 3 is a method for producing a zirconia molded product for forming a dental material, which includes a step of photoforming using a composition containing zirconia particles, a polymerizable monomer, and a photopolymerization initiator. A production method is described in which the average primary particle size of the zirconia particles is 30 nm or less, and the monodispersity of the zirconia particles is 50% or more. Here, stereolithography is a technique of locally curing a layer by irradiating the above composition with light to sequentially form a molded product layer by layer, and is used for a target object (artificial tooth, etc.). It is said that a molded product having a desired shape can be obtained by irradiating light according to the slice data for each layer based on the three-dimensional CAD data corresponding to the three-dimensional shape. In a specific example of Patent Document 3, as the above composition, the dispersion medium is made into an organic solvent from water by adding an organic solvent to an aqueous zirconia slurry in which zirconia fine particles are dispersed in water and then removing water by co-boiling. The organic slurry replaced with is used, and then mixed with a polymerizable monomer, which is obtained by a complicated method. Further, after photoforming, it is dried for a long time (5 days) and then heated to 400 ° C. A ceramic article (artificial tooth) is obtained by obtaining a burnt body and further sintering it at 1050 ° C.
前記特許文献３に開示される方法では、焼結前の成形体を光造形技術により製造できるため、モールド金型などを別途準備することなく、所望の形状の成型体を得ることができる（少量多品種生産に適している）という利点がある半面、前記したような煩雑な方法で３０ｎｍ以下のジルコニア１次粒子が重合性単量体中に分散した原料組成物を調製する必要があり、（たとえば、規格化された）同一の形状を有する成形体、延いてはセラミック物品を大量に製造するには不向きである。 In the method disclosed in Patent Document 3, since the molded product before sintering can be produced by a stereolithography technique, a molded product having a desired shape can be obtained without separately preparing a mold or the like (small amount). While it has the advantage of being suitable for high-mix production), it is necessary to prepare a raw material composition in which zirconia primary particles of 30 nm or less are dispersed in a polymerizable monomer by a complicated method as described above. For example, it is not suitable for mass production of molded articles having the same shape (standardized), and thus ceramic articles.
これに対し、特許文献１や２に記載された方法では、前記コンパウンドは粉体状やペレット状を有して取り扱い易く、しかも成形に際しては、射出成形法、プレス成形法、鋳込み成形法などの成形法が適用できるため、所定形状のセラミック物品を一定の規模以上で量産する場合に適した方法であると言える。 On the other hand, in the methods described in Patent Documents 1 and 2, the compound has a powder or pellet shape and is easy to handle, and in molding, an injection molding method, a press molding method, a casting molding method, or the like is used. Since a molding method can be applied, it can be said that this method is suitable for mass production of ceramic articles having a predetermined shape on a certain scale or more.
しかしながら、コンパウンド調製に際しては、成形性を向上させるためにセラミック無機粉体に熱可塑性樹脂等の有機バインダーを混練する必要があり、そのためには有機バインダーが溶融する様な（例えば１６０℃〜１７０℃といった）高温で加圧式ニーダー、双腕式ニーダー又はスクリュー押出機等の専用の装置を用いて混錬を行う必要がある。そのため、セラミック製歯科加工用ミルブランクのような規格化された形状を有する物品であっても、比較的生産規模の小さい物品を製造する場合には、設備費負担が大きくまたエネルギーコストもかかると言う点で、必ずしも経済的な方法であるとは言えなかった。 However, when preparing the compound, it is necessary to knead an organic binder such as a thermoplastic resin with the ceramic inorganic powder in order to improve the moldability, and for that purpose, the organic binder is melted (for example, 160 ° C. to 170 ° C.). It is necessary to perform kneading at a high temperature using a dedicated device such as a pressurized kneader, a double-armed kneader or a screw extruder. Therefore, even if an article has a standardized shape such as a ceramic mill blank for dental processing, when an article having a relatively small production scale is manufactured, the equipment cost burden is large and the energy cost is also high. In that respect, it was not always an economical method.
そこで、本発明は、加圧式ニーダーやスクリュー押出し機といった大型装置を用いた混練を必要とせず、また１００℃以上といった高温での処理を必要とせずに、十分な成形性を有するセラミック原料コンパウンドを製造する方法を提供することを課題とする。 Therefore, the present invention provides a ceramic raw material compound having sufficient moldability without the need for kneading using a large device such as a pressure kneader or a screw extruder, and without the need for treatment at a high temperature of 100 ° C. or higher. An object of the present invention is to provide a method for manufacturing.
本発明は、下記技術手段により上記課題を解決するものである。 The present invention solves the above problems by the following technical means.
すなわち、本発明の第一の形態は、焼結可能なセラミック原料無機粉体（Ａ）：１００質量部、及び分子内に重合性基を有する有機化合物からなる重合性単量体（Ｂ）：１質量部以上２５質量部未満、を含むセラミック原料コンパウンドの製造方法であって、前記セラミック原料無機粉体（Ａ）１００質量に対して、１質量部以上２５質量部未満となる量の前記重合性単量体（Ｂ）が有機溶媒（Ｃ）に溶解したモノマー溶液（Ｄ）と、前記セラミック無機粉体（Ａ）１００質量部と、を混合して、前記セラミック原料無機粉体（Ａ）が前記モノマー溶液（Ｄ）中に分散したスラリーを調製するスラリー化工程、及び前記スラリー化工程で得られた前記スラリーから前記有機溶媒（Ｃ）を除去する溶媒除去工程、を含んでなることを特徴とする、前記セラミック原料コンパウンドの製造方法（以下、「本発明の原料製法」ともいう。）である。 That is, the first embodiment of the present invention is a polymerizable monomer (B) composed of a sinterable ceramic raw material inorganic powder (A): 100 parts by mass and an organic compound having a polymerizable group in the molecule. A method for producing a ceramic raw material compound containing 1 part by mass or more and less than 25 parts by mass, wherein the polymerization amount is 1 part by mass or more and less than 25 parts by mass with respect to 100 parts by mass of the ceramic raw material inorganic powder (A). The monomer solution (D) in which the sex monomer (B) is dissolved in the organic solvent (C) and 100 parts by mass of the ceramic inorganic powder (A) are mixed to form the ceramic raw material inorganic powder (A). Includes a slurrying step of preparing a slurry dispersed in the monomer solution (D) and a solvent removing step of removing the organic solvent (C) from the slurry obtained in the slurrying step. This is a characteristic method for producing the ceramic raw material compound (hereinafter, also referred to as "the raw material manufacturing method of the present invention").
上記本発明の原料製法においては、前記セラミック原料コンパウンドは重合開始剤を含まないことが好ましく、また、前記セラミック原料コンパウンドは、粉粒体であることが好ましい。さらに、前記重合性単量体（Ｂ）が、分子内に複数の重合性基を有するか、又は１つの重合性基と少なくとも１つの水素結合性基を有する、分子量が５０以上１０００以下の有機化合物からなることが好ましい。 In the raw material production method of the present invention, the ceramic raw material compound preferably does not contain a polymerization initiator, and the ceramic raw material compound is preferably a powder or granular material. Further, the polymerizable monomer (B) has a plurality of polymerizable groups in the molecule, or has one polymerizable group and at least one hydrogen-binding group, and has a molecular weight of 50 or more and 1000 or less. It preferably consists of a compound.
本発明の第二の形態は、本発明の第一の形態である前記方法によりセラミック原料コンパウンド粉粒体を製造する工程、前記工程で得られたセラミック原料コンパウンド粉粒体を成形し、所定の形状を有するグリーン体を得る成形工程、及び前記成形工程で得られたグリーン体を直接又は脱脂処理後に焼結する焼結工程を含んでなることを特徴とする、セラミック製物品の製造方法（以下、「本発明の物品製法」ともいう。）である。 The second embodiment of the present invention is a step of producing a ceramic raw material compound powder and granules by the method according to the first aspect of the present invention, and the ceramic raw material compound powder and granules obtained in the above step are molded and determined. A method for producing a ceramic article, which comprises a molding step of obtaining a green body having a shape and a sintering step of sintering the green body obtained in the molding step directly or after a degreasing treatment (hereinafter,). , Also referred to as "article manufacturing method of the present invention").
本発明の第三の形態は、本発明の物品製法によりジルコニア歯科用ミルブランクを製造する、ジルコニア歯科用ミルブランクの製造方法である。 A third aspect of the present invention is a method for producing a zirconia dental mill blank, which manufactures a zirconia dental mill blank by the article manufacturing method of the present invention.
