CN107001876B - Sheet for forming resin film and composite sheet for forming resin film - Google Patents
Sheet for forming resin film and composite sheet for forming resin film Download PDFInfo
- Publication number
- CN107001876B CN107001876B CN201680003816.7A CN201680003816A CN107001876B CN 107001876 B CN107001876 B CN 107001876B CN 201680003816 A CN201680003816 A CN 201680003816A CN 107001876 B CN107001876 B CN 107001876B
- Authority
- CN
- China
- Prior art keywords
- resin film
- sheet
- forming
- silicon wafer
- forming sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 437
- 239000011347 resin Substances 0.000 title claims abstract description 437
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 113
- 239000010703 silicon Substances 0.000 claims abstract description 113
- 230000003746 surface roughness Effects 0.000 claims abstract description 48
- 239000000945 filler Substances 0.000 claims description 43
- 229920000058 polyacrylate Polymers 0.000 claims description 39
- 229920001187 thermosetting polymer Polymers 0.000 claims description 36
- 230000001681 protective effect Effects 0.000 claims description 29
- 239000000853 adhesive Substances 0.000 claims description 26
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000012790 adhesive layer Substances 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000010030 laminating Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 291
- 150000001875 compounds Chemical class 0.000 description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 45
- -1 2-ethylhexyl Chemical group 0.000 description 30
- 239000004593 Epoxy Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- 239000000178 monomer Substances 0.000 description 26
- 206010040844 Skin exfoliation Diseases 0.000 description 23
- 239000000463 material Substances 0.000 description 21
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 20
- 238000001723 curing Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 14
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- 125000003700 epoxy group Chemical group 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 239000007822 coupling agent Substances 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 239000003086 colorant Substances 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229920006243 acrylic copolymer Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 2
- 238000007648 laser printing Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- CVBWTNHDKVVFMI-LBPRGKRZSA-N (2s)-1-[4-[2-[6-amino-8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]purin-9-yl]ethyl]piperidin-1-yl]-2-hydroxypropan-1-one Chemical compound C1CN(C(=O)[C@@H](O)C)CCC1CCN1C2=NC=NC(N)=C2N=C1SC(C(=C1)Br)=CC2=C1OCO2 CVBWTNHDKVVFMI-LBPRGKRZSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- NWOMMWVCNAOLOG-UHFFFAOYSA-N 1h-imidazol-5-ylmethanediol Chemical compound OC(O)C1=CN=CN1 NWOMMWVCNAOLOG-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-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
- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-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
- 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-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
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
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- 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
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Abstract
The invention provides a resin film forming sheet with excellent re-peeling performance and a composite sheet for forming resin film, which has a structure formed by directly laminating the resin film forming sheet and a support, wherein the resin film forming sheet is a sheet which is pasted on a silicon wafer and is used for forming the resin film on the silicon wafer, and the surface roughness (Ra) of the surface (alpha) of the sheet on the side to be pasted with the silicon wafer is more than 40 nm.
Description
Technical Field
The present invention relates to a sheet for forming a resin film and a composite sheet for forming a resin film.
Background
In recent years, a mounting method called a so-called flip-chip (face down) method has been used to manufacture a semiconductor device. In the flip-chip method, a semiconductor chip (hereinafter, also simply referred to as "chip") having an electrode such as a bump on a circuit surface is used, and the electrode is bonded to a substrate. Therefore, the surface of the chip opposite to the circuit surface (hereinafter also referred to as "the back surface of the chip") may be peeled.
A resin film made of an organic material is formed on the back surface of the chip having undergone the peeling, and the chip may be incorporated in a semiconductor device as a chip with a resin film. The resin film is formed as a protective film for preventing cracks from occurring after a dicing process or packaging, or as an adhesive film for adhering the obtained chip to a pad portion or another member such as another semiconductor chip.
Generally, the chip with a resin film is produced by forming a coating film by applying a solution of a composition containing a resin to the back surface of a wafer by spin coating or the like, drying and curing the coating film to form a resin film, and dicing the resulting wafer with a resin film.
As a material for forming a protective film or an adhesive film provided on the back surface of such a chip or the back surface of a wafer, various resin film-forming sheets have been proposed.
For example, patent document 1 discloses a film for protecting a chip having a structure in which an energy ray curable protective film forming layer is sandwiched by 2 peeling sheets, the energy ray curable protective film forming layer including: a polymer component containing an acrylic copolymer, an energy ray-curable component, a dye or pigment, an inorganic filler, and a photopolymerization initiator.
According to the description of patent document 1, the chip protection film can form a protective film having improved laser marking visibility, hardness, and adhesion to a wafer by irradiation with energy rays, and can simplify the process compared to a conventional chip protection film.
Patent document 2 discloses a dicing tape-integrated wafer back surface protective film including a dicing tape including a base material and an adhesive layer, and a wafer back surface protective film colored and having a predetermined elastic modulus on the adhesive layer of the dicing tape.
According to the description of patent document 2, the wafer back surface protective film can exhibit excellent holding force with respect to the semiconductor wafer in the dicing step of the semiconductor wafer.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-138026
Patent document 2: japanese patent application laid-open No. 2010-199543
Disclosure of Invention
Problems to be solved by the invention
However, in the step of attaching the protective film disclosed in patent documents 1 and 2 to the wafer, if the attachment position of the protective film is displaced or the protective film is attached so as to include foreign matter in a state where foreign matter on the wafer is not found, it is difficult to re-peel the wafer after peeling the protective film.
The protective films disclosed in patent documents 1 and 2 have a problem in removability because of high adhesion to the wafer if they are temporarily attached to the wafer for the purpose of improving adhesion to the wafer during attachment and holding force to the wafer after attachment. On the other hand, if the protective film temporarily attached to the wafer is forcibly peeled off, the wafer may be broken by the peeling force, or a part of the protective film may remain on the wafer. Therefore, it is difficult to reuse the wafer after the wafer is bonded to the protective film.
That is, in patent documents 1 and 2, the protective films described therein have been studied from the viewpoint of adhesion to the wafer at the time of bonding and holding force between the protective films and the wafer after bonding, but there has been no study on removability of the protective films.
The present invention has been made in view of the above problems, and an object thereof is to provide a resin film forming sheet having excellent removability, and a composite sheet for forming a resin film having the resin film forming sheet and a support.
Means for solving the problems
The present inventors have found that the above problems can be solved by adjusting the surface roughness of the surface to which the silicon wafer is bonded to a predetermined value or more, and have completed the present invention.
Namely, the present invention provides the following [1] to [15 ].
[1] A sheet for forming a resin film, which is to be stuck to a silicon wafer and is for forming a resin film on the silicon wafer, wherein,
the surface (alpha) of the sheet to be bonded to the silicon wafer has a surface roughness (Ra) of 40nm or more.
[2] The resin film-forming sheet according to [1], which comprises a polymer component (A) and a curable component (B).
[3] The resin film-forming sheet according to [2], wherein the polymer component (A) comprises an acrylic polymer (A1).
[4] The resin film-forming sheet according to any one of [1] to [3], which contains a thermosetting component (B1).
[5] The resin film-forming sheet according to any one of [1] to [4], which contains a filler (C).
[6] The resin film-forming sheet according to [5], wherein the content of the filler (C) is 10 to 80% by mass based on the total amount of the resin film-forming sheet.
[7] The sheet for forming a resin film according to [5] or [6], wherein the filler (C) has an average particle diameter of 100 to 1000 nm.
[8] The resin film-forming sheet according to any one of [1] to [7], which is a protective film-forming sheet for forming a protective film on a silicon wafer.
[9] The resin film-forming sheet according to any one of [1] to [8], wherein a surface (α) of the resin film-forming sheet is bonded to a silicon wafer, and a gloss value measured from a surface (β') of a resin film formed from the resin film-forming sheet on the side opposite to the silicon wafer is 25 or more.
[10] A composite sheet for forming a resin film, comprising:
the sheet for forming a resin film according to any one of [1] to [9], and
and a support body.
[11] A composite sheet for forming a resin film, comprising:
a resin film-forming sheet bonded to a silicon wafer for forming a resin film on the silicon wafer, and
a support body (I),
the composite sheet has a structure in which the surface (alpha) of the resin film-forming sheet to be bonded to the silicon wafer and the surface (I) of the support (I) having a surface roughness of 40nm or more are directly laminated.
[12] The composite sheet for forming a resin film according to [11], wherein a surface roughness (Ra) of a surface (α) of the sheet for forming a resin film exposed when the support (I) provided in the composite sheet for forming a resin film is removed is 40nm or more.
[13] The composite sheet for forming a resin film according to [11] or [12], wherein the sheet for forming a resin film contains a thermosetting component (B1).
[14] The composite sheet for resin film formation according to [11] or [12], which has a structure in which a2 nd support (II) is further directly laminated on a surface (. beta.) of the sheet for resin film formation on the side opposite to the surface (. alpha.),
the resin film-forming sheet contains a thermosetting component (B1).
[15] The composite sheet for forming a resin film according to [14], wherein the support (II) is an adhesive sheet having an adhesive layer, and the composite sheet has a structure in which the adhesive layer and the surface (. beta.) of the sheet for forming a resin film are directly laminated.
ADVANTAGEOUS EFFECTS OF INVENTION
The resin film-forming sheet of the present invention has excellent removability. Therefore, when it is determined that the re-application is necessary after the resin film forming sheet of the present invention is temporarily attached to the silicon wafer, the resin film forming sheet can be peeled off without causing damage to the silicon wafer and while suppressing generation of residue, and the silicon wafer from which the resin film forming sheet has been peeled off can be reused.
In the present specification, the term "removability of the resin film forming sheet" refers to a property of enabling peeling without causing damage to the silicon wafer and without leaving a part of the resin film forming sheet on the silicon wafer when peeling is performed again after the silicon wafer is attached.
