JP2006256921A - Manufacturing method of silica hollow particle - Google Patents
Manufacturing method of silica hollow particle Download PDFInfo
- Publication number
- JP2006256921A JP2006256921A JP2005078417A JP2005078417A JP2006256921A JP 2006256921 A JP2006256921 A JP 2006256921A JP 2005078417 A JP2005078417 A JP 2005078417A JP 2005078417 A JP2005078417 A JP 2005078417A JP 2006256921 A JP2006256921 A JP 2006256921A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- calcium carbonate
- silicon alkoxide
- hollow particles
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 276
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 133
- 239000002245 particle Substances 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 121
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 60
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 48
- 239000010703 silicon Substances 0.000 claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 46
- 239000012736 aqueous medium Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000010306 acid treatment Methods 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 53
- 239000003960 organic solvent Substances 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 16
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000002296 dynamic light scattering Methods 0.000 abstract description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052753 mercury Inorganic materials 0.000 abstract description 7
- 239000011164 primary particle Substances 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 2
- 230000002093 peripheral effect Effects 0.000 abstract description 2
- 238000002459 porosimetry Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 239000002537 cosmetic Substances 0.000 description 22
- 239000003814 drug Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 16
- 239000000306 component Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 210000004209 hair Anatomy 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 229940088594 vitamin Drugs 0.000 description 12
- 239000011782 vitamin Substances 0.000 description 12
- 229930003231 vitamin Natural products 0.000 description 12
- 235000013343 vitamin Nutrition 0.000 description 12
- 229940079593 drug Drugs 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000004115 Sodium Silicate Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 150000003722 vitamin derivatives Chemical class 0.000 description 8
- 239000006071 cream Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000005426 pharmaceutical component Substances 0.000 description 6
- 238000013268 sustained release Methods 0.000 description 6
- 239000012730 sustained-release form Substances 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002260 anti-inflammatory agent Substances 0.000 description 3
- 229940121363 anti-inflammatory agent Drugs 0.000 description 3
- 230000001139 anti-pruritic effect Effects 0.000 description 3
- 239000003908 antipruritic agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003779 hair growth Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002453 shampoo Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229940035676 analgesics Drugs 0.000 description 2
- 230000000954 anitussive effect Effects 0.000 description 2
- 239000000730 antalgic agent Substances 0.000 description 2
- 239000002220 antihypertensive agent Substances 0.000 description 2
- 229940030600 antihypertensive agent Drugs 0.000 description 2
- 239000003434 antitussive agent Substances 0.000 description 2
- 229940124584 antitussives Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003212 astringent agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000008266 hair spray Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 239000000419 plant extract Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000001370 static light scattering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000829 suppository Substances 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 235000015961 tonic Nutrition 0.000 description 2
- 230000001256 tonic effect Effects 0.000 description 2
- 229960000716 tonics Drugs 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 210000002925 A-like Anatomy 0.000 description 1
- 241001237961 Amanita rubescens Species 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 206010003210 Arteriosclerosis Diseases 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 208000001840 Dandruff Diseases 0.000 description 1
- 206010012335 Dependence Diseases 0.000 description 1
- 201000005569 Gout Diseases 0.000 description 1
- 208000031226 Hyperlipidaemia Diseases 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 101000774651 Naja atra Zinc metalloproteinase-disintegrin-like kaouthiagin-like Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NYZGMENMNUBUFC-UHFFFAOYSA-N P.[S-2].[Zn+2] Chemical compound P.[S-2].[Zn+2] NYZGMENMNUBUFC-UHFFFAOYSA-N 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- PXLVUBPOUFMYMH-UHFFFAOYSA-N [Na+].OB(O)O.OB(O)[O-] Chemical compound [Na+].OB(O)O.OB(O)[O-] PXLVUBPOUFMYMH-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000003266 anti-allergic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001142 anti-diarrhea Effects 0.000 description 1
- 230000003474 anti-emetic effect Effects 0.000 description 1
- 230000003556 anti-epileptic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000000883 anti-obesity agent Substances 0.000 description 1
- 230000002921 anti-spasmodic effect Effects 0.000 description 1
- 239000000043 antiallergic agent Substances 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 239000002111 antiemetic agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- 229940125710 antiobesity agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 229940125716 antipyretic agent Drugs 0.000 description 1
- 239000003435 antirheumatic agent Substances 0.000 description 1
- 229940124575 antispasmodic agent Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000002763 arrhythmic effect Effects 0.000 description 1
- 208000011775 arteriosclerosis disease Diseases 0.000 description 1
- 239000002968 autonomic agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229940124630 bronchodilator Drugs 0.000 description 1
- 239000000168 bronchodilator agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000023852 carbohydrate metabolic process Effects 0.000 description 1
- 235000021256 carbohydrate metabolism Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229940124579 cold medicine Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 230000008260 defense mechanism Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000551 dentifrice Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 229940124568 digestive agent Drugs 0.000 description 1
- 229940079920 digestives acid preparations Drugs 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002934 diuretic Substances 0.000 description 1
- 229940030606 diuretics Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000002895 emetic Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003172 expectorant agent Substances 0.000 description 1
- 230000003419 expectorant effect Effects 0.000 description 1
- 229940066493 expectorants Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004083 gastrointestinal agent Substances 0.000 description 1
- 229940125695 gastrointestinal agent Drugs 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 229960003444 immunosuppressant agent Drugs 0.000 description 1
- 239000003018 immunosuppressive agent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 230000002475 laxative effect Effects 0.000 description 1
- 230000037356 lipid metabolism Effects 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 229940126701 oral medication Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 210000004798 organs belonging to the digestive system Anatomy 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 210000001428 peripheral nervous system Anatomy 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000008257 shaving cream Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000001040 synthetic pigment Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 239000005526 vasoconstrictor agent Substances 0.000 description 1
- 229940124549 vasodilator Drugs 0.000 description 1
- 239000003071 vasodilator agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
Description
本発明は、シリカの殻からなる中空粒子の製造方法に関する。
より詳しくは、本発明は、水系媒質中にて、シリコンアルコキシドを用いて炭酸カルシウム表面にシリカ膜を被覆した後、内部の炭酸カルシウムを溶解させることによりシリカ中空粒子を製造する方法に関する。
The present invention relates to a method for producing hollow particles comprising a silica shell.
More specifically, the present invention relates to a method for producing hollow silica particles by coating a silica film on a calcium carbonate surface using silicon alkoxide in an aqueous medium and then dissolving the internal calcium carbonate.
近年、粒子の形態制御による機能性材料の研究開発が盛んに行われており、そのひとつに中空状粒子の開発が挙げられる。
中空状粒子は、医薬や化粧品の分野では、その内部に有効成分を内包した徐放性医薬や徐放性化粧品のほか、外環境との接触により分解あるいは劣化してしまう成分の保護、ドラッグデリバリーシステムのための担体などへ適用すべく、種々の検討がなされている。
In recent years, research and development of functional materials by particle shape control has been actively conducted, and one of them is the development of hollow particles.
In the field of pharmaceuticals and cosmetics, hollow particles are used for the protection of drugs that are decomposed or deteriorated by contact with the external environment, drug delivery, in addition to sustained-release pharmaceuticals and sustained-release cosmetics encapsulating active ingredients. Various studies have been made to apply to a carrier for a system.
例えば、特許文献１においては、シリコンアルコキシドなどの有機ケイ素化合物と発泡剤とを混合噴霧した後に加水分解することにより中空シリカ粉末が得られることが記載されている。
さらに、特許文献２においては、シリコンアルコキシドに、アルコール、水及び酸触媒を加えて部分加水分解を行った後、フタル酸ジメチルを添加し、この溶液を界面活性剤を含んだアンモニア水溶液中で混合撹拌、乳化し、重縮合反応させることにより球状多孔質シリカ粒子を製造する方法が提案されている。
For example, Patent Document 1 describes that a hollow silica powder can be obtained by hydrolyzing after mixing and spraying an organosilicon compound such as silicon alkoxide and a foaming agent.
Further, in Patent Document 2, alcohol, water, and an acid catalyst are added to silicon alkoxide for partial hydrolysis, dimethyl phthalate is added, and this solution is mixed in an aqueous ammonia solution containing a surfactant. There has been proposed a method of producing spherical porous silica particles by stirring, emulsifying, and causing a polycondensation reaction.
また、特許文献３においては、特定条件下でケイ酸アルカリから、シリカ以外の支持体上に活性シリカを沈殿させた後、該支持体を除去することによって、緻密シリカシェルからなる中空シリカ粒子を製造する方法も提案されている。
上記の通り、シリカの殻からなる中空状粒子については幾つかの検討がなされてきているものの、特許文献１及び２のような界面反応を利用した方法では、ミクロンオーダー以上の粒子径のものしか得られない。
In Patent Document 3, hollow silica particles composed of a dense silica shell are obtained by precipitating active silica on a support other than silica from alkali silicate under specific conditions, and then removing the support. A manufacturing method has also been proposed.
As described above, some studies have been made on hollow particles made of silica shells. However, in the method using the interfacial reaction as described in Patent Documents 1 and 2, only particles having a particle size of micron order or more are used. I can't get it.
さらに、その特許文献３においては、２０ｎｍ以上の中空シリカ粒子が製造できるとの記述はあるものの、本発明者らの実験によれば、ナノオーダーになると凝集が激しくなり、結果的にはミクロンオーダー以上の凝集粒子となってしまうことが確認されている。
しかも、この方法では、中空粒子を構成するシリカ殻は、シリカの微粒子が集合して形成されており、その結果、微細ではあるもののシリカ殻に細孔が存在することも、本発明者らは確認している。
Furthermore, in Patent Document 3, although there is a description that hollow silica particles of 20 nm or more can be produced, according to the experiments by the present inventors, aggregation becomes intense when nano-order is obtained, and as a result, micron-order is obtained. It has been confirmed that the above aggregated particles are formed.
In addition, in this method, the silica shell constituting the hollow particle is formed by agglomeration of silica fine particles, and as a result, although the silica shell is fine, pores exist in the silica shell. I have confirmed.
