JP6505406B2 - Method for producing fibrous shaped body of calcium phosphate - Google Patents
Method for producing fibrous shaped body of calcium phosphate Download PDFInfo
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- JP6505406B2 JP6505406B2 JP2014197727A JP2014197727A JP6505406B2 JP 6505406 B2 JP6505406 B2 JP 6505406B2 JP 2014197727 A JP2014197727 A JP 2014197727A JP 2014197727 A JP2014197727 A JP 2014197727A JP 6505406 B2 JP6505406 B2 JP 6505406B2
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- calcium
- phosphorus
- fibrous
- stock solution
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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 description 111
- 239000001506 calcium phosphate Substances 0.000 title claims description 48
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims description 36
- 235000011010 calcium phosphates Nutrition 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 238000009987 spinning Methods 0.000 claims description 129
- 239000011550 stock solution Substances 0.000 claims description 83
- 229910052698 phosphorus Inorganic materials 0.000 claims description 78
- 239000011574 phosphorus Substances 0.000 claims description 76
- 239000002270 dispersing agent Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 48
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 47
- 239000011575 calcium Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 40
- -1 phosphorus oxo acid Chemical class 0.000 claims description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 35
- 238000000465 moulding Methods 0.000 claims description 34
- 229910052791 calcium Inorganic materials 0.000 claims description 33
- 238000010304 firing Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 26
- 125000004437 phosphorous atom Chemical group 0.000 claims description 15
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 13
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 12
- 229940078499 tricalcium phosphate Drugs 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
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 229960001714 calcium phosphate Drugs 0.000 description 33
- 229960005069 calcium Drugs 0.000 description 30
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 28
- 238000011156 evaluation Methods 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 159000000007 calcium salts Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000012620 biological material Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 3
- 239000004373 Pullulan Substances 0.000 description 3
- 229920001218 Pullulan Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 238000007664 blowing Methods 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
- 235000019821 dicalcium diphosphate Nutrition 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
- 238000002360 preparation method Methods 0.000 description 3
- 235000019423 pullulan Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 230000015572 biosynthetic process Effects 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
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 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
- 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
- PAXPHUUREDAUGV-UHFFFAOYSA-N OP(=O)OP(O)(O)=O Chemical compound OP(=O)OP(O)(O)=O PAXPHUUREDAUGV-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
- 229910000147 aluminium phosphate Inorganic materials 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
- 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
- 229960005188 collagen Drugs 0.000 description 1
- 238000012777 commercial manufacturing Methods 0.000 description 1
- 238000013329 compounding Methods 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
- 238000000151 deposition Methods 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
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 229940014259 gelatin Drugs 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
- 230000003301 hydrolyzing effect Effects 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
- 239000007943 implant Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000011835 investigation Methods 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
- 150000002739 metals Chemical class 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
- 229960000292 pectin Drugs 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 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
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
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- 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 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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- 235000013337 tricalcium citrate Nutrition 0.000 description 1
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- 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
- 238000000733 zeta-potential measurement Methods 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
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 shaped article of calcium phosphate. More specifically, the present invention relates to a method of producing a fibrous shaped article of calcium phosphate in which the content ratio of hydroxyapatite and β-type tricalcium phosphate can be controlled within a desired range and the composition is uniform. The present invention also relates to a method of controlling the content ratio of hydroxyapatite and β-type tricalcium phosphate in the production of a fibrous shaped article 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。 At present, metals, polymers, ceramics, etc. are used as biomaterials, but among them, calcium phosphate ceramics have a property (biocompatibility) which metal and polymers do not directly bond to living tissues, and are artificial It is widely used in bones, artificial joint coatings, dental implants and the like. 