WO2018181765A1 - 粘着シート - Google Patents
粘着シート Download PDFInfo
- Publication number
- WO2018181765A1 WO2018181765A1 PCT/JP2018/013352 JP2018013352W WO2018181765A1 WO 2018181765 A1 WO2018181765 A1 WO 2018181765A1 JP 2018013352 W JP2018013352 W JP 2018013352W WO 2018181765 A1 WO2018181765 A1 WO 2018181765A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- thermally expandable
- resin
- adhesive sheet
- Prior art date
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 115
- 239000000853 adhesive Substances 0.000 title claims abstract description 114
- 239000002245 particle Substances 0.000 claims abstract description 109
- 229920005989 resin Polymers 0.000 claims abstract description 106
- 239000011347 resin Substances 0.000 claims abstract description 106
- 239000000758 substrate Substances 0.000 claims abstract description 93
- 238000003860 storage Methods 0.000 claims abstract description 48
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 255
- 239000010410 layer Substances 0.000 claims description 131
- 238000007789 sealing Methods 0.000 claims description 89
- 239000000463 material Substances 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 53
- 239000000523 sample Substances 0.000 claims description 24
- 239000012790 adhesive layer Substances 0.000 abstract description 36
- 239000004840 adhesive resin Substances 0.000 abstract description 35
- 239000004065 semiconductor Substances 0.000 description 71
- -1 vinyl compound Chemical class 0.000 description 67
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 57
- 239000000203 mixture Substances 0.000 description 47
- 239000000178 monomer Substances 0.000 description 40
- 238000004519 manufacturing process Methods 0.000 description 38
- 239000011342 resin composition Substances 0.000 description 32
- 239000007787 solid Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 25
- 229920006243 acrylic copolymer Polymers 0.000 description 24
- 239000000047 product Substances 0.000 description 21
- 150000002009 diols Chemical class 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 19
- 239000003431 cross linking reagent Substances 0.000 description 19
- 239000000654 additive Substances 0.000 description 18
- 229920005672 polyolefin resin Polymers 0.000 description 17
- 239000004480 active ingredient Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 11
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 10
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 150000003077 polyols Chemical class 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920000103 Expandable microsphere Polymers 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- KUVMKLCGXIYSNH-UHFFFAOYSA-N isopentadecane Chemical compound CCCCCCCCCCCCC(C)C KUVMKLCGXIYSNH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- PHONXVMOPDJLEY-UHFFFAOYSA-N (3-hydroxy-3-phenylpropyl) prop-2-enoate Chemical compound C=CC(=O)OCCC(O)C1=CC=CC=C1 PHONXVMOPDJLEY-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 description 2
- RJWUMFHQJJBBOD-UHFFFAOYSA-N 2-methylheptadecane Chemical compound CCCCCCCCCCCCCCCC(C)C RJWUMFHQJJBBOD-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940067597 azelate Drugs 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- UEVXKGPJXXDGCX-UHFFFAOYSA-N cyclotridecane Chemical compound C1CCCCCCCCCCCC1 UEVXKGPJXXDGCX-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- FNWWOHKUXFTKGN-UHFFFAOYSA-N isoheptadecane Natural products CCCCCCCCCCCCCCC(C)C FNWWOHKUXFTKGN-UHFFFAOYSA-N 0.000 description 2
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- CJBFZKZYIPBBTO-UHFFFAOYSA-N isotetradecane Natural products CCCCCCCCCCCC(C)C CJBFZKZYIPBBTO-UHFFFAOYSA-N 0.000 description 2
- HGEMCUOAMCILCP-UHFFFAOYSA-N isotridecane Natural products CCCCCCCCCCC(C)C HGEMCUOAMCILCP-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 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
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- VCLJODPNBNEBKW-UHFFFAOYSA-N 2,2,4,4,6,8,8-heptamethylnonane Chemical compound CC(C)(C)CC(C)CC(C)(C)CC(C)(C)C VCLJODPNBNEBKW-UHFFFAOYSA-N 0.000 description 1
- MTFZMVUYAILXSB-UHFFFAOYSA-N 2,6,10,10-tetramethylpentadecane Chemical compound CCCCCC(C)(C)CCCC(C)CCCC(C)C MTFZMVUYAILXSB-UHFFFAOYSA-N 0.000 description 1
- GVJRTUUUJYMTNQ-UHFFFAOYSA-N 2-(2,5-dioxofuran-3-yl)acetic acid Chemical compound OC(=O)CC1=CC(=O)OC1=O GVJRTUUUJYMTNQ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 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
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-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
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-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
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- XUKLTPZEKXTPBT-UHFFFAOYSA-N 3-oxatricyclo[5.2.1.01,5]dec-5-ene-2,4-dione Chemical compound C1CC2C=C3C(=O)OC(=O)C13C2 XUKLTPZEKXTPBT-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- MVFNWZHRHUOGKQ-UHFFFAOYSA-N 4-methyl-1,7-dioxacyclotridecane-8,13-dione Chemical compound CC1CCOC(=O)CCCCC(=O)OCC1 MVFNWZHRHUOGKQ-UHFFFAOYSA-N 0.000 description 1
- UZTXSMATBUWDDZ-UHFFFAOYSA-N 4-methyldodecane Chemical compound CCCCCCCCC(C)CCC UZTXSMATBUWDDZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QHZLCTYHMCNIMS-UHFFFAOYSA-L [2-ethylhexanoyloxy(dioctyl)stannyl] 2-ethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(CC)CCCC)(OC(=O)C(CC)CCCC)CCCCCCCC QHZLCTYHMCNIMS-UHFFFAOYSA-L 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- LKMCJXXOBRCATQ-UHFFFAOYSA-N benzylsulfanylbenzene Chemical compound C=1C=CC=CC=1CSC1=CC=CC=C1 LKMCJXXOBRCATQ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- SRONXYPFSAKOGH-UHFFFAOYSA-N cyclopentadecane Chemical compound C1CCCCCCCCCCCCCC1 SRONXYPFSAKOGH-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- STWFZICHPLEOIC-UHFFFAOYSA-N decylcyclohexane Chemical compound CCCCCCCCCCC1CCCCC1 STWFZICHPLEOIC-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RJLZSKYNYLYCNY-UHFFFAOYSA-N ethyl carbamate;isocyanic acid Chemical group N=C=O.CCOC(N)=O RJLZSKYNYLYCNY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- VLHZQNGNJQYAIZ-UHFFFAOYSA-N heptadecylcyclohexane Chemical compound CCCCCCCCCCCCCCCCCC1CCCCC1 VLHZQNGNJQYAIZ-UHFFFAOYSA-N 0.000 description 1
- MSTLSCNJAHAQNU-UHFFFAOYSA-N heptylcyclohexane Chemical compound CCCCCCCC1CCCCC1 MSTLSCNJAHAQNU-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- NRHBFNBZAZZTAU-UHFFFAOYSA-N hexadecylcyclohexane Chemical compound CCCCCCCCCCCCCCCCC1CCCCC1 NRHBFNBZAZZTAU-UHFFFAOYSA-N 0.000 description 1
- QHWAQXOSHHKCFK-UHFFFAOYSA-N hexylcyclohexane Chemical compound CCCCCCC1CCCCC1 QHWAQXOSHHKCFK-UHFFFAOYSA-N 0.000 description 1
- 229920006130 high-performance polyamide Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- CLMFECCMAVQYQA-UHFFFAOYSA-N nonylcyclohexane Chemical compound CCCCCCCCCC1CCCCC1 CLMFECCMAVQYQA-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- MWWVNZNVTGBKQO-UHFFFAOYSA-N octadecylcyclohexane Chemical compound CCCCCCCCCCCCCCCCCCC1CCCCC1 MWWVNZNVTGBKQO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FBXWCEKQCVOOLT-UHFFFAOYSA-N octylcyclohexane Chemical compound CCCCCCCCC1CCCCC1 FBXWCEKQCVOOLT-UHFFFAOYSA-N 0.000 description 1
- ZNUABQHWFGTOCO-UHFFFAOYSA-N pentadecylcyclohexane Chemical compound CCCCCCCCCCCCCCCC1CCCCC1 ZNUABQHWFGTOCO-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 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 1
- 230000000704 physical effect Effects 0.000 description 1
- MXXWOMGUGJBKIW-YPCIICBESA-N piperine Chemical compound C=1C=C2OCOC2=CC=1/C=C/C=C/C(=O)N1CCCCC1 MXXWOMGUGJBKIW-YPCIICBESA-N 0.000 description 1
- 229940075559 piperine Drugs 0.000 description 1
- WVWHRXVVAYXKDE-UHFFFAOYSA-N piperine Natural products O=C(C=CC=Cc1ccc2OCOc2c1)C3CCCCN3 WVWHRXVVAYXKDE-UHFFFAOYSA-N 0.000 description 1
- 235000019100 piperine Nutrition 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- 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
Definitions
- the present invention relates to an adhesive sheet.
- the pressure-sensitive adhesive sheet may be used not only for semi-permanent fixing of members but also for temporary fixing for temporarily fixing building materials, interior materials, electronic parts and the like. Such a pressure-sensitive adhesive sheet for temporarily fixing is required to satisfy both adhesiveness at the time of use and peelability after use.
- Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporarily fixing when cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material. Yes.
- This heat-peelable pressure-sensitive adhesive sheet adjusts the maximum particle size of the heat-expandable microspheres with respect to the thickness of the heat-expandable pressure-sensitive adhesive layer, and calculates the center line average roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating. It is adjusted to 0.4 ⁇ m or less.
- the heat-peelable pressure-sensitive adhesive sheet can secure an area of contact with an adherend when cutting an electronic component and can exhibit adhesiveness that can prevent adhesion failure such as chip jumping.
- the heat-expandable microspheres can be easily peeled off by expanding the thermally expandable microspheres by heating to reduce the contact area with the adherend.
- FOWLP Fean out Wafer Level Package
- the FOWLP 50 is provided with a rewiring layer 53 on the surface of the semiconductor chip 51 sealed with the sealing resin layer 52, and the solder balls 54 and the semiconductor chip 51 are interposed via the rewiring layer 53. Is a semiconductor package electrically connected to each other.
- the FOWLP 50 can be applied to applications where the number of terminals is larger than the area of the semiconductor chip 51 because the terminals that are the solder balls 54 can be expanded to the outside of the semiconductor chip 51 (Fan out). be able to.
- a semiconductor chip is placed on an adhesive sheet, and a sealing resin in a fluid state heated to around 100 ° C. is used as (1) an adhesive sheet around the semiconductor chip and the semiconductor chip. Or the like.
- a sealing resin film is laminated on a semiconductor chip and heated and laminated. The sealing step (1) or (2) is performed. Then, after the sealing step, FOWLP is manufactured through a step of removing the adhesive sheet and forming a redistribution layer and solder balls on the exposed surface of the semiconductor chip.
- the semiconductor chip is not misaligned between the time when the semiconductor chip is placed and the time when the semiconductor chip is sealed with the sealing resin. Adhesiveness to such an extent that the sealing resin does not enter at the adhesive interface is required. On the other hand, after sealing, the peelability which can remove an adhesive sheet easily is calculated
- a heat-peelable adhesive in which a thermally expandable adhesive layer containing thermally expandable microspheres is provided on a substrate. It is also possible to use a sheet.
- the elastic modulus of the thermally expandable pressure-sensitive adhesive layer is reduced by heating in the sealing step, It was found that the mounted semiconductor chip sinks to the adhesive sheet side.
- the sealing resin is cured while the semiconductor chip is sinking to the adhesive sheet side, the surface on the semiconductor chip side including the sealing resin after removing the adhesive sheet is the surface of the semiconductor chip and the surface of the sealing resin.
- the level difference is inferior and the flatness is poor.
- the semiconductor chips may be misaligned, resulting in problems such as the distance between the chips being not constant.
- the semiconductor chip sinks to the pressure-sensitive adhesive sheet side. It is also possible that peeling is difficult without this external force.
- the present invention has been made in view of the above-described problems, and when temporarily fixing an object, it is easy to use a slight force at the time of peeling while suppressing sinking of the object during heating. It aims at providing the adhesive sheet which can be peeled.
- the inventors of the present invention have a configuration of a pressure-sensitive adhesive sheet that includes a resin and a heat-expandable particle and has a heat-expandable base material that is non-adhesive and a pressure-sensitive adhesive layer that includes a pressure-sensitive adhesive resin. It has been found that the above problem can be solved by adjusting the storage elastic modulus E ′ at a predetermined temperature of the substrate to a specific range.
- a pressure-sensitive adhesive sheet comprising a resin and heat-expandable particles having an expansion start temperature (t) of 120 to 250 ° C., having a non-adhesive heat-expandable base material, and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive resin Because The pressure-sensitive adhesive sheet, wherein the thermally expandable substrate satisfies the following requirements (1) to (2).
- Requirement (2) The storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
- -Requirement (3) The storage elastic modulus E '(23) of the said thermally expansible base material in 23 degreeC is 1.0 * 10 ⁇ 6 > Pa or more.
- the above [1], wherein the ratio of the thickness of the thermally expandable substrate to the thickness of the adhesive layer (thermally expandable substrate / adhesive layer) at 23 ° C. is 0.2 or more.
- a thermally expandable substrate comprising a resin and thermally expandable particles having an expansion start temperature (t) of 120 to 250 ° C., non-adhesive, and satisfying the following requirements (1) to (2): -Requirement (1): The storage elastic modulus E '(100) of the said thermally expansible base material in 100 degreeC is 2.0 * 10 ⁇ 5 > Pa or more. Requirement (2): The storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
- the pressure-sensitive adhesive sheet of the present invention can be easily peeled off with a slight force during peeling while suppressing the sinking of the object during heating when temporarily fixing the object.
- the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
- the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically a value measured based on the method described in the examples.
- (meth) acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
- the lower limit value and upper limit value which were described in steps can be combined independently, respectively. For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.
- the pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it includes a resin and heat-expandable particles and has a non-adhesive heat-expandable base material and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive resin.
- 1 and 2 are schematic cross-sectional views of a pressure-sensitive adhesive sheet showing the configuration of the pressure-sensitive adhesive sheet of the present invention.
- a pressure-sensitive adhesive sheet 1a having a pressure-sensitive adhesive layer 12 on a thermally expandable substrate 11 as shown in FIG.
- the adhesive sheet of 1 aspect of this invention is good also as a structure which has the peeling material 13 on the adhesive surface of the adhesive layer 12 like the adhesive sheet 1b shown in FIG.1 (b).
- the pressure-sensitive adhesive sheet according to another aspect of the present invention may have two pressure-sensitive adhesive layers on both sides of the thermally expandable substrate.
- an adhesive sheet having such a configuration for example, as shown in FIG. 2A, both surfaces having a configuration in which the thermally expandable substrate 11 is sandwiched between the first adhesive layer 121 and the second adhesive layer 122.
- the adhesive sheet 2a is mentioned.
- the release material 131 is further provided on the adhesive surface of the first adhesive layer 121, and the release material is further provided on the adhesive surface of the second adhesive layer 122.
- a configuration having 132 is also possible.
- the peeling force when peeling the release material 131 from the first pressure-sensitive adhesive layer 121, and the peeling force when peeling the peeling material 132 from the second pressure-sensitive adhesive layer 122 In the case of the same level, if the two release materials are pulled outward to be peeled off, a phenomenon may occur in which the pressure-sensitive adhesive layer is divided and peeled off along with the two release materials. From the viewpoint of suppressing such a phenomenon, it is preferable to use two types of release materials designed so that the two release materials 131 and 132 have different release forces from the adhesive layer attached to each other.
- a release material in which release treatment is performed on both surfaces of one pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer 121 and the second pressure-sensitive adhesive layer 122. May be a double-sided pressure-sensitive adhesive sheet having a configuration in which a laminate is wound in a roll shape.
- the pressure-sensitive adhesive sheet of one embodiment of the present invention may have a configuration having another layer between the thermally expandable base material and the pressure-sensitive adhesive layer.
- the thermally expandable substrate 11 and the pressure-sensitive adhesive sheets 1a and 1b shown in FIG. 1 and the double-sided pressure-sensitive adhesive sheets 2a and 2b shown in FIG. It is preferable to have a structure in which the pressure-sensitive adhesive layer 12 is directly laminated.
- the heat-expandable base material of the pressure-sensitive adhesive sheet of the present invention comprises a resin and heat-expandable particles having an expansion start temperature (t) of 120 to 250 ° C., and is a non-adhesive base material.
- the storage elastic modulus E '(100) of the said thermally expansible base material in 100 degreeC is 2.0 * 10 ⁇ 5 > Pa or more.
- the storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
- the storage elastic modulus E ′ of the thermally expandable substrate at a predetermined temperature means a value measured by the method described in the examples.
- a sealing resin heated to around 100 ° C. and filled with fluidity is filled on the semiconductor chip, or a sealing resin sheet is laminated on the semiconductor chip.
- the semiconductor chip is sealed by heating and laminating. That is, the above requirement (1) prescribes the storage elastic modulus E ′ of the thermally expandable substrate under the temperature environment in the sealing process, assuming that the temperature environment in the sealing process of the manufacturing process of FOWLP is 100 ° C. Is.
- the heat-expandable pressure-sensitive adhesive layer as the pressure-sensitive adhesive sheet described in Patent Document 1 contains a pressure-sensitive adhesive resin
- the degree of decrease in the storage elastic modulus E ′ becomes very large as the temperature rises.
- the degree of decrease in the storage elastic modulus E ′ of the heat-expandable pressure-sensitive adhesive layer becomes very large, the heat-expandable particles and the pressure-sensitive resin contained in the heat-expandable pressure-sensitive adhesive layer easily flow, and accordingly, The pressure-sensitive adhesive surface of the thermally expandable pressure-sensitive adhesive layer is easily deformed.
- a target such as a semiconductor chip around 100 ° C.
- the weight of the sealing resin is increased.
- the pressure-sensitive adhesive sheet becomes flexible along with the heating and heating, the object is likely to sink into the pressure-sensitive adhesive sheet side.
- the sinking of the object is caused by the occurrence of positional deviation of the object, the occurrence of variation in the distance between the objects, and unevenness on the surface on which the object after sealing is placed, and the flatness is It also causes inferiority. This problem can also occur in a sealing method using a laminate using a sealing resin film.
- the flow of the heat-expandable particles and the pressure-sensitive resin in the heat-expandable pressure-sensitive adhesive layer is the same as described above. Therefore, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer is likely to be deformed, and the above-described problem may occur.
- the pressure-sensitive adhesive sheet of the present invention contains a resin and thermally expandable particles, and has a storage elastic modulus E ′ (100) at 100 ° C. of 2. as defined in the above requirement (1).
- the flow of thermally expandable particles can be moderately suppressed even in a temperature environment in a sealing process such as a FOWLP manufacturing process.
- the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer provided on is difficult to deform.
- the weight of the sealing resin laminated on the object such as a semiconductor chip or the pressure accompanying the lamination using the sealing resin sheet causes the object to sink to the adhesive sheet side, and a flat surface is formed. It is possible to suppress the adverse effects such as difficulty and the occurrence of displacement of the object.
- thermally expandable substrate having a storage elastic modulus E ′ (100) of less than 2.0 ⁇ 10 5 Pa it is thermally expandable under a temperature environment of 100 ° C. assuming a sealing process.
- the fluidity of the thermally expandable particles contained in the substrate is not sufficiently suppressed, and the adhesive surface of the adhesive layer provided on the thermally expandable substrate is likely to be deformed.
- the semiconductor chip is affected by the weight of the sealing resin and the pressure accompanying the lamination using the sealing resin sheet. Sinks on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet, irregularities are seen on the surface of the semiconductor chip after sealing, and it is difficult to form a flat surface.
- the storage elastic modulus E ′ (100) specified in the requirement (1) of the thermally expandable substrate used in one embodiment of the present invention is 2.0 ⁇ 10 5 Pa or more. It is 0 ⁇ 10 5 Pa or more, more preferably 6.0 ⁇ 10 5 Pa or more, further preferably 8.0 ⁇ 10 5 Pa or more, and still more preferably 1.0 ⁇ 10 6 Pa or more.
- the storage elastic modulus E ′ (100) defined by the requirement (1) of the thermally expandable base material is , Preferably 1.0 ⁇ 10 12 Pa or less, more preferably 1.0 ⁇ 10 11 Pa or less, further preferably 1.0 ⁇ 10 10 Pa or less, and even more preferably 1.0 ⁇ 10 9 Pa or less. .
- the said requirement (2) prescribes
- the contact area between the adherend (semiconductor chip and cured sealing resin) and the adhesive surface decreases, and the adherend and the adhesive surface By forming a space between them, the pressure-sensitive adhesive sheet can be easily peeled off from the adherend with a slight force.
- the heat-expandable particles contained in the heat-expandable substrate need to be adjusted so as to easily expand.
- the storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is defined. It can also be said that the index indicates the rigidity of the thermally expandable substrate immediately before expansion. That is, according to the study by the present inventors, the storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is more than 1.0 ⁇ 10 7 Pa. Even if it is attempted to expand the thermally expandable particles by heating to a temperature equal to or higher than the expansion start temperature (t), the expansion is suppressed and the thermally expandable particles are not sufficiently large, and are laminated on the surface of the thermally expandable substrate. It was found that the formation of irregularities on the adhesive surface of the pressure-sensitive adhesive layer was insufficient.
- the storage elastic modulus E ′ (t) defined in the requirement (2) of the thermally expandable substrate used in one embodiment of the present invention is preferably 9.0 ⁇ 10 6 Pa or less, more preferably 8. It is 0 ⁇ 10 6 Pa or less, more preferably 6.0 ⁇ 10 6 Pa or less, and still more preferably 4.0 ⁇ 10 6 Pa or less.
- the storage elastic modulus E ′ (t) specified in (2) is preferably 1.0 ⁇ 10 3 Pa or more, more preferably 1.0 ⁇ 10 4 Pa or more, and further preferably 1.0 ⁇ 10 5 Pa or more. It is.
- the storage elastic modulus E '(23) of the said thermally expansible base material in 23 degreeC is 1.0 * 10 ⁇ 6 > Pa or more.
- a semiconductor chip is usually placed so that its circuit surface is covered with an adhesive surface of an adhesive layer.
- a known apparatus such as a flip chip bonder or a die bonder may be used.
- a force is applied to push the semiconductor chip in the thickness direction of the adhesive sheet.
- the storage elastic modulus E ′ (23) of the thermally expandable base material defined by the above requirement (3) is preferably 5.0 ⁇ 10 6 to 5.0 ⁇ 10 12 Pa, more preferably 1. 0 ⁇ 10 7 to 1.0 ⁇ 10 12 Pa, more preferably 5.0 ⁇ 10 7 to 1.0 ⁇ 10 11 Pa, still more preferably 1.0 ⁇ 10 8 to 1.0 ⁇ 10 10 Pa is there.
- the thickness of the thermally expandable substrate at 23 ° C. is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, still more preferably 25 to 400 ⁇ m, and still more preferably 30 to 300 ⁇ m.
- the thickness of a thermally expansible base material means the value measured by the method as described in an Example.
- the thickness of the thermally expandable substrate is a value before expansion of the thermally expandable particles.
- the thermally expansible base material which the adhesive sheet of 1 aspect of this invention has is a non-adhesive base material.
- whether or not the non-adhesive substrate is determined if the probe tack value measured in accordance with JIS Z0237: 1991 is less than 50 mN / 5 mm ⁇ with respect to the surface of the target substrate.
- the said base material is judged as a "non-adhesive base material".
- the probe tack value on the surface of the thermally expandable substrate used in one embodiment of the present invention is usually less than 50 mN / 5 mm ⁇ , preferably less than 30 mN / 5 mm ⁇ , more preferably less than 10 mN / 5 mm ⁇ , and still more preferably. It is less than 5 mN / 5 mm ⁇ .
- the specific measuring method of the probe tack value on the surface of a thermally expansible base material is based on the method as described in an Example.
- the heat-expandable base material which the adhesive sheet of 1 aspect of this invention has contains resin and heat-expandable particle
- a thermally expansible base material can be formed from the resin composition (y) containing resin and a thermally expansible particle.
- each component contained in the resin composition (y) which is a forming material of a thermally expansible base material is demonstrated.
- the resin contained in the resin composition (y) may be any polymer that can form a thermally expandable substrate that satisfies the above requirements (1) and (2).
- non-adhesive resin may be sufficient and adhesive resin may be sufficient. That is, even if the resin contained in the resin composition (y) is an adhesive resin, the adhesive resin undergoes a polymerization reaction with the polymerizable compound in the process of forming the thermally expandable substrate from the resin composition (y). The obtained resin becomes a non-adhesive resin, and the heat-expandable substrate containing the resin may be non-adhesive.
- the mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1,000 to 1,000,000, more preferably 1,000 to 700,000, and still more preferably 1,000 to 500,000. Further, when the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer It may be.
- the content of the resin is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and still more preferably 65 to 90% with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y). It is 70% by weight, more preferably 70 to 85% by weight.
- the resin contained in the resin composition (y) is selected from acrylic urethane resins and olefin resins. Preferably it contains more than one species.
- the following resin (U1) is preferable.
- urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
- the urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.
- Examples of the polyol used as a raw material for the urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, ester amide type polyols, ester / ether type polyols, and carbonate type polyols. These polyols may be used independently and may use 2 or more types together.
- the polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and even more preferably an ester diol and a carbonate diol.
- ester type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarbox
- alkylene type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.
- alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol
- ethylene glycol, propylene glycol And alkylene glycols such as diethylene glycol and dipropylene glycol
- Examples of the carbonate type diol include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, and 1,3-propylene carbonate diol. 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, and the like.
- polyvalent isocyanate used as a raw material for the urethane prepolymer (UP) examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyvalent isocyanates may be used alone or in combination of two or more. These polyisocyanates may be a trimethylolpropane adduct type modified product, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
- the polyisocyanate used in one embodiment of the present invention is preferably diisocyanate, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
- MDI 4,4′-diphenylmethane diisocyanate
- 2,4-TDI 2,4-tolylene diisocyanate
- 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
- alicyclic diisocyanate examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane.
- IPDI isophorone diisocyanate
- Examples include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and isophorone diisocyanate (IPDI) is preferred.
- the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) is a reaction product of a diol and a diisocyanate, and is a straight chain having ethylenically unsaturated groups at both ends.
- a urethane prepolymer is preferred.
- an NCO group at the end of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting with.
- hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
- the (meth) acrylic acid ester is preferably one or more selected from alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates, and more preferably used in combination with alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
- the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.
- the carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
- hydroxyalkyl (meth) acrylate the same thing as the hydroxyalkyl (meth) acrylate used in order to introduce
- vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate.
- Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide). These may be used alone or in combination of two or more.
- the content of the (meth) acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably based on the total amount (100% by mass) of the vinyl compound. It is 80 to 100% by mass, more preferably 90 to 100% by mass.
- the total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the vinyl compound.
- the amount is 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
- the acrylic urethane-based resin (U1) used in one embodiment of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester and polymerizing both.
- the polymerization is preferably performed by adding a radical initiator.
- the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11 ) / (U12)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and still more preferably 35 by mass ratio. / 65 to 55/45.
- the olefin resin suitable as the resin contained in the resin composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
- the olefin monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and specifically includes ethylene, propylene, butylene, isobutylene, 1-hexene and the like. Among these, ethylene and propylene are preferable.
- olefinic resins for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more 910 kg / m less than 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more 915 kg / m less than 3 ), Medium density polyethylene (MDPE, density: 915 kg / m 3 or more and less than 942 kg / m 3 ), high density polyethylene (HDPE, density: 942 kg / m 3 or more), linear low density polyethylene, etc .; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); Vinyl alcohol copolymer (EVOH); ethylene-propylene Olefinic terpolymers such as-(5-ethylidene-2-norborn
- the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.
- an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride.
- unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride.
- Glutaconic anhydride citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
- unsaturated carboxylic acid or its anhydride may be used independently and may use 2 or more types together.
- an acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin as a main chain.
- a polymer is mentioned.
- the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1-20, more preferably 1-16, and still more preferably 1-12.
- said alkyl (meth) acrylate the same thing as the compound which can be selected as a below-mentioned monomer (a1 ') is mentioned, for example.
- Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin, which is the main chain.
- Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl.
- Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
- the resin composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
- Such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer Polycarbonate; Polyurethane not applicable to acrylic urethane resin; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine resin etc. are mentioned.
- vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol
- polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
- polystyrene acrylonitrile-butadiene-styren
- the content of the resin other than the acrylic urethane-based resin and the olefin-based resin in the resin composition (y) is smaller. Is preferred.
- the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin is preferably less than 30 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y). Less than, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass.
- the heat-expandable particles used in the present invention may be particles having an expansion start temperature (t) adjusted to 120 to 250 ° C., and are appropriately selected according to the application.
- the expansion start temperature (t) of the thermally expandable particles means a value measured based on the following method.
- Measurement method of expansion start temperature (t) of thermally expandable particles To an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, 0.5 mg of thermally expandable particles to be measured is added, and an aluminum lid (diameter 5.6 mm, thickness 0. 1 mm) is prepared.
- the height of the sample is measured from the upper part of the aluminum lid while a force of 0.01 N is applied to the sample by a pressurizer. Then, in a state where a force of 0.01 N is applied by the pressurizer, heating is performed from 20 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min, and the amount of displacement of the pressurizer in the vertical direction is measured.
- the displacement start temperature be the expansion start temperature (t).
- the thermally expandable particles are microencapsulated foaming agents composed of an outer shell composed of a thermoplastic resin and an encapsulated component encapsulated in the outer shell and vaporized when heated to a predetermined temperature.
- a thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
- Examples of the inclusion component contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane.
- the average particle diameter of the thermally expandable particles before expansion at 23 ° C. used in one embodiment of the present invention is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, still more preferably 6 to 60 ⁇ m, still more preferably 10 to 50 ⁇ m.
- the average particle diameter before expansion of the thermally expandable particles is the volume-median particle diameter (D 50 ), and is a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern).
- the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion means a particle diameter corresponding to 50%.
- the 90% particle diameter (D 90 ) before expansion at 23 ° C. of the thermally expandable particles used in one embodiment of the present invention is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, still more preferably 25 to 90 ⁇ m, More preferably, it is 30 to 80 ⁇ m.
- the 90% particle diameter (D 90 ) before expansion of the thermally expandable particles is the expansion measured by using a laser diffraction particle size distribution measuring apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern). In the particle distribution of the previous thermally expandable particles, it means a particle diameter corresponding to 90% of the cumulative volume frequency calculated from the smaller particle diameter of the thermally expandable particles before expansion.
- the maximum volume expansion coefficient when heated to a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles used in one embodiment of the present invention is preferably 1.5 to 100 times, more preferably 2 to 80 times, Preferably it is 2.5 to 60 times, and more preferably 3 to 40 times.
- the content of the heat-expandable particles is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and still more preferably 10% with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y). To 30% by mass, and more preferably 15 to 25% by mass.
- the resin composition (y) used in one embodiment of the present invention may contain a base material additive contained in a base material included in a general pressure-sensitive adhesive sheet as long as the effects of the present invention are not impaired.
- base material additives include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants. These base material additives may be used alone or in combination of two or more.
- the content of each base material additive is preferably 0.0001 to 20 parts by mass with respect to 100 parts by mass of the resin in the resin composition (y). More preferably, it is 0.001 to 10 parts by mass.
- the resin composition (y) used in one embodiment of the present invention is ethylenic having a mass average molecular weight (Mw) of 50000 or less from the viewpoint of forming a thermally expandable substrate that satisfies the above requirements (1) and (2).
- Examples include a solventless resin composition (y1), which is obtained by blending an oligomer having an unsaturated group, an energy beam polymerizable monomer, and the above-described thermally expandable particles, and not blending a solvent. In the solventless resin composition (y1), no solvent is blended, but the energy beam polymerizable monomer contributes to the improvement of the plasticity of the oligomer. By irradiating the coating film formed from the solventless resin composition (y1) with energy rays, it is easy to form a thermally expandable substrate that satisfies the above requirements (1) and (2).
- the mass average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y1) is 50000 or less, preferably 1000 to 50000, more preferably 2000 to 40000, and still more preferably 3000 to 35000. More preferably, it is 4000-30000.
- oligomer As said oligomer, what is necessary is just to have an ethylenically unsaturated group whose mass mean molecular weight is 50000 or less among resin contained in the above-mentioned resin composition (y), but the above-mentioned urethane prepolymer (UP ) Is preferred.
- a modified olefin resin having an ethylenically unsaturated group can also be used.
- the total content of the oligomer and the energy beam polymerizable monomer in the solventless resin composition (y1) is preferably 50 with respect to the total amount (100% by mass) of the solventless resin composition (y1). It is ⁇ 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.
- Examples of the energy ray polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantane ( Cycloaliphatic polymerizable compounds such as (meth) acrylate and tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate and phenol ethylene oxide modified acrylate; Tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- And heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam. These energy beam polymerizable monomers may be used independently and may use 2 or more types together.
- the content ratio [oligomer / energy ray polymerizable monomer] of the oligomer and the energy ray polymerizable monomer in the solventless resin composition (y1) is preferably 20/80 to 90 / in mass ratio. 10, more preferably 30/70 to 85/15, still more preferably 35/65 to 80/20.
- the solventless resin composition (y1) is further blended with a photopolymerization initiator.
- a photopolymerization initiator By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with a relatively low energy beam.
- photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned. These photoinitiators may be used independently and may use 2 or more types together.
- the blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass with respect to the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer.
- the amount is preferably 0.02 to 3 parts by mass.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention only needs to contain a pressure-sensitive adhesive resin, and if necessary, for pressure-sensitive adhesives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator. An additive may be contained.
- the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet of one embodiment of the present invention is non-thermal from the viewpoint of preventing an object such as a mounted semiconductor chip from sinking into the pressure-sensitive adhesive layer due to heating in the sealing step. It is preferable that it is an expandable adhesive layer.
- the adhesive force on the adhesive surface of the adhesive layer on which an object such as a semiconductor chip is placed at 23 ° C. before expansion of the thermally expandable particles is preferably 0.1 to 10 It is 0.0 N / 25 mm, more preferably 0.2 to 8.0 N / 25 mm, still more preferably 0.4 to 6.0 N / 25 mm, and still more preferably 0.5 to 4.0 N / 25 mm. If the adhesive force is 0.1 N / 25 mm or more, the adherend such as a semiconductor chip can be sufficiently fixed to the extent that positional displacement can be prevented in the next step such as a sealing step.
- said adhesive force means the value measured by the method as described in an Example.
- the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer on which an object such as a semiconductor chip is placed at 23 ° C. is preferably 1.0 ⁇ 10 4 to It is 1.0 ⁇ 10 8 Pa, more preferably 5.0 ⁇ 10 4 to 5.0 ⁇ 10 7 Pa, and still more preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa. If the storage shear elastic modulus G ′ (23) of the pressure-sensitive adhesive layer is 1.0 ⁇ 10 4 Pa or more, it is possible to prevent positional deviation when attaching an object such as a semiconductor chip, It is possible to prevent excessive sinking into the adhesive layer.
- the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer is 1.0 ⁇ 10 8 Pa or less, it is easily deformed by heating to a temperature equal to or higher than the expansion start temperature (t) during peeling.
- the expansion of the thermally expandable particles in the thermally expandable substrate irregularities are easily formed on the surface of the pressure-sensitive adhesive layer, and as a result, it can be easily peeled off with a slight force.
- the storage shear modulus G '(23) of an adhesive layer means the value measured by the method as described in an Example.
- the adhesive on which objects, such as a semiconductor chip, are mounted The storage shear modulus G ′ (23) of the layer is preferably within the above range.
- the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer on the side to be attached to the support or the like at 23 ° C. has good adhesion to the support or the like. From the viewpoint, it is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 8 Pa, more preferably 3.0 ⁇ 10 4 to 5.0 ⁇ 10 7 Pa, still more preferably 5.0 ⁇ 10 4 to 1. 0 ⁇ 10 7 Pa.
- the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention is formed by the viewpoint of developing excellent pressure-sensitive adhesive force and the expansion of the thermally expandable particles in the thermally expandable substrate by heat treatment. From the viewpoint of easily forming irregularities on the surface of the pressure-sensitive adhesive layer, the thickness is preferably 1 to 60 ⁇ m, more preferably 2 to 50 ⁇ m, still more preferably 3 to 40 ⁇ m, and still more preferably 5 to 30 ⁇ m.
- the ratio of the thickness of the heat-expandable base material to the thickness of the pressure-sensitive adhesive layer at 23 ° C. heat-expandable base material / pressure-sensitive adhesive layer
- the sealing step from the viewpoint of flattening the surface on the object side after sealing and preventing positional displacement of the object, it is preferably 0.2 or more, more preferably 0.5 or more, and still more preferably.
- a pressure-sensitive adhesive sheet that can be easily peeled with a slight force when peeled, preferably 1000 or less, more preferably 200 or less, More preferably, it is 60 or less, More preferably, it is 30 or less.
- the pressure-sensitive adhesive sheet has a plurality of pressure-sensitive adhesive layers, such as the double-sided pressure-sensitive adhesive sheets 2a and 2b shown in FIG. It means the thickness of the agent layer. That is, for each pressure-sensitive adhesive layer, it is preferable that the thickness and the ratio [thermally expandable substrate / pressure-sensitive adhesive layer] are within the above ranges. Moreover, the thickness of an adhesive layer means the value measured by the method as described in an Example.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention can be formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin. Moreover, in the adhesive sheet which has several adhesive layers like the double-sided adhesive sheet 2a, 2b shown in FIG. 2, each adhesive layer may be formed from the same adhesive composition, and is mutually different. You may form from an adhesive composition.
- each component contained in the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer will be described.
- any polymer may be used as long as the resin has adhesiveness and has a mass average molecular weight (Mw) of 10,000 or more.
- the mass average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and even more preferably 30,000, from the viewpoint of improving the adhesive strength. ⁇ 1 million.
- the adhesive resin examples include rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. These adhesive resins may be used independently and may use 2 or more types together. In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
- the adhesive resin used in one embodiment of the present invention may be an energy ray curable adhesive resin in which a polymerizable functional group is introduced into the side chain of the above-mentioned adhesive resin.
- a polymerizable functional group include a (meth) acryloyl group and a vinyl group.
- energy rays include ultraviolet rays and electron beams, but ultraviolet rays are preferred.
- the content of the adhesive resin is preferably 30 to 99.99% by mass, more preferably 40 to 99.95% by mass, still more preferably based on the total amount (100% by mass) of the active ingredients of the adhesive composition. It is 50 to 99.90% by mass, more preferably 55 to 99.80% by mass, still more preferably 60 to 99.50% by mass.
- “content of each component relative to the total amount of active ingredients of the pressure-sensitive adhesive composition” means “content of each component in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition”. Is synonymous with.
- the adhesive resin preferably contains an acrylic resin.
- the content of the acrylic resin in the adhesive resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass with respect to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition. %, More preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
- the acrylic resin that can be used as an adhesive resin includes, for example, a polymer including a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, a cyclic structure And a polymer containing a structural unit derived from a (meth) acrylate having a hydrogen atom.
- the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, still more preferably 500,000 to 1,100,000. .
- a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”) and a functional group-containing monomer (a2).
- An acrylic copolymer (A1) having a structural unit (a2) derived from ') (hereinafter also referred to as “monomer (a2')") is more preferred.
- the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and still more preferably 4 to 8 from the viewpoint of improving adhesive properties. It is.
- the alkyl group contained in the monomer (a1 ′) may be a linear alkyl group or a branched alkyl group.
- Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate. These monomers (a1 ′) may be used alone or in combination of two or more. As the monomer (a1 ′), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.
- the content of the structural unit (a1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass with respect to the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 70 to 97.0% by mass, and still more preferably 80 to 95.0% by mass.
- a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. examples include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer. These monomers (a2 ′) may be used alone or in combination of two or more. Among these, as the monomer (a2 ′), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.
- Examples of the hydroxyl group-containing monomer include the same hydroxyl group-containing compounds as described above.
- carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
- ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid
- dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
- the content of the structural unit (a2) is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight with respect to all the structural units (100% by weight) of the acrylic copolymer (A1). %, More preferably 1.0 to 30% by mass, and still more preferably 3.0 to 25% by mass.
- the acrylic copolymer (A1) may further have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
- the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1).
- To 100% by mass more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
- Examples of the monomer (a3 ′) include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc.
- olefins such as ethylene, propylene, and isobutylene
- halogenated olefins such as vinyl chloride and vinylidene chloride
- diene monomers such as butadiene, iso
- the acrylic copolymer (A1) may be an energy ray curable acrylic copolymer having a polymerizable functional group introduced in the side chain.
- the polymerizable functional group and the energy ray are as described above.
- the polymerizable functional group includes an acrylic copolymer having the above structural units (a1) and (a2), and a substituent that can be bonded to the functional group of the structural unit (a2) of the acrylic copolymer. And a compound having a polymerizable functional group can be reacted. Examples of the compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate, and the like.
- the pressure-sensitive adhesive composition preferably further contains a cross-linking agent when it contains a pressure-sensitive adhesive resin containing a functional group such as the acrylic copolymer (A1) described above.
- the said crosslinking agent reacts with the adhesive resin which has a functional group, and bridge
- crosslinking agent examples include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents may be used independently and may use 2 or more types together. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.
- the content of the crosslinking agent is appropriately adjusted depending on the number of functional groups that the adhesive resin has, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group, The amount is more preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.
- the pressure-sensitive adhesive composition may further contain a tackifier from the viewpoint of further improving the adhesive strength.
- the “tackifier” is a component that assists in improving the adhesive strength of the above-mentioned adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is distinguished from a functional resin.
- the mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 500 to 8000, and still more preferably 800 to 5000.
- Examples of the tackifier are obtained by copolymerizing C5 fractions such as rosin resin, terpene resin, styrene resin, pentene, isoprene, piperine, 1,3-pentadiene generated by thermal decomposition of petroleum naphtha.
- C9 petroleum resin obtained by copolymerizing C9 fractions such as indene generated by thermal decomposition of petroleum naphtha and vinyltoluene, and hydrogenated resins obtained by hydrogenating these.
- the softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and still more preferably 70 to 150 ° C.
- the “softening point” of the tackifier means a value measured according to JIS K2531.
- a tackifier may be used independently and may use 2 or more types from which a softening point and a structure differ. And when using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifier belongs to the said range.
- the content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.05 to 55% by mass, and still more preferably relative to the total amount (100% by mass) of the active ingredients of the adhesive composition. It is 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, still more preferably 1.0 to 40% by mass.
- ⁇ Photopolymerization initiator> 1 aspect of this invention WHEREIN: When an adhesive composition contains an energy-beam curable adhesive resin as an adhesive resin, it is preferable to contain a photoinitiator further. By forming an adhesive composition containing an energy ray-curable adhesive resin and a photopolymerization initiator, the adhesive layer formed from the adhesive composition can be irradiated with a relatively low energy energy beam. It is possible to sufficiently advance the curing reaction and adjust the adhesive strength to a desired range.
- mode of this invention the same thing as what is mix
- the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.001 parts by mass with respect to 100 parts by mass of the energy ray curable adhesive resin. 05 to 2 parts by mass.
- the pressure-sensitive adhesive composition as a material for forming the pressure-sensitive adhesive layer is a pressure-sensitive adhesive used for general pressure-sensitive adhesives in addition to the above-described additives, as long as the effects of the present invention are not impaired. May contain additives.
- an adhesive additive include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, and the like. These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
- each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 100 parts by mass of the adhesive resin. ⁇ 10 parts by mass.
- the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer, may contain thermally expandable particles as long as the effects of the present invention are not impaired.
- the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably a non-thermally expandable pressure-sensitive adhesive layer. Therefore, the pressure-sensitive adhesive composition, which is a material for forming the pressure-sensitive adhesive layer, is more preferable as the content of thermally expandable particles is as small as possible.
- the content of the heat-expandable particles is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably 0.1% by mass with respect to the total amount (100% by mass) of the active ingredients of the pressure-sensitive adhesive composition. Is more preferably less than 0.01% by mass, particularly preferably less than 0.001% by mass.
- the pressure-sensitive adhesive sheet of one embodiment of the present invention may further include a release material on the adhesive surface of the pressure-sensitive adhesive layer. Good.
- the adhesive sheet which has two adhesive layers like the adhesive sheet 2b of FIG.2 (b) the two peeling materials provided on the sticking surface of each adhesive layer differ in the peeling force difference. It is preferable that it is adjusted as described above.
- the release material a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used. Examples include a release material coated on a release material substrate.
- Examples of the base material for the release material include papers such as high-quality paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; and olefins such as polypropylene resin and polyethylene resin.
- a plastic film such as a resin film;
- release agent examples include silicone-based resins, olefin-based resins, isoprene-based resins, rubber-based elastomers such as butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
- the thickness of the release material is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 170 ⁇ m, and still more preferably 35 to 80 ⁇ m.
- Step (1a) On the release treatment surface of the release material, the resin composition (y), which is a material for forming the thermally expandable substrate, is applied to form a coating film, and the coating film is dried or irradiated with UV. Forming a thermally expandable substrate.
- Another method for producing the pressure-sensitive adhesive sheet of the present invention includes a method (b) having the following steps (1b) to (3b).
- the resin composition (y) and the pressure-sensitive adhesive composition may be further mixed with a diluent solvent to form a solution.
- a diluent solvent examples include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
- the expansion of the thermally expandable particles is prevented in the drying process of forming the thermally expandable substrate from the coating film.
- the drying temperature is preferably less than the expansion start temperature (t) of the thermally expandable particles.
- the pressure-sensitive adhesive sheet of the present invention When temporarily fixing an object, the pressure-sensitive adhesive sheet of the present invention can be easily peeled off with a slight force while peeling while suppressing the sinking of the object during heating. Therefore, the pressure-sensitive adhesive sheet of the present invention is preferably used in a sealing step with heating using a sealing resin, and specifically, preferably used in a sealing step when manufacturing FOWLP. .
- the semiconductor chip is placed on the adhesive surface of the adhesive layer of the adhesive sheet of the present invention, and then the upper surface and the adhesive surface of the semiconductor chip are covered with a sealing resin and heated. Sealing is performed by thermosetting the sealing resin.
- the elastic modulus of each layer constituting the pressure-sensitive adhesive sheet decreases due to heating in the sealing process, and the semiconductor chip placed sinks to the pressure-sensitive adhesive sheet side. Is seen.
- the pressure-sensitive adhesive sheet of the present invention satisfies the above requirement (1), and thus effectively suppresses the sinking of the semiconductor chip to the pressure-sensitive adhesive sheet side, which may occur in the sealing step, and the semiconductor after sealing.
- the surface on the chip side can be flattened, and the occurrence of misalignment of the semiconductor chip can be suppressed.
- the sealing resin an arbitrary one can be appropriately selected from those used as a semiconductor sealing material, and examples thereof include a thermosetting resin and an energy ray curable resin. It is done.
- the form of the sealing resin may be a solid such as a granule or a film at room temperature, or may be a liquid material having fluidity such as a composition, but from the viewpoint of workability. A film-like material is preferable.
- a method of covering the semiconductor chip and its peripheral part using the sealing resin it is appropriately selected and applied according to the type of the sealing material from methods conventionally used in the semiconductor sealing process. For example, a roll laminating method, a vacuum pressing method, a vacuum laminating method, a spin coating method, a die coating method, a transfer molding method, a compression molding mold method, or the like can be applied.
- a sealing process is performed on temperature conditions less than the expansion start temperature (t) of a thermally expansible particle.
- the sealing resin coating process and the thermosetting process may be performed separately. However, when the sealing resin is heated in the coating process, the sealing material is cured as it is by the heating, and the coating process is performed. And thermosetting treatment may be performed simultaneously.
- the pressure-sensitive adhesive sheet can be easily peeled with a slight force by heating to a temperature equal to or higher than the expansion start temperature (t).
- the “temperature higher than the expansion start temperature (t)” when peeling the adhesive sheet is preferably “expansion start temperature (t) + 10 ° C.” or higher and “expansion start temperature (t) + 60 ° C.” or lower. It is more preferable that the expansion start temperature (t) + 15 ° C. or higher and the “expansion start temperature (t) + 40 ° C.” or lower.
- this invention can also provide the usage method of the adhesive sheet of following [1].
- a method for using a pressure-sensitive adhesive sheet wherein the pressure-sensitive adhesive sheet is peeled from the adherend by a heat treatment at a temperature equal to or higher than an expansion start temperature (t) after the pressure-sensitive adhesive sheet of the present invention is attached to the adherend.
- t expansion start temperature
- the particle distribution of the thermally expandable particles before expansion at 23 ° C. was measured using a laser diffraction particle size distribution measuring apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern).
- the particle diameters corresponding to 50% and 90% of the cumulative volume frequency calculated from the smaller particle diameter of the particle distribution are expressed as “average particle diameter (D 50 ) of thermally expandable particles” and “thermally expandable particles”, respectively.
- a viscoelasticity measuring device manufactured by Anton Paar, device name “MCR300”
- a torsional shear method under conditions of a test start temperature of 0 ° C., a test end temperature of 300 ° C., a heating rate of 3 ° C./min, and a frequency of 1 Hz was used to measure the storage shear modulus G ′ of the test sample at a given temperature.
- a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample at a contact load of 0.98 N / cm 2 for 1 second, and then the probe is tested at a speed of 10 mm / second. The force required to move away from the surface was measured. And the measured value was made into the probe tack value of the test sample.
- Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) 80.0 / 20.0 (mass ratio), A solution containing an acrylic copolymer having a Mw of 600,000. Diluting solvent: ethyl acetate, solid content concentration: 40% by mass.
- Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid 86.0 / 8.0 / 5.0 / 1.
- first adhesive layer (X-1) The isocyanate-based crosslinking agent (i) 5.0 parts by mass (solid content ratio) is blended with 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin, and diluted with toluene.
- the composition (x-1) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by stirring uniformly. Then, on the surface of the release agent layer of the above heavy release film, the prepared composition (x-1) was applied to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to have a thickness of 10 ⁇ m.
- the first pressure-sensitive adhesive layer (X-1) was formed.
- the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X-1) at 23 ° C. was 2.5 ⁇ 10 5 Pa.
- Second adhesive layer (X-2) The isocyanate-based crosslinking agent (i) 0.8 parts by mass (solid content ratio) is blended with 100 parts by mass of the acrylic copolymer (ii), which is an adhesive resin, and diluted with toluene, The composition (x-2) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by stirring uniformly. Then, on the surface of the release agent layer of the light release film, the prepared composition (x-2) was applied to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to have a thickness of 10 ⁇ m. The second pressure-sensitive adhesive layer (X-2) was formed. The storage shear modulus G ′ (23) of the second pressure-sensitive adhesive layer (X-2) at 23 ° C. was 9.0 ⁇ 10 4 Pa.
- the product name “Irgacure 184”) 2.0 parts by mass (solid content ratio) and 0.2 parts by mass (solid content ratio) phthalocyanine pigment as an additive were blended to prepare an energy ray curable composition. . And the said heat-expandable particle
- thermally expandable substrate (Y-1) The prepared composition (y-1) was applied on the surface of the release agent layer of the light release film to form a coating film. Then, using an ultraviolet irradiation device (product name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.) and a high-pressure mercury lamp (product name “H04-L41” manufactured by Eye Graphics Co., Ltd.), an illuminance of 160 mW / cm 2 and a light amount of 500 mJ / The coating film was cured by irradiating ultraviolet rays under the condition of cm 2 to form a thermally expandable substrate (Y-1) having a thickness of 50 ⁇ m. The above illuminance and light intensity during ultraviolet irradiation are values measured using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT).
- the isocyanate-based crosslinking agent (i) is 6.3 parts by mass with respect to 100 parts by mass of the solid content of the acrylic urethane-based resin solution obtained in (2) above. Parts (solid content ratio), dioctyltin bis (2-ethylhexanoate) 1.4 parts by mass (solid content ratio) as a catalyst, and the above-mentioned thermally expandable particles (i) were blended, diluted with toluene, and homogeneous And a composition (y-2) having a solid content concentration (active ingredient concentration) of 30% by mass was prepared.
- the content of the heat-expandable particles (i) relative to the total amount (100% by mass) of active ingredients in the obtained composition (y-2) was 20% by mass. Then, on the surface of the release agent for the light release film, the prepared composition (y-2) was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to have a thickness of 50 ⁇ m. A thermally expandable substrate (Y-2) was formed.
- thermally expandable pressure-sensitive adhesive layer (Y-3) To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 6.3 parts by mass (solid content ratio) of the isocyanate-based crosslinking agent (i) and the thermally expandable particles ( i) was mixed, diluted with toluene, and stirred uniformly to prepare a composition (y-3) having a solid content concentration (active ingredient concentration) of 30% by mass. The content of thermally expandable particles (i) relative to the total amount (100% by mass) of active ingredients in the obtained composition (y-3) was 20% by mass.
- the prepared composition (y-3) was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to have a thickness of 50 ⁇ m.
- the heat-expandable pressure-sensitive adhesive layer (Y-3) was formed.
- thermally expandable base material (Y-4)
- the above isocyanate-based material is used with respect to 100 parts by mass of the solid content of the energy ray-curable acrylic copolymer (iii) obtained in (1) above.
- 0.5 parts by mass (solid content ratio) of the crosslinking agent (i), 3.0 parts by mass (solid content ratio) of the photopolymerization initiator (i), and the thermally expandable particles (i) are blended, and toluene.
- the mixture was stirred uniformly to prepare a composition (y-4) having a solid content concentration (active ingredient concentration) of 30% by mass.
- the content of the heat-expandable particles (1) relative to the total amount (100% by mass) of active ingredients in the obtained composition (y-4) was 20% by mass.
- the prepared composition (y-4) was applied to form a coating film. After drying the coating film at 100 ° C. for 120 seconds, an illuminance of 160 mW / cm 2. Irradiation with ultraviolet rays under conditions of a light amount of 500 mJ / cm 2 formed a thermally expandable substrate (Y-4) having a thickness of 50 ⁇ m.
- the above illuminance and light intensity during ultraviolet irradiation are values measured using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT).
- Thermally expandable substrates (Y-1) to (Y-2) and (Y-4) formed in Production Examples 3 to 4 and 6, and a thermally expandable pressure-sensitive adhesive layer (Y-3) formed in Production Example 5 ),
- Example 1 After the exposed surfaces of the first pressure-sensitive adhesive layer (X-1) formed in Production Example 1 and the thermally expandable base material (Y-1) formed in Production Example 3 are bonded together, thermal expansion is performed.
- the light release film / second pressure-sensitive adhesive layer (X-2) / thermally expandable substrate (Y-1) / first pressure-sensitive adhesive layer (X-1) / heavy release film were laminated in this order.
- a sheet (1) was produced.
- Example 2 Lightly peelable film / second adhesive as in Example 1, except that the thermally expandable substrate (Y-1) was replaced with the thermally expandable substrate (Y-2) formed in Production Example 4.
- a pressure-sensitive adhesive sheet (2) was prepared by laminating layer (X-2) / thermally expandable substrate (Y-2) / first pressure-sensitive adhesive layer (X-1) / heavy release film in this order.
- Comparative Example 1 The exposed surfaces of the second pressure-sensitive adhesive layer (X-2) formed in Production Example 2 and the thermally expandable pressure-sensitive adhesive layer (Y-3) formed in Production Example 5 were bonded together. Then, the light release film on the side of the heat-expandable pressure-sensitive adhesive layer (Y-3) is removed, and the first pressure-sensitive adhesive formed in Production Example 1 on the surface of the exposed heat-expandable pressure-sensitive adhesive layer (Y-3). The agent layer (X-1) was bonded. Thus, the light release film / second pressure-sensitive adhesive layer (X-2) / thermally expandable pressure-sensitive adhesive layer (Y-3) / first pressure-sensitive adhesive layer (X-1) / heavy release film was laminated in this order. An adhesive sheet (3) was produced.
- Comparative Example 2 Lightly peelable film / second adhesive as in Example 1, except that the thermally expandable substrate (Y-1) was replaced with the thermally expandable substrate (Y-4) formed in Production Example 6.
- a pressure-sensitive adhesive sheet (4) was prepared by laminating layer (X-2) / thermally expandable substrate (Y-4) / first pressure-sensitive adhesive layer (X-1) / heavy release film in this order.
- Comparative Example 3 The exposed surfaces of the second pressure-sensitive adhesive layer (X-2) formed in Production Example 2 and the heat-expandable pressure-sensitive adhesive layer (Y-3) formed in Production Example 5 were bonded together to form a light release film / A pressure-sensitive adhesive sheet (5) was prepared by laminating the second pressure-sensitive adhesive layer (X-2) / heat-expandable pressure-sensitive adhesive layer (Y-3) / light release film in this order.
- the surfaces were placed at necessary intervals so that the surface was in contact with the adhesive surface. Thereafter, a sealing resin film is laminated on the adhesive surface and the semiconductor chip, and the semiconductor chip is sealed using a vacuum heating and pressure laminator (“7024HP5” manufactured by ROHM and HAAS). Produced.
- the sealing conditions are as follows. -Preheating temperature: 100 ° C for both table and diaphragm ⁇ Vacuum drawing: 60 seconds ⁇ Dynamic press mode: 30 seconds ⁇ Static press mode: 10 seconds ⁇ Sealing temperature: 180 ° C. (temperature lower than 208 ° C. which is the expansion start temperature of thermally expandable particles) ⁇ Sealing time: 60 minutes
- the pressure-sensitive adhesive sheets (1) to (5) are heated for 3 minutes at 240 ° C., which is equal to or higher than the expansion start temperature (208 ° C.) of the thermally expandable particles, and the pressure-sensitive adhesive sheets (1) to (5)
- the sealing body is separated, the semiconductor chip on the surface of the separated sealing body (the surface on which the adhesive sheet has been attached) is observed visually and with a microscope, and the presence or absence of misalignment of the semiconductor chip is confirmed. It was evaluated with.
- A A semiconductor chip in which a positional deviation of 25 ⁇ m or more from before sealing was not confirmed.
- F A semiconductor chip in which a positional deviation of 25 ⁇ m or more occurred before sealing was confirmed.
- the heavy release film of the pressure-sensitive adhesive sheets (1) to (4) and the other light-release film of the pressure-sensitive adhesive sheet (5) are also removed, and the first pressure-sensitive adhesive layer (X-1) or the thermal expansibility that is exposed
- the adhesive surface of the adhesive layer (Y-3) was affixed to a stainless steel plate (SUS304 No. 360 polishing) as an adherend and allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity). This was used as a test sample. Then, using the above test sample, in an environment of 23 ° C.
- the pressure-sensitive adhesive sheet (3) of Comparative Example 1 and the pressure-sensitive adhesive sheet (5) of Comparative Example 3 have a thermally expandable pressure-sensitive adhesive layer, not a thermally expandable substrate, during heating during the sealing step, The sinking of the semiconductor chip occurred, the semiconductor chip was misaligned, and a step was observed on the surface on the semiconductor chip side after the sealing step. Therefore, for example, it is considered that it is not suitable for use in a sealing process when manufacturing FOWLP.
- the pressure-sensitive adhesive sheet (4) of Comparative Example 2 did not change much in the adhesive strength before and after heating at a temperature higher than the expansion start temperature, and could not be said to be peelable by heating.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
このような仮固定用途の粘着シートには、使用時の接着性と、使用後の剥離性との両立が要求される。
この加熱剥離型粘着シートは、熱膨張性粘着層の厚さに対して、熱膨張性微小球の最大粒径を調整し、加熱前の熱膨張性粘着層の表面の中心線平均粗さを0.4μm以下に調整している。
特許文献1には、当該加熱剥離型粘着シートは、電子部品切断時には、被着体との接触面積を確保でき、チップ飛び等の接着不具合を防止し得る接着性を発揮でき、一方で、使用後には、加熱によって、熱膨張性微小球を膨張させて、被着体との接触面積を減少させることで、容易に剥離することができる旨の記載がある。
図3に示すように、FOWLP50は、封止樹脂層52によって封止された半導体チップ51の表面上に、再配線層53を設け、再配線層53を介して、はんだボール54と半導体チップ51とを電気的に接続した半導体パッケージである。
図3に示すように、FOWLP50は、半導体チップ51の外側まではんだボール54である端子を広げること(Fan out)ができるため、半導体チップ51の面積と比べて端子数が多い用途にも適用することができる。
上記の封止工程において用いられる粘着シートには、半導体チップを載置してから封止樹脂で封止するまでの間は、半導体チップの位置ズレが生じず、且つ、半導体チップと粘着シートとの接着界面において封止樹脂が侵入しない程度の接着性が求められる。その一方で、封止後には、粘着シートを容易に除去し得る剥離性が求められる。
しかしながら、本発明者らの検討によれば、特許文献1に記載の粘着シートを、上記封止工程に用いた場合、封止工程における加熱によって、熱膨張性粘着層の弾性率が低下し、載置している半導体チップが粘着シート側に沈み込むことが分かった。
半導体チップが粘着シート側に沈み込んだまま、封止樹脂が硬化されると、粘着シートを除去後の封止樹脂を含む半導体チップ側の表面は、半導体チップの表面と封止樹脂の表面との段差が生じ、平坦性に劣る。また、半導体チップの位置ズレが発生し、チップ間距離が一定とならない等の弊害が生じ得る。
さらに、特許文献1に記載の粘着シートを除去する際に、加熱をして熱膨張性粘着層を膨張させても、半導体チップが粘着シート側に沈み込んでしまっていることにより、ある程度の大きさの外力無しでは剥離が困難となることも考えられる。
[1]樹脂及び膨張開始温度(t)が120~250℃である熱膨張性粒子を含み、非粘着性である熱膨張性基材と、粘着性樹脂を含む粘着剤層とを有する粘着シートであって、
前記熱膨張性基材が、下記要件(1)~(2)を満たす、粘着シート。
・要件(1):100℃における、前記熱膨張性基材の貯蔵弾性率E’(100)が、2.0×105Pa以上である。
・要件(2):前記熱膨張性粒子の膨張開始温度(t)における、前記熱膨張性基材の貯蔵弾性率E’(t)が、1.0×107Pa以下である。
[2]前記熱膨張性基材が、下記要件(3)を満たす、上記[1]に記載の粘着シート。
・要件(3):23℃における、前記熱膨張性基材の貯蔵弾性率E’(23)が、1.0×106Pa以上である。
[3]23℃における、前記熱膨張性基材の厚さと、前記粘着剤層の厚さとの比(熱膨張性基材/粘着剤層)が0.2以上である、上記[1]又は[2]に記載の粘着シート。
[4]23℃における、前記熱膨張性基材の厚さが10~1000μmであり、前記粘着剤層の厚さが1~60μmである、上記[1]~[3]のいずれか一項に記載の粘着シート。
[5]前記熱膨張性基材の表面におけるプローブタック値が、50mN/5mmφ未満である、上記[1]~[4]のいずれか一項に記載の粘着シート。
[6]23℃における、前記粘着剤層の貯蔵せん断弾性率G’(23)が、1.0×104~1.0×108Paである、上記[1]~[5]のいずれか一項に記載の粘着シート。
[7]前記熱膨張性基材の両面に、2つの前記粘着剤層をそれぞれ有する、上記[1]~[6]のいずれか一項に記載の粘着シート。
[8]前記熱膨張性粒子の23℃における膨張前の平均粒子径が、3~100μmである、上記[1]~[7]のいずれか一項に記載の粘着シート。
[9]封止樹脂を使用した、加熱を伴う封止工程で用いられる、上記[1]~[8]のいずれか一項に記載の粘着シート。
[10]樹脂及び膨張開始温度(t)が120~250℃である熱膨張性粒子を含み、非粘着性であり、下記要件(1)~(2)を満たす、熱膨張性基材。
・要件(1):100℃における、前記熱膨張性基材の貯蔵弾性率E’(100)が、2.0×105Pa以上である。
・要件(2):前記熱膨張性粒子の膨張開始温度(t)における、前記熱膨張性基材の貯蔵弾性率E’(t)が、1.0×107Pa以下である。
[11]上記[1]~[9]のいずれか一項に記載の粘着シートを被着体に貼付後、膨張開始温度(t)以上の加熱処理によって、前記被着体から前記粘着シートを剥離する、粘着シートの使用方法。
[12]封止樹脂を使用した、加熱を伴う封止工程で用いる、上記[11]に記載の粘着シートの使用方法。
また、質量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー(GPC)法で測定される標準ポリスチレン換算の値であり、具体的には実施例に記載の方法に基づいて測定した値である。
また、好ましい数値範囲(例えば、含有量等の範囲)について、段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、「好ましくは10~90、より好ましくは30~60」という記載から、「好ましい下限値(10)」と「より好ましい上限値(60)」とを組み合わせて、「10~60」とすることもできる。
本発明の粘着シートは、樹脂及び熱膨張性粒子を含み、非粘着性である熱膨張性基材と、粘着性樹脂を含む粘着剤層とを有するものであれば、特に限定されない。
図1及び2は、本発明の粘着シートの構成を示す、粘着シートの断面模式図である。
なお、本発明の一態様の粘着シートは、図1(b)に示す粘着シート1bのように、粘着剤層12の粘着表面上に、さらに剥離材13を有する構成としてもよい。
このような構成の粘着シートとしては、例えば、図2(a)に示すような、熱膨張性基材11を第1粘着剤層121及び第2粘着剤層122で挟持した構成を有する、両面粘着シート2aが挙げられる。
また、図2(b)に示す両面粘着シート2bのように、第1粘着剤層121の粘着表面上にさらに剥離材131を有し、第2粘着剤層122の粘着表面上にさらに剥離材132を有する構成としてもよい。
このような現象を抑制する観点から、2つの剥離材131、132は、互いに貼付される粘着剤層からの剥離力が異なるように設計された2種の剥離材を用いることが好ましい。
ただし、わずかな力で容易に剥離可能な粘着シートとする観点から、図1に示す粘着シート1a、1b、及び図2に示す両面粘着シート2a、2bのように、熱膨張性基材11と粘着剤層12とが直接積層した構成を有するものであることが好ましい。
本発明の粘着シートが有する熱膨張性基材は、樹脂及び膨張開始温度(t)が120~250℃である熱膨張性粒子を含み、非粘着性の基材であって、下記要件(1)~(2)を満たすものである。
・要件(1):100℃における、前記熱膨張性基材の貯蔵弾性率E’(100)が、2.0×105Pa以上である。
・要件(2):前記熱膨張性粒子の膨張開始温度(t)における、前記熱膨張性基材の貯蔵弾性率E’(t)が、1.0×107Pa以下である。
なお、本明細書において、所定の温度における熱膨張性基材の貯蔵弾性率E’は、実施例に記載の方法により測定された値を意味する。
つまり、上記要件(1)は、FOWLPの製造過程の封止工程における温度環境を100℃と仮定し、封止工程における温度環境下での熱膨張性基材の貯蔵弾性率E’を規定したものである。
ここで、熱膨張性粘着剤層の貯蔵弾性率E’の低下の度合いが非常に大きくなると、熱膨張性粘着剤層に含まれる熱膨張性粒子及び粘着性樹脂が流動し易く、それに伴い、熱膨張性粘着剤層の粘着表面が変形し易くなる。
その結果、半導体チップ等の対象物の上に、例えば、封止樹脂を100℃前後に加熱をして流動性を有する封止樹脂を流し込みながら封止した場合には、当該封止樹脂の重さ及び加熱に伴って粘着シートが柔軟になることによって、対象物が粘着シート側に沈み込みが発生し易くなる。対象物の沈み込みは、対象物の位置ズレの発生、対象物間の距離のバラツキの発生、及び、封止後の対象物が載置された側の表面に凹凸が見られ、平坦性が劣る原因ともなる。なお、この問題は、封止用樹脂フィルムを用いたラミネートによる封止方法でも同様に生じ得る。
また、上記の熱膨張性粘着剤層の表面上に、新たな粘着剤層を設けた粘着シートにおいても、上記と同じく、熱膨張性粘着剤層中の熱膨張性粒子及び粘着性樹脂の流動によって、粘着剤層の粘着表面の変形が生じ易く、上述の問題が生じ得る。
その結果、半導体チップ等の対象物の上に積層された封止樹脂の重さや封止用樹脂シートを用いたラミネートに伴う圧力によって、対象物が粘着シート側に沈み込み、平坦面が形成され難いといった弊害や、対象物の位置ズレの発生を抑制することができる。
その結果、例えば、FOWLPの製造の封止工程で当該熱膨張性基材を有する粘着シートを用いた場合、封止樹脂の重さや封止用樹脂シートを用いたラミネートに伴う圧力によって、半導体チップが粘着シートの粘着剤層側に沈み込み、封止後の半導体チップ側の表面に凹凸が見られ、平坦面が形成され難いといった弊害が生じ得る。
また、封止工程において、半導体チップ等の封止対象物の位置ズレを効果的に抑制する観点から、当該熱膨張性基材の要件(1)で規定する貯蔵弾性率E’(100)は、好ましくは1.0×1012Pa以下、より好ましくは1.0×1011Pa以下、更に好ましくは1.0×1010Pa以下、より更に好ましくは1.0×109Pa以下である。
本発明の粘着シートを被着体から剥離する際には、熱膨張性粒子の膨張開始温度(t)以上の温度まで加熱することで、熱膨張性基材中の熱膨張性粒子が膨張し、熱膨張性基材の表面に凹凸が形成されると共に、その凹凸上に積層している粘着剤層も押し上げられ、粘着表面にも凹凸を形成される。
そして、粘着剤層の粘着表面に凹凸を形成させることで、被着体(半導体チップ及び硬化後の封止樹脂)と粘着表面との接触面積が減少すると共に、被着体と粘着表面との間に空間が生じることで、被着体から粘着シートをわずかな力で容易に剥離することができる。
つまり、本発明者らの検討によれば、熱膨張性粒子の膨張開始温度(t)における、熱膨張性基材の貯蔵弾性率E’(t)が1.0×107Pa超となると、膨張開始温度(t)以上の温度まで加熱して熱膨張性粒子の膨張しようとしても、膨張が抑制されて熱膨張性粒子が十分に大きくならず、熱膨張性基材の表面上に積層している粘着剤層の粘着表面の凹凸形成が不十分となることが分かった。
また、膨張した熱膨張性粒子の流動を抑制し、粘着剤層の粘着表面に形成される凹凸の形状維持性を向上させ、剥離性をより向上させる観点から、当該熱膨張性基材の要件(2)で規定する貯蔵弾性率E’(t)は、好ましくは1.0×103Pa以上、より好ましくは1.0×104Pa以上、更に好ましくは1.0×105Pa以上である。
・要件(3):23℃における、前記熱膨張性基材の貯蔵弾性率E’(23)が、1.0×106Pa以上である。
例えば、半導体チップは、通常、その回路面が、粘着剤層の粘着表面で覆われるように載置される。半導体チップの載置には、例えば、フリップチップボンダーやダイボンダー等の公知の装置が用いられることがある。
ここで、フリップチップボンダーやダイボンダーを用いて、半導体チップを粘着シートの粘着剤層上に載置する際に、半導体チップを粘着シートの厚み方向に押し込む力が加わるため、半導体チップが粘着剤層の厚み方向側に過度に沈み込む恐れがある。
また、フリップチップボンダーやダイボンダーを用いて、半導体チップを粘着シート上に載置する際に、半導体チップを粘着シートの水平方向に移動させる力も加わるため、半導体チップが粘着剤層の水平方向に位置ズレする恐れもある。
しかし、上記要件(3)を満たす熱膨張性基材とすることで、これらの問題を解決することもできる。
なお、本明細書において、熱膨張性基材の厚さは、実施例に記載の方法により測定された値を意味する。また、当該熱膨張性基材の厚さは、熱膨張性粒子の膨張前の値である。
本発明において、非粘着性の基材か否かの判断は、対象となる基材の表面に対して、JIS Z0237:1991に準拠して測定したプローブタック値が50mN/5mmφ未満であれば、当該基材を「非粘着性の基材」と判断する。
ここで、本発明の一態様で用いる熱膨張性基材の表面におけるプローブタック値は、通常50mN/5mmφ未満であるが、好ましくは30mN/5mmφ未満、より好ましくは10mN/5mmφ未満、更に好ましくは5mN/5mmφ未満である。
なお、本明細書において、熱膨張性基材の表面におけるプローブタック値の具体的な測定方法は、実施例に記載の方法による。
また、熱膨張性基材は、樹脂及び熱膨張性粒子を含む樹脂組成物(y)から形成することができる。
以下、熱膨張性基材の形成材料である樹脂組成物(y)に含まれる各成分について説明する。
樹脂組成物(y)に含まれる樹脂としては、上記要件(1)及び(2)を満たす熱膨張性基材を形成可能な重合体であればよい。
なお、樹脂組成物(y)に含まれる樹脂としては、非粘着性樹脂であってもよく、粘着性樹脂であってもよい。
つまり、樹脂組成物(y)に含まれる樹脂が粘着性樹脂であっても、樹脂組成物(y)から熱膨張性基材を形成する過程において、当該粘着性樹脂が重合性化合物と重合反応し、得られる樹脂が非粘着性樹脂となり、当該樹脂を含む熱膨張性基材が非粘着性となればよい。
また、当該樹脂が2種以上の構成単位を有する共重合体である場合、当該共重合体の形態は、特に限定されず、ブロック共重合体、ランダム共重合体、及びグラフト共重合体のいずれであってもよい。
また、上記アクリルウレタン系樹脂としては、以下の樹脂(U1)が好ましい。
・ウレタンプレポリマー(UP)と、(メタ)アクリル酸エステルを含むビニル化合物とを重合してなるアクリルウレタン系樹脂(U1)。
アクリルウレタン系樹脂(U1)の主鎖となるウレタンプレポリマー(UP)としては、ポリオールと多価イソシアネートとの反応物が挙げられる。
なお、ウレタンプレポリマー(UP)は、更に鎖延長剤を用いた鎖延長反応を施して得られたものであることが好ましい。
これらのポリオールは、単独で用いてもよく、2種以上を併用してもよい。
本発明の一態様で用いるポリオールとしては、ジオールが好ましく、エステル型ジオール、アルキレン型ジオール及びカーボネート型ジオールがより好ましく、エステル型ジオール、カーボネート型ジオールが更に好ましい。
具体的には、ポリエチレンアジペートジオール、ポリブチレンアジペートジオール、ポリヘキサメチレンアジペートジオール、ポリヘキサメチレンイソフタレートジオール、ポリネオペンチルアジペートジオール、ポリエチレンプロピレンアジペートジオール、ポリエチレンブチレンアジペートジオール、ポリブチレンヘキサメチレンアジペートジオール、ポリジエチレンアジペートジオール、ポリ(ポリテトラメチレンエーテル)アジペートジオール、ポリ(3-メチルペンチレンアジペート)ジオール、ポリエチレンアゼレートジオール、ポリエチレンセバケートジオール、ポリブチレンアゼレートジオール、ポリブチレンセバケートジオール及びポリネオペンチルテレフタレートジオール等が挙げられる。
これらの多価イソシアネートは、単独で用いてもよく、2種以上を併用してもよい。
また、これらの多価イソシアネートは、トリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、イソシアヌレート環を含有させたイソシアヌレート型変性体であってもよい。
当該直鎖ウレタンプレポリマーの両末端にエチレン性不飽和基を導入する方法としては、ジオールとジイソシアネート化合物とを反応してなる直鎖ウレタンプレポリマーの末端のNCO基と、ヒドロキシアルキル(メタ)アクリレートとを反応させる方法が挙げられる。
(メタ)アクリル酸エステルとしては、アルキル(メタ)アクリレート及びヒドロキシアルキル(メタ)アクリレートから選ばれる1種以上が好ましく、アルキル(メタ)アクリレート及びヒドロキシアルキル(メタ)アクリレートを併用することがより好ましい。
これらは単独で用いてもよく、2種以上を併用してもよい。
当該重合においては、さらにラジカル開始剤を加えて行うことが好ましい。
樹脂組成物(y)に含まれる樹脂として好適な、オレフィン系樹脂としては、オレフィンモノマーに由来の構成単位を少なくとも有する重合体である。
上記オレフィンモノマーとしては、炭素数2~8のα-オレフィンが好ましく、具体的には、エチレン、プロピレン、ブチレン、イソブチレン、1-ヘキセン等が挙げられる。
これらの中でも、エチレン及びプロピレンが好ましい。
上記の不飽和カルボン酸又はその無水物としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、グルタコン酸、テトラヒドロフタル酸、アコニット酸、(メタ)アクリル酸、無水マレイン酸、無水イタコン酸、無水グルタコン酸、無水シトラコン酸、無水アコニット酸、ノルボルネンジカルボン酸無水物、テトラヒドロフタル酸無水物等が挙げられる。
なお、不飽和カルボン酸又はその無水物は、単独で用いてもよく、2種以上を併用してもよい。
上記のアルキル(メタ)アクリレートが有するアルキル基の炭素数としては、好ましくは1~20、より好ましくは1~16、更に好ましくは1~12である。
上記のアルキル(メタ)アクリレートとしては、例えば、後述のモノマー(a1’)として選択可能な化合物と同じものが挙げられる。
上記の水酸基含有化合物としては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類;ビニルアルコール、アリルアルコール等の不飽和アルコール類等が挙げられる。
本発明の一態様において、樹脂組成物(y)には、本発明の効果を損なわない範囲で、アクリルウレタン系樹脂及びオレフィン系樹脂以外の樹脂を含有してもよい。
そのような樹脂としては、例えば、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール等のビニル系樹脂;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂;ポリスチレン;アクリロニトリル-ブタジエン-スチレン共重合体;三酢酸セルロース;ポリカーボネート;アクリルウレタン系樹脂には該当しないポリウレタン;ポリスルホン;ポリエーテルエーテルケトン;ポリエーテルスルホン;ポリフェニレンスルフィド;ポリエーテルイミド、ポリイミド等のポリイミド系樹脂;ポリアミド系樹脂;アクリル樹脂;フッ素系樹脂等が挙げられる。
アクリルウレタン系樹脂及びオレフィン系樹脂以外の樹脂の含有割合としては、樹脂組成物(y)中に含まれる樹脂の全量100質量部に対して、好ましくは30質量部未満、より好ましくは20質量部未満、より好ましくは10質量部未満、更に好ましくは5質量部未満、より更に好ましくは1質量部未満である。
本発明で用いる熱膨張性粒子は、膨張開始温度(t)が120~250℃に調整された粒子であればよく、用途に応じて適宜選択される。
なお、本明細書において、熱膨張性粒子の膨張開始温度(t)は、以下の方法に基づき測定された値を意味する。
[熱膨張性粒子の膨張開始温度(t)の測定法]
直径6.0mm(内径5.65mm)、深さ4.8mmのアルミカップに、測定対象となる熱膨張性粒子0.5mgを加え、その上からアルミ蓋(直径5.6mm、厚さ0.1mm)をのせた試料を作製する。
動的粘弾性測定装置を用いて、その試料にアルミ蓋上部から、加圧子により0.01Nの力を加えた状態で、試料の高さを測定する。そして、加圧子により0.01Nの力を加えた状態で、20℃から300℃まで10℃/minの昇温速度で加熱し、加圧子の垂直方向における変位量を測定し、正方向への変位開始温度を膨張開始温度(t)とする。
マイクロカプセル化発泡剤の外殻を構成する熱可塑性樹脂としては、例えば、塩化ビニリデン-アクリロニトリル共重合体、ポリビニルアルコール、ポリビニルブチラール、ポリメチルメタクリレート、ポリアクリロニトリル、ポリ塩化ビニリデン、ポリスルホン等が挙げられる。
これらの内包成分は、単独で用いてもよく、2種以上を併用してもよい。
熱膨張性粒子の膨張開始温度(t)は、内包成分の種類を適宜選択することで調整可能である。
なお、熱膨張性粒子の膨張前の平均粒子径とは、体積中位粒子径(D50)であり、レーザ回折式粒度分布測定装置(例えば、Malvern社製、製品名「マスターサイザー3000」)を用いて測定した、膨張前の熱膨張性粒子の粒子分布において、膨張前の熱膨張性粒子の粒子径の小さい方から計算した累積体積頻度が50%に相当する粒子径を意味する。
なお、熱膨張性粒子の膨張前の90%粒子径(D90)とは、レーザ回折式粒度分布測定装置(例えば、Malvern社製、製品名「マスターサイザー3000」)を用いて測定した、膨張前の熱膨張性粒子の粒子分布において、膨張前の熱膨張性粒子の粒子径の小さい方から計算した累積体積頻度が90%に相当する粒径を意味する。
本発明の一態様で用いる樹脂組成物(y)は、本発明の効果を損なわない範囲で、一般的な粘着シートが有する基材に含まれる基材用添加剤を含有してもよい。
そのような基材用添加剤としては、例えば、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、スリップ剤、アンチブロッキング剤、着色剤等が挙げられる。
なお、これらの基材用添加剤は、それぞれ単独で用いてもよく、2種以上を併用してもよい。
これらの基材用添加剤を含有する場合、それぞれの基材用添加剤の含有量は、樹脂組成物(y)中の前記樹脂100質量部に対して、好ましくは0.0001~20質量部、より好ましくは0.001~10質量部である。
本発明の一態様で用いる樹脂組成物(y)としては、上記要件(1)及び(2)を満たす熱膨張性基材を形成する観点から、質量平均分子量(Mw)が50000以下のエチレン性不飽和基を有するオリゴマーと、エネルギー線重合性モノマーと、上述の熱膨張性粒子を配合してなり、溶剤を配合しない、無溶剤型樹脂組成物(y1)が挙げられる。
無溶剤型樹脂組成物(y1)では、溶剤を配合しないが、エネルギー線重合性モノマーが、前記オリゴマーの可塑性の向上に寄与するものである。
無溶剤型樹脂組成物(y1)から形成した塗膜に対して、エネルギー線を照射することで、上記要件(1)及び(2)を満たす熱膨張性基材を形成し易い。
なお、当該オリゴマーとしては、エチレン性不飽和基を有する変性オレフィン系樹脂も使用し得る。
これらのエネルギー線重合性モノマーは、単独で用いてもよく、2種以上を併用してもよい。
光重合開始剤を含有することで、比較的低エネルギーのエネルギー線の照射によっても、十分に硬化反応を進行させることができる。
これらの光重合開始剤は、単独で用いてもよく、2種以上を併用してもよい。
本発明の一態様の粘着シートが有する粘着剤層は、粘着性樹脂を含むものであればよく、必要に応じて、架橋剤、粘着付与剤、重合性化合物、重合開始剤等の粘着剤用添加剤を含有してもよい。
なお、封止工程での加熱によって、載置した半導体チップ等の対象物が粘着剤層に沈む込むことを防止する観点から、本発明の一態様の粘着シートが有する粘着剤層は、非熱膨張性粘着剤層であることが好ましい。
当該粘着力が0.1N/25mm以上であれば、半導体チップ等の被着体を、封止工程等の次工程で位置ズレを防止し得る程度に、十分に固定することができる。
一方、当該粘着力が10.0N/25mm以下であれば、剥離時に、膨張開始温度(t)以上の温度まで加熱することで、わずかな力で容易に剥離することができる。
なお、上記の粘着力は、実施例に記載の方法により測定された値を意味する。
当該粘着剤層の貯蔵せん断弾性率G’(23)が1.0×104Pa以上であれば、半導体チップ等の対象物を貼付する際の位置ズレを防止することができ、また、その際の粘着剤層への過度な沈み込むを防止することができる。
一方、当該粘着剤層の貯蔵せん断弾性率G’(23)が1.0×108Pa以下であれば、剥離時に、膨張開始温度(t)以上の温度まで加熱することで変形し易くなり、熱膨張性基材中の熱膨張性粒子の膨張により、粘着剤層の表面に凹凸が形成され易く、その結果、わずかな力で容易に剥離することができる。
なお、本明細書において、粘着剤層の貯蔵せん断弾性率G’(23)は、実施例に記載の方法により測定された値を意味する。
一方、粘着シートを固定するために、23℃における、支持体等と貼付される側の粘着剤層の貯蔵せん断弾性率G’(23)としては、支持体等との密着性を良好とする観点から、好ましくは1.0×104~1.0×108Pa、より好ましくは3.0×104~5.0×107Pa、更に好ましくは5.0×104~1.0×107Paである。
また、粘着剤層の厚さは、実施例に記載の方法により測定された値を意味する。
また、図2に示す両面粘着シート2a、2bのように、複数の粘着剤層を有する粘着シートにおいては、それぞれの粘着剤層を、同一の粘着剤組成物から形成してもよく、互いに異なる粘着剤組成物から形成してもよい。
以下、粘着剤層の形成材料である粘着剤組成物に含まれる各成分について説明する。
本発明の一態様で用いる粘着性樹脂としては、当該樹脂単独で粘着性を有し、質量平均分子量(Mw)が1万以上の重合体であればよい。
本発明の一態様で用いる粘着性樹脂の質量平均分子量(Mw)としては、粘着力の向上の観点から、好ましくは1万~200万、より好ましくは2万~150万、更に好ましくは3万~100万である。
これらの粘着性樹脂は、単独で用いてもよく、2種以上を併用してもよい。
また、これらの粘着性樹脂が、2種以上の構成単位を有する共重合体である場合、当該共重合体の形態は、特に限定されず、ブロック共重合体、ランダム共重合体、及びグラフト共重合体のいずれであってもよい。
当該重合性官能基としては、(メタ)アクリロイル基、ビニル基等が挙げられる。
また、エネルギー線としては、紫外線や電子線が挙げられるが、紫外線が好ましい。
なお、本明細書の以下の記載において、「粘着剤組成物の有効成分の全量に対する各成分の含有量」は、「当該粘着剤組成物から形成される粘着剤層中の各成分の含有量」と同義である。
粘着性樹脂中のアクリル系樹脂の含有割合としては、粘着剤組成物に含まれる粘着性樹脂の全量(100質量%)に対して、好ましくは30~100質量%、より好ましくは50~100質量%、更に好ましくは70~100質量%、より更に好ましくは85~100質量%である。
本発明の一態様において、粘着性樹脂として使用し得る、アクリル系樹脂としては、例えば、直鎖又は分岐鎖のアルキル基を有するアルキル(メタ)アクリレートに由来する構成単位を含む重合体、環状構造を有する(メタ)アクリレートに由来する構成単位を含む重合体等が挙げられる。
なお、モノマー(a1’)が有するアルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。
これらのモノマー(a1’)は、単独で用いてもよく、2種以上を併用してもよい。
モノマー(a1’)としては、ブチル(メタ)アクリレート及び2-エチルヘキシル(メタ)アクリレートが好ましい。
つまり、モノマー(a2’)としては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー等が挙げられる。
これらのモノマー(a2’)は、単独で用いてもよく、2種以上を併用してもよい。
これらの中でも、モノマー(a2’)としては、水酸基含有モノマー及びカルボキシ基含有モノマーが好ましい。
なお、アクリル系共重合体(A1)において、構成単位(a1)及び(a2)の含有量は、アクリル系共重合体(A1)の全構成単位(100質量%)に対して、好ましくは70~100質量%、より好ましくは80~100質量%、更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。
当該重合性官能基及び当該エネルギー線としては、上述のとおりである。
なお、重合性官能基は、上述の構成単位(a1)及び(a2)を有するアクリル系共重合体と、当該アクリル系共重合体の構成単位(a2)が有する官能基と結合可能な置換基と重合性官能基とを有する化合物とを反応させることで導入することができる。
前記化合物としては、例えば、(メタ)アクリロイルオキシエチルイソシアネート、(メタ)アクリロイルイソシアネート、グリシジル(メタ)アクリレート等が挙げられる。
本発明の一態様において、粘着剤組成物は、上述のアクリル系共重合体(A1)のような官能基を含有する粘着性樹脂を含有する場合、さらに架橋剤を含有することが好ましい。
当該架橋剤は、官能基を有する粘着性樹脂と反応して、当該官能基を架橋起点として、粘着性樹脂同士を架橋するものである。
これらの架橋剤は、単独で用いてもよく、2種以上を併用してもよい。
これらの架橋剤の中でも、凝集力を高めて粘着力を向上させる観点、及び入手し易さ等の観点から、イソシアネート系架橋剤が好ましい。
本発明の一態様において、粘着剤組成物は、粘着力をより向上させる観点から、さらに粘着付与剤を含有してもよい。
本明細書において、「粘着付与剤」とは、上述の粘着性樹脂の粘着力を補助的に向上させる成分であって、質量平均分子量(Mw)が1万未満のオリゴマーを指し、上述の粘着性樹脂とは区別されるものである。
粘着付与剤の質量平均分子量(Mw)は、好ましくは400~10000、より好ましくは500~8000、更に好ましくは800~5000である。
なお、本明細書において、粘着付与剤の「軟化点」は、JIS K 2531に準拠して測定した値を意味する。
粘着付与剤は、単独で用いてもよく、軟化点や構造が異なる2種以上を併用してもよい。
そして、2種以上の複数の粘着付与剤を用いる場合、それら複数の粘着付与剤の軟化点の加重平均が、上記範囲に属することが好ましい。
本発明の一態様において、粘着剤組成物が、粘着性樹脂として、エネルギー線硬化型の粘着性樹脂を含む場合、さらに光重合開始剤を含有することが好ましい。
エネルギー線硬化型の粘着性樹脂及び光重合開始剤を含有する粘着剤組成物とすることで、当該粘着剤組成物から形成される粘着剤層は、比較的低エネルギーのエネルギー線の照射によっても、十分に硬化反応を進行させ、粘着力を所望の範囲に調整することが可能となる。
なお、本発明の一態様で用いる光重合開始剤としては、上述の無溶剤型樹脂組成物(y1)に配合されるものと同じものが挙げられる。
本発明の一態様において、粘着剤層の形成材料である粘着剤組成物は、本発明の効果を損なわない範囲で、上述の添加剤以外にも、一般的な粘着剤に使用される粘着剤用添加剤を含有していてもよい。
このような粘着剤用添加剤としては、例えば、酸化防止剤、軟化剤(可塑剤)、防錆剤、顔料、染料、遅延剤、反応促進剤(触媒)、紫外線吸収剤等が挙げられる。
なお、これらの粘着剤用添加剤は、それぞれ単独で用いてもよく、2種以上を併用してもよい。
ただし、上述のとおり、本発明の一態様の粘着シートが有する粘着剤層は、非熱膨張性粘着剤層であることが好ましい。そのため、当該粘着剤層の形成材料である粘着剤組成物は、熱膨張性粒子の含有量が極力少ないほど好ましい。
熱膨張性粒子の含有量は、粘着剤組成物の有効成分の全量(100質量%)に対して、好ましくは5質量%未満、より好ましくは1質量%未満、更に好ましくは0.1質量%未満、より更に好ましくは0.01質量%未満、特に好ましくは0.001質量%未満である。
図1(b)の粘着シート1b及び図2(b)の粘着シート2bのように、本発明の一態様の粘着シートは、粘着剤層の貼付表面に、さらに剥離材を有していてもよい。
なお、図2(b)の粘着シート2bのように、2つの粘着剤層を有する粘着シートでは、それぞれの粘着剤層の貼付表面上に設ける2枚の剥離材は、剥離力の差が異なるように調整されたものであることが好ましい。
剥離材としては、両面剥離処理をされた剥離シートや、片面剥離処理された剥離シート等が用いられ、剥離材用の基材上に剥離剤を塗布したもの等が挙げられる。
本発明の粘着シートの製造方法としては、特に制限はなく、下記工程(1a)及び(2a)を有する製造方法(a)が挙げられる。
・工程(1a):剥離材の剥離処理面上に、熱膨張性基材の形成材料である樹脂組成物(y)を塗布して塗膜を形成し、当該塗膜を乾燥又はUV照射し、熱膨張性基材を形成する工程。
・工程(2a):形成した前記熱膨張性基材の表面上に、粘着剤層の形成材料である粘着剤組成物を塗布して塗膜を形成し、当該塗膜を乾燥し、粘着剤層を形成する工程。
・工程(1b):剥離材の剥離処理面上に、熱膨張性基材の形成材料である樹脂組成物(y)を塗布して塗膜を形成し、当該塗膜を乾燥し、熱膨張性基材を形成する工程。
・工程(2b):剥離材の剥離処理面上に、粘着剤層の形成材料である粘着剤組成物を塗布して塗膜を形成し、当該塗膜を乾燥し、粘着剤層を形成する工程。
・工程(3b):工程(1b)で形成した前記熱膨張性基材の表面と、工程(2b)で形成した粘着剤層の表面とを貼り合せる工程。
塗布方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等が挙げられる。
本発明の粘着シートは、対象物を仮固定する際には、加熱時において当該対象物の沈み込みを抑制しつつ、剥離時には、わずかな力で容易に剥離可能である。
そのため、本発明の粘着シートは、封止樹脂を使用した、加熱を伴う封止工程で用いられることが好ましく、具体的には、FOWLPを製造する際の封止工程で使用されることが好ましい。
この際、一般的な粘着シートを用いた場合には、封止工程での加熱によって、粘着シートを構成する各層の弾性率が低下し、載置している半導体チップが粘着シート側に沈み込みが見られる。
これに対して、本発明の粘着シートは、上記要件(1)を満たすため、封止工程で生じ得る、半導体チップの粘着シート側への沈み込みを効果的に抑制し、封止後の半導体チップ側の表面を平坦にすることができると共に、半導体チップの位置ズレの発生を抑制することができる。
また、封止樹脂の形態としては、室温で、顆粒状、フィルム状等の固形であってもよく、組成物のように流動性がある液状物であってもよいが、作業性の観点から、フィルム状物であることが好ましい。
また、封止樹脂の被覆処理と熱硬化処理は、別々に実施してもよいが、被覆処理において封止樹脂を加熱する場合には、当該加熱によって、そのまま封止材を硬化させ、被覆処理と熱硬化処理とを同時に実施してもよい。
粘着シートを剥離する際の「膨張開始温度(t)以上の温度」としては、「膨張開始温度(t)+10℃」以上「膨張開始温度(t)+60℃」以下であることが好ましく、「膨張開始温度(t)+15℃」以上「膨張開始温度(t)+40℃」以下であることがより好ましい。
[1]上述の本発明の粘着シートを被着体に貼付後、膨張開始温度(t)以上の加熱処理によって、前記被着体から前記粘着シートを剥離する、粘着シートの使用方法。
なお、当該使用方法は、封止樹脂を使用した、加熱を伴う封止工程で用いることが好ましい。
ゲル浸透クロマトグラフ装置(東ソー株式会社製、製品名「HLC-8020」)を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
(測定条件)
・カラム:「TSK guard column HXL-L」「TSK gel G2500HXL」「TSK gel G2000HXL」「TSK gel G1000HXL」(いずれも東ソー株式会社製)を順次連結したもの
・カラム温度:40℃
・展開溶媒:テトラヒドロフラン
・流速:1.0mL/min
株式会社テクロック製の定圧厚さ測定器(型番:「PG-02J」、標準規格:JIS K6783、Z1702、Z1709に準拠)を用いて測定した。
レーザ回折式粒度分布測定装置(例えば、Malvern社製、製品名「マスターサイザー3000」)を用いて、23℃における膨張前の熱膨張性粒子の粒子分布を測定した。
そして、粒子分布の粒子径の小さい方から計算した累積体積頻度が50%及び90%に相当する粒子径を、それぞれ「熱膨張性粒子の平均粒子径(D50)」及び「熱膨張性粒子の90%粒子径(D90)とした。
測定対象が非粘着性の熱膨張性基材である場合、当該熱膨張性基材を縦5mm×横30mm×厚さ200μmの大きさとし、剥離材を除去したものを試験サンプルとした。
動的粘弾性測定装置(TAインスツルメント社製,製品名「DMAQ800」)を用いて、試験開始温度0℃、試験終了温度300℃、昇温速度3℃/分、振動数1Hz、振幅20μmの条件で、所定の温度における、当該試験サンプルの貯蔵弾性率E’を測定した。
測定対象が粘着性を有する熱膨張性粘着剤層及び粘着剤層である場合、当該熱膨張性粘着剤層及び粘着剤層を直径8mm×厚さ3mmとし、剥離材を除去したものを試験サンプルとした。
粘弾性測定装置(Anton Paar社製、装置名「MCR300」)を用いて、試験開始温度0℃、試験終了温度300℃、昇温速度3℃/分、振動数1Hzの条件で、ねじりせん断法によって、所定の温度における、試験サンプルの貯蔵せん断弾性率G’を測定した。
そして、貯蔵弾性率E’の値は、測定した貯蔵せん断弾性率G’の値を基に、近似式「E’=3G’」から算出した。
測定対象となる熱膨張性基材又は熱膨張性粘着剤層を一辺10mmの正方形に切断した後、23℃、50%RH(相対湿度)の環境下で24時間静置し、軽剥離フィルムを除去したものを試験サンプルとした。
23℃、50%RH(相対湿度)の環境下で、タッキング試験機(日本特殊測器株式会社製,製品名「NTS-4800」)を用いて、軽剥離フィルムを除去して表出した、前記試験サンプルの表面におけるプローブタック値を、JIS Z0237:1991に準拠して測定した。
具体的には、直径5mmのステンレス鋼製のプローブを、1秒間、接触荷重0.98N/cm2で、試験サンプルの表面に接触させた後、当該プローブを10mm/秒の速度で、試験サンプルの表面から離すのに必要な力を測定した。そして、その測定した値を、その試験サンプルのプローブタック値とした。
<粘着性樹脂>
・アクリル系共重合体(i):2-エチルヘキシルアクリレート(2EHA)/2-ヒドロキシエチルアクリレート(HEA)=80.0/20.0(質量比)からなる原料モノマーに由来の構成単位を有する、Mw60万のアクリル系共重合体を含む溶液。希釈溶媒:酢酸エチル、固形分濃度:40質量%。
・アクリル系共重合体(ii):n-ブチルアクリレート(BA)/メチルメタクリレート(MMA)/2-ヒドロキシエチルアクリレート(HEA)/アクリル酸=86.0/8.0/5.0/1.0(質量比)からなる原料モノマーに由来の構成単位を有する、Mw60万のアクリル系共重合体を含む溶液。希釈溶媒:酢酸エチル、固形分濃度:40質量%。
<添加剤>
・イソシアネート架橋剤(i):東ソー株式会社製、製品名「コロネートL」、固形分濃度:75質量%。
・光重合開始剤(i):BASF社製、製品名「イルガキュア184」、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン。
<熱膨張性粒子>
・熱膨張性粒子(i):株式会社クレハ製、製品名「S2640」、膨張開始温度(t)=208℃、平均粒子径(D50)=24μm、90%粒子径(D90)=49μm。
<剥離材>
・重剥離フィルム:リンテック株式会社製、製品名「SP-PET382150」、ポリエチレンテレフタレート(PET)フィルムの片面に、シリコーン系剥離剤から形成した剥離剤層を設けたもの、厚さ:38μm。
・軽剥離フィルム:リンテック株式会社製、製品名「SP-PET381031」、PETフィルムの片面に、シリコーン系剥離剤から形成した剥離剤層を設けたもの、厚さ:38μm。
粘着性樹脂である、上記アクリル系共重合体(i)の固形分100質量部に、上記イソシアネート系架橋剤(i)5.0質量部(固形分比)を配合し、トルエンで希釈し、均一に撹拌して、固形分濃度(有効成分濃度)25質量%の組成物(x-1)を調製した。
そして、上記重剥離フィルムの剥離剤層の表面上に、調製した組成物(x-1)を塗布して塗膜を形成し、当該塗膜を100℃で60秒間乾燥して、厚さ10μmの第1粘着剤層(X-1)を形成した。
なお、23℃における、第1粘着剤層(X-1)の貯蔵せん断弾性率G’(23)は、2.5×105Paであった。
粘着性樹脂である、上記アクリル系共重合体(ii)の固形分100質量部に、上記イソシアネート系架橋剤(i)0.8質量部(固形分比)を配合し、トルエンで希釈し、均一に撹拌して、固形分濃度(有効成分濃度)25質量%の組成物(x-2)を調製した。
そして、上記軽剥離フィルムの剥離剤層の表面上に、調製した組成物(x-2)を塗布して塗膜を形成し、当該塗膜を100℃で60秒間乾燥して、厚さ10μmの第2粘着剤層(X-2)を形成した。
なお、23℃における、第2粘着剤層(X-2)の貯蔵せん断弾性率G’(23)は、9.0×104Paであった。
(1)組成物(y-1)の調製
エステル型ジオールと、イソホロンジイソシアネート(IPDI)を反応させて得られた末端イソシアネートウレタンプレポリマーに、2-ヒドロキシエチルアクリレートを反応させて、質量平均分子量(Mw)5000の2官能のアクリルウレタン系オリゴマーを得た。
そして、上記で合成したアクリルウレタン系オリゴマー40質量%(固形分比)に、エネルギー線重合性モノマーとして、イソボルニルアクリレート(IBXA)40質量%(固形分比)、及びフェニルヒドロキシプロピルアクリレート(HPPA)20質量%(固形分比)を配合し、アクリルウレタン系オリゴマー及びエネルギー線重合性モノマーの全量100質量部に対して、さらに光重合開始剤として、1-ヒドロキシシクロヘキシルフェニルケトン(BASF社製、製品名「イルガキュア184」)2.0質量部(固形分比)、及び、添加剤として、フタロシアニン系顔料0.2質量部(固形分比)を配合し、エネルギー線硬化性組成物を調製した。
そして、当該エネルギー線硬化性組成物に、上記熱膨張性粒子(i)を配合し、溶媒を含有しない、無溶剤型の組成物(y-1)を調製した。
なお、組成物(y-1)の全量(100質量%)に対する、熱膨張性粒子(i)の含有量は20質量%であった。
上記軽剥離フィルムの剥離剤層の表面上に、調製した組成物(y-1)を塗布して塗膜を形成した。
そして、紫外線照射装置(アイグラフィクス社製、製品名「ECS-401GX」)及び高圧水銀ランプ(アイグラフィクス社製、製品名「H04-L41」)を用いて、照度160mW/cm2、光量500mJ/cm2の条件で紫外線を照射し、当該塗膜を硬化させ、厚さ50μmの熱膨張性基材(Y-1)を形成した。なお、紫外線照射時の上記の照度及び光量は、照度・光量計(EIT社製、製品名「UV Power Puck II」)を用いて測定した値である。
(1)ウレタンプレポリマーの合成
窒素雰囲気下の反応容器内に、質量平均分子量1,000のカーボネート型ジオール100質量部(固形分比)に対して、イソホロンジイソシアネート(IPDI)を、ポリカーボネート型ジオールの水酸基とイソホロンジイソシアネートのイソシアネート基との当量比が1/1となるように配合し、さらにトルエン160質量部を加え、窒素雰囲気下にて、撹拌しながら、イソシアネート基濃度が理論量に到達するまで、80℃で6時間以上反応させた。
次いで、2-ヒドロキシエチルメタクリレート(2-HEMA)1.44質量部(固形分比)をトルエン30質量部に希釈した溶液を添加して、両末端のイソシアネート基が消滅するまで、更に80℃で6時間反応させ、質量平均分子量2.9万のウレタンプレポリマーを得た。
窒素雰囲気下の反応容器内に、上記(1)で得たウレタンプレポリマー100質量部(固形分比)、メチルメタクリレート(MMA)117質量部(固形分比)、2-ヒドロキシエチルメタクリレート(2-HEMA)5.1質量部(固形分比)、1-チオグリセロール1.1質量部(固形分比)、及びトルエン50質量部を加え、撹拌しながら、105℃まで昇温した。
そして、反応容器内に、さらにラジカル開始剤(株式会社日本ファインケム製、製品名「ABN-E」)2.2質量部(固形分比)をトルエン210質量部で希釈した溶液を、105℃に維持したまま4時間かけて滴下した。
滴下終了後、105℃で6時間反応させ、質量平均分子量10.5万のアクリルウレタン系樹脂の溶液を得た。
上記(2)で得たアクリルウレタン系樹脂の溶液の固形分100質量部に対して、上記イソシアネート系架橋剤(i)6.3質量部(固形分比)、触媒としてジオクチルスズビス(2-エチルヘキサノエート)1.4質量部(固形分比)、及び上記熱膨張性粒子(i)を配合し、トルエンで希釈し、均一に撹拌して、固形分濃度(有効成分濃度)30質量%の組成物(y-2)を調製した。
なお、得られた組成物(y-2)中の有効成分の全量(100質量%)に対する、熱膨張性粒子(i)の含有量は20質量%であった。
そして、上記軽剥離フィルムの剥離剤の表面上に、調製した組成物(y-2)を塗布して塗膜を形成し、当該塗膜を100℃で120秒間乾燥して、厚さ50μmの熱膨張性基材(Y-2)を形成した。
粘着性樹脂である、上記アクリル系共重合体(ii)の固形分100質量部に、上記イソシアネート系架橋剤(i)6.3質量部(固形分比)、及び、上記熱膨張性粒子(i)を配合し、トルエンで希釈し、均一に撹拌して、固形分濃度(有効成分濃度)30質量%の組成物(y-3)を調製した。
なお、得られた組成物(y-3)中の有効成分の全量(100質量%)に対する、熱膨張性粒子(i)の含有量は20質量%であった。
そして、上記軽剥離フィルムの剥離剤層の表面上に、調製した組成物(y-3)を塗布して塗膜を形成し、当該塗膜を100℃で120秒間乾燥して、厚さ50μmの熱膨張性粘着剤層(Y-3)を形成した。
(1)アクリル系共重合体(iii)の合成
n-ブチルアクリレート(BA)52質量部、メチルメタクリレート(MMA)20質量部、及び2-ヒドロキシエチルアクリレート(HEA)28質量部を、酢酸エチル溶媒中で溶液重合し、非エネルギー線硬化性のアクリル系共重合体を得た。
得られた当該アクリル系共重合体の全水酸基数に対して、イソシアネート基数が0.9当量となる量のメタクリロイルオキシエチルイソシアネート(MOI)を、当該アクリル系共重合体を含む溶液に加えて反応させ、側鎖にメタクリロイル基を有する、Mw100万のエネルギー線硬化性のアクリル系共重合体(iii)を得た。
そして、上記(1)で得たエネルギー線硬化性のアクリル系共重合体(iii)の固形分100質量部に対して、上記イソシアネート系架橋剤(i)を0.5質量部(固形分比)、上記光重合開始剤(i)を3.0質量部(固形分比)、上記熱膨張性粒子(i)を配合し、トルエンで希釈し、均一に撹拌して、固形分濃度(有効成分濃度)30質量%の組成物(y-4)を調製した。
なお、得られた組成物(y-4)中の有効成分の全量(100質量%)に対する、熱膨張性粒子(1)の含有量は20質量%であった。
そして、上記軽剥離フィルムの剥離剤層の表面上に、調製した組成物(y-4)を塗布して塗膜を形成し、当該塗膜を100℃で120秒間乾燥後、照度160mW/cm2、光量500mJ/cm2の条件で紫外線を照射して、厚さ50μmの熱膨張性基材(Y-4)を形成した。なお、紫外線照射時の上記の照度及び光量は、照度・光量計(EIT社製、製品名「UV Power Puck II」)を用いて測定した値である。
製造例1で形成した第1粘着剤層(X-1)と、製造例3で形成した熱膨張性基材(Y-1)との表出している表面同士を貼り合わせた後、熱膨張性基材(Y-1)側の軽剥離フィルムを除去し、表出した熱膨張性基材(Y-1)の表面上に、製造例2で形成した第2粘着剤層(X-2)を貼り合わせた。
これにより、軽剥離フィルム/第2粘着剤層(X-2)/熱膨張性基材(Y-1)/第1粘着剤層(X-1)/重剥離フィルムをこの順で積層した粘着シート(1)を作製した。
熱膨張性基材(Y-1)を、製造例4で形成した熱膨張性基材(Y-2)に置き換えた以外は、実施例1と同様にして、軽剥離フィルム/第2粘着剤層(X-2)/熱膨張性基材(Y-2)/第1粘着剤層(X-1)/重剥離フィルムをこの順で積層した粘着シート(2)を作製した。
製造例2で形成した第2粘着剤層(X-2)と、製造例5で形成した熱膨張性粘着剤層(Y-3)との表出している表面同士を貼り合わせた。
そして、熱膨張性粘着剤層(Y-3)側の軽剥離フィルムを除去し、表出した熱膨張性粘着剤層(Y-3)の表面上に、製造例1で形成した第1粘着剤層(X-1)を貼り合わせた。
これにより、軽剥離フィルム/第2粘着剤層(X-2)/熱膨張性粘着剤層(Y-3)/第1粘着剤層(X-1)/重剥離フィルムをこの順で積層した粘着シート(3)を作製した。
熱膨張性基材(Y-1)を、製造例6で形成した熱膨張性基材(Y-4)に置き換えた以外は、実施例1と同様にして、軽剥離フィルム/第2粘着剤層(X-2)/熱膨張性基材(Y-4)/第1粘着剤層(X-1)/重剥離フィルムをこの順で積層した粘着シート(4)を作製した。
製造例2で形成した第2粘着剤層(X-2)と、製造例5で形成した熱膨張性粘着剤層(Y-3)の表出している表面同士を貼り合わせ、軽剥離フィルム/第2粘着剤層(X-2)/熱膨張性粘着剤層(Y-3)/軽剥離フィルムをこの順で積層した粘着シート(5)を作製した。
作製した粘着シート(1)~(5)が有する第2粘着剤層(X-2)側の軽剥離フィルムを除去し、表出した第2粘着剤層(X-2)の粘着表面を支持体と貼付した。
そして、粘着シート(1)~(4)の重剥離フィルム、及び、粘着シート(5)の他方の軽剥離フィルムを除去し、表出した第1粘着剤層(X-1)又は熱膨張性粘着剤層(Y-3)の粘着表面上に、9個の半導体チップ(それぞれのチップサイズは6.4mm×6.4mm、チップ厚さは200μm(♯2000))を、各半導体チップの回路面が当該粘着表面と接するように、必要な間隔であけて載置した。
その後、封止用樹脂フィルムを、粘着表面及び半導体チップの上に積層し、真空加熱加圧ラミネーター(ROHM and HAAS社製の「7024HP5」)を用いて半導体チップを封止し、封止体を作製した。
なお、封止条件は、下記の通りである。
・予熱温度:テーブルおよびダイアフラムとも100℃
・真空引き:60秒間
・ダイナミックプレスモード:30秒間
・スタティックプレスモード:10秒間
・封止温度:180℃(熱膨張性粒子の膨張開始温度である208℃よりも低い温度)
・封止時間:60分間
・A:封止前より25μm以上の位置ズレが生じた半導体チップは確認されなかった。
・F:封止前より25μm以上の位置ズレが生じた半導体チップが確認された。
上述の「封止工程時の半導体チップの位置ズレ評価」で得た、粘着シート(1)~(5)を分離した封止体の半導体チップ側の表面を、接触式表面粗さ計(ミツトヨ社製「SV3000」)を用いて段差を測定し、以下の基準により評価した。
・A:2μm以上の段差が生じている箇所は確認されなかった。
・F:2μm以上の段差が生じている箇所が確認された。
作製した粘着シート(1)~(5)が有する第2粘着剤層(X-2)側の軽剥離フィルムを除去し、表出した第2粘着剤層(X-2)の粘着表面上に、厚さ50μmのポリエチレンテレフタレート(PET)フィルム(東洋紡株式会社製、製品名「コスモシャインA4100」)を積層し、基材付き粘着シートとした。
そして、粘着シート(1)~(4)の重剥離フィルム、及び、粘着シート(5)の他方の軽剥離フィルムも除去し、表出した第1粘着剤層(X-1)又は熱膨張性粘着剤層(Y-3)の粘着表面を、被着体であるステンレス鋼板(SUS304 360番研磨)に貼付し、23℃、50%RH(相対湿度)の環境下で、24時間静置したものを試験サンプルとした。
そして、上記の試験サンプルを用いて、23℃、50%RH(相対湿度)の環境下で、JIS Z0237:2000に基づき、180°引き剥がし法により、引っ張り速度300mm/分にて、23℃における粘着力を測定した。
また、上記の試験サンプルを、ホットプレート上にて、熱膨張性粒子の膨張開始温度(208℃)以上となる240℃で3分間加熱し、標準環境(23℃、50%RH(相対湿度))にて60分間静置した後、JIS Z0237:2000に基づき、180°引き剥がし法により、引っ張り速度300mm/分にて、膨張開始温度以上での加熱後の粘着力も測定した。
なお、被着体であるステンレス鋼板に貼付することができないほどに粘着力の測定が困難である場合には、「測定不能」とし、その粘着力は0(N/25mm)であるとした。
また、粘着シート(1)及び(2)は、加熱前は良好な粘着力を有するものの、膨張開始温度以上での加熱後は測定不能となる程度まで粘着力が低下していることから、剥離時には、わずかな力で容易に剥離可能であることが裏付けられる結果となった。
また、比較例2の粘着シート(4)は、膨張開始温度以上での加熱前後の粘着力はあまり変化しておらず、加熱によって剥離可能なものとはいえない結果となった。
2a、2b 両面粘着シート
11 熱膨張性基材
12 粘着剤層
121 第1粘着剤層
122 第2粘着剤層
13、131、132 剥離材
50 FOWLP
51 半導体チップ
52 封止樹脂層
53 再配線層
54 はんだボール
Claims (12)
- 樹脂及び膨張開始温度(t)が120~250℃である熱膨張性粒子を含み、非粘着性である熱膨張性基材と、粘着性樹脂を含む粘着剤層とを有する粘着シートであって、
前記熱膨張性基材が、下記要件(1)~(2)を満たす、粘着シート。
・要件(1):100℃における、前記熱膨張性基材の貯蔵弾性率E’(100)が、2.0×105Pa以上である。
・要件(2):前記熱膨張性粒子の膨張開始温度(t)における、前記熱膨張性基材の貯蔵弾性率E’(t)が、1.0×107Pa以下である。 - 前記熱膨張性基材が、下記要件(3)を満たす、請求項1に記載の粘着シート。
・要件(3):23℃における、前記熱膨張性基材の貯蔵弾性率E’(23)が、1.0×106Pa以上である。 - 23℃における、前記熱膨張性基材の厚さと、前記粘着剤層の厚さとの比(熱膨張性基材/粘着剤層)が0.2以上である、請求項1又は2に記載の粘着シート。
- 23℃における、前記熱膨張性基材の厚さが10~1000μmであり、前記粘着剤層の厚さが1~60μmである、請求項1~3のいずれか一項に記載の粘着シート。
- 前記熱膨張性基材の表面におけるプローブタック値が、50mN/5mmφ未満である、請求項1~4のいずれか一項に記載の粘着シート。
- 23℃における、前記粘着剤層の貯蔵せん断弾性率G’(23)が、1.0×104~1.0×108Paである、請求項1~5のいずれか一項に記載の粘着シート。
- 前記熱膨張性基材の両面に、2つの前記粘着剤層をそれぞれ有する、請求項1~6のいずれか一項に記載の粘着シート。
- 前記熱膨張性粒子の23℃における膨張前の平均粒子径が、3~100μmである、請求項1~7のいずれか一項に記載の粘着シート。
- 封止樹脂を使用した、加熱を伴う封止工程で用いられる、請求項1~8のいずれか一項に記載の粘着シート。
- 樹脂及び膨張開始温度(t)が120~250℃である熱膨張性粒子を含み、非粘着性であり、下記要件(1)~(2)を満たす、熱膨張性基材。
・要件(1):100℃における、前記熱膨張性基材の貯蔵弾性率E’(100)が、2.0×105Pa以上である。
・要件(2):前記熱膨張性粒子の膨張開始温度(t)における、前記熱膨張性基材の貯蔵弾性率E’(t)が、1.0×107Pa以下である。 - 請求項1~9のいずれか一項に記載の粘着シートを被着体に貼付後、膨張開始温度(t)以上の加熱処理によって、前記被着体から前記粘着シートを剥離する、粘着シートの使用方法。
- 封止樹脂を使用した、加熱を伴う封止工程で用いる、請求項11に記載の粘着シートの使用方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201880022410.2A CN110461974B (zh) | 2017-03-31 | 2018-03-29 | 粘合片 |
KR1020197027699A KR102509242B1 (ko) | 2017-03-31 | 2018-03-29 | 점착 시트 |
JP2019510152A JP6764524B2 (ja) | 2017-03-31 | 2018-03-29 | 粘着シート |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-073236 | 2017-03-31 | ||
JP2017073236 | 2017-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018181765A1 true WO2018181765A1 (ja) | 2018-10-04 |
Family
ID=63676227
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/013352 WO2018181765A1 (ja) | 2017-03-31 | 2018-03-29 | 粘着シート |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6764524B2 (ja) |
KR (1) | KR102509242B1 (ja) |
CN (1) | CN110461974B (ja) |
TW (1) | TWI773746B (ja) |
WO (1) | WO2018181765A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113613893A (zh) * | 2019-03-15 | 2021-11-05 | 琳得科株式会社 | 粘合片及半导体装置的制造方法 |
US11443985B2 (en) | 2018-03-29 | 2022-09-13 | Lintec Corporation | Discrete piece forming device and discrete piece forming method |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018181770A1 (ja) * | 2017-03-31 | 2018-10-04 | リンテック株式会社 | 粘着シート |
KR20220112759A (ko) * | 2019-12-11 | 2022-08-11 | 린텍 가부시키가이샤 | 점착 시트 및 반도체 장치의 제조 방법 |
JPWO2021193850A1 (ja) * | 2020-03-25 | 2021-09-30 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000248240A (ja) * | 1999-03-01 | 2000-09-12 | Nitto Denko Corp | 加熱剥離型粘着シート |
JP2002322359A (ja) * | 2001-04-23 | 2002-11-08 | Nitto Denko Corp | ウレタン−アクリル複合フィルムとその製造法 |
JP2006291137A (ja) * | 2005-04-14 | 2006-10-26 | Nitto Denko Cs System Kk | 粘着テープ類およびその使用方法 |
WO2016076131A1 (ja) * | 2014-11-13 | 2016-05-19 | Dic株式会社 | 両面粘着テープ、物品及び分離方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS594853B2 (ja) | 1981-02-23 | 1984-02-01 | 株式会社日立製作所 | 半導体装置 |
JP3404368B2 (ja) * | 1999-11-04 | 2003-05-06 | 日東電工株式会社 | 粘着テープ |
JP4651799B2 (ja) * | 2000-10-18 | 2011-03-16 | 日東電工株式会社 | エネルギー線硬化型熱剥離性粘着シート、及びこれを用いた切断片の製造方法 |
JP2009275060A (ja) * | 2008-05-12 | 2009-11-26 | Nitto Denko Corp | 粘着シート、その粘着シートを使用した被着体の加工方法、及び粘着シート剥離装置 |
TWI404786B (zh) * | 2010-04-22 | 2013-08-11 | Nanya Plastics Corp | An aqueous hot foam adhesive sheet |
-
2018
- 2018-03-29 WO PCT/JP2018/013352 patent/WO2018181765A1/ja active Application Filing
- 2018-03-29 JP JP2019510152A patent/JP6764524B2/ja active Active
- 2018-03-29 CN CN201880022410.2A patent/CN110461974B/zh active Active
- 2018-03-29 KR KR1020197027699A patent/KR102509242B1/ko active Active
- 2018-03-30 TW TW107111203A patent/TWI773746B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000248240A (ja) * | 1999-03-01 | 2000-09-12 | Nitto Denko Corp | 加熱剥離型粘着シート |
JP2002322359A (ja) * | 2001-04-23 | 2002-11-08 | Nitto Denko Corp | ウレタン−アクリル複合フィルムとその製造法 |
JP2006291137A (ja) * | 2005-04-14 | 2006-10-26 | Nitto Denko Cs System Kk | 粘着テープ類およびその使用方法 |
WO2016076131A1 (ja) * | 2014-11-13 | 2016-05-19 | Dic株式会社 | 両面粘着テープ、物品及び分離方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11443985B2 (en) | 2018-03-29 | 2022-09-13 | Lintec Corporation | Discrete piece forming device and discrete piece forming method |
CN113613893A (zh) * | 2019-03-15 | 2021-11-05 | 琳得科株式会社 | 粘合片及半导体装置的制造方法 |
CN113613893B (zh) * | 2019-03-15 | 2023-11-21 | 琳得科株式会社 | 粘合片及半导体装置的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR102509242B1 (ko) | 2023-03-13 |
CN110461974A (zh) | 2019-11-15 |
TWI773746B (zh) | 2022-08-11 |
TW201842108A (zh) | 2018-12-01 |
JPWO2018181765A1 (ja) | 2020-02-06 |
CN110461974B (zh) | 2022-01-18 |
JP6764524B2 (ja) | 2020-09-30 |
KR20190133167A (ko) | 2019-12-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018181765A1 (ja) | 粘着シート | |
WO2018181770A1 (ja) | 粘着シート | |
JP6761115B2 (ja) | 半導体装置の製造方法及び両面粘着シート | |
JP7273792B2 (ja) | 加工品の製造方法及び粘着性積層体 | |
JP6792700B2 (ja) | 加工検査対象物の加熱剥離方法 | |
WO2018181767A1 (ja) | 半導体装置の製造方法及び粘着シート | |
CN111448275B (zh) | 粘合性层叠体、带树脂膜的加工对象物制造方法及带固化树脂膜的固化密封体的制造方法 | |
WO2019189530A1 (ja) | 粘着性積層体、粘着性積層体の使用方法、及び硬化樹脂膜付き硬化封止体の製造方法 | |
JP7530347B2 (ja) | 粘着シート及び半導体装置の製造方法 | |
CN112203840B (zh) | 粘合性层叠体、粘合性层叠体的使用方法、以及半导体装置的制造方法 | |
JP7267272B2 (ja) | 硬化封止体の製造方法 | |
KR102509251B1 (ko) | 점착 시트 | |
JP7185637B2 (ja) | 半導体装置の製造方法 | |
JP2024107808A (ja) | 粘着シート及び半導体装置の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18775509 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019510152 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20197027699 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18775509 Country of ref document: EP Kind code of ref document: A1 |