JP6321360B2 - Polishing liquid composition for glass hard disk substrate - Google Patents
Polishing liquid composition for glass hard disk substrate Download PDFInfo
- Publication number
- JP6321360B2 JP6321360B2 JP2013252323A JP2013252323A JP6321360B2 JP 6321360 B2 JP6321360 B2 JP 6321360B2 JP 2013252323 A JP2013252323 A JP 2013252323A JP 2013252323 A JP2013252323 A JP 2013252323A JP 6321360 B2 JP6321360 B2 JP 6321360B2
- Authority
- JP
- Japan
- Prior art keywords
- polishing
- acid
- mass
- substrate
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005498 polishing Methods 0.000 title claims description 277
- 239000000758 substrate Substances 0.000 title claims description 180
- 239000000203 mixture Substances 0.000 title claims description 140
- 239000011521 glass Substances 0.000 title claims description 112
- 239000007788 liquid Substances 0.000 title claims description 72
- 238000004140 cleaning Methods 0.000 claims description 93
- 238000000034 method Methods 0.000 claims description 68
- 229910052751 metal Inorganic materials 0.000 claims description 51
- 239000002184 metal Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 24
- -1 amine compound Chemical class 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000005354 aluminosilicate glass Substances 0.000 claims description 16
- 238000007517 polishing process Methods 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 235000005985 organic acids Nutrition 0.000 claims description 9
- 229920003169 water-soluble polymer Polymers 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 230000006866 deterioration Effects 0.000 description 19
- 239000000126 substance Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 9
- 230000003749 cleanliness Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 7
- 235000015165 citric acid Nutrition 0.000 description 7
- 239000008119 colloidal silica Substances 0.000 description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000001630 malic acid Substances 0.000 description 6
- 235000011090 malic acid Nutrition 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000011975 tartaric acid Substances 0.000 description 5
- 235000002906 tartaric acid Nutrition 0.000 description 5
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 5
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000006061 abrasive grain Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 4
- 229920006318 anionic polymer Polymers 0.000 description 4
- 238000003426 chemical strengthening reaction Methods 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YEEGWNXDUZONAA-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-gallabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Ga+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YEEGWNXDUZONAA-UHFFFAOYSA-K 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- VRGNUPCISFMPEM-ZVGUSBNCSA-L zinc;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Zn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VRGNUPCISFMPEM-ZVGUSBNCSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- PCPYTNCQOSFKGG-ONEGZZNKSA-N (1e)-1-chlorobuta-1,3-diene Chemical compound Cl\C=C\C=C PCPYTNCQOSFKGG-ONEGZZNKSA-N 0.000 description 1
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CFKBCVIYTWDYRP-UHFFFAOYSA-N 10-phosphonooxydecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOP(O)(O)=O CFKBCVIYTWDYRP-UHFFFAOYSA-N 0.000 description 1
- AHHIUZANWCTSDS-UHFFFAOYSA-N 12-phosphonooxydodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCCCOP(O)(O)=O AHHIUZANWCTSDS-UHFFFAOYSA-N 0.000 description 1
- HVOBSBRYQIYZNY-UHFFFAOYSA-N 2-[2-(2-aminoethylamino)ethylamino]ethanol Chemical compound NCCNCCNCCO HVOBSBRYQIYZNY-UHFFFAOYSA-N 0.000 description 1
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- WCKIDCVWRJUPFY-UHFFFAOYSA-L zinc;oxalate;dihydrate Chemical compound O.O.[Zn+2].[O-]C(=O)C([O-])=O WCKIDCVWRJUPFY-UHFFFAOYSA-L 0.000 description 1
Description
本開示は、ガラスハードディスク基板用研磨液組成物、ガラスハードディスク基板の製造方法、及び、ガラス基板の研磨方法に関する。 The present disclosure relates to a polishing liquid composition for a glass hard disk substrate, a method for manufacturing a glass hard disk substrate, and a method for polishing a glass substrate.
ハードディスクドライブに搭載されるハードディスクは高速で回転するため消費電力が高く、近年では環境への配慮から、低消費電力化が求められている。消費電力を低減するためには、ハードディスク１枚あたりの記録容量を増大させ、ドライブに搭載されるハードディスクの枚数を減らし、軽量化する方法がある。基板１枚の重量を軽量化するためには、基板の厚さを薄くする必要があり、この観点から、アルミ基板に比べて機械的強度が高いガラス基板の需要が高まり、近年の伸張は著しい。また、基板１枚あたりの記録容量を向上させるためには、単位記録面積を縮小する必要がある。しかし、単位記録面積を縮小すると磁気信号が弱くなる問題が発生する。そこで磁気信号の検出感度を向上するため、磁気ヘッドの浮上高さをより低くするための技術開発が進められている。ガラスハードディスク基板の研磨においては、この磁気ヘッドの低浮上化に対応するため、表面粗さや残留物の低減に対する要求が厳しくなっている。このような要求に対し、酸性の研磨液組成物でガラス基板を研磨する技術が提案されている（例えば、特許文献１参照）。 Since the hard disk mounted on the hard disk drive rotates at a high speed, the power consumption is high. In recent years, low power consumption is demanded in consideration of the environment. In order to reduce power consumption, there is a method of increasing the recording capacity per hard disk, reducing the number of hard disks installed in the drive, and reducing the weight. In order to reduce the weight of one substrate, it is necessary to reduce the thickness of the substrate. From this point of view, the demand for a glass substrate having a higher mechanical strength than that of an aluminum substrate has increased, and the recent growth has been remarkable. . In order to improve the recording capacity per substrate, it is necessary to reduce the unit recording area. However, when the unit recording area is reduced, the magnetic signal becomes weak. Therefore, in order to improve the detection sensitivity of the magnetic signal, technological development for lowering the flying height of the magnetic head has been advanced. In polishing a glass hard disk substrate, in order to cope with the low flying height of the magnetic head, there are strict requirements for reducing the surface roughness and residues. In response to such demands, a technique for polishing a glass substrate with an acidic polishing liquid composition has been proposed (see, for example, Patent Document 1).
酸性の研磨液組成物でガラス基板を研磨する方法は、研磨中にガラス基板に含有されるアルカリイオンが溶出するリーチング作用が起こり、基板表面の硬度が低下して研磨速度が向上するという利点がある。しかしながら、酸性の研磨液組成物でガラス基板を研磨する方法は、ｐＨが低いとリーチング作用が大きく働くため、脆いリーチング層が深くまで生成し、研磨工程後のアルカリ洗浄工程におけるアルカリエッチングにより表面粗さが著しく悪化するという問題があった。このような問題に対し、リーチング層の生成を抑制しながら、研磨速度を向上させるために、研磨液の電解質濃度を上げる添加剤を含有する弱酸性（ｐＨ４〜６）の研磨液でガラス基板を研磨する方法が提案されている（例えば、特許文献２参照）。 The method of polishing a glass substrate with an acidic polishing liquid composition has the advantage that the leaching action of elution of alkali ions contained in the glass substrate occurs during polishing, the hardness of the substrate surface is lowered, and the polishing rate is improved. is there. However, in the method of polishing a glass substrate with an acidic polishing liquid composition, since the leaching action works greatly when the pH is low, a brittle leaching layer is generated deeply, and the surface is roughened by alkali etching in the alkali cleaning step after the polishing step. There was a problem that the quality deteriorated significantly. For such a problem, in order to improve the polishing rate while suppressing the formation of the leaching layer, the glass substrate is coated with a weakly acidic (pH 4 to 6) polishing liquid containing an additive for increasing the electrolyte concentration of the polishing liquid. A polishing method has been proposed (see, for example, Patent Document 2).
特許文献３及び４には、磁気ディスク用ガラス基板の製造に用いる研磨液の添加剤としてカルボン酸、多価アミン、アミノ酸、アミノポリカルボン酸、ホスホン酸類等が開示されている。 Patent Documents 3 and 4 disclose carboxylic acids, polyvalent amines, amino acids, aminopolycarboxylic acids, phosphonic acids and the like as additives for polishing liquids used in the production of glass substrates for magnetic disks.
しかし、前記特許文献２記載の方法では、弱酸性の研磨液組成物でガラス基板を研磨するため、研磨速度が遅く、生産性が低く、特許文献３及び４記載の方法においても、洗浄後の表面粗さ低減と研磨速度とがトレードオフの関係にあるという問題がある。 However, in the method described in Patent Document 2, since the glass substrate is polished with a weakly acidic polishing composition, the polishing rate is slow and the productivity is low. Even in the methods described in Patent Documents 3 and 4, after cleaning, There is a problem that a reduction in surface roughness and a polishing rate are in a trade-off relationship.
そこで、本開示は、一又は複数の実施形態において、ガラス基板を酸性研磨液で研磨する工程と洗浄する工程を有するガラスハードディスク基板の製造方法において、研磨工程において研磨速度を維持したまま、洗浄工程におけるガラス基板の表面粗さの悪化を抑制できるガラスハードディスク基板用研磨液組成物を提供する。 Therefore, in one or a plurality of embodiments of the present disclosure, in the method for manufacturing a glass hard disk substrate having a step of polishing a glass substrate with an acidic polishing liquid and a step of cleaning, the cleaning step while maintaining the polishing rate in the polishing step. The polishing liquid composition for glass hard disk substrates which can suppress the deterioration of the surface roughness of the glass substrate in is provided.
本開示は、一又は複数の実施形態において、シリカ粒子、両性金属の水溶性金属塩、及び水を含有する、ガラスハードディスク基板用研磨液組成物に関する。 In one or a plurality of embodiments, the present disclosure relates to a polishing liquid composition for a glass hard disk substrate, which contains silica particles, a water-soluble metal salt of an amphoteric metal, and water.
本開示は、その他の一又は複数の実施形態において、本開示の研磨液組成物を使用して被研磨ガラス基板を研磨する工程を含むガラスハードディスク基板の製造方法に関し、さらにその他の一又は複数の実施形態において、本開示の研磨液組成物を被研磨ガラス基板の研磨対象面に供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び前記被研磨ガラス基板の少なくとも一方を動かして研磨することを含むガラス基板の研磨方法に関する。 In one or a plurality of other embodiments of the present disclosure, the present disclosure relates to a method for manufacturing a glass hard disk substrate including a step of polishing a glass substrate to be polished using the polishing liquid composition of the present disclosure. In an embodiment, the polishing composition of the present disclosure is supplied to a surface to be polished of a glass substrate to be polished, a polishing pad is brought into contact with the surface to be polished, and at least one of the polishing pad and the glass substrate to be polished is moved. The present invention relates to a method for polishing a glass substrate including polishing.
本開示によれば、一又は複数の実施形態において、研磨工程において研磨速度を維持しつつ、洗浄工程においてガラス基板の表面粗さの悪化を効果的に抑制できる。 According to the present disclosure, in one or a plurality of embodiments, deterioration of the surface roughness of the glass substrate can be effectively suppressed in the cleaning process while maintaining the polishing rate in the polishing process.
本開示は、ガラス基板を酸性研磨液で研磨した後に洗浄をした場合であっても、前記研磨液に両性金属の水溶性金属塩が含まれていると、前記研磨液による研磨速度を維持しつつ、洗浄によるガラス基板の表面粗さの悪化を抑制できるという知見に基づく。 In the present disclosure, even when a glass substrate is cleaned after being polished with an acidic polishing liquid, if the polishing liquid contains a water-soluble metal salt of an amphoteric metal, the polishing rate by the polishing liquid is maintained. However, it is based on the knowledge that deterioration of the surface roughness of the glass substrate due to cleaning can be suppressed.
すなわち、本開示は一態様において、シリカ粒子、両性金属の水溶性金属塩、及び水を含有するガラスハードディスク基板用研磨液組成物（以下、「本開示の研磨液組成物」ともいう）に関する。 That is, in one aspect, the present disclosure relates to a polishing composition for a glass hard disk substrate (hereinafter, also referred to as “the polishing composition of the present disclosure”) containing silica particles, a water-soluble metal salt of an amphoteric metal, and water.
本開示の研磨液組成物により、研磨工程で研磨速度が維持され、かつ、洗浄によるガラス基板の表面粗さの悪化が抑制される理由は明らかではないが、アルカリ洗浄の場合には以下のように推定される。すなわち、研磨時のリーチング作用で溶出するガラス基板のアルカリイオンにかわり本開示の研磨液組成物に含まれる両性金属のイオンがガラス基板表層に吸着することで、生成したリーチング層（脆弱層）へのアルカリイオンの作用が抑制されるため、表面粗さの悪化が抑制されると推定される。但し、本開示は、これらのメカニズムに限定されて解釈されなくてもよい。 The reason why the polishing rate of the present disclosure maintains the polishing rate in the polishing step and suppresses the deterioration of the surface roughness of the glass substrate due to cleaning is not clear, but in the case of alkali cleaning, Is estimated. That is, the amphoteric metal ions contained in the polishing composition of the present disclosure are adsorbed on the surface layer of the glass substrate in place of the alkali ions of the glass substrate that are eluted by the leaching action during polishing, and the generated leaching layer (fragile layer). It is presumed that the deterioration of the surface roughness is suppressed because the action of alkali ions is suppressed. However, the present disclosure is not limited to these mechanisms and need not be interpreted.
［両性金属の水溶性金属塩］
本開示において、「両性金属」とは、酸及びアルカリに溶解する金属をいう。両性金属は、一又は複数の実施形態において、アルミニウム（Ａｌ）、亜鉛（Ｚｎ）、ガリウム（Ｇａ）、スズ（Ｓｎ）、鉛（Ｐｂ）又は、これらの組み合わせが挙げられる。本開示において、「組み合わせ」は、２又はそれ以上の要素の組み合わせをいう。一又は複数の実施形態において、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、両性金属としては、亜鉛又はガリウムが好ましい。
[Water-soluble metal salt of amphoteric metal]
In the present disclosure, “amphoteric metal” refers to a metal that dissolves in acid and alkali. In one or more embodiments, the amphoteric metal may be aluminum (Al), zinc (Zn), gallium (Ga), tin (Sn), lead (Pb), or a combination thereof. In this disclosure, “combination” refers to a combination of two or more elements. In one or a plurality of embodiments, zinc or gallium is preferable as the amphoteric metal from the viewpoint of maintaining the polishing rate and suppressing the deterioration of the surface roughness after cleaning.