本発明のセラミック原料コンパウンドの製造方法（本発明の原料製法）では、有機バインダーとして重合性単量体（Ｂ）を使用しているため、これを有機溶媒（Ｃ）に溶解させて焼結可能なセラミック原料無機粉体（Ａ）と混合してから有機溶媒（Ｃ）を除去すると言う簡単な方法で両者が均一な状態で複合化されたコンパウンドを得ることができる。このため、加圧式ニーダーやスクリュー押出し機等の高価な装置を使用することなく、且つ高温加熱することなく、原料コンパウンドを製造することができる。しかも、得られるセラミック原料コンパウンドは、従来の有機樹脂系バインダーを用いたコンパウンドと同様に、良好な成形性及び成形後における保形性を有する。また、コンパウンドは、取り扱い易く、しかも量産に適した射出出成形法、プレス成形法、鋳込み成形法などの成形法が適用できる粉粒体として得ることができる。 In the method for producing the ceramic raw material compound of the present invention (the raw material manufacturing method of the present invention), since the polymerizable monomer (B) is used as the organic binder, it can be dissolved in the organic solvent (C) and sintered. A compound in which both are in a uniform state can be obtained by a simple method of mixing with a ceramic raw material inorganic powder (A) and then removing the organic solvent (C). Therefore, the raw material compound can be produced without using an expensive device such as a pressure kneader or a screw extruder and without heating at a high temperature. Moreover, the obtained ceramic raw material compound has good moldability and shape retention after molding, similar to a compound using a conventional organic resin-based binder. Further, the compound can be obtained as a powder or granular material to which a molding method such as an injection molding method, a press molding method, or a casting molding method, which is easy to handle and suitable for mass production, can be applied.
したがって、本発明の原料製法で得られた前記セラミック原料コンパウンドを用いる本発明のセラミック製物品の製造方法（本発明の物品製法）は、コンパウンド調製において上記したような高価な装置を用いた加熱混錬法を採用することにコストメリットを見出すことができないような規模でセラミック製物品を製造する場合に適した方法であると言える。 Therefore, the method for producing a ceramic article of the present invention (the method for producing an article of the present invention) using the ceramic raw material compound obtained by the raw material manufacturing method of the present invention is a heating mixture using an expensive device as described above in compound preparation. It can be said that this method is suitable for manufacturing ceramic articles on a scale in which no cost advantage can be found in adopting the smelting method.
本発明の原料製法で製造するセラミック原料コンパウンドは、焼結可能なセラミック原料無機粉体（Ａ）：１００質量部、及び分子内に重合性基を有する有機化合物からなる重合性単量体（Ｂ）：１質量部以上２５質量部未満、を含んでなる。ここで、上記重合性単量体（Ｂ）は有機バインダーとして機能するものである。前記したように、従来のセラミック原料コンパウンドでは、有機バインダーとしては、加熱時に軟化或いは低粘度化して良好な成形性を示し、成形後に常温となった場合には硬化或いは高粘度化して良好な形態保持性を示す高分子量の「有機樹脂」を用いるのが一般的である。これに対して、本発明で使用する前記重合性単量体（Ｂ）は、低分子量であるにもかかわらず、前記特許文献３に記載された方法のように成形時において重合開始剤を配合した重合硬化工程を行わなくても良好な成形性及び成形後における保形性を有する。その理由は、必ずしも明らかではないが、溶媒除去工程や成形工程における、減圧操作や比較的低温での加熱操作、および加圧操作などによりモノマーの一部が自然に重合するためであると推定している。 The ceramic raw material compound produced by the raw material manufacturing method of the present invention is a polymerizable monomer (B) composed of a sinterable ceramic raw material inorganic powder (A): 100 parts by mass and an organic compound having a polymerizable group in the molecule. ): 1 part by mass or more and less than 25 parts by mass. Here, the polymerizable monomer (B) functions as an organic binder. As described above, in the conventional ceramic raw material compound, as an organic binder, it softens or becomes less viscous when heated to show good moldability, and when it reaches room temperature after molding, it cures or becomes more viscous to a good form. It is common to use a high molecular weight "organic resin" that exhibits retention. On the other hand, although the polymerizable monomer (B) used in the present invention has a low molecular weight, a polymerization initiator is blended at the time of molding as in the method described in Patent Document 3. It has good moldability and shape retention after molding without performing the polymerization curing step. The reason is not necessarily clear, but it is presumed that a part of the monomer is naturally polymerized by the depressurizing operation, the heating operation at a relatively low temperature, and the pressurizing operation in the solvent removing step and the molding step. ing.
１．本発明のセラミック原料コンパウンドの製造方法（本発明の原料製法）
本発明の原料製法は、前記セラミック原料無機粉体（Ａ）１００質量に対して、１質量部以上２５質量部未満となる量の前記重合性単量体（Ｂ）が有機溶媒（Ｃ）に溶解したモノマー溶液（Ｄ）と、前記セラミック無機粉体（Ａ）１００質量部と、を混合して、前記セラミック無機粉体（Ａ）が前記モノマー溶液（Ｄ）中に分散したスラリーを調製するスラリー化工程、及び前記スラリー化工程で得られた前記スラリーから前記有機溶媒（Ｃ）を除去する溶媒除去工程、を含んでなることを特徴とする。
1. 1. Method for producing ceramic raw material compound of the present invention (method for producing raw material of the present invention)
In the raw material production method of the present invention, the polymerizable monomer (B) in an amount of 1 part by mass or more and less than 25 parts by mass is used as an organic solvent (C) with respect to 100 parts by mass of the ceramic raw material inorganic powder (A). The dissolved monomer solution (D) and 100 parts by mass of the ceramic inorganic powder (A) are mixed to prepare a slurry in which the ceramic inorganic powder (A) is dispersed in the monomer solution (D). It is characterized by including a slurrying step and a solvent removing step of removing the organic solvent (C) from the slurry obtained in the slurrying step.
まず、本発明の原料製法で使用する各種原材料について説明する。
なお、本明細書においては特に断らない限り、数値ｘ及びｙを用いた「ｘ〜ｙ」という表記は「ｘ以上ｙ以下」を意味するものとする。かかる表記において数値ｙのみに単位を付した場合には、当該単位が数値ｘにも適用されるものとする。また、本明細書において、「（メタ）アクリル系」との用語は「アクリル系」及び「メタクリル系」の両者を意味する。
First, various raw materials used in the raw material manufacturing method of the present invention will be described.
In the present specification, unless otherwise specified, the notation "x to y" using the numerical values x and y means "x or more and y or less". When a unit is attached only to the numerical value y in such a notation, the unit shall be applied to the numerical value x as well. Further, in the present specification, the term "(meth) acrylic type" means both "acrylic type" and "methacryl type".
１−１．セラミック原料無機粉体（Ａ）
セラミック原料無機粉体（Ａ）としては、焼結可能なセラミックの粉体であれば特に限定されず、オキサイドセラミック粉体、非オキサイドセラミック粉体が使用できる。オキサイドセラミックを具体的に例示すると、ジルコニア、アルミナ、シリカ、チタニア、マグネシア、シリカジルコニア、チタン酸バリウム、チタン酸ジルコン酸鉛、二ケイ酸リチウムなどを挙げることができ、非オキサイドセラミックを具体的に例示すると、炭化ジルコニウム、炭化ケイ素、窒化アルミニウム、窒化ケイ素、窒化ホウ素などを挙げることができる。これらの中でも、強度等の観点から、ジルコニア、アルミナ、シリカ、シリカジルコニアの粉体を使用することが好ましい。これらの無機粉体は、２種類以上の無機粉体を混合して使用してもよく、例えばジルコニアとアルミナの混合粉体、ジルコニアとシリカの混合粉体などを用いてもよい。セラミック製歯科加工用ミルブランクのような歯科用途のセラミック物品用のセラミック原料コンパウンドに用いる場合には、色調、強度、靱性の観点からジルコニア粉体を主成分とするセラミック原料無機粉体を使用することが好ましい。ここで、主成分とはセラミック原料無機粉体全体の重量を１００重量部とした時に８０重量部以上であることを指す。
1-1. Ceramic raw material inorganic powder (A)
The ceramic raw material inorganic powder (A) is not particularly limited as long as it is a sinterable ceramic powder, and oxide ceramic powder and non-oxide ceramic powder can be used. Specific examples of oxide ceramics include zirconia, alumina, silica, titania, magnesia, silica zirconia, barium titanate, lead zirconate titanate, lithium disilicate, and the like. Examples thereof include zirconium carbide, silicon carbide, aluminum nitride, silicon nitride, and boron nitride. Among these, it is preferable to use powders of zirconia, alumina, silica, and silica zirconia from the viewpoint of strength and the like. As these inorganic powders, two or more kinds of inorganic powders may be mixed and used, and for example, a mixed powder of zirconia and alumina, a mixed powder of zirconia and silica, and the like may be used. When used in a ceramic raw material compound for ceramic articles for dental applications such as ceramic mill blanks for dental processing, a ceramic raw material inorganic powder containing zirconia powder as a main component is used from the viewpoint of color tone, strength and toughness. Is preferable. Here, the main component means that the weight of the entire ceramic raw material inorganic powder is 80 parts by weight or more when the weight is 100 parts by weight.