そして、近年においては、ナノテクノロジーに代表される超微細化技術の流れに対応すべく、シリカを使った中空状粒子についてもナノサイズのものが嘱望されている。
さらには、ナノサイズの特色をより効果的に発現させるためには、分散性がよいものが望まれているほか、中空状粒子を構成するシリカ殻の性状、特に分子サイズでの細孔の制御が必要となってくる。
In recent years, nano-sized hollow particles using silica have been desired to cope with the trend of ultra-fine technology represented by nanotechnology.
Furthermore, in order to express the nano-size features more effectively, those with good dispersibility are desired, and the properties of the silica shell that constitutes the hollow particles, especially the control of pores at the molecular size Will be needed.
このような状況に鑑み、本発明者らは、シリカの中空状粒子の製造について検討を進めた結果、上記要望を満たすシリカの中空粒子の製造方法を既に見出し特許出願を行っている（特願２００４−７７４５０）。
この方法は、炭酸カルシウムを調製する第１工程、炭酸カルシウムにシリカをコーティングする第２工程、及び炭酸カルシウムを溶解させる第３工程により、シリカの殻からなる中空粒子を製造する方法である。
In view of such a situation, the present inventors have studied the production of silica hollow particles, and as a result, have already found a method for producing silica hollow particles that satisfy the above-mentioned requirements and have filed a patent application (Japanese Patent Application). 2004-77450).
This method is a method for producing hollow particles made of silica shells by a first step of preparing calcium carbonate, a second step of coating calcium carbonate with silica, and a third step of dissolving calcium carbonate.
その方法の第１工程においては、透過型電子顕微鏡法による一次粒子径が２０〜２００ｎｍの炭酸カルシウムを水系にて調製し、静的光散乱法による粒子径が２０〜７００ｎｍになるように熟成させた後、脱水して含水ケーキの状態とし、第２工程においては、第１工程の含水ケーキをアルコール中に分散させ、アンモニア水、水、シリコンアルコキシドを、シリコンアルコキシド／アルコールの体積比を０．００２〜０．１、アンモニア水に含有されるＮＨ3を、シリコンアルコキシド１モルに対して、４〜１５モル、水をシリコンアルコキシド１モルに対して、２５〜２００モルとなるように添加することにより、シリカでコーティングされた炭酸カルシウムを調製した後、アルコール及び水による洗浄を行い、再び含水ケーキとし、第３工程においては、第２工程の含水ケーキを水に分散させ、酸を添加して、液の酸濃度を０．１〜３モル／Ｌとすることにより炭酸カルシウムを溶解させることを特徴とする。 In the first step of the method, calcium carbonate having a primary particle size of 20 to 200 nm by transmission electron microscopy is prepared in an aqueous system and aged to have a particle size of 20 to 700 nm by static light scattering. After that, it is dehydrated to obtain a water-containing cake state. In the second step, the water-containing cake of the first step is dispersed in alcohol, and ammonia water, water, and silicon alkoxide are set to a volume ratio of silicon alkoxide / alcohol of 0. 002 to 0.1, NH 3 contained in ammonia water is added so as to be 4 to 15 mol per mol of silicon alkoxide, and water is added to 25 to 200 mol per mol of silicon alkoxide. After preparing calcium carbonate coated with silica, washing with alcohol and water is carried out again to obtain a water-containing cake. In the process, a wet cake of the second step is dispersed in water, the acid was added, and wherein the dissolving calcium carbonate by the acid concentration in the liquid and 0.1 to 3 mol / L.
そして、この方法では、緻密なシリカ殻からなる高分散の中空粒子であって、透過型電子顕微鏡法による一次粒子径が３０〜３００ｎｍ、静的光散乱法による粒子径が３０〜８００ｎｍ、水銀圧入法により測定される細孔分布において２〜２０ｎｍの細孔が検出されない高分散シリカナノ中空粒子を製造することができる。
しかしながら、この方法においては、炭酸カルシウム粒子表面にシリカを被覆させる際、アルコールを主体とする溶媒を使用する必要があり、その結果安全性を配慮する必要があるという弱点がある。
In this method, highly dispersed hollow particles composed of a dense silica shell, the primary particle size by transmission electron microscopy is 30 to 300 nm, the particle size by static light scattering method is 30 to 800 nm, and mercury intrusion is performed. It is possible to produce highly dispersed silica nano hollow particles in which pores of 2 to 20 nm are not detected in the pore distribution measured by the method.
However, this method has a weak point that when a silica is coated on the surface of calcium carbonate particles, it is necessary to use a solvent mainly composed of alcohol, and as a result, it is necessary to consider safety.
そこで、粒子表面へのシリカ被覆に関する従来技術をみるに、それにはシリコンアルコキシドの加水分解により粒子表面にシリカを沈殿させる方法や、ケイ酸アルカリの中和反応により粒子表面にシリカを沈殿させる方法が知られている。
前者のアルコキシドを用いる方法としては、例えば、特許文献４に記載の親水性有機溶剤中でシリコンアルコキシドの加水分解によりアルミニウム顔料表面にシリカを被覆する方法がる。
Therefore, prior art relating to silica coating on the particle surface includes methods of precipitating silica on the particle surface by hydrolysis of silicon alkoxide and methods of precipitating silica on the particle surface by neutralization reaction of alkali silicate. Are known.
As a method using the former alkoxide, for example, there is a method in which silica is coated on the surface of an aluminum pigment by hydrolysis of silicon alkoxide in a hydrophilic organic solvent described in Patent Document 4.
さらに、その方法には、特許文献５に記載のシリコンアルコキシドを含む溶液にシラノール含有樹脂粒子を浸漬することによるシリカ被覆樹脂粒子の製造方法、特許文献６に記載の水及び触媒用の塩酸等を含むテトラエトキシシランのアルコール溶液等に酸化被膜を形成させたアルミニウム粉体を浸漬することによりシリカ被膜を形成させる方法、また特許文献７に記載の硫化亜鉛蛍光体の粒子表面をシリコンアルコキシドで処理した後加水分解してシリカを被覆させる方法などが挙げられる。 Furthermore, the method includes a method for producing silica-coated resin particles by immersing silanol-containing resin particles in a solution containing silicon alkoxide described in Patent Document 5, water and hydrochloric acid for catalyst described in Patent Document 6, and the like. A method of forming a silica coating by immersing an aluminum powder in which an oxide coating is formed in an alcohol solution of tetraethoxysilane and the like, and treating the particle surface of the zinc sulfide phosphor described in Patent Document 7 with silicon alkoxide Examples thereof include a method of post-hydrolysis to coat silica.
後者のケイ酸アルカリを用いる方法としては、例えば、特許文献８に記載の二酸化チタン粒子が分散された特定温度及び特定ｐＨの水性スラリー中にケイ酸塩を添加することにより二酸化チタン粒子表面にシリカの被覆層を形成する方法、特許文献９に記載のカーボンブラック粒子を懸濁させた水性媒質中にケイ酸ナトリウム水溶液を添加してカーボンブラック粒子表面をシリカにより被覆処理する方法、また特許文献１０に記載の水中にて高分子樹脂膜を有する酸化鉄粒子表面にケイ酸ナトリウムの加水分解によりシリカを被覆させる方法などが挙げられる。 As a method using the latter alkali silicate, for example, silica is added to the surface of the titanium dioxide particles by adding silicate to an aqueous slurry having a specific temperature and a specific pH in which the titanium dioxide particles described in Patent Document 8 are dispersed. A method of forming a coating layer of carbon black particles, a method of coating a surface of carbon black particles with silica by adding an aqueous sodium silicate solution to an aqueous medium in which carbon black particles are suspended, and Patent Document 10 And the method of coating the surface of iron oxide particles having a polymer resin film in water with silica by hydrolysis of sodium silicate.
[先行技術文献]
上述の通り、粒子表面へのシリカ被覆については、アルコールなどの有機溶媒を主体とする液相中でシリコンアルコキシドを用いる方法と、水溶媒中でケイ酸ナトリウムなどの無機化合物を用いた方法とに限定される。
そのシリコンアルコキシドを原料とした被覆においては、粒子表面に平滑かつ不純分の少ない被膜を形成させることができる。
ただし、シリコンアルコキシドは、水を主体とする溶媒中では急激な加水分解反応が起こり、その結果シリカが粒子表面で膜を形成せず、ゲルを形成したり、シリカの単独粒子として析出したりするとされている。
As described above, the silica coating on the particle surface includes a method using silicon alkoxide in a liquid phase mainly composed of an organic solvent such as alcohol and a method using an inorganic compound such as sodium silicate in an aqueous solvent. Limited.
In the coating using the silicon alkoxide as a raw material, a smooth and less impure coating can be formed on the particle surface.
However, silicon alkoxide undergoes a rapid hydrolysis reaction in a solvent mainly composed of water, and as a result, silica does not form a film on the particle surface, forms a gel, or precipitates as a single particle of silica. Has been.
このことから、シリコンアルコキシドを用いる場合には、アルコール等の有機溶媒を主体とする液相中で被覆操作を行うことになる。
しかしながら、有機溶媒を使用するには、その製造装置に防爆構造が要求され、装置が大規模かつ高価なものになるほか、使用済みの有機溶媒を排出することは、近年深刻化している環境保全の問題にとっても、工業的に最適な方法であるとは言い難いのが現状である。
For this reason, when silicon alkoxide is used, the coating operation is performed in a liquid phase mainly composed of an organic solvent such as alcohol.
However, the use of organic solvents requires an explosion-proof structure for the production equipment, making the equipment large and expensive, and discharging used organic solvents has become increasingly serious in recent years. It is difficult to say that this is an industrially optimal method for this problem.
他方、ケイ酸ナトリウム等の無機化合物を用いたシリカ被覆の場合には、水を主体とする溶媒の使用が可能となる。
しかしながら、この際には、被覆される膜は微粒子膜となる傾向にあり、アルコキシドを用いた場合よりも平滑性に欠け、また不純分が混在したものとなってしまう。
例えば、ケイ酸ナトリウムから形成させたシリカ膜の場合、シリカ膜中にナトリウムが混在してしまう。
On the other hand, in the case of silica coating using an inorganic compound such as sodium silicate, a solvent mainly composed of water can be used.
However, in this case, the film to be coated tends to be a fine particle film, which is less smooth than the case where an alkoxide is used, and impure components are mixed.
For example, in the case of a silica film formed from sodium silicate, sodium is mixed in the silica film.
また、好適に被覆を行うためにｐＨを調節する必要があることから、ｐＨ調節剤を添加したり、粒子の凝集を防止するために界面活性剤を添加したりすることから、これらの物質もシリカ膜中に残存することが多々ある。
これらのことからケイ酸ナトリウムなどの無機化合物を使用する方法は、シリカ膜の純度が要求される用途に適用することができていない。
In addition, since it is necessary to adjust the pH in order to perform the coating appropriately, a pH adjusting agent is added, or a surfactant is added to prevent the particles from agglomerating. It often remains in the silica film.
From these facts, the method using an inorganic compound such as sodium silicate cannot be applied to uses where the purity of the silica film is required.
シリカ殻からなる中空粒子については、前述したとおり本発明者らが既に特許出願した方法により、ナノサイズで、分散性に優れ、かつシリカ殻が緻密であるものが製造できるが、その製造方法では、炭酸カルシウム粒子表面へのシリカ被覆の際に溶媒としてアルコールを用いる必要があった。
また、粒子表面へのシリカ被覆に関する従来技術によっても、前記したとおりシリコンアルコキシドをシリカ源として用いる場合にはアルコールなどの有機溶媒を使用しなければならない。
For hollow particles composed of silica shells, nano-sized, excellent dispersibility, and dense silica shells can be manufactured by the method already filed by the inventors as described above. In addition, it was necessary to use alcohol as a solvent when coating the surface of calcium carbonate particles with silica.
In addition, as described above, when silicon alkoxide is used as a silica source, an organic solvent such as alcohol must be used according to the prior art relating to silica coating on the particle surface.
このように溶媒としてアルコールなどの有機溶媒を使用した場合、その製造装置には防爆構造が要求され、装置が大規模かつ高価なものとなるほか、使用済みの有機溶媒を排出することは近年深刻化している環境保全の問題にとっても、工業的に最適な方法であるとは言い難い。
他方、シリカ源としてケイ酸ナトリウムなどを用いれば、水系での被膜が可能となるが、シリカ殻中に不純分が少なからず含有され、また緻密な殻とならないという問題があった。
When an organic solvent such as alcohol is used as a solvent in this way, the manufacturing apparatus is required to have an explosion-proof structure, and the apparatus becomes large and expensive, and it has recently been serious to discharge used organic solvents. It is difficult to say that it is an industrially optimal method even for environmental conservation problems.
On the other hand, when sodium silicate or the like is used as a silica source, an aqueous coating can be made, but there is a problem that the silica shell contains not less impurities and does not form a dense shell.
このような状況の中、シリカ中空粒子を製造する方法について、シリコンアルコキシドを用いた方法とケイ酸ナトリウムなどの無機化合物を用いた方法との各々の短所を解消することができるような方法が嘱望されており、本発明はそれを提供するものである。
すなわち、本発明は、シリコンアルコキシドをシリカ膜形成用原料として用いてシリカ中空粒子を製造する際に有機溶媒を使用しない環境負荷の少ない方法で、高品質のシリカ中空粒子を製造する方法を提供することを発明の解決すべき課題とするものである。
Under such circumstances, a method capable of eliminating the respective disadvantages of the method using silicon alkoxide and the method using an inorganic compound such as sodium silicate as a method for producing silica hollow particles is encouraging. The present invention provides this.
That is, the present invention provides a method for producing high-quality silica hollow particles by a method with little environmental load that does not use an organic solvent when producing silica hollow particles using silicon alkoxide as a raw material for forming a silica film. This is a problem to be solved by the invention.
本発明は、前記課題を解決するためのものであり、水系媒質中にて、コロイド状炭酸カルシウム、シリコンアルコキシド及び塩基触媒を混合し、コロイド状炭酸カルシウム表面に、シリコンアルコキシドの加水分解反応により生成するシリカを析出させた後、酸処理により炭酸カルシウムを溶解させることを特徴とするものである。
この方法では、水系媒質が、７５容量％以上の水からなるのがよく、また塩基触媒としてアンモニア水を使用するのがよい。
The present invention is for solving the above-mentioned problems, and is produced by mixing colloidal calcium carbonate, silicon alkoxide and a base catalyst in an aqueous medium, and hydrolyzing silicon alkoxide on the colloidal calcium carbonate surface. After the silica to be deposited is precipitated, calcium carbonate is dissolved by acid treatment.
In this method, the aqueous medium is preferably composed of 75% by volume or more of water, and ammonia water is preferably used as a base catalyst.
本発明の製造方法は、水系媒質中にて、コロイド状炭酸カルシウム粒子表面にシリカを被覆し、その後酸処理により炭酸カルシウムを溶解除去してシリカ中空粒子を得るものである。
そのため有機溶媒を使用する必要がないことから、製造装置及び周辺装置類がコンパクト化でき、使用済みの有機溶媒を排出することがないので環境への負荷を低減できる。
In the production method of the present invention, silica is coated on the surface of colloidal calcium carbonate particles in an aqueous medium, and then the calcium carbonate is dissolved and removed by acid treatment to obtain silica hollow particles.
Therefore, since it is not necessary to use an organic solvent, the manufacturing apparatus and peripheral devices can be made compact, and since the used organic solvent is not discharged, the burden on the environment can be reduced.
そして、この方法では、緻密なシリカ殻からなる高分散性の中空粒子であって、透過型電子顕微鏡法による一次粒子径が３０〜３００ｎｍ、動的光散乱法による粒子径が３０〜８００ｎｍ、水銀圧入法により測定される細孔分布において２〜２０ｎｍの細孔が検出されないシリカ中空粒子を製造することができる。
さらに、本発明の方法により形成されるシリカ殻は、アルコールなどの有機溶媒系で形成させたものと変わらないことから、膜の平滑性や純度が要求される用途で使用できるほか、従来の有機溶媒系よりも製造コストが低く抑えられることから、より安価で同等性能を有するシリカ中空粒子を提供することが可能となる。
In this method, high-dispersion hollow particles composed of a dense silica shell, the primary particle diameter by transmission electron microscopy is 30 to 300 nm, the particle diameter by dynamic light scattering is 30 to 800 nm, mercury Silica hollow particles in which pores of 2 to 20 nm are not detected in the pore distribution measured by the press-fitting method can be produced.
Further, since the silica shell formed by the method of the present invention is not different from that formed in an organic solvent system such as alcohol, it can be used for applications where smoothness and purity of the film are required. Since the production cost can be kept lower than that of the solvent system, it is possible to provide silica hollow particles that are less expensive and have equivalent performance.
以下に、発明を実施するための最良の形態を含む本発明の実施の態様について詳細に説明するが、本発明はそれによって何等限定されるものではなく、特許請求の範囲の記載によって特定されるものであることはいうまでもない。
本発明のシリカ中空粒子の製造方法は、水系媒質中にて、コロイド状炭酸カルシウム、シリコンアルコキシド及び塩基触媒を混合し、シリコンアルコキシドの加水分解反応により生成するシリカを、コロイド状炭酸カルシウム表面に析出させた後、酸処理して炭酸カルシウムを溶解させることを特徴とする。
本発明では、シリカ殻の原料としてシリコンアルコキシドを使用するにも拘わらず、水系媒質を使用することが大きな特長である。
Hereinafter, embodiments of the present invention including the best mode for carrying out the invention will be described in detail. However, the present invention is not limited thereto, and is specified by the description of the scope of claims. It goes without saying that it is a thing.
In the method for producing hollow silica particles of the present invention, colloidal calcium carbonate, silicon alkoxide and a base catalyst are mixed in an aqueous medium, and silica produced by the hydrolysis reaction of silicon alkoxide is precipitated on the surface of the colloidal calcium carbonate. Then, acid treatment is performed to dissolve calcium carbonate.
In the present invention, it is a great feature that an aqueous medium is used in spite of using silicon alkoxide as a raw material for the silica shell.
本発明でいう水系媒質は、水以外に他の液体が含有されていても何等問題がないが、７５容量％以上の水からなるものがよい。
水の含有量が７５容量％未満の場合、例えば水５０容量％とアルコール５０容量％の混合溶媒を用いた場合、製造装置の面では防爆構造が不必要であることは本発明の課題を達成できるが、廃液の処理や環境面への配慮の意味では、支障をきたすことがある。
したがって、本発明で使用する水系媒質は、７５容量％以上、望ましくは８５容量％以上、より望ましくは９５容量％以上の水からなる媒質がよい。
さらに、最も望ましくは水のみからなる媒質がよく、有機溶媒等の他の液体を含有しないことから、排水処理が簡易あるいは不要で、製造コストを低く抑えることができ、かつ環境負荷を低減できる。
The aqueous medium referred to in the present invention does not cause any problems even if other liquids are contained in addition to water, but is preferably composed of 75% by volume or more of water.
In the case where the water content is less than 75% by volume, for example, when a mixed solvent of 50% by volume of water and 50% by volume of alcohol is used, an explosion-proof structure is unnecessary in terms of manufacturing equipment, thereby achieving the object of the present invention Yes, but it may cause problems in terms of waste liquid treatment and environmental considerations.
Accordingly, the aqueous medium used in the present invention is preferably a medium composed of 75% by volume or more, desirably 85% by volume or more, more desirably 95% by volume or more.
Furthermore, most preferably, a medium consisting only of water is good and does not contain other liquids such as an organic solvent. Therefore, wastewater treatment is simple or unnecessary, the manufacturing cost can be kept low, and the environmental load can be reduced.
また、本発明で使用するコロイド状炭酸カルシウムは、透過型電子顕微鏡観察により測定される一次粒子径が２０〜２００ｎｍの立方体状あるいは菱面体状といった形状の炭酸カルシウムであり、水酸化カルシウムの水スラリーに炭酸ガスを導入することにより炭酸カルシウムを沈殿させる方法などにより調製することができる。
この際、目的とするコロイド状炭酸カルシウムを得るためには、比較的低温下で、沈殿反応の速度が比較的速い条件であることが望ましい。
The colloidal calcium carbonate used in the present invention is calcium carbonate having a cubic or rhombohedral shape with a primary particle diameter of 20 to 200 nm measured by observation with a transmission electron microscope, and is a water slurry of calcium hydroxide. It can be prepared by, for example, a method of precipitating calcium carbonate by introducing a carbon dioxide gas into the water.
At this time, in order to obtain the target colloidal calcium carbonate, it is desirable that the precipitation reaction rate is relatively fast at a relatively low temperature.
このコロイド状炭酸カルシウムは、調製直後（炭酸化反応の終了直後）は、２０〜２００ｎｍの一次粒子が凝集し、数μｍの凝集粒子を形成していることが多い。
したがって、調製直後のコロイド状炭酸カルシウムの水スラリーを室温下で静置したり、加熱下で撹拌するなどにより、動的光散乱法による平均粒子径が２０〜７００ｎｍとなるまで熟成させることが望ましい。
この粒子径まで熟成、分散させることにより、最終的にナノサイズで分散性に優れたシリカ中空粒子を得ることができる。
In many cases, the colloidal calcium carbonate immediately after preparation (immediately after the end of the carbonation reaction) aggregates primary particles of 20 to 200 nm to form aggregated particles of several μm.
Therefore, it is desirable that the water slurry of colloidal calcium carbonate immediately after preparation is aged until the average particle size by dynamic light scattering method becomes 20 to 700 nm by standing at room temperature or stirring under heating. .
By aging and dispersing to this particle size, finally silica hollow particles having a nano size and excellent dispersibility can be obtained.
また、水系媒質中に混合するにあたっては、調製及び熟成を行ったコロイド状炭酸カルシウムの水スラリーをそのまま、又は適宜濃度調整を行ったものを混合することがよい。 つまり、熟成により充分分散させたコロイド状炭酸カルシウム粒子を、そのままの状態で、シリカ被覆の工程に供することで、ナノサイズでかつより分散性に優れたシリカ中空粒子を製造することが可能となる。 In addition, when mixing in an aqueous medium, it is preferable to mix the prepared and aged colloidal calcium carbonate water slurry as it is or after appropriately adjusting the concentration. In other words, by applying the colloidal calcium carbonate particles sufficiently dispersed by aging to the silica coating step as it is, it becomes possible to produce nano-sized silica hollow particles with better dispersibility. .
本発明者らが既に別途出願している特願２００４−７７４５０号の方法においては、アルコールを主体とした溶媒を使用する必要があったため、調製した炭酸カルシウムの水スラリーを一旦ろ過して水分量を低減させ、含水ケーキの状態にしなければならないが、本発明においては、水系媒質を使用するため、調製及び熟成後の水スラリーをそのままの状態で使用できる。
このことにより、製造操作が簡易になるばかりでなく、より分散性に優れたシリカ中空粒子を製造することが可能となる。
In the method of Japanese Patent Application No. 2004-77450, which has already been filed separately by the present inventors, it was necessary to use a solvent mainly composed of alcohol. However, in the present invention, since an aqueous medium is used, the water slurry after preparation and aging can be used as it is.
This not only simplifies the production operation, but also makes it possible to produce silica hollow particles with better dispersibility.
本発明においてシリカ殻の原料として用いるシリコンアルコキシドについては、その加水分解によりシリカを生成するものであれば特段の制約はなく、例えば、トリメトキシシラン、テトラメトキシシラン、トリエトキシシラン、テトラエトキシシラン、トリプロポキシシランなどを用いることができる。
また、塩基触媒としては、アンモニア水やアミン類などを用いることができる。
本発明においては、前記したコロイド状炭酸カルシウム及びシリコンアルコキシドに加えて塩基触媒であるアンモニア水などを、水系媒質中にて混合して、まずシリカにより被覆された炭酸カルシウムを調製する。
The silicon alkoxide used as a raw material for the silica shell in the present invention is not particularly limited as long as it produces silica by hydrolysis, and examples thereof include trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, Tripropoxysilane or the like can be used.
As the base catalyst, aqueous ammonia, amines, and the like can be used.
In the present invention, in addition to the colloidal calcium carbonate and silicon alkoxide, ammonia water as a basic catalyst is mixed in an aqueous medium to first prepare calcium carbonate coated with silica.
これらを混合する際の態様としては、予めコロイド状炭酸カルシウムを分散させた水系媒質中にシリコンアルコキシド及び塩基触媒を添加あるいは滴下する方法、水系媒質とシリコンアルコキシドの混合液中にコロイド状炭酸カルシウム及び塩基触媒を添加する方法、コロイド状炭酸カルシウムを分散させたシリコンアルコキシドを塩基触媒を含有する水系媒質中に添加あるいは滴下する方法などがあり、それについては、水系媒質、コロイド状炭酸カルシウム、シリコンアルコキシド及び塩基触媒とを充分に混合できる方法であればよい。
その他にも、必要に応じて、シリカ中空粒子の分散性をさらに向上させるための分散剤や界面活性剤など適宜添加してもよい。
As an aspect when mixing these, a method in which silicon alkoxide and a base catalyst are added or dropped into an aqueous medium in which colloidal calcium carbonate is dispersed in advance, colloidal calcium carbonate and a mixture of the aqueous medium and silicon alkoxide are added. There are a method of adding a base catalyst, a method of adding or dropping a silicon alkoxide in which colloidal calcium carbonate is dispersed into an aqueous medium containing a base catalyst, etc., and it relates to an aqueous medium, colloidal calcium carbonate, silicon alkoxide. And a method that can sufficiently mix the base catalyst.
In addition, if necessary, a dispersant or a surfactant for further improving the dispersibility of the hollow silica particles may be appropriately added.
また、水系媒質、コロイド状炭酸カルシウム、シリコンアルコキシド、塩基触媒の混合比についても、所望するシリカ殻の厚や性状を勘案して、適宜調節することが望ましい。 例えば、シリカ殻厚を厚くしたい場合には、シリコンアルコキシド／コロイド状炭酸カルシウムの比を大きくすればよく、また、反応時間を短縮したい場合には、塩基触媒／シリコンアルコキシドの比を大きくすればよい。
そして、より好適に高品質のシリカ中空粒子を効率よく製造するためには、次のような条件とすることが望ましい。
Also, the mixing ratio of the aqueous medium, colloidal calcium carbonate, silicon alkoxide, and base catalyst is preferably adjusted as appropriate in consideration of the desired thickness and properties of the silica shell. For example, when the silica shell thickness is desired to be increased, the ratio of silicon alkoxide / colloidal calcium carbonate may be increased, and when the reaction time is desired to be shortened, the ratio of base catalyst / silicon alkoxide may be increased. .
And in order to manufacture a silica hollow particle of high quality more suitably and efficiently, it is desirable to set it as the following conditions.
まず、水系媒質に混合されるコロイド状炭酸カルシウムの量については、その固形分濃度が１〜２０重量％とすることがよい。
その際１重量％未満であると、製造効率が低下し現実的でないほか、場合によってはシリカが殻を形成せずに遊離粒子となってしまうこともある。
逆に２０重量％を超えると、粘度が上昇して均一なシリカ殻形成ができなくなることがある。
First, with respect to the amount of colloidal calcium carbonate mixed in the aqueous medium, the solid content concentration is preferably 1 to 20% by weight.
In this case, if it is less than 1% by weight, the production efficiency is lowered, which is not practical, and in some cases, silica may not form a shell and may become free particles.
On the other hand, if it exceeds 20% by weight, the viscosity may increase and uniform silica shell formation may not be possible.
さらに、シリコンアルコキシドとコロイド状炭酸カルシウムとの比については、シリコンアルコキシド１モルに対してコロイド状炭酸カルシウムを１５ｇ以上とするのがよい。 このようにすることにより、より平滑でかつ高純度のシリカ殻を比較的短時間で形成させることが可能となる。
逆に、１５ｇ未満の場合、シリカが遊離粒子として生成してしまうことがある。
Further, the ratio of silicon alkoxide to colloidal calcium carbonate is preferably 15 g or more of colloidal calcium carbonate per mole of silicon alkoxide. By doing so, it is possible to form a smoother and higher purity silica shell in a relatively short time.
Conversely, if it is less than 15 g, silica may be generated as free particles.
また、塩基触媒としてはアンモニア水が最も好適であり、それとシリコンアルコキシドの比については、シリコンアルコキシド１モルに対して、ＮＨ3が２〜４０モル、望ましくは２〜１０モルとすることがよい。
２モル未満であると反応に要する時間が極端に長くなり製造効率が悪化する。
逆に、４０モルを超えると、シリカ殻の平滑性が低下したり、シリカが殻を形成せず遊離粒子となってしまう場合がある。
As the base catalyst is most preferably aqueous ammonia, the same for the ratio of silicon alkoxide, the silicon alkoxide 1 mole NH 3 is 2 to 40 moles, preferably it is that 2 to 10 mol.
If it is less than 2 mol, the time required for the reaction becomes extremely long, and the production efficiency deteriorates.
On the other hand, when the amount exceeds 40 mol, the smoothness of the silica shell may decrease, or the silica may not form a shell and become free particles.
さらに、コロイド状炭酸カルシウムへのシリカ殻の被覆の際の温度については、特段の制約はないが、６０℃以下、より望ましくは４５℃以下であることがよい。
被覆反応時の温度が高すぎると、シリカ殻の平滑性が低下したり、シリカの遊離粒子が生成することがあり、得られるシリカ中空粒子の性状を悪化させる場合がある。
上記したような条件とすることにより、平滑かつ高純度のシリカ殻をより効率よく形成させることができる。
Further, the temperature at which the silica shell is coated on colloidal calcium carbonate is not particularly limited, but is preferably 60 ° C. or lower, more preferably 45 ° C. or lower.
If the temperature during the coating reaction is too high, the smoothness of the silica shell may be reduced, or free silica particles may be produced, which may deteriorate the properties of the resulting silica hollow particles.
By setting it as the above conditions, a smooth and highly pure silica shell can be formed more efficiently.
そのシリカ殻の形成につづいて、シリカ殻が被覆されたコロイド状炭酸カルシウムを酸処理して、炭酸カルシウムを溶解させ、シリカ殻のみを残存させることで中空粒子とする。
なお、酸処理に際しては、シリカ殻被覆後の液を水で置換したり、脱水洗浄などを行うことにより、未反応のシリコンアルコキシドを除去することが望ましい。
未反応のシリコンアルコキシドが大量に残留している場合、酸処理によりゲルが生成して、シリカ中空粒子の性状を悪化させることがある。
Following the formation of the silica shell, the colloidal calcium carbonate coated with the silica shell is acid-treated to dissolve the calcium carbonate, leaving only the silica shell to form hollow particles.
In the acid treatment, it is desirable to remove the unreacted silicon alkoxide by replacing the liquid after the silica shell coating with water or performing dehydration washing.
When a large amount of unreacted silicon alkoxide remains, a gel is generated by acid treatment, and the properties of the silica hollow particles may be deteriorated.
酸処理に使用する酸としては、塩酸、酢酸、硝酸など、炭酸カルシウムを溶解させることができる酸であれば特段の制約はない。
その酸処理する際の液の酸濃度は０．１〜３モル／Ｌとすることがよい。
０．１モル／Ｌ未満であると、酸処理に要する時間が長くなってしまうほか、場合によっては炭酸カルシウムを完全に溶解させることができなくなることがある。
逆に、３モル／Ｌを超えると、炭酸カルシウムの酸分解反応が急激に起こり、特にシリカ殻が薄い場合には、シリカ殻が破壊されてしまうことがある。
The acid used for the acid treatment is not particularly limited as long as it can dissolve calcium carbonate, such as hydrochloric acid, acetic acid, and nitric acid.
The acid concentration of the liquid during the acid treatment is preferably 0.1 to 3 mol / L.
If it is less than 0.1 mol / L, the time required for the acid treatment becomes longer, and in some cases, calcium carbonate cannot be completely dissolved.
On the other hand, when it exceeds 3 mol / L, the acid decomposition reaction of calcium carbonate occurs abruptly, and particularly when the silica shell is thin, the silica shell may be destroyed.
このように、炭酸カルシウムを酸処理により溶解させることによって、炭酸カルシウムが存在していた部分が中空になり、シリカ殻のみが残存することにより、シリカ中空粒子が得られる。
その酸処理後の液には、炭酸カルシウムの酸処理による溶解に伴い、カルシウム塩が混入するかたちとなる。
このカルシウム塩が用途によっては悪影響を及ぼすこともあるので、必要に応じて、液の水による置換や、脱水洗浄等により、カルシウム塩を除去することがよい。
また、用途に応じては、乾燥させて、乾燥粉の状態としても何等問題ない。
さらに、熱処理を行うことにより、殻中に残留する水分の除去を行ってもよい。
Thus, by dissolving calcium carbonate by acid treatment, the portion where calcium carbonate was present becomes hollow and only the silica shell remains, whereby silica hollow particles are obtained.
The solution after the acid treatment is mixed with calcium salt as the calcium carbonate is dissolved by the acid treatment.
Since this calcium salt may have an adverse effect depending on the application, it is preferable to remove the calcium salt by replacement of the liquid with water, dehydration washing or the like, if necessary.
Also, depending on the application, there is no problem even if it is dried to be in a dry powder state.
Furthermore, moisture remaining in the shell may be removed by performing a heat treatment.
このようにして得られるシリカ粒子は、緻密なシリカ殻からなる高分散の中空粒子であって、透過型電子顕微鏡法による一次粒子径が３０〜３００ｎｍ、動的光散乱法による粒子径が３０〜８００ｎｍ、水銀圧入法により測定される細孔分布において２〜２０ｎｍの細孔が検出されないものとなる。
さらに、得られるシリカ中空粒子は、そのシリカ殻が平滑かつ不純分の少ない高純度のものとなる。
The silica particles thus obtained are highly dispersed hollow particles composed of a dense silica shell, and the primary particle diameter by transmission electron microscopy is 30 to 300 nm, and the particle diameter by dynamic light scattering is 30 to 30. In the pore distribution measured by the mercury intrusion method at 800 nm, pores of 2 to 20 nm are not detected.
Furthermore, the silica hollow particles obtained have a high purity with a smooth silica shell and a low impurity content.
また、本発明の製造方法は、アルコール等の有機溶剤を使用する必要がなく、製造装置に防爆構造が要求されないばかりでなく、廃液処理が簡易でかつ環境負荷の少ない方法でシリカ中空粒子を製造することができる。
したがって、本発明の製造方法によれば、先行技術である有機溶媒と金属アルコキシドを利用した方法と同性能のシリカ中空粒子を、水系媒質中という安全で、排水処理が簡易で、かつ環境負荷が少ない方法で提供することが可能となる。
In addition, the production method of the present invention does not require the use of an organic solvent such as alcohol, and the production apparatus does not require an explosion-proof structure, but also produces silica hollow particles by a method that is simple in waste liquid treatment and has a low environmental impact. can do.
Therefore, according to the production method of the present invention, silica hollow particles having the same performance as the prior art method using an organic solvent and a metal alkoxide are safe in an aqueous medium, easy to treat wastewater, and have an environmental burden. It can be provided in a few ways.
本発明により製造されるシリカ中空粒子は、化学的に安定で人体に無害であるシリカから構成されていることから、医薬品、化粧料、食品関連や香料として利用することができ、特に中空構造の内部に有効成分を内包することにより、中空粒子の特長を生かすことができる。
その内部に内包させる物質及びその応用としては、以下のようなものが例示できる。
医薬類に関しては種々の成分を内包させることができ、該内包により、各種医薬成分は徐放性、放出制御性、保護性、マスキング性等の機能性を有する医薬品とすることができる。
Silica hollow particles produced according to the present invention are composed of silica that is chemically stable and harmless to the human body, and thus can be used as pharmaceuticals, cosmetics, food-related products, and fragrances. By enclosing the active ingredient inside, the features of the hollow particles can be utilized.
Examples of substances encapsulated in the interior and applications thereof include the following.
With regard to pharmaceuticals, various components can be encapsulated, and by the encapsulation, various pharmaceutical components can be made into pharmaceuticals having functions such as sustained release, release controllability, protection, and masking properties.
そして、各種医薬成分が内包されたシリカ中空粒子は、経口薬、エアゾール薬、軟膏剤、坐薬、パップ剤などの形態とすることによって、上記した徐放性、放出制御性、保護性、マスキング性等の機能を有する医薬製剤とすることができる。
その経口薬としては、錠剤、カプセル剤、散剤、顆粒剤、丸剤といった固形製剤のほか、シロップ剤、懸濁剤、乳剤といった液体製剤にも適用できる。
固形製剤の場合、シリカ中空粒子に医薬成分を内包した粒子を含有する粉末を造粒して、錠剤、顆粒剤、丸剤等とするか、粉末状態のまま散剤として使用することもできる。
液体製剤の場合には、有効成分を内包したシリカ中空粒子を液に分散させればよい。
Silica hollow particles encapsulating various pharmaceutical ingredients are in the form of oral medicine, aerosol medicine, ointment, suppository, cataplasm, etc., so that the above-mentioned sustained release, release controllability, protection, masking property It can be set as the pharmaceutical formulation which has the function of these.
The oral drug can be applied to solid preparations such as tablets, capsules, powders, granules and pills, and liquid preparations such as syrups, suspensions and emulsions.
In the case of a solid preparation, a powder containing particles in which a pharmaceutical ingredient is encapsulated in silica hollow particles is granulated to form tablets, granules, pills, or the like, or can be used as a powder in a powder state.
In the case of a liquid preparation, the silica hollow particles containing the active ingredient may be dispersed in the liquid.
エアゾール薬では、医薬成分を内包したシリカ中空粒子を粉末状態のまま使用した粉末吸引剤や、液に分散させて霧状あるいはペースト状の吸入剤としてもよい。
また、軟膏剤あるいは坐薬では、医薬成分を内包したシリカ中空粒子を、油脂、乳剤などの基剤と混練してペースト状又はクリーム状等にすればよい。
パップ剤でも同様に医薬成分を内包したシリカ中空粒子を樹脂などと混練し、シート状に成形して湿布などに使用することができる。
As an aerosol drug, a powder suction agent in which silica hollow particles encapsulating a pharmaceutical component are used in a powder state, or a mist-like or paste-like inhalant by dispersing in a liquid may be used.
In addition, in an ointment or suppository, silica hollow particles encapsulating a pharmaceutical component may be kneaded with a base such as an oil or fat to make a paste or cream.
Similarly, in the case of a poultice, silica hollow particles encapsulating a pharmaceutical ingredient can be kneaded with a resin or the like, molded into a sheet and used for a poultice.
医薬成分を内包したシリカ中空粒子の具体的用途については、内包させる医薬成分の種類によって異なるが、内包させる医薬成分としては、下記に示すような種々のものが適用できる。
例えば、神経系医薬としては、抗てんかん剤、解熱剤、鎮痛剤、総合感冒剤などの中枢神経系用剤や、自律神経剤、鎮けい剤などの末梢神経系用剤等がある。
生体防御機構に作用する医薬としては、免疫抑制剤、免疫促進剤、抗炎症剤、抗アレルギー剤、抗リウマチ剤、インターフェロン様剤などがある。
The specific use of the silica hollow particles encapsulating the pharmaceutical component varies depending on the type of the pharmaceutical component to be encapsulated, but various types of pharmaceutical components to be encapsulated can be applied as shown below.
For example, neurological drugs include agents for central nervous system such as antiepileptics, antipyretic agents, analgesics and general cold medicines, and agents for peripheral nervous systems such as autonomic agents and antispasmodics.
Examples of drugs that act on the biological defense mechanism include immunosuppressants, immune promoters, anti-inflammatory agents, antiallergic agents, antirheumatic agents, interferon-like agents, and the like.
循環器官用医薬としては、不整脈用剤、血管拡張剤、血管収縮剤、血圧降下剤、血圧上昇剤、抗動脈硬化症剤、高脂血症用剤、利尿剤などがある。
呼吸器官用医薬としては、気管支拡張剤、鎮咳剤、去たん剤、鎮咳去たん剤、含嗽剤などがある。
消化器官用医薬としては、抗消化性かいよう剤、制酸剤、健胃消化剤、抗肥満症剤、鎮吐剤、催吐剤、止しゃ剤、下剤、整腸剤、複合胃腸剤などがある。
外皮用医薬としては、外皮用殺菌消毒剤、創傷保護剤、化膿性疾患用剤、鎮痛・鎮痒・収れん・消炎剤、浴剤などがある。
Examples of circulatory organ drugs include arrhythmic agents, vasodilators, vasoconstrictors, antihypertensive agents, antihypertensive agents, anti-arteriosclerosis agents, hyperlipidemia agents, diuretics and the like.
Examples of respiratory organ medicines include bronchodilators, antitussives, expectorants, antitussives, and mouthwashes.
Examples of drugs for digestive organs include an anti-digestive itching agent, an antacid, a healthy stomach digestive agent, an anti-obesity agent, an antiemetic, an emetic, an antidiarrheal, a laxative, an intestinal adjuster, and a complex gastrointestinal agent.
Examples of dermatological drugs include dermatological disinfectants, wound protectants, purulent diseases, analgesics, antipruritics, astringents, anti-inflammatory agents, and baths.
代謝系用医薬としては、ビタミンＡ様剤、ビタミンＤ様剤、ビタミンＢ１様剤、ビタミンＢ２様剤、ビタミンＣ様剤、ビタミンＰ様剤、ビタミンＥ様剤、ビタミンＫ様剤、混合ビタミン様剤などのビタミン様剤のほか、カルシウム剤、無機質製剤、糖類剤、有機酸製剤、タンパクアミノ酸製剤などの滋養強壮薬や、肝臓疾患用剤、解毒剤、習慣性中毒用剤、痛風治療剤、酵素製剤、糖尿病用剤、総合代謝性製剤、尿酸代謝用剤、脂質代謝用剤、糖質代謝用剤などがある。 Metabolic drugs include vitamin A-like, vitamin D-like, vitamin B1-like, vitamin B2-like, vitamin C-like, vitamin P-like, vitamin E-like, vitamin K-like, mixed vitamin-like In addition to vitamin-like agents such as remedies, nutritional tonics such as calcium agents, mineral preparations, saccharide preparations, organic acid preparations, protein amino acid preparations, liver disease agents, antidote agents, addictive addiction agents, gout treatment agents, There are enzyme preparations, diabetic agents, comprehensive metabolic preparations, uric acid metabolism agents, lipid metabolism agents, carbohydrate metabolism agents and the like.
本発明により製造されるシリカ中空粒子は、上記した医薬成分を内包することによって、内包した医薬成分が徐々に放出され長期にわたりその薬効を継続することができるばかりでなく、副作用の低減にも効果的である。
また、空気との接触、光、熱などによって分解あるいは変質し易い成分であっても、シリカ中空粒子に内包することによって、該成分の分解あるいは変質を抑制することができる。
Silica hollow particles produced according to the present invention include not only the above-mentioned pharmaceutical ingredients are encapsulated, but the encapsulated pharmaceutical ingredients are gradually released so that the medicinal effect can be maintained over a long period of time, and also effective in reducing side effects. Is.
Moreover, even if it is a component which is easily decomposed or altered by contact with air, light, heat, or the like, decomposition or alteration of the component can be suppressed by enclosing it in silica hollow particles.
化粧料に関しては、下記に示す各種の保湿剤、植物抽出エキス、化粧料用薬剤、着色料、香料等を内包することができる。
これら化粧料成分を内包することによって、徐放性、放出制御性、保護性、マスキング性等の機能性を有する化粧料とすることができる。
植物抽出エキスとしては、収れん・清涼成分、抗炎症・抗アレルギー成分、殺菌・静菌成分、紫外線防止成分、皮膚賦活成分、保湿成分等がある。
Regarding cosmetics, various moisturizers, plant extracts, cosmetic agents, colorants, fragrances and the like shown below can be included.
By encapsulating these cosmetic ingredients, a cosmetic having functionalities such as sustained release, release controllability, protection and masking can be obtained.
Examples of plant extracts include astringent / cooling components, anti-inflammatory / anti-allergic components, bactericidal / bacteriostatic components, UV protection components, skin activation components, and moisturizing components.
化粧料用薬剤としては、美白用薬剤、ビタミン剤、ホルモン剤、止痒剤、鎮痒剤、抗炎症剤、発毛促進剤、角質軟化剥離剤、収れん剤、酸化防止剤、抗菌剤のほか、ベンゾフェノン系、安息香酸系、ケイ皮酸系、サリチル酸系などの紫外線遮蔽剤等がある。
着色剤としては、有機合成色素、天然色素、無機系着色料等が、香料としては、天然香料、合成香料、調合香料等がある。
Cosmetic agents include whitening agents, vitamins, hormones, antipruritics, antipruritics, anti-inflammatory agents, hair growth promoters, keratin softeners, astringents, antioxidants, antibacterial agents, There are UV-shielding agents such as benzophenone, benzoic acid, cinnamic acid, and salicylic acid.
Examples of the colorant include organic synthetic pigments, natural pigments, inorganic colorants, and examples of the flavor include natural flavors, synthetic flavors, and blended flavors.
上記した化粧料成分を内包することによって、該化粧料成分が徐々に放出され長期にわたりその効能を継続することができるばかりでなく、空気との接触、光、熱などによって分解あるいは変質し易い成分であっても、該成分の分解あるいは変質を抑制することができる。
具体例を挙げて説明すると、ビタミンなどの化粧料用薬剤を内包することにより、ビタミン類の効能である抗酸化作用が長期にわたり発現するほか、空気との接触によるビタミン類の分解や変質を抑制することができる。
Including the cosmetic component described above, the cosmetic component is gradually released and can continue its efficacy over a long period of time, but also easily decomposed or altered by contact with air, light, heat, etc. Even so, decomposition or alteration of the component can be suppressed.
Explaining with specific examples, the inclusion of vitamins and other cosmetic drugs allows the long-term antioxidant effect of vitamins to be exhibited, and also prevents the degradation and alteration of vitamins caused by contact with air. can do.
また、油性成分で構成されている化粧料に関して、水を含んだ抽出物を有効量配合することは種々問題が多く困難であり、例え配合できたとしても有効量に満たなかったり、無理に配合すると白濁してしまい好ましい外観が得られず実用には耐えがたい。
このような場合に、一方の成分をシリカ中空粒子内部に内包することにより、両成分の配合を比較的容易に行うことができる。
そのようなことを狙いとして本発明の製造方法で得たシリカ中空粒子が使用できる化粧料には、石鹸、化粧水、乳液、クリーム、パックなどのスキンケアに用いる基礎化粧品がある。
In addition, regarding cosmetics composed of oily ingredients, it is difficult to formulate an effective amount of an extract containing water. Then, it becomes cloudy and a favorable appearance cannot be obtained, and it is difficult to withstand practical use.
In such a case, both components can be blended relatively easily by enclosing one of the components inside the silica hollow particles.
Cosmetics that can use the silica hollow particles obtained by the production method of the present invention with the aim of such things include basic cosmetics used for skin care such as soaps, lotions, emulsions, creams and packs.
さらに、同様の狙いで該シリカ中空粒子が使用できる化粧料には、ファンデーション、口紅、頬紅、白粉、アイシャドー、アイライナー、マスカラ、眉墨、マニキュア等の肌を変えたり陰影をつけ立体感を出し、仕上げに用いるメーキャップ化粧品、香水、オーデコロン類、ボディーローション、ボディパウダー、石鹸等の芳香用化粧品（フラグランス）、シャンプー、リンス、ヘアコンディショナー、ヘアクリーム、非油性整髪料のヘアリキッド、ヘアスプレー、養毛のためのクリーム、ヘアトニック、ふけ取り用シャンプー、パーマネントウェーブ剤、カラークリーム、カラースプレー、洗毛剤、脱毛剤等の毛髪用化粧品がある。 Furthermore, cosmetics that can use the silica hollow particles for the same purpose have a three-dimensional effect by changing or shading the skin of foundation, lipstick, blusher, white powder, eye shadow, eyeliner, mascara, eyebrow, nail polish, etc. Makeup cosmetics used for finishing, perfumes, eau de colognes, body lotions, body powders, soaps and other fragrance cosmetics (fragrances), shampoos, rinses, hair conditioners, hair creams, non-oil-based hair liquids, hair sprays, There are cosmetics for hair such as creams for hair growth, hair tonics, shampoos for dandruff, permanent wave agents, color creams, color sprays, hair washing agents, hair removal agents and the like.
また、汗防臭剤、天瓜剤、育毛・養毛剤、洗毛剤、脱毛剤、薬用石鹸、薬用歯磨剤、浴用剤、防虫剤、日焼け止めクリーム等の薬用化粧品（医薬部外品）にも同様の狙いで使用できる。
さらに、同様の狙いで男性用化粧品にも使用でき、それには、顔用のシェービングクリーム、アフターローション、スキンミルク、頭髪用のシャンプー、リンス、ヘアリキッド、ヘアクリーム、ポマード、ヘアスプレー、フラグランスのオーデコロン、オードトワレ等がある。
The same applies to medicinal cosmetics (quasi-drugs) such as sweat deodorants, tengu, hair growth and hair nourishing agents, hair wash, hair remover, medicated soap, medicated dentifrice, bath preparation, insect repellent, sunscreen cream, etc. Can be used for the purpose of.
It can also be used in men's cosmetics for similar purposes, including facial shaving cream, after lotion, skin milk, hair shampoo, rinse, hair liquid, hair cream, pomade, hair spray, and fragrance. There are Eau de Cologne and Eau De Toilette.
本発明の製造方法で製造したシリカ中空粒子は、上記したこれらの化粧料に単独で、あるいは部分または一部として使用できる。
このように本発明により製造したシリカ中空粒子は、医薬品、化粧料としての利用価値が高く、シリカ中空粒子を含有する医薬品および化粧料は、徐放性、放出制御性、保護性、マスキング性等の機能性に優れた製品といえる。
The silica hollow particles produced by the production method of the present invention can be used alone or as a part or part of these cosmetics.
Thus, the silica hollow particles produced according to the present invention have high utility value as pharmaceuticals and cosmetics, and pharmaceuticals and cosmetics containing silica hollow particles have sustained release properties, release controllability, protective properties, masking properties, etc. It can be said that this product has excellent functionality.
以下において、本発明の実施例及び比較例を示して更に具体的に説明するが、本発明は、該実施例によって何等限定されるものではなく、特許請求の範囲の記載によって特定されるものであることはいうまでもない。
まず、透過型電子顕微鏡観察により測定される粒子径が５０〜１５０ｎｍであるコロイド状炭酸カルシウム及びテトラエトキシシランを用いて、水系媒質中におけるシリカ被覆操作を経て、シリカ中空粒子の製造を行った。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples, and is specified by the description of the scope of claims. Needless to say.
First, silica hollow particles were produced through a silica coating operation in an aqueous medium using colloidal calcium carbonate and tetraethoxysilane having a particle diameter of 50 to 150 nm measured by observation with a transmission electron microscope.
そのコロイド状炭酸カルシウム３０ｇをイオン交換水５００ｇ中に分散させた後、２９％アンモニア水８７ｇ、テトラエトキシシラン３２ｇを添加し、２４時間撹拌した。
その後、イオン交換水により洗浄してから、１Ｍ塩酸５００ｍＬ中に投入し３０分間撹拌して、炭酸カルシウムを溶解させた。
続いて、イオン交換水により洗浄してから、１０５℃にて乾燥させて、シリカ中空粒子を得た。
After 30 g of the colloidal calcium carbonate was dispersed in 500 g of ion-exchanged water, 87 g of 29% ammonia water and 32 g of tetraethoxysilane were added and stirred for 24 hours.
Then, after washing with ion-exchanged water, it was poured into 500 mL of 1M hydrochloric acid and stirred for 30 minutes to dissolve calcium carbonate.
Then, after wash | cleaning with ion-exchange water, it was made to dry at 105 degreeC, and the silica hollow particle was obtained.
得られた生成物を透過型電子顕微鏡及び走査型電子顕微鏡にて観察したところ、緻密なシリカ殻（殻厚約１０ｎｍ）からなる６０〜１５０ｎｍの中空状粒子であった。
さらに、エネルギー分散型Ｘ線検出器により化学分析を行ったところ、シリコン及び酸素のみが検出され、高純度のシリカ中空粒子であることが確認された。
また、動的光散乱法による平均粒子径は２５０ｎｍであり、かつ水銀圧入法による細孔分布測定では２〜２０ｎｍの細孔が検出されなかったことから、緻密なシリカ殻からなり、かつ分散性がよいことも確認できた。
When the obtained product was observed with a transmission electron microscope and a scanning electron microscope, it was 60 to 150 nm hollow particles composed of a dense silica shell (shell thickness: about 10 nm).
Furthermore, when chemical analysis was performed using an energy dispersive X-ray detector, only silicon and oxygen were detected, confirming that the silica hollow particles had high purity.
Moreover, since the average particle diameter by the dynamic light scattering method is 250 nm and the pore distribution measurement by the mercury intrusion method does not detect 2 to 20 nm pores, it is composed of a dense silica shell and has dispersibility. It was also confirmed that is good.
[比較例１]
実施例１と同じコロイド状炭酸カルシウム及びケイ酸ナトリウムを用いて、水系媒質中でのシリカ被覆操作を経て、シリカ中空粒子の製造を行った。
コロイド状炭酸カルシウム３０ｇをホウ酸ナトリウム−ホウ酸緩衝水溶液５００ｇに分散させた後、ＳｉＯ2含有量が３重量％のケイ酸ナトリウム水溶液３００ｇを、５ｇ／分の速度で滴下して、コロイド状炭酸カルシウム表面にシリカを被覆した。
その後実施例１と同様の酸処理、洗浄、乾燥操作を行い、シリカ中空粒子を得た。
[Comparative Example 1]
Using the same colloidal calcium carbonate and sodium silicate as in Example 1, silica hollow particles were produced through a silica coating operation in an aqueous medium.
After 30 g of colloidal calcium carbonate is dispersed in 500 g of a sodium borate-borate buffer aqueous solution, 300 g of a sodium silicate aqueous solution having a SiO 2 content of 3% by weight is dropped at a rate of 5 g / min. Silica was coated on the calcium surface.
Thereafter, the same acid treatment, washing and drying operations as in Example 1 were carried out to obtain silica hollow particles.
得られた生成物を透過型電子顕微鏡及び走査型電子顕微鏡にて観察したところ、比較的疎なシリカ殻（殻厚約１０ｎｍ）からなる６０〜１５０ｎｍの中空状粒子であった。
さらに、エネルギー分散型Ｘ線検出器により化学分析を行ったところ、シリコン、酸素、ナトリウム、ホウ素が検出され、シリカ以外に、ナトリウムやホウ素といった不純分が含有されることが確認された。
また、動的光散乱法による平均粒子径は１１００ｎｍであり、かつ水銀圧入法による細孔分布測定では２〜２０ｎｍの細孔が検出されたことから、比較的疎なシリカ殻からなり、分散性が低いことも確認できた。
When the obtained product was observed with a transmission electron microscope and a scanning electron microscope, it was 60 to 150 nm hollow particles composed of a relatively sparse silica shell (shell thickness: about 10 nm).
Furthermore, when chemical analysis was performed using an energy dispersive X-ray detector, silicon, oxygen, sodium, and boron were detected, and it was confirmed that impurities such as sodium and boron were contained in addition to silica.
Moreover, since the average particle diameter by dynamic light scattering method is 1100 nm and the pore distribution measurement by mercury intrusion method has detected pores of 2 to 20 nm, it is composed of a relatively sparse silica shell and has dispersibility. Was also confirmed to be low.
[比較例２]
実施例１と同じコロイド状炭酸カルシウム、及びテトラエトキシシランを用いて、有機溶媒中でのシリカ被覆操作を経て、シリカ中空粒子の製造を行った。
コロイド状炭酸カルシウム３０ｇをエチルアルコール５００ｇ中に分散させた後、２９％アンモニア水８７ｇ、テトラエトキシシラン３２ｇを添加し、２４時間撹拌した。
その後、イオン交換水により洗浄してから、１Ｍ塩酸５００ｍＬ中に投入し３０分間撹拌して、炭酸カルシウムを溶解させた。
続いて、イオン交換水により洗浄してから、１０５℃にて乾燥させて、シリカ中空粒子を得た。
[Comparative Example 2]
Using the same colloidal calcium carbonate and tetraethoxysilane as in Example 1, silica hollow particles were produced through a silica coating operation in an organic solvent.
After 30 g of colloidal calcium carbonate was dispersed in 500 g of ethyl alcohol, 87 g of 29% ammonia water and 32 g of tetraethoxysilane were added and stirred for 24 hours.
Then, after washing with ion-exchanged water, it was poured into 500 mL of 1M hydrochloric acid and stirred for 30 minutes to dissolve calcium carbonate.
Then, after wash | cleaning with ion-exchange water, it was made to dry at 105 degreeC, and the silica hollow particle was obtained.
得られた生成物を透過型電子顕微鏡及び走査型電子顕微鏡にて観察したところ、緻密なシリカ殻（殻厚約１０ｎｍ）からなる６０〜１５０ｎｍの中空粒子であった。
さらに、エネルギー分散型Ｘ線検出器により化学分析を行ったところ、シリコン及び酸素のみが検出され、高純度のシリカ中空粒子であることが確認された。
また、動的光散乱法による平均粒子径は４５０ｎｍであり、かつ水銀圧入法による細孔分布測定では２〜２０ｎｍの細孔が検出されなかったことから、緻密なシリカ殻からなり、比較的分散性がよいことも確認できた。
When the obtained product was observed with a transmission electron microscope and a scanning electron microscope, it was 60 to 150 nm hollow particles composed of a dense silica shell (shell thickness: about 10 nm).
Furthermore, when chemical analysis was performed using an energy dispersive X-ray detector, only silicon and oxygen were detected, confirming that the silica hollow particles had high purity.
In addition, the average particle size by dynamic light scattering method is 450 nm, and the pore distribution measurement by mercury intrusion method did not detect 2-20 nm pores. It was also confirmed that the nature is good.
Claims (3)
Use of aqueous ammonia as a base catalyst, and the silicon alkoxide to 1 mole, method for producing hollow silica particles according to claim 1 or 2 and NH 3, characterized in that 2 to 40 mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005078417A JP4861634B2 (en) | 2005-03-18 | 2005-03-18 | Method for producing silica hollow particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005078417A JP4861634B2 (en) | 2005-03-18 | 2005-03-18 | Method for producing silica hollow particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006256921A true JP2006256921A (en) | 2006-09-28 |
| JP4861634B2 JP4861634B2 (en) | 2012-01-25 |
Family
ID=37096568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005078417A Active JP4861634B2 (en) | 2005-03-18 | 2005-03-18 | Method for producing silica hollow particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4861634B2 (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070458A (en) * | 2005-09-07 | 2007-03-22 | Nagoya Institute Of Technology | Heat-insulation paint, heat-insulation film or three-layered heat-insulation film and heat-insulation fiber using hollow nanoparticle made of silica shell |
| JP2007070459A (en) * | 2005-09-07 | 2007-03-22 | Nagoya Institute Of Technology | Anticorrosive film using hollow nanoparticle made of silica shell and anticorrosive paint using hollow nanoparticle made of silica shell |
| JP2007308584A (en) * | 2006-05-18 | 2007-11-29 | Nagoya Institute Of Technology | Antireflection coating material, glare-proof coating material, antireflection membrane, antireflection film and glare-proof film |
| WO2008062605A1 (en) * | 2006-11-21 | 2008-05-29 | Nittetsu Mining Co., Ltd | Resin composition, anti-reflection coating material, anti-dazzling coating material, anti-reflection coating, anti-reflection film, anti-dazzling film, corrosion protective coating, corrosion protective coating material, coating material, and coating film |
| JP2008127470A (en) * | 2006-11-21 | 2008-06-05 | Grandex Co Ltd | Corrosion-preventing film and anticorrosion coating |
| JP2008200922A (en) * | 2007-02-19 | 2008-09-04 | Grandex Co Ltd | Coating film and coating |
| JP2008222459A (en) * | 2007-03-09 | 2008-09-25 | Nagoya Institute Of Technology | Method for preparing hollow silica particle |
| JP2009107857A (en) * | 2007-10-26 | 2009-05-21 | Grandex Co Ltd | Dispersible silica nano hollow particles and method for producing dispersion liquid of silica nano hollow particles |
| WO2009125758A1 (en) | 2008-04-10 | 2009-10-15 | 株式会社クラレ | Leather-like sheet having excellent grip performance and artificial leather product using the same |
| WO2010050263A1 (en) * | 2008-10-31 | 2010-05-06 | 旭硝子株式会社 | Hollow particle, method for producing the same, coating composition and article |
| WO2010074063A1 (en) | 2008-12-25 | 2010-07-01 | 電気化学工業株式会社 | Composite particles, process for producing the composite particles, hollow particles, process for producing the hollow particles, and use of the hollow particles |
| CN101823719A (en) * | 2010-05-18 | 2010-09-08 | 南京大学 | Two-step preparation method of hollow silica particles |
| JP2010215490A (en) * | 2009-02-17 | 2010-09-30 | Nagoya Institute Of Technology | Hollow nanoparticle composed of low density silica shell, and method for producing the same |
| JP2010285335A (en) * | 2008-10-15 | 2010-12-24 | National Institute Of Advanced Industrial Science & Technology | Nanoparticle-dispersed fine glass beads having cavity therein, and method for producing the same |
| JP2011001258A (en) * | 2009-05-19 | 2011-01-06 | Sekisui Chem Co Ltd | Bell-structured particle and method for producing the same |
| JP2011126284A (en) * | 2011-02-01 | 2011-06-30 | Nagoya Institute Of Technology | Three-layer thermal insulating film using nano hollow particle consisting of silica shell |
| JP2012505304A (en) * | 2008-10-14 | 2012-03-01 | ディーエスエム アイピー アセッツ ビー．ブイ． | Stain-resistant particles |
| JP2012132022A (en) * | 2012-03-26 | 2012-07-12 | Grandex Co Ltd | Coating paint |
| JP2012144394A (en) * | 2011-01-12 | 2012-08-02 | Konica Minolta Holdings Inc | Method for producing hollow particle, and optical material and heat insulation material using hollow particle |
| US8435475B2 (en) | 2007-06-26 | 2013-05-07 | Denki Kagaku Kogyo Kabushiki Kaisha | Spherical organic polymer-silicon compound composite particles, hollow particles and their production methods |
| WO2019189020A1 (en) * | 2018-03-26 | 2019-10-03 | Ａｇｃ株式会社 | Manufacturing method for hollow particles |
| CN114455592A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院过程工程研究所 | S-triazinyl modified hollow mesoporous silica and its preparation method and use |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5456951B2 (en) * | 2004-12-08 | 2014-04-02 | 日鉄鉱業株式会社 | Method for producing oxide film-coated fine particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005263550A (en) * | 2004-03-18 | 2005-09-29 | Nagoya Kogyo Univ | High dispersion silica nano hollow particle and its producing method |
-
2005
- 2005-03-18 JP JP2005078417A patent/JP4861634B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005263550A (en) * | 2004-03-18 | 2005-09-29 | Nagoya Kogyo Univ | High dispersion silica nano hollow particle and its producing method |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070458A (en) * | 2005-09-07 | 2007-03-22 | Nagoya Institute Of Technology | Heat-insulation paint, heat-insulation film or three-layered heat-insulation film and heat-insulation fiber using hollow nanoparticle made of silica shell |
| JP2007070459A (en) * | 2005-09-07 | 2007-03-22 | Nagoya Institute Of Technology | Anticorrosive film using hollow nanoparticle made of silica shell and anticorrosive paint using hollow nanoparticle made of silica shell |
| JP4651098B2 (en) * | 2005-09-07 | 2011-03-16 | 国立大学法人 名古屋工業大学 | Anticorrosion film using nano hollow particles made of silica shell and anticorrosion coating using nano hollow particles made of silica shell |
| JP2007308584A (en) * | 2006-05-18 | 2007-11-29 | Nagoya Institute Of Technology | Antireflection coating material, glare-proof coating material, antireflection membrane, antireflection film and glare-proof film |
| JP2008127470A (en) * | 2006-11-21 | 2008-06-05 | Grandex Co Ltd | Corrosion-preventing film and anticorrosion coating |
| WO2008062605A1 (en) * | 2006-11-21 | 2008-05-29 | Nittetsu Mining Co., Ltd | Resin composition, anti-reflection coating material, anti-dazzling coating material, anti-reflection coating, anti-reflection film, anti-dazzling film, corrosion protective coating, corrosion protective coating material, coating material, and coating film |
| JP2008200922A (en) * | 2007-02-19 | 2008-09-04 | Grandex Co Ltd | Coating film and coating |
| JP2008222459A (en) * | 2007-03-09 | 2008-09-25 | Nagoya Institute Of Technology | Method for preparing hollow silica particle |
| US8435475B2 (en) | 2007-06-26 | 2013-05-07 | Denki Kagaku Kogyo Kabushiki Kaisha | Spherical organic polymer-silicon compound composite particles, hollow particles and their production methods |
| JP2009107857A (en) * | 2007-10-26 | 2009-05-21 | Grandex Co Ltd | Dispersible silica nano hollow particles and method for producing dispersion liquid of silica nano hollow particles |
| WO2009125758A1 (en) | 2008-04-10 | 2009-10-15 | 株式会社クラレ | Leather-like sheet having excellent grip performance and artificial leather product using the same |
| JP2012505304A (en) * | 2008-10-14 | 2012-03-01 | ディーエスエム アイピー アセッツ ビー．ブイ． | Stain-resistant particles |
| JP2010285335A (en) * | 2008-10-15 | 2010-12-24 | National Institute Of Advanced Industrial Science & Technology | Nanoparticle-dispersed fine glass beads having cavity therein, and method for producing the same |
| WO2010050263A1 (en) * | 2008-10-31 | 2010-05-06 | 旭硝子株式会社 | Hollow particle, method for producing the same, coating composition and article |
| JP5434928B2 (en) * | 2008-10-31 | 2014-03-05 | 旭硝子株式会社 | Hollow particles, method for producing the same, coating composition and article |
| WO2010074063A1 (en) | 2008-12-25 | 2010-07-01 | 電気化学工業株式会社 | Composite particles, process for producing the composite particles, hollow particles, process for producing the hollow particles, and use of the hollow particles |
| JP5576799B2 (en) * | 2008-12-25 | 2014-08-20 | 電気化学工業株式会社 | Composite particle and method for producing the same, hollow particle, method for producing the same and use |
| JP2010215490A (en) * | 2009-02-17 | 2010-09-30 | Nagoya Institute Of Technology | Hollow nanoparticle composed of low density silica shell, and method for producing the same |
| JP2011001258A (en) * | 2009-05-19 | 2011-01-06 | Sekisui Chem Co Ltd | Bell-structured particle and method for producing the same |
| CN101823719A (en) * | 2010-05-18 | 2010-09-08 | 南京大学 | Two-step preparation method of hollow silica particles |
| JP2012144394A (en) * | 2011-01-12 | 2012-08-02 | Konica Minolta Holdings Inc | Method for producing hollow particle, and optical material and heat insulation material using hollow particle |
| JP2011126284A (en) * | 2011-02-01 | 2011-06-30 | Nagoya Institute Of Technology | Three-layer thermal insulating film using nano hollow particle consisting of silica shell |
| JP2012132022A (en) * | 2012-03-26 | 2012-07-12 | Grandex Co Ltd | Coating paint |
| WO2019189020A1 (en) * | 2018-03-26 | 2019-10-03 | Ａｇｃ株式会社 | Manufacturing method for hollow particles |
| CN114455592A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院过程工程研究所 | S-triazinyl modified hollow mesoporous silica and its preparation method and use |
| CN114455592B (en) * | 2020-11-10 | 2023-10-20 | 中国科学院过程工程研究所 | Hollow mesoporous silica modified by sym-triazinyl, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4861634B2 (en) | 2012-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4861634B2 (en) | Method for producing silica hollow particles | |
| TWI818972B (en) | Composite composition | |
| JP5155658B2 (en) | Surface-treated powder and cosmetics containing the same | |
| TW201836992A (en) | Hydrogen supply material and manufacturing method thereof, and hydrogen supply method | |
| KR20140012981A (en) | Hydrogen-emitting composition | |
| EP1642924B1 (en) | Composite particle and process for producing the same | |
| MX2008007354A (en) | Cosmetic compositions with encapsulated pigments and a method for using. | |
| AU2006274541A2 (en) | Metal oxide coating of water insoluble ingredients | |
| CN110603223B (en) | Hollow particles and cosmetics | |
| JP5921188B2 (en) | Method for producing silica-based particles having an ultraviolet shielding effect, silica-based particles obtained from the method, and a cosmetic comprising the silica-based particles | |
| JP2000327552A (en) | Skin preparation for external use | |
| KR20110062501A (en) | Organic-inorganic composite powder, a preparation method thereof, and a use of the same | |
| EP2111846B1 (en) | Cosmetic preparation containing polyfunctional composite powder | |
| JP2000309503A (en) | Liquid or creamy cosmetic containing cellulose fine particle | |
| JPH03200721A (en) | Composite-type ultraviolet absorber | |
| JP3645764B2 (en) | Porous titanium oxide, method for producing the same, and cosmetics containing the same | |
| JPWO2018225310A1 (en) | Powder modifier and composite powder, and makeup cosmetics | |
| JP2813547B2 (en) | Functional powders for cosmetics | |
| EP3318243A1 (en) | Composite powder in which jade powder particles are impregnated in porous polymer, cosmetic composition containing same and manufacturing method for same | |
| JP2002145717A (en) | Antimicrobial cosmetic | |
| JP2005060263A (en) | Method for producing silica-based fine particle for cosmetic preparation | |
| JP4516729B2 (en) | Iron phosphate-containing composite and cosmetic containing the same | |
| JP2006124656A (en) | Composite particle | |
| JP2593296B2 (en) | Cosmetic composition and method for producing the same | |
| JPH09188611A (en) | Surface-coated flaky powder, its production and cosmetic formulated therewith |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071119 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071120 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100301 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101012 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101208 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111018 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111107 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4861634 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141111 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |