JP4911961B2 - Method for producing anisotropic silica sol - Google Patents
Method for producing anisotropic silica sol Download PDFInfo
- Publication number
- JP4911961B2 JP4911961B2 JP2005352661A JP2005352661A JP4911961B2 JP 4911961 B2 JP4911961 B2 JP 4911961B2 JP 2005352661 A JP2005352661 A JP 2005352661A JP 2005352661 A JP2005352661 A JP 2005352661A JP 4911961 B2 JP4911961 B2 JP 4911961B2
- Authority
- JP
- Japan
- Prior art keywords
- silicic acid
- acid solution
- silica sol
- silica
- water
- 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.)
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims description 204
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 134
- 235000012239 silicon dioxide Nutrition 0.000 claims description 105
- 239000000243 solution Substances 0.000 claims description 104
- 239000000377 silicon dioxide Substances 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 10
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 70
- 229910004298 SiO 2 Inorganic materials 0.000 description 54
- 239000007788 liquid Substances 0.000 description 30
- 239000011734 sodium Substances 0.000 description 28
- 238000005498 polishing Methods 0.000 description 23
- 239000008119 colloidal silica Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000004438 BET method Methods 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 8
- 229910001948 sodium oxide Inorganic materials 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- -1 silica and alumina Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical group 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 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 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical class [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- BSVSPZGXUSFFEG-UHFFFAOYSA-N dihydroxy(oxo)silane;tetrakis(2-hydroxyethyl)azanium Chemical compound O[Si](O)=O.OCC[N+](CCO)(CCO)CCO BSVSPZGXUSFFEG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- NNNSKJSUQWKSAM-UHFFFAOYSA-L magnesium;dichlorate Chemical compound [Mg+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NNNSKJSUQWKSAM-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010452 phosphate Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical class [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Description
本発明は、特に研磨材として好適な異方形状シリカゾルの効率的な製造方法およびその製造方法により得られる異方形状シリカゾルに関する。 The present invention relates to an efficient production method of an anisotropic shaped silica sol particularly suitable as an abrasive and an anisotropic shaped silica sol obtained by the production method.
半導体の集積回路付基板の製造においては、シリコンウェーハ上に銅などの金属で回路を形成する際に凹凸あるいは段差が生じるので、これを研磨して表面の段差がなくなるように回路の金属部分を優先的に除去することが行われている。また、シリコンウェーハ上にアルミ配線を形成し、この上に絶縁膜としてシリカ等の酸化膜を設けると配線による凹凸が生じるので、この酸化膜を研磨して平坦化することが行われている。このような基板の研磨においては、研磨後の表面は段差や凹凸がなく平坦で、さらにミクロな傷等もなく平滑であることが求められており、また研磨速度が速いことも必要である。 In the manufacture of a substrate with a semiconductor integrated circuit, irregularities or steps are formed when forming a circuit with a metal such as copper on a silicon wafer. Removal is performed preferentially. Further, when an aluminum wiring is formed on a silicon wafer and an oxide film such as silica is provided thereon as an insulating film, irregularities due to the wiring are generated. Therefore, the oxide film is polished and flattened. In the polishing of such a substrate, the surface after polishing is required to be flat with no steps or irregularities, smooth without microscopic scratches, etc., and the polishing rate must be high.
さらに、半導体材料は電気・電子製品の小型化や高性能化に伴い高集積化が進展しているが、例えばトランジスタ分離層にＮａやＫ等の不純物等が残存した場合、性能が発揮されなかったり、不具合の原因となることがある。特に研磨した半導体基板や酸化膜表面にＮａが付着すると、Ｎａは拡散性が高く、酸化膜中の欠陥などに捕獲され、半導体基板に回路を形成しても絶縁不良を起こしたり、回路が短絡することがあり、また誘電率が低下することがあった。このため使用条件によって、或いは使用が長期にわたった場合に前記不具合を生じることがあるので、ＮａやＫなどの不純物を殆ど含まない研磨用粒子が求められている。
研磨用粒子としては、従来、シリカゾルやヒュームドシリカ、ヒュームドアルミナなどが用いられている。
In addition, semiconductor materials are becoming more highly integrated as electrical and electronic products become smaller and higher in performance. For example, when impurities such as Na and K remain in the transistor isolation layer, the performance is not exhibited. Or cause malfunctions. In particular, if Na adheres to the polished semiconductor substrate or oxide film surface, Na is highly diffusive and is trapped by defects in the oxide film, causing insulation failure even when a circuit is formed on the semiconductor substrate, or shorting the circuit. In some cases, the dielectric constant may decrease. For this reason, since the said malfunction may arise depending on use conditions or when used over a long term, the abrasive | polishing particle | grains which hardly contain impurities, such as Na and K, are calculated | required.
Conventionally, silica sol, fumed silica, fumed alumina, or the like is used as the abrasive particles.
ＣＭＰで使用される研磨材は、通常、シリカ、アルミナ等の金属酸化物からなる平均粒子径が２００ｎｍ程度の球状の研磨用粒子と、配線・回路用金属の研磨速度を早めるための酸化剤、有機酸等の添加剤及び純水などの溶媒から構成されているが、被研磨材の表面には下地の絶縁膜に形成した配線用の溝パターンに起因した段差（凹凸）が存在するので、主に凸部を研磨除去しながら共面まで研磨し、平坦な研磨面とすることが求められている。しかしながら、従来の球状の研磨用粒子では共面より上の部分を研磨した際に、凹部の下部にあった配線溝内の回路用金属が共面以下まで研磨される問題（ディッシングと呼ばれている。）があった。このようなディッシング（過研磨）が起きると配線の厚みが減少して配線抵抗が増加したり、また、この上に形成される絶縁膜の平坦性が低下するなどの問題が生じるので、ディッシングを抑制することが求められている。 The abrasive used in CMP is usually spherical abrasive particles having an average particle diameter of about 200 nm made of a metal oxide such as silica and alumina, and an oxidizer for increasing the polishing rate of the wiring / circuit metal. It is composed of additives such as organic acids and solvents such as pure water, but there are steps (unevenness) due to the groove pattern for wiring formed on the underlying insulating film on the surface of the material to be polished. It is required to polish the coplanar surface mainly while polishing and removing the convex portions to obtain a flat polished surface. However, with conventional spherical abrasive particles, when the portion above the coplanar surface is polished, the circuit metal in the wiring trench at the bottom of the recess is polished to below the coplanar surface (called dishing) There was.) If such dishing (overpolishing) occurs, the thickness of the wiring decreases and the wiring resistance increases, and the flatness of the insulating film formed thereon deteriorates. There is a need to suppress it.
異形粒子群を含む研磨剤は、この様な凹凸を有する基材の研磨において、凸部の上端面が凹部の底面と同レベルになるまで凹部の研磨が抑制され、凸部の上端面が凹部の底面と同レベルまで研磨された後は凸部、凹部ともに同じ研磨速度で研磨できるので、ディッシング（過研磨）が起きることがなく、研磨後の表面は凹凸が無く平坦性に優れることが知られている。例えば、半導体集積回路の形成などにおける研磨においてディッシングが起きることがないので、得られる集積回路の回路抵抗を増加させることもなく、研磨後の表面は平坦性に優れているので効率的に積層集積回路を形成することができる。 Abrasives containing irregularly shaped particles are used in polishing a substrate having such irregularities, and polishing of the concave portion is suppressed until the upper end surface of the convex portion is at the same level as the bottom surface of the concave portion, and the upper end surface of the convex portion is concave. After polishing to the same level as the bottom surface, both the convex and concave portions can be polished at the same polishing rate, so dishing (overpolishing) does not occur, and the polished surface has no unevenness and is excellent in flatness. It has been. For example, since dishing does not occur during polishing in the formation of semiconductor integrated circuits, etc., without increasing the circuit resistance of the obtained integrated circuit, the surface after polishing is excellent in flatness, so that stacking can be performed efficiently. A circuit can be formed.
また、この様な異形粒子群を含む研磨剤の用途としては、アルミニウムディスク（アルミニウムまたはその基材上のメッキ層）や半導体多層配線基板のアルミニウム配線、光ディスクや磁気ディスク用ガラス基板、液晶ディスプレイ用ガラス基板、フォトマスク用ガラス基板、ガラス質材料の鏡面加工などへの適用が期待されている。 In addition, the abrasives containing such irregularly shaped particles include aluminum disks (aluminum or a plating layer on a base material thereof), aluminum wiring of a semiconductor multilayer wiring board, glass substrates for optical disks and magnetic disks, and liquid crystal displays. Application to glass substrates, glass substrates for photomasks, mirror finishing of glassy materials, and the like is expected.