セラミック原料無機粉体としては、取り扱いが容易でかつ結晶の相変態が生じにくいという理由及び焼結により粒成長が進みすぎないという理由から、平均結晶子径が０．００１μｍ〜５０μｍのものが好適に用いられる。平均結晶子径０．００３μｍ〜２０μｍの粉末を用いることがより好ましい。 As the ceramic raw material inorganic powder, one having an average crystallite diameter of 0.001 μm to 50 μm is preferable because it is easy to handle, phase transformation of crystals is unlikely to occur, and grain growth does not proceed excessively due to sintering. Used for. It is more preferable to use a powder having an average crystallite diameter of 0.003 μm to 20 μm.
さらにセラミック原料無機粉体の凝集粒子の形状（外形）は、球形であっても非球形であってもよく、凝集粒子の平均粒子径も特に限定されないが、取り扱いやすさ及び成形性の観点から、形状は球状もしくは略球形が好ましく、凝集粒子の平均粒子径は５μｍ以上３００μｍ以下が好ましい。ここで、凝集粒子の平均粒子径とは、特記しない限り、走査型電子顕微鏡（ＳＥＭ）による観察に基づいて次のようにして決定された値である。すなわち、ＳＥＭにより観察される前記セラミック原料無機粉体（Ａ）の凝集粒子が球状又は略球状の場合には、ＳＥＭ観察画面において無作為に抽出した１００個の凝集粒子の最大径である凝集粒子径（Ｘｉ）を測定し、測定値に基づき、下記式１により凝集体の平均粒子径を算出することにより決定された値を意味する。また、ＳＥＭにより観察される前記セラミック原料無機粉体（Ａ）の粒子が不定形の場合には最大径を凝集粒子径（Ｘｉ）とみなし、球状の場合と同様に下記式１により凝集体の平均粒子径を算出することにより決定された値を意味する。 Further, the shape (outer shape) of the agglomerated particles of the ceramic raw material inorganic powder may be spherical or non-spherical, and the average particle size of the agglomerated particles is not particularly limited, but from the viewpoint of ease of handling and moldability. The shape is preferably spherical or substantially spherical, and the average particle size of the agglomerated particles is preferably 5 μm or more and 300 μm or less. Here, the average particle size of the agglomerated particles is a value determined as follows based on observation with a scanning electron microscope (SEM) unless otherwise specified. That is, when the aggregated particles of the ceramic raw material inorganic powder (A) observed by SEM are spherical or substantially spherical, the aggregated particles having the maximum diameter of 100 aggregated particles randomly selected on the SEM observation screen. It means a value determined by measuring the diameter (Xi) and calculating the average particle size of the agglomerates by the following formula 1 based on the measured value. Further, when the particles of the ceramic raw material inorganic powder (A) observed by SEM are indefinite, the maximum diameter is regarded as the aggregated particle diameter (Xi), and the aggregate is formed by the following formula 1 as in the case of spherical particles. It means a value determined by calculating the average particle size.
セラミック原料無機粉体（Ａ）は、焼結助剤を含んでもよい。焼結助剤とは、セラミックスを製造する際の焼結を促進させるために添加される無機粉体であり、主材となる焼結可能なセラミックの粉体の種類に応じて、公知のものが使用できる。例えば、主材がアルミナ粉体である場合には、シリカ、マグネシア、カルシア等が好適であり、主材がジルコニア粉体である場合にはアルミナ等が好適である。セラミック原料無機粉体（Ａ）が焼結助剤を含む場合における焼結助剤の添加量は、主材である焼結可能なセラミックの粉体１００質量部に対して、通常、０．００５〜１０質量部の範囲である。 The ceramic raw material inorganic powder (A) may contain a sintering aid. The sintering aid is an inorganic powder added to promote sintering in the production of ceramics, and is known depending on the type of sinterable ceramic powder as the main material. Can be used. For example, when the main material is alumina powder, silica, magnesia, calcia and the like are suitable, and when the main material is zirconia powder, alumina and the like are suitable. When the ceramic raw material inorganic powder (A) contains a sintering aid, the amount of the sintering aid added is usually 0.005 with respect to 100 parts by mass of the sinterable ceramic powder as the main material. It is in the range of 10 parts by mass.
１−２．重合性単量体（Ｂ）（以下、「モノマー」とも言う。）
重合性単量体（モノマー）（Ｂ）としては、分子内に重合性基有する有機化合物からなるものであれば特に限定されないが、有機溶媒に対する溶解性の観点から、その分子量は、５０〜１０００、特に１００〜５００であることが好ましい。また、脱脂、焼成工程により容易に除去できると言う観点から、モノマー分子構成する炭素及び水素以外の元素が酸素及び／又は窒素のみである有機化合物からなることが好ましい。
1-2. Polymerizable monomer (B) (hereinafter, also referred to as "monomer")
The polymerizable monomer (monomer) (B) is not particularly limited as long as it is composed of an organic compound having a polymerizable group in the molecule, but the molecular weight thereof is 50 to 1000 from the viewpoint of solubility in an organic solvent. In particular, it is preferably 100 to 500. Further, from the viewpoint that it can be easily removed by the degreasing and firing steps, it is preferable that the monomer molecule is composed of an organic compound in which elements other than carbon and hydrogen are only oxygen and / or nitrogen.
なお、重合性基とは光や熱などの刺激によって重合し得る官能基を意味し、具体的には、（メタ）アクリル基、ビニル基等のラジカル重合性基、エポキシ基、オキセタン基等のカチオン重合性基、アニオン重合性基などを挙げることができる。 The polymerizable group means a functional group that can be polymerized by a stimulus such as light or heat, and specifically, a radical polymerizable group such as a (meth) acrylic group or a vinyl group, an epoxy group, an oxetane group or the like. Examples thereof include a cationically polymerizable group and an anionic polymerizable group.
セラミック製歯科加工用ミルブランクのような歯科用途のセラミック物品用のセラミック原料コンパウンドに用いるモノマーにおける重合性基は、安全性等の理由から（メタ）アクリル基であることが好ましい。また、セラミック原料コンパウンドの成形性や成形後の形態保持性の観点から、重合性基は、（メタ）アクリル基又はエポキシ基であることが好ましい。更にこれら効果がより高まると言う観点から、モノマーとしては、分子内に複数の重合性基を有するか、又は１つの重合性基と少なくとも１つの水素結合性基を有するものを使用することが好ましい。ここで、水素結合性基とは分子内もしくは分子間で双極子相互作用し得る官能基を意味し、具体的には、カルボキシ基、アミノ基、アミド基、ヒドロキシ基等を挙げることができる。 The polymerizable group in the monomer used in the ceramic raw material compound for ceramic articles for dental applications such as ceramic mill blanks for dental processing is preferably a (meth) acrylic group for safety and other reasons. Further, from the viewpoint of moldability of the ceramic raw material compound and morphological retention after molding, the polymerizable group is preferably a (meth) acrylic group or an epoxy group. From the viewpoint of further enhancing these effects, it is preferable to use a monomer having a plurality of polymerizable groups in the molecule or having one polymerizable group and at least one hydrogen bonding group. .. Here, the hydrogen-bonding group means a functional group capable of dipole interaction within or between molecules, and specific examples thereof include a carboxy group, an amino group, an amide group, and a hydroxy group.
（１）分子内に複数の重合性基を有するとして、好適なものを例示すれば、（メタ）アクリル基を複数有するモノマーとして、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ウレタンジメタクリレート、ビスフェノールＡジグリシジルメタクリレート、１，６−ビス（メタクリルエチルオキシカルボニルアミノ）トリメチルヘキサン、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート等を挙げることができる。 (1) Examples of suitable monomers having a plurality of polymerizable groups in the molecule include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and urethane as monomers having a plurality of (meth) acrylic groups. Examples thereof include dimethacrylate, bisphenol A diglycidyl methacrylate, 1,6-bis (methacrylethyloxycarbonylamino) trimethylhexane, trimethylolpropane trimethacrylate, and trimethylolethanetrimethacrylate.
