JP6654357B2 - Polishing pad, method for manufacturing polishing pad and polishing method - Google Patents
Polishing pad, method for manufacturing polishing pad and polishing method Download PDFInfo
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- JP6654357B2 JP6654357B2 JP2015076238A JP2015076238A JP6654357B2 JP 6654357 B2 JP6654357 B2 JP 6654357B2 JP 2015076238 A JP2015076238 A JP 2015076238A JP 2015076238 A JP2015076238 A JP 2015076238A JP 6654357 B2 JP6654357 B2 JP 6654357B2
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- nonwoven fabric
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- 238000005498 polishing Methods 0.000 title claims description 191
- 238000000034 method Methods 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229920005989 resin Polymers 0.000 claims description 191
- 239000011347 resin Substances 0.000 claims description 191
- 239000004745 nonwoven fabric Substances 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 52
- 238000005470 impregnation Methods 0.000 claims description 44
- 238000007654 immersion Methods 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 230000015271 coagulation Effects 0.000 claims description 20
- 238000005345 coagulation Methods 0.000 claims description 20
- 230000006835 compression Effects 0.000 claims description 20
- 238000007906 compression Methods 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000035699 permeability Effects 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims 2
- 239000000523 sample Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 21
- 230000014759 maintenance of location Effects 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 239000007800 oxidant agent Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 239000012085 test solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- -1 amine compound Chemical class 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- PIODVRGFECLUSY-UHFFFAOYSA-N 2,6-diamino-4-[2-(3,5-diamino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C(N)=C(O)C(N)=CC=1C(C)(C)C1=CC(N)=C(O)C(N)=C1 PIODVRGFECLUSY-UHFFFAOYSA-N 0.000 description 1
- KIAWNCIDEJNMPR-UHFFFAOYSA-N 2,6-diamino-4-methylphenol Chemical compound CC1=CC(N)=C(O)C(N)=C1 KIAWNCIDEJNMPR-UHFFFAOYSA-N 0.000 description 1
- WGFYAPLOOOHKPS-UHFFFAOYSA-N 2-(butan-2-ylamino)-4-[2-[3-(butan-2-ylamino)-4-hydroxyphenyl]propan-2-yl]phenol Chemical compound C1=C(O)C(NC(C)CC)=CC(C(C)(C)C=2C=C(NC(C)CC)C(O)=CC=2)=C1 WGFYAPLOOOHKPS-UHFFFAOYSA-N 0.000 description 1
- DPYAEAOFIKXXMM-UHFFFAOYSA-N 2-(hexan-2-ylamino)-4-[2-[3-(hexan-2-ylamino)-4-hydroxyphenyl]propan-2-yl]phenol Chemical compound CC(CCCC)NC=1C=C(C=CC=1O)C(C)(C)C1=CC(=C(C=C1)O)NC(CCCC)C DPYAEAOFIKXXMM-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- GNBPEYCZELNJMS-UHFFFAOYSA-N 2-methylbutane-1,3-diol Chemical compound CC(O)C(C)CO GNBPEYCZELNJMS-UHFFFAOYSA-N 0.000 description 1
- VFUBIRVDKSDPRZ-UHFFFAOYSA-N 2-methylsulfanylbenzene-1,3-diamine Chemical compound CSC1=C(N)C=CC=C1N VFUBIRVDKSDPRZ-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- HJJZIMFAIMUSBW-UHFFFAOYSA-N 3-methylbutane-1,2-diol Chemical compound CC(C)C(O)CO HJJZIMFAIMUSBW-UHFFFAOYSA-N 0.000 description 1
- OGLLAZUAZSIDFE-UHFFFAOYSA-N 3-methylpentane-1,2-diol Chemical compound CCC(C)C(O)CO OGLLAZUAZSIDFE-UHFFFAOYSA-N 0.000 description 1
- RLWWHEFTJSHFRN-UHFFFAOYSA-N 3-methylpentane-2,3-diol Chemical compound CCC(C)(O)C(C)O RLWWHEFTJSHFRN-UHFFFAOYSA-N 0.000 description 1
- RSXKLLMAPPDZJC-UHFFFAOYSA-N 4-[2-[4-hydroxy-3-(propan-2-ylamino)phenyl]propan-2-yl]-2-(propan-2-ylamino)phenol Chemical compound C1=C(O)C(NC(C)C)=CC(C(C)(C)C=2C=C(NC(C)C)C(O)=CC=2)=C1 RSXKLLMAPPDZJC-UHFFFAOYSA-N 0.000 description 1
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 1
- SPBDXSGPUHCETR-JFUDTMANSA-N 8883yp2r6d Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1[C@@H](OC)C[C@H](O[C@@H]2C(=C/C[C@@H]3C[C@@H](C[C@@]4(O[C@@H]([C@@H](C)CC4)C(C)C)O3)OC(=O)[C@@H]3C=C(C)[C@@H](O)[C@H]4OC\C([C@@]34O)=C/C=C/[C@@H]2C)/C)O[C@H]1C.C1C[C@H](C)[C@@H]([C@@H](C)CC)O[C@@]21O[C@H](C\C=C(C)\[C@@H](O[C@@H]1O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C1)[C@@H](C)\C=C\C=C/1[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\1)O)C[C@H]4C2 SPBDXSGPUHCETR-JFUDTMANSA-N 0.000 description 1
- 241001112258 Moca Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Description
本発明は、研磨パッド、研磨パッドの製造方法及び研磨方法に関する。 The present invention relates to a polishing pad, a method for manufacturing a polishing pad, and a polishing method.
現在、パワーデバイスとして、ＳｉＣやＧａＮ等の半導体を用いたものが知られている。これらの半導体基板を実用するに際して、化学機械研磨（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ：ＣＭＰ）技術が用いられる。 At present, devices using semiconductors such as SiC and GaN are known as power devices. In practical use of these semiconductor substrates, a chemical mechanical polishing (CMP) technique is used.
上述した半導体は、一般的に硬度が高く、耐腐食性に優れるため、ＣＭＰを行うにあたっては、研磨パッドと、研磨液として過マンガン酸カリウム等の強酸化剤を含む溶液とが併用されることがあり、かかる研磨パッドとしては、不織布にポリウレタン樹脂を含浸したパッド等が用いられる（例えば、特許文献１，２参照）。 Since the above-mentioned semiconductors generally have high hardness and excellent corrosion resistance, when performing CMP, a polishing pad and a solution containing a strong oxidizing agent such as potassium permanganate as a polishing solution are used in combination. As such a polishing pad, a pad or the like obtained by impregnating a nonwoven fabric with a polyurethane resin is used (for example, see Patent Documents 1 and 2).
しかしながら、特許文献１，２に記載の技術において用いられる研磨パッドは、過マンガン酸カリウムを含む研磨液に対する耐性がまだ不十分である。すなわち、かかる研磨パッドは、上記研磨液に長時間曝露した場合の劣化を避けることが困難であり、十分に長い寿命が得られないという欠点を有している。 However, the polishing pads used in the techniques described in Patent Literatures 1 and 2 still have insufficient resistance to a polishing liquid containing potassium permanganate. That is, such a polishing pad has a disadvantage that it is difficult to avoid deterioration when exposed to the polishing liquid for a long time, and a sufficiently long life cannot be obtained.
本発明は、上記事情に鑑みてなされたものであり、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分に長い寿命を確保できる研磨パッド、研磨パッドの製造方法及び研磨方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, has excellent chemical resistance, and can ensure a sufficiently long life even when subjected to polishing using a strong oxidizing agent. The aim is to provide a method.
本発明者らは、鋭意研究を重ねた結果、特定の構成及び物性を有する研磨パッドが上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have conducted intensive studies and as a result, found that a polishing pad having a specific configuration and physical properties can solve the above-mentioned problems, and have completed the present invention.
すなわち、本発明は、以下の態様を包含する。
［１］
不織布と、樹脂と、を有する研磨パッドであって、
前記研磨パッドの引張強度に対する、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整した溶液に前記研磨パッドを２５℃で４８時間浸漬したときの前記研磨パッドの引張強度の比が、４５％以上である、研磨パッド。
［２］
前記樹脂が、第１の樹脂と、当該第１の樹脂とは異なる第２の樹脂と、を含み、
前記第２の樹脂が、ＮＣＯ当量５００以下のウレタンプレポリマーと硬化剤との反応物である、［１］に記載の研磨パッド。
［３］
前記樹脂が、第１の樹脂と、当該第１の樹脂とは異なる第２の樹脂と、を含み、
前記不織布、前記第１の樹脂及び前記第２の樹脂の合計に対して、前記不織布の含有量が１０〜５０質量％であり、かつ、前記第１の樹脂の含有量が１０〜６０質量％であり、かつ、前記第２の樹脂の含有量が１０〜７０質量％である、［１］又は［２］に記載の研磨パッド。
［４］
通気度が、６．０ｃｃ／ｃｍ2／秒以上である、［１］〜［３］のいずれかに記載の研磨パッド。
［５］
圧縮率が、０．５〜２０％である、［１］〜［４］のいずれかに記載の研磨パッド。
［６］
圧縮弾性率が、５０〜９８％である、［１］〜［５］のいずれかに記載の研磨パッド。
［７］
Ａ硬度が、５０〜９０°である、［１］〜［６］のいずれかに記載の研磨パッド。
［８］
前記不織布に第１の樹脂を含む樹脂溶液を含浸させ、湿式凝固を行うことにより、樹脂含浸不織布を得る１次含浸工程と、
前記樹脂含浸不織布を、前記第１の樹脂が可溶な溶媒に浸漬する浸漬工程と、
前記浸漬工程の後の前記樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと硬化剤とを含む溶液に含浸する２次含浸工程と、
を有する方法から得られる、［１］〜［７］のいずれかに記載の研磨パッド。
［９］
不織布に第１の樹脂を含む樹脂溶液を含浸させ、湿式凝固を行うことにより、樹脂含浸不織布を得る１次含浸工程と、
前記樹脂含浸不織布を、前記第１の樹脂が可溶な溶媒に浸漬する浸漬工程と、
前記浸漬工程の後の前記樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと硬化剤とを含む溶液に含浸する２次含浸工程と、
を有する、研磨パッドの製造方法。
［１０］
前記第１の樹脂が、Ｎ，Ｎ−ジメチルホルムアルデヒド、ジメチルアセトアミド及びジメチルスルホキシドからなる群より選ばれる１種以上の溶媒に可溶である、［９］に記載の研磨パッドの製造方法。
［１１］
前記溶媒が、Ｎ，Ｎ−ジメチルホルムアルデヒド、ジメチルアセトアミド及びジメチルスルホキシドからなる群より選ばれる１種以上の溶媒を含む、［９］又は［１０］に記載の研磨パッドの製造方法。
［１２］
化合物半導体ウェハを、過マンガン酸カリウムを含む溶液に接触させながら［１］〜［８］のいずれかに記載の研磨パッドにより研磨する、研磨方法。
That is, the present invention includes the following embodiments.
[1]
A polishing pad having a nonwoven fabric and a resin,
The ratio of the tensile strength of the polishing pad when the polishing pad is immersed in a solution adjusted to pH 2 by adding nitric acid to a 3% by mass aqueous solution of potassium permanganate at 25 ° C. for 48 hours with respect to the tensile strength of the polishing pad is , 45% or more.
[2]
The resin includes a first resin and a second resin different from the first resin,
The polishing pad according to [1], wherein the second resin is a reaction product of a urethane prepolymer having an NCO equivalent of 500 or less and a curing agent.
[3]
The resin includes a first resin and a second resin different from the first resin,
The content of the nonwoven fabric is 10 to 50% by mass, and the content of the first resin is 10 to 60% by mass, based on the total of the nonwoven fabric, the first resin, and the second resin. The polishing pad according to [1] or [2], wherein the content of the second resin is 10 to 70% by mass.
[4]
The polishing pad according to any of [1] to [3], wherein the polishing pad has an air permeability of 6.0 cc / cm 2 / sec or more.
[5]
The polishing pad according to any one of [1] to [4], wherein the compression ratio is 0.5 to 20%.
[6]
The polishing pad according to any one of [1] to [5], wherein the compression elastic modulus is 50 to 98%.
[7]
The polishing pad according to any one of [1] to [6], wherein the A hardness is 50 to 90 °.
[8]
A primary impregnation step of impregnating the nonwoven fabric with a resin solution containing a first resin and performing wet coagulation to obtain a resin-impregnated nonwoven fabric;
An immersion step of immersing the resin-impregnated nonwoven fabric in a solvent in which the first resin is soluble;
A second impregnation step of impregnating the resin-impregnated nonwoven fabric after the immersion step with a solution containing a urethane prepolymer having an NCO equivalent of 500 or less and a curing agent;
The polishing pad according to any one of [1] to [7], obtained from the method having:
[9]
A primary impregnation step of impregnating the nonwoven fabric with a resin solution containing the first resin and performing wet coagulation to obtain a resin-impregnated nonwoven fabric;
An immersion step of immersing the resin-impregnated nonwoven fabric in a solvent in which the first resin is soluble;
A second impregnation step of impregnating the resin-impregnated nonwoven fabric after the immersion step with a solution containing a urethane prepolymer having an NCO equivalent of 500 or less and a curing agent;
A method for producing a polishing pad, comprising:
[10]
The method for producing a polishing pad according to [9], wherein the first resin is soluble in one or more solvents selected from the group consisting of N, N-dimethylformaldehyde, dimethylacetamide, and dimethylsulfoxide.
[11]
The method for producing a polishing pad according to [9] or [10], wherein the solvent includes at least one solvent selected from the group consisting of N, N-dimethylformaldehyde, dimethylacetamide, and dimethylsulfoxide.
[12]
A polishing method, wherein the compound semiconductor wafer is polished with the polishing pad according to any one of [1] to [8] while being brought into contact with a solution containing potassium permanganate.
本発明によれば、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分に長い寿命を確保できる研磨パッド、研磨パッドの製造方法及び研磨方法を提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the polishing pad which is excellent in chemical resistance, can ensure a sufficiently long life even when it is subjected to polishing using a strong oxidizing agent, a method for manufacturing the polishing pad, and a polishing method. .
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について詳細に説明する。なお、本実施形態は、本発明を説明するための例示であり、本発明は以下の実施形態のみに限定されない。 Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. Note that the present embodiment is an exemplification for describing the present invention, and the present invention is not limited to only the following embodiment.
［研磨パッド］
本実施形態の研磨パッドは、不織布と、樹脂とを有する研磨パッドであって、当該研磨パッドの引張強度に対する、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整した溶液（以下、単に「試験液」ともいう。）に当該研磨パッドを２５℃で４８時間浸漬したときの当該研磨パッドの引張強度の比（以下、単に「引張強度保持率」ともいう。）が、４５％以上である。このように構成されているため、本実施形態の研磨パッドは、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分に長い寿命を確保することができる。
[Polishing pad]
The polishing pad of the present embodiment is a polishing pad having a nonwoven fabric and a resin, and a solution prepared by adding nitric acid to a 3% by mass aqueous solution of potassium permanganate with respect to the tensile strength of the polishing pad to adjust the pH to 2 (hereinafter, referred to as a polishing pad). , Simply referred to as “test liquid”) when the polishing pad is immersed at 25 ° C. for 48 hours in a tensile strength ratio of 45% (hereinafter, simply referred to as “tensile strength retention”). That is all. With such a configuration, the polishing pad of the present embodiment has excellent chemical resistance, and can secure a sufficiently long life even when subjected to polishing using a strong oxidizing agent.
本実施形態における引張強度保持率の測定方法について説明する。まず、試験液に浸漬する前の研磨パッドの引張強度（ａ）を測定する。上記引張強度は、引張万能試験機（「テンシロン」、Ａ＆Ｄ社製、ＲＴＣ−１２１０Ａ）を用い、日本工業規格（ＪＩＳ Ｋ ６５５０）に準拠して測定することができる。次いで、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整し、試験液とする。このように調製された試験液に、研磨パッドを２５℃で４８時間浸漬する。なお、浸漬の開始から２４時間経過後に試験液及び研磨パッドを収容した容器を振とうする。浸漬の開始から４８時間経過後、研磨パッドを試験液から取り出し、流水洗浄し、５分間の超音波洗浄を行い、さらに流水洗浄し、キッチンペーパーで加圧しながら残留した液を拭き取り、上記と同様にして研磨パッドの引張強度（ｂ）を測定する。引張強度保持率は、引張強度（ａ）と引張強度（ｂ）の値から、以下の式で算出する。
引張強度保持率＝引張強度（ｂ）／引張強度（ａ）×１００ ％
A method for measuring the tensile strength retention in the present embodiment will be described. First, the tensile strength (a) of the polishing pad before immersion in the test solution is measured. The tensile strength can be measured using a tensile universal tester (“Tensilon”, manufactured by A & D, RTC-1210A) in accordance with Japanese Industrial Standards (JIS K 6550). Next, nitric acid is added to a 3% by mass aqueous solution of potassium permanganate to adjust the pH to 2 to prepare a test solution. The polishing pad is immersed in the test liquid thus prepared at 25 ° C. for 48 hours. After 24 hours from the start of the immersion, the container containing the test liquid and the polishing pad is shaken. After 48 hours from the start of immersion, the polishing pad is taken out of the test solution, washed with running water, subjected to ultrasonic cleaning for 5 minutes, further washed with running water, and wiped off the remaining solution while applying pressure with kitchen paper, and the same as above. Then, the tensile strength (b) of the polishing pad is measured. The tensile strength retention is calculated from the values of the tensile strength (a) and the tensile strength (b) by the following formula.
Tensile strength retention = tensile strength (b) / tensile strength (a) × 100%
本実施形態の研磨パッドは、上述のようにして得られる引張強度保持率の値が４５％以上となるように構成されている。引張強度保持率が４５％以上であることから、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分に長い寿命を確保できるものと評価できる。耐薬品性の観点から、引張強度保持率は、好ましくは５０％以上であり、より好ましくは５５％以上である。引張強度保持率を上記の範囲に調整するには、例えば、後述の好ましい製造方法を採用すればよい。後述の好ましい製造方法において、例えば、第２の樹脂のＮＣＯ当量を下げることにより、引張強度保持率は高くなる傾向にある。 The polishing pad of the present embodiment is configured such that the value of the tensile strength retention obtained as described above is 45% or more. Since the tensile strength retention is 45% or more, it can be evaluated as having excellent chemical resistance and ensuring a sufficiently long life even when subjected to polishing using a strong oxidizing agent. From the viewpoint of chemical resistance, the tensile strength retention is preferably 50% or more, and more preferably 55% or more. In order to adjust the tensile strength retention to the above range, for example, a preferable manufacturing method described below may be adopted. In a preferred production method described below, for example, by lowering the NCO equivalent of the second resin, the tensile strength retention tends to increase.
研磨パッドの通気度は、スラリーの保持性の観点から、６．０ｃｃ／ｃｍ2／秒以上であると好ましく、７．０〜３０ｃｃ／ｃｍ2／秒であるとより好ましい。通気度は、フラジール形試験機（例えば、安田精機社製の織布通気度試験機）を用いて、日本工業規格（ＪＩＳ Ｌ １０９６）に準拠して測定され、５枚の試料片の相加平均により求められる。通気度は、例えば、後述の好ましい製造方法において、１次含浸工程と２次含浸工程の間に第１の樹脂が可溶な溶媒に浸漬する浸漬工程を採用することにより、高くなる傾向にある。 The air permeability of the polishing pad is preferably 6.0 cc / cm 2 / sec or more, more preferably 7.0 to 30 cc / cm 2 / sec, from the viewpoint of slurry retention. The air permeability is measured using a Frazier type tester (for example, a woven fabric air permeability tester manufactured by Yasuda Seiki Co., Ltd.) in accordance with Japanese Industrial Standards (JIS L 1096). Determined by the average. The air permeability tends to increase, for example, by adopting an immersion step of immersing in a solvent in which the first resin is soluble between the primary impregnation step and the secondary impregnation step in a preferred production method described later. .
研磨パッドの圧縮率は、非研磨物（以下、単に「ワーク」ともいう。）との良好な密着性を確保する観点及び研磨パッドの変形防止の観点から、０．５％〜２０％であると好ましく、２％〜８％であるとより好ましい。圧縮率は日本工業規格（ＪＩＳ Ｌ １０２１）に準拠して、ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を用いて求められる。具体的には、初荷重で３０秒間加圧した後の厚さｔ0を測定し、次に最終圧力の下で５分間放置後の厚さｔ1を測定する。これらから、圧縮率を下記式により算出する。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とする。
圧縮率（％）＝（ｔ0−ｔ1）／ｔ0×１００
圧縮率は、例えば、後述の好ましい製造方法において、得られる研磨パッドの密度が低くなるように調整することにより、高くなる傾向にある。
The compression ratio of the polishing pad is 0.5% to 20% from the viewpoint of ensuring good adhesion to a non-polishing object (hereinafter, also simply referred to as "work") and preventing deformation of the polishing pad. And more preferably 2% to 8%. The compression ratio is determined using a shopper type thickness measuring device (pressing surface: a circle having a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS L 1021). Specifically, the thickness t 0 after pressing for 30 seconds with the initial load is measured, and then the thickness t 1 after standing for 5 minutes under the final pressure. From these, the compression ratio is calculated by the following equation. At this time, the initial load is 100 g / cm 2 and the final load is 1120 g / cm 2 .
Compression rate (%) = (t 0 −t 1 ) / t 0 × 100
The compression ratio tends to increase, for example, by adjusting the density of the obtained polishing pad to be low in a preferable manufacturing method described later.
研磨パッドの圧縮弾性率は、ワークとの良好な密着性を確保する観点及び研磨パッドの変形防止の観点から、５０％〜９８％であると好ましく、６０％〜９５％であるとより好ましい。圧縮弾性率は、日本工業規格（ＪＩＳ Ｌ １０２１）に準拠し、ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を使用して求めることができる。具体的には、無荷重状態から初荷重を３０秒間かけた後の厚さｔ0を測定し、次に、厚さｔ0の状態から最終荷重を３０秒間かけた後の厚さｔ1を測定する。次に、厚さｔ1の状態から全ての荷重を除き、５分間放置（無荷重状態とした）後、再び初荷重を３０秒間かけた後の厚さｔ0’を測定する。これらから、圧縮弾性率を下記式により算出する。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とする。
圧縮弾性率（％）＝１００×（ｔ0’−ｔ1）／（ｔ0−ｔ1）
圧縮弾性率は、例えば、後述の好ましい製造方法において、第２の樹脂の含有率を高くすることにより、高くなる傾向にある。
The compression elastic modulus of the polishing pad is preferably from 50% to 98%, more preferably from 60% to 95%, from the viewpoint of securing good adhesion to the work and preventing deformation of the polishing pad. The compression modulus can be determined using a Shopper type thickness measuring instrument (pressing surface: a circle having a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS L 1021). Specifically, the thickness t 0 after applying the initial load for 30 seconds from the no-load state is measured, and then the thickness t 1 after applying the final load for 30 seconds from the state of the thickness t 0. Measure. Next, after removing all the loads from the state of the thickness t 1 , the sample is left for 5 minutes (no load state), and the thickness t 0 ′ after the initial load is applied again for 30 seconds is measured. From these, the compression modulus is calculated by the following equation. At this time, the initial load is 100 g / cm 2 and the final load is 1120 g / cm 2 .
Compression modulus (%) = 100 × (t 0 ′ −t 1 ) / (t 0 −t 1 )
The compression elastic modulus tends to increase, for example, by increasing the content of the second resin in a preferable manufacturing method described later.
研磨パッドのＡ硬度は、特に限定されないが、ワークとの良好な密着性を確保する観点及び研磨パッドの変形防止の観点から、５０°〜９０°であると好ましく、６０°〜８５°であるとより好ましい。Ａ硬度は、バネを介して厚さ４．５ｍｍ以上の試験片（研磨パッドが４．５ｍｍ未満の厚さである場合は、厚さが４．５ｍｍ以上になるまで研磨パッドを重ねて試験片を得る。）表面に押針（測定子）を押し付け３０秒後の押針の押し込み深さから求められる。これを３回行って相加平均からＡ硬度が求められる。Ａ硬度は、例えば、後述の好ましい製造方法において、第２の樹脂の含有率を高くすることにより、高くなる傾向にある。 The A hardness of the polishing pad is not particularly limited, but is preferably 50 ° to 90 °, and more preferably 60 ° to 85 °, from the viewpoint of securing good adhesion to the work and preventing deformation of the polishing pad. And more preferred. The A hardness is measured using a test piece having a thickness of 4.5 mm or more via a spring (when the polishing pad has a thickness of less than 4.5 mm, the polishing pad is stacked until the thickness becomes 4.5 mm or more). This is determined from the depth of pressing of the indenter 30 seconds after the indenter (probe) has been pressed against the surface. By performing this three times, the A hardness is determined from the arithmetic average. The A hardness tends to increase, for example, by increasing the content of the second resin in a preferable manufacturing method described later.
研磨パッドの密度は、研磨パッドの永久歪みを抑制する観点、ワークとの接触面積の増大による作用点の圧力低下を抑制する観点、及びスラリー保持性を高める観点から、０．３５〜０．６０であると好ましく、０．３５〜０．５０であるとより好ましい。密度は、日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して測定される。具体的には、厚さの測定で用いたのと同様の試料片の質量を自動天秤で測定後、下記式により密度を算出し、３枚の試料片の相加平均を求める。
密度（ｇ／ｃｍ3）＝質量（ｇ）／（１０（ｃｍ）×１０（ｃｍ）×試料片の厚さ（ｃｍ））
密度は、例えば、後述の好ましい製造方法において、不織布に対する第１の樹脂及び第２の樹脂の含有率を高くすることにより、高くなる傾向にある。
The density of the polishing pad is from 0.35 to 0.60 from the viewpoint of suppressing permanent deformation of the polishing pad, suppressing the pressure drop at the action point due to an increase in the contact area with the work, and increasing the slurry retention. And more preferably 0.35 to 0.50. The density is measured according to Japanese Industrial Standard (JIS K 6505). Specifically, after measuring the mass of a sample piece similar to that used in the thickness measurement with an automatic balance, the density is calculated by the following equation, and the arithmetic mean of three sample pieces is obtained.
Density (g / cm 3 ) = mass (g) / (10 (cm) × 10 (cm) × thickness of sample (cm))
The density tends to increase, for example, by increasing the content of the first resin and the second resin in the nonwoven fabric in a preferable manufacturing method described later.
本実施形態における不織布は、特に限定されるものではなく、種々公知のものを採用できる。上記不織布の例としては、ポリアミド系、ポリエステル系等の不織布を挙げることができる。また、不織布を得る際に繊維を交絡させる方法としても特に限定されず、例えば、ニードルパンチであってもよく、水流交絡であってもよい。不織布は上述した中から１種を単独で用いることができ、２種以上を組み合わせて用いることもできる。 The nonwoven fabric in the present embodiment is not particularly limited, and various known nonwoven fabrics can be adopted. Examples of the nonwoven fabric include polyamide and polyester nonwoven fabrics. Further, the method of entanglement of the fibers when obtaining the nonwoven fabric is not particularly limited, and may be, for example, a needle punch or a hydroentanglement. One of the nonwoven fabrics described above can be used alone, or two or more can be used in combination.
本実施形態における不織布の厚さは、特に限定されないが、研磨パッド厚さの観点から、２〜５ｍｍと好ましい。 The thickness of the nonwoven fabric in the present embodiment is not particularly limited, but is preferably 2 to 5 mm from the viewpoint of the polishing pad thickness.
本実施形態における不織布の繊度は、特に限定されないが、研磨時のスクラッチ発生減少の観点から、２〜６ｄであると好ましい。 The fineness of the nonwoven fabric in the present embodiment is not particularly limited, but is preferably 2 to 6 d from the viewpoint of reducing the occurrence of scratches during polishing.
本実施形態における不織布の目付けは、特に限定されないが、研磨パッド密度や不織布と樹脂の比率の観点から、２００〜１０００ｇ／ｍ2であると好ましい。 The basis weight of the nonwoven fabric in the present embodiment is not particularly limited, but is preferably 200 to 1000 g / m 2 from the viewpoint of the polishing pad density and the ratio of the nonwoven fabric to the resin.
本実施形態における樹脂は、研磨パッドに備えられ得るものであれば特に限定されず、従来公知のものであってもよい。本実施形態においては、上記樹脂が、第１の樹脂と、第１の樹脂とは異なる第２の樹脂とを含むことが好ましい。 The resin in the present embodiment is not particularly limited as long as it can be provided on the polishing pad, and may be a conventionally known resin. In the present embodiment, the resin preferably includes a first resin and a second resin different from the first resin.
上記第１の樹脂としては、いわゆる湿式含浸により不織布に含浸できるものであれば特に限定されず、種々公知のものを適用できる。そのような樹脂（以下、単に「湿式樹脂」ともいう。）の例としては、以下に限定されないが、ポリウレタン、ポリウレタンポリウレア等のポリウレタン系、ポリアクリレート、ポリアクリロニトリル等のアクリル系、ポリ塩化ビニル、ポリ酢酸ビニル、ポリフッ化ビニリデン等のビニル系、ポリサルホン、ポリエーテルサルホン等のポリサルホン系、アセチル化セルロース、ブチリル化セルロース等のアシル化セルロース系、ポリアミド系及びポリスチレン系が挙げられる。ポリウレタン樹脂としては、以下に限定されないが、例えば、ポリエステル系ポリウレタン樹脂、ポリエーテル系ポリウレタン樹脂、及びポリカーボネート系ポリウレタン樹脂が挙げられる。樹脂の１００％モジュラスは、５ＭＰａ〜３０ＭＰａであると好ましく、１０ＭＰａ〜２０ＭＰａであるとより好ましい。樹脂の１００％モジュラスは、その樹脂からなるシートを１００％伸ばしたとき、すなわち元の長さの２倍に伸ばしたとき、に掛かる荷重を単位面積で割った値である。 The first resin is not particularly limited as long as it can impregnate the nonwoven fabric by so-called wet impregnation, and various known resins can be applied. Examples of such a resin (hereinafter, also simply referred to as “wet resin”) include, but are not limited to, polyurethane, polyurethane such as polyurethane polyurea, acrylic such as polyacrylate and polyacrylonitrile, polyvinyl chloride, and the like. Examples thereof include vinyls such as polyvinyl acetate and polyvinylidene fluoride, polysulfones such as polysulfone and polyethersulfone, acylated celluloses such as acetylated cellulose and butyrylated cellulose, polyamides and polystyrenes. Examples of the polyurethane resin include, but are not limited to, a polyester-based polyurethane resin, a polyether-based polyurethane resin, and a polycarbonate-based polyurethane resin. The 100% modulus of the resin is preferably from 5 MPa to 30 MPa, more preferably from 10 MPa to 20 MPa. The 100% modulus of the resin is a value obtained by dividing the load applied when the sheet made of the resin is stretched by 100%, that is, when the sheet is stretched to twice the original length, by the unit area.
上記第２の樹脂としては、いわゆる乾式含浸により不織布に含浸できるものであれば特に限定されず、種々公知のものを適用できる。第２の樹脂（以下、単に「乾式樹脂」ともいう。）は、例えば、末端にイソシアネート基を有するウレタンプレポリマーと、硬化剤であるアミン化合物及び／又は多価アルコール化合物と、それらを溶解可能な溶媒とを含む溶液を用い、乾式法によって得ることができる。ここで、ウレタンプレポリマーとしては特に限定されず、例えば、ヘキサメチレンジイソシアネートとヘキサントリオールとの付加物、２，４−トリレンジイソシアネートとプレンツカテコールとの付加物、トリレンジイソシアネートとヘキサントリオールとの付加物、トリレンジイソシアネートとトリメチロールプロパンとの付加物、キシリレンジイソシアネートとトリメチロールプロパンとの付加物、ヘキサメチレンジイソシアネートとトリメチロールプロパンとの付加物、及びイソシアヌル酸とヘキサメチレンジイソシアネートとの付加物が挙げられる。また、硬化剤のうち、アミン化合物としては、例えば、３，３’−ジクロロ−４，４’−ジアミノジフェニルメタン、４−メチル−２，６−ビス（メチルチオ）−１，３−ベンゼンジアミン、２−メチル−４，６−ビス（メチルチオ）−１，３−ベンゼンジアミン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、２，２−ビス［３−（イソプロピルアミノ）−４−ヒドロキシフェニル］プロパン、２，２−ビス［３−（１−メチルプロピルアミノ）−４−ヒドロキシフェニル］プロパン、２，２−ビス［３−（１−メチルペンチルアミノ）−４−ヒドロキシフェニル］プロパン、２，２−ビス（３，５−ジアミノ−４−ヒドロキシフェニル）プロパン、２，６−ジアミノ−４−メチルフェノール、トリメチルエチレンビス−４−アミノベンゾネート、及びポリテトラメチレンオキサイド−ｄｉ−ｐ−アミノベンゾネートが挙げられる。多価アルコール化合物としては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリメチレングリコール、テトラエチレングリコール、トリエチレングリコール、ジプロピレングリコール、１，４−ブタンジオール、１，３−ブタンジオール、２，３−ブタンジオール、１，２−ブタンジオール、３−メチル−１，２−ブタンジオール、１，２−ペンタンジオール、１，４−ペンタンジオール、２，４−ペンタンジオール、２，３−ジメチルトリメチレングリコール、テトラメチレングリコール、３−メチル−４，３−ペンタンジオール、３−メチル−４，５−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、１，６−ヘキサンジオール、１，５−ヘキサンジオール、１，４−ヘキサンジオール、２，５−ヘキサンジオール、１，４−シクロヘキサンジメタノール、ネオペンチルグリコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、トリメチロールメタンが挙げられる。これらのウレタンプレポリマー及び硬化剤は、それぞれ、１種を単独で又は２種以上を組み合わせて用いられる。溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ−ジメチルホルムアミド、及びＮ，Ｎ−ジメチルアセトアミドが挙げられる。 The second resin is not particularly limited as long as it can impregnate the nonwoven fabric by so-called dry impregnation, and various known resins can be applied. The second resin (hereinafter, also simply referred to as “dry resin”) is, for example, a urethane prepolymer having an isocyanate group at a terminal, an amine compound and / or a polyhydric alcohol compound as a curing agent, and capable of dissolving them. It can be obtained by a dry method using a solution containing a suitable solvent. Here, the urethane prepolymer is not particularly limited, for example, an adduct of hexamethylene diisocyanate and hexanetriol, an adduct of 2,4-tolylene diisocyanate and prenzcatechol, and an adduct of tolylene diisocyanate and hexanetriol. Adducts, adducts of tolylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, adducts of hexamethylene diisocyanate and trimethylolpropane, and adducts of isocyanuric acid and hexamethylene diisocyanate Is mentioned. Among the curing agents, examples of the amine compound include 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4-methyl-2,6-bis (methylthio) -1,3-benzenediamine, -Methyl-4,6-bis (methylthio) -1,3-benzenediamine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis [3- (isopropylamino) -4 -Hydroxyphenyl] propane, 2,2-bis [3- (1-methylpropylamino) -4-hydroxyphenyl] propane, 2,2-bis [3- (1-methylpentylamino) -4-hydroxyphenyl] Propane, 2,2-bis (3,5-diamino-4-hydroxyphenyl) propane, 2,6-diamino-4-methylphenol, trimethylethylenebis 4-amino-benzo sulfonates, and polytetramethylene oxide -di-p-aminobenzoyl titanate and the like. Examples of the polyhydric alcohol compound include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, and 2,3. -Butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene Glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexyl Njioru, 2,5-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerol, trimethylol propane, trimethylol ethane, trimethylol methane. Each of these urethane prepolymers and curing agents is used alone or in combination of two or more. Although it does not specifically limit as a solvent, For example, N, N-dimethylformamide and N, N-dimethylacetamide are mentioned.
本実施形態の研磨パッドにおいて、より良好な耐薬品性を付与する観点から、上記樹脂が、第１の樹脂と、当該第１の樹脂とは異なる第２の樹脂とを含み、当該第２の樹脂が、ＮＣＯ当量５００以下のウレタンプレポリマーと硬化剤との反応物であることが好ましい。同様の観点から、上記ＮＣＯ当量は４５０以下であることがより好ましく、２００以上であることが好ましい。なお、本明細書中において、「ＮＣＯ当量」とは、該当樹脂溶液中のウレタンプレポリマーの平均ＮＣＯ当量を意味する。また、ＮＣＯ当量は周知の方法で測定でき、例えばＪＩＳ Ｋ ７３０１に準拠して測定することができる。 In the polishing pad of the present embodiment, from the viewpoint of imparting better chemical resistance, the resin includes a first resin and a second resin different from the first resin; The resin is preferably a reaction product of a urethane prepolymer having an NCO equivalent of 500 or less and a curing agent. From the same viewpoint, the NCO equivalent is more preferably 450 or less, and more preferably 200 or more. In addition, in this specification, "NCO equivalent" means the average NCO equivalent of the urethane prepolymer in the corresponding resin solution. The NCO equivalent can be measured by a known method, for example, in accordance with JIS K7301.
本実施形態の研磨パッドにおいて、研磨中の引張強度保持の観点から、不織布、第１の樹脂及び第２の樹脂の合計に対して、不織布の含有量が１０〜５０質量％であり、かつ、第１の樹脂の含有量が１０〜６０質量％であり、かつ、第２の樹脂の含有量が１０〜７０質量％であることが好ましい。同様の観点から、不織布の含有量が２０〜４０質量％であり、かつ、第１の樹脂の含有量が２０〜５０質量％であり、かつ、第２の樹脂の含有量が２０〜６０質量％であることがより好ましい。研磨パッドにおける不織布、第１の樹脂及び第２の樹脂の各含有量は、極性溶媒への溶解性(極性)の差や、アミン分解性の差を利用して、溶出する成分の質量又は残渣の質量より、求めることができる。また、後述する１次含浸工程後の研磨パッドの密度と、後述する浸漬工程後の研磨パッドの密度と、後述する２次含浸工程後の研磨パッドの密度と、をそれぞれ測定し、密度差から算出することもできる。なお、密度の測定は上記と同様にして測定できる。 In the polishing pad of the present embodiment, the content of the nonwoven fabric is 10 to 50% by mass with respect to the total of the nonwoven fabric, the first resin, and the second resin, from the viewpoint of maintaining tensile strength during polishing, and It is preferable that the content of the first resin is 10 to 60% by mass and the content of the second resin is 10 to 70% by mass. From the same viewpoint, the content of the nonwoven fabric is 20 to 40% by mass, the content of the first resin is 20 to 50% by mass, and the content of the second resin is 20 to 60% by mass. % Is more preferable. Each content of the nonwoven fabric, the first resin, and the second resin in the polishing pad is determined based on the difference in solubility (polarity) in a polar solvent and the difference in amine decomposability. Can be determined from the mass of Further, the density of the polishing pad after the primary impregnation step described later, the density of the polishing pad after the immersion step described later, and the density of the polishing pad after the secondary impregnation step described later were measured, and the density difference was measured. It can also be calculated. The density can be measured in the same manner as described above.
本実施形態の研磨パッドは、上述の不織布及び樹脂の他、本実施形態の所望の効果を阻害しない範囲において、通常の研磨パッドに含まれ得る各種添加剤を含んでもよい。そのような添加剤としては、以下に限定されないが、例えば、カーボンブラック等の顔料、親水性活性剤及び疎水性活性剤が挙げられる。 The polishing pad of the present embodiment may contain, in addition to the nonwoven fabric and the resin described above, various additives that can be included in a normal polishing pad, as long as the desired effects of the present embodiment are not impaired. Such additives include, but are not limited to, pigments such as carbon black, hydrophilic activators, and hydrophobic activators.
本実施形態の研磨パッドの厚さは、特に限定されないが、ワークとの平坦な接触面を十分に確保する観点、平坦性を確保する観点及びスラリーを貯留する観点から、０．８〜３．０ｍｍであると好ましく、１．０〜１．８ｍｍであるとより好ましい。厚さは、日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して測定される。具体的には、研磨パッドを１０ｃｍ×１０ｃｍ角に切り抜いて得た試料片３枚を用意し、各試料片毎に、厚さ測定器の所定位置にセットした後、４８０ｇ／ｃｍ2の荷重をかけた加圧面を試料片の表面に載せ、５秒経過後に厚さを測定する。１枚の試料片につき、５箇所の厚さを測定し相加平均を算出し、さらに３枚の試料片の相加平均を求める。 Although the thickness of the polishing pad of the present embodiment is not particularly limited, it is 0.8 to 3. from the viewpoint of sufficiently securing a flat contact surface with the workpiece, securing the flatness, and storing the slurry. It is preferably 0 mm, more preferably 1.0 to 1.8 mm. The thickness is measured according to Japanese Industrial Standards (JIS K 6505). Specifically, three sample pieces obtained by cutting a polishing pad into a 10 cm × 10 cm square are prepared, and each sample piece is set at a predetermined position of a thickness measuring instrument, and then a load of 480 g / cm 2 is applied. The applied pressure surface is placed on the surface of the sample piece, and the thickness is measured after 5 seconds. The thickness of one sample piece is measured at five points, an arithmetic average is calculated, and an arithmetic average of three sample pieces is obtained.
［研磨パッドの製造方法］
本実施形態の研磨パッドの製造方法は、上述した本実施形態の研磨パッドの構成が得られる方法である限り、特に限定されるものではない。以下、本実施形態の研磨パッドの好適な製造方法を例示する。
[Method of manufacturing polishing pad]
The method for manufacturing the polishing pad of the present embodiment is not particularly limited as long as the method of obtaining the configuration of the polishing pad of the present embodiment described above is obtained. Hereinafter, a preferred method for manufacturing the polishing pad of the present embodiment will be described.
本実施形態の研磨パッドの製造方法は、不織布に第１の樹脂を含む樹脂溶液を含浸させ、湿式凝固を行うことにより、樹脂含浸不織布を得る１次含浸工程と、樹脂含浸不織布を、第１の樹脂が可溶な溶媒に浸漬する浸漬工程と、浸漬工程の後の樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと硬化剤とを含む溶液に含浸する２次含浸工程と、を有する。本実施形態の研磨パッドの製造方法は、上記のように構成されているため、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分なライフを確保できる研磨パッドを得ることができる。 The method for manufacturing a polishing pad according to the present embodiment includes a first impregnation step of impregnating a resin solution containing a first resin into a nonwoven fabric and performing wet coagulation to obtain a resin-impregnated nonwoven fabric. And a secondary impregnation step of impregnating the resin-impregnated nonwoven fabric after the immersion step with a solution containing a urethane prepolymer having an NCO equivalent of 500 or less and a curing agent. . Since the method for manufacturing a polishing pad of the present embodiment is configured as described above, it is possible to obtain a polishing pad which is excellent in chemical resistance and can secure a sufficient life even when subjected to polishing using a strong oxidizing agent. Can be.
上記１次含浸工程においては、不織布に樹脂溶液を含浸させた上で湿式凝固法により樹脂含浸不織布を得る。湿式凝固法とは、樹脂溶液を、樹脂に対して貧溶媒である凝固液に常温で浸漬することで樹脂を凝固再生させる方法である。本実施形態のように不織布に樹脂溶液を含浸させた上で湿式凝固法を用いる場合、凝固液中では、不織布の繊維に付着している樹脂溶液の表面で樹脂溶液の溶媒と凝固液との置換の進行により樹脂が繊維の表面に凝固再生される。 In the primary impregnation step, the nonwoven fabric is impregnated with a resin solution, and then a resin-impregnated nonwoven fabric is obtained by a wet coagulation method. The wet coagulation method is a method in which a resin solution is immersed in a coagulation liquid, which is a poor solvent for the resin, at room temperature to coagulate and regenerate the resin. When the wet coagulation method is used after impregnating the nonwoven fabric with the resin solution as in the present embodiment, in the coagulation liquid, the solvent of the resin solution and the coagulation liquid on the surface of the resin solution adhering to the fibers of the nonwoven fabric The resin is solidified and regenerated on the fiber surface by the progress of the substitution.
上記１次含浸工程の具体例としては、次のとおりである。まず、上述したような湿式樹脂と、当該湿式樹脂を溶解可能であって、後述の凝固液に混和する溶媒と、必要に応じて研磨パッドに配合するその他の添加剤とを混合し、更に必要に応じて減圧下で脱泡して樹脂溶液を準備する。上記溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、メチルエチルケトン（ＭＥＫ）及びジメチルスルホキシドが挙げられる。樹脂に対する良溶媒を選択する観点、さらに凝固浴に対して均一に混和させて湿式凝固をより容易にする観点から、第１の樹脂が、Ｎ，Ｎ−ジメチルホルムアルデヒド、ジメチルアセトアミド及びジメチルスルホキシドからなる群より選ばれる１種以上の溶媒に可溶であることが好ましい。同様に、上記溶媒が、Ｎ，Ｎ−ジメチルホルムアルデヒド、ジメチルアセトアミド及びジメチルスルホキシドからなる群より選ばれる１種以上の溶媒を含むことが好ましい。 Specific examples of the primary impregnation step are as follows. First, a wet resin as described above, a solvent capable of dissolving the wet resin, a solvent to be mixed with a coagulation liquid described later, and other additives to be added to the polishing pad as necessary are mixed, and further necessary. A resin solution is prepared by defoaming under reduced pressure according to. Although it does not specifically limit as said solvent, For example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), methyl ethyl ketone (MEK), and dimethyl sulfoxide are mentioned. The first resin is composed of N, N-dimethylformaldehyde, dimethylacetamide, and dimethylsulfoxide from the viewpoint of selecting a good solvent for the resin and further facilitating wet coagulation by uniformly mixing with the coagulation bath. Preferably, it is soluble in one or more solvents selected from the group. Similarly, the solvent preferably contains one or more solvents selected from the group consisting of N, N-dimethylformaldehyde, dimethylacetamide and dimethylsulfoxide.
不織布の全体に亘って樹脂を含浸する観点、及び、樹脂の含浸量を十分に確保する観点から、上記樹脂溶液について、Ｂ型回転粘度計を用いて２０℃で測定した粘度が８０００ｃｐ以下であると好ましく、１００ｃｐ〜５０００ｃｐであるとより好ましく、４００ｃｐ〜３０００ｃｐであると更に好ましい。そのような粘度の数値範囲にある樹脂溶液を得る観点から、例えば、ポリウレタン樹脂を、樹脂溶液の全体量に対して５〜２５質量％の範囲、より好ましくは８〜１５質量％の範囲で溶媒に溶解させてもよい。樹脂溶液の粘性は、用いる樹脂の種類及び分子量にも依存するため、これらを総合的に考慮し、樹脂の選定、濃度設定等を行うことが好ましい。 From the viewpoint of impregnating the resin with the entire nonwoven fabric, and from the viewpoint of ensuring a sufficient resin impregnation amount, the viscosity of the above resin solution measured at 20 ° C. using a B-type rotational viscometer is 8000 cp or less. And more preferably 100 cp to 5000 cp, and even more preferably 400 cp to 3000 cp. From the viewpoint of obtaining a resin solution having such a viscosity value range, for example, the polyurethane resin may be used in an amount of 5 to 25% by mass, more preferably 8 to 15% by mass, based on the total amount of the resin solution. May be dissolved. Since the viscosity of the resin solution also depends on the type and molecular weight of the resin to be used, it is preferable to select the resin and set the concentration in consideration of these factors comprehensively.
次に、樹脂溶液に不織布を十分に浸漬した後、樹脂溶液が付着した不織布から、１対のローラ間で加圧可能なマングルローラを用いて樹脂溶液を絞り落とすことで、樹脂溶液の不織布への付着量を所望の量に調整し、不織布に樹脂溶液を均一又は略均一に含浸させる。次いで、樹脂溶液を含浸した不織布を、樹脂に対する貧溶媒、例えば水、を主成分とする凝固液中に浸漬することにより、湿式樹脂を凝固再生させる。凝固液には、樹脂の再生速度を調整するために、樹脂溶液中の溶媒以外の極性溶媒等の有機溶媒を添加してもよい。また、凝固液の温度は、樹脂を凝固できる温度であれば特に限定されず、例えば、１５〜６０℃であってもよい。 Next, after sufficiently immersing the nonwoven fabric in the resin solution, the resin solution is squeezed out of the nonwoven fabric to which the resin solution has adhered using a mangle roller capable of being pressed between a pair of rollers, thereby forming the resin solution into the nonwoven fabric. Is adjusted to a desired amount, and the nonwoven fabric is impregnated with the resin solution uniformly or substantially uniformly. Next, the nonwoven fabric impregnated with the resin solution is immersed in a coagulation liquid containing a poor solvent for the resin, for example, water as a main component, to coagulate and regenerate the wet resin. An organic solvent such as a polar solvent other than the solvent in the resin solution may be added to the coagulation liquid in order to adjust the regeneration speed of the resin. The temperature of the coagulating liquid is not particularly limited as long as the resin can be coagulated, and may be, for example, 15 to 60 ° C.
本実施形態において、上述の湿式凝固を行ったのち、以下のような洗浄・乾燥工程に供することが好ましい。まず、湿式樹脂が凝固再生された不織布を水等の洗浄液中で洗浄し、不織布中に残存するＤＭＦ等の溶媒を除去する。洗浄後、不織布を洗浄液から引き上げ、マングルローラ等を用いて余分な洗浄液を絞り落とす。その後、不織布基材を、１００℃〜１５０℃の乾燥機中で乾燥させてもよい。また、上記乾燥の後、得られる樹脂含浸不織布をさらにスライス、バフ等による加工に供し、表層のスキン層を除去し、所定の厚さにすることが、次工程の浸漬工程の均一性を高める観点から好ましい。 In the present embodiment, after the above-mentioned wet coagulation is performed, it is preferable to perform the following washing and drying steps. First, the nonwoven fabric obtained by coagulating and regenerating the wet resin is washed in a washing liquid such as water to remove a solvent such as DMF remaining in the nonwoven fabric. After washing, the non-woven fabric is pulled up from the washing liquid, and excess washing liquid is squeezed out using a mangle roller or the like. Thereafter, the nonwoven fabric substrate may be dried in a dryer at 100C to 150C. Further, after the drying, the obtained resin-impregnated nonwoven fabric is further subjected to processing by slicing, buffing, and the like, and removing the surface skin layer to a predetermined thickness enhances the uniformity of the next immersion step. Preferred from a viewpoint.
本実施形態における浸漬工程は、上述の樹脂含浸不織布を、上述の湿式樹脂が可溶な溶媒に浸漬させることで、当該湿式樹脂を溶媒に再溶解させる工程である。浸漬工程により、樹脂含浸不織布内部の気泡（例えば閉気孔及び開口部の小さい開気孔）が減少し、不織布と湿式樹脂との密着性が向上すると考えられる。浸漬工程に用いる溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、メチルエチルケトン（ＭＥＫ）、及びジメチルスルホキシドが挙げられる。また、浸漬させる際の温度条件としては、第１の樹脂の気泡を減少させ、かつ、溶媒への樹脂の溶出を防止する観点から、１５．０〜２５．０℃であることが好ましく、浸漬時間としては、同様の観点から、５〜３０秒であることが好ましい。なお、上述の浸漬工程の後に、乾燥工程を設けることが好ましい。 The immersion step in the present embodiment is a step of immersing the above-mentioned resin-impregnated nonwoven fabric in a solvent in which the above-mentioned wet resin is soluble, thereby re-dissolving the wet resin in the solvent. It is considered that the immersion step reduces bubbles (for example, closed pores and open pores with small openings) inside the resin-impregnated nonwoven fabric, and improves adhesion between the nonwoven fabric and the wet resin. The solvent used in the immersion step is not particularly limited, and includes, for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), methyl ethyl ketone (MEK), and dimethyl sulfoxide. In addition, the temperature condition at the time of immersion is preferably 15.0 to 25.0 ° C. from the viewpoint of reducing bubbles of the first resin and preventing the resin from being eluted into the solvent. The time is preferably 5 to 30 seconds from the same viewpoint. Note that a drying step is preferably provided after the above-described immersion step.
本実施形態における２次含浸工程は、浸漬工程の後の樹脂含浸不織布を、ウレタンプレポリマーと硬化剤とを含む溶液に含浸する工程である。２次含浸工程により、上述した湿式樹脂の表面に乾式樹脂が形成されるものと推測される。 The secondary impregnation step in the present embodiment is a step of impregnating the resin-impregnated nonwoven fabric after the immersion step with a solution containing a urethane prepolymer and a curing agent. It is presumed that a dry resin is formed on the surface of the above-mentioned wet resin by the secondary impregnation step.
２次含浸工程の具体例としては、まず、末端にイソシアネート基を有するウレタンプレポリマーと、硬化剤であるアミン化合物及び／又は多価アルコール化合物と、それらを溶解可能な溶媒とを含む溶液を準備する。ここで、ウレタンプレポリマー、アミン化合物、多価アルコール化合物及び溶媒は、上記で例示したものと同様のものを用いることができる。また、これらのウレタンプレポリマー及び硬化剤は、それぞれ、１種を単独で又は２種以上を組み合わせて用いられる。 As a specific example of the secondary impregnation step, first, a solution containing a urethane prepolymer having an isocyanate group at a terminal, an amine compound and / or a polyhydric alcohol compound as a curing agent, and a solvent capable of dissolving them is prepared. I do. Here, the same urethane prepolymer, amine compound, polyhydric alcohol compound and solvent as those exemplified above can be used. These urethane prepolymers and curing agents may be used alone or in combination of two or more.
本実施形態において、耐薬品性をより良好とする観点から、ウレタンプレポリマーのＮＣＯ当量はＮＣＯ当量５００以下が好ましく、４５０以下であることがより好ましく、ＮＣＯ当量の下限値としては２００であることが好ましい。 In the present embodiment, from the viewpoint of improving the chemical resistance, the NCO equivalent of the urethane prepolymer is preferably 500 or less, more preferably 450 or less, and the lower limit of the NCO equivalent is 200. Is preferred.
次に、上記溶液に浸漬工程の後の樹脂含浸不織布を浸漬した後、溶液が付着した樹脂含浸不織布から、１対のローラ間で加圧可能なマングルローラを用いて溶液を絞り落とすことで、溶液の樹脂含浸不織布への付着量を所望の量に調整し、樹脂含浸不織布に溶液を均一又は略均一に含浸させる。次いで、溶液を含浸させた樹脂含浸不織布を乾燥機内で乾燥させる。これにより、ウレタンプレポリマーと硬化剤により重合して、樹脂含浸不織布に乾式樹脂を含浸させた本実施形態の研磨パッドが得られる。乾燥温度としては、例えば、１００℃〜１４０℃であってもよい。 Next, after immersing the resin-impregnated nonwoven fabric after the immersion step in the solution, by squeezing the solution from the resin-impregnated nonwoven fabric to which the solution has adhered using a mangle roller that can be pressed between a pair of rollers, The adhesion amount of the solution to the resin-impregnated nonwoven fabric is adjusted to a desired amount, and the resin-impregnated nonwoven fabric is impregnated with the solution uniformly or substantially uniformly. Next, the resin-impregnated nonwoven fabric impregnated with the solution is dried in a dryer. As a result, the polishing pad of the present embodiment is obtained in which the resin-impregnated nonwoven fabric is impregnated with the dry resin by polymerization with the urethane prepolymer and the curing agent. The drying temperature may be, for example, 100C to 140C.
上述した１次含浸工程、浸漬工程及び２次含浸工程を経ることで、本実施形態の所望の構成を有する研磨パッドが得られる。この研磨パッドは、以下に説明する内容に限定する趣旨ではないが、次のような構成を有しているものと推察される。すなわち、１次含浸工程を経ることで、不織布の表面に湿式樹脂が形成される。特に、１次含浸工程では湿式凝固を採用することにより、湿式樹脂が不織布内で均一付着する。ただし、この段階では、得られる樹脂含浸不織布の樹脂内部において、湿式凝固法に由来する微細な気泡が多く、不織布と湿式樹脂との密着性及び強度は十分とはいえない。次いで、浸漬工程を経ることで、湿式樹脂の微細な気泡に浸漬溶液が充填され、乾燥による加温により湿式樹脂が再溶解し、樹脂含浸不織布内部の微細な気泡（例えば閉気孔及び開口部の小さい開気孔）が減少すると共に、不織布に含浸している樹脂（湿式樹脂）が繊維周辺で高密度化するので、不織布の繊維と湿式樹脂との密着性が向上するとともに強度が向上する。また、微細気泡が減少することで、２次含浸工程における乾式樹脂の含浸の均一化や強度向上につながる。さらに、２次含浸工程を経ることで、不織布繊維上の湿式樹脂の層の表面に、さらに乾式樹脂の層が形成される。浸漬工程を経ずに２次含浸工程に移ると、樹脂含浸不織布内部の気泡内の空間への乾式樹脂の侵入が困難になり、乾式樹脂の付着が不均一になる。この場合、湿式樹脂と乾式樹脂が不均一に付着した状態となり、部分的に弾性特性や剛性特性が不均一になるため、研磨の際に研磨パッド内の樹脂が剥離し、寿命が短くなってしまう。また、強酸化剤への耐性に優れた乾式樹脂の存在しない気泡内に強酸化剤が侵入しやすくなるため、耐薬品性に劣ると共に、寿命が短くなってしまう。一方、本実施形態によると、浸漬工程において、気泡が減少するため、２次含浸工程において含浸可能な空隙が確保されるとともに通気性が改善され、乾式樹脂が侵入し難い箇所が少なくなり、乾式樹脂の存在する領域が増加する。そのため、乾式樹脂の存在しない領域への強酸化剤の侵入が抑制され、耐薬品性が向上し、寿命を長くすることができる。また、不織布に直接付着していない部分の湿式樹脂が減少するため、研磨の際に研磨パッド内の樹脂の剥離が抑制され、寿命を長くすることができる。さらに、乾式樹脂の層は、特定のＮＣＯ当量を有するウレタンプレポリマーを用いて形成されるため、良好な耐薬品性が付与される。このように、本実施形態の研磨パッドにおいては、不織布を基材とし、当該不織布上に湿式樹脂の層が形成され、当該湿式樹脂の層上に乾式樹脂の層が形成されるものと推察される。また、研磨パッドの全体としては、不織布と湿式樹脂の層との間の密着性及び湿式樹脂の層と乾式樹脂の層との密着性は、いずれも良好であるものと推察される。上記の観点から、本実施形態の研磨パッドは、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分なライフを確保することができるものと考えられる。
なお、１次含浸工程と浸漬工程を省略し、２次含浸工程により不織布に乾式樹脂を含浸させた場合、不織布と乾式樹脂の馴染が悪く、繊維と樹脂の密着性に問題が生じ、構造上の安定性を損ねることとなる。また、不織布に乾式樹脂のみを付着させ、湿式樹脂を付着させない場合、研磨パッドとして高硬度、低弾性となり、研磨中の被研磨物に対する追従性が悪く、研磨に支障をきたす。更に、乾式樹脂は湿式樹脂に比べ水分の保持性が悪いため、乾式樹脂のみでは研磨液の十分な保持が困難である。
By going through the above-described primary impregnation step, immersion step and secondary impregnation step, a polishing pad having a desired configuration of the present embodiment can be obtained. This polishing pad is not intended to be limited to the contents described below, but is presumed to have the following configuration. That is, the wet resin is formed on the surface of the nonwoven fabric through the primary impregnation step. In particular, by employing wet coagulation in the primary impregnation step, the wet resin is uniformly adhered in the nonwoven fabric. However, at this stage, in the resin of the obtained resin-impregnated nonwoven fabric, there are many fine bubbles derived from the wet coagulation method, and the adhesion and strength between the nonwoven fabric and the wet resin are not sufficient. Then, through the immersion step, the immersion solution is filled into the fine bubbles of the wet resin, and the wet resin is redissolved by heating by drying, and the fine bubbles inside the resin-impregnated nonwoven fabric (for example, closed pores and openings) Since the resin (wet resin) impregnated in the nonwoven fabric has a high density around the fibers, the adhesion between the fibers of the nonwoven fabric and the wet resin is improved, and the strength is improved. Further, the reduction of fine bubbles leads to uniform impregnation of the dry resin in the secondary impregnation step and improvement in strength. Further, through the secondary impregnation step, a dry resin layer is further formed on the surface of the wet resin layer on the nonwoven fabric fibers. If the process is shifted to the secondary impregnation step without passing through the immersion step, it becomes difficult for the dry resin to enter the space inside the bubbles inside the resin-impregnated nonwoven fabric, and the adhesion of the dry resin becomes uneven. In this case, the wet resin and the dry resin are non-uniformly adhered, and the elasticity and rigidity are partially non-uniform, so that the resin in the polishing pad is peeled off during polishing and the life is shortened. I will. Further, since the strong oxidizing agent easily penetrates into bubbles in which a dry resin having excellent resistance to the strong oxidizing agent does not exist, the chemical resistance is deteriorated and the life is shortened. On the other hand, according to the present embodiment, in the immersion step, air bubbles are reduced, so that voids that can be impregnated in the secondary impregnation step are secured and air permeability is improved, and the number of places where the dry resin hardly penetrates is reduced. The area where the resin is present increases. Therefore, the penetration of the strong oxidizing agent into the region where the dry resin does not exist is suppressed, the chemical resistance is improved, and the life can be prolonged. Further, since the wet resin in the portion not directly attached to the nonwoven fabric is reduced, the resin in the polishing pad is prevented from peeling off during polishing, and the life can be extended. Furthermore, since the dry resin layer is formed using a urethane prepolymer having a specific NCO equivalent, good chemical resistance is imparted. Thus, in the polishing pad of the present embodiment, it is presumed that a nonwoven fabric is used as a base material, a wet resin layer is formed on the nonwoven fabric, and a dry resin layer is formed on the wet resin layer. You. In addition, it is assumed that, as a whole of the polishing pad, the adhesiveness between the nonwoven fabric and the wet resin layer and the adhesiveness between the wet resin layer and the dry resin layer are both good. From the above viewpoint, it is considered that the polishing pad of the present embodiment has excellent chemical resistance and can secure a sufficient life even when subjected to polishing using a strong oxidizing agent.
In addition, when the primary impregnation step and the immersion step are omitted, and the nonwoven fabric is impregnated with the dry resin in the secondary impregnation step, the nonwoven fabric and the dry resin are not well-adapted, and a problem occurs in the adhesion between the fiber and the resin. The stability of the device. In addition, when only a dry resin is adhered to the nonwoven fabric and no wet resin is adhered, the polishing pad becomes high in hardness and low in elasticity, has poor followability to the object to be polished during polishing, and hinders polishing. Further, since dry resin has poorer water retention than wet resin, it is difficult to sufficiently hold the polishing liquid only with dry resin.
本実施形態の研磨パッドが上記のとおりに推察される構成を有していることは、以下に限定されないが、例えば、当該研磨パッドの引張強度保持率の値だけでなく、上述した通気度の値や、研磨パッドにおける不織布、第１の樹脂及び第２の樹脂の各含有量の値等から確認することができる。 It is not limited to the following that the polishing pad of the present embodiment has a configuration inferred as described above, for example, not only the value of the tensile strength retention rate of the polishing pad, but also the above-described air permeability. It can be confirmed from the values and the values of the respective contents of the nonwoven fabric, the first resin and the second resin in the polishing pad.
上述のようにして得られた研磨パッドは、その後、必要に応じて、円形等の所望の形状、寸法に裁断されてもよく、汚れや異物等の付着がないことを確認する等の検査を施されてもよい。 The polishing pad obtained as described above may then be cut into a desired shape and dimensions such as a circle, if necessary, and inspected to confirm that there is no adhesion of dirt or foreign matter. May be applied.
得られた研磨パッドは、その表面が研磨面となるが、その研磨パッドを用いてワークを研磨する場合、予め、研磨パッドの研磨面とは反対側の面に、研磨機の研磨定盤に研磨パッドを貼着するための両面テープ（粘着層及び剥離紙を備えるもの）を貼り合わせてもよい。 The obtained polishing pad has a polishing surface on the surface, but when polishing a work using the polishing pad, a polishing surface of the polishing pad is previously set on a surface opposite to the polishing surface of the polishing pad. A double-sided tape (with an adhesive layer and a release paper) for attaching the polishing pad may be attached.
［研磨方法］
本実施形態の研磨方法は、化合物半導体ウェハを、過マンガン酸カリウムを含む溶液に接触させながら本実施形態の研磨パッドにより研磨する工程を有する。その具体的な一例を説明する。まず、片面研磨機の保持定盤にワークを保持させる。次いで、保持定盤と対向するように配置された研磨定盤に研磨パッドを装着する。研磨定盤に研磨パッドを装着する際、両面テープから剥離紙を剥離して粘着層を露出させた後、露出した粘着層を研磨定盤に接触させ押圧する。そして、ワークと研磨パッドとの間に過マンガン酸カリウム及び必要に応じて砥粒を含む溶液（スラリー）を循環供給すると共に、ワークを研磨パッドの方に所定の研磨圧にて押圧しながら研磨定盤ないし保持定盤を回転させることで、ワークを化学機械研磨により研磨する。この際、本実施形態の研磨パッドを用いることにより、高い研磨レート、長い研磨パッドの寿命と共に、十分に高い被研磨物の平坦性を確保することが可能となる。なお、本実施形態の研磨方法において、過マンガン酸カリウムに加えて又は代えて、過マンガン酸ナトリウムなどの強酸化剤を用いてもよい。
[Polishing method]
The polishing method of the present embodiment includes a step of polishing a compound semiconductor wafer with the polishing pad of the present embodiment while contacting the compound semiconductor wafer with a solution containing potassium permanganate. A specific example will be described. First, a work is held on a holding platen of a single-side polishing machine. Next, a polishing pad is mounted on the polishing platen arranged to face the holding platen. When the polishing pad is mounted on the polishing platen, the release paper is peeled off from the double-sided tape to expose the adhesive layer, and then the exposed adhesive layer is brought into contact with the polishing platen and pressed. Then, a solution (slurry) containing potassium permanganate and, if necessary, abrasive grains is circulated and supplied between the work and the polishing pad, and the work is polished while pressing the work toward the polishing pad at a predetermined polishing pressure. The work is polished by chemical mechanical polishing by rotating the platen or holding platen. In this case, by using the polishing pad of the present embodiment, it is possible to secure a sufficiently high flatness of the object to be polished, together with a high polishing rate and a long life of the polishing pad. In the polishing method of the present embodiment, a strong oxidizing agent such as sodium permanganate may be used in addition to or instead of potassium permanganate.
［研磨パッドの用途］
本実施形態の研磨パッドは、レンズ、平行平面板、反射ミラー等の光学材料、ハードディスク用基板、半導体用シリコンウェハ、液晶ディスプレイ用ガラス基板、サファイヤや窒化ガリウムを始めとする難削材等の研磨に特に好適に用いられる。ただし、本実施形態の研磨パッドの用途はそれらに限定されない。
[Use of polishing pad]
The polishing pad of the present embodiment is used for polishing optical materials such as lenses, plane-parallel plates, reflection mirrors, etc., substrates for hard disks, silicon wafers for semiconductors, glass substrates for liquid crystal displays, and difficult-to-cut materials such as sapphire and gallium nitride. Particularly preferably used. However, the use of the polishing pad of the present embodiment is not limited thereto.
以下、実施例によって本実施形態を更に詳細に説明するが、本実施形態はこれらの実施例に限定されるものではない。 Hereinafter, the present embodiment will be described in more detail by way of examples, but the present embodiment is not limited to these examples.
［使用原料］
実施例及び比較例で用いる１次含浸用の樹脂（１次含浸樹脂）、１次含浸用の架橋剤（１次架橋剤）、１次含浸用の溶媒（１次含浸溶媒）、浸漬工程用の溶媒（浸漬溶媒）、２次含浸用の樹脂（２次含浸樹脂）、２次含浸用の硬化剤（２次硬化剤）としては、下記のものを用いた。
[Raw materials]
Resin for primary impregnation (primary impregnating resin), cross-linking agent for primary impregnation (primary cross-linking agent), solvent for primary impregnation (primary impregnating solvent), and dipping process used in Examples and Comparative Examples As a solvent (immersion solvent), a resin for secondary impregnation (secondary impregnation resin), and a curing agent for secondary impregnation (secondary curing agent), the following were used.
（１次含浸樹脂）
ＵＷ−１：エステル系ウレタン樹脂（ＤＩＣ社製、商品名「クリスボン７６６７」）
Ｓ−７０５：ポリカーボネート系ウレタン樹脂（ＤＩＣ社製、商品名「クリスボンＳ７０５」）
Ｃ−８８６７：エステル系ウレタン樹脂（ＤＩＣ社製、商品名「クリスボン８８６７」）
（１次架橋剤）
ＤＮ−９５０：ウレタンプレポリマー（ＤＩＣ社製、商品名「バーノックＤＮ９５０」）
４０２−Ｂ８０Ｔ：ブロックイソシアネート（旭化成ケミカルズ社製、商品名「デュラネート４０２−Ｂ８０Ｔ」）
（１次含浸溶媒）
Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）
（浸漬溶媒）
ＤＭＦ／水 （質量比６５／３５）
（２次含浸樹脂）
ＵＰ１２０：ウレタンプレポリマー（三菱樹脂社製、商品名「ノバレタン ＵＰ１２０」、ＮＣＯ当量４００）
ＵＰ１２１：ウレタンプレポリマー（三菱樹脂社製、商品名「ノバレタン ＵＰ１２１」、ＮＣＯ当量４４０）
ＤＣ６９１２：ウレタンプレポリマー（東ソー社製、商品名「ＤＣ６９１２」、ＮＣＯ当量５４０）
なお、上記のＮＣＯ当量は、ＪＩＳ Ｋ ７３０１に準拠して測定した。
（２次硬化剤）
Ｅ（ＭＯＣＡ）：硬化剤（ＤＩＣ社製、商品名「パンデックスＥ」）
(Primary impregnated resin)
UW-1: Ester urethane resin (manufactured by DIC, trade name "Chrisbon 7667")
S-705: Polycarbonate urethane resin (trade name “Chrisbon S705” manufactured by DIC)
C-8867: ester-based urethane resin (manufactured by DIC, trade name "Chrisbon 8867")
(Primary crosslinking agent)
DN-950: urethane prepolymer (trade name “Barnock DN950” manufactured by DIC)
402-B80T: blocked isocyanate (trade name “Duranate 402-B80T” manufactured by Asahi Kasei Chemicals Corporation)
(Primary impregnating solvent)
N, N-dimethylformamide (DMF)
(Immersion solvent)
DMF / water (mass ratio 65/35)
(Secondary impregnated resin)
UP120: urethane prepolymer (manufactured by Mitsubishi Plastics, trade name "Novaretane UP120", NCO equivalent 400)
UP121: urethane prepolymer (manufactured by Mitsubishi Plastics, trade name "Novaretane UP121", NCO equivalent 440)
DC6912: urethane prepolymer (manufactured by Tosoh Corporation, trade name "DC6912", NCO equivalent 540)
In addition, the said NCO equivalent was measured based on JISK7301.
(Secondary curing agent)
E (MOCA): Curing agent (trade name “PANDEX E” manufactured by DIC)
［実施例１〜６、比較例１〜２］
（１次含浸工程）
上述の１次含浸樹脂、１次架橋剤、及び１次含浸溶媒を、表１に示す配合で混合し調製した樹脂溶液に、繊維材料がＰＥＴで、厚さが３．５ｍｍで、目付が６２０ｇ／ｍ2である不織布（繊度３ｄ）を浸漬した。浸漬後、１対のローラ間を加圧可能なマングルローラを用いて樹脂溶液を絞り落として、不織布に樹脂溶液を略均一に含浸させた。次いで、室温の水からなる凝固液中に浸漬することにより、１次含浸樹脂を凝固再生させて樹脂含浸不織布を得た。その後、樹脂含浸不織布を凝固液から取り出し、更に水からなる洗浄液に浸漬して、ＤＭＦを除去した後、乾燥させた。乾燥後、バフィングにより表面のスキン層が除去された樹脂含浸不織布を得た。
（浸漬工程）
次いで、ＤＭＦと純水とを６５対３５で混合した浸漬溶媒に、上記で得られた樹脂含浸不織布を浸漬した。その後、洗浄・乾燥を行い、浸漬工程後の樹脂含浸不織布を得た。
（２次含浸工程）
さらに、２次含浸樹脂及び２次硬化剤を表１に示す配合で調製した溶液に、浸漬工程後の樹脂含浸不織布を浸漬した。その後、洗浄・乾燥を行い、実施例１〜６及び比較例２の研磨パッドを得た。
なお、比較例１に関しては、浸漬工程及び２次含浸を行わないことを除き、上記と同様に研磨パッドを作成した。
[Examples 1 to 6, Comparative Examples 1 and 2]
(Primary impregnation step)
A resin solution prepared by mixing the above-mentioned primary impregnating resin, primary crosslinking agent, and primary impregnating solvent with the composition shown in Table 1 is made of PET, the thickness is 3.5 mm, and the basis weight is 620 g. / M 2 (3 d fineness). After immersion, the resin solution was squeezed down using a mangle roller capable of pressing between a pair of rollers, and the nonwoven fabric was impregnated with the resin solution substantially uniformly. Then, the primary impregnated resin was solidified and regenerated by immersion in a coagulation liquid composed of water at room temperature to obtain a resin-impregnated nonwoven fabric. Thereafter, the resin-impregnated nonwoven fabric was taken out of the coagulating liquid, immersed in a washing liquid consisting of water to remove DMF, and then dried. After drying, a resin-impregnated nonwoven fabric from which the surface skin layer was removed by buffing was obtained.
(Immersion process)
Next, the resin-impregnated nonwoven fabric obtained above was immersed in an immersion solvent in which DMF and pure water were mixed at a ratio of 65:35. Thereafter, washing and drying were performed to obtain a resin-impregnated nonwoven fabric after the dipping step.
(Secondary impregnation step)
Further, the resin-impregnated nonwoven fabric after the immersion step was immersed in a solution prepared by mixing the secondary impregnated resin and the secondary curing agent with the compositions shown in Table 1. Thereafter, washing and drying were performed to obtain polishing pads of Examples 1 to 6 and Comparative Example 2.
With respect to Comparative Example 1, a polishing pad was prepared in the same manner as described above, except that the immersion step and the secondary impregnation were not performed.
［物性評価］
上述のようにして得られた各実施例及び比較例の研磨パッドについて、下記のとおりに物性を測定し、品質を評価した。それらの結果を表２に示す。
[Evaluation of the physical properties]
With respect to the polishing pads of the respective examples and comparative examples obtained as described above, the physical properties were measured as described below, and the quality was evaluated. Table 2 shows the results.
（厚さ）
日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して、次のとおりに研磨パッドの厚さを測定した。まず、研磨パッドを１０ｃｍ×１０ｃｍ角に切り抜いて得た試料片３枚を用意し、各試料片毎に、厚さ測定器の所定位置にセットした。その後、４８０ｇ／ｃｍ2の荷重をかけた加圧面を試料片の表面に載せ、５秒経過後に厚さを測定した。その際、１枚の試料片につき、５箇所の厚さを測定し、相加平均を算出し、さらに３枚の試料片の相加平均を求めて研磨パッドの厚さとした。
(thickness)
The thickness of the polishing pad was measured as follows in accordance with Japanese Industrial Standards (JIS K 6505). First, three sample pieces obtained by cutting a polishing pad into a 10 cm × 10 cm square were prepared, and each sample piece was set at a predetermined position on a thickness measuring instrument. Thereafter, a pressed surface with a load of 480 g / cm 2 was placed on the surface of the sample piece, and the thickness was measured after 5 seconds. At that time, the thickness was measured at five locations for one sample piece, the arithmetic average was calculated, and the arithmetic average of the three sample pieces was determined to be the thickness of the polishing pad.
（密度）
日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して、次のとおりに研磨パッドの密度を測定した。すなわち、厚さの測定で用いたものと同様の試料片を用意し、その質量を自動天秤で測定後、下記式により密度を算出し、３枚の試料片の相加平均を求めて研磨パッドの密度とした。
密度（ｇ／ｃｍ3）＝質量（ｇ）／（１０（ｃｍ）×１０（ｃｍ）×試料片の厚さ（ｃｍ））
(density)
The density of the polishing pad was measured as follows in accordance with Japanese Industrial Standards (JIS K 6505). That is, a sample piece similar to that used in the thickness measurement was prepared, the mass was measured with an automatic balance, the density was calculated by the following equation, and the arithmetic average of the three sample pieces was obtained to obtain a polishing pad. Density.
Density (g / cm 3 ) = mass (g) / (10 (cm) × 10 (cm) × thickness of sample (cm))
（不織布、湿式樹脂及び乾式樹脂の各含有量）
研磨パッドにおける不織布、湿式樹脂及び乾式樹脂の各含有量は、上述した１次含浸工程後の研磨パッドの密度と、浸漬工程後の研磨パッドの密度と、２次含浸工程後の研磨パッドの密度と、をそれぞれ測定し、密度差から算出した。なお、密度の測定は上記（密度）と同様にして測定した。
(Contents of nonwoven fabric, wet resin and dry resin)
The respective contents of the nonwoven fabric, the wet resin and the dry resin in the polishing pad are as follows: the density of the polishing pad after the primary impregnation step, the density of the polishing pad after the immersion step, and the density of the polishing pad after the secondary impregnation step. And were respectively measured and calculated from the density difference. The density was measured in the same manner as the above (density).
（通気度）
フラジール形試験機（安田精機社製の織布通気度試験機）を用い、日本工業規格（ＪＩＳ Ｌ １０９６）に準拠して、研磨パッドの通気度を測定した。なお、５枚の試料片の相加平均を研磨パッドの通気度とした。
(Air permeability)
The air permeability of the polishing pad was measured using a Frazier-type tester (woven fabric air permeability tester manufactured by Yasuda Seiki Co., Ltd.) in accordance with Japanese Industrial Standards (JIS L 1096). The arithmetic mean of the five sample pieces was taken as the air permeability of the polishing pad.
（圧縮率）
ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を用い、日本工業規格（ＪＩＳ Ｌ １０２１）に準拠して、次のとおりに研磨パッドの圧縮率を測定した。すなわち、初荷重で３０秒間加圧した後の厚さｔ0を測定し、次に最終圧力の下で５分間放置後の厚さｔ1を測定した。これらから、圧縮率を下記式により算出した。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とした。
圧縮率（％）＝（ｔ0−ｔ1）／ｔ0×１００
(Compression rate)
The compressibility of the polishing pad was measured as follows using a Shopper type thickness measuring device (pressing surface: a circle having a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS L 1021). That is, the thickness t 0 after pressing for 30 seconds with the initial load was measured, and then the thickness t 1 after standing for 5 minutes under the final pressure. From these, the compression ratio was calculated by the following equation. At this time, the initial load was 100 g / cm 2 and the final load was 1120 g / cm 2 .
Compression rate (%) = (t 0 −t 1 ) / t 0 × 100
（圧縮弾性率）
ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を用い、日本工業規格（ＪＩＳ Ｌ １０２１）に準拠して、次のとおりに研磨パッドの圧縮弾性率を測定した。すなわち、無荷重状態から初荷重を３０秒間かけた後の厚さｔ0を測定し、次に、厚さｔ0の状態から最終荷重を３０秒間かけた後の厚さｔ1を測定した。次に、厚さｔ1の状態から全ての荷重を除き、５分間放置（無荷重状態とした）後、再び初荷重を３０秒間かけた後の厚さｔ0’を測定した。これらから、圧縮弾性率を下記式により算出した。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とした。
圧縮弾性率（％）＝１００×（ｔ0’−ｔ1）／（ｔ0−ｔ1）
(Compressive modulus)
The compression elastic modulus of the polishing pad was measured as follows using a Shopper type thickness measuring device (pressing surface: a circle having a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS L 1021). That is, the thickness t 0 after the initial load was applied for 30 seconds from the no-load state was measured, and then the thickness t 1 after the final load was applied for 30 seconds from the state of the thickness t 0 was measured. Next, after removing all the loads from the state of the thickness t 1 , the sample was left for 5 minutes (with no load applied), and the thickness t 0 ′ after applying the initial load again for 30 seconds was measured. From these, the compression modulus was calculated by the following equation. At this time, the initial load was 100 g / cm 2 and the final load was 1120 g / cm 2 .
Compression modulus (%) = 100 × (t 0 ′ −t 1 ) / (t 0 −t 1 )
（Ａ硬度）
研磨パッドのＡ硬度は、次のようにして測定した。すなわち、厚さ４．５ｍｍ以上の試験片（１０ｃｍ×１０ｃｍ）の表面にバネを介して押針（測定子）を押し付け、３０秒後の押針の押し込み深さをＡ型硬度計（日本工業規格、ＪＩＳ Ｋ ７３１１）により測定した。なお、研磨パッドが４．５ｍｍ未満の厚さである場合は、厚さが４．５ｍｍ以上になるまで研磨パッドを重ね、試験片とした。これを３回行って相加平均から研磨パッドのＡ硬度を求めた。
(A hardness)
The A hardness of the polishing pad was measured as follows. That is, a needle (probe) is pressed against the surface of a test piece (10 cm × 10 cm) having a thickness of 4.5 mm or more via a spring via a spring, and the pressing depth of the needle after 30 seconds is measured using an A-type hardness tester (Nippon Kogyo). Standard, JIS K 7311). When the polishing pad had a thickness of less than 4.5 mm, the polishing pad was overlapped until the thickness became 4.5 mm or more to obtain a test piece. This was performed three times, and the A hardness of the polishing pad was determined from the arithmetic average.
（引張強度保持率）
引張万能試験機（「テンシロン」、Ａ＆Ｄ社製、ＲＴＣ−１２１０Ａ）を用い、日本工業規格（ＪＩＳ Ｋ ６５５０）に準拠して、試験液に浸漬する前の研磨パッドの引張強度（ａ）を測定した。次いで、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整し、試験液を調製した。この試験液に、研磨パッドを２５℃で４８時間浸漬した。なお、浸漬の開始から２４時間経過後に試験液と研磨パッドを収容した容器を振とうした。浸漬の開始から４８時間経過後、研磨パッドを試験液から取り出し、流水洗浄し、５分間の超音波洗浄を行った。次いで、流水洗浄し、キッチンペーパーで加圧しながら残留した試験液を拭き取り上記と同様に研磨パッドの引張強度（ｂ）を測定した。このようにして測定された引張強度（ａ）と引張強度（ｂ）の値から、引張強度保持率を以下の式で算出した。
引張強度保持率＝引張強度（ｂ）／引張強度（ａ）×１００ （％）
(Tensile strength retention rate)
Using a tensile universal tester ("Tensilon", manufactured by A & D, RTC-1210A), the tensile strength (a) of the polishing pad before being immersed in the test solution is measured in accordance with Japanese Industrial Standards (JIS K 6550). did. Next, nitric acid was added to a 3% by mass aqueous solution of potassium permanganate to adjust the pH to 2, thereby preparing a test solution. The polishing pad was immersed in this test solution at 25 ° C. for 48 hours. The container containing the test solution and the polishing pad was shaken 24 hours after the start of the immersion. After a lapse of 48 hours from the start of immersion, the polishing pad was taken out of the test solution, washed with running water, and subjected to ultrasonic cleaning for 5 minutes. Next, the sample was washed with running water, the remaining test liquid was wiped off while applying pressure with kitchen paper, and the tensile strength (b) of the polishing pad was measured in the same manner as described above. From the values of the tensile strength (a) and the tensile strength (b) thus measured, the tensile strength retention was calculated by the following equation.
Tensile strength retention = tensile strength (b) / tensile strength (a) × 100 (%)
（樹脂の劣化度）
上記の（引張強度保持率）の測定における超音波洗浄時の研磨パッドを対象として、洗浄後の洗浄液中に残った劣化した樹脂粉末を目視により評価した。その際の基準としては、外観上明確に劣化樹脂が多いものを最大で１０とし、少ないものを最小で１とし、１０段階で評価した。なお、劣化した樹脂の粉末で大きめのものが多く見られたものは、表２中に「×」を併記して示す。この樹脂の劣化度は、研磨パッドを用いて実際に研磨加工を実施した際の樹脂の劣化の度合いを間接的に評価したものであり、数値が低いほど、耐薬品性に優れ、スラリーに含まれる強酸化剤への耐性が高いことを意味する。
(Degradation of resin)
With respect to the polishing pad at the time of ultrasonic cleaning in the above measurement of (tensile strength retention), deteriorated resin powder remaining in the cleaning liquid after cleaning was visually evaluated. As a criterion at that time, a maximum of 10 was clearly evaluated as having a large amount of deteriorated resin, and a minimum of 1 was assumed as a minimum with a small amount of deteriorated resin. The deteriorated resin powder, which is often large, is shown in Table 2 with "x". The degree of deterioration of the resin is an indirect evaluation of the degree of deterioration of the resin when the polishing process is actually performed using a polishing pad. Means high resistance to strong oxidants.
（樹脂の脱落状態）
上記の（引張強度保持率）の測定におけるキッチンペーパーでの拭き取りを行った際、当該キッチンペーパーへの劣化樹脂の付着具合を目視で評価した。その際の基準としては、外観上明確に劣化樹脂の付着が多いものを最大で５とし、少ないものを最小で１とし、５段階で評価した。この樹脂の脱落状態の評価は、研磨パッドを用いて実際に研磨加工を実施した際の樹脂の脱落状態を間接的に評価したものである。数値が低いほど、耐薬品性に優れ、スラリーに含まれる強酸化剤への耐性が高いことを意味する。
(Resin detached state)
When wiping was performed with kitchen paper in the above measurement of (tensile strength retention), the degree of adhesion of the deteriorated resin to the kitchen paper was visually evaluated. As a criterion at that time, a maximum of 5 was observed when the deterioration resin was clearly adhered on the appearance, and a minimum was 1 when the deterioration resin was small. The evaluation of the resin falling state is an indirect evaluation of the resin falling state when polishing is actually performed using a polishing pad. The lower the numerical value, the higher the chemical resistance and the higher the resistance to the strong oxidizing agent contained in the slurry.
（樹脂の劣化状態）
上記の（引張強度保持率）の測定における超音波洗浄の後の研磨パッドを対象として、当該研磨パッド断面の樹脂の劣化具合を電子顕微鏡（ＳＥＭ）で評価した。その際の基準としては、劣化がほとんど進んでいないものを「◎」とし、劣化があまり進んでいないものを「○」とし、劣化が進んでいるものを「△」とし、劣化がかなり進んでいるものを「×」として評価した。また、各例の研磨パッドの断面のＳＥＭ写真（３５〜５００倍）を図１に示す。
(Degradation of resin)
With respect to the polishing pad after the ultrasonic cleaning in the measurement of the (tensile strength retention) described above, the degree of deterioration of the resin on the cross section of the polishing pad was evaluated by an electron microscope (SEM). The criteria at that time were those with little progress in deterioration, ◎, those with little progress as 「, and those with progress as △, Were evaluated as "x". FIG. 1 shows SEM photographs (35 to 500 times) of the cross section of the polishing pad of each example.
本発明の研磨パッドは、レンズ、平行平面板、反射ミラー等の光学材料、ハードディスク用基板、半導体用シリコンウェハ、液晶ディスプレイ用ガラス基板、サファイヤや窒化ガリウムを始めとする難削材等の研磨に特に好適に用いられる。したがって、かかる用途に産業上の利用可能性がある。 The polishing pad of the present invention is used for polishing optical materials such as lenses, parallel flat plates, and reflection mirrors, substrates for hard disks, silicon wafers for semiconductors, glass substrates for liquid crystal displays, and difficult-to-cut materials such as sapphire and gallium nitride. Particularly preferably used. Therefore, such uses have industrial applicability.
Claims (11)
前記樹脂は、第１の樹脂と、当該第１の樹脂とは異なる第２の樹脂と、を含み、
前記研磨パッドの引張強度に対する、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整した溶液に前記研磨パッドを２５℃で４８時間浸漬したときの前記研磨パッドの引張強度の比が、４５％以上であり、
前記第１の樹脂が、ポリウレタン樹脂を含み、
前記第２の樹脂が、ウレタンプレポリマーと硬化剤との反応物であり、
前記ウレタンプレポリマーのＮＣＯ当量が、５００以下である、研磨パッド。 A polishing pad having a nonwoven fabric and a resin,
The resin includes a first resin and a second resin different from the first resin,
The ratio of the tensile strength of the polishing pad when the polishing pad is immersed in a solution adjusted to pH 2 by adding nitric acid to a 3% by mass aqueous solution of potassium permanganate at 25 ° C. for 48 hours with respect to the tensile strength of the polishing pad is , 45% or more,
Wherein the first resin is, only it contains a polyurethane resin,
The second resin is a reaction product of a urethane prepolymer and a curing agent,
A polishing pad, wherein the urethane prepolymer has an NCO equivalent of 500 or less .
前記樹脂含浸不織布を、前記第１の樹脂が可溶な溶媒に浸漬する浸漬工程と、
前記浸漬工程の後の前記樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと硬化剤とを含む溶液に含浸する２次含浸工程と、
を有する方法から得られる、請求項１〜６のいずれか１項に記載の研磨パッド。 A primary impregnation step of impregnating the nonwoven fabric with a resin solution containing the first resin and performing wet coagulation to obtain a resin-impregnated nonwoven fabric;
An immersion step of immersing the resin-impregnated nonwoven fabric in a solvent in which the first resin is soluble;
A second impregnation step of impregnating the resin-impregnated nonwoven fabric after the immersion step with a solution containing a urethane prepolymer having an NCO equivalent of 500 or less and a curing agent;
The polishing pad according to any one of claims 1 to 6 , which is obtained from a method having the following.
前記樹脂含浸不織布を、前記ポリウレタン樹脂が可溶な溶媒に浸漬する浸漬工程と、
前記浸漬工程の後の前記樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと硬化剤とを含む溶液に含浸する２次含浸工程と、
を有する、研磨パッドの製造方法。 A primary impregnation step of impregnating the nonwoven fabric with a resin solution containing a polyurethane resin and performing wet coagulation to obtain a resin-impregnated nonwoven fabric;
An immersion step of immersing the resin-impregnated nonwoven fabric in a solvent in which the polyurethane resin is soluble,
A second impregnation step of impregnating the resin-impregnated nonwoven fabric after the immersion step with a solution containing a urethane prepolymer having an NCO equivalent of 500 or less and a curing agent;
A method for producing a polishing pad, comprising:
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