Drawings
Fig. 1 is a cross-sectional view of a composite sheet for forming a resin film according to an embodiment of the present invention.
Description of the symbols
1a, 1b, 1c, 1d composite sheet for forming resin film
10 sheet for forming resin film
11. 11' support body
12 jig adhesive layer
Detailed Description
In the present specification, the values of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each component are values in terms of standard polystyrene measured by a Gel Permeation Chromatography (GPC) method, specifically, values measured by the methods described in examples.
In the present specification, for example, when the term "(meth) acrylate" is used, both the terms "acrylate" and "methacrylate" are used, and other similar terms are also used.
In the present specification, the term "energy ray" refers to, for example, ultraviolet rays, electron beams, and the like.
[ sheet for Forming resin film ]
The resin film-forming sheet of the present invention is a sheet for forming a resin film on a silicon wafer, which is stuck to the silicon wafer, wherein the surface roughness (Ra) of the surface (alpha) of the sheet to be stuck to the silicon wafer (hereinafter also simply referred to as "surface roughness (Ra) of the surface (alpha)") is 40nm or more.
The resin film-forming sheet of the present invention has a surface (α) with a surface roughness (Ra) of 40nm or more, and therefore, even after the resin film-forming sheet is temporarily attached to a silicon wafer, the resin film-forming sheet can be peeled off without causing breakage of the silicon wafer and while suppressing generation of residue, and has excellent removability.
On the other hand, when a resin film forming sheet having a surface roughness (Ra) of less than 40nm on the surface (α) is to be peeled off after being bonded to a silicon wafer, a residue of the resin film forming sheet may be generated on the silicon wafer. In addition, when the silicon wafer is forcibly peeled off, the silicon wafer may be damaged.
From the above viewpoint, the surface roughness (Ra) of the surface (α) of the resin film-forming sheet of the present invention is preferably 45nm or more, more preferably 50nm or more, further preferably 53nm or more, and further preferably 55nm or more.
The upper limit of the surface roughness (Ra) of the surface (α) is not particularly limited from the viewpoint of improving the removability.
However, the surface roughness (Ra) of the surface (α) of the resin film-forming sheet of the present invention is preferably 150nm or less, more preferably 100nm or less, and still more preferably 80nm or less, from the viewpoint of obtaining a resin film-forming sheet having good adhesion to a silicon wafer.
In the present specification, the surface roughness (Ra) of the surface (α) is a value measured by the method described in examples.
The surface roughness (Ra) of the surface (α) can be adjusted by appropriately setting the type, average particle diameter, content, and the like of the fine particle components such as a filler and a colorant that can be contained in the resin film-forming sheet, for example. In addition, the adjustment may be performed by attaching a support having a rough surface.
In one embodiment of the present invention, the surface roughness (Ra) of the surface (β) of the resin film forming sheet opposite to the surface (α) is not particularly limited, but is preferably 5 to 80nm, more preferably 8 to 60nm, and even more preferably 10 to 45 nm.
When the amount is within this range, the gloss value of the surface (β') of the resin film, which will be described later, formed of the resin film-forming sheet can be easily adjusted to be high. In addition, when a silicon wafer having a resin film formed from a sheet for forming a resin film, a chip obtained from a silicon wafer, or the like is inspected by an electromagnetic wave such as infrared rays, the transmittance of the electromagnetic wave can be increased.
After the surface (α) of the resin film-forming sheet according to one embodiment of the present invention is bonded to a silicon wafer, the gloss value measured from the surface (β') of the resin film formed from the resin film-forming sheet on the side opposite to the silicon wafer is preferably 25 or more, more preferably 30 or more, further preferably 35 or more, and further preferably 40 or more.
When the gloss value of the surface (β') of the resin film is 25 or more, a resin film excellent in the visual recognition of laser printing can be obtained.
In one embodiment of the present invention, the light transmittance at a wavelength of 1250nm of the resin film formed from the resin film-forming sheet and the resin film formed from the resin film-forming sheet is preferably 25% or more, more preferably 30% or more, further preferably 35% or more, and still further preferably 40% or more.
When the light transmittance is 25% or more, the transmittance of infrared rays is good, and infrared ray inspection can be performed on a silicon wafer or a chip provided with a resin film forming sheet or a resin film formed from the resin film forming sheet. That is, cracks and the like generated in the silicon wafer or the chip can be easily found through the resin film forming sheet or the resin film, and thus the product yield can be improved.
The light transmittance at a wavelength of 1250nm of the resin film-forming sheet is a value measured by the method described in examples.
The form of the resin film-forming sheet of the present invention is not particularly limited, and may be, for example, a long tape form or a form of a single-leaf label.
The resin film-forming sheet of the present invention may be a single layer composed of 1 composition or a multilayer composed of 2 or more compositions.
When the resin film-forming sheet according to one embodiment of the present invention is a multilayer body, it is preferable to adjust the types and amounts of the components of the composition (α') as a material for forming the surface (α) so that the surface roughness (Ra) of the surface (α) falls within the above range.
In one embodiment of the present invention, the thickness of the resin film-forming sheet can be appropriately set according to the application, but is preferably 1 to 300 μm, more preferably 3 to 250 μm, still more preferably 5 to 200 μm, and still more preferably 7 to 150 μm.
In particular, when the thickness of the silicon wafer to which the resin film forming sheet is attached is small, the thickness of the resin film forming sheet is preferably 1 to 20 μm, and more preferably 3 to 15 μm.
In the case where the resin film-forming sheet is a multilayer body composed of 2 or more layers, the total thickness of the multilayer body is preferably within the above range.
< Components of sheet for Forming resin film >
The resin film-forming sheet according to one embodiment of the present invention is not particularly limited in its constituent components as long as the surface roughness (Ra) of the surface (α) is within the above range.
However, the resin film-forming sheet according to one embodiment of the present invention is preferably a sheet containing the polymer component (a) and the curable component (B) in order to obtain a resin film-forming sheet having good shape retention properties.
In addition, the resin film-forming sheet according to one embodiment of the present invention preferably contains the filler (C) from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) to the above range and from the viewpoint of adjusting the thermal expansion coefficient of the resin film formed from the resin film-forming sheet to an appropriate range.
Further, the resin film-forming sheet according to one embodiment of the present invention may further contain 1 or more selected from the group consisting of the colorant (D), the coupling agent (E), and the general-purpose additive (F) within a range not to impair the effects of the present invention.
The following describes the components (a) to (F) which can be components of the resin film forming sheet according to one embodiment of the present invention.
[ Polymer component (A) ]
In the present specification, the "polymer component" means a high molecular weight material obtained by polymerization reaction, and is a compound having at least 1 repeating unit.
The resin film-forming sheet used in one embodiment of the present invention can be easily provided with flexibility by containing the polymer component (a), and the sheet-like shape retention property is improved. As a result, the storage modulus of the resin film-forming sheet can be adjusted to the above range.
The weight average molecular weight (Mw) of the polymer component (a) is preferably 2 ten thousand or more, more preferably 2 to 300 ten thousand, further preferably 10 to 200 ten thousand, and further preferably 15 to 150 ten thousand, from the viewpoint of adjusting the storage modulus of the obtained resin film-forming sheet to the above range.
The glass transition temperature (Tg) of the acrylic polymer (A1) is preferably-40 ℃ or higher, more preferably-30 to 50 ℃, still more preferably-20 to 20 ℃, and still more preferably-15 to 0 ℃.
In the present specification, the value of the glass transition temperature (Tg) of an acrylic polymer or the like is the glass transition temperature (Tg) expressed as an absolute temperature (unit: K) to be calculated by the following formula (1)K) Converted to temperature in degrees celsius (unit: c) is used.
[ mathematical formula 1]
[ in the above formula (1), W1、W2、W3、W4… represents the mass fraction (mass) of the monomer component constituting the polymer componentAmount%), Tg1、Tg2、Tg3、Tg4… represents the glass transition temperature (unit: K) of the homopolymer of each monomer component constituting the polymer component.]
In one embodiment of the present invention, the content of the polymer component (a) in the resin film-forming sheet is preferably 5 to 60 mass%, more preferably 8 to 50 mass%, even more preferably 10 to 45 mass%, and even more preferably 15 to 40 mass% with respect to the total amount (100 mass%) of the resin film-forming sheet.
In the present specification, the "content of the component (a) with respect to the total amount of the resin film-forming sheet" is the same as the "content of the component (a) with respect to the total amount of the active ingredients in the composition as the material for forming the resin film-forming sheet". The same applies to the contents of other components described below.
Further, the "active ingredient" mentioned above means an ingredient other than a substance such as a solvent which does not directly or indirectly affect the physical properties of the sheet formed by the reaction in the composition, and specifically means an ingredient other than a solvent such as water and an organic solvent.
The polymer component (a) preferably contains an acrylic polymer (a 1).
The polymer component (a) may contain the acrylic polymer (a1) and the non-acrylic polymer (a 2).
These polymer components may be used alone or in combination of 2 or more.
In one embodiment of the present invention, the content of the acrylic polymer (a1) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass, based on the total amount (100% by mass) of the polymer component (a) contained in the resin film-forming sheet.
(acrylic Polymer (A1))
From the viewpoint of imparting flexibility and film-forming property to the resin film-forming sheet and adjusting the storage modulus of the resin film-forming sheet to the above range, the weight average molecular weight (Mw) of the acrylic polymer (a1) is preferably 2 to 300 ten thousand, more preferably 10 to 150 ten thousand, even more preferably 15 to 120 ten thousand, and even more preferably 25 to 100 ten thousand.
The acrylic polymer (a1) may be a polymer mainly composed of an alkyl (meth) acrylate, and specifically, an acrylic polymer containing a structural unit (a1) derived from an alkyl (meth) acrylate having an alkyl group with 1 to 18 carbon atoms is preferable, and an acrylic copolymer further containing a structural unit (a2) other than the structural unit (a1) may be used.
The acrylic polymer (a1) may be used alone or in combination of 2 or more.
When the acrylic polymer (a1) is a copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.
(structural Unit (a1))
The alkyl group of the alkyl (meth) acrylate constituting the structural unit (a1) has preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms, from the viewpoint of imparting flexibility and film-forming properties to the resin film-forming sheet.
Examples of the alkyl (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.
These alkyl (meth) acrylates may be used alone or in combination of 2 or more.
Among these, alkyl (meth) acrylates having an alkyl group having 1 to 3 carbon atoms are preferable, and methyl (meth) acrylate is more preferable.
The content of the structural unit (a11) derived from an alkyl (meth) acrylate having an alkyl group with 1 to 3 carbon atoms in the acrylic polymer (A1) is preferably 5 to 80% by mass, more preferably 15 to 70% by mass, and still more preferably 25 to 60% by mass, based on the total structural units (100% by mass) of the acrylic polymer (A1).
The alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is preferable, and butyl (meth) acrylate is more preferable.
The content of the structural unit (a12) derived from an alkyl (meth) acrylate having an alkyl group with 4 to 12 carbon atoms in the acrylic polymer (A1) is preferably 5 to 80% by mass, more preferably 15 to 70% by mass, and still more preferably 20 to 60% by mass, based on the total structural units (100% by mass) of the acrylic polymer (A1).
The acrylic polymer (a1) used in one embodiment of the present invention is preferably an acrylic copolymer containing both the structural unit (a11) and the structural unit (a 12).
The acrylic copolymer preferably has a content ratio [ (a11)/(a12) ] (mass ratio) of the structural unit (a11) and the structural unit (a12) of 20/80 to 95/5, more preferably 30/70 to 90/10, still more preferably 40/60 to 85/15, and still more preferably 52/48 to 75/25.
The content of the structural unit (a1) in the acrylic polymer (a1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, still more preferably 55 to 98% by mass, and still more preferably 60 to 97% by mass, based on the total structural units (100% by mass) of the acrylic polymer (a 1).
(structural Unit (a2))
The acrylic polymer (a1) used in one embodiment of the present invention may have a structural unit (a2) other than the above structural unit (a1) within a range not to impair the effects of the present invention.
Examples of the monomer constituting the structural unit (a2) include: functional group-containing monomers such as hydroxyl group-containing monomers, carboxyl group-containing monomers, epoxy group-containing monomers and the like; vinyl ester monomers such as vinyl acetate and vinyl propionate; olefin monomers such as ethylene, propylene and isobutylene; aromatic vinyl monomers such as styrene, methylstyrene, and vinyltoluene; diene monomers such as butadiene and isoprene; nitrile monomers such as (meth) acrylonitrile, and the like.
Among these, the functional group-containing monomer is preferable, and 1 or more selected from the group consisting of a hydroxyl group-containing monomer and an epoxy group-containing monomer is more preferable.
Examples of the hydroxyl group-containing monomer include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
Of these, 2-hydroxyethyl (meth) acrylate is preferred.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid.
Examples of the epoxy group-containing monomer include: epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-hydroxypropyl (meth) acrylate; non-acrylic epoxy group-containing monomers such as glycidyl crotonate and allyl glycidyl ether; and so on.
The acrylic polymer having a Mw of 2 ten thousand or more, which has a structural unit derived from an epoxy group-containing monomer, has thermosetting properties, but is not the curable component (B), and is considered to be included in the concept of the polymer component (a).
The acrylic polymer (a1) used in one embodiment of the present invention preferably contains a structural unit (a21) derived from a hydroxyl group-containing monomer.
The content of the structural unit (a21) derived from the hydroxyl group-containing monomer in the acrylic polymer (a1) is preferably 1 to 40 mass%, more preferably 5 to 30 mass%, even more preferably 8 to 25 mass%, and even more preferably 10 to 20 mass% with respect to the total structural units (100 mass%) of the acrylic polymer (a 1).
In addition, the acrylic polymer (a1) used in one embodiment of the present invention preferably contains a structural unit (a22) derived from an epoxy group-containing monomer.
The content of the structural unit (a22) derived from the epoxy group-containing monomer in the acrylic polymer (a1) is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 8 to 25% by mass, based on the total structural units (100% by mass) of the acrylic polymer (a 1).
In addition, when an epoxy thermosetting component is used as the curable component (B) described later, since a carboxyl group reacts with an epoxy group in the epoxy thermosetting component, the content of a structural unit derived from a carboxyl group-containing monomer in the acrylic polymer (a1) is preferably small.
When the epoxy thermosetting component is used as the curable component (B), the content of the structural unit derived from the carboxyl group-containing monomer is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 2% by mass, and even more preferably 0% by mass, based on the total structural units (100% by mass) of the acrylic polymer (a 1).
The content of the structural unit (a2) in the acrylic polymer (a1) is preferably 1 to 50 mass%, more preferably 2 to 45 mass%, and still more preferably 3 to 40 mass% with respect to the total structural units (100 mass%) of the acrylic polymer (a 1).
(non-acrylic resin (A2))
The resin film-forming sheet according to one embodiment of the present invention may contain a non-acrylic polymer (a2) as a polymer component other than the acrylic polymer (a1) as needed.
Examples of the non-acrylic polymer (a2) include: polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber-based polymers, and the like.
These non-acrylic polymers (A2) may be used alone or in combination of 2 or more.
The weight average molecular weight (Mw) of the non-acrylic polymer (a2) is preferably 2 ten thousand or more, more preferably 2 to 10 ten thousand, and still more preferably 2 to 8 ten thousand.
[ curable component (B) ]
The curable component (B) is a component that functions to cure the resin film-forming sheet to form a hard resin film, and is a compound having a weight average molecular weight (Mw) of less than 2 ten thousand.
The resin film-forming sheet used in the present invention preferably contains at least one of a thermosetting component (B1) and an energy ray-curable component (B2) as the curable component (B), and more preferably contains at least the thermosetting component (B1) from the viewpoint of sufficiently advancing the curing reaction and reducing the cost.
The thermosetting component (B1) is preferably a compound having at least a functional group which reacts by heating.
The energy ray-curable component (B2) contains a compound (B21) having a functional group that reacts upon irradiation with an energy ray, and is polymerized and cured upon irradiation with an energy ray.
The functional groups of these curable components react with each other to form a three-dimensional network structure, thereby achieving curing.
The weight average molecular weight (Mw) of the curable component (B) is preferably less than 20,000, more preferably 10,000 or less, and even more preferably 100 to 10,000, from the viewpoints of suppressing the viscosity of the composition for forming a resin film-forming sheet and improving the handling properties by using the curable component (B) in combination with the component (a).
(thermosetting component (B1))
As the thermosetting component (B1), an epoxy thermosetting component is preferable.
As the epoxy thermosetting component, it is preferable to use a compound (B11) having an epoxy group in combination with a thermosetting agent (B12).
Examples of the compound (B11) having an epoxy group (hereinafter also referred to as "epoxy compound (B11)") include: and epoxy compounds having 2 or more functions in the molecule, such as polyfunctional epoxy resins, bisphenol a diglycidyl ethers and hydrogenated products thereof, novolac-type epoxy resins such as cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, biphenyl-type epoxy resins, bisphenol a-type epoxy resins, bisphenol F-type epoxy resins, and phenylene skeleton-type epoxy resins.
These epoxy compounds (B11) may be used alone or in combination of 2 or more.
Among these, 1 or more selected from the novolac type epoxy resins and the biphenyl type epoxy resins are preferably contained.
In one embodiment of the present invention, the epoxy compound (B11) preferably contains an epoxy compound that is liquid at 25 ℃ (hereinafter also referred to as a "liquid epoxy compound").
By including the liquid epoxy compound in the epoxy compound (B11), the value of the elongation at break of the resin film-forming sheet can be increased, and a resin film-forming sheet excellent in removability can be obtained.
In one embodiment of the present invention, from the above-described viewpoint, the content of the liquid epoxy compound is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more, relative to the total amount (100% by mass) of the epoxy compound (B11) in the resin film-forming sheet.
On the other hand, from the viewpoint of improving the reliability of the chip with a resin film manufactured using the resin film forming sheet, the content of the liquid epoxy compound is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and still further preferably 70% by mass or less, relative to the total amount (100% by mass) of the epoxy compound (B11) in the resin film forming sheet.
In the present specification, the "liquid epoxy compound" refers to an epoxy compound having a viscosity of 40Pa · s or less at 25 ℃. In the present specification, the viscosity of the epoxy compound at 25 ℃ is a value measured at 25 ℃ by using an E-type viscometer based on JIS Z8803.
The content of the epoxy compound (B11) is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, still more preferably 5 to 150 parts by mass, and still more preferably 10 to 100 parts by mass, based on 100 parts by mass of the component (a).
(Heat-curing agent (B12))
The thermosetting agent (B12) functions as a curing agent for the epoxy compound (B11).
As the thermal curing agent, a compound having 2 or more functional groups capable of reacting with an epoxy group in 1 molecule is preferable.
Examples of the functional group include: phenolic hydroxyl, alcoholic hydroxyl, amino, carboxyl, acid anhydride, and the like. Among these functional groups, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable, a phenolic hydroxyl group or an amino group is more preferable, and an amino group is further preferable.
Examples of the phenolic thermosetting agent having a phenolic hydroxyl group include: a polyfunctional phenol resin, biphenol, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, a XYLOK-type phenol resin, an aralkyl-type phenol resin, and the like.
Examples of the amine-based heat-curing agent having an amino group include: dicyandiamide (DICY) and the like.
These heat-curing agents (B12) may be used alone or in combination of 2 or more.
Of these, an amine-based heat curing agent is preferably contained.