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 a bone filler using HAp, various types of molded bodies such as powder, granules, blocks and fibers have been developed, but in powder or granules, the filler itself is a body fluid. There is a problem that it is pushed out, or it moves from the operation part due to a deformation of the operation site, and there is also a problem that it can not be applied to the details of the operation site or the operation site details. On the other hand, a fibrous molded body is advantageous over other dosage forms in that it can be filled to the details of the void and that the fibers are hardly entangled and moved from the operation 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 that it be absorbed in the body and be replaced by autologous tissue. HAp is characterized in that it has high affinity to the living body, has high strength as a filling material, but has low absorbability to the living body. On the other hand, β-TCP, like HAp, has high affinity to the living body and has excellent absorbability, but the material that has been compensated for gradually elutes in a period until bone regeneration is achieved. , It is characterized in that the density and form at the time of compensation can not be maintained sufficiently. Thus, since HAp and β-TCP each have excellent advantages, it is important that the content ratio of HAp and β-TCP contained in calcium phosphate affects the rate of bone formation and degradation in vivo. Parameters (see Non-Patent Document 1). Therefore, when calcium phosphate is used as a biomaterial, there are cases where high strength is required depending on the applied biological site. In that case, it is desirable that the HAp content ratio be high. It is desirable that the TCP content ratio is high. Therefore, when calcium phosphate is manufactured 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, control of the content ratio of HAp and β-TCP in calcium phosphate can be carried out by adjusting the compounding ratio of HAp and β-TCP used as a raw material for production. 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. Therefore, in the production of fibrous shaped articles of calcium phosphate, at present, it is not possible to easily control the content ratio of HAp and β-TCP at a high level while forming 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 calcium phosphate fibrous molding have been conventionally studied. For example, Patent Document 1 discloses a method of producing calcium phosphate fiber by depositing 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。 Further, in Patent Document 2, a spinning stock solution containing an ionic organic polymer compound that forms a water-insoluble calcium salt, a water-soluble calcium phosphate and water, is spun in a curing liquid comprising an aqueous solution containing a water-soluble calcium salt. Discloses a method for producing an apatite fiber body by forming a composite spinneret of a water-insoluble organic polymer compound and a sparingly water-soluble calcium phosphate, and molding the resulting composite spinner body into a desired shape and baking it. It is done. However, in the method of Patent Document 2, since the step of spinning and hardening the spinning stock solution in a hardening solution containing a water-soluble calcium salt is adopted, the reaction difference between the surface and the inside of the produced fiber body, etc. May occur, and 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, etc. of water-insoluble calcium salt, ionic organic polymer compound, water-soluble calcium phosphate, and curing liquid There is a need to control the reaction conditions to a high degree, and there are barriers to commercial manufacturing applications. Furthermore, Patent Document 2 does not disclose any 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。 Further, Patent Document 3 discloses a method of producing a fibrous calcium phosphate molded body by forming a slurry in which calcium phosphate is dispersed from a plurality of dies while forming it into a fibrous form by a slurry blow method. In the method of Patent Document 3, since the slurry in which calcium phosphate is dispersed is molded by the slurry blow method, it is expected that the composition of the surface and the inside of the produced fiber is uniform, but even in Patent Document 3, There is no disclosure of a method for controlling the content ratio of HAp and β-TCP.
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 manufacturing technique of a calcium phosphate fibrous molding wherein the content ratio of HAp and β-TCP can be controlled to a desired range by a simple method and the composition is uniform.
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 conducted intensive studies to solve the above problems, and found that a compound containing calcium and phosphorus, a binder, and a carboxylic acid-based dispersion as a spinning stock solution used for producing a calcium phosphate fibrous molded body. HAp in a fibrous molded body produced by using a slurry containing a hydrolyzing agent and a phosphorus oxo-acid type dispersing agent, and adjusting the ratio of the amount of calcium atoms to the amount of phosphorus atoms contained in the spinning stock solution It has been found that the content ratio of β-TCP can be controlled, and furthermore, the composition of the fibrous molding can be made uniform. The present invention has been completed by further investigation 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, the present invention provides the invention of the aspects listed 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 calcium phosphate fibrous molding, comprising the second step of firing the molding.
Item 2. Item 2. The 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 method according to Item 1 or 2, wherein the molar ratio of the amount of calcium atoms to the amount of phosphorus atoms in the stock solution for spinning is 1.50 to 1.67.
Item 4. The method according to any one of items 1 to 3, wherein the baking in the second step is performed at 100 to 400 ° C. for 1 hour or more, and then the baking is performed at 400 to 1200 ° C. for 0.1 hours or more. Manufacturing method described.
Item 5. A method for controlling the content ratio of hydroxyapatite and β-type tricalcium phosphate in a fibrous shaped body of calcium phosphate,
The composition of the stock solution for spinning used for producing a spinning body is set to contain a compound containing calcium and phosphorus, a binder, a phosphorus oxo acid type dispersing agent, and a carboxylic acid type dispersing agent, and a fibrous molded body According to the content ratio of hydroxyapatite and β-type tricalcium phosphate to be prepared, the amount of phosphorus atoms and the amount of calcium atoms in the spinning solution are controlled.
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, the content ratio of HAp and β-TCP can be adjusted in accordance with the strength and bioabsorbability required for the fibrous molding of calcium phosphate, so that the living body according to the treatment purpose, the treatment site, etc. It is possible to manufacture the material. Therefore, the present invention can be suitably used as a technique for providing, for example, a bioimplant material used for tailor-made treatment and the like. Further, according to the present invention, since the composition (the content ratio of HAp and β-TCP) of the fibrous molded body of calcium phosphate can be made uniform, a high quality biomaterial can also 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. Process for Producing Fibrous Mold of Calcium Phosphate The process of the present invention is a process for producing a fibrous mold of calcium phosphate, which comprises a compound containing calcium and phosphorus, a binder, a carboxylic acid dispersant, and a phosphorus oxo acid It is characterized by including a first step of performing spinning using a stock solution containing a dispersant and a second step of firing the fibrous molded body obtained in the first step. Hereinafter, the manufacturing method of the present invention will be described in 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 oxo acid dispersant is used as a stock solution for spinning. Hereinafter, the components to be mixed with the stock solution to be used in the present invention and the adjustment of the composition of the stock solution according to the content ratio of HAp and β-TCP of the fibrous molded body 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 stock solution for spinning, 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 a calcium atom and a phosphorus atom, but, 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, phosphoric acid 8 Calcium, tetracalcium phosphate and the like can be mentioned. These compounds may be used alone or in combination of two or more. Among the 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。 Also, the properties of the compound containing calcium and phosphorus are not particularly limited, but the dispersibility of the compound in the spinning solution is enhanced to make the composition of the surface and the inside of the fibrous molded body to be made more uniform. From the viewpoint, it is preferable to be in the form of particles. In addition, when the compound containing calcium and phosphorus is in the form of fine particles, the density at the time of sintering becomes high, and the strength of the fibrous molded body can also 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 size 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。 The concentration of the compound containing calcium and phosphorus in the stock solution for spinning is not particularly limited, but may be, for example, 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 is possible to easily carry out the spinning step by making the viscosity of the stock spinning solution in an appropriate range while making the strength of the obtained fibrous molded body good.
（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 stock spinning solution contains a binder in order to provide spinnability. The type of binder is not particularly limited, but preferably includes edible water-soluble polysaccharides. Specific examples of edible water-soluble polysaccharides that can be used as binders include pullulan, agar, carrageenan, alginic acid, alginates, xanthan gum, dextran, locust bean gum, guar gum, pectin, glucomannan, starch, collagen, gelatin, Karaya gum, chitin, chitosan, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, tamarind gum, gum arabic and the like. These binders may be used alone or in combination of two or more. Among these binders, preferred is pullulan in consideration of the solubility in the stock solution for spinning and the impartation of a suitable viscosity to the stock solution for spinning.
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。 The concentration of the binder in the stock solution for spinning is not particularly limited, but may be, for example, 5 to 40% by weight, preferably 5 to 20% by weight, and more preferably 5 to 15% by weight. By satisfying such concentration, the spinnability of the stock spinning solution is enhanced, and it becomes possible to easily carry out the spinning step.
（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 dispersant is a compound which has a carboxyl group and is capable of adsorbing or adhering to a compound containing calcium and phosphorus, and dispersing a compound containing calcium and phosphorus in a spinning solution. In the stock solution for spinning, the carboxylic acid-based dispersant, in a state of being adsorbed or adhered to a compound containing calcium and phosphorus, disperses calcium and phosphorus-containing compounds due to repulsion and steric hindrance of charge by carboxyl group, or calcium and It shows the role of enhancing the wettability of the surface of the compound particle containing phosphorus.
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。 The liquid property of the carboxylic acid-based dispersant is not particularly limited, but when it is added to purified water to be 10% by weight, it exhibits a pH of 3 to 12, preferably 5 to 10, more preferably 6 to 8 Can be 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。 Further, as the carboxylic acid-based dispersant, known ones used for dispersing the inorganic particles may be used, for example, surfactants containing a carboxyl group, water-soluble polymers containing a carboxyl group, carboxyl And low molecular weight compounds containing a group. Preferred examples of the carboxylic acid-based dispersant include surfactants containing a carboxyl group, polymers containing acrylic acid and / or methacrylic acid, and the like. One of these carboxylic acid dispersants may be used alone, or two or more thereof may be used in combination. In addition, the thing in which a carboxylic acid type dispersing agent does not contain a metal cation is preferable.
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。 Examples of carboxylic acid-based dispersants include commercially available products such as trade name "Cerna D-305" (manufactured by Chukyo Yushi Co., Ltd.) and trade name "SN Disperse 5468" (manufactured by San Nopco Co., Ltd.). A commercial item can be used suitably.
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。 The concentration of the carboxylic dispersant in the stock solution for spinning may be appropriately set according to the content ratio of HAp and β-TCP to be prepared in the fibrous molded body, for example, more than 0 to 50% by weight Preferably, it is 0.1 to 40 wt%, more preferably 0.3 to 30 wt%.
（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 oxo acid dispersant)
The phosphorus oxo acid dispersant has a residue of a phosphorus oxo acid (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 be adsorbed or adhered to calcium phosphate particles. It is a compound in which a compound containing phosphorus is dispersed in a spinning stock solution. In the stock solution for spinning, the phosphorus oxo-acid type dispersing agent plays the role of enhancing the dispersibility of calcium phosphate particles or the wettability of the surface of calcium phosphate particles by repulsion or steric hindrance of charge by phosphorus oxo acid residue in a state adsorbed or adhered to calcium phosphate particles. 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 liquid property of the phosphorus oxo acid type dispersant is not particularly limited, but when it is added to purified water to be 5% by weight, it exhibits a pH of 3 to 12, preferably 5 to 10, more preferably 6 to 8 Can be 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。 In addition, as the phosphorus oxo acid based dispersant, known ones used for dispersing inorganic particles may be used. For example, a surfactant containing a phosphorus oxo acid residue, a polymer containing a phosphorus oxo acid residue Etc. More specifically, residues of orthophosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, phosphinic acid, phosphenic acid, phosphenic acid, pyrophosphoric acid, hypophosphoric acid, isohypophosphoric acid, etc. Specific examples of those having a structure include polyphosphoric acid, metaphosphoric acid, dimetaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, isometaphosphoric acid and the like. These phosphorus oxo acid type dispersants may be used alone or in combination of two or more. The phosphorus oxo acid dispersant preferably contains no metal cation and has an action of weakening the dispersion inhibiting effect of metal cations such as calcium and magnesium. As a suitable example of the phosphorus oxo-acid type dispersing agent used by this invention, the polymer containing a phosphonic acid residue is 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 phosphorus oxo acid type dispersants include commercially available products such as trade name "SN Disperse 2060" (manufactured by San Nopco Co., Ltd.) and trade name "sodium hexametaphosphate" (manufactured by Wako Pure Chemical Industries, Ltd.). These commercial 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 oxo-acid-based dispersant in the stock solution for spinning may be appropriately set according to the content ratio of HAp and β-TCP to be prepared in the fibrous molded body, for example, more than 0 to 40% by weight The following may preferably be 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 stock solution used in the present invention may optionally contain a calcium salt other than the compound containing calcium and phosphorus. 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 body to be produced by blending a calcium salt other than the compound. Become. The type of such 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, calcium sulfate and the like. . These calcium salts may be used alone or in a combination of two or more.
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。 Further, the stock solution for spinning used in the present invention contains a solvent as a dispersion medium. The solvent to be blended in the stock solution for spinning is not particularly limited as long as it can dissolve or solubilize the binder, the carboxylic acid type dispersing agent and the phosphorus oxo acid type dispersing agent, and examples thereof include water and polar organic solvents. In particular, water is suitable as a solvent to be used as a spinning solution from the viewpoint of safety and manufacturing cost because water is easy to handle waste liquid and no exhaust device is required for manufacturing facilities.
