JP2021143110A - Particle-linked silica microparticle dispersion and method for producing the same, and abrasive particle dispersion for polishing - Google Patents
Particle-linked silica microparticle dispersion and method for producing the same, and abrasive particle dispersion for polishing Download PDFInfo
- Publication number
- JP2021143110A JP2021143110A JP2020044287A JP2020044287A JP2021143110A JP 2021143110 A JP2021143110 A JP 2021143110A JP 2020044287 A JP2020044287 A JP 2020044287A JP 2020044287 A JP2020044287 A JP 2020044287A JP 2021143110 A JP2021143110 A JP 2021143110A
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- Japan
- Prior art keywords
- particle
- silica fine
- linked
- particles
- fine particles
- Prior art date
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- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 1032
- 239000002245 particle Substances 0.000 title claims abstract description 563
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 510
- 239000006185 dispersion Substances 0.000 title claims abstract description 244
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000011859 microparticle Substances 0.000 title abstract 13
- 238000005498 polishing Methods 0.000 title description 124
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000002296 dynamic light scattering Methods 0.000 claims abstract description 10
- 239000010419 fine particle Substances 0.000 claims description 458
- 239000007788 liquid Substances 0.000 claims description 82
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 43
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims description 33
- 230000002378 acidificating effect Effects 0.000 claims description 32
- 238000004448 titration Methods 0.000 claims description 30
- 239000006061 abrasive grain Substances 0.000 claims description 26
- 239000000084 colloidal system Substances 0.000 claims description 25
- 125000002091 cationic group Chemical group 0.000 claims description 23
- 239000003002 pH adjusting agent Substances 0.000 claims description 23
- 239000006174 pH buffer Substances 0.000 claims description 22
- 238000011282 treatment Methods 0.000 claims description 22
- 125000005372 silanol group Chemical group 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 238000005349 anion exchange Methods 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 7
- 238000010979 pH adjustment Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 56
- -1 potassium hydroxide Chemical class 0.000 description 44
- 239000007787 solid Substances 0.000 description 41
- 239000000758 substrate Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000005259 measurement Methods 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 21
- 239000011164 primary particle Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000003703 image analysis method Methods 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000003729 cation exchange resin Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 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 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 8
- 150000002433 hydrophilic molecules Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 238000011033 desalting Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 208000000260 Warts Diseases 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 201000010153 skin papilloma Diseases 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- 239000001488 sodium phosphate Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
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- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
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- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
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- BMFMQGXDDJALKQ-BYPYZUCNSA-N Argininic acid Chemical compound NC(N)=NCCC[C@H](O)C(O)=O BMFMQGXDDJALKQ-BYPYZUCNSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- 239000004328 sodium tetraborate Substances 0.000 description 1
- KKDONKAYVYTWGY-UHFFFAOYSA-M sodium;2-(methylamino)ethanesulfonate Chemical compound [Na+].CNCCS([O-])(=O)=O KKDONKAYVYTWGY-UHFFFAOYSA-M 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
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- 150000003536 tetrazoles Chemical class 0.000 description 1
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- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
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- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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Images
Abstract
Description
本発明は、粒子連結型シリカ微粒子分散液およびその製造方法、並びに研磨用砥粒分散液に関する。 The present invention relates to a particle-linked silica fine particle dispersion, a method for producing the same, and an abrasive grain dispersion for polishing.
溶媒に分散してなる粒子連結型シリカゾルのうち、球状以外の形状からなる粒子連結型シリカゾルとしては、鎖状、数珠状または長球状のものが知られている。この様な粒子連結型シリカゾルは、例えば、各種研磨剤として使用されている。 Among the particle-linked silica sol dispersed in a solvent, chain-shaped, bead-shaped, or oblong spherical particles are known as the particle-linked silica sol having a shape other than the spherical shape. Such particle-linked silica sol is used as, for example, various abrasives.
特許文献１には、画像解析法により測定される平均粒子径が５〜３００ｎｍの範囲にあるアルミナ−シリカ複合一次粒子が２個以上結合した構造を含む粒子連結型アルミナ−シリカ複合微粒子が分散媒に分散してなる粒子連結型アルミナ−シリカ複合ゾルおよびその製造方法の発明が開示されている。特許文献１では、この粒子連結型アルミナ−シリカ複合微粒子が、アルミナ−シリカ複合一次粒子として、表面に複数の疣状突起を有する球状粒子を含むことを特徴とする。この発明は、通常の粒子連結型シリカ微粒子または非球状アルミナ−シリカ複合微粒子とは異なる特異な構造を有する。このため、例えば、研磨材および研磨用組成物として有用であり、特に高研磨速度の効果において優れるものとされている。しかし、アルミニウムは研磨基板の種類によっては汚染物質となってしまうため、好ましくない。 In Patent Document 1, particle-linked alumina-silica composite fine particles containing a structure in which two or more alumina-silica composite primary particles having an average particle diameter in the range of 5 to 300 nm measured by an image analysis method are bonded are used as a dispersion medium. The invention of a particle-linked alumina-silica composite sol dispersed in the above and a method for producing the same is disclosed. Patent Document 1 is characterized in that the particle-linked alumina-silica composite fine particles include spherical particles having a plurality of wart-like protrusions on the surface as alumina-silica composite primary particles. The present invention has a unique structure different from ordinary particle-linked silica fine particles or non-spherical alumina-silica composite fine particles. Therefore, for example, it is useful as an abrasive and a composition for polishing, and is particularly excellent in the effect of high polishing speed. However, aluminum is not preferable because it becomes a pollutant depending on the type of polishing substrate.
特許文献２には、画像解析法により測定される平均粒子径が５〜３００ｎｍの範囲にあるシリカ一次粒子が２個以上結合した構造を含む粒子連結型シリカ微粒子が分散媒に分散してなる粒子連結型シリカゾルおよびその製造方法の発明が開示されている。特許文献２では、この粒子連結型シリカ微粒子が、シリカ一次粒子として、表面に複数の疣状突起を有する球状粒子を含むことを特徴とする。この発明は、通常の粒子連結型シリカ微粒子または非球状シリカ微粒子とは異なる特異な構造を有することから、例えば、研磨材および研磨用組成物として有用であり、特に高研磨速度の効果において優れるものであるとされている。しかし、結合様態としてテトラポット型を含み、さらには疣状突起を含むことにより局所的な研磨基板への応力集中が発生しやすいためか、スクラッチ等の研磨傷を生じやすい。 Patent Document 2 describes particles obtained by dispersing particle-linked silica fine particles containing two or more bonded primary silica particles having an average particle size in the range of 5 to 300 nm measured by an image analysis method in a dispersion medium. The invention of the articulated silica sol and the method for producing the same is disclosed. Patent Document 2 is characterized in that the particle-connected silica fine particles include spherical particles having a plurality of wart-like protrusions on the surface as silica primary particles. Since the present invention has a unique structure different from ordinary particle-connected silica fine particles or non-spherical silica fine particles, it is useful as, for example, an abrasive and a polishing composition, and is particularly excellent in the effect of high polishing speed. Is said to be. However, since the tetrapod type is included as the bonding mode and the wart-shaped protrusions are included, stress concentration is likely to occur locally on the polishing substrate, and polishing scratches such as scratches are likely to occur.
本発明は、研磨性等の優れた特性を有する粒子連結型シリカ微粒子分散液およびその製造方法並びに砥粒分散液を提供することを課題とする。 An object of the present invention is to provide a particle-linked silica fine particle dispersion having excellent properties such as abrasiveness, a method for producing the same, and an abrasive grain dispersion.
本発明の一態様によれば、シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液であって、前記シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子は、下記［１］の要件を備え、かつ前記シリカ微粒子に包含される立体状分岐構造を有する粒子連結型シリカ微粒子が、下記［２］の要件を備えることを特徴とする粒子連結型シリカ微粒子分散液が提供される。
［１］前記シリカ微粒子の動的光散乱法により測定した平均粒子径（Ｄ１）が、５０ｎｍ以上６００ｎｍ以下の範囲にあること。
［２］前記立体状分岐構造を有する粒子連結型シリカ微粒子が、鎖状で、かつ少なくとも１つの分岐（ａ）を有する構造と、この構造に対する立体構造を有すること。
According to one aspect of the present invention, it is a particle-linked silica fine particle dispersion liquid containing particle-linked silica fine particles having a structure in which silica primary fine particles are linked, and is a particle-linked silica having a structure in which the silica primary fine particles are linked. The silica fine particles contained in the particle-linked silica fine particle dispersion liquid containing fine particles include the following [1], and the particle-connected silica fine particles having a three-dimensional branched structure included in the silica fine particles are described in the following [2]. ] The particle-linked silica fine particle dispersion liquid is provided.
[1] The average particle size (D1) measured by the dynamic light scattering method of the silica fine particles is in the range of 50 nm or more and 600 nm or less.
[2] The particle-connected silica fine particles having the three-dimensional branched structure have a chain-like structure having at least one branch (a) and a three-dimensional structure for this structure.
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、前記立体構造が、下記（１）および（２）の構造のうちの少なくとも１つであることが好ましい。
（１）前記分岐（ａ）に対し、立体方向に伸長してなる分岐（ｂ）
（２）前記分岐（ａ）に対し、立体方向に伸長してなる末端（ｃ）
In the particle-linked silica fine particle dispersion liquid according to one aspect of the present invention, it is preferable that the three-dimensional structure is at least one of the following structures (1) and (2).
(1) A branch (b) extending in a three-dimensional direction with respect to the branch (a).
(2) The end (c) extending in the three-dimensional direction with respect to the branch (a).
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、前記立体状分岐構造を有する粒子連結型シリカ微粒子は、下記［３］および［４］の要件を備えることが好ましい。
［３］５０ｎｍ≦ＤＬａ≦１，０００ｎｍ
ＤＬａ：前記立体状分岐構造を有する粒子連結型シリカ微粒子の長さ方向における最長径（ＤＬ）の平均値
［４］１０ｎｍ≦ＤＴａ≦８００ｎｍ
ＤＴａ：前記立体状分岐構造を有する粒子連結型シリカ微粒子の太さ方向における直径（ＤＴ）の平均値
In the particle-linked silica fine particle dispersion liquid according to one aspect of the present invention, the particle-linked silica fine particles having the three-dimensional branched structure preferably satisfy the following requirements [3] and [4].
[3] 50 nm ≤ DLa ≤ 1,000 nm
DLa: Average value of the longest diameter (DL) in the length direction of the particle-connected silica fine particles having the three-dimensional branched structure [4] 10 nm ≤ DTa ≤ 800 nm
DT: The average value of the diameter (DT) in the thickness direction of the particle-connected silica fine particles having the three-dimensional branched structure.
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、前記立体状分岐構造を有する粒子連結型シリカ微粒子は、下記［５］の要件を備えることが好ましい。
［５］１０％≦Ｃ．Ｖ．≦４０％
Ｃ．Ｖ．：前記立体状分岐構造を有する粒子連結型シリカ微粒子の太さ方向における直径（ＤＴ）の平均変動係数
In the particle-linked silica fine particle dispersion liquid according to one aspect of the present invention, the particle-linked silica fine particles having the three-dimensional branched structure preferably satisfy the following requirements [5].
[5] 10% ≤ C.I. V. ≤40%
C. V. : Average coefficient of variation of diameter (DT) in the thickness direction of the particle-connected silica fine particles having the three-dimensional branched structure
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、前記立体状分岐構造を有する粒子連結型シリカ微粒子は、シリカ一次微粒子の平均連結個数が、５個以上２０個以下の範囲にあることが好ましい。 In the particle-linked silica fine particle dispersion liquid according to one aspect of the present invention, in the particle-linked silica fine particles having the three-dimensional branched structure, the average number of silica primary fine particles connected is in the range of 5 or more and 20 or less. Is preferable.
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、前記シリカ微粒子に含まれるＣａ、ＭｇおよびＡｌの割合が、下記のとおりであることが好ましい。
Ｃａ：２５ｐｐｍ以下
Ｍｇ：２５ｐｐｍ以下
Ａｌ：１５０ｐｐｍ以下
In the particle-linked silica fine particle dispersion liquid according to one aspect of the present invention, the proportions of Ca, Mg and Al contained in the silica fine particles are preferably as follows.
Ca: 25ppm or less Mg: 25ppm or less Al: 150ppm or less
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、前記立体状分岐構造を有する粒子連結型シリカ微粒子を５個数％以上５０個数％以下含むことが好ましい。 The particle-linked silica fine particle dispersion liquid according to one aspect of the present invention preferably contains 5% or more and 50% or less of the particle-linked silica fine particles having the three-dimensional branched structure.
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、前記粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子のシラノール基密度が、０．１個／ｎｍ２以上５．０個／ｎｍ２以下の範囲にあることが好ましい。 In the particle-linked silica fine particle dispersion according to one aspect of the present invention, the silanol group density of the silica fine particles contained in the particle-linked silica fine particle dispersion is 0.1 / nm 2 or more and 5.0 / nm 2. It is preferably in the following range.
本発明の一態様に係る粒子連結型シリカ微粒子分散液において、カチオンコロイド滴定を行った場合に、下記数式（Ｆ１）で表される流動電位変化量（ΔＰＣＤ）と、クニックにおけるカチオンコロイド滴定液の添加量（Ｖ）との比（ΔＰＣＤ／Ｖ）が−３５０以上−１０以下となる流動電位曲線が得られることが好ましい。
ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖ・・・（Ｆ１）
Ｃ：前記クニックにおける流動電位（ｍＶ）
Ｉ：前記流動電位曲線の開始点における流動電位（ｍＶ）
Ｖ：前記クニックにおける前記カチオンコロイド滴定液の添加量（ｍＬ）
When cationic colloid titration is performed in the particle-linked silica fine particle dispersion according to one aspect of the present invention, the flow potential change amount (ΔPCD) represented by the following formula (F1) and the cationic colloid titration solution in the knick are used. It is preferable to obtain a flow potential curve in which the ratio (ΔPCD / V) to the addition amount (V) is −350 or more and −10 or less.
ΔPCD / V = (IC) / V ... (F1)
C: Flow potential (mV) in the knick
I: Flow potential (mV) at the start point of the flow potential curve
V: Addition amount (mL) of the cationic colloid titration solution in the knick
本発明の一態様によれば、前述の本発明の一態様に係る粒子連結型シリカ微粒子分散液を含むことを特徴とする砥粒分散液が提供される。 According to one aspect of the present invention, there is provided an abrasive grain dispersion liquid containing the particle-linked silica fine particle dispersion liquid according to the above-mentioned one aspect of the present invention.
本発明の一態様によれば、下記工程１を含む、前述の本発明の一態様に係る粒子連結型シリカ微粒子分散液の製造方法が提供される。
工程１：ＳｉＯ２濃度１．５質量％以上３０質量％以下のシリカ微粒子分散液に、ｐＨ緩衝剤またはｐＨ調整剤を、下記の割合（ＷＢ／ＷＬＰ１）の範囲内で添加し、続いて、４０℃以上９８℃以下に加熱し、１時間以上保持し、粒子連結型シリカ微粒子分散液を得る工程
０．０１≦ＷＢ／ＷＬＰ１≦０．１
（ここで、ＷＬＰ１は、シリカ微粒子分散液中のシリカ質量であり、ＷＢは、ｐＨ緩衝剤またはｐＨ調整剤の質量である。）
According to one aspect of the present invention, there is provided a method for producing a particle-linked silica fine particle dispersion liquid according to the above-mentioned aspect of the present invention, which comprises the following step 1.
Step 1: A pH buffer or a pH adjuster is added to the silica fine particle dispersion having a SiO 2 concentration of 1.5% by mass or more and 30% by mass or less within the following ratio (WB / WLP 1 ), followed by , 40 ° C. or higher and 98 ° C. or lower, and held for 1 hour or longer to obtain a particle-linked silica fine particle dispersion 0.01 ≤ WB / WLP 1 ≤ 0.1
(Here, WLP 1 is the mass of silica in the silica fine particle dispersion, and WB is the mass of the pH buffer or pH adjuster.)
本発明の一態様に係る粒子連結型シリカ微粒子分散液の製造方法において、前記工程１でｐＨ緩衝剤またはｐＨ調整剤の全量添加後のｐＨが２．０以上６．０以下の範囲にあることが好ましい。 In the method for producing a particle-linked silica fine particle dispersion according to one aspect of the present invention, the pH after the addition of the entire amount of the pH buffer or pH adjuster in step 1 is in the range of 2.0 or more and 6.0 or less. Is preferable.
本発明の一態様に係る粒子連結型シリカ微粒子分散液の製造方法において、前記工程１に続いて、下記工程２を含むことが好ましい。
工程２：前記工程１で得た粒子連結型シリカ微粒子分散液に対し、下記（ｉ）および（ｉｉ）の処理のうちの少なくとも１つにより、ｐＨ１０．０以上にｐＨ調整処理し、続いて酸性珪酸液を、下記の割合（ＷＳ／ＷＬＰ２）となるように連続的または断続的に添加し、粒子成長させる処理を施す工程
０．０１≦ＷＳ／ＷＬＰ２≦１０
（ここで、ＷＬＰ２は、粒子連結型シリカ微粒子分散液中のシリカ質量であり、ＷＳは、酸性珪酸液中のシリカ質量である。）
（ｉ）陰イオン交換処理
（ｉｉ）アルカリ添加
In the method for producing a particle-linked silica fine particle dispersion liquid according to one aspect of the present invention, it is preferable to include the following step 2 following the step 1.
Step 2: The particle-linked silica fine particle dispersion obtained in Step 1 is pH-adjusted to pH 10.0 or higher by at least one of the following treatments (i) and (ii), followed by acidity. Step of continuously or intermittently adding the silicic acid solution in the following ratio (WS / WLP 2 ) to grow particles 0.01 ≤ WS / WLP 2 ≤ 10
(Here, WLP 2 is the mass of silica in the particle-linked silica fine particle dispersion, and WS is the mass of silica in the acidic silicic acid solution.)
(I) Anion exchange treatment (ii) Add alkali
本発明の一態様に係る粒子連結型シリカ微粒子分散液の製造方法において、前記工程２に続いて、下記工程３を含むことが好ましい。
工程３：前記工程２を施している粒子連結型シリカ微粒子分散液に対し、下記（ｉ）および（ｉｉ）の処理のうちの少なくとも１つにより、ｐＨ１０．０以上にｐＨ調整処理し、続いて、酸性珪酸液を下記の割合（ＷＳ／ＷＬＰ２）となるように連続的または断続的に添加し、粒子成長させる処理を施す工程を含むことを特徴とする粒子連結型シリカ微粒子分散液の製造方法。
０．５≦ＷＳ／ＷＬＰ２≦１０
（ここで、ＷＬＰ２は、粒子連結型シリカ微粒子分散液中のシリカ質量であり、ＷＳは、酸性珪酸液中のシリカ質量である。）
（ｉ）陰イオン交換処理
（ｉｉ）アルカリ添加
In the method for producing a particle-linked silica fine particle dispersion liquid according to one aspect of the present invention, it is preferable to include the following step 3 following the step 2.
Step 3: The particle-linked silica fine particle dispersion liquid subjected to the step 2 is subjected to pH adjustment treatment to pH 10.0 or higher by at least one of the following treatments (i) and (ii), followed by a pH adjustment treatment. , Production of a particle-linked silica fine particle dispersion, which comprises a step of continuously or intermittently adding an acidic silicic acid solution at the following ratio (WS / WLP 2) to grow particles. Method.
0.5 ≤ WS / WLP 2 ≤ 10
(Here, WLP 2 is the mass of silica in the particle-linked silica fine particle dispersion, and WS is the mass of silica in the acidic silicic acid solution.)
(I) Anion exchange treatment (ii) Add alkali
本発明の立体状分岐構造を有する粒子連結型シリカ微粒子は、従来の粒子連結型シリカ微粒子あるいは非球状シリカ微粒子とは異なる特異な構造（立体状分岐構造）を有する。そのため、例えば、研磨用途に適用した場合、本発明の立体状分岐構造を有する粒子連結型シリカ微粒子と、研磨機基板との複数の接触点において応力が集中し易いため、高い研磨速度を得ることができる。さらに、連結構造を有することで砥粒の回転運動による動的な接触面積を効果的に得ることができるので、優れた研磨特性を達成できる。このため、本発明の立体状分岐構造を有する粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液は、例えば砥粒分散液および研磨用組成物の原料として有用であり、特に高研磨速度の効果において優れるものである。
また、本発明の粒子連結型シリカ微粒子分散液は、その分散質である粒子連結型シリカ微粒子が、シリカ一次微粒子どうしで結合してなる連結粒子であり、結合剤（例えば、ＣａＯ、ＭｇＯあるいはＡｌ２Ｏ３）を含むことがないので、研磨用途に適用した場合、半導体基板等の汚染の問題を生じることが無く、有用性が高いものといえる。
The particle-linked silica fine particles having the three-dimensional branched structure of the present invention have a unique structure (three-dimensional branched structure) different from the conventional particle-linked silica fine particles or non-spherical silica fine particles. Therefore, for example, when applied to a polishing application, stress is likely to be concentrated at a plurality of contact points between the particle-connected silica fine particles having the three-dimensional branched structure of the present invention and the polishing machine substrate, so that a high polishing rate can be obtained. Can be done. Further, by having the connecting structure, it is possible to effectively obtain a dynamic contact area due to the rotational movement of the abrasive grains, so that excellent polishing characteristics can be achieved. Therefore, the particle-linked silica fine particle dispersion liquid containing the particle-linked silica fine particles having a three-dimensional branched structure of the present invention is useful as, for example, an abrasive grain dispersion liquid and a raw material for a polishing composition, and has a particularly high polishing rate. It is excellent in effect.
Further, the particle-linked silica fine particle dispersion liquid of the present invention is a connecting particle formed by bonding the particle-linked silica fine particles which are the dispersoids of the silica primary fine particles to each other, and is a binder (for example, CaO, MgO or Al). Since it does not contain 2 O 3 ), it can be said that it is highly useful because it does not cause a problem of contamination of semiconductor substrates and the like when applied to polishing applications.
［シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液（連結粒子分散液）］
本発明の粒子連結型シリカ微粒子分散液は、シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液であって、前記シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子が下記［１］の要件を備え、かつ前記シリカ微粒子に包含される立体状分岐構造を有する粒子連結型シリカ微粒子が、下記［２］の要件を備えることを特徴とする。
［１］前記シリカ微粒子の動的光散乱法により測定した平均粒子径（Ｄ１）が、５０ｎｍ以上６００ｎｍ以下の範囲にあること。
［２］前記立体状分岐構造を有する粒子連結型シリカ微粒子が、鎖状で、かつ少なくとも１つの分岐（ａ）を有する構造と、この構造に対する立体構造を有すること。
[Particle-linked silica fine particle dispersion liquid containing particle-linked silica fine particles having a structure in which silica primary fine particles are linked (linked particle dispersion liquid)]
The particle-linked silica fine particle dispersion of the present invention is a particle-linked silica fine particle dispersion containing particle-linked silica fine particles having a structure in which silica primary fine particles are linked, and particles having a structure in which the silica primary fine particles are linked. Particles Concatenated Silica Fine Particles Containing Particles Concatenated Silica Fine Particles A particle-linked silica fine particles containing the following requirements [1] and having a three-dimensional branched structure included in the silica fine particles are described below. It is characterized by having the requirements of [2].
[1] The average particle size (D1) measured by the dynamic light scattering method of the silica fine particles is in the range of 50 nm or more and 600 nm or less.
[2] The particle-connected silica fine particles having the three-dimensional branched structure have a chain-like structure having at least one branch (a) and a three-dimensional structure for this structure.
ここで、シリカ一次微粒子が連結したとは、隣接するシリカ一次微粒子の間に生成した結合によって、隣接するシリカ一次微粒子同士が互いに固定化したことをいう。ここで結合の種類は特に限定されるものではないが、例えば隣接するシリカ一次微粒子のそれぞれの表面シラノール基同士の縮合反応により生じたシロキサン結合等の化学的結合を挙げることができる。
以下、本発明の粒子連結型シリカ微粒子分散液を「粒子連結型シリカ微粒子分散液」または「連結粒子分散液」ともいう。
また、本発明のシリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を「連結粒子」ともいう。本発明のシリカ一次微粒子が連結した構造からなる立体状分岐構造を有する粒子連結型シリカ微粒子を「立体状連結粒子」ともいう。
さらに、本発明のシリカ一次微粒子が連結した構造からなる立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）以外のシリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子（連結粒子）を、「平面状連結粒子」ともいう。
連結粒子は、多数のシリカ一次微粒子が結合した構造を有する。連結粒子において、シリカ一次微粒子１個を含んだ最小の構成単位を、本願においては、便宜上、「単位構造」という場合がある。ここで「単位構造」とは、シリカ一次微粒子１個を含み、更に該シリカ一次微粒子に隣接したシリカ一次微粒子との間に形成されるネック部の一部を含んでなる。本発明における粒子連結型シリカ微粒子は、前記単位構造が連結した構造からなる粒子連結型シリカ微粒子ということもできる。前記立体状連結粒子、前記平面状連結粒子についても同様である。
後述するように、本発明の本発明の粒子連結型シリカ微粒子分散液を製造するための主要な原料のひとつであるシリカ微粒子分散液ないしシリカ微粒子を、それぞれ「原料としたシリカ微粒子分散液」、「原料としたシリカ微粒子」と称する場合がある。
加えて、連結粒子以外のシリカ一次微粒子を「単粒子」という。
本発明の粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子とは、粒子連結型シリカ微粒子分散液に含まれるすべてのシリカ微粒子（連結粒子および単粒子）をいう。
本発明において、粒子の特徴を、透過型顕微鏡写真または走査型顕微鏡写真を用いて特定する場合がある。この場合において、写真の代わりに透過型顕微鏡画像を用いても同様に行うことができる。走査型顕微鏡写真においても、同様に走査型顕微鏡画像を用いることができる。
Here, the fact that the silica primary fine particles are linked means that the adjacent silica primary fine particles are immobilized on each other by the bond formed between the adjacent silica primary fine particles. Here, the type of bond is not particularly limited, and examples thereof include chemical bonds such as a siloxane bond generated by a condensation reaction between the surface silanol groups of the adjacent silica primary fine particles.
Hereinafter, the particle-linked silica fine particle dispersion of the present invention is also referred to as "particle-linked silica fine particle dispersion" or "linked particle dispersion".
Further, the particle-linked silica fine particles having a structure in which the silica primary fine particles of the present invention are linked are also referred to as “linking particles”. The particle-linked silica fine particles having a three-dimensional branched structure having a structure in which the silica primary fine particles of the present invention are linked are also referred to as "three-dimensional linked particles".
Further, the particle-linked silica fine particles (connected particles) having a structure in which the silica primary fine particles other than the particle-linked silica fine particles (three-dimensional linked particles) having a three-dimensional branched structure in which the silica primary fine particles of the present invention are linked are linked. ) Is also referred to as "planar connecting particles".
The connecting particles have a structure in which a large number of primary silica fine particles are bonded. In the linked particles, the smallest structural unit containing one silica primary fine particle may be referred to as a "unit structure" in the present application for convenience. Here, the "unit structure" includes one silica primary fine particle, and further includes a part of a neck portion formed between the silica primary fine particle and the silica primary fine particle adjacent to the silica primary fine particle. The particle-linked silica fine particles in the present invention can also be said to be particle-linked silica fine particles having a structure in which the unit structures are linked. The same applies to the three-dimensional connecting particles and the planar connecting particles.
As will be described later, the silica fine particle dispersion liquid or the silica fine particle dispersion liquid, which is one of the main raw materials for producing the particle-linked silica fine particle dispersion liquid of the present invention of the present invention, is used as a “silica fine particle dispersion liquid as a raw material”, respectively. It may be referred to as "silica fine particles used as a raw material".
In addition, silica primary fine particles other than connecting particles are called "single particles".
The silica fine particles contained in the particle-linked silica fine particle dispersion of the present invention refer to all the silica fine particles (connected particles and single particles) contained in the particle-linked silica fine particle dispersion.
In the present invention, the characteristics of particles may be specified by using a transmission micrograph or a scanning micrograph. In this case, the same can be performed by using a transmission microscope image instead of the photograph. Similarly, a scanning microscope image can be used in a scanning microscope photograph.
前記シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子の動的光散乱法で測定された平均粒子径（Ｄ１）は、５０ｎｍ以上６００ｎｍ以下の範囲、好ましくは８０ｎｍ以上４００ｎｍ以下、より好ましくは１００ｎｍ以上３５０ｎｍ以下の範囲である。
平均粒子径（Ｄ１）が、５０ｎｍ未満であると、十分な研磨速度を得られない場合があり、好ましくない。また、平均粒子径（Ｄ１）が６００ｎｍを超えると、研磨基板に傷が生じる傾向が強まり好ましくない。
The average particle diameter (D1) measured by the dynamic light scattering method of the silica fine particles contained in the particle-linked silica fine particle dispersion containing the particle-linked silica fine particles having a structure in which the primary silica fine particles are linked is 50 nm or more and 600 nm. The range is as follows, preferably 80 nm or more and 400 nm or less, and more preferably 100 nm or more and 350 nm or less.
If the average particle size (D1) is less than 50 nm, a sufficient polishing rate may not be obtained, which is not preferable. Further, if the average particle size (D1) exceeds 600 nm, the polished substrate tends to be scratched, which is not preferable.
［シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子（連結粒子）］
本発明のシリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子（連結粒子）は、立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）と、立体状分岐構造を有する粒子連結型シリカ微粒子以外の粒子連結型シリカ微粒子（平面状連結粒子）とからなる。
[Particle-linked silica fine particles (connected particles) having a structure in which primary silica fine particles are linked]
The particle-linked silica fine particles (linking particles) having a structure in which the silica primary fine particles of the present invention are linked are the particle-linking silica fine particles (three-dimensional connecting particles) having a three-dimensional branched structure and the particle linkage having a three-dimensional branched structure. It is composed of particle-connected silica fine particles (planar connecting particles) other than the type silica fine particles.
前記「シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子」におけるシリカ一次微粒子については、その形状が球状ないし略球状であることが好ましい。なお、係る球状粒子等と共に他の形状の粒子（例えば、卵状、立方体状または棒状の粒子）が少量混在しても構わない。
前記シリカ一次微粒子の粒子径は、均一でもよく、それぞれ互いに異なっていてもよい。ここでシリカ一次微粒子の形状については、透過型電子顕微鏡写真（倍率：２０万倍）から確認することができる。
The shape of the silica primary fine particles in the "particle-connected silica fine particles having a structure in which the silica primary fine particles are connected" is preferably spherical or substantially spherical. It should be noted that a small amount of particles having other shapes (for example, oval-shaped, cubic-shaped or rod-shaped particles) may be mixed together with the spherical particles and the like.
The particle size of the silica primary fine particles may be uniform or different from each other. Here, the shape of the primary silica fine particles can be confirmed from a transmission electron micrograph (magnification: 200,000 times).
前記連結粒子におけるシリカ一次微粒子の平均粒子径（透過型電子顕微鏡写真、倍率２０万倍）は５ｎｍ以上６００ｎｍ以下が好ましく、２０ｎｍ以上４００ｎｍ以下がより好ましく、６０ｎｍ以上３００ｎｍ以下がさらに好ましい。なお、係る平均粒子径を本願では、平均粒子径［Ｆ］で表す。平均粒子径［Ｆ］の測定方法を後記「［３］立体状連結粒子の平均連結個数の測定方法 ２．立体状連結粒子におけるシリカ一次微粒子の平均粒子径［Ｆ］の測定方法」に記した。
連結粒子におけるシリカ一次微粒子の平均粒子径が５ｎｍ未満の場合は、シリカ一次微粒子が凝集して得られる連結粒子が塊状になる傾向がある。また、研磨用途においては、研磨基板への応力集中が得られないためか、十分な研磨速度が得られず好ましくない。シリカ一次微粒子の平均粒子径が６００ｎｍを超える場合は、例えば、研磨用途において、研磨基板と連結粒子との間の接触面積の低下が著しくなり、研磨速度の低下を招くときがある。また、研磨面にスクラッチ（線状痕）が発生しやすくなる場合がある。
立体状連結粒子におけるシリカ一次微粒子と、平面状連結粒子におけるシリカ一次微粒子の平均粒子径と、前記連結粒子におけるシリカ一次微粒子には有意な差は見られない。
The average particle size (transmission electron micrograph, magnification 200,000 times) of the silica primary fine particles in the linked particles is preferably 5 nm or more and 600 nm or less, more preferably 20 nm or more and 400 nm or less, and further preferably 60 nm or more and 300 nm or less. In the present application, the average particle size is represented by the average particle size [F]. The method for measuring the average particle size [F] is described later in "[3] Method for measuring the average number of connected three-dimensionally linked particles 2. Measuring method for the average particle size [F] of silica primary fine particles in the three-dimensionally connected particles". ..
When the average particle size of the silica primary fine particles in the linked particles is less than 5 nm, the linked particles obtained by aggregating the silica primary fine particles tend to be agglomerated. Further, in polishing applications, it is not preferable because sufficient polishing speed cannot be obtained, probably because stress concentration on the polishing substrate cannot be obtained. When the average particle size of the silica primary fine particles exceeds 600 nm, for example, in a polishing application, the contact area between the polishing substrate and the connecting particles is significantly reduced, which may lead to a decrease in the polishing rate. In addition, scratches (linear marks) may easily occur on the polished surface.
There is no significant difference between the average particle size of the silica primary fine particles in the three-dimensional connecting particles and the silica primary fine particles in the planar connecting particles, and the silica primary fine particles in the connecting particles.
［立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）］
本発明における立体状分岐構造を有する粒子連結型シリカ微粒子は、鎖状で、かつ少なくとも１つの分岐（ａ）を有する構造と、この構造に対する立体構造を有することを特徴とする。より具体的には、粒子連結型シリカ微粒子は、図１に示すように、白丸で示すシリカ一次微粒子が鎖状に連結した鎖状構造（Ｃｈ）を有する。さらに、この鎖状構造（Ｃｈ）に、シリカ一次微粒子が連結して、分岐（ａ）を有する。ここで、分岐（ａ）の数は、１つ以上であればよく、特に制限はない。鎖状構造（Ｃｈ）と、分岐（ａ）とは、ほぼ同一平面上に存在する。そして、この平面に交差し、角度をなすような方向（以下、「立体方向」ともいう）に、黒丸で示されたシリカ一次微粒子が結合して、立体構造を有するように、分岐（ｂ）または末端（ｃ）を形成している。
[Particle-connected silica fine particles having a three-dimensional branched structure (three-dimensionally connected particles)]
The particle-connected silica fine particles having a three-dimensional branched structure in the present invention are characterized by having a chain-like structure having at least one branch (a) and a three-dimensional structure for this structure. More specifically, as shown in FIG. 1, the particle-linked silica fine particles have a chain structure (Ch) in which the silica primary fine particles indicated by white circles are linked in a chain. Further, silica primary fine particles are connected to this chain structure (Ch) to have a branch (a). Here, the number of branches (a) may be one or more, and is not particularly limited. The chain structure (Ch) and the branch (a) exist on substantially the same plane. Then, the silica primary fine particles indicated by black circles are bonded in a direction that intersects this plane and forms an angle (hereinafter, also referred to as "three-dimensional direction"), and branches (b) so as to have a three-dimensional structure. Or it forms the end (c).
少なくとも１つの分岐（ａ）を有する構造と、この構造に対する立体構造を有するとは、具体的には次の（１）または（２）の構造のうちの少なくとも１つであることを意味する。
（１）前記分岐（ａ）に対し、立体方向に伸長してなる分岐（ｂ）
（２）前記分岐（ａ）に対し、立体方向に伸長してなる末端（ｃ）
Having a structure having at least one branch (a) and having a three-dimensional structure with respect to this structure specifically means that it is at least one of the following structures (1) or (2).
(1) A branch (b) extending in a three-dimensional direction with respect to the branch (a).
(2) The end (c) extending in the three-dimensional direction with respect to the branch (a).
前記鎖状とは、シリカ微粒子が連結してなる細長い構造を指し、屈曲状ないし直鎖状と呼ぶこともできる。なお、この様な鎖状粒子が両端で結合し、環状を構成してなる粒子連結構造、網目構造、シリカ一次微粒子が凝集してテトラポッド様となった構造およびシリカ一次微粒子の不規則な凝集体（例えば、複数のシリカ一次微粒子を含む塊状の凝集体）は、前記鎖状の範囲には含まれない。 The chain shape refers to an elongated structure formed by connecting silica fine particles, and may also be referred to as a bent shape or a linear shape. It should be noted that such a chain-like particle is bonded at both ends to form an annular particle-connected structure, a network structure, a structure in which silica primary fine particles are aggregated to form a tetrapod-like structure, and irregular coagulation of silica primary fine particles. Aggregates (eg, agglomerates containing a plurality of primary silica fine particles) are not included in the chain range.
前記分岐（ａ）とは、立体状連結粒子の両末端のシリカ一次微粒子を除いた粒子において、直鎖方向以外にシリカ一次微粒子またはシリカ一次微粒子の連結体の末端が結合してなる枝分かれ構造を指す。（立体状連結粒子において分岐（ａ）が結合してなるシリカ一次微粒子を含む鎖状部分を「主鎖」と称する。）
前記分岐（ｂ）とは、立体状連結粒子の両末端のシリカ一次微粒子を除いた粒子において、直鎖方向以外にシリカ一次微粒子またはシリカ一次微粒子の連結体の末端が結合してなる枝分かれ構造であって、前記分岐（ａ）の伸長方向に対し、立体方向に伸長してなる分岐を指す。立体方向については、後記のとおり、透過型電子顕微鏡写真から判定することができる。
前記末端（ｃ）とは、立体状連結粒子の両末端のシリカ一次微粒子を除いた粒子において、直鎖方向以外にシリカ一次微粒子またはシリカ一次微粒子の連結体の末端が結合してなる屈曲構造であって、前記分岐（ａ）の伸長方向に対し、立体方向に伸長してなる屈曲構造を指す。ここで、立体方向については、後記のとおり、透過型電子顕微鏡写真から判定することができる。
前記立体状分岐構造を有する粒子連結型シリカ微粒子におけるシリカ一次微粒子の平均連結個数は、５個以上２０個以下の範囲にあることが好ましい。
The branch (a) is a branched structure in which the ends of the silica primary fine particles or the silica primary fine particles are bonded in addition to the linear direction in the particles excluding the silica primary fine particles at both ends of the three-dimensional connecting particles. Point to. (A chain portion containing silica primary fine particles in which branches (a) are bonded in a three-dimensional connecting particle is referred to as a "main chain".)
The branch (b) is a branched structure in which the ends of the silica primary fine particles or the silica primary fine particles are bonded in addition to the linear direction in the particles excluding the silica primary fine particles at both ends of the three-dimensional connecting particles. Therefore, it refers to a branch that extends in the three-dimensional direction with respect to the extension direction of the branch (a). The stereoscopic direction can be determined from the transmission electron micrograph as described later.
The end (c) is a bent structure in which the ends of the silica primary fine particles or the silica primary fine particles are bonded to each other in addition to the linear direction in the particles excluding the silica primary fine particles at both ends of the three-dimensional connecting particles. It refers to a bent structure that extends in a three-dimensional direction with respect to the extension direction of the branch (a). Here, the three-dimensional direction can be determined from the transmission electron micrograph as described later.
The average number of connected silica primary particles in the particle-connected silica fine particles having a three-dimensional branched structure is preferably in the range of 5 or more and 20 or less.
本発明における立体状分岐構造を有する粒子連結型シリカ微粒子は、要件［２］で規定する鎖状で、かつ少なくとも１つの分岐（ａ）を有する構造と、この構造に対する立体構造を有するものである。係る立体構造については、粒子連結型シリカ微粒子分散液の電子顕微鏡写真（透過型電子顕微鏡写真、ＴＥＭ写真）を用いて確認できる。 The particle-connected silica fine particles having a three-dimensional branched structure in the present invention have a chain-like structure defined in the requirement [2] and a structure having at least one branch (a), and a three-dimensional structure for this structure. .. The three-dimensional structure can be confirmed by using an electron micrograph (transmission electron micrograph, TEM photograph) of the particle-linked silica fine particle dispersion.
本発明の立体状連結粒子は、前記のとおり分岐（ａ）と分岐（ｂ）あるいは分岐（ａ）と末端（ｃ）を有するものであり、分岐（ａ）の伸長方向と分岐（ｂ）の伸長方向は、立体状構造の関係にあり、同様に分岐（ａ）の伸長方向と末端（ｃ）の伸長方向も立体状構造の関係にあるので、該立体状連結粒子を砥粒として研磨基板上に適用した場合、研磨時に本発明の立体状連結粒子は、研磨機基板と複数の接触点において応力集中を受取りやすいので、研磨速度の増進に寄与することができる。
更に立体状連結粒子からなる砥粒は、その回転運動により、研磨基板と動的な接触面積を増大するので、これも研磨速度の増大に寄与することができる。
As described above, the three-dimensionally connected particles of the present invention have a branch (a) and a branch (b) or a branch (a) and a terminal (c), and have an extension direction of the branch (a) and a branch (b). Since the elongation direction has a three-dimensional structure relationship, and similarly, the extension direction of the branch (a) and the extension direction of the terminal (c) also have a three-dimensional structure relationship, the polishing substrate uses the three-dimensional connecting particles as abrasive grains. When applied above, the three-dimensional connecting particles of the present invention can easily receive stress concentration at a plurality of contact points with the polishing machine substrate during polishing, and thus can contribute to an increase in polishing speed.
Further, since the abrasive grains made of the three-dimensionally connected particles increase the dynamic contact area with the polishing substrate due to the rotational movement, this can also contribute to the increase in the polishing rate.
本発明では立体状分岐構造を有する粒子連結型シリカ微粒子の確認を次のように行う。
シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液（ＳｉＯ２濃度１質量％、動的光散乱法で測定された平均粒子径が５０ｎｍ〜６００ｎｍの範囲）の透過型電子顕微鏡写真（倍率：２０万倍）を用意し、少なくとも粒子が連結した形状の任意の２００個の粒子のうち、立体状連結粒子に相当する粒子の個数を測定し、立体状連結粒子の個数割合を算定する。
立体状連結粒子の判定基準は次のとおりである。すなわち、特定の粒子連結型シリカ微粒子に関し、下記の（１）〜（３）の要件を満たすかを確認する。
（１）シリカ一次微粒子の連結個数が５個以上で鎖状構造
（２）主鎖構成粒子のうち、末端の粒子以外の粒子に結合した分岐（分岐（ａ））が少なくとも１箇存在する
（３）当該特定の粒子連結型シリカ微粒子上に重複して、他の一次粒子に比して、濃淡が濃い部分が確認できること。
以上の要件を満たす粒子連結型シリカ微粒子は、分岐（ａ）に対し、立体方向に伸長してなる分岐（ｂ）あるいは立体方向に伸長してなる末端（ｃ）を有すると判定し、分岐（ａ）に対する立体構造を有する立体状連結粒子とする。
In the present invention, the particle-connected silica fine particles having a three-dimensional branched structure are confirmed as follows.
Particle-linked silica fine particle dispersion containing particle-linked silica fine particles having a structure in which primary silica fine particles are linked (SiO 2 concentration 1% by mass, average particle diameter measured by the dynamic light scattering method in the range of 50 nm to 600 nm) Prepare a transmissive electron micrograph (magnification: 200,000 times) of Calculate the number ratio of particles.
The criteria for determining the three-dimensional connected particles are as follows. That is, it is confirmed whether or not the following requirements (1) to (3) are satisfied with respect to the specific particle-connected silica fine particles.
(1) Chain structure with 5 or more connected silica primary fine particles (2) Among the main chain constituent particles, there is at least one branch (branch (a)) bonded to particles other than the terminal particles (branch (a)). 3) It is possible to confirm a portion that overlaps with the specific particle-connected silica fine particles and has a darker shade than the other primary particles.
It is determined that the particle-connected silica fine particles satisfying the above requirements have a branch (b) extending in the three-dimensional direction or a terminal (c) extending in the three-dimensional direction with respect to the branch (a), and the branch (a) is determined to have a branch (c). It is a three-dimensional connecting particle having a three-dimensional structure with respect to a).
［立体状分岐構造を有する粒子連結型シリカ微粒子における長さ方向の平均最長径（ＤＬａ）］
本発明における立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）は、下記の要件［３］を備えることが好ましい。
要件［３］５０ｎｍ≦ＤＬａ≦１，０００ｎｍ
ここで、立体状分岐構造を有する粒子連結型シリカ微粒子の長さ方向における平均最長径（ＤＬａ）は、立体状分岐構造を有する粒子連結型シリカ微粒子５０個の最長径（ＤＬ）をそれぞれ測定し、平均した値である。
具体的には、立体状分岐構造を有する粒子連結型シリカ微粒子における長さ方向の最長径（ＤＬ）は、シリカ微粒子分散液（ＳｉＯ２濃度０．０５質量％）の走査型電子顕微鏡（２０万倍）を用い、立体状連結粒子に該当する粒子５０個について、それぞれの最長径（ＤＬ）をそれぞれ測定し、その平均値を算定する。
[Average longest diameter (DLa) in the length direction of particle-connected silica fine particles having a three-dimensional branched structure]
The particle-connected silica fine particles (three-dimensionally connected particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirement [3].
Requirement [3] 50 nm ≤ DLa ≤ 1,000 nm
Here, the average longest diameter (DLa) of the particle-connected silica fine particles having a three-dimensional branched structure in the length direction is measured by measuring the longest diameter (DL) of 50 particle-connected silica fine particles having a three-dimensional branched structure. , The average value.
Specifically, the longest diameter (DL) in the length direction of the particle-connected silica fine particles having a three-dimensional branched structure is a scanning electron microscope (200,000) of a silica fine particle dispersion (SiO 2 concentration 0.05% by mass). The longest diameter (DL) of each of the 50 particles corresponding to the three-dimensionally connected particles is measured using (times), and the average value is calculated.
立体状連結粒子の長さ方向の平均最長径（ＤＬａ）が、５０ｎｍ以上１，０００ｎｍ以下であると、優れた研磨速度が得られるので、好ましい。
立体状連結粒子の長さ方向の平均最長径（ＤＬａ）が、５０ｎｍ未満であると、十分な研磨速度を得られない場合があり、好ましくない。また、立体状連結粒子の長さ方向の平均最長径（ＤＬａ）が、１，０００ｎｍを超えると、研磨基板上で傷が生じやすくなるため、好ましくない。
立体状連結粒子の長さ方向の最長径（ＤＬａ）は、８０ｎｍ以上６００ｎｍ以下がより好ましく、１００ｎｍ以上６００ｎｍ以下が最も好ましい。
When the average longest diameter (DLa) of the three-dimensionally connected particles in the length direction is 50 nm or more and 1,000 nm or less, an excellent polishing rate can be obtained, which is preferable.
If the average longest diameter (DLa) of the three-dimensionally connected particles in the length direction is less than 50 nm, a sufficient polishing rate may not be obtained, which is not preferable. Further, if the average longest diameter (DLa) of the three-dimensionally connected particles in the length direction exceeds 1,000 nm, scratches are likely to occur on the polished substrate, which is not preferable.
The longest diameter (DLa) of the three-dimensionally connected particles in the length direction is more preferably 80 nm or more and 600 nm or less, and most preferably 100 nm or more and 600 nm or less.
［立体状分岐構造を有する粒子連結型シリカ微粒子における太さ方向の平均直径（ＤＴａ）］
本発明における立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）は、下記の要件［４］を備えることが好ましい。
要件［４］ １０ｎｍ≦ＤＴａ≦８００ｎｍ
ここで、立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）の太さ方向における平均直径ＤＴａは、５０個の立体状連結粒子について、各粒子における極大値（ＤＴｍａｘ）の平均値を、さらに平均した値（［５０個の立体状連結粒子についてＤＴｍａｘを合計した値］／５０）をいう。
立体状連結粒子は、外形的に太さ方向の距離が極小値（ＤＴｍｉｎ）と極大値（ＤＴｍａｘ）をそれぞれ２箇所以上有する。
立体状分岐構造を有する粒子連結型シリカ微粒子における太さ方向とは、長さ方向の最長径（ＤＬ）と直交する方向をいう。
立体状分岐構造を有する粒子連結型シリカ微粒子における外形的な太さ方向の直径ＤＴは、粒子の外縁部と太さ方向の線分とが交わる２交点間の距離をいう。
「粒子連結型シリカ微粒子の外縁部」とは、走査型顕微鏡写真等（ＳＥＭ写真等）を用いて、粒子連結型シリカ微粒子を平面視（写真投影図）した場合における粒子連結型シリカ微粒子の輪郭をいう。
立体状分岐構造を有する粒子連結型シリカ微粒子における外形的な太さ方向の直径ＤＴは、走査型電子顕微鏡（２０万倍）を用いて測定する。
[Average diameter (DTa) in the thickness direction of particle-connected silica fine particles having a three-dimensional branched structure]
The particle-connected silica fine particles (three-dimensionally connected particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirement [4].
Requirement [4] 10 nm ≤ DTa ≤ 800 nm
Here, the average diameter DTa in the thickness direction of the particle-connected silica fine particles (three-dimensionally connected particles) having a three-dimensional branched structure is the average value (DTmax) of the maximum values (DTmax) of each of the 50 three-dimensionally connected particles. Is further averaged ([total value of DTmax for 50 three-dimensional connected particles] / 50).
The three-dimensionally connected particles have two or more externally minimum (DTmin) and maximum (DTmax) distances in the thickness direction.
The thickness direction of the particle-connected silica fine particles having a three-dimensional branched structure means a direction orthogonal to the longest diameter (DL) in the length direction.
The external diameter DT in the thickness direction of the particle-connected silica fine particles having a three-dimensional branched structure refers to the distance between two intersections where the outer edge of the particles and the line segment in the thickness direction intersect.
The "outer edge of the particle-connected silica fine particles" is the outline of the particle-connected silica fine particles when the particle-connected silica fine particles are viewed in a plan view (photo projection drawing) using a scanning micrograph or the like (SEM photograph or the like). To say.
The external diameter DT in the thickness direction of the particle-connected silica fine particles having a three-dimensional branched structure is measured using a scanning electron microscope (200,000 times).
立体状連結粒子の太さ方向における平均直径（ＤＴａ）が、１０ｎｍ以上８００ｎｍ以下であると、実用上の不都合を生じず好ましい。立体状連結粒子の太さ方向における平均直径（ＤＴａ）が、１０ｎｍ未満であると、分散液の著しい増粘を伴い、取り扱い上の不都合を生じるため、好ましくない。また、立体状連結粒子の太さ方向における平均直径（ＤＴａ）が、８００ｎｍを超えると、粒子の沈降性が大きくなり、取り扱い上の不都合を生じるため、好ましくない。
立体状連結粒子の太さ方向における平均最長直径（ＤＴａ）は、２０ｎｍ以上６００ｎｍ以下がより好ましい。４０ｎｍ以上６００ｎｍ以下がさらに好ましく、６０ｎｍ以上６００ｎｍ以下が最も好ましい。
It is preferable that the average diameter (DTa) of the three-dimensionally connected particles in the thickness direction is 10 nm or more and 800 nm or less without causing practical inconvenience. If the average diameter (DTa) of the three-dimensionally connected particles in the thickness direction is less than 10 nm, the dispersion liquid is significantly thickened, which causes inconvenience in handling, which is not preferable. Further, if the average diameter (DTa) of the three-dimensionally connected particles in the thickness direction exceeds 800 nm, the sedimentation property of the particles becomes large, which causes inconvenience in handling, which is not preferable.
The average longest diameter (DTa) of the three-dimensionally connected particles in the thickness direction is more preferably 20 nm or more and 600 nm or less. It is more preferably 40 nm or more and 600 nm or less, and most preferably 60 nm or more and 600 nm or less.
本発明における立体状分岐構造を有する粒子連結型シリカ微粒子の長さ方向の平均最長径（ＤＬａ）が５０ｎｍ以上１０００ｎｍ以下の範囲であり、かつその太さ方向の平均直径（ＤＴａ）が、１０ｎｍ以上８００ｎｍ以下の範囲であることが好ましい。 In the present invention, the average longest diameter (DLa) of the particle-connected silica fine particles having a three-dimensional branched structure in the length direction is in the range of 50 nm or more and 1000 nm or less, and the average diameter (DTa) in the thickness direction thereof is 10 nm or more. The range is preferably 800 nm or less.
［立体状分岐構造を有する粒子連結型シリカ微粒子の太さ方向の直径（ＤＴ）における平均変動係数（Ｃ．Ｖ．）］
本発明における立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）は、下記の要件［５］を備えることが好ましい。
要件［５］１０％≦Ｃ．Ｖ．≦４０％
立体状分岐構造を有する粒子連結型シリカ微粒子の太さ方向の直径（ＤＴ）の変動係数および平均変動係数（Ｃ．Ｖ．）は、次のように求める。
（１）立体状分岐構造を有する粒子連結型シリカ微粒子における最長径ＤＬを求めるときに用いた走査型電子顕微鏡写真を使用する。
（２）最長径ＤＬを２等分し、直交する線分が粒子外縁と交わる２交点を求め、該２交点を結ぶ線分をＤＴとする。
（３）任意に選択した５０個の立体状連結粒子について上記（２）の測定を行い、それらの平均値（ＤＴ５０個の合計／５０）を太さ方向の平均直径ＤＴａとした。
（４）任意に選択した５０個の立体状連結粒子について上記（２）の測定を行い、５０個の立体状連結粒子のそれぞれのＤＴの値について変動係数を求め、それらを平均した値を平均変動係数（Ｃ．Ｖ．）とした。
平均変動係数（Ｃ．Ｖ．）が１０％以上４０％以下の範囲にあると、良好な研磨速度が得られるので好ましい。
平均変動係数（Ｃ．Ｖ．）が１０％未満であると、分岐の形成が不十分であり、所望の研磨特性が得られないため好ましくない。また、平均変動係数（Ｃ．Ｖ．）が４０％を超えると、粒子と基板の接触が不均一になるためか所望の研磨特性が得られず、研磨基板に傷が生じる傾向が強まり、好ましくない。
平均変動係数（Ｃ．Ｖ．）は、１５％以上３５％以下の範囲であることがより好ましい。
[Average coefficient of variation (CV) in diameter (DT) in the thickness direction of particle-connected silica fine particles having a three-dimensional branched structure]
The particle-connected silica fine particles (three-dimensionally connected particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirement [5].
Requirement [5] 10% ≤ C. V. ≤40%
The coefficient of variation and the average coefficient of variation (CV) of the diameter (DT) in the thickness direction of the particle-connected silica fine particles having a three-dimensional branched structure are obtained as follows.
(1) The scanning electron micrograph used when determining the longest diameter DL of the particle-connected silica fine particles having a three-dimensional branched structure is used.
(2) The longest diameter DL is divided into two equal parts, two intersections where orthogonal line segments intersect the outer edge of the particle are obtained, and the line segment connecting the two intersections is defined as DT.
(3) The measurement of (2) above was performed on 50 arbitrarily selected three-dimensionally connected particles, and the average value (total of 50 DTs / 50) was taken as the average diameter DTa in the thickness direction.
(4) The measurement of (2) above was performed on 50 arbitrarily selected three-dimensionally connected particles, the coefficient of variation was obtained for each DT value of the 50 three-dimensionally connected particles, and the averaged values were averaged. The coefficient of variation (CV) was used.
When the average coefficient of variation (CV) is in the range of 10% or more and 40% or less, a good polishing rate can be obtained, which is preferable.
If the average coefficient of variation (CV) is less than 10%, branch formation is insufficient and desired polishing characteristics cannot be obtained, which is not preferable. Further, if the average coefficient of variation (CV) exceeds 40%, the desired polishing characteristics cannot be obtained probably because the contact between the particles and the substrate becomes non-uniform, and the polishing substrate tends to be scratched, which is preferable. No.
The average coefficient of variation (CV) is more preferably in the range of 15% or more and 35% or less.
［立体状分岐構造を有する粒子連結型シリカ微粒子のネック部］
本発明の立体状連結粒子においては、立体状連結粒子生成後の珪酸液等のシリカ補強処理の程度により、隣接するシリカ一次微粒子間に形成されるネック部に違いが生じる。ネック部の深さを、隣接するシリカ一次微粒子（ｐ１）とシリカ一次微粒子（ｐ２）の両方に外接する直線Ｃを引き、シリカ一次微粒子（ｐ１）と（ｐ２）の接合部から該直線Ｃに直交する線分を求め、その線分をネック部深さ（Ｌ）［ｎｍ］とし、Ｌｓ、ＬｍおよびＦを下記のとおり定める。
Ｆ：立体状連結粒子におけるシリカ一次微粒子の平均粒子径（透過型電子顕微鏡）
Ｌ：ネック部深さ
Ｌｓ：同一の立体状連結粒子におけるネック部深さの平均値
Ｌｍ：５０個の立体状連結粒子におけるネック部深さの平均値
このとき、Ｌｍは、下記数式（２−１）で表される範囲を満たすことが好ましい。
０≦Ｌｍ≦Ｆ／３・・・（２−１）
Ｌｍが上記範囲にある場合、一次粒子間のネックは十分にシリカで補強されており、研磨時の荷重を受けても、粒子連結構造及び立体状構造は保持されるので、粒子と研磨基板との高接触面積が得られ、所望の研磨性能を得ることができる。
他方、Ｌｍの値がＦ／３の値より大きい場合、即ち、ネック部の深さの平均値（Ｌｍ）が、前記シリカ一次微粒子の平均粒子径（Ｆ）の３分の１より大きい場合は、一次粒子間のネック部深さが十分にシリカで十分に補強されていない状態であり、研磨時の荷重により立体状連結粒子の構造が崩壊し、研磨速度が低下する場合がある。
Ｌｍが、Ｆ/２を超えると粒子連結状とは見做せない。
Ｌｍは、下記数式（２−２）で表される範囲を満たすことがより好ましく、下記数式（２−３）で表される範囲を満たすことがさらに好ましい。
０＜Ｌｍ＜Ｆ／６・・・（２−２）
０＜Ｌｍ＜Ｆ／９・・・（２−３）
[Neck of particle-connected silica fine particles with a three-dimensional branched structure]
In the three-dimensionally connected particles of the present invention, the neck portion formed between the adjacent silica primary fine particles differs depending on the degree of silica reinforcement treatment such as a silicic acid solution after the three-dimensionally connected particles are generated. The depth of the neck portion is drawn by drawing a straight line C circumscribing both the adjacent silica primary fine particles (p1) and the silica primary fine particles (p2), and from the junction between the silica primary fine particles (p1) and (p2) to the straight line C. Find the line segments that are orthogonal to each other, set the line segment to the neck depth (L) [nm], and define Ls, Lm, and F as follows.
F: Average particle size of silica primary fine particles in three-dimensionally connected particles (transmission electron microscope)
L: Neck depth Ls: Average neck depth of the same three-dimensional connecting particles Lm: Average neck depth of 50 three-dimensional connecting particles At this time, Lm is calculated by the following formula (2-). It is preferable to satisfy the range represented by 1).
0 ≤ Lm ≤ F / 3 ... (2-1)
When Lm is in the above range, the neck between the primary particles is sufficiently reinforced with silica, and the particle connection structure and the three-dimensional structure are maintained even when a load is applied during polishing. High contact area can be obtained, and desired polishing performance can be obtained.
On the other hand, when the value of Lm is larger than the value of F / 3, that is, when the average value (Lm) of the depth of the neck portion is larger than one-third of the average particle size (F) of the silica primary fine particles. In a state where the neck depth between the primary particles is not sufficiently reinforced with silica, the structure of the three-dimensionally connected particles may collapse due to the load during polishing, and the polishing speed may decrease.
If Lm exceeds F / 2, it cannot be regarded as a particle-connected form.
Lm more preferably satisfies the range represented by the following mathematical formula (2-2), and further preferably satisfies the range represented by the following mathematical formula (2-3).
0 <Lm <F / 6 ... (2-2)
0 <Lm <F / 9 ... (2-3)
［立体状分岐構造を有する粒子連結型シリカ微粒子のネック部深さの平均変動係数（Ｃ．Ｖ．（Ｌｍ））］
本発明における立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）は、下記の要件を備えることが好ましい。
０％≦Ｃ．Ｖ．（Ｌｍ）≦４０％
ここで、Ｃ．Ｖ．（Ｌｍ）は、上述のとおりに求めた各粒子のＬｓを５０個の立体連結粒子に対して求め、求めた５０個間での変動係数である。Ｃ．Ｖ．（Ｌｍ）は、０％以上３５％以下の範囲であることがより好ましく、０％以上３０％以下の範囲であることがさらに好ましい。
Ｃ．Ｖ．（Ｌｍ）が上記範囲にある場合、ネック補強が均一になされており、研磨中の粒子崩壊が抑制でき、研磨速度が安定する。
Ｃ．Ｖ．（Ｌｍ）が４０％を超える場合、すなわち粒子間のネック部深さのばらつきが大きい場合は、各粒子と基板との接触面積にもばらつきが生じるためか、研磨速度の低下やスクラッチ等の欠陥が発生しやすい場合がある。
[Average coefficient of variation of neck depth of particle-connected silica fine particles having a three-dimensional branched structure (CV (Lm))]
The particle-connected silica fine particles (three-dimensionally connected particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirements.
0% ≤ C. V. (Lm) ≤40%
Here, C.I. V. (Lm) is the coefficient of variation between the obtained 50 particles obtained by obtaining the Ls of each particle obtained as described above for 50 three-dimensionally connected particles. C. V. (Lm) is more preferably in the range of 0% or more and 35% or less, and further preferably in the range of 0% or more and 30% or less.
C. V. When (Lm) is in the above range, the neck reinforcement is made uniform, particle decay during polishing can be suppressed, and the polishing rate is stable.
C. V. If (Lm) exceeds 40%, that is, if there is a large variation in the neck depth between the particles, the contact area between each particle and the substrate may also vary, resulting in a decrease in polishing speed or defects such as scratches. May easily occur.
［ネック部深さの測定方法］
立体状連結粒子の任意の箇所において、隣接するシリカ一次微粒子（ｐ１）とシリカ一次微粒子（ｐ２）の両方に外接する直線Ｃを引き、シリカ一次微粒子（ｐ１）と（ｐ２）の接合部から該直線Ｃに直交する線分を求め、その線分をネック部分深さ（Ｌ）［ｎｍ］とする。
同一の立体状連結粒子の任意の３箇所で、上記ネック部分深さ（Ｌ）［ｎｍ］を求め、それらの平均値（Ｌｓ）［ｎｍ］を算定する。この測定と算定を５０個の立体状連結粒子について行い、その平均値（Ｌｍ）［ｎｍ］を求める。
[Measurement method of neck depth]
A straight line C circumscribing both the adjacent silica primary fine particles (p1) and the silica primary fine particles (p2) is drawn at an arbitrary position of the three-dimensional connecting particles, and the straight line C is drawn from the junction of the silica primary fine particles (p1) and (p2). A line segment orthogonal to the straight line C is obtained, and the line segment is defined as the neck portion depth (L) [nm].
The neck portion depth (L) [nm] is obtained at any three points of the same three-dimensionally connected particles, and the average value (Ls) [nm] thereof is calculated. This measurement and calculation are performed on 50 three-dimensionally connected particles, and the average value (Lm) [nm] is obtained.
［立体状分岐構造を有する粒子連結型シリカ微粒子におけるシリカ一次微粒子の平均連結個数］
本発明の立体状連結粒子におけるシリカ一次微粒子の平均連結個数は、５個以上２０個以下の範囲にあることが好ましい。
平均連結個数が５個未満であると、動的な接触面積が十分に得られないためか所望の研磨速度が得られないことから好ましくない。また、平均連結個数が２０個を超えると、連結型というよりも凝集塊の形態となり、ディフェクト等の原因となるため好ましくない。
本発明の立体状連結粒子におけるシリカ一次微粒子の平均連結個数は、５個以上１５個以下の範囲がより好ましい。
[Average number of connected silica primary particles in particle-connected silica fine particles having a three-dimensional branched structure]
The average number of silica primary fine particles linked in the three-dimensionally linked particles of the present invention is preferably in the range of 5 or more and 20 or less.
If the average number of connected pieces is less than 5, it is not preferable because a sufficient dynamic contact area cannot be obtained or a desired polishing rate cannot be obtained. Further, if the average number of connected pieces exceeds 20, it becomes a form of agglutinated agglomerates rather than a connected type, which causes defects and the like, which is not preferable.
The average number of silica primary fine particles linked in the three-dimensionally linked particles of the present invention is more preferably in the range of 5 or more and 15 or less.
本発明の立体状連結粒子におけるシリカ一次微粒子の平均連結個数は、立体状連結粒子分散液の走査型電子顕微鏡写真（２０万倍）を用いて測定する。
走査型電子顕微鏡写真を用いて、各立体状連結粒子について、シリカ一次微粒子の連結個数を目視によって、数える。そして、立体状連結粒子５０個の連結個数の平均値を平均連結個数とする。
The average number of silica primary fine particles linked in the three-dimensionally linked particles of the present invention is measured using a scanning electron micrograph (200,000 times) of the three-dimensionally linked particle dispersion.
Using a scanning electron micrograph, the number of silica primary fine particles linked is visually counted for each three-dimensional linked particle. Then, the average value of the number of connected 50 three-dimensionally connected particles is taken as the average number of connected particles.
［立体状分岐構造を有する粒子連結型シリカ微粒子におけるシリカ一次微粒子］
立体状連結粒子におけるシリカ一次微粒子の平均粒子径範囲は、前記連結粒子におけるシリカ一次微粒子の平均粒子径と同様である。即ち、前記立体状連結粒子におけるシリカ一次微粒子の平均粒子径は５ｎｍ以上６００ｎｍ以下が好ましく、２０ｎｍ以上４００ｎｍ以下がより好ましく、６０ｎｍ以上３００ｎｍ以下がさらに好ましい。平均粒子径が５ｎｍ未満の場合は、一次粒子が凝集して得られる連結粒子が塊状になる傾向がある。また、研磨用途においては、応力集中が得られないためか、十分な研磨速度が得られず好ましくない。平均粒子径が６００ｎｍを超える場合は、例えば、研磨用途において、接触面積の低下が著しくなり、研磨速度の低下を招くときがある。また、平均粒子径が６００ｎｍを超える場合は、例えば、研磨面にスクラッチ（線状痕）が発生するときがある。
[Silica primary fine particles in particle-connected silica fine particles having a three-dimensional branched structure]
The average particle size range of the silica primary fine particles in the three-dimensionally connected particles is the same as the average particle size of the silica primary fine particles in the connected particles. That is, the average particle size of the silica primary fine particles in the three-dimensionally connected particles is preferably 5 nm or more and 600 nm or less, more preferably 20 nm or more and 400 nm or less, and further preferably 60 nm or more and 300 nm or less. When the average particle size is less than 5 nm, the connected particles obtained by aggregating the primary particles tend to be agglomerated. Further, in the polishing application, it is not preferable because a sufficient polishing rate cannot be obtained probably because stress concentration cannot be obtained. When the average particle size exceeds 600 nm, for example, in polishing applications, the contact area may be significantly reduced, which may lead to a decrease in polishing speed. When the average particle size exceeds 600 nm, scratches (linear marks) may occur on the polished surface, for example.
［立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）以外の粒子連結型シリカ微粒子（平面状連結粒子）］
本発明の平面状連結粒子は、立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）以外の粒子連結型シリカ微粒子（連結粒子）である。
このため、シリカ一次微粒子が２個以上、連結した粒子であって、立体状連結粒子以外であれば、平面状連結粒子に含まれる。例えば、シリカ一次微粒子が２個連結したものは、分岐構造が想定し得ないため、全て、平面状連結粒子に含まれる。
また、平面状連結粒子は、立体状連結粒子のように鎖状に連結したものに限定されない。例えば、平面状連結粒子には、シリカ一次微粒子が連結粒子の構造における一部または全部が環状に連結したものを含む。
[Particle-connected silica fine particles (planar connecting particles) other than particle-connected silica fine particles (three-dimensional connecting particles) having a three-dimensional branched structure]
The planar connecting particles of the present invention are particle connecting type silica fine particles (connecting particles) other than particle connecting type silica fine particles (three-dimensional connecting particles) having a three-dimensional branched structure.
Therefore, if two or more silica primary fine particles are linked to each other and are other than the three-dimensional linked particles, they are included in the planar linked particles. For example, those in which two primary silica fine particles are connected are all included in the planar connected particles because a branched structure cannot be assumed.
Further, the planar connecting particles are not limited to those connected in a chain like the three-dimensional connecting particles. For example, the planar connecting particles include those in which the silica primary fine particles are partially or wholly connected in a ring shape in the structure of the connecting particles.
［粒子連結型シリカ微粒子（連結粒子）以外のシリカ微粒子（単粒子）］
本発明の粒子連結型シリカ微粒子（連結粒子）以外のシリカ微粒子（単粒子）は、シリカ一次微粒子が２個以上連結したもの以外を含む。シリカ微粒子（単粒子）は、連結粒子を生成するために、反応物として用いたシリカ一次微粒子における未反応のシリカ一次微粒子が主な成分である。
[Silica fine particles (single particles) other than particle-linked silica fine particles (connected particles)]
The silica fine particles (single particles) other than the particle-linked silica fine particles (connected particles) of the present invention include those other than those in which two or more silica primary fine particles are linked. The main component of the silica fine particles (single particles) is unreacted silica primary fine particles in the silica primary fine particles used as a reactant in order to generate linked particles.
［粒子連結型シリカ微粒子分散液のシリカ微粒子が含有するＣａ、ＭｇおよびＡｌの割合］
本発明の粒子連結型シリカ微粒子分散液におけるシリカ微粒子が含有するＣａ、ＭｇおよびＡｌの割合は、それぞれ、２５ｐｐｍ以下、２５ｐｐｍ以下および１５０ｐｐｍ以下が好ましい。各元素の含有割合は、シリカ微粒子の単位質量あたりに含まれる各元素の質量の割合として表す。
本発明の粒子連結型シリカ微粒子分散液のシリカ微粒子は、シリカ一次微粒子またはこれがシリカによって結合したものである。このため、例えば、ＣａＯ、ＭｇＯおよびＡｌ２Ｏ３等の結合剤成分を含有しない。したがって、本発明のシリカ微粒子を含んでなる粒子連結型シリカ微粒子分散液を半導体基板あるいは配線基板等の半導体デバイスの研磨用途に適用した場合、これらの結合剤成分に起因する金属汚染の問題を生じるおそれが低い。
前記粒子連結型シリカ微粒子分散液におけるシリカ微粒子におけるＣａ含有量は１０ｐｐｍ以下、Ｍｇ含有量は１０ｐｐｍ以下およびＡｌ含有量は６０ｐｐｍ以下がより好ましい。
[Ratio of Ca, Mg and Al contained in silica fine particles of particle-linked silica fine particle dispersion]
The proportions of Ca, Mg and Al contained in the silica fine particles in the particle-linked silica fine particle dispersion liquid of the present invention are preferably 25 ppm or less, 25 ppm or less and 150 ppm or less, respectively. The content ratio of each element is expressed as the ratio of the mass of each element contained in the unit mass of the silica fine particles.
The silica fine particles of the particle-linked silica fine particle dispersion liquid of the present invention are silica primary fine particles or those bonded by silica. Therefore, for example, it does not contain a binder component such as CaO, MgO and Al 2 O 3. Therefore, when the particle-connected silica fine particle dispersion liquid containing the silica fine particles of the present invention is applied to a polishing application for a semiconductor device such as a semiconductor substrate or a wiring substrate, a problem of metal contamination due to these binder components arises. Low risk.
It is more preferable that the Ca content in the silica fine particles in the particle-linked silica fine particle dispersion is 10 ppm or less, the Mg content is 10 ppm or less, and the Al content is 60 ppm or less.
本発明の連結粒子分散液は、その分散質として、立体状連結粒子を５個数％以上５０個数％以下含む。
立体状連結粒子の個数割合は５個数％以上５０個数％以下の範囲が好ましい。より好ましくは５個数％以上３０個数％以下の範囲が好ましく、さらに好ましくは５個数％以上２５個数％以下の範囲が好ましい。また、平面状連結粒子の割合は５０個数％以上９５個数％が好ましい。
The linked particle dispersion liquid of the present invention contains 5% or more and 50% or less of three-dimensional linked particles as the dispersoid.
The number ratio of the three-dimensionally connected particles is preferably in the range of 5% by number or more and 50% by number or less. More preferably, the range of 5% by number or more and 30% by number or less is preferable, and further preferably the range of 5% by number or more and 25% by number or less is preferable. Further, the ratio of the planar connecting particles is preferably 50% or more and 95% or more.
立体状連結粒子の個数割合が５個数％以上５０個数％以下の範囲の場合、本発明の粒子連結型シリカ微粒子分散液を研磨用途に適用した場合、前記の研磨速度の増大に効果的に寄与することができる。
立体状連結粒子の個数割合が５個数％未満の場合、砥粒のうち、前記立体状構造を有した立体状連結粒子の割合が低いため、研磨後の基板の表面粗さは低くなるものの、研磨速度も低下する。
立体状連結粒子の個数割合が５０個数％を超える場合、砥粒のうち、前記立体状構造を有した立体状連結粒子の割合が過剰で、研磨速度は増大するものの、研磨基板上でのスクラッチ発生や表面粗さが悪化するといった問題が生じやすくなる。立体状連結粒子個数割合が５０個数％以下の場合、５０%超存在する単粒子や連結度の高くない粒子及び平面状連結粒子が、研磨基板の粗さを良化させ、５０%以下の立体状連結粒子が高い研磨速度を示す。そのため、研磨速度と表面粗さを両立する事ができる。
When the number ratio of the three-dimensionally connected particles is in the range of 5% or more and 50% or less, when the particle-linked silica fine particle dispersion of the present invention is applied to a polishing application, it effectively contributes to the increase in the polishing rate. can do.
When the number ratio of the three-dimensionally connected particles is less than 5%, the ratio of the three-dimensionally connected particles having the three-dimensional structure is low among the abrasive grains, so that the surface roughness of the substrate after polishing is low, but The polishing speed is also reduced.
When the number ratio of the three-dimensionally connected particles exceeds 50%, the ratio of the three-dimensionally connected particles having the three-dimensional structure is excessive among the abrasive grains, and the polishing speed is increased, but scratches on the polishing substrate are made. Problems such as generation and deterioration of surface roughness are likely to occur. When the number ratio of the three-dimensionally connected particles is 50% or less, the single particles existing in excess of 50%, the particles having a low degree of connection, and the planar connected particles improve the roughness of the polishing substrate, and the three-dimensionally connected particles are 50% or less. The shape-connected particles show a high polishing rate. Therefore, both the polishing speed and the surface roughness can be achieved at the same time.
立体状連結粒子の個数％は、次のように求める。連結粒子分散液（固形分濃度０．０５質量％）の透過型顕微鏡写真（２０万倍）により、少なくとも粒子が連結した形状の粒子を２００個任意に選択する。選択した２００個における個々の粒子を立体状連結粒子または平面状連結粒子のいずれかに選別する。そして、立体状連結粒子の個数を２００で除した値を立体状連結粒子の個数％とする。 The number% of the three-dimensional connected particles is calculated as follows. A transmission electron micrograph (200,000 times) of a linked particle dispersion (solid content concentration: 0.05% by mass) is used to arbitrarily select at least 200 particles having a shape in which the particles are linked. The individual particles in the selected 200 are sorted into either three-dimensional connecting particles or planar connecting particles. Then, the value obtained by dividing the number of three-dimensionally connected particles by 200 is defined as the number% of the number of three-dimensionally connected particles.
本発明の粒子連結型シリカ微粒子分散液における、立体状連結粒子の体積％は、４０体積％以上９５体積％の範囲が好ましい。
立体状連結粒子の体積割合が４０体積％以上９５体積％以下の範囲の場合、本発明の粒子連結型シリカ微粒子分散液を研磨用途に適用したとき、前記の研磨速度の増大に効果的に寄与することができる。
立体状連結粒子の体積割合が４０体積％未満の場合、砥粒のうち、前記立体構造を有した立体状連結粒子の割合が低く、研磨速度の増大に対する寄与も少ない。
立体状連結粒子の体積割合が９５体積％を超える場合、砥粒のうち、前記立体構造を有した立体状連結粒子の割合が過剰で、研磨速度は増大するものの、研磨基板上でのスクラッチ発生といった問題が生じやすくなる。
立体状連結粒子の体積割合は好ましくは４５体積％以上９０体積％以下、更に好ましくは５０体積％以上８６体積％以下である。
In the particle-linked silica fine particle dispersion liquid of the present invention, the volume% of the three-dimensionally linked particles is preferably in the range of 40% by volume or more and 95% by volume.
When the volume ratio of the three-dimensionally connected particles is in the range of 40% by volume or more and 95% by volume or less, when the particle-connected silica fine particle dispersion liquid of the present invention is applied to a polishing application, it effectively contributes to the increase in the polishing rate. can do.
When the volume ratio of the three-dimensionally connected particles is less than 40% by volume, the ratio of the three-dimensionally connected particles having the three-dimensional structure is low among the abrasive grains, and the contribution to the increase in the polishing rate is small.
When the volume ratio of the three-dimensionally connected particles exceeds 95% by volume, the ratio of the three-dimensionally connected particles having the three-dimensional structure is excessive in the abrasive grains, and the polishing speed increases, but scratches occur on the polishing substrate. Such problems are likely to occur.
The volume ratio of the three-dimensionally connected particles is preferably 45% by volume or more and 90% by volume or less, and more preferably 50% by volume or more and 86% by volume or less.
立体状連結粒子の体積％（Ｗ）の求め方は、後記のとおりである。 The method of obtaining the volume% (W) of the three-dimensionally connected particles is as described later.
本発明の粒子連結型シリカ微粒子分散液は、立体状連結粒子および平面状連結粒子以外に、発明の効果に大きな影響を与えない範囲で、粒子連結していない単粒子を含んでいてもよい。例えば、砥粒として用いる場合には、粒子連結型シリカ微粒子の体積に対する単粒子の体積の比は、前者１００（体積部）に対し、後者５５（体積部）以下であることが望ましい。（ここで、粒子連結型シリカ微粒子の体積とは、立体状連結粒子の体積と平面状連結粒子の体積の総和を意味する。）粒子連結型シリカ微粒子の体積に対する単粒子の体積の比が上記範囲内であれば、本発明の効果を損なうことがない。なお、単粒子の前記体積比が５５(体積部)を超える場合、砥粒のうち前記立体構造を有した立体状連結粒子の割合が相対的に低く、例えば、研磨速度の増大に対する効果も生じ難くなる。
また、粒子連結型シリカ微粒子の個数に対する単粒子の個数の比は、前者１００（個数部）に対し、後者２１０（個数部）以下であることが望ましい。（ここで、粒子連結型シリカ微粒子の個数とは、立体状連結粒子の個数と平面状連結粒子の個数の総和を意味する。）粒子連結型シリカ微粒子の個数に対する単粒子の個数の比が上記範囲内であれば、本発明の効果を損なうことがない。なお、単粒子の前記個数比が２１０（個数部）を超える場合、砥粒のうち前記立体構造を有した立体状連結粒子の割合が相対的に低く、例えば、研磨速度の増大に対する効果も生じ難くなる。
In addition to the three-dimensionally connected particles and the planarly connected particles, the particle-linked silica fine particle dispersion liquid of the present invention may contain single particles that are not particle-connected as long as the effects of the present invention are not significantly affected. For example, when used as abrasive grains, the ratio of the volume of a single particle to the volume of the particle-connected silica fine particles is preferably 100 (volume part) of the former and 55 (volume part) or less of the latter. (Here, the volume of the particle-connected silica fine particles means the sum of the volumes of the three-dimensionally connected particles and the volume of the planar connected particles.) The ratio of the volume of the single particles to the volume of the particle-connected silica fine particles is described above. If it is within the range, the effect of the present invention is not impaired. When the volume ratio of the single particles exceeds 55 (volume part), the proportion of the three-dimensionally connected particles having the three-dimensional structure in the abrasive grains is relatively low, and for example, an effect on increasing the polishing speed also occurs. It becomes difficult.
Further, the ratio of the number of single particles to the number of particle-connected silica fine particles is preferably 210 (number of parts) or less of the latter 100 (number of parts). (Here, the number of particle-linked silica fine particles means the sum of the number of three-dimensional linked particles and the number of planar linked particles.) The ratio of the number of single particles to the number of particle-linked silica fine particles is the above. If it is within the range, the effect of the present invention is not impaired. When the number ratio of the single particles exceeds 210 (number of parts), the proportion of the three-dimensionally connected particles having the three-dimensional structure in the abrasive grains is relatively low, and for example, an effect on increasing the polishing rate also occurs. It becomes difficult.
［粒子連結型シリカ微粒子分散液のシラノール基密度］
粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子のシラノール基密度は、０．１個／ｎｍ２以上５．０個／ｎｍ２以下の範囲にあることが好ましい。
シラノール基密度は、０．５個／ｎｍ２以上４．５個／ｎｍ２以下であることがより好ましく、１．０個／ｎｍ２以上４．０個／ｎｍ２以下であることがさらに好ましい。
シラノール基密度が０．１個／ｎｍ２以上５．０個／ｎｍ２以下の範囲にあると、そのような粒子連結型シリカ微粒子分散液を研磨用途に適用した場合、研磨性能が向上する。これは粒子連結型シリカ微粒子どうしで、シリカ表面のシラノール基に起因する静電的な反発作用により、粒子連結型シリカ微粒子どうしの凝集が抑制され、効率的な研磨が行われるものと推察される。
粒子連結型シリカ微粒子分散液の表面シラノール基密度が５．０個／ｎｍ２を超える場合は、研磨基材の材質によっては、粒子表面のシラノール基と基板との凝着作用のためか、基板への粒子残りが多く発生する、研磨時に添加する界面活性剤が過剰に必要になる等が生じ好ましくない。また、粒子連結型シリカ微粒子分散液の表面シラノール基密度が０．１個／ｎｍ２未満の場合は、粒子連結型シリカ微粒子のシリカ表面の負電荷が小さくなるので、粒子連結型シリカ微粒子の分散性が低下することがあり、好ましくない。
[Silanol group density of particle-linked silica fine particle dispersion]
The silanol group density of the silica fine particles contained in the particle-linked silica fine particle dispersion is preferably in the range of 0.1 / nm 2 or more and 5.0 / nm 2 or less.
The silanol group density is more preferably 0.5 pieces / nm 2 or more and 4.5 pieces / nm 2 or less, and further preferably 1.0 piece / nm 2 or more and 4.0 pieces / nm 2 or less. ..
When the silanol group density is in the range of 0.1 element / nm 2 or more and 5.0 element / nm 2 or less, the polishing performance is improved when such a particle-linked silica fine particle dispersion is applied to a polishing application. It is presumed that these are particle-linked silica fine particles, and that the electrostatic repulsion caused by the silanol groups on the silica surface suppresses the agglutination of the particle-linked silica fine particles, resulting in efficient polishing. ..
If the surface silanol group density of the particle-linked silica fine particle dispersion exceeds 5.0 elements / nm 2 , it may be due to the adhesion between the silanol groups on the particle surface and the substrate, depending on the material of the polishing substrate. It is not preferable because a large amount of particles remain on the surface and an excessive amount of surfactant to be added at the time of polishing is required. Further, when the surface silanol group density of the particle-linked silica fine particle dispersion is less than 0.1 / nm 2 , the negative charge on the silica surface of the particle-linked silica fine particles becomes small, so that the particle-linked silica fine particles are dispersed. It is not preferable because it may reduce the sex.
［粒子連結型シリカ微粒子分散液のカチオンコロイド滴定］
粒子連結型シリカ微粒子分散液は、流動電位変化量（ΔＰＣＤ）と、クニックにおけるカチオンコロイド滴定液の添加量（Ｖ）との比（ΔＰＣＤ／Ｖ）が、−３５０以上−１０以下であることが好ましい。
ΔＰＣＤ／Ｖが、−３５０以上−１０以下である場合、そのような粒子連結型シリカ微粒子分散液を研磨用途に適用した場合、良好な研磨速度を得ることができる。
ΔＰＣＤ／Ｖが、−３５０未満であると、研磨基板の材質によっては電荷による相互作用が大きくなりすぎるためか基板への粒子残りが多く発生し、好ましくない。また、ΔＰＣＤ／Ｖが、−１０を超えると、粒子連結型シリカ微粒子の分散性が低下することがあり、好ましくない。
ΔＰＣＤ／Ｖは、−３００以上−２０以下がさらに好ましい。ΔＰＣＤ／Ｖは、カチオンコロイド滴定によって求められる。
[Cation colloid titration of particle-linked silica fine particle dispersion]
In the particle-linked silica fine particle dispersion, the ratio (ΔPCD / V) of the amount of change in flow potential (ΔPCD) to the amount of cation colloid titration solution added (V) in the knick is −350 or more and −10 or less. preferable.
When ΔPCD / V is −350 or more and −10 or less, a good polishing rate can be obtained when such a particle-linked silica fine particle dispersion is applied to a polishing application.
If ΔPCD / V is less than −350, a large amount of particles remain on the substrate, which is not preferable, probably because the interaction due to electric charge becomes too large depending on the material of the polishing substrate. Further, when ΔPCD / V exceeds −10, the dispersibility of the particle-linked silica fine particles may decrease, which is not preferable.
ΔPCD / V is more preferably −300 or more and −20 or less. ΔPCD / V is determined by cationic colloid titration.
カチオンコロイド滴定は下記のように行い、ΔＰＣＤ／Ｖを求める。
本発明におけるカチオンコロイド滴定は、カチオンコロイド滴定液（０．００１Ｎポリ塩化ジアリルジメチルアンモニウム溶液）を、固形分濃度を１質量％に調整した連結粒子分散液８０ｇに滴下して行う。
カチオンコロイド滴定液の滴下量（ｍＬ）をｘ軸および前記分散液の流動電位（ｍＶ）をｙ軸とし、前記滴下量と前記流動電位との関係をグラフにした電位流動曲線を得る。
前記電位流動曲線において、滴下量に対する流動電位の変化量が大きく変化する点（変曲点）をクニックとする。クニックにおけるカチオンコロイド滴定液の滴下量（Ｖ、ｍＬ）と、流動電位（Ｃ、ｍＶ）を求める。
また、カチオンコロイド滴定液の滴下前における固形分濃度を１質量％に調整した連結粒子分散液８０ｇの流動電位を流動電位曲線の開始点における流動電位（Ｉ、ｍＶ）とする。
これらの結果から、下記数式（Ｆ１）より、ΔＰＣＤ／Ｖを求める。
ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖ・・・（Ｆ１）
Ｃ：前記クニックにおける流動電位（ｍＶ）
Ｉ：前記流動電位曲線の開始点における流動電位（ｍＶ）
Ｖ：前記クニックにおける前記カチオンコロイド滴定液の添加量（ｍＬ）
Cationic colloid titration is performed as follows to determine ΔPCD / V.
The cationic colloid titration in the present invention is carried out by dropping a cationic colloid titration solution (0.001N polydiallyldimethylammonium chloride solution) into 80 g of a linked particle dispersion having a solid content concentration adjusted to 1% by mass.
A potential flow curve is obtained by graphing the relationship between the dropping amount and the flow potential, with the dropping amount (mL) of the cationic colloid titration solution being the x-axis and the flow potential (mV) of the dispersion liquid being the y-axis.
In the potential flow curve, a point (inflection point) at which the amount of change in the flow potential with respect to the dropping amount changes significantly is defined as a knick. The dropping amount (V, mL) and the flow potential (C, mV) of the cationic colloid titration solution in the knick are determined.
Further, the flow potential of 80 g of the linked particle dispersion liquid in which the solid content concentration before dropping of the cationic colloid titration solution is adjusted to 1% by mass is defined as the flow potential (I, mV) at the start point of the flow potential curve.
From these results, ΔPCD / V is obtained from the following mathematical formula (F1).
ΔPCD / V = (IC) / V ... (F1)
C: Flow potential (mV) in the knick
I: Flow potential (mV) at the start point of the flow potential curve
V: Addition amount (mL) of the cationic colloid titration solution in the knick
連結粒子分散液の固形分濃度は２質量％以上５０質量％以下が好ましい。この範囲であれば、経時での粒子の沈降も生じ難く、貯蔵ないし運送にも適用できる。５０質量％を超えると、粒子の凝集およびそれに伴う沈降が生じやすくなる。特に連結粒子分散液を研磨用途に適用した場合、その様な粒子の凝集あるいは沈降は、研磨砥粒分散液の安定性を損ない、研磨速度や研磨効率を低下させる場合がある。また、研磨処理のために研磨砥粒分散液を保管する容器内あるいは供給する工程で、容器あるいは供給装置内の内壁に付着した研磨砥粒分散液は、容易に乾燥して凝集物となり、再度研磨砥粒分散液に混入して、研磨処理により傷（スクラッチ）発生の原因となることがある。２質量％未満では、連結粒子分散液を各種用途に適用するにあたり濃縮が必要となり、実用的ではない。
前記固形分濃度は５質量％以上３０質量％以下がより好ましい。
ここで固形分濃度は、連結粒子分散液の分散質の濃度を意味し、具体的には、シリカ微粒子の質量（連結粒子（立体状連結粒子および平面状連結粒子））および単粒子を合計した質量）に基づく濃度である。
The solid content concentration of the linked particle dispersion is preferably 2% by mass or more and 50% by mass or less. Within this range, it is difficult for particles to settle over time, and it can be applied to storage or transportation. If it exceeds 50% by mass, agglutination of particles and accompanying sedimentation are likely to occur. In particular, when the linked particle dispersion is applied to a polishing application, such aggregation or sedimentation of particles may impair the stability of the abrasive grain dispersion and reduce the polishing speed and polishing efficiency. Further, in the process of supplying the polishing abrasive grain dispersion liquid in the container for storing the polishing abrasive grain dispersion liquid for the polishing treatment, the polishing abrasive grain dispersion liquid adhering to the inner wall in the container or the supply device is easily dried and becomes agglomerates, and again. It may be mixed with the abrasive grain dispersion liquid and cause scratches due to the polishing process. If it is less than 2% by mass, concentration is required for applying the linked particle dispersion to various uses, which is not practical.
The solid content concentration is more preferably 5% by mass or more and 30% by mass or less.
Here, the solid content concentration means the concentration of the dispersoid of the linked particle dispersion liquid, and specifically, the mass of the silica fine particles (connecting particles (three-dimensional connecting particles and planar connecting particles)) and single particles are totaled. It is a concentration based on mass).
前記連結粒子分散液の溶媒または分散媒については、水、有機溶媒、またはこれらの混合溶媒のいずれであっても良い。有機溶媒としては、アルコール類（メチルアルコール、エチルアルコール、イソプロピルアルコール等）、エーテル類、エステル類およびケトン類等の水溶性の有機溶媒が挙げられる。 The solvent or dispersion medium of the linked particle dispersion may be water, an organic solvent, or a mixed solvent thereof. Examples of the organic solvent include water-soluble organic solvents such as alcohols (methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.), ethers, esters, and ketones.
［粒子連結型シリカ微粒子分散液の製造方法］
＜工程１＞
工程１は、シリカ微粒子分散液（ＳｉＯ２濃度１．５質量％以上３０質量％以下）にｐＨ緩衝剤またはｐＨ調整剤を、下記の割合（ＷＢ／ＷＬＰ１）の範囲内で添加し、続いて、４０℃以上９８℃以下に加熱し、１時間以上保持し、粒子連結型シリカ微粒子分散液を得る工程である。
０．０１≦ＷＢ／ＷＬＰ１≦０．１
（ここで、ＷＬＰ１は、シリカ微粒子分散液中のシリカ質量（ｇ）であり、ＷＢは、ｐＨ緩衝剤の質量（ｇ）またはｐＨ調整剤の質量（ｇ）である。）
[Manufacturing method of particle-linked silica fine particle dispersion]
<Step 1>
In step 1, a pH buffer or pH adjuster is added to the silica fine particle dispersion (SiO 2 concentration of 1.5% by mass or more and 30% by mass or less) within the following ratio (WB / WLP 1 ), followed by This is a step of heating to 40 ° C. or higher and 98 ° C. or lower and holding the mixture for 1 hour or longer to obtain a particle-linked silica fine particle dispersion.
0.01 ≤ WB / WLP 1 ≤ 0.1
(Here, WLP 1 is the mass (g) of silica in the silica fine particle dispersion, and WB is the mass (g) of the pH buffer or the mass (g) of the pH adjuster.)
工程１で使用するシリカ微粒子分散液は、分散媒にシリカ微粒子が分散したものである。
分散媒としては、連結粒子分散液の溶媒または分散媒が挙げられる。
シリカ微粒子としては、連結粒子におけるシリカ一次微粒子と同様の形状および同様の平均粒子径を有することが好ましい。
また、シリカ微粒子が含有するＣａ、ＭｇおよびＡｌ濃度は、シリカ微粒子の単位質量あたり、Ｃａ、ＭｇおよびＡｌの質量として、下記のとおりであることが好ましい。
Ｃａ：２５ｐｐｍ以下
Ｍｇ：２５ｐｐｍ以下
Ａｌ：１５０ｐｐｍ以下
The silica fine particle dispersion liquid used in step 1 is one in which silica fine particles are dispersed in a dispersion medium.
Examples of the dispersion medium include a solvent of a linked particle dispersion liquid or a dispersion medium.
The silica fine particles preferably have the same shape and the same average particle size as the silica primary fine particles in the connecting particles.
The Ca, Mg and Al concentrations contained in the silica fine particles are preferably as follows as the mass of Ca, Mg and Al per unit mass of the silica fine particles.
Ca: 25ppm or less Mg: 25ppm or less Al: 150ppm or less
工程１で使用するシリカ微粒子分散液のＳｉＯ２濃度は、１．５質量％以上３０質量％が好ましい。シリカ微粒子分散液のＳｉＯ２濃度が１．５質量％未満の場合は、ＳｉＯ２濃度が薄いことが影響してシリカ粒子の連結構造が生じ難くなる。また、ＳｉＯ２濃度が３０質量％を超える場合は、シリカ粒子の連結が無秩序に生じるため、粒子の構造が制御できなくなる傾向がある。工程１で使用するシリカ微粒子分散液のＳｉＯ２濃度は、４質量％以上１８質量％以下の範囲がより好ましい。 The SiO 2 concentration of the silica fine particle dispersion used in step 1 is preferably 1.5% by mass or more and 30% by mass. When the SiO 2 concentration of the silica fine particle dispersion is less than 1.5% by mass, the low SiO 2 concentration makes it difficult to form a connected structure of silica particles. Further, when the SiO 2 concentration exceeds 30% by mass, the silica particles are connected in a disorderly manner, so that the structure of the particles tends to be uncontrollable. The SiO 2 concentration of the silica fine particle dispersion used in step 1 is more preferably in the range of 4% by mass or more and 18% by mass or less.
工程１で使用するシリカ微粒子分散液において、ＳｉＯ２／Ｎａ２Ｏ（モル比）は制限されるものではなく、Ｎａを全く含まないものを使用してもよい。 In the silica fine particle dispersion used in step 1, the SiO 2 / Na 2 O (molar ratio) is not limited, and one that does not contain Na at all may be used.
工程１において脱塩する方法としては、陽イオン交換樹脂で、Ｎａ＋イオンをＨ＋イオンに交換する方法が挙げられる。
陽イオン交換樹脂としては、強酸性陽イオン交換樹脂または弱酸性陽イオン交換樹脂等が挙げられ、−ＳＯ３Ｈまたは−ＣＯＯＨ等に置換した構造を有する樹脂が挙げられる。
工程１で使用するシリカ微粒子分散液のｐＨは、シリカ微粒子分散液が安定であればよく、特に制限されない。工程１で使用するシリカ微粒子分散液のｐＨは、２以上１２以下で構わない。ｐＨ調整は、例えば、Ｎａ＋のイオン交換より行うことができる。
Examples of the method of desalting in step 1 include a method of exchanging Na + ions with H + ions with a cation exchange resin.
The cation exchange resin, such as strong acidic cation exchange resin or weakly acidic cation exchange resins. Resin having a structure obtained by replacing the -SO 3 H or -COOH, and the like.
The pH of the silica fine particle dispersion used in step 1 is not particularly limited as long as the silica fine particle dispersion is stable. The pH of the silica fine particle dispersion used in step 1 may be 2 or more and 12 or less. The pH adjustment can be performed, for example, by ion exchange of Na +.
工程１で使用するｐＨ緩衝剤またはｐＨ調整剤は、シリカ微粒子分散液に、ＷＢ／ＷＬＰ１が０．０１以上０．１以下の割合で添加する（ここで、ＷＬＰ１は、シリカ微粒子分散液中のシリカ質量（ｇ）であり、ＷＢは、ｐＨ緩衝剤の質量（ｇ）またはｐＨ調整剤（ｇ）の質量である）。
ＷＢ／ＷＬＰ１が上記範囲でｐＨ緩衝液またはｐＨ調整剤を使用すると、緩衝剤またはｐＨ調整剤の作用により、立体状連結粒子および平面状連結粒子が生成しやすくなる。
ＷＢ／ＷＬＰ１が０．０１未満では、平面状連結粒子および立体状連結粒子が生成し難い。また、ＷＢ／ＷＬＰ１が０．１を超えると、ｐＨ緩衝剤が過剰となり、粒子の凝集が生じやすくなり、塊状の粒子が生成しやすくなる。ＷＢ／ＷＬＰ１は、０.０１５以上０.０７以下がより好ましい。
ｐＨ緩衝剤又はｐＨ調整剤は、通常、それぞれ水に溶解させて水溶液として使用される（これらをそれぞれ、ｐＨ緩衝液又はｐＨ調整液と称する場合がある。）。
The pH buffer or pH adjuster used in step 1 is added to the silica fine particle dispersion at a ratio of WB / WLP 1 of 0.01 or more and 0.1 or less (where WLP 1 is a silica fine particle dispersion). The mass of silica in (g), where WB is the mass of the pH buffer (g) or the mass of the pH regulator (g)).
When the WB / WLP 1 uses a pH buffer solution or a pH adjuster in the above range, the action of the buffer solution or the pH adjuster facilitates the formation of three-dimensional connecting particles and planar connecting particles.
When WB / WLP 1 is less than 0.01, it is difficult to generate planar connecting particles and three-dimensional connecting particles. Further, when WB / WLP 1 exceeds 0.1, the pH buffering agent becomes excessive, particles tend to agglomerate, and agglomerated particles tend to be generated. WB / WLP 1 is more preferably 0.015 or more and 0.07 or less.
The pH buffer or pH adjuster is usually dissolved in water and used as an aqueous solution (these may be referred to as a pH buffer solution or a pH adjuster, respectively).
ｐＨ緩衝剤としては、公知の無機系又は有機系のｐＨ緩衝剤を使用することが望ましい。
ｐＨ緩衝剤の例としては、酢酸アンモニウム、酢酸ナトリウム、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、重炭酸カリウム、リン酸三ナトリウム、リン酸三カリウム、リン酸二ナトリウム、リン酸二カリウム、ホウ酸ナトリウム、ホウ酸カリウム、四ホウ酸ナトリウム（ホウ砂）、四ホウ酸カリウムおよび水酸化アンモニウム等が挙げられる。これらのうち、酢酸アンモニウム又は酢酸ナトリウムが特に好ましい。
また、ｐＨ調整剤としては、公知の無機系又は有機系のｐＨ調整剤を使用することが望ましい。
ｐＨ調整剤の例としては、酸としては、酢酸、ギ酸、炭酸、塩酸、硝酸、リン酸、次亜リン酸、亜リン酸、ホスホン酸、硫酸、ホウ酸、フッ化水素酸、オルトリン酸、ピロリン酸、ポリリン酸、メタリン酸およびヘキサメタリン酸等が挙げられる。
塩基の例としては、水酸化カリウム等のアルカリ金属の水酸化物、アルカリ土類金属の水酸化物およびアンモニア等が挙げられる。これらの中でも、入手容易性から水酸化カリウムまたはアンモニアが好ましい。
As the pH buffer, it is desirable to use a known inorganic or organic pH buffer.
Examples of pH buffers include ammonium acetate, sodium acetate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, Examples thereof include disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (both sand), potassium tetraborate, ammonium hydroxide and the like. Of these, ammonium acetate or sodium acetate is particularly preferred.
Further, as the pH adjusting agent, it is desirable to use a known inorganic or organic pH adjusting agent.
Examples of pH adjusters include acetic acid, formic acid, carbonic acid, hydrochloric acid, nitrate, phosphoric acid, hypophosphite, phosphite, phosphonic acid, sulfuric acid, boric acid, hydrofluoric acid, orthophosphoric acid, as acids. Examples thereof include pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid and hexametaphosphoric acid.
Examples of bases include alkali metal hydroxides such as potassium hydroxide, alkaline earth metal hydroxides and ammonia. Among these, potassium hydroxide or ammonia is preferable because of its availability.
ｐＨ緩衝液またはｐＨ調整剤を用いて調整したシリカ微粒子分散液のｐＨは、２．０以上６．０以下の範囲にあることが好ましい。 The pH of the silica fine particle dispersion adjusted with a pH buffer or a pH adjuster is preferably in the range of 2.0 or more and 6.0 or less.
［加熱等の処理（立体状連結粒子の生成）］
ｐＨをｐＨ緩衝材またはｐＨ調整剤でシリカ微粒子分散液を、４０℃以上９８℃以下に加熱し、例えば、１時間以上６４時間以下に保持することが好ましい。
加熱することにより、隣接するシリカ一次微粒子の間にＳｉＯ２による結合が形成され、連結粒子が生成する。
加熱温度が、４０℃未満であると、連結反応が促進されにくく所望の粒子連結型シリカ粒子が得られないため、好ましくない。加熱温度が９８℃を超えると凝集塊を生じ易く所望の粒子連結型シリカ微粒子を得られないため、好ましくない。
また、保持時間が、１時間未満であると、連結反応が十分に進行しないため、好ましくない、また、保持時間が、６４時間を超えると、工程にかかる費用が高コストとなるために、経済的に好ましくない。
本発明では、工程１のみを経て得られた粒子連結型シリカ微粒子分散液を便宜上、粒子連結型シリカ微粒子分散液（Ｉ）とし、工程１および工程２を経て得られた粒子連結型シリカ微粒子分散液を粒子連結型シリカ微粒子分散液（ＩＩ）と称する場合がある。
[Treatment such as heating (generation of three-dimensional connected particles)]
The pH of the silica fine particle dispersion is preferably heated to 40 ° C. or higher and 98 ° C. or lower with a pH buffer or a pH adjuster, and maintained at, for example, 1 hour or longer and 64 hours or lower.
By heating, a bond by SiO 2 is formed between the adjacent silica primary fine particles, and connecting particles are formed.
If the heating temperature is less than 40 ° C., the linking reaction is not easily promoted and the desired particle-linked silica particles cannot be obtained, which is not preferable. If the heating temperature exceeds 98 ° C., agglomerates are likely to occur and desired particle-linked silica fine particles cannot be obtained, which is not preferable.
Further, if the holding time is less than 1 hour, the ligation reaction does not proceed sufficiently, which is not preferable, and if the holding time exceeds 64 hours, the cost required for the process becomes high, which is economical. It is not preferable.
In the present invention, the particle-linked silica fine particle dispersion obtained through only step 1 is designated as the particle-linked silica fine particle dispersion (I) for convenience, and the particle-linked silica fine particle dispersion obtained through steps 1 and 2 is used. The liquid may be referred to as a particle-linked silica fine particle dispersion liquid (II).
＜工程２＞
工程１で得られた連結粒子は、隣接するシリカ一次微粒子の間にＳｉＯ２による結合が形成されているが、結合した部分（以下、「ネック」ともいう）が小さく、脆い。このため、結合した部分を成長させ、隣接するシリカ一次微粒子の間の結合を強くすることが好ましい。
そこで、ネック部の成長を目的として、加熱による熟成やシリカによる補強等、特に粒子を成長させる工程である工程２を行うことが好ましい。
<Process 2>
The linked particles obtained in step 1 have a bond formed by SiO 2 between adjacent silica primary fine particles, but the bonded portion (hereinafter, also referred to as “neck”) is small and brittle. For this reason, it is preferable to grow the bonded portion and strengthen the bond between the adjacent silica primary fine particles.
Therefore, for the purpose of growing the neck portion, it is preferable to perform step 2 which is a step of growing particles, such as aging by heating and reinforcement with silica.
工程２では、工程１で得た粒子連結型シリカ微粒子分散液に対し、下記（ｉ）および（ｉｉ）の処理のうちの少なくとも１つにより、ｐＨ１０以上にｐＨ調整処理し、続いて酸性珪酸液を、下記の割合（ＷＳ／ＷＬＰ２）となるように連続的または断続的に添加し、粒子成長させる処理を施す。
０．０１≦ＷＳ／ＷＬＰ２≦１０
（ここで、ＷＬＰ２は、粒子連結型シリカ微粒子分散液中のシリカ質量（ｇ）であり、ＷＳは、酸性珪酸液中のシリカ質量（ｇ）である。）
（ｉ）陰イオン交換処理
（ｉｉ）アルカリ添加
In step 2, the particle-linked silica fine particle dispersion obtained in step 1 is subjected to pH adjustment treatment to pH 10 or higher by at least one of the following treatments (i) and (ii), followed by an acidic silicic acid liquid. Is continuously or intermittently added so as to have the following ratio (WS / WLP 2 ), and a treatment for growing particles is performed.
0.01 ≤ WS / WLP 2 ≤ 10
(Here, WLP 2 is the mass of silica (g) in the particle-linked silica fine particle dispersion, and WS is the mass of silica (g) in the acidic silicic acid solution.)
(I) Anion exchange treatment (ii) Add alkali
工程２では、工程１で得られた粒子連結型シリカ微粒子分散液（Ｉ）に陰イオン交換処理およびアルカリ性成分を添加する少なくとも一方の方法を用いて、ｐＨを１０以上にする。
陰イオン交換処理としては、陰イオン交換樹脂を使用した方法が挙げられる。陰イオン交換樹脂としては、強塩基陰イオン交換樹脂または弱塩基性陰イオン交換樹脂等が挙げられ、一級ないし三級アミノ基または四級アンモニウム等に置換した構造を有する樹脂が挙げられる。
また、アルカリ性成分としては、アンモニアおよび水ガラス等を使用できる。アルカリ性成分は、溶液にして用いることもできる。アルカリ性成分を溶解する溶媒は、連結粒子分散液の溶媒または分散媒が挙げられる。溶媒は、工程１で使用した分散媒が好ましく、水がより好ましい。
ｐＨ１０以上に調整した粒子連結型シリカ微粒子分散液のＳｉＯ２濃度は、１質量％以上３０質量％以下が好ましい。
In step 2, the pH is adjusted to 10 or more by using at least one method of anion exchange treatment and addition of an alkaline component to the particle-linked silica fine particle dispersion (I) obtained in step 1.
Examples of the anion exchange treatment include a method using an anion exchange resin. Examples of the anion exchange resin include a strong base anion exchange resin and a weakly basic anion exchange resin, and examples thereof include a resin having a structure substituted with a primary to tertiary amino group or a quaternary ammonium.
Further, as the alkaline component, ammonia, water glass and the like can be used. The alkaline component can also be used as a solution. Examples of the solvent for dissolving the alkaline component include the solvent of the linked particle dispersion and the dispersion medium. As the solvent, the dispersion medium used in step 1 is preferable, and water is more preferable.
The SiO 2 concentration of the particle-linked silica fine particle dispersion adjusted to pH 10 or higher is preferably 1% by mass or more and 30% by mass or less.
工程２では、ｐＨ１０以上に調整した粒子連結型シリカ微粒子分散液に酸性珪酸液を連続的または断続的に、ＷＳ／ＷＬＰ２が０．０１以上１０以下の範囲で添加する（ここで、ＷＬＰ２は、粒子連結型シリカ微粒子分散液中のシリカ質量であり、ＷＳは、酸性珪酸液中のシリカ質量である。）。
ＷＳ／ＷＬＰ２が０．０１未満であると、粒子連結型シリカ微粒子の連結部分の成長が不十分であるためか、所望の研磨特性が得られないため、好ましくない。また、ＷＳ／ＷＬＰ２が１０を超えると、得られた粒子連結型シリカ微粒子の形状が球状に近づき連結形状を保てない場合があるため、好ましくない。ＷＳ／ＷＬＰ２は、０．０２以上９．０以下がより好ましい。
工程２おける温度は、シリカが生成する反応なので、反応物の濃度に依存するが、７０℃以上９８℃以下が好ましい。
工程２における酸性珪酸液の添加は、連続的または断続的に行うことができる。酸性珪酸液を添加することによって、濃度を変化させて、シリカを生成させることが好ましい。
In step 2, the acidic silicic acid solution is continuously or intermittently added to the particle-connected silica fine particle dispersion adjusted to pH 10 or more in the range of 0.01 or more and 10 or less for WS / WLP 2 (here, WLP 2). Is the mass of silica in the particle-linked silica fine particle dispersion, and WS is the mass of silica in the acidic silicic acid solution.)
If WS / WLP 2 is less than 0.01, it is not preferable because the growth of the connecting portion of the particle-linked silica fine particles is insufficient or the desired polishing characteristics cannot be obtained. Further, when WS / WLP 2 exceeds 10, the shape of the obtained particle-connected silica fine particles may approach a spherical shape and the connected shape may not be maintained, which is not preferable. WS / WLP 2 is more preferably 0.02 or more and 9.0 or less.
Since the temperature in step 2 is a reaction in which silica is formed, it depends on the concentration of the reactants, but is preferably 70 ° C. or higher and 98 ° C. or lower.
The addition of the acidic silicic acid solution in step 2 can be carried out continuously or intermittently. It is preferable to change the concentration by adding an acidic silicic acid solution to produce silica.
酸性珪酸液は、珪酸アルカリ金属（珪酸ナトリウム等）を水に溶解させ、アルカリ金属イオンを水素イオンに交換したものである。アルカリ金属イオンを水素イオンに交換する方法としては、陽イオン交換樹脂を使用する方法が挙げられる。酸性珪酸液は、ｐＨが６以下であれば使用することができる。酸性珪酸液のＳｉＯ２濃度としては、１質量％以上６質量％以下のものを使用することができる。
ＳｉＯ２濃度が１質量％未満であると、添加する酸性珪酸液が多量に必要となるため、経済上好ましくない。また、６質量％以上であると、酸性珪酸液自体が不安定であるため、好ましくない。ＳｉＯ２濃度は、１質量％以上５質量％以下がより好ましい。
The acidic silicate solution is obtained by dissolving an alkali metal silicate (sodium silicate or the like) in water and exchanging alkali metal ions with hydrogen ions. Examples of the method for exchanging alkali metal ions with hydrogen ions include a method using a cation exchange resin. The acidic silicic acid solution can be used as long as the pH is 6 or less. As the SiO 2 concentration of the acidic silicic acid liquid, one having a concentration of 1% by mass or more and 6% by mass or less can be used.
If the SiO 2 concentration is less than 1% by mass, a large amount of acidic silicic acid solution to be added is required, which is economically unfavorable. Further, if it is 6% by mass or more, the acidic silicic acid solution itself is unstable, which is not preferable. The SiO 2 concentration is more preferably 1% by mass or more and 5% by mass or less.
＜工程３＞
粒子（特に粒子におけるネック部）をさらに成長させるという観点から、さらに工程３を行ってもよい。
工程３は、工程２を施している粒子連結型シリカ微粒子分散液に対し、ｐＨ１０．０以上にｐＨ調整処理し、続いて、酸性珪酸液を下記の割合（ＷＳ／ＷＬＰ２）となるように連続的または断続的に添加し、粒子成長させる処理を施す工程である。
０．５≦ＷＳ／ＷＬＰ２≦１０
（ここで、ＷＬＰ２は、本工程に用いる原料である粒子連結型シリカ微粒子分散液中のシリカ質量であり、ＷＳは、酸性珪酸液中のシリカ質量である。）
ＷＳ／ＷＬＰ２が０．５未満であると、粒子連結型シリカ微粒子の連結部分の成長が不十分であるためか、所望の研磨特性が得られないため、好ましくない。また、ＷＳ／ＷＬＰ２が１０を超えると、得られた粒子連結型シリカ微粒子の形状が球状に近づき連結形状を保てない場合があるため、好ましくない。ＷＳ／ＷＬＰ２は、０．５以上９．０以下がより好ましい。
工程３の操作は、工程２の操作とほぼ同様である。例えば、工程２で得られた粒子連結型シリカ微粒子分散液（ＩＩ）に対して、さらに、工程３を施すことによって、連結粒子をさらに成長（特にネック部を成長）させることができる。
なお、工程３は、上記の観点から、複数回を繰り返して行ってもよい。
<Step 3>
Step 3 may be further performed from the viewpoint of further growing the particles (particularly the neck portion of the particles).
In step 3, the particle-connected silica fine particle dispersion liquid subjected to step 2 is subjected to pH adjustment treatment to pH 10.0 or higher, and then the acidic silicic acid liquid is adjusted to the following ratio (WS / WLP 2 ). It is a step of continuously or intermittently adding the particles to grow particles.
0.5 ≤ WS / WLP 2 ≤ 10
(Here, WLP 2 is the mass of silica in the particle-linked silica fine particle dispersion liquid which is the raw material used in this step, and WS is the mass of silica in the acidic silicic acid liquid.)
If WS / WLP 2 is less than 0.5, it is not preferable because the growth of the connecting portion of the particle-linked silica fine particles is insufficient or the desired polishing characteristics cannot be obtained. Further, when WS / WLP 2 exceeds 10, the shape of the obtained particle-connected silica fine particles may approach a spherical shape and the connected shape may not be maintained, which is not preferable. WS / WLP 2 is more preferably 0.5 or more and 9.0 or less.
The operation of step 3 is almost the same as the operation of step 2. For example, by further performing step 3 on the particle-linked silica fine particle dispersion liquid (II) obtained in step 2, the linked particles can be further grown (particularly the neck portion is grown).
From the above viewpoint, the step 3 may be repeated a plurality of times.
［粒子連結型シリカ微粒子分散液を含む砥粒分散液］
本発明の連結粒子分散液を含む砥粒分散液（「研磨用組成物」ともいう。）は、さらに他の成分を含むことができる。
他の成分として、研磨促進剤、界面活性剤、親水性化合物、複素環化合物、ｐＨ調整剤およびｐＨ緩衝剤から選ばれる１以上の成分を使用することができる。
[Abrasive grain dispersion liquid containing particle-linked silica fine particle dispersion liquid]
The abrasive grain dispersion liquid (also referred to as “polishing composition”) containing the linked particle dispersion liquid of the present invention may further contain other components.
As other components, one or more components selected from polishing accelerators, surfactants, hydrophilic compounds, heterocyclic compounds, pH adjusters and pH buffers can be used.
研磨促進剤の例としては、硫酸、硝酸、リン酸、シュウ酸、フッ酸等の酸、あるいはこれら酸のナトリウム塩、カリウム塩、アンモニウム塩およびこれらの混合物等が挙げられる。これらの研磨促進剤を含む研磨用組成物の場合、複合成分からなる被研磨材を研磨する際に、被研磨材の特定の成分についての研磨速度を促進することにより、最終的に平坦な研磨面を得ることができる。 Examples of the polishing accelerator include acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid, and hydrofluoric acid, or sodium salts, potassium salts, ammonium salts, and mixtures thereof. In the case of a polishing composition containing these polishing accelerators, when polishing a material to be polished composed of composite components, by accelerating the polishing rate for a specific component of the material to be polished, finally flat polishing is performed. You can get a face.
本発明に係る研磨用組成物が研磨促進剤を含有する場合、その含有量としては、０．１質量％以上１０質量％以下であることが好ましく、０．５質量％以上５質量％以下であることがより好ましい。界面活性剤および／または親水性化合物研磨用組成物の分散性や安定性を向上させるためにカチオン系、アニオン系、ノニオン系、両性系の界面活性剤または親水性化合物を添加することができる。 When the polishing composition according to the present invention contains a polishing accelerator, the content thereof is preferably 0.1% by mass or more and 10% by mass or less, and 0.5% by mass or more and 5% by mass or less. More preferably. Surfactants and / or Hydrophilic Compounds Cationic, anionic, nonionic, amphoteric surfactants or hydrophilic compounds can be added to improve the dispersibility and stability of the polishing composition.
界面活性剤と親水性化合物は、いずれも被研磨面への接触角を低下させる作用を有し、均一な研磨を促す作用を有する。界面活性剤および／または親水性化合物としては、例えば、以下の群から選ばれるものを使用することができる。 Both the surfactant and the hydrophilic compound have an action of lowering the contact angle with the surface to be polished and an action of promoting uniform polishing. As the surfactant and / or hydrophilic compound, for example, those selected from the following groups can be used.
陰イオン界面活性剤として、カルボン酸塩、スルホン酸塩、硫酸エステル塩、およびリン酸エステル塩等が挙げられる。カルボン酸塩として、石鹸、Ｎ−アシルアミノ酸塩、ポリオキシエチレンまたはポリオキシプロピレンアルキルエーテルカルボン酸塩、およびアシル化ペプチド等が挙げられる。スルホン酸塩として、アルキルスルホン酸塩、アルキルベンゼンおよびアルキルナフタレンスルホン酸塩、ナフタレンスルホン酸塩、スルホコハク酸塩、α−オレフィンスルホン酸塩、およびＮ−アシルスルホン酸塩等が挙げられる。硫酸エステル塩として、硫酸化油、アルキル硫酸塩、アルキルエーテル硫酸塩、ポリオキシエチレンまたはポリオキシプロピレンアルキルアリルエーテル硫酸塩、およびアルキルアミド硫酸塩等が挙げられる。リン酸エステル塩として、アルキルリン酸塩、ポリオキシエチレンまたはポリオキシプロピレンアルキルアリルエーテルリン酸塩等が挙げられる。 Examples of anionic surfactants include carboxylic acid salts, sulfonates, sulfate ester salts, and phosphate ester salts. Carboxylates include soaps, N-acylamino acid salts, polyoxyethylene or polyoxypropylene alkyl ether carboxylates, acylated peptides and the like. Examples of the sulfonate include alkyl sulfonate, alkylbenzene and alkyl naphthalene sulfonate, naphthalene sulfonate, sulfosuccinate, α-olefin sulfonate, N-acyl sulfonate and the like. Examples of the sulfate ester include sulfated oil, alkyl sulfate, alkyl ether sulfate, polyoxyethylene or polyoxypropylene alkylallyl ether sulfate, alkylamide sulfate and the like. Examples of the phosphoric acid ester salt include alkyl phosphate, polyoxyethylene, polyoxypropylene alkyl allyl ether phosphate and the like.
陽イオン界面活性剤として、脂肪族アミン塩、脂肪族４級アンモニウム塩、塩化ベンザルコニウム塩、塩化ベンゼトニウム、ピリジニウム塩、およびイミダゾリニウム塩等が挙げられる。両性界面活性剤として、カルボキシベタイン型、スルホベタイン型、アミノカルボン酸塩、イミダゾリニウムベタイン、レシチン、およびアルキルアミンオキサイド等が挙げられる。 Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium chloride salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine, lecithin, alkylamine oxide and the like.
非イオン界面活性剤として、エーテル型、エーテルエステル型、エステル型、含窒素型が挙げられ、エーテル型として、ポリオキシエチレンアルキルおよびアルキルフェニルエーテル、アルキルアリルホルムアルデヒド縮合ポリオキシエチレンエーテル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレンポリオキシプロピレンアルキルエーテルが挙げられ、エーテルエステル型として、グリセリンエステルのポリオキシエチレンエーテル、ソルビタンエステルのポリオキシエチレンエーテル、ソルビトールエステルのポリオキシエチレンエーテル、エステル型として、ポリエチレングリコール脂肪酸エステル、グリセリンエステル、ポリグリセリンエステル、ソルビタンエステル、プロピレングリコールエステル、ショ糖エステル、含窒素型として、脂肪酸アルカノールアミド、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンアルキルアミド等が例示される。その他に、フッ素系界面活性剤等が挙げられる。 Examples of nonionic surfactants include ether type, ether ester type, ester type, and nitrogen-containing type, and ether types include polyoxyethylene alkyl and alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, and polyoxyethylene poly. Examples thereof include oxypropylene block polymer and polyoxyethylene polyoxypropylene alkyl ether. Examples of the ether ester type include polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester, and ester type. Examples of polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester, sucrose ester, and nitrogen-containing type include fatty acid alkanolamide, polyoxyethylene fatty acid amide, and polyoxyethylene alkylamide. In addition, a fluorine-based surfactant and the like can be mentioned.
界面活性剤としては、陰イオン界面活性剤もしくは非イオン系界面活性剤が好ましい。また、塩としては、アンモニウム塩、カリウム塩、ナトリウム塩等が挙げられ、特にアンモニウム塩およびカリウム塩が好ましい。 As the surfactant, an anionic surfactant or a nonionic surfactant is preferable. Examples of the salt include ammonium salt, potassium salt, sodium salt and the like, and ammonium salt and potassium salt are particularly preferable.
さらに、その他の界面活性剤、親水性化合物等としては、エステル（グリセリンエステル、ソルビタンエステルおよびアラニンエチルエステル等）、エーテル（ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリエチレングリコールアルキルエーテル、ポリエチレングリコールアルケニルエーテル、アルキルポリエチレングリコール、アルキルポリエチレングリコールアルキルエーテル、アルキルポリエチレングリコールアルケニルエーテル、アルケニルポリエチレングリコール、アルケニルポリエチレングリコールアルキルエーテル、アルケニルポリエチレングリコールアルケニルエーテル、ポリプロピレングリコールアルキルエーテル、ポリプロピレングリコールアルケニルエーテル、アルキルポリプロピレングリコール、アルキルポリプロピレングリコールアルキルエーテル、アルキルポリプロピレングリコールアルケニルエーテル、およびアルケニルポリプロピレングリコール等）、多糖類（アルギン酸、ペクチン酸、カルボキシメチルセルロース、カードランおよびプルラン等）、アミノ酸塩（グリシンアンモニウム塩およびグリシンナトリウム塩等）、ポリカルボン酸およびその塩（ポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリメタクリル酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリアミド酸、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、ポリアクリルアミド、アミノポリアクリルアミド、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリアミド酸、ポリアミド酸アンモニウム塩、ポリアミド酸ナトリウム塩およびポリグリオキシル酸等）、ビニル系ポリマ（ポリビニルアルコール、ポリビニルピロリドンおよびポリアクロレイン等）、スルホン酸およびその塩（メチルタウリン酸アンモニウム塩、メチルタウリン酸ナトリウム塩、硫酸メチルナトリウム塩、硫酸エチルアンモニウム塩、硫酸ブチルアンモニウム塩、ビニルスルホン酸ナトリウム塩、１−アリルスルホン酸ナトリウム塩、２−アリルスルホン酸ナトリウム塩、メトキシメチルスルホン酸ナトリウム塩、エトキシメチルスルホン酸アンモニウム塩、３−エトキシプロピルスルホン酸ナトリウム塩等）、およびアミド等（プロピオンアミド、アクリルアミド、メチル尿素、ニコチンアミド、コハク酸アミドおよびスルファニルアミド等）が挙げられる。 Further, as other surfactants, hydrophilic compounds and the like, esters (glycerin ester, sorbitan ester, alanine ethyl ester, etc.), ethers (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol alkenyl, etc.) Ether, alkyl polyethylene glycol, alkyl polyethylene glycol alkyl ether, alkyl polyethylene glycol alkenyl ether, alkenyl polyethylene glycol, alkenyl polyethylene glycol alkyl ether, alkenyl polyethylene glycol alkenyl ether, polypropylene glycol alkyl ether, polypropylene glycol alkenyl ether, alkyl polypropylene glycol, alkyl polypropylene Glycolalkyl ethers, alkylpolypropylene glycolalkenyl ethers, alkenylpolypropylene glycols, etc.), polysaccharides (arginic acid, pectinic acid, carboxymethylcellulose, curdran, purulan, etc.), amino acid salts (glycineammonium salt, glycine sodium salt, etc.), polycarboxylic acids Acids and their salts (polyaspartic acid, polyglutamic acid, polylysine, polyappleic acid, polymethacrylic acid, polyammonium methacrylate, polysodium methacrylate, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrene) Sulfonic acid), polyacrylic acid, polyacrylamide, aminopolyacrylamide, ammonium polyacrylic acid salt, sodium polyacrylic acid salt, polyamic acid, ammonium polyamic acid salt, sodium polyamic acid salt and polyglioxylic acid, etc.), vinyl-based polyma ( Polyvinyl alcohol, polyvinylpyrrolidone, polyacrolein, etc.), sulfonic acid and its salts (ammonium methyltaurate, sodium methyltaurate, methylsodium sulfate, ethylammonium sulfate, butylammonium sulfate, sodium vinylsulfonic acid, etc. 1-allyl sulfonic acid sodium salt, 2-allyl sulfonic acid sodium salt, methoxymethyl sulfonic acid sodium salt, ethoxymethyl sulfonic acid ammonium salt, 3-ethoxypropyl sulfonic acid sodium salt, etc.), and amides (propion amide, acrylamide, etc.) Me (Chilurea, nicotinamide, succinate amide, sulfanilamide, etc.) can be mentioned.
なお、適用する被研磨基材がガラス基板等である場合は何れの界面活性剤であっても好適に使用できるが、半導体集積回路用シリコン基板等の場合であって、アルカリ金属、アルカリ土類金属またはハロゲン化物等による汚染の影響を嫌う場合にあっては、酸もしくはそのアンモニウム塩系の界面活性剤を使用することが望ましい。 When the substrate to be polished is a glass substrate or the like, any surfactant can be preferably used, but in the case of a silicon substrate for a semiconductor integrated circuit or the like, alkali metals and alkaline earths are used. When the influence of contamination by metals or halides is disliked, it is desirable to use an acid or an ammonium salt-based surfactant thereof.
本発明に係る研磨用組成物が界面活性剤および／または親水性化合物を含有する場合、その含有量は、総量として、研磨用組成物の１Ｌ中、０．００１ｇ以上１０ｇ以下とすることが好ましく、０．０１ｇ以上５ｇ以下とすることがより好ましく０．１ｇ以上３ｇ以下とすることが特に好ましい。 When the polishing composition according to the present invention contains a surfactant and / or a hydrophilic compound, the total content thereof is preferably 0.001 g or more and 10 g or less in 1 L of the polishing composition. , 0.01 g or more and 5 g or less is more preferable, and 0.1 g or more and 3 g or less is particularly preferable.
界面活性剤および／または親水性化合物の含有量は、充分な効果を得る上で、研磨用組成物の１Ｌ中、０．００１ｇ以上が好ましく、研磨速度低下防止の点から１０ｇ以下が好ましい。 The content of the surfactant and / or the hydrophilic compound is preferably 0.001 g or more in 1 L of the polishing composition, and preferably 10 g or less from the viewpoint of preventing a decrease in the polishing rate, in order to obtain a sufficient effect.
界面活性剤または親水性化合物は１種のみでもよいし、２種以上を使用してもよく、異なる種類のものを併用することもできる。 Only one type of surfactant or hydrophilic compound may be used, two or more types may be used, or different types may be used in combination.
本発明の研磨用組成物については、被研磨基材に金属が含まれる場合に、金属に不動態層または溶解抑制層を形成させて、被研磨基材の侵食を抑制する目的で、複素環化合物を含有させても構わない。ここで、「複素環化合物」とはヘテロ原子を１個以上含んだ複素環を有する化合物である。ヘテロ原子とは、炭素原子、または水素原子以外の原子を意味する。複素環とはヘテロ原子を少なくとも一つ持つ環状化合物を意味する。ヘテロ原子は複素環の環系の構成部分を形成する原子のみを意味し、環系に対して外部に位置していたり、少なくとも一つの非共役単結合により環系から分離していたり、環系のさらなる置換基の一部分であるような原子は意味しない。ヘテロ原子として好ましくは、窒素原子、硫黄原子、酸素原子、セレン原子、テルル原子、リン原子、ケイ素原子、およびホウ素原子等が挙げられるが、これらに限定されるものではない。複素環化合物の例として、イミダゾール、ベンゾトリアゾール、ベンゾチアゾール、テトラゾール等を用いることができる。より具体的には、１，２，３，４−テトラゾール、５−アミノ−１，２，３，４−テトラゾール、５−メチル−１，２，３，４−テトラゾール、１，２，３−トリアゾール、４−アミノ−１，２，３−トリアゾール、４，５−ジアミノ−１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、３，５−ジアミノ−１，２，４−トリアゾール等が挙げられるが、これらに限定されるものではない。 In the polishing composition of the present invention, when the base material to be polished contains a metal, a heterocycle is formed for the purpose of forming a passivation layer or a dissolution suppressing layer on the metal to suppress erosion of the base material to be polished. A compound may be contained. Here, the "heterocyclic compound" is a compound having a heterocycle containing one or more heteroatoms. Heteroatom means an atom other than a carbon atom or a hydrogen atom. A heterocycle means a cyclic compound having at least one heteroatom. Heteroatoms refer only to the atoms that form the constituents of the heterocyclic ring system, and may be located outside the ring system, separated from the ring system by at least one unconjugated single bond, or the ring system. It does not mean an atom that is part of a further substituent of. Preferable examples of the hetero atom include, but are not limited to, a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. As an example of the heterocyclic compound, imidazole, benzotriazole, benzothiazole, tetrazole and the like can be used. More specifically, 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1,2,3- Triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3, Examples thereof include, but are not limited to, 5-diamino-1,2,4-triazole.
本発明に係る研磨用組成物に複素環化合物を配合する場合の含有量については、０．００１質量％以上１．０質量％以下であることが好ましく、０．００１質量％以上０．７質量％以下であることがより好ましく、０．００２質量％以上０．４質量％以下であることがさらに好ましい。 When the heterocyclic compound is blended in the polishing composition according to the present invention, the content is preferably 0.001% by mass or more and 1.0% by mass or less, and 0.001% by mass or more and 0.7% by mass. It is more preferably 0.002% by mass or more and 0.4% by mass or less.
上記各添加剤の効果を高めるため等に必要に応じて酸または塩基を添加して研磨用組成物のｐＨを調節することができる。 The pH of the polishing composition can be adjusted by adding an acid or a base as necessary to enhance the effect of each of the above additives.
本発明に係る研磨用組成物をｐＨ７以上に調整するときは、ｐＨ調整剤として、アルカリ性のものを使用する。望ましくは、水酸化ナトリウム、アンモニア水、炭酸アンモニウム、エチルアミン、メチルアミン、トリエチルアミン、テトラメチルアミン等のアミンが使用される。 When the polishing composition according to the present invention is adjusted to pH 7 or higher, an alkaline pH adjusting agent is used. Desirably, amines such as sodium hydroxide, aqueous ammonia, ammonium carbonate, ethylamine, methylamine, triethylamine, tetramethylamine and the like are used.
研磨用組成物をｐＨ７未満に調整するときは、ｐＨ調整剤として、酸性のものが使用される。例えば、乳酸、クエン酸、リンゴ酸、酒石酸、グリセリン酸等のヒドロキシ酸類が使用される。 When the polishing composition is adjusted to a pH of less than 7, an acidic one is used as the pH adjuster. For example, hydroxy acids such as lactic acid, citric acid, malic acid, tartaric acid and glyceric acid are used.
研磨用組成物のｐＨ値を一定に保持するために、ｐＨ緩衝剤を使用しても構わない。ｐＨ緩衝剤としては、例えば、リン酸２水素アンモニウム、リン酸水素２アンモニウム、４ホウ酸アンモ四水和水等のリン酸塩およびホウ酸塩または有機酸等を使用することができる。 A pH buffer may be used to keep the pH value of the polishing composition constant. As the pH buffer, for example, phosphates such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammo tetrahydrate tetrahydrate, and borates or organic acids can be used.
本発明に係る研磨用組成物については、必要に応じて溶媒を用いることができる。溶媒としては通常、水を用いるが、必要に応じてメチルアルコール、エチルアルコール、イソプロピルアルコール等のアルコール類を用いることができ、他にエーテル類、エステル類、ケトン類等水溶性の有機溶媒を用いることができる。また、水と有機溶媒からなる混合溶媒であってもよい。 A solvent can be used for the polishing composition according to the present invention, if necessary. Water is usually used as the solvent, but alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol can be used if necessary, and other water-soluble organic solvents such as ethers, esters, and ketones are used. be able to. Further, it may be a mixed solvent composed of water and an organic solvent.
本発明に係る研磨用組成物中の研磨用粒子の濃度は、０．５質量％以上５０質量％以下、さらには５量％以上３０質量％以下の範囲にあることが好ましい。濃度が０．５質量％未満の場合は、基材や絶縁膜の種類によっては濃度が低すぎて研磨速度が遅く生産性が問題となることがある。研磨用粒子の濃度が５０質量％を超えると研磨材の安定性が不充分となり、研磨速度や研磨効率がさらに向上することもなく、また研磨処理のために分散液を供給する工程で乾燥物が生成して付着することがあり傷（スクラッチ）発生の原因となることがある。 The concentration of the polishing particles in the polishing composition according to the present invention is preferably in the range of 0.5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less. If the concentration is less than 0.5% by mass, the concentration may be too low depending on the type of the base material or the insulating film, the polishing speed may be slow, and productivity may become a problem. If the concentration of polishing particles exceeds 50% by mass, the stability of the abrasive material becomes insufficient, the polishing speed and polishing efficiency do not further improve, and the dried product is supplied in the process of supplying the dispersion liquid for the polishing process. May be generated and adhered, which may cause scratches.
［実施例および比較例で用いた分析方法］
以下に本発明の好適な実施例を述べる。実施例および比較例における各種特性の測定方法については、特に断りの無い限り、以下に記す方法にて実施した。
[Analytical method used in Examples and Comparative Examples]
Suitable examples of the present invention will be described below. Unless otherwise specified, the methods for measuring various characteristics in Examples and Comparative Examples were as described below.
［１］動的光散乱法による平均粒子径測定方法
動的光散乱法による粒子連結型シリカ微粒子の平均粒子径（Ｄ１）の測定方法は次のとおりである。
試料（粒子連結型シリカ微粒子を含む分散液）を０．５８％アンモニア水にて希釈して、シリカ濃度１質量％に調整し、レーザーパーティクルアナライザー（例えば粒径測定装置（１））を用いて測定する。
［粒径測定装置（１）の概要］
大塚電子株式会社製、型番「ゼータ電位・粒径測定システム ＥＬＳＺ−１０００」（測定原理：動的光散乱法、光源波長：６６５．７０ｎｍ、温度調整範囲：１０〜９０℃、セル：１０ｍｍ角のプラスチックセル）
[1] Method for measuring average particle size by dynamic light scattering method The method for measuring the average particle size (D1) of particle-connected silica fine particles by the dynamic light scattering method is as follows.
A sample (dispersion liquid containing particle-linked silica fine particles) is diluted with 0.58% aqueous ammonia to adjust the silica concentration to 1% by mass, and a laser particle analyzer (for example, a particle size measuring device (1)) is used. taking measurement.
[Overview of particle size measuring device (1)]
Model number "Zeta potential / particle size measurement system ELSZ-1000" manufactured by Otsuka Electronics Co., Ltd. (Measurement principle: dynamic light scattering method, light source wavelength: 665.70 nm, temperature adjustment range: 10 to 90 ° C, cell: 10 mm square Plastic cell)
［２］粒子連結型シリカ微粒子分散液（連結粒子分散液）における立体構造を有する粒子連結型シリカ微粒子（立体状連結粒子）の個数の測定方法および個数割合の算出方法
１．測定試料の調製
（１）粒子連結型シリカ微粒子分散液を濃縮またはイオン交換水を用いて希釈し、固形分濃度０．０５質量％とした。
（２）上記（１）で固形分濃度０．０５質量％とした分散液に超音波をかけてから、その０．１ｇを撮影試料とした。
２．連結粒子および立体状連結粒子の個数割合の測定方法
（１）上記１．で調製した試料を、透過型電子顕微鏡（株式会社日立製作所製、超高分解能走査電子顕微鏡・型番Ｓ−５５００）を用い、２０万倍で撮影した。
（２）得られた写真において、少なくとも粒子が連結した形状を有する粒子を、任意に２００個選択した。
（３）これらの粒子について、立体状連結粒子を特定し、その粒子数を数えた。
立体状連結粒子の判定基準は次のとおりである。すなわち、特定の粒子連結型シリカ微粒子に関し、下記の１）〜３）の要件を満たすかを確認する。
１）シリカ一次微粒子の連結個数が５個以上で鎖状構造
２）主鎖構成粒子のうち、末端の粒子以外の粒子に結合した分岐（分岐（ａ））が少なくとも１箇存在する
３）当該粒子上に重複して、他の一次粒子に比して、濃淡が濃い部分が確認できること。
以上の１）〜３）の要件を満たす粒子連結型シリカ微粒子は、分岐（ａ）に対し、立体方向に伸長してなる分岐（ｂ）あるいは立体方向に伸長してなる末端（ｃ）を有し、立体構造を有すると見做し、立体状連結粒子とする。
（４）立体状連結粒子の個数％は、連結粒子２００個あたりの立体状連結粒子の数を百分率で表したものである。
（５）立体状連結粒子の体積％は、次の様にして求めた。
ＤＬａおよびＤＴａを用いて画像解析法による平均粒子径ＤＬＴを求める。ＤＬＴは以下の式で表される。
ＤＬＴ＝（ＤＬａ＋ＤＴａ）／２
ここで、立体状連結粒子のＤＬＴ（平均粒子径）をＤＬＴｔ、平面状連結粒子のＤＬＴ（平均粒子径）をＤＬＴｐとし、立体状連結粒子の体積をＶＬＴｔ、平面状連結粒子の体積をＶＬＴｐとしたとき、ＶＬＴｔと、ＶＬＴｐは、それぞれ次の様に求められる。
ＶＬＴｔ＝Σ（ＤＬＴｔ／Ｄｐ）３×（立体状連結粒子の個数％）、
ＶＬＴｐ＝Σ（ＤＬＴｐ／Ｄｐ）３×（平面状連結粒子の個数％）、
そして、求めたＶＬＴｔおよびＶＬＴｐから立体状連結粒子の体積％（Ｗ）を以下の式で求めることができる。
Ｗ＝ＶＬＴｔ／（ＶＬＴｐ＋ＶＬＴｔ）×１００
ここで、Ｄｐは、単粒子の平均粒子径［ｎｍ］である。
[2] Method for measuring the number of particle-linked silica fine particles (three-dimensionally linked particles) having a three-dimensional structure in the particle-linked silica fine particle dispersion (linked particle dispersion) and method for calculating the number ratio. Preparation of measurement sample (1) The particle-linked silica fine particle dispersion was concentrated or diluted with ion-exchanged water to a solid content concentration of 0.05% by mass.
(2) After ultrasonic waves were applied to the dispersion having a solid content concentration of 0.05% by mass in (1) above, 0.1 g thereof was used as a photographing sample.
2. Method for measuring the number ratio of linked particles and three-dimensional linked particles (1) 1. The sample prepared in the above was photographed at 200,000 times using a transmission electron microscope (manufactured by Hitachi, Ltd., ultra-high resolution scanning electron microscope, model number S-5500).
(2) In the obtained photograph, at least 200 particles having a shape in which the particles were connected were arbitrarily selected.
(3) For these particles, three-dimensional connected particles were identified and the number of the particles was counted.
The criteria for determining the three-dimensional connected particles are as follows. That is, it is confirmed whether or not the following requirements 1) to 3) are satisfied with respect to the specific particle-connected silica fine particles.
1) Chain structure with 5 or more connected silica primary fine particles 2) At least one branch (branch (a)) bonded to particles other than the terminal particles among the main chain constituent particles 3) Overlapping on the particles, it is possible to confirm the parts with darker shades than other primary particles.
The particle-connected silica fine particles satisfying the above requirements 1) to 3) have a branch (b) extending in the three-dimensional direction or a terminal (c) extending in the three-dimensional direction with respect to the branch (a). However, it is considered to have a three-dimensional structure, and is regarded as a three-dimensional connecting particle.
(4) The number% of the three-dimensionally connected particles is the number of three-dimensionally connected particles per 200 connected particles expressed as a percentage.
(5) The volume% of the three-dimensional connected particles was determined as follows.
The average particle size DLT is determined by an image analysis method using DLa and DTa. DLT is expressed by the following formula.
DLT = (DLa + DTa) / 2
Here, the DLT (average particle size) of the three-dimensional connecting particles is DLTt, the DLT (average particle size) of the planar connecting particles is DLTp, the volume of the three-dimensional connecting particles is VLTt, and the volume of the planar connecting particles is VLTp. Then, VLTt and VLTp are obtained as follows.
VLTt = Σ (DLTt / Dp) 3 × (number% of three-dimensional connected particles),
VLTp = Σ (DLTp / Dp) 3 × (number% of planar connecting particles),
Then, the volume% (W) of the three-dimensionally connected particles can be obtained from the obtained VLTt and VLTp by the following formula.
W = VLTt / (VLTp + VLTt) x 100
Here, Dp is the average particle size [nm] of a single particle.
［３］立体状連結粒子の平均連結個数の測定方法
１．立体状連結粒子の平均連結個数の測定方法
（１）前記［２］と同様に測定した電子顕微鏡写真を用意する。
（２）同写真における立体状連結粒子におけるシリカ一次微粒子の連結個数を目視によって数えた。
（３）任意に選択した５０個の立体状連結粒子について上記（２）を行い、シリカ一次微粒子の連結個数を平均した。この平均値を立体状連結粒子の平均連結個数とした。
２．立体状連結粒子におけるシリカ一次微粒子の平均粒子径［Ｆ］の測定方法
（１）前記［２］と同様に測定した電子顕微鏡写真を用意する。
（２）同写真における立体状連結粒子におけるシリカ一次微粒子の粒子径をそれぞれ測定し、その平均値を求める。
（３）任意に選択した５０個の立体状連結粒子について上記（２）を行い、５０個の平均値を求め、その値を前記平均粒子径［Ｆ］とする。
なお、平面状連結粒子の測定を行う場合も上記と同様である。
[3] Method for measuring the average number of three-dimensionally connected particles 1. Method for measuring the average number of three-dimensionally linked particles (1) Prepare an electron micrograph measured in the same manner as in [2] above.
(2) The number of linked silica primary fine particles in the three-dimensional linked particles in the same photograph was visually counted.
(3) The above (2) was performed on 50 arbitrarily selected three-dimensional linked particles, and the number of linked silica primary fine particles was averaged. This average value was taken as the average number of connected three-dimensionally connected particles.
2. Method for Measuring Average Particle Diameter [F] of Silica Primary Fine Particles in Three-dimensional Connected Particles (1) Prepare an electron micrograph measured in the same manner as in [2] above.
(2) The particle size of the silica primary fine particles in the three-dimensionally connected particles in the same photograph is measured, and the average value is obtained.
(3) The above (2) is performed on 50 arbitrarily selected three-dimensional connected particles, an average value of 50 particles is obtained, and the value is defined as the average particle diameter [F].
The same applies to the measurement of planar connected particles.
［４］立体状分岐構造を有する粒子連結型シリカ微粒子（立体状連結粒子）における長さ方向の平均最長径（ＤＬａ）および太さ方向の平均直径（ＤＴａ）の測定方法
１．測定試料の調製および走査型顕微鏡（ＳＥＭ）を用いた撮影
測定試料の調製およびＳＥＭを用いた撮影は、上記［２］立体状連結粒子の平均連結個数の測定方法における１．に準じて行った。
２．立体状連結粒子における長さ方向の平均最長径（ＤＬａ）の測定方法
（１）上記［２］において、使用した電子顕微鏡写真を用い、立体状連結粒子において、粒子外縁間の２点間を結ぶ線分のうち、その長さが最長となる線分の長さを最長径（ＤＬ）とする。
（２）任意に選択した５０個の立体状連結粒子について上記（１）を行い、それらの平均値（［５０個の立体状連結粒子について、それぞれのＤＬを合計した値］／５０）を長さ方向の平均最長径ＤＬａとした。
３．立体状連結粒子における太さ方向の平均直径（ＤＴａ）の測定方法
（１）上記［２］において、使用した電子顕微鏡写真を用い、立体状連結粒子において、粒子外縁間の２点間を結ぶ線分のうち、その長さが最長となる線分の方向を長さ方向と定め、それに対し、直交する方向を太さ方向とする。
（２）前記ＤＬと直交する線分が粒子外縁と交わる２交点を求め、該２交点間の距離が、最長となる線分をＤＴとする。
（３）任意に選択した５０個の立体状連結粒子について上記（２）の測定を行い、それらの平均値（ＤＴ５０個の合計／５０）を太さ方向の平均直径ＤＴａとした。
４．任意に選択した５０個の立体状連結粒子について上記（２）の測定を行い、５０個の立体状連結粒子のそれぞれのＤＴの値について変動係数を求め、それらを平均した値を平均変動係数（Ｃ．Ｖ．）とした。
[4] Method for measuring average longest diameter (DLa) in the length direction and average diameter (DTa) in the thickness direction of particle-connected silica fine particles (three-dimensionally connected particles) having a three-dimensional branched structure. Preparation of measurement sample and imaging using a scanning electron microscope (SEM) Preparation of a measurement sample and imaging using an SEM are described in the above [2] Method for measuring the average number of concatenated particles. It was done according to.
2. Method for measuring average longest diameter (DLa) in the length direction of three-dimensionally connected particles (1) Using the electron micrograph used in [2] above, in three-dimensionally connected particles, connect two points between the outer edges of the particles. Of the line segments, the length of the line segment having the longest length is defined as the longest diameter (DL).
(2) Perform the above (1) for 50 arbitrarily selected three-dimensionally connected particles, and lengthen their average value ([total DL of 50 three-dimensionally connected particles] / 50). The average longest diameter DLa in the longitudinal direction was used.
3. 3. Method for measuring average diameter (DTa) in the thickness direction of a three-dimensionally connected particle (1) Using the electron micrograph used in the above [2], a line connecting two points between the outer edges of the three-dimensionally connected particles. Of the minutes, the direction of the line segment having the longest length is defined as the length direction, and the direction orthogonal to the direction is defined as the thickness direction.
(2) Two intersections where the line segment orthogonal to the DL intersects the outer edge of the particle is obtained, and the line segment having the longest distance between the two intersections is defined as DT.
(3) The measurement of (2) above was performed on 50 arbitrarily selected three-dimensionally connected particles, and the average value (total of 50 DTs / 50) was taken as the average diameter DTa in the thickness direction.
4. The measurement of (2) above is performed on 50 arbitrarily selected three-dimensionally connected particles, the coefficient of variation is obtained for each DT value of the 50 three-dimensionally connected particles, and the average value is the average coefficient of variation ( C.V.).
［５］シラノール基密度の測定方法
Ｎａタイトレーション法による比表面積測定および平均粒子径測定
１）ＳｉＯ２として１．５ｇに相当する試料をビーカーに採取してから、恒温反応槽（２５℃）に移し、純水を加えて液量を９０ｍＬにする。（以下の操作は、２５℃に保持した恒温反応槽中にて行った。）
２）０．１モル／Ｌ塩酸を加え、ｐＨを３．６にする。
３）塩化ナトリウムを３０ｇ加え、純水で１５０ｍＬに希釈し、１０分間攪拌する。
４）ｐＨ電極をセットし、攪拌しながら０．１モル／Ｌ水酸化ナトリウム水溶液を滴下して、ｐＨ４．０に調整する。
５）ｐＨ４．０に調整した試料を０．１モル／Ｌ水酸化ナトリウム水溶液で滴定し、ｐＨ８．７〜９．３の範囲での滴定量とｐＨ値を４点以上記録して、０．１モル／Ｌ水酸化ナトリウム水溶液の滴定量をＸ、その時のｐＨ値をＹとして、検量線を作る。
６）次の式（２）からＳｉＯ２１．５ｇ当たりのｐＨ４．０から９．０までに要する０．１モル／Ｌ水酸化ナトリウム水溶液の消費量Ｖ（ｍＬ）を求め、後記式（３）に従って比表面積ＳＡ［ｍ２／ｇ］を求める。
Ｖ＝（Ａ×ｆ×１００×１．５）／（Ｗ×Ｃ）・・・（２）
上記式中、
Ａ：ＳｉＯ２１．５ｇ当たりｐＨ４．０から９．０までに要する０．１モル／Ｌ水酸化ナトリウム水溶液の滴定量（ｍＬ）
ｆ：０．１モル／Ｌ水酸化ナトリウム水溶液の力価
Ｗ：試料採取量（ｇ）
Ｃ：試料のＳｉＯ２濃度（質量％）
をそれぞれ表す。
ＳＡ＝２９．０Ｖ−２８・・・（３）
また、比表面積換算粒子径Ｄ２（ｎｍ）は、式（４）から求める。
比表面積換算粒子径Ｄ２（ｎｍ）＝６０００／（ρＳｉＯ２×ＳＡ）・・・（４）
（ここで、ρＳｉＯ２はシリカ粒子の密度２．２［ｇ／ｃｍ３］を表す。）
ここで本発明の連結型微粒子の表面シラノール基密度は、次のように測定するものとする。
初めに、前述の比表面積を測定するシアーズ法の手順１）〜６）によって、ＮａＯＨ滴定量を求める。次に、下記式に基づきシラノール基密度ρを算出することができる。
ρ＝（ａ×ｂ×ＮＡ）÷（ｃ×ｄ１）
上記式中、ρ：シラノール基密度（個／ｎｍ２）、ａ：滴定に用いたＮａＯＨ溶液の濃度（ｍｏｌ／Ｌ）、ｂ：ｐＨ４〜９のＮａＯＨ溶液の滴下量（ｍＬ）、ＮＡ：アボガドロ数、ｃ：シリカ質量（ｇ）、ｄ１：窒素吸着法で求めた比表面積換算粒子径（ｎｍ）
前記ｄ１は以下のように求める。
ＢＥＴ法（窒素吸着法）による比表面積測定および平均粒子径測定
粒子連結型シリカゾル５０ｍＬをＨＮＯ３でｐＨ３．５に調整し、１−プロパノール４０ｍＬを加え、１１０℃で１６時間乾燥した試料について、乳鉢で粉砕後、マッフル炉にて５００℃、１時間焼成し、測定用試料とした。そして、比表面積測定装置（ユアサアイオニクス製、型番マルチソーブ１２）を用いて窒素吸着法（ＢＥＴ法）を用いて、窒素の吸着量から、ＢＥＴ１点法により比表面積を算出した。
具体的には、試料０．５ｇを測定セルに取り、窒素３０ｖ％とヘリウム７０ｖ％との混合ガス気流中、３００℃で２０分間脱ガス処理を行い、その上で試料を上記混合ガス気流中で液体窒素温度に保ち、窒素を試料に平衡吸着させる。次に、上記混合ガスを流しながら試料温度を徐々に室温まで上昇させ、その間に脱離した窒素の量を検出し、予め作成した検量線により、粒子連結型シリカゾルの比表面積を算出した。また、得られた比表面積（ＳＡ）を前記式（４）に代入して比表面積換算粒子径ｄ１を求めた。
[5] Measurement method of silanol group density Specific surface area measurement and average particle size measurement by Na titration method 1) A sample corresponding to 1.5 g of SiO 2 is collected in a beaker and then placed in a constant temperature reaction vessel (25 ° C.). Transfer and add pure water to make the liquid volume 90 mL. (The following operation was performed in a constant temperature reaction vessel kept at 25 ° C.)
2) Add 0.1 mol / L hydrochloric acid to bring the pH to 3.6.
3) Add 30 g of sodium chloride, dilute to 150 mL with pure water, and stir for 10 minutes.
4) Set the pH electrode and add 0.1 mol / L sodium hydroxide aqueous solution while stirring to adjust the pH to 4.0.
5) The sample adjusted to pH 4.0 was titrated with a 0.1 mol / L sodium hydroxide aqueous solution, and the titration amount in the range of pH 8.7 to 9.3 and the pH value were recorded at 4 points or more, and 0. A titration line is prepared by setting the titration amount of 1 mol / L sodium hydroxide aqueous solution to X and the pH value at that time to Y.
6) From the following formula (2), the consumption V (mL) of 0.1 mol / L sodium hydroxide aqueous solution required for pH 4.0 to 9.0 per 1.5 g of SiO 2 was determined, and the following formula (3) ) To determine the specific surface area SA [m 2 / g].
V = (A × f × 100 × 1.5) / (W × C) ・ ・ ・ (2)
In the above formula,
A: Titration (mL) of 0.1 mol / L sodium hydroxide aqueous solution required from pH 4.0 to 9.0 per 1.5 g of SiO 2
f: Titer of 0.1 mol / L sodium hydroxide aqueous solution W: Sampling amount (g)
C: SiO 2 concentration (mass%) of the sample
Represent each.
SA = 29.0V-28 ... (3)
The specific surface area-equivalent particle size D2 (nm) is calculated from the formula (4).
Specific surface area equivalent particle size D2 (nm) = 6000 / (ρ SiO2 x SA) ... (4)
(Here, ρ SiO2 represents the density of silica particles 2.2 [g / cm 3 ].)
Here, the surface silanol group density of the articulated fine particles of the present invention shall be measured as follows.
First, the NaOH titration amount is determined by the above-mentioned steps 1) to 6) of the Sears method for measuring the specific surface area. Next, the silanol group density ρ can be calculated based on the following formula.
ρ = (a × b × NA) ÷ (c × d1)
In the above formula, ρ: silanol group density (pieces / nm 2 ), a: concentration of NaOH solution used for titration (mol / L), b: dropping amount of NaOH solution of pH 4-9 (mL), NA: Avogadro Number, c: Silica mass (g), d1: Specific surface area equivalent particle diameter (nm) determined by nitrogen adsorption method
The d1 is obtained as follows.
Specific surface area measurement and average particle size measurement by BET method (nitrogen adsorption method) 50 mL of particle-connected silica sol was adjusted to pH 3.5 with HNO 3 , 40 mL of 1-propanol was added, and the sample was dried at 110 ° C. for 16 hours. After crushing with a muffle furnace, the sample was calcined at 500 ° C. for 1 hour to prepare a sample for measurement. Then, the specific surface area was calculated from the amount of nitrogen adsorbed by the BET 1-point method using the nitrogen adsorption method (BET method) using a specific surface area measuring device (manufactured by Yuasa Ionics, model number Multisorb 12).
Specifically, 0.5 g of a sample is taken in a measurement cell, degassed at 300 ° C. for 20 minutes in a mixed gas stream of 30 v% nitrogen and 70 v% helium, and then the sample is placed in the mixed gas stream. Keep the temperature at liquid nitrogen and allow nitrogen to equilibrate and adsorb to the sample. Next, the sample temperature was gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that period was detected, and the specific surface area of the particle-connected silica sol was calculated from a calibration curve prepared in advance. Further, the obtained specific surface area (SA) was substituted into the above formula (4) to obtain the specific surface area equivalent particle diameter d1.
［６］カチオンコロイド滴定方法
（１）固形分濃度１質量％に調整した粒子連結型シリカ微粒子分散液８０ｇを試料とする。
（２）試料を攪拌する。
（３）カチオンコロイド滴定液の滴下前における試料の流動電位（ｍＶ）を測定する。
この流動電位（ｍＶ）を流動電位曲線の開始における流動電位Ｉ（ｍＶ）とする。
（４）試料を攪拌し、流動電位を測定しながら、カチオンコロイド滴定液（０．００１Ｎポリ塩化ジアリルジメチルアンモニウム溶液）を滴下する。
（５）カチオンコロイド滴定液の滴下量（ｍＬ）をｘ軸および試料の流動電位（ｍＶ）をｙ軸とし、前記滴下量と前記流動電位との間の関係を描画し、流動電位曲線を得る。
（６）流動電位曲線において、カチオンコロイド滴定液の滴下量に比し、流動電位が大きく変化する点（変曲点）を、クニックとする。このクニックにおけるカチオンコロイド滴定液の添加量Ｖ（ｍＬ）と流動電位Ｃ（ｍＶ）を求める。
（７）クニックにおけるカチオンコロイド滴定液の添加量（Ｖ）との比（ΔＰＣＤ／Ｖ）を、流動電位変化量（ΔＰＣＤ）と、クニックにおけるカチオンコロイド滴定液の添加量（Ｖ）との比（ΔＰＣＤ／Ｖ）を下記数式（Ｆ１）より求める。
ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖ・・・（Ｆ１）
Ｃ：前記クニックにおける流動電位（ｍＶ）
Ｉ：前記流動電位曲線の開始点における流動電位（ｍＶ）
Ｖ：前記クニックにおける前記カチオンコロイド滴定液の添加量（ｍＬ）
をそれぞれ表す。
[6] Cationic colloid titration method (1) 80 g of a particle-linked silica fine particle dispersion adjusted to a solid content concentration of 1% by mass is used as a sample.
(2) Stir the sample.
(3) The flow potential (mV) of the sample before dropping the cationic colloid titration solution is measured.
This flow potential (mV) is defined as the flow potential I (mV) at the start of the flow potential curve.
(4) The sample is stirred, and the cationic colloid titration solution (0.001N polydialyldimethylammonium chloride solution) is added dropwise while measuring the flow potential.
(5) With the dropping amount (mL) of the cationic colloid titration solution on the x-axis and the flow potential (mV) of the sample on the y-axis, the relationship between the dropping amount and the flow potential is drawn to obtain a flow potential curve. ..
(6) In the flow potential curve, a point (inflection point) at which the flow potential changes significantly with respect to the dropping amount of the cationic colloid titration solution is defined as a knick. The addition amount V (mL) and the flow potential C (mV) of the cationic colloid titration solution in this knick are determined.
(7) The ratio (ΔPCD / V) to the amount (V) of the cationic colloid titrator added in the knick, and the ratio (ΔPCD / V) to the amount of change in flow potential (ΔPCD) to the amount (V) of the cationic colloid titrator added in the knick. ΔPCD / V) is calculated from the following formula (F1).
ΔPCD / V = (IC) / V ... (F1)
C: Flow potential (mV) in the knick
I: Flow potential (mV) at the start point of the flow potential curve
V: Addition amount (mL) of the cationic colloid titration solution in the knick
Represent each.
［７］Ｃａ、ＭｇおよびＡｌの含有割合の測定方法
１．試料の調製
固形分濃度２０質量％に調整した粒子連結型シリカ微粒子分散液８０ｇを試料とする。
２．Ｃａ、ＭｇおよびＡｌの含有割合の測定方法
（１）約１ｇの粒子連結型シリカ微粒子分散液を白金皿に精秤する。
（２）上記（１）に、リン酸３ｍＬ、硝酸５ｍＬおよび弗化水素酸１０ｍＬを加えて、サンドバス上で加熱する。
（３）乾固したら、少量の水と硝酸５０ｍＬを加え溶解させて、１００ｍＬのメスフラスコにおさめ、水を加えて、１００ｍＬにする。
（４）次に、１００ｍＬにおさめた溶液から分液１０ｍＬを２０ｍＬのメスフラスコに採取する操作を５回繰り返し、分液１０ｍＬを５個得る。
（５）これを用いて、ＩＣＰプラズマ発光分析装置（ＳＩＩ製、品番ＳＰＳ５５２０）にて、標準添加法で測定を行う。
（６）同様の方法でブランクを測定し、ブランク分を差し引いて調整し、各元素における測定値とする。
（７）上記測定値から、粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子の単位質量あたりに含まれる各元素（Ｃａ、ＭｇおよびＡｌ）の質量の割合を求めた。
[7] Method for measuring the content ratio of Ca, Mg and Al 1. Preparation of sample 80 g of a particle-linked silica fine particle dispersion adjusted to a solid content concentration of 20% by mass is used as a sample.
2. Method for measuring the content ratio of Ca, Mg and Al (1) Approximately 1 g of a particle-linked silica fine particle dispersion is precisely weighed in a platinum dish.
(2) To (1) above, 3 mL of phosphoric acid, 5 mL of nitric acid and 10 mL of hydrofluoric acid are added and heated on a sand bath.
(3) After drying, add a small amount of water and 50 mL of nitric acid to dissolve, put in a 100 mL volumetric flask, and add water to make 100 mL.
(4) Next, the operation of collecting 10 mL of the separated solution from the solution contained in 100 mL into a 20 mL volumetric flask is repeated 5 times to obtain 5 10 mL of the separated solution.
(5) Using this, measurement is performed by a standard addition method with an ICP plasma emission spectrometer (manufactured by SII, product number SPS5520).
(6) The blank is measured by the same method, and the blank is subtracted and adjusted to obtain the measured value for each element.
(7) From the above measured values, the ratio of the mass of each element (Ca, Mg and Al) contained in the unit mass of the silica fine particles contained in the particle-linked silica fine particle dispersion was determined.
［８］ＳｉＯ２絶縁膜（厚み１μｍ）基板に対する研磨特性の評価方法と研磨用砥粒分散液の調製方法
［研磨用砥粒分散液の調製］
実施例および比較例の各々において得られた粒子連結型シリカ微粒子分散液あるいはシリカ微粒子分散液について、それぞれイオン交換水を加えて希釈し、いずれも固形分濃度１．０質量％に調整し、それぞれ硝酸水溶液（濃度５％）を添加してｐＨ６．０に調整し、研磨用砥粒分散液とした。
［研磨試験方法］
被研磨基板として、熱酸化法により作製したＳｉＯ２絶縁膜（厚み１μｍ）基板を準備し、この被研磨基板を研磨装置（ナノファクター株式会社製、ＮＦ３００）にセットし、研磨パッド（ニッタハース社製「ＩＣ−１０００／ＳＵＢＡ４００同心円タイプ」）を使用し、基板荷重０．０４ＭＰａ、テーブル回転速度９０ｒｐｍで研磨用砥粒分散液を２００ｍＬ／分の速度で１分間供給して研磨を行った。
そして、研磨前後の被研磨基板の重量変化を求めて研磨速度（ｎｍ／ｍｉｎ）を算定した。また、研磨基材の表面の平滑性（表面粗さ［Ｒａ］）を原子間力顕微鏡（ＡＦＭ、株式会社日立ハイテクサイエンス社製）を用いて測定した。平滑性と表面粗さは概ね比例関係にあるため、表には表面粗さを記載した。
[8] Method for evaluating polishing characteristics of a SiO 2 insulating film (thickness 1 μm) substrate and method for preparing a polishing abrasive grain dispersion [Preparation of polishing abrasive grain dispersion]
The particle-linked silica fine particle dispersions or silica fine particle dispersions obtained in each of the Examples and Comparative Examples were diluted by adding ion-exchanged water, respectively, and the solid content concentration was adjusted to 1.0% by mass, respectively. An aqueous nitric acid solution (concentration 5%) was added to adjust the pH to 6.0 to prepare an abrasive grain dispersion for polishing.
[Polishing test method]
As a substrate to be polished, a SiO 2 insulating film (thickness 1 μm) substrate manufactured by a thermal oxidation method is prepared, and this substrate to be polished is set in a polishing device (Nanofactor Co., Ltd., NF300) and a polishing pad (manufactured by Nitta Hearth Co., Ltd.). Using "IC-1000 / SUBA400 concentric circle type"), polishing was performed by supplying an abrasive grain dispersion for polishing at a substrate load of 0.04 MPa and a table rotation speed of 90 rpm for 1 minute at a rate of 200 mL / min.
Then, the polishing rate (nm / min) was calculated by obtaining the weight change of the substrate to be polished before and after polishing. Further, the surface smoothness (surface roughness [Ra]) of the polished substrate was measured using an atomic force microscope (AFM, manufactured by Hitachi High-Tech Science Corporation). Since smoothness and surface roughness are generally proportional to each other, the surface roughness is shown in the table.
［原料としたシリカ微粒子の平均粒子径］
本発明の粒子連結型シリカ微粒子分散液を製造するための原料としたシリカ微粒子分散液におけるシリカ微粒子の平均粒子径の測定方法は次のとおりである。
［測定方法］シリカ微粒子分散液（固形分濃度：０．０５質量％）を用いて作成した試料の透過型電子顕微鏡（倍率：２０万倍）で撮影した。その写真を用い、５０個の一次粒子を任意に選択した。任意に選択された各一次粒子を写真投影図（平面視）した場合に、円形のものは、直径を粒子径とした。また、円形以外の一次粒子は、写真投影図（平面視）した場合に粒子の外縁と外縁との間の距離について、最長のものと最短のものを平均した値を粒子径とした。５０個の粒子について、粒子径を合計し、粒子の個数で除した平均値をシリカの平均粒子径とした。
[Average particle size of silica fine particles used as raw material]
The method for measuring the average particle size of silica fine particles in the silica fine particle dispersion used as a raw material for producing the particle-linked silica fine particle dispersion of the present invention is as follows.
[Measurement method] A sample prepared using a silica fine particle dispersion (solid content concentration: 0.05% by mass) was photographed with a transmission electron microscope (magnification: 200,000 times). Using the photograph, 50 primary particles were arbitrarily selected. When each of the arbitrarily selected primary particles was photographicly projected (planar view), the circular one had a diameter as the particle diameter. For primary particles other than a circle, the particle size was defined as the average value of the longest and shortest distances between the outer edges of the particles in a photographic projection drawing (plan view). For 50 particles, the particle size was totaled and the average value divided by the number of particles was taken as the average particle size of silica.
［酸性珪酸液］
珪酸ナトリウム水溶液（ＳｉＯ２濃度５質量％）を陽イオン交換樹脂塔に通すことにより調製し、酸性珪酸液（ＳｉＯ２濃度４．６質量％、ｐＨ２．３、ＳｉＯ２／Ｎａ２Ｏ［モル比］＝１２００）を調製した。
以下、実施例および比較例では、この酸性珪酸液を使用した。
[Acid silicic acid solution]
Prepared by passing an aqueous sodium silicate solution (SiO 2 concentration 5% by mass) through a cation exchange resin tower, and an acidic silicic acid solution (SiO 2 concentration 4.6% by mass, pH 2.3, SiO 2 / Na 2 O [molar ratio). ] = 1200) was prepared.
Hereinafter, in Examples and Comparative Examples, this acidic silicic acid solution was used.
［実施例１］
＜粒子連結型シリカ微粒子分散液の調製＞
シリカ微粒子分散液「カタロイドＳＩ−５０」（平均粒子径３０ｎｍ（ＳＥＭによる画像解析法）、固形分濃度４８質量％、日揮触媒化成（株）製）３，１００ｇを、純水で固形分濃度１５質量％に希釈した。
この希釈したシリカ微粒子分散液に、ｐＨ調整剤として酢酸水溶液（濃度３．０質量％）１，０６０ｇを添加し（ＷＢ／ＷＬＰ１＝０．０２１）、ｐＨを４．６に調整した。
次に、このｐＨを調整したシリカ微粒子分散液を７０℃で２時間保持し、粒子連結型シリカ微粒子分散液を得た。
[Example 1]
<Preparation of particle-connected silica fine particle dispersion>
Silica fine particle dispersion "Cataloid SI-50" (average particle size 30 nm (image analysis method by SEM), solid content concentration 48% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.), solid content concentration 15 with pure water Diluted to mass%.
To this diluted silica fine particle dispersion, 1,060 g of an acetic acid aqueous solution (concentration: 3.0% by mass) was added as a pH adjuster (WB / WLP 1 = 0.021) to adjust the pH to 4.6.
Next, the pH-adjusted silica fine particle dispersion was held at 70 ° C. for 2 hours to obtain a particle-linked silica fine particle dispersion.
得られた粒子連結型シリカ微粒子分散液（固形分濃度１３質量％）１０，６５５ｇを、陰イオン交換によって、脱酢酸した。脱酢酸後のｐＨは１０．４であった。
この脱酢酸した粒子連結型シリカ微粒子分散液５，０６７ｇに、純水４，１２８ｇを加え希釈した。これに、ＪＩＳ３号水ガラス（ＳｉＯ２濃度２４質量％、ＳｉＯ２／Ｎａ２Ｏ（モル比）＝３）２８１ｇを添加した。水ガラス添加後のｐＨは、１０．９であった。
続いて、酸性珪酸液（ＳｉＯ２濃度４．６質量％）３５，８３９ｇ（ＷＳ／ＷＬＰ２＝２．５に相当）を、１４時間かけて、添加した。この操作により、粒子成長させ、併せて一次粒子間のネック部をも成長させた。粒子連結型シリカ微粒子分散液（固形分濃度５．２質量％）を得た。
得られた粒子連結型シリカ微粒子分散液は、前記測定方法によって、立体状分岐構造を有する粒子連結型シリカ微粒子を含むことを確認した。立体状分岐構造（三次元分岐構造）を有する粒子連結型シリカ微粒子の個数割合は、１４％であった。
10,655 g of the obtained particle-linked silica fine particle dispersion (solid content concentration: 13% by mass) was deacetic acidized by anion exchange. The pH after deacetic acid was 10.4.
To 5,067 g of the deacetic acid-linked particle-linked silica fine particle dispersion, 4,128 g of pure water was added and diluted. To this, 281 g of JIS No. 3 water glass (SiO 2 concentration 24% by mass, SiO 2 / Na 2 O (molar ratio) = 3) was added. The pH after adding water glass was 10.9.
Subsequently, 35,839 g (corresponding to WS / WLP 2 = 2.5) of an acidic silicic acid solution (SiO 2 concentration 4.6% by mass) was added over 14 hours. By this operation, the particles were grown, and at the same time, the neck portion between the primary particles was also grown. A particle-linked silica fine particle dispersion (solid content concentration: 5.2% by mass) was obtained.
It was confirmed by the above-mentioned measuring method that the obtained particle-linked silica fine particle dispersion liquid contained particle-linked silica fine particles having a three-dimensional branched structure. The number ratio of the particle-connected silica fine particles having the three-dimensional branched structure (three-dimensional branched structure) was 14%.
限外濾過装置にて、この粒子連結型シリカ微粒子分散液を濃縮し、ＳｉＯ２濃度を１２％に調整した。さらに、ロータリーエバポレータにて、この粒子連結型シリカ微粒子分散液を濃縮し、ＳｉＯ２濃度を４０質量％に調整し、各種測定を行った。 The particle-linked silica fine particle dispersion was concentrated with an ultrafiltration device to adjust the SiO 2 concentration to 12%. Further, the particle-connected silica fine particle dispersion was concentrated by a rotary evaporator, the SiO 2 concentration was adjusted to 40% by mass, and various measurements were performed.
［実施例２］
＜粒子連結型シリカ微粒子分散液の調製＞
シリカ微粒子分散液「カタロイドＳＩ−４５Ｐ」（平均粒子径５０ｎｍ（ＳＥＭによる画像解析法）、固形分濃度４１質量％、日揮触媒化成（株）製）９７６ｇを、純水で固形分濃度５．１質量％に希釈した。
この希釈したシリカ微粒子分散液を、陽イオン交換樹脂（ＳＫ１ＢＨ、三菱ケミカル（株）製）によって、脱塩した。脱塩後のｐＨは３．６であった。
これに、ｐＨ緩衝剤として酢酸アンモニウム水溶液（酢酸濃度７．０質量％、アンモニア濃度６５００ｐｐｍ）１４６ｇを添加し（ＷＢ／ＷＬＰ１＝０．０２６）、ｐＨを４．５に調整した。
次に、このｐＨを調整したシリカ微粒子分散液を８０℃で３３時間保持し、粒子連結型シリカ微粒子分散液を得た。
[Example 2]
<Preparation of particle-connected silica fine particle dispersion>
Silica fine particle dispersion "Cataloid SI-45P" (average particle diameter 50 nm (image analysis method by SEM), solid content concentration 41% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.) 976 g, solid content concentration 5.1 with pure water Diluted to mass%.
This diluted silica fine particle dispersion was desalted with a cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation). The pH after desalting was 3.6.
To this, 146 g of an aqueous ammonium acetate solution (acetic acid concentration 7.0% by mass, ammonia concentration 6500 ppm) was added as a pH buffer (WB / WLP 1 = 0.026), and the pH was adjusted to 4.5.
Next, the pH-adjusted silica fine particle dispersion was held at 80 ° C. for 33 hours to obtain a particle-linked silica fine particle dispersion.
得られた粒子連結型シリカ微粒子分散液（固形分濃度５．０質量％）２，５００ｇを、陰イオン交換によって、脱酢酸した。脱酢酸後のｐＨは９．０であった。
この脱酢酸した粒子連結型シリカ微粒子分散液２，１３４ｇに、純水１０２ｇを加え希釈した。これにアンモニア水溶液（濃度３質量％）を加え、ｐＨを１０．８に調整した。
続いて、酸性珪酸液（ＳｉＯ２濃度４．６質量％）６，３８６ｇ（ＷＳ／ＷＬＰ２＝２．８に相当）を、１８時間かけて、添加した。この操作により、粒子成長させ、併せて一次粒子間のネック部をも成長させた。粒子連結型シリカ微粒子分散液（固形分濃度４．４質量％）を得た。
得られた粒子連結型シリカ微粒子分散液は、前記測定方法によって、立体状分岐構造を有する粒子連結型シリカ微粒子を含むことを確認した。立体状分岐構造（三次元分岐構造）を有する粒子連結型シリカ微粒子の個数割合は、２５％であった。
得られた粒子連結型シリカ微粒子分散液の濃縮および各種測定は、実施例１と、同様に行った。
2,500 g of the obtained particle-linked silica fine particle dispersion (solid content concentration: 5.0% by mass) was deacetic acidized by anion exchange. The pH after deacetic acid was 9.0.
To 2,134 g of the deacetic acid-linked particle-linked silica fine particle dispersion, 102 g of pure water was added and diluted. An aqueous ammonia solution (concentration: 3% by mass) was added thereto to adjust the pH to 10.8.
Subsequently, 6,386 g of an acidic silicic acid solution (SiO 2 concentration 4.6% by mass) (corresponding to WS / WLP 2 = 2.8) was added over 18 hours. By this operation, the particles were grown, and at the same time, the neck portion between the primary particles was also grown. A particle-linked silica fine particle dispersion (solid content concentration 4.4% by mass) was obtained.
It was confirmed by the above-mentioned measuring method that the obtained particle-linked silica fine particle dispersion liquid contained particle-linked silica fine particles having a three-dimensional branched structure. The number ratio of the particle-connected silica fine particles having the three-dimensional branched structure (three-dimensional branched structure) was 25%.
Concentration and various measurements of the obtained particle-linked silica fine particle dispersion were carried out in the same manner as in Example 1.
［実施例３］
＜粒子連結型シリカ微粒子分散液の調製＞
シリカ微粒子分散液「カタロイドＳＩ−８０Ｐ」（平均粒子径１００ｎｍ（ＳＥＭによる画像解析法）、固形分濃度４１質量％、日揮触媒化成（株）製）６３４ｇを、純水で固形分濃度１０．５質量％に希釈した。
この希釈したシリカ微粒子分散液を、陽イオン交換樹脂（ＳＫ１ＢＨ、三菱ケミカル（株）製）によって、脱塩した。脱塩後のｐＨは３．２であった。
これに、ｐＨ緩衝剤として酢酸アンモニウム水溶液（酢酸濃度７．０質量％、アンモニア濃度６５００ｐｐｍ）６１ｇを添加し（ＷＢ／ＷＬＰ１＝０．０１６）、ｐＨを４．５に調整した。
次に、このｐＨを調整したシリカ微粒子分散液を９０℃で２０時間保持し、粒子連結型シリカ微粒子分散液を得た。
[Example 3]
<Preparation of particle-connected silica fine particle dispersion>
Silica fine particle dispersion "Cataloid SI-80P" (average particle size 100 nm (image analysis method by SEM), solid content concentration 41% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.) 634 g, solid content concentration 10.5 with pure water Diluted to mass%.
This diluted silica fine particle dispersion was desalted with a cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation). The pH after desalting was 3.2.
To this, 61 g of an aqueous ammonium acetate solution (acetic acid concentration 7.0% by mass, ammonia concentration 6500 ppm) was added as a pH buffer (WB / WLP 1 = 0.016), and the pH was adjusted to 4.5.
Next, the pH-adjusted silica fine particle dispersion was held at 90 ° C. for 20 hours to obtain a particle-linked silica fine particle dispersion.
得られた粒子連結型シリカ微粒子分散液（固形分濃度９．５質量％）８００ｇを、陰イオン交換によって、脱酢酸した。脱酢酸後のｐＨは１０．１であった。
この脱酢酸した粒子連結型シリカ微粒子分散液７００ｇに、純水１，６３３ｇを加え希釈した。これにアンモニア水溶液（濃度３質量％）を加え、ｐＨを１１．０に調整した。
続いて、酸性珪酸液（ＳｉＯ２濃度４．６質量％）を純水で希釈した希釈酸性珪酸液（ＳｉＯ２濃度２．３質量％）４,４６８ｇを、２４時間かけて、添加した（ＷＳ／ＷＬＰ２＝１．５に相当）。この操作により、粒子成長させ、併せて一次粒子間のネック部をも成長させた。粒子連結型シリカ微粒子分散液（固形分濃度２．５質量％）を得た。
得られた粒子連結型シリカ微粒子分散液は、前記測定方法によって、立体状分岐構造を有する粒子連結型シリカ微粒子を含むことを確認した。立体状分岐構造（三次元分岐構造）を有する粒子連結型シリカ微粒子の個数割合は、１４％であった。
得られた粒子連結型シリカ微粒子分散液の濃縮および各種測定は、実施例１と、同様に行った。
800 g of the obtained particle-linked silica fine particle dispersion (solid content concentration: 9.5% by mass) was deacetic acidized by anion exchange. The pH after deacetic acid was 10.1.
To 700 g of this deacetic acid-linked particle-linked silica fine particle dispersion, 1,633 g of pure water was added and diluted. An aqueous ammonia solution (concentration: 3% by mass) was added thereto to adjust the pH to 11.0.
Subsequently, 4,468 g of a diluted acidic silicate solution (SiO 2 concentration 2.3% by mass) obtained by diluting the acidic silicate solution (SiO 2 concentration 4.6% by mass) with pure water was added over 24 hours (WS). / WLP 2 = 1.5). By this operation, the particles were grown, and at the same time, the neck portion between the primary particles was also grown. A particle-linked silica fine particle dispersion (solid content concentration 2.5% by mass) was obtained.
It was confirmed by the above-mentioned measuring method that the obtained particle-linked silica fine particle dispersion liquid contained particle-linked silica fine particles having a three-dimensional branched structure. The number ratio of the particle-connected silica fine particles having the three-dimensional branched structure (three-dimensional branched structure) was 14%.
Concentration and various measurements of the obtained particle-linked silica fine particle dispersion were carried out in the same manner as in Example 1.
［実施例４］
＜粒子連結型シリカ微粒子分散液の調製＞
シリカ微粒子分散液「カタロイドＳＳ−１６０」（平均粒子径１６０ｎｍ（ＳＥＭによる画像解析法）、固形分濃度１４質量％、日揮触媒化成（株）製）９２７ｇを、純水で固形分濃度１１質量％に希釈した。
この希釈したシリカ微粒子分散液を、陽イオン交換樹脂（ＳＫ１ＢＨ、三菱ケミカル（株）製）によって、脱塩した。脱塩後のｐＨは２．７であった。
これに、ｐＨ緩衝剤として酢酸アンモニウム水溶液（酢酸濃度７．０質量％、アンモニア濃度６５００ｐｐｍ）１２２ｇを添加し（ＷＢ／ＷＬＰ１＝０．０６６）、ｐＨを４．４に調整した。
次に、このｐＨを調整したシリカ微粒子分散液を９０℃で５４時間保持し、粒子連結型シリカ微粒子分散液を得た。
[Example 4]
<Preparation of particle-connected silica fine particle dispersion>
Silica fine particle dispersion "Cataloid SS-160" (average particle size 160 nm (image analysis method by SEM), solid content concentration 14% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.) 927 g, solid content concentration 11% by mass with pure water Diluted to.
This diluted silica fine particle dispersion was desalted with a cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation). The pH after desalting was 2.7.
To this, 122 g of an aqueous ammonium acetate solution (acetic acid concentration 7.0% by mass, ammonia concentration 6500 ppm) was added as a pH buffer (WB / WLP 1 = 0.066), and the pH was adjusted to 4.4.
Next, the pH-adjusted silica fine particle dispersion was held at 90 ° C. for 54 hours to obtain a particle-linked silica fine particle dispersion.
得られた粒子連結型シリカ微粒子分散液（固形分濃度９．５質量％）９１５ｇを、陰イオン交換によって、脱酢酸した。脱酢酸後のｐＨは１０．５であった。
この脱酢酸した粒子連結型シリカ微粒子分散液７４０ｇに、純水１，５９３ｇを加え希釈した。
続いて、酸性珪酸液（ＳｉＯ２濃度４．６質量％）を純水で希釈した希釈酸性珪酸液（ＳｉＯ２濃度１．２質量％）２，４７２ｇを、４８時間かけて、添加した（ＷＳ／ＷＬＰ２＝０．４に相当）。この操作により、粒子成長させ、併せて一次粒子間のネック部をも成長させた。粒子連結型シリカ微粒子分散液（固形分濃度２質量％）を得た。
915 g of the obtained particle-linked silica fine particle dispersion (solid content concentration: 9.5% by mass) was deacetic acidized by anion exchange. The pH after deacetic acid was 10.5.
To 740 g of this deacetic acid-linked particle-linked silica fine particle dispersion, 1,593 g of pure water was added and diluted.
Subsequently, 2,472 g of a diluted acidic silicic acid solution (SiO 2 concentration 1.2% by mass) obtained by diluting the acidic silicic acid solution (SiO 2 concentration 4.6% by mass) with pure water was added over 48 hours (WS). / WLP 2 = 0.4). By this operation, the particles were grown, and at the same time, the neck portion between the primary particles was also grown. A particle-linked silica fine particle dispersion (solid content concentration: 2% by mass) was obtained.
更に、得られた粒子連結型シリカ微粒子分散液３，０００ｇにアンモニア水（濃度５質量％）と珪酸液を同時添加してビルトアップし、立体状連結粒子を得た。
得られた粒子連結型シリカ微粒子分散液に、アンモニア水溶液（濃度３質量％）の９９ｇと、前記希釈酸性珪酸液（ＳｉＯ２濃度１．２質量％）６，１９４ｇとを４８時間かけて同時に添加した（ＷＳ／ＷＬＰ２＝１．２）。粒子連結型シリカ微粒子分散液（固形分濃度１．８質量％）を得た。
得られた粒子連結型シリカ微粒子分散液は、前記測定方法によって、立体状分岐構造を有する粒子連結型シリカ微粒子を含むことを確認した。立体状分岐構造（三次元分岐構造）を有する粒子連結型シリカ微粒子の個数割合は、７％であった。
得られた粒子連結型シリカ微粒子分散液の濃縮および各種測定は、実施例１と、同様に行った。
Further, aqueous ammonia (concentration: 5% by mass) and a silicic acid solution were simultaneously added to 3,000 g of the obtained particle-linked silica fine particle dispersion to build up the particles to obtain three-dimensional linked particles.
To the obtained particle-linked silica fine particle dispersion, 99 g of an aqueous ammonia solution (concentration: 3% by mass) and 6,194 g of the diluted acidic silicic acid solution (SiO 2 concentration: 1.2% by mass) were simultaneously added over 48 hours. (WS / WLP 2 = 1.2). A particle-linked silica fine particle dispersion (solid content concentration 1.8% by mass) was obtained.
It was confirmed by the above-mentioned measuring method that the obtained particle-linked silica fine particle dispersion liquid contained particle-linked silica fine particles having a three-dimensional branched structure. The number ratio of the particle-connected silica fine particles having the three-dimensional branched structure (three-dimensional branched structure) was 7%.
Concentration and various measurements of the obtained particle-linked silica fine particle dispersion were carried out in the same manner as in Example 1.
［実施例５］
シリカ微粒子分散液「カタロイドＳＩ−５０」（平均粒子径３０ｎｍ（ＳＥＭによる画像解析法）、固形分濃度４８質量％、日揮触媒化成（株）製）３，１００ｇを、純水で固形分濃度１５質量％に希釈した。
これに、ｐＨ調整剤として酢酸水溶液（濃度３．０質量％）１，０６０ｇを添加し（ＷＢ／ＷＬＰ１＝０．０２１）、ｐＨを４．６に調整した。
次に、このｐＨを調整したシリカ微粒子分散液を７０℃で２時間保持し、粒子連結型シリカ微粒子分散液を得た。
[Example 5]
Silica fine particle dispersion "Cataloid SI-50" (average particle size 30 nm (image analysis method by SEM), solid content concentration 48% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.), solid content concentration 15 with pure water Diluted to mass%.
To this, 1,060 g of an aqueous acetic acid solution (concentration: 3.0% by mass) was added as a pH adjuster (WB / WLP 1 = 0.021), and the pH was adjusted to 4.6.
Next, the pH-adjusted silica fine particle dispersion was held at 70 ° C. for 2 hours to obtain a particle-linked silica fine particle dispersion.
得られた粒子連結型シリカ微粒子分散液（固形分濃度１３．０質量％）１０，６５５ｇから、５，０６７ｇを小分けした。この小分けした粒子連結型シリカ微粒子分散液に脱酢酸処理をすることなく、純水４，１２８ｇを加えて希釈した。
この希釈した粒子連結型シリカ微粒子分散液の全量に、ＪＩＳ３号水ガラス（ＳｉＯ２濃度２４質量％、ＳｉＯ２／Ｎａ２Ｏ（モル比）＝３）４５９ｇを添加した。水ガラス添加後のｐＨは、１０．９であった。
続いて、酸性珪酸液（ＳｉＯ２濃度４．６質量％）３５，８３９ｇ（ＷＳ／ＷＬＰ２＝２．５に相当）を、１４時間かけて、添加した。粒子成長させ、併せて一次粒子間のネック部をも成長させた。粒子連結型シリカ微粒子分散液（固形分濃度５．２質量％）を調製した。
得られた粒子連結型シリカ微粒子分散液は、前記測定方法によって、立体状分岐構造を有する粒子連結型シリカ微粒子を含むことを確認した。立体状分岐構造（三次元分岐構造）を有する粒子連結型シリカ微粒子の個数割合は、１４％であった。
得られた粒子連結型シリカ微粒子分散液の濃縮および各種測定は、実施例１と、同様に行った。
From 10,655 g of the obtained particle-linked silica fine particle dispersion (solid content concentration 13.0% by mass), 5,067 g was subdivided. This subdivided particle-linked silica fine particle dispersion was diluted by adding 4,128 g of pure water without deacetic acid treatment.
459 g of JIS No. 3 water glass (SiO 2 concentration 24% by mass, SiO 2 / Na 2 O (molar ratio) = 3) was added to the total amount of the diluted particle-linked silica fine particle dispersion. The pH after adding water glass was 10.9.
Subsequently, 35,839 g (corresponding to WS / WLP 2 = 2.5) of an acidic silicic acid solution (SiO 2 concentration 4.6% by mass) was added over 14 hours. The particles were grown, and the neck between the primary particles was also grown. A particle-linked silica fine particle dispersion (solid content concentration: 5.2% by mass) was prepared.
It was confirmed by the above-mentioned measuring method that the obtained particle-linked silica fine particle dispersion liquid contained particle-linked silica fine particles having a three-dimensional branched structure. The number ratio of the particle-connected silica fine particles having the three-dimensional branched structure (three-dimensional branched structure) was 14%.
Concentration and various measurements of the obtained particle-linked silica fine particle dispersion were carried out in the same manner as in Example 1.
［実施例６］
シリカ微粒子分散液「カタロイドＳＩ−５０」（平均粒子径３０ｎｍ（ＳＥＭによる画像解析法）、固形分濃度４８質量％、日揮触媒化成（株）製）３，１００ｇを、純水で固形分濃度１５質量％に希釈した。
これに、ｐＨ調整剤として酢酸水溶液（濃度３．０質量％）１，０６０ｇを添加し（ＷＢ／ＷＬＰ１＝０．０２１）、ｐＨを４．６に調整した。
次に、このｐＨを調整したシリカ微粒子分散液を７０℃で２時間保持し、粒子連結型シリカ微粒子分散液を得た。
得られた粒子連結型シリカ微粒子分散液は、ＳｉＯ２濃度１３質量％であった。前記測定方法によって、立体状分岐構造を有する粒子連結型シリカ微粒子を含むことを確認した。立体状分岐構造（三次元分岐構造）を有する粒子連結型シリカ微粒子の個数割合は、１５％であった。
得られた粒子連結型シリカ微粒子分散液の濃縮および各種測定は、実施例１と、同様に行った。
[Example 6]
Silica fine particle dispersion "Cataloid SI-50" (average particle size 30 nm (image analysis method by SEM), solid content concentration 48% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.), solid content concentration 15 with pure water Diluted to mass%.
To this, 1,060 g of an aqueous acetic acid solution (concentration: 3.0% by mass) was added as a pH adjuster (WB / WLP 1 = 0.021), and the pH was adjusted to 4.6.
Next, the pH-adjusted silica fine particle dispersion was held at 70 ° C. for 2 hours to obtain a particle-linked silica fine particle dispersion.
The obtained particle-linked silica fine particle dispersion had a SiO 2 concentration of 13% by mass. By the above measurement method, it was confirmed that the particle-connected silica fine particles having a three-dimensional branched structure were contained. The number ratio of the particle-connected silica fine particles having the three-dimensional branched structure (three-dimensional branched structure) was 15%.
Concentration and various measurements of the obtained particle-linked silica fine particle dispersion were carried out in the same manner as in Example 1.
［比較例１］
＜シリカ微粒子分散液（シリカ微粒子の平均粒子径６０ｎｍ）の調製＞
エタノール１２,０９０ｇと正珪酸エチル６，３６３．９ｇとを混合し、混合液ａとした。次に、超純水６,１２０ｇとアンモニア水溶液（濃度２９質量％）４４４．９ｇとを混合し、混合液ｂとした。
続いて、超純水１９２．９ｇとエタノール４４４．９ｇとを混合して敷き水とし、敷き水を撹拌しながら７５℃に調整した。そこに、混合液ａおよび混合液ｂを、各々１０時間で添加が終了するように、同時に添加した。
添加終了後、液温を７５℃のまま３時間保持することにより熟成させ、シリカ微粒子分散液９,６４６．３ｇ得た。このシリカ微粒子分散液のＳｉＯ２固形分濃度を１９質量％に調整し、動的光散乱法（大塚電子社製ＰＡＲ−III）により平均粒子径を測定した。平均粒子径６０ｎｍであった。
[Comparative Example 1]
<Preparation of silica fine particle dispersion (average particle size of silica fine particles 60 nm)>
12,090 g of ethanol and 6,363.9 g of ethyl orthosilicate were mixed to prepare a mixed solution a. Next, 6,120 g of ultrapure water and 444.9 g of an aqueous ammonia solution (concentration 29% by mass) were mixed to prepare a mixed solution b.
Subsequently, 192.9 g of ultrapure water and 444.9 g of ethanol were mixed to prepare bedding water, and the bedding water was adjusted to 75 ° C. with stirring. The mixed liquid a and the mixed liquid b were simultaneously added thereto so that the addition was completed in 10 hours each.
After completion of the addition, the liquid temperature was kept at 75 ° C. for 3 hours for aging to obtain 9,646.3 g of a silica fine particle dispersion liquid. The SiO 2 solid content concentration of this silica fine particle dispersion was adjusted to 19% by mass, and the average particle size was measured by a dynamic light scattering method (PAR-III manufactured by Otsuka Denshi Co., Ltd.). The average particle size was 60 nm.
［比較例２］
ヒュームドシリカ（日本アエロジル社製、ＡＥＲＯＳＩＬ５０）３００ｇにイオン交換水３，９８６ｇを加え、φ０．２５ｍｍの高純度シリカビーズ（大研化学工業株式会社製、アシザワファインテック社製ビーズミルＬＭＺ０６）を用い、湿式解砕、粉砕をした。固形分濃度７質量％のシリカ微粒子分散液４，２８６ｇを得た。このシリカ微粒子分散液２，５７１ｇに超純水３３８７．７ｇとアンモニア２９．７ｇ（３質量％）を加えて混合した。ＳｉＯ２固形分濃度３質量％の分散液６０００ｇを得た。
このシリカ微粒子分散液に含まれるシリカ微粒子の平均粒子径は３２ｎｍ（ＳＥＭによる画像解析法）であり、前述の画像解析法により短径／長径比を算出すると、０．４４であった。
[Comparative Example 2]
Add 3,986 g of ion-exchanged water to 300 g of fumed silica (AEROSIL50, manufactured by Aerosil Japan), and use high-purity silica beads with a diameter of 0.25 mm (bead mill LMZ06, manufactured by Ashizawa Finetech, manufactured by Daiken Kagaku Kogyo Co., Ltd.). Wet crushing and crushing. 4,286 g of a silica fine particle dispersion having a solid content concentration of 7% by mass was obtained. To 2,571 g of this silica fine particle dispersion, 3387.7 g of ultrapure water and 29.7 g (3% by mass) of ammonia were added and mixed. 6000 g of a dispersion liquid having a SiO 2 solid content concentration of 3% by mass was obtained.
The average particle size of the silica fine particles contained in the silica fine particle dispersion was 32 nm (image analysis method by SEM), and the minor axis / major axis ratio was 0.44 when the minor axis / major axis ratio was calculated by the above-mentioned image analysis method.
［比較例３］
シリカ微粒子分散液「カタロイドＳＩ−５０」（平均粒子径３０ｎｍ（ＳＥＭによる画像解析法）、固形分濃度４８質量％、日揮触媒化成（株）製）３，１００ｇを、純水で固形分濃度１５質量％に希釈した。これに、ｐＨ調整剤として酢酸水溶液（濃度２０．０質量％）１，０６０ｇを添加し（ＷＢ／ＷＬＰ１＝０．１４２）、ｐＨを４．４に調整した。
次に、このｐＨを調整したシリカ微粒子分散液を７０℃で２４時間保持したところ、係る保持中にシリカ微粒子の過剰で不定形な凝集が発生し、更に沈降する凝集体も発生し、本発明に係る粒子連結型シリカ微粒子分散液を得ることができなかった。
[Comparative Example 3]
Silica fine particle dispersion "Cataloid SI-50" (average particle size 30 nm (image analysis method by SEM), solid content concentration 48% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.), solid content concentration 15 with pure water Diluted to mass%. To this, 1,060 g of an aqueous acetic acid solution (concentration 20.0% by mass) was added as a pH adjuster (WB / WLP 1 = 0.142) to adjust the pH to 4.4.
Next, when the silica fine particle dispersion liquid having adjusted pH was held at 70 ° C. for 24 hours, excessive and irregular agglomeration of silica fine particles was generated during the holding, and further settling agglomerates were also generated. It was not possible to obtain the particle-linked silica fine particle dispersion liquid according to the above.
［比較例４］
シリカ微粒子分散液「カタロイドＳＩ−４５Ｐ」（平均粒子径５０ｎｍ（ＳＥＭによる画像解析法）、固形分濃度４１質量％、日揮触媒化成（株）製）９７６ｇを用いた。
[Comparative Example 4]
976 g of silica fine particle dispersion "Cataloid SI-45P" (average particle size 50 nm (image analysis method by SEM), solid content concentration 41% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.) was used.
各種測定の結果を表１〜表３に示す。表１には、連結粒子分散液におけるシリカ微粒子の特徴と連結粒子分散液のΔＰＣＤ／Ｖを示す。表２には、連結粒子中の立体状連結粒子の割合を示す。表３には、立体状連結粒子の特徴を示す。なお、表２において、連結粒子個数［ｃ］は、立体状連結粒子の個数［ａ］と平面状連結粒子の個数［ｂ］との合計を表し、連結粒子体積［Ｃ］は、立体状連結粒子の体積［Ａ］と平面状連結粒子の体積［Ｂ］との合計を表す。
表４および表５には、ネック部分深さの平均値（Ｌｍ）の測定結果と、研磨速度および面精度の試験結果を示す。
The results of various measurements are shown in Tables 1 to 3. Table 1 shows the characteristics of the silica fine particles in the linked particle dispersion and the ΔPCD / V of the linked particle dispersion. Table 2 shows the ratio of the three-dimensional connected particles in the connected particles. Table 3 shows the characteristics of the three-dimensional connecting particles. In Table 2, the number of connected particles [c] represents the total of the number of three-dimensionally connected particles [a] and the number of planarly connected particles [b], and the volume of connected particles [C] is three-dimensionally connected. It represents the sum of the volume of particles [A] and the volume of planar connected particles [B].
Tables 4 and 5 show the measurement results of the average value (Lm) of the neck portion depth and the test results of the polishing speed and the surface accuracy.
表１〜表３に示す結果からも明らかなように、実施例１〜６によれば、立体状分岐構造を有する本発明の粒子連結型シリカ微粒子分散液が得られたことが確認された。また、表４および表５に示す結果からも明らかなように、実施例１〜６で得られた粒子連結型シリカ微粒子分散液によれば、研磨性等の優れた特性を有することが確認された。 As is clear from the results shown in Tables 1 to 3, it was confirmed that according to Examples 1 to 6, the particle-linked silica fine particle dispersion liquid of the present invention having a three-dimensional branched structure was obtained. Further, as is clear from the results shown in Tables 4 and 5, it was confirmed that the particle-linked silica fine particle dispersions obtained in Examples 1 to 6 have excellent properties such as abrasiveness. rice field.
本発明の粒子連結型シリカ微粒子分散液は、研磨材および研磨用組成物として有用である。例えば、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およびガラス質材料の鏡面加工等の研磨剤または研磨用組成物に利用が可能である。また、樹脂成型物やコーテイング被膜の充填剤、化粧料の成分、吸着剤、凝集促進剤、滓下げ剤、増粘剤および土壌硬化剤等としても利用可能である。 The particle-linked silica fine particle dispersion of the present invention is useful as an abrasive and a composition for polishing. For example, aluminum wiring of aluminum discs (plating layer on aluminum or its base material) and semiconductor multilayer wiring boards, glass substrates for optical disks and magnetic disks, glass substrates for liquid crystal displays, glass substrates for photomasks, and mirror processing of glassy materials. It can be used as an abrasive or a composition for polishing. It can also be used as a filler for resin molded products and coating films, cosmetic components, adsorbents, aggregation promoters, slag-lowering agents, thickeners, soil hardeners and the like.
Claims (14)
前記シリカ一次微粒子が連結した構造からなる粒子連結型シリカ微粒子を含む粒子連結型シリカ微粒子分散液に含まれるシリカ微粒子は、下記［１］の要件を備え、かつ前記シリカ微粒子に包含される立体状分岐構造を有する粒子連結型シリカ微粒子が、下記［２］の要件を備えることを特徴とする粒子連結型シリカ微粒子分散液。
［１］前記シリカ微粒子の動的光散乱法により測定した平均粒子径（Ｄ１）が、５０ｎｍ以上６００ｎｍ以下の範囲にあること。
［２］前記立体状分岐構造を有する粒子連結型シリカ微粒子が、鎖状で、かつ少なくとも１つの分岐（ａ）を有する構造と、この構造に対する立体構造を有すること。 A particle-linked silica fine particle dispersion containing particle-linked silica fine particles having a structure in which silica primary fine particles are linked.
The silica fine particles contained in the particle-linked silica fine particle dispersion liquid containing the particle-linked silica fine particles having a structure in which the silica primary fine particles are linked have the following requirements [1] and are contained in the silica fine particles in a three-dimensional shape. A particle-linked silica fine particle dispersion liquid, wherein the particle-linked silica fine particles having a branched structure satisfy the following requirements [2].
[1] The average particle size (D1) measured by the dynamic light scattering method of the silica fine particles is in the range of 50 nm or more and 600 nm or less.
[2] The particle-connected silica fine particles having the three-dimensional branched structure have a chain-like structure having at least one branch (a) and a three-dimensional structure for this structure.
（１）前記分岐（ａ）に対し、立体方向に伸長してなる分岐（ｂ）
（２）前記分岐（ａ）に対し、立体方向に伸長してなる末端（ｃ） The particle-linked silica fine particle dispersion liquid according to claim 1, wherein the three-dimensional structure is at least one of the following structures (1) and (2).
(1) A branch (b) extending in a three-dimensional direction with respect to the branch (a).
(2) The end (c) extending in the three-dimensional direction with respect to the branch (a).
［３］５０ｎｍ≦ＤＬａ≦１，０００ｎｍ
ＤＬａ：前記立体状分岐構造を有する粒子連結型シリカ微粒子の長さ方向における最長径（ＤＬ）の平均値
［４］１０ｎｍ≦ＤＴａ≦８００ｎｍ
ＤＴａ：前記立体状分岐構造を有する粒子連結型シリカ微粒子の太さ方向における直径（ＤＴ）の平均値 The particle-linked silica fine particle dispersion according to claim 1 or 2, wherein the particle-linked silica fine particles having a three-dimensional branched structure have the following requirements [3] and [4].
[3] 50 nm ≤ DLa ≤ 1,000 nm
DLa: Average value of the longest diameter (DL) in the length direction of the particle-connected silica fine particles having the three-dimensional branched structure [4] 10 nm ≤ DTa ≤ 800 nm
DT: The average value of the diameter (DT) in the thickness direction of the particle-connected silica fine particles having the three-dimensional branched structure.
［５］１０％≦Ｃ．Ｖ．≦４０％
Ｃ．Ｖ．：前記立体状分岐構造を有する粒子連結型シリカ微粒子の太さ方向における直径（ＤＴ）の平均変動係数 The particle-linked silica fine particle dispersion according to any one of claims 1 to 3, wherein the particle-linked silica fine particles having a three-dimensional branched structure satisfy the requirements of the following [5].
[5] 10% ≤ C.I. V. ≤40%
C. V. : Average coefficient of variation of diameter (DT) in the thickness direction of the particle-connected silica fine particles having the three-dimensional branched structure
Ｃａ：２５ｐｐｍ以下
Ｍｇ：２５ｐｐｍ以下
Ａｌ：１５０ｐｐｍ以下 The particle-linked silica fine particle dispersion according to any one of claims 1 to 5, wherein the ratio of Ca, Mg and Al contained in the silica fine particles is as follows.
Ca: 25ppm or less Mg: 25ppm or less Al: 150ppm or less
ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖ・・・（Ｆ１）
Ｃ：前記クニックにおける流動電位（ｍＶ）
Ｉ：前記流動電位曲線の開始点における流動電位（ｍＶ）
Ｖ：前記クニックにおける前記カチオンコロイド滴定液の添加量（ｍＬ） When cationic colloid titration is performed, the ratio (ΔPCD / V) of the flow potential change amount (ΔPCD) represented by the following formula (F1) to the addition amount (V) of the cationic colloid titration solution in the knick is -350. The particle-linked silica fine particle dispersion liquid according to any one of claims 1 to 8, wherein a flow potential curve of -10 or less can be obtained.
ΔPCD / V = (IC) / V ... (F1)
C: Flow potential (mV) in the knick
I: Flow potential (mV) at the start point of the flow potential curve
V: Addition amount (mL) of the cationic colloid titration solution in the knick
工程１：ＳｉＯ２濃度１．５質量％以上３０質量％以下のシリカ微粒子分散液に、ｐＨ緩衝剤またはｐＨ調整剤を、下記の割合（ＷＢ／ＷＬＰ１）の範囲内で添加し、続いて、４０℃以上９８℃以下に加熱し、１時間以上保持し、粒子連結型シリカ微粒子分散液を得る工程
０．０１≦ＷＢ／ＷＬＰ１≦０．１
（ここで、ＷＬＰ１は、シリカ微粒子分散液中のシリカ質量であり、ＷＢは、ｐＨ緩衝剤またはｐＨ調整剤の質量である。） The method for producing a particle-linked silica fine particle dispersion liquid according to claim 1, which comprises the following step 1.
Step 1: A pH buffer or a pH adjuster is added to the silica fine particle dispersion having a SiO 2 concentration of 1.5% by mass or more and 30% by mass or less within the following ratio (WB / WLP 1 ), followed by , 40 ° C. or higher and 98 ° C. or lower, and held for 1 hour or longer to obtain a particle-linked silica fine particle dispersion 0.01 ≤ WB / WLP 1 ≤ 0.1
(Here, WLP 1 is the mass of silica in the silica fine particle dispersion, and WB is the mass of the pH buffer or pH adjuster.)
工程２：前記工程１で得た粒子連結型シリカ微粒子分散液に対し、下記（ｉ）および（ｉｉ）の処理のうちの少なくとも１つにより、ｐＨ１０．０以上にｐＨ調整処理し、続いて酸性珪酸液を、下記の割合（ＷＳ／ＷＬＰ２）となるように連続的または断続的に添加し、粒子成長させる処理を施す工程
０．０１≦ＷＳ／ＷＬＰ２≦１０
（ここで、ＷＬＰ２は、粒子連結型シリカ微粒子分散液中のシリカ質量であり、ＷＳは、酸性珪酸液中のシリカ質量である。）
（ｉ）陰イオン交換処理
（ｉｉ）アルカリ添加 The method for producing a particle-linked silica fine particle dispersion liquid according to claim 11 or 12, which comprises the following step 2 following the step 1.
Step 2: The particle-linked silica fine particle dispersion obtained in Step 1 is pH-adjusted to pH 10.0 or higher by at least one of the following treatments (i) and (ii), followed by acidity. Step of continuously or intermittently adding the silicic acid solution in the following ratio (WS / WLP 2 ) to grow particles 0.01 ≤ WS / WLP 2 ≤ 10
(Here, WLP 2 is the mass of silica in the particle-linked silica fine particle dispersion, and WS is the mass of silica in the acidic silicic acid solution.)
(I) Anion exchange treatment (ii) Add alkali
工程３：前記工程２を施している粒子連結型シリカ微粒子分散液に対し、下記（ｉ）および（ｉｉ）の処理のうちの少なくとも１つにより、ｐＨ１０．０以上にｐＨ調整処理し、続いて、酸性珪酸液を下記の割合（ＷＳ／ＷＬＰ２）となるように連続的または断続的に添加し、粒子成長させる処理を施す工程を含むことを特徴とする粒子連結型シリカ微粒子分散液の製造方法。
０．５≦ＷＳ／ＷＬＰ２≦１０
（ここで、ＷＬＰ２は、粒子連結型シリカ微粒子分散液中のシリカ質量であり、ＷＳは、酸性珪酸液中のシリカ質量である。）
（ｉ）陰イオン交換処理
（ｉｉ）アルカリ添加 The method for producing a particle-linked silica fine particle dispersion liquid according to claim 13, which comprises the following step 3 following the step 2.
Step 3: The particle-linked silica fine particle dispersion liquid subjected to the step 2 is subjected to pH adjustment treatment to pH 10.0 or higher by at least one of the following treatments (i) and (ii), followed by a pH adjustment treatment. , Production of a particle-linked silica fine particle dispersion, which comprises a step of continuously or intermittently adding an acidic silicic acid solution at the following ratio (WS / WLP 2) to grow particles. Method.
0.5 ≤ WS / WLP 2 ≤ 10
(Here, WLP 2 is the mass of silica in the particle-linked silica fine particle dispersion, and WS is the mass of silica in the acidic silicic acid solution.)
(I) Anion exchange treatment (ii) Add alkali
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005119911A (en) * | 2003-10-17 | 2005-05-12 | Speedfam Co Ltd | Method for refining colloidal silica |
| US20080038995A1 (en) * | 2003-08-14 | 2008-02-14 | Small Robert J | Periodic Acid Compositions For Polishing Ruthenium/Low K Substrates |
| JP2009188058A (en) * | 2008-02-04 | 2009-08-20 | Nippon Chem Ind Co Ltd | Polishing colloidal silica for semiconductor wafer, and method for producing same |
| WO2010021400A1 (en) * | 2008-08-22 | 2010-02-25 | 国立大学法人東京大学 | Silica nanoparticle structure and process for production of same |
| WO2010035613A1 (en) * | 2008-09-26 | 2010-04-01 | 扶桑化学工業株式会社 | Colloidal silica containing silica secondary particles having bent structure and/or branched structure, and method for producing same |
| JP2010143784A (en) * | 2008-12-18 | 2010-07-01 | Adeka Corp | Silica sol comprising branched chain silica particles and method for producing the same |
| JP2018168031A (en) * | 2017-03-30 | 2018-11-01 | 株式会社フジミインコーポレーテッド | Manufacturing method for silica sol |
| WO2019163992A1 (en) * | 2018-02-26 | 2019-08-29 | 日産化学株式会社 | Method for producing silica sol having elongated particle shape |
-
2020
- 2020-03-13 JP JP2020044287A patent/JP7455623B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080038995A1 (en) * | 2003-08-14 | 2008-02-14 | Small Robert J | Periodic Acid Compositions For Polishing Ruthenium/Low K Substrates |
| JP2005119911A (en) * | 2003-10-17 | 2005-05-12 | Speedfam Co Ltd | Method for refining colloidal silica |
| JP2009188058A (en) * | 2008-02-04 | 2009-08-20 | Nippon Chem Ind Co Ltd | Polishing colloidal silica for semiconductor wafer, and method for producing same |
| WO2010021400A1 (en) * | 2008-08-22 | 2010-02-25 | 国立大学法人東京大学 | Silica nanoparticle structure and process for production of same |
| WO2010035613A1 (en) * | 2008-09-26 | 2010-04-01 | 扶桑化学工業株式会社 | Colloidal silica containing silica secondary particles having bent structure and/or branched structure, and method for producing same |
| JP2010143784A (en) * | 2008-12-18 | 2010-07-01 | Adeka Corp | Silica sol comprising branched chain silica particles and method for producing the same |
| JP2018168031A (en) * | 2017-03-30 | 2018-11-01 | 株式会社フジミインコーポレーテッド | Manufacturing method for silica sol |
| WO2019163992A1 (en) * | 2018-02-26 | 2019-08-29 | 日産化学株式会社 | Method for producing silica sol having elongated particle shape |
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