異形粒子を含むシリカゾルの製造方法としては、特開平１−３１７１１５号公報（特許文献１）に、動的光散乱法による測定粒子径（D1）と窒素ガス吸着法による測定粒子径（D2）の比D1/D2が５以上であり、D1は40〜500ミリミクロン、そして電子顕微鏡観察による５〜40ミリミクロンの範囲内の一様な太さで一平面内のみの伸長を有する細長い形状の非晶質コロイダルシリカ粒子が液状媒体中に分散されてなるシリカゾルの製造方法として、（ａ）所定の活性珪酸のコロイド水溶液に、水溶性のカルシウム塩またはマグネシウム塩などを含有する水溶液を、所定量添加し、混合する工程、（ｂ） 更に、アルカリ金属酸化物、水溶性有機塩基又はそれらの水溶性珪酸塩をSiO2/M2O（但し、Ｍは上記アルカリ金属原子又は有機塩基の分子を表わす。）モル比として20〜200となるように加えて混合する工程、（ｃ）前工程によって得られた混合物を60〜150℃で0.5〜40時間加熱する工程からなる製造方法が開示されている。 As a method for producing the silica sol comprising irregular particles, in Japanese Unexamined 1-317115 (Patent Document 1), particle diameter measured by the measuring particle size (D 1) and the nitrogen gas adsorption method by dynamic light scattering method (D 2 ) Ratio D 1 / D 2 is 5 or more, D 1 is 40-500 millimicrons, and stretched only in one plane with uniform thickness in the range of 5-40 millimicrons by electron microscope observation As a method for producing a silica sol in which long and narrow amorphous colloidal silica particles are dispersed in a liquid medium, (a) an aqueous solution containing a water-soluble calcium salt or magnesium salt in a predetermined colloidal aqueous solution of active silica (B) Further, an alkali metal oxide, a water-soluble organic base or a water-soluble silicate thereof is added to SiO 2 / M 2 O (where M is the alkali metal atom or organic group). Represents a base molecule .) A production method comprising a step of adding and mixing so as to have a molar ratio of 20 to 200, and (c) a step of heating the mixture obtained in the previous step at 60 to 150 ° C. for 0.5 to 40 hours is disclosed. .
特開平４−６５３１４号公報（特許文献２）には、動的光散乱法による測定粒子径（D1ミリミクロン）と窒素ガス吸着法による測定粒子径（D2ミリミクロン）の比D1/D2が３以上５未満であって、このD1は40〜500ミリミクロンであり、そして電子顕微鏡観察による５ミリミクロンより大きいが100ミリミクロン以下の範囲内の一様な太さで一平面内のみの伸長を有する細長い形状の非晶質コロイダルシリカ粒子が液状媒体中に分散されてなるSiO2濃度50重量％以下の安定なシリカゾルの製造方法として、細長い形状のシリカゾルに活性珪酸の水溶液の添加を始めると、原料ゾルのコロイダルシリカ粒子の崩壊が起らずに、元の細長い形状の粒子表面上に、加えられた活性珪酸がシロキサン結合を介して沈積することによって太さの増大した細長い形状のコロイダルシリカが得られることについて開示されている。 Japanese Patent Laid-Open No. 4-65314 (Patent Document 2) describes a ratio D 1 / D of a measured particle diameter (D 1 millimicron) by a dynamic light scattering method and a measured particle diameter (D 2 millimicron) by a nitrogen gas adsorption method. D 2 is 3 or more and less than 5, and this D 1 is 40 to 500 millimicrons, and is flat with a uniform thickness in the range of 5 millimicrons but less than 100 millimicrons by electron microscopy. As a method for producing a stable silica sol having a SiO 2 concentration of 50% by weight or less, in which elongated amorphous colloidal silica particles having only an internal extension are dispersed in a liquid medium, an aqueous solution of active silicic acid is added to the elongated silica sol. When the addition is started, the colloidal silica particles of the raw material sol do not collapse, and the added active silicic acid is deposited on the surface of the original elongated particles through deposition of siloxane bonds to increase the thickness. Jo colloidal silica is disclosed about what obtained.
特開平４−１８７５１２号公報（特許文献３）には、ＳｉＯ2として0.05〜5.0wt％のアルカリ金属珪酸塩水溶液に、珪酸液を添加して混合液のＳｉＯ2/M2O（モル比、Ｍはアルカリ金属又は第４級アンモニウム）を30〜60とした後に、Ｃａ,Ｍｇ,Ａｌ,Ｉｎ,Ｔｉ,Ｚｒ,Ｓｎ,Ｓｉ,Ｓｂ,Ｆｅ,Ｃｕおよび希土類金属からなる群から選ばれた１種または２種以上の金属の化合物を添加し（添加時期は、前記珪酸液添加の前または添加中でも良い）、 この混合液を60℃以上の任意の温度で一定時間維持し、更に珪酸液を添加して反応液中のＳｉＯ2/M2O（モル比）を60〜100としてなる実質的に鎖状形状のシリカ微粒子が分散したゾルの製造方法が開示されている。 The JP-A 4-187512 (Patent Document 3), the alkali metal silicate aqueous solution 0.05～5.0Wt% as SiO 2, SiO 2 / M 2 O of the mixture by adding silicic acid solution (molar ratio, 1 is selected from the group consisting of Ca, Mg, Al, In, Ti, Zr, Sn, Si, Sb, Fe, Cu and rare earth metals after M is alkali metal or quaternary ammonium) Add a seed or a compound of two or more metals (the timing of addition may be before or during the addition of the silicic acid solution), maintain this mixed solution at an arbitrary temperature of 60 ° C. or higher for a certain period of time, and further add the silicic acid solution. There is disclosed a method for producing a sol in which silica fine particles having a substantially chain shape are dispersed by adding SiO 2 / M 2 O (molar ratio) in a reaction solution to 60 to 100.
特許第３４４１１４２号公報（特許文献４）には、電子顕微鏡写真の画像解析により求められる７〜1000ｎｍの長径と 0.3〜0.8 の短径／長径比を有するコロイダルシリカ粒子の数が全粒子中50％以上を占めるシリカの安定なゾルからなる半導体ウェーハーの研磨剤が提案されている。 In Japanese Patent No. 3441142 (Patent Document 4), the number of colloidal silica particles having a major axis of 7 to 1000 nm and a minor axis / major axis ratio of 0.3 to 0.8 determined by image analysis of an electron micrograph is 50% of all particles. A semiconductor wafer polishing agent made of a stable sol of silica occupying the above has been proposed.
特開平７−１１８００８号公報（特許文献５）には、活性珪酸のコロイド水溶液に、水溶性のカルシウム塩、マグネシウム塩又はこれらの混合物の水溶液を添加し、得られた水溶液にアルカリ性物質を加え、得られた混合物の一部を６０℃以上に加熱してヒール液とし、残部をフィード液として、当該ヒール液に当該フィード液を添加し、当該添加の間に、水を蒸発させる事によりＳｉＯ2濃度６〜３０重量％まで濃縮することよりなる細長い形状のシリカゾルの製造法が開示されている。 In JP-A-7-118008 (Patent Document 5), an aqueous solution of a water-soluble calcium salt, magnesium salt or a mixture thereof is added to an aqueous colloidal solution of active silicic acid, and an alkaline substance is added to the obtained aqueous solution. A part of the obtained mixture is heated to 60 ° C. or more to obtain a heel liquid, the remainder is used as a feed liquid, the feed liquid is added to the heel liquid, and water is evaporated during the addition to evaporate SiO 2. A process for producing an elongated silica sol comprising concentrating to a concentration of 6-30% by weight is disclosed.
特開平８−２７９４８０号公報（特許文献６）には、(1)珪酸アルカリ水溶液を鉱酸で中和しアルカリ性物質を添加して加熱熟成する方法、(2)珪酸アルカリ水溶液を陽イオン交換処理して得られる活性珪酸にアルカリ性物質を添加して加熱熟成する方法、(3)エチルシリケート等のアルコキシシランを加水分解して得られる活性珪酸を加熱熟成する方法、または、(4)シリカ微粉末を水性媒体中で直接に分散する方法等によって製造されるコロイダルシリカ水溶液は、通常、４〜１,０００ｎｍ（ナノメートル）、好ましくは７〜５００ｎｍの粒子径を有するコロイド状シリカ粒子が水性媒体に分散したものであり、ＳｉＯ2 として０．５〜５０重量％、好ましくは０．５〜３０重量％の濃度を有する。上記シリカ粒子の粒子形状は、球状、いびつ状、偏平状、板状、細長い形状、繊維状等が挙げられることが記載されている。 In JP-A-8-279480 (Patent Document 6), (1) a method in which an alkali silicate aqueous solution is neutralized with mineral acid, an alkaline substance is added and heat-aged, and (2) the alkali silicate aqueous solution is subjected to cation exchange treatment. A method of heating and aging by adding an alkaline substance to the obtained active silicic acid, (3) a method of heating and aging the active silicic acid obtained by hydrolyzing alkoxysilane such as ethyl silicate, or (4) fine silica powder Colloidal silica aqueous solution produced by, for example, a method of directly dispersing in an aqueous medium usually contains colloidal silica particles having a particle diameter of 4 to 1,000 nm (nanometer), preferably 7 to 500 nm. is obtained by dispersing 0.5 to 50% by weight SiO 2, preferably has a concentration of 0.5 to 30 wt%. It is described that the particle shape of the silica particles includes a spherical shape, a distorted shape, a flat shape, a plate shape, an elongated shape, and a fibrous shape.