The content of the thermosetting agent (B12) is preferably 0.1 to 500 parts by mass, more preferably 0.5 to 300 parts by mass, and still more preferably 1 to 200 parts by mass, based on 100 parts by mass of the epoxy compound (B11).
(curing Accelerator (B13))
The resin film-forming sheet according to one embodiment of the present invention may further contain a curing accelerator (B13) in order to adjust the curing rate of the sheet by heating.
The curing accelerator (B13) is preferably used in combination with the epoxy compound (B11) as the thermosetting component (B1).
Examples of the curing accelerator (B13) include: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-benzeneImidazoles such as yl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenyl radical
Tetraphenylboron salts such as tetraphenylboron salt and triphenylphosphine tetraphenylboron ester.
These curing accelerators (B13) may be used alone or in combination of 2 or more.
From the viewpoint of improving the adhesiveness of a resin film formed from a sheet for forming a resin film, the content of the curing accelerator (B13) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and still more preferably 0.3 to 4 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12).
(energy ray-curable component (B2))
As the energy ray-curable component (B2), a compound (B21) having a functional group which reacts by irradiation with an energy ray may be used alone, but it is preferable to use the compound (B21) in combination with a photopolymerization initiator (B22). The energy ray-curable component (B2) is preferably a component that is cured by ultraviolet rays.
(Compound (B21) having functional group that reacts when irradiated with energy ray.)
Examples of the compound (B21) having a functional group that reacts upon irradiation with an energy ray (hereinafter also referred to as "energy ray-reactive compound (B21)") include: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, oligoester (meth) acrylate, urethane (meth) acrylate oligomer, epoxy (meth) acrylate, polyether (meth) acrylate, itaconic acid oligomer, and the like.
These energy line-reactive compounds (B21) may be used alone or in combination of 2 or more.
The weight average molecular weight (Mw) of the energy ray-reactive compound (B21) is preferably 100 to 30,000, more preferably 200 to 20,000, and still more preferably 300 to 10,000.
The content of the energy ray-reactive compound (B21) is preferably 1 to 1500 parts by mass, more preferably 3 to 1200 parts by mass, and still more preferably 5 to 1000 parts by mass, based on 100 parts by mass of the component (a).
(photopolymerization initiator (B22))
By using the energy ray-reactive compound (B21) in combination with the photopolymerization initiator (B22), the polymerization/curing time can be shortened, and the resin film-forming sheet can be cured even when the amount of light irradiation is reduced.
Examples of the photopolymerization initiator (B22) include: benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, and the like.
More specific examples of the photopolymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, butanedione, β -chloroanthraquinone, 2,4, 6-trimethylbenzyldiphenyl phosphine oxide, and the like.
These photopolymerization initiators may be used alone or in combination of 2 or more.
The content of the photopolymerization initiator (B22) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the energy ray-reactive compound (B21), from the viewpoint of sufficiently performing the curing reaction of the resin film-forming sheet and suppressing the generation of residues.
In one embodiment of the present invention, the content of the curable component (B) in the resin film-forming sheet is preferably 5 to 50 mass%, more preferably 8 to 40 mass%, even more preferably 10 to 30 mass%, and even more preferably 12 to 25 mass%, relative to the total amount (100 mass%) of the resin film-forming sheet.
The "content of the curable component (B)" refers to the total content of the thermosetting component (B1) containing the epoxy compound (B11), the thermosetting agent (B12) and the curing accelerator (B13) and the energy ray-curable component (B2) containing the energy ray-reactive compound (B21) and the photopolymerization initiator (B22).
[ Filler (C) ]
The resin film-forming sheet according to one embodiment of the present invention preferably contains a filler (C).
By including the filler (C), the surface roughness (Ra) of the surface (α) of the resin film-forming sheet can be easily adjusted to the above range.
In addition, the resin film forming sheet containing the filler (C) can adjust the coefficient of thermal expansion of the formed resin film to an appropriate range, and optimize the coefficient of thermal expansion of the chip with the resin film, thereby improving the reliability of the semiconductor device in which the chip is incorporated. In addition, the moisture absorption rate of the resin film formed from the resin film forming sheet can be reduced.
Examples of the filler (C) include: an organic filler such as a polymethyl methacrylate filler or rubber-based particles, and an inorganic filler such as silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, or boron nitride powder, or beads obtained by spheroidizing these materials, single crystal fibers, or glass fibers.
These fillers (C) may be used alone or in combination of 2 or more.
Among these, in the case where the resin film-forming sheet is thermosetting, an inorganic filler is preferable, and silica or alumina is more preferable, from the viewpoint of excellent heat resistance and the like.
In one embodiment of the present invention, the average particle diameter of the filler (C) is preferably 3 to 20 μm, and more preferably 5 to 15 μm, from the viewpoint of easily adjusting the surface roughness (Ra) of the surface (α) of the resin film-forming sheet to be formed to the above range.
If the filler has an average particle diameter within the above range, the surface roughness (Ra) of the surface (α) of the resin film-forming sheet to be formed can be easily adjusted to the above range even when the content of the filler (C) is small.
However, by adding a large amount of the filler (C) or forming a configuration of forming a composite sheet for forming a resin film described later, the surface roughness (Ra) of the surface (α) of the formed sheet for forming a resin film can be adjusted to the above range even when the filler (C) having a small average particle diameter is used.
The average particle diameter of the filler (C) in the above case is preferably 100 to 1000nm, more preferably 200 to 900nm, still more preferably 200 to 800nm, still more preferably 300 to 750nm, and still more preferably 400 to 700 nm.
When the average particle diameter of the filler (C) is 100nm or more, the surface roughness (Ra) of the surface (α) of the resin film-forming sheet can be easily adjusted to the above range by adjusting the content of the filler (C).
When the average particle diameter of the filler (C) is 1000nm or less, the following advantages (1) to (4) are obtained.
(1) The gloss value measured from the surface (beta') of the resin film formed from the resin film forming sheet on the side opposite to the silicon wafer after the surface (alpha) of the resin film forming sheet is adhered to the silicon wafer can be improved.
(2) The sheet for forming a resin film and the resin layer can easily have improved transparency to electromagnetic waves such as infrared rays. As a result, when the inspection by electromagnetic waves is performed on a silicon wafer, a chip, or the like having a resin film forming sheet and a resin layer, the efficiency of the inspection work is improved because the electromagnetic waves have high transmittance.
(3) In a process for irradiating a silicon wafer having a sheet for forming a resin film and the resin film with a laser beam, the problem of laser beam diffusion due to the presence of the sheet for forming a resin film and the resin film is easily avoided.
(4) In the case of producing a resin film-forming sheet having a small thickness of, for example, 20 μm or less, adverse effects such as poor formation of a coating film due to a filler having a large particle diameter can be easily avoided in the step of applying a composition as a material for forming the resin film-forming sheet.
In the case where the resin film-forming sheet according to one embodiment of the present invention is a multilayer body formed of 2 or more compositions, it is preferable to adjust the surface roughness (Ra) of the surface (α) by adding the filler (C) having an average particle diameter in the above range to the composition as the forming material on the surface (α) side of the resin film-forming sheet.
On the other hand, from the viewpoint of improving the gloss value measured from the surface (β ') of the resin film formed from the resin film-forming sheet on the side opposite to the silicon wafer, it is preferable to blend a filler (C') having a small average particle diameter different from the above range in the composition as the forming material on the surface (β) side.
The filler (C') has an average particle diameter of usually 1 to 400nm, preferably 1 to 250nm, and more preferably 1 to 100 nm.
In the present specification, the average particle diameter of the fillers (C) and (C') is a value measured by a dynamic light scattering particle size distribution tester (Nanotrack Wave-UT151, manufactured by japan ltd).
In one embodiment of the present invention, the content of the filler (C) in the resin film-forming sheet is preferably 10 to 80 mass%, more preferably 20 to 70 mass%, even more preferably 30 to 65 mass%, and even more preferably 40 to 60 mass% with respect to the total amount (100 mass%) of the resin film-forming sheet, from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the resin film-forming sheet to the above range, and from the viewpoint of improving the reliability of the resin film-provided chip produced using the resin film-forming sheet.
In one embodiment of the present invention, the total content of the polymer component (a), the curable component (B), and the filler (C) in the resin film-forming sheet is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and still further preferably 90% by mass or more, relative to the total amount (100% by mass) of the resin film-forming sheet.
[ colorant (D) ]
The resin film-forming sheet according to one embodiment of the present invention may further contain a colorant (D).
By containing the colorant (D) in the resin film forming sheet, when the semiconductor chip having the resin film formed from the resin film forming sheet is incorporated into a device, grinding marks generated at the time of grinding of the semiconductor wafer are not easily visually recognized, and the appearance of the semiconductor chip can be finished.
As the colorant (D), organic or inorganic pigments and dyes can be used.
As the dye, any of acid dyes, reactive dyes, direct dyes, disperse dyes, cationic dyes, and the like can be used, for example.
The pigment is not particularly limited, and may be appropriately selected from known pigments, for example, phthalocyanine-based blue pigments, isoindoline-based yellow pigments, and pyrrolopyrroledione-based red pigments, and black pigments such as carbon black, iron oxide, manganese dioxide, aniline black, and activated carbon.
These colorants (D) may be used alone or in combination of 2 or more.
By using a phthalocyanine-based blue pigment, an isoindoline-based yellow pigment, and a pyrrolopyrroledione-based red pigment in combination, a resin film having improved light transmittance in the red region and low visible light transmittance can be easily obtained.
The average particle diameter of the colorant (D) is preferably 400nm or less, more preferably 300nm or less, further preferably 200nm or less, further preferably 100nm or less, and further preferably 10nm or more, more preferably 20nm or more.
