JP2007153671A - Method for manufacturing anisotropic-shape silica sol - Google Patents
Method for manufacturing anisotropic-shape silica sol Download PDFInfo
- Publication number
- JP2007153671A JP2007153671A JP2005351259A JP2005351259A JP2007153671A JP 2007153671 A JP2007153671 A JP 2007153671A JP 2005351259 A JP2005351259 A JP 2005351259A JP 2005351259 A JP2005351259 A JP 2005351259A JP 2007153671 A JP2007153671 A JP 2007153671A
- Authority
- JP
- Japan
- Prior art keywords
- silica sol
- sio
- silicate
- silicic acid
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 217
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 100
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 84
- 239000007864 aqueous solution Substances 0.000 claims abstract description 57
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 48
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical group NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 16
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 15
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Chemical group CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Chemical group CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 113
- 239000002245 particle Substances 0.000 claims description 69
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 10
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 abstract description 34
- 239000000203 mixture Substances 0.000 abstract description 34
- 239000003082 abrasive agent Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 73
- 239000011734 sodium Substances 0.000 description 54
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 44
- 239000004115 Sodium Silicate Substances 0.000 description 42
- 229910052911 sodium silicate Inorganic materials 0.000 description 42
- 239000000377 silicon dioxide Substances 0.000 description 24
- 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
- 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 14
- 238000004438 BET method Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003729 cation exchange resin Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- -1 silica and alumina 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000002242 deionisation method Methods 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
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 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
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 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
- 239000012535 impurity Substances 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
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium 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
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000000108 ultra-filtration Methods 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 239000004111 Potassium silicate Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 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
- 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 229910021485 fumed silica Inorganic materials 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
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron 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
- 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
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 230000001376 precipitating effect Effects 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
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction 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
Abstract
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, abrasives containing such irregularly shaped particles include aluminum disks (plated layer on aluminum or its base), aluminum wiring of semiconductor multilayer wiring boards, 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. SiO 2 / M 2 O production processes for substantially sol silica fine strand shape is dispersed consisting of (molar ratio) as a 60 to 100 in the reaction solution were added are disclosed.
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 composed of 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-A-2001-150334 (Patent Document 11), an acidic aqueous solution of active silicic acid as SiO 2 concentration of about 2-6% by weight obtained by decationizing treating 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, 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、水溶性珪酸塩の水溶液に対して珪酸液を添加して、ＳｉＯ2／Ｍ2Ｏ［Ｍはアルカリ金属、第３級アンモニウム、第４級アンモニウムまたはグアニジンから選ばれる］（モル比）が３０〜６５の範囲の混合液を調製し、該混合液に６０〜２００℃の温度で、再度珪酸液を断続的または連続的に添加することによりシリカゾルを調製し、該シリカゾルをｐＨ７〜９の範囲にて、６０〜９８℃で加熱することを特徴とするものである。 In the method for producing an anisotropic silica sol of the present invention, a silicic acid solution is added to an aqueous solution of a water-soluble silicate, and SiO 2 / M 2 O [M is an alkali metal, tertiary ammonium, quaternary ammonium or (Selected from guanidine) (molar ratio) is prepared in the range of 30 to 65, and the silica sol is added to the mixture at a temperature of 60 to 200 ° C. by adding the silicic acid solution intermittently or continuously again. The silica sol is prepared and heated at 60 to 98 ° C. in the pH range of 7 to 9.
前記シリカゾルにｐＨ調整剤を添加したり、イオン交換樹脂による脱イオンにより、ｐＨ７〜９の範囲にすることが好ましい。
前記混合液に対する前記珪酸液の添加量が、ＳｉＯ2／Ｍ2Ｏ［Ｍはアルカリ金属第３級アンモニウム、第４級アンモニウムまたはグアニジンから選ばれる］（モル比）が３０〜１５０の範囲となる量であることが好ましい。
前記水溶性珪酸塩が、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ものであることが好ましい。
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ることが好ましい。
It is preferable to add a pH adjuster to the silica sol or to make the pH within a range of 7 to 9 by deionization with an ion exchange resin.
The addition amount of the silicic acid solution to the mixed solution is in the range of SiO 2 / M 2 O [M is selected from alkali metal tertiary ammonium, quaternary ammonium or guanidine] (molar ratio) in the range of 30 to 150. An amount is preferred.
The water-soluble silicate is preferably selected from alkali metal silicate, tertiary ammonium silicate, quaternary ammonium silicate, or guanidine silicate.
The silicic acid solution is preferably prepared by dealkalizing a water-soluble silicate selected from alkali metal silicate, tertiary ammonium silicate, quaternary ammonium silicate or guanidine silicate.
本発明の異方形状シリカゾルは、前記いずれかの方法によって得られる平均粒子径が４〜２０ｎｍの範囲にあり、短径／長径比が０．０５〜０．５の範囲にある異方形状シリカゾルである。 The anisotropic shaped silica sol of the present invention has an average particle diameter obtained by any of the above methods in the range of 4 to 20 nm, and a short diameter / long diameter ratio in the range of 0.05 to 0.5. It is.
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。
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。
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.
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(モル比)が１００〜５,０００、ＳｉＯ2濃度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 (molar ratio) of 100 to 5,000, SiO 2 concentration of 10% by weight or less, preferably 2 to 7% by weight. Gelation at normal temperature hardly occurs, is relatively stable, and is practically used as a raw material.
水溶性珪酸塩
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。
Water-soluble silicate 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, and quaternary composed of quaternary ammonium and silicic acid. Examples thereof include ammonium silicate and guanidine silicate composed of guanidine and silicic acid.