本開示において、「水溶性」とは、２０℃の水１００ｇに対する溶解度が２ｇ以上であることをいう。水溶性金属塩における両性金属の対イオン（陰イオン）としては、水溶性の塩を形成できれば特に限定されないが、一又は複数の実施形態において、硫酸、硝酸、塩酸等の無機陰イオン、又は、クエン酸、酒石酸、シュウ酸等の有機陰イオンが挙げられる。 In the present disclosure, “water-soluble” means that the solubility in 100 g of water at 20 ° C. is 2 g or more. The counter ion (anion) of the amphoteric metal in the water-soluble metal salt is not particularly limited as long as a water-soluble salt can be formed. In one or a plurality of embodiments, inorganic anions such as sulfuric acid, nitric acid, hydrochloric acid, or Organic anions such as citric acid, tartaric acid and oxalic acid can be mentioned.
両性金属の水溶性金属塩としては、一又は複数の実施形態において、無機酸又は有機酸と金属カチオンの組み合わせが挙げられるが、水溶性金属塩の量産性の観点から、無機酸と金属カチオンの組み合わせが好ましい。両性金属の水溶性金属塩の具体例としては、硫酸亜鉛、硝酸亜鉛、塩化亜鉛、クエン酸亜鉛、酒石酸亜鉛、シュウ酸亜鉛、硫酸ガリウム、硝酸ガリウム、塩化ガリウム、クエン酸ガリウム、酒石酸ガリウム、シュウ酸ガリウム、及びこれらの組み合わせ等が挙げられる。 Examples of the water-soluble metal salt of the amphoteric metal include, in one or more embodiments, a combination of an inorganic acid or an organic acid and a metal cation. From the viewpoint of mass production of the water-soluble metal salt, an inorganic acid and a metal cation are used. A combination is preferred. Specific examples of water-soluble metal salts of amphoteric metals include zinc sulfate, zinc nitrate, zinc chloride, zinc citrate, zinc tartrate, zinc oxalate, gallium sulfate, gallium nitrate, gallium chloride, gallium citrate, gallium tartrate, Examples thereof include gallium acid and combinations thereof.
本開示の研磨液組成物中における両性金属の水溶性金属塩の含有量は、一又は複数の実施形態において、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、０．００１質量％以上が好ましく、より好ましくは０．０１質量％以上、さらに好ましくは０．０３質量％以上、更により好ましくは０．０６質量％以上である。また、本開示の研磨液組成物中における両性金属の水溶性金属塩の含有量は、一又は複数の実施形態において、同様の観点から、１０質量％以下が好ましく、より好ましくは７質量％以下、さらに好ましくは５質量％以下である。また、本開示の研磨液組成物中における両性金属の水溶性金属塩の含有量は、一又は複数の実施形態において、同様の観点から、０．００１質量％以上１０質量％以下が好ましく、より好ましくは０．０１質量％以上７質量％以下、さらに好ましくは０．０３質量％以上５質量％以下である。なお、本開示において「研磨液組成物中における含有成分の含有量」とは、研磨液組成物を研磨に使用する時点での前記成分の含有量をいう（以下同じ）。したがって、本開示の研磨液組成物が濃縮物として作製された場合には、前記成分の含有量はその濃縮分だけ高くなりうる。 In one or more embodiments, the content of the water-soluble metal salt of the amphoteric metal in the polishing liquid composition of the present disclosure is 0.001 from the viewpoint of maintaining the polishing rate and suppressing the deterioration of the surface roughness after cleaning. It is preferably at least 0.01% by mass, more preferably at least 0.01% by mass, even more preferably at least 0.03% by mass, and even more preferably at least 0.06% by mass. Further, the content of the water-soluble metal salt of the amphoteric metal in the polishing liquid composition of the present disclosure is preferably 10% by mass or less, more preferably 7% by mass or less from the same viewpoint in one or more embodiments. More preferably, it is 5% by mass or less. Further, the content of the water-soluble metal salt of the amphoteric metal in the polishing liquid composition of the present disclosure is preferably 0.001% by mass or more and 10% by mass or less from the same viewpoint in one or more embodiments. Preferably they are 0.01 mass% or more and 7 mass% or less, More preferably, they are 0.03 mass% or more and 5 mass% or less. In addition, in this indication, "content of the component in polishing liquid composition" means content of the said component at the time of using polishing liquid composition for grinding | polishing (hereinafter the same). Therefore, when the polishing liquid composition of the present disclosure is prepared as a concentrate, the content of the components can be increased by the concentration.
［シリカ砥粒］
本開示の研磨液組成物は、研磨速度向上の観点から、シリカ粒子を研磨砥粒として含有することが好ましい。本開示に使用されるシリカ粒子としては、コロイダルシリカ、ヒュームドシリカ、表面修飾したシリカ等のシリカが挙げられるが、一又は複数の実施形態において、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、コロイダルシリカが好ましい。また、シリカ粒子の使用形態としては、一又は複数の実施形態において、スラリー状であることが好ましい。
[Silica abrasive grains]
The polishing composition of the present disclosure preferably contains silica particles as abrasive grains from the viewpoint of improving the polishing rate. Examples of the silica particles used in the present disclosure include colloidal silica, fumed silica, and surface-modified silica. In one or a plurality of embodiments, the polishing rate is maintained and the surface roughness after cleaning is adjusted. From the viewpoint of suppressing deterioration, colloidal silica is preferable. Moreover, as a usage form of a silica particle, it is preferable that it is a slurry form in one or some embodiment.
前記コロイダルシリカは、一又は複数の実施形態において、珪酸ナトリウム等の珪酸アルカリ金属塩を原料とし、水溶液中で縮合反応させて粒子を成長させる水ガラス法で得られうる。あるいは、前記コロイダルシリカは、テトラエトキシシラン等のアルコキシシランを原料とし、アルコール等の水溶性有機溶媒を含有する水溶液中で縮合反応させて成長させるアルコキシシラン法で得られうる。また、前記ヒュームドシリカは、一又は複数の実施形態において、四塩化珪素等の揮発性珪素化合物を原料とし、酸素水素バーナーによる１０００℃以上の高温下で加水分解させて成長させる気相法で得られうる。 In one or a plurality of embodiments, the colloidal silica can be obtained by a water glass method in which alkali metal silicate such as sodium silicate is used as a raw material and a particle is grown by condensation reaction in an aqueous solution. Alternatively, the colloidal silica can be obtained by an alkoxysilane method in which an alkoxysilane such as tetraethoxysilane is used as a raw material and grown by condensation reaction in an aqueous solution containing a water-soluble organic solvent such as alcohol. Further, in one or a plurality of embodiments, the fumed silica is a vapor phase method in which a volatile silicon compound such as silicon tetrachloride is used as a raw material and is hydrolyzed at a high temperature of 1000 ° C. or higher with an oxygen hydrogen burner. Can be obtained.
シリカ粒子の一次粒子の平均粒子径は、一又は複数の実施形態において、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、５ｎｍ以上２００ｎｍ以下が好ましく、より好ましくは７ｎｍ以上１００ｎｍ以下、さらに好ましくは９ｎｍ以上８０ｎｍ以下、さらにより好ましくは１０ｎｍ以上５０ｎｍ以下である。ここで、シリカ粒子の一次粒子の平均粒子径は、実施例に記載の方法により測定される。 In one or a plurality of embodiments, the average particle diameter of primary particles of silica particles is preferably 5 nm or more and 200 nm or less, more preferably 7 nm or more and 100 nm, from the viewpoint of maintaining the polishing rate and suppressing the deterioration of the surface roughness after cleaning. Hereinafter, it is more preferably 9 nm to 80 nm, and still more preferably 10 nm to 50 nm. Here, the average particle diameter of the primary particles of the silica particles is measured by the method described in the examples.
研磨液組成物中におけるシリカ粒子の含有量は、一又は複数の実施形態において、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、好ましくは１質量％以上２０質量％以下、より好ましくは２質量％以上１９質量％以下、さらに好ましくは３質量％以上１８質量％以下、さらにより好ましくは５質量％以上１６質量％以下である。 In one or more embodiments, the content of the silica particles in the polishing liquid composition is preferably 1% by mass or more and 20% by mass or less from the viewpoint of maintaining the polishing rate and suppressing the deterioration of the surface roughness after cleaning. More preferably, they are 2 mass% or more and 19 mass% or less, More preferably, they are 3 mass% or more and 18 mass% or less, More preferably, they are 5 mass% or more and 16 mass% or less.
［酸］
本開示の研磨液組成物は、一又は複数の実施形態において、研磨速度向上の観点から、酸を含有することが好ましい。使用される酸としては、無機酸及び有機酸の少なくとも一方が挙げられる。無機酸としては、硝酸、硫酸、亜硫酸、過硫酸、塩酸、過塩素酸、リン酸、ホスホン酸、ホスフィン酸、ピロリン酸、トリポリリン酸、アミド硫酸等が挙げられる。有機酸としては、メタンジスルホン酸、エタンジスルホン酸、フェノールジスルホン酸、ナフタレンジスルホン酸等の含硫黄有機酸、２−アミノエチルホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、エタン−１，１，−ジホスホン酸、エタン−１，１，２−トリホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸、エタン−１−ヒドロキシ−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、２−ホスホノブタン−１，２−ジカルボン酸、１−ホスホノブタン−２，３，４−トリカルボン酸、α−メチルホスホノコハク酸等の含リン有機酸、シュウ酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、イタコン酸、フタル酸、ニトロトリ酢酸、ニトロ酢酸、エチレンジアミンテトラ酢酸、オキサロ酢酸等のカルボン酸、リンゴ酸、酒石酸、クエン酸、イソクエン酸、グリコール酸等の分子内に水酸基を有する有機カルボン酸、グルタミン酸、ピコリン酸、アスパラギン酸等のアミノカルボン酸等が挙げられる。一方、基板製造における排水による水質汚染の基準であるＣＯＤ値低減の観点から、無機酸の使用が好ましく、リン酸、硫酸がより好ましい。また循環研磨における研磨液の耐久性向上の観点から、多価カルボン酸、分子内に水酸基を有する有機カルボン酸、含リン無機酸及び含リン有機酸から選ばれる一種以上が好ましく、多価カルボン酸、分子内に水酸基を有する有機カルボン酸、及び含リン有機酸から選ばれる一種以上がより好ましく、さらに好ましくは多価カルボン酸、分子内に水酸基を有する有機カルボン酸である。具体的には、１−ヒドロキシエチリデン−１，１−ジホスホン酸、グリコール酸、コハク酸、リンゴ酸、酒石酸、及びクエン酸から選ばれる一種以上が好ましく、１−ヒドロキシエチリデン−１，１−ジホスホン酸、グリコール酸、リンゴ酸、及びクエン酸から選ばれる一種以上がより好ましく、入手容易性も考慮すると、グリコール酸、リンゴ酸、及びクエン酸から選ばれる一種以上がさらに好ましい。これらの化合物は単独で用いてもよいし、混合して用いてもよい。
[acid]
In one or more embodiments, the polishing composition of the present disclosure preferably contains an acid from the viewpoint of improving the polishing rate. Examples of the acid used include at least one of an inorganic acid and an organic acid. Examples of inorganic acids include nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, amidosulfuric acid and the like. Examples of organic acids include sulfur-containing organic acids such as methanedisulfonic acid, ethanedisulfonic acid, phenoldisulfonic acid, naphthalenedisulfonic acid, 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid). Acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ethane-1,1, -diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1- Diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α- Phosphorus organic acids such as tilphosphonosuccinic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, nitrotriacetic acid, nitroacetic acid, ethylenediaminetetraacetic acid, oxaloacetic acid, etc. Examples thereof include organic carboxylic acids having a hydroxyl group in the molecule such as carboxylic acid, malic acid, tartaric acid, citric acid, isocitric acid and glycolic acid, and aminocarboxylic acids such as glutamic acid, picolinic acid and aspartic acid. On the other hand, from the viewpoint of reducing the COD value, which is a standard for water pollution caused by wastewater in substrate production, the use of inorganic acids is preferred, and phosphoric acid and sulfuric acid are more preferred. In addition, from the viewpoint of improving the durability of the polishing liquid in cyclic polishing, one or more selected from polyvalent carboxylic acids, organic carboxylic acids having a hydroxyl group in the molecule, phosphorus-containing inorganic acids and phosphorus-containing organic acids are preferable. One or more selected from organic carboxylic acids having a hydroxyl group in the molecule and phosphorus-containing organic acids are more preferred, polyvalent carboxylic acids being more preferred, and organic carboxylic acids having a hydroxyl group in the molecule. Specifically, at least one selected from 1-hydroxyethylidene-1,1-diphosphonic acid, glycolic acid, succinic acid, malic acid, tartaric acid, and citric acid is preferable, and 1-hydroxyethylidene-1,1-diphosphonic acid is preferable. One or more selected from glycolic acid, malic acid, and citric acid is more preferable, and in view of availability, one or more selected from glycolic acid, malic acid, and citric acid is more preferable. These compounds may be used alone or in combination.
前記酸は塩の形態であってもよい。これらの酸の塩を用いる場合、特に限定はなく、具体的には、アルカリ金属、アルカリ土類金属、アンモニウム、アルキルアンモニウム等との塩が挙げられる。これらの中でも、研磨速度向上、粗さ低減の観点からアルカリ金属又はアンモニウムとの塩が好ましい。 The acid may be in the form of a salt. When these acid salts are used, there is no particular limitation, and specific examples include salts with alkali metals, alkaline earth metals, ammonium, alkylammonium, and the like. Among these, a salt with an alkali metal or ammonium is preferable from the viewpoint of improving the polishing rate and reducing the roughness.
研磨液組成物における酸の含有量は、一又は複数の実施形態において、研磨速度向上の観点及び循環研磨における耐久性向上の観点から、０．０５質量％以上が好ましく、より好ましくは０．１質量％以上、さらに好ましくは０．１５質量％以上である。また、前記酸の含有量は、研磨装置の腐食をさらに抑制できるため、１０質量％以下が好ましく、より好ましくは７．５質量％以下、さらに好ましくは５．５質量％以下、さらにより好ましくは２質量％以下である。また、研磨液組成物における酸の含有量は、一又は複数の実施形態において、上述の観点から、０．０５質量％以上１０質量％以下が好ましく、より好ましくは０．１質量％以上７．５質量％以下、さらに好ましくは０．１５質量％以上５．５質量％以下、さらにより好ましくは０．１５質量％以上２質量％以下である。なお、上述の酸の含有量は、研磨液組成物中の酸が複数種類の場合、全ての酸の合計含有量を示す。 In one or a plurality of embodiments, the acid content in the polishing composition is preferably 0.05% by mass or more, more preferably 0.1% from the viewpoint of improving the polishing rate and improving the durability in the circular polishing. It is at least mass%, more preferably at least 0.15 mass%. The acid content is preferably 10% by mass or less, more preferably 7.5% by mass or less, still more preferably 5.5% by mass or less, and still more preferably, since the corrosion of the polishing apparatus can be further suppressed. 2% by mass or less. In addition, in one or a plurality of embodiments, the acid content in the polishing composition is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7. It is 5 mass% or less, More preferably, it is 0.15 mass% or more and 5.5 mass% or less, More preferably, it is 0.15 mass% or more and 2 mass% or less. In addition, content of the above-mentioned acid shows the total content of all the acids, when there are two or more types of acids in polishing liquid composition.
［アミン化合物］
本開示の研磨液組成物は、一又は複数の実施形態において、洗浄後の表面粗さの低減の観点や研磨速度維持の観点、循環研磨における耐久性向上の観点、及び、ガラス基板の清浄性向上の観点から、アミン化合物を含有することが好ましく、多価アミン化合物を含有することがより好ましい。なお、本開示において清浄性とは研磨工程において基板表面に残留する物質を除去する性能を指す。研磨後に基板表面に残留する物質には、例えば砥粒、研磨中に発生する研磨クズ、研磨パッドのカス、ステンレスなどの研磨機に使用される部材などが挙げられる。
[Amine compound]
In one or a plurality of embodiments, the polishing liquid composition of the present disclosure includes a viewpoint of reducing surface roughness after cleaning, a viewpoint of maintaining a polishing speed, a viewpoint of improving durability in cyclic polishing, and a cleanliness of a glass substrate. From the viewpoint of improvement, an amine compound is preferably contained, and a polyvalent amine compound is more preferably contained. In this disclosure, cleanliness refers to the ability to remove substances remaining on the substrate surface in the polishing process. Examples of the substance remaining on the substrate surface after polishing include abrasive grains, polishing scraps generated during polishing, polishing pad debris, and members used in polishing machines such as stainless steel.
本開示の研磨液組成物に使用される多価アミン化合物中に含まれる窒素原子の数は、研磨速度を維持する観点から、１０個以下が好ましく、８個以下がより好ましく、６個以下がさらに好ましく、４個以下がさらにより好ましく、洗浄工程における表面粗さの悪化を抑制する観点から、２個以上である。 From the viewpoint of maintaining the polishing rate, the number of nitrogen atoms contained in the polyvalent amine compound used in the polishing liquid composition of the present disclosure is preferably 10 or less, more preferably 8 or less, and 6 or less. More preferably, 4 or less is even more preferable, and 2 or more from the viewpoint of suppressing deterioration of the surface roughness in the cleaning step.
本開示の研磨液組成物に使用される多価アミン化合物中に含まれる窒素原子の数は、清浄性を向上する観点から、２個以上が好ましく、３個以上がより好ましい。 From the viewpoint of improving cleanliness, the number of nitrogen atoms contained in the polyvalent amine compound used in the polishing liquid composition of the present disclosure is preferably 2 or more, and more preferably 3 or more.
また、前記多価アミン化合物の分子量は、研磨速度を維持する観点から、５００以下が好ましく、４００以下がより好ましく、３００以下がさらに好ましく、２００以下がさらにより好ましく、洗浄工程における表面粗さの悪化を抑制し、さらに清浄性を向上させる観点から、４０以上が好ましく、６０以上がより好ましく、８０以上がさらに好ましく、１００以上がさらにより好ましい。したがって、研磨速度を維持し、洗浄工程における表面粗さの悪化を抑制し、さらに清浄性を向上させる観点から、好ましくは４０以上５００以下、より好ましくは６０以上４００以下、さらに好ましくは８０以上３００以下、さらにより好ましくは１００以上２００以下である。研磨液組成物に含有される多価アミン化合物は、一種類でもよく、二種類以上でもよい。また、前記多価アミン化合物は、塩の形態であってもよく、例えば、塩酸、硫酸、リン酸等の無機酸、有機酸等との塩、アニオン性界面活性剤との塩が挙げられる。 The molecular weight of the polyvalent amine compound is preferably 500 or less, more preferably 400 or less, still more preferably 300 or less, and even more preferably 200 or less, in view of maintaining the polishing rate. From the viewpoint of suppressing deterioration and further improving cleanliness, 40 or more is preferable, 60 or more is more preferable, 80 or more is more preferable, and 100 or more is even more preferable. Therefore, from the viewpoint of maintaining the polishing rate, suppressing the deterioration of the surface roughness in the cleaning process, and further improving the cleanliness, it is preferably 40 or more and 500 or less, more preferably 60 or more and 400 or less, and still more preferably 80 or more and 300. Hereinafter, it is still more preferably 100 or more and 200 or less. The polyvalent amine compound contained in the polishing composition may be one type or two or more types. The polyvalent amine compound may be in the form of a salt, and examples thereof include salts with inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids, and salts with anionic surfactants.
前記多価アミン化合物の具体例としては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラアミン、テトラエチレンペンタアミン、ペンタエチレンヘキサアミン、２−［（２−アミノエチル）アミノ］エタノール（Ａ−ＥＡ）、２−［メチル［２−（ジメチルアミノ）エチル］アミノ］エタノール、２，２′−（エチレンビスイミノ）ビスエタノール、Ｎ−（２−ヒドロキシエチル）−Ｎ′−（２−アミノエチル）エチレンジアミン、２，２′−（２−アミノエチルイミノ）ジエタノール、Ｎ１，Ｎ４−ビス（ヒドロキシエチル）ジエチレントリアミン、Ｎ１，Ｎ７−ビス（ヒドロキシエチル）ジエチレントリアミン、１，３−ジアミノ−２−プロパノール、ピペラジン、１−メチルピペラジン、３−（１−ピペラジニル）−１−プロパンアミン、１−（２−アミノエチル）ピペラジン、４−メチルピペラジン−１−アミン、１−ピペラジンメタンアミン、４−エチル−１−ピペラジンアミン、１−メチル−４−（２−アミノエチル）ピペラジン、１−（２−ヒドロキシエチル）ピペラジンが挙げられるが、研磨速度を維持し、洗浄工程での表面粗さの悪化を抑制し、清浄性を向上させる観点から、２−［（２−アミノエチル）アミノ］エタノール、１−（２−アミノエチル）ピペラジン、１−（２−ヒドロキシエチル）ピペラジン、ジエチレントリアミン、トリエチレンテトラアミンが好ましく、２−［（２−アミノエチル）アミノ］エタノール、１−（２−アミノエチル）ピペラジン、１−（２−ヒドロキシエチル）ピペラジン、ジエチレントリアミンがより好ましく、２−［（２−アミノエチル）アミノ］エタノール、１−（２−アミノエチル）ピペラジン、ジエチレントリアミンがさらに好ましく、ジエチレントリアミンがさらにより好ましい。又、特に、研磨速度を維持する観点からは、１−（２−ヒドロキシエチル）ピペラジン、２−［（２−アミノエチル）アミノ］エタノールが好ましい。 Specific examples of the polyvalent amine compound include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, 2-[(2-aminoethyl) amino] ethanol (A-EA), 2- [Methyl [2- (dimethylamino) ethyl] amino] ethanol, 2,2 ′-(ethylenebisimino) bisethanol, N- (2-hydroxyethyl) -N ′-(2-aminoethyl) ethylenediamine, 2, 2 '-(2-aminoethylimino) diethanol, N1, N4-bis (hydroxyethyl) diethylenetriamine, N1, N7-bis (hydroxyethyl) diethylenetriamine, 1,3-diamino-2-propanol, piperazine, 1-methylpiperazine , 3- (1-Piperazinyl)- -Propanamine, 1- (2-aminoethyl) piperazine, 4-methylpiperazine-1-amine, 1-piperazinemethanamine, 4-ethyl-1-piperazineamine, 1-methyl-4- (2-aminoethyl) Examples include piperazine and 1- (2-hydroxyethyl) piperazine. From the viewpoint of maintaining the polishing rate, suppressing deterioration of the surface roughness in the cleaning step, and improving cleanliness, 2-[(2-amino Ethyl) amino] ethanol, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine, diethylenetriamine and triethylenetetraamine are preferred, and 2-[(2-aminoethyl) amino] ethanol, 1- (2-Aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine, and diethylenetriamine are more preferred. Properly, 2 - [(2-aminoethyl) amino] ethanol, 1- (2-aminoethyl) piperazine, diethylenetriamine more preferably, diethylenetriamine even more preferred. In particular, 1- (2-hydroxyethyl) piperazine and 2-[(2-aminoethyl) amino] ethanol are preferable from the viewpoint of maintaining the polishing rate.
研磨液組成物における、多価アミン化合物の含有量は、研磨速度の維持及び基板の清浄性向上の観点から、５質量％以下が好ましく、４質量％以下がより好ましく、３質量％以下がさらに好ましく、１質量％以下がさらにより好ましく、０．５質量％以下がさらにより好ましく、０．１質量％以下がさらにより好ましく、洗浄工程における表面粗さの悪化を抑制する観点、基板の清浄性向上の観点及び循環研磨における研磨液の耐久性向上の観点から、研磨液組成物における、多価アミン化合物の含有量は、０．００１質量％以上が好ましく、０．００５質量％以上がより好ましく、０．０１質量％以上がさらに好ましい。したがって、研磨速度を維持し、洗浄工程における表面粗さの悪化を抑制する観点、基板の清浄性向上の観点及び循環研磨における研磨液の耐久性向上の観点から、０．００１質量％以上５質量％以下が好ましく、０．００５質量％以上４質量％以下がより好ましく、０．０１質量％以上３質量％以下がさらに好ましく、０．０１質量％以上１質量％以下がさらにより好ましく、０．０１質量％以上０．５質量％以下がさらにより好ましく、０．０１質量％以上０．１質量％以下がさらにより好ましい。なお、前記含有量は、研磨液組成物中の多価アミン化合物が複数種類の場合、全多価アミン化合物の合計含有量を示す。 The content of the polyvalent amine compound in the polishing liquid composition is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less from the viewpoint of maintaining the polishing rate and improving the cleanliness of the substrate. Preferably, 1% by mass or less is even more preferable, 0.5% by mass or less is further more preferable, 0.1% by mass or less is even more preferable, from the viewpoint of suppressing deterioration of surface roughness in the cleaning process, the cleanliness of the substrate From the viewpoint of improvement and the viewpoint of improving the durability of the polishing liquid in cyclic polishing, the content of the polyvalent amine compound in the polishing liquid composition is preferably 0.001% by mass or more, and more preferably 0.005% by mass or more. 0.01% by mass or more is more preferable. Therefore, from the viewpoint of maintaining the polishing rate and suppressing the deterioration of the surface roughness in the cleaning process, from the viewpoint of improving the cleanliness of the substrate, and from the viewpoint of improving the durability of the polishing liquid in cyclic polishing, 0.001% by mass or more and 5% by mass. % Or less, more preferably 0.005% by mass or more and 4% by mass or less, still more preferably 0.01% by mass or more and 3% by mass or less, still more preferably 0.01% by mass or more and 1% by mass or less. 01 mass% or more and 0.5 mass% or less are still more preferable, and 0.01 mass% or more and 0.1 mass% or less are still more preferable. In addition, the said content shows the total content of all the polyvalent amine compounds, when there are multiple types of polyvalent amine compounds in the polishing composition.
研磨液組成物における多価アミン化合物と酸の質量比（多価アミン化合物の質量／酸の質量）は、研磨速度を維持し、洗浄工程における表面粗さの悪化を抑制する観点、清浄性の向上の観点、並びに循環研磨における耐久性向上の観点から、０．００１以上１．０以下が好ましく、より好ましくは０．００５以上０．５以下、さらに好ましくは０．０１以上０．３以下である。 The mass ratio of the polyvalent amine compound and the acid in the polishing composition (the mass of the polyvalent amine compound / the mass of the acid) maintains the polishing rate and suppresses the deterioration of the surface roughness in the cleaning process. From the viewpoint of improvement, and from the viewpoint of improving durability in cyclic polishing, 0.001 or more and 1.0 or less are preferable, more preferably 0.005 or more and 0.5 or less, and still more preferably 0.01 or more and 0.3 or less. is there.
［水溶性高分子］
本開示の研磨液組成物は、一又は複数の実施形態において、研磨速度向上の観点から、水溶性高分子を含有することが好ましく、アニオン性基を有する水溶性高分子（以下「アニオン性高分子」とも言う。）を含有することがより好ましい。
[Water-soluble polymer]
In one or a plurality of embodiments, the polishing liquid composition of the present disclosure preferably contains a water-soluble polymer from the viewpoint of improving the polishing rate, and includes a water-soluble polymer having an anionic group (hereinafter referred to as “anionic high polymer”). More preferably, it is also referred to as “molecule”.
アニオン性高分子のアニオン性基としては、カルボン酸基、スルホン酸基、硫酸エステル基、リン酸エステル基、ホスホン酸基等が挙げられる。これらのアニオン性基は塩の形態であってもよい。アニオン性基が塩を形成する場合、特に限定はなく、具体的には、金属、アンモニウム、アルキルアンモニウム等との塩が挙げられる。金属の具体例としては、周期律表（長周期型）１Ａ、１Ｂ、２Ａ、２Ｂ、３Ａ、３Ｂ、４Ａ、６Ａ、７Ａ又は８族に属する金属が挙げられる。アルキルアンモニウムの具体例としては、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウム等が挙げられる。中でも、作業性の観点からナトリウム塩が好ましい。 Examples of the anionic group of the anionic polymer include a carboxylic acid group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, and a phosphonic acid group. These anionic groups may be in the form of a salt. When the anionic group forms a salt, there is no particular limitation, and specific examples include salts with metals, ammonium, alkylammonium, and the like. Specific examples of the metal include metals belonging to the periodic table (long-period type) 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A, or Group 8. Specific examples of alkylammonium include tetramethylammonium, tetraethylammonium, tetrabutylammonium and the like. Among these, sodium salt is preferable from the viewpoint of workability.
アニオン性高分子は、例えば、スルホン酸基を有する単量体、カルボン酸基を有する単量体等のアニオン性基を有する単量体を重合することにより得られうる。これら単量体の重合は、ランダム、ブロック、又はグラフトのいずれでもよい。 The anionic polymer can be obtained, for example, by polymerizing a monomer having an anionic group such as a monomer having a sulfonic acid group or a monomer having a carboxylic acid group. The polymerization of these monomers may be random, block or graft.
スルホン酸基を有する単量体の具体例としては、イソプレンスルホン酸、２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸、スチレンスルホン酸、メタリルスルホン酸、ビニルスルホン酸、アリルスルホン酸、イソアミレンスルホン酸、ナフタレンスルホン酸等が挙げられる。カルボン酸基を有する単量体としては、例えば、イタコン酸、（メタ）アクリル酸、マレイン酸等が挙げられる。リン酸エステル基又はホスホン酸基を有する単量体としては、例えば、ビニルホスホン酸、メタクロイルオキシメチルリン酸、メタクロリルオキシエチルリン酸、メタクロイルオキシブチルリン酸、メタクロリルオキシヘキシルリン酸、メタクロリルオキシオクチルリン酸、メタクロリルオキシデシルリン酸、メタクロリルオキシラウリルリン酸、メタロイルオキシステアリルリン酸、メタクロイルオキシ１、４−ジメチルシクロヘキシルリン酸が挙げられる。 Specific examples of the monomer having a sulfonic acid group include isoprene sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, iso Examples include amylene sulfonic acid and naphthalene sulfonic acid. Examples of the monomer having a carboxylic acid group include itaconic acid, (meth) acrylic acid, maleic acid and the like. Examples of the monomer having a phosphate ester group or a phosphonic acid group include vinylphosphonic acid, methacryloyloxymethyl phosphoric acid, methacryloyloxyethyl phosphoric acid, methacryloyloxybutyl phosphoric acid, methacryloyloxyhexyl phosphoric acid, Examples include methacrylyloxyoctyl phosphoric acid, methacrylyloxydecyl phosphoric acid, methacryloyloxylauryl phosphoric acid, metalloyloxystearyl phosphoric acid, methacryloyloxy 1,4-dimethylcyclohexylphosphoric acid.
また、アニオン性高分子には、上記以外の単量体を用いることもできる。他の単量体としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレン等の芳香族ビニル化合物、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸オクチル等の（メタ）アクリル酸アルキルエステル類、ブタジエン、イソプレン、２−クロル−１，３−ブタジエン、１−クロル−１，３−ブタジエン等の脂肪族共役ジエン、（メタ）アクリロニトリル等のシアン化ビニル化合物が挙げられる。 Moreover, monomers other than the above can also be used for the anionic polymer. Examples of other monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic acid alkyl esters such as octyl, aliphatic conjugated dienes such as butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3-butadiene, and cyanation of (meth) acrylonitrile A vinyl compound is mentioned.
アニオン性高分子としては、一又は複数の実施形態において、ポリアクリル酸、（メタ）アクリル酸／イソプレンスルホン酸共重合体、（メタ）アクリル酸／２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸共重合体（ＡＡ−ＡＭＰＳ）、（メタ）アクリル酸／イソプレンスルホン酸／２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸共重合体、（メタ）アクリル酸／マレイン酸共重合体、ナフタレンスルホン酸ホルムアルデヒド縮合物、メチルナフタレンスルホン酸ホルムアルデヒド縮合物、アントラセンスルホン酸ホルムアルデヒド縮合物、メラミンスルホン酸ホルムアルデヒド縮合物、リグニンスルホン酸、変成リグニンスルホン酸、アミノアリールスルホン酸−フェノール−ホルムアルデヒド縮合物、スチレン／イソプレンスルホン酸共重合体、スチレン／スチレンスルホン酸共重合体、（メタ）アクリル酸アルキルエステル／スチレンスルホン酸共重合体が挙げられるが、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、ポリアクリル酸、（メタ）アクリル酸／２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸共重合体、ナフタレンスルホン酸ホルマリン縮合物、スチレン／イソプレンスルホン酸共重合体、及びスチレン／スチレンスルホン酸共重合体から選ばれる１種以上が好ましく、（メタ）アクリル酸／２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸共重合体、及びスチレン／スチレンスルホン酸共重合体から選ばれる１種以上がより好ましい。 As an anionic polymer, in one or a plurality of embodiments, polyacrylic acid, (meth) acrylic acid / isoprenesulfonic acid copolymer, (meth) acrylic acid / 2- (meth) acrylamide-2-methylpropanesulfone Acid copolymer (AA-AMPS), (meth) acrylic acid / isoprenesulfonic acid / 2- (meth) acrylamide-2-methylpropanesulfonic acid copolymer, (meth) acrylic acid / maleic acid copolymer, naphthalene Sulfonic acid formaldehyde condensate, methylnaphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, lignin sulfonic acid, modified lignin sulfonic acid, aminoaryl sulfonic acid-phenol-formaldehyde condensate, styrene / Isoprene sulfonic acid copolymer, styrene / styrene sulfonic acid copolymer, (meth) acrylic acid alkyl ester / styrene sulfonic acid copolymer, but maintaining the polishing rate and worsening the surface roughness after cleaning From the viewpoint of suppression, polyacrylic acid, (meth) acrylic acid / 2- (meth) acrylamide-2-methylpropanesulfonic acid copolymer, naphthalenesulfonic acid formalin condensate, styrene / isoprenesulfonic acid copolymer, and styrene 1 type or more selected from / styrene sulfonic acid copolymer is preferable, and is selected from (meth) acrylic acid / 2- (meth) acrylamide-2-methylpropanesulfonic acid copolymer and styrene / styrene sulfonic acid copolymer One or more selected from the above are more preferable.
水溶性高分子の重量平均分子量は、一又は複数の実施形態において、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、５００以上１２万以下であることが好ましく、１０００以上１０万以下がより好ましく、１０００以上３万以下がさらに好ましく、１０００以上１万以下がさらにより好ましく、１５００以上８０００以下がさらにより好ましい。該重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて実施例に記載の方法により求めることができる。 In one or a plurality of embodiments, the weight average molecular weight of the water-soluble polymer is preferably 500 or more and 120,000 or less, from the viewpoint of maintaining the polishing rate and suppressing the deterioration of the surface roughness after cleaning, and preferably 1000 or more and 10 or less. Is more preferably from 1,000 to 30,000, still more preferably from 1,000 to 10,000, and even more preferably from 1500 to 8,000. The weight average molecular weight can be determined by the method described in Examples using gel permeation chromatography (GPC).
研磨液組成物における水溶性高分子の含有量は、一又は複数の実施形態において、研磨速度の維持及び洗浄後の表面粗さの悪化抑制の観点から、０．００１質量％以上１質量％以下が好ましく、より好ましくは０．００５質量％以上０．５質量％以下、さらに好ましくは０．０１質量％以上０．２質量％以下、さらにより好ましくは０．０１質量％以上０．１質量％以下、さらにより好ましくは０．０１５質量％以上０．０７５質量％以下、さらにより好ましくは０．０２質量％以上０．０７５質量％以下である。 In one or a plurality of embodiments, the content of the water-soluble polymer in the polishing composition is 0.001% by mass or more and 1% by mass or less from the viewpoint of maintaining the polishing rate and suppressing the deterioration of the surface roughness after cleaning. Is preferable, more preferably 0.005% by mass to 0.5% by mass, still more preferably 0.01% by mass to 0.2% by mass, and still more preferably 0.01% by mass to 0.1% by mass. Hereinafter, it is still more preferably 0.015 mass% or more and 0.075 mass% or less, and still more preferably 0.02 mass% or more and 0.075 mass% or less.
［水］
本開示の研磨液組成物は、媒体として水を含有する。水は、一又は複数の実施形態において、蒸留水、イオン交換水、純水及び超純水等が使用され得る。本開示の研磨液組成物中の水の含有量は、研磨液組成物の取扱いがさらに容易になるため、５５質量％以上が好ましく、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは８５質量％以上である。また、前記水の含有量は、研磨速度向上の観点から、９９質量％以下が好ましく、より好ましくは９８質量％以下、さらに好ましくは９７質量％以下である。したがって、前記媒体の含有量は、５５質量％以上９９質量％以下が好ましく、より好ましくは７０質量％以上９８質量％以下、さらに好ましくは８０質量％以上９７質量％以下、さらにより好ましくは８５質量％以上９７質量％以下である。
[water]
The polishing liquid composition of the present disclosure contains water as a medium. In one or more embodiments, water may be distilled water, ion exchange water, pure water, ultrapure water, or the like. The water content in the polishing liquid composition of the present disclosure is preferably 55% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more because the handling of the polishing liquid composition is further facilitated. Especially preferably, it is 85 mass% or more. In addition, the water content is preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably 97% by mass or less, from the viewpoint of improving the polishing rate. Therefore, the content of the medium is preferably 55% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, still more preferably 80% by mass or more and 97% by mass or less, and still more preferably 85% by mass. % To 97% by mass.
［その他の成分］
本開示の研磨液組成物は、さらに、殺菌剤、抗菌剤、増粘剤、分散剤、防錆剤等を含んでもよい。これらの成分の研磨液組成物中の含有量は、研磨特性の観点から、５質量％以下が好ましく、より好ましくは３質量％以下、さらに好ましくは１質量％以下である。
[Other ingredients]
The polishing composition of the present disclosure may further contain a bactericidal agent, an antibacterial agent, a thickener, a dispersant, a rust inhibitor, and the like. The content of these components in the polishing liquid composition is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less from the viewpoint of polishing characteristics.
［研磨液組成物のｐＨ］
本開示の研磨液組成物のｐＨは、研磨速度向上及び洗浄工程での表面粗さ低減の観点、循環研磨における耐久性向上の観点、研磨機の腐食防止及び作業者の安全性向上の観点から、１．０以上４．７以下であり、好ましくは１．０以上４．５未満、より好ましくは１．５以上４．３以下、さらに好ましくは１．６以上４．１以下、さらにより好ましくは１．７以上４．１以下、さらにより好ましくは１．８以上４．１以下である。なお、上記のｐＨは、２５℃における研磨液組成物のｐＨであり、ｐＨメータ（東亜電波工業株式会社、ＨＭ−３０Ｇ）を用いて測定でき、電極の研磨液組成物への浸漬後３分後の数値である。詳しくは実施例に記載の方法により求めることができる。
[PH of polishing composition]
The pH of the polishing liquid composition of the present disclosure is from the viewpoint of improving the polishing rate and reducing the surface roughness in the cleaning process, from the viewpoint of improving durability in the cyclic polishing, from the viewpoint of preventing corrosion of the polishing machine and improving worker safety. 1.0 or more and 4.7 or less, preferably 1.0 or more and less than 4.5, more preferably 1.5 or more and 4.3 or less, still more preferably 1.6 or more and 4.1 or less, and even more preferably. Is 1.7 or more and 4.1 or less, and more preferably 1.8 or more and 4.1 or less. In addition, said pH is pH of polishing liquid composition in 25 degreeC, can be measured using a pH meter (Toa Denpa Kogyo KK, HM-30G), and 3 minutes after immersion in polishing liquid composition of electrode It is the latter number. In detail, it can obtain | require by the method as described in an Example.
［研磨液組成物の調製方法］
本開示の研磨液組成物は、各成分を公知の方法で混合することにより、調製することができる。研磨液組成物は、経済性の観点から、通常、濃縮液として製造され、これを使用時に希釈する場合が多い。研磨液組成物は、そのまま使用してもよいし、濃縮液であれば希釈して使用すればよい。濃縮液を希釈する場合、その希釈倍率は、特に制限されず、前記濃縮液における各成分の濃度（研磨材の含有量等）や研磨条件等に応じて適宜決定できる。
[Method for preparing polishing liquid composition]
The polishing liquid composition of this indication can be prepared by mixing each component by a well-known method. The polishing composition is usually produced as a concentrated solution from the viewpoint of economy, and it is often diluted at the time of use. The polishing composition may be used as it is, or diluted if it is a concentrated solution. When diluting the concentrate, the dilution ratio is not particularly limited, and can be appropriately determined according to the concentration of each component in the concentrate (abrasive content, etc.), polishing conditions, and the like.
研磨液組成物のｐＨは、前記成分の混合後、所定のｐＨに調整してもよいし、混合前にそれぞれ調整していてもよい。ｐＨの調整は、酸、水溶性金属塩、多価アミン化合物、及びそれら以外のｐＨ調整剤により行うことができる。 The pH of the polishing composition may be adjusted to a predetermined pH after mixing the components, or may be adjusted before mixing. The pH can be adjusted with an acid, a water-soluble metal salt, a polyvalent amine compound, and other pH adjusters.
［被研磨ガラス基板］
本開示の研磨液組成物の研磨対象である被研磨ガラス基板は、一又は複数の実施形態において、ガラスハードディスク基板の製造工程にあるガラス基板である。前記ガラス基板としては、アルミノ珪酸ガラス、ホウ珪酸ガラス、アルミノホウ珪酸ガラス、化学強化工程でナトリウムがカリウムに置換されたアルミノ珪酸ガラス等のＳｉ以外の金属原子を含有するガラスが挙げられるが、研磨速度向上の観点から、アルミノ珪酸ガラス基板、及び化学強化工程でナトリウムがカリウムに置換されたアルミノ珪酸ガラスが好ましく、アルミノ珪酸ガラス基板がより好ましい。また、本発明に用いられる被研磨ガラスハードディスク基板は、一又は複数の実施形態において、水平磁気記録用基板、垂直磁気記録用基板、熱アシスト記録（ＨＡＭＲ）用基板のいずれにも用いることができる。
[Polished glass substrate]
In one or a plurality of embodiments, a glass substrate to be polished that is a polishing target of the polishing composition of the present disclosure is a glass substrate that is in a manufacturing process of a glass hard disk substrate. Examples of the glass substrate include aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, and glass containing metal atoms other than Si, such as aluminosilicate glass in which sodium is replaced with potassium in a chemical strengthening step, From the viewpoint of improvement, an aluminosilicate glass substrate and an aluminosilicate glass in which sodium is substituted with potassium in the chemical strengthening step are preferable, and an aluminosilicate glass substrate is more preferable. The glass hard disk substrate to be polished used in the present invention can be used for any of a horizontal magnetic recording substrate, a vertical magnetic recording substrate, and a thermally assisted recording (HAMR) substrate in one or a plurality of embodiments. .
アルミノ珪酸ガラス基板は、その構成元素としてＯ（酸素）以外ではＳｉを最も多く含み、次いでＡｌ（アルミニウム）を多く含む。通常、Ｓｉの含有量は１５〜４０質量％であり、Ａｌの含有量は２〜２５質量％で、他にもＮａ、Ｋ、Ｔｉ、Ｚｎ、Ｓ、Ｃａ、Ｐ、Ｂ、Ｚｒ、Ｆｅ、Ｓｒ、Ｎｂ、Ｂａ、Ｎｉなどを含むことがある。ハードディスク用として用いられる場合には、アルミノ珪酸ガラス基板は、研磨速度の向上及び基板の透明性維持の観点から、Ａｌの含有量は、３質量％以上２０質量％以下が好ましく、４質量％以上１５質量％以下がより好ましい。なお、アルミノ珪酸ガラス基板中に含まれるＳｉ及びＡｌの含有量は実施例に示す方法により求めることができる。 The aluminosilicate glass substrate contains Si as a constituent element other than O (oxygen), and then contains a large amount of Al (aluminum). Usually, the Si content is 15 to 40% by mass, the Al content is 2 to 25% by mass, and Na, K, Ti, Zn, S, Ca, P, B, Zr, Fe, May contain Sr, Nb, Ba, Ni, etc. When used for hard disks, the aluminosilicate glass substrate is preferably 3% by mass or more and 20% by mass or less, preferably 4% by mass or more, from the viewpoint of improving the polishing rate and maintaining the transparency of the substrate. 15 mass% or less is more preferable. In addition, content of Si and Al contained in an aluminosilicate glass substrate can be calculated | required by the method shown in an Example.
［ガラスハードディスク基板の製造方法］
一般に、ガラスハードディスク基板は、溶融ガラスの型枠プレス又はシートガラスから切り出す方法によってガラス基材を得る工程から、形状加工工程、端面研磨工程、粗研削工程、精研削工程、粗研磨工程、仕上げ研磨工程、化学強化工程を経て製造される。化学強化工程は仕上げ研磨工程の前に施しても良い。また各工程の間には洗浄工程が含まれることがある。研磨工程後のガラスハードディスク基板は、磁性膜の形成を含む記録部形成工程を経ることで磁気ディスク化されたガラスハードディスク基板となる。本開示の研磨液組成物は、仕上げ研磨工程における研磨に使用されることが好ましい。
[Glass hard disk substrate manufacturing method]
In general, a glass hard disk substrate is obtained from a process of obtaining a glass substrate by a mold press of molten glass or a method of cutting out from sheet glass, a shape processing process, an end surface polishing process, a rough grinding process, a fine grinding process, a rough polishing process, and a finish polishing. It is manufactured through a process and a chemical strengthening process. The chemical strengthening step may be performed before the finish polishing step. In addition, a cleaning process may be included between the processes. The glass hard disk substrate after the polishing process becomes a glass hard disk substrate formed into a magnetic disk through a recording portion forming process including the formation of a magnetic film. The polishing liquid composition of the present disclosure is preferably used for polishing in the final polishing step.
したがって、本開示は、その他の態様において、本開示の研磨液組成物を使用して被研磨ガラス基板を研磨する工程を含むガラスハードディスク基板の製造方法（以下、「本開示の基板製造方法」ともいう）に関する。 Accordingly, in another aspect, the present disclosure provides a glass hard disk substrate manufacturing method (hereinafter referred to as “substrate manufacturing method of the present disclosure”) including a step of polishing a glass substrate to be polished using the polishing composition of the present disclosure. Say).
［ガラス基板の研磨工程］
本開示の基板製造方法における被研磨ガラス基板を研磨する工程は、一又は複数の実施形態において、被研磨ガラス基板の研磨対象面に本開示の研磨液組成物を供給し、前記研磨対象面に研磨パッドを接触させ、所定の圧力（荷重）をかけながら、研磨パッドや被研磨基板を動かすこと等によって行う工程である。上述したとおり、この工程は、ガラスハードディスク基板の研磨工程の最終工程である仕上げ研磨工程であることが好ましい。また、仕上げ研磨工程では、一又は複数の実施形態において、本開示の研磨液組成物を用いて循環研磨してもよい。本開示において、循環研磨とは、ガラス基板の研磨工程において、使用した研磨液を再度研磨機に投入し、研磨液を研磨機内で循環させて再利用する手法をいう。研磨後の廃液を一度全量回収してから研磨機に再投入してもよいし、廃液を回収タンクに戻しながら連続的に研磨機に再投入してもよい。
[Glass substrate polishing process]
In one or a plurality of embodiments, the step of polishing the glass substrate to be polished in the substrate manufacturing method of the present disclosure is performed by supplying the polishing liquid composition of the present disclosure to the surface to be polished of the glass substrate to be polished and applying the polishing target surface to the surface to be polished. This is a step performed by moving the polishing pad or the substrate to be polished while bringing the polishing pad into contact and applying a predetermined pressure (load). As described above, this step is preferably a final polishing step which is the final step of the glass hard disk substrate polishing step. In the final polishing step, in one or a plurality of embodiments, cyclic polishing may be performed using the polishing liquid composition of the present disclosure. In the present disclosure, the term “circular polishing” refers to a technique in which, in the polishing process of the glass substrate, the used polishing liquid is again put into the polishing machine, and the polishing liquid is circulated in the polishing machine and reused. The entire amount of the waste liquid after polishing may be recovered once and then re-entered into the polishing machine, or may be continuously re-introduced into the polishing machine while returning the waste liquid to the recovery tank.
［研磨機］
ガラス基板の研磨に用いられる研磨機としては、特に制限はなく、被研磨基板を保持する冶具（キャリア：アラミド製等）と研磨布（研磨パッド）とを備える研磨機を用いることができる。中でも、両面研磨機が好適に用いられる。
[Polishing machine]
There is no restriction | limiting in particular as a grinder used for grinding | polishing of a glass substrate, A grinder provided with the jig (carrier: product made from an aramid etc.) and polishing cloth (polishing pad) which hold | maintain a to-be-polished substrate can be used. Among these, a double-side polishing machine is preferably used.
［研磨パッド］
研磨パッドの材質としては、有機高分子等が挙げられ、前記有機高分子としては、ポリウレタン等が挙げられる。前記研磨パッドの形状は、不織布状が好ましい。例えば、粗研磨工程ではスウェード調のウレタン製硬質パッド、仕上げ研磨工程ではスウェード調のウレタン製軟質パッドが好適に用いられる。
[Polishing pad]
Examples of the material for the polishing pad include organic polymers, and examples of the organic polymer include polyurethane. The shape of the polishing pad is preferably a nonwoven fabric. For example, a suede-like urethane hard pad is suitably used in the rough polishing process, and a suede-like urethane soft pad is suitably used in the final polishing process.
研磨機を用いる研磨は、一又は複数の実施形態において、被研磨ガラス基板をキャリアで保持し研磨パッドを貼り付けた１対の研磨定盤で挟み込み、本開示の研磨液組成物を研磨パッドと被研磨基板との間に供給し、所定の圧力の下で研磨定盤及び／又は被研磨基板を動かすことにより、本開示の研磨液組成物を被研磨ガラス基板に接触させながら被研磨基板を研磨する方法が挙げられる。 In one or a plurality of embodiments, polishing using a polishing machine is performed by sandwiching a glass substrate to be polished by a pair of polishing surface plates to which a polishing pad is attached and holding the polishing pad. The substrate to be polished is brought into contact with the glass substrate to be polished while the polishing liquid composition of the present disclosure is brought into contact with the glass substrate by moving the polishing platen and / or the substrate to be polished under a predetermined pressure. A method of polishing is mentioned.
被研磨ガラス基板を研磨する工程における研磨荷重は、研磨速度を向上させる観点から、好ましくは３ｋＰａ以上、４ｋＰａ以上がより好ましく、５ｋＰａ以上がさらに好ましく、６ｋＰａ以上がさらにより好ましい。研磨中に研磨機に振動が発生しないように安定に研磨できるという観点から、好ましくは４０ｋＰａ以下、３０ｋＰａ以下がより好ましく、２０ｋＰａ以下がさらに好ましく、１５ｋＰａ以下がさらにより好ましい。従って、研磨速度を維持し、安定に研磨できるという観点から、好ましくは３ｋＰａ以上４０ｋＰａ以下、より好ましくは４ｋＰａ以上３０ｋＰａ以下、さらに好ましくは５ｋＰａ以上２０ｋＰａ以下、さらにより好ましくは６ｋＰａ以上１５ｋＰａ以下である。ここで、「研磨荷重」とは、研磨時に被研磨基板を挟み込む定盤から被研磨ガラス基板の研磨対象面に加えられる圧力をいう。 From the viewpoint of improving the polishing rate, the polishing load in the step of polishing the glass substrate to be polished is preferably 3 kPa or more, more preferably 4 kPa or more, further preferably 5 kPa or more, and further preferably 6 kPa or more. From the viewpoint that stable polishing can be performed so that vibration does not occur in the polishing machine during polishing, it is preferably 40 kPa or less, more preferably 30 kPa or less, still more preferably 20 kPa or less, and even more preferably 15 kPa or less. Therefore, from the viewpoint of maintaining the polishing rate and enabling stable polishing, it is preferably 3 kPa to 40 kPa, more preferably 4 kPa to 30 kPa, further preferably 5 kPa to 20 kPa, and even more preferably 6 kPa to 15 kPa. Here, the “polishing load” refers to a pressure applied to the surface to be polished of the glass substrate to be polished from a surface plate that sandwiches the substrate to be polished during polishing.
本開示の研磨液組成物の供給方法は、予め本開示の研磨液組成物の構成成分が十分に混合された状態で研磨パッドとガラス基板の間にポンプ等で供給する方法、研磨の直前の供給ライン内等で構成成分を混合して供給する方法、シリカ粒子スラリーと両性金属の水溶性金属塩を含有する水溶液とを別々に研磨装置に供給する方法等を用いることができる。 The method of supplying the polishing liquid composition of the present disclosure is a method of supplying a polishing pad and a glass substrate with a pump or the like in a state in which the constituents of the polishing liquid composition of the present disclosure are sufficiently mixed in advance. For example, a method in which constituent components are mixed and supplied in a supply line or the like, a method in which a silica particle slurry and an aqueous solution containing a water-soluble metal salt of an amphoteric metal are separately supplied to a polishing apparatus can be used.
本開示の研磨液組成物の供給速度は、コスト低減の観点及び研磨速度の向上の観点から、被研磨基板１ｃｍ2あたり０．０１ｍＬ／分以上１．０ｍＬ／分以下が好ましく、より好ましくは０．０２５ｍＬ／分以上０．６ｍＬ／分以下、さらに好ましくは０．０５ｍＬ／分以上０．４ｍＬ／分以下、さらにより好ましくは０．１ｍＬ／分以上０．４ｍＬ／分以下である。また循環研磨をする場合であれば研磨液組成物を再利用できるので供給流量は上記記載の流量よりも多くなってもよい。 The supply rate of the polishing liquid composition of the present disclosure is preferably 0.01 mL / min or more and 1.0 mL / min or less per 1 cm 2 of the substrate to be polished from the viewpoint of cost reduction and improvement of the polishing rate, and more preferably 0. 0.025 mL / min to 0.6 mL / min, more preferably 0.05 mL / min to 0.4 mL / min, and even more preferably 0.1 mL / min to 0.4 mL / min. In addition, since the polishing composition can be reused in the case of cyclic polishing, the supply flow rate may be higher than the flow rate described above.
［ガラス基板の洗浄工程］
本開示の基板製造方法は、一又は複数の実施形態において、本開示の研磨液組成物を用いた研磨が施されたガラス基板（被洗浄基板）を、上述の洗浄剤組成物を用いて洗浄する工程を含む。洗浄工程における被洗浄基板には、本開示の研磨液組成物を使用した研磨工程の直後のガラス基板や、研磨工程後に乾燥を防ぐための水等への浸漬工程、予備洗浄として水洗浄工程や酸洗浄工程等を経たガラス基板が含まれる。この洗浄工程は、一又は複数の実施形態において、（ａ）被洗浄基板を洗浄剤組成物に浸漬するか、及び／又は、（ｂ）洗浄剤組成物を射出して被洗浄基板の表面上に洗浄剤組成物を供給することにより行われる。
[Glass substrate cleaning process]
In one or a plurality of embodiments, the substrate manufacturing method of the present disclosure is a method of cleaning a glass substrate (substrate to be cleaned) that has been polished using the polishing liquid composition of the present disclosure, using the cleaning composition described above. The process of carrying out is included. The substrate to be cleaned in the cleaning process includes a glass substrate immediately after the polishing process using the polishing composition of the present disclosure, a dipping process in water to prevent drying after the polishing process, a water cleaning process as preliminary cleaning, A glass substrate that has undergone an acid cleaning step or the like is included. In one or a plurality of embodiments, this cleaning step includes (a) immersing the substrate to be cleaned in the cleaning composition, and / or (b) injecting the cleaning composition on the surface of the substrate to be cleaned. Is performed by supplying a cleaning composition to
前記方法（ａ）において、被洗浄基板の洗浄剤組成物への浸漬条件としては、特に制限はないが、例えば、洗浄剤組成物の温度は、安全性及び操業性の観点から２０℃以上１００℃以下であると好ましく、浸漬時間は、洗浄剤組成物による洗浄性と生産効率の観点から１０秒以上３０分以内であると好ましい。また、残留物の除去性及び残留物の分散性を高める観点から、洗浄剤組成物には超音波振動が付与されていると好ましい。超音波の周波数としては、好ましくは２０ｋＨｚ以上２０００ｋＨｚ以下であり、より好ましくは４０ｋＨｚ以上２０００ｋＨｚ以下であり、さらに好ましくは４０ｋＨｚ以上１５００ｋＨｚ以下である。 In the method (a), the conditions for immersing the substrate to be cleaned in the cleaning composition are not particularly limited. For example, the temperature of the cleaning composition is 20 ° C. or more and 100 from the viewpoint of safety and operability. The immersion time is preferably 10 ° C. or less and within 30 minutes from the viewpoint of the cleanability and production efficiency of the cleaning composition. Moreover, it is preferable that ultrasonic vibration is given to the cleaning composition from the viewpoint of improving the removability of the residue and the dispersibility of the residue. The frequency of the ultrasonic wave is preferably 20 kHz or more and 2000 kHz or less, more preferably 40 kHz or more and 2000 kHz or less, and further preferably 40 kHz or more and 1500 kHz or less.
前記方法（ｂ）では、残留物の洗浄性や油分の溶解性を促進させる観点から、超音波振動が与えられている洗浄剤組成物を射出して、被洗浄基板の表面に洗浄剤組成物を接触させて当該表面を洗浄するか、又は、洗浄剤組成物を被洗浄基板の表面上に射出により供給し、洗浄剤組成物が供給された当該表面を洗浄用ブラシでこすることにより洗浄することが好ましい。さらには、超音波振動が与えられている洗浄剤組成物を射出により洗浄対象の表面に供給し、かつ、洗浄剤組成物が供給された当該表面を洗浄用ブラシでこすることにより洗浄することが好ましい。 In the method (b), from the viewpoint of promoting the cleaning property of the residue and the solubility of the oil, the cleaning agent composition to which ultrasonic vibration is applied is injected to the cleaning substrate surface. The surface is contacted to clean the surface, or the cleaning composition is supplied by injection onto the surface of the substrate to be cleaned and then cleaned by rubbing the surface supplied with the cleaning composition with a cleaning brush. It is preferable to do. Furthermore, the cleaning composition to which ultrasonic vibration is applied is supplied to the surface to be cleaned by injection, and the surface to which the cleaning composition is supplied is cleaned by rubbing with a cleaning brush. Is preferred.
洗浄剤組成物を被洗浄基板の表面上に供給する手段としては、スプレーノズル等の公知の手段を用いることができる。また、洗浄用ブラシとしては、特に制限はなく、例えばナイロンブラシやＰＶＡ（ポリビニルアルコール）スポンジブラシ等の公知のものを使用することができる。超音波の周波数としては、前記方法（ａ）で好ましく採用される値と同様であればよい。 As means for supplying the cleaning composition onto the surface of the substrate to be cleaned, known means such as a spray nozzle can be used. Moreover, there is no restriction | limiting in particular as a brush for washing | cleaning, For example, well-known things, such as a nylon brush and a PVA (polyvinyl alcohol) sponge brush, can be used. The ultrasonic frequency may be the same as the value preferably adopted in the method (a).
洗浄工程では、前記方法（ａ）及び／又は前記方法（ｂ）に加えて、揺動洗浄、スピンナー等の回転を利用した洗浄、パドル洗浄等の公知の洗浄を用いる工程を１つ以上含んでもよい。 In addition to the method (a) and / or the method (b), the cleaning step may include one or more steps using known cleaning such as rocking cleaning, cleaning using rotation of a spinner, paddle cleaning, and the like. Good.
［洗浄剤組成物］
洗浄剤組成物は、アルカリ剤、水、及び必要に応じて各種添加剤を含有するものが使用できる。
[Cleaning composition]
As the cleaning composition, one containing an alkaline agent, water, and various additives as required can be used.
［アルカリ剤］
前記洗浄剤組成物で使用されるアルカリ剤は、無機アルカリ剤及び有機アルカリ剤のうちのいずれであってもよい。無機アルカリ剤としては、例えば、アンモニア、水酸化カリウム、及び水酸化ナトリウム等が挙げられる。有機アルカリ剤としては、例えば、ヒドロキシアルキルアミン、テトラメチルアンモニウムハイドロオキサイド、及びコリンからなる群より選ばれる一種以上が挙げられる。これらのアルカリ剤は、単独で用いてもよく、二種以上を混合して用いてもよい。
[Alkaline agent]
The alkaline agent used in the cleaning composition may be either an inorganic alkaline agent or an organic alkaline agent. Examples of the inorganic alkaline agent include ammonia, potassium hydroxide, and sodium hydroxide. Examples of the organic alkali agent include one or more selected from the group consisting of hydroxyalkylamine, tetramethylammonium hydroxide, and choline. These alkaline agents may be used alone or in combination of two or more.
ヒドロキシアルキルアミンとしては、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルエタノールアミン、メチルジエタノールアミン、モノプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン、メチルプロパノールアミン、メチルジプロパノールアミン、アミノエチルエタノールアミン等が挙げられる。なかでも、製品安定性及び環境保全性を向上させる観点から、モノエタノールアミン、メチルジエタノールアミン及びアミノエチルエタノールアミンが好ましく、モノエタノールアミン及びアミノエチルエタノールアミンがより好ましい。これらのヒドロキシアルキルアミンは単独で用いても良く、二種以上を混合して用いても良い。 Examples of the hydroxyalkylamine include monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylpropanolamine, methyldipropanolamine, aminoethylethanolamine. Etc. Of these, monoethanolamine, methyldiethanolamine and aminoethylethanolamine are preferred, and monoethanolamine and aminoethylethanolamine are more preferred from the viewpoint of improving product stability and environmental preservation. These hydroxyalkylamines may be used alone or in combination of two or more.
前記アルカリ剤のうち、洗浄剤組成物の基板上の残留物の分散性の向上、保存安定性の向上、及び特にガラスに対するエッチング制御の容易化の観点から、水酸化カリウム、水酸化ナトリウム、モノエタノールアミン、メチルジエタノールアミン、及びアミノエチルエタノールアミンからなる群から選ばれる少なくとも１種が好ましく、水酸化カリウム及び水酸化ナトリウムからなる群から選ばれる少なくとも１種がより好ましい。 Among the alkali agents, potassium hydroxide, sodium hydroxide, mono-oxide are used from the viewpoint of improving the dispersibility of the residue on the substrate of the cleaning composition, improving the storage stability, and particularly facilitating the etching control for glass. At least one selected from the group consisting of ethanolamine, methyldiethanolamine, and aminoethylethanolamine is preferable, and at least one selected from the group consisting of potassium hydroxide and sodium hydroxide is more preferable.
洗浄剤組成物中におけるアルカリ剤の含有量は、洗浄剤組成物の基板上の残留物に対する洗浄性を発現させ、かつ、取扱時の安全性を高める観点から、０．１質量％以上１０質量％以下であると好ましく、０．３質量％以上３質量％以下であるとより好ましい。 The content of the alkaline agent in the cleaning composition is 0.1% by mass or more and 10% by mass from the viewpoint of expressing the cleaning property for the residue on the substrate of the cleaning composition and enhancing the safety during handling. % Or less, and more preferably 0.3% by mass or more and 3% by mass or less.
洗浄剤組成物のｐＨは、基板上の残留物の分散性を向上させる観点から、８．０以上１３．０以下であり、好ましくは９．０以上１３．０以下、より好ましくは１０．０以上１３．０以下、さらに好ましくは１１．０以上１３．０以下である。なお、上記のｐＨは、２５℃における洗浄剤組成物のｐＨであり、ｐＨメータ（東亜電波工業株式会社、ＨＭ−３０Ｇ）を用いて測定でき、電極の洗浄剤組成物への浸漬後３分後の数値である。 The pH of the cleaning composition is from 8.0 to 13.0, preferably from 9.0 to 13.0, more preferably 10.0 from the viewpoint of improving the dispersibility of the residue on the substrate. It is 13.0 or less, more preferably 11.0 or more and 13.0 or less. In addition, said pH is pH of the cleaning composition at 25 degreeC, can be measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), 3 minutes after immersion in the cleaning composition of an electrode It is the latter number.
［各種添加剤］
前記洗浄剤組成物には、アルカリ剤以外に、非イオン界面活性剤、キレート剤、エーテルカルボキシレート、脂肪酸、アニオン性界面活性剤、水溶性高分子、消泡剤（成分に該当する界面活性剤は除く。）、アルコール類、防腐剤、酸化防止剤等が含まれていても良い。
[Various additives]
In addition to alkaline agents, the detergent composition includes nonionic surfactants, chelating agents, ether carboxylates, fatty acids, anionic surfactants, water-soluble polymers, antifoaming agents (surfactants corresponding to the components) May be included), alcohols, preservatives, antioxidants, and the like.
前記洗浄剤組成物に含まれる水以外の成分の含有量は、コスト低減や各種添加剤の充分な効果が発現される濃縮度である事と保存安定性向上との両立の観点から、水の含有量と水以外の成分の含有量の合計を１００質量％とすると、好ましくは１０質量％以上６０質量％以下であり、より好ましくは１５質量％以上５０質量％以下であり、さらに好ましくは１５質量％以上４０質量％以下である。 The content of the components other than water contained in the cleaning composition is water from the viewpoint of coexistence of cost reduction and a concentration that exhibits a sufficient effect of various additives and an improvement in storage stability. When the total of the content and the content of components other than water is 100% by mass, it is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and even more preferably 15%. It is not less than 40% by mass.
前記洗浄剤組成物は、希釈して用いられる。希釈倍率は、洗浄効率を考慮すると、好ましくは１０倍以上５００倍以下、より好ましくは２０倍以上２００倍以下、更に好ましくは５０倍以上１００倍以下である。希釈用の水は、下記と同様のものでよい。 The cleaning composition is used after being diluted. In consideration of cleaning efficiency, the dilution rate is preferably 10 to 500 times, more preferably 20 to 200 times, and still more preferably 50 to 100 times. The water for dilution may be the same as described below.
［水］
前記洗浄剤組成物に含まれる水は、溶媒としての役割を果たすことができるものであれば特に制限はなく、例えば、超純水、純水、イオン交換水、又は蒸留水等を挙げることができるが、超純水、純水、又はイオン交換水が好ましく、超純水がより好ましい。尚、純水及び超純水は、例えば、水道水を活性炭に通し、イオン交換処理し、さらに蒸留したものを、必要に応じて所定の紫外線殺菌灯を照射、又はフィルターに通すことにより得ることができる。尚、洗浄剤組成物は、溶媒として上記水に加えて水系溶媒（例えば、エタノール等のアルコール）をさらに含んでいてもよいが、洗浄剤組成物に含まれる溶媒は水のみからなると好ましい。
[water]
The water contained in the cleaning composition is not particularly limited as long as it can serve as a solvent, and examples thereof include ultrapure water, pure water, ion exchange water, or distilled water. However, ultrapure water, pure water, or ion exchange water is preferable, and ultrapure water is more preferable. Pure water and ultrapure water can be obtained, for example, by passing tap water through activated carbon, subjecting it to ion exchange treatment, and further distilling it, irradiating it with a predetermined ultraviolet germicidal lamp or passing it through a filter as necessary. Can do. The cleaning composition may further contain an aqueous solvent (for example, an alcohol such as ethanol) in addition to the above water as a solvent. However, it is preferable that the solvent contained in the cleaning composition consists only of water.
［磁性膜の形成工程］
本開示の基板製造方法は、一又は複数の実施形態において、被研磨ガラス基板の研磨工程及び洗浄工程後のガラス基板上に磁性膜を形成する工程、或いは、磁性膜の形成を含む記録部形成工程を有してもよい。
[Magnetic film formation process]
In one or a plurality of embodiments, a substrate manufacturing method of the present disclosure includes a step of forming a magnetic film on a glass substrate after a polishing step and a cleaning step of a glass substrate to be polished, or a recording unit formation including formation of a magnetic film You may have a process.
［ガラス基板の研磨方法］
本開示は、その他の態様において、被研磨ガラス基板の研磨対象面に本開示の研磨液組成物を供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び前記被研磨基板の少なくとも一方を動かして研磨することを含むガラス基板の研磨方法に関する。本開示の研磨方法における、研磨液組成物の供給方法、研磨条件、実施形態は、上述の研磨工程における研磨と同様とすることができる。
[Glass substrate polishing method]
In another aspect, the present disclosure provides the polishing liquid composition of the present disclosure to a surface to be polished of a glass substrate to be polished, contacts the polishing pad with the surface to be polished, and includes at least the polishing pad and the substrate to be polished. The present invention relates to a method for polishing a glass substrate including moving one side and polishing. In the polishing method of the present disclosure, the method for supplying the polishing composition, the polishing conditions, and the embodiment can be the same as those in the polishing step described above.
上述した実施形態に関し、本開示はさらに以下の一又は複数の実施形態にかかる組成物、製造方法、或いは用途を開示する。 Regarding the above-described embodiment, the present disclosure further discloses a composition, a production method, or an application according to one or more of the following embodiments.
＜１＞ シリカ粒子、両性金属の水溶性金属塩、及び水を含有する、ガラスハードディスク基板用研磨液組成物。 <1> A polishing liquid composition for a glass hard disk substrate, comprising silica particles, a water-soluble metal salt of an amphoteric metal, and water.
＜２＞ 研磨液組成物中における両性金属の水溶性金属塩の含有量は、０．００１質量％以上が好ましく、より好ましくは０．０１質量％以上、さらに好ましくは０．０３質量％以上である、＜１＞記載のガラスハードディスク基板用研磨液組成物。
＜３＞ 研磨液組成物中における両性金属の水溶性金属塩の含有量は、１０質量％以下が好ましく、より好ましくは７質量％以下、さらに好ましくは５質量％以下である、＜１＞又は＜２＞記載のガラスハードディスク基板用研磨液組成物。
＜４＞ 研磨液組成物中における両性金属の水溶性金属塩の含有量は、０．００１質量％以上１０質量％以下が好ましく、より好ましくは０．０１質量％以上７質量％以下、さらに好ましくは０．０３質量％以上５質量％以下である、＜１＞から＜３＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜５＞ シリカ粒子の一次粒子の平均粒子径は、５ｎｍ以上２００ｎｍ以下が好ましく、より好ましくは７ｎｍ以上１００ｎｍ以下、さらに好ましくは９ｎｍ以上８０ｎｍ以下、さらにより好ましくは１０ｎｍ以上５０ｎｍ以下である、＜１＞から＜４＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜６＞ 研磨液組成物中におけるシリカ粒子の含有量は、好ましくは１質量％以上２０質量％以下、より好ましくは２質量％以上１９質量％以下、さらに好ましくは３質量％以上１８質量％以下、さらにより好ましくは５質量％以上１６質量％以下である、＜１＞から＜５＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜７＞ 両性金属の水溶性金属塩が、アルミニウム（Ａｌ）、亜鉛（Ｚｎ）、ガリウム（Ｇａ）、スズ（Ｓｎ）、鉛（Ｐｂ）及びこれらの組み合わせからなる群から選択される金属の水溶性金属塩である、＜１＞から＜６＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜８＞ さらに酸を含有する、＜１＞から＜７＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜９＞ 酸が、無機酸、有機酸、及びこれらの組み合わせからなる群から選択される酸である、＜８＞記載のガラスハードディスク基板用研磨液組成物。
＜１０＞ さらにアミン化合物及び水溶性高分子の少なくとも一方を含有する、＜１＞から＜９＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜１１＞ アルミノ珪酸ガラス基板を研磨するための、＜１＞から＜１０＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜１２＞ ガラス基板が熱アシスト記録（ＨＡＭＲ）用アルミノ珪酸ガラス基板である、＜１＞から＜１１＞のいずれかに記載のガラスハードディスク基板用研磨液組成物。
＜１３＞ ＜１＞から＜１２＞のいずれかに記載の研磨液組成物を使用して被研磨ガラス基板を研磨する工程を含む、ガラスハードディスク基板の製造方法。
＜１４＞ さらに、前記研磨工程の後のガラス基板を、洗浄剤組成物を用いて洗浄する工程を含む、＜１３＞記載のガラスハードディスク基板の製造方法。
＜１５＞ さらに、ガラス基板上に磁性膜を形成する工程を含む、＜１３＞又は＜１４＞に記載のガラスハードディスク基板の製造方法。
＜１６＞ 被研磨ガラス基板の研磨対象面に＜１＞から＜１２＞のいずれかに記載の研磨液組成物を供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び前記被研磨ガラス基板の少なくとも一方を動かして研磨することを含む、ガラス基板の研磨方法。
＜１７＞ 前記研磨液組成物を循環使用して被研磨ガラス基板を研磨する工程を含む、＜１６＞記載のガラス基板の研磨方法。
<2> The content of the water-soluble metal salt of the amphoteric metal in the polishing composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.03% by mass or more. A polishing composition for a glass hard disk substrate according to <1>.
<3> The content of the amphoteric metal water-soluble metal salt in the polishing composition is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less, <1> or <2> The polishing liquid composition for glass hard disk substrates as described.
<4> The content of the water-soluble metal salt of the amphoteric metal in the polishing composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 7% by mass, and still more preferably. Is a polishing liquid composition for glass hard disk substrates according to any one of <1> to <3>, which is 0.03% by mass or more and 5% by mass or less.
<5> The average particle diameter of primary particles of silica particles is preferably 5 nm to 200 nm, more preferably 7 nm to 100 nm, still more preferably 9 nm to 80 nm, and even more preferably 10 nm to 50 nm, <1 > To <4> The polishing liquid composition for a glass hard disk substrate according to any one of the above.
<6> The content of silica particles in the polishing composition is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 19% by mass or less, and further preferably 3% by mass or more and 18% by mass or less. The polishing composition for a glass hard disk substrate according to any one of <1> to <5>, further preferably 5% by mass to 16% by mass.
<7> A water-soluble metal salt of an amphoteric metal selected from the group consisting of aluminum (Al), zinc (Zn), gallium (Ga), tin (Sn), lead (Pb), and combinations thereof. The polishing liquid composition for glass hard disk substrates according to any one of <1> to <6>, which is a conductive metal salt.
<8> The polishing composition for a glass hard disk substrate according to any one of <1> to <7>, further containing an acid.
<9> The polishing liquid composition for a glass hard disk substrate according to <8>, wherein the acid is an acid selected from the group consisting of inorganic acids, organic acids, and combinations thereof.
<10> The polishing composition for a glass hard disk substrate according to any one of <1> to <9>, further comprising at least one of an amine compound and a water-soluble polymer.
<11> The polishing composition for a glass hard disk substrate according to any one of <1> to <10>, for polishing an aluminosilicate glass substrate.
<12> The polishing liquid composition for a glass hard disk substrate according to any one of <1> to <11>, wherein the glass substrate is an aluminosilicate glass substrate for heat-assisted recording (HAMR).
<13> A method for producing a glass hard disk substrate, comprising a step of polishing a glass substrate to be polished using the polishing composition according to any one of <1> to <12>.
<14> The method for producing a glass hard disk substrate according to <13>, further comprising a step of cleaning the glass substrate after the polishing step using a cleaning composition.
<15> The method for producing a glass hard disk substrate according to <13> or <14>, further comprising a step of forming a magnetic film on the glass substrate.
<16> The polishing liquid composition according to any one of <1> to <12> is supplied to the surface to be polished of the glass substrate to be polished, the polishing pad is brought into contact with the surface to be polished, and the polishing pad and the object to be polished A method for polishing a glass substrate, comprising polishing by moving at least one of the polished glass substrates.
<17> The method for polishing a glass substrate according to <16>, which comprises a step of polishing the glass substrate to be polished using the polishing composition in a circulating manner.
［実施例１〜３６及び比較例１〜１４］
１．被研磨ガラス基板の調製
セリア砥粒を含有する研磨液組成物であらかじめ粗研磨したアルミノ珪酸ガラス基板を被研磨ガラス基板として用意した。基板中に含まれる構成元素は、Ｓｉの含有量は２０質量％、Ａｌの含有量は５質量％であった。構成元素は、ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）法を用い以下の測定条件で測定した。
[Examples 1-36 and Comparative Examples 1-14]
1. Preparation of glass substrate to be polished An aluminosilicate glass substrate coarsely polished in advance with a polishing composition containing ceria abrasive grains was prepared as a glass substrate to be polished. Constituent elements contained in the substrate had a Si content of 20% by mass and an Al content of 5% by mass. The constituent elements were measured using the ESCA (Electron Spectroscopy for Chemical Analysis) method under the following measurement conditions.
〔ＥＳＣＡ測定条件〕
・試料作製
アルミノ珪酸ガラス基板を１ｃｍ×１ｃｍに切断し、カーボン製両面テープ上に乗せ固定した。表面のゴミ等を除くためにＡｒスパッタを加速電圧２ｋＶで６分間かけ、ＥＳＣＡ測定を実施した。
・測定
機器：アルバックファイ製 ＰＨＩ Ｑｕａｎｔｅｒａ ＳＸＭ
Ｘ線源：単色化ＡｌＫα線、１４８６．６ｅＶ、２５Ｗ、１５ｋＶ
ビーム径：１００μｍ
Ｘ線入射角：４５°
測定範囲：５００×５００（μｍ2）
Ｐａｓｓ ｅｎｅｒｇｙ：２８０．０(ｓｕｒｖｅｙ）、１４０．０ｅＶ(ｎａｒｒｏｗ）
Ｓｔｅｐ ｓｉｚｅ：１．００(ｓｕｒｖｅｙ)、０．２５０ｅＶ(ｎａｒｒｏｗ)
測定元素：Ｃ，Ｎ，Ｏ，Ｎａ，Ｍｇ，Ａｌ，Ｓｉ，Ｓ，Ｋ，Ｔｉ，Ｚｒ，Ｎｂ
帯電補正：Ｎｅｕｔｒａｌｉｚｅｒ及びＡｒ+照射
[ESCA measurement conditions]
-Sample preparation The aluminosilicate glass substrate was cut into 1 cm x 1 cm and placed on a carbon double-sided tape and fixed. In order to remove dust on the surface, Ar sputtering was performed for 6 minutes at an acceleration voltage of 2 kV, and ESCA measurement was performed.
・ Measurement equipment: PHI Quantera SXM manufactured by ULVAC-PHI
X-ray source: Monochromatic AlKα ray, 1486.6 eV, 25 W, 15 kV
Beam diameter: 100 μm
X-ray incident angle: 45 °
Measurement range: 500 × 500 (μm 2 )
Pass energy: 280.0 (survey), 140.0 eV (narrow)
Step size: 1.00 (survey), 0.250 eV (narrow)
Measurement elements: C, N, O, Na, Mg, Al, Si, S, K, Ti, Zr, Nb
Charging correction: Neutralizer and Ar + irradiation
２．研磨液組成物の調製
イオン交換水に下記表１に示す有機酸（クエン酸、グルコン酸、リンゴ酸、又は酒石酸のいずれか、和光純薬工業社製、１．０質量％）を添加した後、下記の添加剤を下記表１の添加量になるように添加し、さらにコロイダルシリカ（平均粒子径：２５ｎｍ）を研磨液組成物中８質量％になるよう添加し、硫酸（和光純薬工業社製）を用いてｐＨを１．９に調整して実施例１〜２７及び比較例１〜５の研磨液組成物を得た。
2. Preparation of polishing liquid composition After adding an organic acid (either citric acid, gluconic acid, malic acid, or tartaric acid, manufactured by Wako Pure Chemical Industries, 1.0% by mass) shown in Table 1 below to ion-exchanged water The following additives are added so as to have the addition amount shown in Table 1 below, and colloidal silica (average particle size: 25 nm) is further added to 8% by mass in the polishing composition, and sulfuric acid (Wako Pure Chemical Industries, Ltd.) is added. Was used to adjust the pH to 1.9, and polishing compositions of Examples 1 to 27 and Comparative Examples 1 to 5 were obtained.
また、イオン交換水に下記の添加剤を下記表２〜４の添加量になるように添加し、さらにコロイダルシリカ（平均粒子径：２５ｎｍ）を研磨液組成物中８質量％になるよう添加し、下記表２〜４記載の有機酸（クエン酸、グルコン酸、リンゴ酸、又は酒石酸のいずれか、和光純薬工業社製）を用いて所定のｐＨに調整して実施例２８〜３６及び比較例６〜１４の研磨液組成物を得た。 Further, the following additives are added to ion-exchanged water so as to have the addition amounts shown in Tables 2 to 4 below, and colloidal silica (average particle size: 25 nm) is further added to 8% by mass in the polishing composition. In Examples 28 to 36 and Comparative Examples, the organic acids (citric acid, gluconic acid, malic acid, or tartaric acid, manufactured by Wako Pure Chemical Industries, Ltd.) described in Tables 2 to 4 below were adjusted to a predetermined pH. The polishing liquid composition of Examples 6-14 was obtained.
〔添加剤〕
実施例１〜６、２５〜３６：硫酸亜鉛７水和物（和光純薬工業社製）
実施例７：硝酸亜鉛（和光純薬工業社製）
実施例８：塩化亜鉛（和光純薬工業社製）
実施例９〜１４：硝酸ガリウム（ナカライテスク社製）
実施例１５：硫酸ガリウム(高純度化学研究所製)
実施例１６：塩化ガリウム（和光純薬工業社製）
実施例１７：クエン酸亜鉛２水和物（三津和化学薬品社製）
実施例１８：クエン酸ガリウムｎ水和物（三津和化学薬品社製）
実施例１９：酒石酸亜鉛（関東化学社製)
実施例２０：シュウ酸亜鉛２水和物（関東化学社製）
実施例２１：硫酸亜鉛７水和物（和光純薬工業社製）＋硫酸ナトリウム（和光純薬工業社製）
実施例２２：硫酸亜鉛７水和物（和光純薬工業社製）＋硫酸マグネシウム（和光純薬工業社製）
実施例２３：硫酸亜鉛７水和物（和光純薬工業社製）＋ＡＡ−ＡＭＰＳ［アクリル酸／アクリルアミド−２−メチルプロパンスルホン酸共重合体ナトリウム塩（共重合モル比８９／１１、重量平均分子量２，０００、東亞合成社製）］
実施例２４：硫酸亜鉛７水和物（和光純薬工業社製）＋Ａ−ＥＡ［２−アミノエチルエタノールアミン、日本乳化剤社製］
比較例１：なし
比較例２：硫酸ナトリウム（和光純薬工業社製）
比較例３：硫酸マグネシウム（和光純薬工業社製）
比較例４：ＡＡ−ＡＭＰＳ［アクリル酸／アクリルアミド−２−メチルプロパンスルホン酸共重合体ナトリウム塩（共重合モル比８９／１１、重量平均分子量２，０００、東亞合成社製）］
比較例５：Ａ−ＥＡ［２−アミノエチルエタノールアミン、日本乳化剤社製］
〔Additive〕
Examples 1-6, 25-36: Zinc sulfate heptahydrate (Wako Pure Chemical Industries, Ltd.)
Example 7: Zinc nitrate (Wako Pure Chemical Industries, Ltd.)
Example 8: Zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.)
Examples 9 to 14: Gallium nitrate (manufactured by Nacalai Tesque)
Example 15: Gallium sulfate (manufactured by High Purity Chemical Laboratory)
Example 16: Gallium chloride (Wako Pure Chemical Industries, Ltd.)
Example 17: Zinc citrate dihydrate (Mitsuwa Chemical Co., Ltd.)
Example 18: Gallium citrate n hydrate (Mitsuwa Chemical Co., Ltd.)
Example 19: Zinc tartrate (manufactured by Kanto Chemical Co., Inc.)
Example 20: Zinc oxalate dihydrate (manufactured by Kanto Chemical Co., Inc.)
Example 21: Zinc sulfate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) + Sodium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.)
Example 22: Zinc sulfate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) + Magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.)
Example 23: Zinc sulfate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) + AA-AMPS [acrylic acid / acrylamido-2-methylpropanesulfonic acid copolymer sodium salt (copolymerization molar ratio 89/11, weight average molecular weight 2,000, manufactured by Toagosei)
Example 24: Zinc sulfate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) + A-EA [2-aminoethylethanolamine, manufactured by Nippon Emulsifier Co., Ltd.]
Comparative Example 1: None Comparative Example 2: Sodium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.)
Comparative Example 3: Magnesium sulfate (Wako Pure Chemical Industries, Ltd.)
Comparative Example 4: AA-AMPS [acrylic acid / acrylamido-2-methylpropanesulfonic acid copolymer sodium salt (copolymerization molar ratio 89/11, weight average molecular weight 2,000, manufactured by Toagosei Co., Ltd.)]
Comparative Example 5: A-EA [2-aminoethylethanolamine, manufactured by Nippon Emulsifier Co., Ltd.]
〔シリカ粒子の一次粒子平均粒子径の測定方法〕
コロイダルシリカを含む試料を、透過型電子顕微鏡「ＪＥＭ−２０００ＦＸ」（８０ｋＶ、１〜５万倍、日本電子社製）により当該製造業者が添付した説明書に従って試料を観察し、ＴＥＭ（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）像を写真撮影した。この写真をスキャナで画像データとしてパソコンに取り込み、解析ソフト「ＷｉｎＲＯＯＦ ｖｅｒ．３．６」（販売元：三谷商事）を用いて、個々のシリカ粒子の円相当径を計測し、粒子径を求めた。このようにして、１０００個のシリカ粒子の粒子径を求めた後、これらの平均値を算出し、この平均値を一次粒子の平均粒子径とした。
[Measurement method of primary particle average particle diameter of silica particles]
A sample containing colloidal silica was observed with a transmission electron microscope “JEM-2000FX” (80 kV, 1 to 50,000 times, manufactured by JEOL Ltd.) according to the instructions attached by the manufacturer, and TEM (Transmission Electron Microscope) was observed. ) Photographed the statue. This photograph was taken into a personal computer as image data by a scanner, and the equivalent diameter of each silica particle was measured using analysis software “WinROOF ver. 3.6” (distributor: Mitani Corp.) to obtain the particle diameter. . Thus, after calculating | requiring the particle diameter of 1000 silica particles, these average values were computed and this average value was made into the average particle diameter of a primary particle.
〈重合平均分子量の測定〉
水溶性高分子化合物の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法を下記の条件で適用して得たクロマトグラム中のピークに基づき算出した。
装置：ＨＬＣ−８３２０ ＧＰＣ(東ソー株式会社製、検出器一体型)
カラム：ＴＳＫｇｅｌ α−Ｍ＋ＴＳＫｇｅｌ α−Ｍ（カチオン、東ソー株式会社製）
溶離液：エタノール／水（＝３／７）に対して、ＬｉＢｒ（５０ｍｍｏｌ／Ｌ（０．４３質量％））、ＣＨ3ＣＯＯＨ（１６６．７ｍｍｏｌ／Ｌ（１．０質量％））を添加
流量：０．６ｍＬ／ｍｉｎ
カラム温度：４０℃
検出器：ＲＩ
標準物質：ポリエチレングリコール
<Measurement of polymerization average molecular weight>
The weight average molecular weight of the water-soluble polymer compound was calculated based on the peak in the chromatogram obtained by applying the gel permeation chromatography (GPC) method under the following conditions.
Apparatus: HLC-8320 GPC (manufactured by Tosoh Corporation, integrated detector)
Column: TSKgel α-M + TSKgel α-M (cation, manufactured by Tosoh Corporation)
Eluent: LiBr (50 mmol / L (0.43% by mass)) and CH 3 COOH (166.7 mmol / L (1.0% by mass)) added to ethanol / water (= 3/7) : 0.6 mL / min
Column temperature: 40 ° C
Detector: RI
Reference material: Polyethylene glycol
３．研磨方法
実施例１〜３６、比較例１〜１４の研磨液組成物を用いた研磨は、下記の標準研磨試験の条件で行った。
〔研磨条件〕
研磨試験機：スピードファム社製「両面９Ｂ研磨機」
研磨パッド：スウェードタイプ（厚さ０．９ｍｍ、平均開孔径３０μｍ、材質:発泡ウレタン）
研磨液組成物供給量：１００ｍＬ／分（被研磨基板１ｃｍ2あたりの供給速度：約０．３ｍＬ／分）
下定盤回転数：３２．５ｒｐｍ
研磨荷重：８．４ｋＰａ
キャリア：アラミド製、厚さ０．４５ｍｍ
研磨時間：２０分
被研磨基板：アルミノ珪酸ガラス基板（外径６５ｍｍ、内径２０ｍｍ、厚さ０．６３５ｍｍ）
投入基板枚数：１０枚
リンス条件：荷重＝２．０ｋＰａ、時間＝２分、イオン交換水供給量＝約２Ｌ／分
研磨後の基板を下記洗浄条件で洗浄し評価を実施した。
3. Polishing Method Polishing using the polishing composition of Examples 1 to 36 and Comparative Examples 1 to 14 was performed under the conditions of the following standard polishing test.
[Polishing conditions]
Polishing tester: "Fast double-sided 9B polishing machine" manufactured by Speedfam
Polishing pad: Suede type (thickness 0.9mm, average pore diameter 30μm, material: urethane foam)
Polishing liquid composition supply amount: 100 mL / min (supply rate per 1 cm 2 of polishing substrate: about 0.3 mL / min)
Lower platen rotation speed: 32.5 rpm
Polishing load: 8.4 kPa
Carrier: Aramid, thickness 0.45mm
Polishing time: 20 minutes Polished substrate: aluminosilicate glass substrate (outer diameter 65 mm, inner diameter 20 mm, thickness 0.635 mm)
Number of input substrates: 10 rinse conditions: load = 2.0 kPa, time = 2 minutes, ion exchange water supply amount = about 2 L / min The substrate after polishing was cleaned under the following cleaning conditions and evaluated.
４．洗浄方法
研磨したアルミノ珪酸ガラス基板を、洗浄装置にて以下の条件で洗浄した。
（１）洗浄−１：ＫＯＨ水溶液からなるｐＨ１２．０のアルカリ性洗浄剤組成物を入れた樹脂槽（４０℃）に被洗浄基板を浸漬し、超音波を照射しながら１２０秒間洗浄する。
（２）すすぎ−１：被洗浄基板を、超純水を入れた樹脂槽（４０℃）に移し、超音波（１２０ｋＨｚ）を照射しながら１２０秒間すすぎを行う。
（３）再度（１）と（２）を繰り返す。
（４）洗浄−２：樹脂槽内から被洗浄基板を、洗浄ブラシがセットされたスクラブ洗浄ユニットに移し、洗浄ブラシに常温の洗浄剤組成物を射出し、該洗浄剤組成物の存在下で洗浄ブラシを該基板の両面に４００ｒｐｍで回転させながら押し当てることにより、洗浄を５秒間行う。洗浄剤組成物には、「（１）洗浄−１」で用いた洗浄剤組成物と同組成のものを用いる。
（５）すすぎ−２：次のスクラブ洗浄ユニットに被洗浄基板を移し、常温の超純水を射出し、洗浄ブラシを該基板の両面に４００ｒｐｍで回転させながら押し当てることにより、すすぎを５秒間行う。
（６）再度（４）と（５）を繰り返す。
（７）すすぎ−３:超純水を入れた樹脂槽に移し、１０分間すすぎを行う。
（８）乾燥：温純水（６０℃）を入れた樹脂槽に移し、６０秒間浸漬した後、２５０ｍｍ／分の速度で被洗浄基板を引き上げ、４２０秒間放置し、完全に基板表面を乾燥させる。
4). Cleaning Method The polished aluminosilicate glass substrate was cleaned with a cleaning apparatus under the following conditions.
(1) Cleaning-1: The substrate to be cleaned is immersed in a resin tank (40 ° C.) containing a pH 12.0 alkaline cleaning composition made of an aqueous KOH solution and cleaned for 120 seconds while being irradiated with ultrasonic waves.
(2) Rinse-1: The substrate to be cleaned is transferred to a resin tank (40 ° C.) containing ultrapure water, and rinsed for 120 seconds while irradiating ultrasonic waves (120 kHz).
(3) Repeat (1) and (2) again.
(4) Cleaning-2: The substrate to be cleaned is transferred from the resin tank to a scrub cleaning unit in which a cleaning brush is set, and a normal temperature cleaning composition is injected onto the cleaning brush, and in the presence of the cleaning composition. Cleaning is performed for 5 seconds by pressing the cleaning brush against both sides of the substrate while rotating the substrate at 400 rpm. The cleaning composition having the same composition as the cleaning composition used in “(1) Cleaning-1” is used.
(5) Rinsing-2: The substrate to be cleaned is transferred to the next scrub cleaning unit, ultra-pure water at room temperature is injected, and the cleaning brush is pressed against both surfaces of the substrate while rotating at 400 rpm, thereby rinsing for 5 seconds. Do.
(6) Repeat (4) and (5) again.
(7) Rinse-3: Move to a resin tank containing ultrapure water and rinse for 10 minutes.
(8) Drying: Transfer to a resin tank containing warm pure water (60 ° C.) and immerse for 60 seconds, then lift the substrate to be cleaned at a rate of 250 mm / min and leave for 420 seconds to completely dry the substrate surface.
５．評価方法
研磨速度、及び表面粗さの評価は、以下のように行った。
5. Evaluation Method The polishing rate and the surface roughness were evaluated as follows.
〔研磨速度の測定方法〕
研磨前後の基板の質量差（ｇ）を該基板の密度（２．４６ｇ／ｃｍ3）、基板の表面積（３０．０４ｃｍ2）、及び研磨時間（分）で除した単位時間当たりの研磨量を計算し、研磨速度（μｍ／分）を算出した。実施例１〜実施例２７及び比較例１〜５の研磨速度については、下記表１に、比較例１を１００とした相対値として示す。実施例２８〜３１及び比較例６〜９の研磨速度については、下記表２に、比較例６を１００とした相対値として示す。実施例３２〜３３及び比較例１０〜１１の研磨速度については、下記表３に、比較例１０を１００とした相対値として示す。実施例３４〜３６及び比較例１２〜１４の研磨速度については、比較例１２を１００とした相対値として示す。
[Measurement method of polishing rate]
The amount of polishing per unit time obtained by dividing the mass difference (g) of the substrate before and after polishing by the density of the substrate (2.46 g / cm 3 ), the surface area of the substrate (30.04 cm 2 ), and the polishing time (minutes). The polishing rate (μm / min) was calculated. The polishing rates of Examples 1 to 27 and Comparative Examples 1 to 5 are shown in Table 1 as relative values with Comparative Example 1 as 100. About the polishing rate of Examples 28-31 and Comparative Examples 6-9, it shows as a relative value which set Comparative Example 6 to 100 in the following Table 2. The polishing rates of Examples 32-33 and Comparative Examples 10-11 are shown in Table 3 below as relative values with Comparative Example 10 taken as 100. About the polishing rate of Examples 34-36 and Comparative Examples 12-14, it shows as a relative value which set Comparative Example 12 to 100.
〔表面粗さの測定方法〕
前述の研磨方法により得られた同じ研磨処理を施した基板１０枚のうち、無作為に３枚選択し、洗浄剤組成物を用いた洗浄を行い、それぞれの表面粗さを測定した。表面粗さは、各々の基板の両面を、以下に示す条件にて、ＡＦＭ（Ｄｉｇｉｔａｌ Ｉｎｓｔｒｕｍｅｎｔ ＮａｎｏＳｃｏｐｅ ＩＩＩａ Ｍｕｌｔｉ Ｍｏｄｅ ＡＦＭ）を用いて測定し、平均値を算出した。実施例１〜２７及び比較例１〜５の表面粗さ（ＡＦＭ−Ｒａ）については、下記表１に、比較例１を１００とした相対値として示す。実施例２８〜３１及び比較例６〜９の表面粗さ（ＡＦＭ−Ｒａ）については、下記表２に、比較例６を１００とした相対値として示す。実施例３２〜３３及び比較例１０〜１１の表面粗さ（ＡＦＭ−Ｒａ）については、下記表３に、比較例１０を１００とした相対値として示す。実施例３４〜３６及び比較例１２〜１４の表面粗さ（ＡＦＭ−Ｒａ）については、比較例１２を１００とした相対値として示す。
（ＡＦＭの測定条件）
Ｍｏｄｅ： Ｔａｐｐｉｎｇ ｍｏｄｅ
Ａｒｅａ： １×１μｍ
Ｓｃａｎ ｒａｔｅ： １．０Ｈｚ
Ｃａｎｔｉｌｅｖｅｒ： ＮＣＨ−１０Ｖ
Ｌｉｎｅ： ５１２×５１２
[Measurement method of surface roughness]
Of the 10 substrates subjected to the same polishing treatment obtained by the above polishing method, 3 were selected at random, washed with the cleaning composition, and the surface roughness was measured. The surface roughness was measured using AFM (Digital Instrument Nanoscope IIIa Multi Mode AFM) on both surfaces of each substrate under the following conditions, and the average value was calculated. About the surface roughness (AFM-Ra) of Examples 1-27 and Comparative Examples 1-5, it shows as a relative value which set Comparative Example 1 to 100 in the following Table 1. About the surface roughness (AFM-Ra) of Examples 28-31 and Comparative Examples 6-9, it shows as a relative value which set Comparative Example 6 to 100 in the following Table 2. About the surface roughness (AFM-Ra) of Examples 32-33 and Comparative Examples 10-11, it shows as a relative value which set Comparative Example 10 to 100 in the following Table 3. About the surface roughness (AFM-Ra) of Examples 34-36 and Comparative Examples 12-14, it shows as a relative value which set Comparative Example 12 to 100.
(AFM measurement conditions)
Mode: Tapping mode
Area: 1 × 1μm
Scan rate: 1.0 Hz
Cantilever: NCH-10V
Line: 512 × 512
上記表１〜４に示すとおり、実施例１〜３６の研磨液組成物は、比較例１〜１４に比べて優れた研磨速度が維持され、かつ、洗浄後の基板表面の表面粗さの悪化が抑制された。 As shown in the above Tables 1 to 4, the polishing liquid compositions of Examples 1 to 36 maintained an excellent polishing rate as compared with Comparative Examples 1 to 14, and deteriorated the surface roughness of the substrate surface after cleaning. Was suppressed.
Claims (11)
前記両性金属の水溶性金属塩が、亜鉛（Ｚｎ）、ガリウム（Ｇａ）及びこれらの組み合わせからなる群から選択される金属の水溶性金属塩である、ガラスハードディスク基板用研磨液組成物。 A polishing composition for a glass hard disk substrate obtained by mixing silica particles, a water-soluble metal salt of an amphoteric metal, and water ,
The polishing composition for glass hard disk substrates, wherein the water-soluble metal salt of the amphoteric metal is a water-soluble metal salt of a metal selected from the group consisting of zinc (Zn), gallium (Ga), and combinations thereof.
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