（２）１つの重合性基と少なくとも１つの水素結合性基を有するものを例示すれば、重合性基がエポキシ基であるものとして、メタクリル酸グリシジル、４−ヒドロキシブチルアクリレートグリシジルエーテル等を、重合性基が（メタ）アクリル基であるものとして、メタクリル酸、フタル酸２−メタクリロイルオキシエチル、ヘキサヒドロフタル酸２−メタクリロイルオキシエチル、２−メタクリロイルオキシエチルサクシネート、１１−メタクリロキシ−１，１−ウンデカンジカルボン酸、４−メタクリロキシエチルトリメリット酸等を挙げることができる。 (2) For example, those having one polymerizable group and at least one hydrogen-binding group are polymerized with glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether or the like, assuming that the polymerizable group is an epoxy group. As the sex group is a (meth) acrylic group, methacrylic acid, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, 2-methacryloyloxyethyl succinate, 11-methacryloyl-1,1- Examples thereof include undecanedicarboxylic acid and 4-methacryloxyethyl trimellitic acid.
これらモノマーは１種を単独で使用しても、２種以上を混合して使用してもよい。 These monomers may be used alone or in combination of two or more.
本発明におけるモノマーの含有量は、前記セラミック原料無機粉体（Ａ）１００質量部に対して１質量部以上２５質量部未満である必要がある。モノマーの含有量が１質量部未満の場合、モノマーの添加理由である成型性の向上が得られず、一方、含有量が２５質量部以上の場合、脱脂後や焼成後に十分な強度が得られないことがあるばかりでなく、成型の際にセラミック原料無機粉体（Ａ）とモノマー（Ｂ）で一部分離してしまうことがある。モノマーの上記含有量は４〜１５質量部であることが好ましい。なお、モノマー（Ｂ）は、スラリー化工程や溶媒除去工程において、その一部が重合して比較的低分子量の重合体やオリゴマーとなっている可能性があるが、その量を定量することは困難であるので、本発明では、セラミック原料コンパウンドにおけるモノマー（Ｂ）の含有量は、これらを含めた量（別言すれば、混合したモノマー量）で表している。 The content of the monomer in the present invention needs to be 1 part by mass or more and less than 25 parts by mass with respect to 100 parts by mass of the ceramic raw material inorganic powder (A). When the content of the monomer is less than 1 part by mass, the moldability which is the reason for adding the monomer cannot be improved, while when the content is 25 parts by mass or more, sufficient strength can be obtained after degreasing or firing. Not only may it not be present, but it may also be partially separated by the ceramic raw material inorganic powder (A) and the monomer (B) during molding. The content of the monomer is preferably 4 to 15 parts by mass. It should be noted that the monomer (B) may be partially polymerized into a polymer or oligomer having a relatively low molecular weight in the slurrying step or the solvent removing step, but the amount thereof cannot be quantified. Since it is difficult, in the present invention, the content of the monomer (B) in the ceramic raw material compound is represented by the amount including these (in other words, the amount of the mixed monomer).
１−３．有機溶媒（Ｃ）
有機溶媒（Ｃ）としては、前記モノマー（Ｂ）を溶解し、且つ沸点が、使用する前記モノマー（Ｂ）の沸点より低いものであれば、公知の有機溶媒が特に制限されず使用できる。溶媒除去工程における除去性の観点から、有機溶媒としては、常温常圧（２５℃、１気圧下）での沸点が２００℃以下、特に１２０℃以下のものを使用することが好ましい。
1-3. Organic solvent (C)
As the organic solvent (C), a known organic solvent can be used without particular limitation as long as the monomer (B) is dissolved and the boiling point is lower than the boiling point of the monomer (B) to be used. From the viewpoint of removability in the solvent removing step, it is preferable to use an organic solvent having a boiling point of 200 ° C. or lower, particularly 120 ° C. or lower, at normal temperature and pressure (25 ° C. and 1 atm).
好適に使用できる有機溶媒を例示すれば、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、アセトン、ジエチルエーテル、ヘキサン、トルエン、ジクロロメタン、クロロホルムなどを挙げることができる。 Examples of preferably usable organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, diethyl ether, hexane, toluene, dichloromethane, chloroform and the like.
これら溶媒は１種を単独で使用しても、２種以上を混合して使用してもよく、２種以上を混合して使用する場合は互いに相溶するものが好ましい。また、モノマーの溶解を阻害しない量であれば水を含んでもよい。 One of these solvents may be used alone, or two or more of them may be mixed and used, and when two or more of these solvents are mixed and used, those that are compatible with each other are preferable. Further, water may be contained as long as it does not inhibit the dissolution of the monomer.
１−４．その他添加物等
本発明の原料製法を用いて作製されるセラミック原料粉体には、混合段階において前記セラミック原料無機粉体（Ａ）及び前記モノマー（Ｂ）の他に、無機顔料、有機顔料、蛍光剤、紫外線吸収剤、無機粉体分散剤等の添加材を配合することができる。また、効果に悪影響を与えない範囲で、前記モノマー（Ｂ）以外の有機成分として他の有機物を添加することもできる。ただし、操作性の観点から、重合開始剤は含まないことが好ましい。なお、重合開始剤とは、ラジカル重合開始剤のような前記モノマー（Ｂ）を重合硬化させる機能を有する化合物又は化合物の組み合わせを意味する。
1-4. Other Additives, etc. In addition to the ceramic raw material inorganic powder (A) and the monomer (B), inorganic pigments, organic pigments, etc. Additives such as a fluorescent agent, an ultraviolet absorber, and an inorganic powder dispersant can be blended. Further, other organic substances may be added as organic components other than the monomer (B) as long as the effect is not adversely affected. However, from the viewpoint of operability, it is preferable that the polymerization initiator is not contained. The polymerization initiator means a compound or a combination of compounds having a function of polymerizing and curing the monomer (B) such as a radical polymerization initiator.
次に、本発明の原料製法におけるスラリー化工程及び溶媒除去工程について説明する。 Next, the slurrying step and the solvent removing step in the raw material manufacturing method of the present invention will be described.
１−５．スラリー化工程
スラリー化工程では、前記セラミック原料無機粉体（Ａ）１００質量に対して、１質量部以上２５質量部未満となる量の前記重合性単量体（Ｂ）が有機溶媒（Ｃ）に溶解したモノマー溶液（Ｄ）と、前記セラミック原料無機粉体（Ａ）１００質量部と、を混合して、前記セラミック無機粉体（Ａ）が前記モノマー溶液（Ｄ）中に分散したスラリーを調製する。
1-5. Slurrying Step In the slurrying step, the polymerizable monomer (B) in an amount of 1 part by mass or more and less than 25 parts by mass is the organic solvent (C) with respect to 100 parts by mass of the ceramic raw material inorganic powder (A). The monomer solution (D) dissolved in the mixture and 100 parts by mass of the ceramic raw material inorganic powder (A) were mixed to obtain a slurry in which the ceramic inorganic powder (A) was dispersed in the monomer solution (D). Prepare.
モノマー溶液（Ｄ）を調製する際に使用する有機溶媒（Ｃ）の量は、均一混合性、操作性及び溶媒除去性の観点から、使用するモノマー（Ｂ）を溶解できる量で且つセラミック原料無機粉体（Ａ）とモノマー（Ｂ）の総量：１００質量部に対して、５０質量部以上であることが好ましく、１００〜３０００質量部、特に１００〜２０００質量部とすることがより好ましい。 The amount of the organic solvent (C) used when preparing the monomer solution (D) is an amount capable of dissolving the monomer (B) to be used from the viewpoint of uniform miscibility, operability and solvent removal property, and the ceramic raw material is inorganic. Total amount of powder (A) and monomer (B): 50 parts by mass or more, more preferably 100 to 3000 parts by mass, and particularly preferably 100 to 2000 parts by mass with respect to 100 parts by mass.
スラリーの調製は、容器内でモノマー溶液（Ｄ）とセラミック原料無機粉体（Ａ）とを混合し、撹拌等により均一化することにより好適に行うことができる。均一化方法としては、撹拌、振盪、振動、超音波等による方法が採用できる。さらに、分散性向上の観点から、ホモジナイザーやボールミル等と用いた分散処理を行ってもよい。また、混合に際しては、結果として前記セラミック無機粉体（Ａ）が前記モノマー溶液（Ｄ）中に分散したスラリーが得られる方法であれば特に限定されないが、予めモノマー溶液（Ｄ）を調製し、これとセラミック原料無機粉体（Ａ）を混合するのが一般的である。このとき、より短時間でスラリーを均一化するという観点から、セラミック原料無機粉体（Ａ）を事前に有機溶媒及び／又は水と混合してスラリー化しておき、これをモノマー溶液（Ｄ）と混合してもよい。この時、前記有機溶媒はモノマー溶液（Ｄ）で使用した有機溶媒（Ｃ）と同じものであっても、異なるものであってもよいが、均一に混合するという観点から互いに相溶し、且つ、モノマー（Ｂ）の溶解を阻害しない有機溶媒及び／又は水を使用することが好ましい。 The slurry can be preferably prepared by mixing the monomer solution (D) and the ceramic raw material inorganic powder (A) in a container and homogenizing them by stirring or the like. As the homogenization method, a method of stirring, shaking, vibration, ultrasonic waves or the like can be adopted. Further, from the viewpoint of improving the dispersibility, a dispersion treatment using a homogenizer, a ball mill or the like may be performed. Further, upon mixing, the method is not particularly limited as long as the method can obtain a slurry in which the ceramic inorganic powder (A) is dispersed in the monomer solution (D) as a result, but the monomer solution (D) is prepared in advance. It is common to mix this with the ceramic raw material inorganic powder (A). At this time, from the viewpoint of homogenizing the slurry in a shorter time, the ceramic raw material inorganic powder (A) is mixed with an organic solvent and / or water in advance to form a slurry, which is then combined with the monomer solution (D). It may be mixed. At this time, the organic solvent may be the same as or different from the organic solvent (C) used in the monomer solution (D), but they are compatible with each other from the viewpoint of uniform mixing. , It is preferable to use an organic solvent and / or water that does not inhibit the dissolution of the monomer (B).
１−６．溶媒除去工程
溶媒除去工程では、スラリー化工程にて調製したスラリーから有機溶媒（Ｃ）を除去しセラミック原料コンパウンドを作製する。
1-6. Solvent removal step In the solvent removal step, the organic solvent (C) is removed from the slurry prepared in the slurrying step to prepare a ceramic raw material compound.
溶媒除去の方法としては、前記有機溶媒（Ｃ）をスラリーから除去できる方法であれば特に限定されないが、溶媒除去にかかる時間の短さや溶媒をほぼ全て除去できるという観点から、減圧乾燥法及び／又は加熱乾燥法を採用することが好ましい。ここで、減圧乾燥法とは、例えば８００ヘクトパスカル以下での減圧下にて溶媒を除去する方法であり、加熱乾燥法とは、室温以上の温度にて溶媒を除去する方法であり、減圧下で加熱することにより、有機溶媒の沸点よりも低い温度で有機溶媒の除去（乾燥）を行うことができる。高温下での処理を必要としないと言う観点から、加熱乾燥法を採用する場合でも、適宜減圧乾燥法と併用する等して１００℃以下の温度で乾燥させることが好ましい。溶媒除去工程を得ることにより、焼結可能なセラミック原料無機粉体（Ａ）：１００質量部、及び分子内に重合性基を有する有機化合物からなる重合性単量体（Ｂ）：１質量部以上２５質量部未満、を含むセラミック原料コンパウンドを得ることができる。 The method for removing the solvent is not particularly limited as long as it can remove the organic solvent (C) from the slurry, but from the viewpoint of shortening the time required for removing the solvent and removing almost all the solvent, the vacuum drying method and / Alternatively, it is preferable to adopt a heat drying method. Here, the vacuum drying method is a method of removing the solvent under reduced pressure of, for example, 800 hectopascals or less, and the heat drying method is a method of removing the solvent at a temperature of room temperature or higher, under reduced pressure. By heating, the organic solvent can be removed (dried) at a temperature lower than the boiling point of the organic solvent. From the viewpoint that treatment at a high temperature is not required, even when the heat drying method is adopted, it is preferable to dry at a temperature of 100 ° C. or lower by appropriately using it in combination with a vacuum drying method. A polymerizable monomer (B) composed of 100 parts by mass of a ceramic raw material inorganic powder (A) that can be sintered by obtaining a solvent removing step and an organic compound having a polymerizable group in the molecule: 1 part by mass. A ceramic raw material compound containing more than 25 parts by mass can be obtained.
本発明の原料製法では、有機バインダーとして低分子量の重合性単量体（Ｂ）を用いているため、取り扱い易い粉粒体の形態で上記セラミック原料コンパウンドを得ることができる。ここで、粉粒体とは、粉体及び粒体の総称であり、具体的には、前記セラミック原料無機粉体（Ａ）を構成する１次粒子の表面に前記重合性単量体（Ｂ）が付着した粒子：ａ１、当該粒子ａ１が凝集した凝集粒子：ａ２、及び当該凝集粒子ａ２が解砕された粒子：ａ３、並びに前記セラミック原料無機粉体（Ａ）を構成する凝集粒子の表面に前記重合性単量体（Ｂ）が付着した凝集粒子：ａ４、当該凝集粒子ａ４が凝集した凝集粒子：ａ５、及び当該凝集粒子ａ５が解砕された粒子：ａ６からなる群より選ばれる少なくとも１種の粒子を含む粉体を意味する。なお、前記重合性単量体（Ｂ）を介して無機粒子が結合する場合であってもその結合力は弱いので簡単に解砕することができる。 In the raw material production method of the present invention, since the low molecular weight polymerizable monomer (B) is used as the organic binder, the ceramic raw material compound can be obtained in the form of powders and granules that are easy to handle. Here, the powder or granular material is a general term for powder and granular material, and specifically, the polymerizable monomer (B) is formed on the surface of the primary particles constituting the ceramic raw material inorganic powder (A). ) Attached particles: a1, aggregated particles a1 in which the particles a1 are aggregated: a2, particles in which the aggregated particles a2 are crushed: a3, and the surfaces of the aggregated particles constituting the ceramic raw material inorganic powder (A). At least selected from the group consisting of agglomerated particles a4 to which the polymerizable monomer (B) is attached, agglomerated particles a4 in which the agglomerated particles a4 are agglomerated: a5, and particles in which the agglomerated particles a5 are crushed: a6. It means a powder containing one kind of particles. Even when the inorganic particles are bonded via the polymerizable monomer (B), the bonding force is weak and the particles can be easily crushed.
また、本発明の原料製法で得られる前記コンパウンドは、従来の有機樹脂系バインダーを用いたコンパウンドと同様に、良好な成形性及び成形後における保形性を有する。したがって、セラミック原料コンパウンドを成形する方法としては様々な方法が適用できる。たとえば、有機バインダーとしてオレフィン樹脂系有機バインダーのような熱可塑性樹脂を用いた場合には、加圧式ニーダーやスクリュー押出し機を用いて混錬する必要があるばかりでなく、混錬後の複合化物は冷えると固化するため、熱時に切断されてペレット状のコンパウンドとされるのが一般的であり、これを成形するためには、再度加熱して可塑性を付与する必要がある。このため、成形方法は、そのような工程を含む射出成形法のような方法に限定されてしまう。射出成形法は、装置自体が高価であるばかりでなく再加熱にエネルギーや手間がかかるため、樹脂系バインダーを用いる場合には、コンパウンド化時と合わせて二重に負担がかかると言える。これに対し、本発明の原料製法で粉粒体のコンパウンドを製造した場合には、それをそのまま型に入れて圧縮するだけで所望の形状に成形することが可能であるので、成形時の負担を軽減することができる。 In addition, the compound obtained by the raw material manufacturing method of the present invention has good moldability and shape retention after molding, similar to a compound using a conventional organic resin-based binder. Therefore, various methods can be applied as a method for molding the ceramic raw material compound. For example, when a thermoplastic resin such as an olefin resin-based organic binder is used as the organic binder, it is necessary not only to knead using a pressure kneader or a screw extruder, but also the compounded product after kneading Since it solidifies when cooled, it is generally cut at the time of heat to form a pellet-like compound, and in order to form this, it is necessary to heat it again to impart plasticity. Therefore, the molding method is limited to a method such as an injection molding method including such a step. In the injection molding method, not only the apparatus itself is expensive, but also energy and labor are required for reheating. Therefore, when a resin-based binder is used, it can be said that a double burden is applied together with the compounding. On the other hand, when a powder / granular material compound is produced by the raw material manufacturing method of the present invention, it can be molded into a desired shape simply by putting it in a mold and compressing it. Can be reduced.