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 stock solution for spinning is not particularly limited, and may be, for example, 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。
(Adjustment of HAp and β-TCP content ratio based on composition setting of spinning solution)
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 body to be produced by adjusting the composition of the spinning stock solution. Specifically, the content ratio of HAp and β-TCP in the fibrous molded body to be produced can be controlled according to the ratio of calcium atoms and phosphorus atoms contained in the above-mentioned stock solution for spinning. Therefore, the ratio of the amount of phosphorus atoms to 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 stock solution for spinning is the total amount of the phosphorus atoms contained in the compound containing calcium and phosphorus and the phosphorus atoms contained in the phosphorus oxo-acid-based dispersant. In addition, the amount of calcium atoms contained in the stock solution for spinning is the calcium atoms contained in the compounds containing calcium and phosphorus and the calcium salts contained in calcium salts (other than the compounds containing calcium and phosphorus) added as needed. It is 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 stock solution for spinning (hereinafter sometimes referred to as "Ca / P ratio"), the more in the fibrous molded body to be produced As the amount of HAp is large and the amount of β-TCP is small, and the lower the Ca / P ratio, the amount of HAp in the fibrous molded body to be produced is small and the amount of β-TCP is large. 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 stock solution for spinning (hereinafter sometimes referred to as "Ca / P ratio") is 1. When set to 64, it is possible to control the Hap content to 85.9% by weight and the β-TCP content to 14.1% by weight in the fibrous molded body to be produced, and the Ca / P ratio in the spinning stock solution is 1 When set to .53, it is possible to control the HAp content in the fibrous molded body to be produced 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。 Based on this point, the Ca / P ratio in the spinning stock solution should be, for example, in the range of 1.50 to 1.67, preferably 1.50 to 1.66, in the fibrous molded body to be produced It may be 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 stock solution for spinning can be adjusted by appropriately setting the content thereof in accordance with the type of the compound containing calcium and phosphorus and the type of the phosphorus oxo acid based dispersant blended in the stock solution for spinning.
（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 solution)
The preparation method of the spinning stock solution is not particularly limited, but in order to uniformly disperse the compound containing calcium and phosphorus, the compound, a carboxylic acid dispersant, and a phosphorus oxo acid dispersant are added to a solvent After thorough mixing, it is preferable to add and mix a binder. The addition of the binder may be carried out 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。 The temperature conditions for preparing the stock solution for spinning are not particularly limited, and examples thereof include 0 to 100 ° C., preferably 10 to 80 ° C., and more preferably 20 to 50 ° C. Under such temperature conditions, the volatilization of the solvent and the decomposition of the binder, the carboxylic acid-based dispersant, and the phosphorus oxo-acid-based dispersant can be suppressed.
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 stock solution for spinning is not particularly limited. For example, a container rotation type device in which the container itself rotates, vibrates and swings; a mechanical stirring type device in which the blades placed in the container rotate; powder in a twisted tube Non-stirring type devices for flowing the body; high-speed shear impact type devices rotating at high speed; planetary stirring type devices for stirring by material convection by centrifugal force. Among these devices, the planetary stirring device, in particular, the planetary stirring device having a defoaming function can suppress the formation of fine air bubbles in the spinning solution, and the voids caused by the air bubbles in the fibrous molded product. It is preferably used because the occurrence can be suppressed.
［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 of spinning the spinning stock solution is not particularly limited, and any conventionally known spinning method of inorganic fibers may be adopted. For example, the spinning stock solution is supplied to a rotor A method of fiberization by centrifugal force (spinning method), a method of fiberization by blowing off a spinning solution with high speed air or steam, or the like (blowing method) may be mentioned. Specific examples of the spinning method include force spinning and electron spinning. Further, as a blowing method, for example, a method of using a device described in JP-A-61-174460 to remove water from a spinning stock solution jetted from a die by an infrared heater and collect it with a net type drum, etc. Be
［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。
[Firing process]
The fibrous shaped body spun using the above-mentioned stock solution for spinning is subjected to a firing step. Removal of the binder, the carboxylic acid-based dispersant and the phosphorus oxo-acid-based dispersant in the fibrous molded body by performing the firing step; HAp and β-TCP crystal phase formation; strength and 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 of the firing step are not particularly limited, but it is preferable to perform two-step firing in which the firing conditions are changed. Specifically, as the two-step baking method, after performing the first-step baking under the conditions of 100 to 400 ° C., preferably 250 ° C. to 350 ° C. for 1 hour or more, preferably 12 to 24 hours, 400 The method of performing 2nd step baking on the conditions of -1200 degreeC, preferably 500 degreeC-1150 degreeC for 0.1 hours or more, preferably 0.5 to 10 hours is mentioned. Note that the second-step firing may be performed at a temperature higher than the first-step firing, and for example, the second-step firing temperature may be set to be about 300 ° C. or more higher than the first-step firing temperature. Just do it. By baking under such conditions, it becomes possible to burn out the binder and the dispersant while suppressing the loss 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 molded body]
In the production method of the present invention, the fibrous molding may be produced as a monofilament or may be produced as 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。 Moreover, the fibrous molded body obtained by the production method of the present invention is suitably used for bone grafting materials, scaffolding materials for regenerative therapeutic materials, biomedical implant materials such as artificial bones and artificial teeth, etc. It can also be used in 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。 In addition, the fibrous molded body obtained by the production method of the present invention may be further subjected to a forming treatment such as granulation, compression and the like, and may be formed into a granular, spherical, plate or block shape.
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 of controlling the content ratio of HAp and β-TCP The control method of the present invention is a method of controlling the content ratio of HAp and β-TCP in a fibrous shaped article of calcium phosphate, and the spinning used for producing a spun product The composition of the stock solution is set to include a compound containing calcium and phosphorus, a binder, a phosphorus oxo acid type dispersing agent, and a carboxylic acid type dispersing agent, and HAp and β-TCP to be prepared in the fibrous molded body The ratio of the amount of calcium atoms to the amount of phosphorus atoms in the stock solution for spinning 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 of controlling the content ratio of HAp and β-TCP to be provided to the fibrous molded body in the production of a fibrous molded body of calcium phosphate, specifically, to a 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 It is carried out through the second step of adjusting the ratio of atomic amounts.
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。 The spinning stock solution having the composition set by the control method of the present invention is subjected to the above-mentioned spinning step and firing step to produce a fibrous shaped article of calcium phosphate having a target content ratio of HAp to β-TCP.
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 method of adjusting the composition and the like of the stock solution for controlling the type and concentration of each component of the stock solution used and the content ratio of HAp and β-TCP in the fibrous molding, etc. It is as having described in the column of "1. The manufacturing method of the fibrous cast 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, the present invention will be specifically described by way of examples, but the present invention is not construed as being limited to the examples.
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 to 4
1. Production of fibrous moldings
30.0 g of HAp slurry (manufactured by Tomita Seiyaku Co., Ltd .; average particle size of HAp, solid content 45.4% by weight) 30.0 g, phosphorus oxo acid based dispersant ("SN Disperse 2060", manufactured by Sannopco Co., Ltd., phosphorus The amount of the content shown in Table 1 (7.4 wt%) and the amount of the concentration shown in Table 1 of the carboxylic acid dispersant ("Celna D-305" manufactured by Chukyo Yushi Co., Ltd.) are each accurately determined. Weighed, added to a 50 mL container and stirred for 5 minutes with a vortex. After stirring, it was transferred to a 50 mL beaker and stirred with a magnetic stirrer at room temperature for 15 minutes. Then, 4.26 g of Japanese Pharmacopoeia pullulan was added, and mixed by stirring at room temperature for 15 minutes with a stirrer. This was used as a spinning stock solution.
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。
This spinning stock solution is applied to two 7 cm 2 circular plates (in such an amount that the spinning stock solution becomes about 0.1 ml / cm 2 on one circular plate), and the two circular plates are sandwiched to sandwich the spinning stock solution. I overlapped it. Next, the two circular plates were pulled apart, and dried (hair-dryer; 1200 W, 50-60 Hz) by air blow at the moment when the stock spinning solution became thread-like, to obtain a fibrous molded body. The dried fibrous molded body was fired under the following firing conditions.
(Firing conditions)
After the temperature was raised to 320 ° C. for 24 hours (temperature rise: 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 fired 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 performance of fibrous molded body and spinning stock solution <Measurement of HAp and β-TCP content of fibrous molded body>
The content of HAp and β-TCP was measured for the fibrous molded body after firing. The measurement of the content of HAp and β-TCP was performed by the following method. First, apatite HAP monoclinic crystals (manufactured by Wako Pure Chemical Industries, Ltd.) and apatite β-TCP trigonal crystals (manufactured by Wako Pure Chemical Industries, Ltd.) are each fired at 1000 ° C., and then a predetermined ratio (β-TCP = 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 A standard sample was prepared by mixing so as to be 5% by weight by weight. Next, measure the integrated intensity of the signal derived from β-TCP (around 2θ / θ = 31.2 °) using a powder X-ray diffraction apparatus as a standard sample, and from the β-TCP content (mixing amount) and the integrated intensity ratio A calibration curve was created. The integral strength of the signal derived from β-TCP (around 2θ / θ = 31.2 °) is measured using a powder X-ray diffractometer for the fibrous molded body after firing, and HAp and β-TCP are measured using the above calibration curve. The content of was calculated. In addition, the Ca / P ratio of the fibrous molded body after firing was calculated by the following equation.
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 solution>
A dispersion having the same composition as the spinning stock solution was prepared except that the binder was not blended. 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 measurement of the zeta potential was performed using a zeta potential measurement device (manufactured by 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 solution>
A dispersion having the same composition as the spinning stock solution was prepared except that the binder was not blended. Purified water was added to 200 μL of the dispersion to make exactly 10 mL, and an evaluation dispersion 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 solution>
At the time of the spinning process using the spinning solution, the spinnability of the spinning solution was evaluated according to the following judgment criteria.
Judgment criteria of spinnability O: Stringing of the stock spinning solution was confirmed in the spinning step, and spinning was possible.
X: In the spinning process, the spinning solution was insufficiently stringed 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 The results of evaluating the HAp and β-TCP content of the fibrous molded body after firing, the pH and the dispersibility (zeta potential) of the spinning stock solution, and the spinnability of the spinning stock solution are shown in Table 2. Further, the relationship between the content of the phosphorus oxo-acid-based dispersant blended in the stock solution for spinning and the content of β-TCP of the fibrous molded body after firing is shown in FIG. Furthermore, the result of having observed the external appearance property of the fibrous molding after baking is shown to FIGS. From these results, in any of Examples 1 to 4, it was confirmed that the spinnability of the stock solution for spinning was excellent, and that a fibrous molded body could be produced. In addition, a high correlation is recognized between the Ca / P ratio in the spinning stock and the β-TCP content of the fibrous molded body after firing, and the fibrous molding is controlled by controlling the Ca / P ratio in the spinning stock. It has also been confirmed that the body's β-TCP content 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 to 7
1. Production of fibrous molded body and evaluation of spinnability of fibrous molded body and spinning stock solution The above-mentioned practice except that the phosphorus oxo acid type dispersing agent and the carboxylic acid type dispersing agent in the spinning stock solution were set to the concentration shown in Table 3. A fibrous molded body was produced under the same conditions as in Example 1. Moreover, evaluation of the fibrous molded body and performance evaluation of the spinning solution were performed under the same conditions as in Example 1 above.
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 The results of evaluating the HAp and β-TCP content of the fibrous molded body after firing, the pH and the dispersibility (zeta potential) of the spinning stock solution, and the spinnability of the spinning stock solution are shown in Table 4. 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 the dispersibility was improved by using the carboxylic acid-based dispersant in combination, and spinning became possible. Also, in the case where the concentration of the phosphorus oxo-acid-based dispersant in the stock solution for spinning is set to 7.2% by weight or more, and the carboxylic acid-based dispersant is further used in combination (Examples 6 and 7), both dispersants disperse each other Without inhibiting the effect, the dispersibility (zeta potential) of the stock spinning solution was good and spinning was possible, and a fibrous molding having 100% by weight of β-TCP 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 the preparation of a spinning stock solution, phosphorus oxo type dispersant and carboxylic type dispersant of the type and content shown in Table 5 were used A fibrous molded product was manufactured under the same conditions as in Example 1 except for the above. The phosphorus content of sodium hexametaphosphate used in Example 9 is 30.55% by weight. Moreover, evaluation of the fibrous molded body and performance evaluation of the spinning solution were performed under the same conditions as in Example 1 above.
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 The results of evaluating the HAp and β-TCP content of the fibrous molded body after firing, the pH and the dispersibility (zeta potential) of the spinning stock solution, and the spinnability of the spinning stock solution are shown in Table 6. Furthermore, the result of having observed the external appearance property of the fibrous molding after baking is shown to FIG. 9 and 10. FIG. From these results, even when the type of the phosphorus oxo acid type dispersing agent or the carboxylic acid type dispersing agent is changed, the fibrous molded body β-TCP content can be controlled by controlling the Ca / P ratio in the spinning stock solution. 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. Production of fibrous shaped body and evaluation of spinnability of fibrous shaped body and stock solution for spinning The content of the phosphorus oxo acid dispersant and the carboxylic acid based dispersant in the stock solution for spinning is set to the content shown in Table 7; The fibrous molding was produced under the same conditions as in Example 1. Moreover, evaluation of the fibrous molded body and performance evaluation of the spinning solution were performed under the same conditions as in Example 1 above. 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 molded body>
The fibrous molded body after drying (before firing) was randomly sampled from three places, and fired under the same conditions as in Example 1, respectively. The β-TCP content of each fibrous molded body after firing was calculated in the same manner 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 The HAp and β-TCP content of the fibrous molding after firing, the pH and dispersibility of the spinning stock solution (zeta potential), the spinnability of the spinning stock solution, and the composition uniformity of the fibrous molding were evaluated. Shown in 8. Moreover, the result of having observed the external appearance property of the fibrous molding after baking is shown in FIG. From these results, it has been confirmed that the dispersibility of the spinning stock solution can be improved and the uniformity of the composition of the fibrous molded body can be improved by using a phosphorus oxo acid type dispersing agent and a carboxylic acid type dispersing agent 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 contents of the phosphorus oxo-acid dispersant and the carboxylic-acid dispersant in the stock solution for spinning were set to the contents shown in Table 9. Also, the performance evaluation of the stock solution for spinning was performed under the same conditions as in Example 1 above. Furthermore, the composition uniformity of the fibrous molded body was measured under the same conditions as in Example 10 above.
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 The pH and dispersibility (zeta potential) of the stock solution for spinning, the spinnability of the stock solution for spinning, and the composition uniformity of the fibrous molded body were evaluated. The results are shown in Table 10. From these results, when the absolute value of the zeta potential is 27.4 or more, more preferably, the zeta potential is more than −27.4 and less than 6.4, high viscosity of the spinning stock solution and no stringing are confirmed, and spinning Was confirmed to be difficult. In addition, when only the carboxylic acid type dispersing agent is used as the dispersing agent (Comparative Example 1), spinning is difficult, and when only the phosphorus oxo acid type dispersing agent is used (Comparative Example 2), the composition of the fibrous molding is Since it was nonuniform, it was confirmed that by using a carboxylic acid-based dispersing agent and a phosphorus oxo-acid-based dispersing agent in combination as a dispersing agent, it is possible to achieve both spinnability and uniformity of the composition of the fibrous molding. The
Claims (4)
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。 Spinning that contains a compound containing calcium and phosphorus, a binder, a carboxylic acid dispersant, and a phosphorus oxo acid dispersant, and the molar ratio of the amount of calcium atoms to the amount of phosphorus atoms is 1.50 to 1.67 A method for producing a calcium phosphate fibrous molding, comprising a first step of spinning using a stock solution, and a second step of firing the fibrous molding obtained in the first step.
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 shaped body of calcium phosphate,
The composition of the stock solution for spinning used for producing a spinning body is set to contain a compound containing calcium and phosphorus, a binder, a phosphorus oxo acid type dispersing agent, and a carboxylic acid type dispersing agent, and a fibrous molded body According to the content ratio of hydroxyapatite and β-type tricalcium phosphate to be prepared, the amount of phosphorus atoms and the amount of calcium atoms in the spinning solution are controlled.
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