JP6462459B2 - Method for producing silica particles - Google Patents
Method for producing silica particles Download PDFInfo
- Publication number
- JP6462459B2 JP6462459B2 JP2015072673A JP2015072673A JP6462459B2 JP 6462459 B2 JP6462459 B2 JP 6462459B2 JP 2015072673 A JP2015072673 A JP 2015072673A JP 2015072673 A JP2015072673 A JP 2015072673A JP 6462459 B2 JP6462459 B2 JP 6462459B2
- Authority
- JP
- Japan
- Prior art keywords
- silica particles
- particles
- silica
- dispersion
- silicon
- 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.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 330
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims description 185
- 239000006185 dispersion Substances 0.000 claims description 101
- 239000002210 silicon-based material Substances 0.000 claims description 68
- 239000000377 silicon dioxide Substances 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 58
- 238000000746 purification Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000010304 firing Methods 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011342 resin composition Substances 0.000 claims description 27
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000010335 hydrothermal treatment Methods 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000003456 ion exchange resin Substances 0.000 claims description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 13
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 239000003729 cation exchange resin Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 description 41
- 239000007789 gas Substances 0.000 description 37
- 239000010419 fine particle Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 230000008569 process Effects 0.000 description 21
- 230000007062 hydrolysis Effects 0.000 description 17
- 238000006460 hydrolysis reaction Methods 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 230000004927 fusion Effects 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011362 coarse particle Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 8
- 230000005070 ripening Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 208000010392 Bone Fractures Diseases 0.000 description 5
- 206010017076 Fracture Diseases 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000011361 granulated particle Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 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 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006059 cover glass Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- LZKBJDFRBKBJLP-UHFFFAOYSA-N 3-[diethoxy(3-methylbutan-2-yloxy)silyl]propylurea Chemical compound CC(C)C(C)O[Si](OCC)(OCC)CCCNC(N)=O LZKBJDFRBKBJLP-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 206010010214 Compression fracture Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- BPCRGIAAAKYTMD-UHFFFAOYSA-N bis(1,1,1,2,3,3,3-heptafluoropropan-2-yloxy)-[1,1,1,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-icosafluoro-2-(trifluoromethyl)decan-2-yl]oxy-(1,1,2,2,2-pentafluoroethyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(C(F)(F)F)(C(F)(F)F)O[Si](OC(F)(C(F)(F)F)C(F)(F)F)(OC(F)(C(F)(F)F)C(F)(F)F)C(F)(F)C(F)(F)F BPCRGIAAAKYTMD-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
- YEROEIVBCZSQJY-UHFFFAOYSA-N dimethoxymethyl(3,3,3-trifluoropropyl)silane Chemical compound COC(OC)[SiH2]CCC(F)(F)F YEROEIVBCZSQJY-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- QNKXRZAXBKSFQC-UHFFFAOYSA-N trimethoxy-[3-[2-(oxiran-2-ylmethoxy)ethoxy]propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCCOCC1CO1 QNKXRZAXBKSFQC-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、液晶表示装置におけるスペーサ、半導体デバイスの封止材用フィラー及びギャップ調整を必要とするデバイスのギャップ調整フィラー等として用いられるシリカ粒子の製造方法に関する。 The present invention relates to a method for producing silica particles used as spacers in liquid crystal display devices, fillers for encapsulating semiconductor devices, gap adjusting fillers for devices that require gap adjustment, and the like.
シリカ粒子は、液晶表示装置の面内用スペーサ、シール用スペーサの他、樹脂組成物の充填剤、フィラー等として、各種用途に使用されている。
このようなシリカ粒子を製造する方法としては、例えば、加水分解が可能なシリコン化合物を水と触媒とを含む有機溶媒中で加水分解、縮合することによって得られるシリカ粒子を噴霧乾燥(スプレードライ)し、その後、1000〜1200℃の範囲内で焼成する方法が提案されている(特許文献1参照)。
このように1000〜1200℃の比較的高温で焼成して緻密化を進めると、粒子の吸湿性が低下することが経験的に知られているが、高温で処理すればするほど、シリカ粒子同士が融着し、特に狭いギャップへの注入性、埋め込み性や、樹脂と混練した際の混練物の濾過性の問題となることがあった。
Silica particles are used in various applications as fillers and fillers for resin compositions in addition to in-plane spacers and sealing spacers for liquid crystal display devices.
As a method for producing such silica particles, for example, silica particles obtained by hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst are spray-dried (spray drying). And after that, the method of baking within the range of 1000-1200 degreeC is proposed (refer patent document 1).
As described above, it is empirically known that when the particles are baked at a relatively high temperature of 1000 to 1200 ° C. and densified, the hygroscopicity of the particles decreases. May cause problems such as injectability into a narrow gap, embedding property, and filterability of a kneaded product when kneaded with a resin.
更に、融着した粒子を粉砕装置で処理することも経験的になされているが、粉砕された粒子の破壊面はシロキサン結合が切れて、シラノール基を発生させ易くし、結果的に親水性の表面になり易い。焼成によって緻密化された表面はシラノール基が少なく、比較的疎水性な表面となるが、粉砕によってシロキサン結合が切断され、シラノール基が形成された結果、新たに生じた親水性の表面が増加していくと一次粒子がゆるく会合した凝集体を形成し易くなり、後に樹脂成分と共に混練した時に分散が不充分となり、濾過性の低下および注入性の低下を引き起こす結果となる。
従って、いまだ十分に分散性に優れた均一なシリカ粒子が得られているとはいえず、さらなる品質の向上が求められている。
Furthermore, the fused particles are treated empirically with a pulverizer, but the fracture surface of the pulverized particles breaks the siloxane bond, making it easier to generate silanol groups, resulting in hydrophilic properties. It is easy to become the surface. The surface that has been densified by baking has few silanol groups and becomes a relatively hydrophobic surface, but the siloxane bond is cut by pulverization and silanol groups are formed, resulting in an increase in newly generated hydrophilic surfaces. As a result, it becomes easy to form an aggregate in which the primary particles are loosely associated with each other, resulting in insufficient dispersion when kneaded with the resin component later, resulting in a decrease in filterability and a decrease in injectability.
Therefore, it cannot be said that uniform silica particles excellent in dispersibility are obtained yet, and further improvement in quality is required.
本発明の課題は、シリカ粒子同士の融着を抑制して、シリカ粒子の凝集を抑制し、分散性に優れた均一な粒子径のシリカ粒子(粒子径変動係数の小さいシリカ粒子)を製造する方法を提供することにある。 An object of the present invention is to produce silica particles having a uniform particle diameter (silica particles having a small particle diameter variation coefficient) excellent in dispersibility by suppressing the fusion of silica particles to suppress aggregation of silica particles. It is to provide a method.
本発明者らは、系中に残存する反応が不十分な含珪素化合物が、乾燥時に粒子間に付着し、焼成時にシリカ粒子同士の融着を促進させていることを知見し、乾燥工程に供する分散液中に存在する反応が不十分な含珪素化合物を所定量以下とすることにより、この問題を解決することができることを見いだし、本発明を完成するに至った。 The present inventors have found that the silicon-containing compound with insufficient reaction remaining in the system adheres between the particles during drying and promotes the fusion of the silica particles during firing. It has been found that this problem can be solved by setting the amount of the silicon-containing compound with insufficient reaction present in the dispersion to be provided to a predetermined amount or less, and the present invention has been completed.
すなわち、本発明は、加水分解可能な含珪素化合物を原料として、シリカ粒子の分散液を調製する分散液調製工程と、該調製したシリカ粒子分散液を乾燥する乾燥工程と、該乾燥したシリカ粒子を焼成する焼成工程と、該焼成したシリカ粒子を解砕する解砕工程と、を備えたシリカ粒子の製造方法であって、前記乾燥工程に供するシリカ微粒子分散液中の反応が不十分な含珪素化合物の含有量を50ppm以下としたシリカ粒子の製造方法に関する。 That is, the present invention includes a dispersion preparation step of preparing a dispersion of silica particles using a hydrolyzable silicon-containing compound as a raw material, a drying step of drying the prepared silica particle dispersion, and the dried silica particles A method for producing silica particles comprising: a firing step for firing the silica particles; and a crushing step for crushing the fired silica particles, wherein the reaction in the silica fine particle dispersion used for the drying step is insufficient. The present invention relates to a method for producing silica particles with a silicon compound content of 50 ppm or less.
本発明のシリカ粒子の製造方法は、分散液調製工程と乾燥工程との間に、調製したシリカ粒子分散液から、反応が不十分な含珪素化合物を分離除去する精製工程を備えることが好ましい。また、分散液調製工程と乾燥工程との間に、望ましくは前記精製工程の後乾燥工程の前に、シリカ粒子分散液を水熱処理する水熱処理工程と、該水熱処理した分散液から反応が不十分な含珪素化合物を分離除去する水熱後精製工程とを備えることが好ましい。 The method for producing silica particles of the present invention preferably includes a purification step of separating and removing a silicon-containing compound with insufficient reaction from the prepared silica particle dispersion between the dispersion preparation step and the drying step. Further, between the dispersion preparation step and the drying step, preferably, before the post-drying step after the purification step, there is no reaction from the hydrothermal treatment step of hydrothermally treating the silica particle dispersion and the hydrothermally treated dispersion. It is preferable to include a hydrothermal post-purification step for separating and removing a sufficient silicon-containing compound.
ここで、精製工程及び水熱後精製工程において分離除去する「反応が不十分な含珪素化合物」とは、調製目的とするシリカ粒子まで反応が進んでいない含珪素化合物を意味し、例えば、未反応の原料含珪素化合物やその低分子加水分解物(1〜4量体程度)等であり、その粒径としては例えば5nm以下程度のものである。
また、「反応が不十分な含珪素化合物の含有量」の測定は、分散液を遠心機で十分に処理して目的のシリカ粒子を沈降させ、上澄みを分取し、その上澄みを弗化水素酸、硫酸、硝酸の順で前処理した後、硝酸に溶解させ、ICP質量分析装置(Agilent製:型式Agilent 7500S)を用いてSiを定量することにより行い、このSiの含有量を「反応が不十分な含珪素化合物の含有量」とする。
Here, the “silicon-containing compound with insufficient reaction” that is separated and removed in the purification step and the post-hydrothermal purification step means a silicon-containing compound in which the reaction has not progressed to the target silica particles. The raw material of the reaction is a silicon-containing compound or a low-molecular hydrolyzate thereof (about 1 to 4 mer), and the particle size is, for example, about 5 nm or less.
In addition, the measurement of “content of silicon-containing compound with insufficient reaction” is carried out by sufficiently treating the dispersion with a centrifuge to settle the target silica particles, separating the supernatant, and removing the supernatant by hydrogen fluoride. After pre-treating in the order of acid, sulfuric acid, and nitric acid, it is dissolved in nitric acid, and Si is quantified using an ICP mass spectrometer (manufactured by Agilent: Model Agilent 7500S). "Insufficient silicon-containing compound content".
本発明のシリカ粒子の製造方法によれば、焼成時におけるシリカ粒子同士の融着を抑制できることにより、より均一な粒子径のシリカ粒子を得ることができる。これにより、樹脂に対する分散性が向上し、かかるシリカ粒子を含有した樹脂組成物は、濾過性に優れ、狭ギャップへの注入性にも優れている。 According to the method for producing silica particles of the present invention, it is possible to obtain silica particles having a more uniform particle diameter by suppressing fusion of silica particles during firing. Thereby, the dispersibility with respect to resin improves, and the resin composition containing this silica particle is excellent in filterability, and excellent in the injection | pouring property to a narrow gap.
本発明のシリカ微粒子の製造方法は、加水分解可能な含珪素化合物を原料として、シリカ粒子の分散液を調製する分散液調製工程と、該調製したシリカ粒子分散液を乾燥する乾燥工程と、該乾燥したシリカ粒子を焼成する焼成工程と、該焼成したシリカ粒子を解砕する解砕工程とを備えており、乾燥工程に供するシリカ微粒子分散液中の反応が不十分な含珪素化合物の含有量を50ppm以下とすることを特徴とする。本発明の製造方法においては、上記のように、反応が不十分な含珪素化合物が50ppm以下となるように含珪素化合物を系中から分離除去するものであるが、30ppm以下まで分離除去することがより好ましく、25ppm以下まで分離除去することが更に好ましい。通常、原料含珪素化合物の反応を十分に進めるような操作を行ったとしても、乾燥工程前の分散液には通常100ppmを超える含珪素化合物が存在するが、本発明においてはこれを分離除去して、その含有量を低下させるものである。 The method for producing silica fine particles of the present invention comprises a dispersion preparation step of preparing a dispersion of silica particles using a hydrolyzable silicon-containing compound as a raw material, a drying step of drying the prepared silica particle dispersion, A content of a silicon-containing compound that includes a firing step for firing the dried silica particles and a pulverization step for pulverizing the fired silica particles, and the reaction in the silica fine particle dispersion used for the drying step is insufficient. Is 50 ppm or less. In the production method of the present invention, as described above, the silicon-containing compound is separated and removed from the system so that the silicon-containing compound with insufficient reaction is 50 ppm or less. Is more preferable, and it is more preferable to separate and remove to 25 ppm or less. Usually, even if the operation of sufficiently proceeding the reaction of the raw material silicon-containing compound is carried out, the silicon-containing compound in excess of 100 ppm usually exists in the dispersion before the drying step. In the present invention, this is separated and removed. Therefore, the content is reduced.
具体的には、例えば、分散液調製工程と乾燥工程との間に、調製したシリカ粒子分散液から、反応が不十分な含珪素化合物を分離除去する精製工程を備える。また、精製工程とは別に、又は精製工程の後乾燥工程の前に、シリカ粒子分散液を水熱処理する水熱処理工程と、該水熱処理した分散液から反応が不十分な含珪素化合物を分離除去する水熱後精製工程とを備える。これらの工程の詳細については、後述する。 Specifically, for example, a purification step of separating and removing a silicon-containing compound with insufficient reaction from the prepared silica particle dispersion is provided between the dispersion preparation step and the drying step. Also, separately from the purification step or before the post-drying step of the purification step, a hydrothermal treatment step of hydrothermally treating the silica particle dispersion, and separating and removing silicon-containing compounds that are insufficiently reacted from the hydrothermal treatment dispersion And a hydrothermal post-purification step. Details of these steps will be described later.