２．本発明のセラミック製物品の製造方法（本発明の物品製法）
前記したように、セラミック原料コンパウンドの製造工程として前記本発明の原料製法で粉粒体のコンパウンドを製造する工程を含む本発明の物品製法は、セラミック原料コンパウンドの製造工程として前記本発明の原料製法を採用することによる利点を有するだけでなく、このような粉粒体のコンパウンドを用いることによる利点を有するものであり、コンパウンド調製において上記したような高価な装置を用いた加熱混錬法を採用することにコストメリットを見出すことができないような規模でセラミック製物品を製造する方法、特にジルコニア歯科用ミルブランクのような歯科用セラミック物品を製造する方法として好適である。
2. Method for manufacturing ceramic article of the present invention (manufacturing method for article of the present invention)
As described above, the article manufacturing method of the present invention including the step of manufacturing the powder / granular compound by the raw material manufacturing method of the present invention as the manufacturing process of the ceramic raw material compound is the raw material manufacturing method of the present invention as the manufacturing process of the ceramic raw material compound. Not only has the advantage of adopting the above, but also has the advantage of using such a compound of powder and granules, and the heat kneading method using the above-mentioned expensive equipment is adopted in the compound preparation. It is suitable as a method for producing ceramic articles on a scale for which no cost advantage can be found, particularly as a method for producing dental ceramic articles such as zirconia dental mill blanks.
以下、本発明の物品製法について詳しく説明する。
本発明の物品製法は、本発明の原料製法により、セラミック原料コンパウンド粉粒体を製造する工程、前記工程で得られたセラミック原料コンパウンド粉粒体を成形し、所定の形状を有するグリーン体を得る成形工程、及び前記成形工程で得られたグリーン体を直接又は脱脂処理後に焼結する焼結工程を含んでなることを特徴とする。
Hereinafter, the method for producing an article of the present invention will be described in detail.
The article manufacturing method of the present invention is a step of producing a ceramic raw material compound powder and granules by the raw material manufacturing method of the present invention, and the ceramic raw material compound powder and granules obtained in the above step are molded to obtain a green body having a predetermined shape. It is characterized by including a molding step and a sintering step of sintering the green body obtained in the molding step directly or after a degreasing treatment.
２−１．セラミック原料コンパウンド粉粒体を製造する工程
当該工程では、本発明の原料製法により、焼結可能なセラミック原料無機粉体（Ａ）：１００質量部、及び分子内に重合性基を有する有機化合物からなる重合性単量体（Ｂ）：１質量部以上２５質量部未満、を含むセラミック原料コンパウンドを粉粒体の形態で得る。具体的には前記ａ１乃至ａ６からなる群より選ばれる少なくとも１種の粒子を含む粉体を製造する。前記したように、前記重合性単量体（Ｂ）を介して無機粒子が結合する場合であってもその結合力は弱いので簡単に解砕することができるので、必要に応じて解砕を行うことにより、若干大きめにシフトするものの、使用したセラミック原料無機粉体（Ａ）と同程度の粒度分布とすることもできる。取り扱いの容易さ及び圧縮成形時の生成性の観点から、必要に応じて解砕を行うことにより、使用したセラミック原料無機粉体（Ａ）と同程度の粒度分布とすることが好ましい。
2-1. Step of manufacturing ceramic raw material compound powder In this step, ceramic raw material inorganic powder (A) that can be sintered by the raw material manufacturing method of the present invention is made from 100 parts by mass and an organic compound having a polymerizable group in the molecule. (B): A ceramic raw material compound containing 1 part by mass or more and less than 25 parts by mass is obtained in the form of powder or granular material. Specifically, a powder containing at least one kind of particles selected from the group consisting of a1 to a6 is produced. As described above, even when the inorganic particles are bonded via the polymerizable monomer (B), the bonding force is weak and the particles can be easily crushed. Therefore, crushing is performed as necessary. By doing so, it is possible to obtain a particle size distribution similar to that of the used ceramic raw material inorganic powder (A), although the particle size shifts to a slightly larger size. From the viewpoint of ease of handling and productivity during compression molding, it is preferable that the particle size distribution is about the same as that of the used ceramic raw material inorganic powder (A) by crushing as necessary.
２−２．成形工程
成型工程では、前記工程で得られたセラミック原料コンパウンド粉粒体を用いて所定形状の圧縮成形体又はグリーン体を得る。このとき成形方法は、原料として前記セラミック原料コンパウンド粉粒体を用いる以外は、従来の方法と特に変わる点は無く、プレス成形、押出成形、射出成形、鋳込成形、テープ成形、積層造形による成形、粉末造形による成形等、粉体成形法或いはグリーン体成型法として知られている方法が特に制限なく使用できる。また、多段階的な成形を施してもよい。例えば、本発明のセラミック原料コンパウンド粉粒体を一軸プレス成形した後に、さらにＣＩＰ（Ｃｏｌｄ Ｉｓｏｓｔａｔｉｃ Ｐｒｅｓｓｉｎｇ；冷間静水等方圧プレス）処理を施したものでもよい。高密度の成形に向いているという観点から、成型方法としてはプレス成型を用いるのがより好ましく、例えば、１軸プレス成型、２軸プレス成型、ＨＩＰ（Ｈｏｔ Ｉｓｏｓｔａｔｉｃ Ｐｒｅｓｓｉｎｇ；熱間等方圧プレス）成型、ＣＩＰ（Ｃｏｌｄ Ｉｓｏｓｔａｔｉｃ Ｐｒｅｓｓｉｎｇ；冷間静水等方圧プレス）成型等が挙げられる。
2-2. Molding step In the molding step, the ceramic raw material compound powder and granules obtained in the above step are used to obtain a compression molded body or a green body having a predetermined shape. At this time, the molding method is not particularly different from the conventional method except that the ceramic raw material compound powder and granules are used as the raw material, and molding by press molding, extrusion molding, injection molding, casting molding, tape molding, and laminated molding. , A method known as a powder molding method or a green body molding method, such as molding by powder molding, can be used without particular limitation. Moreover, you may perform multi-step molding. For example, the ceramic raw material compound powder or granular material of the present invention may be uniaxially press-molded and then further subjected to CIP (Cold Isostatic Pressing) treatment. From the viewpoint of being suitable for high-density molding, it is more preferable to use press molding as a molding method. For example, uniaxial press molding, biaxial press molding, HIP (Hot Isostatic Pressing) Examples thereof include molding and CIP (Cold Isostatic Pressing) molding.
また、成形工程において、複数種のセラミック原料コンパウンド粉粒体を積層し成形してもよい。 Further, in the molding step, a plurality of types of ceramic raw material compound powders and granules may be laminated and molded.
成型工程で得られる圧縮成形体又はグリーン体の形状は、目的とするセラミック物品の形状に応じて適宜決定すればよいが、歯科用ミルブランクを製造する場合には、円盤状のもの（ディスクタイプ）、或いは直方体又は略直方体形状のもの（ブロックタイプ）とすることが一般的である。 The shape of the compression molded product or the green body obtained in the molding process may be appropriately determined according to the shape of the target ceramic article, but when manufacturing a dental mill blank, it is a disk shape (disc type). ), Or a rectangular parallelepiped or a substantially rectangular parallelepiped shape (block type).
２−３．焼結工程
焼結工程では、前記成形工程で得られた圧縮成形体又はグリーン体を焼結温度で一定時間加熱して、焼結体を得る。ここで、焼結（焼成或いは焼き締めとも呼ばれる。）とは、その温度（或いは温度範囲）で一定時間保持して、圧縮成形体又はグリーン体をセラミック原料無機粉体の融点以下の温度に加熱して、粉末粒子を互いに表面拡散（凝着、融着）させて多結晶体に変化させることを意味する。但し、必ずしも完全に焼結させる必要はなく、用途によっては、焼結に至らない温度で焼成した所謂「仮焼体」の状態であってもよい。たとえば、ジルコニア歯科用ミルブランクは所謂ジルコニア仮焼体の状態で提供され、使用時にＣＡＤ／ＣＡＭシステムを用いて歯冠形状に切削加工されてから本焼結を行うことも多い（例えば国際公開ＷＯ２０１６／１０４７２４パンフレット参照。）。本発明の物品製法の目的物であるセラミック製物品は、このような仮焼体をも含む概念である。また、上記焼結温度とは、その温度（或いは一定の温度範囲内）に一定時間保持して、所望の程度に焼結（仮焼を含む）を進行させる温度（或いは温度範囲）をいう。強度や加工性の観点から、６００℃〜１８００℃が好ましい。
2-3. Sintering step In the sintering step, the compression molded body or green body obtained in the molding step is heated at the sintering temperature for a certain period of time to obtain a sintered body. Here, sintering (also referred to as firing or baking) means that the compression molded body or the green body is heated to a temperature equal to or lower than the melting point of the ceramic raw material inorganic powder by holding the compression molded body or the green body at that temperature (or temperature range) for a certain period of time. Then, it means that the powder particles are surface-diffused (adhered, fused) with each other to change into a polycrystal. However, it is not always necessary to completely sinter, and depending on the application, it may be in a so-called "temporarily fired body" state in which it is fired at a temperature that does not lead to sintering. For example, a zirconia dental mill blank is provided in a so-called zirconia calcined body state, and is often cut into a crown shape at the time of use using a CAD / CAM system before the main sintering (for example, international publication WO2016). / 104724 See pamphlet.). The ceramic article, which is the object of the article manufacturing method of the present invention, is a concept including such a calcined body. Further, the above-mentioned sintering temperature means a temperature (or temperature range) in which sintering (including calcining) proceeds to a desired degree by holding the temperature (or within a certain temperature range) for a certain period of time. From the viewpoint of strength and workability, 600 ° C to 1800 ° C is preferable.
また、本発明の物品製法では、焼結工程における焼結を行う前に脱脂処理を行うこともできる。ここで、脱脂処理とは、前記成形工程で得られた圧縮成形体又はグリーン体に含まれる水分、溶媒、バインダーなどを揮発除去或いは分解除去する処理を意味する。これら処理は、通常、１００℃以上、１１００℃以下であって且つ焼結温度よりも低い温度で行われる。 Further, in the article manufacturing method of the present invention, degreasing treatment can be performed before sintering in the sintering step. Here, the degreasing treatment means a treatment for volatilizing or decomposing or decomposing water, a solvent, a binder and the like contained in the compression molded product or the green product obtained in the molding step. These treatments are usually carried out at a temperature of 100 ° C. or higher and 1100 ° C. or lower and lower than the sintering temperature.
脱脂処理の方法としては、従来から知られている方法が特に制限されず使用でき、連続的に行っても、多段階的に行ってもよい。また、有機物を効率的に除去するため、酸素を含む空気雰囲気下で行うことが好ましい。なお、脱脂処理は、その前工程である成形工程及び／又はその後に行われる焼結工程と同一の装置を用いた方法、例えばＳＰＳ（放電プラズマ焼結：Ｓｐａｒｋ Ｐｌａｓｍａ Ｓｉｎｔｅｒｉｎｇ）法やＨＰ（ホットプレス）法等により、連続的に行うこともできる。 As a method of degreasing treatment, a conventionally known method can be used without particular limitation, and may be continuously performed or may be performed in multiple steps. Further, in order to efficiently remove organic substances, it is preferable to carry out in an air atmosphere containing oxygen. The degreasing treatment is performed by a method using the same equipment as the molding step which is the previous step and / or the sintering step performed after that, for example, the SPS (discharge plasma sintering: Spark Plasma Sintering) method or the HP (hot press). ) It can be done continuously by the method or the like.
本発明の物品製法は、ジルコニア歯科用ミルブランクの製法として好適に採用できる。歯科用ジルコニアとしては、イットリア、カルシア、マグネシア、セリア、酸化エルビウム等の安定化剤、アルミナ等の焼結助剤、及び、酸化鉄、酸化コバルト等の顔料を含むものが一般的であり、本発明で製造されるジルコニア歯科用ミルブランクにおいてもこれらが含まれていてもよい。本発明の物品製法により好適に製造されるジルコニア歯科用ミルブランクは、特に限定されるものではないが、強度と審美性の観点から、焼結後に正方晶が主成分となる部分安定化ジルコニアからなるものが好ましい。 The article manufacturing method of the present invention can be suitably adopted as a manufacturing method for a zirconia dental mill blank. Dental zirconia generally contains stabilizers such as yttria, calcia, magnesia, ceria, and erbium oxide, sintering aids such as alumina, and pigments such as iron oxide and cobalt oxide. These may also be contained in the zirconia dental mill blank manufactured by the present invention. The zirconia dental mill blank preferably produced by the article manufacturing method of the present invention is not particularly limited, but from the viewpoint of strength and aesthetics, from partially stabilized zirconia containing tetragonal crystals as the main component after sintering. Is preferable.
以下、本発明を具体的に説明するために、実施例および比較例を挙げて説明するが、本発明はこれらにより何等制限されるものではない。まず、以下に、各実施例および比較例のサンプルの作製に用いた物質の略称・略号等について説明する。 Hereinafter, the present invention will be described with reference to Examples and Comparative Examples in order to specifically explain the present invention, but the present invention is not limited thereto. First, the abbreviations and abbreviations of the substances used for preparing the samples of each Example and Comparative Example will be described below.
＜セラミック原料コンパウンドの原材料＞
１．セラミック原料無機粉体（Ａ）
・ＴＺ−６Ｙ：東ソー株式会社製ジルコニア、バインダー未含有品、平均一次粒径４０ｎｍ、凝集粒子の平均粒子径４０μｍ、イットリア含有量６ｍｏｌ％ 。
<Raw materials for ceramic raw material compounds>
1. 1. Ceramic raw material inorganic powder (A)
TZ-6Y: Zirconia manufactured by Tosoh Corporation, binder-free product, average primary particle size 40 nm, average particle size of aggregated particles 40 μm, yttria content 6 mol%.
２．重合性単量体（Ｂ）
・３Ｇ（トリエチレングリコールジメタクリレート）：新中村化学工業株式会社製、分子量＝１２３、分子内にメタクリル基を２つ有する
・ＵＤＭＡ（１，６−ビス（メタクリルエチルオキシカルボニルアミノ）トリメチルヘキサン）：デグッサ製、分子量＝４７１、分子内にメタクリル基を２つ有する
・ＣＢ−１（２−メタクリロイロキシエチルフタル酸）：新中村化学工業株式会社製、分子量＝２７８、分子内にメタクリル基１つとカルボキシ基１つを有する
・ＧＭＡ（メタクリル酸グリシジル）：富士フィルム和光純薬株式会社製、分子量＝１４２、分子内にメタクリル基１つとエポキシ基１つを有する
・ＯＸＴ−２１１（（３−エチルオキセタン３−イル）メチルフェノール）：東亜合成株式会社製、分子量＝１９２、分子内にオキセタン基を１つ有する
・ＯＸＥ−３０（（３−エチルオキセタン３−イル）メチルメタクリレート）：大阪有機化学工業株式会社製、分子量＝１８４、分子内にメタクリル基１つとオキセタン基１つを有する。
2. Polymerizable monomer (B)
・ 3G (triethylene glycol dimethacrylate): manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight = 123, having two methacryl groups in the molecule ・ UDMA (1,6-bis (methacrylethyloxycarbonylamino) trimethylhexane): Made by Degussa, molecular weight = 471, having two methacryl groups in the molecule ・ CB-1 (2-methacryloyloxyethyl phthalic acid): manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight = 278, having one methacryl group in the molecule Has one carboxy group ・ GMA (glycidyl methacrylate): manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight = 142, has one methacryl group and one epoxy group in the molecule ・ OXT-211 ((3-ethyloxetane) 3-Il) methylphenol): manufactured by Toa Synthetic Co., Ltd., molecular weight = 192, having one oxetane group in the molecule ・ OXE-30 ((3-ethyloxetan 3-yl) methyl methacrylate): Osaka Organic Chemical Industry Co., Ltd. Manufactured by the company, the molecular weight is 184, and it has one methacryl group and one oxetane group in the molecule.
３．重合性単量体（Ｂ）以外の有機化合物
・１，５−ペンタンジオール：富士フィルム和光純薬株式会社製、分子量＝１０４、分子内に２つのヒドロキシ基を有する
・ＰＥＧ２００（ポリエチレングリコール）：富士フィルム和光純薬株式会社製、平均分子量＝１８０〜２２０
・ＰＥＧ４００（ポリエチレングリコール）：富士フィルム和光純薬株式会社製、平均分子量＝３６０〜４４０
・ＰＥＧ２００００００（ポリエチレングリコール）：富士フィルム和光純薬株式会社製、分子量＝約２００万。
3. 3. Organic compounds other than polymerizable monomer (B) ・ 1,5-pentanediol: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight = 104, having two hydroxy groups in the molecule ・ PEG200 (polyethylene glycol): Fuji Film manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight = 180-220
-PEG400 (polyethylene glycol): manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., average molecular weight = 360-440
-PEG2000000 (polyethylene glycol): manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight = about 2 million.
４．有機溶媒（Ｃ）
・エタノール：富士フィルム和光純薬株式会社製。
4. Organic solvent (C)
-Ethanol: Made by Fuji Film Wako Pure Chemical Industries, Ltd.
実施例１
ＴＺ−６Ｙ １０ｇとエタノール ９０ｇを秤量後、１５分間超音波（アズワン株式会社製 卓上型超音波洗浄機ＭＯＤＥＬ ＶＳ−１５０、５０ｋＨｚ）をあてることでＴＺ−６Ｙ分散液を得た。３Ｇ １．２１ｇとエタノール ５ｇを秤量、撹拌子を用いて混合し、３Ｇ溶液を得た。ＴＺ−６Ｙ分散液に３Ｇ分散液を加え、２時間撹拌子を用いて混合した。その後、エバポレーターを用い、常温下にて減圧することでエタノールを除去し、セラミック原料コンパウンド粉体を得た。
Example 1
After weighing 10 g of TZ-6Y and 90 g of ethanol, a TZ-6Y dispersion was obtained by applying ultrasonic waves (Desktop ultrasonic cleaner MODEL VS-150, 50 kHz manufactured by AS ONE Corporation) for 15 minutes. 1.21 g of 3G and 5 g of ethanol were weighed and mixed using a stir bar to obtain a 3G solution. A 3G dispersion was added to the TZ-6Y dispersion and mixed using a stirrer for 2 hours. Then, ethanol was removed by reducing the pressure at room temperature using an evaporator to obtain a ceramic raw material compound powder.
得られたセラミック原料コンパウンド粉体１ｇを直径１６ｍｍのプレス用金型を用いて最大荷重１ｔで一軸プレスし成型体を作製した。合計４枚の成型体を作製し、その結果を評価した。以下に評価基準を示す。
評価基準：
◎：４枚全て、問題なく成型可能であった。
○：３枚が、問題なく成形可能であった。
△：２枚が、問題なく成型可能であった。
×：１枚しか成型できなかった、もしくは、１枚も成型できなかった。
評価結果を表１に示す。
1 g of the obtained ceramic raw material compound powder was uniaxially pressed with a pressing die having a diameter of 16 mm under a maximum load of 1 ton to prepare a molded product. A total of 4 molded bodies were prepared and the results were evaluated. The evaluation criteria are shown below.
Evaluation criteria:
⊚: All four sheets could be molded without any problem.
◯: Three sheets could be molded without any problem.
Δ: Two sheets could be molded without any problem.
X: Only one sheet could be molded, or none could be molded.
The evaluation results are shown in Table 1.
実施例２〜８
モノマー（Ｂ）の原料及び配合重量を表１に示すように変える他は実施例１と同様にしてセラミック原料コンパウンド粉体を調製し、同様に成型性の評価を行った。結果を表１に示す。
Examples 2-8
A ceramic raw material compound powder was prepared in the same manner as in Example 1 except that the raw material and compounding weight of the monomer (B) were changed as shown in Table 1, and the moldability was evaluated in the same manner. The results are shown in Table 1.
比較例１
ＴＺ−６Ｙ １０ｇとエタノール ９０ｇを秤量、混合後、１５分間超音波を当てることでＴＺ−６Ｙ分散液を得た。ＴＺ−６Ｙ分散液を２時間撹拌子を用いて混合した。その後、エバポレーターを用い、常温下にて減圧することでエタノールを除去し、セラミック原料コンパウンド粉体を得た。その後、実施例１と同様にして成型性評価を行った、結果を表１に示す。
Comparative Example 1
10 g of TZ-6Y and 90 g of ethanol were weighed and mixed, and then ultrasonic waves were applied for 15 minutes to obtain a TZ-6Y dispersion. The TZ-6Y dispersion was mixed using a stir bar for 2 hours. Then, ethanol was removed by reducing the pressure at room temperature using an evaporator to obtain a ceramic raw material compound powder. Then, the moldability was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
比較例２〜４
モノマー（Ｂ）の原料及び配合重量を表１に示すように変える他は実施例１と同様にしてセラミック原料コンパウンド粉体を調製し、実施例１と同様にして成型性評価を行った、結果を表１に示す。
Comparative Examples 2-4
A ceramic raw material compound powder was prepared in the same manner as in Example 1 except that the raw material and compounding weight of the monomer (B) were changed as shown in Table 1, and the moldability was evaluated in the same manner as in Example 1. Is shown in Table 1.
比較例５
ＴＺ−６Ｙ １０ｇとエタノール ９０ｇを秤量、混合後、１５分間超音波を当てることでＴＺ−６Ｙ分散液を得た。ＰＥＧ２００００００ ０．５１ｇとエタノール ５ｇを秤量、混合し、ＰＥＧ２００００００分散液を得た。ＴＺ−６Ｙ分散液にＰＥＧ２００００００分散液を加え、２時間撹拌子を用いて混合した。その後、エバポレーターを用い、常温下にて減圧することでエタノールを除去し、セラミック原料コンパウンド粉体を得た。その後、実施例１と同様にして成型性評価を行った、結果を表１に示す。
Comparative Example 5
10 g of TZ-6Y and 90 g of ethanol were weighed and mixed, and then ultrasonic waves were applied for 15 minutes to obtain a TZ-6Y dispersion. 0.51 g of PEG2000000 and 5 g of ethanol were weighed and mixed to obtain a PEG2000000 dispersion. The PEG2000000 dispersion was added to the TZ-6Y dispersion and mixed using a stir bar for 2 hours. Then, ethanol was removed by reducing the pressure at room temperature using an evaporator to obtain a ceramic raw material compound powder. Then, the moldability was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
表１示されるように実施例１〜８では、良好な成型性を示した。これに対し、バインダーとなる有機化合物を含まない比較例１、及び、バインダーとしてモノマーでない低分子量の有機化合物を添加した比較例２〜４では成形性が極めて低かった。さらに、バインダーとしてモノマーではない高分子量の有機化合物を添加した比較例５では、揮発性溶媒中に溶けず、結果として無機粉体とバインダーが均一複合化された粉体を得ることができず、成型性極めて低かった。 As shown in Table 1, Examples 1 to 8 showed good moldability. On the other hand, in Comparative Example 1 containing no organic compound as a binder and Comparative Examples 2 to 4 in which a low molecular weight organic compound other than a monomer was added as a binder, the moldability was extremely low. Further, in Comparative Example 5 in which a high molecular weight organic compound other than a monomer was added as the binder, it was not soluble in the volatile solvent, and as a result, a powder in which the inorganic powder and the binder were uniformly composited could not be obtained. The moldability was extremely low.
Claims (6)
前記セラミック原料無機粉体（Ａ）１００質量に対して、１質量部以上２５質量部未満となる量の前記重合性単量体（Ｂ）が有機溶媒（Ｃ）に溶解したモノマー溶液（Ｄ）と、前記セラミック原料無機粉体（Ａ）１００質量部と、を混合して、前記セラミック無機粉体（Ａ）が前記モノマー溶液（Ｄ）中に分散したスラリーを調製するスラリー化工程、及び
前記スラリー化工程で得られた前記スラリーから前記有機溶媒（Ｃ）を除去する溶媒除去工程、
を含んでなることを特徴とする、前記セラミック原料コンパウンドの製造方法。 Sinterable ceramic raw material inorganic powder (A): 100 parts by mass, and a polymerizable monomer (B) composed of an organic compound having a polymerizable group in the molecule: 1 part by mass or more and less than 25 parts by mass. A method for producing ceramic raw material compounds.
A monomer solution (D) in which the polymerizable monomer (B) in an amount of 1 part by mass or more and less than 25 parts by mass is dissolved in an organic solvent (C) with respect to 100 parts by mass of the ceramic raw material inorganic powder (A). And 100 parts by mass of the ceramic raw material inorganic powder (A), and a slurrying step of preparing a slurry in which the ceramic inorganic powder (A) is dispersed in the monomer solution (D), and the above. A solvent removing step of removing the organic solvent (C) from the slurry obtained in the slurrying step.
The method for producing a ceramic raw material compound, which comprises the above.
前記工程で得られたセラミック原料コンパウンド粉粒体を成形し、所定の形状を有するグリーン体を得る成形工程、及び
前記成形工程で得られたグリーン体を直接又は脱脂処理後に焼結する焼結工程
を含んでなることを特徴とする、セラミック製物品の製造方法。 A step of producing a ceramic raw material compound powder or granular material by the method according to any one of claims 1 to 4.
A molding step of molding the ceramic raw material compound powder and granules obtained in the above step to obtain a green body having a predetermined shape, and a sintering step of sintering the green body obtained in the molding step directly or after degreasing treatment. A method for producing a ceramic article, which comprises.
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| JPH0867571A (en) * | 1994-08-31 | 1996-03-12 | Kyocera Corp | Composition for molding ceramic |
| JPH10279364A (en) * | 1997-04-01 | 1998-10-20 | Toray Ind Inc | Ceramic green sheet |
| JP2001278670A (en) * | 2000-03-30 | 2001-10-10 | Toshiba Corp | Method for manufacturing sintered ceramic |
| US20050065259A1 (en) * | 2001-11-09 | 2005-03-24 | Alevtina Smirnova | Method of preparing thin-walled articles |
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