JP4979930B2 - Method for producing anisotropic silica sol - Google Patents
Method for producing anisotropic silica sol Download PDFInfo
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- JP4979930B2 JP4979930B2 JP2005351260A JP2005351260A JP4979930B2 JP 4979930 B2 JP4979930 B2 JP 4979930B2 JP 2005351260 A JP2005351260 A JP 2005351260A JP 2005351260 A JP2005351260 A JP 2005351260A JP 4979930 B2 JP4979930 B2 JP 4979930B2
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- silica sol
- silica
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims description 167
- 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 93
- 239000002245 particle Substances 0.000 claims description 85
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 206010029412 Nightmare Diseases 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 50
- 239000007864 aqueous solution Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 30
- 238000005498 polishing Methods 0.000 description 23
- -1 silica and alumina Chemical class 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000008119 colloidal silica Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 238000004438 BET method Methods 0.000 description 15
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000012528 membrane Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000000108 ultra-filtration Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000002156 mixing Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 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 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent 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
- 239000003082 abrasive agent Substances 0.000 description 3
- 230000004931 aggregating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 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
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 230000007257 malfunction Effects 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
- 239000000178 monomer Substances 0.000 description 2
- 150000007524 organic acids Chemical class 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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 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
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- 238000000746 purification Methods 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
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003892 spreading Methods 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
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
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７〜1000 nm 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 electron micrographs is 50 in all particles. A semiconductor wafer polishing agent comprising a stable sol of silica occupying more than 100% 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.
本発明の異方形状シリカゾルの製造方法は、平均粒子径が３〜２５ｎｍの範囲にあるシリカ微粒子が分散した、ｐＨが２〜８の範囲にあるシリカゾルに、該シリカゾルのシリカ固形分１００重量部に対して、ポリ金属塩化合物を０．０１〜７０重量部添加し、５０〜１６０℃で加熱することを特徴とするものである。 In the method for producing the anisotropic shaped silica sol of the present invention, silica fine particles having an average particle size in the range of 3 to 25 nm are dispersed, and the silica sol in the range of pH 2 to 8 is mixed with 100 parts by weight of silica solid content of the silica sol. In contrast, 0.01 to 70 parts by weight of a polymetal salt compound is added and heated at 50 to 160 ° C.
イオン交換、イオン交換樹脂による脱イオン、またはｐＨ調整剤を添加することにより、前記ｐＨ２〜８の範囲のシリカゾルを調製することが好ましい。
前記ポリ金属塩化合物が、ポリ硫酸第二鉄、ポリ硫酸アルミニウム、ポリ硫酸カリウム、ポリ塩化第二鉄、ポリ塩化アルミニウム、ポリ塩化カルシウムまたはこれらの複合体から選ばれる１種または２種以上であることが好ましい。
本発明の異方形状シリカゾルは、前記製造方法によって得られる平均粒子径４．０〜３０ｎｍ、短径／長径比が、０．０５〜０．８０の範囲にある異方形状シリカゾルである。
It is preferable to prepare the silica sol in the range of pH 2 to 8 by adding ion exchange, deionization with an ion exchange resin, or adding a pH adjuster.
The polymetal salt compound is one or two or more selected from polyferric sulfate, aluminum polysulfate, potassium polysulfate, polyferric chloride, polyaluminum chloride, polycalcium chloride or a complex thereof. It is preferable.
The anisotropic shaped silica sol of the present invention is an anisotropic shaped silica sol having an average particle diameter of 4.0 to 30 nm and a minor axis / major axis ratio in the range of 0.05 to 0.80 obtained by the above production method.
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。
本発明に係る異方形状シリカゾルの製造方法は、シリカゾルにポリ金属塩化合物を添加後加熱することにより、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。
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.
The method for producing an anisotropic silica sol according to the present invention can produce an anisotropic silica sol very easily by heating after adding a polymetal salt compound to the silica sol.
［異方形状シリカゾルの製造方法］
原料シリカゾル
本発明に係る異方形状シリカゾルの製造方法においては、原料となるシリカゾルとして、ＢＥＴ法により求められた平均粒子径が３〜２５ｎｍのシリカ微粒子が分散したシリカゾルが使用される。また、好適には平均粒子径４〜２３ｎｍのものが使用される。原料となるシリカゾルの平均粒子径は、本発明の異方形状シリカゾルの製造方法により、原料シリカゾルを異方形状にする上で、重要な条件となる。平均粒子径が３ｎｍ未満の場合、本発明の異方形状シリカゾルの製造方法を適用しても、粒子同士の架橋で球状化が早く、異方形状化し難く、他方、２５ｎｍを越える場合は、粒子の安定性が高く、異方形状化し難い。このため平均粒子径が３〜２５ｎｍの範囲にあるシリカゾルが原料として好適に使用される。
なお、後述するように、本発明において「異方形状」シリカゾルとは、球状シリカゾル以外を意味しており、特に、短径／長径比が０．８０以下のものを云う。
[Method for producing anisotropic silica sol]
Raw material silica sol In the method for producing an anisotropic silica sol according to the present invention, a silica sol in which silica fine particles having an average particle diameter of 3 to 25 nm determined by the BET method are dispersed is used as a raw material silica sol. Further, those having an average particle diameter of 4 to 23 nm are preferably used. The average particle diameter of the silica sol used as a raw material is an important condition for making the raw silica sol into an anisotropic shape by the method for producing an anisotropic silica sol of the present invention. When the average particle diameter is less than 3 nm, even when the method for producing the anisotropic silica sol of the present invention is applied, the particles are rapidly spheroidized by cross-linking and difficult to be anisotropically formed. Is highly stable and difficult to be anisotropically shaped. Therefore, silica sol having an average particle diameter in the range of 3 to 25 nm is preferably used as a raw material.
As will be described later, in the present invention, the “anisotropic shape” silica sol means other than the spherical silica sol, and in particular, the one having a minor axis / major axis ratio of 0.80 or less.
原料となるシリカゾルのｐＨは、２〜８の範囲にあるものが使用される。原料となるシリカゾルのｐＨについても、原料シリカゾルを異方形状化させるうえで重要な条件となる。
ｐＨが２未満の場合は、酸性が強すぎるため、シリカゾルの安定性が損なわれるため、異方形状シリカゾルを調製することは容易ではない。他方、ｐＨが８を越える場合は、シリカ微粒子は、粒子の負電位が大きくなり、粒子間の反発が増加することと溶解度が高いために、粒子間のネック成長が早くなり、異方形状化し難く、好ましくない。ｐＨが２〜８の範囲にあるシリカゾルは、粒子成長させた場合、粒子同士の架橋が起こり易く、架橋した粒子の結合部に過飽和状態にある溶液から、シリカが粒子間結合部に析出しやすく、本発明の異方形状シリカゾルの製造方法においては、更にポリ金属塩化合物がシリカ微粒子間の架橋剤として作用するため、シリカ微粒子の異方形状化が促進されるものと推察される。ｐＨの範囲については、好適にはｐＨ２．５〜７．５が推奨される。
The silica sol used as a raw material has a pH in the range of 2-8. The pH of the raw silica sol is also an important condition for making the raw silica sol anisotropic.
When the pH is less than 2, the acidity is too strong, and the stability of the silica sol is impaired. Therefore, it is not easy to prepare an anisotropic silica sol. On the other hand, when the pH exceeds 8, the silica fine particles have a large negative potential, increase repulsion between particles, and have high solubility, so that the neck growth between particles is accelerated and anisotropic shape is formed. It is difficult and undesirable. Silica sols having a pH in the range of 2 to 8 tend to cause cross-linking of particles when particles are grown, and silica is likely to precipitate from the solution in a supersaturated state at the bonded portion of the crosslinked particles. In the method for producing the anisotropic shaped silica sol of the present invention, it is presumed that the anisotropic formation of the silica fine particles is promoted because the polymetal salt compound further acts as a crosslinking agent between the silica fine particles. Regarding the pH range, pH 2.5 to 7.5 is recommended.
なお、原料となるシリカゾルについては、必要に応じてイオン交換樹脂で脱イオン若しくはｐＨ調整剤を添加することにより、ｐＨ２〜８の範囲に調整しても良い。イオン交換樹脂は、塩基性型交換樹脂及び酸性型交換樹脂が使用可能であり、ｐＨ調整剤としては、シリカゾルに添加されてｐＨを調整し、異方形状シリカゾルの生成を阻害する効果を有しない水溶性の物質であれば使用可能である。また、ｐＨ調整剤としては、例えば、水酸化ナトリウム水溶液、硫酸水溶液、塩酸水溶液、硝酸水溶液などを挙げることができる。 In addition, about the silica sol used as a raw material, you may adjust to the range of pH 2-8 by adding deionization or a pH adjuster with an ion exchange resin as needed. As the ion exchange resin, a basic type exchange resin and an acid type exchange resin can be used. As a pH adjuster, the pH adjuster is added to the silica sol to adjust the pH, and has no effect of inhibiting the formation of the anisotropic shaped silica sol. Any water-soluble substance can be used. Examples of the pH adjuster include a sodium hydroxide aqueous solution, a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, and a nitric acid aqueous solution.
原料シリカゾル中のシリカ微粒子の形状については、球状シリカまたは非球状シリカのいずれも適用可能である。しかしながら、本発明の製造方法は、球状シリカゾルからなる原料をもとに非球状シリカゾルを調製することを可能とするものであり、原料となるシリカゾルとして、球状シリカゾルを用いた場合に、その優れた効果が顕著に現れるものとなる。この様な球状シリカゾルについては、その短径/長径比率は、通常は０．８以上のものである。 As for the shape of the silica fine particles in the raw material silica sol, either spherical silica or non-spherical silica is applicable. However, the production method of the present invention makes it possible to prepare a non-spherical silica sol based on a raw material consisting of a spherical silica sol, and when the spherical silica sol is used as the raw material silica sol, its excellent The effect becomes prominent. For such a spherical silica sol, the minor axis / major axis ratio is usually 0.8 or more.
原料となるシリカゾルのＳｉＯ2固形分濃度については、通常は１〜５０重量％の範囲のものが使用される。また、好適には３〜３０重量％のものが使用される。１重量％未満では、効率的にシリカゾルの生産を行うには不向きである。他方、５０重量％を越えるとシリカゾルの安定性が低下し、凝集し易くなるので望ましくない。
原料となるシリカゾルの製造方法は、限定されるものではなく、公知のシリカゾル製造方法で調製されたシリカゾルを適用することができる。
Regarding the SiO 2 solid content concentration of the silica sol used as a raw material, a concentration in the range of 1 to 50% by weight is usually used. Moreover, the thing of 3 to 30 weight% is used suitably. If it is less than 1% by weight, it is not suitable for producing silica sol efficiently. On the other hand, if it exceeds 50% by weight, the stability of the silica sol is lowered and it tends to aggregate, which is not desirable.
The manufacturing method of the silica sol used as a raw material is not limited, The silica sol prepared with the well-known silica sol manufacturing method can be applied.
原料シリカゾルとしては、水系溶媒のシリカゾルが好ましい。水系溶媒のシリカゾルの場合、上記ｐＨ範囲に調整することにより、シリカゾルの異方形状化を行うことができる。原料としてオルガノゾルを使用する場合には、ポリ金属塩化物の析出による凝集体の生成の影響で、ポリ金属塩化合物が架橋剤として機能しなくなることもあり、望ましくない。 As the raw material silica sol, an aqueous solvent silica sol is preferable. In the case of silica sol as an aqueous solvent, the silica sol can be anisotropically shaped by adjusting to the above pH range. When an organosol is used as a raw material, the polymetal salt compound may not function as a cross-linking agent due to the formation of aggregates due to the precipitation of polymetal chloride, which is not desirable.
ポリ金属塩化合物
本発明において使用されるポリ金属塩化合物とは、鉄、アルミニウム、カリウム、またはカルシウムから選ばれる金属塩の２量体以上の重合体構造をとるものであり、２種以上のポリ金属塩化合物の複合体であっても良い。これらは、水系溶媒中において、優れた凝集能力を発揮するものとして知られている。具体的には、ポリ硫酸第二鉄、ポリ硫酸アルミニウム、ポリ塩化第二鉄、ポリ塩化アルミニウム、ポリ塩化カルシウム、ポリ硫酸カリウム、またはこれらの複合体から選ばれる１種または２種以上である。
Polymetal salt compound The polymetal salt compound used in the present invention has a polymer structure of a dimer or more of a metal salt selected from iron, aluminum, potassium, or calcium. It may be a complex of metal salt compounds. These are known to exhibit an excellent aggregation ability in an aqueous solvent. Specifically, it is one or more selected from polyferric sulfate, polyaluminum sulfate, polyferric chloride, polyaluminum chloride, polycalcium chloride, potassium polysulfate, or a complex thereof.
ポリ硫酸第二鉄は、水溶性の無機高分子化合物で、［Ｆｅ2（ＯＨ）n（ＳＯ4）3-n/2］m （但し、ｎ＜２、ｍ＞１０である。）の一般式で表されるものであり、通常、硫酸第１鉄、硫酸、水及び酸素とを原料として調製した硫酸第１鉄含有硫酸酸性溶液中の第１鉄イオンの全てを第２鉄イオンに酸化することによって製造される液状の物質であり、水系の凝集剤として知られている。
ポリ硫酸アルミニウムは、一般式[Al2(OH)n(SO4)3-2/n]（但し、１＜ｎ＜５、ｍ＜１０である。）で表されるものであり、例えば、水酸化アルミニウムと硫酸を反応させて調製することができる。凝集剤であるポリ塩化アルミニウムに添加して、その凝集性能を向上させる凝集性能向上剤として知られている。
Polyferric sulfate is a water-soluble inorganic polymer compound, and is generally [Fe 2 (OH) n (SO 4 ) 3−n / 2 ] m (where n <2, m> 10). It is expressed by the formula, and normally all ferrous ions in ferric sulfate-containing sulfuric acid acidic solution prepared using ferrous sulfate, sulfuric acid, water and oxygen as raw materials are oxidized to ferric ions. It is a liquid substance produced by doing so and is known as an aqueous flocculant.
The polyaluminum sulfate is represented by the general formula [Al 2 (OH) n (SO 4 ) 3−2 / n ] (where 1 <n <5, m <10). It can be prepared by reacting aluminum hydroxide and sulfuric acid. It is known as an aggregating performance improver that is added to polyaluminum chloride as an aggregating agent to improve its aggregating performance.
ポリ塩化第二鉄は、一般式〔Ｆｅ2（ＯＨ）nＣｌ6-n〕m （ただし、ｎ＜２、ｍ＞１）で示される水溶性の無機高分子化合物であり、水系の凝集剤として知られている。
ポリ塩化アルミニウムは、一般式〔Ａｌ2（ＯＨ）nＣｌ6-n〕m （ただし、１＜ｎ＜５、ｍ＜１０）で表される。例えば、塩酸と水酸化アルミニウムを反応させて得られる塩基性塩化アルミニウムに、アルミナ濃度、塩基度を調節する目的で、各種添加剤を混合反応させる方法により製造される。工業用水、飲料水などの用水等の処理に使用される浄化剤としての用途に使用されている。この他、ポリ塩化カルシウムやポリ硫酸カリウムも使用可能である。
Polyferric chloride is a water-soluble inorganic polymer compound represented by the general formula [Fe 2 (OH) n Cl 6-n ] m (where n <2, m> 1), and is an aqueous flocculant. Known as.
Polyaluminum chloride is represented by the general formula [Al 2 (OH) n Cl 6-n ] m (where 1 <n <5, m <10). For example, it is manufactured by a method in which various additives are mixed and reacted with basic aluminum chloride obtained by reacting hydrochloric acid and aluminum hydroxide for the purpose of adjusting alumina concentration and basicity. It is used for applications as a purification agent used in the treatment of industrial water, drinking water and the like. In addition, poly calcium chloride and potassium polysulfate can be used.
本発明に係る異方形状シリカゾルの製造方法においては、ポリ金属塩化合物が、原料シリカゾルのシリカ微粒子に対する架橋剤として作用することにより、異方形状のシリカ微粒子が形成されものと考えられる。また、シリカ微粒子が均等に結合することなく、異方形状化する理由については、特に、原料シリカゾルのｐＨ範囲（２〜８）とポリ金属塩化合物の有するＯＨ基の特性が、シリカ微粒子同士を異方形状に結合することに有利に作用するためと思われる。即ち、ポリ金属塩化合物の有する複数のＯＨ基がシリカ微粒子表面のシラノール基と反応して、異方形状化が促進されるものと推察される。
さらに、原料シリカゾルのシリカ固形分に対する、ポリ金属塩化合物の添加量、加熱温度および加熱時間の条件を調整することによって、良好な性状の異方形状シリカゾルが得られる。
In the method for producing the anisotropic shaped silica sol according to the present invention, it is considered that the anisotropically shaped silica fine particles are formed by the polymetal salt compound acting as a crosslinking agent for the silica fine particles of the raw material silica sol. Further, the reason why the silica fine particles are anisotropically formed without evenly bonding is that the pH range (2 to 8) of the raw material silica sol and the characteristics of the OH group of the polymetal salt compound are different from each other. It seems to be advantageous for bonding to an anisotropic shape. That is, it is presumed that the plurality of OH groups possessed by the polymetal salt compound react with silanol groups on the surface of the silica fine particles to promote anisotropic shape formation.
Furthermore, an anisotropic shaped silica sol having good properties can be obtained by adjusting the addition amount of the polymetal salt compound, the heating temperature and the heating time with respect to the silica solid content of the raw silica sol.
なお、ポリ金属塩化合物に代えて、単量体の金属塩を適用した場合は、単量体のＯＨ基は、二量体以上の場合より、反応性が高いため、シリカゾルと反応してゲル化を招き易いため、本発明の異方形状シリカゾルの製造方法には使用できない。 In addition, when a metal salt of a monomer is applied instead of the polymetal salt compound, the OH group of the monomer is more reactive than the case of a dimer or more, and thus reacts with the silica sol and gels. Therefore, it cannot be used in the method for producing the anisotropic silica sol of the present invention.
ポリ金属塩化合物の添加量については、原料シリカゾルのシリカ固形分１００重量部に対して、ポリ塩化金属化合物を０．０１〜７０重量部が使用される。ポリ塩化金属化合物の添加量が０．０１重量部未満では、異方形状のシリカゾルの生成量が少なく、工業的には有用ではない。他方、ポリ金属塩化合物の添加量が７０重量部を越える場合は、ポリ金属塩化合物同士が相互作用して、凝集しやすくなり、好ましくない。ポリ塩化金属化合物の添加量としては、好適には１〜６８重量部が推奨される。 About the addition amount of a polymetal salt compound, 0.01-70 weight part of polychlorinated metal compounds are used with respect to 100 weight part of silica solid content of raw material silica sol. When the addition amount of the polychlorinated metal compound is less than 0.01 parts by weight, the amount of anisotropically formed silica sol is small, which is not industrially useful. On the other hand, when the addition amount of the polymetal salt compound exceeds 70 parts by weight, the polymetal salt compounds interact with each other and tend to aggregate, which is not preferable. The added amount of the polychlorinated metal compound is preferably 1 to 68 parts by weight.
加熱処理
本発明製造方法においては、ｐＨ２〜８の範囲にある原料シリカゾルにポリ塩化金属化合物を添加してから、５０〜１６０℃にて加熱を行い、異方形状シリカゾルを調製する。５０〜１６０℃の範囲での加熱を行うことにより、ポリ金属塩化合物のＯＨ基とシリカ微粒子のシラノール基との反応が進行し、シリカ微粒子が異方形状化する。
加熱温度が５０℃未満では、上記反応が充分に進行しないため、異方形状シリカゾルが生成し難くなる。他方、１６０℃以上では、シリカ粒子の溶解性が大きくなり、球状化しやすく、充分な異方性が起こりにくい。従って、加熱温度については、好適には７０〜１５５℃の範囲が推奨される。
加熱時間は、生成するシリカゾル中における異方形状シリカゾルの割合に影響するものであるが、通常は１〜７２時間、好ましくは２〜６０時間の加熱が行われる。
Heat treatment In the production method of the present invention, the polysilicic acid metal compound is added to the raw material silica sol in the range of pH 2 to 8, and then heated at 50 to 160 ° C to prepare an anisotropic silica sol. By heating in the range of 50 to 160 ° C., the reaction between the OH group of the polymetal salt compound and the silanol group of the silica fine particles proceeds, and the silica fine particles become anisotropic.
When the heating temperature is less than 50 ° C., the above reaction does not proceed sufficiently, so that it becomes difficult to produce an anisotropic shaped silica sol. On the other hand, at 160 ° C. or higher, the solubility of the silica particles is increased, the particles are easily spheroidized, and sufficient anisotropy is unlikely to occur. Accordingly, the heating temperature is preferably in the range of 70 to 155 ° C.
The heating time affects the proportion of the anisotropic shaped silica sol in the silica sol to be generated, but is usually 1 to 72 hours, preferably 2 to 60 hours.
［異方形状シリカゾル］
前記した本発明の製造方法によって、異方形状シリカゾル得られる。このシリカゾルの平均粒子径は４．０〜３０ｎｍ、短径／長径比は０．０５〜０．８０である。なお、この平均粒子径についてもＢＥＴ法により求められるものである。
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０．１０〜０．６０の範囲のものが好適である。
[Anisotropic silica sol]
An anisotropic shaped silica sol can be obtained by the production method of the present invention described above. The silica sol has an average particle size of 4.0 to 30 nm and a minor axis / major axis ratio of 0.05 to 0.80. This average particle size is also determined by the BET method.
This anisotropic shaped silica sol preferably has an average particle diameter of 5 to 25 nm and a minor axis / major axis ratio of 0.10 to 0.60 in terms of abrasive application.
本発明の異方形状シリカゾルは、必要に応じて濃縮したり、希釈したりして用いることができる。濃縮方法としては、加熱して水分を蒸発させる方法、限外濾過膜を用いる方法などがある。シリカゾルの濃度はＳｉＯ2として通常、１〜５０重量％の範囲に調整される。 The anisotropic silica sol of the present invention can be used after being concentrated or diluted as necessary. Examples of the concentration method include a method of evaporating moisture by heating, a method of using an ultrafiltration membrane, and the like. The concentration of the silica sol is usually as SiO 2, is adjusted to a range of 1 to 50 wt%.
さらに、本発明の異方形状シリカゾルは、必要に応じて有機溶媒で溶媒置換してオルガノゾルとすることもできる。この溶媒置換に用いられる有機溶媒としては、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。 Furthermore, the anisotropic shaped silica sol of the present invention may be substituted with an organic solvent as needed to obtain an organosol. Organic solvents used for this solvent replacement include alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol; acetic acid methyl ester, acetic acid ethyl ester Esters such as: diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .; ketones such as acetone, methyl ethyl ketone, acetylacetone, acetoacetate Amides such as N-methylpyrrolidone and dimethylformamideThese 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.
本発明に係る異方形状シリカゾルの製造方法は、基本的に既存の球状シリカゾルをｐＨ２〜８の範囲にて、ポリ金属塩化合物を添加して、加熱することにより、異方形状シリカゾルの製造を行なうことができるものであり、異方形状シリカゾルの製造方法としては、極めて実用性が高いものである。この製造方法は、例えば、研磨剤として利用されるシリカゾルの製造に適用される。 The method for producing an anisotropic shaped silica sol according to the present invention basically produces an anisotropic shaped silica sol by adding a polymetal salt compound and heating an existing spherical silica sol in the range of pH 2-8. As a method for producing an anisotropic shaped silica sol, it is extremely practical. This production method is applied, for example, to the production of silica sol used as an abrasive.
また、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。
Further, 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, and material surfaces. It is applicable to hydrophilic coating materials, binders and the like.
ＢＥＴ法により測定される平均粒子径が５．０ｎｍ、比表面積が５４５ｍ2／ｇ、ＳｉＯ2濃度が２０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−５５０）を純水で希釈して、ＳｉＯ2濃度を３重量％に調整した後、５％硫酸水溶液を用いてｐＨ３に調整した。
このシリカゾル５００ｇにポリ塩化アルミニウムの１０％水溶液をポリ塩化アルミニウム換算で１０．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して１２０℃で３時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１２重量％まで濃縮した。
Silica sol (catalyst SI-550, produced by Catalytic Chemical Industry Co., Ltd.) having an average particle size of 5.0 nm, a specific surface area of 545 m 2 / g, and a SiO 2 concentration of 20% by weight measured by the BET method is diluted with pure water. The SiO 2 concentration was adjusted to 3% by weight, and then adjusted to pH 3 using a 5% aqueous sulfuric acid solution.
To 500 g of this silica sol, 10.0 g of a 10% aqueous solution of polyaluminum chloride was added in terms of polyaluminum chloride, sufficiently stirred and mixed at room temperature, heated and stirred at 120 ° C. for 3 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 12% by weight with an ultrafiltration membrane.
本発明のシリカゾルの平均粒子径はＢＥＴ法により測定される比表面積から算定される。具体的には、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）により測定する。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×（試料の密度）の式から平均粒子径を求めた。
ここで得られたシリカゾルの平均粒子径は６．０ｎｍ、比表面積は４５５ｍ2／ｇとなった。
The average particle size of the silica sol of the present invention is calculated from the specific surface area measured by the BET method. Specifically, after the silica sol was dried with a freeze dryer, the specific surface area of a sample dried at 110 ° C. for 20 hours was measured, and then nitrogen adsorption was performed using a specific surface area measuring device (manufactured by Yuasa Ionics, Multisorb 12). Measured by the method (BET method). And the specific surface area (SA) was calculated | required from the nitrogen adsorption amount by BET method, and the average particle diameter was calculated | required from the type | formula of particle diameter (Dp) = 6000 / SAx (sample density).
The silica sol thus obtained had an average particle size of 6.0 nm and a specific surface area of 455 m 2 / g.
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、平均値は０．１５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。これ以降の実施例、比較例についても同様に表１に記載した。
Regarding 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. (Maximum length) and short diameter (maximum thickness) were measured, and the value of the short diameter / long diameter ratio was calculated. The average value was 0.15. The above preparation conditions, the average particle diameter of silica sol The minor axis / major axis ratio is shown in Table 1. The following examples and comparative examples are also shown in Table 1.
ＢＥＴ法により測定される平均粒子径が４．３ｎｍ、比表面積が６３４ｍ2／ｇ、ＳｉＯ2濃度が１２重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−５５０）を純水で希釈して、ＳｉＯ2濃度を１０重量％に調整した後、５％塩酸水溶液にてｐＨ５に調整した。
このシリカゾル５００ｇにポリ硫酸第２鉄の１０％水溶液をポリ硫酸第２鉄換算で３．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して８０℃で１５時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１１重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は５．０ｎｍ、比表面積は５４０ｍ2／ｇとなった。また、短径／長径比の平均値は０．３２となった
A silica sol (catalyst SI-550, manufactured by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter measured by the BET method of 4.3 nm, a specific surface area of 634 m 2 / g, and a SiO 2 concentration of 12% by weight is diluted with pure water. The SiO 2 concentration was adjusted to 10% by weight and then adjusted to pH 5 with a 5% aqueous hydrochloric acid solution.
To 500 g of this silica sol, 3.0 g of a 10% aqueous solution of polyferric sulfate was added in terms of polyferric sulfate, sufficiently stirred and mixed at room temperature, then heated and stirred at 80 ° C. for 15 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 11% by weight with an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 5.0 nm and a specific surface area of 540 m 2 / g. The average value of the minor axis / major axis ratio was 0.32.
ＢＥＴ法により測定される平均粒子径が７．０ｎｍ、比表面積が３９０ｍ2／ｇ、ＳｉＯ2濃度が３０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−３５０）を純水で希釈して、ＳｉＯ2濃度を１０重量％に調整した後、５％硫酸水溶液にてｐＨ６に調整した。
このシリカゾル５００ｇにポリ塩化アルミニウムの１０％水溶液をポリ塩化アルミニウム換算で５．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して１２０℃で５時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１２重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は８．０ｎｍ、比表面積は３３５ｍ2／ｇとなった。また、短径／長径比の平均値は０．３１となった
A silica sol (catalyst SI-350, manufactured by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter of 7.0 nm, a specific surface area of 390 m 2 / g, and a SiO 2 concentration of 30% by weight measured by the BET method is diluted with pure water. The SiO 2 concentration was adjusted to 10% by weight, and then adjusted to pH 6 with a 5% aqueous sulfuric acid solution.
To 500 g of this silica sol, 5.0 g of a 10% aqueous solution of polyaluminum chloride was added in terms of polyaluminum chloride. After sufficiently stirring and mixing at room temperature, the mixture was heated and stirred at 120 ° C. for 5 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 12% by weight with an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 8.0 nm and a specific surface area of 335 m 2 / g. The average value of the minor axis / major axis ratio was 0.31.
ＢＥＴ法により測定される平均粒子径が７．０ｎｍ、比表面積が３９０ｍ2／ｇ、ＳｉＯ2濃度が３０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−３５０）を純水で希釈して、ＳｉＯ2濃度を１５重量％に調整した後、５％硫酸水溶液にてｐＨ５に調整した。
このシリカゾル５００ｇにポリ塩化アルミニウムの１０％水溶液をポリ塩化アルミニウム換算で８．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して１５０℃で３時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１２重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は９．０ｎｍ、比表面積は３０１ｍ2／ｇとなった。また、短径／長径比の平均値は０．４０となった
A silica sol (catalyst SI-350, manufactured by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter of 7.0 nm, a specific surface area of 390 m 2 / g, and a SiO 2 concentration of 30% by weight measured by the BET method is diluted with pure water. Then, after adjusting the SiO 2 concentration to 15% by weight, the pH was adjusted to 5 with a 5% aqueous sulfuric acid solution.
To 500 g of this silica sol, 8.0 g of a 10% aqueous solution of polyaluminum chloride was added in terms of polyaluminum chloride, and the mixture was sufficiently stirred and mixed at room temperature, followed by heating and stirring at 150 ° C. for 3 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 12% by weight with an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 9.0 nm and a specific surface area of 301 m 2 / g. The average value of the minor axis / major axis ratio was 0.40.
ＢＥＴ法により測定される平均粒子径が１８ｎｍ、比表面積が１５２ｍ2／ｇ、ＳｉＯ2濃度が４０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−４０）を純水で希釈して、ＳｉＯ2濃度を２０重量％に調整した後、５％硫酸水溶液にてｐＨ７に調整した。
このシリカゾル５００ｇにポリ塩化アルミニウムの１０％水溶液をポリ塩化アルミニウム換算で５．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して１５０℃で３時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度２０重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は２０ｎｍ、比表面積は１３５ｍ2／ｇとなった。また、短径／長径比の平均値は０．５０となった
Silica sol (catalyst SI-40, manufactured by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter of 18 nm, a specific surface area of 152 m 2 / g, and a SiO 2 concentration of 40% by weight measured by the BET method is diluted with pure water, After adjusting the SiO 2 concentration to 20% by weight, the pH was adjusted to 7 with a 5% aqueous sulfuric acid solution.
To 500 g of this silica sol, 5.0 g of a 10% aqueous solution of polyaluminum chloride was added in terms of polyaluminum chloride, and the mixture was sufficiently stirred and mixed at room temperature, and then heated and stirred at 150 ° C. for 3 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 20% by weight using an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 20 nm and a specific surface area of 135 m 2 / g. The average value of the minor axis / major axis ratio was 0.50.
ＢＥＴ法により測定される平均粒子径が２０ｎｍ、比表面積が１３６ｍ2／ｇ、ＳｉＯ2濃度が４０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−４０）を純水で希釈して、ＳｉＯ2濃度を２０重量％に調整した後、５％水酸化ナトリウムにてｐＨ６に調整した。
このシリカゾル５００ｇにポリ硫酸第２鉄の１０％水溶液をポリ硫酸第２鉄換算で２．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して１５０℃で３時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１５重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は２２ｎｍ、比表面積は１２４ｍ2／ｇとなった。また、短径／長径比の平均値は０．３０となった
A silica sol (catalyst chemical industry make, Catalloy SI-40) having an average particle diameter of 20 nm, a specific surface area of 136 m 2 / g, and a SiO 2 concentration of 40% by weight measured by the BET method is diluted with pure water, After adjusting the SiO 2 concentration to 20% by weight, the pH was adjusted to 6 with 5% sodium hydroxide.
To 500 g of this silica sol, 2.0 g of a 10% aqueous solution of polyferric sulfate was added in terms of polyferric sulfate. The mixture was thoroughly stirred and mixed at room temperature, then heated and stirred at 150 ° C. for 3 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 15% by weight with an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 22 nm and a specific surface area of 124 m 2 / g. Moreover, the average value of the minor axis / major axis ratio was 0.30.
ＢＥＴ法により測定される平均粒子径が７．０ｎｍ、比表面積が３９０ｍ2／ｇ、ＳｉＯ2濃度が３０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−３５０）を純水で希釈して、ＳｉＯ2濃度を１５重量％に調整した後、５％水酸化ナトリウムにてｐＨ１１に調整した。
このシリカゾル５００ｇにポリ塩化アルミニウムの１０％水溶液をポリ塩化アルミニウム換算で５．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して８０℃で１５時間撹拌した。次いで、室温まで冷却したところ、シリカゾルはゲル化した。また、シリカゾルの長径（最大の長さ）と短径（最大の太さ）は測定することが出来なかった。
A silica sol (catalyst SI-350, manufactured by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter of 7.0 nm, a specific surface area of 390 m 2 / g, and a SiO 2 concentration of 30% by weight measured by the BET method is diluted with pure water. Then, after adjusting the SiO 2 concentration to 15% by weight, the pH was adjusted to 11 with 5% sodium hydroxide.
To 500 g of this silica sol, 5.0 g of a 10% aqueous solution of polyaluminum chloride was added in terms of polyaluminum chloride. After sufficiently stirring and mixing at room temperature, the mixture was heated and stirred at 80 ° C. for 15 hours. Subsequently, when cooled to room temperature, the silica sol gelled. Further, the major axis (maximum length) and minor axis (maximum thickness) of silica sol could not be measured.
ＢＥＴ法により測定される平均粒子径が７．０ｎｍ、比表面積が３９０ｍ2／ｇ、ＳｉＯ2濃度が３０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−３５０）を純水で希釈して、ＳｉＯ2濃度を１５重量％に調整した後、５％硫酸水溶液にてｐＨ６に調整した。
このシリカゾル５００ｇにポリ塩化アルミニウムの１０％水溶液をポリ塩化アルミニウム換算で５．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して４０℃で５０時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１２重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は７．０ｎｍ、比表面積は３８９ｍ2／ｇとなった。また、短径／長径比の平均値は０．９５となった
A silica sol (catalyst SI-350, manufactured by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter of 7.0 nm, a specific surface area of 390 m 2 / g, and a SiO 2 concentration of 30% by weight measured by the BET method is diluted with pure water. The SiO 2 concentration was adjusted to 15% by weight, and then adjusted to pH 6 with a 5% aqueous sulfuric acid solution.
To 500 g of this silica sol, 5.0 g of a 10% aqueous solution of polyaluminum chloride was added in terms of polyaluminum chloride, and after sufficiently stirring and mixing at room temperature, the mixture was heated and stirred at 40 ° C. for 50 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 12% by weight with an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 7.0 nm and a specific surface area of 389 m 2 / g. Moreover, the average value of the minor axis / major axis ratio was 0.95.
ＢＥＴ法により測定される平均粒子径が８０ｎｍ、比表面積が３４ｍ2／ｇ、ＳｉＯ2濃度が４０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−８０）を純水で希釈して、ＳｉＯ2濃度を２０重量％に調整した後、５％硫酸水溶液にてｐＨ３に調整した。
このシリカゾル５００ｇにポリ塩化アルミニウムの１０％水溶液をポリ塩化アルミニウム換算で３．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して１５０℃で３時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１５重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は８０ｎｍ、比表面積は３４ｍ2／ｇとなった。また、短径／長径比の平均値は０．９７となった
Silica sol (catalyst SI-80, produced by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter of 80 nm, a specific surface area of 34 m 2 / g, and a SiO 2 concentration of 40% by weight measured by the BET method is diluted with pure water, After adjusting the SiO 2 concentration to 20% by weight, the pH was adjusted to 3 with a 5% aqueous sulfuric acid solution.
To 500 g of this silica sol, 3.0 g of a 10% aqueous solution of polyaluminum chloride was added in terms of polyaluminum chloride, and after sufficiently stirring and mixing at room temperature, the mixture was heated and stirred at 150 ° C. for 3 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 15% by weight with an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 80 nm and a specific surface area of 34 m 2 / g. Moreover, the average value of the minor axis / major axis ratio was 0.97.
ＢＥＴ法により測定される平均粒子径が７．０ｎｍ、比表面積が３９０ｍ2／ｇ、ＳｉＯ2濃度が３０重量％のシリカゾル（触媒化成工業株式会社製、カタロイドＳＩ−３５０）を純水で希釈して、ＳｉＯ2濃度を１０重量％に調整した後、５％水酸化ナトリウムにてｐＨ６に調整した。
このシリカゾル５００ｇに塩化アルミニウムの１０％水溶液を塩化アルミニウム換算で５．０ｇ添加し、常温で充分に攪拌、混合した後、加熱して１２０℃で５時間撹拌した。次いで、室温まで冷却し、得られたシリカゾルを限外濾過膜でＳｉＯ2濃度１２重量％まで濃縮した。
ここで得られたシリカゾルの平均粒子径は８．０ｎｍ、比表面積は３４０ｍ2／ｇとなった。また、短径／長径比の平均値は０．８７となった
A silica sol (catalyst SI-350, manufactured by Catalytic Chemical Industry Co., Ltd.) having an average particle diameter of 7.0 nm, a specific surface area of 390 m 2 / g, and a SiO 2 concentration of 30% by weight measured by the BET method is diluted with pure water. The SiO 2 concentration was adjusted to 10% by weight, and then adjusted to pH 6 with 5% sodium hydroxide.
To 500 g of this silica sol, 5.0 g of a 10% aqueous solution of aluminum chloride was added in terms of aluminum chloride, and the mixture was sufficiently stirred and mixed at room temperature, then heated and stirred at 120 ° C. for 5 hours. Next, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 12% by weight with an ultrafiltration membrane.
The silica sol thus obtained had an average particle size of 8.0 nm and a specific surface area of 340 m 2 / g. Moreover, the average value of the minor axis / major axis ratio was 0.87.
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