JP2016069745A - Calcium phosphate fibrous molded body production method - Google Patents
Calcium phosphate fibrous molded body production method Download PDFInfo
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- JP2016069745A JP2016069745A JP2014197727A JP2014197727A JP2016069745A JP 2016069745 A JP2016069745 A JP 2016069745A JP 2014197727 A JP2014197727 A JP 2014197727A JP 2014197727 A JP2014197727 A JP 2014197727A JP 2016069745 A JP2016069745 A JP 2016069745A
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- Prior art keywords
- phosphorus
- calcium
- molded body
- spinning
- fibrous molded
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 116
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 40
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 40
- 238000009987 spinning Methods 0.000 claims abstract description 144
- 239000002270 dispersing agent Substances 0.000 claims abstract description 77
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 72
- 239000011574 phosphorus Substances 0.000 claims abstract description 68
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011575 calcium Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 16
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 46
- -1 phosphorus oxo-acid Chemical class 0.000 claims description 32
- 238000010304 firing Methods 0.000 claims description 23
- 239000011550 stock solution Substances 0.000 claims description 18
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 12
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 11
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 11
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 11
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 3
- 239000002002 slurry Substances 0.000 abstract description 8
- 229960001714 calcium phosphate Drugs 0.000 description 33
- 229960005069 calcium Drugs 0.000 description 31
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 31
- 238000000465 moulding Methods 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 159000000007 calcium salts Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012620 biological material Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000004373 Pullulan Substances 0.000 description 3
- 229920001218 Pullulan Polymers 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 3
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 description 3
- 229940043256 calcium pyrophosphate Drugs 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 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 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 235000019423 pullulan Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000004068 calcium phosphate ceramic Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000004804 polysaccharides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- GIXFALHDORQSOQ-UHFFFAOYSA-N 2,4,6,8-tetrahydroxy-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000934878 Sterculia Species 0.000 description 1
- 240000004584 Tamarindus indica Species 0.000 description 1
- 235000004298 Tamarindus indica Nutrition 0.000 description 1
- GBXPSMDBZOHGBW-UHFFFAOYSA-L [O-]P(O)(O)=O.[O-]P(O)(O)=O.OP(O)(O)=O.OP(O)(O)=O.OP(O)(O)=O.P.[Ca+2] Chemical compound [O-]P(O)(O)=O.[O-]P(O)(O)=O.OP(O)(O)=O.OP(O)(O)=O.OP(O)(O)=O.P.[Ca+2] GBXPSMDBZOHGBW-UHFFFAOYSA-L 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229940023476 agar Drugs 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000010478 bone regeneration Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- HUSUHZRVLBSGBO-UHFFFAOYSA-L calcium;dihydrogen phosphate;hydroxide Chemical compound O.[Ca+2].OP([O-])([O-])=O HUSUHZRVLBSGBO-UHFFFAOYSA-L 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- AZSFNUJOCKMOGB-UHFFFAOYSA-N cyclotriphosphoric acid Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 239000000551 dentifrice Substances 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 239000000231 karaya gum Substances 0.000 description 1
- 229940039371 karaya gum Drugs 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
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- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Abstract
Description
本発明は、リン酸カルシウムの繊維状成型体の製造方法に関する。より詳細には、本発明は、ハイドロキシアパタイトとβ型リン酸三カルシウムの含有比を所望の範囲に制御でき、且つ組成が均一なリン酸カルシウムの繊維状成型体を製造する方法に関する。また、本発明は、リン酸カルシウムの繊維状成型体の製造においてハイドロキシアパタイトとβ型リン酸三カルシウムの含有比を制御する方法に関する。 The present invention relates to a method for producing a fibrous molded body of calcium phosphate. More specifically, the present invention relates to a method for producing a fibrous molded body of calcium phosphate that can control the content ratio of hydroxyapatite and β-type tricalcium phosphate within a desired range and has a uniform composition. The present invention also relates to a method for controlling the content ratio between hydroxyapatite and β-type tricalcium phosphate in the production of a fibrous molded product of calcium phosphate.
現在、生体材料として金属、高分子、セラミックス等が使用されているが、その中でもリン酸カルシウム系セラミックスは生体組織と直接結合するという金属や高分子にはない性質(生体親和性)を有し、人工骨、人工関節コーティング、歯科用インプラント分野等で広く使用されている。特に、リン酸カルシウム系セラミックスの中でも、ハイドロキシアパタイト（以下、HApと表記することもある）及びβ型リン酸三カルシウム（以下、β-TCPと表記することもある）は生体材料として多く利用されている。 Currently, metals, polymers, ceramics, etc. are used as biomaterials. Among them, calcium phosphate ceramics have properties (biocompatibility) that are not found in metals and polymers that bind directly to living tissue, and are artificial. Widely used in the fields of bones, artificial joint coatings, dental implants, etc. In particular, among calcium phosphate ceramics, hydroxyapatite (hereinafter also referred to as HAp) and β-type tricalcium phosphate (hereinafter also referred to as β-TCP) are widely used as biomaterials. .
従来、HApを用いた骨充填材としては、粉末状、顆粒状、ブロック状、繊維状等の様々な形態の成型体が開発されているが、粉末状や顆粒状では充填材自身が体液により押し出されたり、術部位の変形によって術部から移動してしまうという問題があり、更にブロック状では複雑な形状をとりにくいという加工性の問題や術部位細部に適用できないといった問題があった。一方、繊維状の成型体では、空隙部の細部にまで充填できる点や、充填後に繊維が絡まって術部位から移動することが殆どない点で、他の剤型に比べて有利である。 Conventionally, as bone fillers using HAp, various forms of powders, granules, blocks, fibers, etc. have been developed, but in powders and granules, the fillers themselves are made of body fluids. There is a problem that it is pushed out or moves from the surgical site due to deformation of the surgical site, and there is a problem that it is difficult to take a complicated shape in the block shape and it cannot be applied to the details of the surgical site. On the other hand, the fibrous molded body is advantageous compared to other dosage forms in that it can be filled up to the details of the voids, and the fiber hardly gets entangled and moves from the surgical site after filling.
また、リン酸カルシウムを生体材料として使用する場合、体内で吸収され、自家組織に置換されることが望ましいと考えられている。HApは、生体への親和性が高く、補填材として高い強度を有しているが生体への吸収性が低いという特徴を持っている。一方、β-TCPは、HApと同様に生体への親和性が高く、優れた吸収性を有しているが、補填した材料は骨再生が成されるまでの期間に少しずつ溶出してしまい、補填時の密度や形態を十分に保つことができないという特徴をもっている。このように、HAp及びβ-TCPはそれぞれ優れた利点を有していることから、リン酸カルシウムに含まれるHApとβ-TCPの含有比が生体内での骨形成速度及び分解速度に影響を与える重要なパラメーターになっている(非特許文献１)。そのため、リン酸カルシウムを生体材料として使用する場合、適用する生体部位によっては高い強度が必要になるケースがあり、その場合はHAp含有比が高い方が望ましく、逆に高い吸収性が求められるケースではβ-TCP含有比が高いことが望ましい。そこで、リン酸カルシウムを生体材料として製造する際には、求められる特性に応じてHApとβ-TCPの含有比を調節することが求められている。 In addition, when calcium phosphate is used as a biomaterial, it is considered desirable to be absorbed in the body and replaced with autologous tissue. HAp is characterized by high affinity to the living body and high strength as a filling material but low absorbability to the living body. On the other hand, β-TCP, like HAp, has a high affinity to the living body and excellent absorbability, but the supplemented material elutes little by little until bone regeneration is achieved. It has the feature that the density and form at the time of compensation cannot be kept sufficiently. Thus, since HAp and β-TCP have excellent advantages, the content ratio of HAp and β-TCP contained in calcium phosphate has an important effect on the bone formation rate and degradation rate in vivo. (Non-Patent Document 1). Therefore, when calcium phosphate is used as a biomaterial, there are cases where high strength is required depending on the biological site to be applied, in which case it is desirable that the HAp content ratio is high, and conversely in cases where high absorbency is required, β -A high TCP content ratio is desirable. Therefore, when producing calcium phosphate as a biomaterial, it is required to adjust the content ratio of HAp and β-TCP according to the required characteristics.
一方、リン酸カルシウム中のHApとβ-TCPの含有比の制御は、製造原料として使用するHAp及びβ-TCPの配合比を調整することによって行うことができる。しかしながら、このような方法では、原料として使用されるHApとβ-TCPの比を厳密に制御し、更に粒度分布や嵩密度等の物性の異なるこれら原料を均一に混合する必要がある。そのため、リン酸カルシウムの繊維状成型体の製造において、繊維状に成型しつつHApとβ-TCPの含有比を高度に制御することを容易に実施できないのが現状である。 On the other hand, the control of the content ratio of HAp and β-TCP in calcium phosphate can be performed by adjusting the blending ratio of HAp and β-TCP used as production raw materials. However, in such a method, it is necessary to strictly control the ratio of HAp and β-TCP used as raw materials and to uniformly mix these raw materials having different physical properties such as particle size distribution and bulk density. For this reason, in the production of a calcium phosphate fibrous molded body, it is difficult to easily control the content ratio of HAp and β-TCP while molding into a fibrous form.
一方、リン酸カルシウムの繊維状成型体を製造する技術については、従来、種々検討されている。例えば、特許文献１には、熱可塑性高分子表面にハイドロキシアパタイトを析出させてリン酸カルシウムファイバーを製造する方法が開示されている。しかしながら、特許文献１には、HApとβ-TCPの含有比を制御する手法については開示されていない。 On the other hand, various techniques for producing a fibrous molded body of calcium phosphate have been conventionally studied. For example, Patent Document 1 discloses a method for producing calcium phosphate fibers by precipitating hydroxyapatite on the surface of a thermoplastic polymer. However, Patent Document 1 does not disclose a method for controlling the content ratio of HAp and β-TCP.
また、特許文献２には、水不溶性のカルシウム塩を形成するイオン性有機高分子化合物と水僅溶性リン酸カルシウムと水とを含む紡糸原液を水溶性カルシウム塩を含有する水溶液からなる硬化液中で紡糸して水不溶性有機高分子化合物と水僅溶性リン酸カルシウムとの複合紡糸体を形成し、得られた複合紡糸体を所望の形状に成型して焼成することによって、アパタイト繊維体を製造する方法が開示されている。しかしながら、特許文献２の方法では、水溶性カルシウム塩を含有する硬化液中で、紡糸原液を紡糸して硬化させる工程を採用しているため、製造される繊維体の表面と内部の反応差等が生じ、組成の均一性が得られない可能性がある。そのため、特許文献２の方法では、組成の均一な繊維体を得るには、水不溶性のカルシウム塩、イオン性有機高分子化合物、水僅溶性リン酸カルシウム、及び硬化液の種類、濃度、反応速度等、反応条件を高度に制御する必要があり、商業的な製造への適用に障壁がある。更に、特許文献２でも、HApとβ-TCPの含有比を制御する手法については開示されていない。 In Patent Document 2, a spinning stock solution containing an ionic organic polymer compound that forms a water-insoluble calcium salt, a water-insoluble calcium phosphate, and water is spun in a hardening solution composed of an aqueous solution containing a water-soluble calcium salt. Discloses a method for producing an apatite fiber body by forming a composite spinning body of a water-insoluble organic polymer compound and a water-insoluble calcium phosphate, and molding the obtained composite spinning body into a desired shape and firing it. Has been. However, since the method of Patent Document 2 employs a step of spinning and curing a spinning stock solution in a curing solution containing a water-soluble calcium salt, the difference in reaction between the surface and the inside of the produced fiber body, etc. May occur, and the uniformity of the composition may not be obtained. Therefore, in the method of Patent Document 2, in order to obtain a fibrous body having a uniform composition, the type, concentration, reaction rate, and the like of water-insoluble calcium salt, ionic organic polymer compound, water-insoluble calcium phosphate, and hardening liquid, The reaction conditions need to be highly controlled and there are barriers to commercial production applications. Furthermore, Patent Document 2 does not disclose a method for controlling the content ratio of HAp and β-TCP.
更に、特許文献３には、リン酸カルシウムを分散させたスラリーを複数のダイから吐出しながらスラリーブロー法により繊維状に成形することにより繊維状リン酸カルシウム成形体を製造する方法が開示されている。特許文献３の方法では、リン酸カルシウムを分散させたスラリーをスラリーブロー法によって成型しているため、製造された繊維の表面及び内部の組成は均一であることが予想されるが、特許文献３でも、HApとβ-TCPの含有比を制御する手法については開示されていない。 Furthermore, Patent Document 3 discloses a method for producing a fibrous calcium phosphate molded body by forming a slurry in which calcium phosphate is dispersed into a fiber by a slurry blowing method while discharging the slurry from a plurality of dies. In the method of Patent Document 3, because the slurry in which calcium phosphate is dispersed is molded by the slurry blow method, the surface and internal composition of the manufactured fiber is expected to be uniform. A method for controlling the content ratio of HAp and β-TCP is not disclosed.
本発明の目的は、簡易な手法によって、HApとβ-TCPの含有比を所望の範囲に制御でき、しかも組成が均一なリン酸カルシウムの繊維状成型体の製造技術を提供することである。 An object of the present invention is to provide a technique for producing a fibrous molded product of calcium phosphate having a uniform composition in which the content ratio of HAp and β-TCP can be controlled within a desired range by a simple technique.
本発明者等は、前記課題を解決すべく鋭意検討を行ったところ、リン酸カルシウムの繊維状成型体の製造に使用される紡糸原液として、カルシウム及びリンを含む化合物と、バインダーと、カルボン酸系分散剤と、リンオキソ酸系分散剤とを含むスラリーを使用し、当該紡糸原液に含まれるカルシウム原子の量とリン原子の量の比率を調節することによって、製造される繊維状成型体中のHApとβ-TCPの含有比を制御でき、更には繊維状成型体の組成を均一にできることを見出した。本発明は、これらの知見に基づいて、更に検討を重ねることにより完成したものである。 The inventors of the present invention have intensively studied to solve the above problems, and as a spinning dope used for the production of a calcium phosphate fibrous molding, a compound containing calcium and phosphorus, a binder, and a carboxylic acid dispersion HAp in the fibrous molded article produced by using a slurry containing an agent and a phosphorus oxoacid-based dispersant and adjusting the ratio of the amount of calcium atoms and the amount of phosphorus atoms contained in the spinning dope It has been found that the content ratio of β-TCP can be controlled and the composition of the fibrous molded body can be made uniform. The present invention has been completed by further studies based on these findings.
即ち、本発明は、下記に掲げる態様の発明を提供する。
項１． カルシウム及びリンを含む化合物と、バインダーと、カルボン酸系分散剤と、リンオキソ酸系分散剤とを含む紡糸原液を使用して紡糸を行う第１工程、及び
前記第１工程で得られた繊維状成型体を焼成する第２工程
を含むことを特徴とする、リン酸カルシウムの繊維状成型体の製造方法。
項２． 前記カルシウム及びリンを含む化合物が、ハイドロキシアパタイト及びβ型リン酸三カルシウムよりなる群から選択される少なくとも１種である、項１に記載の製造方法。
項３． 前記紡糸原液においてリン原子の量に対するカルシウム原子の量のモル比が１．５０〜１．６７である、項１又は２に記載の製造方法。
項４． 前記第２工程が、１００〜４００℃で１時間以上の条件で焼成を行った後に、更に４００〜１２００℃で０．１時間以上の条件で焼成が行われる、項１〜３のいずれかに記載の製造方法。
項５． リン酸カルシウムの繊維状成型体におけるハイドロキシアパタイトとβ型リン酸三カルシウムの含有比を制御する方法であって、
紡糸体の製造に使用される紡糸原液の組成を、カルシウムとリンを含む化合物と、バインダーと、リンオキソ酸系分散剤と、カルボン酸系分散剤とを含むように設定し、且つ
繊維状成型体に備えさせるべきハイドロキシアパタイトとβ型リン酸三カルシウムの含有比に応じて、前記紡糸原液中のリン原子の量とカルシウム原子の量を調節することを特徴とする、制御方法。
That is, this invention provides the invention of the aspect hung up below.
Item 1. A first step of spinning using a spinning stock solution containing a compound containing calcium and phosphorus, a binder, a carboxylic acid-based dispersant, and a phosphorus oxo-acid-based dispersant; and the fibrous form obtained in the first step A method for producing a fibrous molded body of calcium phosphate, comprising a second step of firing the molded body.
Item 2. Item 2. The production method according to Item 1, wherein the compound containing calcium and phosphorus is at least one selected from the group consisting of hydroxyapatite and β-type tricalcium phosphate.
Item 3. Item 3. The production method according to Item 1 or 2, wherein a molar ratio of the amount of calcium atoms to the amount of phosphorus atoms in the spinning dope is 1.50 to 1.67.
Item 4. Item 2. The firing according to any one of Items 1 to 3, wherein after the second step is performed at 100 to 400 ° C for 1 hour or longer, further baking is performed at 400 to 1200 ° C for 0.1 hour or longer. The manufacturing method as described.
Item 5. A method for controlling the content ratio of hydroxyapatite and β-type tricalcium phosphate in a fibrous molded product of calcium phosphate,
The composition of the spinning dope used for the production of the spinning body is set so as to include a compound containing calcium and phosphorus, a binder, a phosphorus oxoacid dispersant, and a carboxylic acid dispersant, and a fibrous molded body A control method characterized by adjusting the amount of phosphorus atoms and the amount of calcium atoms in the spinning dope according to the content ratio of hydroxyapatite and β-type tricalcium phosphate to be prepared in the above.
本発明によれば、リン酸カルシウムの繊維状成型体に求められる強度や生体吸収性に応じて、HApとβ-TCPの含有比を調整することができるので、治療目的や治療個所等に応じた生体材料を製造することが可能になっている。そのため、本発明は、例えば、テーラーメイド治療等に使用される生体インプラント材料を提供する技術として好適に使用できる。また、本発明によれば、リン酸カルシウムの繊維状成型体の組成（HApとβ-TCPの含有比）を均一にできるので、高品質な生体材料を提供することもできる。 According to the present invention, since the content ratio of HAp and β-TCP can be adjusted according to the strength and bioabsorbability required for the calcium phosphate fibrous molded body, the living body according to the therapeutic purpose, treatment location, etc. It is possible to produce materials. Therefore, this invention can be used conveniently as a technique which provides the biological implant material used for a tailor-made treatment etc., for example. Furthermore, according to the present invention, the composition of the calcium phosphate fibrous molding (content ratio of HAp and β-TCP) can be made uniform, so that a high-quality biomaterial can be provided.
１．リン酸カルシウムの繊維状成型体の製造方法
本発明の製造方法は、リン酸カルシウムの繊維状成型体の製造方法であって、カルシウム及びリンを含む化合物と、バインダーと、カルボン酸系分散剤と、リンオキソ酸系分散剤とを含む紡糸原液を使用して紡糸を行う第１工程、及び前記第１工程で得られた繊維状成型体を焼成する第２工程を含むことを特徴とする。以下、本発明の製造方法について詳述する。
1. Manufacturing method of calcium phosphate fibrous molded body The manufacturing method of the present invention is a manufacturing method of a calcium phosphate fibrous molded body, which includes a compound containing calcium and phosphorus, a binder, a carboxylic acid-based dispersant, and a phosphorus oxoacid system. It includes a first step of spinning using a spinning dope containing a dispersant and a second step of firing the fibrous molded body obtained in the first step. Hereafter, the manufacturing method of this invention is explained in full detail.
［紡糸原液］
本発明の製造方法では、紡糸原液として、カルシウム及びリンを含む化合物と、バインダーと、カルボン酸系分散剤と、リンオキソ酸系分散剤とを含む分散液を使用する。以下、本発明で使用する紡糸原液に配合する成分、製造する繊維状成型体のHApとβ-TCPの含有比に応じた紡糸原液の組成調節等について説明する。
[Spinning stock solution]
In the production method of the present invention, a dispersion containing a compound containing calcium and phosphorus, a binder, a carboxylic acid dispersant, and a phosphorus oxoacid dispersant is used as the spinning dope. Hereinafter, the composition of the spinning dope according to the components to be blended in the spinning dope used in the present invention and the content ratio of HAp and β-TCP of the fibrous molded article to be produced will be described.
（カルシウム及びリンを含む化合物）
紡糸原液には、繊維状成型体のカルシウム源及びリン源として、カルシウム及びリンを含む化合物を配合する。カルシウム及びリンを含む化合物としては、カルシウム原子及びリン原子を含んでいることを限度として特に制限されないが、例えば、HAp、β-TCP、無水リン酸水素カルシウム、リン酸水素カルシウム水和物、リン酸ニ水素カルシウム、α型メタリン酸カルシウム、β型メタリン酸カルシウム、γ型メタリン酸カルシウム、α型ピロリン酸カルシウム、β型ピロリン酸カルシウム、γ型ピロリン酸カルシウム、リン酸三カルシウム、α型リン酸三カルシウム、リン酸八カルシウム、リン酸四カルシウム等が挙げられる。これらの化合物は、１種単独で使用してもよく、また２種以上を組み合わせて使用してもよい。これらカルシウム及びリンを含む化合物の中でも、HAp及びβ-TCPの少なくとも1種を使用することが好ましい。
(Compound containing calcium and phosphorus)
In the spinning dope, a compound containing calcium and phosphorus is blended as a calcium source and a phosphorus source of the fibrous molded body. The compound containing calcium and phosphorus is not particularly limited as long as it contains calcium atom and phosphorus atom. For example, HAp, β-TCP, anhydrous calcium hydrogen phosphate, calcium hydrogen phosphate hydrate, phosphorus Calcium dihydrogen phosphate, α-type calcium metaphosphate, β-type calcium metaphosphate, γ-type calcium metaphosphate, α-type calcium pyrophosphate, β-type calcium pyrophosphate, γ-type calcium pyrophosphate, tricalcium phosphate, α-type tricalcium phosphate, eight phosphate phosphate Examples include calcium and tetracalcium phosphate. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Among these compounds containing calcium and phosphorus, it is preferable to use at least one of HAp and β-TCP.
また、カルシウム及びリンを含む化合物の性状についても特に制限されないが、紡糸原液中での当該化合物の分散性を高め、製造される繊維状成型体の表面及び内部の組成をより一層均一にするという観点から、微粒子状であることが好ましい。また、カルシウム及びリンを含む化合物が微粒子状であれば、焼結時の密度が高くなり、繊維状成型体の強度を良好にすることもできる。カルシウム及びリンを含む化合物が微粒子状である場合、その平均粒子径として、具体的には２０μm以下、好ましくは０．０１〜１０μm、更に好ましくは０．１〜２μmが挙げられる。ここで、平均粒子径については、レーザー回折・散乱式粒度分布測定法によって測定される値である。 Further, the properties of the compound containing calcium and phosphorus are not particularly limited, but the dispersibility of the compound in the spinning dope is enhanced, and the surface and internal composition of the produced fibrous molded body is made more uniform. From the viewpoint, it is preferably fine particles. Moreover, if the compound containing calcium and phosphorus is in the form of fine particles, the density during sintering is increased, and the strength of the fibrous molded body can be improved. When the compound containing calcium and phosphorus is in the form of fine particles, the average particle diameter is specifically 20 μm or less, preferably 0.01 to 10 μm, more preferably 0.1 to 2 μm. Here, the average particle diameter is a value measured by a laser diffraction / scattering particle size distribution measurement method.
また、カルシウム及びリンを含む化合物の紡糸原液中の濃度については、特に制限されないが、例えば、５〜７０重量％、好ましくは１０〜６０重量％、更に好ましくは２５〜５０重量％が挙げられる。このような濃度を充足することによって、得られる繊維状成型体の強度を良好にしつつ、紡糸原液の粘性を適度な範囲にして紡糸工程を容易に実施することが可能になる。 Further, the concentration of the compound containing calcium and phosphorus in the spinning dope is not particularly limited, and examples thereof include 5 to 70% by weight, preferably 10 to 60% by weight, and more preferably 25 to 50% by weight. By satisfying such a concentration, it becomes possible to easily carry out the spinning process by making the viscosity of the spinning dope in an appropriate range while improving the strength of the obtained fibrous molded body.
（バインダー）
紡糸原液には、紡糸性を備えさせるために、バインダーを含有する。バインダーの種類については、特に制限されないが、好ましくは可食性の水溶性多糖類が挙げられる。バインダーとして使用できる可食性の水溶性多糖類として、具体的には、プルラン、寒天、カラギナン、アルギン酸、アルギン酸塩類、キサンタンガム、デキストラン、ローカストビーンガム、グアーガム、ペクチン、グルコマンナン、デンプン、コラーゲン、ゼラチン、カラヤガム、キチン、キトサン、ポリビニルアルコール、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、タマリンドガム、アラビアガム等が挙げられる。これらのバインダーは、１種単独で使用してもよく、また２種以上を組み合わせて使用してもよい。これらのバインダーの中でも、紡糸原液への溶解性と紡糸原液に適した粘性を付与することを考慮すると、好ましくはプルランが挙げられる。
(binder)
The spinning dope contains a binder in order to provide spinnability. The type of the binder is not particularly limited, and preferably an edible water-soluble polysaccharide. As edible water-soluble polysaccharides that can be used as binders, specifically, pullulan, agar, carrageenan, alginic acid, alginates, xanthan gum, dextran, locust bean gum, guar gum, pectin, glucomannan, starch, collagen, gelatin, Examples include karaya gum, chitin, chitosan, polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, tamarind gum, and gum arabic. These binders may be used individually by 1 type, and may be used in combination of 2 or more type. Among these binders, pullulan is preferably used in consideration of solubility in the spinning dope and imparting viscosity suitable for the spinning dope.
また、バインダーの紡糸原液中の濃度については、特に制限されないが、例えば、５〜４０重量％、好ましくは５〜２０重量％、更に好ましくは５〜１５重量％が挙げられる。このような濃度を充足することによって、紡糸原液の紡糸性が高められ、紡糸工程を容易に実施することが可能になる。 Further, the concentration of the binder in the spinning dope is not particularly limited, and examples thereof include 5 to 40% by weight, preferably 5 to 20% by weight, and more preferably 5 to 15% by weight. By satisfying such a concentration, the spinnability of the spinning dope is improved, and the spinning process can be easily performed.
（カルボン酸系分散剤）
カルボン酸系分散剤とは、カルボキシル基を有し、カルシウム及びリンを含む化合物に吸着又は接着可能であって、カルシウム及びリンを含む化合物を紡糸原液中で分散させる化合物である。紡糸原液中で、カルボン酸系分散剤は、カルシウム及びリンを含む化合物に吸着又は接着した状態で、カルボキシル基による電荷の反発や立体障害によってカルシウム及びリンを含む化合物同士の分散性、又はカルシウム及びリンを含む化合物粒子表面の濡れ性を高める役割を示す。
(Carboxylic acid dispersant)
The carboxylic acid-based dispersant is a compound that has a carboxyl group, can be adsorbed or adhered to a compound containing calcium and phosphorus, and disperses the compound containing calcium and phosphorus in a spinning dope. In the spinning dope, the carboxylic acid-based dispersant is adsorbed or adhered to the compound containing calcium and phosphorus, and the dispersibility between the compounds containing calcium and phosphorus due to charge repulsion or steric hindrance by the carboxyl group, or calcium and phosphorus. The role which improves the wettability of the compound particle surface containing phosphorus is shown.
カルボン酸系分散剤の液性については、特に制限されないが、精製水に１０重量％となるように添加した際に、ｐＨ３〜１２、好ましくはｐＨ５〜１０、更に好ましくはｐＨ６〜８を示すものが挙げられる。 Although it does not restrict | limit especially about the liquid property of a carboxylic acid type dispersing agent, When it adds to purified water so that it may become 10 weight%, pH 3-12, Preferably pH 5-10, More preferably, it shows pH 6-8 Is mentioned.
また、カルボン酸系分散剤としては、無機粒子を分散させるために用いられている公知のものを使用すればよいが、例えば、カルボキシル基を含む界面活性剤、カルボキシル基を含む水溶性ポリマー、カルボキシル基を含む低分子化合物等が挙げられる。カルボン酸系分散剤の好適な例として、カルボキシル基を含む界面活性剤、アクリル酸及び／又はメタクリル酸を含むポリマー等が挙げられる。これらのカルボン酸系分散剤は、１種単独で使用してもよく、また２種以上を組み合わせて使用してもよい。なお、カルボン酸系分散剤は、金属カチオンを含まないものが好ましい。 In addition, as the carboxylic acid-based dispersant, a known one used for dispersing inorganic particles may be used. For example, a surfactant containing a carboxyl group, a water-soluble polymer containing a carboxyl group, a carboxyl And low molecular weight compounds containing a group. Preferable examples of the carboxylic acid dispersant include a surfactant containing a carboxyl group, a polymer containing acrylic acid and / or methacrylic acid, and the like. These carboxylic acid dispersants may be used alone or in combination of two or more. The carboxylic acid dispersant preferably does not contain a metal cation.
カルボン酸系分散剤としては、商品名「セルナＤ-３０５」（中京油脂株式会社製）、商品名「ＳＮディスパーサント５４６８」(サンノプコ株式会社製)等の市販品があり、本発明ではこれらの市販品を好適に使用することができる。 As the carboxylic acid-based dispersant, there are commercially available products such as trade name “Celna D-305” (manufactured by Chukyo Yushi Co., Ltd.), trade name “SN Dispersant 5468” (manufactured by San Nopco Co., Ltd.). A commercial item can be used conveniently.
また、カルボン酸系分散剤の紡糸原液中の濃度については、繊維状成型体に備えさせるべきHAp及びβ-TCPの含有比に応じて適宜設定すればよいが、例えば、０超〜５０重量％、好ましくは０．１〜４０重量％、更に好ましくは０．３〜３０重量％が挙げられる。 Further, the concentration of the carboxylic acid dispersant in the spinning dope may be appropriately set according to the content ratio of HAp and β-TCP to be provided in the fibrous molded body. For example, more than 0 to 50% by weight , Preferably 0.1 to 40% by weight, more preferably 0.3 to 30% by weight.
（リンオキソ酸系分散剤）
リンオキソ酸系分散剤は、リン原子にヒドロキシル基とオキソ基が結合しているリンオキソ酸の残基（以下、リンオキソ酸残基）を有し、リン酸カルシウム粒子に吸着又は接着可能であって、カルシウム及びリンを含む化合物を紡糸原液中で分散させる化合物である。紡糸原液中で、リンオキソ酸系分散剤は、リン酸カルシウム粒子に吸着又は接着した状態で、リンオキソ酸残基による電荷の反発や立体障害によってリン酸カルシウム粒子同士の分散性又はリン酸カルシウム粒子表面の濡れ性を高める役割を示す。
(Phosphorus acid dispersant)
The phosphorus oxo acid dispersant has a phosphorus oxo acid residue (hereinafter referred to as a phosphorus oxo acid residue) in which a hydroxyl group and an oxo group are bonded to a phosphorus atom, and can adsorb or adhere to calcium phosphate particles, A compound in which a compound containing phosphorus is dispersed in a spinning dope. In the spinning dope, the phosphorous acid dispersant is adsorbed or adhered to the calcium phosphate particles, and improves the dispersibility between the calcium phosphate particles or the wettability of the calcium phosphate particle surface due to repulsion of charges and steric hindrance. Indicates.
リンオキソ酸系分散剤の液性については、特に制限されないが、精製水に５重量％となるように添加した際に、ｐＨ３〜１２、好ましくはｐＨ５〜１０、更に好ましくはｐＨ６〜８を示すものが挙げられる。 The liquidity of the phosphorus oxoacid dispersant is not particularly limited, but when added to purified water so as to be 5% by weight, it exhibits pH 3 to 12, preferably pH 5 to 10, more preferably pH 6 to 8. Is mentioned.
また、リンオキソ酸系分散剤としては、無機粒子を分散させるために用いられている公知のものを使用すればよいが、例えば、リンオキソ酸残基を含む界面活性剤、リンオキソ酸残基を含むポリマー等が挙げられる。より具体的には、オルトリン酸、亜リン酸、ホスホン酸、亜ホスホン酸、ホスフィン酸、亜ホスフィン酸、ホスフェン酸、亜ホスフェン酸、ピロリン酸、次リン酸、イソ次リン酸等の残基を構造中に有するもので具体的にはポリリン酸、メタリン酸、ジメタリン酸、トリメタリン酸、テトラメタリン酸、ヘキサメタリン酸、イソメタリン酸等が挙げられる。これらのリンオキソ酸系分散剤は、１種単独で使用してもよく、また２種以上を組み合わせて使用してもよい。なお、リンオキソ酸系分散剤は、金属カチオンを含まず、カルシウムやマグネシウム等金属カチオンによる分散阻害効果を弱める作用を持つものが好ましい。本発明で使用されるリンオキソ酸系分散剤の好適な一例として、ホスホン酸残基を含むポリマーが挙げられる。 Further, as the phosphooxo acid-based dispersant, known ones used for dispersing inorganic particles may be used. For example, surfactants containing phosphooxoacid residues, polymers containing phosphooxoacid residues, and the like. Etc. More specifically, residues such as orthophosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, phosphinic acid, phosphenic acid, phosphinic acid, pyrophosphoric acid, hypophosphoric acid, isophosphoric acid, etc. Specific examples thereof include polyphosphoric acid, metaphosphoric acid, dimetaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, and isometaphosphoric acid. These phosphorus oxo acid dispersants may be used alone or in combination of two or more. The phosphorus oxo acid dispersant preferably does not contain a metal cation and has an action of weakening the dispersion inhibition effect by a metal cation such as calcium or magnesium. As a suitable example of the phosphorus oxoacid dispersant used in the present invention, a polymer containing a phosphonic acid residue can be mentioned.
リンオキソ酸系分散剤としては、商品名「ＳＮディスパーサント２０６０」（サンノプコ株式会社製）、商品名「ヘキサメタりん酸ナトリウム」（和光純薬工業株式会社製）等の市販品があり、本発明ではこれらの市販品を使用することができる。 Examples of the phosphorus oxo acid dispersant include commercial products such as trade name “SN Dispersant 2060” (manufactured by San Nopco Co., Ltd.) and trade name “sodium hexametaphosphate” (manufactured by Wako Pure Chemical Industries, Ltd.). These commercially available products can be used.
また、リンオキソ酸系分散剤の紡糸原液中の濃度については、繊維状成型体に備えさせるべきHAp及びβ-TCPの含有比に応じて適宜設定すればよいが、例えば、０超〜４０重量％以下、好ましくは０．１〜３０重量％、更に好ましくは０．３〜１０重量％が挙げられる。 The concentration of the phosphorus oxoacid dispersant in the spinning dope may be appropriately set according to the content ratio of HAp and β-TCP to be provided in the fibrous molded body. For example, more than 0 to 40% by weight Hereinafter, it is preferably 0.1 to 30% by weight, more preferably 0.3 to 10% by weight.
（その他の成分）
本発明で使用される紡糸原液には、必要に応じて、前記カルシウム及びリンを含む化合物以外のカルシウム塩を含んでいてもよい。特に、前記カルシウム及びリンを含む化合物としてβ-TCPを使用する場合には、当該化合物以外のカルシウム塩を配合することによって、製造される繊維状成型体のHAp含有比を増加させることが可能になる。このようなカルシウム塩の種類については、特に制限されないが、例えば、硝酸カルシウム、酸化カルシウム、水酸化カルシウム、塩化カルシウム、炭酸カルシウム、シュウ酸カルシウム、クエン酸カルシウム、乳酸カルシウム、硫酸カルシウム等が挙げられる。これらのカルシウム塩は１種単独で使用してもよく、また２種以上を組み合わせて使用してもよい。
(Other ingredients)
The spinning dope used in the present invention may contain a calcium salt other than the compound containing calcium and phosphorus, if necessary. In particular, when β-TCP is used as the compound containing calcium and phosphorus, it is possible to increase the HAp content ratio of the fibrous molded article to be manufactured by adding a calcium salt other than the compound. Become. The type of the calcium salt is not particularly limited, and examples thereof include calcium nitrate, calcium oxide, calcium hydroxide, calcium chloride, calcium carbonate, calcium oxalate, calcium citrate, calcium lactate, and calcium sulfate. . These calcium salts may be used individually by 1 type, and may be used in combination of 2 or more type.
また、本発明で使用される紡糸原液には、分散媒として溶媒が含まれる。紡糸原液に配合される溶媒は、バインダー、カルボン酸系分散剤及びリンオキソ酸系分散剤を溶解又は可溶化させ得ることを限度として特に制限されないが、例えば、水、極性有機溶媒等が挙げられる。特に、水は、廃液処理が容易であり、製造設備に排気装置が不要であるため、安全性や製造コストの観点から、紡糸原液に使用される溶媒として好適である。 The spinning dope used in the present invention contains a solvent as a dispersion medium. The solvent blended in the spinning dope is not particularly limited as long as it can dissolve or solubilize the binder, the carboxylic acid dispersant, and the phosphorus oxo acid dispersant, and examples thereof include water and polar organic solvents. In particular, water is suitable as a solvent used in the spinning dope from the viewpoint of safety and manufacturing cost because the waste liquid treatment is easy and an exhaust device is not required in the manufacturing facility.
紡糸原液中の溶媒の濃度については、特に制限されないが、例えば５〜８０重量％好ましくは２０〜７０重量％、更に好ましくは３０〜５０重量％が挙げられる。 The concentration of the solvent in the spinning dope is not particularly limited, and examples thereof include 5 to 80% by weight, preferably 20 to 70% by weight, and more preferably 30 to 50% by weight.
（紡糸原液の組成設定に基づくHAp及びβ-TCPの含有比の調節）
本発明の製造方法では、前記紡糸原液の組成を調節することによって、製造される繊維状成型体中のHApとβ-TCPの含有比を制御することが可能になる。具体的には、前記紡糸原液に含まれるカルシウム原子とリン原子の比率に応じて、製造される繊維状成型体中のHApとβ-TCPの含有比を制御することができる。従って、製造される繊維状成型体において備えさせるべきHApとβ-TCPの含有比に応じて、前記紡糸原液に含まれるリン原子の量とカルシウム原子の量の比率を設定すればよい。ここで、紡糸原液に含まれるリン原子の量は、前記カルシウム及びリンを含む化合物に含まれるリン原子と、前記リンオキソ酸系分散剤に含まれるリン原子の合計量である。また、紡糸原液に含まれるカルシウム原子の量は、前記カルシウム及びリンを含む化合物に含まれるカルシウム原子と、必要に応じて添加されるカルシウム塩（前記カルシウム及びリンを含む化合物以外）に含まれるカルシウム原子の合計量である。
(Adjusting the content ratio of HAp and β-TCP based on the composition of the spinning dope)
In the production method of the present invention, it is possible to control the content ratio of HAp and β-TCP in the fibrous molded article produced by adjusting the composition of the spinning dope. Specifically, the content ratio of HAp and β-TCP in the produced fibrous molded body can be controlled according to the ratio of calcium atoms and phosphorus atoms contained in the spinning dope. Therefore, the ratio of the amount of phosphorus atoms and the amount of calcium atoms contained in the spinning stock solution may be set according to the content ratio of HAp and β-TCP to be provided in the fibrous molded body to be produced. Here, the amount of phosphorus atoms contained in the spinning dope is the total amount of phosphorus atoms contained in the calcium and phosphorus-containing compound and phosphorus atoms contained in the phosphorus oxoacid dispersant. In addition, the amount of calcium atoms contained in the spinning dope is the calcium atoms contained in the compound containing calcium and phosphorus and calcium contained in the calcium salt (other than the compound containing calcium and phosphorus) added as necessary. The total amount of atoms.
より具体的には、紡糸原液中のリン原子の量に対するカルシウム原子の量のモル比（以下、「Ｃａ／Ｐ比」と表記することもある）が高い程、製造される繊維状成型体中のHAp量が多くβ-TCP量が少なくなり、また、当該Ｃａ／Ｐ比が低い程、製造される繊維状成型体中のHAp量が少なくβ-TCP量が多くなる。例えば、後述する実施例に示されているように、紡糸原液に含まれるリン原子の総量に対するカルシウム原子の総量のモル比（以下、「Ｃａ／Ｐ比」と表記することもある）を１．６４に設定すると、製造される繊維状成型体におけるHap含有量を８５．９重量％且つβ-TCP含有量を１４．１重量％に制御でき、また、紡糸原液中のＣａ／Ｐ比を１．５３に設定すると、製造される繊維状成型体におけるHAp含有量を２１．０重量％且つβ-TCP含有量を７９．０重量％に制御することが可能になっている。 More specifically, the higher the molar ratio of the amount of calcium atoms to the amount of phosphorus atoms in the spinning dope (hereinafter sometimes referred to as “Ca / P ratio”), the higher the produced fibrous molded body. The amount of HAp is large and the amount of β-TCP is small, and the lower the Ca / P ratio is, the smaller the amount of HAp in the produced fibrous molded body is, and the larger the amount of β-TCP. For example, as shown in Examples described later, the molar ratio of the total amount of calcium atoms to the total amount of phosphorus atoms contained in the spinning dope (hereinafter sometimes referred to as “Ca / P ratio”) is 1. If it is set to 64, the Hap content in the produced fibrous molded body can be controlled to 85.9% by weight and the β-TCP content to 14.1% by weight, and the Ca / P ratio in the spinning dope is 1 When set to .53, it is possible to control the HAp content in the produced fibrous molded body to 21.0 wt% and the β-TCP content to 79.0 wt%.
かかる点を踏まえて、紡糸原液中のＣａ／Ｐ比は、例えば１．５０〜１．６７、好ましくは１．５０〜１．６６の範囲内で、製造される繊維状成型体において備えさせるべきHApとβ-TCPの含有比に応じて設定すればよい。 In consideration of such points, the Ca / P ratio in the spinning dope should be provided in the fibrous molded article to be produced, for example, within the range of 1.50 to 1.67, preferably 1.50 to 1.66. What is necessary is just to set according to the content ratio of HAp and β-TCP.
紡糸原液中のＣａ／Ｐ比は、紡糸原液に配合するカルシウム及びリンを含む化合物の種類とリンオキソ酸系分散剤の種類に応じて、これらの含有量を適宜設定することによって調節できる。 The Ca / P ratio in the spinning dope can be adjusted by appropriately setting these contents according to the type of the compound containing calcium and phosphorus and the kind of the phosphorus oxoacid dispersant to be blended in the spinning dope.
（紡糸原液の調製）
紡糸原液の調製方法については、特に制限されないが、前記カルシウム及びリンを含む化合物を均一に分散させるために、当該化合物と、カルボン酸系分散剤と、リンオキソ酸系分散剤とを溶媒中に添加して十分に混合した後に、バインダーを添加して混合することが好ましい。また、バインダーの添加は、バインダーを溶媒に溶解又は可溶化させてバインダー溶液を調製し、当該バインダー溶液を添加することによって行ってもよい。
(Preparation of spinning dope)
The method for preparing the spinning dope is not particularly limited, but in order to uniformly disperse the compound containing calcium and phosphorus, the compound, a carboxylic acid-based dispersant, and a phosphorus oxoacid-based dispersant are added to a solvent. It is preferable that the binder is added and mixed after sufficiently mixing. The binder may be added by dissolving or solubilizing the binder in a solvent to prepare a binder solution and adding the binder solution.
紡糸原液を調製する際の温度条件については、特に制限されないが、例えば、０〜１００℃、好ましくは１０〜８０℃、更に好ましくは２０〜５０℃が挙げられる。このような温度条件であれば、溶媒の揮発や、バインダー、カルボン酸系分散剤、及びリンオキソ酸系分散剤の分解を抑制することができる。 Although it does not restrict | limit especially about the temperature conditions at the time of preparing a spinning undiluted solution, For example, 0-100 degreeC, Preferably it is 10-80 degreeC, More preferably, 20-50 degreeC is mentioned. Under such temperature conditions, it is possible to suppress the volatilization of the solvent and the decomposition of the binder, the carboxylic acid dispersant, and the phosphorus oxo acid dispersant.
紡糸原液を調製する装置については、特に制限されないが、例えば、容器自体が回転、振動、揺動する容器回転型装置；容器内に入れた羽根が回転する機械撹拌型装置；ねじれた管内に粉体を流す無撹拌型装置；高速回転する高速せん断衝撃型装置；遠心力による材料対流で撹拌する遊星式攪拌型装置等が挙げられる。これらの装置の中でも、遊星式攪拌型装置、特に脱泡機能を備えた遊星式撹拌型装置は、紡糸原液中の微細な気泡の生成を抑制でき、繊維状成型体において気泡に起因する空隙の発生を抑制できるので、好適に使用される。 The apparatus for preparing the spinning dope is not particularly limited. For example, a container rotating type apparatus in which the container itself rotates, vibrates, or rocks; a mechanical stirring type apparatus in which blades in the container rotate; a powder in a twisted tube Examples include a non-stirring type device for flowing the body; a high-speed shearing impact type device that rotates at high speed; and a planetary stirring type device that stirs by material convection by centrifugal force. Among these devices, the planetary stirring type device, particularly the planetary stirring type device having a defoaming function, can suppress the generation of fine bubbles in the spinning dope, and the voids caused by the bubbles in the fibrous molded body can be suppressed. Since generation | occurrence | production can be suppressed, it is used suitably.
［紡糸工程］
本発明の製造方法において、前記紡糸原液を紡糸する方法については、特に制限されず、従来公知の無機繊維の紡糸方法を採用すればよいが、例えば、紡糸原液を、ロータに供給し、ロータの遠心力により繊維化する方法(スピニング法)、高速空気や水蒸気で紡糸原液吹き飛ばすことにより繊維化する方法(ブローイング法)等が挙げられる。スピニング法としては、具体的には、フォーススピニング法やエレクロンスピニング法等が挙げられる。また、ブローイング法としては、例えば、特開昭６１−１７４４６０号公報に記載の装置を用いて、ダイから噴射した紡糸原液を赤外線ヒーターにより水分を除去してネット型ドラムで回収する方法等が挙げられる。
[Spinning process]
In the production method of the present invention, the method for spinning the spinning dope is not particularly limited, and a conventionally known spinning method of inorganic fibers may be adopted. For example, the spinning dope is supplied to the rotor, Examples thereof include a method of fiberizing by a centrifugal force (spinning method), a method of fiberizing by blowing off a spinning stock solution with high-speed air or steam (blowing method), and the like. Specific examples of the spinning method include a force spinning method and an electron spinning method. Examples of the blowing method include a method of recovering a spinning stock solution injected from a die by using an apparatus described in JP-A-61-174460 and removing the moisture with an infrared heater and collecting it with a net-type drum. It is done.
［焼成工程］
前記紡糸原液を用いて紡糸された繊維状成型体は、焼成工程に供される。焼成工程を行うことによって、繊維状成型体中のバインダー、カルボン酸系分散剤、及びリンオキソ酸系分散剤の除去；HAp及びβ-TCPの結晶相形成；繊維状成型体の強度、溶解性、繊維径の制御等を行うことが可能になる。
[Baking process]
The fibrous molded body spun using the spinning dope is subjected to a firing step. By performing the firing step, removal of binder, carboxylic acid-based dispersant, and phosphorus oxo-acid-based dispersant in the fibrous molded body; HAp and β-TCP crystal phase formation; strength, solubility of the fibrous molded body, It becomes possible to control the fiber diameter and the like.
焼成工程の条件については、特に制限されないが、焼成条件を変えた２段階での焼成を行うことが好ましい。２段階の焼成方法としては、具体的には、１００〜４００℃、好ましくは２５０℃〜３５０℃で１時間以上、好ましくは１２〜２４時間の条件で１段階目の焼成を行った後に、４００〜１２００℃、好ましくは５００℃〜１１５０℃で０．１時間以上、好ましくは０．５〜１０時間の条件で２段階目の焼成を行う方法が挙げられる。なお、２段階目の焼成は、１段階目の焼成よりも高い温度で行えばよく、例えば、２段階目の焼成温度が１段階目の焼成温度よりも３００℃程度以上高くなるように設定すればよい。このような条件で焼成することにより、HAp中の水酸基消失や、β-TCPのα-TCPへの結晶相転移を抑制しつつ、バインダー及び分散剤を焼失させることが可能になる。 The conditions for the firing step are not particularly limited, but it is preferable to perform firing in two stages with different firing conditions. Specifically, as the two-stage baking method, after performing the first-stage baking at 100 to 400 ° C., preferably 250 to 350 ° C. for 1 hour or longer, preferably 12 to 24 hours, 400 A method of performing the second stage baking at a temperature of ˜1200 ° C., preferably 500 ° C. to 1150 ° C. for 0.1 hour or longer, preferably 0.5 to 10 hours, is mentioned. The second stage baking may be performed at a higher temperature than the first stage baking. For example, the second stage baking temperature is set to be about 300 ° C. higher than the first stage baking temperature. That's fine. By baking under such conditions, it becomes possible to burn out the binder and the dispersant while suppressing the disappearance of hydroxyl groups in HAp and the crystal phase transition of β-TCP to α-TCP.
［繊維状成型体］
本発明の製造方法では、繊維状成型体をモノフィラメントとして製造してもよく、またマルチフィラメントとして製造してもよい。
[Fibrous molding]
In the production method of the present invention, the fibrous molded body may be produced as a monofilament or a multifilament.
また、本発明の製造方法で得られた繊維状成型体は、骨補填材、再生治療材料用の足場材料、人工骨、人工歯等の生体インプラント材料に好適に用いられる他、医薬品、歯磨き剤、フィルター、抗菌剤、吸着剤、触媒、触媒担体、化粧品等に使用することもできる。 In addition, the fibrous molded body obtained by the production method of the present invention is preferably used for bone implants, scaffolding materials for regenerative treatment materials, bioimplant materials such as artificial bones and artificial teeth, as well as pharmaceuticals and dentifrices. , Filters, antibacterial agents, adsorbents, catalysts, catalyst carriers, cosmetics and the like.
また、本発明の製造方法で得られた繊維状成型体は、更に、造粒、圧縮等の成型処理に供して、顆粒状、球状、プレート状、ブロック状等に成形することもできる。 Moreover, the fibrous molded body obtained by the production method of the present invention can be further subjected to a molding process such as granulation and compression to be molded into granules, spheres, plates, blocks, and the like.
２．HAp及びβ-TCPの含有比の制御方法
本発明の制御方法は、リン酸カルシウムの繊維状成型体におけるHApとβ-TCPの含有比を制御する方法であって、紡糸体の製造に使用される紡糸原液の組成を、カルシウムとリンを含む化合物と、バインダーと、リンオキソ酸系分散剤と、カルボン酸系分散剤とを含むように設定し、且つ繊維状成型体に備えさせるべきHApとβ-TCPの含有比に応じて、前記紡糸原液中のカルシウム原子の量とリン原子の量の比率を調節することを特徴とする。
2. Method for controlling the content ratio of HAp and β-TCP The control method of the present invention is a method for controlling the content ratio of HAp and β-TCP in a fibrous molded product of calcium phosphate, which is used for producing a spun body. The composition of the stock solution is set to include a compound containing calcium and phosphorus, a binder, a phosphorus oxoacid dispersant, and a carboxylic acid dispersant, and HAp and β-TCP to be provided in the fibrous molded body The ratio of the amount of calcium atoms and the amount of phosphorus atoms in the spinning dope is adjusted according to the content ratio of.
本発明の制御方法は、リン酸カルシウムの繊維状成型体の製造において、繊維状成型体に備えさせるべきHApとβ-TCPの含有比を制御する方法であり、具体的には、繊維状成型体に備えさせるべきHApとβ-TCPの含有比を決定する第１工程、及び当該第１工程で決定されたHApとβ-TCPの含有比に基づいて、前記紡糸原液中のカルシウム原子の量とリン原子の量の比率を調節する第２工程を経て実施される。 The control method of the present invention is a method for controlling the content ratio of HAp and β-TCP to be provided in a fibrous molded body in the production of a calcium phosphate fibrous molded body. Based on the first step of determining the content ratio of HAp and β-TCP to be provided, and the content ratio of HAp and β-TCP determined in the first step, the amount of calcium atoms and phosphorus in the spinning stock solution This is carried out through a second step of adjusting the atomic ratio.
本発明の制御方法によって設定された組成の紡糸原液は、前述する紡糸工程及び焼成工程に供することによって、目的のHApとβ-TCPの含有比を有するリン酸カルシウムの繊維状成型体が製造される。 A spinning dope having a composition set by the control method of the present invention is subjected to the spinning step and the firing step described above, whereby a fibrous molded body of calcium phosphate having a target content ratio of HAp and β-TCP is produced.
本発明の制御方法において、使用される紡糸原液の各成分の種類や濃度、繊維状成型体におけるHApとβ-TCPの含有比を制御するための紡糸原液の組成の調節方法等については、前記「１．リン酸カルシウムの繊維状成型体の製造方法」の欄に記載の通りである。 In the control method of the present invention, the type and concentration of each component of the spinning dope used, the method for adjusting the composition of the spinning dope for controlling the content ratio of HAp and β-TCP in the fibrous molding, etc. It is as described in the column of “1. Manufacturing method of fibrous molded product of calcium phosphate”.
以下、実施例を挙げて本発明を具体的に説明するが、本発明は実施例に限定して解釈されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is limited to an Example and is not interpreted.
実施例１〜４
１．繊維状成型体の製造
HApスラリー(富田製薬株式会社製；HApの平均粒子径１．８μm、固形分量４５．４重量％)を３０．０g、リンオキソ酸系分散剤（「SNディスパーサント２０６０」、サンノプコ株式会社製、リン含有量７．４重量％)を表１に示す濃度となる量、カルボン酸系分散剤（「セルナD-３０５」、中京油脂株式会社製）を表１に示す濃度となる量をそれぞれ正確に量りとり、５０ｍＬ容器に加えボルテックスにて５分間撹拌した。撹拌後５０mLビーカーに移し、マグネチックスターラーにて室温で１５分間撹拌した。次いで、日本薬局方プルランを４．２６g添加し、スターラーにて１５分間室温で撹拌混合した。これを紡糸原液とした。
Examples 1-4
1. Manufacture of fibrous moldings
30.0 g of HAp slurry (Tomita Pharmaceutical Co., Ltd .; HAp average particle size 1.8 μm, solid content 45.4% by weight), phosphorus oxoacid dispersant (“SN Dispersant 2060”, San Nopco Co., Ltd., phosphorus The amount of 7.4 wt.%) Is the concentration shown in Table 1, and the amount of carboxylic acid dispersant ("Selna D-305", manufactured by Chukyo Yushi Co., Ltd.) is the concentration shown in Table 1. The sample was weighed and added to a 50 mL container and stirred for 5 minutes by vortexing. After stirring, the mixture was transferred to a 50 mL beaker and stirred with a magnetic stirrer at room temperature for 15 minutes. Next, 4.26 g of Japanese Pharmacopoeia pullulan was added and stirred and mixed at room temperature for 15 minutes with a stirrer. This was used as a spinning dope.
この紡糸原液を７ｃｍ2の円形状板２枚に塗り（１枚の円形状板に紡糸原液が約０．１ｍｌ／ｃｍ2となる量）、紡糸原液を挟むように２枚の円形状板を重ねあわせた。次いで、２枚の円形状板を引き離し、紡糸原液が糸状になる瞬間にエアーブローにて乾燥(ヘア―ドライヤー；１２００Ｗ、５０−６０Ｈｚ)を行い、繊維状成型体を得た。乾燥後の繊維状成型体を下記焼成条件で焼成を行った。
（焼成条件）
３２０℃まで２４時間で昇温した(昇温温度：１３．３℃/ｈｒ)後に、３２０℃にて１時間保持した。その後１０００℃まで１３.６時間(５０℃/ｈｒ)で昇温した後に１０００℃にて２時間焼成した。
Apply this spinning stock solution to two 7 cm 2 circular plates (amount of spinning stock solution of about 0.1 ml / cm 2 on one circular plate), and place two circular plates so as to sandwich the spinning stock solution. Overlapped. Next, the two circular plates were separated and dried by air blow (hair-dryer; 1200 W, 50-60 Hz) at the moment when the spinning solution became a yarn to obtain a fibrous molded body. The fibrous molded body after drying was fired under the following firing conditions.
(Baking conditions)
After raising the temperature to 320 ° C. in 24 hours (temperature raising temperature: 13.3 ° C./hr), the temperature was maintained at 320 ° C. for 1 hour. Thereafter, the temperature was raised to 1000 ° C. for 13.6 hours (50 ° C./hr) and then calcined at 1000 ° C. for 2 hours.
２．繊維状成型体及び紡糸原液の性能の評価
＜繊維状成型体のHApとβ-TCPの含有量の測定＞
焼成後の繊維状成型体について、HApとβ-TCPの含有量を測定した。HApとβ-TCPの含有量の測定は以下の方法にて行った。先ず、アパタイトHAP単斜晶（和光純薬工業株式会社製）及びアパタイトβ-TCP三方晶（和光純薬工業株式会社製）をそれぞれ１０００℃で焼成した後、所定の割合（β-TCP＝０．５重量％、１．０重量％、１．５重量％、２．０重量％、３．０重量％、５．０重量％、８．０重量％、１５．０重量％、２０．０重量％、５０．０重量％）になるように混合して標準サンプルを作成した。次に標準サンプルを粉末Ｘ線回析装置によりβ-TCP由来のシグナル（２θ/θ＝３１．２°付近）の積分強度を測定し、β-TCP含有量（混合量）及び積分強度比から検量線を作成した。焼成後の繊維状成型体を粉末X線回折装置によりβ-TCP由来のシグナル（２θ/θ＝３１．２°付近）の積分強度を測定し、前記検量線を使用してHAp及びβ-TCPの含有量を算出した。また、焼成後の繊維状成型体のCa/P比に関しては以下の式にて算出した。
Ca/P=((１０x/１００４)+(３y/３１０))/((６x/１００４)+(２y/３１０))
ｘ：HApの含有量(重量％)
ｙ：β-TCPの含有量(重量％)
2. Evaluation of the performance of fibrous moldings and spinning dope <Measurement of HAp and β-TCP content of fibrous moldings>
About the fibrous molded object after baking, content of HAp and (beta) -TCP was measured. The content of HAp and β-TCP was measured by the following method. First, after apatite HAP monoclinic crystal (manufactured by Wako Pure Chemical Industries, Ltd.) and apatite β-TCP trigonal crystal (manufactured by Wako Pure Chemical Industries, Ltd.) are each fired at 1000 ° C., a predetermined ratio (β-TCP = 0) 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 3.0 wt%, 5.0 wt%, 8.0 wt%, 15.0 wt%, 20.0 Wt%, 50.0 wt%) to prepare a standard sample. Next, the integrated intensity of the β-TCP-derived signal (2θ / θ = around 31.2 °) was measured using a powder X-ray diffractometer for the standard sample. A calibration curve was created. Measure the integrated intensity of the β-TCP-derived signal (2θ / θ = around 31.2 °) with the powder X-ray diffractometer after firing, and use the calibration curve to determine HAp and β-TCP The content of was calculated. Further, the Ca / P ratio of the fibrous molded body after firing was calculated by the following formula.
Ca / P = ((10x / 1004) + (3y / 310)) / ((6x / 1004) + (2y / 310))
x: HAp content (% by weight)
y: β-TCP content (% by weight)
＜繊維状成型体の外観性状の観察＞
焼成後の繊維状成型体について、電子顕微鏡にて外観性状の観察を行った。
<Observation of appearance of fibrous molded body>
The appearance of the fibrous molded body after firing was observed with an electron microscope.
＜紡糸原液の分散性の評価＞
バインダーを配合しなかったこと以外は、前記紡糸原液と同組成となる分散液を調製した。当該分散液２００μＬに精製水を加えて正確に１０ｍＬ（５０倍希釈）として、評価用分散液を調製した。この評価用分散液のゼータ電位を測定した。ゼータ電位の測定は、ゼータ電位測定装置(大塚電子株式会社製)及び１２μｌ容のフローセルを用いて行った。
<Evaluation of dispersibility of spinning dope>
A dispersion having the same composition as the spinning dope was prepared except that no binder was added. Purified water was added to 200 μL of the dispersion to make exactly 10 mL (50-fold dilution) to prepare a dispersion for evaluation. The zeta potential of this evaluation dispersion was measured. The zeta potential was measured using a zeta potential measuring device (Otsuka Electronics Co., Ltd.) and a 12 μl flow cell.
＜紡糸原液のｐＨの評価＞
バインダーを配合しなかったこと以外は、前記紡糸原液と同組成となる分散液を調製した。当該分散液２００μＬに精製水を加えて正確に１０ｍＬとして、評価用分散液を調製した。この評価用分散液のｐＨを、ｐＨメーターを用いて測定した。
<Evaluation of pH of spinning dope>
A dispersion having the same composition as the spinning dope was prepared except that no binder was added. Purified water was added to 200 μL of the dispersion to make exactly 10 mL, and a dispersion for evaluation was prepared. The pH of this evaluation dispersion was measured using a pH meter.
＜紡糸原液の紡糸性の評価＞
前記紡糸原液を用いた紡糸工程時に、紡糸原液の紡糸性を以下の判定基準に従って評価した。
紡糸性の判定基準
○：紡糸工程において紡糸原液の糸引きが確認され、紡糸できた。
×：紡糸工程において紡糸原液の糸引きが不十分であり、紡糸できなかった。
<Evaluation of spinnability of spinning dope>
During the spinning process using the spinning dope, the spinnability of the spinning dope was evaluated according to the following criteria.
Judgment criteria for spinnability ◯: In the spinning process, spinning of the spinning solution was confirmed and spinning was possible.
X: In the spinning process, the spinning solution was not sufficiently drawn, and could not be spun.
３．結果
焼成後の繊維状成型体のHAp及びβ-TCPの含有量、紡糸原液のｐＨ及び分散性（ゼータ電位）、並びに紡糸原液の紡糸性を評価した結果を表２に示す。また、紡糸原液に配合したリンオキソ酸系分散剤の含有量と、焼成後の繊維状成型体のβ-TCPの含有量の関係を図１に示す。更に、焼成後の繊維状成型体の外観性状を観察した結果を図２〜５に示す。これら結果から、実施例１〜４のいずれでも、紡糸原液の紡糸性が優れており、繊維状成型体を製造できることが確認された。また、紡糸原中のＣａ／Ｐ比と、焼成後の繊維状成型体のβ-TCP含有量に高い相関性が認められ、紡糸原中のＣａ／Ｐ比をコントロールすることにより、繊維状成型体のβ-TCP含有量を調節できることも確認された。
3. Results Table 2 shows the results of evaluating the contents of HAp and β-TCP, the pH and dispersibility of the spinning dope (zeta potential), and the spinning property of the spinning dope after firing. FIG. 1 shows the relationship between the content of the phosphorus oxoacid dispersant blended in the spinning dope and the content of β-TCP in the fibrous molded body after firing. Furthermore, the result of having observed the external appearance property of the fibrous molding after baking is shown to FIGS. From these results, it was confirmed that in any of Examples 1 to 4, the spinning property of the spinning dope was excellent and a fibrous molded body could be produced. In addition, a high correlation was found between the Ca / P ratio in the spinning raw material and the β-TCP content of the fibrous molded body after firing, and by controlling the Ca / P ratio in the spinning raw material, the fibrous molding It was also confirmed that the β-TCP content of the body can be adjusted.
実施例５〜７
１．繊維状成型体の製造、並びに繊維状成型体及び紡糸原液の紡糸性の評価
紡糸原液中のリンオキソ酸系分散剤及びカルボン酸系分散剤を表３に示す濃度に設定したこと以外は、前記実施例１と同条件で繊維状成型体の製造を行った。また、前記実施例１と同条件で、繊維状成型体の評価及び紡糸原液の性能評価を行った。
Examples 5-7
1. Production of fibrous molded body, and evaluation of spinnability of fibrous molded body and spinning stock solution The above-described implementation was carried out except that the concentrations of the phosphoroxo acid dispersant and carboxylic acid dispersant in the spinning stock solution were set to the concentrations shown in Table 3. A fibrous molded body was produced under the same conditions as in Example 1. Further, under the same conditions as in Example 1, evaluation of the fibrous molded body and performance evaluation of the spinning dope were performed.
２．結果
焼成後の繊維状成型体のHAp及びβ-TCPの含有量、紡糸原液のｐＨ及び分散性（ゼータ電位）、並びに紡糸原液の紡糸性を評価した結果を表４に示す。更に、焼成後の繊維状成型体の外観性状を観察した結果を図６〜８に示す。これら結果から、カルボン酸系分散剤を併用することで分散性が向上し、紡糸可能となることが確認できた。また、紡糸原液中のリンオキソ酸系分散剤濃度を７．２重量％以上に設定し、更にカルボン酸系分散剤を併用させた場合（実施例６及び７）においても、両分散剤は互いに分散効果を阻害することなく、かつ紡糸原液の分散性(ゼータ電位)が良好で紡糸が可能であり、β-TCPが１００重量％の繊維状成型体を製造できた。
2. Results Table 4 shows the results of evaluating the contents of HAp and β-TCP, the pH and dispersibility (seta potential) of the spinning dope, and the spinning property of the spinning dope after firing. Furthermore, the result of having observed the external appearance property of the fibrous molding after baking is shown to FIGS. From these results, it was confirmed that dispersibility was improved by using a carboxylic acid-based dispersant in combination, and spinning became possible. Further, when the concentration of the phosphorus oxoacid dispersant in the spinning dope is set to 7.2% by weight or more and a carboxylic acid dispersant is used in combination (Examples 6 and 7), both dispersants are dispersed in each other. Spinning was possible without impairing the effect, and the spinning stock solution was excellent in dispersibility (zeta potential), and a fibrous molded body having β-TCP of 100% by weight could be produced.
実施例８及び９
１．繊維状成型体の製造、並びに繊維状成型体及び紡糸原液の紡糸性の評価
紡糸原液の調製において、表５に示す種類及び含有量のリンオキソ酸系分散剤及びカルボン酸系分散剤を使用したこと以外は、前記実施例１と同条件で繊維状成型体の製造を行った。なお、実施例９で使用したヘキサメタリン酸ナトリウムのリン含有量は３０．５５重量％である。また、前記実施例１と同条件で、繊維状成型体の評価及び紡糸原液の性能評価を行った。
Examples 8 and 9
1. Production of fibrous molded body and evaluation of spinnability of fibrous molded body and spinning stock solution In preparation of spinning stock solution, the types and contents shown in Table 5 were used with phosphorous acid dispersant and carboxylic acid dispersant Except for the above, a fibrous molded body was produced under the same conditions as in Example 1. In addition, the phosphorus content of the sodium hexametaphosphate used in Example 9 is 30.55 weight%. Further, under the same conditions as in Example 1, evaluation of the fibrous molded body and performance evaluation of the spinning dope were performed.
２．結果
焼成後の繊維状成型体のHAp及びβ-TCPの含有量、紡糸原液のｐＨ及び分散性（ゼータ電位）、並びに紡糸原液の紡糸性を評価した結果を表６に示す。更に、焼成後の繊維状成型体の外観性状を観察した結果を図９及び１０に示す。これら結果から、リンオキソ酸系分散剤又はカルボン酸系分散剤の種類を変更した場合でも、紡糸原液中のＣａ／Ｐ比をコントロールすることにより、繊維状成型体β-TCP含有量を制御できることが確認できた。
2. Results Table 6 shows the results of evaluation of the content of HAp and β-TCP, the pH and dispersibility (seta potential) of the spinning dope, and the spinning property of the spinning dope after firing. Furthermore, the result of having observed the external appearance property of the fibrous molded object after baking is shown to FIG. From these results, it is possible to control the content of the fibrous molded body β-TCP by controlling the Ca / P ratio in the spinning dope even when the type of the phosphorus oxoacid dispersant or the carboxylic acid dispersant is changed. It could be confirmed.
実施例１０
１．繊維状成型体の製造、並びに繊維状成型体及び紡糸原液の紡糸性の評価
紡糸原液中のリンオキソ酸系分散剤及びカルボン酸系分散剤を表７に示す含有量に設定したこと以外は、前記実施例１と同条件で繊維状成型体の製造を行った。また、前記実施例１と同条件で、繊維状成型体の評価及び紡糸原液の性能評価を行った。更に、以下の方法で、繊維状成型体の組成均一性を測定した。
Example 10
1. Manufacture of fibrous molded body, and evaluation of spinnability of fibrous molded body and spinning raw solution Except that the contents of phosphoroxo acid-based dispersant and carboxylic acid-based dispersant in the spinning raw solution were set to the contents shown in Table 7, A fibrous molded body was produced under the same conditions as in Example 1. Further, under the same conditions as in Example 1, evaluation of the fibrous molded body and performance evaluation of the spinning dope were performed. Furthermore, the composition uniformity of the fibrous molded body was measured by the following method.
＜繊維状成型体の組成均一性の測定＞
乾燥後（焼成前）の繊維状成型体をランダムに３か所からサンプリングし、それぞれ実施例１と同様の条件で焼成した。焼成後の各繊維状成型体について、前記と同様の方法でβ-TCP含有量を算出し、各β-TCP含有量の相対標準偏差(CV値)を算出した。
<Measurement of composition uniformity of fibrous molding>
The fibrous molded body after drying (before firing) was sampled at random from three locations and fired under the same conditions as in Example 1. For each fibrous molded body after firing, the β-TCP content was calculated by the same method as described above, and the relative standard deviation (CV value) of each β-TCP content was calculated.
２．結果
焼成後の繊維状成型体のHAp及びβ-TCPの含有量、紡糸原液のｐＨ及び分散性（ゼータ電位）、紡糸原液の紡糸性、繊維状成型体の組成均一性を評価した結果を表８に示す。また、焼成後の繊維状成型体の外観性状を観察した結果を図１１に示す。これら結果から、リンオキソ酸系分散剤及びカルボン酸系分散剤を併用することによって紡糸原液の分散性を向上させ、繊維状成型体の組成の均一性を向上させ得ることが確認できた。
2. Results: Table shows the results of evaluating the HAp and β-TCP contents, the spinning solution pH and dispersibility (zeta potential), the spinning property of the spinning solution, and the composition uniformity of the fibrous product after firing. It is shown in FIG. Moreover, the result of having observed the external appearance property of the fibrous molding after baking is shown in FIG. From these results, it was confirmed that the dispersibility of the spinning dope could be improved and the uniformity of the composition of the fibrous molded body could be improved by using a phosphorus oxoacid dispersant and a carboxylic acid dispersant in combination.
比較例１及び２
紡糸原液中のリンオキソ酸系分散剤及びカルボン酸系分散剤を表９に示す含有量に設定したこと以外は、前記実施例１と同条件で繊維状成型体の製造を行った。また、前記実施例１と同条件で、紡糸原液の性能評価を行った。更に、前記実施例１０と同条件で、繊維状成型体の組成均一性の測定を行った。
Comparative Examples 1 and 2
A fibrous molded body was produced under the same conditions as in Example 1 except that the phosphorus oxoacid dispersant and carboxylic acid dispersant in the spinning dope were set to the contents shown in Table 9. Further, the performance evaluation of the spinning dope was performed under the same conditions as in Example 1. Furthermore, the composition uniformity of the fibrous molded body was measured under the same conditions as in Example 10.
２．結果
紡糸原液のｐＨ及び分散性（ゼータ電位）、紡糸原液の紡糸性、繊維状成型体の組成均一性を評価した結果を表１０に示す。これら結果から、ゼータ電位の絶対値が２７．４以上、より好ましくはゼータ電位が‐２７．４より大きく６．４未満の場合では、紡糸原液の高粘度でかつ糸引きは確認されず、紡糸が困難になることが確認できた。また、分散剤としてカルボン酸系分散剤のみを用いた場合(比較例１)では紡糸が困難であり、リンオキソ酸系分散剤のみを用いた場合(比較例２)では繊維状成型体の組成が不均一であったことから、分散剤としてカルボン酸系分散剤とリンオキソ酸系分散剤を併用することによって、紡糸性と繊維状成型体の組成の均一性の両立が可能になることが確認された。
2. Results Table 10 shows the results of evaluating the pH and dispersibility (zeta potential) of the spinning dope, the spinning property of the spinning dope, and the composition uniformity of the fibrous molded body. From these results, when the absolute value of the zeta potential is 27.4 or more, more preferably when the zeta potential is greater than −27.4 and less than 6.4, the spinning dope has high viscosity and no stringing is confirmed, and Was confirmed to be difficult. In addition, when only the carboxylic acid-based dispersant is used as the dispersant (Comparative Example 1), spinning is difficult, and when only the phosphoroxo acid-based dispersant is used (Comparative Example 2), the composition of the fibrous molded body is It was confirmed that the use of both a carboxylic acid dispersant and a phosphorus oxoacid dispersant as a dispersant makes it possible to achieve both spinnability and uniformity in the composition of the fibrous molded body. It was.
Claims (5)
前記第１工程で得られた繊維状成型体を焼成する第２工程
を含むことを特徴とする、リン酸カルシウムの繊維状成型体の製造方法。 A first step of spinning using a spinning stock solution containing a compound containing calcium and phosphorus, a binder, a carboxylic acid-based dispersant, and a phosphorus oxo-acid-based dispersant; and the fibrous form obtained in the first step A method for producing a fibrous molded body of calcium phosphate, comprising a second step of firing the molded body.
紡糸体の製造に使用される紡糸原液の組成を、カルシウムとリンを含む化合物と、バインダーと、リンオキソ酸系分散剤と、カルボン酸系分散剤とを含むように設定し、且つ
繊維状成型体に備えさせるべきハイドロキシアパタイトとβ型リン酸三カルシウムの含有比に応じて、前記紡糸原液中のリン原子の量とカルシウム原子の量を調節することを特徴とする、制御方法。 A method for controlling the content ratio of hydroxyapatite and β-type tricalcium phosphate in a fibrous molded product of calcium phosphate,
The composition of the spinning dope used for the production of the spinning body is set so as to include a compound containing calcium and phosphorus, a binder, a phosphorus oxoacid dispersant, and a carboxylic acid dispersant, and a fibrous molded body A control method characterized by adjusting the amount of phosphorus atoms and the amount of calcium atoms in the spinning dope according to the content ratio of hydroxyapatite and β-type tricalcium phosphate to be prepared in the above.
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