特開平１１−２１４３３８号公報（特許文献７）には、コロイダルシリカ粒子を主材とした研磨材を用いるシリコンウェハーの研磨方法であって、蒸留により精製した珪酸メチルを、メタノール溶媒中でアンモニア又はアンモニアとアンモニウム塩を触媒として水と反応させることにより得られるコロイダルシリカ粒子を用い、且つ該コロイダルシリカ粒子の長径／短径比が、１．４以上であることを特徴とするシリコンウェハーの研磨方法が提案されている。 Japanese Patent Laid-Open No. 11-214338 (Patent Document 7) discloses a silicon wafer polishing method using an abrasive mainly composed of colloidal silica particles, in which methyl silicate purified by distillation is converted into ammonia or methanol in a methanol solvent. A method for polishing a silicon wafer, characterized by using colloidal silica particles obtained by reacting with ammonia and ammonium salt as a catalyst, and having a major axis / minor axis ratio of 1.4 or more. Has been proposed.
国際公開番号ＷＯ００／１５５５２（特許文献８）には、平均粒子径１０〜８０ｎｍの球状コロイダルシリカ粒子とこの球状コロイダルシリカ粒子を接合する金属酸化物含有シリカからなり、動的光散乱法による測定粒子径（Ｄ1）と球状コロイダルシリカ粒子の平均粒子径（窒素吸着法による測定粒子径／Ｄ2）の比Ｄ1／Ｄ2が３以上であって、このＤ1は５０〜５００ｎｍであり、球状コロイダルシリカ粒子が一平面内のみにつながった数珠状コロイダルシリカ粒子が分散されてなるシリカゾルが記載されている。
また、その製造方法として、（ａ）所定の活性珪酸のコロイド水溶液又は酸性シリカゾルに、水溶性金属塩の水溶液を、前記コロイド水溶液又は酸性シリカゾルのＳｉＯ2に対して、金属酸化物として１〜１０重量％となる量を加えて混合液１を調製する工程、（ｂ）前記混合液１に、平均粒子径１０〜８０ｎｍ、ｐＨ２〜６の酸性球状シリカゾルを、この酸性球状シリカゾルに由来するシリカ含量（Ａ）とこの混合液１に由来するシリカ含量（Ｂ）の比Ａ／Ｂ（重量比）が５〜１００、かつ、この酸性球状シリカゾルとこの混合液１との混合により得られる混合液２の全シリカ含量（Ａ＋Ｂ）が混合液２においてＳｉＯ2濃度５〜４０重量％となる量加えて混合する工程、および、（ｃ）得られた混合液２にアルカリ金属水酸化物、水溶性有機塩基又は水溶性珪酸塩をｐＨが７〜１１となるように加えて混合し、加熱する工程からなる前記シリカゾルの製造方法が記載されている。
International Publication No. WO00 / 15552 (Patent Document 8) includes spherical colloidal silica particles having an average particle diameter of 10 to 80 nm and metal oxide-containing silica that joins the spherical colloidal silica particles, and measurement particles by a dynamic light scattering method. The ratio D 1 / D 2 of the diameter (D 1 ) and the average particle diameter of the spherical colloidal silica particles (measured particle diameter by nitrogen adsorption method / D 2 ) is 3 or more, and this D 1 is 50 to 500 nm, A silica sol is described in which beaded colloidal silica particles in which spherical colloidal silica particles are connected only in one plane are dispersed.
Further, as a production method thereof, (a) an aqueous solution of a water-soluble metal salt is added to a predetermined colloidal aqueous solution or acidic silica sol of active silicic acid as a metal oxide with respect to SiO 2 of the colloidal aqueous solution or acidic silica sol as 1 to 10 A step of preparing a mixed solution 1 by adding an amount of% by weight; (b) an acidic spherical silica sol having an average particle size of 10 to 80 nm and a pH of 2 to 6 is added to the mixed solution 1, and the silica content derived from the acidic spherical silica sol The ratio A / B (weight ratio) of (A) and the silica content (B) derived from the mixed liquid 1 is 5 to 100, and the mixed liquid 2 obtained by mixing the acidic spherical silica sol and the mixed liquid 1 All silica content (a + B) a step of adding and mixing amount corresponding to SiO 2 concentration of 5 to 40 wt% in the mixture 2, and an alkali metal hydroxide to the mixture 2 obtained (c), a water-soluble organic of It describes a method for producing the silica sol comprising a step of adding an organic base or a water-soluble silicate so that the pH is 7 to 11, mixing, and heating.
特開２００１−１１４３３号公報（特許文献９）には、ＳｉＯ2として０．５〜１０重量％を含有し、かつ、ｐＨが２〜６である、活性珪酸のコロイド水溶液に、水溶性のII価又はIII価の金属の塩を単独又は混合して含有する水溶液を、同活性珪酸のコロイド水溶液のＳｉＯ2に対して、金属酸化物（II価の金属の塩の場合はＭＯとし、III価の金属の塩の場合はＭ2Ｏ3とする。但し、ＭはII価又はIII価の金属原子を表し、Ｏは酸素原子を表す。）として１〜１０重量％となる量を加えて混合し、得られた混合液（１）に、平均粒子径１０〜１２０ｎｍ、ｐＨ２〜６の酸性球状シリカゾルを、この酸性球状シリカゾルに由来するシリカ含量（Ａ）とこの混合液（１）に由来するシリカ含量（Ｂ）の比Ａ／Ｂ（重量比）が５〜１００、かつ、この酸性球状シリカゾルとこの混合液（１）との混合により得られる混合液（２）の全シリカ含量（Ａ＋Ｂ）が混合液（２）においてＳｉＯ2濃度５〜４０重量％となるように加えて混合し混合液（２）にアルカリ金属水酸化物等をｐＨが７〜１１となるように加えて混合し、得られた混合液（３）を１００〜２００℃で０．５〜５０時間加熱する数珠状のシリカゾルの製造方法が記載されている。 JP-A-2001-11433 (Patent Document 9) describes a water-soluble II in an aqueous colloidal solution of active silicic acid containing 0.5 to 10% by weight as SiO 2 and having a pH of 2 to 6. an aqueous solution containing valence or III valent metal salt singly or as a mixture thereof, with respect to SiO 2 colloid solution having the same active silicic acid in the case of the metal oxide (II valent metal salt and MO, the III In the case of a metal salt of M 2 O 3 , M represents a II or III valent metal atom, and O represents an oxygen atom). Then, an acidic spherical silica sol having an average particle size of 10 to 120 nm and a pH of 2 to 6 is added to the obtained mixed liquid (1), and the silica content (A) derived from the acidic spherical silica sol and the mixed liquid (1). The ratio A / B (weight ratio) of silica content (B) is 5 to 100, and this acid Spherical silica sol and the mixture (1) and the resulting mixture by mixing (2) the total silica content (A + B) is added and mixed so that SiO 2 concentration of 5 to 40 wt% in the mixture (2) A bead of alkali metal hydroxide added to the mixture (2) and mixed so that the pH is 7 to 11, and the resulting mixture (3) is heated at 100 to 200 ° C. for 0.5 to 50 hours. A process for producing a silica sol is described.
特開２００１−４８５２０号公報（特許文献１０）には、シリカ濃度１〜８モル／リットル、酸濃度０．００１８〜０．１８モル／リットルで水濃度２〜３０モル／リットルの範囲の組成で、溶剤を使用しないでアルキルシリケートを酸触媒で加水分解した後、シリカ濃度が０．２〜１．５モル／リットルの範囲となるように水で希釈し、次いでｐＨが７以上となるようにアルカリ触媒を加え加熱して珪酸の重合を進行させて、電子顕微鏡観察による太さ方向の平均直径が５〜１００ｎｍであり、長さがその１.５〜５０倍の長さの細長い形状の非晶質シリカ粒子が液状分散体中に分散されているシリカゾルの製造方法が記載されている。 Japanese Patent Laid-Open No. 2001-48520 (Patent Document 10) describes a composition having a silica concentration of 1 to 8 mol / liter, an acid concentration of 0.0018 to 0.18 mol / liter, and a water concentration of 2 to 30 mol / liter. The alkyl silicate is hydrolyzed with an acid catalyst without using a solvent, diluted with water so that the silica concentration is in the range of 0.2 to 1.5 mol / liter, and then the pH is 7 or more. An alkali catalyst is added and heated to advance the polymerization of silicic acid, and the average diameter in the thickness direction by electron microscope observation is 5 to 100 nm, and the length is 1.5 to 50 times that of a long and thin shape. A method for producing a silica sol in which crystalline silica particles are dispersed in a liquid dispersion is described.
特開２００１−１５０３３４号公報（特許文献１１）には、水ガラスなどのアルカリ金属珪酸塩の水溶液を脱陽イオン処理することにより得られるＳｉＯ2濃度２〜６重量％程度の活性珪酸の酸性水溶液に、アルカリ土類金属、例えば、Ca、Mｇ、Baなどの塩をその酸化物換算で上記活性珪酸のＳｉＯ2に対し 100〜1500 ppmの重量比で添加し、更にこの液中ＳｉＯ2/M2O (M は、アルカリ金属原子、NH4 又は第４級アンモニウム基を表す。) モル比が20〜150 となる量の同アルカリ物質を添加することにより得られる液を当初ヒール液とし、同様にして得られる２〜６重量％のＳｉＯ2濃度と20〜150 のＳｉＯ2/M2O (M は、上記に同じ。) モル比を有する活性珪酸水溶液をチャージ液として、60〜150 ℃で前記当初ヒール液に前記チャージ液を、１時間当たり、チャージ液ＳｉＯ2／当初ヒール液ＳｉＯ2の重量比として0.05〜1.0 の速度で、液から水を蒸発除去しながら（又はせずに）、添加してなる歪な形状を有するシリカゾルの製造方法が記載されている。 JP 2001-150334 A (Patent Document 11) discloses an acidic aqueous solution of activated silicic acid having a SiO 2 concentration of about 2 to 6% by weight obtained by decation treatment of an aqueous solution of an alkali metal silicate such as water glass. In addition, an alkaline earth metal, for example, a salt of Ca, Mg, Ba or the like is added at a weight ratio of 100 to 1500 ppm with respect to SiO 2 of the above active silicic acid in terms of its oxide, and SiO 2 / M 2 O (M represents an alkali metal atom, NH 4 or a quaternary ammonium group.) The liquid obtained by adding the same alkali substance in an amount that the molar ratio is 20 to 150 is the initial heel liquid. An active silicic acid aqueous solution having a SiO 2 concentration of 2 to 6% by weight and SiO 2 / M 2 O of 20 to 150 (M is the same as above) obtained as a charge liquid at 60 to 150 ° C. The charge liquid is added to the initial heel liquid per hour. At a rate of the charge liquid SiO 2 / initial 0.05-1.0 as a weight ratio of the heel solution SiO 2, (without or) a while evaporating off water from the liquid, method for producing a silica sol having a distorted shape obtained by adding the Are listed.
特開２００３−１３３２６７号公報（特許文献１２）には、ディッシング（過研磨）を抑制し、基板表面を平坦に研磨することができる研磨用粒子として、平均粒子径が５〜３００ｎｍの範囲にある１次粒子が２個以上結合した異形粒子群を含むことを特徴とする研磨用粒子、特には研磨用粒子中の全１次粒子の粒子数に占める、前記異形粒子群を構成する１次粒子の粒子数が５〜１００％の範囲にある研磨用粒子が有効でることについて記載がある。 In JP-A-2003-133267 (Patent Document 12), the average particle diameter is in the range of 5 to 300 nm as polishing particles capable of suppressing dishing (overpolishing) and polishing the substrate surface flatly. Abrasive particles comprising a group of irregularly shaped particles in which two or more primary particles are bonded, and in particular, the primary particles constituting the irregularly shaped particle group in the total number of primary particles in the abrasive particles There is a description that polishing particles having a particle number of 5 to 100% are effective.
特開２００４−２８８７３２号公報（特許文献１３）には、非真球状コロイダルシリカ、酸化剤および有機酸を含有し、残部が水であることを特徴とする半導体研磨用スラリーについて開示されており、その中で、非真球状コロイダルシリカの（長径／短径）が１．２〜５．０のものが提案されており、特開２００４−３１１６５２号公報（特許文献１４）にも同様な非真球状コロイダルシリカが開示されている。 JP 2004-288732 A (Patent Document 13) discloses a slurry for semiconductor polishing characterized by containing non-spherical colloidal silica, an oxidizing agent and an organic acid, and the balance being water. Among them, non-spherical colloidal silica (major axis / minor axis) having a major axis / minor axis of 1.2 to 5.0 has been proposed, and a similar non-true one is also disclosed in Japanese Patent Application Laid-Open No. 2004-311652 (Patent Document 14). Spherical colloidal silica is disclosed.
本発明は、特に研磨材として好適な異方形状シリカゾルおよびその製造方法を提供するものであり、所定のシリカゾルを原料として、異方形状のシリカゾルを調製することを可能とする製造方法を提供することを目的とする。 The present invention provides an anisotropic silica sol particularly suitable as an abrasive and a method for producing the same, and provides a production method capable of preparing an anisotropic silica sol using a predetermined silica sol as a raw material. For the purpose.
本出願の第１の発明は、珪酸液（ａ）にアルカリ性水溶液を添加してｐＨを１０．０〜１２．０に調整し、６０〜１５０℃の温度条件下、珪酸液（ｂ）と２価以上の水溶性金属塩との混合物を連続的にまたは断続的に添加することを特徴とする異方形状シリカゾルの製造方法である。
本出願の第２の発明は、前記異方形状シリカゾルの製造方法において、前記珪酸液（ａ）と前記珪酸液（ｂ）のそれぞれのシリカ固形分の重量比が５０：５０〜９５：５の範囲にあり、前記珪酸液（ａ）と前記珪酸液（ｂ）のシリカ固形分の合計重量に対する前記２価以上の水溶性金属塩の割合が、該水溶性金属塩の酸化物換算重量で１００〜２０００ｐｐｍの範囲にあることを特徴とする異方形状シリカゾルの製造方法である。
In the first invention of the present application, an alkaline aqueous solution is added to the silicic acid solution (a) to adjust the pH to 10.0 to 12.0, and under the temperature condition of 60 to 150 ° C., the silicic acid solution (b) and 2 A method for producing an anisotropic shaped silica sol, comprising continuously or intermittently adding a mixture with a water-soluble metal salt having a valence higher than that.
According to a second invention of the present application, in the method for producing the anisotropic silica sol, the weight ratio of the silica solids of the silicic acid solution (a) and the silicic acid solution (b) is 50:50 to 95: 5. The ratio of the divalent or higher water-soluble metal salt to the total weight of the silica solids of the silicic acid solution (a) and the silicic acid solution (b) is 100 in terms of oxide weight of the water-soluble metal salt. It is the manufacturing method of the anisotropic shape silica sol characterized by being in the range of -2000 ppm.
本出願の第３の発明は、前記異方形状シリカゾルの製造方法において、前記珪酸液が、アルカリ金属珪酸塩、第３級アンモニウム珪酸塩、第４級アンモニウム珪酸塩またはグアニジン珪酸塩から選ばれる水溶性珪酸塩を脱アルカリすることにより調製されたものであって、シリカ固形分濃度が１〜１０重量％の範囲であることを特徴とする異方形状シリカゾルの製造方法である。
本出願の第４の発明は、前記異方形状シリカゾルの製造方法において、前記２価以上の水溶性金属塩が、マグネシウム、カルシウム、バリウム、マンガン、鉄、チタニウム、ジルコニウム、アルミニウム、スズ、鉛またはアンチモンから選ばれる金属のハロゲン化物、シリル化物、硫酸塩、チオ硫酸塩、リン酸塩または有機酸の金属塩であることを特徴とする異方形状シリカゾルの製造方法である。
According to a third invention of the present application, in the method for producing the anisotropic shaped silica sol, the silicic acid solution is an aqueous solution selected from alkali metal silicate, tertiary ammonium silicate, quaternary ammonium silicate, or guanidine silicate. It is prepared by dealkalizing a functional silicate and has a silica solid content concentration in the range of 1 to 10% by weight.
According to a fourth invention of the present application, in the method for producing the anisotropic silica sol, the divalent or higher water-soluble metal salt is magnesium, calcium, barium, manganese, iron, titanium, zirconium, aluminum, tin, lead, or A method for producing an anisotropic silica sol, characterized by being a metal halide, silylated, sulfate, thiosulfate, phosphate or metal salt of an organic acid selected from antimony.
本出願の第５の発明は、前記異方形状シリカゾルに製造方法において、前記珪酸液（ｂ）と２価以上の水溶性金属塩との混合物を５分〜２４時間かけて添加することを特徴とする異方形状シリカゾルの製造方法である。
本出願の第６の発明は、前記異方形状シリカゾルの製造方法によって得られる平均粒子径が１０〜５０ｎｍの範囲にあり、短径／長径比が０．０１〜０．５の範囲にある異方形状シリカゾルである。
According to a fifth aspect of the present application, in the method for producing the anisotropic silica sol, the mixture of the silicic acid solution (b) and a divalent or higher water-soluble metal salt is added over 5 minutes to 24 hours. This is a method for producing an anisotropic shaped silica sol.
According to a sixth aspect of the present application, the average particle diameter obtained by the method for producing an anisotropic shaped silica sol is in the range of 10 to 50 nm, and the minor axis / major axis ratio is in the range of 0.01 to 0.5. It is a square silica sol.
本発明に係る異方形状シリカゾルの製造方法によれば、基本的に既存の球状シリカゾルの製造プロセスをそのまま利用して、異方形状シリカゾルを製造することができ、異方形状シリカゾルを極めて容易に製造することができるものである。特に、本発明の製造方法は、細長い異方形状シリカゾルを製造することのに好適である。 According to the method for producing an anisotropic shaped silica sol according to the present invention, an anisotropic shaped silica sol can be produced using the existing spherical silica sol production process as it is, and the anisotropic shaped silica sol can be produced very easily. It can be manufactured. In particular, the production method of the present invention is suitable for producing an elongated anisotropic shaped silica sol.
本発明に係る異方形状シリカゾルは、研磨剤として優れた研磨特性を有する。特に実用上問題となるレベルのスクラッチを抑制できるものである。即ち、当該異方形状シリカゾルは研磨時において研磨面で粒子配列が起こり、スクラッチの少ない各種の基板研磨面を提供することができる。
The anisotropic shaped silica sol according to the present invention has excellent polishing characteristics as an abrasive. In particular, it is possible to suppress a level of scratch that is a practical problem. That is, the anisotropic shaped silica sol causes particle alignment on the polishing surface during polishing, and can provide various substrate polishing surfaces with less scratches.
［異方形状シリカゾルの製造方法］
珪酸液
本発明製造方法において使用される珪酸液とは、水溶性珪酸塩を脱アルカリすることにより調製されるものであり、通常は珪酸塩の水溶液を陽イオン交換樹脂で処理するなどの方法で脱アルカリして得られる珪酸の低重合物の水溶液である。この種の珪酸液は、通常、ｐＨは２〜４、ＳｉＯ2／Ｎａ2Ｏが１００〜５,０００、ＳｉＯ2濃度約１０重量％以下、好ましくは２〜７重量％のものが、常温でのゲル化が生じ難く、比較的安定であり、実用的に原料として使用される。
[Method for producing anisotropic silica sol]
Silicic acid solution The silicic acid solution used in the production method of the present invention is prepared by dealkalizing a water-soluble silicate. Usually, the silicate aqueous solution is treated with a cation exchange resin. This is an aqueous solution of a low polymer of silicic acid obtained by dealkalization. This type of silicic acid solution usually has a pH of 2 to 4, SiO 2 / Na 2 O of 100 to 5,000, and a SiO 2 concentration of about 10% by weight or less, preferably 2 to 7% by weight. Gelation hardly occurs, is relatively stable, and is practically used as a raw material.
前記水溶性珪酸塩としては、アルカリ金属と珪酸とからなるアルカリ金属珪酸塩、第３級アンモニウムと珪酸からなる第３級アンモニウム珪酸塩、第４級アンモニウムと珪酸からなる第４級アンモニウム珪酸塩およびグアニジンと珪酸とからなるグアニジン珪酸塩などが挙げられる。
アルカリ金属珪酸塩としては、珪酸ナトリウム（水硝子）、珪酸カリウム、珪酸リチウムなどがあり、第３級アンモニウム珪酸塩としては珪酸トリエタノールアミン、第４級アンモニウム珪酸塩としては、珪酸テトラメタノールアンモニウム、珪酸テトラエタノールアンモニウムなどが挙げられる。
Examples of the water-soluble silicate include alkali metal silicate composed of alkali metal and silicic acid, tertiary ammonium silicate composed of tertiary ammonium and silicic acid, quaternary ammonium silicate composed of quaternary ammonium and silicic acid, and Examples thereof include guanidine silicate composed of guanidine and silicic acid.
Examples of the alkali metal silicate include sodium silicate (water glass), potassium silicate, and lithium silicate. The tertiary ammonium silicate includes triethanolamine silicate, the quaternary ammonium silicate includes tetramethanol ammonium silicate, Examples include tetraethanolammonium silicate.
アルカリ性水溶液
アルカリ性水溶液としては、珪酸液のｐＨを調整できるものであって、本発明の異方形状シリカゾルの生成に悪影響を与えないものであれば、制限なく使用できる。具体例としては、水酸化ナトリウム水溶液、水酸化カリウム水溶液、アンモニア水溶液、有機アミン系塩類や水溶性珪酸塩の水溶液などが挙げられる。
Alkaline aqueous solution The alkaline aqueous solution can be used without limitation as long as it can adjust the pH of the silicic acid solution and does not adversely affect the formation of the anisotropic silica sol of the present invention. Specific examples include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution, an aqueous solution of an organic amine salt or a water-soluble silicate, and the like.
本発明の製造方法では、最初に珪酸液（以下、「珪酸液（ａ）」と称する。）に、アルカリ性水溶液を加えて、ｐＨを１０．０〜１２．０の範囲に調整する。ｐＨをこの範囲に調整するとシリカが過飽和となり、シリカ微粒子が析出する。このシリカ微粒子を種粒子として、粒子成長させて、異方形状シリカゾルを調製する。珪酸液のｐＨが１０.０未満の場合は過飽和度が高く凝集し易くなり、他方、ｐＨが１２.０を越える場合はシリカ溶解度が高く、溶解して粒子が生成しない。このｐＨ範囲については、好適には、１０．３〜１１．５の範囲が推奨される。 In the production method of the present invention, first, an alkaline aqueous solution is added to a silicic acid solution (hereinafter referred to as “silicic acid solution (a)”) to adjust the pH to a range of 10.0 to 12.0. When the pH is adjusted within this range, the silica becomes supersaturated and silica fine particles are precipitated. Using this silica fine particle as a seed particle, particle growth is carried out to prepare an anisotropic shaped silica sol. When the pH of the silicic acid solution is less than 10.0, the degree of supersaturation is high and the particles tend to aggregate. On the other hand, when the pH exceeds 12.0, the silica solubility is high and the particles are not dissolved and formed. About this pH range, the range of 10.3-11.5 is recommended suitably.
粒子成長
ｐＨ１０．０〜１２．０の範囲に調整された珪酸液を加熱して、６０〜１５０℃の温度条件下、別の珪酸液（以下、「珪酸液（ｂ）」と称する。）と２価以上の水溶性金属塩の混合物を連続的にまたは断続的に添加することにより、シリカ微粒子を成長させてシリカゾルを調製する。
The silicic acid solution adjusted to a particle growth pH of 10.0 to 12.0 is heated to obtain another silicic acid solution (hereinafter referred to as “silicic acid solution (b)”) under a temperature condition of 60 to 150 ° C. A silica sol is prepared by growing silica fine particles by continuously or intermittently adding a mixture of divalent or higher water-soluble metal salts.
前記２価以上の水溶性金属塩の金属の例としては、マグネシウム、カルシウム、バリウム、マンガン、鉄、チタニウム、ジルコニウム、アルミニウム、スズ、鉛、アンチオモンなどを挙げることができる。これらの金属を含む水溶性金属塩としては、これらの金属のハロゲン化物、ヘキサフルオロシリル化物、硫酸塩、チオ硫酸塩、リン酸塩、塩素酸類塩、硝酸類塩等の無機金属塩が挙げられる。また、有機酸の金属塩も水溶性であれば用いることができる。 Examples of the metal of the divalent or higher water-soluble metal salt include magnesium, calcium, barium, manganese, iron, titanium, zirconium, aluminum, tin, lead, and antimony. Examples of water-soluble metal salts containing these metals include inorganic metal salts such as halides, hexafluorosilylates, sulfates, thiosulfates, phosphates, chlorates, and nitrates of these metals. . Also, a metal salt of an organic acid can be used if it is water-soluble.
具体的には、塩化マンガン、塩化マグネシウム、塩化カルシウム、塩化バリウム、塩化アルミニウム、塩化スズ、塩化鉛、塩化ストロンチウム、硫酸マグネシウム、硫酸カルシウム、硫酸アルミニウム、硫酸カリウムアルミニウム、塩素酸マグネシウム、リン酸マグネシウム、硝酸マグネシウム、硝酸カルシウム、硝酸バリウム、硝酸アルミニウム、水酸化ストロンチウム、乳酸アルミニウム、ジルコニウムアセチルアセトネート、酢酸ジルコニル、硫酸ジルコニル、炭酸ジルコニウムアンモニウム、ステアリン酸ジルコニル、オクチル酸ジルコニル、硝酸ジルコニル、オキシ塩化ジルコニウム、ヒドロキシ塩化ジルコニウム、塩化第２鉄、塩化第１鉄、塩化第１錫等が挙げられるが、これらに限定されるものではない。 Specifically, manganese chloride, magnesium chloride, calcium chloride, barium chloride, aluminum chloride, tin chloride, lead chloride, strontium chloride, magnesium sulfate, calcium sulfate, aluminum sulfate, potassium aluminum sulfate, magnesium chlorate, magnesium phosphate, Magnesium nitrate, calcium nitrate, barium nitrate, aluminum nitrate, strontium hydroxide, aluminum lactate, zirconium acetylacetonate, zirconyl acetate, zirconyl sulfate, ammonium zirconium carbonate, zirconyl octylate, zirconyl octylate, zirconyl nitrate, zirconium oxychloride, hydroxy Examples include, but are not limited to, zirconium chloride, ferric chloride, ferrous chloride, and stannous chloride.
また、ここで使用する珪酸液（ｂ）は、前記出発珪酸液である珪酸液（ａ）と同様に、通常、ｐＨは２〜４、ＳｉＯ2／Ｎａ2Ｏが１００〜５０００、ＳｉＯ2濃度約１０重量％以下、好ましくは２〜７重量％のものである。
この珪酸液（ｂ）と２価以上の水溶性金属塩の混合物を調製し、この混合物を、珪酸液（ａ）にアルカリ性水溶液を添加して、ｐＨ１０．０〜１２．０に調整された珪酸液に６０〜１５０℃の温度範囲で連続的にまたは断続的に添加する。
The silicic acid solution (b) used here is usually pH 2 to 4, SiO 2 / Na 2 O 100 to 5000, SiO 2 concentration, like the silicic acid solution (a) which is the starting silicic acid solution. About 10% by weight or less, preferably 2-7% by weight.
A mixture of this silicic acid solution (b) and a divalent or higher water-soluble metal salt is prepared, and this mixture is added with an aqueous alkaline solution to the silicic acid solution (a) to adjust the pH to 10.0 to 12.0. It is continuously or intermittently added to the liquid in a temperature range of 60 to 150 ° C.
珪酸液（ａ）にアルカリ性水溶液を添加して、ｐＨ１０．０〜１２．０に調整された珪酸液に対して使用する、珪酸液（ｂ）と２価以上の水溶性金属塩との混合物の使用量については、次のように設定される。
水溶性金属塩の使用量については、該水溶性金属塩の金属酸化物に換算して、珪酸液（ａ）と珪酸液（ｂ）のシリカ固形分の合計重量に対して、１００〜２０００ｐｐｍの範囲で使用される。１００ｐｐｍ未満では、異方性が得られにくく、他方、２０００ｐｐｍを越える場合は、シリカゾルが凝集するといった問題がある。水溶液金属塩の添加量については、好適には１２０〜１,５００ｐｐｍの範囲が推奨される。なお、ここで水溶性金属塩の使用量を、該水溶性金属塩の金属酸化物に換算する場合、１酸化物型の金属酸化物に換算する。従って、例えば、Ａｌ2Ｏ3の場合は、Ａｌ2Ｏ3に相当する使用量の１／２がこれに相当する。
A mixture of a silicic acid solution (b) and a divalent or higher water-soluble metal salt used for a silicic acid solution adjusted to pH 10.0 to 12.0 by adding an alkaline aqueous solution to the silicic acid solution (a) The usage amount is set as follows.
About the usage-amount of water-soluble metal salt, it converts into the metal oxide of this water-soluble metal salt, and is 100-2000 ppm with respect to the total weight of the silica solid content of silicic acid liquid (a) and silicic acid liquid (b). Used in range. If it is less than 100 ppm, it is difficult to obtain anisotropy. On the other hand, if it exceeds 2000 ppm, there is a problem that silica sol aggregates. About the addition amount of aqueous metal salt, the range of 120-1500 ppm is recommended suitably. In addition, here, when converting the usage-amount of water-soluble metal salt into the metal oxide of this water-soluble metal salt, it converts into 1 oxide type metal oxide. Thus, for example, in the case of Al 2 O 3, 1/2 of the amount corresponding to Al 2 O 3 corresponds to this.
珪酸液（ｂ）の使用量については、珪酸液（ａ）と珪酸液（ｂ）のシリカ固形分比率で、５０：５０〜９５：５の範囲で使用される。珪酸液（ｂ）の使用量が、この範囲を下回る場合は、連結した粒子間の強度が小さく、凝集し易くなり、他方、珪酸液（ｂ）の使用量が、この範囲を超える場合は、連結した粒子の成長が大きくなり、異方性が小さくなり易い。珪酸液（ａ）と珪酸液（ｂ）のシリカ固形分比率の好適な範囲としては、５０：５０〜７５：２５の範囲が推奨される。 About the usage-amount of silicic acid liquid (b), it is used in the range of 50: 50-95: 5 by the silica solid content ratio of silicic acid liquid (a) and silicic acid liquid (b). When the amount of the silicic acid liquid (b) is less than this range, the strength between the connected particles is small, and it tends to aggregate. On the other hand, when the amount of the silicic acid liquid (b) exceeds this range, The growth of connected particles increases and the anisotropy tends to decrease. As a suitable range of the silica solid content ratio of the silicic acid liquid (a) and the silicic acid liquid (b), a range of 50:50 to 75:25 is recommended.
以上の条件を満たすように珪酸液（ｂ）と２価以上の水溶性金属塩の混合物は調製されて、珪酸液（ａ）にアルカリ性水溶液を添加して、ｐＨ１０．０〜１２．０に調整された珪酸液に６０〜１５０℃の温度範囲で連続的にまたは断続的に添加される。珪酸液（ｂ）と２価以上の水溶性金属塩の混合については、格別に制限はなく、常温で珪酸液（ｂ）に２価以上の水溶性金属塩を添加し、攪拌することにより行うことができる。 A mixture of the silicic acid solution (b) and a divalent or higher water-soluble metal salt is prepared so as to satisfy the above conditions, and an alkaline aqueous solution is added to the silicic acid solution (a) to adjust the pH to 10.0 to 12.0. The resulting silicic acid solution is continuously or intermittently added in a temperature range of 60 to 150 ° C. The mixing of the silicic acid liquid (b) and the water-soluble metal salt having a valence of 2 or more is not particularly limited. be able to.
ｐＨ調整した珪酸液への前記混合物の添加に当たっては、珪酸液（ｂ）と２価以上の水溶性金属塩の混合物を連続的にまたは断続的に添加する方法がとられる。通常、５分から２４時間かけて、ゲル化を招かないように添加が行なわれる。前記混合物の添加終了後は、直ちに次の工程を行なっても構わないが、１〜３時間保持し、徐冷してから次の工程に進んでもよく、また、数時間かけて放冷することにより、常温にしてから次の工程に進んでも良い。 In the addition of the mixture to the pH-adjusted silicic acid solution, a method of continuously or intermittently adding a mixture of the silicic acid solution (b) and a divalent or higher water-soluble metal salt is employed. Usually, the addition is performed over 5 minutes to 24 hours so as not to cause gelation. After completion of the addition of the mixture, the next step may be performed immediately, but it may be held for 1 to 3 hours, gradually cooled before proceeding to the next step, or allowed to cool for several hours. Thus, the process may proceed to the next step after the room temperature is reached.
本発明に係る異方形状シリカゾルの製造方法により、効率的に異方形状シリカゾルを調製できることについては、珪酸液と２価以上の水溶性金属塩との混合物を徐々にｐＨ１０．０〜１２．０、温度範囲６０〜１５０℃の珪酸液に添加することにより、金属塩が、シリカ微粒子間の連結剤として作用する結果、「シリカ−金属塩−シリカ−金属塩−・・・」の構造をとり、シリカ微粒子が細長く成長するものと推測される。また、本発明に係る異方形状シリカゾルの製造方法では、前記珪酸液と２価以上の水溶性金属塩との混合物を徐々に添加するため、珪酸液の凝集が生じ難く、得られる異方形状シリカゾルの大きさを制御する上でも好適である。 Regarding the ability to efficiently prepare an anisotropic shaped silica sol by the method for producing an anisotropic shaped silica sol according to the present invention, a mixture of a silicic acid solution and a divalent or higher water-soluble metal salt is gradually adjusted to pH 10.0 to 12.0. By adding to a silicic acid solution having a temperature range of 60 to 150 ° C., the metal salt acts as a linking agent between silica fine particles, resulting in the structure of “silica-metal salt-silica-metal salt-. It is estimated that the silica fine particles grow elongated. Further, in the method for producing an anisotropic shaped silica sol according to the present invention, since the mixture of the silicic acid solution and the divalent or higher water-soluble metal salt is gradually added, the silicic acid solution hardly aggregates and the obtained anisotropic shape is obtained. It is also suitable for controlling the size of the silica sol.
［異方形状シリカゾル］
本発明の異方形状シリカゾルは、前記した製造方法によって得られる非球状のシリカ微粒子が分散したゾルであり、シリカ微粒子の平均粒子径が３〜３０ｎｍであり、短径／長径比が０．０１〜０．５の範囲にある。
平均粒子径が３ｎｍ未満の場合は、安定性がない。他方、３０ｎｍを越える場合は、粒子間の相互作用が大きく高粘度となる。短径／長径比が０．０１未満の場合は、粘度が高くなり、凝集しやすい。他方、０．５を越える場合は、粘度はひくく、異方性の特性が小さくなる。この異方形状シリカゾルは、研磨剤用途からは、平均粒子径が５〜２５ｎｍ、短径／長径比が０．１０〜０．３５の範囲のものが好適である。
[Anisotropic silica sol]
The anisotropic shaped silica sol of the present invention is a sol in which non-spherical silica fine particles obtained by the above-described production method are dispersed, the average particle size of the silica fine particles is 3 to 30 nm, and the minor axis / major axis ratio is 0.01. It is in the range of ~ 0.5.
When the average particle size is less than 3 nm, there is no stability. On the other hand, when it exceeds 30 nm, the interaction between particles is large and the viscosity becomes high. When the minor axis / major axis ratio is less than 0.01, the viscosity increases and the particles tend to aggregate. On the other hand, if it exceeds 0.5, the viscosity becomes low and the anisotropic characteristics become small. This anisotropic shaped silica sol preferably has an average particle diameter in the range of 5 to 25 nm and a minor axis / major axis ratio of 0.10 to 0.35 in terms of abrasive use.
前記平均粒子径については、ＢＥＴ法により測定したものである。また、短径／長径比については、走査型電子顕微鏡により撮影された写真をもとに、後記するように所定数のシリカ微粒子について、短径／長径の長さを測定し、そこから短径／長径比の値を算出し、更にその平均値をとったものである。 The average particle diameter is measured by the BET method. As for the minor axis / major axis ratio, the length of the minor axis / major axis was measured for a predetermined number of silica fine particles based on a photograph taken with a scanning electron microscope, and the minor axis was calculated therefrom. / Long diameter ratio is calculated, and the average value is further calculated.
本発明の異方形状シリカゾルのＳｉＯ2濃度は、通常は、１〜５０重量％の範囲にあるものが好適に使用される。
本発明の異方形状シリカゾルは、このまま目的の用途に供されることもあり、また、用途によっては限外過または蒸発等の手段によって濃縮される。また、溶媒置換等の方法によって、有機溶媒と置換し、オルガノゾルとすることもできる。
The SiO 2 concentration of the anisotropic shaped silica sol of the present invention is preferably suitably in the range of 1 to 50% by weight.
The anisotropic shaped silica sol of the present invention may be used for the intended use as it is, and depending on the use, it is concentrated by means such as ultrafiltration or evaporation. Further, it can be substituted with an organic solvent by a method such as solvent substitution to obtain an organosol.
このような有機溶媒としては、メタノール、エタノール、プロパノール、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、エチレングリコール、ヘキシレングリコールなどのアルコール類；酢酸メチルエステル、酢酸エチルエステルなどのエステル類；ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルなどのエーテル類；アセトン、メチルエチルケトン、アセチルアセトン、アセト酢酸エステルなどのケトン類、Ｎ−メチルピロリドン、ジメチルホルムアミド等のアミド類などが挙げられる。これらは単独で使用しても良く、また２種以上混合して使用しても良い。 Examples of such organic solvents include methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol and other alcohols; esters such as acetic acid methyl ester and acetic acid ethyl ester Ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, acetylacetone and acetoacetate, N- Examples include amides such as methylpyrrolidone and dimethylformamide. These may be used singly or in combination of two or more.
また、本発明の異方形状シリカゾルは、シランカップリング剤で表面処理して疎水性を付与して用いることもでき、必要に応じてシリカゾル中のアルカリをイオン交換樹脂等によって除去して用いることもできる。 Further, the anisotropic shaped silica sol of the present invention can be used by applying a surface treatment with a silane coupling agent to impart hydrophobicity, and if necessary, remove the alkali in the silica sol with an ion exchange resin or the like. You can also.
本発明に係る製造方法により得られる異方形状シリカゾルは、微細で異方形状なシリカゾルであり、研磨剤用途を始め、インク用吸収性微粒子、塗料等の展着性補助剤、材料表面の親水性コーティング材、バインダー等に適用可能である。
The anisotropic shaped silica sol obtained by the production method according to the present invention is a fine and anisotropic shaped silica sol, which is used for abrasives, absorbent fine particles for ink, spreading aids such as paints, etc. It can be applied to an adhesive coating material and a binder.
還流器および攪拌機付セパラブルフラスコにシリカ固形分４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液４．５ｇを添加し、攪拌混合した。添加後のｐＨは１１．１だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化マグネシウム０．０２ｇの混合物を３時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
In a separable flask equipped with a reflux condenser and a stirrer, 500 g of a silica solution (a) (SiO 2 / Na 2 O molar ratio 1200, pH 2.5) having a silica solid content of 4.5% by weight was added, and 10% aqueous sodium hydroxide solution was added thereto. 4.5 g was added and mixed with stirring. The pH after the addition was 11.1.
The solution was heated at 80 ° C. for 1 hour, and the temperature was kept at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) A mixture of 220 g and magnesium chloride 0.02 g was added dropwise over 3 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
このシリカゾルについてのＢＥＴ法により測定される比表面積から算定される平均粒子径については、シリカゾルを凍結乾燥機で乾燥させた後、１１０℃で２０時間乾燥した試料について比表面積を測定した後、比表面積測定装置（湯浅アイオニクス製、マルチソーブ１２）を用いて窒素吸着法（ＢＥＴ法）により測定した。
そして、ＢＥＴ法による窒素吸着量から比表面積（ＳＡ）を求め、粒子径（Ｄｐ）＝６０００／ＳＡ×〔粒子の密度〕の式から平均粒子径を求めたところ７ｎｍとなった。
For the average particle size calculated from the specific surface area measured by the BET method for this silica sol, the silica sol was dried with a freeze dryer and then the specific surface area was measured for a sample dried at 110 ° C. for 20 hours. The surface area was measured by a nitrogen adsorption method (BET method) using a surface area measuring device (manufactured by Yuasa Ionics, Multisorb 12).
Then, the specific surface area (SA) was determined from the amount of nitrogen adsorbed by the BET method, and the average particle diameter was determined from the formula of particle diameter (Dp) = 6000 / SA × [particle density].
また、シリカゾルの短径／長径比については、透過型電子顕微鏡（型番Ｈ−８００、日立製作所製）を使用して、倍率２５０,０００倍の写真を撮影し、任意の１０個のシリカ微粒子について、長径（最大の長さ）と短径（最大の太さ）を測定し、それぞれ短径／長径比の値を算出したところ、平均値は０．２０となった。
以上の調製条件、シリカゾルの平均粒子径および短径／長径比について、表１に示した。また、これ以降の実施例と比較例についても同様に記載した。
As for the minor axis / major axis ratio of the silica sol, a transmission electron microscope (model number H-800, manufactured by Hitachi, Ltd.) was used to take a photograph at a magnification of 250,000 times, and about 10 arbitrary silica fine particles. When the major axis (maximum length) and minor axis (maximum thickness) were measured and the ratio of minor axis / major axis ratio was calculated, the average value was 0.20.
The above preparation conditions, the average particle diameter of silica sol, and the minor axis / major axis ratio are shown in Table 1. Moreover, it described similarly about the Example and comparative example after this.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化カリウム水溶液４．４ｇを添加し、攪拌混合した。添加後のｐＨは１０．５だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化マンガン０．０４ｇの混合物を９時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
このシリカゾルのＢＥＴ法による平均粒子径を求めたところ６ｎｍとなった。また、短径／長径比の値は０．３０となった。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. 4.4 g of an aqueous potassium oxide solution was added and mixed with stirring. The pH after addition was 10.5.
The solution was heated at 80 ° C. for 1 hour, and the temperature was kept at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) A mixture of 220 g and manganese chloride 0.04 g was added dropwise over 9 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
The average particle diameter of this silica sol determined by the BET method was 6 nm. Further, the value of the minor axis / major axis ratio was 0.30.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液４．５ｇを添加し、攪拌混合した。添加後のｐＨは１１．１だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化マグネシウム０．０３ｇの混合物を４時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
このシリカゾルのＢＥＴ法による平均粒子径を求めたところ９ｎｍとなった。また、短径／長径比の値は０．２０となった。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. 4.5 g of an aqueous sodium oxide solution was added and mixed with stirring. The pH after the addition was 11.1.
The solution was heated at 80 ° C. for 1 hour, and the temperature was kept at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) A mixture of 220 g and magnesium chloride 0.03 g was added dropwise over 4 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
The average particle diameter of this silica sol determined by the BET method was 9 nm. Moreover, the value of the minor axis / major axis ratio was 0.20.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．１）５００ｇを入れ、そこに１０％アンモニア水溶液１０．５ｇを添加し、攪拌混合した。添加後のｐＨは１１．１だった。
この溶液を１２０℃で１時間加熱してから、温度を１２０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化マグネシウム０．０１ｇの混合物を４時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
このシリカゾルのＢＥＴ法による平均粒子径を求めたところ２１ｎｍとなった。また、短径／長径比の値は０．２１となった。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.1) having a silica solid content concentration of 4.5% by weight was placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% ammonia was added thereto. 10.5 g of an aqueous solution was added and mixed with stirring. The pH after the addition was 11.1.
The solution was heated at 120 ° C. for 1 hour, and the temperature was maintained at 120 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) A mixture of 220 g and 0.01 g of magnesium chloride was added dropwise over 4 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
The average particle size of this silica sol determined by the BET method was 21 nm. Further, the value of the minor axis / major axis ratio was 0.21.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液５．０ｇを添加し、攪拌混合した。添加後のｐＨは１１．３だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化アルミニウム０．０１ｇの混合物を３時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
このシリカゾルのＢＥＴ法による平均粒子径を求めたところ８ｎｍとなった。また、短径／長径比の値は０．０５となった。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. Sodium oxide aqueous solution 5.0g was added and it stirred and mixed. The pH after addition was 11.3.
The solution was heated at 80 ° C. for 1 hour, and the temperature was kept at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) A mixture of 220 g and 0.01 g of aluminum chloride was added dropwise over 3 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
The average particle diameter of this silica sol determined by the BET method was 8 nm. Further, the value of the ratio of minor axis / major axis was 0.05.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度２．２重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ３．１）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液を２．５ｇを添加し、攪拌混合した。添加後のｐＨは１０．１だった。
この溶液を９８℃で１時間加熱してから、温度を９８℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）４５０ｇと塩化マグネシウム０．０５ｇの混合物を１０時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
このシリカゾルのＢＥＴ法による平均粒子径を求めたところ１５ｎｍとなった。また、短径／長径比の値は０．２５となった。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 3.1) having a silica solid content concentration of 2.2 wt% was placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water was added thereto. 2.5 g of an aqueous sodium oxide solution was added and mixed with stirring. The pH after the addition was 10.1.
The solution was heated at 98 ° C. for 1 hour, and the temperature was maintained at 98 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) A mixture of 450 g and 0.05 g of magnesium chloride was added dropwise over 10 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
The average particle diameter of this silica sol determined by the BET method was 15 nm. Further, the value of the minor axis / major axis ratio was 0.25.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液１．５ｇを添加し、攪拌混合した。添加後のｐＨは８．２だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化マグネシウム０．０２ｇの混合物を３時間かけて滴下したところ凝集した。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. A sodium oxide aqueous solution (1.5 g) was added and mixed with stirring. The pH after the addition was 8.2.
The solution was heated at 80 ° C. for 1 hour, and the temperature was kept at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) When a mixture of 220 g and 0.02 g of magnesium chloride was added dropwise over 3 hours, the mixture aggregated.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液１０ｇを添加し、攪拌混合した。添加後のｐＨは１２．５だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化マグネシウム０．０２ｇの混合物を３時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
このシリカゾルのＢＥＴ法による平均粒子径を求めたところ６ｎｍとなった。また、短径／長径比の値は０．６となった。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. 10 g of an aqueous sodium oxide solution was added and mixed with stirring. The pH after addition was 12.5.
The solution was heated at 80 ° C. for 1 hour, and the temperature was kept at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) A mixture of 220 g and magnesium chloride 0.02 g was added dropwise over 3 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
The average particle diameter of this silica sol determined by the BET method was 6 nm. Further, the value of the minor axis / major axis ratio was 0.6.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液４．５ｇを添加し、攪拌混合した。添加後のｐＨは１１．１だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇのみを３時間かけて滴下し、シリカゾルを得た。そして、このシリカゾルをエバポレーターにてＳｉＯ2濃度２０重量％まで濃縮してシリカゾルを調製した。
このシリカゾルのＢＥＴ法による平均粒子径を求めたところ６ｎｍとなった。また、短径／長径比の値は０．９となった。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. 4.5 g of an aqueous sodium oxide solution was added and mixed with stirring. The pH after the addition was 11.1.
The solution was heated at 80 ° C. for 1 hour, and the temperature was kept at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a) Similarly) Only 220 g was dropped over 3 hours to obtain a silica sol. Then, this silica sol was concentrated with an evaporator to a SiO 2 concentration of 20% by weight to prepare a silica sol.
The average particle diameter of this silica sol determined by the BET method was 6 nm. Further, the value of the minor axis / major axis ratio was 0.9.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液４．５ｇを添加し、攪拌混合した。添加後のｐＨは１１．１だった。
この溶液を８０℃で１時間加熱してから、温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇと塩化マグネシウム３ｇの混合物を４時間かけて滴下したところ凝集した。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. 4.5 g of an aqueous sodium oxide solution was added and mixed with stirring. The pH after the addition was 11.1.
The solution was heated at 80 ° C. for 1 hour, and the temperature was maintained at 80 ° C., while the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na 2 O molar ratio and pH were the same as that of the silicic acid solution (a). Similarly) When a mixture of 220 g and 3 g of magnesium chloride was added dropwise over 4 hours, the mixture aggregated.
還流器および攪拌機付セパラブルフラスコにシリカ固形分濃度４．５重量％の珪酸液（ａ）（ＳｉＯ2／Ｎａ2Ｏモル比１,２００、ｐＨ２．５）５００ｇを入れ、そこに１０％水酸化ナトリウム水溶液４．５ｇを添加し、攪拌混合した。添加後のｐＨは１１．１だった。
この溶液を８０℃で１時間加熱してから、塩化マグネシウム０．０２ｇのみを全量同時に添加し、更に温度を８０℃に保持しながら、珪酸液（ｂ）（シリカ固形分濃度、ＳｉＯ2／Ｎａ2Ｏモル比およびｐＨは珪酸液（ａ）と同様）２２０ｇを３時間かけて滴下しところ凝集した。
500 g of silicic acid solution (a) (SiO 2 / Na 2 O molar ratio 1,200, pH 2.5) having a silica solid content concentration of 4.5% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and 10% water is added thereto. 4.5 g of an aqueous sodium oxide solution was added and mixed with stirring. The pH after the addition was 11.1.
After heating this solution at 80 ° C. for 1 hour, only 0.02 g of magnesium chloride was added simultaneously, and while maintaining the temperature at 80 ° C., the silicic acid solution (b) (silica solid content concentration, SiO 2 / Na The 2 O molar ratio and pH were the same as in the silicic acid solution (a)), and 220 g was added dropwise over 3 hours, and agglomerated.
Claims (3)
前記珪酸液（ａ）と前記珪酸液（ｂ）のそれぞれのシリカ固形分の重量比が５０：５０〜９５：５の範囲にあり、前記珪酸液（ａ）と前記珪酸液（ｂ）のシリカ固形分の合計重量に対する前記２価以上の水溶性金属塩の割合が、該水溶性金属塩の酸化物換算重量で１００〜２ ,０００ｐｐｍの範囲にあることを特徴とする異方形状シリカゾルの製造方法。 An alkaline aqueous solution is added to the silicic acid solution (a) to adjust the pH to 10.0 to 12.0, and from the silicic acid solution (b) and magnesium chloride, manganese chloride, or aluminum chloride under a temperature condition of 60 to 150 ° C. A method of producing an anisotropic shaped silica sol by continuously or intermittently adding a mixture with a water-soluble metal salt having two or more valences selected ,
The silica solids weight ratio of the silicic acid solution (a) and the silicic acid solution (b) is in the range of 50:50 to 95: 5, and the silica of the silicic acid solution (a) and the silicic acid solution (b). Production of anisotropic silica sol, wherein the ratio of the divalent or higher water-soluble metal salt to the total weight of the solid content is in the range of 100 to 2,000 ppm in terms of oxide weight of the water-soluble metal salt. Method.
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| JP2022091234A (en) * | 2020-12-09 | 2022-06-21 | 日揮触媒化成株式会社 | Dispersion of modified silica-based fine particles and method for producing the same |
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