CN107075322A - The processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer - Google Patents
The processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer Download PDFInfo
- Publication number
- CN107075322A CN107075322A CN201580056130.XA CN201580056130A CN107075322A CN 107075322 A CN107075322 A CN 107075322A CN 201580056130 A CN201580056130 A CN 201580056130A CN 107075322 A CN107075322 A CN 107075322A
- Authority
- CN
- China
- Prior art keywords
- semiconductor wafer
- adhesive tape
- polymer
- adhesive
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 128
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 123
- 238000003672 processing method Methods 0.000 title claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 161
- 230000001070 adhesive effect Effects 0.000 claims abstract description 161
- 229920000642 polymer Polymers 0.000 claims abstract description 140
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 78
- 239000012790 adhesive layer Substances 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 40
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 238000007711 solidification Methods 0.000 claims abstract description 17
- 230000008023 solidification Effects 0.000 claims abstract description 17
- 238000003847 radiation curing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 96
- -1 isocyanic acid 2- (methyl) acryloyloxyethyl ester Chemical class 0.000 claims description 51
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 44
- 239000003431 cross linking reagent Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 18
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 13
- 238000001723 curing Methods 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 114
- 238000004519 manufacturing process Methods 0.000 description 60
- 239000010408 film Substances 0.000 description 50
- 239000002585 base Substances 0.000 description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 26
- 229920006243 acrylic copolymer Polymers 0.000 description 24
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 17
- 229920002635 polyurethane Polymers 0.000 description 16
- 239000004814 polyurethane Substances 0.000 description 16
- 238000000227 grinding Methods 0.000 description 14
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 11
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 11
- 229920001684 low density polyethylene Polymers 0.000 description 11
- 239000004702 low-density polyethylene Substances 0.000 description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 230000006978 adaptation Effects 0.000 description 10
- 230000006870 function Effects 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000003292 glue Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 125000003566 oxetanyl group Chemical group 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000002285 radioactive effect Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000004026 adhesive bonding Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical class C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GNBCKKSGQPLTRW-UHFFFAOYSA-N C(C=C)(=O)OC.C(N)(O)=O Chemical compound C(C=C)(=O)OC.C(N)(O)=O GNBCKKSGQPLTRW-UHFFFAOYSA-N 0.000 description 2
- 241001050985 Disco Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012945 sealing adhesive Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical class CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical class C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical class ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000003855 Adhesive Lamination Methods 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 244000004005 Nypa fruticans Species 0.000 description 1
- 235000005305 Nypa fruticans Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QDHUQRBYCVAWEN-UHFFFAOYSA-N amino prop-2-enoate Chemical class NOC(=O)C=C QDHUQRBYCVAWEN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- AJKZIPCWVAURSI-UHFFFAOYSA-N carbamic acid;2-methylprop-2-enoic acid Chemical compound NC(O)=O.CC(=C)C(O)=O AJKZIPCWVAURSI-UHFFFAOYSA-N 0.000 description 1
- NYVPYOCCTPDTKV-UHFFFAOYSA-N carbamic acid;isocyanic acid Chemical group N=C=O.NC(O)=O NYVPYOCCTPDTKV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XRXDLBRJHUCCHH-UHFFFAOYSA-N diiodomethane Chemical compound ICI.ICI XRXDLBRJHUCCHH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- AUCNMQYOQYTGPE-UHFFFAOYSA-N n-(hydroxymethyl)-n-methylprop-2-enamide Chemical class OCN(C)C(=O)C=C AUCNMQYOQYTGPE-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
- H01L21/683—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 for supporting or gripping
- H01L21/6835—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 for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesive Tapes (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A kind of processing method with projection semiconductor wafer surface protection adhesive tape and with projection semiconductor wafer, this is the band projection semiconductor wafer surface protection adhesive tape with ultra-violet solidified adhesive phase on base material film with adhesive tape with the protection of projection semiconductor wafer surface, wherein, it is less than more than 10,000 200 ten thousand and group with the carbon-carbon double bond of type containing radiation-curing that the adhesive phase, which contains weight average molecular weight, (methyl) acrylate copolymer of hydroxyl and carboxyl, the surface free energy of the adhesive layer surface of ultraviolet pre-irradiation is 25.5mN/m less than 35mN/m, the surface of the adhesive phase after the solidification that ultraviolet irradiates high more than 5mN/m of surface free energy compared with the surface of the adhesive phase of ultraviolet pre-irradiation, and it is small to the contact angle of diiodomethane, the hydroxyl value for constituting the polymer of above-mentioned adhesive layer surface is 30mgKOH/g~100mgKOH/g, the acid number for constituting the polymer of above-mentioned adhesive layer surface is 5mgKOH/g~65mgKOH/g.
Description
Technical field
The present invention relates to the processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer.More specifically,
It is related to the surface protection adhesive tape and semiconductor wafer of the semiconductor wafer used when by grinding semiconductor wafer into film etc.
Processing method.
Background technology
Semiconductor package part is obtained by the manufacture of following methods：Semiconductor die is being made in the section such as high purity silicon monocrystalline
After piece, by ion implanting, etching etc. in wafer surface formation integrated circuit, semiconductor package part is thus manufactured.By right
The back side for being formed with the semiconductor wafer of integrated circuit is ground, ground, and it is desired to be processed into semiconductor wafer
Thickness.Now, in order to protect the integrated circuit to be formed in semiconductor wafer surface, semiconductor wafer surface protection adhesive tape is used
(being hereinafter also referred to as " surface protection band ").
The semiconductor wafer being ground through the back side is overleaf ground terminate after be accommodated in wafer case, be carried to cutting action,
It is processed into semiconductor chip.
In the past, it is necessary to which being ground etc. by the back side makes the thickness of semiconductor wafer be 200 μm~400 μm or so.But, with
High-density installation technology is improved, it is necessary to minimize semiconductor chip in recent years, and the filming of semiconductor wafer is continued to develop.
According to the difference of the species of semiconductor chip, it is necessary to make semiconductor wafer be as thin as 100 μm or so.Moreover, can pass through to increase
The quantity of the manufactured semiconductor chip of disposable processing, it is intended to use large-scale chip.A diameter of 5 inches or 6 English before this
Very little chip is main flow, on the other hand, and the semiconductor wafer of 8 inches~12 inches of diameter is processed into semiconductor chip in recent years
Become main flow.
The filming of semiconductor wafer and the trend of maximization there are the flash memory field of NAND or NOR-type or conduct
It is particularly significant in the fields such as the DRAM of volatile memory.For example, by the grinding semiconductor wafer of 12 inches of diameter to thickness 150
Situation below μm is also not uncommon for.
Generally, semiconductor wafer is taken out piecewise by mechanical arm from the special box referred to as wafer case, using positioned at
Semiconductor wafer fixation in equipment for grinding is kept with fixture, carries out back side grinding.The semiconductor wafer being ground through the back side
It is contained by mechanical arm to wafer case and is delivered to subsequent processing.Now, if the warpage of semiconductor wafer is big, suction can be produced
It is attached bad or produce chip in the worst cases and depart from and the problems such as drop from absorption arm during transport.But due to referred to as
The appearance or the exploitation of special adhesive tape of the film grinding special machine of system (in-line system) in line, the problem are obtained
To solution (for example, see patent document 1 and 2).It is therefore contemplated that the trend that chip changes to filming can increasingly accelerate from now on.
Chip after grinding, which is mounted to, to be cut crystal zone or cuts on brilliant viscous epitaxial, and surface protection band is peeled off afterwards.To large-scale
In the case that the back side of semiconductor wafer is ground and makes wafer film, if not suppressing to be attached at the face side of the chip
The peeling force of the surface protection band on surface, the then load that chip is applied to when peeling off surface protection band is excessive, and chip is easily broken
Split.
In addition, for discrete chip, in order to improve performance, also in iterative method filming.Due to the discrete
Chip implements the difference in height different sizes on special surface treatment or surface, therefore easily residual when peeling off surface protection band
Glue, the raising of fissility becomes one of important topic.
For surface protection band, high chip confining force is needed in the grinding process of chip back surface, when peeling off
It is required that low adhesion power.Therefore, the adhesive tape with ultra-violet solidified adhesive phase was widely used in the past as surface protection
Band.Surface protection band with ultra-violet solidified adhesive phase can be fitted in the state of with high adhesion partly leads
Body chip, therefore excellent adhesion, show high chip confining force.On the other hand, consolidated before stripping by irradiation ultraviolet radiation
Change, bonding force can be reduced, therefore further improve fissility.(for example, see patent document 3).
But, the reactivity of ultra-violet solidified adhesive phase is high, if thus wafer surface be modified, bond sometimes
Oxidant layer is reacted into branch and the wafer surface and is peeling bad or wafer breakage.In addition, wafer surface is provided with sometimes
Insulating resin layer comprising polyimides etc. and conductor wirings pattern, if there is insulating resin layer in wafer surface, surface is protected
The bonding force increase of protecting band, fissility reduction.
In this condition, as improvement method of the surface protection band from the fissility of semiconductor surface, in patent document 4
Describe to the contact angle of diiodomethane (diiodomethane), as index, the character to adhesive layer surface is adjusted.
In addition, as improving method of the surface protection band from the fissility of semiconductor surface, under having recorded in patent document 5
State content：Also the surface free energy of adhesive phase will not only be made to the contact angle of diiodomethane (diiodomethane) as index
For index, the character to adhesive layer surface is adjusted.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-151355 publications
Patent document 2：Japanese Unexamined Patent Publication 2003-261842 publications
Patent document 3：Japanese Unexamined Patent Publication 9-298173 publications
Patent document 4：Japanese Unexamined Patent Publication 2009-242776 publications
Patent document 5：No. 2013/122060 pamphlet of International Publication No.
The content of the invention
Invent problem to be solved
But, as described in above-mentioned patent document 4, the adhesive layer surface for making surface protection band is specific property
Shape and improve in the case of the fissility of semiconductor wafer, in conveying operation or when storing to wafer case, semiconductor wafer
Peripheral part (edge) is sometimes prone to peel off (i.e. it is easy to occurring marginal swell) from adhesive tape.If generation marginal swell, cutting after
When crystal zone is fitted, edge break or wafer breakage are likely to occur due to the pressurization produced by roller.In addition, being protected by the surface
In the case that protecting band is applied to band projection (electrode) semiconductor wafer, it can not obtain abundant with the wafer surface with projection sometimes
Adaptation, be easily mixed into air (air) between surface protection band and wafer surface.
On the other hand, the surface protection band described in patent document 5 shines due to eliminating the complicated ultraviolet of process management
It is pressure sensitive to penetrate adhesive used in process, thus adhesive phase.Therefore, in patent document 5, it is not conceived to adhesive
Adhesive used is the improvement of the surface protection bands of radiation-curing type such as ultraviolet in layer.
The problem of the present invention is to provide a kind of semiconductor wafer surface protection adhesive tape and has used the half of the adhesive tape
The processing method of conductor chip, even if the semiconductor wafer surface protection adhesive tape is applied to the recessed of projection semiconductor wafer
Adaptation is also excellent in the case of nonreentrant surface, and is less susceptible to occur marginal swell, and then, even if on the surface of semiconductor wafer
Protection band binding face also can easily be shelled in the case of there is insulating barrier or conductor wirings pattern in the case of not damage wafers
From the cull of the wafer surface after stripping is also few, and adhesive used is radiation-curing type in adhesive phase.
Scheme for solving problem
The present inventor is in view of above-mentioned problem has made intensive studies.As a result find, make ultra-violet solidified adhesive
During the character that the contact angle of surface free energy rise and diiodomethane diminishes after being irradiated for ultraviolet, even with projection semiconductor
The convex-concave surface of chip etc., is also sufficiently carried out closely sealed, nor easily occurs marginal swell, and then, even if in semiconductor die
Be present insulating barrier or conductor wirings pattern in the surface protection band binding face of piece, easily can also shell the adhesive tape from semiconductor wafer
From may also suppress the cull of the wafer surface after stripping.The present invention be based on these technological thoughts further repeatedly research and
Complete.
That is, main points of the invention are as described below.
(1) a kind of band projection semiconductor wafer surface protection adhesive tape, it is with ultra-violet solidified on base material film
Adhesive phase band projection semiconductor wafer surface protection adhesive tape, it is characterised in that
It is less than more than 10,000 200 ten thousand and with the carbon-to-carbon pair of type containing radiation-curing that the adhesive phase, which contains weight average molecular weight,
(methyl) acrylate copolymer of the group of key, hydroxyl and carboxyl,
The surface free energy of the adhesive layer surface of ultraviolet pre-irradiation be 25.5mN/m less than 35mN/m,
The surface of the adhesive phase after the solidification that ultraviolet irradiates and the table of the adhesive phase of ultraviolet pre-irradiation
High more than the 5mN/m of surface free energy is compared in face,
The surface of the adhesive phase after the solidification that ultraviolet irradiates and the table of the adhesive phase of ultraviolet pre-irradiation
Face is compared, small to the contact angle of diiodomethane,
Above-mentioned (methyl) acrylate copolymer is to make the importing radiation-curing type carbon-to-carbon double bond base with hydroxyl and carboxyl
Polymer before group and polymer obtained from the compound reaction with radiation-curing type carbon-to-carbon double bond group, are being formed
In whole monomer components of polymer before the importing radiation-curing type carbon-to-carbon double bond group, (methyl) acrylic acid is included
1mol%~10mol%,
The hydroxyl value for constituting the polymer of above-mentioned adhesive layer surface is 30mgKOH/g~100mgKOH/g,
The acid number for constituting the polymer of above-mentioned adhesive layer surface is 5mgKOH/g~65mgKOH/g.
(2) the band projection semiconductor wafer surface protection adhesive tape as described in (1), it is characterised in that above-mentioned that there is radiation
The compound of line curing type carbon-to-carbon double bond group is isocyanic acid 2- (methyl) acryloyloxyethyl ester.
(3) the band projection semiconductor wafer surface protection adhesive tape as described in (2), it is characterised in that relative to above-mentioned (first
Base) 100 mass parts of acrylate copolymer, the blend amount of above-mentioned isocyanic acid 2- (methyl) acryloyloxyethyl ester for 1 mass parts~
20 mass parts.
(4) the band projection semiconductor wafer surface protection adhesive tape as any one of (1)~(3), it is characterised in that
Relative to the above-mentioned mass parts of (methyl) acrylate copolymer 100, the mass parts of mass parts of mixture crosslinking agent 0.1~5.
(5) the band projection semiconductor wafer surface protection adhesive tape as any one of (1)~(4), it is characterised in that
The acid number for constituting the polymer of above-mentioned adhesive layer surface is 10mgKOH/g~35mgKOH/g.
(6) a kind of processing method with projection semiconductor wafer, it is convex for the band any one of use (1)~(5)
The processing method with projection semiconductor wafer of block semiconductor wafer surface protection adhesive tape, it is characterised in that the processing method
Including following processes (A)~(D).
Process (A), has the above-mentioned band projection semiconductor wafer of surface laminating of projection in the formation with projection semiconductor wafer
The process of surface protection adhesive tape；
Process (B), to above-mentioned with projection semiconductor wafer and above-mentioned band projection semiconductor wafer surface protection adhesive tape
Binding face opposite side the process that is ground of surface；
Process (C), makes above-mentioned band projection to above-mentioned band projection semiconductor wafer surface protection adhesive tape irradiation ultraviolet radiation
The process that semiconductor wafer surface protection adhesive tape solidifies；And
Process (D), above-mentioned band projection semiconductor wafer surface protection adhesive tape is peeled off from above-mentioned band projection semiconductor wafer
Process.
(7) processing method with projection semiconductor wafer as described in (6), it is characterised in that above-mentioned band projection semiconductor
Chip has insulating barrier with the above-mentioned binding face with projection semiconductor wafer surface protection adhesive tape.
(8) processing method with projection semiconductor wafer as described in (6) or (7), it is characterised in that the height of above-mentioned projection
Spend for more than 15 μm.
When in this specification, referring to " surface of adhesive phase " or " adhesive layer surface ", as long as not special declaration, then be
Refer to the surface with the binding face opposite side of base material film.
In this specification, referred in semiconductor wafer laminated semiconductor wafer surface protection with adhesive tape, towards semiconductor die
Piece surface laminating adhesive layer surface.
In this specification, term " (methyl) acrylic acid " is with any one of acrylic acid and methacrylic acid or includes both
Implication use.This is also identical in the case of term " (methyl) acryloyl group ", " (methyl) acrylamide ".
The effect of invention
Even if the semiconductor wafer surface protection adhesive tape of the present invention is applied to the projection such as band solder projection or golden projection
Semiconductor wafer convex-concave surface when be not easy to be mixed into air, excellent adhesion is not easy to occur marginal swell.In addition, this
The fissility of the semiconductor wafer surface protection adhesive tape of invention is also excellent, even if fitting in large-scale semiconductor wafer surface simultaneously
In the case of being ground to the chip back surface and being processed into less than 100 μm of thin film wafers, also can not damage wafers feelings
Easily peeled off under condition, may also suppress the cull of the wafer surface after stripping.Even if in addition, to semiconductor wafer surface
Protection has that insulating barrier or conductor wirings pattern similarly show good fissility with adhesive tape gluing face.
Therefore, semiconductor wafer surface protection of the invention with adhesive tape suitably as apparent height as discrete chip
Semiconductor wafer of the difference than larger semiconductor wafer, with the salient pole being made up of insulating barrier and conductor wirings pattern, use
In the surface protection adhesive tape of the semiconductor wafer with solder projection or golden projection applied to flip-chip mounting means etc..
In addition, according to the processing method of the semiconductor wafer of the present invention, thin film semiconductor can be obtained with high finished product rate brilliant
Piece.That is, the processing method of semiconductor wafer of the invention is suitably as the manufacture method of thin film semiconductor's chip.
The above and other feature and advantage of the present invention can be suitably further clear and definite by following contents referring to the drawings.
Brief description of the drawings
Fig. 1 is the sectional view for an embodiment for showing the semiconductor wafer surface protection adhesive tape of the present invention.
Embodiment
<<Semiconductor wafer surface protection adhesive tape>>
Referring to the drawings, the preferred semiconductor wafer surface protection to the present invention is (hereinafter referred to as " of the invention with adhesive tape
Adhesive tape ") illustrate.As shown in schematical sectional view in Fig. 1, adhesive tape 10 of the invention in base material film 11 at least
One side is formed with adhesive phase 12, makes adhesive phase 12 be bonded with semiconductor wafer 13 and uses.
Below, embodiments of the present invention are described in detail.
<Adhesive phase>
The adhesive phase of the adhesive tape of the present invention can be individual layer, or the different two or more adhesive phases of composition
The sandwich construction of lamination.Adhesive phase at least its surface of the adhesive tape of the present invention is ultra-violet solidified, preferred adhesive
Layer is generally ultra-violet solidified.In the adhesive tape of the present invention, adhesive layer surface after the solidification that ultraviolet irradiates with it is ultraviolet
The adhesive layer surface of line pre-irradiation compare high more than the 5mN/m of surface free energy, and with the adhesive phase of ultraviolet pre-irradiation
Compare to diiodomethane (CH on surface2I2) contact angle it is small.
(surface free energy of adhesive layer surface)
In the present invention, the surface free energy of adhesive layer surface is the value obtained using Owens and Wendt methods, to viscous
The contact angle to pure water and diiodomethane of mixture layer surface is measured (drop volume：The μ L of pure water 2, the μ L of diiodomethane 3, reading
Take the time：After being added dropwise 30 seconds, determine atmosphere：23 DEG C of temperature, relative humidity 50%), the simultaneous equations of following formula 1 is solved, by
This obtains the surface free energy of adhesive layer surface.It should be noted that in this specification, following " surfaces of solids " refer to glue
Mixture layer surface.
【Number 1】
<Formula 1>
rs=γs p+γs d (1)
72.8(1+cosθ1 H(51.0 γ of)=2s p)1/2+2(21.8γs d)1/2 (2a)
50.8(1+cosθ1 I(2.3 γ of)=2s p)1/2+2(48.5rs d)1/2 (2b)
γs：Surface free energy
γs p：The polar component of surface free energy
γs d：The dispersive component of surface free energy
θ1 H：Contact angle of the pure water to the surface of solids
θl I：Diiodomethane (CH2I2) to the contact angle of the surface of solids
Herein, formula (1) is Fowkes-Owens formulas, and it distinguishes the component of surface free energy, it is believed that surface free energy γsIt is
The polar component γ of surface free energys pThe dispersive component γ of (being only London (London) power) with surface free energys d(include moral
Visit (Debye) power or hydrogen bond force) sum.Above-mentioned formula (2a) and (2b) are by for solid s and interface as liquid 1 interface
Tension force γs 1Spread F owkes models relational expression combined with Young formulas obtained from relational expression, wherein, formula (2a) be pure water
In the case of relational expression, formula (2b) be diiodomethane in the case of relational expression.
The surface tension γ of pure water1, surface tension polar component γ1 p, surface tension dispersive component γ1 dIt is followed successively by respectively
72.8mN/m, 51.0mN/m, 21.8mN/m, the surface tension γ of diiodomethane1, surface tension polar component γ1 p, surface tension
Dispersive component γ1 dBe followed successively by 50.8mN/m, 2.3mN/m, 48.5mN/m respectively, thus plug these values into above-mentioned formula (2a) and
In (2b).
It should be noted that pure water is different from the polar component and dispersive component of diiodomethane, thus surface as described above
Tension force is different.Because, pure water and diiodomethane are different in terms of hydrogen bond, the difference of electronegativity is whether there is, therewith pole together
Property is significantly different.Particularly, in the case of water, the hydrogen bond such as-OH and-O- is strong, and the ratio of polar component is big.
In adhesive, by assigning hydroxyl or carboxyl into polymer, thus it is possible to vary polar component.Thus, to water
Contact angle changes, thus can change surface free energy.In stripping tape, thus it is speculated that causing cull because condensing deficiency
In the case of generation, dispersive component is top dog, and cull is there occurs on the surface for implementing special activation process
In the case of, polar component is top dog.Therefore, in order to solve the cull to the surface of various characters the problem of, control pair
The surface free energy of the contact angle of water or diiodomethane, i.e. adhesive layer surface is critically important.
Ultra-violet solidified adhesive is irradiated by ultraviolet and bonding force is reduced, thus, the stripping with semiconductor wafer
Improved from property.So, ultra-violet solidified adhesive phase is different from the adhesive phase of pressure sensitive, the meeting after ultraviolet pre-irradiation
Occur the physical property or structure change of adhesive phase.
Ultra-violet solidified adhesive phase generally comprises Photoepolymerizationinitiater initiater, even if thus also can before ultraviolet curing
React and occur be bonded with such as wafer surface because of the influence of heat or light.When the bonding becomes stripping the reason for cull.This
Inventor has found, relatively low by the way that the surface free energy of the adhesive layer surface before ultraviolet curing is suppressed to a certain extent,
The reaction of above-mentioned ultraviolet pre-irradiation can be suppressed while cohesive is maintained, can prevent through when chip and adhesive tape it is viscous
Connect.
On the other hand, it can be seen from the research of the present inventor, after uv irradiation, even if the surface of adhesive layer surface
Free energy is high to a certain degree, is not easy to peeling-off bad.Think that its reason is：Except making bonding because ultraviolet irradiates
Beyond agent solidification, bonding force reduction, caused curing reaction is irradiated by ultraviolet and above-mentioned Photoepolymerizationinitiater initiater is disappeared
Consumption, so as to be reduced with the reactivity of wafer surface.And then, the inventors discovered that, by the way that ultraviolet is irradiated after adhesive phase
The surface free energy on surface is improved to a certain extent, and the conveying or box in device effectively can prevent edge grand when storing
Rise.If generation marginal swell, as described above, easily occurring edge break the pressure of roller generation when cutting crystal zone laminating, most
Bad situation can cause wafer breakage.
In the adhesive tape of the present invention, the surface free energy and ultraviolet of the adhesive layer surface after the solidification that ultraviolet irradiates
The surface free energy of the adhesive layer surface of pre-irradiation is compared, preferably high more than 6mN/m, more preferably high more than 7mN/m.In addition,
In the adhesive tape of the present invention, surface free energy and the ultraviolet pre-irradiation of the adhesive layer surface after the solidification that ultraviolet irradiates
The difference of the surface free energy of adhesive phase is usually below 15mN/m, also preferably below 12mN/m.
In addition, for the adhesive tape of the present invention, the surface free energy of the adhesive layer surface of ultraviolet pre-irradiation is
25.5mN/m is less than 35mN/m, more preferably 28mN/m~33mN/m.
(to the contact angle of diiodomethane)
If being conceived to the contact angle to diiodomethane, adhesive layer surface is coloured to the big meaning of contact angle of diiodomethane
Component is dissipated greatly, in this case, the molecular separating force for constituting the polymer of adhesive becomes strong and is difficult to extend.After uv irradiation,
The crosslink density of adhesive is substantially increased, if therefore constitute adhesive polymer molecular separating force it is too strong, can become it is hard and
It is crisp, easily cause cull because glue ruptures in the stripping of adhesive tape.Conversely, adhesive layer surface is small to the contact angle of diiodomethane
In the case of, the molecular separating force for constituting the polymer of adhesive is weak, so even also possessing after the solidification that ultraviolet irradiates
For the flexibility of stretching, glue is not easily broken, when being peeled off from projections such as projections, glue be also not secured to the projections such as projection and
Easily come off.Therefore, after the solidification of the adhesive phase irradiated through ultraviolet, contact angle of the adhesive layer surface to diiodomethane
Preferably as low as to a certain degree.
On the other hand, there is the chip of the big projection such as projection or high difference of height surface protection band is fitted in into surface
When, if the adaptation of the chip and adhesive phase is insufficient, it is likely that be involved in air and fitted.If being involved in air,
Hindered due to solidifying caused by the oxygen in air, even if irradiation ultraviolet radiation is also possible to not solidify.In this case, constitute
Crosslinking between the polymer molecule of adhesive becomes insufficient, if therefore the polymer of ultraviolet pre-irradiation molecular separating force not
Height, then easily occur cohesion destruction.That is, before the curing reaction irradiated through ultraviolet, adhesive layer surface is to diiodomethane
Contact angle is preferably big to a certain degree.
In the adhesive tape of the present invention, preferably the adhesive layer surface of ultraviolet pre-irradiation to the contact angle (I) of diiodomethane with
Adhesive layer surface after the solidification that ultraviolet irradiates meets (I) to the contact angle (II) of diiodomethane>(II) relation, and
Its poor (I-II) is 5 degree~20 degree.
In addition, in the adhesive tape of the present invention, the adhesive layer surface of ultraviolet pre-irradiation is preferred to the contact angle of diiodomethane
For 50 degree~80 degree, more preferably 55 degree~75 degree, particularly preferably 55 degree~66.5 degree.
In the present invention, in order to determine the surface free energy of the adhesive phase after solidification and the contact angle of diiodomethane be entered
Capable " the ultraviolet irradiation " that is used to solidify adhesive phase refers to, is 500mJ/cm according to accumulative exposure2Mode to viscous
Mixture layer overall exposure ultraviolet.High-pressure sodium lamp can be for example used in ultraviolet irradiation.
On the composition of the adhesive phase of the present invention, adhesive phase is illustrated for the situation of single layer structure first.
In the adhesive tape of the present invention, adhesive phase is constituted and constituted by what can be irradiated and solidified by ultraviolet.The adhesive phase
Containing polymer, Photoepolymerizationinitiater initiater and crosslinking agent are preferably comprised.The adhesive phase can also as needed contain and be used to prevent
Only soak or improve additive or plasticizer of sliding etc..
(adhesive)
In the adhesive tape of the present invention, as long as adhesive used in adhesive phase is because ultraviolet irradiates and solidifies just without spy
Do not limit, at least containing a kind there is at least one can irradiate and carry out the polymerization of the reactive group of polymerisation by ultraviolet
Thing (hereinafter referred to " ultra-violet solidified polymer ").
Above-mentioned adhesive is preferably used as main component using ultra-violet solidified polymer.More specifically, purple is preferably comprised
More than the mass % of outside line curable polymer 50, further preferably more than 80 mass %, further preferably 90 mass % with
On.
The reactive group of polymerisation can be irradiated and carried out by ultraviolet as above-mentioned, and preferably ethylenic is unsaturated
Group, the group with carbon-to-carbon double bond, for example, can enumerate vinyl, pi-allyl, styryl, (methyl) acryloyl-oxy
Base, (methyl) Acryloyl amino etc..
Above-mentioned ultra-violet solidified polymer is not particularly limited, can for example enumerate (methyl) acrylate copolymer,
Polyester, ethene or styrol copolymer, polyurethane.It should be noted that in the present invention, these ultra-violet solidified polymer can
So that one kind is used alone, it can also be used in combination of two or more.
It is more than 10,000 200 that adhesive phase in the present invention, which contains as the weight average molecular weight of ultra-violet solidified polymer,
Less than ten thousand (methyl) acrylate copolymer is as neccessary composition, and being somebody's turn to do (methyl) acrylate copolymer has radiation-curing type
Carbon-to-carbon double bond, hydroxyl and carboxyl.
In the present invention, (methyl) acrylate copolymer that above-mentioned weight average molecular weight is less than more than 10,000 200 ten thousand can be used
Commercially available material, can also use the material synthesized by conventional method.In the case where being synthesized, (methyl) acrylic acid gathers
Compound is preferably to make the polymer imported before radiation-curing type carbon-to-carbon double bond group with hydroxyl and carboxyl with having radiation
Polymer obtained from the compound reaction of line curing type carbon-to-carbon double bond group.In this case, radioactive ray are imported in formation to consolidate
In whole monomer components of polymer before change type carbon-to-carbon double bond group, preferably comprise (methyl) acrylic acid 1mol%~
10mol%.
In the present invention, as the compound with radiation-curing type carbon-to-carbon double bond group, preferably make isocyanide described later
Sour 2- (methyl) acryloyloxyethyl esters and material obtained from hydroxyl polymer-containing described later reaction.
It should be noted that in the present invention, relative to the mass parts of (methyl) acrylate copolymer 100, isocyanic acid 2- (first
Base) blend amount of acryloyloxyethyl ester is preferably the mass parts of 1 mass parts~20, the mass parts of more preferably 6 mass parts~20.
As the synthetic method of above-mentioned ultra-violet solidified polymer, such as following methods are because easy and easy and preferred：
(a) in the case of for the polymer with ethylenic unsaturated group, make compound with ethylenic unsaturated group with
Polymer is reacted, the method for obtaining being imported with the polymer of ethylenic unsaturated group；(b) using with ethylenic insatiable hunger
With a kind of method of the oligomer of group [for example, carbamate (methyl) acrylic acid oligomer etc.] as crosslinking agent,
The method of wherein preferred above-mentioned (a).
In the method for above-mentioned (a), as the compound with ethylenic unsaturated group, using unsaturated with the ethylenic
Group has the compound of the structure of different reactive groups (being referred to as reactive group α), and conduct is imported with ethylenic
The polymer of unsaturated group, is carried out using the reactive group α with the compound with this with ethylenic unsaturated group
The polymer (hereinafter referred to " polymer with reactive group β ") of the reactive group β of reaction structure, makes reactivity
Group α and β is reacted.
Such for example preferred one of reactive group α, β is carries out the group of nucleophillic attack, and another one is to bear nucleophilic
The group of attack or the group for bearing addition reaction.As such reactive group, for example, it can enumerate hydroxyl, amino, mercapto
Base, carboxyl, epoxy radicals, oxetanyl, NCO, group, halogen atom, alkoxy or the virtue of the acid anhydrides of formation ring-type
Epoxide carbonyl etc..
Herein, in the case where any one of reactive group α and β are hydroxyl, amino, sulfydryl, carboxyl, another reaction
Property group can for epoxy radicals, oxetanyl, NCO, formed ring-type acid anhydrides group, halogen atom, alkoxy
Or aryloxycarbonyl.
The reactive group α that compound with ethylenic unsaturated group has is preferably the base for bearing nucleophillic attack
The group of addition reaction bears in group, for example preferably epoxy radicals, oxetanyl, NCO, the acid for forming ring-type
Group, halogen atom, alkoxy or the aryloxycarbonyl of acid anhydride, more preferably epoxy radicals, oxetanyl, NCO or
The group of the acid anhydrides of formation ring-type, more preferably epoxy radicals, oxetanyl or NCO, further preferably
For NCO.
On the other hand, the reactive group β that being imported with the polymer of ethylenic unsaturated group has is preferably to carry out
The group of nucleophillic attack, such as preferably hydroxyl, amino, sulfydryl or carboxyl, more preferably hydroxyl, amino or sulfydryl, enter one
Step preferably hydroxyl, amino or carboxyl, more preferably hydroxyl or carboxyl, wherein preferably hydroxyl.
There is reactivity as the compound with ethylenic unsaturated group and reactive group α or for synthesizing
The monomer with reactive group β of group β polymer, can enumerate following compound.
- reactive group for carboxyl compound-
(methyl) acrylic acid, cinnamic acid, itaconic acid, fumaric acid etc.
- reactive group for hydroxyl compound-
There is (methyl) acrylic acid hydroxy alkyl ester of hydroxyl in alcohol portion [for example, (methyl) acrylic acid -2- hydroxyl ethyl esters, (first
Base) 2-hydroxypropyl acrylate, trimethylolpropane list (methyl) acrylate, ethylene glycol list (methyl) acrylate, diethyl two
Alcohol list (methyl) acrylate], have in amine portion hydroxyl alkylamine N- (hydroxyalkyl) alkyl (methyl) acrylamide [example
Such as, N- methylols (methyl) acrylamide, N, double methylol (methyl) acrylamides of N-], allyl alcohol etc.
- reactive group for amino compound-
There is (methyl) acrylate of amino in alcohol portion [for example, (methyl) acrylic acid 2- (alkyl amino)
Ethyl ester, (methyl) acrylic acid 3- (alkyl amino) propyl ester], (methyl) acrylamide etc.
- reactive group for ring-type acid anhydrides compound-
Maleic anhydride, itaconic anhydride, fumaric acid anhydride, phthalic anhydride etc.
- reactive group be epoxy radicals or oxetanyl compound-
(methyl) glycidyl acrylate, allyl glycidyl ether, 3- ethyl -3- hydroxymethyl-oxetanes etc.
- reactive group for NCO compound-
Isocyanic acid (methyl) acryloyloxyalkyl is [for example, isocyanic acid 2- (methyl) acryloyloxyethyl ester, isocyanic acid
2- (methyl) acryloxies propyl ester], will be polynary different using the compound with hydroxyl or carboxyl and ethylenic unsaturated group
A part for the NCO of cyanate esters carries out the compound of urethane [for example, 2~10 functions
The urethane acrylate oligomer of (methyl) acrylic acid] etc.
It should be noted that as above-mentioned urethane acrylate oligomer, being such as preferably to make (methyl) propylene
The alcohol portions such as acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, pentaerythrite three (methyl) acrylate have the (first of hydroxyl
Base) acrylic acid hydroxy alkyl ester and toluene di-isocyanate(TDI), methylenediphenyl diisocyanate, hexamethylene diisocyanate, naphthalene
It is more than the diisocyanate such as diisocyanate, methylene bis cyclohexyl isocyanates, IPDI or 3 functions
Isocyanates has the oligomer of at least one NCO obtained from being reacted.Alternatively, it is also possible to for except (methyl) third
Also enter outside olefin(e) acid hydroxy alkyl ester and multicomponent isocyanate with polyol compound, PTMEG compound or polyester-diol compound
Oligomer obtained from row reaction.
- reactive group for halogen atom compound-
Halogenation triazines such as the chloro- 6- methoxyl groups -1,3,5- triazines of the chloro- 1,3,5- triazines of 2,4,6- tri-, 2,4- bis- etc.
It is used as the above-mentioned compound with ethylenic unsaturated group and reactive group α, preferably above-mentioned reactive base
Group is the compound of NCO, on the other hand, as the monomer of the synthesis for the polymer with reactive group β,
It is preferred that it is the compound of hydroxyl that above-mentioned reactive group, which is the compound or reactive group of carboxyl, more preferably reactive group is
The compound of hydroxyl.
The method of above-mentioned (b) uses above-mentioned carbamate (methyl) acrylate oligomer (as described later, oligomer
Also it is one kind of crosslinking agent), (methyl) acrylic copolymer and carbamate (methyl) acrylate oligomer can be made common
Deposit and constitute ultra-violet solidified adhesive phase.As (methyl) acrylic copolymer, preferably make (methyl) acrylic acid with
Material obtained from (methyl) acrylic ester polymerization.Constitute (methyl) acrylic copolymer (methyl) acrylate component it is excellent
Form slection state is identical with the material illustrated by the copolymer composition described later as in the polymer with reactive group β.
The above-mentioned monomer component with reactive group β accounts for the whole for constituting the above-mentioned polymer with reactive group β
The ratio of monomer component is preferably 5 moles of %~50 mole %, more preferably 20 moles of %~40 mole %.
In addition, making the compound with ethylenic unsaturated group and reactive group α with having reactive group β's
Polymer reacted and to reactive group β polymer import ethylenic unsaturated group when, preferably with respect to tool
The mass parts of polymer 100 for having reactive group β make compound with reactive group α react the mass parts of 1 mass parts~40,
More preferably react the mass parts of 1 mass parts~30, further preferably the mass parts of 1 mass parts of reaction~20, particularly preferably 1 mass of reaction
Part~10 mass parts.
Pass through the reactive group β of the remained unreacted after above-mentioned reactive group α and β reaction, it is possible to use aftermentioned
The regulation resin properties such as crosslinking agent.
The above-mentioned polymer with reactive group β preferably has above-mentioned monomer component and work with reactive group β
Its constituent is used as (methyl) acrylate component of copolymer composition.
It is used as (methyl) acrylate, preferably one kind or two or more (methyl) alkyl acrylate.It is somebody's turn to do (methyl)
The alcohol portion of acrylate does not have above-mentioned reactive group β.It is preferred that the alcohol portion of above-mentioned (methyl) acrylate is unsubstituted.
As such (methyl) acrylate, the carbon number in alcohol portion is preferably 1~12.The carbon number in alcohol portion is more excellent
Elect 1~10, more preferably 4~10 as, wherein preferred alcohols portion is the material of branched alkyl, particularly preferred (methyl) propylene
Acid -2- ethylhexyl esters.
In addition, being used as composition comprising two or more (methyl) acrylate components in above-mentioned ultraviolet polymerizing polymer
In the case of composition, it is 1~8 (methyl) acrylic acid to be somebody's turn to do in (methyl) acrylate component and preferably comprise the carbon number in alcohol portion
Ester composition, wherein preferably comprising (methyl) ethyl acrylate composition.
Below, the concrete example that the monomer in polymer is introduced to as above-mentioned copolymer composition is enumerated.
- Arrcostab of (methyl) acrylic acid-
As the Arrcostab of (methyl) acrylic acid, the carbon number in preferred alcohols portion is 1~12 material, for example, can enumerate
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) third
Olefin(e) acid isobutyl ester, (methyl) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl)
Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate etc..They can be used alone, can also
Two or more is used in mixed way.By the way that two or more is shared, the various functions as adhesive can have been given play to, and then can be simultaneous
Turn round and look at the tracing ability and the non-polluting including preventing cull to the difference in height of semiconductor wafer surface.
- monomer beyond the Arrcostab of (methyl) acrylic acid-
As the monomer beyond the Arrcostab of (methyl) acrylic acid, vinyl acetate, styrene or (methyl) can be enumerated
Acrylamide, such as N, N- acrylamides, N, N- acrylamides, NIPA, N- acryloyls
Morpholine etc..They may be used alone, can also be 2 or more kinds in combination.
The ratio that above-mentioned copolymer composition accounts for the whole monomer components for constituting the above-mentioned polymer with reactive group β is preferred
For 5 moles of %~50 mole %, more preferably 20 moles of %~40 mole %.
Above-mentioned surface free energy or adhesive layer surface in the present invention can pass through to the contact angle of diiodomethane or water
Adjust the species and content of ultra-violet solidified polymer and the polymer shared with the polymer and freely control.
Wherein, preferably constituted by adjusting ultra-violet solidified polymer the monomer component with reactive group β,
The species and content ratio of copolymer composition, (methyl) acrylic component of (methyl) alkyl acrylate composition etc etc. is carried out
Control.
For example, (containing for hydroxyl, carboxyl or amino in the reactive group β of the polymer with reactive group β
Amide groups) in the case of, reactive group β can react with the compound with reactive group α and ethylenic unsaturated group,
But make unreacted hydroxyl, carboxyl or amino remaining.Furthermore it is possible to by existing in the polymer with reactive group β
2 kinds of reactivity group base β (for example, carboxyl and hydroxyl), and only make the part (a such as only part for hydroxyl) of one of which with
Reactive group α is reacted, so that the part and the reactive group of another one of the reactive group (hydroxyl) of one
(carboxyl) is remained, control surface free energy or adhesive phase table so as to the species or amount according to the reactive group remained
In face of the contact angle of water.
In this case, the polarity of such as carboxyl is higher than hydroxyl or amino, surface free energy or contact angle can significantly change.
In addition, for example by also including as the association produced by carboxyl, amino (amide-containing) mutual hydrogen bond
Puppet is crosslinked and cohesiveness is also improved, thus can also adjust the contact angle to diiodomethane.
Conversely, in the case where the reactive group β of remaining is mainly hydroxyl, the polarity not up to degree of carboxyl, thus
Influence to the surface free energy or adhesive layer surface of adhesive layer surface to the contact angle of water is small, but due to being hardly formed
By hydroxyl produced pseudo- crosslinking each other, thus can in the case where having little influence on the contact angle to diiodomethane adjustment table
Face free energy.
Have it should be noted that the reactive group β remained in ultra-violet solidified polymer amount is also depended on
The blend amount of reactive group α compound, can also be adjusted according to the species and blend amount of aftermentioned crosslinking agent.That is,
The surface free energy of adhesive layer surface can be adjusted by crosslinking agent.
In the present invention, relative to the above-mentioned mass parts of (methyl) acrylate copolymer 100, the preferably mass of mixture crosslinking agent 0.1
Part~5 mass parts.
For the polar component of the surface free energy that controls adhesive phase, contained by the preferred adhesive phase of adhesive tape of the invention
Ultra-violet solidified polymer include hydroxyl, hydroxyl and carboxyl or hydroxyl and amino (amide-containing).Wherein, preferably comprise
Hydroxyl and carboxyl.
The hydroxyl value for constituting the polymer of adhesive layer surface is preferably 5mgKOH/g~100mgKOH/g, is more preferably
10mgKOH/g~100mgKOH/g, more preferably 20mgKOH/g~100mgKOH/g, particularly preferably 30mgKOH/g~
100mgKOH/g.By being set in the range of this, cohesiveness or the residual hydroxyl by being not involved in crosslinking can be controlled by crosslinking agent
Base carrys out control surface free energy.In addition, constitute adhesive layer surface polymer acid number be preferably 0mgKOH/g~
70mgKOH/g, more preferably 5mgKOH/g~65mgKOH/g, more preferably 10mgKOH/g~65mgKOH/g or
5mgKOH/g~35mgKOH/g, particularly preferably 10mgKOH/g~35mgKOH/g, most preferably 15mgKOH/g~
35mgKOH/g.Wherein, the hydroxyl value for preferably comprising the polymer of adhesive layer surface is 10mgKOH/g~100mgKOH/g and acid
It is worth for 5mgKOH/g~65mgKOH/g, the hydroxyl value of more preferably polymer is 20mgKOH/g~100mgKOH/g and acid number is
10mgKOH/g~65mgKOH/g, the hydroxyl value of further preferred polymer is 30mgKOH/g~100mgKOH/g and acid number is
10mgKOH/g~35mgKOH/g, the hydroxyl value of particularly preferred polymer is 30mgKOH/g~100mgKOH/g and acid number is
15mgKOH/g~35mgKOH/g.It should be noted that in the present invention, polymer hydroxyl value for 30mgKOH/g~
In the case of 100mgKOH/g, the acid number of polymer is 5mgKOH/g~65mgKOH/g (preferably 5mgKOH/g~35mgKOH/
G) it is also preferred mode.In addition, the acidic group preferably carboxyl mainly having in the polymer of composition adhesive layer surface.
Above-mentioned acid number is the polymer using ultraviolet pre-irradiation (before solidification) as sample and according to JIS K5601-2-1:
1999 acid numbers determined.In addition, hydroxyl value is the hydroxyl value determined according to JIS K 0070.
It should be noted that in this specification, " hydroxyl value " be the polymer of ultraviolet pre-irradiation (before solidification) solid into
The hydroxyl value divided, i.e., obtain the hydroxyl value obtained by the hydroxyl required for being acylated using KOH；" acid number " be ultraviolet pre-irradiation (Gu
Before change) polymer solid constituent acid number, i.e., by the use of as required by the KOH for neutralizing the alkali required for the acidic-group such as carboxyl
The acid number gone out.
In above-mentioned adhesive phase the weight average molecular weight of ultra-violet solidified polymer used be 10000~2000000, it is excellent
Elect 50000~2000000 as, in addition, in the case where the polymer and other polymer are shared, the polymerization preferably shared
The weight average molecular weight of thing is also within the above range.
If the weight average molecular weight of polymer used is excessive in above-mentioned adhesive phase, polymerization is difficult, abbe number is uprised,
So as to the polymer containing low molecule amount, thus cohesiveness is possible to step-down.On the other hand, if molecular weight is too small, polymer
The cohesiveness meeting step-down of itself, thus easily become cull Producing reason.In the adhesive tape of the present invention, used in adhesive phase
The weight average molecular weight of polymer is preferably 200000~800000.
Weight average molecular weight is calculated as follows：By gel permeation chromatography, (Waters societies manufacture, the name of an article：150-C ALC/
GPC) to being dissolved in tetrahydrofuran obtained from 1% solution be measured, the value determined is converted as polystyrene
Weight average molecular weight and calculate.
(Photoepolymerizationinitiater initiater)
The adhesive phase of the present invention particularly preferably contains Photoepolymerizationinitiater initiater.Triggered by the photopolymerization for adjusting adhesive phase
The blend amount of agent, can control the bonding force after crosslinking.As such Photoepolymerizationinitiater initiater, specifically, benzene can be enumerated
Acyloin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzyldiphenyl thioether, tetramethylthiuram monosulfide, idol
Nitrogen bis-isobutyronitrile, two benzils, diacetyl, β-chloroanthraquinone etc..Photoepolymerizationinitiater initiater is generally with relative to ethylenic insatiable hunger
With the polymer of group and the mass parts of total amount 100 of the compound with ethylenic unsaturated group are the matter of 0.1 mass parts~10
The ratio of amount part is used.By the ultra-violet solidified adhesive phase irradiation ultraviolet radiation to being thusly-formed, it can be greatly reduced
Bonding force, easily can peel off the adhesive tape from clung body.
(crosslinking agent)
In the present invention, crosslinking agent is preferably comprised in adhesive phase.It is used as the reactive group of the crosslinkable groups of crosslinking agent
The crosslinking agent preferably reacted with the reactive group β of the polymer with reactive group β.
For example, in the case where the reactive group β of the resin with reactive group β is carboxyl or hydroxyl, being used as friendship
The reactive group for joining the crosslinkable groups of agent is preferably acid anhydrides, NCO, epoxy radicals, the halogen atom of ring-type, more preferably
For NCO or epoxy radicals.
By using such crosslinking agent, the anti-of the polymer with reactive group β can be adjusted according to its blend amount
Answering property group β remaining quantity, can be by surface free energy control in desired scope.
In addition, by using crosslinking agent, the cohesiveness of adhesive phase can also be controlled.
As the crosslinking agent for being preferred for above-mentioned adhesive phase, polyhydric isocyanate compound, polynary epoxy can be enumerated
Compound, polynary nitrogen heterocycle propane compound, chelate compound etc.., specifically, can be with as polyhydric isocyanate compound
Enumerate toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, IPDI
With their addition product type etc..
As polynary epoxide, ethylene glycol diglycidylether, terephthalic acid diglycidyl ester can be enumerated
Acrylate etc..Polynary nitrogen heterocycle propane compound can enumerate three -2,4,6- (1- '-aziridinos) -1,3,5- triazines, three [1-
(2- methyl)-'-aziridino] phosphine oxide, six [1- (2- methyl)-'-aziridino] triphosphoric acid triazines etc..In addition, as sequestration
Compound, can enumerate ethyl acetoacetate aluminum-diisopropoxide, three (ethyl acetoacetate) aluminium etc..
Alternatively, it is also possible to which there is at least two above ethylenic not using intramolecular in adhesive used in the present invention
The crosslinking agent of saturated group, the crosslinking agent for preferably using oligomer or polymer, crosslinking agent are itself served as ultra-violet solidified
Resin.
There is the low molecular compound of at least two above ethylenic unsaturated group as intramolecular, for example, can enumerate
Trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, pentaerythrite 4 third
Olefin(e) acid ester, dipentaerythritol monohydroxypentaacryande, dipentaerythritol acrylate, 1,4 butanediol diacrylate,
1,6 hexanediyl esters, polyethyleneglycol diacrylate, oligoester acrylate etc..
In addition, urethane acrylate oligomer can also be used, specifically, can be extensively using making tool
There is (methyl) acrylate of hydroxyl (for example, (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, poly- second
Glycol (methyl) acrylate) with terminal isocyanate carbamate prepolymer reaction obtained from material, the terminal isocyanate
Acid esters carbamate prepolymer is to make the polyol compound and polyhydric isocyanate compound (example of polyester-type or polyether-type etc.
Such as, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, 1,3- XDIs, Isosorbide-5-Nitrae-benzene two are sub-
Methyl diisocyanate, diphenyl methane 4,4- diisocyanate etc.) reaction obtained from.
Relative to the mass parts of polymer 100 for constituting adhesive phase, the content of crosslinking agent is preferably 0.1 mass parts~5.0
Mass parts, the more preferably mass parts of 0.5 mass parts~4.0.
(additive)
In the present invention, in addition to those specified above, adhesive phase can also contain additive.
As such additive, such as, as preventing from soaking or improving the additive of sliding, it can enumerate poly-
Silicone acrylate (for example, silicone diacrylate, the acrylate of polysiloxanes six), ultraviolet curing accelerator.
In addition, as the additive, the amino acrylates as water-proofing agent can also be included.In addition, as the additive, can also
Include plasticizer.The surfactant used during alternatively, it is also possible to included in the polymerization of polymer.
(storage modulus)
The storage modulus of adhesive or adhesive phase to the present invention is not particularly limited, if in view of cull or to bumps
The tracing ability of shape, then the storage modulus of preferred ultraviolet pre-irradiation be 30000Pa~75000Pa, more preferably 35000Pa~
60000Pa.(it is 500mJ/cm according to accumulative exposure after the solidification that ultraviolet irradiates2Mode to adhesive phase integrally according to
Penetrate ultraviolet and make after it solidifies) the storage modulus of adhesive be preferably more than 100000Pa.
In the adhesive tape of the present invention, as described above, adhesive phase can form to constitute two or more different adhesive laminations
Sandwich construction.In the case where adhesive phase is sandwich construction, the composition at least making the layer on the surface of composition adhesive phase is
The composition of above-mentioned adhesive phase (i.e. as the mode illustrated by the composition of the adhesive phase of single layer structure).Additionally, it is preferred that multilayer
All adhesive phases of structure are the composition of above-mentioned adhesive phase (i.e. as illustrated by the composition of the adhesive phase of single layer structure
Mode).
(thickness of adhesive phase)
The thickness of adhesive phase is not particularly limited, preferably 10 μm~300 μm, more preferably 30 μm~200 μm, enter
One step is preferably 40 μm~200 μm.
In addition, adhesive phase can be arranged on the two sides of base material film according to purpose.
In order to form adhesive phase on base material film, as set forth above, it is possible to by conventional method at least single of base material film
At least one adhesive of face coating.
(other layers)
In the present invention, the intermediate layers such as priming coat can be arranged as required between base material film and adhesive phase.
<Release liner>
The adhesive tape of the present invention can have release liner over the binder layer.As release liner, it is stripped using through silicone
Polyethylene terephthalate film of processing etc..Alternatively, it is also possible to be stripped poly- the third of processing using without silicone as needed
Alkene film etc..
<Base material film>
As the material of base material film used in the present invention, to protect semiconductor wafer from carrying out grinding to the back side
When by impact be main purpose, water is cleaned etc. has water resistance and retentivity with processing component especially important.As
Such base material film, for example, can enumerate the base material film described in Japanese Unexamined Patent Publication 2004-186429 publications.
It should be noted that the base material film used in the present invention can use base material film used generally in adhesive tape, example
Polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, vinyl-vinyl acetate copolymer, ethene-the third can such as be enumerated
It is the homopolymer or copolymer of the alpha-olefins such as olefin(e) acid ester copolymer, ionomer, polyethylene terephthalate, makrolon, poly-
The thermoplastic elastomer (TPE)s such as the engineering plastics such as methyl methacrylate, polyurethane, styrene-ethylene-butadiene or amylene based copolymer,
Can also be two or more base material film mixed or the base material film of multiple stratification in the group selected from these.
Among these, optimal ethylene-vinyl acetate copolymer, vinyl-acrylate copolymer, amino first in the present invention
The copolymer of acid esters acrylate oligomer and isobornyl acrylate.It should be noted that urethane acrylate is low
The copolymer of polymers and isobornyl acrylate can be using the Photoepolymerizationinitiater initiater illustrated within the adhesive layer come to amino first
Acid esters acrylate oligomer and isobornyl acrylate are manufactured.
In addition, the base material film of the preferred visible light permeability of base material film, the base material film of further preferred ultraviolet permeability.Separately
Outside, the thickness of base material film is not particularly limited, preferably 50 μm~500 μm.If the thickness of base material film is less than 50 μm, enter
Thickness and precision is easily deteriorated during row manufacture, and rigidity is low, thus the retentivity shortcoming of chip, and conveying mistake is caused sometimes.
Conversely, if the thickness of base material film is more than 500 μm, cause conveying mistake because the warpage after grinding becomes greatly, or because rigidity is too strong
And adhesive tape can not be made.The thickness of base material film is more preferably 80 μm~300 μm, more preferably 100 μm~300 μm.
And then, as base material film, can also use adhesive carry out ultraviolet curing and membranization into base material film.For example
It can use by the base material film manufactured by the method for Japanese Unexamined Patent Publication 11-343469 publications etc..
<<The processing method of semiconductor wafer and semiconductor wafer>>
The semiconductor wafer of the adhesive tape of the application present invention is not particularly limited, the semiconductor of all modes is can apply to
Chip.
The processing method of the semiconductor wafer of the adhesive tape of the present invention has been used (to be hereinafter referred to " processing side of the invention
Method ") at least include following processes (A)~(D).
(A) in the process of the surface laminating of semiconductor wafer adhesive tape of the invention；
(B) to the surface (back side of chip) with the binding face opposite side of the adhesive tape of the present invention of above-mentioned semiconductor wafer
The process being ground；
(C) radioactive ray are irradiated to the adhesive tape of the present invention and makes the process of the adhesive tape solidification of the present invention；
(D) process that the adhesive tape of the present invention is peeled off from above-mentioned semiconductor wafer.
The radioactive ray of irradiation refer to the ionization of the light or electron ray of ultraviolet etc etc in above-mentioned operation (C)
Radioactive ray.The radioactive ray of irradiation are preferably ultraviolet in above-mentioned operation (C).The accumulative irradiation of radioactive ray in above-mentioned operation (C)
Amount is preferably 300mJ/cm2~1000mJ/cm2Left and right.
The adhesive tape of the present invention is also suitable for the surface for the semiconductor wafer for having insulating barrier as the binding face in the adhesive tape
Protection band.That is, even if there is the insulating barrier for including polyimide resin etc. in semiconductor wafer surface, it can also take into account good
Adaptation and good fissility.
Even if in addition, the binding face in adhesive tape has the projections such as electrode, good adaptation can also be taken into account and good
Fissility.Even if for example, the height of the projection such as electrode is more than 15 μm and then is more than 50 μm, can also take into account good close
Conjunction property and good fissility.From practicality, the height of above-mentioned projection is less than 300 μm.
In addition, the thickness that thin film semiconductor's chip that the back side is ground has been carried out by the processing method of the present invention is preferably
20 μm~500 μm, more preferably 50 μm~200 μm.
By using the processing method of the present invention, thin film semiconductor's chip can be obtained with high finished product rate.That is, it is of the invention
The processing method of semiconductor wafer is suitably as the manufacture method of thin film semiconductor's chip.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiments.
Embodiment 1
Urethane acrylate system oligomer (the Xin Zhong villages chemical industry strain formula meeting that mixture weight average molecular weight is 3500
Society manufacture) 50 mass parts, the mass parts of isobornyl acrylate 50, Irgacure184 (the BASF societies systems as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain ultraviolet-curing resin composition., will be resulting by pond mould (fountain die) mode
PET film (the Dongli Ltd. that ultraviolet-curing resin composition is applied to as cast donor sheets using 270 μm of thickness
Manufacture：38 μm of thickness) on, form resin composition layer.Just after coating, the further lamination identical on resin composition layer
PET film, afterwards using high-pressure sodium lamp (160W/cm, height 10cm) with light quantity 500mJ/cm2Condition carry out ultraviolet irradiation,
Thus make resin composition layer crosslinked/cured, obtain the base material film that thickness is 270 μm.
Mixture methacrylic acid 1.5mol%, acrylic acid-2-ethyl caproite 64mol%, acrylic acid -2- hydroxyl ethyl esters
34.5mol%, is polymerize in the solution, so as to obtain polymer solution.In the solution, relative to the mass of polymer 100
The mass parts of part mixing isocyanic acid 2- methacryloyloxyethyls 18 (Showa Denko K. K's manufacture, Karenz MOI), to
Hydroxyl imports ethylenic unsaturated group, thus synthesizes the acrylic copolymer polymer (weight containing ethylenic unsaturated group
Average molecular weight：400000；Hydroxyl value 99.1mgKOH/g；Acid number 10.5mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONET L
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 2.5 mass parts, (the BASF societies systems of Irgacure 184 as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 40 μm, adhesive composition is applied to by lamination in above-mentioned two sides
On the above-mentioned base material film that PET film is peeled off, fitted with transparent release liner (50 μm of thickness), so as to obtain the glue of 310 μm of thickness
Band.
<Embodiment 2>
Mixture methacrylic acid 2.0mol%, acrylic acid-2-ethyl caproite 70mol%, acrylic acid -2- hydroxyl ethyl esters
28mol% is polymerize in the solution, so as to obtain polymer solution.In the solution, it is mixed relative to the mass parts of polymer 100
The mass parts of isocyanic acid 2- methacryloyloxyethyls 10 (Showa Denko K. K's manufacture, Karenz MOI) are closed, to hydroxyl
Ethylenic unsaturated group is imported, the acrylic copolymer polymer containing ethylenic unsaturated group is thus synthesized and (divides equally again
Son amount：500000, hydroxyl value 50.8mgKOH/g, acid number 10.5mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONET L
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 0.5 mass parts, (the BASF societies systems of Irgacure 184 as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
Pad on (50 μm of thickness), fitted with 100 μm ethane-acetic acid ethyenyl ester (EVA) film of thickness, so as to obtain 230 μm of thickness
Adhesive tape.
<Embodiment 3>
Mixture methacrylic acid 4.0mol%, acrylic acid-2-ethyl caproite 76mol%, acrylic acid -2- hydroxyl ethyl esters
20mol%, is polymerize in the solution, so as to obtain polymer solution.In the solution, relative to the mass parts of polymer 100
The mass parts of isocyanic acid 2- acryloyloxyethyl esters 10 (Showa Denko K. K's manufacture, Karenz AOI) are mixed, are led to hydroxyl
Enter ethylenic unsaturated group, thus synthesize the acrylic copolymer polymer (Weight-average molecular containing ethylenic unsaturated group
Amount：350000, hydroxyl value 33.8mgKOH/g, acid number 19.9mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONET L
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 1.5 mass parts and TETRAD-X (Mitsubishi Gas Chemical Co., Ltd's manufacture) 0.3
Mass parts, Irgacure 651 (manufacture of BASF societies) 5.0 mass parts as Photoepolymerizationinitiater initiater, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm low density polyethylene (LDPE) (LDPE) film of the adhesive phase formed and thickness is fitted, so as to obtain thickness
230 μm of adhesive tape.
<Embodiment 4>
Mixture methacrylic acid 6.0mol%, ethyl acrylate 74mol%, acrylic acid -2- hydroxyl ethyl ester 20mol%, molten
It is polymerize in liquid, so as to obtain polymer solution.In the solution, relative to the mass parts of polymer 100 mixing isocyanic acid 2-
The mass parts of methacryloyloxyethyl 10 (Showa Denko K. K's manufacture, Karenz MOI), ethylenic is imported to hydroxyl
Unsaturated group, thus synthesizes the acrylic copolymer polymer (weight average molecular weight containing ethylenic unsaturated group：700000,
Hydroxyl value 33.7mgKOH/g, acid number 33.1mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONETL
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 0.9 mass parts, the EsacureKIP-150 as Photoepolymerizationinitiater initiater
(manufacture of Lamberte societies) 5.0 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
Pad on (50 μm of thickness), fitted with 100 μm of EVA film of thickness, so as to obtain the adhesive tape of 230 μm of thickness.
<Embodiment 5>
Mixture methacrylic acid 1.0mol%, acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters
21mol%, is polymerize in the solution, so as to obtain polymer solution.In the solution, relative to the mass parts of polymer 100
The mass parts of isocyanic acid 2- methacryloyloxyethyls 10 (Showa Denko K. K's manufacture, Karenz MOI) are mixed, to hydroxyl
Base imports ethylenic unsaturated group, and thus synthesizing the acrylic copolymer polymer containing ethylenic unsaturated group, (weight is equal
Molecular weight：750000, hydroxyl value 33.7mgKOH/g, acid number 5.6mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONETL
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 2.0 mass parts, the EsacureKIP-150 as Photoepolymerizationinitiater initiater
(manufacture of Lamberte societies) 5.0 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 150 μm, resulting adhesive composition is applied to transparent stripping
Pad on (50 μm of thickness), fitted with 80 μm polypropylene (PP) film of thickness, so as to obtain the adhesive tape of 230 μm of thickness.
<Embodiment 6>
Mixture methacrylic acid 1.0mol%, acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters
21mol%, is polymerize in the solution, so as to obtain polymer solution.In the solution, relative to the mass parts of polymer 100
The mass parts of isocyanic acid 2- methacryloyloxyethyls 6 (Showa Denko K. K's manufacture, Karenz MOI) are mixed, to hydroxyl
Ethylenic unsaturated group is imported, the acrylic copolymer polymer containing ethylenic unsaturated group is thus synthesized and (divides equally again
Son amount：600000, hydroxyl value 55.6mgKOH/g, acid number 5.9mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONETL
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 0.5 mass parts, the EsacureKIP-150 as Photoepolymerizationinitiater initiater
(manufacture of Lamberte societies) 5.0 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 150 μm, resulting adhesive composition is applied to transparent stripping
Pad on (50 μm of thickness), fitted with 150 μm of EVA film of thickness, so as to obtain the adhesive tape of 300 μm of thickness.
<Comparative example 1>
Mixture acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters 21mol%, methacrylic acid 1mol%,
It is polymerize in the solution, so as to obtain the polymer solution that weight average molecular weight is 700,000.In the solution, relative to the polymer
100 mass parts mixing isocyanic acid 2- methacryloyloxyethyls 10 mass parts (Showa Denko K. K's manufacture, Karenz
MOI), ethylenic unsaturated group is imported to hydroxyl, thus synthesizes the acrylic copolymer containing ethylenic unsaturated group and gather
Compound (weight average molecular weight：600000, hydroxyl value 50.1mgKOH/g, acid number 6.1mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONET L
(manufacture of Japanese polyurethane industry society) 1.5 mass parts, the Irgacure 184 (manufacture of BASF societies) 3.0 as Photoepolymerizationinitiater initiater
Mass parts, Ebecryl 350 (manufacture of DAICEL-ALLNEX societies) 0.3 mass parts as additive, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of EVA film of the adhesive phase formed and thickness is fitted, so as to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 2>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 30mol%, acrylic acid -2- hydroxyl ethyl esters
10mol%, methyl acrylate 40mol%, are polymerize in the solution, so that it is molten to obtain the polymer that weight average molecular weight is 600,000
Liquid.The hydroxyl value of the polymer is that 28.1mgKOH/g, acid number are 60.8mgKOH/g.
In the polymer solution, relative to the mass parts of polymer 100, mixture is used as the 6 of ultraviolet reaction resin
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of Xin Zhong villages) 100 mass parts of function and 3 functions
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of Xin Zhong villages) 50 mass parts, it is used as crosslinking agent
CORONET L (Nippon Polyurethane Industry Co., Ltd.'s manufacture) 4.0 mass parts, the Irgacure 184 as Photoepolymerizationinitiater initiater
(manufacture of BASF societies) 10 mass parts, Ebecryl350 (manufacture of DAICEL-ALLNEX Co., Ltd.) 0.5 mass as additive
Part, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm LDPE (low density polyethylene (LDPE)) film of the adhesive phase formed and thickness is fitted, so as to obtain thickness
230 μm of adhesive tape.
<Comparative example 3>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 30mol%, acrylic acid -2- hydroxyl ethyl esters
10mol%, methyl acrylate 40mol%, are polymerize in the solution, so that it is molten to obtain the polymer that weight average molecular weight is 600,000
Liquid.The hydroxyl value of the polymer is that 33.5mgKOH/g, acid number are 48.6mgKOH/g.
In the polymer solution, relative to the mass parts of polymer 100, mixture is used as the 5 of ultraviolet reaction resin
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of Xin Zhong villages) 100 mass parts of function and 3 functions
The carbamic acid of urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of Xin Zhong villages) 10 mass parts and 2 functions
Ester acrylate oligomer (manufacture of chemical industry Co., Ltd. of Xin Zhong villages) 30 mass parts, the CORONET L (days as crosslinking agent
This polyurethane industrial Co., Ltd. manufacture) 4.0 mass parts, the Irgacure 184 (manufacture of BASF societies) as Photoepolymerizationinitiater initiater
5 mass parts, Ebecryl 350 (manufacture of DAICEL-ALLNEX Co., Ltd.) 0.5 mass parts as additive, are bonded
Agent composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of LDPE films of the adhesive phase formed and thickness are fitted, so as to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 4>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 35mol%, acrylic acid -2- hydroxyl ethyl esters 5mol%,
Methyl acrylate 40mol%, is polymerize in the solution, so as to obtain the polymer solution that weight average molecular weight is 200,000.This gathers
The hydroxyl value of compound is that 5.5mgKOH/g, acid number are 60.8mgKOH/g.
In the polymer solution, relative to the mass parts of polymer 100, mixture is used as the 6 of ultraviolet reaction resin
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of Xin Zhong villages) 80 mass parts and the ammonia of 2 functions of function
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of Xin Zhong villages) 20 mass parts, it is used as crosslinking agent
CORONET L (Nippon Polyurethane Industry Co., Ltd.'s manufacture) 4.0 mass parts, the Irgacure 184 as Photoepolymerizationinitiater initiater
(manufacture of BASF societies) 2.5 mass parts, Ebecryl350 (manufacture of DAICEL-ALLNEX Co., Ltd.) 0.5 matter as additive
Part is measured, adhesive composition is obtained.
In the way of the thickness of adhesive is 150 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of LDPE films of the adhesive phase formed and thickness are fitted, so as to obtain the adhesive tape of 250 μm of thickness.
<Comparative example 5>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 60mol%, methyl acrylate 20mol%, molten
It is polymerize in liquid, so as to obtain the polymer solution that weight average molecular weight is 400,000.The hydroxyl value of the polymer is 0mgKOH/g, acid
It is worth for 48.8mgKOH/g.
In the polymer solution, relative to the mass parts of polymer 100, mixture as crosslinking agent CORONET L (days
This polyurethane industrial Co., Ltd. manufacture) 1.0 mass parts, TETRAD-X (Mitsubishi Gas Chemical Co., Ltd's manufacture) 1.0 mass
Part, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of LDPE films of the adhesive phase formed and thickness are fitted, so as to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 6>
Mixture acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters 21mol%, methacrylic acid 1mol%,
It is polymerize in the solution, so as to obtain the polymer solution that weight average molecular weight is 700,000.In the solution, relative to the polymer
100 mass parts mixing isocyanic acid 2- methacryloyloxyethyls 5.0 mass parts (Showa Denko K. K's manufacture, Karenz
MOI), ethylenic unsaturated group is imported to hydroxyl, thus synthesizes the acrylic copolymer containing ethylenic unsaturated group and gather
Compound (weight average molecular weight：700000, hydroxyl value 38.0mgKOH/g, acid number 6.5mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONET L
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 1.0 mass parts, TETRAD-X (Mitsubishi Gas Chemical Co., Ltd's manufacture) 0.5 matter
Part, Irgacure 184 (manufacture of BASF societies) 5.0 mass parts as Photoepolymerizationinitiater initiater are measured, adhesive composition is obtained.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of EVA film of the adhesive phase formed and thickness is fitted, so as to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 7>
Using the mass parts of acrylic acid-2-ethyl caproite 95, the mass parts of acrylic acid -2- hydroxyl ethyl esters 5, it is used as optical free radical initiator
Irgacure 651 (BASF societies manufacture, 50% ethyl acetate solution) 0.2 mass parts and the mass parts of lauryl mercaptan 0.01 it is molten
Solution obtains solution in ethyl acetate.The solution irradiation ultraviolet radiation is polymerize, the ethyl acetate for obtaining polymer is molten
Liquid.And then, the mass parts of solid constituent 100 relative to the solution make isocyanic acid 2- methacryloyloxyethyl (Showa electricians
Co., Ltd.'s manufacture, Karenz MOI) 3.5 mass parts are reacted, and it is that 700,000, hydroxyl value is to have synthesized weight average molecular weight
11.1mgKOH/g, acid number are handed over for 0.9mgKOH/g's as (methyl) acrylic resin for containing ethylenic unsaturated group
Conjuncted acrylic copolymer.
Mixture is used as Photoepolymerizationinitiater initiater in the acrylic copolymer polymer of the unsaturated group containing ethylenic
(manufacture of BASF societies) 1.0 mass parts of Irgacure 184 and the U-324A (in new as urethane acrylate oligomer
Chemical industry Co., Ltd. of village manufactures) 2.0 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of EVA film of the adhesive phase formed and thickness is fitted, so as to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 8>
Using the mass parts of acrylic acid-2-ethyl caproite 95, the mass parts of acrylic acid -2- hydroxyl ethyl esters 5, it is used as optical free radical initiator
Irgacure 651 (BASF societies manufacture, 50% ethyl acetate solution) 0.2 mass parts and the mass parts of lauryl mercaptan 0.01
It is dissolved in ethyl acetate, obtains solution.The solution irradiation ultraviolet radiation is polymerize, the ethyl acetate for obtaining polymer is molten
Liquid.And then, the mass parts of solid constituent 100 relative to the solution make isocyanic acid 2- methacryloyloxyethyl (Showa electricians
Co., Ltd.'s manufacture, Karenz MOI) 3.5 mass parts are reacted, and it is that 700,000, hydroxyl value is to have synthesized weight average molecular weight
12.2mgKOH/g, acid number are handed over for 0.9mgKOH/g's as (methyl) acrylic resin for containing ethylenic unsaturated group
Conjuncted acrylic copolymer.
Mixture is used as Photoepolymerizationinitiater initiater in the acrylic copolymer polymer of the unsaturated group containing ethylenic
Irgacure 184 (manufacture of BASF societies) 1.0 mass parts, U-324A (the Xin Zhong villages as urethane acrylate oligomer
Chemical industry Co., Ltd. manufactures) 2.0 mass parts and SE4050 (Co., Ltd. Admatechs manufactures) 150 matter as filler
Part is measured, adhesive composition is obtained.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of EVA film of the adhesive phase formed and thickness is fitted, so as to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 9>
Mixture methacrylic acid 2.0mol%, acrylic acid-2-ethyl caproite 71mol%, acrylic acid -2- hydroxyl ethyl esters
27mol%, is polymerize in the solution, so as to obtain the polymer solution that weight average molecular weight is 200,000.In the solution, relative to
The mass parts of the mass parts of polymer 100 mixing isocyanic acid 2- acryloyloxyethyl esters 20 (Showa Denko K. K's manufacture,
Karenz AOI), ethylenic unsaturated group is imported to hydroxyl, the acrylic acid containing ethylenic unsaturated group is thus synthesized and is total to
Polymerized polymers (weight average molecular weight：300000, hydroxyl value 12.3mgKOH/g, acid number 7.8mgKOH/g).
In the acrylic copolymer polymer of the unsaturated group containing ethylenic mixture as crosslinking agent CORONET L
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 1.5 mass parts, (the BASF societies systems of Irgacure 184 as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 150 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of LDPE films of the adhesive phase formed and thickness are fitted, so as to obtain the adhesive tape of 250 μm of thickness.
<Comparative example 10>
Mixture butyl acrylate 96mol%, acrylic acid -2- hydroxyl ethyl ester 4mol%, are polymerize, so as to obtain in the solution
Weight average molecular weight is 700,000 polymer solution.The hydroxyl value of the polymer is that 16.7mgKOH/g, acid number are 0mgKOH/g.
In the polymer solution, relative to the mass parts of polymer 100, mixture as crosslinking agent CORONET L (days
This polyurethane industrial Co., Ltd. manufactures) 2.5 mass parts, obtain adhesive composition.
In the way of the thickness of adhesive is 130 μm, resulting adhesive composition is applied to transparent stripping
On pad, 100 μm of LDPE films of the adhesive phase formed and thickness are fitted, so as to obtain the adhesive tape of 230 μm of thickness.
Following experiment is carried out for the adhesive tape made in above-described embodiment and comparative example, its performance is evaluated.Evaluation result
It is recorded in table 1 below and 2.
<Measure/analysis>
The measure of contact angle and the calculating of surface free energy：
The face for being not provided with adhesive phase of base material film is fixed to the flat chip in surface using two-sided tape.
Thereafter, release liner is peeled off, diiodomethane and pure water is added dropwise to mutually different position over the binder layer,
The FACE contact angle meter CA-S150 types manufactured using Kyowa Chemical Industry Co., Ltd are measured to each contact angle θ.
Then, it is sharp in order to determine the adhesive phase for irradiating and solidifying through ultraviolet to diiodomethane and the contact angle of pure water
Adhesive tape is fixed to the flat chip in surface with method same as described above.Then, entered using high-pressure sodium lamp from release liner side
Row ultraviolet irradiates, and accumulative exposure is reached 500mJ/cm2.After ultraviolet irradiation, place 1 hour, thereafter by release liner
Peel off, and diiodomethane and pure water are added dropwise to mutually different position, manufactured using Kyowa Chemical Industry Co., Ltd
FACE contact angle meter CA-S150 types are measured to each contact angle θ.
Contact angle θ obtained above value is substituted into above-mentioned<Formula 1>Simultaneous equations, calculate adhesive layer surface
Surface free energy.
Hydroxyl value：
It is measured according to JIS K 0070.
Acid number：
According to JIS K5601-2-1:1999 are measured.
<Test example 1>The evaluation of marginal swell
The DR8500III (trade name) manufactured using Dong Jing machines society, on 725 μm of thickness, the silicon wafer of 8 inches of diameter
Form thick about 10 μm of polyimide film [HD-8820 (trade name, the manufacture of HD MicroSystems Co., Ltd.)], using by
O2The etching that plasma is carried out is cleaned to wafer surface.By the adhesive tape gluing made in above-described embodiment and comparative example extremely
The chip with polyimides.Thereafter, using the grinder [DFG8760 of Co., Ltd. DISCO manufactures with Xian Nei mechanisms
(trade name)] be ground to thickness for 250 μm.25 operations are implemented to each adhesive tape.By the wafer storage after grinding defeated
In the box sent, lid is closed, visually the protuberance at observation edge.
(edge part protuberance metewand)
A：25 wholes can't see protuberance
B：It was observed that protuberance for less than 12
C：It was observed that protuberance for more than 13
<Test example 2>Fissility is tested
The fissility experiment of the chip of bumpless：
By the adhesive tape gluing made in embodiment and comparative example to the band utilized with the preparation of the above-mentioned identical method of test example 1
The surface of the chip of polyimides.Thereafter, using the grinder [DFG8760 of Co., Ltd. DISCO manufactures with Xian Nei mechanisms
(trade name)] be ground to thickness for 75 μm, use chip mounter RAD2700 (trade name, Lintec plant with Xian Nei mechanisms
Formula commercial firm manufactures) adhesive tape is peeled off from the chip after grinding.Herein, the adhesive tape for applying the comparative example 5 of Pressuresensitive Adhesive enters
Gone 50 DEG C heating peel off.In addition, applying the embodiment 1~6 of ultraviolet-curing adhesive, comparative example 1~4,6~10
Adhesive tape using high-pressure sodium lamp to add up exposure as 500mJ/cm2Mode irradiation ultraviolet radiation after peeled off.
(fissility metewand)
A：Adhesive tape can all be peeled off
B：Peeling-off mistake (heat sealing adhesive bad or adhesive tape cutting) can not peel off
The fissility experiment of bumped wafer：
By the adhesive tape gluing made in above-described embodiment and comparative example to the weldering with 100 μm of height, 200 μm of projection spacing
Expect projection 8 inches of diameter it is with projection silicon wafer and further in 50 μm of height, the copper pillar bumps of 100 μm of projection spacing
The surface of chip with 7 μm of polyimide films [HD-8820 (trade name, the manufacture of HD MicroSystems Co., Ltd.)].
Using the chip identical method with above-mentioned bumpless by the grinding wafer with solder projection to 100 μ m-thicks, by band
The grinding wafer of copper pillar bumps to 50 μ m-thicks, and using with above-mentioned bumpless chip identical method from the chip after grinding by glue
Band is peeled off.
(fissility metewand)
A：Adhesive tape can all be peeled off
B：Peeling-off mistake (because heat sealing adhesive is bad or adhesive tape cutting caused by peel off mistake) or can not peel off
<Test example 3>Cull is evaluated
Using light microscope to having peeled off the chip with solder projection of adhesive tape in above-mentioned test example 2 and convex with copper post
The wafer surface of the chip of block is observed, and the presence or absence of cull is evaluated.
(cull metewand)
A：Without cull
B：Any one of chip with copper pillar bumps or the chip with solder projection have cull
C：Chip with solder projection and the chip with copper pillar bumps have cull
<Test example 4>Fitness test
The DR8500III (trade name) manufactured using Dong Jing machines society, in operating temperature and roll temperature：Normal temperature (23
DEG C), laminate pressure：By the adhesive tape gluing made in above-described embodiment and comparative example to 100 μ of height under conditions of 0.4MPa
M, 8 inches of the diameter of the solder projection of 200 μm of projection the spacing surface with projection silicon wafer.
Adaptation now is confirmed by visual observation, whetheing there is air between investigation adhesive tape and chip is mixed into.
(metewand of adaptation)
A：Also it was mixed into after laminating more than 48 hours without air
B：After laminating more than 24 to 48 hours between have being mixed into for air
C：After firm laminating~there is being mixed into for air between 24 hours
Show the result in table 1 below.
The adhesive tape of comparative example 1~4 is the example of the surface free energy reduction in the adhesive face after ultraviolet (UV) irradiation.If
Using the adhesive tape of comparative example 1~4, then the result for occurring the marginal swell caused by box is stored with high probability can be obtained.And then, than
Compared with being poor result at least one assessment item of the adhesive tape in fissility, cull and adaptation of example 1~4.
The adhesive tape of comparative example 5 and 10 has used Pressuresensitive Adhesive, as a result easily occurs marginal swell (comparative example 5), separately
Outside, substantial amounts of cull (comparative example 5 and 10) is produced when peeling off.
Although the surface free energy that the adhesive tape of comparative example 6~8 is the adhesive face after UV irradiations rises its degree and is less than
The example of scope given to this invention.If using the adhesive tape of comparative example 6~8, obtaining the result that cull occurs after stripping.
And then, the adhesive tape of comparative example 6~8 turns into poor at least one assessment item in marginal swell, fissility and adaptation
As a result.
The surface free energy of the adhesive of the UV pre-irradiations of the adhesive tape of comparative example 9 is less than value given to this invention
Value.Its result：Peeling force from projection chip is not enough, although do not have cull in the chip with solder projection, but with polyamides
The copper pillar bumps chip of imines film has cull.
On the other hand, in the case of using the adhesive tape of embodiment 1~6, all non-flanged is swelled.In addition, even for tool
The surface for having the projection of 100 μm of height also shows that excellent adaptation, even if also unconfirmed to sky more than 48 hours after laminating
Gas is mixed into.And then, when peeling off, adhesive tape will not be cut off, and cull does not also occur.
With reference to embodiments thereof, the present invention is described, but applicants contemplate that, as long as no specifying, then originally
Invention is not limited in any details of explanation, should not violate spirit and scope shown in appended claims
In the case of carry out wide in range explanation.
This application claims the Japanese Patent Application 2014-205465's for carrying out patent submission in Japan based on October 6th, 2014
Priority, by it with reference to this and using its content as this specification contents a part introduce.
Symbol description
10 adhesive tapes
11 base material films
12 adhesive phases
13 semiconductor wafers
Claims (8)
1. a kind of band projection semiconductor wafer surface protection adhesive tape, it is to have ultra-violet solidified bonding on base material film
The band projection semiconductor wafer surface protection adhesive tape of oxidant layer, it is characterised in that
It is less than more than 10,000 200 ten thousand and with the carbon-to-carbon double bond of type containing radiation-curing that the adhesive phase, which contains weight average molecular weight,
(methyl) acrylate copolymer of group, hydroxyl and carboxyl,
The surface free energy of the adhesive layer surface of ultraviolet pre-irradiation be 25.5mN/m less than 35mN/m,
The surface of the adhesive phase after the solidification that ultraviolet irradiates and the surface phase of the adhesive phase of ultraviolet pre-irradiation
High more than the 5mN/m of specific surface free energy,
The surface of the adhesive phase after the solidification that ultraviolet irradiates and the surface phase of the adhesive phase of ultraviolet pre-irradiation
Than, it is small to the contact angle of diiodomethane,
(methyl) acrylate copolymer is made before the importing radiation-curing type carbon-to-carbon double bond group with hydroxyl and carboxyl
Polymer with radiation-curing type carbon-to-carbon double bond group compound reaction obtained from polymer, formed this lead
In the whole monomer components for entering the polymer before radiation-curing type carbon-to-carbon double bond group, (methyl) acrylic acid 1mol% is included
~10mol%,
The hydroxyl value for constituting the polymer of described adhesive layer surface is 30mgKOH/g~100mgKOH/g,
The acid number for constituting the polymer of described adhesive layer surface is 5mgKOH/g~65mgKOH/g.
2. band projection semiconductor wafer surface protection adhesive tape as claimed in claim 1, it is characterised in that described that there is radiation
The compound of line curing type carbon-to-carbon double bond group is isocyanic acid 2- (methyl) acryloyloxyethyl ester.
3. band projection semiconductor wafer surface protection adhesive tape as claimed in claim 2, it is characterised in that relative to described
The mass parts of (methyl) acrylate copolymer 100, the blend amount of isocyanic acid 2- (methyl) acryloyloxyethyl ester is 1 mass parts
~20 mass parts.
4. such as band projection semiconductor wafer surface protection adhesive tape according to any one of claims 1 to 3, it is characterised in that
Relative to the mass parts of (methyl) acrylate copolymer 100, the mass parts of mass parts of mixture crosslinking agent 0.1~5.
5. such as band projection semiconductor wafer surface protection adhesive tape according to any one of claims 1 to 4, it is characterised in that
The acid number for constituting the polymer of described adhesive layer surface is 10mgKOH/g~35mgKOH/g.
6. a kind of processing method with projection semiconductor wafer, it is the band projection any one of usage right requirement 1~5
The processing method with projection semiconductor wafer of semiconductor wafer surface protection adhesive tape, it is characterised in that the processing method bag
Include following processes (A)~(D)：
Process (A), has the surface laminating band projection semiconductor wafer surface of projection in the formation with projection semiconductor wafer
The process of protection adhesive tape；
Process (B), to the projection semiconductor wafer and patch with projection semiconductor wafer surface protection adhesive tape
The process that the surface of conjunction face opposite side is ground；
Process (C), makes the band projection partly lead the band projection semiconductor wafer surface protection with adhesive tape irradiation ultraviolet radiation
The process that body wafer surface protection adhesive tape solidifies；And
Process (D), from described with the projection semiconductor wafer stripping work with projection semiconductor wafer surface protection adhesive tape
Sequence.
7. the processing method as claimed in claim 6 with projection semiconductor wafer, it is characterised in that the band projection semiconductor
Chip has insulating barrier with the binding face with projection semiconductor wafer surface protection adhesive tape.
8. the processing method with projection semiconductor wafer as claimed in claims 6 or 7, it is characterised in that the height of the projection
Spend for more than 15 μm.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014010821 | 2014-01-23 | ||
| JP2014-205465 | 2014-10-06 | ||
| JP2014205465A JP5718515B1 (en) | 2014-01-23 | 2014-10-06 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
| PCT/JP2015/062946 WO2016056269A1 (en) | 2014-01-23 | 2015-04-30 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107075322A true CN107075322A (en) | 2017-08-18 |
| CN107075322B CN107075322B (en) | 2018-09-18 |
Family
ID=53277434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580056130.XA Active CN107075322B (en) | 2014-01-23 | 2015-04-30 | The processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5718515B1 (en) |
| KR (1) | KR101840179B1 (en) |
| CN (1) | CN107075322B (en) |
| TW (1) | TWI573852B (en) |
| WO (1) | WO2016056269A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240869A (en) * | 2018-03-09 | 2019-09-17 | 三菱化学株式会社 | Active energy ray-curable removable adhesive composition and exfoliated bonding sheet |
| CN113272399A (en) * | 2019-04-26 | 2021-08-17 | 积水化学工业株式会社 | Adhesive tape |
| CN113795380A (en) * | 2018-12-25 | 2021-12-14 | 积水化学工业株式会社 | Adhesive tape |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5718515B1 (en) * | 2014-01-23 | 2015-05-13 | 古河電気工業株式会社 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
| JP6382239B2 (en) * | 2016-01-18 | 2018-08-29 | 古河電気工業株式会社 | Adhesive tape for electronic parts |
| JP6382240B2 (en) * | 2016-01-18 | 2018-08-29 | 古河電気工業株式会社 | Adhesive tape for electronic parts |
| JP6904368B2 (en) | 2017-01-23 | 2021-07-14 | 東京エレクトロン株式会社 | Semiconductor substrate processing method and semiconductor substrate processing equipment |
| JP6324573B1 (en) * | 2017-03-31 | 2018-05-16 | 古河電気工業株式会社 | Adhesive composition, method for producing semiconductor wafer surface protective tape using the same, and semiconductor wafer surface protective tape |
| WO2019082959A1 (en) * | 2017-10-27 | 2019-05-02 | リンテック株式会社 | Film for protective film formation use, composite sheet for protective film formation use, and method for manufacturing semiconductor chip |
| JP7079609B2 (en) * | 2018-01-19 | 2022-06-02 | 日東電工株式会社 | Masking tape for forming electromagnetic wave shield |
| KR102228537B1 (en) * | 2018-03-23 | 2021-03-15 | 주식회사 엘지화학 | Back-grinding tape |
| KR102220313B1 (en) | 2018-06-20 | 2021-02-25 | 주식회사 엘지화학 | Adhesieve composition |
| JP2020150196A (en) * | 2019-03-15 | 2020-09-17 | 日東電工株式会社 | Dicing tape with adhesive film |
| WO2020225919A1 (en) * | 2019-05-09 | 2020-11-12 | 昭和電工マテリアルズ株式会社 | Adhesive set, and structure manufacturing method |
| CN114144443B (en) * | 2019-07-02 | 2024-05-14 | 摩根粘合剂有限责任公司 | Method for promoting curing of silicone composition |
| JP6756398B1 (en) * | 2019-10-11 | 2020-09-16 | 住友ベークライト株式会社 | Adhesive tape |
| JP7453831B2 (en) | 2020-03-31 | 2024-03-21 | マクセル株式会社 | Laminated body with self-healing properties, method for manufacturing the same, and method for using the same |
| WO2022201789A1 (en) * | 2021-03-22 | 2022-09-29 | リンテック株式会社 | Semiconductor processing adhesive tape, and method for manufacturing semiconductor device |
| JP7479336B2 (en) | 2021-08-06 | 2024-05-08 | 古河電気工業株式会社 | Semiconductor manufacturing process transport tape |
| CN118176270A (en) * | 2021-11-12 | 2024-06-11 | 电化株式会社 | Adhesive tape and processing method |
| WO2023188714A1 (en) * | 2022-03-31 | 2023-10-05 | デンカ株式会社 | Adhesive tape and processing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102714151A (en) * | 2010-03-31 | 2012-10-03 | 古河电气工业株式会社 | Adhesive sheet for semiconductor wafer processing |
| CN103525324A (en) * | 2012-07-06 | 2014-01-22 | 古河电气工业株式会社 | Adhesive tape for surface protection of a semiconductor wafer and method of producing a semiconductor wafer |
| JP2014175334A (en) * | 2013-03-06 | 2014-09-22 | Furukawa Electric Co Ltd:The | Adhesive tape for semiconductor wafer surface protection |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4251915B2 (en) * | 2003-05-26 | 2009-04-08 | 株式会社巴川製紙所 | Adhesive sheet |
| JP2005235889A (en) * | 2004-02-18 | 2005-09-02 | Furukawa Electric Co Ltd:The | Method for protecting surface of wafer |
| JP5184161B2 (en) * | 2008-03-17 | 2013-04-17 | 古河電気工業株式会社 | Semiconductor processing tape |
| JP4810565B2 (en) * | 2008-11-26 | 2011-11-09 | 日東電工株式会社 | Dicing die-bonding film and method for manufacturing semiconductor device |
| JP2010129700A (en) * | 2008-11-26 | 2010-06-10 | Nitto Denko Corp | Dicing die-bonding film and method for producing semiconductor device |
| JP5566774B2 (en) * | 2010-05-20 | 2014-08-06 | 古河電気工業株式会社 | Radiation curable semiconductor wafer surface protection adhesive tape |
| JP5053455B1 (en) * | 2011-10-28 | 2012-10-17 | 古河電気工業株式会社 | Dicing tape for semiconductor processing |
| JP5653990B2 (en) * | 2012-12-07 | 2015-01-14 | 古河電気工業株式会社 | Manufacturing method of adhesive tape for semiconductor wafer surface protection |
| KR101985049B1 (en) * | 2012-02-17 | 2019-05-31 | 후루카와 덴키 고교 가부시키가이샤 | Semiconductor-wafer-surface-protective adhesive tape |
| JP2013213075A (en) * | 2012-03-30 | 2013-10-17 | Sekisui Chem Co Ltd | Semiconductor processing adhesive tape |
| WO2014080918A1 (en) * | 2012-11-20 | 2014-05-30 | 古河電気工業株式会社 | Method for manufacturing semiconductor chips and surface protective tape for thin-film grinding used in same |
| JP2014141603A (en) * | 2013-01-25 | 2014-08-07 | Toyo Ink Sc Holdings Co Ltd | Adhesive agent composition excellent in dielectric property, adhesive agent sheet using the same and printed wiring board |
| JP2014154704A (en) * | 2013-02-08 | 2014-08-25 | Hitachi Chemical Co Ltd | Dicing/die bonding integrated tape |
| JP5379919B1 (en) * | 2013-02-13 | 2013-12-25 | 古河電気工業株式会社 | Adhesive tape for semiconductor processing |
| JP5718515B1 (en) * | 2014-01-23 | 2015-05-13 | 古河電気工業株式会社 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
| JP5654157B2 (en) * | 2014-04-18 | 2015-01-14 | 古河電気工業株式会社 | Adhesive tape for semiconductor wafer surface protection |
-
2014
- 2014-10-06 JP JP2014205465A patent/JP5718515B1/en active Active
-
2015
- 2015-04-30 TW TW104113815A patent/TWI573852B/en active
- 2015-04-30 WO PCT/JP2015/062946 patent/WO2016056269A1/en active Application Filing
- 2015-04-30 CN CN201580056130.XA patent/CN107075322B/en active Active
- 2015-04-30 KR KR1020177011335A patent/KR101840179B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102714151A (en) * | 2010-03-31 | 2012-10-03 | 古河电气工业株式会社 | Adhesive sheet for semiconductor wafer processing |
| CN103525324A (en) * | 2012-07-06 | 2014-01-22 | 古河电气工业株式会社 | Adhesive tape for surface protection of a semiconductor wafer and method of producing a semiconductor wafer |
| JP2014175334A (en) * | 2013-03-06 | 2014-09-22 | Furukawa Electric Co Ltd:The | Adhesive tape for semiconductor wafer surface protection |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240869A (en) * | 2018-03-09 | 2019-09-17 | 三菱化学株式会社 | Active energy ray-curable removable adhesive composition and exfoliated bonding sheet |
| CN113795380A (en) * | 2018-12-25 | 2021-12-14 | 积水化学工业株式会社 | Adhesive tape |
| CN113795380B (en) * | 2018-12-25 | 2024-05-03 | 积水化学工业株式会社 | Adhesive tape |
| CN113272399A (en) * | 2019-04-26 | 2021-08-17 | 积水化学工业株式会社 | Adhesive tape |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201614022A (en) | 2016-04-16 |
| KR20170055552A (en) | 2017-05-19 |
| WO2016056269A1 (en) | 2016-04-14 |
| JP2015157931A (en) | 2015-09-03 |
| JP5718515B1 (en) | 2015-05-13 |
| TWI573852B (en) | 2017-03-11 |
| CN107075322B (en) | 2018-09-18 |
| KR101840179B1 (en) | 2018-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107075322B (en) | The processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer | |
| KR101722137B1 (en) | Dicing film and dicing die-bonding film | |
| CN108307635B (en) | Adhesive tape for processing workpiece | |
| CN103975421B (en) | Semiconductor wafer adhesive sheet for processing and employ the processing method of semiconductor wafer of this bonding sheet | |
| CN104271694B (en) | Sheet having adhesive resin layer attached thereto, and method for producing semiconductor device | |
| CN104837942B (en) | Holding membrane forming film | |
| CN104541360B (en) | Manufacturing method with protective film cambial cutting sheet and chip | |
| CN104040696A (en) | Dicing sheet with protective film-forming layer, and method for producing chip | |
| CN102337089B (en) | Wafer processing adhesive tape and method for processing semiconductor therewith | |
| CN101638566B (en) | Re-releasable adhesive agent and re-releasable adhesive sheet | |
| CN103525324B (en) | Adhesive tape for surface protection of a semiconductor wafer and method of producing a semiconductor wafer | |
| CN109075055A (en) | The processing method that adhesive tape and semiconductor wafer are used in semiconductor wafer surface protection | |
| CN102971839A (en) | Multilayer adhesive sheet and method for manufacturing electronic component | |
| CN103797567A (en) | Dicing sheet with protective film forming layer and chip fabrication method | |
| CN104937712A (en) | Protective film-forming film and protective film-forming composite sheet | |
| CN101275062A (en) | Adhesive composition, adhesive sheet and production process for semiconductor device | |
| CN110272696A (en) | Grinding back surface adhesive tape | |
| CN103109354A (en) | Method for manufacturing electronic component | |
| CN104160491A (en) | Sheet for forming resin film for chips | |
| CN107112229A (en) | Semiconductor wafer surface protection adhesive tape | |
| KR20130105434A (en) | Adhesive composition, adhesive sheet and method for manufacturing semiconductor device | |
| CN107960131A (en) | The processing method of semiconductor wafer processing adhesive tape and semiconductor wafer | |
| CN105981137B (en) | The manufacturing method of the semiconductor device of protective film and the use protective film | |
| CN106716603A (en) | Adhesive tape for protecting semiconductor wafer surface | |
| KR102407903B1 (en) | Surface protective sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |