WO2022070936A1 - 研磨パッド及び研磨パッドの製造方法 - Google Patents
研磨パッド及び研磨パッドの製造方法 Download PDFInfo
- Publication number
- WO2022070936A1 WO2022070936A1 PCT/JP2021/034032 JP2021034032W WO2022070936A1 WO 2022070936 A1 WO2022070936 A1 WO 2022070936A1 JP 2021034032 W JP2021034032 W JP 2021034032W WO 2022070936 A1 WO2022070936 A1 WO 2022070936A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- polishing pad
- resin
- hole
- translucent
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 1331
- 238000000034 method Methods 0.000 title description 129
- 238000004519 manufacturing process Methods 0.000 title description 53
- 229920005989 resin Polymers 0.000 claims abstract description 644
- 239000011347 resin Substances 0.000 claims abstract description 644
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 188
- 239000000178 monomer Substances 0.000 claims description 172
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 99
- -1 polyxysilyl viologen Polymers 0.000 claims description 52
- 125000000524 functional group Chemical group 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 24
- 230000000149 penetrating effect Effects 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical class C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000004386 diacrylate group Chemical group 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 7
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 229940105990 diglycerin Drugs 0.000 claims description 5
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 5
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims description 5
- 239000004386 Erythritol Substances 0.000 claims description 4
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 4
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 4
- 235000019414 erythritol Nutrition 0.000 claims description 4
- 229940009714 erythritol Drugs 0.000 claims description 4
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 3
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 175
- 230000003287 optical effect Effects 0.000 abstract description 18
- 239000010410 layer Substances 0.000 description 440
- 239000002002 slurry Substances 0.000 description 192
- 229920005749 polyurethane resin Polymers 0.000 description 78
- 239000000243 solution Substances 0.000 description 68
- 229920000178 Acrylic resin Polymers 0.000 description 61
- 239000004925 Acrylic resin Substances 0.000 description 61
- 238000005259 measurement Methods 0.000 description 54
- 239000011248 coating agent Substances 0.000 description 49
- 238000000576 coating method Methods 0.000 description 49
- 239000000758 substrate Substances 0.000 description 38
- 229920000139 polyethylene terephthalate Polymers 0.000 description 37
- 239000005020 polyethylene terephthalate Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 36
- 239000000463 material Substances 0.000 description 35
- 239000002585 base Substances 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 239000000126 substance Substances 0.000 description 28
- 238000001514 detection method Methods 0.000 description 25
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- 229920006267 polyester film Polymers 0.000 description 24
- 239000010453 quartz Substances 0.000 description 24
- 230000007423 decrease Effects 0.000 description 23
- 239000011521 glass Substances 0.000 description 20
- 230000015271 coagulation Effects 0.000 description 19
- 238000005345 coagulation Methods 0.000 description 19
- 238000007517 polishing process Methods 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 230000002093 peripheral effect Effects 0.000 description 17
- 238000005520 cutting process Methods 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 239000012780 transparent material Substances 0.000 description 15
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 14
- 239000003999 initiator Substances 0.000 description 14
- 229920002635 polyurethane Polymers 0.000 description 14
- 239000004814 polyurethane Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 13
- 229920005668 polycarbonate resin Polymers 0.000 description 13
- 239000004431 polycarbonate resin Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229920001225 polyester resin Polymers 0.000 description 12
- 239000004645 polyester resin Substances 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000001678 irradiating effect Effects 0.000 description 11
- 239000007921 spray Substances 0.000 description 11
- 239000002344 surface layer Substances 0.000 description 11
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 10
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 10
- 238000009832 plasma treatment Methods 0.000 description 10
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 238000004891 communication Methods 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000010559 graft polymerization reaction Methods 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 229920002492 poly(sulfone) Polymers 0.000 description 8
- 229920005672 polyolefin resin Polymers 0.000 description 8
- 229920005990 polystyrene resin Polymers 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000005553 drilling Methods 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 229940105570 ornex Drugs 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 238000004049 embossing Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 235000013772 propylene glycol Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000000411 transmission spectrum Methods 0.000 description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920002396 Polyurea Polymers 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012461 cellulose resin Substances 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 101100064324 Arabidopsis thaliana DTX48 gene Proteins 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000006061 abrasive grain Substances 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- ZTVZLYBCZNMWCF-UHFFFAOYSA-N homocystine Chemical compound [O-]C(=O)C([NH3+])CCSSCCC([NH3+])C([O-])=O ZTVZLYBCZNMWCF-UHFFFAOYSA-N 0.000 description 3
- 150000002440 hydroxy compounds Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000010893 paper waste Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004420 Iupilon Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- NFTVTXIQFYRSHF-UHFFFAOYSA-N 1-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)C(C)OC(=O)C=C NFTVTXIQFYRSHF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- ZBRZSJUFJUMKIM-UHFFFAOYSA-N 3-(1-phenylpropan-2-ylamino)propanenitrile;hydrochloride Chemical compound Cl.N#CCCNC(C)CC1=CC=CC=C1 ZBRZSJUFJUMKIM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000005526 alkyl sulfate group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940098237 dicel Drugs 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- YEIGUXGHHKAURB-UHFFFAOYSA-N viridine Natural products O=C1C2=C3CCC(=O)C3=CC=C2C2(C)C(O)C(OC)C(=O)C3=COC1=C23 YEIGUXGHHKAURB-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/26—Lapping pads for working plane surfaces characterised by the shape of the lapping pad surface, e.g. grooved
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/005—Control means for lapping machines or devices
- B24B37/013—Devices or means for detecting lapping completion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/22—Rubbers synthetic or natural
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67092—Apparatus for mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D7/00—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor
- B24D7/12—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor with apertures for inspecting the surface to be abraded
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
Definitions
- the present invention relates to a polishing pad and a manufacturing method thereof, and particularly to a polishing pad for chemical mechanical polishing (CMP) having a light transmitting region and a manufacturing method thereof. More specifically, the present invention relates to a polishing pad provided with an end point detection window in which the polishing end point can be optically detected.
- CMP chemical mechanical polishing
- CMP chemical mechanical polishing
- a semiconductor manufacturing process particularly, flattening of an interlayer insulating film, metal plug formation, or embedded wiring formation in a multilayer wiring forming process.
- CMP is a technique for polishing using a slurry in which abrasive grains are dispersed in a state where the surface to be polished of the wafer is pressed against the polished surface of the polishing pad.
- the polishing pads used for CMP are roughly classified into hard polishing pads and soft polishing pads.
- the hard polishing pads are a dry molding method in which a curable composition containing a urethane prepolymer is cast into a mold and cured.
- the wet film forming method in which a urethane resin solution is formed in a coagulation bath and dried is the mainstream.
- low defects and step elimination properties of the object to be polished have been highly required, and the number of cases where a soft polishing pad is used in a finish polishing process or the like is increasing.
- the number of layers and high definition of semiconductor devices has dramatically increased, and the yield and throughput (yield) of semiconductor devices have been required to be further improved.
- Sex is required.
- Optical measurement is a method of observing the surface of a wafer through a measurement window provided on the polishing pad.
- a window for measurement is provided on the polishing pad for optical measurement, since the polishing pad is generally not transparent, it is necessary to arrange a transparent material different from the polishing pad in the portion to be the window.
- the light transmittance of this transparent material decreases due to various factors such as scratches on the surface during polishing and dew condensation on the back surface of the transparent material due to the slurry leaking from the gap between the polished region and the transparent material. Therefore, it is difficult to maintain high accuracy in determining the polishing end point from the initial stage of polishing to the final stage of polishing.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2008-221367
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-221367
- a polishing pad has been proposed that prevents moisture derived from the slurry from condensing on the back surface of the light transmittance region and prevents a decrease in light transmittance even when the water leaks from the seam with the region to the back surface side of the light transmittance region. ..
- Patent Document 2 a slurry is formed during polishing by adhering and fixing a light transmitting region to an inner wall of a through hole provided in a polishing substrate with a photocuring adhesive. Polishing pads that can prevent leakage from gaps have been proposed.
- Patent Document 3 the surface of the light transmitting region on the polished surface side is roughened in advance by roughening the surface by sandblasting, etc., from the initial stage of polishing to the final stage of polishing.
- a polishing pad that prevents the occurrence of an end point detection error due to a decrease in light transmittance has been proposed.
- Patent Document 4 Japanese Patent Application Laid-Open No. 2014-104521 states that the window hits the wafer by lowering the window surface from the polished surface of the polishing layer to have recesses. There have been proposed polishing pads that can prevent the window surface from being scratched and reduce polishing scratches on the wafer.
- the polishing pads of Patent Documents 1 and 2 both focus on solving the problem of dew condensation caused by leakage to the side surface or the back surface of the translucent member, and are on the surface of the translucent member. We do not pay attention to the variation in light transmittance due to the presence or absence of slurry. Similarly, with respect to the polishing pad of Patent Document 3, attention is not paid to the variation in light transmittance due to the presence or absence of slurry on the surface of the translucent member. Further, since the polishing pad of Patent Document 3 roughens the window surface, it is difficult to obtain high light transmittance in the first place, and the roughening of the window surface due to the slurry, abrasive grains, dressing, etc. during polishing is different.
- the first aspect of the present invention has been made in view of the above, and an object of the present invention is to provide a polishing pad capable of suppressing variation in light transmittance due to the presence of slurry on the surface of a translucent member. And.
- the present inventors have different light transmittances depending on whether the slurry is present or not on the surface of the translucent member, which causes variation in the light transmittance and makes it difficult to determine the polishing end point with high accuracy.
- the present invention was completed by solving the problem by reducing the water contact angle of the surface of the translucent member on the polished surface side.
- Optical measurement is a method of observing the surface of the wafer through a measurement window provided on the polishing pad.
- a window for measurement is provided on the polishing pad for optical measurement, since the polishing pad is generally not transparent, it is necessary to arrange a transparent material different from the polishing pad in the portion to be the window.
- the light transmittance of this transparent material decreases due to various factors such as scratches on the surface during polishing and dew condensation on the back surface of the transparent material due to the slurry leaking from the gap between the polished region and the transparent material. Therefore, it is difficult to maintain high accuracy in determining the polishing end point from the initial stage of polishing to the final stage of polishing.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2008-221367
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-221367
- a polishing pad has been proposed that prevents moisture derived from the slurry from condensing on the back surface of the light transmitting region even when leaking from the seam with the transmitting region to the back surface side of the light transmitting region, and prevents a decrease in light transmittance.
- Patent Document 5 describes glass as a polishing pad for solving the problem that the surface of a window member is roughened by a slurry and light is scattered to reduce the light transmittance.
- a polishing pad having a water-repellent surface of a window member made of an inorganic transparent material such as the above has been proposed.
- Japanese Patent Application Laid-Open No. 2004-327974 constitutes a window as a polishing pad that solves the problem that the polishing performance is deteriorated because the window member does not have the ability to hold and discharge the slurry.
- a polishing pad in which a water-soluble substance is dispersed and contained in a matrix material has been proposed.
- the polishing pad of Patent Document 1 focuses on solving the problem of dew condensation that leaks to the back surface of the translucent member, and whether or not slurry is present on the surface of the translucent member. We are not paying attention to the variation in light transmittance caused by slurry.
- the polishing pad of Patent Document 5 uses glass as the window member in order to solve the decrease in light transmittance due to the surface of the window member being scraped and roughened by the slurry. Since the window member is harder than the polishing layer, the window member is arranged so that the surface of the window member is located below the surface of the polishing layer, so that the surface of the window member and the surface of the object to be polished are separated from each other. Slurry is likely to intervene.
- the problem is solved by making the surface of the window member water-repellent in order to discharge the slurry, but it is present on the surface of the translucent member during polishing in which the polishing liquid is continuously supplied. It is difficult to reduce the slurry to zero, and the slurry present in a small amount becomes droplet-like due to water repellency, which may cause variations in light transmittance.
- the polishing pad of Patent Document 6 disperses the water-soluble substance in the matrix constituting the window, so that the water-soluble substance comes into contact with water and is released during use, and forms pores for holding the slurry. As a result, the ability to retain and discharge the slurry can be obtained, and it is premised that the water-soluble substance is dispersed throughout the matrix material.
- Patent Document 6 does not pay attention to the variation in light transmittance due to the presence or absence of slurry on the surface of the translucent member. Further, when the hydrophilic substance is kneaded into the matrix material by the method of Patent Document 6, the matrix material and the hydrophilic substance are mixed and the entire window has hydrophilicity, so that the window swells and deforms due to the slurry and is polished. It may also come off the area or cause slurry leakage.
- the second aspect of the present invention has been made in view of the above, and an object of the present invention is to provide a polishing pad capable of suppressing variation in light transmittance due to the presence of slurry on the surface of a translucent member. And.
- the present inventors have different light transmittances depending on whether the slurry is present or not on the surface of the translucent member, which causes variation in the light transmittance and makes it difficult to determine the polishing end point with high accuracy.
- the present invention was completed by solving the problem by coating the surface of the translucent member on the polished surface side with a hydrophilic resin.
- Optical measurement is a method of observing the surface of the wafer through a measurement window provided on the polishing pad.
- a window for measurement is provided on the polishing pad for optical measurement, since the polishing pad is generally not transparent, it is necessary to arrange a transparent material different from the polishing pad in the portion to be the window.
- the light transmittance of this transparent material decreases due to various factors such as scratches on the surface during polishing and dew condensation on the back surface of the transparent material due to the slurry leaking from the gap between the polished region and the transparent material. Therefore, it is difficult to maintain high accuracy in determining the polishing end point from the initial stage of polishing to the final stage of polishing.
- Patent Document 4 Japanese Patent Application Laid-Open No. 2014-104521
- Patent Document 4 states that the window member is recessed from the polished surface in order to suppress the occurrence of polishing scratches due to contact with the object to be polished.
- a polishing pad with a window member arranged at the position has been proposed.
- Patent Document 1 when the back surface of the window member is hydrolyzed, the slurry leaks from the joint between the polished region and the window member to the back surface side of the window member.
- Patent Document 1 there has been proposed a polishing pad that prevents moisture derived from the slurry from condensing on the back surface of the window member and prevents a decrease in light transmittance.
- the polishing pad of Patent Document 4 has a problem that the light transmittance decreases with time because the polishing debris contained in the slurry sinks into the recessed window region and adheres to the window surface.
- the polishing pad of Patent Document 1 focuses on solving the problem of dew condensation that leaks to the side surface or the back surface of the window member, and adheres polishing debris to the surface of the window member on the polishing surface side. It does not improve the problem of sticking.
- the third aspect of the present invention has been made in view of the above, and provides a polishing pad capable of reducing adhesion and adhesion of polishing debris to the surface of the translucent resin member (window member) on the polishing surface side.
- the purpose is to do.
- the present inventors have adhered polishing debris to the surface of the translucent resin member (window member) on the polished surface side by graft-polymerizing a hydrophilic monomer on the surface of the translucent resin member on the polished surface side. We have found that sticking can be reduced and completed the third invention.
- Optical measurement is a method of observing the surface of the wafer through a measurement window provided on the polishing pad.
- a window for measurement is provided on the polishing pad for optical measurement, since the polishing pad is generally not transparent, it is necessary to arrange a transparent material different from the polishing pad in the portion to be the window. If the surface of this transparent material is damaged during polishing, the light transmittance will decrease. Therefore, it is difficult to maintain high accuracy in determining the polishing end point from the initial stage of polishing to the final stage of polishing.
- Patent Document 4 Japanese Unexamined Patent Publication No. 2002-1652
- the polishing pad of Patent Document 4 has a problem that the polishing slurry sinks into the recessed window region and the light transmittance is lowered.
- the polishing pad of Patent Document 7 can promote the discharge of the polishing slurry from the upper surface of the transparent window by providing a window groove in the vicinity of the transparent window, but the value of the light transmittance varies and accurate optical. There is a problem that measurement is difficult.
- the fourth aspect of the present invention has been made in view of the above, and an object of the present invention is to provide a polishing pad capable of suppressing variations in light transmittance.
- the fourth invention occurs between the case where the slurry is present and the case where the slurry is not present on the surface of the translucent resin member by applying a specific resin to the surface of the translucent resin member on the polished surface side. It suppresses large variations in light transmittance, which enables more accurate determination of the polishing end point.
- the first to fourth inventions provide the following.
- a polishing pad having a translucent member and a polishing layer.
- the polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent member is arranged.
- the polishing pad having a water contact angle of 80 degrees or less on the surface on the polishing surface side.
- a polishing pad having a translucent member and a polishing layer The polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent member is arranged.
- the polishing pad whose surface on the polishing surface side is coated with a hydrophilic resin.
- the hydrophilic resin is a resin having an ion-bonding hydrophilic group.
- a polishing pad having a translucent resin member and a polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent resin member is present.
- the resin member is the polishing pad on which a hydrophilic monomer is graft-polymerized on the surface on the polishing surface side.
- An ion complex is formed in the grafted surface resin with a complex-forming polymer selected from polyethylene glycol, polyvinylpyrrolidone, polyxysilyl viologen, polyethyleneimine and polyvinylpyridinium chloride, and polyvinylbenzyltrimethylammonium chloride.
- a polishing pad having a translucent resin member and a polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent resin member is present.
- the resin member is a polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups and having a -C 2-4 alkylene-O- unit at least on the surface on the surface side of the polished surface.
- the polishing pad Having a resin containing a structural unit derived from an acrylate monomer, The polishing pad.
- the polyfunctional (meth) acrylate monomer is described below: A monomer in which a compound having a -C 2-4 alkylene-O- unit and (meth) acrylic acid are ester-bonded, and a trihydric or higher alcohol to which C 2-4 alkylene oxide is added and (meth) acrylic acid.
- the polishing pad according to [13], wherein is at least one selected from the group consisting of ester-bonded monomers.
- the polyfunctional (meth) acrylate monomer is polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, ethoxy.
- the polishing pad according to any one of [13] to [16], which is at least one selected from the group consisting of trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate.
- polishing pad as described in the section.
- the polishing pad When the polished surface has a groove and the polished surface is the upper surface and the opposite surface is the lower surface, is the uppermost portion of the translucent member at the same position as the lowermost portion of the groove?
- the polishing pad When the through hole of the polishing layer is used as the first through hole, the polishing pad further includes another layer having a second through hole having a diameter corresponding to a circle smaller than that of the first through hole.
- the other layer is located on the side opposite to the polishing surface of the polishing layer.
- the first through hole and the second through hole overlap at least partially.
- the translucent member is arranged so that the translucent member exists in the first through hole, [1] to The polishing pad according to any one of [19].
- a polishing pad having a translucent member and a polishing layer.
- the polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent member is arranged.
- the polishing pad having a water contact angle of 80 degrees or less on the surface on the polishing surface side.
- [1-2] The polishing pad according to [1-1], wherein the uppermost portion of the translucent member is lower than the polishing surface when the polishing surface is the upper surface and the opposite surface is the lower surface.
- [1-3] The polishing pad according to [1] or [1-2], wherein the water contact angle of the surface of the translucent member opposite to the polishing surface side is more than 80 degrees.
- Any one of [1-1] to [1-3], wherein the visible light transmittance when the translucent member is irradiated with light having a wavelength of 380 nm to 780 nm is 60% or more. Polishing pad described in. [1-5] The polishing pad according to any one of [1-1] to [1-4], wherein the polishing surface has a groove.
- the polishing pad When the through hole of the polishing layer is used as the first through hole, the polishing pad further includes another layer having a second through hole having a diameter equivalent to a circle smaller than that of the first through hole. Including, The other layer is located on the side opposite to the polishing surface of the polishing layer.
- the first through hole and the second through hole overlap at least partially.
- the translucent member is arranged so that the translucent member exists in the first through hole [1-1]. ]
- the translucent member is arranged so that the translucent member exists in the through hole in the step of providing the through hole in the polishing layer and when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad. Step, where the translucent member is arranged such that one surface thereof is on the polished surface side.
- the second invention also provides the following.
- a polishing pad having a translucent member and a polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent member is arranged.
- the polishing pad whose surface on the polishing surface side is coated with a hydrophilic resin.
- the hydrophilic resin is a resin having an ion-bonding hydrophilic group.
- the surface of the translucent member coated with the resin on the polished surface side has a water contact angle of 50 degrees or less.
- the polished surface is the upper surface and the opposite surface is the lower surface, the uppermost portion of the translucent member coated with the resin is at the same position as or lower than the lowermost portion of the groove. , [2-7] or [2-8].
- polishing pad The item according to any one of [2-1] to [2-9], wherein the shape of the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad is circular.
- Polishing pad When the through hole of the polishing layer is used as the first through hole, the polishing pad further includes another layer having a second through hole having a diameter equivalent to a circle smaller than that of the first through hole. Including, The other layer is located on the side opposite to the polishing surface of the polishing layer. When the polishing pad is viewed from the polishing surface side in the thickness direction, the first through hole and the second through hole overlap at least partially.
- the translucent member When viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, the translucent member is arranged so that the translucent member exists in the first through hole [2-1]. ] To the polishing pad according to any one of [2-10]. [2-12] A step of preparing a translucent member whose at least one surface is coated with a hydrophilic resin and a polishing layer. The translucent member is arranged so that the translucent member exists in the through hole in the step of providing the through hole in the polishing layer and when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad. Step, where the coated surface of the translucent member is arranged so as to be on the polished surface side.
- the third aspect of the present invention also provides the following.
- the polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent resin member is present.
- the resin member is the polishing pad on which a hydrophilic monomer is graft-polymerized on the surface on the polishing surface side.
- the grafted surface resin has an ion complex formed of a complex-forming polymer selected from polyethylene glycol, polyvinylpyrrolidone, polyxysilyl viologen, polyethyleneimine and polyvinylpyridinium chloride.
- polishing pad When the through hole of the polishing layer is used as the first through hole, the polishing pad further includes another layer having a second through hole having a diameter equivalent to a circle smaller than that of the first through hole. Including, The other layer is located on the side opposite to the polishing surface of the polishing layer. When the polishing pad is viewed from the polishing surface side in the thickness direction, the first through hole and the second through hole overlap at least partially.
- the translucent resin member When viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, the translucent resin member is arranged so that the translucent resin member exists in the first through hole [3]. -1] The polishing pad according to any one of [3-9]. [3-11] A step of preparing a polishing layer and a translucent resin member having a hydrophilic monomer graft-polymerized on at least one surface thereof. The translucent resin member is provided so that the translucent resin member exists in the through hole when viewed in the polishing pad thickness direction from the polishing surface side of the polishing pad and the step of providing the through hole in the polishing layer. The step of arranging, where the grafted surface of the translucent resin member is arranged so as to be on the polished surface side.
- a polishing pad having a translucent resin member and a polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, and the translucent resin member is present.
- the resin member is a polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups and having a -C 2-4 alkylene-O- unit at least on the surface on the surface side of the polished surface.
- the polishing pad Having a resin containing a structural unit derived from an acrylate monomer, The polishing pad.
- the polyfunctional (meth) acrylate monomer is described below. A monomer in which a compound having a -C 2-4 alkylene-O- unit and (meth) acrylic acid are ester-bonded, and a trihydric or higher alcohol to which C 2-4 alkylene oxide is added and (meth) acrylic acid. 4-1.
- the polishing pad according to [4-1] wherein is at least one selected from the group consisting of ester-bonded monomers.
- the trihydric or higher alcohol is selected from the group consisting of glycerin, diglycerin, triglycerin, trimethylolpropane, trimethylolpropane, erythritol, pentaerythritol and dipentaerythritol [4-2].
- the polishing pad described in. [4-4] The item according to any one of [4-1] to [4-3], wherein the -C 2-4 alkylene-O- unit is derived from ethylene oxide and / or propylene oxide. Polishing pad.
- the polyfunctional (meth) acrylate monomer is polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate.
- the polishing pad according to any one of [4-1] to [4-4], which is at least one selected from the group consisting of ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate. ..
- polishing pad The item according to any one of [4-1] to [4-9], wherein the shape of the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad is circular. Polishing pad. [4-11] When the through hole of the polishing layer is used as the first through hole, the polishing pad further includes another layer having a second through hole having a diameter equivalent to a circle smaller than that of the first through hole. Including, The other layer is located on the side opposite to the polishing surface of the polishing layer. When the polishing pad is viewed from the polishing surface side in the thickness direction, the first through hole and the second through hole overlap at least partially.
- the translucent resin member When viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, the translucent resin member is arranged so that the translucent resin member exists in the first through hole [4]. -1] The polishing pad according to any one of [4-10]. [4-12] To the polyfunctional (meth) acrylate monomer having a polishing layer and two or more polymerizable functional groups and having a -C 2-4 alkylene-O- unit. A step of preparing a translucent resin member having a resin containing a derived structural unit on at least one surface, The translucent resin member is provided so that the translucent resin member exists in the through hole when viewed in the polishing pad thickness direction from the polishing surface side of the polishing pad and the step of providing the through hole in the polishing layer.
- the step of arranging, here, the surface having the resin containing the structural unit derived from the polyfunctional (meth) acrylate monomer of the translucent resin member is arranged so as to be on the polished surface side.
- the polishing end point can be determined with high accuracy.
- the polishing end point can be determined with high accuracy.
- the polishing pad capable of suppressing variation in light transmittance.
- the polishing end point can be determined with high accuracy.
- FIG. 1 is a perspective view seen in the thickness direction from the polished surface of the polishing pad of one aspect of the present invention.
- FIG. 2A is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 2B is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 3A is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 3B is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 4A is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 4B is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 4C is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 5A is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 5B is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 6A is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- FIG. 6B is a schematic cross-sectional view (cut end face) in the thickness direction of the polishing pad according to one aspect of the present invention.
- the polishing pad of the first aspect of the present invention is a polishing pad having a translucent member and a polishing layer, the polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad is the above-mentioned polishing pad. It has a through hole that penetrates from the polishing surface to the opposite surface, and the translucent member is transparent in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the polishing pad is arranged so that a light-transmitting member is present, and the water contact angle of the surface of the transparent member on the polishing surface side is 80 degrees or less.
- the polishing layer is a layer having a surface (polished surface) that comes into contact with the object to be polished and is polished when the object to be polished such as a semiconductor device is polished.
- the object to be polished is not particularly limited, and examples thereof include a product substrate including a plurality of memory dies or processor dies, a test substrate, a bare substrate, and a gate substrate.
- the substrate can be from various stages of integrated circuit manufacturing, for example, the substrate can be a bare wafer, or it can be one or more deposition layers and / or pattern forming layers.
- the polishing pad of the first aspect of the present invention has a translucent member, that is, a window member.
- a translucent member that is, a window member.
- a visible light (white light) laser, lamp, or the like is used for optical end point detection.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the translucent member is polished as shown in FIGS. 2A and 3A. When arranged so as to be in contact with (or adhere to) the side surface (side wall) of the through hole provided in the layer, or (2) a circle of the through hole having the polishing layer in the lower layer of the polishing layer as shown in FIG. 4A.
- Another layer having a through hole having a circle equivalent diameter smaller than the equivalent diameter is provided, and the translucent member is arranged on the exposed portion 7 caused by the difference in size between the through hole of the polishing layer and the through hole of the other layer.
- the translucent member is sandwiched between the polishing layer and another layer as shown in FIG. 5A, and a part of the translucent member is arranged so as to be exposed in the through hole.
- through holes are provided in both the polishing layer and the other layer, and the translucent member is arranged so as to be in contact with (or adhere to) the side surface of either or both of the through holes. It is a concept including the case of. Among these, (1), (2) or (4) is preferable, (1) or (2) is more preferable, and (2) is even more preferable.
- the translucent member is preferably a transparent resin member.
- the transparent resin member is not particularly limited as long as it has transparency enough to transmit light, and for example, heat of a polyurethane resin, a polyester resin, a phenol resin, a urea resin, a melamine resin, an epoxy resin, an acrylic resin, or the like.
- Thermoplastic resins such as polyethylene and polypropylene
- rubbers such as butadiene rubber and isoprene rubber
- photocurable resins that are cured by light such as ultraviolet rays and electron beams
- photosensitive resins can be used.
- acrylic resin, polyurethane resin, polyester resin, and polystyrene resin are preferable, and acrylic resin is more preferable.
- the surface of the translucent member on the polished surface side is preferably hydrophilized.
- the translucent member may be hydrophilized not only on the surface on the polished surface side but also on the surface (back surface) and the side surface opposite to the polished surface, but it is costly to hydrophilize the back surface and the side surface as well.
- the hydrophilization of the back surface and the side surface is not related to the effect of the present invention, it is preferable that only the surface surface on the polished surface side is hydrophilized. By hydrophilizing the surface on the polished surface side, it becomes easy to obtain a translucent member having a water contact angle of 80 degrees or less on the surface on the polished surface side.
- Examples of the means for hydrophilization include physicochemical treatment such as plasma treatment and ultraviolet irradiation treatment, mechanical treatment such as roll blast treatment and embossing treatment, and chemical treatment such as chemical treatment and surface grafting treatment. Be done. Among these, plasma treatment or roll blast treatment is preferable, and plasma treatment is more preferable.
- Plasma processing is a process of hitting the surface of a material with a plasma beam emitted from a rod called an electrode using a high-voltage power supply.
- the roll blasting process is a process of rotating a roll with abrasive grains at high speed to modify the surface.
- the uppermost portion of the translucent member when the polishing surface is the upper surface and the opposite surface is the lower surface, the uppermost portion of the translucent member may be at the same height as the polishing surface and is lower than the polishing surface. It may be, but it is preferably lower than the polished surface (FIG. 2A). Since the uppermost portion of the translucent member is lower than the polished surface, it is possible to prevent the occurrence of polishing scratches due to the translucent member that is harder than the polishing layer.
- the slurry enters the recess surrounded by the translucent member and the side surface of the through hole, and most of the slurry moves to the side surface of the through hole by centrifugal force to form a groove. Since it is discharged through the light-transmitting member, a small amount of slurry may or may not remain on the surface of the translucent member. However, when a conventional polishing pad is used, the light transmittance differs between the case where a small amount of slurry remains in the translucent member and the case where it does not remain, so that the polishing end point is determined with high accuracy. It's difficult.
- the surface of the translucent member is made hydrophilic so that it becomes more compatible with the slurry, and even when a small amount of slurry is present, it can be applied to the window surface.
- the fluctuation of the light transmittance is reduced from the initial stage to the final stage of polishing, and even if the uppermost portion of the translucent member is located lower than the polishing surface, the uppermost portion 4'of the translucent member is particularly present.
- the polishing end point can be determined with high accuracy even if it is at the same position as or lower than the bottom 8'of the groove.
- the polishing pad of the first aspect of the present invention has a water contact angle of 80 degrees or less on the surface of the translucent member on the polishing surface side.
- the water contact angle is preferably 5 to 80 degrees, more preferably 5 to 50 degrees, even more preferably 5 to 30 degrees, and even more preferably 5 to 20 degrees.
- Window members used in conventional polishing pads generally have a water contact angle of more than 80 degrees.
- the window member is preferably hydrophobic with a water contact angle of more than 80 degrees, and in the present invention, it is preferable to hydrophilize only the surface on the polished surface side so that the water contact angle is 80 degrees or less.
- the method of setting the water contact angle of the surface of the translucent member on the polished surface side to 80 degrees or less there is no particular limitation on the method of setting the water contact angle of the surface of the translucent member on the polished surface side to 80 degrees or less, but the surface on the polished surface side is hydrophilized and the water on the surface on the polished surface side is treated. It is preferable to use one having a contact angle of 80 degrees or less.
- the hydrophilization treatment means include the above.
- the water contact angle on the surface on the polished surface side may be 80 degrees or less, and the water contact angle on the back surface or the side surface is not particularly limited. Therefore, the water contact angle on the back surface and the side surface may be more than 80 degrees. That is, the back surface and the side surface of the translucent member may not be hydrophilized.
- the visible light transmittance in the present specification, it may be simply referred to as light transmittance
- the translucent member when the translucent member is irradiated with light having a wavelength of 380 nm to 780 nm is determined. It is preferably 60% or more, more preferably 62% or more, further preferably 65% or more, further preferably 70% or more, further preferably 75% or more, and even more preferably 80. % Or more is even more preferable, and 85% or more is even more preferable.
- the light transmittance when water is adhered to the surface of the translucent member is preferably 60% or more, more preferably 62% or more.
- the light transmittance when water is not adhered to the surface of the translucent member is preferably 60% or more, more preferably 62% or more. It is more preferably 65% or more, even more preferably 70% or more, even more preferably 75% or more, even more preferably 80% or more, and even more preferably 85% or more. Even more preferable.
- the polishing pad according to the first aspect of the present invention has the light transmittance when water is not adhered to the surface of the translucent member and the light transmittance when water is adhered to the surface of the translucent member.
- the difference from the above is preferably 30% or less, more preferably 20% or less, further preferably 15% or less, still more preferably 10% or less, and 8% or less. It is even more preferably, and even more preferably 6% or less, and even more preferably 5% or less.
- the difference in light transmittance is less likely to occur between the case where the slurry is present on the surface of the translucent member and the case where there is no slurry, and the determination of the polishing end point is made with high accuracy. Can be done.
- the light transmittance can be measured by measuring a transmission spectrum having a wavelength of 300 to 1000 nm with a spectrophotometer and determining it as the visible light transmittance (%) of the Japanese Industrial Standards (JIS A5759: 2008). That is, the transmittance of each wavelength in the range of 380 to 780 nm is measured, and the weight obtained from the spectral distribution of CIE (International Lighting Commission) daylight D65, the wavelength distribution of CIE bright adaptation standard relative visibility, and the wavelength interval. It is the transmittance obtained by multiplying the transmittance at each wavelength by the weight coefficient and averaging the valence coefficient.
- CIE International Lighting Commission
- the measurement of the light transmittance when water is adhered to the surface of the translucent member is 0.01 for a translucent member cut out to a size of 9 mm ⁇ 50 mm by a spray. (Approximately 0.03 mL) of water was adhered to the entire surface of the translucent member on the polished surface side, and then the translucent member was placed perpendicular to the ground and allowed to stand for 60 seconds to drain water. This can be done using a light member.
- the through hole is a hole that penetrates from the polishing surface to the opposite surface when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the through hole preferably penetrates the polishing layer parallel to the thickness direction or perpendicular to the polishing surface.
- One through hole may be provided in the polishing layer, or two or more through holes that are separated from each other and independent of each other may be provided.
- Examples of the shape of the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad or the shape of the through hole on the polishing surface include a circle, an ellipse, a triangle, a quadrangle, a hexagon, and an octagon. ..
- the same or different shapes may be a shape in which the same or different shapes partially overlap each other. Among these, a circular shape that does not form a corner where polishing debris easily collects is particularly preferable.
- the circle-equivalent diameter is the diameter of a perfect circle corresponding to the area of the figure to be measured.
- the circle-equivalent diameter of the through hole is the circle-equivalent diameter of the through hole when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction, and when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction. When the shape of the through hole is circular, it corresponds to the diameter.
- the equivalent circle diameter of the through hole is not particularly limited, but is preferably 5 to 40 mm, more preferably 5 to 30 mm, and even more preferably 10 to 28 mm.
- the area of the through holes on the polished surface is preferably 0.003 to 0.5%, more preferably 0.004 to 0.4%, based on the total area of the polished surface. Even more preferably, it is 003 to 0.3%.
- the resin constituting the polishing layer includes polyurethane resins such as polyurethane and polyurethane polyurea; acrylic resins such as polyacrylate and polyacrylonitrile; vinyl resins such as polyvinyl chloride, polyvinyl acetate and polyvinylidene fluoride; polysulfone and poly.
- polysulfone-based resins such as ether sulfone
- acylated cellulose-based resins such as acetylated cellulose and butyrylated cellulose
- polyamide-based resins and polystyrene-based resins.
- polyurethane resin is more preferable in consideration of compression characteristics and flexibility.
- the polishing layer may be composed of one kind of resin or may be made of two or more kinds of resins. Further, the polishing layer preferably has open cells.
- the open bubbles referred to here refer to foaming having a space in which adjacent bubbles are connected to each other by communication holes.
- a resin by a wet film forming method, a dry molding, or a foam by injection molding may be used. It is preferably a wet film forming method, and good bending and stretching motion can be expected.
- the resin formed by the wet film forming method means a resin (preferably polyurethane resin) formed by the wet film forming method.
- the wet film forming method is a method in which a resin to be formed is dissolved in an organic solvent, the resin solution is applied to a sheet-shaped substrate, and then the resin is passed through a coagulating solution to solidify the resin.
- the wet-formed resin generally has a plurality of teardrop-shaped bubbles (a shape having anisotropy and a structure having a large diameter from the polished surface to the bottom of the polishing pad). Therefore, the wet-formed resin can be rephrased as a resin having a plurality of tear-shaped bubbles.
- the plurality of tear-shaped bubbles are preferably in the form of open cells.
- the polishing pad of the first aspect of the present invention preferably has a groove on the polished surface of the polishing layer.
- the groove does not penetrate the polishing layer and can be distinguished from the through hole.
- Examples of the groove include an embossed groove obtained by embossing the polished surface and a cutting groove obtained by cutting with a cutting tool. Of these, the embossed groove is preferable.
- the depth of the groove is not particularly limited as long as it is smaller than the thickness of the polishing layer, but is preferably 50 to 90%, more preferably 60 to 80% of the thickness of the polishing layer.
- the groove depth is deep.
- the processing pressure or the processing temperature which causes deformation of the base material (PET) on the back surface of the polishing layer and deterioration of the surface of the polishing layer.
- the cross-sectional shape of the groove is not particularly limited, and may be an arc shape, a U shape, a V shape, a rectangular shape, a trapezoidal shape, or another polygonal shape, and a combination of these two or more shapes. It may be.
- the number and shape of the grooves are not particularly limited, and the number and shape of the grooves may be appropriately adjusted according to the purpose of use of the polishing pad and the like. Examples of the shape include a grid shape, a radial shape, a concentric circle shape, a honeycomb shape, and the like, and these may be combined.
- the surface of the polishing layer may be opened by grinding (buffing) or sliced.
- polishing pad of the first aspect of the present invention when the polishing surface is the upper surface and the opposite surface is the lower surface, even if the uppermost portion 4'of the translucent member is located higher than the lowermost portion 8'of the groove. , It may be in the same position as the bottom 8'or lower than the bottom 8', but it is preferably in the same position as or lower than the bottom 8'of the groove. It is more preferable that the uppermost portion 4'of the translucent member is located lower than the lowermost portion 8'of the groove. Polishing pads generally end their life when polished to the point where the grooves on the polished surface are gone, but the grooves disappear when the top of the translucent member is at or below the bottom of the groove. Up to can use polishing pads.
- the polishing pad of one aspect of the present invention polishing pad of FIG. 4A
- the slurry and polishing debris that have entered the recess in the first through hole are placed on the side surface of the first through hole by the centrifugal force during the polishing process. Since it moves and becomes difficult to see from the second through hole having a small equivalent circle diameter, it is possible to prevent a decrease in light transmittance.
- the light transmittance is unlikely to decrease due to the slurry, so that stable light detection is possible. Is possible.
- the polishing pad according to the first aspect of the present invention has a water contact angle of 80 degrees or less on the surface of the translucent member on the polished surface side, so that the presence or absence of slurry on the surface of the translucent member on the polished surface side is present. Has little effect on light transmittance. As a result, the polishing end point can be determined with high accuracy. Further, in the polishing pad of the first aspect of the present invention, when the polishing surface is the upper surface and the opposite surface is the lower surface, the translucent member is provided even if the translucent member is at the same height as the polishing surface. The effect is exhibited even if the position is lower than the polished surface, but the effect is more exhibited especially when the translucent member is located at a position lower than the polished surface.
- the translucent member when the translucent member is located at a position lower than the polished surface, there is a recess (for example, a columnar recess) surrounded by the surface of the translucent member and the side surface of the through hole. Slurry enters. Most of the slurry that has entered the recess moves to the side surface under the influence of centrifugal force and is discharged through the embossed groove, so the slurry exists in the region where the laser light on the surface of the translucent member is transmitted over time.
- a recess for example, a columnar recess
- timing at which the slurry flows into the recess There may be a timing at which the slurry flows into the recess (a timing at which a large amount of slurry flows into the recess, a timing at which the slurry cannot be discharged, etc.) and a timing at which the slurry does not exist.
- the slurry adheres in the form of water droplets or streaks on the window surface without being familiar, so that the parallel light transmittance when the slurry does not exist in the region through which the laser light is transmitted.
- the parallel light transmittance when the slurry is present is significantly reduced due to the scattering of light by the water droplet-like slurry, and the light transmittance during the polishing process tends to vary.
- the water contact angle of the surface of the translucent member on the polished surface side is lowered (hydrophilicized) so that the slurry is not made into water droplets but spreads on the window surface. Therefore, it is possible to suppress the scattering of light and reduce the fluctuation of the light transmittance between the case where the slurry is attached and the case where the slurry is not attached, thereby reducing the variation in the light transmittance during the polishing process. It can be suppressed.
- the polishing pad according to the first aspect of the present invention can be manufactured, for example, by the method described in the section "Method for manufacturing the polishing pad according to the first aspect".
- the polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad has a through hole penetrating from the polishing surface to the opposite surface thereof.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the polishing pad whose surface on the polishing surface side of the translucent member is coated with a hydrophilic resin.
- the polishing layer is a layer having a surface (polished surface) that comes into contact with the object to be polished and is polished when the object to be polished such as a semiconductor device is polished.
- the object to be polished is not particularly limited, and examples thereof include a product substrate including a plurality of memory dies or processor dies, a test substrate, a bare substrate, and a gate substrate.
- the substrate can be from various stages of integrated circuit manufacturing, for example, the substrate can be a bare wafer, or it can be one or more deposition layers and / or pattern forming layers.
- the surface of the translucent member coated with the hydrophilic resin on the polished surface side refers to the coated surface on the surface of the translucent member on the polished surface side.
- the surface of the translucent member coated with the hydrophilic resin on the polished surface side is abbreviated as "the surface of the translucent member” or “the surface of the translucent member on the polished surface side”. I have something to do.
- the uppermost portion of the translucent member coated with the hydrophilic resin is the surface of the translucent member 4 on the polished surface side when the polished surface is the upper surface and the opposite surface is the lower surface. Refers to the upper surface of the coating portion 9 in.
- the polishing pad of the second aspect of the present invention has a translucent member, that is, a window member.
- a translucent member that is, a window member.
- a visible light (white light) laser, lamp, or the like is used for optical end point detection.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the thickness is from the polishing surface of the polishing pad.
- the translucent member is arranged so that the translucent member can be confirmed when the inside of the through hole is viewed in the vertical direction.
- the translucent member is polished as shown in FIGS. 2B and 3B. When it is arranged so as to be in contact with (or adhere to) the side surface (side wall) of the through hole provided in the layer, or (2) the penetration of the polishing layer in the lower layer of the polishing layer as shown in FIG. 4B or FIG. 4C.
- Another layer having a through hole having a circle equivalent diameter smaller than the circle equivalent diameter of the hole is provided, and a translucent member is provided on the exposed portion 7 caused by the difference in size between the through hole of the polishing layer and the through hole of the other layer.
- the translucent member is sandwiched between the polishing layer and another layer as shown in FIG. 5B, and a part of the translucent member is arranged so as to be exposed in the through hole.
- a through hole is provided in both the polishing layer and the other layer, and the translucent member is in contact with (or adheres to) the side surface of either or both of the through holes. It is a concept including the case where is arranged. Among these, (1), (2) or (4) is preferable, (1) or (2) is more preferable, and (2) is even more preferable.
- the translucent member is preferably a transparent resin member.
- the transparent resin member is not particularly limited as long as it has transparency enough to transmit light, and for example, heat of a polyurethane resin, a polyester resin, a phenol resin, a urea resin, a melamine resin, an epoxy resin, an acrylic resin, or the like.
- Thermoplastic resins such as polyethylene and polypropylene
- rubbers such as butadiene rubber and isoprene rubber
- photocurable resins that are cured by light such as ultraviolet rays and electron beams
- photosensitive resins can be used.
- acrylic resin, polyurethane resin, polyester resin, and polystyrene resin are preferable, and acrylic resin is more preferable.
- the surface of the translucent member on the polished surface side is preferably coated with a hydrophilic resin.
- the translucent member may be coated not only on the surface on the polished surface side but also on the surface (back surface) and the side surface opposite to the polished surface with the hydrophilic resin, but the back surface and the side surface may also be coated. While it leads to an increase in cost, the hydrophilicity of the back surface and the side surface is not related to the effect of the present invention, so that it is preferable that only the surface surface on the polished surface side is coated with the hydrophilic resin.
- the hydrophilic resin is preferably a resin having a water contact angle of 80 degrees or less when coated on a flat surface, and more preferably a resin having a water contact angle of 50 degrees or less.
- the hydrophilic resin is preferably a resin having an ion-bonding hydrophilic group.
- the resin having an ionic bonding hydrophilic group is a resin containing an ionic bonding hydrophilic group consisting of a cation and an anion.
- the cation and anion are preferably organic cations or organic anions, and more preferably composed of organic cations and organic anions. Further, it is preferable that one of the cation and the anion is covalently bonded to the atom constituting the resin.
- the resin having an ionic bonding hydrophilic group may be a resin containing an ionic bonding hydrophilic group represented by the formula: A + B- ( A + is a cation and B- is an anion). It is more preferable that the resin contains an ion-binding hydrophilic group represented by ⁇ A + B ⁇ or ⁇ B ⁇ A + .
- the ionic-bonding hydrophilic group may be added to the resin, for example, by polymerizing a monomer or oligomer containing an ionic-bonding hydrophilic group together with other monomers or oligomers, if necessary, and is used for coating.
- the side chain of the polymer and the ionic bonding hydrophilic group may be covalently bonded to the resin.
- the resin containing an ionic-binding hydrophilic group has an ionic-binding hydrophilic group in a part or all of the structural units (monomers) constituting the resin.
- the monomer constituting the resin has an ionically bonding hydrophilic group
- the monomer (before UV irradiation) preferably has a functional group having an unsaturated double bond in the side chain, and has an ethylenically unsaturated bond. It is preferable to have a functional group (for example, a vinyl group, an allyl group, an acrylic group, a methacryl group, an acryloyl group, a methacryloyl group, etc.). Since the monomer constituting the resin has an unsaturated double bond in its side chain, the resin can be cured by UV irradiation.
- the monomer containing an ionic bonding hydrophilic group may be synthesized or a commercially available one may be used. Examples of commercially available monomers containing an ionic bonding hydrophilic group include amino ions (manufactured by Nippon Embroidery Co., Ltd.).
- the cation portion of the ionic-bonding hydrophilic group is covalently bonded to the monomer (preferably the side chain of the monomer) constituting the resin, and the anionic portion of the ionic-bonding hydrophilic group It may be ionically bonded with (preferably having a ⁇ A + B— structure at the end of the side chain), or a monomer (preferably) in which the anionic portion of the ionic bonding hydrophilic group constitutes the resin.
- the resin containing an ion-bonding hydrophilic group preferably having a ⁇ B — A + structure at the end of the side chain.
- the cation portion of the ion-binding hydrophilic group is covalently bonded to the monomer constituting the resin and the anionic portion of the ion-binding hydrophilic group is ion-bonded.
- the resin containing an ion-binding hydrophilic group a resin having an ion-binding hydrophilic group in the side chain is preferable.
- the type of the ionic bonding hydrophilic group is not particularly limited, and examples thereof include a hydrophilic group containing an ammonium cation, a phosphonium cation, a sulfonium cation, an imidazolium cation, and a pyridinium cation.
- a hydrophilic group containing an ammonium cation is preferable, and ⁇ A + B ⁇ (A + is an ammonium cation and B ⁇ is an anion) is more preferable, and ⁇ NR 3 + B ⁇ (R is). (Representing a substituent such as a hydrogen atom or an alkyl group) is even more preferable.
- the hydrophilic group represented by ⁇ NR 3 + X ⁇ is preferable (in the formula, R independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, respectively.
- X - represents an anion).
- X - is not particularly limited, but is an alkyl sulfate anion or a sulfonic acid anion (for example, alkyl sulfate ion, polyoxyalkylene alkyl ether sulfate ion, polyoxyalkylene alkylphenyl ether sulfate ion, alkyl sulfonic acid ion, alkyl benzene). It is preferable to contain sulfonic acid ion etc.). It is presumed that these ionic structures are difficult to elute from the resin because the terminal groups have hydrophobicity while having hydrophilicity.
- Examples of the monomer having an ionic bonding hydrophilic group include the following monomers (constituent units) shown in Japanese Patent No. 6209639.
- R b1 is a hydrogen atom or a methyl group
- R b2 is a hydrogen atom or a substituted or unsubstituted C 1-6 alkyl group
- nb is an integer of 1 to 6
- Y b - is as follows. It is an anion represented by the formula (2').
- R' is a substituted or unsubstituted C 12-14 linear alkyl group
- A' is a C 2-4 linear or branched alkylene group
- m is A.
- the average number of added moles of O is 2 to 50.
- Specific examples thereof include salts of (meth) acrylic monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate and polyoxyalkylene alkyl ether sulfate esters.
- hydrophilic resin a resin containing an ionic bonding hydrophilic group is preferable, a resin having a hydrophilic group containing an ammonium cation is more preferable, and a resin containing a hydrophilic group (-NR 3 + X- ) composed of an ammonium cation and an anion is preferable. Is even more preferable, and an acrylic resin containing a hydrophilic group consisting of an ammonium cation and an anion is even more preferable.
- a photocurable resin containing a hydrophilic group composed of an ammonium cation and an anion is also preferable
- a photocurable acrylic resin containing a hydrophilic group composed of an ammonium cation and an anion is also preferable.
- the resin containing an ion-bonding hydrophilic group include Acryt 8WX (modified acrylate polymer, manufactured by Taisei Fine Chemical Co., Ltd.), which is a photocurable polymer containing an ammonium cation.
- the method of coating with a hydrophilic resin is not particularly limited.
- coating with a hydrophilic resin includes a hydrophilic photocurable resin, preferably a photocurable resin containing an ion-binding hydrophilic group, and a photopolymerization initiator. Is mixed, applied to the surface of the translucent member, and then cured by irradiating with ultraviolet rays or the like. At this time, in addition to the hydrophilic photocurable resin, a photocurable resin serving as a binder may be mixed.
- a coating can be obtained by applying the solution after polymerization to the surface of the end point detection window and drying it.
- photopolymerization a coating can be obtained by applying a monomer solution to the surface of the end point detection window and irradiating with ultraviolet rays.
- the photocurable resin used as the binder is not particularly limited, and conventionally known photocurable resins can be used.
- a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule can be mentioned, and commercially available products include NK ester (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and Aronix (Toa). Examples thereof include synthetic (manufactured by Synthetic Co., Ltd.), KAYARAD (manufactured by Nippon Kayaku Co., Ltd.), and funkryl (manufactured by Hitachi Kasei Co., Ltd.).
- the photocurable resin is preferably transparent enough to allow light to pass through after curing.
- the photopolymerization initiator is not particularly limited as long as it can cure the photocurable resin by irradiation with ultraviolet rays, electron beams, or the like, and conventionally known photopolymerization initiators can be used.
- a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator and the like can be mentioned, and examples of commercially available products include Irgacure (manufactured by IGM Resin B.V.).
- the uppermost portion of the translucent member coated with the hydrophilic resin is at the same height as the polishing surface. It may be lower than the polished surface, but preferably lower than the polished surface (FIG. 2B). Since the uppermost portion of the translucent member coated with the hydrophilic resin is lower than the polished surface, it is possible to prevent the occurrence of polishing scratches due to the translucent member harder than the polishing layer.
- the slurry enters the recess surrounded by the translucent member and the side surface of the through hole, and most of the slurry moves to the side surface of the through hole by centrifugal force to form a groove. Since it is discharged through the light-transmitting member, a small amount of slurry may or may not remain on the surface of the translucent member. However, when a conventional polishing pad is used, there is a difference in light transmittance between the case where a small amount of slurry remains on the surface of the translucent member and the case where it does not remain, so that the polishing end point is made highly accurate. Difficult to judge.
- the surface of the translucent member on the polishing surface side is coated with the above resin to improve the compatibility with the slurry, and a small amount of slurry is present. Even in this case, by spreading evenly on the window surface, the fluctuation of the light transmittance is reduced from the initial stage to the final stage of polishing, and even if the uppermost portion of the translucent member is located lower than the polished surface, the translucent member is particularly suitable. Even if the uppermost portion 4'is at the same position as or lower than the lowermost portion 8'of the groove, the polishing end point can be determined with high accuracy.
- the water contact angle of the surface of the translucent member coated with the hydrophilic resin on the polishing surface side is preferably 50 degrees or less, and preferably 30 degrees or less. Even more preferably, it is even more preferably 20 degrees or less, and even more preferably 5 to 20 degrees. When the water contact angle is within the above range, it becomes easy to suppress the variation in the light transmittance due to the presence or absence of the slurry on the surface of the translucent member.
- the water contact angle on the back surface or the side surface of the translucent member is not particularly limited, and the water contact angle on the back surface or the side surface may be more than 50 degrees or more than 80 degrees.
- window members used in conventional polishing pads generally have a water contact angle of more than 80 degrees.
- the window may be swollen and deformed by the slurry, and may be peeled off from the polished area or cause slurry leakage. Therefore, the window member is preferably hydrophobic with a water contact angle of more than 80 degrees, and in the present invention, it is preferable to coat only the surface on the polished surface side with a hydrophilic resin so that the water contact angle is 50 degrees or less.
- the polishing pad of the second aspect of the present invention has a visible light transmittance when water is not attached to the surface of a translucent member coated with a hydrophilic resin (in the present specification, it is simply referred to as light transmittance).
- the difference between the visible light transmittance when water is adhered to the surface of the translucent member is preferably 10% or less, more preferably 8% or less, and 6% or less. Is even more preferably, and even more preferably within 5%.
- the difference in light transmittance is less likely to occur between the case where the slurry is present on the surface of the resin-coated translucent member and the case where there is no slurry, and the polishing end point.
- the light transmittance when water is adhered to the surface of the translucent member coated with the hydrophilic resin is preferably 60% or more, preferably 62%.
- the above is more preferable, 65% or more is even more preferable, 70% or more is even more preferable, 75% or more is even more preferable, and 80% or more is even more preferable.
- the polishing pad according to the second aspect of the present invention preferably has a light transmittance of 60% or more when water is not adhered to the surface of the translucent member coated with the hydrophilic resin.62 % Or more is more preferable, 65% or more is even more preferable, 70% or more is even more preferable, 75% or more is even more preferable, and 80% or more is even more preferable. Even more preferably, it is 85% or more.
- the light transmittance can be measured by measuring a transmission spectrum having a wavelength of 300 to 1000 nm with a spectrophotometer and determining it as the visible light transmittance (%) of the Japanese Industrial Standards (JIS A5759: 2008).
- the transmittance of each wavelength in the range of 380 to 780 nm of each wavelength is measured, and the weight obtained from the spectral distribution of CIE (International Lighting Commission) daylight D65, the wavelength distribution of CIE bright adaptation standard relative visual sensitivity, and the wavelength interval. It is the transmittance obtained by multiplying the transmittance at each wavelength by the weight coefficient and averaging the valence coefficient. Further, the measurement of the light transmittance when water is adhered to the surface of the translucent member coated with the hydrophilic resin is a sufficient amount (for example, a translucent member cut into a size of 9 mm ⁇ 50 mm) by spraying.
- a sufficient amount for example, a translucent member cut into a size of 9 mm ⁇ 50 mm
- the translucent member After adhering water (about 0.01 to 0.03 mL) to the entire surface of the translucent member on the polished surface side, the translucent member is placed perpendicular to the ground and allowed to stand for 60 seconds. This can be done by using a translucent member that has been drained.
- the through hole is a hole that penetrates from the polishing surface to the opposite surface when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the through hole preferably penetrates the polishing layer parallel to the thickness direction or perpendicular to the polishing surface.
- One through hole may be provided in the polishing layer, or two or more through holes that are separated from each other and independent of each other may be provided.
- Examples of the shape of the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad or the shape of the through hole on the polishing surface include a circle, an ellipse, a triangle, a quadrangle, a hexagon, and an octagon. ..
- the same or different shapes may be a shape in which the same or different shapes partially overlap each other. Among these, a circular shape that does not form a corner where polishing debris easily collects is particularly preferable.
- the circle-equivalent diameter is the diameter of a perfect circle corresponding to the area of the figure to be measured.
- the circle-equivalent diameter of the through hole is the circle-equivalent diameter of the through hole when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction, and when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction. When the shape of the through hole is circular, it corresponds to the diameter.
- the equivalent circle diameter of the through hole is not particularly limited, but is preferably 5 to 40 mm, more preferably 5 to 30 mm, and even more preferably 10 to 28 mm.
- the area of the through holes on the polished surface is preferably 0.003 to 0.5%, more preferably 0.004 to 0.4%, based on the total area of the polished surface. Even more preferably, it is 005 to 0.3%.
- the resin constituting the polishing layer includes polyurethane resins such as polyurethane and polyurethane polyurea; acrylic resins such as polyacrylate and polyacrylonitrile; vinyl resins such as polyvinyl chloride, polyvinyl acetate and polyvinylidene fluoride; polysulfone and poly.
- polysulfone-based resins such as ether sulfone
- acylated cellulose-based resins such as acetylated cellulose and butyrylated cellulose
- polyamide-based resins and polystyrene-based resins.
- polyurethane resin is more preferable in consideration of compression characteristics and flexibility.
- the polishing layer may be composed of one kind of resin or may be made of two or more kinds of resins. Further, the polishing layer preferably has open cells.
- the open bubbles referred to here refer to foaming having a space in which adjacent bubbles are connected to each other by communication holes.
- a resin by a wet film forming method, a dry molding, or a foam by injection molding may be used. It is preferably a wet film forming method, and good bending and stretching motion can be expected.
- the resin formed by the wet film forming method means a resin (preferably polyurethane resin) formed by the wet film forming method.
- the wet film forming method is a method in which a resin to be formed is dissolved in an organic solvent, the resin solution is applied to a sheet-shaped substrate, and then the resin is passed through a coagulating solution to solidify the resin.
- the wet-formed resin generally has a plurality of teardrop-shaped bubbles (a shape having anisotropy and a structure having a large diameter from the polished surface to the bottom of the polishing pad). Therefore, the wet-formed resin can be rephrased as a resin having a plurality of tear-shaped bubbles.
- the plurality of tear-shaped bubbles are preferably in the form of open cells.
- the polishing layer constituting the polishing pad of the second aspect of the present invention is preferably a resin sheet (preferably a polyurethane sheet) formed by a wet film forming method, and is a polyurethane sheet containing a plurality of tear-shaped bubbles. It is even more preferable that the polyurethane sheet contains a plurality of teardrop-shaped bubbles and has open cells in which some or all of the bubbles are connected by communication holes.
- the polishing pad of the second aspect of the present invention preferably has a groove on the polished surface of the polishing layer.
- the groove does not penetrate the polishing layer and can be distinguished from the through hole.
- Examples of the groove include an embossed groove obtained by embossing the polished surface and a cutting groove obtained by cutting with a cutting tool. Of these, the embossed groove is preferable.
- the depth of the groove is not particularly limited as long as it is smaller than the thickness of the polishing layer, but is preferably 50 to 90%, more preferably 60 to 80% of the thickness of the polishing layer.
- the groove depth is deep.
- the processing pressure or the processing temperature which causes the base material (PET) on the back surface of the polishing layer to be deformed or the surface of the polishing layer to deteriorate. There is a possibility that it will happen.
- the groove depth is within the above range, these problems are unlikely to occur.
- the cross-sectional shape of the groove is not particularly limited, and may be an arc shape, a U shape, a V shape, a rectangular shape, a trapezoidal shape, or another polygonal shape, and a combination of these two or more shapes. It may be.
- the number and shape of the grooves are not particularly limited, and the number and shape of the grooves may be appropriately adjusted according to the purpose of use of the polishing pad and the like. Examples of the shape include a grid shape, a radial shape, a concentric circle shape, a honeycomb shape, and the like, and these may be combined.
- the surface of the polishing layer may be opened by grinding (buffing) or sliced.
- the uppermost portion 4'(that is, the coating portion 9) of the translucent member coated with the hydrophilic resin is used.
- the top surface may be higher than the bottom 8'of the groove, the same position as the bottom 8', or lower than the bottom 8', but with the bottom 8'of the groove. It is preferably at the same position or at a lower position, and more preferably at a position where the uppermost portion 4'of the translucent member is lower than the lowermost portion 8'of the groove.
- the polishing pad generally ends its life when it is polished until the groove provided on the polished surface disappears, but when the uppermost portion of the translucent member is at the same position as or lower than the lowermost portion of the groove, the groove is formed. You can use the polishing pad until it is gone. Further, in the conventional polishing pad, if the uppermost portion 4'of the translucent member is located at the same position as or lower than the lowermost portion 8'of the groove, the slurry and polishing debris are less likely to be discharged from the groove. , The problem that the light transmittance decreases with time may occur. On the other hand, in the polishing pad of one aspect of the present invention (polishing pad of FIG. 4B or FIG.
- the slurry and polishing debris that have entered the recess in the first through hole have the first through hole due to the centrifugal force during the polishing process. Since it moves to the side surface of the scouring pad and becomes difficult to see from the second through hole having a small equivalent circle diameter, it is possible to prevent a decrease in the light transmittance. Furthermore, even if only a small amount of slurry is present on the surface of the translucent member after most of the slurry has moved to the side surface of the recess, the light transmittance is unlikely to decrease due to the slurry, so that stable light detection is possible. Is possible.
- the polishing pad of the second aspect of the present invention polishes a translucent member by coating the surface of the translucent member on the polished surface side with a hydrophilic resin, preferably a resin containing an ion-bonding hydrophilic group.
- a hydrophilic resin preferably a resin containing an ion-bonding hydrophilic group.
- the light transmittance hardly changes depending on the presence or absence of the slurry on the surface on the surface side.
- the polishing end point can be determined with high accuracy.
- the polishing pad of the second aspect of the present invention when the polishing surface is the upper surface and the opposite surface is the lower surface, the surface of the translucent member coated with resin on the polishing surface side is the same height as the polishing surface.
- timing at which the slurry flows into the recess There may be a timing at which the slurry flows into the recess (a timing at which a large amount of slurry flows into the recess, a timing at which the slurry cannot be discharged, etc.) and a timing at which the slurry does not exist.
- the slurry adheres in the form of water droplets or streaks on the window surface without being familiar, so that the parallel light transmittance when the slurry does not exist in the region through which the laser light is transmitted.
- the parallel light transmittance when the slurry is present is significantly reduced due to the scattering of light by the water droplet-like slurry, and the light transmittance during the polishing process tends to vary.
- the surface of the translucent member on the polished surface side is coated with a hydrophilic resin, preferably a resin containing an ion-binding hydrophilic group, so that the slurry is not formed into water droplets. Since it can be wetted and spread on the window surface, it is possible to suppress the scattering of light and reduce the fluctuation of the light transmittance depending on whether the slurry is attached or not, which makes it possible to reduce the fluctuation of the light transmittance during the polishing process. It is possible to suppress the variation in the light transmittance of.
- the polishing pad of the second aspect of the present invention can be manufactured, for example, by the method described in the section "Method of manufacturing the polishing pad of the second aspect".
- the polishing pad of the third aspect of the present invention is a polishing pad having a translucent resin member and a polishing layer, the polishing layer includes a polishing surface for polishing an object to be polished, and the polishing pad is
- the translucent resin member has a through hole penetrating from the polishing surface to the opposite surface, and the translucent resin member is inside the through hole when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction.
- the translucent resin member is arranged so as to be present in the polishing pad, and the translucent resin member is the polishing pad on which a hydrophilic monomer is graft-polymerized on the surface on the polishing surface side thereof.
- the polishing pad according to the third aspect of the present invention is a polishing pad having a translucent resin member and a polishing layer, and the polishing layer includes a polishing surface for polishing an object to be polished, and the polishing is performed.
- the pad has a through hole penetrating from the polished surface to the opposite surface thereof, and the translucent resin member penetrates when viewed from the polished surface side of the polishing pad in the thickness direction of the polishing pad.
- the translucent resin member is arranged so as to exist in the pores, and the resin on the surface of the translucent resin member on the polished surface side has a polymer containing a hydrophilic monomer as a constituent unit in its side chain. It may be paraphrased as the polishing pad having.
- the polishing layer is a layer having a surface (polished surface) that comes into contact with the object to be polished and is polished when the object to be polished such as a semiconductor device is polished.
- the object to be polished is not particularly limited, and examples thereof include a product substrate including a plurality of memory dies or processor dies, a test substrate, a bare substrate, and a gate substrate.
- the substrate can be from various stages of integrated circuit manufacturing, for example, the substrate can be a bare wafer, or it can be one or more deposition layers and / or pattern forming layers.
- the polishing pad of the third aspect of the present invention has a translucent resin member, that is, a window member.
- a translucent resin member that is, a window member.
- a visible light (white light) laser, lamp, or the like is used for optical end point detection.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- Another layer having a through hole having a circle equivalent diameter smaller than the circle equivalent diameter of the through hole is provided, and the through portion 7 is transparent due to the difference in size between the through hole of the polishing layer and the through hole of the other layer.
- a part of the translucent resin member is exposed in the through hole.
- a through hole is provided in both the polishing layer and the other layer so as to be in contact with (or adhere to) the side surface of either or both of the through holes. It is a concept including the case where the translucent resin member is arranged. Among these, (1), (2) or (4) is preferable, (1) or (2) is more preferable, and (2) is even more preferable.
- the translucent resin member is not particularly limited as long as it is a resin having transparency to the extent that light is transmitted, and for example, a polyurethane resin, a polyester resin, a phenol resin, a urea resin, a melamine resin, an epoxy resin, and the like.
- Thermosetting resin such as acrylic resin, polyurethane resin, polyester resin, polyamide resin, cellulose resin, acrylic resin, polycarbonate resin, halogen resin (polyvinyl chloride, polytetrafluoroethylene, polyfluorovinylidene, etc.), polystyrene resin, And thermoplastic resins such as olefin resins (polyethylene, polypropylene, etc.), rubbers such as butadiene rubber and isoprene rubber, photocurable resins that are cured by light such as ultraviolet rays and electron beams, and photosensitive resins can be used. .. Among these, acrylic resin, polyurethane resin, polyester resin, and polystyrene resin are preferable, and acrylic resin is more preferable.
- the translucent resin member has a certain degree of transparency when the visible light transmittance (sometimes referred to simply as the light transmittance in the present specification) when irradiated with light having a wavelength of 380 nm to 780 nm is 60% or more. It is more preferable, 65% or more to have a certain degree of transparency, 70% or more to have a certain degree of transparency, and 75% or more to have a certain degree of transparency. It is even more preferable to have a certain degree of transparency at 80% or more.
- the visible light transmittance can be measured by measuring a transmission spectrum having a wavelength of 300 to 1000 nm with a spectrophotometer and obtaining it as the visible light transmittance (%) of the Japanese Industrial Standards (JIS A5759: 2008).
- a hydrophilic monomer is graft-polymerized on the surface of the translucent resin member on the polishing surface side.
- a hydrophilic monomer is graft-polymerized on the surface of the translucent resin member on the polished surface side
- the translucent resin on the surface on the polished surface side is hydrophilic. It means that the monomers are bonded by graft polymerization. Therefore, the resin present on the surface of the translucent resin member on the polished surface side has a polymer having a hydrophilic monomer as a constituent unit in its side chain.
- the polishing pad according to the third aspect of the present invention is a translucent resin because a hydrophilic monomer is graft-polymerized on the surface of the translucent resin member on the polishing surface side (hereinafter, may be referred to as grafting). It is possible to reduce the adhesion and adhesion of polishing debris to the surface of the member. The reason why the adhesion / adhesion of polishing debris to the surface of the translucent resin member can be reduced by grafting is not clear, but it is presumed as follows. That is, in the polishing pad of the third aspect of the present invention, the resin on the surface of the translucent resin member on the polishing surface side has a long side chain due to grafting.
- This long side chain adsorbs water molecules to form a film of water, and the polishing debris that has flowed to the surface of the translucent resin member does not easily adhere to or adhere to the surface of the translucent resin member, and is also polished. It is presumed that the polishing debris can be prevented from adhering and sticking to the surface of the translucent resin member by causing the polishing debris to flow out from the surface of the translucent resin member by the centrifugal force at the time.
- Plasma graft polymerization is a method of forming a graft polymerization surface by reacting a monomer such as acrylic acid with a radical formed by plasma surface treatment as a starting point (Journal of the Textile Society, 1985, Vol. 41, No. No. 10, pp. 388-393).
- the plasma treatment refers to a treatment of irradiating a solid surface with plasma generated by the ionization action of the inert gas by discharging in an inert gas atmosphere.
- the inert gas in the plasma treatment include nitrogen gas, argon gas, oxygen gas, helium gas, neon gas, xenon gas and the like.
- the plasma can be generated by any of the known methods for generating the plasma.
- a monomer can be placed under vacuum between parallel plate electrodes connected to a high frequency generator and plasma can be generated using either the outside or inside parallel plate of the vacuum chamber.
- an electric field may be generated by an external induction coil to generate plasma of ionized gas, or conversely, plasma may be generated by directly putting the charged electrodes in a vacuum chamber at intervals.
- the translucent resin member is taken out from the plasma processing apparatus and immersed in an aqueous solution containing the hydrophilic monomer. It is preferable to graft-polymerize the hydrophilic unsaturated monomer to the translucent resin member.
- the hydrophilic monomer refers to a monomer having a functional group capable of adsorbing water molecules around it.
- a hydrophilic monomer having an unsaturated double bond is preferable, and a hydrophilic monomer having a vinyl group or an allylic group is more preferable.
- the hydrophilic monomer used for grafting is not particularly limited as long as it is a hydrophilic monomer, and conventionally known monomers can be used.
- hydrophilic monomers examples include acrylamide, methacrylicamide, N-vinylpyrrolidone; acrylic acid, methacrylic acid, P-styrene sulfonic acid, vinyl sulfonic acid, 2-methacryloyloxyethyl sulfonic acid, 3-methacryloyloxy-2.
- acrylic monomers are preferable, and acrylic acid, methacrylic acid, 2 hydroxyethyl methacrylate, 2 hydroxyethyl acrylate, acrylamide, methacrylic acid, 2acrylamide-2-methylpropanesulfonic acid, N, N dimethylaminoethyl methacrylate or N. , N Dimethylaminoethyl acrylate is more preferable, acrylic acid and methacrylic acid are even more preferable, and acrylic acid is even more preferable.
- the hydrophilic monomer one kind may be used alone, or two or more kinds may be used in combination.
- the translucent resin member may be formed into a complex by further reacting a polymer with a graft polymer formed by grafting the surface on the polished surface side.
- the graft polymer contains or consists of a monomer having a carboxylic acid group such as an acrylic monomer (for example, acrylic acid or methacrylic acid) or maleic anhydride.
- examples of the complex-forming polymer include cationic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyxysilyl viologen, polyethyleneimine and polyvinylpyridinium chloride, and polyvinylbenzyltrimethylammonium chloride.
- the graft polymer contains or consists of a basic monomer such as acrylamide, methacrylamide, vinylpyridine, N, N-dimethylaminoethyl methacrylate or N, N-dimethylaminoethyl acrylate (cationic).
- a basic monomer such as acrylamide, methacrylamide, vinylpyridine, N, N-dimethylaminoethyl methacrylate or N, N-dimethylaminoethyl acrylate (cationic).
- examples of the complex-forming polymer include anionic polymers such as polyacrylic acid, polymethacrylic acid, poly2-acrylamide-2methylpropanesulfonic acid, polystyrenesulfonic acid, and polyvinylsulfonic acid.
- the surface resin grafted with the acrylic monomer is a complex-forming polymer selected from polyethylene glycol, polyvinylpyrrolidone, polyxysilylbiologen, polyethyleneimine, polyvinylpyridinium chloride and polyvinylbenzyltrimethylammonium chloride between the molecules. It is preferably linked by interaction, and more preferably linked by intermolecular interaction with polyvinylbenzyltrimethylammonium chloride. Intermolecular interactions, such as hydrogen bonds and ionic bonds, act between the polymer chain and the complex-forming polymer by graft polymerization to form a complex consisting of an ionic complex.
- the ion present in the graft group and the counterion of the complex-forming polymer increase the adsorption points of water molecules, so that the contact angle is further lowered and the translucent resin member.
- the hydrophilicity of the surface can be further enhanced.
- dirt such as polishing debris is less likely to adhere or adhere.
- the composite formation with the composite-forming polymer can be formed, for example, by immersing the translucent resin member graft-polymerized with the hydrophilic monomer in the composite-forming polymer aqueous solution for a predetermined time.
- the translucent resin member may be grafted not only with the resin on the surface on the polished surface side but also on the surface (back surface) and the side surface opposite to the polished surface, but the back surface and the side surface are also grafted. While doing so leads to increased costs, backside and side surface grafting has nothing to do with the effectiveness of the invention. Further, when the resin on the side surface or the back surface of the translucent resin member is grafted, the surface in contact with the polishing layer becomes hydrophilic, so that the translucent resin member swells and deforms due to the slurry and peels off from the polishing area. May cause slurry leakage. For the above reasons, it is preferable that only the resin on the surface on the polished surface side is grafted.
- the polishing pad of the third aspect of the present invention has a water contact angle of 80 degrees or less on the surface of the translucent resin member on the polishing surface side.
- the water contact angle is preferably 60 degrees or less, more preferably 50 degrees or less, even more preferably 30 degrees or less, even more preferably 20 degrees or less, and 1 to 20 degrees. Is even more preferably 2 to 15 degrees, even more preferably 3 to 10 degrees.
- the water contact angle is within the above range, it is easy to prevent the polishing debris from adhering to or sticking to the surface of the translucent resin member (window member) on the polishing surface side.
- the reason why it becomes easy to prevent the polishing debris from adhering to or sticking to the surface of the translucent resin member (window member) on the polishing surface side is as follows. ..
- the resin on the surface of the translucent resin member on the polished surface side has a long side chain due to grafting, and water molecules are adsorbed on the side chain. Since the adjacent side chains have the same charge, they repel each other, so that many water molecules are adsorbed and the wettability is improved. At this time, the water on the surface of the translucent resin member on the polished surface side is considered to be improved.
- the contact angle is hydrophilic with a contact angle of 80 degrees or less, water molecules adhering to the side chain portion are likely to form a water film, and the abrasive debris is easily discharged from the translucent resin member together with the slurry, resulting in this. It is considered that the adhesion and sticking of polishing debris can be suppressed.
- the polishing pad of the third aspect of the present invention is not particularly limited in the water contact angle of the back surface and the side surface of the translucent resin member. Therefore, the water contact angle on the back surface and the side surface may be more than 80 degrees. That is, the back surface and the side surface of the translucent resin member may not be grafted.
- Window members used in conventional polishing pads generally have a water contact angle of more than 80 degrees. When a window having a water contact angle of 80 degrees or less on the entire surface of the window member is used, the window may be swollen and deformed by the slurry, and may be peeled off from the polished area or cause slurry leakage.
- a window member having a hydrophobic water contact angle of more than 80 degrees is preferable, and it is preferable that only the surface on the polished surface side has a water contact angle of 80 degrees or less.
- only the resin on the surface on the polished surface side is grafted, so that the water contact angle on the surface on the polished surface side is 80 degrees or less (the water contact angle on the side surface and the back surface is more than 80 degrees). Yes) It is preferable to use a translucent resin member.
- the grafted surface 9 (upper surface of the translucent resin member) of the translucent resin member is polished. It may be the same as the surface or lower than the polished surface, but is preferably lower than the polished surface (FIG. 2B). Since the grafted surface 9 of the translucent resin member is lower than the polished surface, it is possible to prevent the occurrence of polishing scratches due to the translucent resin member that is harder than the polishing layer. Further, when the upper surface of the translucent resin member is lower than the polished surface, the polishing debris generally enters the recess surrounded by the translucent resin member and the side surface of the through hole and adheres to the surface of the translucent resin member.
- the polishing pad of the third aspect of the present invention the resin existing on the surface of the translucent resin member is grafted with a hydrophilic monomer, so that even if the polishing debris enters the recess, it does.
- the polishing debris can be poured out together with the slurry to the side surface of the recess or the groove portion, and it becomes easy to prevent the polishing debris from adhering to or sticking to the surface of the translucent resin member.
- the through hole is a hole that penetrates from the polishing surface to the opposite surface when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the through hole preferably penetrates the polishing layer parallel to the thickness direction or perpendicular to the polishing surface.
- One through hole may be provided in the polishing layer, or two or more through holes that are separated from each other and independent of each other may be provided.
- Examples of the shape of the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad or the shape of the through hole on the polishing surface include a circle, an ellipse, a triangle, a quadrangle, a hexagon, and an octagon. ..
- the same or different shapes may be a shape in which the same or different shapes partially overlap each other. Among these, a circular shape that does not form a corner where polishing debris easily collects is particularly preferable.
- the circle-equivalent diameter is the diameter of a perfect circle corresponding to the area of the figure to be measured.
- the circle-equivalent diameter of the through hole is the circle-equivalent diameter of the through hole when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction, and when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction. When the shape of the through hole is circular, it corresponds to the diameter.
- the equivalent circle diameter of the through hole is not particularly limited, but is preferably 5 to 40 mm, more preferably 5 to 30 mm, and even more preferably 10 to 28 mm.
- the area of the through holes on the polished surface is preferably 0.003 to 0.5%, more preferably 0.004 to 0.4%, based on the total area of the polished surface. Even more preferably, it is 05 to 0.3%.
- the resin constituting the polishing layer includes polyurethane resins such as polyurethane and polyurethane polyurea; acrylic resins such as polyacrylate and polyacrylonitrile; vinyl resins such as polyvinyl chloride, polyvinyl acetate and polyvinylidene fluoride; polysulfone and poly.
- polysulfone-based resins such as ether sulfone
- acylated cellulose-based resins such as acetylated cellulose and butyrylated cellulose
- polyamide-based resins and polystyrene-based resins.
- polyurethane resin is more preferable in consideration of compression characteristics and flexibility.
- the polishing layer may be composed of one kind of resin or may be made of two or more kinds of resins. Further, the polishing layer preferably has open cells.
- the open bubbles referred to here refer to foaming having a space in which adjacent bubbles are connected to each other by communication holes.
- a resin by a wet film forming method, a dry molding, or a foam by injection molding may be used. It is preferably a wet film forming method, and good bending and stretching motion can be expected.
- the resin formed by the wet film forming method means a resin (preferably polyurethane resin) formed by the wet film forming method.
- the wet film forming method is a method in which a resin to be formed is dissolved in an organic solvent, the resin solution is applied to a sheet-shaped substrate, and then the resin is passed through a coagulating solution to solidify the resin.
- the wet-formed resin generally has a plurality of teardrop-shaped bubbles (a shape having anisotropy and a structure having a large diameter from the polished surface to the bottom of the polishing pad). Therefore, the wet-formed resin can be rephrased as a resin having a plurality of tear-shaped bubbles.
- the plurality of tear-shaped bubbles are preferably in the form of open cells.
- the polishing pad of the third aspect of the present invention preferably has a groove on the polished surface of the polishing layer.
- the groove does not penetrate the polishing layer and can be distinguished from the through hole.
- Examples of the groove include an embossed groove obtained by embossing the polished surface and a cutting groove obtained by cutting with a cutting tool. Of these, the embossed groove is preferable.
- the depth of the groove is not particularly limited as long as it is smaller than the thickness of the polishing layer, but is preferably 50 to 90%, more preferably 60 to 80% of the thickness of the polishing layer.
- the groove depth is deep.
- the processing pressure or the processing temperature which causes deformation of the base material (PET) on the back surface of the polishing layer and deterioration of the surface of the polishing layer.
- the cross-sectional shape of the groove is not particularly limited, and may be an arc shape, a U shape, a V shape, a rectangular shape, a trapezoidal shape, or another polygonal shape, and a combination of these two or more shapes. It may be.
- the number and shape of the grooves are not particularly limited, and the number and shape of the grooves may be appropriately adjusted according to the purpose of use of the polishing pad and the like. Examples of the shape include a grid shape, a radial shape, a concentric circle shape, a honeycomb shape, and the like, and these may be combined.
- the surface of the polishing layer may be opened by grinding (buffing) or sliced.
- the grafted surface 9 of the translucent resin member (that is, the upper surface 4 of the translucent resin member).
- ' May be higher than the bottom 8'of the groove, at the same position as the bottom 8', or lower than the bottom 8', but with the bottom 8'of the groove. It is preferably at the same position or lower, and more preferably the grafted surface 9 of the translucent resin member is at a position lower than the bottom 8'of the groove.
- Polishing pads generally end their life when polished to the point where the grooves on the polished surface are exhausted, but if the top of the translucent resin member is at or below the bottom of the groove, the groove will be You can use the polishing pad until it is gone. Further, in the conventional polishing pad, generally, when the upper surface 4'of the translucent resin member is located at the same position as or lower than the lowermost portion 8'of the groove, the slurry and the polishing debris are discharged from the groove. Since it becomes difficult, there may be a problem that the light transmittance decreases with time.
- the polishing debris is hard to adhere to and adhere to the surface of the translucent resin member, it is possible to suppress a decrease in the light reduction rate.
- the polishing pad of one aspect of the present invention (polishing pad of FIG. 4B or FIG. 4C)
- the polishing debris that has entered the recess in the first through hole is applied to the side surface of the first through hole by the centrifugal force during the polishing process. Even if a part of the moving portion remains without being discharged from the groove, it becomes difficult to see from the second through hole having a small equivalent circle diameter, so that it is possible to further prevent a decrease in the light transmittance. This enables stable light detection.
- the polishing pad according to the third aspect of the present invention can be manufactured, for example, by the method described in the section "Method for manufacturing the polishing pad according to the third aspect".
- the polishing pad according to the fourth aspect of the present invention is a polishing pad having a translucent resin member and a polishing layer, wherein the polishing layer has a polishing surface for polishing an object to be polished, and the polishing pad is
- the translucent resin member has a through hole penetrating from the polished surface to the opposite surface thereof, and the translucent resin member is inside the through hole when viewed from the polished surface side of the polishing pad in the thickness direction of the polishing pad.
- the translucent resin member is arranged so as to be present in the transparent resin member, and the translucent resin member is a polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups at least on the surface on the surface side of the polished surface.
- the polishing pad having a resin containing a structural unit derived from the polyfunctional (meth) acrylate monomer having a -C 2-4 alkylene-O- unit.
- a resin containing a structural unit derived from a polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups and having a -C 2-4 alkylene-O- unit. May be abbreviated as a resin containing a structural unit derived from a polyfunctional (meth) acrylate monomer.
- a polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups and having a -C 2-4 alkylene-O- unit can be used as a polyfunctional (meth) acrylate.
- monomer usually abbreviated as monomer.
- the polishing layer is a layer having a surface (polished surface) that comes into contact with the object to be polished and is polished when the object to be polished such as a semiconductor device is polished.
- the object to be polished is not particularly limited, and examples thereof include a product substrate including a plurality of memory dies or processor dies, a test substrate, a bare substrate, and a substrate such as a gate substrate.
- the substrate can be from various stages of integrated circuit manufacturing, for example, the substrate can be a bare wafer, or it can be one or more deposition layers and / or pattern forming layers. Further, referring to FIGS.
- At least the surface of the translucent resin member on the polished surface side is transparent when the polished surface is the upper surface and the opposite surface is the lower surface. Refers to the surface portion 9 on the polished surface side of the light resin member 4.
- the polishing pad of the fourth aspect of the present invention has a translucent resin member, that is, a window member.
- a translucent resin member that is, a window member.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- they are arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad means from the polishing surface of the polishing pad. It is intended that the translucent resin member is arranged so that the translucent resin member can be confirmed when the inside of the through hole is viewed in the thickness direction.
- the polishing layer When the member is arranged so as to be in contact with (or adhere to) the side surface (side wall) of the through hole provided in the polishing layer, or (2) the polishing layer is placed in the lower layer of the polishing layer as shown in FIG. 4B or FIG. 4C. Another layer having a through hole having a circle equivalent diameter smaller than the circle equivalent diameter of the through hole is provided, and the through portion 7 is transparent due to the difference in size between the through hole of the polishing layer and the through hole of the other layer.
- arranging the light-transmitting resin member, or (3) sandwiching the light-transmitting resin member between the polishing layer and another layer as shown in FIG. 5B a part of the light-transmitting resin member is exposed in the through hole. It is a concept including the case where it is arranged so as to be used. Among these, (1) or (2) is preferable, and (2) is more preferable.
- the translucent resin member is not particularly limited as long as it is a resin having transparency to the extent that light is transmitted, and for example, a polyurethane resin, a polyester resin, a phenol resin, a urea resin, a melamine resin, an epoxy resin, and the like.
- Thermosetting resin such as acrylic resin, polyurethane resin, polyester resin, polyamide resin, cellulose resin, acrylic resin, polycarbonate resin, halogen resin (polyvinyl chloride, polytetrafluoroethylene, polyfluorovinylidene, etc.), polystyrene resin, And thermoplastic resins such as olefin resins (polyethylene, polypropylene, etc.), rubbers such as butadiene rubber and isoprene rubber, photocurable resins that are cured by ultraviolet rays, electron beams, and the like, and photosensitive resins can be used.
- acrylic resin, polyurethane resin, polyester resin, and polystyrene resin are preferable, and acrylic resin is more preferable.
- the translucent resin member is not particularly limited as long as it is a resin having transparency enough to transmit light, but the visible light transmittance when irradiated with light having a wavelength of 380 nm to 780 nm (in the present specification). , It may be simply referred to as light transmittance), but it is preferable that it has a certain degree of transparency at 60% or more, more preferably it has a certain degree of transparency at 65% or more, and a certain degree of transparency at 70% or more. It is even more preferable to have, it is even more preferable to have a certain degree of transparency at 75% or more, and even more preferably to have a certain degree of transparency at 80% or more.
- the visible light transmittance can be measured by measuring a transmission spectrum having a wavelength of 300 to 1000 nm with a spectrophotometer and obtaining it as the visible light transmittance (%) of the Japanese Industrial Standards (JIS A5759: 2008).
- the polishing pad of the fourth aspect of the present invention is a polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups on at least the surface of the translucent resin member on the polishing surface side thereof, and is ⁇ C 2 -4 It has a resin containing a structural unit derived from the polyfunctional (meth) acrylate monomer having an alkylene-O- unit. "Having a -C 2-4 alkylene-O- unit” means having one or two or more basic units of -C 2-4 alkylene-O-.
- Having one SI base unit or having multiple SI base units repeats can be rephrased as having (-C 2-4 alkylene-O-) n (n is an integer greater than or equal to 1).
- the number of basic units or the number of n is not particularly limited, but 1 to 30 is preferable, 2 to 28 is more preferable, 3 to 25 is even more preferable, and 4 to 25 is even more preferable.
- the polyfunctional (meth) acrylate monomer may have one type of -C 2-4alkylene -O- unit and may have two or more different types of -C 2-4alkylene -O- unit. May be good.
- the number of -C 2-4alkylene -O- per polyfunctional (meth) acrylate monomer is preferably 1 to 30, more preferably 2 to 28, still more preferably 3 to 25, and further preferably 4 to 25. More preferred.
- the -C 2-4 alkylene-O- unit is preferably the -C 2-3 alkylene-O- unit.
- the -C 2-4 alkylene-O- unit is derived from ethylene oxide (-CH 2 -CH 2 -O-) and / or derived from propylene oxide (-CH 2 -CH (CH 3 )).
- -O- or -CH (CH 3 ) -CH 2 -O- (preferably -CH 2 -CH (CH 3 ) -O-)) is preferable.
- the polyfunctional (meth) acrylate monomer is preferably a polyfunctional (meth) acrylate monomer having -CH 2 -CH 2 -O- unit and / or -CH 2 -CH (CH 3 ) -O- unit.
- the polyfunctional (meth) acrylate monomer contains -C 2-4 alkylene-O- units.
- the -C 2-4 alkylene-O- unit may be present in any polyfunctional (meth) acrylate monomer, for example, may be ester-bonded to the carboxyl group of the (meth) acrylic acid (meth). Meta) It may be bonded to a group bonded to the carboxyl group of acrylic acid (ester bond, amide bond, etc.) (ester bond, ether bond, etc.).
- the translucent resin member may be coated with a resin containing a structural unit derived from a polyfunctional (meth) acrylate monomer at least on the surface of the translucent resin member on the polished surface side, and the translucent resin member itself.
- the resin may be composed of a resin containing a structural unit derived from the polyfunctional (meth) acrylate monomer, but at least the surface of the translucent resin member on the polished surface side is derived from the polyfunctional (meth) acrylate monomer. More preferably, it is coated with a resin containing a structural unit.
- the translucent resin member may be coated not only on the surface on the polished surface side but also on the surface (back surface) and the side surface opposite to the polished surface with the resin, but also on the back surface and the side surface. This leads to an increase in cost, but since the coating on the back surface and the side surface has nothing to do with the effect of the present invention, it is preferable that only the surface surface on the polished surface side is coated with the resin.
- the thickness of the surface layer of the translucent member coated with the resin is not particularly limited, but is preferably 1 to 50 ⁇ m. When the thickness of the surface layer is within the above range, high light transmittance can be obtained.
- Examples of the polyfunctional (meth) acrylate monomer include a monomer in which a compound having (i) -C 2-4alkylene-O-unit and (meth) acrylic acid are ester-bonded, and (ii) C 2-4 alkylene oxide. It is preferable that it is at least one selected from the group consisting of a monomer in which a trihydric or higher alcohol to which is added and (meth) acrylic acid are ester-bonded.
- a monomer in which a compound having a —C 2-3alkylene -O— unit and (meth) acrylic acid are ester-bonded is preferable.
- As the monomer (ii), a monomer in which ethylene oxide and / or a trihydric or higher alcohol to which propylene oxide is added and (meth) acrylic acid are ester-bonded is preferable.
- the polyfunctional (meth) acrylate monomer of (i) above is a compound in which a compound having a -C 2-4alkylene -O- unit and (meth) acrylic acid are ester-bonded, and a (meth) acryloyl group is contained in the molecule. It is a compound having both -C 2-4 alkylene-O- units.
- a bifunctional (meth) acrylate monomer is preferable. Since the resin containing the structural unit derived from the bifunctional (meth) acrylate is relatively excellent in flexibility, it has high adhesion to the substrate and can prevent peeling.
- the number of -C 2-4alkylene -O- per one polyfunctional (meth) acrylate monomer of (i) is preferably 1 to 30, more preferably 4 to 30, and even more preferably 5 to 25. 9 to 25 are even more preferable.
- Examples of compounds having the -C 2-4 alkylene-O- unit include ethylene oxide, propylene oxide, tetramethylene glycol, diethylene oxide, dipropylene oxide, ditetramethylene glycol, triethylene oxide, tripropylene oxide, and tri. Examples thereof include compounds in which (poly) ethylene oxide, (poly) propylene oxide, (poly) tetramethylene glycol and the like, and mono (meth) acrylic acid are bonded, such as tetramethylene glycol.
- a compound in which (poly) ethylene oxide and / or (poly) propylene oxide and mono (meth) acrylic acid are bonded is preferable.
- a polyfunctional, preferably bifunctional (meth) acrylate monomer can be obtained.
- the monomer of (i) above include (poly) C such as (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and (poly) tetramethylene glycol di (meth) acrylate.
- Examples thereof include methoxy- (poly) C 2-4 alkylene glycol di (meth) acrylates such as 2-4 alkylene glycol di (meth) acrylates and methoxy- (poly) ethylene glycol (meth) acrylates.
- (poly) C 2-3 alkylene glycol di (meth) acrylate ((poly) ethylene glycol di (meth) acrylate and / or (poly) propylene glycol di (meth) acrylate) is preferable, and (poly) ethylene.
- Glycoldi (meth) acrylates are more preferred.
- (poly) ethylene glycol includes one ethylene glycol (monoethylene glycol) and two or more ethylene glycols (diethylene glycol, triethylene glycol, tetraethylene glycol, etc.). It is used as a concept that includes both.
- (poly) propylene glycol is used as a concept that includes both one propylene glycol (monopropylene glycol) and two or more propylene glycols (dipropylene glycol, tripropylene glycol, tetrapropylene glycol, etc.). Be done.
- (poly) tetramethylene glycol includes one tetramethylene glycol (monotetramethylene glycol) and two or more tetramethylene glycols (ditetramethylene glycol, tritetramethylene glycol, tetratetramethylene glycol, etc.). It is used as a concept that includes both of.
- the mass average molecular weight of the monomer of (i) is preferably 200 to 1500, preferably 300 to 1200, even more preferably 400 to 1400, and even more preferably 500 to 1300. It is preferably 600 to 1200, even more preferably.
- the polyfunctional (meth) acrylate monomer of (ii) is an ester bond of a trihydric or higher alcohol to which a C 2-4 alkylene oxide is added and (meth) acrylic acid, and (meth) is contained in the molecule. It is a compound having both an acryloyl group and a -C 2-4 alkylene-O- unit.
- 3 to 6 functional (meth) acrylate monomers are preferable, 3 to 5 functional (meth) acrylate monomers are more preferable, and 3 to 4 functional (meth) acrylate monomers are more preferable.
- Acrylate monomers are even more preferred.
- Such a polyfunctional (meth) acrylate can accelerate the curing rate at the time of polymerization, increase the crosslink density, and contribute to the improvement of water resistance.
- the number of basic units of C 2-4 alkylene oxide (-C 2 to 4 alkylene-O-) per one polyfunctional (meth) acrylate monomer of (ii) is preferably 1 to 30, preferably 3 to 30. More preferably, 3 to 25 is even more preferable.
- the trihydric or higher alcohol is preferably at least one selected from the group consisting of glycerin, diglycerin, triglycerin, trimethylolpropane, ditrimethylolpropane, erythritol, pentaerythritol, and dipentaerythritol, and is preferably glycerin. It is more preferably at least one selected from the group consisting of diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol, and at least selected from the group consisting of glycerin, pentaerythritol and trimethylolpropane.
- the trihydric or higher alcohol to which C 2-4 alkylene oxide is added is a trihydric or higher alcohol to which C 2-3 alkylene oxide (ethylene oxide (EO) and / or propylene oxide (PO)) is added.
- EO ethylene oxide
- PO propylene oxide
- Examples of the monomer of (ii) above include C 2-4 alkoxylated pentaerythritol tetra (meth) acrylate, C 2-4 alkoxylated glycerin tri (meth) acrylate, and C 2-4 alkoxylated trimethylolpropane tri (meth).
- Acrylate, dipentaerythritol hexaacrylate can be mentioned.
- C 2-3 alkoxylated pentaerythritol tetra (meth) acrylate, C 2-3 alkoxylated glycerin tri (meth) acrylate and / or C 2-3 alkoxylated trimethylolpropane tri (meth) acrylate are preferable.
- More preferred are C 2-3 alkoxylated pentaerythritol tetra (meth) acrylates and / or C 2-3 alkoxylated glycerintri (meth) acrylates.
- the mass average molecular weight of the monomer of (ii) is preferably 200 to 2000, preferably 300 to 1500, even more preferably 400 to 1300, and even more preferably 500 to 1200. preferable.
- Examples of the polyfunctional (meth) acrylate monomers of (i) and (ii) include polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated glycerin triacrylate, and propoxy. It is preferably at least one selected from the group consisting of glycerin triacrylate, ethoxylated trimethylol propanetriacrylate, and propoxylated trimethylol propanetriacrylate, preferably polyethylene glycol diacrylate, polypropylene glycol diacrylate, and ethoxylated pentaerythritol.
- it is at least one selected from the group consisting of tetraacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated glycerin triacrylate, and propoxylated glycerin triacrylate, and polyethylene glycol diacrylate, ethoxylated pentaerythritol tetraacrylate, and the like. Even more preferably, it is at least one selected from the group consisting of propoxylated pentaerythritol tetraacrylate and ethoxylated glycerin triacrylate.
- EBECRYL 11 polyethylene glycol diacrylate
- A-1000 manufactured by Shin Nakamura Chemical Industry Co., Ltd.
- EBECRYL40 C 2 -3 Alkylated pentaerythritol tetraacrylate
- A-GLY-20E ethoxylated glycerin triacrylate
- the content of the monomer in the resin containing the structural unit derived from the polyfunctional (meth) acrylate monomer is preferably 30 to 100 parts by mass, preferably 40 to 100 parts by mass with respect to 100 parts by mass of all the monomer components constituting the resin. Parts are more preferable, 45 to 100 parts by mass is even more preferable, 70 to 100 parts by mass is even more preferable, 80 to 100 parts by mass is even more preferable, and 100 parts by mass may be used.
- the content of the monomer is preferably 40 to 60 parts by mass with respect to 100 parts by mass of all the constituents of the resin.
- the mass average molecular weight of the resin containing the structural unit derived from the polyfunctional (meth) acrylate monomer is not particularly limited, and those having various mass average molecular weights can be used.
- the mass average molecular weight of the resin may be 500 to 30,000.
- the molecular weight is 500 or more, high hydrophilicity is exhibited, and sufficient durability can be obtained by increasing the molecular weight at the time of cross-linking.
- the molecular weight is 30,000 or less, uniform coating is possible without increasing the viscosity too much.
- the mass average molecular weight of the resin may be 600 to 20000 or 700 to 15000.
- the polyfunctional (meth) acrylate monomer has two or more polymerizable functional groups.
- the polyfunctional (meth) acrylate monomer preferably has 2 to 6 polymerizable functional groups, more preferably 2 to 5 polymerizable functional groups, and 2 to 4 polymerizable functional groups. It is more preferable to have.
- As the polymerizable functional group an ethylenically unsaturated double bond (unsaturated double bond between carbon atoms) is preferable, and an ethylenically unsaturated double bond (unsaturated between carbon atoms) present in the (meth) acryloyl group is preferable. Double bond) is more preferred.
- the resin containing the structural unit derived from polyfunctional (meth) acrylate may further contain the structural unit derived from urethane (meth) acrylate.
- Urethane (meth) acrylate is a compound having a urethane bond obtained by reacting an isocyanate group with a hydroxy group and a (meth) acryloyl group.
- the urethane (meth) acrylate preferably has two or more polymerizable functional groups, more preferably 2 to 4 polymerizable functional groups, and further preferably 2 to 3 polymerizable functional groups. More preferably, it is even more preferable to have two polymerizable functional groups.
- the polymerizable functional group an ethylenically unsaturated double bond (unsaturated double bond between carbon atoms) is preferable, and an ethylenically unsaturated double bond (unsaturated between carbon atoms) present in the (meth) acryloyl group is preferable. Double bond) is more preferred.
- the urethane (meth) acrylate examples include an aliphatic urethane (meth) acrylate and an aromatic urethane (meth) acrylate. Further, the urethane (meth) acrylate preferably does not have a structure derived from polysiloxane. Urethane (meth) acrylate is obtained, for example, by reacting a hydroxy compound having at least two (meth) acryloyl groups with isocyanate. Examples of the isocyanate include aliphatic polyisocyanates and aromatic polyisocyanates.
- Aliphatic urethane (meth) acrylates are obtained, for example, by reacting a hydroxy compound having at least two (meth) acryloyl groups with an aliphatic isocyanate.
- the aliphatic isocyanate include aliphatic diisocyanates and aliphatic triisocyanates.
- Aromatic urethane (meth) acrylates are obtained, for example, by reacting a hydroxy compound having at least two (meth) acryloyl groups with an aromatic isocyanate.
- aromatic isocyanate include aromatic diisocyanate and aromatic triisocyanate.
- the content of the urethane (meth) acrylate is 100% by mass of all the monomer components constituting the resin. It is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less. Further, the constituent component derived from the urethane (meth) acrylate monomer is preferably 40 to 60 parts by mass with respect to 100 parts by mass of all the monomer components of the resin.
- the method of coating with a resin containing a structural unit derived from the polyfunctional (meth) acrylate monomer is not particularly limited, and for example, the polyfunctional (meth) acrylate monomer and other monomers or oligomers (preferably acrylic) as needed. It can be carried out by polymerizing (solution polymerization / photopolymerization) with a system monomer or oligomer by a conventional method. Among these, photopolymerization is preferable. When solution polymerization is used, the polymerization reaction may proceed to obtain a coating while a solution containing the monomer or the like and a polymerization initiator (catalyst or the like) is applied to the surface of the translucent resin member and dried. can.
- a polymerization initiator catalyst or the like
- a coating can be obtained by applying a solution containing the monomer and the like and a photopolymerization initiator to the surface of the translucent resin member and irradiating with ultraviolet rays.
- the photopolymerization initiator is not particularly limited as long as it can cure the photocurable resin by irradiation with ultraviolet rays, electron beams, or the like, and conventionally known photopolymerization initiators can be used.
- a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator and the like can be mentioned, and examples of commercially available products include Irgacure (manufactured by IGM Resin B.V.).
- the uppermost portion of the translucent resin member may be at the same height as the polishing surface. It may be lower, but preferably lower than the polished surface (FIG. 2B). Since the uppermost portion of the translucent resin member is lower than the polished surface, it is possible to prevent the occurrence of polishing scratches due to the translucent resin member that is harder than the polishing layer.
- the slurry enters the recess surrounded by the translucent resin member and the side surface of the through hole, and most of the slurry moves to the side surface of the through hole by centrifugal force. Since the slurry is discharged through the groove, a small amount of slurry may or may not remain on the surface of the translucent resin member.
- the light transmittance differs depending on whether a small amount of slurry remains on the surface of the translucent resin member or not, so the polishing end point can be determined with high accuracy. Difficult to do.
- a resin containing a structural unit derived from the polyfunctional (meth) acrylate monomer is present on the surface of the translucent resin member on the polishing surface side, so that the slurry is present. Even if a small amount of slurry is present, it spreads evenly on the window surface, reducing the fluctuation of the light transmission rate from the beginning to the end of polishing, and the top of the translucent resin member is polished. Even if the position is lower than the surface, the polishing end point can be determined with high accuracy.
- the polishing pad of the fourth aspect of the present invention has a visible light transmittance when water is not adhered to the surface of the translucent resin member on the polishing surface side (in the present specification, it may be simply referred to as light transmittance). ) And the visible light transmittance when water is adhered to the surface of the translucent resin member on the polished surface side, preferably within 10%.
- the difference in light transmittance is within the above range, the difference in light transmittance is less likely to occur between the case where the slurry is present on the surface of the translucent resin member and the case where there is no slurry, and the determination of the polishing end point is highly accurate. Can be done.
- the light transmittance can be measured by measuring a transmission spectrum having a wavelength of 300 to 1000 nm with a spectrophotometer and determining it as the visible light transmittance (%) of the Japanese Industrial Standards (JIS A5759: 2008). That is, the transmittance of each wavelength in the range of 380 to 780 nm of each wavelength is measured, and the weight obtained from the spectral distribution of CIE (International Lighting Commission) daylight D65, the wavelength distribution of CIE bright adaptation standard relative visual sensitivity, and the wavelength interval. It is the transmittance obtained by multiplying the transmittance at each wavelength by the weight coefficient and averaging the valence coefficient.
- CIE International Lighting Commission
- the measurement of the light transmittance when water is adhered to the surface of the translucent resin member on the polished surface side is measured by spraying a sufficient amount (for example, a translucent resin member cut into a size of 9 mm ⁇ 50 mm).
- a sufficient amount for example, a translucent resin member cut into a size of 9 mm ⁇ 50 mm.
- the translucent resin member is placed perpendicular to the ground and allowed to stand for 60 seconds. This can be done by using a translucent resin member that has been drained.
- the through hole is a hole that penetrates from the polishing surface to the opposite surface when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the through hole preferably penetrates the polishing layer parallel to the thickness direction or perpendicular to the polishing surface.
- One through hole may be provided in the polishing layer, or two or more through holes that are separated from each other and independent of each other may be provided.
- Examples of the shape of the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad or the shape of the through hole on the polishing surface include a circle, an ellipse, a triangle, a quadrangle, a hexagon, and an octagon. ..
- the same or different shapes may be a shape in which the same or different shapes partially overlap each other.
- a circular shape is particularly preferable because it does not form a corner where polishing debris easily collects.
- the circle-equivalent diameter is the diameter of a perfect circle corresponding to the area of the figure to be measured.
- the circle-equivalent diameter of the through hole is the circle-equivalent diameter of the through hole when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction, and when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction. When the shape of the through hole is circular, it corresponds to the diameter.
- the equivalent circle diameter of the through hole is not particularly limited, but is preferably 5 to 40 mm, more preferably 5 to 30 mm, and even more preferably 8 to 28 mm.
- the area of the through holes on the polished surface is preferably 0.003 to 0.5%, more preferably 0.004 to 0.4%, based on the total area of the polished surface. Even more preferably, it is 005 to 0.3%.
- the resin constituting the polishing layer includes polyurethane resins such as polyurethane and polyurethane polyurea; acrylic resins such as polyacrylate and polyacrylonitrile; vinyl resins such as polyvinyl chloride, polyvinyl acetate and polyvinylidene fluoride; polysulfone and poly.
- polysulfone-based resins such as ether sulfone
- acylated cellulose-based resins such as acetylated cellulose and butyrylated cellulose
- polyamide-based resins and polystyrene-based resins.
- polyurethane resin is more preferable in consideration of compression characteristics and flexibility.
- the polishing layer may be composed of one kind of resin or may be made of two or more kinds of resins. Further, the polishing layer preferably has open cells.
- the open bubbles referred to here refer to foaming having a space in which adjacent bubbles are connected to each other by communication holes.
- a resin by a wet film forming method, a dry molding, or a foam by injection molding may be used. It is preferably a wet film forming method, and good bending and stretching motion can be expected.
- the resin formed by the wet film forming method means a resin (preferably polyurethane resin) formed by the wet film forming method.
- the wet film forming method is a method in which a resin to be formed is dissolved in an organic solvent, the resin solution is applied to a sheet-shaped substrate, and then the resin is passed through a coagulating solution to solidify the resin.
- the wet-formed resin generally has a plurality of teardrop-shaped bubbles (a shape having anisotropy and a structure having a large diameter from the polished surface to the bottom of the polishing pad). Therefore, the wet-formed resin can be rephrased as a resin having a plurality of tear-shaped bubbles.
- the plurality of tear-shaped bubbles are preferably in the form of open cells.
- the polishing layer constituting the polishing pad of the fourth aspect of the present invention is preferably a resin sheet (preferably a polyurethane sheet) formed by a wet film forming method, and is a polyurethane sheet containing a plurality of tear-shaped bubbles. It is even more preferable that the polyurethane sheet contains a plurality of teardrop-shaped bubbles and has open cells in which some or all of the bubbles are connected by communication holes.
- the polishing pad of the fourth aspect of the present invention preferably has a groove on the polished surface of the polishing layer.
- the groove does not penetrate the polishing layer and can be distinguished from the through hole.
- Examples of the groove include an embossed groove obtained by embossing the polished surface and a cutting groove obtained by cutting with a cutting tool. Of these, the embossed groove is preferable.
- the depth of the groove is not particularly limited as long as it is smaller than the thickness of the polishing layer, but is preferably 50 to 90%, more preferably 60 to 80% of the thickness of the polishing layer.
- the groove depth is deep.
- the processing pressure or the processing temperature which causes the base material (PET) on the back surface of the polishing layer to be deformed or the surface of the polishing layer to deteriorate. There is a possibility that it will happen.
- the groove depth is within the above range, these problems are unlikely to occur.
- the cross-sectional shape of the groove is not particularly limited, and may be an arc shape, a U shape, a V shape, a rectangular shape, a trapezoidal shape, or another polygonal shape, and a combination of these two or more shapes. It may be.
- the number and shape of the grooves are not particularly limited, and the number and shape of the grooves may be appropriately adjusted according to the purpose of use of the polishing pad and the like. Examples of the shape include a grid shape, a radial shape, a concentric circle shape, a honeycomb shape, and the like, and these may be combined.
- the surface of the polishing layer may be opened by grinding (buffing) or sliced.
- the polishing pad of the fourth aspect of the present invention is derived from the uppermost portion 4'(that is, polyfunctional (meth) acrylate monomer) of the translucent resin member when the polishing surface is the upper surface and the opposite surface is the lower surface.
- the upper surface of the resin containing the structural unit) may be located higher than the bottom 8'of the groove, at the same position as the bottom 8', or lower than the bottom 8', but the groove may be located. It is preferable that the top 4'of the translucent resin member is at the same position as or higher than the bottom 8', and it is more preferable that the top 4'of the translucent resin member is higher than the bottom 8'of the groove. ..
- polishing pad of one aspect of the present invention (polishing pad of FIG.
- the slurry and polishing debris that have entered the recess in the first through hole move to the groove due to the centrifugal force during the polishing process, and the light transmittance. Can be prevented from decreasing. Furthermore, even if only a small amount of slurry is present on the surface of the translucent resin member after most of the slurry has moved to the groove, stable light detection is possible because the light transmittance is unlikely to decrease due to the slurry. It becomes.
- the polishing pad according to the fourth aspect of the present invention has a wettability to a slurry because at least the surface of the translucent member on the polishing surface side has a resin containing a structural unit derived from a polyfunctional (meth) acrylate monomer. It is improved and the light transmittance hardly changes depending on the presence or absence of the slurry on the surface of the translucent member on the polished surface side. As a result, the polishing end point can be determined with high accuracy. Further, in the polishing pad of the fourth aspect of the present invention, when the polishing surface is the upper surface and the opposite surface is the lower surface, even if the surface of the translucent member on the polishing surface side is at the same height as the polishing surface.
- the effect is exhibited even if the surface is lower than the polished surface, but the effect is more exhibited especially when the surface of the translucent member on the polished surface side is lower than the polished surface. That is, when the surface of the translucent member on the polished surface side is lower than the polished surface, a recess (for example, a columnar recess) surrounded by the surface of the translucent member and the side surface of the through hole. Exists, and the slurry enters here. Most of the slurry that has entered the recess can move to the side surface under the influence of centrifugal force and be discharged through the embossed groove. Therefore, the slurry exists in the region where the laser light is transmitted on the surface of the translucent member over time.
- a recess for example, a columnar recess
- the slurry adheres to the surface of the translucent member on the polishing surface side because the resin containing the structural unit derived from the polyfunctional (meth) acrylate monomer is contained. It is possible to reduce the fluctuation of the light transmittance that occurs between the case where the light is present and the case where the light is not adhered, and thereby it is possible to suppress the variation in the light transmittance during the polishing process.
- the polishing pad according to the fourth aspect of the present invention is resistant to the light-transmitting resin member because it has a resin containing a structural unit derived from a polyfunctional (meth) acrylate monomer, at least on the surface on the polishing surface side thereof. It has high chemical properties and can prevent deterioration of the translucent resin member both when an acidic slurry is used and when an alkaline slurry is used.
- the polishing pad according to the fourth aspect of the present invention can be manufactured, for example, by the method described in the section "Method for manufacturing the polishing pad according to the fourth aspect".
- the shore A hardness means a value measured according to the Japanese Industrial Standards (JIS K7311).
- the shore A hardness of the polishing layer is preferably 5 to 70 degrees (°), more preferably 8 to 65 degrees.
- the polishing layer is preferably softer than the translucent member or the translucent resin member, and is more than the translucent member or the translucent resin member. It is more preferable that the shore A hardness is low.
- the compressibility is an index of softness
- the compressive elastic modulus is an index of ease of return to compressive deformation.
- the compressibility and compressive elastic modulus can be determined by using a shopper type thickness measuring instrument (pressurized surface: circular with a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS L1021). Specifically, it is as follows. The thickness t 0 after the initial load is applied for 30 seconds from the unloaded state is measured, and then the thickness t 1 after the final load is applied for 5 minutes from the state of the thickness t 0 is measured.
- the load is 1120 g / cm 2 ).
- the compressibility of the polishing layer is preferably 1 to 60%, more preferably 3 to 50%.
- the compressive elastic modulus of the polishing layer is preferably 50 to 100%, more preferably 60 to 98%.
- the polishing layer is compressed when the object to be polished passes over the through hole, and the polishing property is excellent in recovery after being pushed by the object to be polished.
- the bending and stretching motion of the layer creates a flow of slurry inside the through hole, the slurry circulates without staying in the through hole, and the polishing debris that has entered the through hole together with the slurry is discharged to the outside of the through hole by the operation of compression and recovery. It will be easier. This makes it easier to prevent the polishing debris from accumulating in the through holes.
- the thickness can be determined by using a shopper type thickness measuring instrument (pressurized surface: circular with a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS K6505). Specifically, it is as follows. Prepare a sample of 10 cm square in length and width. Place the sample on the measuring instrument with the surface facing up. A pressurized surface with a load of 100 g / cm 2 is placed on the sample, and the thickness after 5 seconds is measured. Measure 5 points per sheet and use the average value as the thickness. If a 10 cm square sample cannot be obtained, the average of 5 locations is used.
- the thickness of the polishing layer is not particularly limited, but is preferably 0.5 to 2 mm, and even more preferably 0.75 to 1.55 mm.
- the polishing pad of the first to fourth aspects of the present invention may have a layer (other layer) other than the polishing layer.
- the other layer may be one layer or two or more layers on the surface of the polishing layer opposite to the polishing surface.
- the other layer has through holes like the polished layer. Further, the shapes of the through holes of the polishing layer and the through holes of other layers may be the same or different, but when the polishing pad is viewed from the polishing surface side in the thickness direction, the polishing layer may be different. It is preferable that the through-holes of the above and the through-holes of other layers are at least partially overlapped with each other. As a result, when the light is applied to the translucent member or the translucent resin member, the light is transmitted through the translucent member or the translucent resin member.
- the polishing pad when the polishing pad has another layer, the other having a through hole (second through hole) having a diameter equivalent to a circle smaller than the through hole (first through hole) existing in the polishing layer. It may have a layer (FIG. 4A or FIG. 4B).
- the other layer is a layer located on the side opposite to the polishing surface of the polishing layer.
- the first through hole and the second through hole are at least partially overlapped when viewed from the polishing surface side in the thickness direction.
- the translucent member or the translucent resin member is present in the first through hole. It is preferable that the resin member is arranged.
- the outer peripheral portion of the first through hole 5 covers a part or all of the outer peripheral portion of the second through hole 6. It is preferable that the first through hole 5 is provided so that the outer peripheral portion thereof covers the entire outer peripheral portion of the second through hole 6, and the first through hole 5 and the second through hole 5 are provided. It is even more preferable that both the holes 6 have a cylindrical shape, and the central axis of the cylinder of the first through hole 5 and the central axis of the cylinder of the second through hole 6 coincide with each other (see FIG. 4A or FIG. 4B).
- the diameter of the first through hole 5 is larger than the diameter of the second through hole 6, and the first through hole is like a double circle. It means that the outer peripheral portion of the through hole 5 exists outside the outer peripheral portion of the second through hole 6.
- the first through hole and the second through hole are at least partially overlapped when viewed in the thickness direction from the polished surface side
- the first through hole is when viewed in the thickness direction from the polished surface side. 1
- the polishing pad of this embodiment has the same as the first through hole because the opening position of the first through hole and the opening position of the second through hole are at least partially coincident when viewed in the thickness direction.
- the second through hole is connected in the thickness direction of the polishing pad.
- the polishing pad of this embodiment is described so that the translucent member 4 or the translucent resin member 4 is present in the first through hole 5 when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad. It is preferable that a translucent member or a translucent resin member is arranged. Further, it is preferable that the translucent member 4 or the translucent resin member 4 is provided in the first through hole 5. Here, when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, the translucent member or the translucent resin member is present in the first through hole.
- the sex resin member is arranged means that the translucent member or the translucent resin member can be confirmed when the inside of the first through hole is viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad. ..
- the first through hole 5 is a part of the other layer 3 (hereinafter referred to as an exposed portion 7 of the other layer) and the second through hole when the polishing pad 1 is viewed from the polishing surface side in the thickness direction. It is preferable to arrange so that at least a part of 6 is exposed. Thereby, the translucent member 4 or the translucent resin member 4 can be arranged in the first through hole 5 and on the second through hole 6 and the exposed portion 7 of the other layer 3.
- the first through hole 5 is arranged so that a part of the other layer 3 and all of the second through hole 6 are exposed when the first through hole 5 is viewed from the polished surface side. .. Further, it is preferable that the translucent member 4 or the translucent resin member 4 is provided in the first through hole 5 and is adhered to the exposed portion 7 of the other layer 3.
- the first through hole 5 is the polishing on the second through hole 6 and the exposed portion 7. It is provided in layer 2.
- a further layer may be provided between the other layer 3 provided with the exposed portion 7 and the polishing layer 2, and in this case, the through holes existing in the further layer are the polishing layer 2. It has the same cross-sectional shape as the through hole (first through hole) (cross-sectional shape in the horizontal direction with the polished surface), and completely overlaps with the first through hole 5 when viewed in the thickness direction from the polished surface. Is preferable.
- the translucent member 4 or the translucent resin member 4 is arranged on the second through hole 6 and the exposed portion 7 and inside the first through hole 5 of the polishing layer 2 and the through hole of another layer. It is preferable that it is.
- One second through hole may be provided in the other layer, or two or more through holes that are separated from each other and independent of each other may be provided. It is preferable that the number of first through holes and the number of second through holes are equal. When a plurality of first through holes and a plurality of second through holes are provided, each first through hole shall be provided on each second through hole provided in another layer and its exposed portion. Is preferable.
- the second through hole preferably penetrates the other layer parallel to the thickness direction or perpendicular to the polished surface.
- the polishing pad of the first to fourth aspects of the present invention has the same cross-sectional shape of the first through hole and the cross-sectional shape of the second through hole when cut perpendicularly to the thickness direction. Although they may have different shapes, they preferably have the same shape.
- the shape of the second through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad, the cross-sectional shape of the second through hole when cut perpendicular to the thickness direction of the polishing pad, and / or Examples of the shape of the second through hole on the surface of the other layer include a circle, an ellipse, a triangle, a quadrangle, a hexagon, an octagon, and a shape in which these shapes are combined.
- the same or different shapes may be a shape in which the same or different shapes partially overlap each other. Of these, a circular shape is particularly preferable.
- the circle-equivalent diameter of the second through hole is the circle-equivalent diameter of the second through hole when viewed from the polishing surface side of the polishing pad in the polishing pad thickness direction, and is the polishing pad.
- the equivalent circle diameter of the first through hole is larger than the equivalent circle diameter of the second through hole.
- the equivalent circle diameter of the first through hole is larger than the equivalent circle diameter of the second through hole
- the equivalent circle diameter of the second through hole is not particularly limited, but the equivalent circle diameter of the second through hole is preferably 1 to 20 mm. 2 to 18 mm is more preferable, and 5 to 15 mm is even more preferable.
- the difference between the equivalent circle diameter of the first through hole and the equivalent circle diameter of the second through hole is not particularly limited, but the equivalent circle diameter of the first through hole is 5 to 30 mm from the equivalent circle diameter of the second through hole. Larger is preferable, 6 to 25 mm larger is more preferable, and 7 to 20 mm larger is even more preferable.
- the outer peripheral portion of the first through hole is provided so as to cover the entire outer peripheral portion of the second through hole, and the first through hole is provided.
- the equivalent circle diameter is preferably 5 to 30 mm larger than the equivalent circle diameter of the second through hole, more preferably 6 to 25 mm larger, even more preferably 7 to 20 mm larger, and even more preferably 8 to 20 mm larger. Preferably, it is 9 to 20 mm larger, even more preferably 10 to 20 mm larger.
- the outer peripheral portion of the first through hole is provided so as to cover the entire outer peripheral portion of the second through hole, and the first through hole is provided.
- the equivalent circle diameter of the second through hole is preferably 1.5 to 4 times, more preferably 2 to 4 times, and even more preferably 2.5 to 3 times the equivalent circle diameter of the second through hole. preferable.
- the shortest distance between the outer peripheral portion of the second through hole and the outer peripheral portion of the first through hole is preferably larger than 0, the shortest distance is more preferably 2 to 15 mm, and the shortest distance is 3 to 12 mm. It is even more preferable that the distance is 4 to 10 mm.
- the difference in size between the first through hole and the second through hole is within the above range, the slurry and polishing debris that have entered the recess in the first through hole will be removed from the first through hole by the centrifugal force during the polishing process. Since it moves to the outer peripheral side and becomes difficult to see from the second through hole having a small equivalent circle diameter, it is possible to prevent the optical path from being blocked by polishing debris when the translucent member or the translucent resin member is irradiated with light. .. Therefore, excellent light transmittance can be maintained, and stable end point detection signal intensity can be obtained during polishing.
- the area of the exposed portion is sufficiently large, the adhesive strength between the translucent member or the translucent resin member and the other layer can be maintained, and the peeling of the translucent member or the translucent resin member is prevented. can. Further, even if most of the slurry moves to the side surface of the recess and only a small amount of slurry is present on the surface of the translucent member or the translucent resin member, the first to fourth aspects of the present invention. Since the polishing pad is unlikely to have variations in light transmittance depending on the presence or absence of slurry, stable light detection is possible.
- the polishing pad of the first to fourth aspects of the present invention contains another layer
- a sheet-like translucent member or a translucent resin member is used between the polishing layer and the other layer. It may be sandwiched between them and arranged so that a part of the translucent member or the translucent resin member is exposed in the through hole (FIG. 5A or FIG. 5B).
- the through hole existing in the other layer (second through hole) and the through hole existing in the polishing layer (first through hole) are at least partially. It is preferable that they overlap, and it is more preferable that they completely overlap.
- the polishing layer preferably has open cells having communication holes.
- the polishing layer has open cells having communication holes, open bubbles also open on the side surface of the first through hole provided in the polishing layer, so that a part of them communicates to the polishing surface or the groove region.
- the slurry and polishing debris that have entered the first through hole during polishing move to the side surface of the first through hole due to the centrifugal force generated during the polishing process, and pass through the open air bubbles having the communication holes to the polishing surface and the groove. Since it is discharged to the region, it is possible to prevent a decrease in light transmittance over time due to accumulation of polishing debris in the first through hole, which leads to a longer life of the polishing pad.
- the polishing pad of the first to fourth aspects of the present invention contains another layer
- through holes are provided in both the polishing layer and the other layer provided under the polishing layer, and any one of them is provided.
- the translucent member or the translucent resin member may be arranged so as to be in contact with (or adhere to) the side surface (preferably the side surface of the other layer) of both through holes (FIG. 6A or FIG. 6B).
- the through hole existing in the other layer (second through hole) and the through hole existing in the polishing layer (first through hole) are at least partially. It is preferable that they overlap, and it is more preferable that they completely overlap.
- the translucent member or the translucent resin member is adhered to the side surface of the second through hole. Further, it is preferable that the translucent member or the translucent resin member does not exist in the first through hole. Since the translucent member or the translucent resin member is adhered to the side surface of the second through hole of the other layer, the thickness of the polishing layer that can be used for polishing is maximized, and polishing is performed due to wear during dressing or polishing. Even if the surface is scraped, the translucent member or the translucent resin member does not protrude from the polished surface, and the occurrence of scratches can be reduced.
- the softer the polishing layer of the polishing pad the more there is a risk that the polishing pad will sink due to the polishing pad being pressed against the wafer, and the translucent member or the translucent resin member will protrude.
- the resulting polishing pad cannot be used for polishing the object to be polished. Since the polishing pad of this embodiment can prevent the translucent member or the translucent resin member from protruding, the life of the polishing pad can be extended. Further, if the translucent member or the translucent resin member is not bonded to the polishing layer but is arranged so as to adhere to the side surface of the second through hole, the polishing debris that has entered the first through hole is placed on the groove or the polishing surface.
- polishing layer is provided with an expansion / contraction mechanism so that it can be easily discharged, distortion is unlikely to occur at the adhesive portion of the translucent member or the translucent resin member, which causes the translucent member or the translucent resin member to be distorted. Peeling can be suppressed.
- Materials constituting the other layer include polyethylene (PE), polypropylene (PP), polyethylene-based sheets such as ethylene / propylene copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN).
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- Etc. polyester-based sheets, vinyl chloride-based sheets, vinyl acetate-based sheets, polyimide-based sheets, polyamide-based sheets, fluororesin-based sheets, resin-impregnated non-woven fabrics, non-woven fabrics, woven fabrics, and the like.
- the other layer is preferably a non-porous sheet in which the slurry does not penetrate into the inside.
- the other layers are polyester from the viewpoint of physical properties (for example, dimensional stability, thickness accuracy, processability, tensile strength), economy, and the like.
- PET polyethylene terephthalate
- a sheet such as a PET sheet coated with an adhesive on one side or both sides is used as another layer.
- the other layer can be adhered to the polishing layer or another layer via this pressure-sensitive adhesive.
- a sheet such as a PET sheet to which no adhesive is applied is prepared as another layer, and a polishing layer or another layer and an adhesive are prepared separately from this, and the other layer is prepared via the adhesive. Can also be adhered to the polishing layer or another layer.
- the method for manufacturing a polishing pad according to the first aspect of the present invention includes a step of preparing a polishing layer and a translucent member having a water contact angle of at least one surface of 80 degrees or less, a step of providing a through hole in the polishing layer, and a step of providing a through hole. And a step of arranging the translucent member so that the translucent member can be seen in the through hole (here, the one side of the translucent member is arranged so as to be on the polished surface side). , A method for manufacturing a polishing pad. Each process will be described.
- Step of preparing a polishing layer and a translucent member having a water contact angle of at least one surface of 80 degrees or less> a polishing layer and a translucent member having a water contact angle of at least one surface of 80 degrees or less are prepared.
- the polishing layer and the translucent member the above-mentioned ones can be used respectively.
- commercially available ones may be used or manufactured ones may be used.
- the polishing layer can be obtained as commercial products.
- the polishing layer can be manufactured by forming a wet film of a polyurethane resin with reference to Japanese Patent No. 5421635 and Japanese Patent No. 5844189 and laminating it with a flexible sheet made of PET resin.
- the method for manufacturing a polishing pad according to the first aspect of the present invention may further include a step of hydrophilizing at least one surface (preferably only the surface on the polishing surface side) of the translucent member. This makes it possible to obtain a translucent member having a water contact angle of 80 degrees or less on the surface on the polished surface side.
- Examples of the method for hydrophilization treatment include the above.
- a through hole is provided in the polishing layer.
- the through hole is a hole penetrating from the polished surface of the polishing layer to the opposite surface thereof.
- a through hole is provided by making a hole in the thickness direction of the polishing layer using a die such as a circle, an ellipse, or a polygon (preferably a circular die). Can be done.
- the equivalent circle diameter of the through hole in any polishing layer cross section obtained by cutting the polishing layer of the polishing pad perpendicular to the thickness direction is the diameter of the through hole in any other polishing layer cross section. It can be the same as the diameter equivalent to a circle.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the translucent member is arranged so that one surface thereof is on the polished surface side.
- the translucent member is provided in the through hole in the polishing layer.
- a method of arranging the translucent member so as to be in contact with (or adhere to) the side surface of the above, and (2) another layer having a through hole having a smaller circular equivalent diameter is provided in the lower layer of the polishing layer as shown in FIG. 4A.
- the translucent member By arranging the translucent member on the exposed part caused by the difference in size between the through hole of the polishing layer and the through hole of the other layer, the translucent member can be seen in the through hole.
- a translucent member is provided with a through hole having the same shape in both the polishing layer and the other layer provided under the polishing layer as in 6A, and is in contact with (or adheres to) the side surface of either or both of the through holes.
- the method of arranging the light is mentioned. Among these, (1), (2) or (4) is preferable, (1) or (2) is more preferable, and (2) is even more preferable.
- the method for manufacturing a polishing pad according to the first aspect of the present invention may include a step of preparing a layer other than the polishing layer, and a step of bonding a layer other than the polishing layer (another layer) and the polishing layer. You may have.
- the other layer has the same or different through-holes as the through-holes of the polished layer.
- the through hole in the other layer may be provided before the other layer is bonded to the polishing layer, or may be provided after the other layer is bonded to the polishing layer. Examples of the other layer and the through hole include the same as described above.
- the method for manufacturing a polishing pad according to the first aspect of the present invention includes a step of providing a second through hole having a diameter equivalent to a circle smaller than the through hole (first through hole) provided in the polishing layer in another layer. You may be doing it.
- the polishing pad of the first aspect of the present invention When the polishing pad of the first aspect of the present invention is used, the polishing pad is attached to the polishing surface plate of the polishing machine so that the polishing surface of the polishing layer faces the object to be polished. Then, while supplying the slurry, the polishing surface plate is rotated to polish the processed surface of the object to be polished.
- the object to be polished processed by the polishing pad of the first aspect of the present invention include bare silicon and a semiconductor device.
- the polishing pad of the first aspect of the present invention is suitable for polishing semiconductor devices, particularly finish polishing, and is preferable.
- the slurry any slurry containing water (aqueous slurry) can be used without particular limitation. For example, colloidal silica slurry, cerium oxide slurry and the like can be mentioned.
- a light beam is irradiated to the wafer through the polishing pad through the translucent member in the through hole, and the interference signal generated by the reflection is emitted.
- the surface characteristics of the object to be polished such as a semiconductor wafer and the time when the surface state is reached while polishing the object to be polished.
- the method for manufacturing a polishing pad according to the second aspect of the present invention includes a step of preparing a translucent member whose at least one surface is coated with a hydrophilic resin and a polishing layer, a step of providing a through hole in the polishing layer, and a step of providing a through hole in the polishing layer.
- a translucent member whose at least one surface is coated with a hydrophilic resin and a polishing layer are prepared.
- the polishing layer, the translucent member, and the hydrophilic resin the above-mentioned ones can be used.
- the polishing layer and the translucent member commercially available ones may be used or manufactured ones may be used.
- polishing layer for example, it can be manufactured by forming a wet film of a polyurethane resin with reference to Japanese Patent No. 5421635 and Japanese Patent No. 5844189 and laminating it with a flexible sheet made of PET resin.
- the method for producing a polishing pad according to the second aspect of the present invention may further include a step of coating at least one surface (preferably only the surface on the polishing surface side) of the translucent member with a hydrophilic resin.
- the method of coating at least one surface of the translucent member with a hydrophilic resin is not particularly limited, and the resin can be coated on the surface of the translucent member by using, for example, a polymerization reaction or a photocuring reaction.
- the hydrophilic resin may be mixed with the photocurable resin and the photopolymerization initiator, applied to the surface of the translucent member, and then cured by irradiating with ultraviolet rays or the like. Examples of the photocurable resin and the photopolymerization initiator include those mentioned above.
- a through hole is provided in the polishing layer.
- the through hole is a hole penetrating from the polished surface of the polishing layer to the opposite surface thereof.
- a through hole is provided by making a hole in the thickness direction of the polishing layer using a die such as a circle, an ellipse, or a polygon (preferably a circular die). Can be done.
- the equivalent circle diameter of the through hole in any polishing layer cross section obtained by cutting the polishing layer of the polishing pad perpendicular to the thickness direction is the diameter of the through hole in any other polishing layer cross section. It can be the same as the diameter equivalent to a circle.
- the translucent member is arranged so that the translucent member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the coated surface of the translucent member is arranged so as to be on the polished surface side.
- the translucent member is provided in the through hole in the polishing layer.
- the translucent member is visible in the through hole.
- a through hole having the same shape is provided in both the polishing layer and the other layer provided under the polishing layer, and the through hole is made to be in contact with (or adhere to) the side surface of either or both of the through holes.
- Examples include a method of arranging a light member. Among these, (1), (2) or (4) is preferable, (1) or (2) is more preferable, and (2) is even more preferable.
- the method for manufacturing a polishing pad according to the second aspect of the present invention may include a step of preparing a layer other than the polishing layer, and a step of bonding a layer other than the polishing layer (another layer) and the polishing layer. You may have.
- the other layer has the same or different through-holes as the through-holes of the polished layer.
- the through hole in the other layer may be provided before the other layer is bonded to the polishing layer, or may be provided after the other layer is bonded to the polishing layer. Examples of the other layer and the through hole include the same as described above.
- the method for manufacturing a polishing pad according to the second aspect of the present invention includes a step of providing a second through hole having a diameter equivalent to a circle smaller than the through hole (first through hole) provided in the polishing layer in another layer. You may be doing it.
- the polishing pad of the second aspect of the present invention When the polishing pad of the second aspect of the present invention is used, the polishing pad is attached to the polishing surface plate of the polishing machine so that the polishing surface of the polishing layer faces the object to be polished. Then, while supplying the slurry, the polishing surface plate is rotated to polish the processed surface of the object to be polished.
- the object to be polished processed by the polishing pad of the second aspect of the present invention include bare silicon and a semiconductor device.
- the polishing pad of the second aspect of the present invention is suitable for polishing semiconductor devices, particularly finish polishing, and is preferable.
- the slurry any slurry containing water (aqueous slurry) can be used without particular limitation. For example, colloidal silica slurry, cerium oxide slurry and the like can be mentioned.
- a light beam is irradiated to the wafer through the polishing pad through the translucent member in the through hole, and the interference signal generated by the reflection is emitted.
- the surface characteristics of the object to be polished such as a semiconductor wafer and the time when the surface state is reached while polishing the object to be polished.
- the method for manufacturing a polishing pad according to a third aspect of the present invention includes a step of preparing a polishing layer and a translucent resin member having a hydrophilic monomer graft-polymerized on at least one surface thereof, and a step of providing through holes in the polishing layer. , And the step of arranging the translucent resin member so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad (here, the translucent resin member).
- Step of preparing a polishing layer and a translucent resin member having a hydrophilic monomer graft-polymerized on at least one surface a polishing layer and a translucent resin member having a hydrophilic monomer graft-polymerized on at least one surface are prepared.
- the hydrophilic monomer is graft-polymerized on at least one surface means that the hydrophilic monomer is bonded to the translucent resin on at least one surface by graft polymerization.
- the translucent resin member it is preferable that the hydrophilic monomer is graft-polymerized on only one surface.
- the polishing layer and the translucent resin member the above-mentioned ones can be used respectively.
- polishing layer and the translucent resin member commercially available ones may be used or manufactured ones may be used.
- Commercially available translucent resin members include "Diafoil T910E” and “Diafoil T600E” manufactured by Mitsubishi Chemical Co., Ltd., “Cosmo Shine A4300”, “Cosmo Shine A2330” and “Cosmo Shine” manufactured by Toyo Spinning Co., Ltd. TA017 ”,“ Cosmo Shine TA015 ”,“ Cosmo Shine TA042 ”,“ Cosmo Shine TA044 ”,“ Cosmo Shine TA048 ”,“ Soft Shine TA009 ”,“ Acryplen HBXN47 ”manufactured by Mitsubishi Chemical Co., Ltd.
- polishing layer for example, it can be manufactured by forming a wet film of a polyurethane resin with reference to Japanese Patent No. 5421635 and Japanese Patent No. 5844189 and laminating it with a flexible sheet made of PET resin.
- the method for manufacturing a polishing pad according to a third aspect of the present invention may further include a step of plasma grafting the at least one surface of the translucent resin member.
- Examples of the method for plasma grafting include the above. By plasma grafting the at least one surface of the translucent resin member, a translucent resin member having a hydrophilic monomer graft-polymerized on at least one surface can be obtained.
- a through hole is provided in the polishing layer.
- the through hole is a hole penetrating from the polished surface of the polishing layer to the opposite surface thereof.
- a through hole is provided by making a hole in the thickness direction of the polishing layer using a die such as a circle, an ellipse, or a polygon (preferably a circular die). Can be done.
- the equivalent circle diameter of the through hole in any polishing layer cross section obtained by cutting the polishing layer of the polishing pad perpendicular to the thickness direction is the diameter of the through hole in any other polishing layer cross section. It can be the same as the diameter equivalent to a circle.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the grafted surface of the translucent resin member is arranged so as to be on the polished surface side.
- the translucent resin member is provided in the polishing layer as shown in FIGS. 2B and 3B.
- the translucent resin member is placed in the through hole by providing another layer having A method of arranging the translucent resin member so as to be visible, or (3) sandwiching the translucent resin member between the polishing layer and another layer as shown in FIG. 5B, and penetrating a part of the translucent resin member.
- both the polishing layer and the other layer provided under the polishing layer are provided with through holes having the same shape, and are in contact with the side surfaces of either or both of the through holes.
- Examples thereof include a method of arranging the translucent resin member so as to (or adhere).
- (1), (2) or (4) is preferable, (1) or (2) is more preferable, and (2) is even more preferable.
- the method for manufacturing a polishing pad according to a third aspect of the present invention may include a step of preparing a layer other than the polishing layer, and a step of bonding a layer other than the polishing layer (another layer) and the polishing layer. You may have.
- the other layer has the same or different through-holes as the through-holes of the polished layer.
- the through hole in the other layer may be provided before the other layer is bonded to the polishing layer, or may be provided after the other layer is bonded to the polishing layer. Examples of the other layer and the through hole include the same as described above.
- the method for manufacturing a polishing pad according to a third aspect of the present invention includes a step of providing a second through hole having a diameter equivalent to a circle smaller than the through hole (first through hole) provided in the polishing layer in another layer. You may be doing it.
- the polishing pad of the third aspect of the present invention When the polishing pad of the third aspect of the present invention is used, the polishing pad is attached to the polishing surface plate of the polishing machine so that the polishing surface of the polishing layer faces the object to be polished. Then, while supplying the slurry, the polishing surface plate is rotated to polish the processed surface of the object to be polished.
- the object to be polished processed by the polishing pad of the third aspect of the present invention include bare silicon and a semiconductor device.
- the polishing pad of the third aspect of the present invention is suitable for polishing semiconductor devices, particularly finish polishing, and is preferable.
- the slurry any slurry containing water (aqueous slurry) can be used without particular limitation. For example, colloidal silica slurry, cerium oxide slurry and the like can be mentioned.
- a light beam is irradiated to the wafer through the polishing pad through the translucent resin member in the through hole, and the interference signal generated by the reflection thereof.
- the method for producing a polishing pad according to a fourth aspect of the present invention comprises a polishing layer, a polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups, and a -C 2-4 alkylene-O- unit.
- a step of arranging the translucent resin member so that the translucent resin member exists in the through hole when viewed in the thickness direction of the polishing pad (here, the polyfunctionality of the translucent resin member (here, the polyfunctionality of the translucent resin member).
- Meta A method for manufacturing a polishing pad, comprising (arranged so that the surface having a resin containing a structural unit derived from an acrylate monomer is on the polishing surface side). Each process will be described.
- Step of preparing a translucent resin member having at least one surface of the containing resin> In this step, a structural unit derived from the polyfunctional (meth) acrylate monomer having two or more polymerizable functional groups and having the -C 2-4 alkylene-O- unit is used.
- a translucent resin member having a resin containing the resin on at least one surface and a polishing layer are prepared.
- the above-mentioned resins can be used as the resin containing the polishing layer, the translucent resin member, and the structural unit derived from the polyfunctional (meth) acrylate monomer.
- the polishing layer and the translucent resin member commercially available ones may be used or manufactured ones may be used.
- Commercially available translucent resin members include "Diafoil T910E” and "Diafoil T600E” manufactured by Mitsubishi Chemical Co., Ltd., "Cosmo Shine A4300", “Cosmo Shine A2330” and “Cosmo Shine” manufactured by Toyo Spinning Co., Ltd.
- the polishing layer when the polishing layer is manufactured, for example, it can be manufactured by forming a wet film of a polyurethane resin with reference to Japanese Patent No. 5421635 and Japanese Patent No. 5844189 and laminating it with a flexible sheet made of PET resin.
- the method for producing a polishing pad according to a fourth aspect of the present invention further includes a step of coating at least one surface of the translucent resin member with a resin containing a structural unit derived from a polyfunctional (meth) acrylate monomer. May be good.
- the method of coating at least one surface of the translucent resin member with the resin is not particularly limited, and the resin can be coated on the surface of the translucent resin member by using, for example, a polymerization reaction or a photocuring reaction.
- the resin may be mixed with a photocurable resin and a photopolymerization initiator, applied to the surface of the translucent resin member, and then cured by irradiating with ultraviolet rays or the like.
- the method for producing a polishing pad according to a fourth aspect of the present invention includes a step of applying a mixture containing a monomer component containing a polyfunctional (meth) acrylate monomer and a photopolymerization initiator onto a translucent resin member, and a step of applying the mixture. It may further include a step of photopolymerizing the mixture.
- a through hole is provided in the polishing layer.
- the through hole is a hole penetrating from the polished surface of the polishing layer to the opposite surface thereof.
- a through hole is provided by making a hole in the thickness direction of the polishing layer using a die such as a circle, an ellipse, or a polygon (preferably a circular die). Can be done.
- the equivalent circle diameter of the through hole in any polishing layer cross section obtained by cutting the polishing layer of the polishing pad perpendicular to the thickness direction is the diameter of the through hole in any other polishing layer cross section. It can be the same as the diameter equivalent to a circle.
- the translucent resin member is arranged so that the translucent resin member exists in the through hole when viewed from the polishing surface side of the polishing pad in the thickness direction of the polishing pad.
- the surface of the translucent resin member having the resin containing the structural unit derived from the polyfunctional (meth) acrylate monomer is arranged so as to be on the polished surface side.
- the translucent resin member is provided in the polishing layer as shown in FIGS. 2B and 3B.
- the translucent resin member is placed in the through hole by providing another layer having A method of arranging the translucent resin member so as to be visible, or (3) sandwiching the translucent resin member between the polishing layer and another layer as shown in FIG. 5B, and penetrating a part of the translucent resin member. Examples include a method of exposing the inside of the hole. Among these, (1) or (2) is preferable, and (2) is more preferable.
- the method for manufacturing a polishing pad according to a fourth aspect of the present invention may include a step of preparing a layer other than the polishing layer, and the layer other than the polishing layer (other layer) and the polishing layer are bonded together. It may have a process.
- the other layer has the same or different through-holes as the through-holes of the polished layer.
- the through hole in the other layer may be provided before the other layer is bonded to the polishing layer, or may be provided after the other layer is bonded to the polishing layer. Examples of the other layer and the through hole include the same as described above.
- the method for manufacturing a polishing pad according to a fourth aspect of the present invention includes a step of providing a second through hole having a diameter equivalent to a circle smaller than the through hole (first through hole) provided in the polishing layer in another layer. You may be doing it.
- the polishing pad of the fourth aspect of the present invention When the polishing pad of the fourth aspect of the present invention is used, the polishing pad is attached to the polishing surface plate of the polishing machine so that the polishing surface of the polishing layer faces the object to be polished. Then, while supplying the slurry, the polishing surface plate is rotated to polish the processed surface of the object to be polished.
- the object to be polished processed by the polishing pad of the fourth aspect of the present invention include bare silicon and a semiconductor device.
- the polishing pad of the fourth aspect of the present invention is suitable for polishing semiconductor devices, particularly finish polishing, and is preferable.
- the slurry any slurry containing water (aqueous slurry) can be used without particular limitation. For example, colloidal silica slurry, cerium oxide slurry and the like can be mentioned.
- a light beam is irradiated to the wafer through the polishing pad through the translucent resin member in the through hole, and the interference signal generated by the reflection thereof.
- Example 1-1 A 20 cm ⁇ 20 cm transparent acrylic resin film (manufactured by Mitsubishi Chemical Corporation, Acryprene HBS006, thickness 150 ⁇ m) was prepared, and one surface of the film was hydrophilized by plasma processing. As a result, the translucent member of Example 1-1 was obtained.
- Example 1-2 A 20 cm ⁇ 20 cm transparent acrylic resin film (manufactured by Mitsubishi Chemical Corporation, Acryprene HBS006, thickness 150 ⁇ m) was prepared, and one surface of the film was hydrophilized by roll blasting. As a result, a translucent member of Example 1-2 was obtained.
- Comparative Example 1-1 A 20 cm ⁇ 20 cm transparent acrylic resin film (manufactured by Mitsubishi Chemical Corporation, Acryprene HBS006, thickness 150 ⁇ m) was prepared, and this was used as a translucent member of Comparative Example 1-1.
- the visible light transmittance of the translucent members of Examples 1-1 to 1-2 and Comparative Example 1-1 was measured by the following method using an ultraviolet-visible near-infrared spectrophotometer V-770 (manufactured by JASCO Corporation). Measured at. The visible light transmittance is 2 when water is attached to the surface of the translucent member (the surface processed for Examples 1-1 to 1-2) and when water is not attached. The measurement was performed under the conditions. 1. 1. Measurement when water is attached (1) Insert a quartz glass cell and measure the blank. (2) The translucent members of Examples 1-1 to 1-2 and Comparative Example 1-1 are cut out to a size of 9 mm ⁇ 50 mm.
- the translucent member is placed on the Kimwipe, and the surface of the translucent member is placed 20 cm away from the surface (only the processed surface for Examples 1-1 to 1-2, and one surface for Comparative Example 1-1).
- (Only) is sprayed with purified water 3 times (capacity 50 ml, PP bottle) (spray amount per spray: about 0.160 to 0.165 ml, surface of translucent member after 3 sprays) Amount applied to: about 0.01 to 0.03 ml).
- the translucent member was placed in a vertical state and allowed to stand for 60 seconds.
- a translucent member is installed in the quartz glass cell so that the surface not sprayed with water and the inner surface of the quartz glass cell come into contact with each other.
- a translucent member is arranged on the inner wall of the quartz glass cell so that the surface treatment surface faces the surface opposite to the light source and the translucent member is in full contact with the light source side of the quartz cell.
- V-770 ultraviolet-visible near-infrared spectrophotometer
- the water contact angle of the surface of the translucent member of Comparative Example 1-1 is more than 80 degrees, there is a large difference in visible light transmittance between the case where the surface has water and the case where there is no water. rice field.
- the translucent members of Examples 1-1 to 1-2 have a water contact angle of 80 degrees or less on the surface, the visible light transmittance is between the case where the surface has water and the case where there is no water. There was almost no difference. Therefore, in the polishing pad including the translucent member of Examples 1-1 to 1-2, the visible light transmittance does not vary depending on whether the slurry is present or not on the surface, and the polishing end point can be determined. It can be done with higher accuracy.
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 ⁇ m is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- a translucent member prepare an acrylic resin film (manufactured by Mitsubishi Chemical Co., Ltd., acrylicplen HBS006, thickness 150 ⁇ m) with one side plasma-treated, cut out three sheets to a diameter of 17 mm, and form a ring in the first through hole.
- a polishing pad was manufactured by adhering the exposed double-sided tape and the translucent member so that the surface-treated surface side of the translucent member was the polished surface side.
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 ⁇ m is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- Double-sided tape with a thickness of about 0.1 mm PET base material thickness 0.023 mm, adhesiveness on the front and back surfaces of the PET base material
- the component thickness was 0.04 mm).
- a circular die with a diameter of 20 mm is used at equal intervals so that the release paper of the double-sided tape can be penetrated on the concentric circles from the center of the polishing pad on the grooved surface side to the position that is 1/2 of the radius of the polishing pad.
- a hole was made and a first through hole was provided.
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 ⁇ m is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- Another layer was bonded to the surface side where the polyurethane resin film of the resin base material was not bonded via a heat-meltable adhesive.
- a non-woven fabric produced by a needle punching method from a polyester fiber having a fineness of 2 dtex and a fiber length of 51 mm was used, and the thickness was 0.50 mm and the density was 0.35 g / cm 3 .
- a double-sided tape having a release paper on one side was adhered to the side on which the non-woven polyurethane resin film was not bonded.
- a circular die with a diameter of 20 mm is used at equal intervals so that the polishing pad penetrates from the polishing surface to the double-sided tape on a concentric circle at a position that is 1/2 of the radius of the polishing pad from the center position of the polishing pad on the grooved surface side.
- As a translucent member three acrylic resin / polycarbonate resin sheets (Technoloy C001, thickness 500 ⁇ m, manufactured by Sumitomo Chemical Co., Ltd.) with one side plasma-treated were cut out to a diameter of 20 mm and placed on the side surface of the circular translucent member.
- a polishing pad was manufactured by applying a hot melt adhesive and adhering the surface-treated surface side of the translucent member to the side surface in the second through hole so that the surface side was the polished surface side. Since the light transmittance of the polishing pads of Production Examples 1-1 to 1-3 does not fluctuate greatly depending on the presence or absence of the aqueous slurry, the polishing end point can be detected with high accuracy.
- DPHA dipentaerythritol hexaacrylate
- NK ester A-DPH acrylate polymer having an ionic bond hydrophilic group (group containing ammonium cation) (Taisei Fine Chemical Co., Ltd.) ) 25 parts by weight (i.e., 10% by mass of 8WX-030 with respect to the total solid content of DPHA and 8WX-030), 1-hydroxycyclohexylphenylketone (IGM Resin B). .V.
- Irgacure 184) 3 parts by weight was blended and diluted with propylene glycol monomethyl ether so that the non-volatile content was 30% to prepare a coating solution (* 8 WX was added at 10%).
- the obtained coating liquid was applied to an acrylic resin sheet (manufactured by Mitsubishi Chemical Corporation, Acryprene HBS006, thickness 150 ⁇ m) with a bar coater, and pre-dried at 80 ° C. for 1 minute.
- ultraviolet irradiation was performed under air using a high-pressure mercury lamp to prepare a coating film having a film thickness of 5 ⁇ m on an acrylic resin sheet.
- the obtained acrylic resin sheet with a coating film was used as an end point detection window.
- Example 2-2 Apply in the same manner as in Example 2-1 except that the DPHA is changed to 50 parts by mass and 8WX-030 by 125 parts by mass (that is, 8WX-030 which is 50% by mass with respect to the total solid content of DPHA and 8WX-030).
- An acrylic resin sheet with a film was prepared and used as an end point detection window.
- Example 2-3 Apply in the same manner as in Example 2-1 except that it was changed to 30 parts by mass of DPHA and 175 parts by mass of 8WX-030 (that is, 8WX-030 which is 70% by mass with respect to the total solid content of DPHA and 8WX-030).
- An acrylic resin sheet with a film was prepared and used as an end point detection window.
- Example 2-4 Apply in the same manner as in Example 2-1 except that the DPHA is changed to 100 parts by mass and 8WX-030 parts by mass (that is, 8WX-030 which is 0% by mass with respect to the total solid content of DPHA and 8WX-030).
- An acrylic resin sheet with a film was prepared and used as an end point detection window.
- the water contact angle of the surface is measured by the above method, and the one with a water contact angle of 20 degrees or less is ⁇ , the one with a water contact angle greater than 20 degrees and 50 degrees or less is ⁇ , and the one with a water contact angle greater than 50 degrees and 80 degrees or less is ⁇ . Those larger than 80 degrees were evaluated as x. The results are shown in Table 2.
- the visible light transmittances of the translucent members of Examples 2-1 to 2-4 and Comparative Example 2-1 are as follows using an ultraviolet-visible near-infrared spectrophotometer V-770 (manufactured by JASCO Corporation). It was measured by the method of. 1. 1. Measurement when water is attached (1) Insert a quartz glass cell and measure the blank. (2) The translucent members of Examples 2-1 to 2-4 and Comparative Example 2-1 are cut out to a size of 9 mm ⁇ 50 mm. (3) Place the translucent member on a paper waste cloth (Kim Towel, manufactured by Nippon Paper Crecia Co., Ltd.), and coat the surface of the translucent member from a position 20 cm away (coating treatment for Examples 2-1 to 2-4).
- V-770 ultraviolet-visible near-infrared spectrophotometer
- the translucent member is arranged on the inner wall of the quartz glass cell so that the surface of the translucent member with the coating film is opposite to the light source and the translucent member is in full contact with the light source side of the quartz cell.
- V-770 ultraviolet-visible near-infrared spectrophotometer
- the polishing pads containing the translucent members of Examples 2-1 to 2-4, particularly Examples 2-1 to 2-3 have a visible light transmittance depending on whether the slurry is present on the surface or not. It is possible to determine the polishing end point with higher accuracy without causing variation in the polishing.
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 ⁇ m is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- the acrylic resin sheet with the coating film of Example 2-1 was prepared, three sheets were cut out so as to have a diameter of 17 mm, and the double-sided tape exposed in a ring shape and the translucent member were formed in the first through hole.
- a polishing pad was manufactured by adhering the translucent member so that the side with the coating film was on the polishing surface side.
- ⁇ Manufacturing Example 2-2> To 100 parts by mass of a solution containing 100% modulus 7.8 MPa polyester polyurethane resin (30 parts by mass) and DMF (70 parts by mass), 60 parts by mass of DMF and 5 parts by mass of water are separately added and mixed to contain the resin. A solution was obtained. The insoluble component was removed by filtering the obtained resin-containing solution. The solution was cast on a polyester film using a knife coater so that the coating thickness was 0.8 mm. Then, the polyester film cast with the resin-containing solution is immersed in a coagulation bath (the coagulation liquid is water) to coagulate the resin-containing solution, and then the polyester film is peeled off, washed and dried to form a teardrop shape inside.
- a coagulation bath the coagulation liquid is water
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 ⁇ m is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- Double-sided tape with a thickness of about 0.1 mm PET base material thickness 0.023 mm, adhesiveness on the front and back surfaces of the PET base material
- the component thickness was 0.04 mm).
- a circular die with a diameter of 20 mm is used at equal intervals so that the release paper of the double-sided tape can be penetrated on the concentric circles from the center of the polishing pad on the grooved surface side to the position that is 1/2 of the radius of the polishing pad.
- a hole was made and a first through hole was provided.
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 ⁇ m is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- Another layer was bonded to the surface side where the polyurethane resin film of the resin base material was not bonded via a heat-meltable adhesive.
- a non-woven fabric produced by a needle punching method from a polyester fiber having a fineness of 2 dtex and a fiber length of 51 mm was used, and the thickness was 0.50 mm and the density was 0.35 g / cm 3 .
- a double-sided tape having a release paper on one side was adhered to the side on which the non-woven polyurethane resin film was not bonded.
- a circular die with a diameter of 20 mm is used at equal intervals so that the polishing pad penetrates from the polishing surface to the double-sided tape on a concentric circle at a position that is 1/2 of the radius of the polishing pad from the center position of the polishing pad on the grooved surface side.
- the translucent member three acrylic resin sheets with a coating film of Example 2-1 were cut out so as to have a diameter of 20 mm, a hot melt adhesive was applied to the side surface of the circular translucent member, and the inside of the second through hole was formed.
- a polishing pad was manufactured by adhering the side surface of the translucent member with the coating film of the translucent member so that the side with the coating film was on the polished surface side. Since the light transmittance of the polishing pads of Production Examples 2-1 to 2-3 does not fluctuate greatly depending on the presence or absence of the aqueous slurry, the polishing end point can be detected with high accuracy.
- Plasma polymerization was carried out on an acrylic resin sheet (manufactured by Mitsubishi Chemical Corporation, Accliplen HBS006) having a length of 20 mm, a width of 20 mm and a thickness of 0.15 mm using argon gas at a flow rate of 10 sccs, a reaction time of 2 minutes and a pressure of 50 Pa. Next, it was immersed in an aqueous solution of 40 mol% acrylic acid, subjected to a graft polymerization reaction at 80 ° C. for 1 hour while bubbling nitrogen gas, ultrasonically washed in distilled water for 2 hours, and vacuum dried at 80 ° C. for 6 hours. Was given.
- a cross-polymer complex formation reaction was carried out while stirring the graft-polymerized acrylic resin sheet in 25 ml of a 5 wt% aqueous solution of polyvinylbenzyltrimethylammonium chloride (molecular weight 43000) for 30 minutes. The film was then washed with water and then dried to form a polymer composite. The obtained translucent resin member was used as the translucent resin member of Example 3-2.
- ⁇ Contact angle maintenance evaluation> In order to evaluate the change over time of hydrophilicity, water contact 2 days and 2 weeks after the translucent resin members of Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-2 were prepared. The angle was measured. The water contact angle was measured by the following method using an automatic contact angle meter DropMaster DM500 (manufactured by Kyowa Interface Science Co., Ltd.). (1) Put distilled water in a syringe, attach a dispenser, and set it in DM500. (2) Cut the measurement sample into a size of 5 mm x 50 mm and attach it to the stage. (3) Launch the analysis software, select the contact angle measurement [droplet method], and set each parameter.
- DropMaster DM500 manufactured by Kyowa Interface Science Co., Ltd.
- polishing pads were manufactured as follows. Resin by adding 60 parts by mass of DMF and 5 parts by mass of water separately to 100 parts by mass of a solution containing (30 parts by mass) and DMF (70 parts by mass) of 100% modulus 7.8 MPa polyester polyurethane resin. The contained solution was obtained. The insoluble component was removed by filtering the obtained resin-containing solution. The solution was cast on a polyester sheet using a knife coater so that the coating thickness was 0.8 mm.
- the polyester sheet obtained by casting the resin-containing solution was immersed in a coagulation bath (the coagulation liquid was water), the resin-containing solution was coagulated, and then the polyester sheet was peeled off, washed and dried to obtain a polyurethane resin sheet. ..
- the surface of the obtained polyurethane resin sheet is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 mm is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin sheet.
- the surface was embossed, and a grid pattern groove was provided on the surface with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm.
- a grooved polyurethane resin sheet is punched into a circle with a diameter of 740 mm by punching, and on a concentric circle at a position that is 1/2 of the radius from the center of the circular polyurethane resin sheet on the grooved surface side. Three holes were independently drilled and the first through hole was provided.
- the adhesive component thickness on the front and back surfaces of the PET substrate was 004 mm), and the excess double-sided tape was cut so that it had the same diameter as the polyurethane resin sheet. Subsequently, a circular die with a diameter of 9 mm was fitted into the first through hole with a diameter of 18 mm, and a second through hole was opened so that the double-sided tape and the release paper could pass through. At this time, drilling was performed so that the center of the first through hole and the center of the second through hole were substantially the same. Three transparent resin members produced in Example 3-1 and Example 3-2, Comparative Example 3-1 and Comparative Example 3-2 were cut out so as to have a diameter of 17 mm, and exposed in a ring shape in the first through hole.
- a polishing pad was manufactured by adhering the double-sided tape and the transparent resin member.
- a pattern substrate having a line of tungsten (W) and a space of TEOS (silicon oxide film) was prepared, and 500 substrates were polished under the following conditions using each polishing pad.
- the cross section of the translucent resin member was observed with an energy dispersive X-ray spectroscope (EDS), and it was evaluated whether or not the residue adhered to the surface of the translucent resin member on the polished surface side.
- Polishing machine used EBARA F-REX300 Polishing pressure: 2.5psi Polishing pad: Polishing pad: Fujibo Ehime Co., Ltd.
- H600 Abrasive Planar, model number "BSL8176C” Dresser: 3M diamond dresser, model number "A188" Pad break 30N x 30 minutes, diamond dresser 54rpm, surface plate rotation speed 80rpm, ultrapure water 200mL / min Conditioning: Ex-situ, 30N, 4 scans, 16 seconds Polishing: Surface plate rotation speed 70 rpm, head rotation speed 71 rpm, slurry flow rate 200 mL / min Polishing time: Approximately 60 seconds The results are shown in Table 3.
- Example 3-1 subjected to the graft polymerization treatment maintained a low contact angle even after 2 weeks
- Example 3-2 in which the graft polymer was complex had a lower contact angle than Example 3-1. The contact angle could be maintained even after 2 weeks. Further, in any of Examples 3-1 and 3-2, the Si element could not be confirmed by the measurement of EDS.
- the polishing pad including the translucent resin member of Examples 3-1 to 3-2 reduces adhesion and adhesion of polishing debris to the surface of the translucent resin member (window member) on the polishing surface side. It was found that stable light detection is possible.
- ⁇ Polishing pad of the fourth aspect >> ⁇ Example 4-1> 50 parts by mass of aliphatic urethane acrylate (“EBECRYL2000” manufactured by Daicel Ornex) and 50 parts by mass of polyethylene glycol diacrylate (“EBECRYL 11” manufactured by Dicel Ornex, mass average molecular weight 700, ethylene oxide unit per monomer) The number: 13) was mixed, and 5 parts by mass of a photopolymerization initiator (“IRGACURE184” manufactured by BASF) was added and uniformly mixed using a mixing / stirring device to obtain a resin composition.
- EBECRYL2000 aliphatic urethane acrylate
- EBECRYL 11 polyethylene glycol diacrylate
- IRGACURE184 manufactured by BASF
- the composition was applied to an acrylic resin sheet (manufactured by Nitto Jushi Kogyo Co., Ltd., Clarex S, thickness 400 ⁇ m) on one side so as to be uniform using a bar coater, and then left in an oven kept at 50 ° C. for 10 minutes. After drying, the resin composition was cured by irradiating it with ultraviolet rays having an integrated ultraviolet irradiation amount of 900 mJ / cm 2 with an 80 W / cm metal halide lamp to form a surface layer having a thickness of 3.5 ⁇ m. A layered acrylic resin sheet was used as the end point detection window.
- Example 4-2 58 parts by mass of polyethylene glycol diacrylate (“A-1000” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., mass average molecular weight 1140, number of ethylene oxide units per monomer: 23), 39 parts by mass of C 2-3 alkoxylated penta Erislitol tetraacrylate (“EBECRYL40” manufactured by Dycel Ornex Co., Ltd., mass average molecular weight 571, number of ethylene / propylene oxide units per monomer: 4), 3 parts by mass of photopolymerization initiator (“IRGACURE184” manufactured by BASF), A resin composition was obtained by uniformly mixing 100 parts by mass of propylene glycol monomethyl ether as a solvent using a mixing and stirring device. The obtained resin composition was applied to an acrylic resin sheet in the same manner as in Example 4-1 to form a surface layer and used as an end point detection window.
- a resin composition was obtained by uniformly mixing 100 parts by mass of propylene glycol monomethyl ether as a solvent using
- Example 4-3 67 parts by mass of ethoxylated glycerin triacrylate (“A-GLY-20E” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., mass average molecular weight 1134, number of ethylene oxide units per monomer: 20) and 28 parts by mass of C 2-3 Alkylated pentaerythritol tetraacrylate (“EBECRYL40” manufactured by Dycel Ornex Co., Ltd., mass average molecular weight 571, number of ethylene / propylene oxide units per monomer: 4), 5 parts by mass of photopolymerization initiator (“IRGACURE 184” manufactured by BASF Co., Ltd.) ”), 100 parts by mass of propylene glycol monomethyl ether as a solvent was uniformly mixed using a mixing / stirring device to obtain a resin composition. The obtained resin composition was applied to an acrylic resin sheet in the same manner as in Example 4-1 to form a surface layer and used as an end point detection window.
- A-GLY-20E
- the visible light transmittance of the translucent resin members of Examples 4-1 to 4-3 and Comparative Example 4-1 was measured using an ultraviolet-visible near-infrared spectrophotometer V-770 (manufactured by JASCO Corporation). It was measured by the following method. 1. 1. Measurement when water is attached (1) Insert a quartz glass cell and measure the blank. (2) The translucent resin members of Examples 4-1 to 4-3 and Comparative Example 4-1 are cut into a size of 9 mm ⁇ 50 mm. (3) Place the translucent resin member on a paper waste cloth (Kim Towel, manufactured by Nippon Paper Cresia Co., Ltd.), and place the surface of the translucent resin member from a position 20 cm away (for Examples 4-1 to 4-3).
- V-770 ultraviolet-visible near-infrared spectrophotometer
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 mm is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- a translucent member As a translucent member, as a translucent member, an acrylic resin sheet with a surface layer of Example 4-1 was prepared, three sheets were cut out so as to have a diameter of 17 mm, and a double-sided tape exposed in a ring shape in the first through hole. And the translucent member were adhered so that the surface-treated surface side of the translucent member was the polished surface side, and a polishing pad was manufactured.
- a polyurethane resin film having a plurality of bubbles and having the plurality of bubbles connected to each other and communicated with each other was obtained.
- the surface of the obtained polyurethane resin film is buffed to a thickness of 0.73 mm, and then a PET resin base material having a thickness of 0.188 mm is bonded to the side opposite to the buffed surface with an adhesive to form a polyurethane resin film.
- the surface was embossed from the surface side of the above, and grooves having a rectangular cross section with a groove width of 1 mm, a groove spacing of 4 mm, and a groove depth of 0.45 mm were provided on the surface.
- Double-sided tape with a thickness of about 0.1 mm PET base material thickness 0.023 mm, adhesiveness on the front and back surfaces of the PET base material
- the component thickness was 0.04 mm).
- a circular die with a diameter of 9 mm is used at equal intervals so that the release paper of the double-sided tape can be penetrated on the concentric circles from the center of the polishing pad on the grooved surface side to the position that is 1/2 of the radius of the polishing pad.
- a hole was made and a first through hole was provided.
- the release paper of the double-sided tape was peeled off, and the acrylic resin sheet with the surface layer of Example 4-1 cut into the same size as the polishing layer was prepared as a translucent member, and the adhesive portion of the double-sided tape and the surface of the acrylic resin sheet were prepared. It was pasted together with the layer side.
- a double-sided tape with a thickness of about 0.11 mm having a release paper on one side (PET base material thickness 0.023 mm, adhesive component thickness on the front and back surfaces of the PET base material is 0.04 mm) was prepared.
- a second through hole is provided by drilling three holes with a diameter of 9 mm at positions overlapping the first through hole when viewed in the thickness direction, and the surface side of the acrylic resin film translucent member without the coating film is attached.
- a polishing pad was manufactured by adhering to.
- the polishing end point can be detected with high accuracy.
- the polishing pad of the present invention it is possible to provide a polishing pad capable of suppressing variations in light transmittance.
- the second aspect of the present invention it is possible to provide a polishing pad capable of suppressing variation in light transmittance.
- the third aspect of the present invention it is possible to provide a polishing pad capable of reducing adhesion and adhesion of polishing debris to the surface of the translucent resin member (window member) on the polishing surface side.
- the fourth aspect of the present invention it is possible to provide a polishing pad capable of suppressing variations in light transmittance. Therefore, the polishing pad of the present invention is extremely useful in industry.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
近年、半導体素子の多層化、高精細化が飛躍的に進み、半導体素子の歩留まり及びスループット(収量)の更なる向上が要求され、研磨パッドに対してはディフェクトフリーとともに、ディッシングのない高平坦化性が要望されている。これらの要求を満たして高精度のCMPを行うためには、研磨終点の判定が必要となり、希望の表面特性や平面状態に到達した時点を検知しなければならず、光学的測定による終点の検出が行われてきている。
同じく、特開2004-343090号公報(特許文献2)には、光透過領域を光硬化接着剤によって研磨基体に設けられた貫通孔の内壁に接着させて固定することにより、研磨中にスラリーが隙間から漏れることを防止できる研磨パッドが提案されている。
特許第4931133号公報(特許文献3)には、サンドブラスト処理を施すなどして光透過領域の研磨面側の表面を粗面化処理で予め粗面化にすることで、研磨初期から研磨終盤にかけて光透過率の低下に伴う終点検出エラーの発生を防ぐ研磨パッドが提案されている。
特許文献3の研磨パッドについても同様に、透光性部材の表面にスラリーが存在するか否かに起因する光透過率のバラツキには着目していない。また、特許文献3の研磨パッドは、窓表面を荒らしてしまうため、そもそも高い光透過率を得ることが難しく、また、研磨中のスラリーや砥粒、ドレッシングなどによる窓表面の荒れ方はそれぞれ異なるため、常に光透過率を一定に保つことが困難という問題もある。
特許文献4の研磨パッドは、凹部を有するため、当該凹部に入り込んだスラリーの多くが遠心力により凹部側面に移動した後、研磨面に設けられた溝から排出され、特に軟質研磨パッドへ応用した場合には軟質な研磨層によるスラリーの流動が起こりやすく、透光性部材に光を照射した際に透光性部材の表面にスラリーが存在するときとそうでないときとが生じやすくなる。しかしながら、引用文献4は、この問題を認識しておらず、どのように解決するのかについても言及されていない。
また、特開2003-285257号公報(特許文献5)には、スラリーによって窓部材表面が粗面化して光が散乱して光透過率が低下するという問題を解決するための研磨パッドとして、ガラスなどの無機透明材料からなる窓部材の表面を撥水化した研磨パッドが提案されている。
さらに、特開2004-327974号公報(特許文献6)には、窓部材がスラリーの保持や排出能力を有さないことにより研磨性能が低下するという問題を解決する研磨パッドとして、窓を構成するマトリックス材中に水溶性物質を分散・含有させた研磨パッドが提案されている。
特許文献5の研磨パッドは、スラリーによって窓部材表面が削れて粗面化することに起因する光透過率の低下を解決するため、窓部材としてガラスを採用したものである。窓部材は研磨層と比較して硬いため、窓部材表面が研磨層表面より下に位置するように窓部材を配されることに起因して、窓部材表面と被研磨物表面との間にスラリーが介在しやすくなる。そのスラリーを排出するため、窓部材表面を撥水化することによって当該問題を解決するものであるが、研磨液の供給が連続的に行われる研磨中において、透光性部材の表面に介在するスラリーをゼロにすることは難しく、少量存在するスラリーが撥水化によって液滴状となり、光透過率のバラツキの原因となる恐れがある。
特許文献6の研磨パッドは、窓を構成するマトリックス中に水溶性物質を分散させることにより、使用時に水溶性物質が水と接触して遊離し、スラリーを保持するための空孔を形成し、これによりスラリーの保持や排出能力が得られるものであり、マトリックス材全体に水溶性物質が分散されていることが前提となっている。特許文献6は、特許文献1と同様に、透光性部材の表面にスラリーが存在するか否かに起因する光透過率のバラツキには着目していない。また、特許文献6の方法でマトリックス材に親水性物質を練り込んだ場合、マトリックス材と親水性物質とが混在し、窓全体が親水性を有するため、スラリーによって窓が膨潤・変形し、研磨領域から剥がれ落ちたり、スラリー漏れを引き起こしたりする恐れもある。
〔1〕 透光性部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ
前記透光性部材の研磨面側の表面の水接触角が80度以下である、前記研磨パッド。
〔2〕 前記透光性部材の研磨面側とは反対の表面の水接触角が80度超である、〔1〕に記載の研磨パッド。
〔3〕 透光性部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ
前記透光性部材の研磨面側の表面が、親水性樹脂でコーティングされている、前記研磨パッド。
〔4〕 前記親水性樹脂が、イオン結合性の親水基を有する樹脂である、〔3〕に記載の研磨パッド。
〔5〕 前記イオン結合性の親水基を有する樹脂が、イオン結合性の親水基を側鎖に有する樹脂である、〔4〕に記載の研磨パッド。
〔6〕 前記イオン結合性の親水基を有する樹脂は、イオン結合性の親水基のカチオン部が樹脂を構成するモノマーと共有結合しており且つイオン結合性の親水基のアニオン部とイオン結合している、〔4〕又は〔5〕に記載の研磨パッド。
〔7〕 前記イオン結合性の親水基が、アンモニウムカチオンを含む、〔4〕~〔6〕のいずれか1項に記載の研磨パッド。
〔8〕 前記樹脂でコーティングされた透光性部材の研磨面側の表面が、50度以下の水接触角を有する、〔3〕~〔7〕のいずれか1項に記載の前記研磨パッド。
〔9〕 透光性樹脂部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ
前記透光性樹脂部材は、その研磨面側の表面に親水性モノマーがグラフト重合されている、前記研磨パッド。
〔10〕 前記透光性樹脂部材の研磨面側の表面の水接触角が80度以下である、〔9〕に記載の研磨パッド。
〔11〕 前記親水性モノマーが、アクリル系モノマーである、〔9〕又は〔10〕に記載の研磨パッド。
〔12〕 グラフト化された前記表面の樹脂が、ポリエチレングリコール、ポリビニルピロリドン、ポリキシリルビオローゲン、ポリエチレンイミン及びポリビニルピリジニウムクロライド、ポリビニルベンジルトリメチルアンモニウムクロライドから選択される複合体形成ポリマーでイオンコンプレックスが形成されている、〔11〕に記載の研磨パッド。
〔13〕 透光性樹脂部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ
前記透光性樹脂部材は、少なくともその研磨面側の表面において、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する、
前記研磨パッド。
〔14〕 前記多官能(メタ)アクリレートモノマーが、下記:
-C2-4アルキレン-O-単位を有する化合物と(メタ)アクリル酸とがエステル結合されたモノマー、及び
C2-4アルキレンオキサイドが付加された3価以上のアルコールと(メタ)アクリル酸とがエステル結合されたモノマー
からなる群から選択される少なくとも1種である、〔13〕に記載の研磨パッド。
〔15〕 前記3価以上のアルコールが、グリセリン、ジグリセリン、トリグリセリン、トリメチロールプロパン、ジトリメチロールプロパン、エリスリトール、ペンタエリスリトール及びジペンタエリスリトールからなる群から選択される、〔14〕に記載の研磨パッド。
〔16〕 前記-C2-4アルキレン-O-単位が、エチレンオキサイド及び/又はプロピレンオキサイドに由来するものである、〔13〕~〔15〕のいずれか1項に記載の研磨パッド。
〔17〕 前記多官能(メタ)アクリレートモノマーが、ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、プロポキシ化ペンタエリスリトールテトラアクリレート、エトキシ化グリセリントリアクリレート、プロポキシ化グリセリントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、プロポキシ化トリメチロールプロパントリアクリレートからなる群から選択される少なくとも1種である、〔13〕~〔16〕のいずれか1項に記載の研磨パッド。
〔18〕 前記研磨面を上面としその反対面を下面とした場合に、前記透光性樹脂部材の研磨面側の表面が前記研磨面よりも低い、〔1〕~〔17〕のいずれか1項に記載の研磨パッド。
〔19〕 前記研磨面が溝を有し、且つ前記研磨面を上面としその反対面を下面とした場合に、前記透光性部材の最上部が前記溝の最下部と同じ位置にあるかそれよりも低い、〔1〕~〔18〕に記載の研磨パッド。
〔20〕 前記研磨層が有する貫通孔を第1貫通孔とするとき、前記研磨パッドは、前記第1貫通孔よりも小さい円相当径を有する第2貫通孔を有する他の層を更に含み、
前記他の層は、前記研磨層の研磨面とは反対側に位置しており、
前記研磨パッドを研磨表面側から厚さ方向に見た場合に、前記第1貫通孔と前記第2貫通孔とが少なくとも部分的に重なっており、
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性部材が前記第1貫通孔内に存在するように前記透光性部材が配置されている、〔1〕~〔19〕のいずれか1項に記載の研磨パッド。
〔1-1〕 透光性部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ
前記透光性部材の研磨面側の表面の水接触角が80度以下である、前記研磨パッド。
〔1-2〕 前記研磨面を上面としその反対面を下面とした場合に、前記透光性部材の最上部が前記研磨面よりも低い、〔1-1〕に記載の研磨パッド。
〔1-3〕 前記透光性部材の研磨面側とは反対の表面の水接触角が80度超である、〔1〕又は〔1-2〕に記載の研磨パッド。
〔1-4〕 380nm~780nmの波長の光を透光性部材に照射したときの可視光線透過率が、60%以上である、〔1-1〕~〔1-3〕のいずれか1項に記載の研磨パッド。
〔1-5〕 前記研磨面が溝を有する、〔1-1〕~〔1-4〕のいずれか1項に記載の研磨パッド。
〔1-6〕 前記溝がエンボス溝である、〔1-5〕に記載の研磨パッド。
〔1-7〕 前記研磨面を上面としその反対面を下面とした場合に、前記透光性部材の最上部が前記溝の最下部と同じ位置にあるかそれよりも低い、〔1-5〕又は〔1-6〕に記載の研磨パッド。
〔1-8〕 研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の前記貫通孔の形状が円形である、〔1-1〕~〔1-7〕のいずれか1項に記載の研磨パッド。
〔1-9〕 前記研磨層が有する貫通孔を第1貫通孔とするとき、前記研磨パッドは、前記第1貫通孔よりも小さい円相当径を有する第2貫通孔を有する他の層を更に含み、
前記他の層は、前記研磨層の研磨面とは反対側に位置しており、
前記研磨パッドを研磨表面側から厚さ方向に見た場合に、前記第1貫通孔と前記第2貫通孔とが少なくとも部分的に重なっており、
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性部材が前記第1貫通孔内に存在するように前記透光性部材が配置されている、〔1-1〕~〔1-8〕のいずれか1項に記載の研磨パッド。
〔1-10〕 研磨層と、少なくとも一面の水接触角が80度以下である透光性部材とを用意する工程、
研磨層に貫通孔を設ける工程、及び
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性部材が貫通孔内に存在するように前記透光性部材を配置する工程、ここで前記透光性部材の前記一面が研磨面側になるように配置されている、
を含む、〔1-1〕~〔1-9〕のいずれか1項に記載の研磨パッドの製造方法。
〔2-1〕 透光性部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ
前記透光性部材の研磨面側の表面が、親水性樹脂でコーティングされている、前記研磨パッド。
〔2-2〕 前記親水性樹脂が、イオン結合性の親水基を有する樹脂である、〔2-1〕に記載の研磨パッド。
〔2-3〕 前記イオン結合性の親水基を有する樹脂が、イオン結合性の親水基を側鎖に有する樹脂である、〔2-2〕に記載の研磨パッド。
〔2-4〕 前記イオン結合性の親水基を有する樹脂は、イオン結合性の親水基のカチオン部が樹脂を構成するモノマーと共有結合しており且つイオン結合性の親水基のアニオン部とイオン結合している、〔2-2〕又は〔2-3〕に記載の研磨パッド。
〔2-5〕 前記イオン結合性の親水基が、アンモニウムカチオンを含む、〔2-2〕~〔2-4〕のいずれか1項に記載の研磨パッド。
〔2-6〕 前記樹脂でコーティングされた透光性部材の研磨面側の表面が、50度以下の水接触角を有する、〔2-1〕~〔2-5〕のいずれか1項に記載の前記研磨パッド。
〔2-7〕 前記研磨面が溝を有する、〔2-1〕~〔2-6〕のいずれか1項に記載の研磨パッド。
〔2-8〕 前記溝がエンボス溝である、〔2-7〕に記載の研磨パッド。
〔2-9〕 前記研磨面を上面としその反対面を下面とした場合に、前記樹脂でコーティングされた透光性部材の最上部が前記溝の最下部と同じ位置にあるかそれよりも低い、〔2-7〕又は〔2-8〕に記載の研磨パッド。
〔2-10〕 研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の前記貫通孔の形状が円形である、〔2-1〕~〔2-9〕のいずれか1項に記載の研磨パッド。
〔2-11〕 前記研磨層が有する貫通孔を第1貫通孔とするとき、前記研磨パッドは、前記第1貫通孔よりも小さい円相当径を有する第2貫通孔を有する他の層を更に含み、
前記他の層は、前記研磨層の研磨面とは反対側に位置しており、
前記研磨パッドを研磨表面側から厚さ方向に見た場合に、前記第1貫通孔と前記第2貫通孔とが少なくとも部分的に重なっており、
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性部材が前記第1貫通孔内に存在するように前記透光性部材が配置されている、〔2-1〕~〔2-10〕のいずれか1項に記載の研磨パッド。
〔2-12〕 少なくとも一面が親水性樹脂でコーティングされている透光性部材と、研磨層とを用意する工程、
研磨層に貫通孔を設ける工程、及び
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性部材が貫通孔内に存在するように前記透光性部材を配置する工程、ここで前記透光性部材のコーティング面が研磨面側になるように配置されている、
を含む、〔2-1〕~〔2-11〕のいずれか1項に記載の研磨パッドの製造方法。
〔3-1〕 透光性樹脂部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ
前記透光性樹脂部材は、その研磨面側の表面に親水性モノマーがグラフト重合されている、前記研磨パッド。
〔3-2〕 前記透光性樹脂部材の研磨面側の表面の水接触角が80度以下である、〔3-1〕に記載の研磨パッド。
〔3-3〕 前記親水性モノマーが、アクリル系モノマーである、〔1〕又は〔2〕に記載の研磨パッド。
〔3-4〕 グラフト化された前記表面の樹脂が、ポリエチレングリコール、ポリビニルピロリドン、ポリキシリルビオローゲン、ポリエチレンイミン及びポリビニルピリジニウムクロライドから選択される複合体形成ポリマーでイオンコンプレックスが形成されている、〔3-3〕に記載の研磨パッド。
〔3-5〕 前記研磨面を上面としその反対面を下面とした場合に、前記透光性樹脂部材のグラフト化された表面が前記研磨面よりも低い、〔3-1〕~〔3-4〕のいずれか1項に記載の研磨パッド。
〔3-6〕 前記研磨面が溝を有する、〔3-1〕~〔3-5〕のいずれか1項に記載の研磨パッド。
〔3-7〕 前記溝がエンボス溝である、〔3-6〕に記載の研磨パッド。
〔3-8〕 前記研磨面を上面としその反対面を下面とした場合に、前記透光性樹脂部材のグラフト化された表面が前記溝の最下部と同じ位置にあるかそれよりも低い、〔3-6〕又は〔3-7〕に記載の研磨パッド。
〔3-9〕 研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の前記貫通孔の形状が円形である、〔3-1〕~〔3-8〕のいずれか1項に記載の研磨パッド。
〔3-10〕 前記研磨層が有する貫通孔を第1貫通孔とするとき、前記研磨パッドは、前記第1貫通孔よりも小さい円相当径を有する第2貫通孔を有する他の層を更に含み、
前記他の層は、前記研磨層の研磨面とは反対側に位置しており、
前記研磨パッドを研磨表面側から厚さ方向に見た場合に、前記第1貫通孔と前記第2貫通孔とが少なくとも部分的に重なっており、
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性樹脂部材が前記第1貫通孔内に存在するように前記透光性樹脂部材が配置されている、〔3-1〕~〔3-9〕のいずれか1項に記載の研磨パッド。
〔3-11〕 研磨層と、少なくとも一面に親水性モノマーがグラフト重合されている透光性樹脂部材とを用意する工程、
研磨層に貫通孔を設ける工程、及び
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性樹脂部材が貫通孔内に存在するように前記透光性樹脂部材を配置する工程、ここで前記透光性樹脂部材のグラフト化した面が研磨面側になるように配置されている、
を含む、〔3-1〕~〔3-10〕のいずれか1項に記載の研磨パッドの製造方法。
〔3-12〕 前記透光性樹脂部材の前記少なくとも一面を、プラズマグラフト処理する工程を更に含む、〔3-11〕に記載の製造方法。
〔4-1〕 透光性樹脂部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ
前記透光性樹脂部材は、少なくともその研磨面側の表面において、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する、
前記研磨パッド。
〔4-2〕 前記多官能(メタ)アクリレートモノマーが、下記:
-C2-4アルキレン-O-単位を有する化合物と(メタ)アクリル酸とがエステル結合されたモノマー、及び
C2-4アルキレンオキサイドが付加された3価以上のアルコールと(メタ)アクリル酸とがエステル結合されたモノマー
からなる群から選択される少なくとも1種である、〔4-1〕に記載の研磨パッド。
〔4-3〕 前記3価以上のアルコールが、グリセリン、ジグリセリン、トリグリセリン、トリメチロールプロパン、ジトリメチロールプロパン、エリスリトール、ペンタエリスリトール及びジペンタエリスリトールからなる群から選択される、〔4-2〕に記載の研磨パッド。
〔4-4〕 前記-C2-4アルキレン-O-単位が、エチレンオキサイド及び/又はプロピレンオキサイドに由来するものである、〔4-1〕~〔4-3〕のいずれか1項に記載の研磨パッド。
〔4-5〕 前記多官能(メタ)アクリレートモノマーが、ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、プロポキシ化ペンタエリスリトールテトラアクリレート、エトキシ化グリセリントリアクリレート、プロポキシ化グリセリントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、プロポキシ化トリメチロールプロパントリアクリレートからなる群から選択される少なくとも1種である、〔4-1〕~〔4-4〕のいずれか1項に記載の研磨パッド。
〔4-6〕 前記研磨面を上面としその反対面を下面とした場合に、前記透光性樹脂部材の研磨面側の表面が前記研磨面よりも低い、〔4-1〕~〔4-5〕のいずれか1項に記載の研磨パッド。
〔4-7〕 前記研磨面が溝を有する、〔4-1〕~〔4-6〕のいずれか1項に記載の研磨パッド。
〔4-8〕 前記溝がエンボス溝である、〔4-7〕に記載の研磨パッド。
〔4-9〕 前記研磨面を上面としその反対面を下面とした場合に、前記透光性樹脂部材の研磨面側の表面が前記溝の最下部と同じ位置にあるかそれよりも高い、〔4-7〕又は〔4-8〕に記載の研磨パッド。
〔4-10〕 研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の前記貫通孔の形状が円形である、〔4-1〕~〔4-9〕のいずれか1項に記載の研磨パッド。
〔4-11〕 前記研磨層が有する貫通孔を第1貫通孔とするとき、前記研磨パッドは、前記第1貫通孔よりも小さい円相当径を有する第2貫通孔を有する他の層を更に含み、
前記他の層は、前記研磨層の研磨面とは反対側に位置しており、
前記研磨パッドを研磨表面側から厚さ方向に見た場合に、前記第1貫通孔と前記第2貫通孔とが少なくとも部分的に重なっており、
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性樹脂部材が前記第1貫通孔内に存在するように前記透光性樹脂部材が配置されている、〔4-1〕~〔4-10〕のいずれか1項に記載の研磨パッド。
〔4-12〕 研磨層と、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を少なくとも一面に有する透光性樹脂部材とを用意する工程、
研磨層に貫通孔を設ける工程、及び
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性樹脂部材が貫通孔内に存在するように前記透光性樹脂部材を配置する工程、ここで前記透光性樹脂部材の前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する面が研磨面側になるように配置される、
を含む、〔4-1〕~〔4-11〕のいずれか1項に記載の研磨パッドの製造方法。
本発明の第2の態様によれば、光透過率のバラツキを抑えることができる研磨パッドを提供することができる。これにより、研磨終点判定を高精度に行うことができる。
本発明の第3の態様によれば、透光性樹脂部材(窓部材)の研磨面側の表面への研磨屑の付着、固着を低減することのできる研磨パッドを提供することができる。これにより、安定した光検出が可能となる。
本発明の第4の態様によれば、光透過率のバラツキを抑えることができる研磨パッドを提供することができる。これにより、研磨終点判定を高精度に行うことができる。
本発明の第1の態様の研磨パッドは、透光性部材及び研磨層を有する研磨パッドであって、前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ前記透光性部材の研磨面側の表面の水接触角が80度以下である、前記研磨パッドである。
本発明の第1の態様の研磨パッドは、透光性部材、即ち窓部材を有する。透光性部材を通して被研磨物に光を照射することにより、被研磨物が希望の表面特性や平面状態に到達した時点を検出することができる。光学的終点検出には、可視光(白色光)のレーザーやランプ等を用いる。
透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されている。ここで、「研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されている」とは、研磨パッドの研磨面から厚さ方向に貫通孔内を見た場合に、透光性部材が確認できるように配置されていることを意図したものであり、(1)図2A、図3Aのように透光性部材が研磨層に設けられた貫通孔の側面(側壁)に接する(又は接着する)ようにして配置されている場合や、(2)図4Aのように研磨層の下層に研磨層の有する貫通孔の円相当径よりも小さい円相当径を有する貫通孔を有する他の層を設け、研磨層の貫通孔と他の層の貫通孔のサイズの差から生じる露出部7上に透光性部材を配置する場合や、(3)図5Aのように透光性部材を研磨層と他の層との間に挟み込み、透光性部材の一部が貫通孔内に露出するように配置されている場合や、(4)図6Aのように研磨層と他の層の両方に貫通孔を設け、そのいずれか又は両方の貫通孔の側面と接する(又は接着する)ようにして透光性部材が配置されている場合を含む概念である。これらの中でも、(1)、(2)又は(4)が好ましく、(1)又は(2)がより好ましく、(2)がさらにより好ましい。
親水化処理する手段としては、例えばプラズマ処理、紫外線照射処理などの物理化学的処理、ロールブラスト処理、エンボス処理などの機械的処理、化学薬品処理や表面グラフト化処理などの化学的処理などが挙げられる。これらの中でも、プラズマ処理又はロールブラスト処理が好ましく、プラズマ処理がより好ましい。
プラズマ処理とは、高圧電源を用いて、電極と呼ばれるロッドから出るプラズマビームで材料表面を叩く処理である。材料の表面はビームにより放出されたイオンや電子が樹脂表面の分子の化学結合を切断し、樹脂の種類に応じて親水性の官能基(OH(水酸基)、CO(カルボニル基)、COOH(カルボキシル基)等)が生成される。
ロールブラスト処理とは、砥粒の付いたロールを高速回転させ表面改質を行う処理である。
本発明の第1の態様の研磨パッドは、透光性部材の研磨面側の表面の水接触角が80度以下である。水接触角は、5~80度であることが好ましく、5~50度であることがより好ましく、5~30度であることがさらにより好ましく、5~20度であることがさらにより好ましい。水接触角が上記範囲内であると、透光性部材の表面にスラリーが存在するか否かに起因する光透過率のバラツキを抑えることができる。これにより、より高精度な研磨終点の判定が可能となる。
従来の研磨パッドで使用されている窓部材は、一般に水接触角が80度超である。80度以下の親水性を持つ窓を用いた場合、スラリーによって窓が膨潤、変形し、研磨領域から剥がれ落ちたり、スラリー漏れを引き起こす可能性がある。そのため、窓部材は水接触角が80度超の疎水性が好ましく、本発明ではその研磨面側の表面だけを水接触角が80度以下になるよう親水化処理を行うことが好ましい。本発明において、透光性部材の研磨面側の表面の水接触角を80度以下とする方法に特に制限はないが、研磨面側の表面を親水化処理して研磨面側の表面の水接触角を80度以下としたものを用いることが好ましい。親水化処理手段としては、上記のものが挙げられる。
透光性部材としては、研磨面側の表面の水接触角が80度以下であればよく、裏面や側面の水接触角に特に制限はない。従って、裏面や側面の水接触角は80度超であってよい。すなわち、透光性部材の裏面や側面は、親水化処理が施されていなくてもよい。
本発明の第1の態様の研磨パッドは、380nm~780nmの波長の光を透光性部材に照射したときの可視光線透過率(本明細書において、単に光透過率ということがある)が、60%以上であることが好ましく、62%以上であることがより好ましく、65%以上であることがさらにより好ましく、70%以上がさらにより好ましく、75%以上であることがさらにより好ましく、80%以上であることがさらにより好ましく、85%以上であることがさらにより好ましい。
本発明の第1の態様の研磨パッドは、透光性部材の表面に水を付着させたときの前記光透過率が、60%以上であることが好ましく、62%以上であることがより好ましく、65%以上であることがさらにより好ましく、70%以上がさらにより好ましく、75%以上であることがさらにより好ましく、80%以上であることがさらにより好ましい。
本発明の第1の態様の研磨パッドは、透光性部材の表面に水を付着させていないときの前記光透過率が、60%以上であることが好ましく、62%以上であることがより好ましく、65%以上であることがさらにより好ましく、70%以上がさらにより好ましく、75%以上であることがさらにより好ましく、80%以上であることがさらにより好ましく、85%以上であることがさらにより好ましい。
本発明の第1の態様の研磨パッドは、透光性部材の表面に水を付着させていないときの前記光透過率と透光性部材の表面に水を付着させたときの前記光透過率との差が、30%以内であることが好ましく、20%以内であることがより好ましく、15%以内であることがさらにより好ましく、10%以内であることがさらにより好ましく、8%以内であることがさらにより好ましく、6%以内であることがさらにより好ましく、5%以内であることがさらにより好ましい。光透過率の差が上記範囲内であることにより、透光性部材の表面にスラリーがある場合とない場合との間で光透過率の差が生じにくくなり、研磨終点の判定を高精度に行うことが出来る。
光透過率の測定は、分光光度計で波長300~1000nmの透過スペクトルを測定し、日本工業規格(JIS A5759:2008)の可視光線透過率(%)として求めることが出来る。すなわち、各波長 380~780nmの範囲の各波長の透過率を測定し、CIE(国際照明委員会)昼光 D65の分光分布,CIE 明順応標準比視感度の波長分布及び波長間隔から得られる重価係数を各波長での透過率に乗じて加重平均することによって求められる透過率である。
また、透光性部材の表面に水を付着させたときの光透過率の測定は、スプレーにより十分量(例えば、9mm×50mmの大きさに切り出した透光性部材に対して、0.01~0.03mL程度)の水を透光性部材の研磨面側の表面全体に付着させた後、透光性部材を地面に対して垂直にして60秒間静置することで水切りを行った透光性部材を用いて行うことが出来る。
貫通孔は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、研磨面からその反対面へと貫通している孔である。貫通孔は、厚み方向に対して平行に又は研磨面に対して垂直に研磨層を貫通していることが好ましい。
貫通孔は研磨層中に1個設けられていてもよく、互いに離間し且つ独立している2個以上の貫通孔が設けられていてもよい。
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の貫通孔の形状又は研磨面における貫通孔の形状としては、円形、楕円形、三角形、四角形、六角形、八角形等が挙げられる。或いは、同一又は異なる複数の上記形状が互いに部分的に重なり合った形状であってもよい。これらの中でも、研磨屑が溜りやすい隅部を形成しない円形が特に好ましい。
本明細書及び特許請求の範囲において、円相当径とは、測定対象の図形が有する面積に相当する、真円の直径のことである。
貫通孔の円相当径は、研磨パッドの研磨面側から研磨パッド厚さ方向に見たときの貫通孔の円相当径であり、研磨パッドの研磨面側から研磨パッド厚さ方向に見た時の貫通孔の形状が円形である場合は直径に相当する。
貫通孔の円相当径に特に制限はないが、5~40mmが好ましく、5~30mmがより好ましく、10~28mmがさらにより好ましい。
また、研磨面における貫通孔の面積は、研磨面の全面積に対して0.003~0.5%であることが好ましく、0.004~0.4%であることがより好ましく、0.003~0.3%であることがさらにより好ましい。
研磨層を構成する樹脂としては、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樹脂;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樹脂;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樹脂;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樹脂;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樹脂;ポリアミド系樹脂;及びポリスチレン系樹脂などが挙げられる。これらの中でも、圧縮特性や柔軟性を考慮すれば、ポリウレタン樹脂がより好ましい。
研磨層は1種類の樹脂から構成されていてもよく、2種以上の樹脂から構成されていてもよい。
また、研磨層は連続気泡を有するものが好ましい。ここでいう連続気泡とは隣り合う気泡同士が互いに連通孔によりつながった空間を有する発泡を示す。具体的には湿式成膜法による樹脂や乾式成形、射出成形によるフォームでよい。好ましくは湿式成膜法によるもので、良好な屈伸運動が期待できる。
本明細書において、湿式成膜法による樹脂とは、湿式成膜法により成膜された樹脂(好ましくはポリウレタン樹脂)を意味する。湿式成膜法は、成膜する樹脂を有機溶媒に溶解させ、その樹脂溶液をシート状の基材に塗布後に凝固液中に通して樹脂を凝固させる方法である。湿式成膜された樹脂は、一般に、複数の涙形状(teardrop-shaped)気泡(異方性があり、研磨パッドの研磨面から底部に向けて径が大きい構造を有する形状)を有する。従って、湿式成膜された樹脂は、複数の涙形状気泡を有する樹脂と言い換えることもできる。複数の涙形状気泡は連続気泡の形態であることが好ましい。
本発明の第1の態様の研磨パッドは、研磨層の研磨面に溝が設けられていることが好ましい。溝は研磨層を貫通しておらず、貫通孔と区別することができる。
溝としては、研磨面にエンボス加工を施すことで得られるエンボス溝、切削工具により切削加工を施すことで得られる切削溝が挙げられる。これらの中でもエンボス溝が好ましい。エンボス溝などの溝を設けることにより、研磨面にバリが出にくく、仕上げ研磨に適した研磨パッドを得ることができる。
溝の深さは研磨層の厚みよりも小さい限り特に制限はないが、研磨層の厚みの50~90%であることが好ましく、60~80%であることがより好ましい。被研磨物の研磨により溝が消失すると研磨スラリーの流排出性が失われ研磨性能が低下するため研磨パッドは寿命となることから、溝深さは深いことが好ましい。他方、エンボス溝の溝深さを大きくするためには加工圧力を上げる、或いは加工温度を上げる必要があり、それにより研磨層裏面の基材(PET)が変形したり、研磨層表面が劣化する可能性がある。溝の深さが上記範囲内であると、これらの問題が生じにくい。
溝の断面形状は特に限定されず、円弧状であってもよく、U字状、V字状、矩形状、台形状及びその他の多角形状であってもよく、これら2種以上の形状の組み合わせであってもよい。また、溝の数や形状も特に制限はなく、研磨パッドの使用目的などに合わせて適宜溝数や形状を調整すればよい。形状としては、格子状、放射状、同心円状、ハニカム状などが挙げられ、それらを組み合わせてもよい。
また、本発明の第1の態様の研磨パッドは、研磨層の表面を研削(バフ処理)により開口していてもよく、スライスしていてもよい。
また、従来の研磨パッドは、透光性部材の最上部4’を溝の最下部8’と同じ位置にあるかそれよりも低い位置にすると、スラリーや研磨屑が溝から排出されにくくなるため、経時的に光透過率が低下するという問題が生じ得る。これに対し、本発明の一態様の研磨パッド(図4Aの研磨パッド)は、第1貫通孔内の凹部に入り込んだスラリーや研磨屑が研磨加工中の遠心力により第1貫通孔の側面に移動し、円相当径の小さい第2貫通孔からは見えにくくなるため、光透過率の低下を防ぐことが出来る。さらに、大部分のスラリーが凹部の側面に移動した後、少量のスラリーのみが透光性部材の表面に存在していたとしても、スラリーによる光透過率の低下が生じにくいため、安定した光検出が可能となる。
本発明の第1の態様の研磨パッドは、透光性部材の研磨面側の表面の水接触角が80度以下であることにより、透光性部材の研磨面側の表面でのスラリーの有無が光透過率にほとんど影響を与えない。これにより、研磨終点を高精度に判定することができる。
また、本発明の第1の態様の研磨パッドは、研磨面を上面としその反対面を下面とした場合に、透光性部材が研磨面と同じ高さにあっても、透光性部材が研磨面よりも低い位置にあってもその効果を発揮するが、特に透光性部材が研磨面よりも低い位置にある場合にその効果をよりよく発揮する。すなわち、透光性部材が研磨面よりも低い位置にある場合には、透光性部材の表面と貫通孔の側面とで囲まれた凹部(例えば、円柱状の凹部)が存在し、ここにスラリーが入り込む。凹部内に入り込んだスラリーの多くは、遠心力の影響を受けて側面に移動しエンボス溝を介して排出されるため、経時的に透光性部材表面のレーザー光が透過する領域にスラリーが存在するタイミング(凹部内にスラリーが多く流入したタイミングや排出しきれなかったタイミング等)と存在しないタイミングが生じ得る。透光性部材表面の撥水性が高い場合、窓表面上でスラリーは馴染むことなく水滴状あるいは筋状に付着しているため、レーザー光が透過する領域にスラリーが存在しないときの平行光線透過率に対し、スラリーが存在するときの平行光線透過率は水滴状のスラリーによる光の散乱のために大幅に低下し、研磨加工時の光透過率にバラツキが生じやすい。本発明の第1の態様の研磨パッドは、透光性部材の研磨面側の表面の水接触角を低くする(親水化する)ことにより、スラリーを水滴状にせず窓表面に濡れ広がらせることができるため、光の散乱を抑制し、スラリーが付着している場合と付着していない場合とで光透過率の変動を小さくすることができ、これにより研磨加工時の光透過率のバラツキを抑えることができる。
本発明の第2の態様の研磨パッドは、前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ前記透光性部材の研磨面側の表面が、親水性樹脂でコーティングされている、前記研磨パッドである。
本明細書において、親水性樹脂でコーティングされた透光性部材の研磨面側の表面とは、透光性部材の研磨面側の表面にあるコーティング面を指す。
また、本明細書において、親水性樹脂でコーティングされた透光性部材の研磨面側の表面を、「透光性部材の表面」又は「透光性部材の研磨面側の表面」などと略記することがある。
また、本明細書において、親水性樹脂でコーティングされた透光性部材の最上部とは、研磨面を上面としその反対面を下面とした場合における、透光性部材4の研磨面側の表面にあるコーティング部9の上面を指す。
本発明の第2の態様の研磨パッドは、透光性部材、即ち窓部材を有する。透光性部材を通して被研磨物に光を照射することにより、被研磨物が希望の表面特性や平面状態に到達した時点を検出することができる。光学的終点検出には、可視光(白色光)のレーザーやランプ等を用いる。
透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されている。ここで、「研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されている」とは、研磨パッドの研磨面から厚さ方向に貫通孔内を見た場合に、透光性部材が確認できるように配置されていることを意図したものであり、(1)図2B、図3Bのように透光性部材が研磨層に設けられた貫通孔の側面(側壁)に接する(又は接着する)ようにして配置されている場合や、(2)図4B或いは図4Cのように研磨層の下層に研磨層の有する貫通孔の円相当径よりも小さい円相当径を有する貫通孔を有する他の層を設け、研磨層の貫通孔と他の層の貫通孔のサイズの差から生じる露出部7上に透光性部材を配置する場合や、(3)図5Bのように透光性部材を研磨層と他の層との間に挟み込み、透光性部材の一部が貫通孔内に露出するように配置されている場合や、(4)図6Bのように研磨層と他の層の両方に貫通孔を設け、そのいずれか又は両方の貫通孔の側面と接する(又は接着する)ようにして透光性部材が配置されている場合を含む概念である。これらの中でも、(1)、(2)又は(4)が好ましく、(1)又は(2)がより好ましく、(2)がさらにより好ましい。
透光性部材は、研磨面側の表面が、親水性樹脂でコーティングされていることが好ましい。透光性部材は、研磨面側の表面だけではなく、研磨面とは反対側の面(裏面)や側面も親水性樹脂でコーティングされていてもよいが、裏面や側面をもコーティングすることはコストの増加につながる一方で、裏面や側面の親水化は本発明の効果と関係がないため、研磨面側の表面のみが、親水性樹脂でコーティングされていることが好ましい。研磨面側の表面を親水性樹脂でコーティングすることにより、透光性部材の表面にスラリーが存在するか否かに起因する光透過率のバラツキを抑えることができる。これにより、より高精度な研磨終点の判定が可能となる。
親水性樹脂としては、イオン結合性の親水基を有する樹脂であることが好ましい。イオン結合性の親水基を有する樹脂は、カチオンとアニオンからなるイオン結合性の親水基を含む樹脂である。カチオンとアニオンは有機カチオン又は有機アニオンであることが好ましく、有機カチオンと有機アニオンからなることがより好ましい。さらに、カチオン又はアニオンの一方が樹脂を構成する原子と共有結合していることが好ましい。樹脂を構成する原子と共有結合していることで、イオン結合性の親水基を含む樹脂からのイオン結合性の親水基の溶出を抑制し、研磨液の汚染を防止することができる。
イオン結合性の親水基を有する樹脂は、式:A+B-(A+はカチオンであり、B-はアニオンである。)で表されるイオン結合性の親水基を含む樹脂であることが好ましく、-A+B-又は-B-A+で表されるイオン結合性の親水基を含む樹脂であることがより好ましい。イオン結合性の親水基は、例えば、イオン性結合性の親水基を含むモノマー又はオリゴマーを、必要に応じて他のモノマーやオリゴマーなどとともに重合することにより樹脂中に付与してもよく、コーティング用のポリマーの側鎖とイオン結合性の親水基とを共有結合することにより樹脂中に付与してもよい。
これらの中でもイオン結合性の親水基を含む樹脂は、樹脂を構成する構成単位(モノマー)の一部又は全部がイオン性結合性の親水基を有することが好ましい。
樹脂を構成するモノマーがイオン性結合性の親水基を有する場合、(UV照射前の)当該モノマーは側鎖に不飽和二重結合を有する官能基を有することが好ましく、エチレン性不飽和結合を有する官能基(例えば、ビニル基、アリル基、アクリル基、メタクリル基、アクリロイル基、メタクリロイル基等)を有することが好ましい。樹脂を構成するモノマーがその側鎖に不飽和二重結合を有することにより、当該樹脂はUV照射によって硬化することができる。
イオン結合性の親水基を含むモノマーは、合成してもよく、市販のものを用いてもよい。市販のイオン結合性の親水基を含むモノマーとしては、例えば、アミノイオン(日本乳化剤(株)製)等が挙げられる。
イオン結合性の親水基を含む樹脂としては、イオン結合性の親水基を側鎖に有する樹脂であることが好ましい。
-A+B-のイオン結合性の親水基としては、-NR3 +X-で示す親水基が好ましい(式中、Rはそれぞれ独立して水素原子又は置換若しくは非置換のアルキル基を表し、X-はアニオンを表す)。
また、X-は特に限定はされないが、アルキルを有する硫酸アニオンやスルホン酸アニオン(例えば、アルキル硫酸イオン、ポリオキシアルキレンアルキルエーテル硫酸イオン、ポリオキシアルキレンアルキルフェニルエーテル硫酸イオン、アルキルスルホン酸イオン、アルキルベンゼンスルホン酸イオン等)を含むことが好ましい。これらのイオン構造は、親水性を有しながらも末端基が疎水性を有するため、樹脂から溶出しにくくなるものと推測される。
(式中、Rb1は水素原子またはメチル基であり、Rb2は水素原子または置換もしくは非置換のC1-6アルキル基であり、nbは1~6の整数であり、Yb -は下記式(2’)で表されるアニオンである。)
(式中、R’は置換もしくは非置換のC12-14の直鎖状のアルキル基であり、A’はC2-4の直鎖状又は分岐鎖状のアルキレン基であり、mはA’Oの平均付加モル数であって2~50である。)
その具体例としては、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート等の(メタ)アクリル系単量体と、ポリオキシアルキレンアルキルエーテル硫酸エステルとの塩等を挙げることができる。
イオン結合性の親水基を含む樹脂の例としては、アンモニウムカチオンを含む光硬化性ポリマーであるアクリット 8WX(変性アクリレートポリマー、大成ファインケミカル(株)製)などが挙げられる。
また、イオン結合性の親水基を含むモノマーを、必要に応じて他のモノマー(好ましくはアクリル系モノマー)とともに、常法により重合(溶液重合・光重合)することによっても行うことができる。溶液重合を用いる場合には、重合後の溶液を終点検出窓表面に塗布し、乾燥することでコーティングを得ることができる。光重合を用いる場合には、モノマー溶液を終点検出窓表面に塗布し、紫外線照射をすることでコーティングを得ることができる。
バインダーとなる光硬化型樹脂としては、特に制限はなく、従来から知られている光硬化型樹脂を用いることができる。例えば、1分子中に2以上の(メタ)アクリロイル基を有する多官能(メタ)アクリレート化合物を挙げることができ、市販品としては、NKエステル(新中村化学工業(株)製)、アロニックス(東亞合成(株)製)、KAYARAD(日本化薬(株)製)、ファンクリル(日立化成(株)製)等を挙げることができる。光硬化型樹脂は、その硬化後に光が透過できる程度の透明性を有するものであることが好ましい。
光重合開始剤としては、紫外線や電子線などの照射により光硬化型樹脂を硬化させることが出来るものであれば特に制限はなく、従来から知られている光重合開始剤を用いることができる。例えば、ラジカル重合開始剤、カチオン重合開始剤、アニオン重合開始剤等を挙げることができ、市販品としては、イルガキュア(IGM Resin B.V.製)等を挙げることができる。
本発明の第2の態様の研磨パッドは、研磨面を上面としその反対面を下面とした場合に、親水性樹脂でコーティングされた透光性部材の最上部が研磨面と同じ高さにあってもよく研磨面より低くてもよいが、研磨面よりも低いことが好ましい(図2B)。親水性樹脂でコーティングされた透光性部材の最上部が研磨面よりも低いことにより、研磨層よりも硬い透光性部材に起因する研磨傷の発生を防ぐことができる。また、透光性部材の最上部が研磨面よりも低いと、透光性部材と貫通孔の側面で囲まれた凹部にスラリーが入り込み、その多くは遠心力により貫通孔側面に移動し溝を介して排出されるため、少量のスラリーが透光性部材の表面に残っている場合と残っていない場合が生じやすくなる。しかしながら、従来の研磨パッドを用いた場合には、少量のスラリーが透光性部材の表面に残っている場合と残っていない場合とで光透過率に差が出るため、研磨終点を高精度に判定することが難しい。これに対し、本発明の第2の態様の研磨パッドは、透光性部材の研磨面側の表面を上記樹脂でコーティングすることでスラリーとの馴染みがよくなり、少量のスラリーが存在するような場合でも窓表面に均一に広がることで、研磨初期から終盤まで光透過率の変動が少なくなり、透光性部材の最上部が研磨面よりも低い位置にあっても、特に透光性部材の最上部4’が溝の最下部8’と同じ位置にあるかそれよりも低い位置にあっても、研磨終点を高精度に判定することができる。
本発明の第2の態様の研磨パッドは、親水性樹脂でコーティングされた透光性部材の研磨面側の表面の水接触角が50度以下であることが好ましく、30度以下であることがさらにより好ましく、20度以下であることがさらにより好ましく、5~20度であることがさらにより好ましい。水接触角が上記範囲内であると、透光性部材の表面にスラリーが存在するか否かに起因する光透過率のバラツキを抑えやすくなる。
透光性部材の裏面や側面の水接触角に特に制限はなく、裏面や側面の水接触角は50度超であってもよく、80度超であってもよい。すなわち、透光性部材の裏面や側面は、コーティング処理が施されていなくてもよい。従来の研磨パッドで使用されている窓部材は、一般に水接触角が80度超である。80度以下の親水性を持つ窓を用いた場合、スラリーによって窓が膨潤、変形し、研磨領域から剥がれ落ちたり、スラリー漏れを引き起こしたりする可能性がある。そのため、窓部材は水接触角が80度超の疎水性が好ましく、本発明ではその研磨面側の表面だけを水接触角が50度以下になるよう親水性樹脂でコーティングすることが好ましい。
本発明の第2の態様の研磨パッドは、親水性樹脂でコーティングされた透光性部材の表面に水を付着させていないときの可視光線透過率(本明細書において、単に光透過率ということがある)と前記透光性部材の表面に水を付着させたときの可視光線透過率との差が、10%以内であることが好ましく、8%以内であることがより好ましく、6%以内であることがさらにより好ましく、5%以内であることがさらにより好ましい。光透過率の差が上記範囲内であることにより、前記樹脂でコーティングされた透光性部材の表面にスラリーがある場合とない場合との間で光透過率の差が生じにくくなり、研磨終点の判定を高精度に行うことが出来る。
本発明の第2の態様の研磨パッドは、親水性樹脂でコーティングされた透光性部材の表面に水を付着させたときの前記光透過率が、60%以上であることが好ましく、62%以上であることがより好ましく、65%以上であることがさらにより好ましく、70%以上がさらにより好ましく、75%以上であることがさらにより好ましく、80%以上であることがさらにより好ましい。
本発明の第2の態様の研磨パッドは、親水性樹脂でコーティングされた透光性部材の表面に水を付着させていないときの前記光透過率が、60%以上であることが好ましく、62%以上であることがより好ましく、65%以上であることがさらにより好ましく、70%以上がさらにより好ましく、75%以上であることがさらにより好ましく、80%以上であることがさらにより好ましく、85%以上であることがさらにより好ましい。
光透過率の測定は、分光光度計で波長300~1000nmの透過スペクトルを測定し、日本工業規格(JIS A5759:2008)の可視光線透過率(%)として求めることが出来る。すなわち、各波長380~780nmの範囲の各波長の透過率を測定し、CIE(国際照明委員会)昼光D65の分光分布、CIE明順応標準比視感度の波長分布及び波長間隔から得られる重価係数を各波長での透過率に乗じて加重平均することによって求められる透過率である。
また、親水性樹脂でコーティングされた透光性部材の表面に水を付着させたときの光透過率の測定は、スプレーにより十分量(例えば、9mm×50mmの大きさに切り出した透光性部材に対して、0.01~0.03mL程度)の水を透光性部材の研磨面側の表面全体に付着させた後、透光性部材を地面に対して垂直にして60秒間静置することで水切りを行った透光性部材を用いて行うことが出来る。
貫通孔は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、研磨面からその反対面へと貫通している孔である。貫通孔は、厚み方向に対して平行に又は研磨面に対して垂直に研磨層を貫通していることが好ましい。
貫通孔は研磨層中に1個設けられていてもよく、互いに離間し且つ独立している2個以上の貫通孔が設けられていてもよい。
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の貫通孔の形状又は研磨面における貫通孔の形状としては、円形、楕円形、三角形、四角形、六角形、八角形等が挙げられる。或いは、同一又は異なる複数の上記形状が互いに部分的に重なり合った形状であってもよい。これらの中でも、研磨屑が溜りやすい隅部を形成しない円形が特に好ましい。
本明細書及び特許請求の範囲において、円相当径とは、測定対象の図形が有する面積に相当する、真円の直径のことである。
貫通孔の円相当径は、研磨パッドの研磨面側から研磨パッド厚さ方向に見たときの貫通孔の円相当径であり、研磨パッドの研磨面側から研磨パッド厚さ方向に見た時の貫通孔の形状が円形である場合は直径に相当する。
貫通孔の円相当径に特に制限はないが、5~40mmが好ましく、5~30mmがより好ましく、10~28mmがさらにより好ましい。
また、研磨面における貫通孔の面積は、研磨面の全面積に対して0.003~0.5%であることが好ましく、0.004~0.4%であることがより好ましく、0.005~0.3%であることがさらにより好ましい。
研磨層を構成する樹脂としては、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樹脂;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樹脂;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樹脂;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樹脂;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樹脂;ポリアミド系樹脂;及びポリスチレン系樹脂などが挙げられる。これらの中でも、圧縮特性や柔軟性を考慮すれば、ポリウレタン樹脂がより好ましい。
研磨層は1種類の樹脂から構成されていてもよく、2種以上の樹脂から構成されていてもよい。
また、研磨層は連続気泡を有するものが好ましい。ここでいう連続気泡とは隣り合う気泡同士が互いに連通孔によりつながった空間を有する発泡を示す。具体的には湿式成膜法による樹脂や乾式成形、射出成形によるフォームでよい。好ましくは湿式成膜法によるもので、良好な屈伸運動が期待できる。
本明細書において、湿式成膜法による樹脂とは、湿式成膜法により成膜された樹脂(好ましくはポリウレタン樹脂)を意味する。湿式成膜法は、成膜する樹脂を有機溶媒に溶解させ、その樹脂溶液をシート状の基材に塗布後に凝固液中に通して樹脂を凝固させる方法である。湿式成膜された樹脂は、一般に、複数の涙形状(teardrop-shaped)気泡(異方性があり、研磨パッドの研磨面から底部に向けて径が大きい構造を有する形状)を有する。従って、湿式成膜された樹脂は、複数の涙形状気泡を有する樹脂と言い換えることもできる。複数の涙形状気泡は連続気泡の形態であることが好ましい。
本発明の第2の態様の研磨パッドを構成する研磨層は、湿式成膜法により成膜された樹脂シート(好ましくはポリウレタンシート)であることが好ましく、複数の涙形状気泡を含むポリウレタンシートであることがより好ましく、複数の涙形状気泡を含み且つ当該気泡の一部又は全部が連通孔によりつながった連続気泡を有するポリウレタンシートであることがさらにより好ましい。
本発明の第2の態様の研磨パッドは、研磨層の研磨面に溝が設けられていることが好ましい。溝は研磨層を貫通しておらず、貫通孔と区別することができる。
溝としては、研磨面にエンボス加工を施すことで得られるエンボス溝、切削工具により切削加工を施すことで得られる切削溝が挙げられる。これらの中でもエンボス溝が好ましい。エンボス溝などの溝を設けることにより、研磨面にバリが出にくく、仕上げ研磨に適した研磨パッドを得ることができる。
溝の深さは研磨層の厚みよりも小さい限り特に制限はないが、研磨層の厚みの50~90%であることが好ましく、60~80%であることがより好ましい。被研磨物の研磨により溝が消失すると研磨スラリーの流排出性が失われ研磨性能が低下するため研磨パッドは寿命となることから、溝深さは深いことが好ましい。他方、エンボス溝の溝深さを大きくするためには加工圧力を上げる、或いは加工温度を上げる必要があり、それにより研磨層裏面の基材(PET)が変形したり、研磨層表面が劣化したりする可能性がある。溝の深さが上記範囲内であると、これらの問題が生じにくい。
溝の断面形状は特に限定されず、円弧状であってもよく、U字状、V字状、矩形状、台形状及びその他の多角形状であってもよく、これら2種以上の形状の組み合わせであってもよい。また、溝の数や形状も特に制限はなく、研磨パッドの使用目的などに合わせて適宜溝数や形状を調整すればよい。形状としては、格子状、放射状、同心円状、ハニカム状などが挙げられ、それらを組み合わせてもよい。
また、本発明の第2の態様の研磨パッドは、研磨層の表面を研削(バフ処理)により開口していてもよく、スライスしていてもよい。
また、従来の研磨パッドは、透光性部材の最上部4’を溝の最下部8’と同じ位置にあるかそれよりも低い位置にすると、スラリーや研磨屑が溝から排出されにくくなるため、経時的に光透過率が低下するという問題が生じ得る。これに対し、本発明の一態様の研磨パッド(図4B或いは図4Cの研磨パッド)は、第1貫通孔内の凹部に入り込んだスラリーや研磨屑が研磨加工中の遠心力により第1貫通孔の側面に移動し、円相当径の小さい第2貫通孔からは見えにくくなるため、光透過率の低下を防ぐことが出来る。さらに、大部分のスラリーが凹部の側面に移動した後、少量のスラリーのみが透光性部材の表面に存在していたとしても、スラリーによる光透過率の低下が生じにくいため、安定した光検出が可能となる。
本発明の第2の態様の研磨パッドは、親水性樹脂、好ましくはイオン結合性の親水基を含む樹脂で透光性部材の研磨面側の表面をコーティングすることにより、透光性部材の研磨面側の表面でのスラリーの有無によって光透過率がほとんど変わらない。これにより、研磨終点を高精度に判定することができる。
また、本発明の第2の態様の研磨パッドは、研磨面を上面としその反対面を下面とした場合に、樹脂でコーティングされた透光性部材の研磨面側の表面が研磨面と同じ高さにあっても、研磨面よりも低い位置にあってもその効果を発揮するが、特に透光性部材の研磨面側の表面が研磨面よりも低い位置にある場合にその効果をよりよく発揮する。すなわち、透光性部材の研磨面側の表面が研磨面よりも低い位置にある場合には、樹脂でコーティングされた透光性部材の表面と貫通孔の側面とで囲まれた凹部(例えば、円柱状の凹部)が存在し、ここにスラリーが入り込む。凹部内に入り込んだスラリーの多くは、遠心力の影響を受けて側面に移動しエンボス溝を介して排出されるため、経時的に透光性部材表面のレーザー光が透過する領域にスラリーが存在するタイミング(凹部内にスラリーが多く流入したタイミングや排出しきれなかったタイミング等)と存在しないタイミングが生じ得る。透光性部材表面の撥水性が高い場合、窓表面上でスラリーは馴染むことなく水滴状あるいは筋状に付着しているため、レーザー光が透過する領域にスラリーが存在しないときの平行光線透過率に対し、スラリーが存在するときの平行光線透過率は水滴状のスラリーによる光の散乱のために大幅に低下し、研磨加工時の光透過率にバラツキが生じやすい。本発明の第2の態様の研磨パッドは、透光性部材の研磨面側の表面を親水性樹脂、好ましくはイオン結合性の親水基を含む樹脂でコーティングすることにより、スラリーを水滴状にせず窓表面に濡れ広がらせることができるため、光の散乱を抑制し、スラリーが付着している場合と付着していない場合とで光透過率の変動を小さくすることができ、これにより研磨加工時の光透過率のバラツキを抑えることができる。
本発明の第3の態様の研磨パッドは、透光性樹脂部材及び研磨層を有する研磨パッドであって、前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ前記透光性樹脂部材は、その研磨面側の表面に親水性モノマーがグラフト重合されている、前記研磨パッドである。
また、本発明の第3の態様の研磨パッドは、透光性樹脂部材及び研磨層を有する研磨パッドであって、前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ前記透光性樹脂部材の研磨面側の表面の樹脂は、親水性モノマーを構成単位として含む重合体をその側鎖に有する、前記研磨パッドと言い換えてもよい。
本発明の第3の態様の研磨パッドは、透光性樹脂部材、即ち窓部材を有する。透光性樹脂部材を通して被研磨物に光を照射することにより、被研磨物が希望の表面特性や平面状態に到達した時点を検出することができる。光学的終点検出には、可視光(白色光)のレーザーやランプ等を用いる。
透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されている。ここで、「研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されている」とは、研磨パッドの研磨面から厚さ方向に貫通孔内を見た場合に、透光性樹脂部材が確認できるように配置されていることを意図したものであり、(1)図2B、図3Bのように透光性樹脂部材が研磨層に設けられた貫通孔の側面(側壁)に接する(又は接着する)ようにして配置されている場合や、(2)図4B或いは図4Cのように研磨層の下層に研磨層の有する貫通孔の円相当径よりも小さい円相当径を有する貫通孔を有する他の層を設け、研磨層の貫通孔と他の層の貫通孔のサイズの差から生じる露出部7上に透光性樹脂部材を配置する場合や、(3)図5Bのように透光性樹脂部材を研磨層と他の層との間に挟み込み、透光性樹脂部材の一部が貫通孔内に露出するように配置されている場合や、(4)図6Bのように研磨層と他の層の両方に貫通孔を設け、そのいずれか又は両方の貫通孔の側面と接する(又は接着する)ようにして透光性樹脂部材が配置されている場合を含む概念である。これらの中でも、(1)、(2)又は(4)が好ましく、(1)又は(2)がより好ましく、(2)がさらにより好ましい。
本発明の第3の態様の研磨パッドは、透光性樹脂部材の研磨面側の表面に親水性モノマーがグラフト重合されている。
本明細書及び特許請求の範囲において、「透光性樹脂部材の研磨面側の表面に親水性モノマーがグラフト重合されている」とは、研磨面側の表面の透光性樹脂に、親水性モノマーがグラフト重合により結合していることをいう。したがって、透光性樹脂部材の研磨面側の表面に存在する樹脂は、その側鎖に、親水性モノマーを構成単位として含む重合体を有する。
プラズマ処理とは、不活性ガス雰囲気下で放電することにより、前記不活性ガスの電離作用によって生じるプラズマを固体表面に照射する処理をいう。
前記プラズマ処理における不活性ガスとしては、窒素ガス、アルゴンガス、酸素ガス、ヘリウムガス、ネオンガスおよびキセノンガス等が挙げられる。
プラズマの生成は、プラズマを生成するための公知方法のいずれによっても行なうことが出来る。例えば、高周波発生器に連結された平行板電極の間にモノマーを真空下で入れ、真空室の外部又は内部のいずれかの平行板を用いてプラズマを生成させることが出来る。また外部誘導コイルによって電場をつくらせ、イオン化ガスのプラズマを発生させてもよく、また反対に荷電した電極に間隔をおいて直接真空室に入れてプラズマを生成させてもよい。
親水性モノマーとしては、不飽和二重結合を有する親水性モノマーが好ましく、ビニル基またはアリル基を有する親水性モノマーがより好ましい。
グラフト化に用いる親水性モノマーとしては、親水性のモノマーであれば特に制限はなく、従来知られたモノマーを用いることが出来る。親水性モノマーの例としては、アクリルアミド、メタクリルアミド、N-ビニルピロリドン;アクリル酸、メタクリル酸、P-スチレンスルホン酸、ビニルスルホン酸、2-メタアクリロイルオキシエチルスルホン酸、3-メタアクリロイルオキシ-2-ヒドロキシプロピルスルホン酸、アリルスルホン酸、メタクリルスルホン酸、並びにこれらの酸のアンモニウム塩、及びアルカリ金属塩、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルアクリレート及びジエチルアミノエルメタクリレート、2ビニルビリジン及び4ビニルビリジンの塩酸、硝酸、ジメチル硫酸、ジエチル硫酸又は塩化エチルの4級化物が挙げられる。これらの中でも、アクリル系モノマーが好ましく、アクリル酸、メタクリル酸、2ヒドロキシエチルメタクリレート、2ヒドロキシエチルアクリレート、アクリルアミド、メタクリルアミド、2アクリルアミド-2-メチルプロパンスルホン酸、N,Nジメチルアミノエチルメタクリレート又はN,Nジメチルアミノエチルアクリレートがより好ましく、アクリル酸、メタクリル酸がさらにより好ましく、アクリル酸がさらにより好ましい。
親水性モノマーとしては1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これらの中でも、アクリル系モノマーでグラフト化した表面の樹脂が、ポリエチレングリコール、ポリビニルピロリドン、ポリキシリルビオローゲン、ポリエチレンイミン、ポリビニルピリジニウムクロライド及びポリビニルベンジルトリメチルアンモニウムクロライドから選択される複合体形成ポリマーで分子間相互作用により結びついていることが好ましく、ポリビニルベンジルトリメチルアンモニウムクロライドで分子間相互作用により結びついていることがより好ましい。グラフト重合による高分子鎖と複合体形成ポリマーとの間に分子間相互作用、例えば、水素結合、イオン結合などが働いてイオンコンプレックスからなる複合体が形成される。
複合体形成ポリマーと複合体を形成することにより、グラフト基に存在するイオンと複合体形成ポリマーの対イオンにより、水分子の吸着点が増えるため、接触角がさらに低下し、透光性樹脂部材表面の親水性を更に高めることができる。また、表面に水膜が形成されやすくなるため、研磨屑等の汚れが付着・固着しにくくなる。
複合体形成ポリマーによる複合体化は、例えば、親水性モノマーをグラフト重合させた透光性樹脂部材を複合体形成ポリマー水溶液中に所定時間浸漬することにより、形成させることができる。
本発明の第3の態様の研磨パッドは、透光性樹脂部材の研磨面側の表面の水接触角が80度以下である。水接触角は、60度以下であることが好ましく、50度以下であることがより好ましく、30度以下であることがさらにより好ましく、20度以下であることがさらにより好ましく、1~20度であることがさらにより好ましく、2~15度であることがさらにより好ましく、3~10度であることがさらにより好ましい。水接触角が上記範囲内であると、透光性樹脂部材(窓部材)の研磨面側の表面への研磨屑の付着、固着を防ぎやすい。
水接触角が上記範囲内であることにより、透光性樹脂部材(窓部材)の研磨面側の表面への研磨屑の付着、固着を防ぎやすくなる理由としては、以下のように推察される。
上記の通り、本発明の第3の態様の研磨パッドは、グラフト化により、透光性樹脂部材の研磨面側の表面の樹脂が長い側鎖を有し、側鎖に水分子が吸着しつつ、隣り合う側鎖同士は同じ電荷を帯びているため反発するため、水分子が多数吸着し、濡れ性が向上すると考えられるが、このとき、透光性樹脂部材の研磨面側の表面の水接触角が80度以下の親水性であることにより、側鎖部分に付着した水分子が水の膜を形成しやすくなり研磨屑がスラリーとともに透光性樹脂部材から排出されやすくなるため、結果として研磨屑の付着や固着を抑えることができるものと考えられる。
従来の研磨パッドで使用されている窓部材は、一般に水接触角が80度超である。窓部材の全面が80度以下の水接触角を持つ窓を用いた場合、スラリーによって窓が膨潤、変形し、研磨領域から剥がれ落ちたり、スラリー漏れを引き起こす可能性がある。そのため、窓部材材料としては水接触角が80度超の疎水性を有する窓部材が好ましく、研磨面側の表面だけを80度以下の水接触角とすることが好ましい。本発明としては、研磨面側の表面の樹脂のみがグラフト化されており、これにより研磨面側の表面の水接触角が80度以下である(側面や裏面の水接触角は80度超である)透光性樹脂部材を用いることが好ましい。
貫通孔は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、研磨面からその反対面へと貫通している孔である。貫通孔は、厚み方向に対して平行に又は研磨面に対して垂直に研磨層を貫通していることが好ましい。
貫通孔は研磨層中に1個設けられていてもよく、互いに離間し且つ独立している2個以上の貫通孔が設けられていてもよい。
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の貫通孔の形状又は研磨面における貫通孔の形状としては、円形、楕円形、三角形、四角形、六角形、八角形等が挙げられる。或いは、同一又は異なる複数の上記形状が互いに部分的に重なり合った形状であってもよい。これらの中でも、研磨屑が溜りやすい隅部を形成しない円形が特に好ましい。
本明細書及び特許請求の範囲において、円相当径とは、測定対象の図形が有する面積に相当する、真円の直径のことである。
貫通孔の円相当径は、研磨パッドの研磨面側から研磨パッド厚さ方向に見たときの貫通孔の円相当径であり、研磨パッドの研磨面側から研磨パッド厚さ方向に見た時の貫通孔の形状が円形である場合は直径に相当する。
貫通孔の円相当径に特に制限はないが、5~40mmが好ましく、5~30mmがより好ましく、10~28mmがさらにより好ましい。
また、研磨面における貫通孔の面積は、研磨面の全面積に対して0.003~0.5%であることが好ましく、0.004~0.4%であることがより好ましく、0.05~0.3%であることがさらにより好ましい。
研磨層を構成する樹脂としては、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樹脂;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樹脂;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樹脂;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樹脂;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樹脂;ポリアミド系樹脂;及びポリスチレン系樹脂などが挙げられる。これらの中でも、圧縮特性や柔軟性を考慮すれば、ポリウレタン樹脂がより好ましい。
研磨層は1種類の樹脂から構成されていてもよく、2種以上の樹脂から構成されていてもよい。
また、研磨層は連続気泡を有するものが好ましい。ここでいう連続気泡とは隣り合う気泡同士が互いに連通孔によりつながった空間を有する発泡を示す。具体的には湿式成膜法による樹脂や乾式成形、射出成形によるフォームでよい。好ましくは湿式成膜法によるもので、良好な屈伸運動が期待できる。
本明細書において、湿式成膜法による樹脂とは、湿式成膜法により成膜された樹脂(好ましくはポリウレタン樹脂)を意味する。湿式成膜法は、成膜する樹脂を有機溶媒に溶解させ、その樹脂溶液をシート状の基材に塗布後に凝固液中に通して樹脂を凝固させる方法である。湿式成膜された樹脂は、一般に、複数の涙形状(teardrop-shaped)気泡(異方性があり、研磨パッドの研磨面から底部に向けて径が大きい構造を有する形状)を有する。従って、湿式成膜された樹脂は、複数の涙形状気泡を有する樹脂と言い換えることもできる。複数の涙形状気泡は連続気泡の形態であることが好ましい。
本発明の第3の態様の研磨パッドは、研磨層の研磨面に溝が設けられていることが好ましい。溝は研磨層を貫通しておらず、貫通孔と区別することができる。
溝としては、研磨面にエンボス加工を施すことで得られるエンボス溝、切削工具により切削加工を施すことで得られる切削溝が挙げられる。これらの中でもエンボス溝が好ましい。エンボス溝などの溝を設けることにより、研磨面にバリが出にくく、仕上げ研磨に適した研磨パッドを得ることができる。
溝の深さは研磨層の厚みよりも小さい限り特に制限はないが、研磨層の厚みの50~90%であることが好ましく、60~80%であることがより好ましい。被研磨物の研磨により溝が消失すると研磨スラリーの流排出性が失われ研磨性能が低下するため研磨パッドは寿命となることから、溝深さは深いことが好ましい。他方、エンボス溝の溝深さを大きくするためには加工圧力を上げる、或いは加工温度を上げる必要があり、それにより研磨層裏面の基材(PET)が変形したり、研磨層表面が劣化する可能性がある。溝の深さが上記範囲内であると、これらの問題が生じにくい。
溝の断面形状は特に限定されず、円弧状であってもよく、U字状、V字状、矩形状、台形状及びその他の多角形状であってもよく、これら2種以上の形状の組み合わせであってもよい。また、溝の数や形状も特に制限はなく、研磨パッドの使用目的などに合わせて適宜溝数や形状を調整すればよい。形状としては、格子状、放射状、同心円状、ハニカム状などが挙げられ、それらを組み合わせてもよい。
また、本発明の第3の態様の研磨パッドは、研磨層の表面を研削(バフ処理)により開口していてもよく、スライスしていてもよい。
また、従来の研磨パッドにおいては、一般に、透光性樹脂部材の上面4’を溝の最下部8’と同じ位置にあるかそれよりも低い位置にすると、スラリーや研磨屑が溝から排出されにくくなるため、経時的に光透過率が低下するという問題が生じ得る。これに対し、本発明の第3の態様の研磨パッドは、研磨屑が透光性樹脂部材の表面に付着・固着しづらいため、光低下率の低下を抑えることができる。また、特に本発明の一態様の研磨パッド(図4B或いは図4Cの研磨パッド)では、第1貫通孔内の凹部に入り込んだ研磨屑が研磨加工中の遠心力により第1貫通孔の側面に移動した後、その一部が溝から排出されずに残っていたとしても、円相当径の小さい第2貫通孔からは見えにくくなるため、光透過率の低下を更に防ぐことが出来る。これにより、安定した光検出が可能となる。
本発明の第4の態様の研磨パッドは、透光性樹脂部材及び研磨層を有する研磨パッドであって、前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ前記透光性樹脂部材は、少なくともその研磨面側の表面において、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する、前記研磨パッドである。
以下、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を、多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂と略記することがある。同様に、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する多官能(メタ)アクリレートモノマーを、多官能(メタ)アクリレートモノマーと略記することがある。
また、図2B、図3B、図4B、図4C、図5Bを参照すると、透光性樹脂部材の少なくとも研磨面側の表面は、研磨面を上面としその反対面を下面とした場合における、透光性樹脂部材4の研磨面側の表面部9を指す。
本発明の第4の態様の研磨パッドは、透光性樹脂部材、即ち窓部材を有する。透光性樹脂部材を通して被研磨物に光を照射することにより、被研磨物が希望の表面特性や平面状態に到達した時点を検出することができる。光学的終点検出には、可視光(白色光)のレーザーやランプ等を用いる。
本発明の第4の態様の研磨パッドは、透光性樹脂部材の少なくともその研磨面側の表面において、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する。
「-C2-4アルキレン-O-単位を有する」とは、-C2-4アルキレン-O-の基本単位を1個又は2個以上有することをいう。基本単位を1個有するか或いは複数の基本単位の繰り返しを有する場合、(-C2-4アルキレン-O-)nを有すると言い換えることができる(nは1以上の整数である)。基本単位の数又はnの数に特に制限はないが、1~30が好ましく、2~28がより好ましく、3~25がさらにより好ましく、4~25がさらにより好ましい。
多官能(メタ)アクリレートモノマーは、1種類の-C2-4アルキレン-O-単位を有していてもよく、2種以上の異なる-C2-4アルキレン-O-単位を有していてもよい。
多官能(メタ)アクリレートモノマー1個あたりの-C2-4アルキレン-O-の数は、1~30が好ましく、2~28がより好ましく、3~25がさらにより好ましく、4~25がさらにより好ましい。
-C2-4アルキレン-O-単位は、-C2-3アルキレン-O-単位であることが好ましい。また、-C2-4アルキレン-O-単位は、エチレンオキサイドに由来するもの(-CH2-CH2-O-)及び/又はプロピレンオキサイドに由来するもの(-CH2-CH(CH3)-O-又は-CH(CH3)-CH2-O-(好ましくは-CH2-CH(CH3)-O-))であることが好ましい。多官能(メタ)アクリレートモノマーは、-CH2-CH2-O-単位及び/又は-CH2-CH(CH3)-O-単位を有する多官能(メタ)アクリレートモノマーであることが好ましい。
また、透光性樹脂部材は、研磨面側の表面だけではなく、研磨面とは反対側の面(裏面)や側面も前記樹脂でコーティングされていてもよいが、裏面や側面をもコーティングすることはコストの増加につながる一方で、裏面や側面のコーティングは本発明の効果と関係がないため、研磨面側の表面のみが、前記樹脂でコーティングされていることが好ましい。
前記樹脂でコーティングされた透光性部材の表面層の厚みに特に制限はないが、1~50μmであることが好ましい。表面層の厚みが前記範囲内であれば、高い光透過率が得られる。
(i)のモノマーとしては、-C2-3アルキレン-O-単位を有する化合物と(メタ)アクリル酸がエステル結合されたモノマーが好ましい。
(ii)のモノマーとしては、エチレンオキサイド及び/又はプロピレンオキサイドが付加された3価以上のアルコールと(メタ)アクリル酸とがエステル結合されたモノマーが好ましい。
上記(i)の多官能性(メタ)アクリレートモノマーとしては、2官能性(メタ)アクリレートモノマーが好ましい。2官能性(メタ)アクリレート由来の構成単位を含む樹脂は比較的柔軟性に優れるため、基材への密着性が高く剥離を防止できる。
上記(i)の多官能(メタ)アクリレートモノマー1個あたりの-C2-4アルキレン-O-の数は、1~30が好ましく、4~30がより好ましく、5~25がさらにより好ましく、9~25がさらにより好ましい。
-C2-4アルキレン-O-単位を有す化合物の例としては、エチレンオキサイド、プロピレンオキサイド、テトラメチレングリコール、ジエチレンオキサイド、ジプロピレンオキサイド、ジテトラメチレングリコール、トリエチレンオキサイド、トリプロピレンオキサイド、トリテトラメチレングリコールなどの、(ポリ)エチレンオキサイド、(ポリ)プロピレンオキサイド、(ポリ)テトラメチレングリコールなどとモノ(メタ)アクリル酸とが結合してなる化合物が挙げられる。これらの中でも、(ポリ)エチレンオキサイド及び/又は(ポリ)プロピレンオキサイドとモノ(メタ)アクリル酸とが結合してなる化合物が好ましい。当該化合物と他の(メタ)アクリル酸とを更に反応させることにより、多官能性、好ましくは2官能性の(メタ)アクリレートモノマーを得ることができる。
上記(i)のモノマーの例としては、(ポリ)エチレングリコールジ(メタ)アクリレート、(ポリ)プロピレングリコールジ(メタ)アクリレート、(ポリ)テトラメチレングリコールジ(メタ)アクリレートなどの(ポリ)C2-4アルキレングリコールジ(メタ)アクリレート、メトキシ-(ポリ)エチレングリコール(メタ)アクリレートなどのメトキシ-(ポリ)C2-4アルキレングリコールジ(メタ)アクリレートが挙げられる。これらの中でも、(ポリ)C2-3アルキレングリコールジ(メタ)アクリレート((ポリ)エチレングリコールジ(メタ)アクリレート及び/又は(ポリ)プロピレングリコールジ(メタ)アクリレート)が好ましく、(ポリ)エチレングリコールジ(メタ)アクリレートがより好ましい。
同様に、(ポリ)プロピレングリコールは、1個のプロピレングリコール(モノプロピレングリコール)と、2個以上のプロピレングリコール(ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコールなど)との両方を含む概念として用いられる。
同様に、(ポリ)テトラメチレングリコールは、1個のテトラメチレングリコール(モノテトラメチレングリコール)と、2個以上のテトラメチレングリコール(ジテトラメチレングリコール、トリテトラメチレングリコール、テトラテトラメチレングリコールなど)との両方を含む概念として用いられる。
上記(i)のモノマーの質量平均分子量は、200~1500であることが好ましく、300~1200であることが好ましく、400~1400であることがさらにより好ましく、500~1300であることがさらにより好ましく、600~1200であることがさらにより好ましい。
上記(ii)の多官能性(メタ)アクリレートモノマーとしては、3~6官能性(メタ)アクリレートモノマーが好ましく、3~5官能性(メタ)アクリレートモノマーがより好ましく、3~4官能性(メタ)アクリレートモノマーがさらにより好ましい。このような多官能性(メタ)アクリレートは、重合時の硬化速度を早め、架橋密度を高めることができ耐水性向上に寄与する。
上記(ii)の多官能(メタ)アクリレートモノマー1個あたりのC2-4アルキレンオキサイド(-C2~4アルキレン-O-)の基本単位の数は、1~30が好ましく、3~30がより好ましく、3~25がさらにより好ましい。
3価以上のアルコールとしては、グリセリン、ジグリセリン、トリグリセリン、トリメチロールプロパン、ジトリメチロールプロパン、エリスリトール、ペンタエリスリトール、ジペンタエリスリトールからなる群から選択される少なくとも1種であることが好ましく、グリセリン、ジグリセリン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールからなる群から選択される少なくとも1種であることがより好ましく、グリセリン、ペンタエリスリトール、トリメチロールプロパンからなる群から選択される少なくとも1種であることがさらにより好ましく、グリセリン、ペンタエリスリトールからなる群から選択される少なくとも1種であることがさらにより好ましい。
また、C2-4アルキレンオキサイドが付加された3価以上のアルコールとしては、C2-3アルキレンオキサイド(エチレンオキサイド(EO)及び/又はプロピレンオキサイド(PO))が付加された3価以上のアルコールであることが好ましい。
上記(ii)のモノマーの例としては、C2-4アルコキシ化ペンタエリスリトールテトラ(メタ)アクリレート、C2-4アルコキシ化グリセリントリ(メタ)アクリレート、C2-4アルコキシ化トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールヘキサアクリレートが挙げられる。これらの中でも、C2-3アルコキシ化ペンタエリスリトールテトラ(メタ)アクリレート、C2-3アルコキシ化グリセリントリ(メタ)アクリレート及び/又はC2-3アルコキシ化トリメチロールプロパントリ(メタ)アクリレートが好ましく、C2-3アルコキシ化ペンタエリスリトールテトラ(メタ)アクリレート及び/又はC2-3アルコキシ化グリセリントリ(メタ)アクリレートがより好ましい。
重合性官能基としては、エチレン性不飽和二重結合(炭素原子間の不飽和二重結合)が好ましく、(メタ)アクリロイル基に存在するエチレン性不飽和二重結合(炭素原子間の不飽和二重結合)がより好ましい。
ウレタン(メタ)アクリレートは、イソシアネート基とヒドロキシ基を反応させたウレタン結合と(メタ)アクリロイル基を有する化合物である。ウレタン(メタ)アクリレートは、2以上の重合性官能基を有することが好ましく、2~4個の重合性官能基を有することがより好ましく、2~3個の重合性官能基を有することがさらにより好ましく、2個の重合性官能基を有することがさらにより好ましい。重合性官能基としては、エチレン性不飽和二重結合(炭素原子間の不飽和二重結合)が好ましく、(メタ)アクリロイル基に存在するエチレン性不飽和二重結合(炭素原子間の不飽和二重結合)がより好ましい。
ウレタン(メタ)アクリレートとしては、例えば、脂肪族ウレタン(メタ)アクリレート、芳香族ウレタン(メタ)アクリレートなどが挙げられる。また、ウレタン(メタ)アクリレートは、ポリシロキサン由来の構造を有さないことが好ましい。
ウレタン(メタ)アクリレートは、例えば、少なくとも2つの(メタ)アクリロイル基を有するヒドロキシ化合物とイソシアネートとの反応によって得られる。前記イソシアネートとしては、例えば、脂肪族ポリイソシアネート又は芳香族ポリイソシアネートが挙げられる。
脂肪族ウレタン(メタ)アクリレートは、例えば、少なくとも2つの(メタ)アクリロイル基を有するヒドロキシ化合物と脂肪族イソシアネートとの反応によって得られる。前記脂肪族イソシアネートとしては、例えば、脂肪族ジイソシアネート、脂肪族トリイソシアネートなどが挙げられる。
芳香族ウレタン(メタ)アクリレートは、例えば、少なくとも2つの(メタ)アクリロイル基を有するヒドロキシ化合物と芳香族イソシアネートとの反応によって得られる。前記芳香族イソシアネートとしては、例えば、芳香族ジイソシアネート、芳香族トリイソシアネートなどが挙げられる。
多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂がウレタン(メタ)アクリレート由来の構成単位を含む場合、当該ウレタン(メタ)アクリレートの含有量は、前記樹脂を構成する全モノマー成分100質量部に対して、70質量部以下であることが好ましく、60質量部以下であることがより好ましく、55質量部以下であることがさらにより好ましい。また、ウレタン(メタ)アクリレートモノマーに由来する構成成分は、上記樹脂の全モノマー成分100質量部に対して、40~60質量部であることも好ましい。
溶液重合を用いる場合には、前記モノマー等と重合開始剤(触媒等)とを含む溶液を透光性樹脂部材の表面に塗布して乾燥する間に、重合反応が進み、コーティングを得ることができる。
光重合を用いる場合には、前記モノマー等と光重合開始剤を含む溶液を透光性樹脂部材の表面に塗布し、紫外線照射をすることでコーティングを得ることができる。
光重合開始剤としては、紫外線や電子線などの照射により光硬化型樹脂を硬化させることが出来るものであれば特に制限はなく、従来から知られている光重合開始剤を用いることができる。例えば、ラジカル重合開始剤、カチオン重合開始剤、アニオン重合開始剤等を挙げることができ、市販品としては、イルガキュア(IGM Resin B.V.製)等を挙げることができる。
本発明の第4の態様の研磨パッドは、研磨面を上面としその反対面を下面とした場合に、透光性樹脂部材の最上部が研磨面と同じ高さにあってもよく研磨面より低くてもよいが、研磨面よりも低いことが好ましい(図2B)。透光性樹脂部材の最上部が研磨面よりも低いことにより、研磨層よりも硬い透光性樹脂部材に起因する研磨傷の発生を防ぐことができる。また、透光性樹脂部材の最上部が研磨面よりも低いと、透光性樹脂部材と貫通孔の側面で囲まれた凹部にスラリーが入り込み、その多くは遠心力により貫通孔側面に移動し溝を介して排出されるため、少量のスラリーが透光性樹脂部材の表面に残っている場合と残っていない場合が生じやすくなる。従来の研磨パッドを用いた場合には、少量のスラリーが透光性樹脂部材の表面に残っている場合と残っていない場合とで光透過率に差が出るため、研磨終点を高精度に判定することが難しい。これに対し、本発明の第4の態様の研磨パッドは、透光性樹脂部材の研磨面側の表面に前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂が存在することでスラリーとの馴染みがよくなり、少量のスラリーが存在するような場合でも窓表面に均一に広がることで、研磨初期から終盤まで光透過率の変動が少なくなり、透光性樹脂部材の最上部が研磨面よりも低い位置にあっても、研磨終点を高精度に判定することができる。
本発明の第4の態様の研磨パッドは、透光性樹脂部材の研磨面側の表面に水を付着させていないときの可視光線透過率(本明細書において、単に光透過率ということがある)と前記透光性樹脂部材の研磨面側の表面に水を付着させたときの可視光線透過率との差が10%以内であることが好ましい。光透過率の差が上記範囲内であることにより、透光性樹脂部材の表面にスラリーがある場合とない場合との間で光透過率の差が生じにくくなり、研磨終点の判定を高精度に行うことが出来る。
光透過率の測定は、分光光度計で波長300~1000nmの透過スペクトルを測定し、日本工業規格(JIS A5759:2008)の可視光線透過率(%)として求めることが出来る。すなわち、各波長380~780nmの範囲の各波長の透過率を測定し、CIE(国際照明委員会)昼光D65の分光分布、CIE明順応標準比視感度の波長分布及び波長間隔から得られる重価係数を各波長での透過率に乗じて加重平均することによって求められる透過率である。
また、透光性樹脂部材の研磨面側の表面に水を付着させたときの光透過率の測定は、スプレーにより十分量(例えば、9mm×50mmの大きさに切り出した透光性樹脂部材に対して、0.01~0.03mL程度)の水を透光性樹脂部材の研磨面側の表面全体に付着させた後、透光性樹脂部材を地面に対して垂直にして60秒間静置することで水切りを行った透光性樹脂部材を用いて行うことが出来る。
貫通孔は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、研磨面からその反対面へと貫通している孔である。貫通孔は、厚み方向に対して平行に又は研磨面に対して垂直に研磨層を貫通していることが好ましい。
貫通孔は研磨層中に1個設けられていてもよく、互いに離間し且つ独立している2個以上の貫通孔が設けられていてもよい。
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の貫通孔の形状又は研磨面における貫通孔の形状としては、円形、楕円形、三角形、四角形、六角形、八角形等が挙げられる。或いは、同一又は異なる複数の上記形状が互いに部分的に重なり合った形状であってもよい。これらの中でも、研磨屑が溜りやすい隅部を形成しないため、円形が特に好ましい。
本明細書及び特許請求の範囲において、円相当径とは、測定対象の図形が有する面積に相当する、真円の直径のことである。
貫通孔の円相当径は、研磨パッドの研磨面側から研磨パッド厚さ方向に見たときの貫通孔の円相当径であり、研磨パッドの研磨面側から研磨パッド厚さ方向に見た時の貫通孔の形状が円形である場合は直径に相当する。
貫通孔の円相当径に特に制限はないが、5~40mmが好ましく、5~30mmがより好ましく、8~28mmがさらにより好ましい。
また、研磨面における貫通孔の面積は、研磨面の全面積に対して0.003~0.5%であることが好ましく、0.004~0.4%であることがより好ましく、0.005~0.3%であることがさらにより好ましい。
研磨層を構成する樹脂としては、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樹脂;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樹脂;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樹脂;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樹脂;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樹脂;ポリアミド系樹脂;及びポリスチレン系樹脂などが挙げられる。これらの中でも、圧縮特性や柔軟性を考慮すれば、ポリウレタン樹脂がより好ましい。
研磨層は1種類の樹脂から構成されていてもよく、2種以上の樹脂から構成されていてもよい。
また、研磨層は連続気泡を有するものが好ましい。ここでいう連続気泡とは隣り合う気泡同士が互いに連通孔によりつながった空間を有する発泡を示す。具体的には湿式成膜法による樹脂や乾式成形、射出成形によるフォームでよい。好ましくは湿式成膜法によるもので、良好な屈伸運動が期待できる。
本明細書において、湿式成膜法による樹脂とは、湿式成膜法により成膜された樹脂(好ましくはポリウレタン樹脂)を意味する。湿式成膜法は、成膜する樹脂を有機溶媒に溶解させ、その樹脂溶液をシート状の基材に塗布後に凝固液中に通して樹脂を凝固させる方法である。湿式成膜された樹脂は、一般に、複数の涙形状(teardrop-shaped)気泡(異方性があり、研磨パッドの研磨面から底部に向けて径が大きい構造を有する形状)を有する。従って、湿式成膜された樹脂は、複数の涙形状気泡を有する樹脂と言い換えることもできる。複数の涙形状気泡は連続気泡の形態であることが好ましい。
本発明の第4の態様の研磨パッドを構成する研磨層は、湿式成膜法により成膜された樹脂シート(好ましくはポリウレタンシート)であることが好ましく、複数の涙形状気泡を含むポリウレタンシートであることがより好ましく、複数の涙形状気泡を含み且つ当該気泡の一部又は全部が連通孔によりつながった連続気泡を有するポリウレタンシートであることがさらにより好ましい。
本発明の第4の態様の研磨パッドは、研磨層の研磨面に溝が設けられていることが好ましい。溝は研磨層を貫通しておらず、貫通孔と区別することができる。
溝としては、研磨面にエンボス加工を施すことで得られるエンボス溝、切削工具により切削加工を施すことで得られる切削溝が挙げられる。これらの中でもエンボス溝が好ましい。エンボス溝などの溝を設けることにより、研磨面にバリが出にくく、仕上げ研磨に適した研磨パッドを得ることができる。
溝の深さは研磨層の厚みよりも小さい限り特に制限はないが、研磨層の厚みの50~90%であることが好ましく、60~80%であることがより好ましい。被研磨物の研磨により溝が消失すると研磨スラリーの流排出性が失われ研磨性能が低下するため研磨パッドは寿命となることから、溝深さは深いことが好ましい。他方、エンボス溝の溝深さを大きくするためには加工圧力を上げる、或いは加工温度を上げる必要があり、それにより研磨層裏面の基材(PET)が変形したり、研磨層表面が劣化したりする可能性がある。溝の深さが上記範囲内であると、これらの問題が生じにくい。
溝の断面形状は特に限定されず、円弧状であってもよく、U字状、V字状、矩形状、台形状及びその他の多角形状であってもよく、これら2種以上の形状の組み合わせであってもよい。また、溝の数や形状も特に制限はなく、研磨パッドの使用目的などに合わせて適宜溝数や形状を調整すればよい。形状としては、格子状、放射状、同心円状、ハニカム状などが挙げられ、それらを組み合わせてもよい。
また、本発明の第4の態様の研磨パッドは、研磨層の表面を研削(バフ処理)により開口していてもよく、スライスしていてもよい。
本発明の第4の態様の研磨パッドは、透光性部材の少なくとも研磨面側の表面が、多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有することにより、スラリーに対する濡れ性が向上し、透光性部材の研磨面側の表面でのスラリーの有無によって光透過率がほとんど変わらない。これにより、研磨終点を高精度に判定することができる。
また、本発明の第4の態様の研磨パッドは、研磨面を上面としその反対面を下面とした場合に、透光性部材の研磨面側の表面が研磨面と同じ高さにあっても、研磨面よりも低い位置にあってもその効果を発揮するが、特に透光性部材の研磨面側の表面が研磨面よりも低い位置にある場合にその効果をよりよく発揮する。すなわち、透光性部材の研磨面側の表面が研磨面よりも低い位置にある場合には、透光性部材の表面と貫通孔の側面とで囲まれた凹部(例えば、円柱状の凹部)が存在し、ここにスラリーが入り込む。凹部内に入り込んだスラリーの多くは、遠心力の影響を受けて側面に移動しエンボス溝を介して排出され得るため、経時的に透光性部材表面のレーザー光が透過する領域にスラリーが存在するタイミング(凹部内にスラリーが多く流入したタイミングや排出しきれなかったタイミング等)と存在しないタイミングとが生じ得る。本発明の第4の態様の研磨パッドは、透光性部材の研磨面側の表面に前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂が含まれることにより、スラリーが付着している場合と付着していない場合との間で生じる光透過率の変動を小さくすることができ、これにより研磨加工時の光透過率のバラツキを抑えることができる。
また、本発明の第4の態様の研磨パッドは、透光性樹脂部材が、少なくともその研磨面側の表面において、多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有するため、耐薬品性が高く、酸性スラリーを用いた場合にもアルカリ性スラリーを用いた場合にも透光性樹脂部材の劣化を防ぐことができる。
(ショアA硬度)
本明細書において、ショアA硬度とは、日本工業規格(JIS K7311)に準じて測定した値を意味する。
本発明の第1~第4の態様の研磨パッドは、研磨層のショアA硬度が、5~70度(°)であることが好ましく、8~65度であることがより好ましい。研磨層のショアA硬度が上記範囲内であると、研磨屑が被研磨物に過度に接触されることが抑制されるため、スクラッチが発生しにくくなる。
また、本発明の第1~第4の態様の研磨パッドは、研磨層が透光性部材又は透光性樹脂部材よりも軟質であることが好ましく、透光性部材又は透光性樹脂部材よりもショアA硬度が低いことがより好ましい。
本明細書において、圧縮率とは、軟らかさの指標であり、圧縮弾性率とは、圧縮変形に対する戻りやすさの指標である。
圧縮率及び圧縮弾性率は、日本工業規格(JIS L1021)に従い、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出来る。具体的には、以下の通りである。
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5分間かけた後の厚さ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。
圧縮率は、圧縮率(%)=100×(t0-t1)/t0の式で算出することができる(なお、初荷重は100g/cm2、最終荷重は1120g/cm2である)。
圧縮弾性率は、圧縮弾性率(%)=100×(t0’-t1)/(t0-t1)の式で算出することが出来る(なお、初荷重は100g/cm2、最終荷重は1120g/cm2である)。
研磨層の圧縮率は、1~60%が好ましく、3~50%がより好ましい。研磨層の圧縮弾性率は、50~100%であることが好ましく、60~98%であることがより好ましい。圧縮率及び圧縮弾性率が上記範囲内であると、貫通孔上を被研磨物が通過する際に研磨層が圧縮され、また、被研磨物によって押し込まれた後の回復性に優れるため、研磨層の屈伸運動により貫通孔内部でスラリーの流れができ、貫通孔内にスラリーが留まることなく循環し、スラリーと共に貫通孔内に入った研磨屑が圧縮・回復の動作で貫通孔外に排出されやすくなる。これにより、貫通孔内に研磨屑が堆積することが防ぎやすくなる。
厚みは、日本工業規格(JIS K6505)に従い、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出来る。具体的には、以下の通りである。
縦、横10cm角の試料を準備する。試料の表面を上にして測定器に載せる。荷重100g/cm2をかけた加圧面を試料上に下し、5秒後の厚さを測定する。1枚につき5ヶ所測定しその平均値を厚さとする。なお、10cm角の試料が取れない場合は5ヶ所の平均とする。
研磨層の厚みに特に制限はないが、0.5~2mmであることが好ましく、0.75~1.55mmがさらにより好ましい。
本発明の第1~第4の態様の研磨パッドは、研磨層以外の層(他の層)を有していてもよい。他の層は、研磨層の研磨面とは反対側の面に1層または2層以上存在してもよい。他の層は、研磨層と同様に貫通孔を有する。
また、研磨層の貫通孔と他の層の貫通孔の形状は、同じであってもよく、異なっていてもよいが、研磨パッドを研磨面側から厚さ方向に見た場合に、研磨層の貫通孔と他の層の貫通孔とが少なくとも部分的に重なっていることが好ましい。これにより、透光性部材又は透光性樹脂部材に光を照射した場合に光が透光性部材又は透光性樹脂部材を透過する。
この態様の研磨パッドは、研磨面側から厚さ方向に見た場合に、第1貫通孔と第2貫通孔とが少なくとも部分的に重なっていることが好ましい。また、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、透光性部材又は透光性樹脂部材が第1貫通孔内に存在するように前記透光性部材又は透光性樹脂部材が配置されていることが好ましい。
第1貫通孔の外周部が第2貫通孔の外周部の全部を覆うとは、第1貫通孔5の径が第2貫通孔6の径よりも大きく、二重丸のように、第1貫通孔5の外周部が第2貫通孔6の外周部の外側に存在していることをいう。
ここで、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、透光性部材又は透光性樹脂部材が第1貫通孔内に存在するように前記透光性部材又は透光性樹脂部材が配置されているとは、研磨パッドの研磨面側から研磨パッド厚さ方向に第1貫通孔内を見た場合に、透光性部材又は透光性樹脂部材が確認できることをいう。
また、第1貫通孔5は、研磨パッド1を研磨面側から厚さ方向に見た場合に、他の層3の一部(以下、他の層の露出部7という)と第2貫通孔6の少なくとも一部とが露出されるように配置されることが好ましい。これにより、透光性部材4又は透光性樹脂部材4を、第1貫通孔5内であって且つ他の層3の第2貫通孔6及び露出部7上に配することができる。好ましくは、第1貫通孔5は、第1貫通孔5を研磨面側から見た場合に、他の層3の一部と第2貫通孔6の全てとが露出されるように配置される。また、透光性部材4又は透光性樹脂部材4は、第1貫通孔5内に設けられ、且つ他の層3の露出部7と接着されていることが好ましい。
図4A又は図4Bを参照すると、本発明の第1~第4の態様の研磨パッド1の厚さ方向断面において、第1貫通孔5は、第2貫通孔6と露出部7上にある研磨層2に設けられている。なお、露出部7を備える他の層3と研磨層2との間に更なる他の層を有していてもよく、この場合、更なる他の層に存在する貫通孔は研磨層2の貫通孔(第1貫通孔)と同一の断面形状(研磨面と水平方向の断面形状)を有し、研磨面から厚さ方向に見た場合に第1貫通孔5と完全に重なっていることが好ましい。透光性部材4又は透光性樹脂部材4は、第2貫通孔6と露出部7上であって且つ研磨層2の第1貫通孔5と更なる他の層の貫通孔の内部に配置されていることが好ましい。
本発明の第1~第4の態様の研磨パッドは、厚さ方向に対して垂直に切断した場合の第1貫通孔の断面形状と第2貫通孔の断面形状とが同じ形状を有していても異なる形状を有していてもよいが、同じ形状を有することが好ましい。
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合の第2貫通孔の形状、研磨パッドの厚さ方向に対して垂直に切断した場合の第2貫通孔の断面形状、及び/又は他の層表面における第2貫通孔の形状としては、円形、楕円形、三角形、四角形、六角形、八角形やこれらの形状が複合された形状等が挙げられる。或いは、同一又は異なる複数の上記形状が互いに部分的に重なり合った形状であってもよい。これらの中でも、円形が特に好ましい。
本明細書及び特許請求の範囲において、第2貫通孔の円相当径は、研磨パッドの研磨面側から研磨パッド厚さ方向に見たときの第2貫通孔の円相当径であり、研磨パッドの研磨面側から研磨パッド厚さ方向に見た時の第2貫通孔の形状が円形である場合は直径に相当する。
第1貫通孔の円相当径は第2貫通孔の円相当径より大きいことが好ましい。第1貫通孔の円相当径が第2貫通孔の円相当径より大きい限り第2貫通孔の円相当径に特に制限はないが、第2貫通孔の円相当径は1~20mmが好ましく、2~18mmがより好ましく、5~15mmがさらにより好ましい。また、第1貫通孔の円相当径と第2貫通孔の円相当径との差に特に制限はないが、第1貫通孔の円相当径が第2貫通孔の円相当径より5~30mm大きいことが好ましく、6~25mm大きいことがより好ましく、7~20mm大きいことがさらにより好ましい。
また、研磨パッドの研磨面側から厚さ方向に見た場合に、第1貫通孔の外周部が第2貫通孔の外周部の全部を覆うようにして設けられており、且つ第1貫通孔の円相当径が第2貫通孔の円相当径よりも5~30mm大きいことが好ましく、6~25mm大きいことがより好ましく、7~20mm大きいことがさらにより好ましく、8~20mm大きいことがさらにより好ましく、9~20mm大きいことがさらにより好ましく、10~20mm大きいことがさらにより好ましい。
また、研磨パッドの研磨面側から厚さ方向に見た場合に、第1貫通孔の外周部が第2貫通孔の外周部の全部を覆うようにして設けられており、且つ第1貫通孔の円相当径が、第2貫通孔の円相当径の1.5~4倍であることが好ましく、2~4倍であることがより好ましく、2.5~3倍であることがさらにより好ましい。
第1貫通孔と第2貫通孔との大きさの違いが上記範囲内であると、第1貫通孔内の凹部に入り込んだスラリーや研磨屑は研磨加工中の遠心力により第1貫通孔の外周側に移動し、円相当径の小さい第2貫通孔からは見えにくくなるため、透光性部材又は透光性樹脂部材に光を照射した際に研磨屑による光路の塞ぎを防ぐことが出来る。従って、優れた光透過率を維持することができ、研磨中に安定した終点検出の信号強度を得ることができる。また、露出部の面積が十分に広いため、透光性部材又は透光性樹脂部材と他の層との接着強度を保つことができ、透光性部材又は透光性樹脂部材の剥離を防止できる。
また、大部分のスラリーが凹部の側面に移動し、少量のスラリーのみが透光性部材又は透光性樹脂部材の表面に存在していたとしても、本発明の第1~第4の態様の研磨パッドはスラリーの有無による光透過率のバラツキが生じにくいため、安定した光検出が可能となる。
研磨層が連通孔を持つ連続気泡を有すると、研磨層に設けた第1貫通孔の側面にも連続気泡が開くため、その一部が研磨表面又は溝領域まで連通する。これにより、研磨中に第1貫通孔内に入り込んだスラリーや研磨屑が、研磨加工時に発生する遠心力により第1貫通孔側面に移動し、連通孔を持つ連続気泡を通って研磨面や溝領域へと排出されるため、研磨屑が第1貫通孔内に蓄積することによる経時的な光透過率の低下を防ぐことができ、研磨パッドの長寿命化につながる。
透光性部材又は透光性樹脂部材が他の層の第2貫通孔の側面に接着されていることにより、研磨に利用可能な研磨層の厚みが最大となり、ドレッシングや研磨中の摩耗により研磨面が削られても透光性部材又は透光性樹脂部材が研磨面に突出することがなく、スクラッチの発生を低減することができる。一般に、研磨パッドの研磨層が軟質であればあるほど、研磨パッドがウエハに押し付けられることにより研磨パッドが沈み込み、透光性部材又は透光性樹脂部材が突出してしまうリスクがあり、突出が生じた研磨パッドは被研磨物の研磨に用いることができなくなる。この態様の研磨パッドは、透光性部材又は透光性樹脂部材の突出を防ぐことができるため、研磨パッドの長寿命化を図ることができる。また、透光性部材又は透光性樹脂部材を研磨層に接合させず、第2貫通孔の側面に接着するように配置させると、第1貫通孔に入った研磨屑が溝や研磨表面に排出されやすくなるよう研磨層に伸縮機構を持たせたとしても、透光性部材又は透光性樹脂部材の接着部で歪みが発生しにくく、これにより透光性部材又は透光性樹脂部材の剥離を抑制することができる。
他の層を構成する材料としては、ポリエチレン(PE)、ポリプロピレン(PP)、エチレン・プロピレン共重合体等のポリオレフィン系シート、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、ポリエチレンナフタレート(PEN)等のポリエステル系シート、塩化ビニル系シート、酢酸ビニル系シート、ポリイミド系シート、ポリアミド系シート、フッ素樹脂系シートや樹脂含浸不織布、不織布や織布等が挙げられる。また、他の層は、スラリーが内部に浸透しない非多孔質なシートであることが好ましい。これら中でも、スラリーが内部に浸透しない非多孔質なシートであって、物理的特性(例えば、寸法安定性、厚み精度、加工性、引張強度)、経済性等の観点から、他の層はポリエステル系シートがより好ましく、そのなかでもポリエチレンテレフタレート(以下、PETと略記する。)製シートが特に好ましい。
他の層と研磨層とを貼り合わせる方法又は他の層と別の他の層とを貼り合わせる方法としては、例えば、片面又は両面に粘着剤を塗着したPETシート等のシートを他の層として用い、この粘着剤を介して他の層と研磨層又は別の他の層とを接着させることができる。粘着剤を塗着していないPETシート等のシートを他の層として用意し、これとは別に研磨層又は別の他の層と粘着剤とを用意して、粘着剤を介して他の層と研磨層又は別の他の層とを接着させることもできる。
本発明の第1の態様の研磨パッドの製造方法は、研磨層と、少なくとも一面の水接触角が80度以下である透光性部材とを用意する工程、研磨層に貫通孔を設ける工程、及び前記透光性部材が前記貫通孔内に見えるように前記透光性部材を配置する工程(ここで前記透光性部材の前記一面が研磨面側になるように配置されている)を含む、研磨パッドの製造方法である。
各工程について説明する。
本工程において、研磨層と、少なくとも一面の水接触角が80度以下である透光性部材とを用意する。
研磨層及び透光性部材としては、それぞれ上記のものを用いることが出来る。研磨層及び透光性部材は、それぞれ市販のものを用いてもよく、製造したものを用いてもよい。市販の透光性部材としては、ポリエステル樹脂からなる三菱ケミカル株式会社製「ダイアホイルT910E」、「ダイアホイルT600E」、東洋紡株式会社製「コスモシャインA4300」、「コスモシャインA2330」、「コスモシャインTA017」、「コスモシャインTA015」、「コスモシャインTA042」、「コスモシャインTA044」、「コスモシャインTA048」、「ソフトシャインTA009」、ポリメチルメタクリレート樹脂からなる三菱ケミカル株式会社製「アクリプレンHBXN47」、「アクリプレンHBS010」、帝人化成株式会社製「パンライトフィルムPC-2151」、株式会社カネカ製「サンデュレンSD009」、「サンデュレンSD010」、ポリカーボネート樹脂からなる住友化学株式会社製「C000」、帝人化成株式会社製「ユーピロンH-3000」、アクリル樹脂/ポリカーボネート樹脂からなる住友化学株式会社製「C001」、アクリル樹脂からなる住友化学株式会社製「S000」、「S001G」、「S014G」、三菱ケミカル株式会社製「アクリプレンHBS006」、脂環式ポリオレフィン樹脂からなる日本ゼオン株式会社製「ゼオノアZF14」、「ゼオノアZF16」、JSR株式会社製「アートンフィルム」等を市販品として入手することができる。研磨層を製造する場合は、例えば、特許第5421635号、特許第5844189号を参照してポリウレタン樹脂を湿式成膜し、PET樹脂からなる可撓性シートと貼り合わせることで製造することができる。
本工程において、研磨層に貫通孔を設ける。貫通孔は、研磨層の研磨面からその反対面へと貫通している孔である。研磨層に貫通孔を設ける方法としては、例えば、円形、楕円形、多角形等の抜型(好ましくは円形の抜型)を用いて研磨層の厚さ方向に穴を開けることにより貫通孔を設けることができる。抜型を用いることにより、研磨パッドの研磨層を厚さ方向に対して垂直に切断して得られる任意の研磨層断面における貫通孔の円相当径が、他の任意の研磨層断面における貫通孔の円相当径と同一とすることができる。
本工程において、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、透光性部材が貫通孔内に存在するように透光性部材を配置する。このとき、透光性部材の前記一面が研磨面側になるように配置される。
透光性部材が貫通孔内に存在するように透光性部材を配置する方法としては、例えば、(1)図2A、図3Aのように透光性部材を研磨層に設けられた貫通孔の側面に接する(又は接着する)ようにして、透光性部材を配置する方法や、(2)図4Aのように研磨層の下層により小さい円相当径の貫通孔を有する他の層を設け、研磨層の貫通孔と他の層の貫通孔のサイズの差から生じる露出部上に透光性部材を配置することにより、透光性部材が貫通孔内に見えるように透光性部材を配置する方法や、(3)図5Aのように透光性部材を研磨層と他の層との間に挟み込み、透光性部材の一部分を貫通孔内に露出させる方法や、(4)図6Aのように研磨層とその下層に設けた他の層の両方に同じ形状の貫通孔を設け、そのいずれか又は両方の貫通孔の側面と接する(又は接着する)ようにして透光性部材を配置する方法などが挙げられる。これらの中でも、(1)、(2)又は(4)が好ましく、(1)又は(2)がより好ましく、(2)がさらにより好ましい。
また、本発明の第1の態様の研磨パッドの製造方法は、研磨層が備える貫通孔(第1貫通孔)よりも小さい円相当径を有する第2貫通孔を他の層に設ける工程を有していてもよい。
本発明の第1の態様の研磨パッドにより加工される被研磨物としては、ベアシリコン、半導体デバイスが挙げられる。中でも、本発明の第1の態様の研磨パッドは、半導体デバイスの研磨、特に仕上げ研磨に適しており好ましい。
スラリーとしては、水を含むスラリー(水性スラリー)であれば特に制限なく用いることが出来る。例えば、コロイダルシリカスラリー、酸化セリウムスラリーなどが挙げられる。
本発明の第2の態様の研磨パッドの製造方法は、少なくとも一面が親水性樹脂でコーティングされている透光性部材と、研磨層とを用意する工程、研磨層に貫通孔を設ける工程、及び研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性部材が貫通孔内に存在するように前記透光性部材を配置する工程(ここで前記透光性部材のコーティング面が研磨面側になるように配置されている)を含む、研磨パッドの製造方法である。
各工程について説明する。
本工程において、少なくとも一面が親水性樹脂でコーティングされている透光性部材と、研磨層とを用意する。
研磨層、透光性部材及び親水性樹脂としては、それぞれ上記のものを用いることが出来る。研磨層及び透光性部材は、それぞれ市販のものを用いてもよく、製造したものを用いてもよい。市販の透光性部材としては、ポリエステル樹脂からなる三菱ケミカル株式会社製「ダイアホイルT910E」、「ダイアホイルT600E」、東洋紡株式会社製「コスモシャインA4300」、「コスモシャインA2330」、「コスモシャインTA017」、「コスモシャインTA015」、「コスモシャインTA042」、「コスモシャインTA044」、「コスモシャインTA048」、「ソフトシャインTA009」、ポリメチルメタクリレート樹脂からなる三菱ケミカル株式会社製「アクリプレンHBXN47」、「アクリプレンHBS010」、帝人化成株式会社製「パンライトフィルムPC-2151」、株式会社カネカ製「サンデュレンSD009」、「サンデュレンSD010」、ポリカーボネート樹脂からなる住友化学株式会社製「C000」、帝人化成株式会社製「ユーピロンH-3000」、アクリル樹脂/ポリカーボネート樹脂からなる住友化学株式会社製「C001」、アクリル樹脂からなる住友化学株式会社製「S000」、「S001G」、「S014G」、三菱ケミカル株式会社製「アクリプレンHBS006」、脂環式ポリオレフィン樹脂からなる日本ゼオン株式会社製「ゼオノアZF14」、「ゼオノアZF16」、JSR株式会社製「アートンフィルム」等を市販品として入手することができる。研磨層を製造する場合は、例えば、特許第5421635号、特許第5844189号を参照してポリウレタン樹脂を湿式成膜し、PET樹脂からなる可撓性シートと貼り合わせることで製造することができる。
透光性部材の少なくとも一面を親水性樹脂でコーティングする方法に特に制限はなく、例えば重合反応や光硬化反応などを利用して前記樹脂を透光性部材の表面にコーティングすることが出来る。
光硬化反応を利用する場合には、親水性樹脂を光硬化型樹脂及び光重合開始剤と混合し、透光性部材の表面に塗布した後、紫外線などを照射して硬化させればよい。光硬化型樹脂及び光重合開始剤としては、上記のものを挙げることができる。
本工程において、研磨層に貫通孔を設ける。貫通孔は、研磨層の研磨面からその反対面へと貫通している孔である。研磨層に貫通孔を設ける方法としては、例えば、円形、楕円形、多角形等の抜型(好ましくは円形の抜型)を用いて研磨層の厚さ方向に穴を開けることにより貫通孔を設けることができる。抜型を用いることにより、研磨パッドの研磨層を厚さ方向に対して垂直に切断して得られる任意の研磨層断面における貫通孔の円相当径が、他の任意の研磨層断面における貫通孔の円相当径と同一とすることができる。
本工程において、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、透光性部材が貫通孔内に存在するように透光性部材を配置する。このとき、透光性部材のコーティング面が研磨面側になるように配置される。
透光性部材が貫通孔内に存在するように透光性部材を配置する方法としては、例えば、(1)図2B、図3Bのように透光性部材を研磨層に設けられた貫通孔の側面に接する(又は接着する)ようにして、透光性部材を配置する方法や、(2)図4B或いは図4Cのように研磨層の下層により小さい円相当径の貫通孔を有する他の層を設け、研磨層の貫通孔と他の層の貫通孔のサイズの差から生じる露出部上に透光性部材を配置することにより、透光性部材が貫通孔内に見えるように透光性部材を配置する方法や、(3)図5Bのように透光性部材を研磨層と他の層との間に挟み込み、透光性部材の一部分を貫通孔内に露出させる方法や、(4)図6Bのように研磨層とその下層に設けた他の層の両方に同じ形状の貫通孔を設け、そのいずれか又は両方の貫通孔の側面と接する(又は接着する)ようにして透光性部材を配置する方法などが挙げられる。これらの中でも、(1)、(2)又は(4)が好ましく、(1)又は(2)がより好ましく、(2)がさらにより好ましい。
また、本発明の第2の態様の研磨パッドの製造方法は、研磨層が備える貫通孔(第1貫通孔)よりも小さい円相当径を有する第2貫通孔を他の層に設ける工程を有していてもよい。
本発明の第2の態様の研磨パッドにより加工される被研磨物としては、ベアシリコン、半導体デバイスが挙げられる。中でも、本発明の第2の態様の研磨パッドは、半導体デバイスの研磨、特に仕上げ研磨に適しており好ましい。
スラリーとしては、水を含むスラリー(水性スラリー)であれば特に制限なく用いることが出来る。例えば、コロイダルシリカスラリー、酸化セリウムスラリーなどが挙げられる。
本発明の第3の態様の研磨パッドの製造方法は、研磨層と、少なくとも一面に親水性モノマーがグラフト重合されている透光性樹脂部材とを用意する工程、研磨層に貫通孔を設ける工程、及び研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性樹脂部材が貫通孔内に存在するように前記透光性樹脂部材を配置する工程(ここで前記透光性樹脂部材のグラフト化した面が研磨面側になるように配置されている)を含む、請求項1~10のいずれか1項に記載の研磨パッドの製造方法。
である。
各工程について説明する。
本工程において、研磨層と、少なくとも一面に親水性モノマーがグラフト重合されている透光性樹脂部材とを用意する。
本明細書及び特許請求の範囲において、「少なくとも一面に親水性モノマーがグラフト重合されている」とは、少なくとも一面の透光性樹脂に親水性モノマーがグラフト重合により結合されていることをいう。
透光性樹脂部材としては、一面のみが親水性モノマーがグラフト重合されていることが好ましい。
研磨層及び透光性樹脂部材としては、それぞれ上記のものを用いることが出来る。研磨層及び透光性樹脂部材は、それぞれ市販のものを用いてもよく、製造したものを用いてもよい。市販の透光性樹脂部材としては、ポリエステル樹脂からなる三菱ケミカル株式会社製「ダイアホイルT910E」、「ダイアホイルT600E」、東洋紡株式会社製「コスモシャインA4300」、「コスモシャインA2330」、「コスモシャインTA017」、「コスモシャインTA015」、「コスモシャインTA042」、「コスモシャインTA044」、「コスモシャインTA048」、「ソフトシャインTA009」、ポリメチルメタクリレート樹脂からなる三菱ケミカル株式会社製「アクリプレンHBXN47」、「アクリプレンHBS010」、帝人化成株式会社製「パンライトフィルムPC-2151」、株式会社カネカ製「サンデュレンSD009」、「サンデュレンSD010」、ポリカーボネート樹脂からなる住友化学株式会社製「C000」、帝人化成株式会社製「ユーピロンH-3000」、アクリル樹脂/ポリカーボネート樹脂からなる住友化学株式会社製「C001」、アクリル樹脂からなる住友化学株式会社製「S000」、「S001G」、「S014G」、三菱ケミカル株式会社製「アクリプレンHBS006」、脂環式ポリオレフィン樹脂からなる日本ゼオン株式会社製「ゼオノアZF14」、「ゼオノアZF16」、JSR株式会社製「アートンフィルム」等を市販品として入手することができる。研磨層を製造する場合は、例えば、特許第5421635号、特許第5844189号を参照してポリウレタン樹脂を湿式成膜し、PET樹脂からなる可撓性シートと貼り合わせることで製造することができる。
本工程において、研磨層に貫通孔を設ける。貫通孔は、研磨層の研磨面からその反対面へと貫通している孔である。研磨層に貫通孔を設ける方法としては、例えば、円形、楕円形、多角形等の抜型(好ましくは円形の抜型)を用いて研磨層の厚さ方向に穴を開けることにより貫通孔を設けることができる。抜型を用いることにより、研磨パッドの研磨層を厚さ方向に対して垂直に切断して得られる任意の研磨層断面における貫通孔の円相当径が、他の任意の研磨層断面における貫通孔の円相当径と同一とすることができる。
本工程において、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、透光性樹脂部材が貫通孔内に存在するように透光性樹脂部材を配置する。このとき、透光性樹脂部材のグラフト化した面が研磨面側になるように配置される。
透光性樹脂部材が貫通孔内に存在するように透光性樹脂部材を配置する方法としては、例えば、(1)図2B、図3Bのように透光性樹脂部材を研磨層に設けられた貫通孔の側面に接する(又は接着する)ようにして、透光性樹脂部材を配置する方法や、(2)図4B或いは図4Cのように研磨層の下層により小さい円相当径の貫通孔を有する他の層を設け、研磨層の貫通孔と他の層の貫通孔のサイズの差から生じる露出部上に透光性樹脂部材を配置することにより、透光性樹脂部材が貫通孔内に見えるように透光性樹脂部材を配置する方法や、(3)図5Bのように透光性樹脂部材を研磨層と他の層との間に挟み込み、透光性樹脂部材の一部分を貫通孔内に露出させる方法や、(4)図6Bのように研磨層とその下層に設けた他の層の両方に同じ形状の貫通孔を設け、そのいずれか又は両方の貫通孔の側面と接する(又は接着する)ようにして透光性樹脂部材を配置する方法などが挙げられる。これらの中でも、(1)、(2)又は(4)が好ましく、(1)又は(2)がより好ましく、(2)がさらにより好ましい。
また、本発明の第3の態様の研磨パッドの製造方法は、研磨層が備える貫通孔(第1貫通孔)よりも小さい円相当径を有する第2貫通孔を他の層に設ける工程を有していてもよい。
本発明の第3の態様の研磨パッドにより加工される被研磨物としては、ベアシリコン、半導体デバイスが挙げられる。中でも、本発明の第3の態様の研磨パッドは、半導体デバイスの研磨、特に仕上げ研磨に適しており好ましい。
スラリーとしては、水を含むスラリー(水性スラリー)であれば特に制限なく用いることが出来る。例えば、コロイダルシリカスラリー、酸化セリウムスラリーなどが挙げられる。
本発明の第4の態様の研磨パッドの製造方法は、研磨層と、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を少なくとも一面に有する透光性樹脂部材とを用意する工程、研磨層に貫通孔を設ける工程、及び研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性樹脂部材が貫通孔内に存在するように前記透光性樹脂部材を配置する工程(ここで前記透光性樹脂部材の前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する面が研磨面側になるように配置される)を含む、研磨パッドの製造方法である。
各工程について説明する。
本工程において、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を少なくとも一面に有する透光性樹脂部材と、研磨層とを用意する。
研磨層、透光性樹脂部材及び多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂としては、それぞれ上記のものを用いることが出来る。研磨層及び透光性樹脂部材は、それぞれ市販のものを用いてもよく、製造したものを用いてもよい。市販の透光性樹脂部材としては、ポリエステル樹脂からなる三菱ケミカル株式会社製「ダイアホイルT910E」、「ダイアホイルT600E」、東洋紡株式会社製「コスモシャインA4300」、「コスモシャインA2330」、「コスモシャインTA017」、「コスモシャインTA015」、「コスモシャインTA042」、「コスモシャインTA044」、「コスモシャインTA048」、「ソフトシャインTA009」、ポリメチルメタクリレート樹脂からなる三菱ケミカル株式会社製「アクリプレンHBXN47」、「アクリプレンHBS010」、帝人化成株式会社製「パンライトフィルムPC-2151」、株式会社カネカ製「サンデュレンSD009」、「サンデュレンSD010」、ポリカーボネート樹脂からなる住友化学株式会社製「C000」、帝人化成株式会社製「ユーピロンH-3000」、アクリル樹脂/ポリカーボネート樹脂からなる住友化学株式会社製「C001」、アクリル樹脂からなる住友化学株式会社製「S000」、「S001G」、「S014G」、三菱ケミカル株式会社製「アクリプレンHBS006」、脂環式ポリオレフィン樹脂からなる日本ゼオン株式会社製「ゼオノアZF14」、「ゼオノアZF16」、JSR株式会社製「アートンフィルム」等を市販品として入手することができる。研磨層を製造する場合は、例えば、特許第5421635号、特許第5844189号を参照してポリウレタン樹脂を湿式成膜し、PET樹脂からなる可撓性シートと貼り合わせることで製造することができる。
透光性樹脂部材の少なくとも一面を前記樹脂でコーティングする方法に特に制限はなく、例えば重合反応や光硬化反応などを利用して前記樹脂を透光性樹脂部材の表面にコーティングすることが出来る。
光硬化反応を利用する場合には、前記樹脂を光硬化型樹脂及び光重合開始剤と混合し、透光性樹脂部材の表面に塗布した後、紫外線などを照射して硬化させればよい。光硬化型樹脂及び光重合開始剤としては、上記のものを挙げることができる。
従って、本発明の第4の態様の研磨パッドの製造方法は、多官能(メタ)アクリレートモノマーを含むモノマー成分と光重合開始剤とを含む混合物を透光性樹脂部材上に塗布する工程、及び前記混合物を光重合させる工程を更に含んでいてもよい。
本工程において、研磨層に貫通孔を設ける。貫通孔は、研磨層の研磨面からその反対面へと貫通している孔である。研磨層に貫通孔を設ける方法としては、例えば、円形、楕円形、多角形等の抜型(好ましくは円形の抜型)を用いて研磨層の厚さ方向に穴を開けることにより貫通孔を設けることができる。抜型を用いることにより、研磨パッドの研磨層を厚さ方向に対して垂直に切断して得られる任意の研磨層断面における貫通孔の円相当径が、他の任意の研磨層断面における貫通孔の円相当径と同一とすることができる。
本工程において、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、透光性樹脂部材が貫通孔内に存在するように透光性樹脂部材を配置する。このとき、透光性樹脂部材の前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する面が研磨面側になるように配置される。
透光性樹脂部材が貫通孔内に存在するように透光性樹脂部材を配置する方法としては、例えば、(1)図2B、図3Bのように透光性樹脂部材を研磨層に設けられた貫通孔の側面に接する(又は接着する)ようにして、透光性樹脂部材を配置する方法や、(2)図4B或いは図4Cのように研磨層の下層により小さい円相当径の貫通孔を有する他の層を設け、研磨層の貫通孔と他の層の貫通孔のサイズの差から生じる露出部上に透光性樹脂部材を配置することにより、透光性樹脂部材が貫通孔内に見えるように透光性樹脂部材を配置する方法や、(3)図5Bのように透光性樹脂部材を研磨層と他の層との間に挟み込み、透光性樹脂部材の一部分を貫通孔内に露出させる方法などが挙げられる。これらの中でも、(1)又は(2)が好ましく、(2)がより好ましい。
また、本発明の第4の態様の研磨パッドの製造方法は、研磨層が備える貫通孔(第1貫通孔)よりも小さい円相当径を有する第2貫通孔を他の層に設ける工程を有していてもよい。
本発明の第4の態様の研磨パッドにより加工される被研磨物としては、ベアシリコン、半導体デバイスが挙げられる。中でも、本発明の第4の態様の研磨パッドは、半導体デバイスの研磨、特に仕上げ研磨に適しており好ましい。
スラリーとしては、水を含むスラリー(水性スラリー)であれば特に制限なく用いることが出来る。例えば、コロイダルシリカスラリー、酸化セリウムスラリーなどが挙げられる。
[実施例1-1]
20cm×20cmの透明なアクリル樹脂フィルム(三菱ケミカル(株)製、アクリプレン HBS006、厚さ150μm)を用意し、この一面を、プラズマ加工することにより親水化処理した。これにより、実施例1-1の透光性部材を得た。
20cm×20cmの透明なアクリル樹脂フィルム(三菱ケミカル(株)製、アクリプレン HBS006、厚さ150μm)を用意し、この一面を、ロールブラスト加工することにより親水化処理した。これにより、実施例1-2の透光性部材を得た。
20cm×20cmの透明なアクリル樹脂フィルム(三菱ケミカル(株)製、アクリプレン HBS006、厚さ150μm)を用意し、これを比較例1-1の透光性部材とした。
実施例1-1~1-2及び比較例1-1の透光性部材の水接触角を、自動接触角計DropMaster DM500(協和界面科学社製)を用いて、以下の方法により測定した。
(1)注射筒に蒸留水を入れディスペンサを取り付け、DM500にセットする。
(2)測定試料を5mm×50mmのサイズにカットし、ステージに貼り付ける。
(3)解析ソフトを立ち上げ、接触角測定[液滴法]を選択し、各パラメータを設定する。
測定までの待ち時間:1000ms
測定時間間隔:1000ms
連続測定回数:180回
(4)測定する液滴量、イメージモニタ上の注射針位置を設定し、イメージモニタのフォーカス値を最適化する。
(5)試料に液滴を着滴させ測定を開始し、測定開始から20秒後の水接触角を読み取る。
水接触角測定試験の結果を表1に示す。
実施例1-1~1-2及び比較例1-1の透光性部材の可視光線透過率を、紫外可視近赤外分光光度計V-770(日本分光社製)を用いて以下の方法で測定した。なお、可視光線透過率は、透光性部材の表面(実施例1-1~1-2については加工処理した表面)に水が付着している場合と、水が付着していない場合の2条件で測定を行った。
1.水が付着している場合の測定
(1)石英ガラスセルを入れてブランクを測定する。
(2)実施例1-1~1-2、比較例1-1の透光性部材を9mm×50mmの大きさに切り出す。
(3)透光性部材をキムワイプ上に置き、20cm離れた位置から透光性部材の表面(実施例1-1~1-2については加工処理した表面のみ、比較例1-1については一面のみ)にスプレー(容量50ml、PP製ボトル)にて精製水を3回噴霧する(スプレーの1回あたりの散布量:約0.160~0.165ml、3回噴霧後の透光性部材表面への塗布量:約0.01~0.03ml)。噴霧後、透光性部材を垂直状態にして60秒間静置した。水を噴霧していない表面と石英ガラスセル内面とが触れるようにして石英ガラスセル内に透光性部材を設置する。
(3)石英ガラスセルの内壁に、表面処理面が光源と反対面になる向きで、透光性部材を石英セルの光源側に全面接触させるように配置する。
(4)紫外可視近赤外分光光度計V-770(日本分光社製)を用い、250nm~1000nmの光に対する直進透過率を測定する。
(5)JIS A5759:2008に基づき380~780nmの波長に対する可視光線透過率を算出する。
(1)石英ガラスセルを入れてブランクを測定する。
(2)実施例1-1~1-2、比較例1-1の透光性部材を9mm×50mmの大きさに切り出す。
(3)石英ガラスセルの内壁に、表面処理面が光源と反対面になる向きで、透光性部材を石英セルの光源側に全面接触させるように配置する。
(4)紫外可視近赤外分光光度計V-770(日本分光社製)を用い、250nm~1000nmの光に対する直進透過率を測定する。
(5)JIS A5759:2008に基づき380~780nmの波長に対する可視光線透過率を算出する。
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。
得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.8mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188μmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm、溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、直径18mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に片側に離型紙を有する両面テープを接着し、直径18mmの第1貫通孔に直径9mmの円形抜型を嵌め込み、両面テープと離型紙を貫通させるよう第2貫通孔を開けた。この時、第1貫通孔の中心と第2貫通孔の中心が略同一となるよう穴あけを行った。透光性部材として、片面をプラズマ処理したアクリル樹脂フィルム(三菱ケミカル(株)製、アクリプレン HBS006、厚み150μm)を用意し、直径17mmとなるよう3枚切り出し、第1貫通孔内にリング状に露出した両面テープと透光性部材を、透光性部材の表面処理した面側が研磨面側になるように接着させ研磨パッドを製造した。
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。
得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.8mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188μmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm、溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に、片側に離型紙を有する厚さ約0.1mmの両面テープ(PET基材厚み0.023mm、PET基材の表面及び裏面における粘着性成分厚みは共に0.04mm)を接着した。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、両面テープの離型紙まで貫通させるよう、直径20mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔を設けた。両面テープの離型紙を剥がし、透光性部材として、片面をプラズマ処理した研磨層と同径のアクリル樹脂フィルム(三菱ケミカル(株)製、アクリプレン HBS006、厚み150μm)を用意し、両面テープの粘着部と透光性部材の表面処理した面側とを貼り合わせた。他の層として片面に離型紙を有する厚さ約0.1mmの両面テープ(PET基材厚み0.023mm、PET基材の表面及び裏面における粘着性成分厚みは共に0.04mm)を用意し、厚さ方向に見た場合に第1貫通孔と重なる位置に3か所穴を開けることで第2貫通孔を設け、透光性部材の表面処理を行っていない面側に接着させることで研磨パッドを製造した。
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。
得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.8mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188μmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm、溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に、熱溶融性接着剤を介し他の層を貼り合わせた。他の層としては繊度2dtex、繊維長51mmのポリエステル繊維からニードルパンチ法により製造した不織布を用い、厚さは0.50mm、密度は0.35g/cm3であった。不織布のポリウレタン樹脂フィルムが貼り合わされていない面側に、片面に離型紙を有する両面テープを接着した。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、研磨表面から両面テープまで貫通させるよう、直径20mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔と第2貫通孔を設けた。透光性部材として、片面をプラズマ処理したアクリル樹脂/ポリカーボネート樹脂シート(住友化学(株)製、テクノロイ C001、厚み500μm)を直径20mmとなるよう3枚切り出し、円形の透光性部材の側面にホットメルト接着剤を塗布し、第2貫通孔内の側面に透光性部材の表面処理した面側が研磨面側になるように接着させることで研磨パッドを製造した。
製造例1-1~1-3の研磨パッドは、水性スラリーの有無によって光透過率が大きく変動しないため、研磨終点を高精度に検出することができる。
[実施例2-1]
ジペンタエリスリトールヘキサアクリレート(DPHA)(新中村化学工業(株)製、NKエステルA-DPH)90重量部、イオン結合性の親水基(アンモニウムカチオンを含む基)を有するアクリレートポリマー(大成ファインケミカル(株)製 アクリット 8WX-030(40%溶液))25重量部(すなわち、DPHAと8WX-030の固形分の合計に対して10質量%の8WX-030)、1-ヒドロキシシクロヘキシルフェニルケトン(IGM Resin B.V.製、イルガキュア184)3重量部を配合し、不揮発分が30%となるようにプロピレングリコールモノメチルエーテルで希釈し、塗工液を調製した(※8WXを10%添加)。得られた塗工液を、アクリル樹脂シート(三菱ケミカル(株)製、アクリプレンHBS006、厚み150μm)にバーコーターで塗工し、80℃で1分間の予備乾燥を行った。次に、空気下で高圧水銀灯を用いて紫外線照射を行い、アクリル樹脂シート上に膜厚5μmの塗膜を作製した。得られた塗膜付きのアクリル樹脂シートを終点検出窓として用いた。
市販のアクリル樹脂シート(三菱ケミカル(株)製、アクリプレンHBS006、厚み150μm)を終点検出窓として用いた。
DPHA 50質量部、8WX-030 125質量部(すなわち、DPHAと8WX-030の固形分の合計に対して50質量%の8WX-030)に変更した以外、実施例2-1と同様にして塗膜付きのアクリル樹脂シートを作製し、終点検出窓として用いた。
DPHA 30質量部、8WX-030 175質量部(すなわち、DPHAと8WX-030の固形分の合計に対して70質量%の8WX-030)に変更した以外、実施例2-1と同様にして塗膜付きのアクリル樹脂シートを作製し、終点検出窓として用いた。
DPHA 100質量部、8WX-030 0質量部(すなわち、DPHAと8WX-030の固形分の合計に対して0質量%の8WX-030)に変更した以外、実施例2-1と同様にして塗膜付きのアクリル樹脂シートを作製し、終点検出窓として用いた。
接触角計(協和界面科学(株)製、DropMaster500)を用い、注射針から水滴1滴(2μL)を滴下し、3秒後の接触角を測定した。
実施例2-1~2-4及び比較例2-1の透光性部材の可視光線透過率を、紫外可視近赤外分光光度計V-770(日本分光(株)製)を用いて以下の方法で測定した。
1.水が付着している場合の測定
(1)石英ガラスセルを入れてブランクを測定する。
(2)実施例2-1~2-4、比較例2-1の透光性部材を9mm×50mmの大きさに切り出す。
(3)透光性部材を紙ウエス(キムタオル、日本製紙クレシア(株)製)上に置き、20cm離れた位置から透光性部材の表面(実施例2-1~2-4についてはコーティング処理した表面のみ、比較例2-1については一面のみ)にスプレー(容量50mL、PP製ボトル)にて精製水を3回噴霧する(1回あたりの散布量:0.160~0.165mL、透光性部材表面への水付着量:0.01~0.03mL)。噴霧後、透光性部材を垂直状態にして60秒間静置した。水を噴霧していない表面と石英ガラスセル内面とが触れるようにして石英ガラスセル内に透光性部材を設置する。
(3)石英ガラスセルの内壁に、透光性部材の塗膜が付いた面が光源と反対面になる向きで、透光性部材を石英セルの光源側に全面接触させるように配置する。
(4)紫外可視近赤外分光光度計V-770(日本分光(株)製)を用い、250~1000nmの光に対する直進透過率を測定する。
(5)JIS A5759:2008に基づき380~780nmの波長に対する可視光線透過率を算出する。
(1)石英ガラスセルを入れてブランクを測定する。
(2)実施例2-1~2-4、比較例2-1の透光性部材を9mm×50mmの大きさに切り出す。
(3)石英ガラスセルの内壁に、透光性部材の塗膜が付いた面が光源と反対面になる向きで、透光性部材を石英セルの光源側に全面接触させるように配置する。
(4)紫外可視近赤外分光光度計V-770(日本分光(株)製)を用い、250~1000nmの光に対する直進透過率を測定する。
(5)JIS A5759:2008に基づき380~780nmの波長に対する可視光線透過率を算出する。
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。
得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.8mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188μmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm、溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、直径18mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に片側に離型紙を有する両面テープを接着し、直径18mmの第1貫通孔に直径9mmの円形抜型を嵌め込み、両面テープと離型紙を貫通させるよう第2貫通孔を開けた。この時、第1貫通孔の中心と第2貫通孔の中心が略同一となるよう穴あけを行った。透光性部材として、実施例2-1の塗膜付きアクリル樹脂シートを用意し、直径17mmとなるよう3枚切り出し、第1貫通孔内にリング状に露出した両面テープと透光性部材を、透光性部材の塗膜が付いた側が研磨面側になるように接着させ研磨パッドを製造した。
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。
得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.8mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188μmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm、溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に、片側に離型紙を有する厚さ約0.1mmの両面テープ(PET基材厚み0.023mm、PET基材の表面及び裏面における粘着性成分厚みは共に0.04mm)を接着した。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、両面テープの離型紙まで貫通させるよう、直径20mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔を設けた。両面テープの離型紙を剥がし、透光性部材として、実施例2-1の塗膜付きアクリル樹脂シートを用意し、両面テープの粘着部と透光性部材の塗膜が付いた面側とを貼り合わせた。他の層として片面に離型紙を有する厚さ約0.1mmの両面テープ(PET基材厚み0.023mm、PET基材の表面及び裏面における粘着性成分厚みは共に0.04mm)を用意し、厚さ方向に見た場合に第1貫通孔と重なる位置に3か所穴を開けることで第2貫通孔を設け、アクリル樹脂フィルム透光性部材の塗膜が付いていない面側に接着させることで研磨パッドを製造した。
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。
得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.8mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188μmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm、溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に、熱溶融性接着剤を介し他の層を貼り合わせた。他の層としては繊度2dtex、繊維長51mmのポリエステル繊維からニードルパンチ法により製造した不織布を用い、厚さは0.50mm、密度は0.35g/cm3であった。不織布のポリウレタン樹脂フィルムが貼り合わされていない面側に、片面に離型紙を有する両面テープを接着した。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、研磨表面から両面テープまで貫通させるよう、直径20mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔と第2貫通孔を設けた。透光性部材として、実施例2-1の塗膜付きアクリル樹脂シートを直径20mmとなるよう3枚切り出し、円形の透光性部材の側面にホットメルト接着剤を塗布し、第2貫通孔内の側面に透光性部材の透光性部材の塗膜が付いた側が研磨面側になるように接着させることで研磨パッドを製造した。
製造例2-1~2-3の研磨パッドは、水性スラリーの有無によって光透過率が大きく変動しないため、研磨終点を高精度に検出することができる。
<実施例3-1>
縦20mm、横20mm、厚さ0.15mmのアクリル樹脂シート(三菱ケミカル(株)製、アクリプレンHBS006)に対し、アルゴンガスを流量10sccs、反応時間2分、圧力50Paとしてプラズマ処理を行った。次いで、アクリル酸40mol%の水溶液中に浸漬し、窒素ガスをバブリングさせながら80℃で1時間グラフト重合反応を行った後、蒸留水中で2時間超音波洗浄を行い、80℃で6時間真空乾燥を施した。得られた透光性樹脂部材を、実施例3-1の透光性樹脂部材として用いた。
縦20mm、横20mm、厚さ0.15mmのアクリル樹脂シート(三菱ケミカル(株)製、アクリプレンHBS006)に対し、アルゴンガスを流量10sccs、反応時間2分、圧力50Paとしてプラズマ重合を行った。次いで、アクリル酸40mol%の水溶液中に浸漬し、窒素ガスをバブリングさせながら80℃で1時間グラフト重合反応を行った後、蒸留水中で2時間超音波洗浄を行い、80℃で6時間真空乾燥を施した。グラフト重合済みのアクリル樹脂シートをポリビニルベンジルトリメチルアンモニウムクロライド(分子量43000)の5重量%水溶液25ml中に30分間撹拌しながら高分子間錯形成反応を行なつた。次いでこのフィルムを水洗後、乾燥し、ポリマー複合体を形成した。得られた透光性樹脂部材を、実施例3-2の透光性樹脂部材として用いた。
縦20mm、横20mm、厚さ0.15mmのアクリル樹脂シート(三菱ケミカル(株)製、アクリプレンHBA001PアクリプレンHBS006)を、比較例3-1の透光性樹脂部材として用いた。
縦20mm、横20mm、厚さ0.15mmのアクリル樹脂シート(三菱ケミカル(株)製、アクリプレンHBA001PアクリプレンHBS007)に対し、アルゴンガスを流量10sccs、反応時間2分、圧力50Paとしてプラズマ処理を行った。得られた透光性樹脂部材を、比較例3-2の透光性樹脂部材として用いた。
親水性の経時変化を評価するため、実施例3-1~3-2、比較例3-1~3-2の透光性樹脂部材を作製してから2日後、2週間後における水の接触角を測定した。水接触角は、自動接触角計DropMaster DM500(協和界面科学社製)を用いて、以下の方法により測定した。
(1)注射筒に蒸留水を入れディスペンサを取り付け、DM500にセットする。
(2)測定試料を5mm×50mm の サイズにカットし、ステージに貼り付ける。
(3)解析ソフトを立ち上げ、接触角測定[液滴法]を選択し、各パラメータを設定する。
測定までの待ち時間:1000ms
測定時間間隔:1000ms
連続測定回数:180回
(4)測定する液滴量、イメージモニタ上の注射針位置を設定し、イメージモニタのフォーカス値を最適化する。
(5)試料に液滴を着滴させ測定を開始し、測定開始から10秒後の水接触角を読み取る。
水接触角測定試験の結果を表3に示す。
測定の結果、2日後、2週間後の接触角がいずれも80度(°)以下である場合を〇、そうではない場合を×として評価した。
実施例3-1~3-2、比較例3-1~3-2の透光性樹脂部材を用いて、以下のようにして研磨パッドを製造した。
100%モジュラス7. 8MPaのポリエステル系ポリウレタン樹脂の(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルシート上にナイフコータを用いて塗布厚みが0. 8mmとなるようキャストした。その後、樹脂含有溶液をキヤストしたポリエステルシートを凝固浴(凝固液は水)に浸漬し、該樹脂含有溶液を凝固させた後、ポリエステルシートを剥離し洗浄・乾燥させて、ポリウレタン樹脂シートを得た。得られたポリウレタン樹脂シートの表面をバフ処理し厚みを0. 73mmとしたのち、バフ処理面と反対面側に厚み0. 188mmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂シートの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm、溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。溝付きポリウレタン樹脂シートを直径740mmの円形に抜型により打ち抜き、溝処理面側の円形ポリウレタン樹脂シートの中心から半径の1/2となる位置の同心円上に、直径18mmの円形抜型で等間隔且つ互いに独立して3か所に穴を開け、第1貫通孔を設けた。上記樹脂基材のポリウレタン樹脂シートが貼り合わされていない面側に、第2の層として片側に離型紙を有する厚さ約0. 1mm、直径790mmの円形両面テープ(PET基材厚み0. 023mm、PET基材の表面及び裏面における粘着性成分厚みは共に004mm)を接着し、ポリウレタン樹脂シートと同じ径になるよう、余剰の両面テープをカットした。続いて直径18mmの第1貫通孔に直径9mmの円形抜型を嵌め込み、両面テープと離型紙を貫通させるよう第2貫通孔を開けた。この時、第1貫通孔の中心と第2貫通孔の中心が略同一となるよう穴あけを行った。実施例3-1、実施例3-2、比較例3-1、比較例3-2で作製した透明樹脂部材をそれぞれ直径17mmとなるよう3枚切り出し、第1貫通孔内にリング状に露出した両面テープと透明樹脂部材を接着させ研磨パッドを製造した。
次に、研磨対象物として、ラインがタングステン(W)であり、スペースがTEOS(酸化ケイ素膜)であるパターン基板を準備し、各研磨パッドを用いて下記条件で500枚の基板を研磨したのち、エネルギー分散型X線分光器(EDS)で透光性樹脂部材の断面を観察し、透光性樹脂部材の研磨面側の表面に残留物が付着しているかどうかを評価した。
使用研磨機:EBARA F-REX300
研磨圧力:2.5psi
研磨パッド:研磨パッド:フジボウ愛媛(株)社製 H600
研磨剤:Planar社製、型番「BSL8176C」
ドレッサー:3M社製ダイヤモンドドレッサー、型番「A188」
パッドブレイク 30N×30分、ダイヤモンドドレッサー54rpm、定盤回転数80rpm、超純水200mL/min
コンディショニング:Ex-situ、30N、4スキャン、16秒
研磨:定盤回転数70rpm、ヘッド回転数71rpm、スラリー流量200mL/min
研磨時間:約60秒
その結果を表3に示す。
プラズマ処理のみ行った比較例3-2では、2日後の接触角は未処理品より小さくなっているものの、2週間後には未処理品同等の接触角になっており、プラズマ処理による表面改質効果が失われていた。また、EDSの測定では透光性樹脂部材表面にSi元素が確認でき、親水性が十分ではない窓部表面にSiが堆積したものと考えられる。
一方、グラフト重合処理を施した実施例3-1は2週間たっても低い接触角が維持され、グラフトポリマーを複合体化した実施例3-2は実施例3-1よりさらに接触角が低くなり、2週間後もその接触角が維持できていた。また、実施例3-1、3-2のどちらでもEDSの測定でSi元素は確認できなかった。
以上の結果、実施例3-1~3-2の透光性樹脂部材を含む研磨パッドは、透光性樹脂部材(窓部材)の研磨面側の表面への研磨屑の付着、固着を低減することができ、安定した光検出が可能となることが分かった。
<実施例4-1>
50質量部の脂肪族ウレタンアクリレート(ダイセルオルネクス社製「EBECRYL2000」)および50質量部のポリエチレングリコールジアクリレート(ダイセルオルネクス社製「EBECRYL 11」、質量平均分子量700、モノマーあたりのエチレンオキサイド単位の数:13)とを混合し、さらに、5質量部の光重合開始剤(BASF社製「IRGACURE184」添加し、混合攪拌装置を用いて均一に混合し樹脂組成物を得た。得られた樹脂組成物をアクリル樹脂シート(日東樹脂工業株式会社製、クラレックスS、厚み400μm)にバーコーターを用い、均一になるように片面に塗布した。その後に50℃に保ったオーブン内に10分間放置、乾燥させた。乾燥後、80W/cmメタルハライドランプにて紫外線積算照射量900mJ/cm2の紫外線を照射し、樹脂組成物を硬化させ厚み3.5μmの表面層を形成した。得られた表面層付きアクリル樹脂シートを終点検出窓として用いた。
58質量部のポリエチレングリコールジアクリレート(新中村化学工業株式会社製「A-1000」、質量平均分子量1140、モノマーあたりのエチレンオキサイド単位の数:23)、39質量部のC2-3アルコキシ化ペンタエリスリトールテトラアクリレート(ダイセルオルネクス株式会社製「EBECRYL40」、質量平均分子量571、モノマーあたりのエチレン/プロピレンオキサイド単位の数:4)、3質量部の光重合開始剤(BASF社製「IRGACURE184」)、溶剤として100質量部のプロピレングリコールモノメチルエーテルを混合攪拌装置を用いて均一に混合し樹脂組成物を得た。得られた樹脂組成物を実施例4-1と同様にアクリル樹脂シートに塗布し、表面層を形成し終点検出窓として用いた。
67質量部のエトキシ化グリセリントリアクリレート(新中村化学工業株式会社製「A-GLY-20E」、質量平均分子量1134、モノマーあたりのエチレンオキサイド単位の数:20)と28質量部のC2-3アルコキシ化ペンタエリスリトールテトラアクリレート(ダイセルオルネクス株式会社製「EBECRYL40」、質量平均分子量571、モノマーあたりのエチレン/プロピレンオキサイド単位の数:4)、5質量部の光重合開始剤(BASF社製「IRGACURE184」)、溶剤として100質量部のプロピレングリコールモノメチルエーテルを混合攪拌装置を用いて均一に混合し樹脂組成物を得た。得られた樹脂組成物を実施例4-1と同様にアクリル樹脂シートに塗布し、表面層を形成し終点検出窓として用いた。
市販のアクリル樹脂シート(日東樹脂工業株式会社製、クラレックスS、厚み400μm)を終点検出窓として用いた。
接触角計(協和界面科学(株)製、DropMas ter500)を用い、注射針から水滴1滴(2μL)を滴下し、3秒後の接触角を測定した。
上記の方法で表面の水接触角を測定し、表面層形成前の水接触角より40度以上低下したものを○×と評価した。その結果を、表4に示す。
実施例4-1~4-3及び比較例4-1の透光性樹脂部材の可視光線透過率を、紫外可視近赤外分光光度計V-770 (日本分光(株)製)を用いて以下の方法で測定した。
1.水が付着している場合の測定
(1)石英ガラスセルを入れてブランクを測定する。
(2)実施例4-1~4-3、比較例4-1の透光性樹脂部材を9mm×50mmの大きさに切り出す。
(3)透光性樹脂部材を紙ウエス(キムタオル、日本製紙クレシア(株)製)上に置き、20cm離れた位置から透光性樹脂部材の表面(実施例4-1~4-3についてはコーティング処理した表面のみ、比較例4-1については一面のみ)にスプレー(容量50mL、PP製ボトル)にて精製水を3回噴霧する(1回あたりの散布量:0.160~0.165mL、透光性樹脂部材表面への水付着量:0.01~0.03mL)。噴霧後、透光性樹脂部材を垂直状態にして60秒間静置した。水を噴霧していない表面と石英ガラスセル内面とが触れるようにして石英ガラスセル内に透光性樹脂部材を設置する。
(3)石英ガラスセルの内壁に、透光性樹脂部材の塗膜が付いた面が光源と反対面になる向きで、透光性樹脂部材を石英セルの光源側に全面接触させるように配置する。
(4)紫外可視近赤外分光光度計V-770(日本分光(株)製)を用い、250~1000nnlの光に対する直進透過率を測定する。
(5)J ISA5759:2008に基づき380~780nmの波長に対する可視光線透過率を算出する。
(1)石英ガラスセルを入れてブランクを測定する。
(2)実施例4-1~4-3、比較例4-1の透光性樹脂部材を9mm×50mmの大きさに切り出す。
(3)石英ガラスセルの内壁に、透光性樹脂部材の塗膜が付いた面が光源と反対面になる向きで、透光性樹脂部材を石英セルの光源側に全面接触させるように配置する。
(4)紫外可視近赤外分光光度計V-770(日本分光(株)製)を用い、250~1000nmの光に対する直進透過率を測定する。
(5)J ISA5759:2008に基づき380~780nmの波長に対する可視光線透過率を算出する。
15mm×15mmの大きさの実施例4-1~4-3のサンプルを、40℃の酸性スラリー/アルカリ性スラリーそれぞれに24時間浸漬させ、取り出し表面の水分を紙ウエス(キムタオル、日本製紙クレシア(株)製)でふき取り表面層の状態を観察した。目視で剥がれや歪みが確認できない場合を〇として評価した。酸性スラリー及びアルカリ性スラリーとしては、それぞれ下記のものを用いた。その結果を、表4に示す。
酸性スラリー:過マンガン酸カリウム系スラリー(FUJIMI社:DSC-201)、pH2
アルカリ性スラリー:コロイダルシリカスラリー(キャボット社製スラリー:SS25、KOH入り)、pH11
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.81mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188mmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm,溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、直径18mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に片側に離型紙を有する両面テープを接着し、直径18mmの第1貫通孔に直径9mmの円形抜型を嵌め込み、両面テープと離型紙を貫通させるよう第2貫通孔を開けた。この時、第1貫通孔の中心と第2貫通孔の中心が略同一となるよう穴あけを行った。透光性部材として、透光性部材として、実施例4-1の表面層付きアクリル樹脂シートを用意し、直径17mmとなるよう3枚切り出し、第1貫通孔内にリング状に露出した両面テープと透光性部材を、透光性部材の表面処理した面側が研磨面側になるように接着させ研磨パッドを製造した。
100%モジュラス7.8MPaのポリエステル系ポリウレタン樹脂(30質量部)及びDMF(70質量部)を含む溶液100質量部に、別途DMF60質量部、水5質量部を添加し、混合することにより樹脂含有溶液を得た。得られた樹脂含有溶液を、濾過することにより、不溶成分を除去した。前記溶液をポリエステルフィルム上にナイフコータを用いて塗布厚みが0.81mmとなるようキャストした。その後、樹脂含有溶液をキャストしたポリエステルフィルムを凝固浴(凝固液は水)に浸漬し、前記樹脂含有溶液を凝固させた後、ポリエステルフィルムを剥離し洗浄・乾燥させて、内部に涙型形状の複数の気泡を有し且つ当該複数の気泡が互いに繋がり合って連通しているポリウレタン樹脂フィルムを得た。得られたポリウレタン樹脂フィルムの表面をバフ処理し厚みを0.73mmとしたのち、バフ処理面と反対面側に厚み0.188mmのPET製の樹脂基材を接着剤で貼り合わせ、ポリウレタン樹脂フィルムの表面側からエンボス加工を施し、表面に溝幅を1mm、溝間隔を4mm,溝深さを0.45mmとした断面矩形状で格子パターンの溝を設けた。樹脂基材のポリウレタン樹脂フィルムが貼り合わされていない面側に、片側に離型紙を有する厚さ約0.1mmの両面テープ(PET基材厚み0.023mm、PET基材の表面及び裏面における粘着性成分厚みは共に0.04mm)を接着した。溝処理面側の研磨パッドの中心となる位置から研磨パッドの半径の1/2となる位置の同心円上に、両面テープの離型紙まで貫通させるよう、直径9mmの円形抜型で等間隔に3か所穴を開け、第1貫通孔を設けた。両面テープの離型紙を剥がし、透光性部材として、研磨層と同じ大きさに裁断した実施例4-1の表面層付きアクリル樹脂シートを用意し、両面テープの粘着部とアクリル樹脂シートの表面層側とを貼り合わせた。他の層として片面に離型紙を有する厚さ約0.11mmの両面テープ(PET基材厚み0.023mm,PET基材の表面及び裏面における粘着性成分厚みは共に0.04mm)を用意し、厚さ方向に見た場合に第1貫通孔と重なる位置に直径9mmの穴を3か所開けることで第2貫通孔を設け、アクリル樹脂フィルム透光性部材の塗膜が付いていない面側に接着させることで研磨パッドを製造した。
本発明の第2の態様によれば、光透過率のバラツキを抑えることができる研磨パッドを提供することができる。
本発明の第3の態様によれば、透光性樹脂部材(窓部材)の研磨面側の表面への研磨屑の付着、固着を低減することのできる研磨パッドを提供することができる。
本発明の第4の態様によれば、光透過率のバラツキを抑えることができる研磨パッドを提供することができる。
よって、本発明の研磨パッドは、産業上極めて有用である。
2…研磨層
3…他の層
4…透光性部材又は透光性樹脂部材
4’…透光性部材又は透光性樹脂部材の最上部
5…貫通孔(第1貫通孔)
6…第2貫通孔
7…露出部
8…溝
8’…溝の最下部
9…コーティング部(第2の態様)、グラフト化された表面部(第3の態様)又は透光性樹脂部材の研磨面側の表面部(第4の態様)
Claims (20)
- 透光性部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ
前記透光性部材の研磨面側の表面の水接触角が80度以下である、前記研磨パッド。 - 前記透光性部材の研磨面側とは反対の表面の水接触角が80度超である、請求項1に記載の研磨パッド。
- 透光性部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性部材が存在するように配置されており、且つ
前記透光性部材の研磨面側の表面が、親水性樹脂でコーティングされている、前記研磨パッド。 - 前記親水性樹脂が、イオン結合性の親水基を有する樹脂である、請求項3に記載の研磨パッド。
- 前記イオン結合性の親水基を有する樹脂が、イオン結合性の親水基を側鎖に有する樹脂である、請求項4に記載の研磨パッド。
- 前記イオン結合性の親水基を有する樹脂は、イオン結合性の親水基のカチオン部が樹脂を構成するモノマーと共有結合しており且つイオン結合性の親水基のアニオン部とイオン結合している、請求項4又は5に記載の研磨パッド。
- 前記イオン結合性の親水基が、アンモニウムカチオンを含む、請求項4~6のいずれか1項に記載の研磨パッド。
- 前記樹脂でコーティングされた透光性部材の研磨面側の表面が、50度以下の水接触角を有する、請求項3~7のいずれか1項に記載の前記研磨パッド。
- 透光性樹脂部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ
前記透光性樹脂部材は、その研磨面側の表面に親水性モノマーがグラフト重合されている、前記研磨パッド。 - 前記透光性樹脂部材の研磨面側の表面の水接触角が80度以下である、請求項9に記載の研磨パッド。
- 前記親水性モノマーが、アクリル系モノマーである、請求項9又は10に記載の研磨パッド。
- グラフト化された前記表面の樹脂が、ポリエチレングリコール、ポリビニルピロリドン、ポリキシリルビオローゲン、ポリエチレンイミン及びポリビニルピリジニウムクロライド、ポリビニルベンジルトリメチルアンモニウムクロライドから選択される複合体形成ポリマーでイオンコンプレックスが形成されている、請求項11に記載の研磨パッド。
- 透光性樹脂部材及び研磨層を有する研磨パッドであって、
前記研磨層は、被研磨物を研磨するための研磨面を備え、前記研磨パッドは前記研磨面からその反対面へと貫通している貫通孔を有しており、
前記透光性樹脂部材は、研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、貫通孔内に透光性樹脂部材が存在するように配置されており、且つ
前記透光性樹脂部材は、少なくともその研磨面側の表面において、2以上の重合性官能基を有する多官能(メタ)アクリレートモノマーであって且つ-C2-4アルキレン-O-単位を有する前記多官能(メタ)アクリレートモノマーに由来する構成単位を含む樹脂を有する、
前記研磨パッド。 - 前記多官能(メタ)アクリレートモノマーが、下記:
-C2-4アルキレン-O-単位を有する化合物と(メタ)アクリル酸とがエステル結合されたモノマー、及び
C2-4アルキレンオキサイドが付加された3価以上のアルコールと(メタ)アクリル酸とがエステル結合されたモノマー
からなる群から選択される少なくとも1種である、請求項13に記載の研磨パッド。 - 前記3価以上のアルコールが、グリセリン、ジグリセリン、トリグリセリン、トリメチロールプロパン、ジトリメチロールプロパン、エリスリトール、ペンタエリスリトール及びジペンタエリスリトールからなる群から選択される、請求項14に記載の研磨パッド。
- 前記-C2-4アルキレン-O-単位が、エチレンオキサイド及び/又はプロピレンオキサイドに由来するものである、請求項13~15のいずれか1項に記載の研磨パッド。
- 前記多官能(メタ)アクリレートモノマーが、ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、プロポキシ化ペンタエリスリトールテトラアクリレート、エトキシ化グリセリントリアクリレート、プロポキシ化グリセリントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、プロポキシ化トリメチロールプロパントリアクリレートからなる群から選択される少なくとも1種である、請求項13~16のいずれか1項に記載の研磨パッド。
- 前記研磨面を上面としその反対面を下面とした場合に、前記透光性樹脂部材の研磨面側の表面が前記研磨面よりも低い、請求項1~17のいずれか1項に記載の研磨パッド。
- 前記研磨面が溝を有し、且つ前記研磨面を上面としその反対面を下面とした場合に、前記透光性部材の最上部が前記溝の最下部と同じ位置にあるかそれよりも低い、請求項1~18に記載の研磨パッド。
- 前記研磨層が有する貫通孔を第1貫通孔とするとき、前記研磨パッドは、前記第1貫通孔よりも小さい円相当径を有する第2貫通孔を有する他の層を更に含み、
前記他の層は、前記研磨層の研磨面とは反対側に位置しており、
前記研磨パッドを研磨表面側から厚さ方向に見た場合に、前記第1貫通孔と前記第2貫通孔とが少なくとも部分的に重なっており、
研磨パッドの研磨面側から研磨パッド厚さ方向に見た場合に、前記透光性部材が前記第1貫通孔内に存在するように前記透光性部材が配置されている、請求項1~19のいずれか1項に記載の研磨パッド。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202180067394.0A CN116490322A (zh) | 2020-09-30 | 2021-09-16 | 研磨垫和研磨垫的制造方法 |
EP21875238.4A EP4223452A1 (en) | 2020-09-30 | 2021-09-16 | Polishing pad and method for manufacturing polishing pad |
IL301788A IL301788A (en) | 2020-09-30 | 2021-09-16 | Polishing pad and method for manufacturing a polishing pad |
US18/247,158 US20230415300A1 (en) | 2020-09-30 | 2021-09-16 | Polishing pad and method for manufacturing polishing pad |
KR1020237014231A KR20230073325A (ko) | 2020-09-30 | 2021-09-16 | 연마 패드 및 연마 패드의 제조 방법 |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-164766 | 2020-09-30 | ||
JP2020164767A JP2022056818A (ja) | 2020-09-30 | 2020-09-30 | 研磨パッド及び研磨パッドの製造方法 |
JP2020-164765 | 2020-09-30 | ||
JP2020-164767 | 2020-09-30 | ||
JP2020164766A JP2022056817A (ja) | 2020-09-30 | 2020-09-30 | 研磨パッド及び研磨パッドの製造方法 |
JP2020164765A JP2022056816A (ja) | 2020-09-30 | 2020-09-30 | 研磨パッド及び研磨パッドの製造方法 |
JP2021-055069 | 2021-03-29 | ||
JP2021055069A JP2022152340A (ja) | 2021-03-29 | 2021-03-29 | 研磨パッド及び研磨パッドの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022070936A1 true WO2022070936A1 (ja) | 2022-04-07 |
Family
ID=80950320
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/034032 WO2022070936A1 (ja) | 2020-09-30 | 2021-09-16 | 研磨パッド及び研磨パッドの製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230415300A1 (ja) |
EP (1) | EP4223452A1 (ja) |
KR (1) | KR20230073325A (ja) |
IL (1) | IL301788A (ja) |
TW (1) | TW202225286A (ja) |
WO (1) | WO2022070936A1 (ja) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002001652A (ja) | 2000-06-22 | 2002-01-08 | Nikon Corp | 研磨パッド及び研磨装置及び素子製造方法 |
JP2003285257A (ja) | 2002-03-28 | 2003-10-07 | Toray Ind Inc | 研磨パッド、研磨装置および半導体の製造方法 |
JP2004327974A (ja) | 2003-04-09 | 2004-11-18 | Jsr Corp | 研磨パッド、その製造法と製造用金型および半導体ウエハの研磨方法 |
JP2004343090A (ja) | 2003-04-22 | 2004-12-02 | Jsr Corp | 研磨パッドおよび半導体ウェハの研磨方法 |
US20050266771A1 (en) * | 2001-12-28 | 2005-12-01 | Applied Materials, Inc., A Delaware Corporation | Polishing pad with window |
JP2008221367A (ja) | 2007-03-09 | 2008-09-25 | Toyo Tire & Rubber Co Ltd | 研磨パッド |
JP4931133B2 (ja) | 2007-03-15 | 2012-05-16 | 東洋ゴム工業株式会社 | 研磨パッド |
JP5421635B2 (ja) | 2009-03-30 | 2014-02-19 | 富士紡ホールディングス株式会社 | 研磨パッド |
JP2014104521A (ja) | 2012-11-26 | 2014-06-09 | Toyo Tire & Rubber Co Ltd | 研磨パッド |
JP5844189B2 (ja) | 2012-03-26 | 2016-01-13 | 富士紡ホールディングス株式会社 | 研磨パッド及び研磨パッドの製造方法 |
JP6209639B2 (ja) | 2016-03-31 | 2017-10-04 | 大成ファインケミカル株式会社 | 親水性共重合体およびその製造方法、ならびに当該親水性共重合体を含む活性エネルギー線硬化型組成物および塗膜 |
US20200164482A1 (en) * | 2018-11-28 | 2020-05-28 | Taiwan Semiconductor Manufacturing Co., Ltd. | Multi-layered windows for use in chemical-mechanical planarization systems |
-
2021
- 2021-09-14 TW TW110134177A patent/TW202225286A/zh unknown
- 2021-09-16 IL IL301788A patent/IL301788A/en unknown
- 2021-09-16 WO PCT/JP2021/034032 patent/WO2022070936A1/ja active Application Filing
- 2021-09-16 EP EP21875238.4A patent/EP4223452A1/en active Pending
- 2021-09-16 US US18/247,158 patent/US20230415300A1/en active Pending
- 2021-09-16 KR KR1020237014231A patent/KR20230073325A/ko unknown
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002001652A (ja) | 2000-06-22 | 2002-01-08 | Nikon Corp | 研磨パッド及び研磨装置及び素子製造方法 |
US20050266771A1 (en) * | 2001-12-28 | 2005-12-01 | Applied Materials, Inc., A Delaware Corporation | Polishing pad with window |
JP2003285257A (ja) | 2002-03-28 | 2003-10-07 | Toray Ind Inc | 研磨パッド、研磨装置および半導体の製造方法 |
JP2004327974A (ja) | 2003-04-09 | 2004-11-18 | Jsr Corp | 研磨パッド、その製造法と製造用金型および半導体ウエハの研磨方法 |
JP2004343090A (ja) | 2003-04-22 | 2004-12-02 | Jsr Corp | 研磨パッドおよび半導体ウェハの研磨方法 |
JP2008221367A (ja) | 2007-03-09 | 2008-09-25 | Toyo Tire & Rubber Co Ltd | 研磨パッド |
JP4931133B2 (ja) | 2007-03-15 | 2012-05-16 | 東洋ゴム工業株式会社 | 研磨パッド |
JP5421635B2 (ja) | 2009-03-30 | 2014-02-19 | 富士紡ホールディングス株式会社 | 研磨パッド |
JP5844189B2 (ja) | 2012-03-26 | 2016-01-13 | 富士紡ホールディングス株式会社 | 研磨パッド及び研磨パッドの製造方法 |
JP2014104521A (ja) | 2012-11-26 | 2014-06-09 | Toyo Tire & Rubber Co Ltd | 研磨パッド |
JP6209639B2 (ja) | 2016-03-31 | 2017-10-04 | 大成ファインケミカル株式会社 | 親水性共重合体およびその製造方法、ならびに当該親水性共重合体を含む活性エネルギー線硬化型組成物および塗膜 |
US20200164482A1 (en) * | 2018-11-28 | 2020-05-28 | Taiwan Semiconductor Manufacturing Co., Ltd. | Multi-layered windows for use in chemical-mechanical planarization systems |
Non-Patent Citations (1)
Title |
---|
SEN'I GAKKAISHI, vol. 41, no. 10, 1985, pages 388 - 393 |
Also Published As
Publication number | Publication date |
---|---|
TW202225286A (zh) | 2022-07-01 |
US20230415300A1 (en) | 2023-12-28 |
EP4223452A1 (en) | 2023-08-09 |
IL301788A (en) | 2023-05-01 |
KR20230073325A (ko) | 2023-05-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5105559B2 (ja) | 研磨パッド用クッション層の製造方法 | |
TW564202B (en) | Abrasive article having a window system for polishing wafers, and methods | |
JP5223336B2 (ja) | 研磨パッドおよび研磨装置 | |
KR20040093402A (ko) | 연마 패드 및 반도체 웨이퍼의 연마 방법 | |
KR20130081229A (ko) | 화학 기계적 평탄화를 위한 계면활성제를 포함하는 고정 연마 패드 | |
KR20110113635A (ko) | 표면 처리된 나노-세리아 충전재를 포함하는 구조화 고정 연마 용품, 및 그의 제조 및 사용 방법 | |
EP2327088A2 (en) | Structured abrasive article, method of making the same, and use in wafer planarization | |
JP2004343090A (ja) | 研磨パッドおよび半導体ウェハの研磨方法 | |
TW200905739A (en) | Polishing pad | |
KR20160026740A (ko) | 반사 방지 적층체, 편광판, 커버 유리, 화상 표시 장치, 및 반사 방지 적층체의 제조 방법 | |
WO2022070936A1 (ja) | 研磨パッド及び研磨パッドの製造方法 | |
JPWO2008053948A1 (ja) | 化学機械研磨パッドの製造方法および被研磨体の加工方法 | |
CN116490322A (zh) | 研磨垫和研磨垫的制造方法 | |
JP2022056817A (ja) | 研磨パッド及び研磨パッドの製造方法 | |
JP2022056818A (ja) | 研磨パッド及び研磨パッドの製造方法 | |
JP4845347B2 (ja) | 研磨パッドおよびその製造方法 | |
JP2022056816A (ja) | 研磨パッド及び研磨パッドの製造方法 | |
TW201627658A (zh) | 拋光層分析器及方法 | |
JP2016128205A (ja) | 化学機械研磨パッドの製造方法 | |
KR102173453B1 (ko) | 디스플레이 연마용 세정 패드 및 이의 제조방법 | |
JP2007067143A (ja) | 研磨パッド用感光性樹脂組成物 | |
JP2021137892A (ja) | 研磨パッド及び研磨パッドの製造方法 | |
JP2006015421A (ja) | 研磨パッドおよび研磨装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21875238 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202180067394.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 20237014231 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021875238 Country of ref document: EP Effective date: 20230502 |