In one embodiment of the present invention, the content of the colorant (D) in the resin film-forming sheet is preferably 0.01 to 20 mass%, more preferably 0.05 to 15 mass%, even more preferably 0.1 to 10 mass%, and even more preferably 0.15 to 5 mass% with respect to the total amount (100 mass%) of the resin film-forming sheet.
[ coupling agent (E) ]
The resin film-forming sheet according to one embodiment of the present invention may further contain a coupling agent (E).
By containing the coupling agent (E), the water resistance of the resin film formed from the resin film-forming sheet can be improved without deteriorating the heat resistance. In addition, it is also advantageous to improve the adhesion of the end portion after the silicon wafer is bonded.
The coupling agent (E) is preferably a compound that reacts with the functional groups of the components (a) and (B), and more preferably a silane coupling agent.
Examples of the silane coupling agent include: gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma- (methacryloxypropyl) trimethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, beta-3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, gamma-aminopropyl-trimethoxysilane, gamma-mercaptomethyldimethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, beta-3-glycidoxypropyl-ethyltrimethoxysilane, gamma, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.
These coupling agents (E) may be used alone or in combination of 2 or more.
As the coupling agent (E), an oligomer type coupling agent is preferable.
The molecular weight of the coupling agent (E) which also includes an oligomer-type coupling agent is preferably 100 to 15000, more preferably 150 to 10000, still more preferably 200 to 5000, yet more preferably 250 to 3000, and yet more preferably 350 to 2000.
In one embodiment of the present invention, the content of the coupling agent (E) in the resin film-forming sheet is preferably 0.01 to 3.0 mass%, more preferably 0.03 to 1.5 mass%, even more preferably 0.05 to 0.8 mass%, and even more preferably 0.1 to 0.3 mass% with respect to the total amount (100 mass%) of the resin film-forming sheet.
[ general additive (F) ]
The resin film-forming sheet used in one embodiment of the present invention may contain, if necessary, a general-purpose additive (F) in addition to the above components within a range that does not impair the effects of the present invention.
Examples of the general-purpose additive (F) include: cross-linking agent, plasticizer, leveling agent, antistatic agent, antioxidant, ion trapping agent, getter, chain transfer agent and the like.
The content of each of these general-purpose additives (F) in the resin film forming sheet according to one embodiment of the present invention is preferably 0 to 10 mass%, more preferably 0 to 5 mass%, and still more preferably 0 to 2 mass% with respect to the total amount (100 mass%) of the resin film forming sheet.
< method for producing sheet for forming resin film >
The method for producing the resin film-forming sheet of the present invention is not particularly limited, and the resin film can be produced by a known method.
For example, after preparing a resin film-forming composition containing the above components as a material for forming a resin film-forming sheet, a solution of the resin film-forming composition is obtained by appropriately adding an organic solvent to dilute the composition. Then, a solution of the resin film-forming composition is applied to a support described later by a known coating method to form a coating film, and the coating film is dried to produce a resin film-forming sheet.
From the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the obtained resin film-forming sheet to the above range, the method for producing a resin film-forming sheet preferably includes a step of applying a resin film-forming composition, which is a material for forming a resin film-forming sheet, to the surface of a support having a surface with a surface roughness (Ra) of 40nm or more to form a coating film, and drying the coating film.
The resin film-forming composition may be diluted with a solvent as appropriate to form a solution of the resin film-forming composition.
The surface roughness (Ra) of the surface of the support is preferably 40nm or more, more preferably 70nm or more, further preferably 100nm or more, further preferably 200nm or more, further preferably 300nm or more, and further preferably 1000nm or less, more preferably 800nm or less, and further preferably 500nm or less.
In the case where the resin film forming sheet according to one embodiment of the present invention is a multilayer body, the method for producing the resin film forming sheet may include, for example, the steps of: coating a solution of the resin film-forming composition on 2 or more supports to form coating films, laminating the coating films, and drying.
As the organic solvent used for preparing the solution of the composition for forming a resin film, for example: toluene, ethyl acetate, methyl ethyl ketone, and the like.
The solid content concentration of the solution of the resin film-forming composition when the organic solvent is blended is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 65% by mass.
Examples of the coating method include: spin coating, spray coating, bar coating, knife coating, roll coating, knife coating, blade coating, die coating, gravure coating, and the like.
< use of sheet for Forming resin film >
The resin film forming sheet according to one embodiment of the present invention can be attached to the back surface of a work such as a flip chip semiconductor wafer or a silicon wafer such as a semiconductor chip to form a resin film on the work. The resin film has a function as a protective film for protecting the back surface of a work such as a semiconductor wafer or a semiconductor chip. For example, in the case of being attached to a semiconductor wafer, the resin film has a function of reinforcing the wafer, and thus can prevent breakage of the wafer and the like.
That is, the resin film forming sheet according to the embodiment of the present invention is preferably a protective film forming sheet for forming a protective film on a silicon wafer.
In addition, the resin film formed from the resin film forming sheet according to one embodiment of the present invention can also be provided with a function as an adhesive sheet. That is, when the resin film formed using the resin film forming sheet according to one embodiment of the present invention functions as an adhesive film, the chip having the resin film can be bonded to another member (chip mounting portion) such as a pad portion or another semiconductor chip, and thus, productivity for manufacturing a semiconductor device can be improved.
That is, the resin film forming sheet according to one embodiment of the present invention may be used as an adhesive film forming sheet for forming an adhesive film on a silicon wafer.
[ constitution of composite sheet for Forming resin film ]
The composite sheet for forming a resin film of the present invention (hereinafter also simply referred to as "composite sheet") comprises the sheet for forming a resin film of the present invention and a support.
The form of the composite sheet according to an embodiment of the present invention is not particularly limited, and may be, for example, a long tape form or a form of a single-leaf label.
Fig. 1 is a sectional view of a composite sheet for forming a resin film according to an embodiment of the present invention.
As a composite sheet according to an embodiment of the present invention, a composite sheet 1a having a structure in which a resin film forming sheet 10 is directly laminated on a support 11 as shown in fig. 1(a) can be cited.
The shape of the sheet 10 for forming a resin film, which is the composite sheet according to one embodiment of the present invention, may be substantially the same as the shape of the silicon wafer to be adhered or may include a silicon wafer.
In the composite sheet 1a of fig. 1(a), the support 11 and the resin film forming sheet 10 have substantially the same shape, but as shown in fig. 1(b), a composite sheet 1b in which the shape of the resin film forming sheet 10 is smaller than that of the support 11 may be used.
As a composite sheet according to an embodiment of the present invention, a composite sheet 1c having an annular jig adhesive layer 12 as shown in fig. 1(c) can be mentioned.
The annular jig bonding layer 12 is provided for the purpose of improving the bonding force to a jig such as an annular frame when bonding the jig to the jig, and may be formed of a double-sided adhesive sheet having a base material (core material) or an adhesive.
In the composite sheet 1c shown in fig. 1(c), a structure in which the composite sheet 1a of fig. 1(a) is further provided with a jig bonding layer 12 is shown, but as the composite sheet according to an embodiment of the present invention, a composite sheet in which the jig bonding layer 12 is provided on the surface of the support 11 of the composite sheet 1b of fig. 1(b) may be mentioned.
The composite sheet according to an embodiment of the present invention may be a composite sheet 1d having a structure in which a resin film forming sheet 10 is supported by 2 support members 11 and 11' as shown in fig. 1 (d).
Similarly to the structure of the composite sheet 1d, a support different from the support 11 may be provided on the surface of the composite sheet 1b of fig. 1(b) exposed to the resin film forming sheet 10.
Similarly, a support different from the support 11 may be provided on the surface of the resin film forming sheet 10 and the surface of the jig adhesive layer 12 of the composite sheet 1c shown in fig. 1 (c).
< support >
The support of the composite sheet according to one embodiment of the present invention is a sheet material that functions as a release sheet for preventing dust and the like from adhering to the surface of the resin film forming sheet, a dicing sheet for protecting the surface of the resin film forming sheet in a dicing step and the like, and the like.
The support used in the present invention preferably has a structure of a resin film.
Examples of the resin film include: polyethylene films such as Low Density Polyethylene (LDPE) films and Linear Low Density Polyethylene (LLDPE) films, ethylene-propylene copolymer films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polyethylene naphthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films, ionomer resin films, ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylate copolymer films, polystyrene films, polycarbonate films, polyimide films, fluororesin films, and the like.
The substrate used in one embodiment of the present invention may be a single-layer film composed of 1 kind of resin film, or may be a laminated film obtained by laminating 2 or more kinds of resin films.
The resin film may be a crosslinked film.
Further, a sheet obtained by coloring these resin films, a sheet obtained by printing, or the like can be used.
The resin film may be a film obtained by forming a sheet of a thermoplastic resin by extrusion molding, a stretched film, or a film obtained by forming a curable resin into a thin film by a predetermined method and curing the thin film to form a sheet.
Among these resin films, a substrate including a polypropylene film is preferable from the viewpoint of excellent heat resistance, expansion suitability due to appropriate flexibility, and easiness in maintaining pickup suitability.
The structure of the substrate including the polypropylene film may be a single-layer structure composed of only the polypropylene film, or a multi-layer structure composed of the polypropylene film and another resin film.
When the sheet for forming a resin film is thermosetting, the resin film constituting the base material has heat resistance, and thus damage to the base material due to heat can be suppressed, and occurrence of defects in the manufacturing process of a semiconductor device can be suppressed.
When the support is used as a release sheet for preventing dust or the like from adhering to the surface of the resin film forming sheet, the support is preferably a resin film that can be easily released from the resin film forming sheet when the support is attached to a silicon wafer or when the support is cut.
Further, as the support, a resin film obtained by subjecting the surface of the resin film to a peeling treatment may be used.
As a method of the peeling treatment, a method of providing a peeling film formed of a peeling agent on the surface of the resin film is preferable.
Examples of the release agent include release agents containing resins selected from acrylic resins, alkyd resins, silicone resins, fluorine resins, unsaturated polyester resins, polyolefin resins, and wax resins.
When the support is used as a dicing sheet for fixing the resin film forming sheet in a dicing step or the like, the support is preferably an adhesive sheet having an adhesive layer formed of an adhesive on the resin film.
The pressure-sensitive adhesive resin contained in the pressure-sensitive adhesive includes, for example, acrylic resins, urethane resins, rubber resins, silicone resins, vinyl ether resins, and the like, when the structure of the pressure-sensitive adhesive resin is focused on, and energy ray curable resins, and the like, when the function is focused on.
In one embodiment of the present invention, a binder containing an energy ray curable resin is preferable from the viewpoint of improving the pickup property.
The thickness of the support is suitably selected depending on the application, but is preferably 10 to 500. mu.m, more preferably 20 to 350. mu.m, and still more preferably 30 to 200. mu.m.
The thickness of the support is not limited to the thickness of the resin film constituting the support, and includes the thickness of the pressure-sensitive adhesive layer or the release film when the pressure-sensitive adhesive layer or the release film is provided.
< jig adhesion layer >
The jig bonding layer may be formed of a double-sided adhesive sheet having a base material (core material) or an adhesive composition containing an adhesive.
As the substrate (core material), a resin film that can be used as the substrate is exemplified, and a polypropylene film is preferable.
Examples of the binder include: acrylic resins, urethane resins, rubber resins, silicone resins, vinyl ether resins, and the like.
The thickness of the jig bonding layer is preferably 1 to 80 μm, more preferably 5 to 60 μm, and further preferably 10 to 40 μm.
[ composite sheet for forming resin film according to another embodiment of the present invention ]
As another embodiment of the present invention, the following composite sheet for forming a resin film (hereinafter also referred to as "composite sheet (1)") can be mentioned.
The composite sheet (1) according to one embodiment of the present invention is a composite sheet having a support (I) and a resin film forming sheet for forming a resin film on a silicon wafer by being stuck to the silicon wafer, and has the same structure as the composite sheets 1a to 1d shown in fig. 1.
The composite sheet (1) has a structure in which the surface (alpha) of the resin film-forming sheet to be bonded to the silicon wafer and the surface (I) of the support (I) having a surface roughness of 40nm or more are directly laminated.
It is considered that the surface (α) of the resin film-forming sheet exposed when the support (I) is removed from the composite sheet (1) is transferred to exhibit a surface roughness (Ra) that is comparable to or less than the irregularities having a surface roughness (Ra) of 40nm or more formed on the surface (I) of the support (I).
Therefore, it is considered that the surface roughness (Ra) of the surface (α) of the resin film forming sheet after the support (I) is removed from the composite sheet (1) is a predetermined value or more to the extent that the effect of improving the removability is exerted, and the effect of improving the removability is exhibited as in the case of the resin film forming sheet of the present invention.
The resin film-forming sheet included in the composite sheet (1) according to one embodiment of the present invention preferably has thermosetting properties.
In the case of the resin film forming sheet having thermosetting properties, the uneven shape on the surface (α) of the resin film forming sheet is likely to be deformed in the heating step after the resin film forming sheet is bonded to the silicon wafer, and therefore voids due to the uneven shape on the surface (α) of the resin film forming sheet are less likely to be generated at the interface with the silicon wafer. As a result, scattering of light due to the voids on the resin film formed on the silicon wafer can be suppressed, and observation such as inspection of the silicon wafer or chip having the resin film with the naked eye or electromagnetic waves such as infrared rays can be easily performed.
The resin film-forming sheet included in the composite sheet (1) according to one embodiment of the present invention preferably contains the thermosetting component (B1) from the viewpoint of imparting thermosetting properties.
The surface roughness (Ra) of the resin film-forming sheet after the removal of the support (I) of the composite sheet (1) is preferably 40nm or more, more preferably 45nm or more, further preferably 50nm or more, further preferably 53nm or more, further preferably 55nm or more, and further preferably 200nm or less, more preferably 150nm or less, and further preferably 100nm or less.
The surface roughness (Ra) of the surface (I) of the support (I) is preferably 40nm or more, more preferably 70nm or more, further preferably 100nm or more, further preferably 200nm or more, further preferably 300nm or more, and further preferably 1000nm or less, more preferably 800nm or less, and further preferably 500nm or less.
The support (I) of the composite sheet (1) is not particularly limited as long as it is a support that can be peeled off with the surface roughness (Ra) within the above range by surface treatment, but is preferably formed of paper or a resin film, and more preferably formed of a resin film from the viewpoint of reducing the possibility of generation of dust.
Examples of the method for adjusting the surface roughness (Ra) of the surface (I) of the support (I) include: a method of incorporating a filler into a resin film constituting the support (I), a method of providing a release film formed of a release agent containing a filler, and the like.
In the case where the support (I) is made of a resin film produced by melt extrusion, the resin film can be produced by injecting a molten resin onto a rough-surface-shaped roll to adjust the surface roughness (Ra) to the above range.
The surface roughness (Ra) of the surface (I) of the support (I) can be adjusted by using a material such as paper or nonwoven fabric, which is rough in nature.
The composite sheet (1) may be a composite sheet having a structure in which the second support (II) is further directly laminated on the surface (β) of the resin film forming sheet opposite to the surface (α), as in the composite sheet 1d shown in fig. 1 (d).
The sheet for forming a resin film included in the composite sheet preferably has thermosetting properties. Therefore, the resin film-forming sheet preferably contains the thermosetting component (B1).
In the composite sheet (1) having a structure in which the resin film-forming sheet is sandwiched between the support (I) and the support (II) as shown in fig. 1(d), after the surface (α) of the resin film-forming sheet is bonded to the silicon wafer, the resin film-forming sheet is thermally cured in a state in which the support (II) and the resin film-forming sheet are laminated without peeling off the support (II), and the gloss value measured from the surface (β') of the formed resin film opposite to the silicon wafer tends to be high. The gloss value is higher than the gloss value of the surface (β ') of a resin film formed from a composite sheet without a support (II) and the gloss value of the surface (β') of a resin film formed by heat curing in a state where the surface (β) of a resin film forming sheet is exposed after peeling the support (II).
That is, even when the gloss value of the surface (β') of the resin film is lowered due to, for example, the use of a filler having a large average particle diameter as the filler (C), the resin film having high visibility in laser printing can be formed by thermally curing the resin film-forming sheet in a state in which the support (II) and the resin film-forming sheet are laminated without peeling the support (II) after the composite sheet (1) is attached to the silicon wafer.
In order to impart thermosetting properties to the resin film-forming sheet, the resin film-forming sheet may contain the thermosetting component (B1) described above.
The support (II) may be made of the same material as the support included in the composite sheet of the present invention, and specifically, may be: the resin film, the resin film having a release film, the adhesive sheet having an adhesive layer, and the like.
When the support (II) is an adhesive sheet having an adhesive layer, the composite sheet (1) preferably has a structure in which the adhesive layer and the surface (β) of the resin film-forming sheet are directly laminated. In this configuration, the gloss value of the surface (β') of the resin film formed can be improved by forming a pressure-sensitive adhesive layer from a pressure-sensitive adhesive containing an energy ray-curable resin, curing the pressure-sensitive adhesive layer by irradiation with energy rays in advance to obtain a pressure-sensitive adhesive layer, and thermally curing the resin film-forming sheet in a state where the support (II) and the resin film-forming sheet are laminated.
[ method for regenerating silicon wafer ]
As a method for regenerating a silicon wafer by peeling a resin film forming sheet of the present invention from a laminate obtained by sticking a silicon wafer and the surface (α) of the resin film forming sheet, for example, a method for regenerating a silicon wafer comprising the following steps (1) to (2) can be mentioned.
Step (1): a step of bonding the adhesive layer of an adhesive sheet having a base material and an adhesive layer to a surface (β) of the resin film-forming sheet of the laminate opposite to the surface (α) to which the silicon wafer is bonded;
step (2): and (2) pulling the adhesive sheet bonded in the step (1) to peel off the resin film-forming sheet bonded to the silicon wafer.
The method for recycling a silicon wafer described above is a recycling method using the properties of the resin film-forming sheet of the present invention having excellent removability, and can realize detachment without causing damage to the silicon wafer and without generating residue when the sheet is to be detached after being attached to the silicon wafer.
The method for regenerating a silicon wafer is applicable not only to a laminate obtained immediately after the silicon wafer and the surface (α) of the resin film forming sheet of the present invention are bonded, but also to a laminate obtained after about 24 hours has elapsed after the bonding and having improved adhesion between the silicon wafer and the resin film forming sheet.
< step (1) >
The step (1) is a step of bonding the adhesive layer of an adhesive sheet having a substrate and an adhesive layer to the surface (β) of the resin film-forming sheet of the laminate opposite to the surface (α) to which the silicon wafer is bonded.
The silicon wafer is not limited to the wafer before the singulation, and may be a wafer which has been already singulated by, for example, a DBG (dicing before grinding) method in which a groove is provided from a surface of the silicon wafer on the opposite side to the surface to be ground and ground until reaching the groove, thereby singulating the silicon wafer into chips.
The pressure-sensitive adhesive sheet used in this step is a pressure-sensitive adhesive sheet having a substrate and a pressure-sensitive adhesive layer. When the composite sheet (1) having the support (II) formed of an adhesive sheet is bonded to a silicon wafer, the support (II) may be used as the "adhesive sheet" in the present step.
The substrate is preferably a resin film, and examples of the resin film include the resin films described in the above-mentioned items of the support.
The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer is not particularly limited as long as it has a pressure-sensitive adhesive strength sufficient to enable the resin film-forming sheet to be peeled from the silicon wafer in the step (2).
Specific examples of the binder include: acrylic adhesives, urethane adhesives, silicone adhesives, and the like.
The shape of the pressure-sensitive adhesive sheet is not particularly limited, but from the viewpoint of handling in the subsequent step (2), a pressure-sensitive adhesive sheet having the same shape as or a shape larger than the resin film-forming sheet is preferable.
The method of attaching the surface (β) to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet in this step may be performed by a machine or by a manual operation.
In the case where the surface (α) of the resin film-forming sheet included in the composite sheet according to the above-described embodiment of the present invention is bonded to a silicon wafer and an adhesive sheet such as a dicing sheet as a support is already laminated on the surface (β), the adhesive sheet can be used as the adhesive sheet in the present step.
< step (2) >
The step (2) is a step of pulling the adhesive sheet bonded in the step (1) to peel off the resin film forming sheet bonded to the silicon wafer.
In this step, since the surface roughness (Ra) of the surface (α) of the resin film-forming sheet of the present invention to be bonded to the silicon wafer is adjusted to the above range, the resin film-forming sheet can be pulled off together by pulling the adhesive sheet bonded to the surface (β) in the step (1), and the resin film-forming sheet can be peeled from the silicon wafer.
The peeling speed and peeling angle of the pressure-sensitive adhesive sheet are not particularly limited and can be set as appropriate.
In the present step, the adhesive sheet may be pulled mechanically, but from the viewpoint of workability, it is preferable to pull the adhesive sheet manually and peel the resin film-forming sheet from the silicon wafer.
In this step, after peeling the sheet for forming a resin film, the surface of the silicon wafer may be washed with an organic solvent such as ethanol as necessary.
Through the above steps, the silicon wafer to which the resin film forming sheet is temporarily attached can be regenerated.
Examples
< measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) >
The measurement was performed under the following conditions using a gel permeation chromatography apparatus (product name "HLC-8220 GPC" manufactured by Tosoh corporation), and the value measured in terms of standard polystyrene was used.
(measurement conditions)
Column chromatography: "TSK guard column HXL-L", "TSK gel GMHXL (. times.2)" "TSK gel G2000 HXL" (all manufactured by Tosoh Corp.) were connected in this order.
Column temperature: 40 deg.C
Elution solvent: tetrahydrofuran (THF)
Flow rate: 1.0mL/min
< average particle diameter of component in composition for Forming resin film >
The particle size distribution was measured using a dynamic light scattering particle size distribution measuring instrument (product name "Nanotrack Wave-UT 151", manufactured by Nikkiso K.K.).
< measurement of surface roughness (Ra) >
The surface roughness (Ra) of the surface of the measurement object was measured at a magnification of 10 times in the PSI mode using an optical interference type surface shape measuring apparatus (product name "WYKO WT 1100" manufactured by Veeco metals Group corporation).
< evaluation of removability of resin film-forming sheet >
The support (I) of the composite sheets for forming a resin film prepared in examples and comparative examples was removed, and the surface (α) of the exposed sheet for forming a resin film was laminated on the polished surface of a silicon wafer polished with #2000 (diameter: 200mm, thickness: 280 μm), and bonded while heating to 70 ℃ using a tape mounter (product name "Adwil RAD-3600F/12" manufactured by Lingdeko Co., Ltd.).
After the application, the support (II) of the composite sheet for forming a resin film was also removed at room temperature (25 ℃ C.), and the surface of the adhesive layer of a commercially available general-purpose dicing tape (manufactured by Lindceko, Ltd., trade name "Adwill D-510T") was applied to the exposed surface of the sheet for forming a resin film.
Next, whether or not the resin film forming sheet can be peeled off from the silicon wafer together by pulling the general-purpose dicing tape by a manual operation and whether or not there is a residue on the surface of the silicon wafer after the peeling were observed, and the removability of the resin film forming sheet was evaluated according to the following criteria.
A: the resin film forming sheet can be completely peeled off from the silicon wafer. On the silicon wafer after peeling, no residue of the resin film forming sheet was observed, which could be visually confirmed.
B: the sheet for forming a resin film can be peeled off from the silicon wafer. Some residues of the resin film forming sheet were observed on the silicon wafer after peeling, but the residues were removed completely by wiping with ethanol.
C: even if the silicon wafer is damaged during the peeling or the peeling can be performed without causing the damage of the silicon wafer, the residue of the resin film forming sheet is observed on the silicon wafer after the peeling to such an extent that the wiping with ethanol is difficult.
< measurement of gloss value of resin film >
The support (I) of the composite sheets for forming a resin film produced in examples and comparative examples was removed, and the surface (α) of the exposed sheet for forming a resin film was laminated on the polished surface of a silicon wafer (diameter 200mm, thickness 280 μm) polished by #2000, and the sheet was bonded while heating to 70 ℃ using a tape mounter (product name "Adwil RAD-3600F/12" manufactured by Lingdeko Co., Ltd.).
After the adhesion, the support (II) of the composite sheet for forming a resin film was also removed, and the sheet for forming a resin film was put into a heating furnace at 130 ℃ for 2 hours to cure the sheet, thereby forming a resin film on a silicon wafer.
Next, the specular gloss of the surface of the resin film formed on the side opposite to the side having the silicon wafer was measured using a gloss meter (product name "VG 2000" manufactured by japan electrochromic industries) at 60 degrees based on JIS Z8741. The value of the specular gloss was defined as the gloss value of the resin film.
< measurement of light transmittance of resin film at wavelength 1250nm >
The support (I) of the composite sheets for forming a resin film prepared in examples and comparative examples was removed, and the exposed surface (α) of the sheet for forming a resin film was laminated on a flat surface of a glass plate having a thickness of 2mm, and was bonded while being heated to 70 ℃.
After the bonding, the support (II) of the composite sheet for forming a resin film was also removed, and the sheet for forming a resin film was put into a heating furnace at 130 ℃ for 2 hours to cure the sheet, thereby forming a resin film on a glass plate.
Subsequently, the transmittance of the resin film on the glass plate was measured by a spectrophotometer (UV-VIS-NIRSPEROTOMETER UV-3600, product name of Shimadzu corporation), and the transmittance (%) at a wavelength of 1250nm was extracted.
The measurement was performed using a large sample cell "MPC-3100" (product name) attached to the spectrophotometer without using a built-in integrating sphere. The transmittance at a wavelength of 1250nm of the resin film was calculated by taking the difference from the previously measured transmittance at a wavelength of 1250nm of the glass plate alone.
Example 1
Each component of the kind and amount shown in table 1 was added and diluted with methyl ethyl ketone to prepare a solution of the resin film-forming composition having an effective component concentration of 51 mass%.
Next, as a support (II), a solution of the resin film-forming composition was applied to a release-treated surface of a polyethylene terephthalate (PET) film (trade name "SP-PET 381031", manufactured by Lindelco Ltd., thickness: 38 μm) subjected to a release treatment, and dried to form a resin film-forming sheet having a thickness of 25 μm.
Further, a release-treated surface of a release paper (product name "SP-8 LK blue", manufactured by Linekco Ltd., thickness: 88 μm) having a surface roughness (Ra) of 370nm, which was formed by coating a cellophane with a polyolefin and subjecting the cellophane to a silicone release treatment was attached as a support (I) to the exposed surface of the formed sheet for forming a resin film, and the sheet for forming a resin film was laminated at room temperature (25 ℃ C.) by a laminating apparatus (product name "VA-400", manufactured by Dachen laminating apparatus Co., Ltd.) to prepare a composite sheet for forming a resin film comprising the support (I)/the sheet for forming a resin film/the support (II).
Comparative example 1
A composite sheet for forming a resin film comprising a support (I)/a sheet for forming a resin film/a support (II) was produced in the same manner as in example 1, except that a release-treated surface of a polyethylene terephthalate (PET) film (trade name "SP-PET 251130", manufactured by Lingdeko Co., Ltd., thickness: 25 μm) which had been subjected to a release treatment was bonded as the support (I) to the exposed surface of the sheet for forming a resin film formed in the same manner as in example 1.
Details of each component described in table 1 used for the preparation of the resin film-forming composition are as follows.
< Polymer component (A) >
[ A-1 ]: an acrylic copolymer obtained by copolymerizing Methyl Acrylate (MA), n-Butyl Acrylate (BA), Glycidyl Methacrylate (GMA), and 2-hydroxyethyl acrylate (HEA) (BA/MA/GMA/HEA: 37/28/20/15 (mass%), Mw: 80 ten thousand, Tg ═ 10.1 ℃).
< curable component (B) >
(B-1): bisphenol a epoxy resin (trade name "jER 828" manufactured by mitsubishi chemical corporation, epoxy equivalent of 184 to 194g/eq, Mn of 370, viscosity of 120 to 150P (12 to 15Pa · s) at 25 ℃), liquid epoxy resin, and a compound corresponding to the above component (B11).
(B-2): bisphenol a epoxy resin (product name "jER 1055" manufactured by mitsubishi chemical corporation, epoxy equivalent of 800 to 900g/eq, Mn of 1600, solid epoxy resin, compound corresponding to the above component (B11)).
(B-3): a dicyclopentadiene type epoxy resin (a compound having an epoxy equivalent of 255 to 260g/eq and an Mw of less than 2 ten thousand, a solid epoxy resin, or a compound corresponding to the above component (B11), which is manufactured by DIC corporation and has a trade name of "Epiclon HP-7200 HH").
(B-4): dicyandiamide (a compound corresponding to the above-mentioned component (B12) with an amine-based curing agent having an active hydrogen content of 21g/eq, trade name "ADEKA hardereh-3636 AS", manufactured by ADEKA corporation).
(B-5): 2-phenyl-4, 5-dihydroxymethylimidazole (product name "CUREZOL 2 PHZ" manufactured by Shikoku Kogyo Co., Ltd., curing accelerator, compound corresponding to the above-mentioned component (B13)).
< Filler (C) >
(C-1): a silica filler (trade name "SC 2050 MA" manufactured by Admatechs corporation, average particle diameter 500 nm).
< colorant (D) >
(D-1): carbon black (trade name "# MA 650" manufactured by Mitsubishi chemical corporation, average particle diameter: 28 nm).
< silane coupling agent (E) >
[ E-1 ]: silane coupling agent (3-glycidoxypropylmethyldimethoxysilane, product name "KBM-402" from shin-Etsu chemical Co., Ltd., Mn: 220.3).
The resin film-forming sheets prepared in examples and comparative examples were subjected to measurement and evaluation of physical properties based on the methods described above, and the results are shown in table 1.
[ Table 1]
As is clear from table 1, the resin film-forming sheet included in the composite sheet for forming a resin film produced in example 1, which is one embodiment of the present invention, has excellent removability. Further, the gloss value and the light transmittance at a wavelength of 1250nm of the resin film formed from the sheet for forming a resin film were also high.
On the other hand, the resin film-forming sheet included in the composite sheet for forming a resin film produced in comparative example 1 had a small surface roughness (Ra) value of the surface (α), and therefore was difficult to peel after being stuck to a silicon wafer, and had a result of poor removability.
Industrial applicability
The resin film-forming sheet according to one embodiment of the present invention is suitable as a material for forming a protective film for protecting the back surface of a semiconductor chip, or a material for forming an adhesive film that can be bonded to a pad portion or other portions.
Claims (25)
1. A sheet for forming a resin film, which is a sheet for forming a resin film on a silicon wafer, the sheet for forming a resin film being stuck to the silicon wafer, the sheet for forming a resin film comprising a polymer component (A) containing an acrylic polymer (A1) having a glass transition temperature Tg of-40 to-10.1 ℃,
wherein the surface (alpha) of the sheet on the side to be bonded to the silicon wafer has a surface roughness (Ra) of 40nm or more,
the surface roughness was measured by using an optical interference type surface shape measuring apparatus at a magnification of 10 times in a PSI mode on the surface of the object to be measured.
2. The sheet for forming a resin film according to claim 1, comprising a curable component (B).
3. The resin film-forming sheet according to claim 1, comprising a thermosetting component (B1).
4. The resin film-forming sheet according to claim 2, comprising a thermosetting component (B1).
5. The sheet for forming a resin film according to claim 1, comprising a filler (C).
6. The sheet for forming a resin film according to claim 2, comprising a filler (C).
7. The sheet for forming a resin film according to claim 3, comprising a filler (C).
8. The sheet for forming a resin film according to claim 4, comprising a filler (C).
9. The resin film-forming sheet according to claim 5, wherein the content of the filler (C) is 10 to 80% by mass based on the total amount of the resin film-forming sheet.
10. The resin film-forming sheet according to claim 6, wherein the content of the filler (C) is 10 to 80% by mass based on the total amount of the resin film-forming sheet.
11. The resin film-forming sheet according to claim 7, wherein the content of the filler (C) is 10 to 80% by mass based on the total amount of the resin film-forming sheet.
12. The resin film-forming sheet according to claim 8, wherein the content of the filler (C) is 10 to 80% by mass based on the total amount of the resin film-forming sheet.
13. The sheet for forming a resin film according to any one of claims 5 to 12, wherein the filler (C) has an average particle diameter of 100 to 1000 nm.
14. The sheet for forming a resin film according to any one of claims 1 to 12, which is a protective film-forming sheet for forming a protective film on a silicon wafer.
15. The resin film-forming sheet according to claim 13, which is a protective film-forming sheet for forming a protective film on a silicon wafer.
16. The sheet for forming a resin film according to any one of claims 1 to 12, wherein a surface (α) of the sheet for forming a resin film is bonded to a silicon wafer, and then a gloss value measured from a surface (β') of the resin film formed from the sheet for forming a resin film on the side opposite to the silicon wafer is 25 or more.
17. The sheet for forming a resin film according to claim 13, wherein a gloss value measured from a surface (β') of a resin film formed from the sheet for forming a resin film on the side opposite to a silicon wafer after the surface (α) of the sheet for forming a resin film is attached to the silicon wafer is 25 or more.
18. The sheet for forming a resin film according to claim 14, wherein a gloss value measured from a surface (β') of a resin film formed from the sheet for forming a resin film on the side opposite to a silicon wafer after the surface (α) of the sheet for forming a resin film is attached to the silicon wafer is 25 or more.
19. The sheet for forming a resin film according to claim 15, wherein a gloss value measured from a surface (β') of a resin film formed from the sheet for forming a resin film on the side opposite to a silicon wafer after the surface (α) of the sheet for forming a resin film is attached to the silicon wafer is 25 or more.
20. A composite sheet for forming a resin film, comprising:
the sheet for forming a resin film according to any one of claims 1 to 19, and
and a support body.
21. A composite sheet for forming a resin film, comprising:
a resin film forming sheet for forming a resin film on a silicon wafer, and a support (I) which are bonded to the silicon wafer,
the sheet for forming a resin film comprises an acrylic polymer (A1) having a glass transition temperature Tg of-40 to-10.1 ℃,
the composite sheet has a structure in which the surface (alpha) of the resin film-forming sheet to be bonded to the silicon wafer and the surface (I) of the support (I) having a surface roughness of 40nm or more are directly laminated,
the surface roughness was measured by using an optical interference type surface shape measuring apparatus at a magnification of 10 times in a PSI mode on the surface of the object to be measured.
22. The composite sheet for forming resin film according to claim 21, wherein a surface roughness (Ra) of a surface (α) of the sheet for forming resin film exposed when a support (I) provided in the composite sheet for forming resin film is removed is 40nm or more.
23. The composite sheet for forming a resin film according to claim 21 or 22, wherein the sheet for forming a resin film contains a thermosetting component (B1).
24. The composite sheet for forming a resin film according to claim 21 or 22, which has a structure in which a2 nd support (II) is further directly laminated on a surface (β) of the resin film forming sheet on the opposite side to the surface (α),
the resin film-forming sheet contains a thermosetting component (B1).
25. The composite sheet for forming resin film according to claim 24, wherein the support (II) is an adhesive sheet having an adhesive layer,
the composite sheet has a structure in which the adhesive layer and the surface (beta) of the resin film-forming sheet are directly laminated.
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| CN202011201640.0A CN112625609B (en) | 2015-03-30 | 2016-03-25 | Sheet for forming resin film and composite sheet for forming resin film |
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| JP2015069795 | 2015-03-30 | ||
| JP2015-069795 | 2015-03-30 | ||
| PCT/JP2016/059573 WO2016158727A1 (en) | 2015-03-30 | 2016-03-25 | Sheet for forming resin film and composite sheet for forming resin film |
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| WO2020026666A1 (en) * | 2018-08-01 | 2020-02-06 | 株式会社有沢製作所 | Resin composition for resists and use thereof |
| JP6854983B1 (en) * | 2019-04-26 | 2021-04-07 | リンテック株式会社 | A method for manufacturing a third laminated body, a method for manufacturing a fourth laminated body, a method for manufacturing a semiconductor device with a back surface protective film, and a third laminated body. |
| JP7457513B2 (en) | 2020-02-03 | 2024-03-28 | リンテック株式会社 | PRODUCTION METHOD OF PROTECTIVE FILM-FORMING FILM, COMPOSITE SHEET FOR PROTECTIVE FILM-FORMING, AND APPARATUS |
| JP2022146565A (en) | 2021-03-22 | 2022-10-05 | リンテック株式会社 | Protective film-forming film, protective film-forming composite sheet, and wafer recycling method |
| CN117433564B (en) * | 2023-12-05 | 2024-03-01 | 北京航空航天大学 | Polarization sensor error online calibration method based on sun sensor assistance |
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| JP2009138026A (en) | 2007-12-03 | 2009-06-25 | Furukawa Electric Co Ltd:The | Energy ray-curable chip protecting film |
| JP5805367B2 (en) | 2009-01-30 | 2015-11-04 | 日東電工株式会社 | Dicing tape integrated wafer back surface protection film |
| JP4851613B2 (en) * | 2009-12-22 | 2012-01-11 | 古河電気工業株式会社 | Adhesive tape for semiconductor wafer surface protection |
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2016
- 2016-03-25 KR KR1020177013455A patent/KR102499451B1/en active IP Right Grant
- 2016-03-25 CN CN201680003816.7A patent/CN107001876B/en active Active
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Patent Citations (4)
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| JPS63193982A (en) * | 1987-02-09 | 1988-08-11 | Bridgestone Corp | Pressure-sensitive adhesive sheet having modified section |
| WO2010024121A1 (en) * | 2008-09-01 | 2010-03-04 | 日東電工株式会社 | Process for production of dicing/die bondind film |
| JP2011228637A (en) * | 2010-03-30 | 2011-11-10 | Furukawa Electric Co Ltd:The | Chip protecting film |
| CN104277728A (en) * | 2013-07-03 | 2015-01-14 | 早川橡胶株式会社 | Adhesive tape for flat-panel displays |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6562172B2 (en) | 2019-08-21 |
| CN112625609A (en) | 2021-04-09 |
| TW201708477A (en) | 2017-03-01 |
| SG11201704075PA (en) | 2017-10-30 |
| CN107001876A (en) | 2017-08-01 |
| JP2019096913A (en) | 2019-06-20 |
| JPWO2016158727A1 (en) | 2018-01-25 |
| KR20170134960A (en) | 2017-12-07 |
| JP6501428B2 (en) | 2019-04-17 |
| WO2016158727A1 (en) | 2016-10-06 |
| KR102499451B1 (en) | 2023-02-13 |
| CN112625609B (en) | 2022-11-08 |
| TWI695872B (en) | 2020-06-11 |
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