以下、本発明のシリカ粒子の製造方法における各工程を順に説明する。
[分散液調製工程]
分散液調製工程は、シリカ粒子分散液を調製する工程であり、各種の調製方法を採用することができる。例えば、特開平11−228698号公報、特開平11−228699号公報等に開示された含珪素化合物を加水分解する方法や、これに準じた方法が挙げられる。本工程において調製されるシリカ微粒子の平均粒子径としては、10nm〜1μm程度であることが好ましく、20nm〜1μm程度であることがより好ましい。なお、本明細書において述べる各シリカ粒子の平均粒子径は、1μm未満の粒子は堀場製作所製の粒度分布測定装置LA−950V2を用い、1μm以上の場合はベックマン・コールター社製のコールターカウンターIIIを用いて測定する。
Hereinafter, each process in the manufacturing method of the silica particle of this invention is demonstrated in order.
[Dispersion preparation process]
The dispersion preparation step is a step of preparing a silica particle dispersion, and various preparation methods can be employed. Examples thereof include a method of hydrolyzing a silicon-containing compound disclosed in JP-A-11-228698, JP-A-11-228699, and the like, and a method according thereto. The average particle size of the silica fine particles prepared in this step is preferably about 10 nm to 1 μm, and more preferably about 20 nm to 1 μm. In addition, the average particle diameter of each silica particle described in this specification uses a particle size distribution measuring apparatus LA-950V2 manufactured by HORIBA, Ltd. for particles having a particle diameter of less than 1 μm, and in the case of 1 μm or more, a Coulter Counter III manufactured by Beckman Coulter is used. Use to measure.
ここでは、分散液調製工程が、種粒子調製工程と粒子成長工程を備え、必要に応じて熟成工程を備える場合を説明する。具体的には、下記式(1)で表される加水分解可能な含珪素化合物を加水分解して種粒子を調製し、次いで粒子成長(ビルドアップ)させてシリカ粒子の分散液を調製し、更に必要に応じて分散液の熟成を行う方法について説明する。
Rn−SiX4−n・・・(1)
(但し、式中、Rは炭素数1〜10の置換または非置換の炭化水素基であって、互いに同一であっても異なっていてもよい。Xは炭素数1〜4のアルコキシ基、水酸基、ハロゲンまたは水素である。nは0〜3の整数である。)
Here, the case where the dispersion liquid preparation step includes a seed particle preparation step and a particle growth step, and includes an aging step as necessary will be described. Specifically, a hydrolyzable silicon-containing compound represented by the following formula (1) is hydrolyzed to prepare seed particles, and then particle growth (build-up) is performed to prepare a dispersion of silica particles. Further, a method for aging the dispersion as necessary will be described.
R n —SiX 4-n (1)
(In the formula, R is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. , Halogen or hydrogen, n is an integer of 0 to 3.)
具体的に、前述の式(1)で表される加水分解性含珪素化合物(加水分解性有機珪素化合物)としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(βメトキシエトキシ)シラン、3,3,3−トリフルオロプロピルトリメトキシシラン、メチル−3,3,3−トリフルオロプロピルジメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、γ−グリシドキシメチルトリメトキシシラン、γ−グリシドキシメチルトリエトキシシラン、γ−グリシドキシエチルトリメトキシシラン、γ−グリシドキシエチルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−(β−グリシドキシエトキシ)プロピルトリメトキシシラン、γ−(メタ)アクリロオキシメチルトリメトキシシラン、γ−(メタ)アクリロオキシメチルトリエトキシシラン、γ−(メタ)アクリロオキシエチルトリメトキシシラン、γ−(メタ)アクリロオキシエチルトリエトキシシラン、γ−(メタ)アクリロオキシプロピルトリメトキシシラン、γ−(メタ)アクリロオキシプロピルトリエトキシシラン、ブチルトリメトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリエトキシシラン、ブチルトリエトキシシラン、3−ウレイドイソプロピルプロピルトリエトキシシラン、N−β(アミノエチル)γ-アミノプロピルメチルジメトキシシラン、N−β(アミノエチル)γ−アミノプロピルトリメトキシシラン、N-フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、パ−フルオロオクチルエチルトリメトキシシラン、パ−フルオロオクチルエチルトリエトキシシラン、パ−フルオロオクチルエチルトリイソプロポキシシラン、トリフルオロプロピルトリメトキシシラン、トリデカフルオロオクチルトリメトキシシラン、ヘプタデカトリフルオロデシルトリメトキシシラン、ジメトキシメチルトリフルオロプロピルシラン、ペンタデカトリフルオロデシルトリメトキシシラン、ヘプタデカトリフルオロデシルトリプロポキシシラン、トリメチルシラノール、メチルトリクロロシラン、3−グリシドキシプロピルメチルジエトキシシラン,3−メタクリロキシプロピルメチルジメトキシシラン,3−メタクリロキシプロピルメチルジエトキシシラン、N−2−(アミノエチル)−3−アミノプロピルメチルジメトキシシラン、3−メルカプトプロピルメチルジメトキシシラン、およびこれらの化合物を2種以上含む混合物が挙げられる。 Specifically, as the hydrolyzable silicon-containing compound (hydrolyzable organosilicon compound) represented by the above formula (1), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxy Silane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) E) Ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glyce Sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) Acryloxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- ( (Meth) acryloxypropyltriethoxysilane, butyltrimeth Xysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyl Triethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecatrifluorode Rutrimethoxysilane, dimethoxymethyltrifluoropropylsilane, pentadecatrifluorodecyltrimethoxysilane, heptadecatrifluorodecyltripropoxysilane, trimethylsilanol, methyltrichlorosilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryl Roxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and two or more of these compounds A mixture is mentioned.
(1)種粒子調製工程
まず、水とアルコールに加水分解用触媒を加えて混合溶媒とする。この混合溶媒に式(1)で示した含珪素化合物を添加すると、シリカ微粒子(種粒子ということもある)の分散液(A液)が得られる。すなわち、シリカ種粒子は含珪素化合物の加水分解物である。
混合溶媒に含珪素化合物を添加する際、できるだけ短時間で、できれば一気に添加することが好ましい。短時間で添加することによって、均一な粒子径の種粒子が作製できる。これを後述する粒子成長工程で粒子成長させると、均一な粒子径の(すなわち、粒子径変動係数の小さい)シリカ粒子が得られる。
アルコールとしてはメタノール、エタノール、プロパノール、ブタノール等を用いることができる。なお、必要に応じて他の有機溶媒を併用してもよい。このとき、混合溶媒中の水/アルコール重量比は1/1〜3/1の範囲にあることが好ましい。この範囲にあれば、比較的単分散のシリカ種粒子が得られ、均一な粒子径のシリカ粒子の作製に有効である。
加水分解用触媒としては、アルカリ金属水酸化物、塩基性窒素化合物等の塩基性化合物を用いることができる。ここでは、アンモニアが推奨される。アンモニアは、加水分解能だけでなく、各工程における分散液のpH調整に有効で、かつ、最終的に得られる解砕シリカ粒子中にアンモニアは不純物として残存することがない。
加水分解用触媒や含珪素化合物の種類によって、混合溶媒中の加水分解用触媒の濃度は異なるものの、1〜7.5質量%の範囲にあることが好ましい。加水分解用触媒の濃度がこの範囲にあれば、種粒子に適した比較的単分散のシリカ微粒子が得られる。更に、加水分解用触媒の濃度は3〜5質量%がより好ましい。
(1) Seed particle preparation step First, a hydrolysis catalyst is added to water and alcohol to obtain a mixed solvent. When the silicon-containing compound represented by the formula (1) is added to this mixed solvent, a dispersion (liquid A) of silica fine particles (sometimes referred to as seed particles) is obtained. That is, silica seed particles are a hydrolyzate of a silicon-containing compound.
When adding the silicon-containing compound to the mixed solvent, it is preferable to add the silicon-containing compound in a short time if possible. By adding in a short time, seed particles having a uniform particle size can be produced. When particles are grown in a particle growth step described later, silica particles having a uniform particle size (that is, a small particle size variation coefficient) are obtained.
As the alcohol, methanol, ethanol, propanol, butanol or the like can be used. In addition, you may use another organic solvent together as needed. At this time, the water / alcohol weight ratio in the mixed solvent is preferably in the range of 1/1 to 3/1. Within this range, relatively monodispersed silica seed particles can be obtained, which is effective for producing silica particles having a uniform particle diameter.
As the hydrolysis catalyst, basic compounds such as alkali metal hydroxides and basic nitrogen compounds can be used. Here, ammonia is recommended. Ammonia is effective not only in hydrolyzing ability but also in adjusting the pH of the dispersion in each step, and ammonia does not remain as an impurity in the finally obtained crushed silica particles.
Although the concentration of the hydrolysis catalyst in the mixed solvent varies depending on the type of the hydrolysis catalyst and the silicon-containing compound, it is preferably in the range of 1 to 7.5% by mass. If the concentration of the catalyst for hydrolysis is within this range, relatively monodispersed silica fine particles suitable for seed particles can be obtained. Furthermore, the concentration of the catalyst for hydrolysis is more preferably 3 to 5% by mass.
シリカ種粒子の分散液(A液)の濃度はRn−SiO(4−n)/2として0.01〜5質量%の範囲にあることが好ましい。分散液(A液)の濃度がこの範囲にあれば、所望の粒子径を有するシリカ種粒子を得ることができる。より好ましくは、0.1〜1質量%の範囲である。また、分散液(A液)の温度は5〜40℃の範囲が、pHは8〜13が好ましい。より好ましいpHの範囲は10〜12である。このように、温度とpHを適正な範囲にすることにより、シリカ種粒子の平均粒子径を5nm〜0.8μmの間に制御することができ、標準偏差を0.5μm以下にすることができる。
更に、シリカ微粒子の分散液(A液)に、pH調整剤を添加することが好ましい。本実施例ではアンモニア水を加える。必要に応じて水を加えてもよい。このようにして、pHが10〜13の範囲のシリカ微粒子の分散液(B液)が得られる。シリカ微粒子の分散液(B液)の温度を5〜40℃の範囲にすることが好ましい。また、分散液の電導度は80〜200μs/cmの範囲が好ましい。シリカ微粒子の分散液(B液)のpH、温度および電導度をこのような範囲とすることによってシリカ微粒子は凝集することなく、より均一な粒子径となり、種粒子として好適に用いることができる。
Dispersion of silica seed particles concentration of (A solution) is preferably in the range of 0.01 to 5 mass% as R n -SiO (4-n) / 2. When the concentration of the dispersion (liquid A) is within this range, silica seed particles having a desired particle diameter can be obtained. More preferably, it is the range of 0.1-1 mass%. Moreover, the temperature of a dispersion liquid (A liquid) has the preferable range of 5-40 degreeC, and pH 8-13 is preferable. A more preferred pH range is 10-12. As described above, by setting the temperature and pH within appropriate ranges, the average particle diameter of the silica seed particles can be controlled between 5 nm and 0.8 μm, and the standard deviation can be reduced to 0.5 μm or less. .
Furthermore, it is preferable to add a pH adjuster to the silica fine particle dispersion (liquid A). In this embodiment, ammonia water is added. Water may be added as necessary. In this manner, a dispersion of silica fine particles (liquid B) having a pH in the range of 10 to 13 is obtained. It is preferable that the temperature of the silica fine particle dispersion (liquid B) be in the range of 5 to 40 ° C. The conductivity of the dispersion is preferably in the range of 80 to 200 μs / cm. By setting the pH, temperature, and conductivity of the dispersion of silica fine particles (liquid B) in such a range, the silica fine particles do not agglomerate and have a more uniform particle size, and can be suitably used as seed particles.
(2)粒子成長工程
次いで、粒子成長工程を行う。すなわち、シリカ微粒子の分散液(B液)に加水分解可能な含珪素化合物と加水分解用触媒を連続的にあるいは断続的に添加する。ここでは、含珪素化合物と加水分解用触媒を同時かつ連続的に添加する。同時に添加することにより、粒子成長工程で分散液のpHの変動を小さくすることが可能となり、粒子成長用の含珪素化合物の加水分解およびシリカ微粒子(種粒子)表面への析出速度が一定となり、均一な粒子径のシリカ粒子が得られる。
このとき、含珪素化合物の添加量は、前述の分散液(A液)のRn−SiO(4−n)/2量の2〜200倍の範囲にあることが好ましい。この範囲にあれば、平均粒子径が後述する10nm〜1μmの範囲にあるシリカ粒子を、凝集することなく単分散で得られる。より好ましくは、10〜150倍である。1μm以上のシリカ粒子を得たい場合には、ここで得られた粒子を種粒子として、同様の粒子成長工程を更に行えばよい。このように、粒子成長工程を繰り返すことで、10μm程度までシリカ粒子を成長させることができる。
(2) Particle growth step Next, a particle growth step is performed. That is, a hydrolyzable silicon-containing compound and a hydrolysis catalyst are continuously or intermittently added to a dispersion of silica fine particles (liquid B). Here, the silicon-containing compound and the hydrolysis catalyst are added simultaneously and continuously. By adding at the same time, it is possible to reduce the fluctuation of the pH of the dispersion in the particle growth process, the hydrolysis rate of the silicon-containing compound for particle growth and the deposition rate on the surface of the silica fine particles (seed particles) become constant, Silica particles having a uniform particle diameter can be obtained.
At this time, the addition amount of the silicon-containing compound is preferably in the range of 2 to 200 times the R n -SiO (4-n) / 2 the amount of the dispersion liquid of the aforementioned (A solution). If it exists in this range, the silica particle which has an average particle diameter in the range of 10 nm-1 micrometer mentioned later is obtained by monodispersion, without agglomerating. More preferably, it is 10 to 150 times. When it is desired to obtain silica particles of 1 μm or more, a similar particle growth step may be further performed using the particles obtained here as seed particles. Thus, silica particles can be grown to about 10 μm by repeating the particle growth step.
この工程で、含珪素化合物と加水分解用触媒(アンモニア水)の添加時間は、シリカ粒子の作製量によっても異なるが、1〜48時間である。特に、2〜24時間が好ましい。添加時間がこの範囲にあれば、凝集することなく単分散のシリカ粒子を作製することができる。また、粒子成長中には分散液のpHを8〜13にする。pHの変動幅は±1.0が好ましく、±0.5の範囲にあることがより好ましい。
またこのとき、シリカ微粒子(SiO2)1モルに対して、水を4〜200モル加えることが好ましい。特に、6〜100モルが適している。水が4モル未満であると、加水分解が生じ難く、球状の粒子が得られない場合がある。水が200モル以上であると、加水分解速度が速くなるため、粒子成長が生じずに自己核生成が生じる場合がある。更に加水分解用の触媒は種類にもよるが、系内に0.5〜7.5%存在するように添加することが好ましい。0.5%未満の場合は、粒子成長をせず目的の粒子サイズにならない場合がある。7.5%より多い場合は粒子成長に影響は及ぼさないがコスト的観点から好ましくない。
このように、シリカ微粒子の分散液(B液)に含珪素化合物と加水分解用触媒を同時かつ連続的に添加することでシリカ微粒子が成長し、シリカ粒子の分散液(C液)が得られる。以上のような方法により、平均粒子径10nm〜1μmのシリカ粒子の分散液を作製することができる。
In this step, the addition time of the silicon-containing compound and the hydrolysis catalyst (ammonia water) is 1 to 48 hours, although it varies depending on the amount of silica particles produced. In particular, 2 to 24 hours are preferable. If the addition time is within this range, monodispersed silica particles can be produced without agglomeration. Further, the pH of the dispersion is adjusted to 8 to 13 during particle growth. The fluctuation range of pH is preferably ± 1.0, and more preferably in the range of ± 0.5.
At this time, silica fine particles (SiO 2) with respect to 1 mole, it is preferable to add water 4 to 200 mol. In particular, 6 to 100 mol is suitable. If the amount of water is less than 4 mol, hydrolysis hardly occurs and spherical particles may not be obtained. If the water is 200 mol or more, the hydrolysis rate increases, so that particle growth does not occur and autonucleation may occur. Furthermore, although it depends on the kind of the catalyst for hydrolysis, it is preferable to add it so that it is present in the system at 0.5 to 7.5%. If it is less than 0.5%, there is a case where particle growth does not occur and the target particle size is not achieved. If it exceeds 7.5%, the particle growth is not affected, but it is not preferable from the viewpoint of cost.
Thus, the silica fine particles grow by adding the silicon-containing compound and the hydrolysis catalyst simultaneously and continuously to the silica fine particle dispersion (liquid B), and a silica particle dispersion (liquid C) is obtained. . By the above method, a dispersion of silica particles having an average particle diameter of 10 nm to 1 μm can be produced.
(粒子熟成工程)
更に、上述の粒子成長工程の後に、必要に応じて粒子熟成処理を行うことができる。ここで、粒子熟成工程とは、35〜100℃に加温して所定時間保持する工程をいう。
具体的には、粒子成長工程を経たシリカ粒子の分散液(C液)を、35〜100℃に加温し、所定時間撹拌する。するとシリカ粒子の分散液が熟成し、シリカ粒子の分散液(D液)が得られる。40〜80℃の範囲で熟成させることがより好ましい。この温度範囲内であれば分散液(C液)の温度は変動しても構わない。
また、熟成時の分散液のpHを8〜13にする。このとき、分散液のpHの変動幅を±1.0にする。±0.5の範囲に制御することが、より好ましい。熟成時間は温度によっても異なるが概ね1〜24時間である。このような条件で熟成することによって、含珪素化合物の加水分解物の縮合が進むとともに、より均一な粒子径の(粒子径変動係数の小さい)シリカ粒子が得られる。
(Particle ripening process)
Furthermore, a particle ripening treatment can be performed as necessary after the above-described particle growth step. Here, the particle ripening step refers to a step of heating to 35 to 100 ° C. and holding for a predetermined time.
Specifically, the silica particle dispersion (liquid C) that has undergone the particle growth step is heated to 35 to 100 ° C. and stirred for a predetermined time. Then, a dispersion of silica particles is aged, and a dispersion of silica particles (liquid D) is obtained. It is more preferable to age in the range of 40-80 degreeC. Within this temperature range, the temperature of the dispersion liquid (liquid C) may vary.
Further, the pH of the dispersion during aging is adjusted to 8 to 13. At this time, the fluctuation range of the pH of the dispersion is set to ± 1.0. It is more preferable to control within a range of ± 0.5. The aging time varies depending on the temperature, but is generally 1 to 24 hours. By aging under such conditions, condensation of the hydrolyzate of the silicon-containing compound proceeds and silica particles having a more uniform particle size (small particle size variation coefficient) can be obtained.
(濾過工程)
更に、必要に応じて濾過工程を設けてもよい。濾過工程の前に前述の粒子熟成工程を行っているか否かは問わない。濾過によって、所定の平均粒子径よりも大きい、シリカ粒子の凝集体を分離できる。この時点で所定の平均粒子径よりも大きい凝集体が残存していると、焼成工程での焼成により、解砕が困難な焼成シリカ粒子が生成する可能性がある。
(Filtering process)
Furthermore, you may provide the filtration process as needed. It does not matter whether or not the above-described particle ripening step is performed before the filtration step. By filtration, an aggregate of silica particles larger than a predetermined average particle diameter can be separated. If aggregates larger than the predetermined average particle size remain at this time, there is a possibility that calcined silica particles that are difficult to disintegrate are generated by the calcining in the calcining step.
[精製工程]
本発明の製造法においては、前述した分散液調製工程と後述する乾燥工程との間に、調製したシリカ粒子分散液から、反応が不十分な含珪素化合物を分離除去する精製工程を備えていることが好ましい。これにより、乾燥工程、焼成工程におけるシリカ粒子同士の融着、すなわちネック部の生成及び成長の促進を抑制して、より分散性に優れ均一なシリカ粒子の製造が可能となる。分散液中の含珪素化合物を分離除去する方法としては、含珪素化合物を分離除去できるものであれば特に限定されるものではなく、イオン交換樹脂を用いた処理、イオン交換膜を用いた処理、限外膜を用いた濾過、遠心機を用いた分離、デカンテーション等を例示することができ、これらの中でも、イオン成分の交換と共に吸着等の分離除去作用を期待できるイオン交換樹脂を用いた処理が好ましい。含珪素化合物は、陰イオン交換樹脂を用いて分離することができるが、更に陽イオン樹脂を用いることにより、ナトリウムイオン等を除去することができることから、双方のイオン交換樹脂を用いて分離除去することが好ましい。
[Purification process]
The production method of the present invention includes a purification step for separating and removing a silicon-containing compound with insufficient reaction from the prepared silica particle dispersion between the dispersion preparation step described above and the drying step described later. It is preferable. Thereby, fusion of the silica particles in the drying step and the firing step, that is, generation of a neck portion and promotion of growth can be suppressed, and uniform silica particles having excellent dispersibility can be produced. The method for separating and removing the silicon-containing compound in the dispersion is not particularly limited as long as it can separate and remove the silicon-containing compound. The treatment using an ion exchange resin, the treatment using an ion exchange membrane, Examples include filtration using an ultra-membrane, separation using a centrifuge, decantation, etc. Among these, treatment using an ion exchange resin that can be expected to have separation and removal effects such as adsorption as well as exchange of ion components Is preferred. The silicon-containing compound can be separated using an anion exchange resin, but sodium ions and the like can be removed by using a cation resin. It is preferable.
陰イオン交換樹脂としてOH型陰イオン交換樹脂を用いることが好ましく、ビーズ状、繊維状等、その形態は問わない。また、処理方法としては、分散液中にイオン交換樹脂を投入してバッチ方式で処理する方法や、カラムにイオン交換樹脂を充填して通液する方法等、従来公知の方法を用いることができる。
陽イオン交換樹脂としてH型陽イオン交換樹脂を用いることが好ましく、ビーズ状、繊維状等、その形態は問わない。また、上記同様、処理方法としては、分散液中にイオン交換樹脂を投入してバッチ方式で処理する方法や、カラムにイオン交換樹脂を充填して通液する方法等、従来公知の方法を用いることができる。
陽イオン交換樹脂と陰イオン交換樹脂の処理を交互に複数回行うことにより、含珪素化合物及びナトリウムイオン等のアルカリ成分をより効果的に分離除去することができ、シリカ粒子同士の融着をより抑制することが可能となる。
It is preferable to use an OH type anion exchange resin as the anion exchange resin, and any form such as beads or fibers may be used. In addition, as a processing method, a conventionally known method such as a method in which an ion exchange resin is introduced into a dispersion and a batch method is used, or a method in which a column is filled with an ion exchange resin and passed therethrough can be used. .
It is preferable to use an H-type cation exchange resin as the cation exchange resin, and any form such as beads or fibers may be used. Similarly to the above, as a processing method, a conventionally known method such as a method in which an ion exchange resin is introduced into a dispersion and a batch method is used, a method in which a column is filled with an ion exchange resin, and the like is used. be able to.
By alternately performing the treatment of the cation exchange resin and the anion exchange resin a plurality of times, alkali components such as silicon-containing compounds and sodium ions can be separated and removed more effectively, and the silica particles can be more fused. It becomes possible to suppress.
[水熱処理工程]
上記精製工程に続いて、又は上記精製工程を行うことなく、水熱処理を行うことが好ましい。本工程により、シリカ粒子内部に存在する反応が不十分な含珪素化合物を粒子外部(分散液中)に排出することができ、続く水熱後精製工程により、この分散液中に排出された含珪素化合物を分離除去することができることから、焼成時のシリカ粒子同士の融着を抑制できることができる。すなわち、シリカ粒子内部に反応が不十分な含珪素化合物が残存していると、乾燥の際、含珪素化合物が粒子表面に出現し、かかる含珪素化合物が、シリカ粒子同士の融着、すなわちネック部の生成及び成長を促進させると考えられるが(図1参照)、これを抑制することができる。
[Hydrothermal treatment process]
It is preferable to perform the hydrothermal treatment subsequent to the purification step or without performing the purification step. By this step, the silicon-containing compound with insufficient reaction existing inside the silica particles can be discharged to the outside of the particles (in the dispersion), and the hydrothermal post-purification step includes the silicon-containing compound discharged into this dispersion. Since the silicon compound can be separated and removed, the fusion of the silica particles during firing can be suppressed. That is, if a silicon-containing compound with insufficient reaction remains in the silica particles, the silicon-containing compound appears on the particle surface during drying, and the silicon-containing compound is fused between the silica particles, that is, the neck Although it is thought that the production | generation and growth of a part are promoted (refer FIG. 1), this can be suppressed.
また、本工程においては、シリカ粒子内部に存在する反応が不十分な含珪素化合物と同時に、シリカ粒子表面に存在(付着)している反応が不十分な含珪素化合物も分散液中に排出することができると考えられ、次工程の水熱後精製工程で、これも同時に分離除去されることから、焼成時のシリカ粒子同士の融着をより抑制することができる。また、もともとシリカ粒子外部(分散液中)に存在する反応が不十分な含珪素化合物も、次工程の水熱後精製工程で同時に分離除去することができることから、これによってもシリカ粒子同士の融着を抑制することができる。更に、ナトリウムイオン等のアルカリ成分も、焼成時のシリカ粒子同士の融着を促進させる原因となるが、このアルカリ成分も同時にシリカ粒子内部から排出することができると考えられ、これを次工程の水熱後精製工程で取り除くことにより、シリカ粒子同士の融着をより効果的に抑制することができる。 In addition, in this step, the silicon-containing compound present in the silica particles and the insufficiently-reacted silicon-containing compound present (attached) on the surface of the silica particles is also discharged into the dispersion. This is considered to be possible, and in the subsequent post-hydrothermal purification step, this is also separated and removed at the same time, so that the fusion of the silica particles during firing can be further suppressed. In addition, since the silicon-containing compound which is originally present outside the silica particles (in the dispersion) and has insufficient reaction can be separated and removed at the same time in the subsequent hydrothermal purification step, it is also possible to melt the silica particles. Wear can be suppressed. Furthermore, although alkali components such as sodium ions also cause the fusion of silica particles during firing, it is considered that this alkali component can also be discharged from the inside of the silica particles at the same time. By removing in the post-hydrothermal purification step, the fusion of the silica particles can be more effectively suppressed.
本工程における水熱処理条件としては、シリカ粒子内部に存在する反応が不十分な含珪素化合物を粒子外部に排出することができる条件であれば特に制限されるものではなく、バッチ式で行っても、連続式で行ってもよい。温度としては、100℃を超えて300℃以下であることが好ましく、150〜250℃であることがより好ましい。圧力は、通常、各処理温度での飽和圧力であり、更に加圧してもよい。また、処理時間としては、1〜24時間であることが好ましく、3〜15時間であることがより好ましい。これらの条件で水熱処理を行うことにより、シリカ粒子内部に存在する反応が不十分な含珪素化合物をより効果的に粒子外部に排出することができる。 The hydrothermal treatment conditions in this step are not particularly limited as long as the silicon-containing compound with insufficient reaction existing inside the silica particles can be discharged to the outside of the particles. You may carry out by a continuous type. As temperature, it is preferable that it is 300 degreeC or less exceeding 100 degreeC, and it is more preferable that it is 150-250 degreeC. The pressure is usually a saturation pressure at each processing temperature, and may be further pressurized. Moreover, as processing time, it is preferable that it is 1 to 24 hours, and it is more preferable that it is 3 to 15 hours. By performing hydrothermal treatment under these conditions, a silicon-containing compound with insufficient reaction existing inside the silica particles can be more effectively discharged to the outside of the particles.
なお、本工程における水熱処理は、前述の粒子熟成処理を兼ねることができ、この場合、熟成工程を省略して、より効率的にシリカ粒子の製造を行うことが可能となる。すなわち、この場合、分散液調製工程は、種粒子調製工程と、粒子成長工程とを具備し、粒子熟成工程を具備しない工程となる。 The hydrothermal treatment in this step can also serve as the above-described particle ripening treatment, and in this case, the ripening step can be omitted and silica particles can be produced more efficiently. That is, in this case, the dispersion preparation step includes a seed particle preparation step and a particle growth step, and does not include a particle ripening step.
[水熱後精製工程]
本工程は、上記水熱処理工程で、シリカ粒子内部から分散液中に排出された含珪素化合物を取り除く工程であり、本発明においては、水熱処理工程と共に行われる工程である。すなわち、本工程を行わない場合(反応が不十分な含珪素化合物を分離除去しない場合)、分散液中に残った反応が不十分な含珪素化合物により、続く乾燥工程において、シリカ粒子同士の融着を促進させることとなり、結果としてシリカ粒子の凝集をもたらすこととなる。
[Post-hydrothermal purification process]
This step is a step of removing the silicon-containing compound discharged from the inside of the silica particles into the dispersion in the hydrothermal treatment step, and in the present invention, this step is performed together with the hydrothermal treatment step. That is, when this step is not performed (when a silicon-containing compound with insufficient reaction is not separated and removed), a silica-containing compound with insufficient reaction remaining in the dispersion liquid causes the silica particles to melt in the subsequent drying step. Adhesion is promoted, resulting in agglomeration of silica particles.
本工程における含珪素化合物を分離除去する方法としては、含珪素化合物を分離除去できるものであれば特に限定されるものではなく、イオン交換樹脂を用いた処理、イオン交換膜を用いた処理、限外膜を用いた濾過、遠心機を用いた分離、デカンテーション等を例示することができ、これらの中でも、イオン成分の交換と共に吸着等の分離除去作用を期待できるイオン交換樹脂を用いた処理が好ましい。含珪素化合物は、陰イオン交換樹脂を用いて分離することができるが、更に陽イオン樹脂を用いることにより、ナトリウムイオン等を除去することができることから、双方のイオン交換樹脂を用いて分離除去することが好ましい。 The method for separating and removing the silicon-containing compound in this step is not particularly limited as long as the silicon-containing compound can be separated and removed, and treatment using an ion exchange resin, treatment using an ion exchange membrane, Examples include filtration using an outer membrane, separation using a centrifuge, decantation, etc. Among these, treatment using an ion exchange resin that can be expected to have separation and removal effects such as adsorption as well as exchange of ion components preferable. The silicon-containing compound can be separated using an anion exchange resin, but sodium ions and the like can be removed by using a cation resin. It is preferable.
陰イオン交換樹脂としては、OH型陰イオン交換樹脂を用いることが好ましく、ビーズ状、繊維状等、その形態は問わない。また、処理方法としては、分散液中にイオン交換樹脂を投入してバッチ方式で処理する方法や、カラムにイオン交換樹脂を充填して通液する方法等、従来公知の方法を用いることができる。
陽イオン交換樹脂としては、H型陽イオン交換樹脂を用いることが好ましく、ビーズ状、繊維状等、その形態は問わない。また、上記同様、処理方法としては、分散液中にイオン交換樹脂を投入してバッチ方式で処理する方法や、カラムにイオン交換樹脂を充填して通液する方法等、従来公知の方法を用いることができる。
陽イオン交換樹脂と陰イオン交換樹脂の処理を交互に複数回行うことにより、含珪素化合物及びナトリウムイオン等のアルカリ成分をより効果的に分離除去することができ、シリカ粒子同士の融着をより抑制することが可能となる。
As the anion exchange resin, it is preferable to use an OH type anion exchange resin, and any form such as beads or fibers may be used. In addition, as a processing method, a conventionally known method such as a method in which an ion exchange resin is introduced into a dispersion and a batch method is used, or a method in which a column is filled with an ion exchange resin and passed therethrough can be used. .
As the cation exchange resin, it is preferable to use an H-type cation exchange resin, and the form thereof may be any shape such as beads or fibers. Similarly to the above, as a processing method, a conventionally known method such as a method in which an ion exchange resin is introduced into a dispersion and a batch method is used, a method in which a column is filled with an ion exchange resin, and the like is used. be able to.
By alternately performing the treatment of the cation exchange resin and the anion exchange resin a plurality of times, alkali components such as silicon-containing compounds and sodium ions can be separated and removed more effectively, and the silica particles can be more fused. It becomes possible to suppress.
[噴霧乾燥工程]
次に、水熱処理、及び反応が不十分な含珪素化合物の分離除去処理が行われたシリカ分散液の乾燥を行う。乾燥方法としては、シリカ分散液(C液)を噴霧乾燥する方法が好ましい。噴霧乾燥シリカ粒子(噴霧乾燥により得られる造粒粒子であり、シリカ粒子の均一な集合体粒子)の平均粒子径は1〜100μmが適している。特に、1〜70μmの範囲が好ましい。噴霧乾燥シリカ粒子の平均粒子径が1μm未満の場合は、流動性が低く、焼成工程で均一に焼成できないことがある。その場合、解砕工程の処理条件によっては、元の粒子径になるように解砕できない虞がある。噴霧乾燥シリカ粒子の平均粒子径が100μmを超えると、粒子が大きすぎて解砕工程で元の粒子径になるまで解砕できない虞がある。できたとしても長時間の解砕を要する。また、吸湿性の低い、樹脂への分散性に優れた解砕シリカ粒子を得ることが困難となる。
また、噴霧乾燥シリカ粒子の水分含有量は0.01〜10質量%が適している。特に、0.1〜7質量%の範囲が好ましい。水分含有量を0.01質量%未満とすることは困難であり、できたとしても噴霧乾燥工程で静電気による凝集が起き、これをこのまま焼成したのでは、解砕工程で元の粒子径になるまで解砕できないことがある。また、水分含有量が10質量%を超えると、焼成工程で融着が促進され、解砕工程で元の粒子径になるまで解砕できないことがある。
[Spray drying process]
Next, the silica dispersion that has been subjected to hydrothermal treatment and separation and removal treatment of the silicon-containing compound with insufficient reaction is dried. As a drying method, a method of spray-drying a silica dispersion (liquid C) is preferable. The average particle size of spray-dried silica particles (granulated particles obtained by spray-drying and uniform aggregate particles of silica particles) is suitably 1 to 100 μm. The range of 1-70 micrometers is especially preferable. When the average particle diameter of the spray-dried silica particles is less than 1 μm, the fluidity is low, and it may not be possible to perform uniform firing in the firing step. In that case, depending on the processing conditions of the crushing step, there is a possibility that the crushing cannot be performed to the original particle size. If the average particle size of the spray-dried silica particles exceeds 100 μm, the particles may be too large to be crushed until the original particle size is obtained in the crushing step. Even if it can, it takes a long time to disintegrate. In addition, it becomes difficult to obtain crushed silica particles having low hygroscopicity and excellent dispersibility in the resin.
Moreover, 0.01-10 mass% is suitable for the water content of the spray-dried silica particle. In particular, the range of 0.1 to 7% by mass is preferable. It is difficult to reduce the water content to less than 0.01% by mass, and even if it can be done, agglomeration due to static electricity occurs in the spray drying process, and if this is baked as it is, the original particle size is obtained in the crushing process. May not be crushed. On the other hand, if the water content exceeds 10% by mass, fusion may be promoted in the firing step, and it may not be pulverized until the original particle size is obtained in the pulverization step.
噴霧乾燥方法としては、後述する解砕シリカ粒子が結果的に得られれば特に制限はないが、回転ディスク法、加圧ノズル法、2流体ノズル法等、従来の方法を採用できる。特に、2流体ノズル法が好適である。
噴霧乾燥における熱風の温度は、出口温度で120〜300℃が適している。特に、130〜250℃が好ましい。入口温度にも依るが、出口温度が120℃未満の場合、未乾燥粒子が得られたり、造粒粒子が緻密になるため、これらの造粒粒子を焼成すると、粒子の接点数が増加し合着が起きやすいので、結果として融着が起きやすくなる。解砕工程を用いても、融着した粒子を均一に解砕することは困難である。また、出口温度が300℃を越える場合には、造粒粒子の水分は少なくなるものの、焼成工程で融着する粒子が増大する。そのため、全ての融着粒子を解砕することは難しい。
噴霧乾燥に用いるシリカ分散液の濃度は1〜40質量%が適している。特に、10〜30質量%の範囲が好ましい。シリカ分散液の濃度が1質量%未満だと、生産性が低下するだけでなく、得られる粒子(造粒粒子)の粒子径が小さくなる。即ち、シリカ粒子の集合数の少ないシリカ分散液(造粒粒子)となるため、流動性が低下し、焼成工程で均一に焼成できないことがある。その場合に、解砕工程の処理条件によっては、元の粒子径になるように解砕できない虞がある。一方、シリカ分散液の濃度が40質量%を超えると、分散液の安定性が低下するため、シリカ粒子の均一な集合体粒子が得られ難い。そのため、焼成工程で均一な焼成ができず、解砕工程の処理条件によっては、元の粒子径になるように解砕できない虞がある。
The spray drying method is not particularly limited as long as crushed silica particles to be described later can be obtained as a result, but conventional methods such as a rotating disk method, a pressurized nozzle method, and a two-fluid nozzle method can be employed. In particular, the two-fluid nozzle method is suitable.
The temperature of hot air in spray drying is suitably 120 to 300 ° C. at the outlet temperature. In particular, 130-250 degreeC is preferable. Although it depends on the inlet temperature, when the outlet temperature is less than 120 ° C, undried particles are obtained or the granulated particles become dense. Since wearing tends to occur, fusion is likely to occur as a result. Even if the crushing step is used, it is difficult to uniformly crush the fused particles. On the other hand, when the outlet temperature exceeds 300 ° C., the water content of the granulated particles decreases, but the number of particles fused in the firing process increases. Therefore, it is difficult to crush all the fused particles.
The concentration of the silica dispersion used for spray drying is suitably 1 to 40% by mass. The range of 10 to 30% by mass is particularly preferable. When the concentration of the silica dispersion is less than 1% by mass, not only the productivity is lowered, but also the particle diameter of the obtained particles (granulated particles) is reduced. That is, since it becomes a silica dispersion (granulated particles) with a small number of aggregated silica particles, the fluidity is lowered, and it may not be uniformly fired in the firing step. In that case, depending on the processing conditions of the crushing step, there is a possibility that the crushing cannot be performed to the original particle size. On the other hand, when the concentration of the silica dispersion exceeds 40% by mass, the stability of the dispersion decreases, and it is difficult to obtain uniform aggregate particles of silica particles. Therefore, uniform firing cannot be performed in the firing step, and depending on the processing conditions of the crushing step, there is a possibility that the original particle size cannot be crushed.
[焼成工程]
焼成工程では、乾燥工程で乾燥されたシリカ粒子を好ましくは600〜1200℃で焼成し焼成シリカ粒子10を得る(図1参照)。得られた焼成シリカ粒子10は、通常、例えば2個のシリカ粒子(一次粒子)11がネック部12で融着しており、更に、これらが凝集して集合体粒子(図示せず)となる。しかしながら、本発明の製造方法においては、水熱処理等を施していることから、ネック部12の生成及び成長が抑制され、生成したネック部12の分離面14も非常に小さいものとなっている。ここで、焼成温度が600℃未満の場合は、得られる粒子(焼成シリカ粒子)の緻密化が充分に進んでおらず吸湿性が高くなる傾向にあり、一方、焼成温度が1200℃を超える場合は、シリカ粒子の集合体粒子が焼結し易いので、解砕工程で元の粒子径になるまで解砕すること、すなわち、一次粒子とすることが困難となる傾向にある。通常、焼成は空気雰囲気で行えるが、焼成後に冷却する際には、露点が0℃以下のガス雰囲気にすることが結露に伴う吸湿を抑制する観点から好ましい。露点−10℃以下のガス雰囲気が更に好ましい。
[Baking process]
In the firing step, the silica particles dried in the drying step are preferably fired at 600 to 1200 ° C. to obtain the fired silica particles 10 (see FIG. 1). In the obtained fired silica particles 10, for example, two silica particles (primary particles) 11 are usually fused at the neck portion 12, and these are aggregated to form aggregate particles (not shown). . However, in the manufacturing method of the present invention, since the hydrothermal treatment or the like is performed, the generation and growth of the neck portion 12 are suppressed, and the separation surface 14 of the generated neck portion 12 is very small. Here, when the calcination temperature is less than 600 ° C., the resulting particles (calcined silica particles) are not sufficiently densified and the hygroscopicity tends to increase, whereas the calcination temperature exceeds 1200 ° C. Since the aggregate particles of silica particles are easily sintered, it tends to be difficult to crush until the original particle size is obtained in the crushing step, that is, to make primary particles. Usually, firing can be performed in an air atmosphere, but when cooling after firing, it is preferable to use a gas atmosphere having a dew point of 0 ° C. or less from the viewpoint of suppressing moisture absorption due to condensation. A gas atmosphere having a dew point of −10 ° C. or lower is more preferable.
本発明において、水熱処理工程を備えている場合、シリカ粒子の緻密化が進んでおり、焼成温度を低くすることができる。例えば、800℃以上1000℃未満であっても吸湿性の極めて低い高品質のシリカ粒子を製造することができる。 In the present invention, when the hydrothermal treatment step is provided, the densification of the silica particles has progressed, and the firing temperature can be lowered. For example, even when the temperature is 800 ° C. or higher and lower than 1000 ° C., high-quality silica particles having extremely low hygroscopicity can be produced.
[解砕工程]
続く解砕工程では、焼成工程において凝集したシリカ粒子の集合体を分離し、一次粒子径に分散されたシリカ粒子とする。解砕処理は、ボールミルやハンマーミル等の従来公知の粉砕装置を用いて行うこともできるが、解砕用容器内に導入するガスによって旋回流を発生させ、旋回流中に焼成シリカ粒子を供給し、焼成シリカ粒子を解砕する方法が好ましい。例えば、解砕用容器内に亜音速以上のガスをノズルから導入して亜音速以上の旋回流を発生させ、この均一旋回流中に焼成工程で得られた焼成シリカ粒子10を固気比(固体(g/Hr)/気体(m3/Hr))が4.4〜36.3g/m3、好ましくは、6.6〜30.3g/m3の範囲内となるように供給する。これにより、焼成シリカ粒子の集合体粒子が焼成前のシリカ粒子の粒子径になるまで、粒子が破壊されることなく解砕される。これにより、解砕シリカ粒子が得られる。
ここで、図1に示すように、焼成シリカ粒子10の集合体粒子を均一旋回流に供給して解砕すると、集合体粒子同士の接触により、集合体粒子の接触部分が分離して焼成シリカ粒子10が得られる。更に、焼成シリカ粒子10の融着部分であるネック部12が開裂し、一次粒子径に分散された解砕シリカ粒子13が得られる。
[Crushing process]
In the subsequent crushing step, the aggregate of the silica particles aggregated in the firing step is separated to obtain silica particles dispersed in the primary particle size. The crushing treatment can be performed using a conventionally known crushing device such as a ball mill or a hammer mill, but a swirling flow is generated by the gas introduced into the crushing vessel, and calcined silica particles are supplied into the swirling flow. A method of crushing the fired silica particles is preferable. For example, a gas having a subsonic speed or higher is introduced from a nozzle into a crushing container to generate a swirling flow having a subsonic speed or higher, and the solid-gas ratio ( The solid (g / Hr) / gas (m 3 / Hr)) is supplied in a range of 4.4 to 36.3 g / m 3 , preferably 6.6 to 30.3 g / m 3 . Thus, the particles are crushed without being destroyed until the aggregated particles of the fired silica particles have the particle diameter of the silica particles before firing. Thereby, crushed silica particles are obtained.
Here, as shown in FIG. 1, when the aggregate particles of the fired silica particles 10 are supplied to a uniform swirl flow and crushed, the contact portions of the aggregate particles are separated by the contact between the aggregate particles, and the fired silica is separated. Particles 10 are obtained. Furthermore, the neck part 12 which is the fused part of the fired silica particles 10 is cleaved, and the crushed silica particles 13 dispersed in the primary particle diameter are obtained.
上述の均一な旋回流を用いた解砕によって得られる解砕シリカ粒子13は、粒子同士の衝突等ではなく旋回流中の剪断により解砕されるので、粒子の破壊面が発生し難い。また、ネック部12で開裂した際に生じる分離面14は、解砕される力で活性面となっても、破壊面に比べて面積が小さい。そのため、旋回流中の解砕は粒子表面の親水性と疎水性は制御され、吸湿性が低く、凝集体が発生し難く、分散性に優れた解砕シリカ粒子13が得られ易い。 The crushed silica particles 13 obtained by pulverization using the above-described uniform swirl flow are crushed not by collision between particles but by shear in the swirl flow, so that a particle fracture surface is unlikely to occur. Moreover, even if the separation surface 14 generated when cleaving at the neck portion 12 becomes an active surface due to the crushing force, the area is smaller than the fracture surface. Therefore, in the crushing in the swirling flow, the hydrophilicity and hydrophobicity of the particle surface are controlled, the hygroscopicity is low, the aggregates are hardly generated, and the crushed silica particles 13 excellent in dispersibility are easily obtained.
更に、本発明の製造方法においては、水熱処理等を施していることから、ネック部12の成長が抑制されており、ネック部12の分離面14は非常に小さいものとなっており、吸湿性が低く、凝集体が発生し難く、分散性に優れた解砕シリカ粒子13がより得られ易い。 Furthermore, in the manufacturing method of the present invention, since the hydrothermal treatment or the like is performed, the growth of the neck portion 12 is suppressed, and the separation surface 14 of the neck portion 12 is very small, and is hygroscopic. The crushed silica particles 13 having a low particle size, hardly generating aggregates, and having excellent dispersibility are more easily obtained.
ここで、導入ガスとしては、空気、酸素ガス、不活性ガス等を用いることができる。安全性や経済性の観点から空気が推奨される。更に、解砕用容器に導入するガスの露点は0℃以下が好ましい。ガスの露点が0℃を超えていると、解砕により解砕シリカ粒子に現れた活性表面に、水分に依るシラノール基が生成し易くなるからである。シラノール基を持つ解砕シリカ粒子が配合された樹脂組成物から得られる硬化物は、長時間外気に触れると吸湿し、充分な信頼性が得られない。このような理由から、導入ガスの露点は−10℃以下が好ましく、−20℃以下がより好ましい。露点が0℃以下の導入ガスは、圧縮ガス、エアドライヤー、あるいは吸着剤による吸着除去法等の、公知の方法で調製することができる。解砕時の温度は、結露しない範囲であれば、制限はない。
更に、導入ガスの圧力は0.1〜1.5MPaの範囲にあることが好ましい。導入ガスの圧力が0.1MPa未満の場合は、ガスの旋回速度が足りず、解砕が不充分となる場合がある。導入ガスの圧力が1.5MPaを超えると、集合体粒子の解砕にとどまらず、粒子同士の衝突が増えて、粒子が破壊する虞がある。したがって、高圧側を抑えた0.1〜1.0MPaの範囲がより好ましい。また、膨張潜熱によるジュール・トムソン効果により局部的に低温となり、粒子の活性表面から水分を吸着することがある。このように、導入ガスの圧力が適正でないと、吸湿性の低い、樹脂への分散性に優れた解砕シリカ粒子を得ることが困難となる。
また、導入ガスの線速は、亜音速以上が好ましく、遷音速〜超音速がより好ましい。導入ガスの線速が亜音速未満であると、旋回速度が足りず解砕が不充分となる場合がある。また、超音速を超えると、集合体粒子の解砕にとどまらず、粒子同士の衝突が増えて粒子が破壊する虞がある。なお、導入ガスの見掛けの線速は、導入ガスの圧力から算出することができる。
Here, air, oxygen gas, inert gas, etc. can be used as introduction gas. Air is recommended for safety and economic reasons. Furthermore, the dew point of the gas introduced into the crushing container is preferably 0 ° C. or less. This is because if the dew point of the gas exceeds 0 ° C., silanol groups due to moisture are easily generated on the active surface that appears on the crushed silica particles by pulverization. A cured product obtained from a resin composition in which crushed silica particles having a silanol group are blended absorbs moisture when exposed to the outside air for a long time, and sufficient reliability cannot be obtained. For these reasons, the dew point of the introduced gas is preferably −10 ° C. or lower, and more preferably −20 ° C. or lower. The introduced gas having a dew point of 0 ° C. or lower can be prepared by a known method such as a compressed gas, an air dryer, or an adsorption removal method using an adsorbent. If the temperature at the time of crushing is a range which does not condense, there will be no restriction | limiting.
Furthermore, the pressure of the introduced gas is preferably in the range of 0.1 to 1.5 MPa. When the pressure of the introduced gas is less than 0.1 MPa, the gas swirling speed is insufficient, and the crushing may be insufficient. When the pressure of the introduced gas exceeds 1.5 MPa, there is a possibility that not only the aggregate particles are crushed but also the collision between the particles increases and the particles are destroyed. Therefore, the range of 0.1-1.0 MPa which suppressed the high voltage | pressure side is more preferable. In addition, the Joule-Thomson effect caused by the latent heat of expansion may locally lower the temperature and adsorb moisture from the active surface of the particles. Thus, if the pressure of the introduced gas is not appropriate, it becomes difficult to obtain crushed silica particles having low hygroscopicity and excellent dispersibility in the resin.
The linear velocity of the introduced gas is preferably subsonic or higher, and more preferably transonic to supersonic. If the linear velocity of the introduced gas is less than the subsonic speed, the turning speed may be insufficient and the crushing may be insufficient. Further, when the supersonic speed is exceeded, not only the aggregate particles are crushed but also the collision between the particles may increase and the particles may be destroyed. Note that the apparent linear velocity of the introduced gas can be calculated from the pressure of the introduced gas.
更に、一定の粉砕チャンバー容積に対する旋回流に供給する焼成シリカ粒子と導入ガスの量比(固気比:g/m3)は、4.4〜36.3g/m3が好ましく、6.6〜30.3g/m3がより好ましい。固気比が、4.4g/m3未満であると、焼成シリカ粒子の供給量が安定しない場合があり、36.3g/m3を超えると、解砕が不充分となる場合がある。ここで、固気比は、単位時間あたりの、焼成シリカ粒子(固体)供給量と、導入ガス(気体)の風量の比(固体(g/Hr)/気体(m3/Hr))で算出することができる。なお、旋回流の流れが維持されて、粉砕チャンバー容積/固気比が維持されれば、粉砕チャンバーの大きさに制限されるものではない。 Further, the amount ratio of the calcined silica particles and introducing the gas supplied to the swirling flow for a fixed grinding chamber volume (solid-gas ratio: g / m 3) is preferably from 4.4~36.3g / m 3, 6.6 ˜30.3 g / m 3 is more preferable. If the solid-gas ratio is less than 4.4 g / m 3 , the supply amount of the fired silica particles may not be stable, and if it exceeds 36.3 g / m 3 , crushing may be insufficient. Here, the solid-gas ratio is calculated by the ratio of the supply amount of calcined silica particles (solid) and the flow rate of introduced gas (gas) per unit time (solid (g / Hr) / gas (m 3 / Hr)). can do. The size of the grinding chamber is not limited as long as the swirling flow is maintained and the grinding chamber volume / solid-gas ratio is maintained.
図2は本発明に好適な解砕装置を示すモデル図である。焼成シリカ粒子は解砕用容器1に設けられた導入口3から解砕用容器1内に供給される。導入口3と焼成シリカ粒子の貯留部4は一つの密閉空間5にあり、密閉空間5に導入ガスが充填されることが好ましい。また、導入ガスは複数(例えば、7個)のガス導入部2から容器内に流入する。
ここで、高圧ガスにより発生する旋回流により解砕を行う解砕装置としては、アイシンナノテクノロジーズ社製のナノジェットマイザーシリーズや、サンレックス工業株式会社製のナノグラインディングミルシリーズ等が挙げられる。
解砕用容器1内の表面の材質は炭化珪素(SiC)が適している。特に、900℃以上で焼成されたSiCを用いることが好ましい。材質がSiCである解砕用容器1を用いると、ジルコニウム(Zr)、鉄(Fe)、ウラン(U)、トリウム(Th)等の不純物を含まない解砕シリカ粒子を得ることができる。そのため、信頼性に優れた電子デバイス(半導体チップ、液晶シール材等)が実現できる。
FIG. 2 is a model diagram showing a crushing apparatus suitable for the present invention. The calcined silica particles are supplied into the crushing container 1 from the inlet 3 provided in the crushing container 1. It is preferable that the inlet 3 and the storage part 4 of the baked silica particles are in one sealed space 5 and the sealed space 5 is filled with the introduced gas. Further, the introduced gas flows into the container from a plurality of (for example, seven) gas introducing portions 2.
Here, examples of the crushing apparatus that performs crushing by the swirling flow generated by the high-pressure gas include the NanoJet Mizer series manufactured by Aisin Nano Technologies, the Nano Grinding Mill series manufactured by Sanrex Industry Co., Ltd., and the like.
Silicon carbide (SiC) is suitable for the material of the surface in the crushing container 1. In particular, it is preferable to use SiC fired at 900 ° C. or higher. When the crushing container 1 made of SiC is used, crushed silica particles that do not contain impurities such as zirconium (Zr), iron (Fe), uranium (U), and thorium (Th) can be obtained. Therefore, an electronic device (semiconductor chip, liquid crystal sealing material, etc.) excellent in reliability can be realized.
このようにして調製した解砕シリカ粒子は平均粒径が5nm〜0.95μm、更には20nm〜0.95μmの範囲にあることが好ましい。解砕シリカ粒子の平均粒径が5nm未満の場合は、樹脂への分散性が不充分となる場合がある。また、解砕シリカ粒子の平均粒径が0.95μmを超えると、集積度の高い半導体素子等に用いる場合にギャップが狭いために、充填性が低下する場合がある。
また、解砕シリカ粒子は粒子径が均一であることが好ましい。すなわち、粒子径変動係数(CV値)はより低いことが好ましい。CV値が高い粒子では、ギャップが狭い場合、注入性や充填性が低下する。粒子径変動係数(CV値)は下記の式(2)によって算出できる。
The crushed silica particles thus prepared preferably have an average particle size in the range of 5 nm to 0.95 μm, more preferably 20 nm to 0.95 μm. When the average particle size of the crushed silica particles is less than 5 nm, the dispersibility in the resin may be insufficient. On the other hand, when the average particle size of the crushed silica particles exceeds 0.95 μm, the gap may be narrow when used for a highly integrated semiconductor device or the like, which may reduce the filling property.
The crushed silica particles preferably have a uniform particle size. That is, the particle diameter variation coefficient (CV value) is preferably lower. In the case of particles having a high CV value, when the gap is narrow, the injection property and the filling property are lowered. The particle diameter variation coefficient (CV value) can be calculated by the following equation (2).
なお、粒子径変動係数(CV値)を求める際の平均粒子径は、走査型電子顕微鏡(日本電子(株)製:JSM−5300型)により写真を撮影し、この画像の250個の粒子について画像解析装置(旭化成(株)製:IP−1000)を用いて測定される。
また、解砕シリカ粒子中には平均粒子径の4倍以上の粒子径を持つ粗大粒子が存在することがあるが、この粗大粒子の割合は5質量%以下であることが好ましい。粗大粒子の割合が5重量%を超えると、樹脂への分散性が低下するとともに、樹脂組成物は粒子径によって注入性、充填性が低下する場合がある。粗大粒子の割合は2質量%以下が、より好ましい。
In addition, the average particle diameter at the time of calculating | requiring a particle diameter variation coefficient (CV value) took a photograph with the scanning electron microscope (The JEOL Co., Ltd. product: JSM-5300 type | mold), About 250 particles of this image It is measured using an image analysis device (Asahi Kasei Co., Ltd .: IP-1000).
In the crushed silica particles, coarse particles having a particle size of 4 times or more the average particle size may be present, and the proportion of the coarse particles is preferably 5% by mass or less. When the ratio of coarse particles exceeds 5% by weight, the dispersibility in the resin is lowered, and the resin composition may have poor injectability and filling properties depending on the particle diameter. The ratio of coarse particles is more preferably 2% by mass or less.
また、解砕シリカ粒子の吸湿量は0.2質量%以下であることが好ましい。解砕シリカ粒子の吸湿量が0.2質量%を超えると、樹脂への分散性が低下するとともに、粒子を配合した樹脂組成物を硬化させて得られる硬化物が吸湿しやすく、電子デバイス等の信頼性が低下する場合がある。より好ましくは、解砕シリカ粒子の吸湿量を0.1質量%以下にする。
ここでは、吸湿量を以下のように求める。質量(WD)の焼成シリカ微粒子(B1)を、温度25℃、湿度90%の環境下に暴露し、48時間経過後の質量(WH)を測定する。このとき、吸湿量Q(質量%)は下記の式(3)によって算出できる。
吸湿量Q(質量%)=((WH)−(WD))/(WD)×100・・・(3)
Further, the moisture absorption amount of the crushed silica particles is preferably 0.2% by mass or less. When the moisture absorption amount of the crushed silica particles exceeds 0.2% by mass, the dispersibility in the resin decreases, and the cured product obtained by curing the resin composition containing the particles easily absorbs moisture, such as an electronic device. Reliability may be reduced. More preferably, the moisture absorption of the crushed silica particles is 0.1% by mass or less.
Here, the amount of moisture absorption is obtained as follows. The mass (W D ) of the fired silica fine particles (B1) is exposed to an environment at a temperature of 25 ° C. and a humidity of 90%, and the mass (W H ) after 48 hours is measured. At this time, the moisture absorption Q (mass%) can be calculated by the following equation (3).
Moisture absorption Q (mass%) = ((W H ) − (W D )) / (W D ) × 100 (3)
[分級工程]
解砕工程にて得られた解砕シリカ粒子を分級装置により分級し、平均粒子径の4倍以上の粒径を持つ粗大粒子を除去し、この粗大粒子の割合を5質量%以下、好ましくは2質量%以下とすることができる。また、分級装置により、平均粒子径が所定範囲内の解砕シリカ粒子を多く得ることができる(すなわち、CV値を低くすることができる)。ここで、分級装置としては、ドナルドソン社製のドレセレック、セイシン企業社製のスピンエアシーブ、日清エンジニアリング社製のエアロファインクラシファイア、パウダーシステムズ社製のハイプレック分級機、ホソカワミクロン社製のツインターボプレックス等が使用できる。
[Classification process]
The pulverized silica particles obtained in the pulverization step are classified by a classifier to remove coarse particles having a particle size of 4 times or more of the average particle size, and the proportion of coarse particles is preferably 5% by mass or less, preferably It can be 2 mass% or less. Moreover, with the classifier, many crushed silica particles having an average particle diameter within a predetermined range can be obtained (that is, the CV value can be lowered). Here, as the classifiers, there are Donaresson made by Donaldson, Spin Air Sheave made by Seishin Enterprise, Aerofine Classifier made by Nissin Engineering, Hyprec Classifier made by Powder Systems, and Twin Turbo made by Hosokawa Micron. Plex etc. can be used.
[シリカ粒子を含む樹脂組成物の製造]
本発明の樹脂組成物の製造方法としては、上記本発明の製造方法により製造したシリカ粒子を含有させることができる方法であれば特に制限されるものではなく、従来公知の混合装置を用いて製造することができる。
樹脂は、用途によって適宜選択できる。例えば、エポキシ系樹脂、ポリイミド系樹脂、ビスマレイミド系樹脂、アクリル系樹脂、メタクリル系樹脂、シリコン系樹脂、BTレジン、シアネート系樹脂から選ばれる1種または2種以上であることが好ましい。
このような樹脂を用いると、解砕シリカ粒子が均一に分散し、得られる樹脂組成物はギャップが狭い場合であっても注入性、充填性に優れている。更に、硬化させた後も吸湿性がなく、信頼性に優れた電子デバイス等を得ることができる。
樹脂組成物中の解砕シリカ粒子の含有量は5〜75質量%、更には10〜70質量%の範囲にあることが好ましい。樹脂組成物中の解砕シリカ粒子の含有量が5質量%未満の場合は、粒子が少ないので膨張率が樹脂のみの場合と大きく変わらず、例えばバンプ周辺にクラックが発生する場合がある。樹脂組成物中の解砕シリカ粒子の含有量が75質量%を超えると樹脂組成物の粘度が高くなり、注入性、充填性、浸透性等が不充分となる場合がある。
[Production of resin composition containing silica particles]
The method for producing the resin composition of the present invention is not particularly limited as long as it can contain the silica particles produced by the production method of the present invention, and is produced using a conventionally known mixing apparatus. can do.
The resin can be appropriately selected depending on the application. For example, one or more selected from epoxy resins, polyimide resins, bismaleimide resins, acrylic resins, methacrylic resins, silicon resins, BT resins, and cyanate resins are preferable.
When such a resin is used, the crushed silica particles are uniformly dispersed, and the resulting resin composition is excellent in injectability and filling properties even when the gap is narrow. Furthermore, it is possible to obtain an electronic device or the like that is not hygroscopic even after being cured and has excellent reliability.
The content of crushed silica particles in the resin composition is preferably in the range of 5 to 75 mass%, more preferably 10 to 70 mass%. When the content of the crushed silica particles in the resin composition is less than 5% by mass, since the number of particles is small, the expansion coefficient is not significantly different from that of the resin alone, and cracks may occur around the bumps, for example. If the content of the crushed silica particles in the resin composition exceeds 75% by mass, the viscosity of the resin composition increases, and the injectability, filling property, permeability, etc. may be insufficient.
以下、実施例により本発明をより詳細に説明するが、本発明の範囲はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the scope of the present invention is not limited to this.
[実施例1]
《解砕シリカ粒子の調製》
(種粒子調製工程)
まず、水、アルコールと加水分解用触媒を加えて混合溶媒を調製した。本実施例では、水4424g、エチルアルコール(関東化学社製)3702g、及び濃度28質量%アンモニア水(関東化学社製。加水分解用触媒の一例)762gを容量2L(Lはリットルを意味する。以下同様)のガラス製反応器に入れ撹拌した。この溶液の液温を35±0.5℃に調節して、反応器にテトラエトキシシラン(多摩化学社製。含珪素化合物の一例)157.6gを一気に加えた。その後、1時間撹拌した。1時間撹拌することにより、テトラエトキシシランは加水分解・縮合し、シリカ微粒子(種粒子)の分散液(A液)が得られた。このとき、シリカ微粒子の平均粒子径は0.083μm、平均粒子径の標準偏差は0.072μmとなった。
[Example 1]
<< Preparation of crushed silica particles >>
(Seed particle preparation process)
First, a mixed solvent was prepared by adding water, alcohol and a catalyst for hydrolysis. In this example, 4424 g of water, 3702 g of ethyl alcohol (manufactured by Kanto Chemical Co., Inc.), and 762 g of ammonia water having a concentration of 28% by mass (manufactured by Kanto Chemical Co., Ltd., an example of a catalyst for hydrolysis) have a capacity of 2 L (L means liter). The same applies hereinafter) and stirred in a glass reactor. The liquid temperature of this solution was adjusted to 35 ± 0.5 ° C., and 157.6 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., an example of a silicon-containing compound) was added all at once to the reactor. Then, it stirred for 1 hour. By stirring for 1 hour, tetraethoxysilane was hydrolyzed and condensed, and a dispersion (liquid A) of silica fine particles (seed particles) was obtained. At this time, the average particle diameter of the silica fine particles was 0.083 μm, and the standard deviation of the average particle diameter was 0.072 μm.
このシリカ微粒子の分散液(A液)のpHを調整するために、28重量%アンモニア水(関東化学社製。pH調整剤の一例)1222gと水200gを加え、撹拌しながら液温を35±0.5℃に調整した。これにより、シリカ微粒子の分散液(B液)を得る。この分散液(B液)のpHは12.2で、電導度は196μS/cmであった。 In order to adjust the pH of this silica fine particle dispersion (liquid A), 1222 g of 28 wt% ammonia water (manufactured by Kanto Chemical Co., Inc., an example of a pH adjusting agent) and 200 g of water were added, and the liquid temperature was adjusted to 35 ± while stirring. Adjusted to 0.5 ° C. Thereby, a dispersion of silica fine particles (liquid B) is obtained. The pH of this dispersion (liquid B) was 12.2, and the conductivity was 196 μS / cm.
(粒子成長工程)
第一滴下装置に粒子成長用の加水分解可能な含珪素化合物としてテトラエトキシシラン9940gを入れた。第二滴下装置には、濃度8質量%アンモニア水(加水分解用触媒の一例)8820gを入れた。35±0.5℃に管理された分散液(B液)に、第一滴下装置と第二滴下装置を用いてテトラエトキシシランとアンモニア水を12時間かけて滴下した。滴下期間中にpHが11.5を下回らないようにした。また、滴下終了後のシリカ粒子の分散液(C液)の電導度は96.1μS/cmで、同様に、滴下期間中90μS/cmを下回ることはなかった。
(Particle growth process)
In the first dropping device, 9940 g of tetraethoxysilane was added as a hydrolyzable silicon-containing compound for particle growth. In the second dropping device, 8820 g of 8 mass% ammonia water (an example of a catalyst for hydrolysis) was put. Tetraethoxysilane and aqueous ammonia were added dropwise to the dispersion (liquid B) controlled at 35 ± 0.5 ° C. over 12 hours using the first dropping device and the second dropping device. The pH was kept below 11.5 during the dropping period. In addition, the conductivity of the dispersion (liquid C) of the silica particles after completion of the dropping was 96.1 μS / cm, and similarly, it did not fall below 90 μS / cm during the dropping period.
(粒子熟成工程)
滴下終了後、シリカ粒子の分散液(C液)の液温を60±0.5℃に調節し、1時間撹拌して熟成させ、シリカ粒子(A1)の分散液(D液)を調製した。このとき、シリカ粒子(A1)の平均粒子径は0.27μmであり、平均粒子径の標準偏差は0.07μmであった。また、この時の分散液のpHは11.7であった。
(Particle ripening process)
After completion of the dropping, the temperature of the silica particle dispersion (liquid C) was adjusted to 60 ± 0.5 ° C. and stirred for 1 hour to age, thereby preparing a dispersion (liquid D) of silica particles (A1). . At this time, the average particle diameter of the silica particles (A1) was 0.27 μm, and the standard deviation of the average particle diameter was 0.07 μm. Further, the pH of the dispersion at this time was 11.7.
(濾過・水置換工程)
このようにして得られたシリカ粒子(A1)の分散液(D液)を0.5μmのナイロンフィルターで濾過して、シリカ粒子の凝集粒子を除去した。更に、蒸留装置を用いて水溶媒に置換した。その後、シリカ濃度が35質量%になるまで濃縮して、シリカ粒子(A1)の分散液(D’液)を得た。このようにして得られたシリカ粒子(A1)の分散液(D’液)は、pH8.05、電気電導度106(μS/cm)であった。
(Filtration / water replacement process)
The silica particle (A1) dispersion (D liquid) thus obtained was filtered through a 0.5 μm nylon filter to remove the aggregated particles of the silica particles. Furthermore, it replaced with the water solvent using the distillation apparatus. Then, it concentrated until the silica density | concentration became 35 mass%, and obtained the dispersion liquid (D 'liquid) of the silica particle (A1). The dispersion (D ′ liquid) of silica particles (A1) thus obtained had a pH of 8.05 and an electric conductivity of 106 (μS / cm).
(精製工程)
シリカ粒子(A1)の分散液(D’液)8000gを撹拌し、その中に陽イオン交換樹脂(ローム&ハース社製:デュオライトC255LFH)を2460g投入した。投入後10分間撹拌した後、ステンレス金網(メッシュサイズ:325)を用いて樹脂を分離した。分離した状態で、続いて樹脂に押水として純水200gをかけ入れ、同様に回収した。これにより得られたシリカ粒子(A1)の分散液(E−1)7060gは、pH3.56、電気電導度35.4μS/cmであった。引き続き、シリカ粒子(A1)の分散液(E−1)中に陰イオン交換樹脂(ローム&ハース社製:デュオライトUP5000)580gを投入し10分間撹拌した後、ステンレス金網(メッシュサイズ:325)を用いて樹脂を分離した。分離した状態で、続いて樹脂に押水として純水400gをかけ入れ、同様に回収した。これにより得られたシリカ粒子(A1)の分散液(E−2)7180gは、固形分濃度32.0%、pH4.18、電気電導度5.2μS/cmであった。引き続き、このシリカ粒子(A1)の分散液(E−2)6240gを撹拌し、その中に陽イオン交換樹脂(ローム&ハース社製:デュオライトC255LFH)120g投入した。投入後10分間撹拌した後、ステンレス金網(メッシュサイズ:325)を用いて樹脂を分離した。これにより得られたシリカ粒子(A1)の分散液(E−3)6160gは、固形分濃度32.0%、pH3.92、電気電導度11.8μS/cmであった。引き続き、このシリカ粒子(A1)の分散液(E−3)5340gを撹拌し、その中に陰イオン交換樹脂(ローム&ハース社製:デュオライトUP5000)100gを投入した。投入後10分間撹拌した後、ステンレス金網(メッシュサイズ:325)を用いて樹脂を分離した。これにより得られたシリカ粒子(A1)の分散液(E液)5340gは、固形分濃度32.0%、pH4.07、電気電導度7.81μS/cmであった。
《反応が不十分な含珪素化合物含有量の測定》
シリカ粒子分散液(E液)を十分に遠心機で処理し、目的のシリカ粒子を沈降させ、上澄みを分取した。その上澄みを弗化水素酸、硫酸、硝酸の順で前処理した後、硝酸に溶解させ、ICP質量分析装置(Agilent製:型式Agilent 7500S)を用いてSiを定量し、目的のシリカ粒子以外の含珪素化合物量を測定した(表2参照)。
(Purification process)
8000 g of a dispersion (D ′ solution) of silica particles (A1) was stirred, and 2460 g of a cation exchange resin (Rohm & Haas Co., Ltd .: Duolite C255LFH) was charged therein. After stirring for 10 minutes, the resin was separated using a stainless wire mesh (mesh size: 325). In a separated state, 200 g of pure water was subsequently poured into the resin as water to be recovered in the same manner. The resulting dispersion (E-1) 7060 g of silica particles (A1) had a pH of 3.56 and an electrical conductivity of 35.4 μS / cm. Subsequently, 580 g of an anion exchange resin (Rohm & Haas: Duolite UP5000) was added to the dispersion (E-1) of silica particles (A1) and stirred for 10 minutes, and then a stainless wire mesh (mesh size: 325). Was used to separate the resin. In a separated state, 400 g of pure water was subsequently poured into the resin as water to be recovered in the same manner. 7180 g of the dispersion (E-2) of silica particles (A1) thus obtained had a solid content concentration of 32.0%, a pH of 4.18, and an electric conductivity of 5.2 μS / cm. Subsequently, 6240 g of the dispersion (E-2) of the silica particles (A1) was stirred, and 120 g of a cation exchange resin (Rohm & Haas: Duolite C255LFH) was added thereto. After stirring for 10 minutes, the resin was separated using a stainless wire mesh (mesh size: 325). 6160 g of the dispersion (E-3) of silica particles (A1) obtained in this manner had a solid content concentration of 32.0%, a pH of 3.92, and an electric conductivity of 11.8 μS / cm. Subsequently, 5340 g of the dispersion (E-3) of silica particles (A1) was stirred, and 100 g of an anion exchange resin (Rohm & Haas: Duolite UP5000) was charged therein. After stirring for 10 minutes, the resin was separated using a stainless wire mesh (mesh size: 325). As a result, 5340 g of a dispersion (liquid E) of silica particles (A1) obtained as described above had a solid content concentration of 32.0%, pH 4.07, and electric conductivity of 7.81 μS / cm.
<Measurement of content of silicon-containing compound with insufficient reaction>
The silica particle dispersion (liquid E) was sufficiently treated with a centrifuge to precipitate the target silica particles, and the supernatant was collected. The supernatant was pretreated in the order of hydrofluoric acid, sulfuric acid, and nitric acid, dissolved in nitric acid, and Si was quantified using an ICP mass spectrometer (manufactured by Agilent: Model Agilent 7500S). The amount of silicon-containing compound was measured (see Table 2).
(噴霧乾燥工程)
シリカ粒子(A1)の分散液(E液)を、噴霧乾燥装置(大川原化工機株式会社製:FOC−25型。スプレードライヤ)を用いて噴霧乾燥してシリカ粉体(噴霧乾燥シリカ粒子)を造粒した。このとき、噴霧乾燥装置の入口温度を250℃、出口温度を150℃とした。シリカ粉体の水分含有量は7質量%である。シリカ粉体を構成するシリカ粒子(A1)の平均粒子径を測定した(表1参照)。
(Spray drying process)
The silica particle (A1) dispersion (liquid E) is spray-dried using a spray dryer (Okawara Koki Co., Ltd .: FOC-25 type, spray dryer) to obtain silica powder (spray-dried silica particles). Granulated. At this time, the inlet temperature of the spray dryer was 250 ° C. and the outlet temperature was 150 ° C. The water content of the silica powder is 7% by mass. The average particle diameter of the silica particles (A1) constituting the silica powder was measured (see Table 1).
(焼成工程)
次に、シリカ粉体を炭化珪素(SiC)製のるつぼ(焼成用容器)に入れ、電気炉を用いて900℃で10時間焼成した。これを冷却して焼成シリカ粒子が得られた。
(Baking process)
Next, the silica powder was put into a crucible made of silicon carbide (SiC) (baking container) and fired at 900 ° C. for 10 hours using an electric furnace. This was cooled to obtain calcined silica particles.
《圧縮破壊強度の測定》
シリカ粒子同士の融着の程度を評価するため、島津製作所製微小圧縮試験機(MCT−W500)を用い、焼成したシリカ粒子(解砕前)の圧縮破壊強度を測定した(表2参照)。
<Measurement of compressive fracture strength>
In order to evaluate the degree of fusion between silica particles, the compression fracture strength of the fired silica particles (before pulverization) was measured using a micro compression tester (MCT-W500) manufactured by Shimadzu Corporation (see Table 2).
(解砕工程)
続いて、この焼成シリカ粒子を、高圧ガスによる旋回流が発生している解砕装置(アイシンナノテクノロジーズ社製:ナノジェットマイザーNJ−100)に投入して、焼成シリカ粒子を解砕し、解砕シリカ粒子(B1)を得た。このとき、高圧ガスとして、エアドライヤーにより圧力が1.0MPaの場合に露点−10℃に制御された乾燥空気を用いた。また、焼成シリカ粒子の導入口を密閉するように囲いを設けた。そこへ露点−10℃の乾燥空気が導入される。露点が−10℃の環境から焼成シリカ粒子を供給し、焼成シリカ粒子とともに導入される乾燥空気も露点−10℃の空気とした。
(Crushing process)
Subsequently, the calcined silica particles are introduced into a crushing apparatus (Aisin Nano Technologies, Inc .: NanoJet Mizer NJ-100) in which a swirling flow is generated by high-pressure gas, and the calcined silica particles are crushed and disintegrated. Crushed silica particles (B1) were obtained. At this time, as the high-pressure gas, dry air controlled at a dew point of −10 ° C. when the pressure was 1.0 MPa by an air dryer was used. Moreover, the enclosure was provided so that the inlet of the baked silica particle might be sealed. There, dry air having a dew point of −10 ° C. is introduced. The calcined silica particles were supplied from an environment having a dew point of −10 ° C., and the dry air introduced together with the calcined silica particles was also air having a dew point of −10 ° C.
本装置の運転条件は、解砕圧力(解砕部における旋回流空気圧)を0.85MPa、焼成シリカ粒子の導入部における圧力を1.0MPa、原料の導入速度を5kg/Hr、旋回流の速度(線速)を391m/s、固気比を22.6g/m3と設定した。 The operating conditions of the apparatus are as follows: the crushing pressure (swirl air pressure in the crushing part) is 0.85 MPa, the pressure in the introduction part of the calcined silica particles is 1.0 MPa, the raw material introduction speed is 5 kg / Hr, and the speed of the swirl flow (Linear speed) was set to 391 m / s, and the solid-gas ratio was set to 22.6 g / m 3 .
得られた解砕シリカ粒子(B1)について、平均粒子径、粒子径変動係数(CV値)を測定した(表2参照)。更に、以下のように、粗大粒子の含有量、吸湿性(吸着水量)、不純物(Fe、Zr、U、Th)含有量を測定した(表2参照)。 About the obtained crushed silica particles (B1), the average particle size and the particle size variation coefficient (CV value) were measured (see Table 2). Furthermore, the content of coarse particles, hygroscopicity (adsorption water amount), and impurity (Fe, Zr, U, Th) content were measured as follows (see Table 2).
《粗大粒子の測定》
平均粒子径を測定する際に、粒子径の大きな粒子の分布が観察された場合、平均粒子径の4倍以上の粒子の割合(重量割合)を求め粗大粒子の含有量とした(表2参照)。
《吸湿性の測定》
解砕シリカ粒子(B1)を、温度25℃、湿度90%の環境下に暴露し、48時間経過後の質量(WH)を測定し、解砕シリカ粒子の質量(WD)からの増加量((WH)−(WD))を(WD)で除して吸着水分量Q(質量%)を下記(3)式より求めた(表2参照)。
Q=((WH)−(WD))/(WD)×100(%)・・・(3)
《不純物含有量の測定》
解砕シリカ粒子(B1)を硫酸・硝酸・弗化水素酸で前処理した後、硝酸に溶解させ、ICP質量分析装置(Agilent製:型式Agilent 7500S)を用いて不純物含有量を測定した(表2参照)。
<Measurement of coarse particles>
When the average particle size is measured, if a distribution of particles having a large particle size is observed, the ratio (weight ratio) of the particles 4 times or more the average particle size is obtained and used as the content of coarse particles (see Table 2). ).
<Measurement of hygroscopicity>
The crushed silica particles (B1) are exposed to an environment of a temperature of 25 ° C. and a humidity of 90%, the mass (W H ) after 48 hours is measured, and the increase from the mass (W D ) of the crushed silica particles The amount ((W H ) − (W D )) was divided by (W D ) to determine the amount of adsorbed moisture Q (mass%) from the following equation (3) (see Table 2).
Q = ((W H ) − (W D )) / (W D ) × 100 (%) (3)
<Measurement of impurity content>
The crushed silica particles (B1) were pretreated with sulfuric acid / nitric acid / hydrofluoric acid, dissolved in nitric acid, and the impurity content was measured using an ICP mass spectrometer (manufactured by Agilent: Model Agilent 7500S) (Table). 2).
以上のように製造されたシリカ粒子を樹脂に含有させて樹脂組成物を製造し、分散性、濾過性、注入性についての評価を行った。 The silica particles produced as described above were contained in a resin to produce a resin composition, and the dispersibility, filterability, and injectability were evaluated.
《分散性の評価》
次のように、樹脂組成物を作製し、分散性を評価した。エポキシアクリレート樹脂(共栄社化学(株)製:3000A)とエポキシアクリレート樹脂(共栄社化学(株)製:M600A)を重量比85:15で混合した樹脂25.5gに、解砕シリカ粒子(B1)4.5gを混合し、自転・公転ミキサー(シンキー社製:あわとり練太郎AR−100)を用いて、2000rpmで10分間混練した。次いで、三本ロールミル(EXAKT社製:EXAKT50)に1回通過させて樹脂組成物(ペースト1)を作製した。樹脂組成物について、以下の基準で分散性を評価した(表2参照)。
微細な粒子凝集体が全く認められない。 : ◎
微細な粒子凝集体が殆ど認められない。 : ○
微細な粒子凝集体が僅かに認められる。 : △
比較的大きな粒子凝集体が認められる。 : ×
<Evaluation of dispersibility>
Resin compositions were prepared and evaluated for dispersibility as follows. To 25.5 g of a resin prepared by mixing an epoxy acrylate resin (manufactured by Kyoeisha Chemical Co., Ltd .: 3000A) and an epoxy acrylate resin (manufactured by Kyoeisha Chemical Co., Ltd .: M600A) at a weight ratio of 85:15, crushed silica particles (B1) 4 0.5 g was mixed and kneaded at 2000 rpm for 10 minutes using a rotation / revolution mixer (Sinky Corporation: Awatori Nertaro AR-100). Subsequently, the resin composition (paste 1) was produced by passing once through a three-roll mill (EXAKT: EXAKT50). The resin composition was evaluated for dispersibility according to the following criteria (see Table 2).
No fine particle aggregates are observed. : ◎
Almost no fine particle aggregates are observed. : ○
Slight fine particle aggregates are observed. : △
Relatively large particle aggregates are observed. : ×
《濾過性の評価》
次のように、樹脂組成物を作製し、分散性を評価した。エポキシアクリレート樹脂(共栄社化学(株)製:3000A)とエポキシアクリレート樹脂(共栄社化学(株)製:M600A)を重量比85:15で混合した樹脂51.0gに、焼成シリカ微粒子(B1)9.0gを混合し、自転・公転ミキサー(シンキー社製:あわとり練太郎AR−100)を用いて、2000rpmで10分間混練した。次いで、三本ロールミル(EXAKT社製:EXAKT50)に1回通過させて樹脂組成物(ペースト1)を作製した。得られた樹脂組成物を、SUS製のカラムに充填し、40度に加温した状態で、0.4MPaの窒素で加圧し、3μmの金属製フィルター(日本金網商工(株)社製:NKSスーパーポアA3)で濾過を行った。樹脂組成物について、以下の基準で濾過性を評価した(表2参照)。
濾過速度の低下が全く認められない。 : ◎
濾過速度の低下が殆ど認められない。 : ○
濾過速度の低下が僅かに認められる。 : △
濾過速度の低下が認められる。 : ×
<< Evaluation of filterability >>
Resin compositions were prepared and evaluated for dispersibility as follows. 8. To 51.0 g of a resin prepared by mixing an epoxy acrylate resin (manufactured by Kyoeisha Chemical Co., Ltd .: 3000A) and an epoxy acrylate resin (manufactured by Kyoeisha Chemical Co., Ltd .: M600A) at a weight ratio of 85:15, 0 g was mixed and kneaded at 2000 rpm for 10 minutes using a rotation / revolution mixer (manufactured by Shinky Corporation: Awatori Nertaro AR-100). Subsequently, the resin composition (paste 1) was produced by passing once through a three-roll mill (EXAKT: EXAKT50). The obtained resin composition was packed in a SUS column, heated to 40 degrees, and pressurized with 0.4 MPa of nitrogen, and a 3 μm metal filter (manufactured by Nippon Kinnet Shoko Co., Ltd .: NKS) Filtration was performed with Superpore A3). The filterability of the resin composition was evaluated according to the following criteria (see Table 2).
No decrease in filtration rate is observed. : ◎
Almost no decrease in filtration rate is observed. : ○
A slight decrease in filtration rate is observed. : △
A decrease in filtration rate is observed. : ×
《注入性の評価》
次のように、樹脂組成物を作製し、注入性を評価した。ビスフェノールF型エポキシ樹脂(新日鐵住金化学(株)社製:YDF8170)と液状フェノール樹脂(明和化成(株)社製:MEH8000)とイミダゾール(四国化成工業(株)社製:2E4MZ)と解砕シリカ粒子(B1)を重量比31.0:19.0:0.26:50.0で混合し、自転・公転ミキサー(シンキー社製:あわとり練太郎AR−100)を用いて、2000rpmで10分間混練した。次いで、三本ロールミル(EXAKT社製:EXAKT50)に5回通過させて樹脂組成物(ペースト1)15gを作製した。得られた樹脂組成物について、110℃で注入性の評価を行った。注入性の評価は、ガラスの上に、ギャップ約20μmの松浪硝子工業(株)社製のギャップカバーグラス(CG00024)を貼り付けたものを用い、開口部(ギャップカバーグラスの短辺)に、シリンジを用いて満遍なく各実施例及び比較例の樹脂組成物を載置した。載置した樹脂組成物は、110℃に加熱されることで粘度が下がり、毛管現象により、ギャップカバーガラス内を対辺(開口部)まで進んでいく。その際、以下の基準で注入性を評価した(表2参照)。
注入口付近に微細な粒子凝集体が全く認められない。 : ◎
注入口付近に微細な粒子凝集体が殆ど認められない。 : ○
注入口付近に微細な粒子凝集体が僅かに認められる。 : △
注入口付近に比較的大きな粒子凝集体が認められる。 : ×
<Evaluation of injectability>
The resin composition was produced as follows and the injectability was evaluated. Bisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .: YDF8170), liquid phenolic resin (manufactured by Meiwa Kasei Co., Ltd .: MEH8000) and imidazole (manufactured by Shikoku Chemicals Co., Ltd .: 2E4MZ) The crushed silica particles (B1) were mixed at a weight ratio of 31.0: 19.0: 0.26: 50.0 and 2000 rpm using a rotating / revolving mixer (Shinky Corp .: Awatori Netaro AR-100). For 10 minutes. Subsequently, the resin composition (paste 1) 15g was produced by making it pass 5 times through a three roll mill (EXAKT product: EXAKT50). About the obtained resin composition, injection property evaluation was performed at 110 degreeC. The evaluation of pouring property was made by attaching a gap cover glass (CG00024) manufactured by Matsunami Glass Industry Co., Ltd. with a gap of about 20 μm on the glass, and opening the opening (short side of the gap cover glass). The resin composition of each Example and Comparative Example was placed evenly using a syringe. The placed resin composition decreases in viscosity when heated to 110 ° C., and proceeds to the opposite side (opening) in the gap cover glass by capillary action. At that time, the injectability was evaluated according to the following criteria (see Table 2).
No fine particle aggregates are observed near the inlet. : ◎
Almost no fine particle aggregates are observed near the inlet. : ○
Slightly fine particle aggregates are observed near the inlet. : △
Relatively large particle aggregates are observed near the inlet. : ×
[実施例2]
テトラエトキシシランの代わりにテトラメトキシシラン用いた以外は実施例1と同様にして解砕シリカ粒子(B2)を得た。
[Example 2]
Crushed silica particles (B2) were obtained in the same manner as in Example 1 except that tetramethoxysilane was used instead of tetraethoxysilane.
[実施例3]
実施例1において、精製工程の後に、水熱処理工程及び水熱後精製工程を行い、解砕シリカ粒子(B3)を得た。水熱処理工程及び水熱後精製工程は、次のように行った。
[Example 3]
In Example 1, after the purification step, a hydrothermal treatment step and a hydrothermal post-purification step were performed to obtain crushed silica particles (B3). The hydrothermal treatment process and the hydrothermal post-purification process were performed as follows.
(水熱処理工程)
シリカ粒子(A1)の分散液(E液)5000gに、純水11000gを撹拌しながら加えて希釈し、固形分濃度10%とした。希釈後の液16000gに28重量%アンモニア水(関東化学社製)148gを添加し、pHを12.5に調整した。その時の電気電導度は343μS/cmであった。続いてこれを小型圧力容器(耐圧硝子工業株式会社製TAS−50型)へ充填し、圧力1.6MPa、撹拌速度200r.p.m、加熱温度200℃で11時間処理を行った。室温まで冷却後、抜き出したシリカ粒子(A1)の分散液(F液)15976gは、固形分濃度9.9%、pH10.51、電気電導度887μS/cmであった。
(Hydrothermal process)
To 5000 g of a dispersion (E liquid) of silica particles (A1), 11000 g of pure water was added with stirring to dilute to a solid content concentration of 10%. 148 g of 28 wt% ammonia water (manufactured by Kanto Chemical Co., Inc.) was added to 16000 g of the diluted liquid, and the pH was adjusted to 12.5. The electrical conductivity at that time was 343 μS / cm. Subsequently, this was filled into a small pressure vessel (TAS-50 type manufactured by Pressure Glass Industrial Co., Ltd.), and the pressure was 1.6 MPa, the stirring speed was 200 r. p. m, and the treatment was performed at a heating temperature of 200 ° C. for 11 hours. After cooling to room temperature, the extracted silica particle (A1) dispersion (F solution) 15976 g had a solid content concentration of 9.9%, pH of 10.51, and electric conductivity of 887 μS / cm.
(水熱後精製工程)
水熱処理後のシリカ粒子(A1)の分散液(F液)を用い、水熱前精製工程と同様にイオン交換を行った。陽イオン交換、陰イオン交換、陽イオン交換、陰イオン交換の順に行い、蒸留装置を用いて濃縮し、固形分35.0%、pH4.00、電気電導度8.00μS/cmのシリカ粒子(A1)の分散液(G液)を得た。
(Purification process after hydrothermal)
Using a dispersion (F liquid) of silica particles (A1) after hydrothermal treatment, ion exchange was performed in the same manner as in the hydrothermal pre-purification step. Cation exchange, anion exchange, cation exchange, anion exchange are carried out in this order, concentrated using a distillation apparatus, and silica particles having a solid content of 35.0%, a pH of 4.00, and an electric conductivity of 8.00 μS / cm ( A dispersion (liquid G) of A1) was obtained.
[実施例4]
テトラエトキシシランの代わりにテトラメトキシシラン用いた以外は実施例3と同様にして解砕シリカ粒子(B4)を得た。
[Example 4]
Crushed silica particles (B4) were obtained in the same manner as in Example 3 except that tetramethoxysilane was used instead of tetraethoxysilane.
[実施例5]
実施例1において、精製工程に代えて、水熱処理工程及び水熱後精製工程を行い、解砕シリカ粒子(B5)を得た。水熱処理工程及び水熱後精製工程については、実施例3と同様の操作を行った。
[Example 5]
In Example 1, it replaced with the refinement | purification process and the hydrothermal treatment process and the hydrothermal post-purification process were performed, and the crushed silica particle (B5) was obtained. About the hydrothermal treatment process and the hydrothermal post-purification process, the same operation as Example 3 was performed.
[比較例1]
実施例1の精製工程を省略して解砕シリカ粒子(C1)を得た。
[Comparative Example 1]
By omitting the purification step of Example 1, crushed silica particles (C1) were obtained.
以上のように製造されたシリカ粒子の製造条件の概要を表1に示し、測定・評価結果を表2に示す。 The outline of the production conditions of the silica particles produced as described above is shown in Table 1, and the measurement / evaluation results are shown in Table 2.
表2に示すように、本発明の実施例においては、乾燥工程に用いる分散液中の含珪素化合物が低減されており、これにより、焼成粒子の圧縮破壊強度が低減している。すなわち、焼成時のシリカ粒子同士の融着におけるネック部の生成及び成長が抑制されたことがわかる。そして、本発明の実施例においては、比較例に比べ、吸湿性が低く、粒子径変動係数の小さい均一な粒子径のシリカ粒子を得ることができた。特に水熱処理を施した場合に、吸湿性を抑制できた。また、本発明の実施例により製造されたシリカ粒子を含有した樹脂組成物は、比較例で製造されたものに比べ、濾過性に優れ、狭ギャップへの注入性にも優れていた。 As shown in Table 2, in the examples of the present invention, the silicon-containing compound in the dispersion used in the drying step is reduced, thereby reducing the compressive fracture strength of the fired particles. That is, it can be seen that the generation and growth of the neck portion in the fusion of the silica particles during firing was suppressed. And in the Example of this invention, the silica particle of the uniform particle diameter with a low hygroscopicity and a small particle diameter variation coefficient was able to be obtained compared with the comparative example. In particular, when the hydrothermal treatment was performed, the hygroscopicity could be suppressed. Moreover, the resin composition containing the silica particle manufactured by the Example of this invention was excellent in filterability compared with what was manufactured by the comparative example, and was excellent also in the injection property to a narrow gap.
さらに、反応が不十分な含珪素化合物及びアルカリ成分(ナトリウム及びアンモニア)の分散液中の濃度の推移を表3〜表5に示す。アルカリ成分の濃度の測定方法は、以下に示す通りである。なお、反応が不十分な含珪素化合物の測定方法については、実施例1に示した方法と同様である。 Furthermore, transition of the concentration in the dispersion of the silicon-containing compound and the alkali components (sodium and ammonia) that are insufficiently reacted is shown in Tables 3 to 5. The method for measuring the concentration of the alkali component is as follows. The method for measuring a silicon-containing compound with insufficient reaction is the same as the method shown in Example 1.
《ナトリウム量の測定》
シリカ分散液に硫酸と弗化水素酸を加え、硫酸白煙が発生するまで加熱する。硝酸と水を加えて加温溶解し、一定量に希釈後、ICP質量分析装置を使用して不純分ナトリウム濃度を求めた。
<Measurement of sodium content>
Add sulfuric acid and hydrofluoric acid to the silica dispersion and heat until white sulfuric acid smoke is generated. Nitric acid and water were added and dissolved by heating. After dilution to a certain amount, the concentration of impure sodium was determined using an ICP mass spectrometer.
《アンモニア量の測定》
シリカ分散液に水酸化ナトリウム水溶液を添加してシリカ粒子を溶解した後、加熱して発生したアンモニアガスを希硫酸(H2SO4:0.05mol/L)を含む水溶液に吸収させる。次いで、これにメチルレッド溶液を2〜3滴たらして、水酸化ナトリウム水溶液(NaOH:0.1mol/L)で滴定し、該分散液中に含まれるアンモニアの量を測定した。
<Measurement of ammonia amount>
An aqueous sodium hydroxide solution is added to the silica dispersion to dissolve the silica particles, and then the ammonia gas generated by heating is absorbed into an aqueous solution containing dilute sulfuric acid (H 2 SO 4 : 0.05 mol / L). Next, 2 to 3 drops of methyl red solution were added thereto, and titrated with an aqueous sodium hydroxide solution (NaOH: 0.1 mol / L), and the amount of ammonia contained in the dispersion was measured.
表3〜表5に示すように、本発明においては、反応が不十分な含珪素化合物に加えて、シリカ粒子同士の融着に影響を与えるアルカリ成分(ナトリウム及びアンモニア)も同時に低減させることができることがわかる。 As shown in Tables 3 to 5, in the present invention, in addition to the silicon-containing compound that is insufficiently reacted, alkali components (sodium and ammonia) that affect the fusion between the silica particles can be simultaneously reduced. I understand that I can do it.
1 解砕用容器
2 ガス導入部
3 導入口
4 貯留部
5 密閉空間
10 焼成シリカ粒子
11 シリカ粒子
12 ネック部
13 解砕シリカ粒子
14 分離面
15 破壊面
DESCRIPTION OF SYMBOLS 1 Container for crushing 2 Gas introduction part 3 Inlet 4 Reservation part 5 Sealed space 10 Firing silica particle 11 Silica particle 12 Neck part 13 Crushing silica particle 14 Separation surface 15 Destruction surface
Claims (5)
前記シリカ粒子分散液から、反応が不十分な含珪素化合物を分離除去する精製工程と、
前記精製工程で得られたシリカ粒子分散液を乾燥して、乾燥シリカ粒子を調製する乾燥工程と、
前記乾燥シリカ粒子を焼成して、焼成シリカ粒子を調製する焼成工程と、
前記焼成シリカ粒子を解砕する解砕工程と、を備えたシリカ粒子の製造方法であって、
前記乾燥工程に供するシリカ粒子分散液は、反応が不十分な含珪素化合物を50ppm以下含有することを特徴とするシリカ粒子の製造方法。 Using a hydrolyzable silicon-containing compound as a raw material, a dispersion preparation step for preparing a silica particle dispersion,
A purification step of separating and removing a silicon-containing compound with insufficient reaction from the silica particle dispersion;
Drying the silica particle dispersion obtained in the purification step to prepare dry silica particles; and
A firing step of firing the dried silica particles to prepare the fired silica particles;
A crushing step of crushing the calcined silica particles, and a method for producing silica particles,
The silica particle dispersion used in the drying step contains 50 ppm or less of a silicon-containing compound that is insufficiently reacted.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015072673A JP6462459B2 (en) | 2015-03-31 | 2015-03-31 | Method for producing silica particles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015072673A JP6462459B2 (en) | 2015-03-31 | 2015-03-31 | Method for producing silica particles |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2016190770A JP2016190770A (en) | 2016-11-10 |
JP2016190770A5 JP2016190770A5 (en) | 2018-05-10 |
JP6462459B2 true JP6462459B2 (en) | 2019-01-30 |
Family
ID=57245741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015072673A Active JP6462459B2 (en) | 2015-03-31 | 2015-03-31 | Method for producing silica particles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6462459B2 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018096876A1 (en) * | 2016-11-24 | 2018-05-31 | 株式会社トクヤマ | Sol-gel silica powder and method for producing same |
CN111094184A (en) * | 2017-08-31 | 2020-05-01 | 株式会社德山 | Surface-treated sol-gel silica and method for producing same |
JPWO2019177004A1 (en) * | 2018-03-15 | 2021-02-25 | 株式会社トクヤマ | Composite oxide powder and its manufacturing method |
JP7470508B2 (en) * | 2018-11-22 | 2024-04-18 | 株式会社日本触媒 | Silica powder, method for producing silica powder, and method for producing calcined silica powder |
CN110282631B (en) * | 2019-03-15 | 2022-10-21 | 深圳市本征方程石墨烯技术股份有限公司 | Silicon dioxide and preparation method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4184683B2 (en) * | 2002-03-19 | 2008-11-19 | 宇部日東化成株式会社 | Metal oxide spherical particles and method for producing the same |
JP4731137B2 (en) * | 2004-07-06 | 2011-07-20 | 日揮触媒化成株式会社 | Method for producing silica-based fine particles |
WO2006009132A1 (en) * | 2004-07-21 | 2006-01-26 | Catalysts & Chemicals Industries Co., Ltd. | Silica-based fine particles, method for production thereof, coating for forming coating film and base material having coating film formed thereon |
WO2015016359A1 (en) * | 2013-08-01 | 2015-02-05 | 日揮触媒化成株式会社 | Method for producing crushed silica particles, and resin composition containing said particles |
-
2015
- 2015-03-31 JP JP2015072673A patent/JP6462459B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2016190770A (en) | 2016-11-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6440551B2 (en) | Method for producing silica particles | |
US10358353B2 (en) | Method for producing disintegrated silica particles | |
JP6462459B2 (en) | Method for producing silica particles | |
KR101808859B1 (en) | Method for producing spherical alumina powder | |
JP5148971B2 (en) | Spherical silica particles and method for producing the same | |
JP5253124B2 (en) | Porous silica particles and method for producing the same | |
EP3009480A1 (en) | Silica-containing resin composition and method for producing same, and molded article produced from silica-containing resin composition | |
JP4043103B2 (en) | Fused spherical silica and method for producing the same | |
TW201831402A (en) | Silica particle dispersion and method for producing same | |
KR20230002311A (en) | Method for producing surface-treated silica powder, resin composition and slurry | |
JP5480497B2 (en) | Method for producing surface-encapsulated silica-based particles, surface-encapsulated silica-based particles, and a resin composition for semiconductor encapsulation obtained by mixing the particles | |
JP6329776B2 (en) | Sealing material for mold underfill | |
JP2014214061A (en) | Hydrophobic inorganic oxide powder, and method of producing the same | |
JP2019112614A (en) | COMPOSITE MATERIAL CONTAINING AT LEAST ONE FIRST MATERIAL AND PARTICLE HAVING NEGATIVE HEAT EXPANSION COEFFICIENT α, AND ADHESIVE MATERIAL CONTAINING THE COMPOSITE MATERIAL | |
JP2014214061A5 (en) | ||
CN110885637A (en) | Preparation method of rare earth fluoride polishing powder and rare earth fluoride polishing solution | |
JP2013249218A (en) | Synthetic amorphous silica powder and method of producing the same | |
JP5975589B2 (en) | Paste for mounting semiconductor devices | |
JP4006220B2 (en) | Surface-modified spherical silica, method for producing the same, and resin composition for semiconductor encapsulant | |
JP7470508B2 (en) | Silica powder, method for producing silica powder, and method for producing calcined silica powder | |
KR100814479B1 (en) | Preparing of spherical improved a specific surface | |
KR100722379B1 (en) | A method of preparing transparent silica glass | |
KR100722378B1 (en) | A method of preparing transparent silica glass | |
JP2018030759A (en) | Irregularly shaped silica powder, method for producing the same, and resin composition containing the same | |
JP2023110669A (en) | Method for adjusting particle diameter of silica particles and method for producing silica particles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180315 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180315 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180920 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181022 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181127 |
|
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: 20181204 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181227 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6462459 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
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 |