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。
水溶性珪酸塩を原料として、珪酸液を調製する場合は、水溶性珪酸塩を水溶液にして、前記の通り脱陽イオン処理などが行なわれる。このような水溶性珪酸塩の水溶性については、通常はＳｉＯ2／Ｍ2Ｏ（モル比、Ｍはアルカリ金属、第３級アンモニウム、第４級アンモニウムまたはグアニジンから選ばれる）が約１〜４．５のものが好適に用いられる。また、このような水溶性珪酸塩の濃度については、格別に制限はないが、実用上は１５〜３５重量％のものが使用される。なお、珪酸液を添加するにあたり、適宜、更に水希釈して使用しても良い。
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.
When preparing a silicic acid solution using a water-soluble silicate as a raw material, the water-soluble silicate is used as an aqueous solution, and decation treatment or the like is performed as described above. As for the water solubility of such water-soluble silicates, SiO 2 / M 2 O (molar ratio, M is selected from alkali metals, tertiary ammonium, quaternary ammonium or guanidine) is usually about 1-4. .5 is preferably used. Further, the concentration of such a water-soluble silicate is not particularly limited, but a concentration of 15 to 35% by weight is practically used. In addition, when adding a silicic acid liquid, you may dilute and use it further suitably.
水溶性珪酸塩の水溶液と珪酸液の混合
本発明製造方法においては、最初に前記珪酸液を水溶性珪酸塩の水溶液に添加する。これにより粒子が調製され、得られた粒子を種粒子として、後の工程で粒子成長を行なう。
水溶性珪酸塩の水溶液に対する、珪酸液の添加量は、水溶性珪酸塩の水溶液に所定の珪酸液の全量を添加して混合液とした段階で、ＳｉＯ2／Ｍ2Ｏ（モル比、Ｍはアルカリ金属、第３級アンモニウム、第４級アンモニウムまたはグアニジンから選ばれる。）が３０〜６５、好ましくは３３〜６３の範囲となるように添加する。
前記ＳｉＯ2／Ｍ2Ｏの値が３０未満の場合は、最終的に得られるシリカゾル中のシリカ微粒子の形状が球状に近いものになる。他方、ＳｉＯ2／Ｍ2Ｏの値が６５を越える場合は、製造工程中でシリカゾルの安定性が低下し、ゲル化を起こし易くなるため好ましくない。
Mixing of an aqueous solution of a water-soluble silicate and a silicate solution In the production method of the present invention, first, the silicate solution is added to an aqueous solution of a water-soluble silicate. As a result, particles are prepared, and the obtained particles are used as seed particles for particle growth in a later step.
The addition amount of the silicic acid solution relative to the aqueous solution of the water-soluble silicate is SiO 2 / M 2 O (molar ratio, M Is selected from alkali metals, tertiary ammonium, quaternary ammonium or guanidine) is added in a range of 30 to 65, preferably 33 to 63.
When the value of SiO 2 / M 2 O is less than 30, the shape of the silica fine particles in the finally obtained silica sol becomes nearly spherical. On the other hand, when the value of SiO 2 / M 2 O exceeds 65, it is not preferable because the stability of the silica sol is lowered during the production process and gelation is likely to occur.
珪酸液を水溶性珪酸塩の水溶液に添加する際の温度は、５０℃以下、好ましくは４０℃以下で行なわれる。 珪酸液を水溶性珪酸塩の水溶液に添加する際の温度が５０℃を超える場合は、ゲル化が発生し易くなり好ましくない。通常は、常温以上、５０℃以下の範囲で行なわれる。珪酸液の水溶性珪酸塩の水溶液への添加が終了した後は、好適には０．１〜５時間、充分に攪拌する。 The temperature for adding the silicic acid solution to the aqueous solution of the water-soluble silicate is 50 ° C. or less, preferably 40 ° C. or less. If the temperature when adding the silicic acid solution to the aqueous solution of the water-soluble silicate exceeds 50 ° C., gelation tends to occur, which is not preferable. Usually, it is carried out in the range of room temperature to 50 ° C. After the addition of the silicic acid solution to the aqueous solution of the water-soluble silicate, it is preferably stirred sufficiently for 0.1 to 5 hours.
粒子成長
珪酸液と水溶性珪酸塩の水溶液からなる混合液を加熱して、６０〜２００℃にて、更に珪酸液を断続的にまたは連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。ここで使用する珪酸液としては、前記と同様な条件の珪酸液が使用できる。即ち、ｐＨは２〜４、ＳｉＯ2／Ｎａ2Ｏ(モル比)が１００〜５,０００、ＳｉＯ2濃度１０重量％以下、好ましくは２〜７重量％のものが使用される。
珪酸液の添加量については、格別に制限されるものではないが、通常は所定の珪酸液の全量を添加した段階で、ＳｉＯ2／Ｍ2Ｏの値（モル比）が３０〜１５０の範囲となるように添加される。特にＳｉＯ2／Ｍ2Ｏの値（モル比）が６０〜１５０の範囲にある場合は、シリカ粒子は安定であり好ましい。
Silica sol is grown by heating a liquid mixture consisting of an aqueous solution of particle-growth silicate solution and water-soluble silicate, and further adding the silicate solution intermittently or continuously at 60 to 200 ° C. To prepare. As a silicic acid liquid used here, the silicic acid liquid of the same conditions as the above can be used. That is, the pH is 2 to 4, the SiO 2 / Na 2 O (molar ratio) is 100 to 5,000, and the SiO 2 concentration is 10 wt% or less, preferably 2 to 7 wt%.
The addition amount of the silicic acid solution is not particularly limited, but usually the SiO 2 / M 2 O value (molar ratio) is in the range of 30 to 150 at the stage when the total amount of the predetermined silicic acid solution is added. To be added. In particular, when the SiO 2 / M 2 O value (molar ratio) is in the range of 60 to 150, the silica particles are stable and preferable.
主として混合液を安定させることを目的として、珪酸液の添加前に６０〜９８℃にて３０分から３時間程度、静置させることにより、熟成してから、珪酸液の添加を開始しても良い。
水溶性珪酸塩の水溶液への珪酸液の添加に当たっては、珪酸液を断続的にまたは連続的に添加する方法がとられる。通常は５分から７２時間かけて、混合液のゲル化を招かないように添加が行なわれる。珪酸液の添加終了後は、直ちに次の工程を行なっても良いが、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。
Mainly for the purpose of stabilizing the mixed solution, the addition of the silicic acid solution may be started after aging by allowing it to stand for 30 minutes to 3 hours at 60 to 98 ° C. before adding the silicic acid solution. .
In adding the silicic acid solution to the aqueous solution of the water-soluble silicate, a method of adding the silicic acid solution intermittently or continuously is employed. Usually, addition is performed over 5 minutes to 72 hours so as not to cause gelation of the mixed solution. After completion of the addition of the silicic acid solution, the next step may be performed immediately, but it may be maintained for 1 to 3 hours, gradually cooled before proceeding to the next step, or allowed to cool for several hours. The process may proceed to the next step after the room temperature is reached.
加熱工程
次に得られたシリカゾルをｐＨ７〜９の範囲にて、６０〜９８℃にて加熱することにより、非球状のシリカ微粒子が分散した異方形状シリカゾルを調製する。
加熱前のシリカゾルのｐＨが７〜９の範囲にない場合は、限外濾過による脱イオン、イオン交換樹脂（陽イオン交換樹脂または陰イオン交換樹脂）による脱イオン若しくはｐＨ調整剤を添加して、ｐＨを７〜９の範囲に調整する。なお、ｐＨ調製剤としては、酸性側に調整する場合は、通常、硫酸、塩酸、硝酸などの水溶液が使用できる。アルカリ性側に調整する場合は、通常、水酸化ナトリウム水溶液、アンモニア水溶液などが使用できる。ｐＨが７未満の場合は、シリカゾルがゲル化し易くなる。他方、ｐＨが９を越える場合は、最終的に得られるシリカゾルのシリカ微粒子が球状になり易くなる。加熱前のｐＨの調整範囲としては、好適にはｐＨ７．８〜８．８の範囲が推奨される。
Heating step Next, the obtained silica sol is heated in the range of pH 7 to 9 at 60 to 98 ° C to prepare an anisotropic shaped silica sol in which non-spherical silica fine particles are dispersed.
When the pH of the silica sol before heating is not in the range of 7-9, deionization by ultrafiltration, deionization by ion exchange resin (cation exchange resin or anion exchange resin) or pH adjuster is added, Adjust the pH to a range of 7-9. In addition, as a pH adjuster, when adjusting to an acidic side, aqueous solutions, such as a sulfuric acid, hydrochloric acid, nitric acid, can usually be used. When adjusting to the alkaline side, sodium hydroxide aqueous solution, ammonia aqueous solution, etc. can be normally used. When the pH is less than 7, the silica sol is easily gelled. On the other hand, when the pH exceeds 9, the silica fine particles of the finally obtained silica sol tend to be spherical. As the pH adjustment range before heating, a pH range of 7.8 to 8.8 is recommended.
加熱時間については、格別に制限されるものではないが、通常は１時間〜２５時間程度、６０〜９８℃で加熱を行なう。加熱温度が６０℃未満の場合は、成長が遅く、不安定であり、他方、９８℃以上の場合は、ｐＨ変動が大きくなり易く、制御し難いので好ましくない。
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、シリカ粒子が連結することと、シリカがｐＨ７〜９で過飽和状態となり、シリカ粒子同士の連結部分に析出することによるものと推察される。
Although it does not restrict | limit especially about a heating time, Usually, it heats at 60-98 degreeC for about 1 hour-25 hours. When the heating temperature is less than 60 ° C., the growth is slow and unstable. On the other hand, when the heating temperature is 98 ° C. or more, the pH fluctuation tends to be large and difficult to control.
About the anisotropically shaped silica sol production method according to the present invention, the anisotropically shaped silica sol can be efficiently prepared. The silica particles are connected, and the silica is supersaturated at pH 7 to 9, and the silica particles are connected to each other. This is presumably due to precipitation.
［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４〜２０ｎｍであり、短径／長径比が０．０５〜０．５の範囲にある。
平均粒子径が４ｎｍ未満の場合は、シリカゾルの性状が不安定である。他方、２０ｎｍを越える場合は、調製段階において成長速度が遅くなり、また、シリカ粒子間の連結部分にシリカを析出させて安定した異方形状シリカゾルを得ることが容易ではなくなる。
[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 4 to 20 nm, and the minor axis / major axis ratio is 0.05. It is in the range of ~ 0.5.
When the average particle diameter is less than 4 nm, the properties of the silica sol are unstable. On the other hand, when it exceeds 20 nm, the growth rate is slow in the preparation stage, and it is not easy to obtain a stable anisotropic silica sol by precipitating silica at the connecting portion between silica particles.
また、短径／長径比が０．０５未満の場合は、異方性に基づく特性が発揮され難い。他方、０．５を越える場合は、粘度が高くなるため、濃度を高くすることができなくなり、実用上問題が生じやすくなる。
本発明の異方形状シリカゾルについては、好適には平均粒子径が４〜１５ｎｍの範囲にあるものが推奨される。また、短径／長径比については０．０５〜０．４５の範囲のものが推奨される。
In addition, when the minor axis / major axis ratio is less than 0.05, it is difficult to exhibit characteristics based on anisotropy. On the other hand, if it exceeds 0.5, the viscosity becomes high, so that the concentration cannot be increased, and problems in practice are likely to occur.
Regarding the anisotropic shaped silica sol of the present invention, those having an average particle diameter in the range of 4 to 15 nm are recommended. Also, a minor diameter / major diameter ratio in the range of 0.05 to 0.45 is recommended.
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比表面積は、１５０〜７００ｍ2／ｇの範囲にある。
本発明の異方形状シリカゾルのＳｉＯ2濃度は、通常、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 specific surface area of the anisotropic shaped silica sol of the present invention is in the range of 150 to 700 m 2 / g.
The SiO 2 concentration of the anisotropic shaped silica sol of the present invention is usually preferably 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 methyl acetate and ethyl acetate 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、ＳｉＯ2濃度が２４重量％でＮａ2Ｏ濃度が８．１６重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水８９５ｇを添加して、珪酸ナトリウム水溶液９１４ｇを調製した。
次に、この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１,２００）を、３５℃の温度条件下、１,９００ｇ添加することにより、珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比６０）を得た。
18.7 g of a sodium silicate aqueous solution (SiO 2 / Na 2 O molar ratio 3) having a SiO 2 concentration of 24% by weight and a Na 2 O concentration of 8.16% by weight is placed in a separable flask equipped with a reflux condenser and a stirrer, and water 895g was added and 914g of sodium silicate aqueous solution was prepared.
Next, sodium silicate (SiO 2 / Na 2 O molar ratio: 3) having a SiO 2 concentration of 4.82% by weight was passed through the cation exchange resin tower through this sodium silicate aqueous solution to obtain a SiO 2 concentration of 4.82. By adding 1,900 g of a weight percent silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1,200) under a temperature condition of 35 ° C., a mixed solution comprising a silicic acid solution and an aqueous sodium silicate solution (SiO 2 / Na 2 O molar ratio 60) was obtained.
得られた混合液を加温し、８０℃の温度で３０分間熟成した。８０℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液３２９ｇを２時間かけて添加して、ｐＨ８．７のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
このシリカゾルを７０℃にて１２時間加熱した後、エバポレーターにてＳｉＯ2濃度２０重量％まで濃縮した。
The resulting mixture was warmed and aged at 80 ° C. for 30 minutes. While maintaining at 80 ° C., 329 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to this solution over 2 hours to obtain a silica sol having a pH of 8.7. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
The silica sol was heated at 70 ° C. for 12 hours, and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator.
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×〔粒子の密度〕 （本発明においては、シリカ粒子であり、密度は２．２となる。）」の式から平均粒子径を求めたところ、６ｎｍ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. Measurement is performed by a nitrogen adsorption method (BET method) using a surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12). Then, the specific surface area (SA) is determined from the amount of nitrogen adsorbed by the BET method, and “particle diameter (Dp) = 6000 / SA × [particle density] (in the present invention, silica particles, and the density is 2.2). The average particle size was determined from the formula of “)” to be 6 nm.
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、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。これ以降の実施例と比較例についても同様に表１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. The major axis (maximum length) and the minor axis (maximum thickness) were measured, and the ratio of the minor axis / major axis ratio was calculated. The average value was 0.15. The particle diameter and the minor axis / major axis ratio are shown in Table 1. The subsequent examples and comparative examples are also shown in Table 1.
還流器および攪拌機付セパラブルフラスコに、ＳｉＯ2濃度２４重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水９１３ｇを添加して、珪酸ナトリウム水溶液９３１ｇを調製した。
次に、この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１,２００）を１,２３５ｇ添加することにより珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比４０）を得た。
18.7 g of a sodium silicate aqueous solution (SiO 2 / Na 2 O molar ratio 3) having a SiO 2 concentration of 24% by weight was added to a separable flask equipped with a reflux condenser and a stirrer, and further 913 g of water was added to prepare 931 g of an aqueous sodium silicate solution. did.
Then, the aqueous sodium silicate solution, SiO 2 concentration obtained by passing a SiO 2 concentration of 4.82 wt% of sodium silicate (SiO 2 / Na 2 O molar ratio 3) to a cation exchange resin column 4.82 By adding 1,235 g of a weight percent silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1,200), a mixed solution (SiO 2 / Na 2 O molar ratio comprising a silicic acid solution and an aqueous sodium silicate solution) 40) was obtained.
得られた液を加温し、８０℃の温度で３０分間熟成した。その後、さら８０℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液９９５ｇを３時間かけて添加して、ｐＨ８．５のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
このシリカゾルを８０℃にて１３時間加熱した後、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は、６ｎｍとなった。また、このシリカゾルの短径／長径比は、０．１７となった。
The obtained liquid was heated and aged at 80 ° C. for 30 minutes. Thereafter, 995 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to this solution over a period of 3 hours while maintaining at 80 ° C. to obtain a silica sol having a pH of 8.5. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
The silica sol was heated at 80 ° C. for 13 hours and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 6 nm. Further, the minor axis / major axis ratio of this silica sol was 0.17.
還流器および攪拌機付セパラブルフラスコにＳｉＯ2濃度２４重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水８３７ｇを添加して、珪酸ナトリウム水溶液８５５ｇを調製した。
次に、この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１２００）を１,０６７ｇ添加することにより珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比３５）を得た。
18.7 g of a sodium silicate aqueous solution (SiO 2 / Na 2 O molar ratio 3) having a SiO 2 concentration of 24 wt% was placed in a separable flask equipped with a reflux condenser and a stirrer, and 837 g of water was further added to prepare 855 g of an aqueous sodium silicate solution. .
Next, sodium silicate (SiO 2 / Na 2 O molar ratio: 3) having a SiO 2 concentration of 4.82% by weight was passed through the cation exchange resin tower through this sodium silicate aqueous solution to obtain a SiO 2 concentration of 4.82. By adding 1,067 g of a weight percent silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1200), a mixed liquid consisting of a silicic acid solution and an aqueous sodium silicate solution (SiO 2 / Na 2 O molar ratio 35) Got.
得られた液を加温し、９８℃の温度で３０分間熟成した。その後、さら９８℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液１,１６２ｇを４時間かけて添加して、ｐＨ８．９のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
このシリカゾルのｐＨが８．５になるように２．５％硫酸水溶液を加え、９０℃にて８時間加熱した後、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は、１２ｎｍだった。また、このシリカゾルの短径／長径比は、０．４０となった。
The resulting liquid was heated and aged at 98 ° C. for 30 minutes. Thereafter, 1,162 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to this solution over a period of 4 hours, and a silica sol having a pH of 8.9 was obtained. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
A 2.5% aqueous sulfuric acid solution was added so that the silica sol had a pH of 8.5, and the mixture was heated at 90 ° C. for 8 hours, and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 12 nm. Further, the minor axis / major axis ratio of this silica sol was 0.40.
還流器および攪拌機付セパラブルフラスコにＳｉＯ2濃度２４重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水８９６ｇを添加して、珪酸ナトリウム水溶液９１４ｇを調製した。
次に、この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１２００）を１,９００ｇ添加することにより珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比６０）を得た。
18.7 g of a sodium silicate aqueous solution (SiO 2 / Na 2 O molar ratio 3) having a SiO 2 concentration of 24 wt% was placed in a separable flask equipped with a reflux condenser and a stirrer, and 896 g of water was further added to prepare 914 g of an aqueous sodium silicate solution. .
Next, sodium silicate (SiO 2 / Na 2 O molar ratio: 3) having a SiO 2 concentration of 4.82% by weight was passed through the cation exchange resin tower through this sodium silicate aqueous solution to obtain a SiO 2 concentration of 4.82. wt% silicate solution (pH2.3, SiO 2 / Na 2 O molar ratio = 1200) consisting of silicic acid solution and an aqueous sodium silicate solution by the addition of 1,900g mixture (SiO 2 / Na 2 O molar ratio of 60) Got.
得られた液を加温し、８０℃の温度で３０分間熟成した。その後、さら８０℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液３２９ｇを５時間かけて添加して、ｐＨ８．６のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
このシリカゾルを８０℃にて１４時間加熱した後、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は、６ｎｍだった。また、このシリカゾルの短径／長径比は、０．２２となった。
The obtained liquid was heated and aged at 80 ° C. for 30 minutes. Thereafter, 329 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to this solution over a period of 5 hours while maintaining the temperature at 80 ° C. to obtain a silica sol having a pH of 8.6. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
The silica sol was heated at 80 ° C. for 14 hours and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 6 nm. Further, the minor axis / major axis ratio of this silica sol was 0.22.
還流器および攪拌機付セパラブルフラスコにＳｉＯ2濃度２４重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水８９６ｇを添加して、実施例１と同様な珪酸ナトリウム水溶液９１４ｇを調製し、珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１２００）を１９００ｇ添加することにより珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比６０）を得た。 18.7 g of a sodium silicate aqueous solution (SiO 2 / Na 2 O molar ratio 3) having a SiO 2 concentration of 24% by weight was added to a separable flask equipped with a reflux condenser and a stirrer, and 896 g of water was further added. aqueous sodium 914g prepared, the aqueous sodium silicate solution, SiO 2 concentration obtained by passing a SiO 2 concentration of 4.82 wt% of sodium silicate (SiO 2 / Na 2 O molar ratio 3) to a cation exchange resin column By adding 1900 g of a 4.82 wt% silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1200), a mixed solution (SiO 2 / Na 2 O molar ratio 60 comprising a silicic acid solution and an aqueous sodium silicate solution) )
得られた液を加温し、７０℃の温度で３０分間熟成した。その後、さら７０℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液３２９ｇを２時間かけて添加して、ｐＨ７．８のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
このシリカゾルのｐＨが８．３になるように５％水酸化ナトリウム水溶液を加え、７０℃にて１２時間加熱した後、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は、５ｎｍだった。また、このシリカゾルの短径／長径比は、０．３０となった。
The obtained liquid was heated and aged at 70 ° C. for 30 minutes. Thereafter, 329 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to this solution over a period of 2 hours while maintaining at 70 ° C. to obtain a silica sol having a pH of 7.8. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
A 5% aqueous sodium hydroxide solution was added so that the silica sol had a pH of 8.3, and the mixture was heated at 70 ° C. for 12 hours, and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 5 nm. Further, the minor axis / major axis ratio of this silica sol was 0.30.
還流器および攪拌機付セパラブルフラスコにＳｉＯ2濃度２４重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水８９６ｇを添加して、珪酸ナトリウム水溶液９１４ｇを調製した。
次いで、この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１２００）を１９００ｇ添加することにより、珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比６０）を得た。
Reflux condenser and SiO 2 concentration of 24 wt% aqueous solution of sodium silicate into a separable flask equipped with a stirrer (SiO 2 / Na 2 O molar ratio 3) 18.7 g was placed, further water was added 896 g, to prepare an aqueous solution of sodium silicate 914g .
Next, sodium silicate (SiO 2 / Na 2 O molar ratio: 3) having a SiO 2 concentration of 4.82% by weight was passed through the cation exchange resin tower through this sodium silicate aqueous solution to obtain a SiO 2 concentration of 4.82%. % Of silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1200) is added to obtain a mixed solution (SiO 2 / Na 2 O molar ratio of 60) composed of silicic acid solution and sodium silicate aqueous solution. It was.
得られた液を加温し、６５℃の温度で３０分間熟成した。その後、さら６５℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液３２９ｇを２時間かけて添加して、ｐＨ７．５のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
このシリカゾルのｐＨが８．２になるように５％水酸化ナトリウムを加え、６５℃にて１８時間加熱した後、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は、５ｎｍだった。また、このシリカゾルの短径／長径比は、０．３１となった。
The resulting liquid was heated and aged at 65 ° C. for 30 minutes. Thereafter, 329 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to the solution over a period of 2 hours while maintaining the temperature at 65 ° C. to obtain a silica sol having a pH of 7.5. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
5% sodium hydroxide was added so that the silica sol had a pH of 8.2, and the mixture was heated at 65 ° C. for 18 hours, and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 5 nm. Further, the minor axis / major axis ratio of this silica sol was 0.31.
実施例１と同様に珪酸ナトリウム水溶液９１４ｇを調製し、この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１２００）を１９００ｇ添加することにより、珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比６０）を得た。
得られた液を加温し、５０℃の温度で３０分間熟成した。その後、さら５０℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液３２９ｇを２時間かけて添加して、ｐＨ９．２のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
In the same manner as in Example 1, 914 g of an aqueous sodium silicate solution was prepared, and sodium silicate having a SiO 2 concentration of 4.82% by weight (SiO 2 / Na 2 O molar ratio 3) was passed through the cation exchange resin tower through this sodium silicate aqueous solution. By adding 1900 g of a silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1200) having a SiO 2 concentration of 4.82% by weight, a mixed solution comprising a silicic acid solution and an aqueous sodium silicate solution ( A SiO 2 / Na 2 O molar ratio of 60) was obtained.
The obtained liquid was heated and aged at 50 ° C. for 30 minutes. Thereafter, 329 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to the solution over a period of 2 hours while maintaining the temperature at 50 ° C. to obtain a silica sol having a pH of 9.2. It shows the SiO 2 / Na 2 O molar ratio of the silica sol in Table 1.
このシリカゾルのｐＨが８．５になるように２．５％硫酸水溶液を加え、８０℃にて１２時間加熱した後、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は、４ｎｍだった。また、このシリカゾルの短径／長径比は、０．０３となった。
A 2.5% aqueous sulfuric acid solution was added so that the silica sol had a pH of 8.5, and the mixture was heated at 80 ° C. for 12 hours, and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 4 nm. Further, the minor axis / major axis ratio of this silica sol was 0.03.
還流器および攪拌機付セパラブルフラスコにＳｉＯ2濃度２４重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水９２４ｇを添加して、実施例１と同様に珪酸ナトリウム水溶液９４２ｇを調製した。この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１２００）を５６５ｇ添加することにより、珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比２０）を得た。
得られた液を加温し、８０℃の温度で３０分間熟成した。その後、さらに６５℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液１,６６４ｇを２時間かけて添加して、ｐＨ９．１のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
18.7 g of a sodium silicate aqueous solution (SiO 2 / Na 2 O molar ratio 3) having a SiO 2 concentration of 24% by weight was added to a separable flask equipped with a reflux condenser and a stirrer, and further 924 g of water was added thereto. 942 g of aqueous sodium solution was prepared. A sodium silicate (SiO 2 / Na 2 O molar ratio: 3) having a SiO 2 concentration of 4.82% by weight was passed through the cation exchange resin tower through this sodium silicate aqueous solution, and the SiO 2 concentration was 4.82% by weight. By adding 565 g of a silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1200), a mixed solution (SiO 2 / Na 2 O molar ratio 20) composed of the silicic acid solution and a sodium silicate aqueous solution was obtained.
The obtained liquid was heated and aged at 80 ° C. for 30 minutes. Thereafter, 1,664 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to this solution over a period of 2 hours, and a silica sol having a pH of 9.1 was obtained. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
このシリカゾルのｐＨが８．４になるように２．５％硫酸水溶液を加え、７０℃にて１２時間加熱した後、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は、９ｎｍだった。また、このシリカゾルの短径／長径比は、０．０４となった。
A 2.5% aqueous sulfuric acid solution was added so that the silica sol had a pH of 8.4, and the mixture was heated at 70 ° C. for 12 hours, and then concentrated to an SiO 2 concentration of 20 wt% by an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 9 nm. Further, the minor axis / major axis ratio of this silica sol was 0.04.
還流器および攪拌機付セパラブルフラスコにＳｉＯ2濃度２４重量％の珪酸ナトリウム水溶液（ＳｉＯ2／Ｎａ2Ｏモル比３）１８．７ｇ入れ、さらに水６８５ｇを添加して、実施例１と同様に珪酸ナトリウム水溶液７０３ｇを調製した。この珪酸ナトリウム水溶液に、ＳｉＯ2濃度４．８２重量％の珪酸ナトリウム（ＳｉＯ2／Ｎａ2Ｏモル比３）を陽イオン交換樹脂塔に通すことにより得られたＳｉＯ2濃度４．８２重量％の珪酸液（ｐＨ２．３、ＳｉＯ2／Ｎａ2Ｏモル比＝１２００）を１７３ｇ添加することにより、珪酸液と珪酸ナトリウム水溶液からなる混合液（ＳｉＯ2／Ｎａ2Ｏモル比１０）を得た。
得られた液を加温し、８０℃の温度で３０分間熟成した。その後、さら８０℃に保持した状態で、この液に前記珪酸液と同じ組成の珪酸液８６２ｇを２時間かけて添加して、ｐＨ９．０のシリカゾルを得た。このシリカゾルのＳｉＯ2／Ｎａ2Ｏモル比を表１に示す。
18.7 g of a sodium silicate aqueous solution (SiO 2 / Na 2 O molar ratio 3) having a SiO 2 concentration of 24% by weight was added to a separable flask equipped with a reflux condenser and a stirrer, and 685 g of water was further added. A sodium aqueous solution (703 g) was prepared. A sodium silicate (SiO 2 / Na 2 O molar ratio: 3) having a SiO 2 concentration of 4.82% by weight was passed through the cation exchange resin tower through this sodium silicate aqueous solution, and the SiO 2 concentration was 4.82% by weight. By adding 173 g of a silicic acid solution (pH 2.3, SiO 2 / Na 2 O molar ratio = 1200), a mixed solution (SiO 2 / Na 2 O molar ratio 10) composed of a silicic acid solution and a sodium silicate aqueous solution was obtained.
The obtained liquid was heated and aged at 80 ° C. for 30 minutes. Thereafter, 862 g of a silicic acid solution having the same composition as that of the silicic acid solution was added to the solution over a period of 2 hours while maintaining the temperature at 80 ° C. to obtain a silica sol having a pH of 9.0. Table 1 shows the SiO 2 / Na 2 O molar ratio of this silica sol.
このシリカゾルのｐＨが８．４になるように２．５％硫酸水溶液を加え、８０℃にて１２時間加熱した後、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は、１２ｎｍだった。また、このシリカゾルの短径／長径比は、０．０３となった。
A 2.5% aqueous sulfuric acid solution was added so that the silica sol had a pH of 8.4, and the mixture was heated at 80 ° C. for 12 hours, and then concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a silica sol.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 12 nm. Further, the minor axis / major axis ratio of this silica sol was 0.03.
実施例１と同様にしてｐＨ８．７のシリカゾルを調製し、そのｐＨが６．５になるように２．５％硫酸水溶液を加え、７０℃にて１２時間加熱を行なったところゲル化した。
A silica sol having a pH of 8.7 was prepared in the same manner as in Example 1, 2.5% sulfuric acid aqueous solution was added so that the pH was 6.5, and the mixture was heated at 70 ° C. for 12 hours to gel.
実施例１と同様にしてｐＨ８．７のシリカゾルを調製し、そのｐＨが１０．０になるように５％水酸化ナトリウム水溶液を加え、７０℃にて１２時間加熱した後、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は、７ｎｍだった。また、このシリカゾルの短径／長径比は、０．０１となった。
Example 1 silica sol pH8.7 was prepared in the same manner as the 5% sodium hydroxide aqueous solution so that the pH is 10.0 was added and after heating at 70 ° C. 12 h, SiO in an evaporator 2 A silica sol was prepared by concentrating to a concentration of 20% by weight.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 7 nm. Further, the minor axis / major axis ratio of this silica sol was 0.01.
実施例１と同様にしてｐＨ８．７のシリカゾルを調製し、そのｐＨが８．５になるように２．５％硫酸水溶液を加え、４０℃にて１２時間加熱した後、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は、５ｎｍだった。また、このシリカゾルの短径／長径比は、０．０１となった。
Example 1 silica sol pH8.7 was prepared in the same manner as the 2.5% aqueous solution of sulfuric acid so that the pH became 8.5 was added and after heating at 40 ° C. 12 h, SiO in an evaporator 2 A silica sol was prepared by concentrating to a concentration of 20% by weight.
The average particle diameter calculated from the specific surface area measured by the BET method for this silica sol was 5 nm. Further, the minor axis / major axis ratio of this silica sol was 0.01.
Claims (6)
An anisotropic silica sol having an average particle diameter of 4 to 20 nm obtained by the method according to any one of claims 1 to 5 and a minor axis / major axis ratio of 0.05 to 0.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005351259A JP4911960B2 (en) | 2005-12-05 | 2005-12-05 | Method for producing anisotropic silica sol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005351259A JP4911960B2 (en) | 2005-12-05 | 2005-12-05 | Method for producing anisotropic silica sol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007153671A true JP2007153671A (en) | 2007-06-21 |
| JP4911960B2 JP4911960B2 (en) | 2012-04-04 |
Family
ID=38238487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005351259A Active JP4911960B2 (en) | 2005-12-05 | 2005-12-05 | Method for producing anisotropic silica sol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4911960B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009184855A (en) * | 2008-02-04 | 2009-08-20 | Nippon Chem Ind Co Ltd | COLLOIDAL SILICA COMPOSED OF SILICA PARTICLES WITH FIXED epsilon-CAPROLACTAM |
| JP2009184853A (en) * | 2008-02-04 | 2009-08-20 | Nippon Chem Ind Co Ltd | Colloidal silica composed of silica particles with fixed piperidine |
| JP2009263484A (en) * | 2008-04-24 | 2009-11-12 | Nippon Chem Ind Co Ltd | Colloidal silica for polishing semiconductor wafer, and method for manufacturing the same |
| JP2010024119A (en) * | 2008-07-24 | 2010-02-04 | Jgc Catalysts & Chemicals Ltd | Method for producing confetti-like silica sol |
| JP2010143784A (en) * | 2008-12-18 | 2010-07-01 | Adeka Corp | Silica sol comprising branched chain silica particles and method for producing the same |
| JP2010528969A (en) * | 2007-06-07 | 2010-08-26 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Silica-based sol |
| JP2016000693A (en) * | 2015-09-03 | 2016-01-07 | 日揮触媒化成株式会社 | Silica particle, production method thereof and semiconductor mounting paste |
| US9272916B2 (en) | 2007-11-30 | 2016-03-01 | Jgc Catalysts And Chemicals Ltd. | Non-spherical silica sol, process for producing the same, and composition for polishing |
| JP2019518690A (en) * | 2016-03-30 | 2019-07-04 | ダウ グローバル テクノロジーズ エルエルシー | Composite containing semiconductor nanocrystals and method for preparing the same |
| WO2024047768A1 (en) * | 2022-08-30 | 2024-03-07 | 株式会社アドマテックス | Method for producing spherical silica particles |
| WO2024047769A1 (en) * | 2022-08-30 | 2024-03-07 | 株式会社アドマテックス | Spherical silica particles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01317115A (en) * | 1988-03-16 | 1989-12-21 | Nissan Chem Ind Ltd | Silica sol having long and thin particle form and production thereof |
| JP2007145633A (en) * | 2005-11-25 | 2007-06-14 | Catalysts & Chem Ind Co Ltd | Manufacturing method of anisotropic-shape silica sol |
-
2005
- 2005-12-05 JP JP2005351259A patent/JP4911960B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01317115A (en) * | 1988-03-16 | 1989-12-21 | Nissan Chem Ind Ltd | Silica sol having long and thin particle form and production thereof |
| JP2007145633A (en) * | 2005-11-25 | 2007-06-14 | Catalysts & Chem Ind Co Ltd | Manufacturing method of anisotropic-shape silica sol |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010528969A (en) * | 2007-06-07 | 2010-08-26 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Silica-based sol |
| US9487917B2 (en) | 2007-06-07 | 2016-11-08 | Akzo Nobel N.V. | Silica-based sols |
| US8846772B2 (en) | 2007-06-07 | 2014-09-30 | Akzo Nobel N.V. | Silica-based sols |
| JP2013166691A (en) * | 2007-06-07 | 2013-08-29 | Akzo Nobel Nv | Silica-based sol |
| US9272916B2 (en) | 2007-11-30 | 2016-03-01 | Jgc Catalysts And Chemicals Ltd. | Non-spherical silica sol, process for producing the same, and composition for polishing |
| US10160894B2 (en) | 2007-11-30 | 2018-12-25 | Jgc Catalysts And Chemicals Ltd. | Non-spherical silica sol, process for producing the same, and composition for polishing |
| JP2009184855A (en) * | 2008-02-04 | 2009-08-20 | Nippon Chem Ind Co Ltd | COLLOIDAL SILICA COMPOSED OF SILICA PARTICLES WITH FIXED epsilon-CAPROLACTAM |
| JP2009184853A (en) * | 2008-02-04 | 2009-08-20 | Nippon Chem Ind Co Ltd | Colloidal silica composed of silica particles with fixed piperidine |
| JP2009263484A (en) * | 2008-04-24 | 2009-11-12 | Nippon Chem Ind Co Ltd | Colloidal silica for polishing semiconductor wafer, and method for manufacturing the same |
| JP2010024119A (en) * | 2008-07-24 | 2010-02-04 | Jgc Catalysts & Chemicals Ltd | Method for producing confetti-like silica sol |
| JP2010143784A (en) * | 2008-12-18 | 2010-07-01 | Adeka Corp | Silica sol comprising branched chain silica particles and method for producing the same |
| JP2016000693A (en) * | 2015-09-03 | 2016-01-07 | 日揮触媒化成株式会社 | Silica particle, production method thereof and semiconductor mounting paste |
| JP2019518690A (en) * | 2016-03-30 | 2019-07-04 | ダウ グローバル テクノロジーズ エルエルシー | Composite containing semiconductor nanocrystals and method for preparing the same |
| WO2024047768A1 (en) * | 2022-08-30 | 2024-03-07 | 株式会社アドマテックス | Method for producing spherical silica particles |
| WO2024047769A1 (en) * | 2022-08-30 | 2024-03-07 | 株式会社アドマテックス | Spherical silica particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4911960B2 (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4911960B2 (en) | Method for producing anisotropic silica sol | |
| JP5127452B2 (en) | Method for producing deformed silica sol | |
| JP5602358B2 (en) | Non-spherical silica sol, method for producing the same, and polishing composition | |
| JP4963825B2 (en) | Polishing silica sol and polishing composition containing the same | |
| JP4911961B2 (en) | Method for producing anisotropic silica sol | |
| JP5084670B2 (en) | Silica sol and method for producing the same | |
| JP5188175B2 (en) | Silica sol and method for producing the same | |
| WO2010052945A1 (en) | Aspherical silica sol, process for producing the same, and composition for polishing | |
| JP2008137822A (en) | Konpeito-like inorganic oxide sol, its production method, and abrasive including the oxide sol | |
| JPWO2004074180A1 (en) | Alkali-resistant cocoon-type colloidal silica particles and method for producing the same | |
| JP4911955B2 (en) | Method for producing anisotropic silica sol | |
| KR100491070B1 (en) | Cerium and/or Lanthanum Phosphate Sol, Preparation Method, and Polishing Suspension, Anti-corrosion Agent and Anti-UV Agent Comprising Them | |
| JP4549878B2 (en) | Method for producing high-purity aqueous silica sol | |
| JP6207345B2 (en) | Method for producing silica particles | |
| JP2926915B2 (en) | Elongated silica sol and method for producing the same | |
| JP4979930B2 (en) | Method for producing anisotropic silica sol | |
| JP4949209B2 (en) | Non-spherical alumina-silica composite sol, method for producing the same, and polishing composition | |
| JP4936720B2 (en) | Anisotropic shaped alumina hydrate sol and process for producing the same | |
| JP5346167B2 (en) | Particle-linked alumina-silica composite sol and method for producing the same | |
| JP3993995B2 (en) | Method for producing silica sol | |
| JP2009091197A (en) | Warty-surfaced sphere-form inorganic oxide sol, method for producing same, and abrasive containing the sol | |
| JP2011016702A (en) | Particle-linked silica sol and method for producing the same | |
| JP5646143B2 (en) | Flaky composite silica fine particle dispersion and method for producing the same | |
| JP2023139490A (en) | Silica-based particle dispersion, polishing slurry for polishing magnetic disk substrate containing the same, composition for polishing magnetic disk substrate containing the same, and method for producing silica-based particle group | |
| JP2024511723A (en) | Cerium oxide particles, their manufacturing process and their use in chemical mechanical polishing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20081024 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110204 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110215 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110404 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120117 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120117 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4911960 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150127 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |