TWI846784B - Adhesive tape and method for manufacturing electronic components - Google Patents
Adhesive tape and method for manufacturing electronic components Download PDFInfo
- Publication number
- TWI846784B TWI846784B TW108146625A TW108146625A TWI846784B TW I846784 B TWI846784 B TW I846784B TW 108146625 A TW108146625 A TW 108146625A TW 108146625 A TW108146625 A TW 108146625A TW I846784 B TWI846784 B TW I846784B
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive layer
- curing
- curing adhesive
- weight
- adhesive tape
- Prior art date
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000012790 adhesive layer Substances 0.000 claims abstract description 223
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 168
- 238000010943 off-gassing Methods 0.000 claims abstract description 21
- 238000001723 curing Methods 0.000 claims description 68
- 239000000853 adhesive Substances 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 53
- 230000001070 adhesive effect Effects 0.000 claims description 51
- 239000000945 filler Substances 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 41
- 239000004593 Epoxy Substances 0.000 claims description 40
- 125000000524 functional group Chemical group 0.000 claims description 39
- 229920005601 base polymer Polymers 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229920006243 acrylic copolymer Polymers 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 7
- 125000001302 tertiary amino group Chemical group 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 239000000377 silicon dioxide Substances 0.000 description 31
- 239000000758 substrate Substances 0.000 description 29
- -1 amino, carbonyl Chemical group 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 27
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 25
- 238000005259 measurement Methods 0.000 description 19
- 239000000523 sample Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- 229920000058 polyacrylate Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 239000003505 polymerization initiator Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 238000005187 foaming Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000003512 tertiary amines Chemical group 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 4
- SLVZOGVXUWUDJW-UHFFFAOYSA-L C(C=C)(=O)[O-].C(C=C)(=O)[O-].[Si+2] Chemical compound C(C=C)(=O)[O-].C(C=C)(=O)[O-].[Si+2] SLVZOGVXUWUDJW-UHFFFAOYSA-L 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000001993 wax Substances 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 1
- ZAMZCSIXTWIEDY-UHFFFAOYSA-N (2-propylphenyl)methanol Chemical compound CCCC1=CC=CC=C1CO ZAMZCSIXTWIEDY-UHFFFAOYSA-N 0.000 description 1
- BWZAUXRKSMJLMH-UHFFFAOYSA-N 1,1-diethoxyethylbenzene Chemical compound CCOC(C)(OCC)C1=CC=CC=C1 BWZAUXRKSMJLMH-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-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
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- IYGMGXHFRPYMGB-UHFFFAOYSA-N 1-(6,6-dimethylheptylperoxy)-6,6-dimethylheptane Chemical compound CC(CCCCCOOCCCCCC(C)(C)C)(C)C IYGMGXHFRPYMGB-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NXQNMWHBACKBIG-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O NXQNMWHBACKBIG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-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
- 239000003480 eluent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 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
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本發明之目的在於提供一種黏著帶及使用該黏著帶之電子零件之製造方法,該黏著帶於電子零件之製造中亦可用於不透光之支持體,且即便於進行高溫處理之情形時亦可抑制自被黏著體及支持體之剝離或糊劑殘留。本發明係一種黏著帶,其係具有非紫外線硬化型黏著劑層及積層於上述非紫外線硬化型黏著劑層上之紫外線硬化型黏著劑層者,上述非紫外線硬化型黏著劑層於23℃之拉伸強度為5.0 N/10 mm以上且20.0 N/10 mm以下,並且將上述非紫外線硬化型黏著劑層於260℃加熱15分鐘時之釋氣量為10000 ppm以下。The object of the present invention is to provide an adhesive tape and a method for manufacturing electronic components using the adhesive tape, wherein the adhesive tape can be used for a light-proof support in the manufacture of electronic components and can inhibit peeling from the adherend and the support or paste residue even when subjected to high temperature treatment. The present invention is an adhesive tape having a non-UV curing adhesive layer and a UV curing adhesive layer laminated on the non-UV curing adhesive layer, wherein the tensile strength of the non-UV curing adhesive layer at 23°C is greater than 5.0 N/10 mm and less than 20.0 N/10 mm, and the outgassing amount of the non-UV curing adhesive layer when heated at 260°C for 15 minutes is less than 10000 ppm.
Description
本發明係關於一種黏著帶及使用該黏著帶之電子零件之製造方法。The present invention relates to an adhesive tape and a method for manufacturing an electronic component using the adhesive tape.
於半導體晶片之製造步驟中,為了使晶圓或半導體晶片於加工時容易使用,並防止破損,而使用黏著帶。例如,於對自高純度之單晶矽等切割之厚膜晶圓進行研磨直至特定厚度而製成薄膜晶圓之情形時,在厚膜晶圓上貼合黏著帶後進行研磨。In the manufacturing process of semiconductor chips, adhesive tape is used to make the wafer or semiconductor chip easy to use during processing and to prevent damage. For example, when a thick film wafer cut from high-purity single crystal silicon is polished to a specific thickness to produce a thin film wafer, the adhesive tape is attached to the thick film wafer and then polished.
對於此種黏著帶所使用之接著劑組成物,要求於加工步驟中僅可能牢固地固定晶圓或半導體晶片等被黏著體之高接著性,以及於步驟結束後可剝離而不會損傷晶圓或半導體晶片等被黏著體(以下亦稱為「高接著易剝離」)。 作為實現高接著易剝離之接著劑組成物,專利文獻1中揭示有使用藉由照射紫外線等光而硬化從而使黏著力降低之光硬化型黏著劑之黏著帶。藉由使用光硬化型黏著劑作為黏著劑,於加工步驟中可確實地固定被黏著體,並且藉由照射紫外線等可容易地剝離。 先前技術文獻 專利文獻The adhesive composition used in such an adhesive tape is required to have high adhesion to firmly fix the adherend such as a wafer or a semiconductor chip during the processing step, and to be able to be peeled off without damaging the adherend such as a wafer or a semiconductor chip after the step is completed (hereinafter also referred to as "high adhesion and easy peeling"). As an adhesive composition for achieving high adhesion and easy peeling, Patent Document 1 discloses an adhesive tape using a light-curing adhesive that is cured by irradiating light such as ultraviolet rays to reduce the adhesive force. By using a light-curing adhesive as an adhesive, the adherend can be firmly fixed during the processing step, and can be easily peeled off by irradiating ultraviolet rays, etc. Prior art literature Patent literature
專利文獻1:日本特開平5-32946號公報Patent document 1: Japanese Patent Application Publication No. 5-32946
發明所欲解決之課題Invent the problem you want to solve
近年來,隨著半導體製品之薄化、小型化,基板亦薄至100 μm以下(以下將薄化之基板稱為薄基板),為了防止於製造基板時產生翹曲或損傷,而使用黏著帶。於此種薄基板之製造中,經由無支持型黏著帶將成為基板之基礎的聚醯亞胺膜等基材固定於支持體,其後進行配線等處理。然而,就成本或使用性之觀點而言,用於製造薄基板之支持體多數情況為銅、鋁、玻璃環氧化物等不透明之素材,此種不透明之支持體存在無法使習知之使用光硬化型黏著劑之黏著帶硬化之問題。針對該問題,提出有具有硬化型黏著劑層及非硬化型黏著劑層之黏著帶。於將硬化型黏著劑層貼附於薄基板等被黏著體並使之硬化後,將非硬化型黏著劑層貼附於支持體,藉此即便於支持體為不透明之情形時亦可使黏著帶硬化。In recent years, with the thinning and miniaturization of semiconductor products, substrates have also become thinner to less than 100 μm (hereinafter, thinned substrates are referred to as thin substrates). In order to prevent warping or damage during the manufacture of substrates, adhesive tapes are used. In the manufacture of such thin substrates, a base material such as a polyimide film that serves as the basis of the substrate is fixed to a support body via an unsupported adhesive tape, and then wiring and other processes are performed. However, from the perspective of cost or usability, the support body used to manufacture thin substrates is mostly an opaque material such as copper, aluminum, and glass epoxy. Such an opaque support body has the problem that the adhesive tape using a conventional light-curing adhesive cannot be cured. In response to this problem, an adhesive tape having a curing adhesive layer and a non-curing adhesive layer has been proposed. After the curable adhesive layer is attached to an adherend such as a thin substrate and cured, the non-curable adhesive layer is attached to a support, thereby curing the adhesive tape even when the support is opaque.
另一方面,於薄基板等電子零件之製造步驟中,有進行150℃以上加熱之高溫處理之情況。於在伴隨此種高溫處理之步驟中使用習知之具有硬化型黏著劑層及非硬化型黏著劑層之黏著帶之情形時,有非硬化型黏著劑層無法充分耐熱而自支持體剝離之情況。高溫處理之溫度隨著技術之進步而逐漸變高,因此尋求即便對不透明之支持體亦可使用、且具有進一步之耐熱性之黏著帶。On the other hand, in the manufacturing process of electronic parts such as thin substrates, high temperature treatment of heating at 150°C or above is sometimes performed. When a conventional adhesive tape having a hardening adhesive layer and a non-hardening adhesive layer is used in the step accompanying such high temperature treatment, the non-hardening adhesive layer may not be able to resist the heat sufficiently and may be peeled off from the support. The temperature of the high temperature treatment is gradually increasing with the advancement of technology, so an adhesive tape that can be used even for an opaque support and has further heat resistance is sought.
本發明之目的在於提供一種黏著帶及使用該黏著帶之電子零件之製造方法,該黏著帶於電子零件之製造中亦可用於不透光之支持體,且即便於進行高溫處理之情形時亦可抑制自被黏著體及支持體之剝離或糊劑殘留。 解決課題之技術手段The purpose of the present invention is to provide an adhesive tape and a method for manufacturing electronic components using the adhesive tape. The adhesive tape can also be used for opaque supports in the manufacture of electronic components, and can inhibit peeling from the adherend and the support or paste residue even when subjected to high temperature treatment. Technical means to solve the problem
本發明之第1態樣係一種黏著帶,其係具有非紫外線硬化型黏著劑層及積層於上述非紫外線硬化型黏著劑層上之紫外線硬化型黏著劑層者,上述非紫外線硬化型黏著劑層於23℃之拉伸強度為5.0 N/10 mm以上且20.0 N/10 mm以下,並且將上述非紫外線硬化型黏著劑層於260℃加熱15分鐘時之釋氣量為10000 ppm以下。 本發明之第2態樣係一種黏著帶,其係具有非紫外線硬化型黏著劑層及積層於上述非紫外線硬化型黏著劑層上之紫外線硬化型黏著劑層者,將上述非紫外線硬化型黏著劑層於260℃加熱15分鐘時之釋氣量為10000 ppm以下,並且上述非紫外線硬化型黏著劑層含有(A')作為基礎聚合物之(甲基)丙烯酸系共聚物、(B)作為硬化劑之含有三級胺結構之環氧系化合物及(C)填料,上述(甲基)丙烯酸系共聚物包含烷基之碳數為4〜12之(甲基)丙烯酸烷基酯92〜97重量%作為構成成分。 以下詳細闡述本發明。The first aspect of the present invention is an adhesive tape having a non-UV curing adhesive layer and a UV curing adhesive layer laminated on the non-UV curing adhesive layer, wherein the tensile strength of the non-UV curing adhesive layer at 23°C is greater than 5.0 N/10 mm and less than 20.0 N/10 mm, and the amount of outgassing of the non-UV curing adhesive layer when heated at 260°C for 15 minutes is less than 10,000 ppm. The second aspect of the present invention is an adhesive tape having a non-ultraviolet curing adhesive layer and a UV curing adhesive layer laminated on the non-ultraviolet curing adhesive layer, wherein the amount of outgassing of the non-ultraviolet curing adhesive layer when heated at 260°C for 15 minutes is less than 10,000 ppm, and the non-ultraviolet curing adhesive layer contains (A') a (meth) acrylic copolymer as a base polymer, (B) an epoxy compound containing a tertiary amine structure as a curing agent, and (C) a filler, and the (meth) acrylic copolymer contains 92 to 97% by weight of an alkyl (meth)acrylate having an alkyl group with 4 to 12 carbon atoms as a constituent component. The present invention is described in detail below.
本發明之黏著帶具有非紫外線硬化型黏著劑層及積層於上述非紫外線硬化型黏著劑層上之紫外線硬化型黏著劑層。 藉由黏著帶具有紫外線硬化型黏著劑層,可利用充分之黏著力貼附於被黏著體而保護被黏著體,並且於貼附後使紫外線硬化型黏著劑層硬化,藉此即便於進行高溫處理之情形時亦可確實地保護被黏著體。又,於無需保護後,可容易地剝離黏著帶而不損傷被黏著體。進而,藉由黏著帶具有非紫外線硬化型黏著劑層,可於將紫外線硬化型黏著劑層貼附於被黏著體,並使紫外線硬化型黏著劑層硬化後,將非紫外線硬化型黏著劑層貼附於支持體,因此即便於支持體為不透明之情形時亦可使紫外線硬化型黏著劑層硬化。再者,就可簡化製造步驟之觀點而言,亦可於將黏著帶貼附於被黏著體後馬上照射紫外線,而使紫外線硬化型黏著劑層硬化。The adhesive tape of the present invention has a non-ultraviolet curing adhesive layer and an ultraviolet curing adhesive layer laminated on the non-ultraviolet curing adhesive layer. Since the adhesive tape has an ultraviolet curing adhesive layer, it can be attached to the adherend with sufficient adhesive force to protect the adherend, and the ultraviolet curing adhesive layer is cured after attachment, thereby reliably protecting the adherend even when high-temperature treatment is performed. In addition, when protection is no longer needed, the adhesive tape can be easily peeled off without damaging the adherend. Furthermore, since the adhesive tape has a non-ultraviolet curing adhesive layer, the non-ultraviolet curing adhesive layer can be attached to the support after the ultraviolet curing adhesive layer is attached to the adherend and cured, so that the ultraviolet curing adhesive layer can be cured even when the support is opaque. Furthermore, from the viewpoint of simplifying the manufacturing steps, the ultraviolet curing adhesive layer can be cured by irradiating ultraviolet rays immediately after the adhesive tape is attached to the adherend.
於本發明之較佳實施態樣中,上述非紫外線硬化型黏著劑層為紫外線穿透性。此處,所謂紫外線穿透性,意指上述紫外線硬化型黏著劑層中所含之紫外線聚合起始劑之吸光波段與上述非紫外線硬化型黏著劑層之透光波段重合,較佳為尤其是上述紫外線聚合起始劑之吸光波段與上述非紫外線硬化型黏著劑層之吸光度為0.2以下之波段重合。藉由上述非紫外線硬化型黏著劑層為紫外線穿透性,可隔著非紫外線硬化型黏著劑層對紫外線硬化型黏著劑層照射紫外線。In a preferred embodiment of the present invention, the non-ultraviolet curing adhesive layer is ultraviolet-transmissive. Here, the so-called ultraviolet-transmissive means that the absorption band of the ultraviolet polymerization initiator contained in the ultraviolet curing adhesive layer overlaps with the light transmission band of the non-ultraviolet curing adhesive layer, and preferably, the absorption band of the ultraviolet polymerization initiator overlaps with the band of the non-ultraviolet curing adhesive layer with an absorbance of 0.2 or less. Since the non-ultraviolet curing adhesive layer is ultraviolet-transmissive, the ultraviolet curing adhesive layer can be irradiated with ultraviolet light through the non-ultraviolet curing adhesive layer.
於本發明之第1態樣中,上述非紫外線硬化型黏著劑層於23℃之拉伸強度為5.0 N/10 mm以上且20.0 N/10 mm以下。 於本發明之第2態樣中,上述非紫外線硬化型黏著劑層於23℃之拉伸強度較佳為5.0 N/10 mm以上且20.0 N/10 mm以下。 藉由上述非紫外線硬化型黏著劑層之拉伸強度為上述範圍,於剝離時黏著帶不易被拉斷。就進一步抑制黏著帶於剝離時被拉斷之觀點而言,上述非紫外線硬化型黏著劑層之拉伸強度之較佳下限為5.5 N/10 mm,更佳下限為6.0 N/10 mm,較佳上限為19.5 N/10 mm,更佳上限為19.0 N/10 mm。 再者,關於上述非紫外線硬化型黏著劑層之拉伸強度,可將非紫外線硬化型黏著劑層切割成厚度200 μm、寬度10 mm作為樣品,於23℃、50%RH之條件,使用TENSILON UCE500(Orientec公司製造),以速度300 mm/分鐘、標線間距離40 mm測定拉伸強度。In the first embodiment of the present invention, the tensile strength of the non-UV curing adhesive layer at 23°C is 5.0 N/10 mm or more and 20.0 N/10 mm or less. In the second embodiment of the present invention, the tensile strength of the non-UV curing adhesive layer at 23°C is preferably 5.0 N/10 mm or more and 20.0 N/10 mm or less. Since the tensile strength of the non-UV curing adhesive layer is within the above range, the adhesive tape is not easily broken during peeling. From the viewpoint of further suppressing the adhesive tape from being pulled apart during peeling, the preferred lower limit of the tensile strength of the non-UV curing adhesive layer is 5.5 N/10 mm, and the more preferred lower limit is 6.0 N/10 mm. The preferred upper limit is 19.5 N/10 mm, and the more preferred upper limit is 19.0 N/10 mm. In addition, regarding the tensile strength of the non-UV curing adhesive layer, the non-UV curing adhesive layer can be cut into a sample with a thickness of 200 μm and a width of 10 mm, and the tensile strength can be measured at 23°C and 50% RH using TENSILON UCE500 (manufactured by Orientec) at a speed of 300 mm/min and a distance between markings of 40 mm.
上述非紫外線硬化型黏著劑層於將上述非紫外線硬化型黏著劑層於260℃加熱15分鐘時之釋氣量為10000 ppm以下。 於伴隨高溫處理之電子零件之製造中,使用通常之具有非紫外線硬化型黏著劑層及紫外線硬化型黏著劑層之黏著帶以保護電子零件之情形時,高溫處理之熱會使非紫外線硬化型黏著劑層分解而產生大量釋氣。所產生之釋氣使非紫外線硬化型黏著劑層發泡而降低其強度與黏著力,因此產生於剝離時支持體與非紫外線硬化型黏著劑層之間發生剝離,於被黏著體側殘留有黏著帶(糊劑殘留)之問題。於本發明之黏著帶時,上述非紫外線硬化型黏著劑層之釋氣產生量較少,即,上述非紫外線硬化型黏著劑層不易因熱分解,藉此可抑制非紫外線硬化型黏著劑層之發泡,使黏著帶不易殘留於被黏著體。就進一步抑制黏著帶向被黏著體之糊劑殘留之觀點而言,上述釋氣量較佳為7500 ppm以下,更佳為5500 ppm以下,進而較佳為4000 ppm以下,尤佳為3500 ppm以下。上述釋氣量之下限並無特別限定,越低越佳,例如較佳下限為1000 ppm。The amount of outgassing of the non-UV curing adhesive layer when the non-UV curing adhesive layer is heated at 260°C for 15 minutes is less than 10,000 ppm. In the manufacture of electronic parts accompanied by high temperature treatment, when a conventional adhesive tape having a non-UV curing adhesive layer and a UV curing adhesive layer is used to protect the electronic parts, the heat of the high temperature treatment will decompose the non-UV curing adhesive layer and generate a large amount of outgassing. The outgassing generated causes the non-UV curing adhesive layer to foam and reduce its strength and adhesion, thus causing the support and the non-UV curing adhesive layer to peel off during peeling, leaving adhesive tape (paste residue) on the adherend side. In the adhesive tape of the present invention, the amount of outgassing generated by the non-UV curing adhesive layer is relatively small, that is, the non-UV curing adhesive layer is not easily decomposed by heat, thereby suppressing the foaming of the non-UV curing adhesive layer, making it difficult for the adhesive tape to remain on the adherend. From the viewpoint of further suppressing the residual paste of the adhesive tape on the adherend, the above-mentioned outgassing amount is preferably 7500 ppm or less, more preferably 5500 ppm or less, further preferably 4000 ppm or less, and particularly preferably 3500 ppm or less. There is no particular limitation on the lower limit of the above-mentioned outgassing amount, and the lower the better. For example, the preferred lower limit is 1000 ppm.
上述釋氣量例如可作為將上述非紫外線硬化型黏著劑層裁切成5 mm×5 mm,使用熱脫附GC-MS(熱脫附裝置:TurboMatrix 350,PerkinElmer公司製造;GC-MS裝置:JMS Q1000,日本電子公司製造)測定時之氣體量(甲苯換算ppm:μg/g)獲得。 再者,詳細之測定條件如下所述。 樣品加熱條件:260℃、15 min(20 mL/min) 二次脫附:350℃、40 min 分流:入口25 mL/min、出口25 mL/min 注入量:2.5% 管柱:EQUITY-1(無極性,SIGMA-ALDRICH公司製造)0.32 mm×60 m×0.25 μm GC升溫:40℃(4 min)→以10℃/min之速度升溫→300℃(10 min) He流量:1.5 mL/min 離子化電壓:70 eV MS測定範圍:29〜600 amu(scan 500 ms) MS溫度:離子源溫度230℃,介面溫度250℃The above-mentioned outgassing amount can be obtained, for example, as the gas volume (toluene conversion ppm: μg/g) when the above-mentioned non-UV curing adhesive layer is cut into 5 mm×5 mm and measured using thermal desorption GC-MS (thermal desorption device: TurboMatrix 350, manufactured by PerkinElmer; GC-MS device: JMS Q1000, manufactured by NEC Corporation). In addition, the detailed measurement conditions are as follows. Sample heating conditions: 260℃, 15 min (20 mL/min) Secondary desorption: 350℃, 40 min Flow split: inlet 25 mL/min, outlet 25 mL/min Injection volume: 2.5% Column: EQUITY-1 (non-polar, manufactured by SIGMA-ALDRICH) 0.32 mm×60 m×0.25 μm GC temperature rise: 40℃ (4 min) → temperature rise at a rate of 10℃/min → 300℃ (10 min) He flow rate: 1.5 mL/min Ionization voltage: 70 eV MS measurement range: 29~600 amu (scan 500 ms) MS temperature: ion source temperature 230℃, interface temperature 250℃
上述非紫外線硬化型黏著劑層之黏著強度較佳為10〜300 gf/3 mmϕ。 藉由上述非紫外線硬化型黏著劑層之黏著強度為上述範圍,非紫外線硬化型黏著劑層與支持體更確實地接著,可於剝離時使黏著帶更容易地自紫外線硬化型黏著劑層與被黏著體之界面剝離。就使黏著帶更加容易地自紫外線硬化型黏著劑層與被黏著體之界面剝離之觀點而言,上述黏著強度之更佳下限為15 gf/3 mmϕ,進而較佳下限為20 gf/3 mmϕ,更佳上限為270 gf/3 mmϕ,進而較佳上限為250 gf/3 mmϕ。 再者,上述黏著強度可藉由如下方式測定:將非紫外線硬化型黏著劑層切割成10 mm×10 mm而製作測定樣品,對所獲得之測定樣品進行探針黏性測定。再者,所使用之測定工具或測定條件可設為如下。 黏性試驗機:TAC1000,RHESCA公司製造(或其同等品) 探針直徑:3 mmϕ 壓接負載:100 g 壓接時間:1秒 接觸速度:30 mm·min 剝離速度:600 mm/minThe adhesive strength of the non-UV curing adhesive layer is preferably 10 to 300 gf/3 mmφ. When the adhesive strength of the non-UV curing adhesive layer is within the above range, the non-UV curing adhesive layer and the support are more securely bonded, and the adhesive tape can be more easily peeled off from the interface between the UV curing adhesive layer and the adherend during peeling. From the viewpoint of making it easier to peel the adhesive tape from the interface between the UV-curing adhesive layer and the adherend, the lower limit of the above-mentioned adhesive strength is preferably 15 gf/3 mmϕ, and further preferably 20 gf/3 mmϕ, and the upper limit is preferably 270 gf/3 mmϕ, and further preferably 250 gf/3 mmϕ. Furthermore, the above-mentioned adhesive strength can be measured by cutting the non-UV-curing adhesive layer into 10 mm×10 mm to prepare a measurement sample, and performing a probe viscosity measurement on the obtained measurement sample. Furthermore, the measurement tool or measurement conditions used can be set as follows. Adhesion tester: TAC1000, manufactured by RHESCA (or equivalent) Probe diameter: 3 mmφ Compression load: 100 g Compression time: 1 second Contact speed: 30 mm·min Peeling speed: 600 mm/min
上述非紫外線硬化型黏著劑層之凝膠分率較佳為80%以上。 藉由上述非紫外線硬化型黏著劑層之凝膠分率為80%以上,非紫外線硬化型黏著劑層之耐化學品性提高,因此於伴隨化學處理之步驟中亦可使用本發明之黏著帶。 就進一步提高耐化學品性之觀點而言,上述凝膠分率更佳為95%以上,進而較佳為97%以上。上述凝膠分率之上限並無特別限定,通常為100%以下。再者,凝膠分率可藉由以下方法測定。 僅刮取所獲得之黏著帶之非紫外線硬化型黏著劑層0.1 g,並浸漬於乙酸乙酯50 mL中,利用振動機於溫度23度、120 rpm之條件振動24小時(以下,將所刮取之非紫外線硬化型黏著劑層稱為黏著劑組成物)。振動後,使用金屬絲網(網眼#200目),將乙酸乙酯與吸收乙酸乙酯後膨潤之黏著劑組成物分離。將分離後之黏著劑組成物於110℃之條件乾燥1小時。測定乾燥後之連同金屬絲網在內之黏著劑組成物之重量,使用下述式算出非紫外線硬化型黏著劑層之凝膠分率。 凝膠分率(重量%)=100×(W1 -W2 )/W0 (W0 :初期黏著劑組成物重量,W1 :乾燥後之連同金屬絲網在內之黏著劑組成物重量,W2 :金屬絲網之初期重量)The gel fraction of the non-UV curing adhesive layer is preferably 80% or more. By having a gel fraction of 80% or more, the chemical resistance of the non-UV curing adhesive layer is improved, so the adhesive tape of the present invention can also be used in the step of accompanying chemical treatment. From the perspective of further improving chemical resistance, the gel fraction is more preferably 95% or more, and further preferably 97% or more. The upper limit of the gel fraction is not particularly limited, and is usually 100% or less. Furthermore, the gel fraction can be measured by the following method. Only 0.1 g of the non-UV curing adhesive layer of the obtained adhesive tape was scraped off and immersed in 50 mL of ethyl acetate. The non-UV curing adhesive layer was vibrated for 24 hours at 23 degrees and 120 rpm using a vibrator (hereinafter, the scraped non-UV curing adhesive layer is referred to as the adhesive composition). After vibration, a metal wire mesh (mesh size #200) was used to separate the ethyl acetate from the adhesive composition that swelled after absorbing the ethyl acetate. The separated adhesive composition was dried at 110°C for 1 hour. The weight of the adhesive composition including the metal wire mesh after drying was measured, and the gel fraction of the non-UV curing adhesive layer was calculated using the following formula. Gel fraction (weight %) = 100 × (W 1 - W 2 ) / W 0 (W 0 : initial weight of adhesive composition, W 1 : weight of adhesive composition including metal mesh after drying, W 2 : initial weight of metal mesh)
構成上述非紫外線硬化型黏著劑層之非紫外線硬化型黏著劑只要為非紫外線硬化型且滿足上述拉伸強度及釋氣量,則並無特別限定,較佳為基礎聚合物具有能夠與環氧基反應之官能基。 作為上述能夠與環氧基反應之官能基,例如可列舉:羧基、羥基、酚基、酯基、胺基、羰基、甲氧基及磺基等。其中,就反應性較高而言,較佳為選自由羧基、羥基、酚基、酯基及胺基所組成之群中之至少1種。The non-UV curing adhesive constituting the above-mentioned non-UV curing adhesive layer is not particularly limited as long as it is non-UV curing and satisfies the above-mentioned tensile strength and outgassing amount. It is preferred that the base polymer has a functional group capable of reacting with an epoxy group. As the above-mentioned functional group capable of reacting with an epoxy group, for example, there can be listed: carboxyl, hydroxyl, phenolic, ester, amino, carbonyl, methoxy and sulfonic groups. Among them, in terms of higher reactivity, it is preferred to select at least one of the group consisting of carboxyl, hydroxyl, phenolic, ester and amino groups.
作為上述基礎聚合物,例如可列舉:丙烯酸系聚合物、聚矽氧系聚合物、胺酯系聚合物等。 於本發明之第1態樣中,上述非紫外線硬化型黏著劑層較佳為含有(A)作為基礎聚合物之(甲基)丙烯酸系共聚物,其包含(a)烷基之碳數為4〜12之(甲基)丙烯酸烷基酯92〜97重量%及(b)含羧基之單體3.0〜8.0重量%作為構成成分,且(c)重量平均分子量為70萬以上(d)分子量分佈為2〜6。 於本發明之第2態樣中,上述非紫外線硬化型黏著劑層含有(A')作為基礎聚合物之(甲基)丙烯酸系共聚物,其包含烷基之碳數為4〜12之(甲基)丙烯酸烷基酯92〜97重量%作為構成成分。於本發明之第2態樣中,亦較佳為上述(甲基)丙烯酸系共聚物包含烷基之碳數為4〜12之(甲基)丙烯酸烷基酯92〜97重量%、含羧基之單體3.0〜8.0重量%,且重量平均分子量為70萬以上、分子量分佈為2〜6。As the above-mentioned base polymer, for example, acrylic polymers, silicone polymers, amine polymers, etc. can be listed. In the first aspect of the present invention, the above-mentioned non-UV curing adhesive layer preferably contains (A) as a base polymer (meth) acrylic copolymer, which contains (a) 92 to 97% by weight of (meth) acrylic acid alkyl esters having 4 to 12 carbon atoms in the alkyl group and (b) 3.0 to 8.0% by weight of carboxyl-containing monomers as constituents, and (c) a weight average molecular weight of 700,000 or more (d) a molecular weight distribution of 2 to 6. In the second aspect of the present invention, the above-mentioned non-UV curing adhesive layer contains (A') as a base polymer (meth) acrylic copolymer, which contains 92 to 97% by weight of (meth) acrylic acid alkyl esters having 4 to 12 carbon atoms in the alkyl group as constituents. In the second aspect of the present invention, it is also preferred that the (meth)acrylic acid copolymer comprises 92 to 97% by weight of an alkyl (meth)acrylate having an alkyl group with 4 to 12 carbon atoms, 3.0 to 8.0% by weight of a carboxyl group-containing monomer, and has a weight average molecular weight of more than 700,000 and a molecular weight distribution of 2 to 6.
藉由使用上述烷基之碳數為4〜12之(甲基)丙烯酸烷基酯作為構成成分,可製成黏著力更優異(較佳為具有紫外線穿透性)之非紫外線硬化型黏著劑層。又,藉由使用含羧基之單體作為構成成分,可提高非紫外線硬化型黏著劑之凝集力,賦予更大之黏著力。進而,於上述紫外線硬化型黏著劑層含有聚矽氧化合物之情形時,由於作為極性基之羧基阻礙低極性之聚矽氧化合物之接近,故而可抑制聚矽氧化合物向非紫外線硬化型黏著劑層側滲出。By using the above-mentioned (meth) acrylate alkyl ester having an alkyl group with 4 to 12 carbon atoms as a constituent, a non-UV curing adhesive layer with better adhesion (preferably with UV transmittance) can be prepared. In addition, by using a carboxyl group-containing monomer as a constituent, the cohesive force of the non-UV curing adhesive can be increased, giving greater adhesion. Furthermore, when the above-mentioned UV curing adhesive layer contains a polysilicone compound, since the carboxyl group as a polar group blocks the approach of the low-polarity polysilicone compound, the polysilicone compound can be inhibited from permeating to the non-UV curing adhesive layer.
作為上述烷基之碳數為4〜12之(甲基)丙烯酸烷基酯,例如可列舉:(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯等。其中,就黏著力優異而言,較佳為丙烯酸丁酯。Examples of the (meth)acrylic acid alkyl esters having an alkyl group with 4 to 12 carbon atoms include butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, etc. Among them, butyl acrylate is preferred in terms of excellent adhesion.
作為上述含羧基之單體,例如可列舉:丙烯酸、甲基丙烯酸等。其中,就可賦予高黏著力而言,較佳為丙烯酸。Examples of the carboxyl group-containing monomer include acrylic acid and methacrylic acid. Of these, acrylic acid is preferred in terms of imparting high adhesion.
藉由上述烷基之碳數為4〜12之(甲基)丙烯酸烷基酯之含量為92〜97重量%,可製成黏著力更優異之黏著帶。藉由含羧基之單體為3.0重量%以上,於上述紫外線硬化型黏著劑層含有聚矽氧化合物之情形時,可進一步抑制聚矽氧化合物向非紫外線硬化型黏著劑層之滲出。藉由含羧基之單體為8.0重量%以下,可將(甲基)丙烯酸系共聚物之酸性度調整為合適之範圍,於上述紫外線硬化型黏著劑層含有聚矽氧化合物之情形時,可進一步抑制聚矽氧化合物向非紫外線硬化型黏著劑層之滲出。就進一步抑制滲出之觀點而言,上述(甲基)丙烯酸系共聚物中之上述(甲基)丙烯酸烷基酯之含量之更佳下限為93重量%,進而較佳下限為94重量%,且更佳上限為96重量%。就進一步抑制滲出之觀點而言,上述(甲基)丙烯酸系共聚物中之含羧基之單體之含量之更佳下限為4.0重量%,且更佳上限為7.0重量%,進而較佳上限為6.0重量%。By having an alkyl (meth)acrylate content of 4 to 12 carbon atoms in the alkyl group of 92 to 97% by weight, an adhesive tape with better adhesion can be produced. By having a carboxyl-containing monomer content of 3.0% by weight or more, when the UV-curing adhesive layer contains a polysilicone compound, the permeation of the polysilicone compound into the non-UV-curing adhesive layer can be further suppressed. By having a carboxyl-containing monomer content of 8.0% by weight or less, the acidity of the (meth)acrylic copolymer can be adjusted to a suitable range, and when the UV-curing adhesive layer contains a polysilicone compound, the permeation of the polysilicone compound into the non-UV-curing adhesive layer can be further suppressed. From the viewpoint of further suppressing the exudation, the lower limit of the content of the alkyl (meth)acrylate in the (meth)acrylic copolymer is preferably 93% by weight, further preferably 94% by weight, and further preferably 96% by weight. From the viewpoint of further suppressing the exudation, the lower limit of the content of the carboxyl group-containing monomer in the (meth)acrylic copolymer is preferably 4.0% by weight, and further preferably 7.0% by weight, and further preferably 6.0% by weight.
藉由上述(甲基)丙烯酸系共聚物具有70萬以上之較大之重量平均分子量與2〜6之較窄之分子量分佈,可容易地將上述非紫外線硬化型黏著劑層之拉伸強度與上述釋氣量調節至上述範圍內。再者,此處,所謂分子量分佈係指重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn)。上述重量平均分子量之更佳下限為75萬,進而較佳下限為80萬。上述重量平均分子量之上限並無特別限定,就使用性之觀點而言,例如較佳上限為120萬。又,上述分子量分佈之更佳下限為2.5,進而較佳下限為3,且更佳上限為5.5,進而較佳上限為5。上述重量平均分子量及分子量分佈可採用GPC測定法確定,具體而言,可採用實施例中所示之方法。 作為獲得具有上述重量平均分子量及分子量分佈之上述(甲基)丙烯酸系共聚物之方法,例如可列舉:溶液聚合、乳化聚合、活性自由基聚合等。Since the (meth) acrylic copolymer has a relatively large weight average molecular weight of more than 700,000 and a relatively narrow molecular weight distribution of 2 to 6, the tensile strength of the non-UV curing adhesive layer and the above-mentioned outgassing amount can be easily adjusted to the above-mentioned range. Furthermore, here, the so-called molecular weight distribution refers to the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The preferred lower limit of the above-mentioned weight average molecular weight is 750,000, and the further preferred lower limit is 800,000. The upper limit of the above-mentioned weight average molecular weight is not particularly limited, and from the perspective of usability, for example, the preferred upper limit is 1.2 million. In addition, the preferred lower limit of the above-mentioned molecular weight distribution is 2.5, and the further preferred lower limit is 3, and the further preferred upper limit is 5.5, and the further preferred upper limit is 5. The weight average molecular weight and molecular weight distribution can be determined by GPC measurement, and specifically, the method shown in the embodiment can be used. Methods for obtaining the (meth)acrylic acid copolymer having the weight average molecular weight and molecular weight distribution include, for example, solution polymerization, emulsion polymerization, and living free radical polymerization.
於本發明之第1態樣中,上述非紫外線硬化型黏著劑層較佳為含有(B)作為硬化劑之環氧系化合物,更佳為含有包含三級胺結構之環氧系化合物。 於本發明之第2態樣中,上述非紫外線硬化型黏著劑層含有(B)作為硬化劑之包含三級胺結構之環氧系化合物。 藉由上述非紫外線硬化型黏著劑層含有環氧系化合物,可使上述基礎聚合物交聯,而提高非紫外線硬化型黏著劑層之耐化學品性及耐熱性。又,交聯後之基礎聚合物凝膠分率提高,成為不易移動之分子結構。因此,於上述紫外線硬化型黏著劑層含有聚矽氧化合物之情形時,可阻礙聚矽氧化合物向非紫外線硬化型黏著劑層之滲出,即便於經過長期保管後亦可發揮充分之黏著力。作為上述環氧系化合物,例如可列舉:N,N,N',N'-四縮水甘油基-1,3-苯二(甲胺)、甲基縮水甘油醚、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、雙-(3,4-環氧環己基)己二酸酯、雙酚A二縮水甘油醚、雙酚A之二縮水甘油醚縮合物、酚醛清漆樹脂或甲酚樹脂之表氯醇改質物等。其中,較佳為包含三級胺結構之環氧系化合物。In the first aspect of the present invention, the non-UV curing adhesive layer preferably contains (B) an epoxy compound as a curing agent, and more preferably contains an epoxy compound containing a tertiary amine structure. In the second aspect of the present invention, the non-UV curing adhesive layer contains (B) an epoxy compound containing a tertiary amine structure as a curing agent. By containing an epoxy compound in the non-UV curing adhesive layer, the base polymer can be crosslinked, thereby improving the chemical resistance and heat resistance of the non-UV curing adhesive layer. In addition, the gel fraction of the crosslinked base polymer is increased, and a molecular structure that is not easy to move is formed. Therefore, when the UV-curable adhesive layer contains a polysilicone compound, the polysilicone compound can be prevented from permeating into the non-UV-curable adhesive layer, and sufficient adhesion can be exerted even after long-term storage. Examples of the epoxy compound include: N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine), methyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis-(3,4-epoxycyclohexyl) adipate, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether condensate, epichlorohydrin modified products of novolac resin or cresol resin, and the like. Among them, epoxy compounds containing a tertiary amine structure are preferred.
與環氧系化合物進行交聯反應前之基礎聚合物凝膠分率較低,為分子容易移動之結構,因此於上述紫外線硬化型黏著劑層含有聚矽氧化合物之情形時,聚矽氧化合物容易滲出。因此,若交聯反應之速度較慢,則會導致聚矽氧化合物向非紫外線硬化型黏著劑層大量滲出。若上述非紫外線硬化型黏著劑層中存在三級胺基,則三級胺基作為交聯反應之觸媒發揮作用,基礎聚合物之交聯反應之速度加快,因此反應於早期完成。藉由在早期完成交聯反應,聚矽氧化合物不易滲出至非紫外線硬化型黏著劑層,因此可製成即便於經過長期保管後亦具有充分之黏著力之黏著帶。作為上述具有三級胺之環氧化合物,可列舉N,N,N',N'-四縮水甘油基-1,3-苯二(甲胺)等。The base polymer before the crosslinking reaction with the epoxy compound has a low gel fraction and a structure in which the molecules can easily move. Therefore, when the above-mentioned UV-curing adhesive layer contains polysilicone, the polysilicone easily permeates. Therefore, if the crosslinking reaction rate is slow, the polysilicone will permeate into the non-UV-curing adhesive layer in large quantities. If the non-UV-curing adhesive layer contains tertiary amine groups, the tertiary amine groups act as catalysts for the crosslinking reaction, and the crosslinking reaction rate of the base polymer is accelerated, so the reaction is completed at an early stage. By completing the crosslinking reaction at an early stage, the polysilicone compound is not easy to penetrate into the non-UV curing adhesive layer, so that an adhesive tape having sufficient adhesion even after long-term storage can be produced. Examples of the above-mentioned epoxy compound having a tertiary amine include N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) and the like.
上述非紫外線硬化型黏著劑層中之硬化劑(上述環氧系化合物)之含量相對於上述基礎聚合物100重量份,較佳下限為0.1重量份,更佳下限為0.2重量份,進而較佳下限為0.3重量份,且較佳上限為0.5重量份,更佳上限為0.45重量份,進而較佳上限為0.4重量份。藉由上述環氧系化合物之含量為上述範圍內,可使上述基礎聚合物充分且快速地交聯,而可進一步抑制聚矽氧化合物向非紫外線硬化型黏著劑層之滲出。The content of the curing agent (the epoxy compound) in the non-UV curing adhesive layer is preferably 0.1 parts by weight, more preferably 0.2 parts by weight, and further preferably 0.3 parts by weight, and the upper limit is preferably 0.5 parts by weight, more preferably 0.45 parts by weight, and further preferably 0.4 parts by weight, relative to 100 parts by weight of the base polymer. When the content of the epoxy compound is within the above range, the base polymer can be fully and quickly crosslinked, and the permeation of the polysilicone compound into the non-UV curing adhesive layer can be further suppressed.
於本發明之第1態樣中,上述非紫外線硬化型黏著劑層較佳為含有(C)填料。 於本發明之第2態樣中,上述非紫外線硬化型黏著劑層含有(C)填料。 藉由上述非紫外線硬化型黏著劑層含有填料,可提高耐熱性。作為上述填料,例如可列舉:二氧化矽填料、鋁填料、鈣填料、硼填料、鎂填料、氧化鋯填料等。其中,較佳為二氧化矽填料。In the first aspect of the present invention, the non-UV curing adhesive layer preferably contains (C) filler. In the second aspect of the present invention, the non-UV curing adhesive layer contains (C) filler. The heat resistance can be improved by the non-UV curing adhesive layer containing filler. Examples of the filler include: silica filler, aluminum filler, calcium filler, boron filler, magnesium filler, zirconia filler, etc. Among them, silica filler is preferred.
就於上述紫外線硬化型黏著劑層含有聚矽氧化合物之情形時可進一步抑制聚矽氧化合物之滲出之方面而言,上述二氧化矽填料較佳為二氧化矽填料氧化物。由於二氧化矽填料氧化物具有親水性基且極性較高,故而藉由使非紫外線硬化型黏著劑層含有二氧化矽填料氧化物,可阻礙極性較低之物質接近。因此,於上述紫外線硬化型黏著劑層含有低極性之聚矽氧化合物之情形時,可抑制聚矽氧化合物向非紫外線硬化型黏著劑層滲出。In the case where the UV-curable adhesive layer contains a polysilicone compound, the silica filler is preferably a silica filler oxide, which can further suppress the permeation of the polysilicone compound. Since the silica filler oxide has a hydrophilic group and is highly polar, the non-UV-curable adhesive layer can be blocked from approaching substances with lower polarity by containing the silica filler oxide. Therefore, when the UV-curable adhesive layer contains a polysilicone compound with low polarity, the permeation of the polysilicone compound into the non-UV-curable adhesive layer can be suppressed.
上述二氧化矽填料氧化物並無特別限定,例如可列舉:矽-鋁-硼複合氧化物、矽-鈦複合氧化物、二氧化矽-二氧化鈦複合氧化物、鎂-鋁-矽複合氧化物、六甲基環三矽氧烷、四甲氧基矽烷、氯矽烷、單矽烷等。其中,就具有與通常用作無機填充劑之二氧化矽類似之物性之方面而言,較佳為矽-鋁-硼複合氧化物、矽-鈦複合氧化物、二氧化矽-二氧化鈦複合氧化物。The silica filler oxide is not particularly limited, and examples thereof include silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, silicon dioxide-titania composite oxide, magnesium-aluminum-silicon composite oxide, hexamethylcyclotrisiloxane, tetramethoxysilane, chlorosilane, monosilane, etc. Among them, silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, and silicon dioxide-titania composite oxide are preferred in terms of having physical properties similar to those of silica commonly used as an inorganic filler.
於上述二氧化矽填料為二氧化矽填料氧化物之情形時,上述二氧化矽填料氧化物較佳為表面之至少一部分經疏水化處理。藉由將二氧化矽填料氧化物所存在之親水性基中之至少一部分取代為疏水性基,可提高於基礎聚合物中之分散性。上述疏水性基並無特別限定,例如可列舉:甲基、乙基、丙基、丁基等。其中,就於基礎聚合物中之分散性之觀點而言,上述疏水化處理後之二氧化矽填料氧化物較佳為具有單甲基矽基、二甲基矽基或三甲基矽基。尤其是就抑制聚矽氧化合物向非紫外線硬化型黏著劑層之滲出之效果與於基礎聚合物中之分散性的平衡性優異之方面而言,更佳為上述二氧化矽填料氧化物之至少一部分具有單甲基矽基。再者,如上所述,二氧化矽填料氧化物係藉由其親水性來阻礙聚矽氧化合物之接近,因此表面全部經疏水性基取代之二氧化矽填料氧化物難以發揮作為二氧化矽填料氧化物之效果。When the silica filler is a silica filler oxide, the silica filler oxide is preferably treated with hydrophobic treatment on at least a portion of the surface. By replacing at least a portion of the hydrophilic groups present in the silica filler oxide with hydrophobic groups, the dispersibility in the base polymer can be improved. The hydrophobic group is not particularly limited, and examples thereof include methyl, ethyl, propyl, butyl, etc. Among them, from the viewpoint of dispersibility in the base polymer, the silica filler oxide after the hydrophobic treatment preferably has a monomethylsilyl group, a dimethylsilyl group, or a trimethylsilyl group. In particular, in terms of the excellent balance between the effect of suppressing the permeation of the polysilicone compound into the non-UV curing adhesive layer and the dispersibility in the base polymer, it is more preferable that at least a portion of the above-mentioned silica filler oxide has a monomethylsilyl group. Furthermore, as mentioned above, the silica filler oxide blocks the approach of the polysilicone compound by its hydrophilicity, so the silica filler oxide whose surface is completely substituted with hydrophobic groups is difficult to exert the effect of a silica filler oxide.
於上述二氧化矽填料氧化物之至少一部分具有單甲基矽基、二甲基矽基或三甲基矽基之情形時,上述二氧化矽填料氧化物較佳為具有以原體比表面積計100 m2 /g以上之上述官能基,更佳為具有140 m2 /g以上。藉由二氧化矽填料氧化物於表面在上述範圍內具有上述官能基,可進一步提高二氧化矽填料氧化物於基礎聚合物中之分散性。When at least a portion of the silica filler oxide has a monomethylsilyl group, a dimethylsilyl group or a trimethylsilyl group, the silica filler oxide preferably has the functional group of 100 m 2 /g or more, more preferably 140 m 2 /g or more, based on the bulk specific surface area. When the silica filler oxide has the functional group within the above range on the surface, the dispersibility of the silica filler oxide in the base polymer can be further improved.
上述填料之平均粒徑並無特別限定,較佳下限為0.06 μm,更佳下限為0.07 μm,且較佳上限為2 μm,更佳上限為1 μm。藉由填料之平均粒徑為上述範圍,可進一步提高於非紫外線硬化型黏著劑中之分散性。The average particle size of the filler is not particularly limited, but the preferred lower limit is 0.06 μm, and the more preferred lower limit is 0.07 μm, and the preferred upper limit is 2 μm, and the more preferred upper limit is 1 μm. When the average particle size of the filler is within the above range, the dispersibility in the non-UV curing adhesive can be further improved.
上述填料之含量並無特別限定,相對於上述基礎聚合物100重量份之較佳下限為3重量份,較佳上限為20重量份。藉由填料之含量為3重量份以上,可進一步提高所獲得之黏著帶之耐熱性。藉由二氧化矽填料之含量為20重量份以下,可製成具有充分之黏著力之黏著帶。就進一步提高黏著帶之耐熱性之觀點而言,相對於上述基礎聚合物100重量份之上述二氧化矽填料之含量之更佳下限為6重量份,進而較佳下限為8重量份,且更佳上限為18重量份,進而較佳上限為15重量份,尤佳上限為13重量份。The content of the above-mentioned filler is not particularly limited. The preferred lower limit is 3 parts by weight relative to 100 parts by weight of the above-mentioned base polymer, and the preferred upper limit is 20 parts by weight. By having a filler content of more than 3 parts by weight, the heat resistance of the obtained adhesive tape can be further improved. By having a silica filler content of less than 20 parts by weight, an adhesive tape with sufficient adhesion can be prepared. From the viewpoint of further improving the heat resistance of the adhesive tape, the preferred lower limit of the content of the above-mentioned silica filler relative to 100 parts by weight of the above-mentioned base polymer is 6 parts by weight, and further the preferred lower limit is 8 parts by weight, and the preferred upper limit is 18 parts by weight, and further the preferred upper limit is 15 parts by weight, and the particularly preferred upper limit is 13 parts by weight.
上述非紫外線硬化型黏著劑層亦可含有黏著賦予劑。 藉由上述非紫外線硬化型黏著劑層含有黏著賦予劑,可進一步提高黏著力。然而,黏著賦予劑於高溫處理時亦會導致產生釋氣,因此較佳為儘量不使用或減少使用量。因此,於使用黏著賦予劑之情形時,上述非紫外線硬化型黏著劑層較佳為相對於上述(甲基)丙烯酸系共聚物100重量份,含有30重量份以下之黏著賦予劑。藉由將黏著賦予劑之含量設為上述範圍,可抑制因熱引起之產生釋氣之情況,而容易調節為上述釋氣量。上述黏著賦予劑之更佳上限為20重量份,進而較佳上限為10重量份。上述黏著賦予劑之下限並無特別限定,就儘量減少釋氣之產生量之觀點而言,較佳為0重量份,就進一步提高黏著力之觀點而言,較佳為3重量份。The above-mentioned non-UV curing adhesive layer may also contain an adhesive agent. By containing an adhesive agent in the above-mentioned non-UV curing adhesive layer, the adhesion can be further improved. However, the adhesive agent will also cause outgassing when treated at high temperature, so it is better not to use it or reduce the amount used as much as possible. Therefore, when using an adhesive agent, the above-mentioned non-UV curing adhesive layer preferably contains 30 parts by weight or less of the adhesive agent relative to 100 parts by weight of the above-mentioned (meth) acrylic copolymer. By setting the content of the adhesive agent to the above range, the generation of outgassing caused by heat can be suppressed, and it is easy to adjust to the above-mentioned outgassing amount. The upper limit of the above-mentioned adhesion-imparting agent is more preferably 20 parts by weight, and further preferably 10 parts by weight. The lower limit of the above-mentioned adhesion-imparting agent is not particularly limited, but is preferably 0 parts by weight from the viewpoint of minimizing the amount of outgassing, and is preferably 3 parts by weight from the viewpoint of further improving the adhesion.
上述非紫外線硬化型黏著劑層亦可含有塑化劑、樹脂、界面活性劑、蠟、微粒子填充劑等公知之添加劑。上述添加劑可使用1或2種以上。The non-UV curing adhesive layer may also contain known additives such as plasticizers, resins, surfactants, waxes, and microparticle fillers. One or more of the additives may be used.
上述非紫外線硬化型黏著劑層之厚度並無特別限定,較佳下限為5 μm,更佳下限為10 μm,且較佳上限為100 μm,更佳上限為60 μm。若上述非紫外線硬化型黏著劑層之厚度為上述範圍,則能夠以充分之黏著力與支持體接著,確實地固定被黏著體。The thickness of the non-UV curing adhesive layer is not particularly limited, and the preferred lower limit is 5 μm, the more preferred lower limit is 10 μm, and the preferred upper limit is 100 μm, the more preferred upper limit is 60 μm. If the thickness of the non-UV curing adhesive layer is within the above range, it can be bonded to the support with sufficient adhesion to securely fix the adherend.
作為構成上述紫外線硬化型黏著劑層之上述紫外線硬化型黏著劑成分,例如可列舉以聚合性聚合物為主成分、且含有紫外線聚合起始劑作為聚合起始劑之紫外線硬化型黏著劑。上述聚合性聚合物例如可藉由預先合成於分子內具有官能基之(甲基)丙烯酸系聚合物(以下稱為含官能基之(甲基)丙烯酸系聚合物),使其和於分子內具有會與上述官能基反應之官能基及自由基聚合性不飽和鍵之化合物(以下稱為含官能基之不飽和化合物)進行反應而獲得。As the UV-curable adhesive component constituting the UV-curable adhesive layer, for example, there can be cited a UV-curable adhesive having a polymerizable polymer as a main component and containing a UV polymerization initiator as a polymerization initiator. The polymerizable polymer can be obtained by, for example, pre-synthesizing a (meth)acrylic polymer having a functional group in the molecule (hereinafter referred to as a (meth)acrylic polymer containing a functional group) and reacting it with a compound having a functional group that reacts with the functional group and a free radical polymerizable unsaturated bond in the molecule (hereinafter referred to as an unsaturated compound containing a functional group).
上述含官能基之(甲基)丙烯酸系聚合物係以烷基之碳數通常處於2〜18之範圍之丙烯酸烷基酯及/或甲基丙烯酸烷基酯為主要單體,使其與含官能基之單體、及進而視需要之能夠與該等共聚合之其他改質用單體藉由常規方法進行共聚合,藉此而獲得者。上述含官能基之(甲基)丙烯酸系聚合物之重量平均分子量通常為20萬〜200萬左右。再者,於本說明書中,重量平均分子量通常可藉由GPC法確定,具體而言,可採用實施例中所示之方法。The above-mentioned (meth) acrylic polymer containing a functional group is obtained by copolymerizing an alkyl acrylate and/or alkyl methacrylate whose alkyl group has a carbon number of 2 to 18 as a main monomer with a monomer containing a functional group and, if necessary, other monomers for modification that can copolymerize with the above-mentioned monomers by a conventional method. The weight average molecular weight of the above-mentioned (meth) acrylic polymer containing a functional group is generally about 200,000 to 2,000,000. In addition, in this specification, the weight average molecular weight can generally be determined by the GPC method, and specifically, the method shown in the examples can be adopted.
作為上述含官能基之單體,例如可列舉:含羧基之單體、含羥基之單體、含環氧基之單體、含異氰酸基之單體、含胺基之單體等。作為上述含羧基之單體,可列舉:丙烯酸、甲基丙烯酸等。作為上述含羥基之單體,可列舉:丙烯酸羥基乙酯、甲基丙烯酸羥基乙酯等。作為上述含環氧基之單體,可列舉:丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等。作為上述含異氰酸基之單體,可列舉:丙烯酸異氰酸基乙酯、甲基丙烯酸異氰酸基乙酯等。作為上述含胺基之單體,可列舉:丙烯酸胺基乙酯、甲基丙烯酸胺基乙酯等。Examples of the above-mentioned monomers containing functional groups include carboxyl group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, isocyanate group-containing monomers, and amino group-containing monomers. Examples of the above-mentioned monomers containing carboxyl group include acrylic acid and methacrylic acid. Examples of the above-mentioned monomers containing hydroxyl group include hydroxyethyl acrylate and hydroxyethyl methacrylate. Examples of the above-mentioned monomers containing epoxy group include glycidyl acrylate and glycidyl methacrylate. Examples of the above-mentioned monomers containing isocyanate group include isocyanate ethyl acrylate and isocyanate ethyl methacrylate. Examples of the above-mentioned monomers containing amino group include aminoethyl acrylate and aminoethyl methacrylate.
作為上述能夠共聚合之其他改質用單體,例如可列舉:乙酸乙烯酯、丙烯腈、苯乙烯等通常之用於(甲基)丙烯酸系聚合物之各種單體。Examples of the other copolymerizable modifying monomers include various monomers commonly used in (meth)acrylic acid polymers, such as vinyl acetate, acrylonitrile, and styrene.
作為與上述含官能基之(甲基)丙烯酸系聚合物進行反應之含官能基之不飽和化合物,可根據上述含官能基之(甲基)丙烯酸系聚合物之官能基,使用與上述含官能基之單體相同者。例如於上述含官能基之(甲基)丙烯酸系聚合物之官能基為羧基之情形時,使用含環氧基之單體或含異氰酸基之單體。於該含官能基之(甲基)丙烯酸系聚合物之官能基為羥基之情形時,使用含異氰酸基之單體。於該含官能基之(甲基)丙烯酸系聚合物之官能基為環氧基之情形時,使用含羧基之單體或丙烯醯胺等含醯胺基之單體。於該含官能基之(甲基)丙烯酸系聚合物之官能基為胺基之情形時,使用含環氧基之單體。As the functional group-containing unsaturated compound that reacts with the functional group-containing (meth)acrylic polymer, the same as the functional group-containing monomer can be used according to the functional group of the functional group-containing (meth)acrylic polymer. For example, when the functional group of the functional group-containing (meth)acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer is used. When the functional group of the functional group-containing (meth)acrylic polymer is a hydroxyl group, an isocyanate group-containing monomer is used. When the functional group of the functional group-containing (meth)acrylic polymer is an epoxy group, a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide is used. When the functional group of the functional group-containing (meth)acrylic polymer is an amino group, an epoxy group-containing monomer is used.
上述紫外線聚合起始劑例如可列舉藉由照射波長200〜410 nm之紫外線而活化者。作為此種紫外線聚合起始劑,例如可列舉:苯乙酮衍生物化合物、安息香醚系化合物、縮酮衍生物化合物、氧化膦衍生物化合物、雙(η5-環戊二烯基)二茂鈦衍生物化合物、二苯甲酮、米其勒酮、氯9-氧硫 、十二烷基9-氧硫 、二甲基9-氧硫 、二乙基9-氧硫 、α-羥基環己基苯基酮、2-羥基甲基苯基丙烷等。作為上述苯乙酮衍生物化合物,可列舉甲氧基苯乙酮等。作為上述安息香醚系化合物,可列舉:安息香丙醚、安息香異丁醚等。作為上述縮酮衍生物化合物,可列舉:苯偶醯二甲基縮酮、苯乙酮二乙基縮酮等。該等紫外線聚合起始劑可單獨使用,亦可併用2種以上。The above-mentioned ultraviolet polymerization initiator can be, for example, activated by irradiation with ultraviolet light of a wavelength of 200 to 410 nm. As such ultraviolet polymerization initiators, for example, acetophenone derivative compounds, benzoin ether compounds, ketal derivative compounds, phosphine oxide derivative compounds, bis(η5-cyclopentadienyl)titaniumocene derivative compounds, benzophenone, michler's ketone, chloro-9-oxysulfur , dodecyl 9-oxysulfide , dimethyl 9-oxysulfide , diethyl 9-sulfoxide , α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenyl propane, etc. Examples of the above-mentioned acetophenone derivative compounds include methoxyacetophenone, etc. Examples of the above-mentioned benzoin ether compounds include benzoin propyl ether, benzoin isobutyl ether, etc. Examples of the above-mentioned ketal derivative compounds include benzoyl dimethyl ketal, acetophenone diethyl ketal, etc. These ultraviolet polymerization initiators may be used alone or in combination of two or more.
上述紫外線硬化型黏著劑層較佳為含有自由基聚合性之多官能低聚物或單體。藉由上述紫外線硬化型黏著劑層含有自由基聚合性之多官能低聚物或單體,紫外線硬化性提高。 上述多官能低聚物或單體較佳為重量平均分子量為1萬以下者,更佳為其重量平均分子量為5000以下且分子內之自由基聚合性不飽和鍵之數量為2〜20個者,以藉由照射紫外線使紫外線硬化型黏著劑層效率良好地三維網狀化。上述重量平均分子量例如可採用GPC測定法確定,具體而言可採用實施例中所示之方法。The above-mentioned UV-curable adhesive layer preferably contains a free radical polymerizable multifunctional oligomer or monomer. The UV curability is improved by the above-mentioned UV-curable adhesive layer containing a free radical polymerizable multifunctional oligomer or monomer. The above-mentioned multifunctional oligomer or monomer preferably has a weight average molecular weight of 10,000 or less, and more preferably has a weight average molecular weight of 5,000 or less and the number of free radical polymerizable unsaturated bonds in the molecule is 2 to 20, so that the UV-curable adhesive layer can be efficiently three-dimensionally networked by irradiating ultraviolet rays. The above-mentioned weight average molecular weight can be determined, for example, by GPC measurement, and specifically, the method shown in the embodiment can be adopted.
上述多官能低聚物或單體例如可列舉:三羥甲基丙烷三丙烯酸酯、四羥甲基甲烷四丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇單羥基五丙烯酸酯、二新戊四醇六丙烯酸酯或上述相同之甲基丙烯酸酯類等。除此以外,可列舉:1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、市售之寡酯丙烯酸酯、上述相同之甲基丙烯酸酯類等。該等多官能低聚物或單體可單獨使用,亦可併用2種以上。Examples of the multifunctional oligomers or monomers include trihydroxymethylpropane triacrylate, tetrahydroxymethylmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, or the same methacrylates as above. In addition, examples include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylates, and the same methacrylates as above. These multifunctional oligomers or monomers may be used alone or in combination of two or more.
上述紫外線硬化型黏著劑層較佳為含有聚矽氧化合物。 藉由上述紫外線硬化型黏著劑層含有聚矽氧化合物,由於在紫外線硬化型黏著劑層與被黏著體之界面滲出聚矽氧化合物,故而於處理結束後可容易地剝離黏著帶。又,由於聚矽氧化合物之耐熱性優異,故而即便於進行伴隨150℃以上之加熱之處理之情形時,亦可抑制紫外線硬化型黏著劑層被烤焦等,抑制糊劑殘留。The UV-curable adhesive layer preferably contains polysilicone. Since the UV-curable adhesive layer contains polysilicone, the adhesive tape can be easily peeled off after the treatment because the polysilicone seeps out at the interface between the UV-curable adhesive layer and the adherend. In addition, since polysilicone has excellent heat resistance, even when the treatment is accompanied by heating at 150°C or above, the UV-curable adhesive layer can be prevented from being scorched, thereby preventing the adhesive from remaining.
上述聚矽氧化合物較佳為具有能夠與上述紫外線硬化型黏著劑成分交聯之官能基。 藉由聚矽氧化合物具有能夠與紫外線硬化型黏著劑成分交聯之官能基,經過紫外線照射,聚矽氧化合物與紫外線硬化型黏著劑成分發生化學反應而摻入至紫外線硬化型黏著劑成分中,因此抑制聚矽氧化合物附著於被黏著體而引起之污染。上述聚矽氧化合物之官能價例如為2〜6價,較佳為2〜4價,更佳為2價。上述官能基根據紫外線硬化型黏著劑成分中所含之官能基而適當決定,例如於紫外線硬化型黏著劑成分係以(甲基)丙烯酸烷基酯系聚合性聚合物為主成分之光硬化型黏著劑之情形時,選擇能夠與(甲基)丙烯酸基交聯之官能基。 上述能夠與(甲基)丙烯酸基交聯之官能基為具有不飽和雙鍵之官能基,具體而言,例如選擇含有乙烯基、(甲基)丙烯酸基、烯丙基、馬來醯亞胺基等之聚矽氧化合物。The polysilicone compound preferably has a functional group capable of crosslinking with the UV-curing adhesive component. Since the polysilicone compound has a functional group capable of crosslinking with the UV-curing adhesive component, the polysilicone compound reacts with the UV-curing adhesive component and is incorporated into the UV-curing adhesive component after irradiation with ultraviolet light, thereby suppressing the contamination caused by the polysilicone compound adhering to the adherend. The functional valence of the polysilicone compound is, for example, 2 to 6, preferably 2 to 4, and more preferably 2. The functional group is appropriately determined according to the functional group contained in the UV-curing adhesive component. For example, when the UV-curing adhesive component is a light-curing adhesive with a (meth) alkyl ester polymer as the main component, a functional group capable of crosslinking with a (meth) acrylic acid group is selected. The functional group capable of crosslinking with a (meth) acrylic acid group is a functional group having an unsaturated double bond. Specifically, for example, a polysiloxane containing a vinyl group, a (meth) acrylic acid group, an allyl group, a maleimide group, etc. is selected.
上述聚矽氧化合物之重量平均分子量較佳為300〜50000。 藉由聚矽氧化合物之重量平均分子量為300以上,可利用其較大之分子尺寸而進一步抑制向非紫外線硬化型黏著劑層之滲出。藉由重量平均分子量為50000以下,可進一步抑制向紫外線硬化型黏著劑層與被黏著體之界面滲出而接著亢進。上述聚矽氧化合物之重量平均分子量之更佳下限為400,進而較佳下限為500,且更佳上限為10000,進而較佳上限為5000。再者,於本發明中,聚矽氧化合物之重量平均分子量可藉由GPC分析確定,具體而言可採用實施例中所示之方法。The weight average molecular weight of the polysilicone compound is preferably 300 to 50,000. When the weight average molecular weight of the polysilicone compound is 300 or more, its larger molecular size can be used to further suppress the permeation into the non-UV curing adhesive layer. When the weight average molecular weight is 50,000 or less, the permeation into the interface between the UV curing adhesive layer and the adherend and the subsequent hyperplasia can be further suppressed. The weight average molecular weight of the polysilicone compound is preferably 400, and further preferably 500, and the upper limit is preferably 10,000, and further preferably 5,000. Furthermore, in the present invention, the weight average molecular weight of the polysilicone compound can be determined by GPC analysis, and specifically, the method shown in the embodiment can be adopted.
作為具有上述官能基及重量平均分子量之聚矽氧化合物,例如可列舉矽二丙烯酸酯。若使用矽二丙烯酸酯,則耐熱性及剝離性更加良好。As the polysilicone compound having the above functional group and weight average molecular weight, for example, silicon diacrylate can be cited. When silicon diacrylate is used, heat resistance and peeling property are further improved.
上述聚矽氧化合物之較佳之含量相對於上述聚合性聚合物100重量份,下限為1重量份,上限為50重量份,更佳下限為10重量份,更佳上限為40重量份。藉由上述聚矽氧化合物之含量為上述範圍,能夠以充分之黏著力保護被黏著體,並且於保護結束後可更容易地剝離黏著帶。The preferred content of the polysilicone compound is 1 part by weight and 50 parts by weight relative to 100 parts by weight of the polymerizable polymer, with a more preferred lower limit of 10 parts by weight and a more preferred upper limit of 40 parts by weight. When the content of the polysilicone compound is within the above range, the adherend can be protected with sufficient adhesion, and the adhesive tape can be more easily peeled off after the protection is completed.
上述紫外線硬化型黏著劑層亦可含有發煙二氧化矽等無機填料、塑化劑、樹脂、界面活性劑、蠟、微粒子填充劑等公知之添加劑。The UV-curable adhesive layer may also contain known additives such as inorganic fillers such as fuming silica, plasticizers, resins, surfactants, waxes, and microparticle fillers.
上述紫外線硬化型黏著劑層之厚度並無特別限定,較佳為下限為5 μm、上限為100 μm。若上述紫外線硬化型黏著劑層之厚度為上述範圍,則能夠以充分之黏著力保護被黏著體,進而亦可抑制於剝離時糊劑殘留。就進一步提高黏著力並進一步抑制於剝離時糊劑殘留之觀點而言,上述紫外線硬化型黏著劑層之厚度之更佳下限為10 μm,更佳上限為60 μm。The thickness of the UV-curable adhesive layer is not particularly limited, but preferably has a lower limit of 5 μm and an upper limit of 100 μm. If the thickness of the UV-curable adhesive layer is within the above range, the adherend can be protected with sufficient adhesion, and the residual paste during peeling can be suppressed. From the perspective of further improving the adhesion and further suppressing the residual paste during peeling, the thickness of the UV-curable adhesive layer has a better lower limit of 10 μm and a better upper limit of 60 μm.
本發明之黏著帶較佳為不具有基材之無支持型雙面黏著帶。於具有基材之支持型之情形時,不存在聚矽氧化合物向支持體側之界面滲出之情況,但必須使用耐熱性基材,因此與無支持型相比成本較高。The adhesive tape of the present invention is preferably a double-sided adhesive tape without a substrate. In the case of a supported type with a substrate, there is no polysilicone compound seeping out to the interface of the support body side, but a heat-resistant substrate must be used, so the cost is higher than that of the unsupported type.
本發明之黏著帶較佳為於上述非紫外線硬化型黏著劑層之與積層有上述紫外線硬化型黏著劑層之面為相反側之面積層有(較佳為紫外線穿透性之)脫模膜。 藉由使非紫外線硬化型黏著劑層上具有脫模膜,可於向被黏著體貼附之前保護非紫外線硬化型黏著劑層,並且可提高黏著帶之使用性。又,於脫模膜為紫外線穿透性之情形時,可於非紫外線硬化型黏著劑層經保護之狀態下進行下述硬化步驟。The adhesive tape of the present invention preferably has a release film (preferably UV-transmissive) on the surface of the non-UV-curing adhesive layer opposite to the surface on which the UV-curing adhesive layer is layered. By providing a release film on the non-UV-curing adhesive layer, the non-UV-curing adhesive layer can be protected before being attached to the adherend, and the usability of the adhesive tape can be improved. In addition, when the release film is UV-transmissive, the following curing step can be performed while the non-UV-curing adhesive layer is protected.
上述脫模膜並無特別限定,例如可列舉:聚萘二甲酸乙二酯(PEN)、聚醯亞胺(PI)、聚醚醚酮(PEEK)、聚苯硫醚(PPS)、聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚對苯二甲酸己二酯、聚萘二甲酸丁二酯、對苯二甲酸丁二醇聚四亞甲基二醇共聚物、對苯二甲酸丁二醇聚己內酯共聚物等紫外線穿透性膜。其中,較佳為聚對苯二甲酸乙二酯(PET)。The mold release film is not particularly limited, and examples thereof include: polyethylene naphthalate (PEN), polyimide (PI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polybutylene naphthalate, butylene terephthalate polytetramethylene glycol copolymer, butylene terephthalate polycaprolactone copolymer and other ultraviolet light-transmitting films. Among them, polyethylene terephthalate (PET) is preferred.
本發明之黏著帶只要紫外線硬化型黏著劑層與非紫外線硬化型黏著劑層位於最外層(與被黏著體接觸之層),則亦可於紫外線硬化型黏著劑層與非紫外線硬化型黏著劑層之間進而具有其他層。As long as the UV-curing adhesive layer and the non-UV-curing adhesive layer are located at the outermost layer (the layer in contact with the adherend), the adhesive tape of the present invention may further have other layers between the UV-curing adhesive layer and the non-UV-curing adhesive layer.
本發明之黏著帶於硬化前在23℃之拉伸強度較佳為2.5〜10 N/10 mm。 藉由硬化前之黏著帶之拉伸強度為上述範圍,可使黏著帶於剝離時不易拉斷。就進一步抑制黏著帶於剝離時被拉斷之觀點而言,上述黏著帶於硬化前之拉伸強度之更佳下限為3.0 N/10 mm,進而較佳下限為3.5 N/10 mm,且更佳上限為9.5 N/10 mm,進而較佳上限為9.0 N/10 mm。再者,上述黏著帶於硬化前之拉伸強度可藉由與上述非紫外線硬化型黏著劑層之拉伸強度相同之方法進行測定。The tensile strength of the adhesive tape of the present invention at 23°C before curing is preferably 2.5 to 10 N/10 mm. By having the tensile strength of the adhesive tape before curing be within the above range, the adhesive tape is not easily pulled apart during peeling. From the viewpoint of further suppressing the adhesive tape from being pulled apart during peeling, the better lower limit of the tensile strength of the adhesive tape before curing is 3.0 N/10 mm, and further the better lower limit is 3.5 N/10 mm, and the better upper limit is 9.5 N/10 mm, and further the better upper limit is 9.0 N/10 mm. Furthermore, the tensile strength of the adhesive tape before curing can be measured by the same method as the tensile strength of the non-UV curing adhesive layer.
本發明之黏著帶較佳為上述紫外線硬化型黏著劑層之凝膠分率於紫外線硬化後為80%以上。 藉由紫外線硬化型黏著劑層之凝膠分率為上述下限值以上,可進一步提高黏著帶之耐化學品性,並且可進一步抑制聚矽氧化合物隨時間經過向非紫外線硬化型黏著劑層滲出之情況。上述紫外線硬化型黏著劑層之凝膠分率之更佳下限為85%,進而較佳下限為90%。上述紫外線硬化型黏著劑層之凝膠分率之上限並無特別限定,較佳為99%。又,於黏著帶具有紫外線硬化型黏著劑層與非紫外線硬化型黏著劑層以外之層之情形時,較佳為該層亦滿足上述凝膠分率。The adhesive tape of the present invention preferably has a gel fraction of 80% or more in the UV-curing adhesive layer after UV curing. By having a gel fraction of the UV-curing adhesive layer of more than the above lower limit, the chemical resistance of the adhesive tape can be further improved, and the polysilicone compound can be further inhibited from seeping into the non-UV-curing adhesive layer over time. The better lower limit of the gel fraction of the UV-curing adhesive layer is 85%, and the further better lower limit is 90%. The upper limit of the gel fraction of the UV-curing adhesive layer is not particularly limited, and is preferably 99%. Furthermore, when the adhesive tape has a layer other than the UV-curing adhesive layer and the non-UV-curing adhesive layer, it is preferred that the layer also satisfies the above-mentioned gel fraction.
製造本發明之黏著帶之方法並無特別限定,可使用先前公知之方法。例如可藉由以下方法製造:於經過脫模處理之膜上塗佈上述紫外線硬化型黏著劑成分之溶液,使其乾燥而形成紫外線硬化型黏著劑層,於另一經過脫模處理之膜上藉由相同方法形成非紫外線硬化型黏著劑層後,貼合紫外線硬化型黏著劑層與非紫外線硬化型黏著劑層。The method for manufacturing the adhesive tape of the present invention is not particularly limited, and a previously known method can be used. For example, the adhesive tape can be manufactured by the following method: a solution of the above-mentioned UV-curable adhesive component is applied on a film that has been subjected to a demolding treatment, and the solution is dried to form a UV-curable adhesive layer, and a non-UV-curable adhesive layer is formed on another film that has been subjected to a demolding treatment by the same method, and then the UV-curable adhesive layer and the non-UV-curable adhesive layer are laminated.
本發明之黏著帶之用途並無特別限定,可尤佳地用作使用不透明支持體、且藉由伴隨高溫處理之製造步驟製造電子基板或半導體晶片等電子零件時之保護帶。 作為此種電子零件之製造方法,例如可列舉以下之電子零件之製造方法。即,包括下述步驟之方法:被黏著體貼附步驟,其係自上述紫外線硬化型黏著劑層貼附於被黏著體;硬化步驟,其係照射紫外線而使上述紫外線硬化型黏著劑層硬化;支持體貼附步驟,其係於上述非紫外線硬化型黏著劑層上貼附支持體;熱處理步驟,其係將上述被黏著體於150℃以上之高溫進行處理;及剝離步驟,其係將自上述黏著帶剝離上述被黏著體。此種電子零件之製造方法可尤其有利地表現出本發明之效果。The use of the adhesive tape of the present invention is not particularly limited, and it can be particularly preferably used as a protective tape when manufacturing electronic components such as electronic substrates or semiconductor chips using an opaque support and a manufacturing step accompanied by high temperature treatment. As a manufacturing method for such electronic components, for example, the following manufacturing methods for electronic components can be listed. That is, the method includes the following steps: an adherend attaching step, which is to attach the adherend from the above-mentioned UV-curing adhesive layer; a curing step, which is to irradiate UV rays to cure the above-mentioned UV-curing adhesive layer; a support attaching step, which is to attach the support to the above-mentioned non-UV-curing adhesive layer; a heat treatment step, which is to treat the above-mentioned adherend at a high temperature of more than 150°C; and a peeling step, which is to peel the above-mentioned adherend from the above-mentioned adhesive tape. This method for manufacturing electronic components can particularly advantageously show the effect of the present invention.
又,本發明之一亦為一種電子零件之製造方法,該方法包括下述步驟:被黏著體貼附步驟,其係將本發明之黏著帶自紫外線硬化型黏著劑層貼附於被黏著體;硬化步驟,其係照射紫外線而使上述紫外線硬化型黏著劑層硬化;支持體貼附步驟,其係於上述非紫外線硬化型黏著劑層上貼附支持體;熱處理步驟,其係將上述被黏著體於150℃以上之高溫進行處理;及剝離步驟,其係自上述黏著帶剝離上述被黏著體。Furthermore, one of the present inventions is also a method for manufacturing electronic components, which includes the following steps: an adherend attaching step, which is to attach the adhesive tape of the present invention to the adherend from the UV-curing adhesive layer; a curing step, which is to irradiate UV rays to harden the above-mentioned UV-curing adhesive layer; a support attaching step, which is to attach a support to the above-mentioned non-UV-curing adhesive layer; a heat treatment step, which is to treat the above-mentioned adherend at a high temperature of more than 150°C; and a peeling step, which is to peel the above-mentioned adherend from the above-mentioned adhesive tape.
於本發明之電子零件之製造方法中,首先進行貼附步驟:將具有紫外線硬化型黏著劑層及非紫外線硬化型黏著劑層之本發明之黏著帶自上述紫外線硬化型黏著劑層貼附於被黏著體。 作為上述被黏著體,可列舉:矽晶圓、半導體晶片、製造電子基板時之基礎基材、電子零件之材料等。作為上述基材,可列舉:聚醯亞胺膜、玻璃環氧基板等。In the manufacturing method of the electronic component of the present invention, the attaching step is first performed: the adhesive tape of the present invention having a UV-curing adhesive layer and a non-UV-curing adhesive layer is attached to the adherend from the UV-curing adhesive layer. As the above-mentioned adherend, there can be listed: silicon wafers, semiconductor chips, base substrates when manufacturing electronic substrates, materials for electronic components, etc. As the above-mentioned substrates, there can be listed: polyimide films, glass epoxy substrates, etc.
於本發明之電子零件之製造方法中,繼而進行硬化步驟:照射紫外線使上述紫外線硬化型黏著劑層硬化。 藉由使紫外線硬化型黏著劑層硬化,可抑制糊劑殘留,容易自處理結束後之被黏著體剝離黏著帶。於本發明之電子零件之製造方法中,由於在將黏著帶貼附於支持體之前使紫外線硬化型黏著劑層硬化,故而即便支持體為不透光之素材,亦可使紫外線硬化型黏著劑層硬化。又,於黏著帶之非紫外線硬化型黏著劑層為紫外線穿透性之情形時,即便自非紫外線硬化型黏著劑層側向紫外線硬化型黏著劑層照射紫外線,亦可使紫外線硬化型黏著劑層充分地硬化。再者,由於將紫外線硬化型黏著劑層貼附於被黏著體後再硬化,故而即便於在進行被黏著體之處理前使紫外線硬化型黏著劑層硬化之情形時,黏著帶亦不會立即自被黏著體剝離。In the manufacturing method of the electronic component of the present invention, a curing step is then performed: irradiating ultraviolet rays to cure the above-mentioned ultraviolet curing adhesive layer. By curing the ultraviolet curing adhesive layer, the paste residue can be suppressed, and the adhesive tape can be easily peeled off from the adherend after the treatment. In the manufacturing method of the electronic component of the present invention, since the ultraviolet curing adhesive layer is cured before the adhesive tape is attached to the support, the ultraviolet curing adhesive layer can be cured even if the support is a light-opaque material. Furthermore, when the non-UV curing adhesive layer of the adhesive tape is UV-transmissive, the UV curing adhesive layer can be fully cured even when UV rays are irradiated from the non-UV curing adhesive layer to the UV curing adhesive layer. Furthermore, since the UV curing adhesive layer is cured after being attached to the adherend, the adhesive tape will not immediately peel off the adherend even when the UV curing adhesive layer is cured before the adherend is treated.
使上述紫外線硬化型黏著劑層硬化之光照射條件可根據所使用之上述聚合性聚合物與上述紫外線聚合起始劑之組合而適當調節。例如於使用側鏈具有乙烯基等不飽和雙鍵之聚合性聚合物、與會於波長200〜410 nm之光活化之紫外線聚合起始劑之情形時,藉由照射波長365 nm以上之光,可使上述紫外線硬化型黏著劑層交聯、硬化。 對此種紫外線硬化型黏著劑層,例如較佳為以5 mW以上之照度照射波長365 nm之光,更佳為以10 mW以上之照度照射,進而較佳為以20 mW以上之照度照射,尤佳為以50 mW以上之照度照射。又,較佳為以300 mJ以上之累計照度照射波長365 nm之光,更佳為以500 mJ以上且10000 mJ以下之累計照度照射,進而較佳為以500 mJ以上且7500 mJ以下之累計照度照射,尤佳為以1000 mJ以上且5000 mJ以下之累計照度照射。The light irradiation conditions for curing the above-mentioned UV-curable adhesive layer can be appropriately adjusted according to the combination of the above-mentioned polymerizable polymer and the above-mentioned UV polymerization initiator used. For example, when using a polymerizable polymer having unsaturated double bonds such as vinyl groups in the side chain and a UV polymerization initiator activated by light of a wavelength of 200 to 410 nm, the above-mentioned UV-curable adhesive layer can be crosslinked and cured by irradiating light of a wavelength of 365 nm or more. For such a UV-curable adhesive layer, for example, it is preferred to irradiate with light of a wavelength of 365 nm at an illumination of 5 mW or more, more preferably at an illumination of 10 mW or more, further preferably at an illumination of 20 mW or more, and even more preferably at an illumination of 50 mW or more. Furthermore, it is preferred to irradiate with light of a wavelength of 365 nm at a cumulative illuminance of 300 mJ or more, more preferably at a cumulative illuminance of 500 mJ or more and 10000 mJ or less, further preferably at a cumulative illuminance of 500 mJ or more and 7500 mJ or less, and particularly preferably at a cumulative illuminance of 1000 mJ or more and 5000 mJ or less.
於本發明之電子零件之製造方法中,繼而進行支持體貼附步驟:於非紫外線硬化型黏著劑層上貼附支持體。 於本發明之電子零件之製造方法中,由於黏著帶之黏著劑層分為紫外線硬化型黏著劑層與非紫外線硬化型黏著劑層,故而即便於在支持體貼附前進行硬化步驟之情形時,非紫外線硬化型黏著劑層亦不會硬化。因此,能夠以充分之黏著力將黏著帶貼附於支持體。再者,於黏著帶具有上述紫外線穿透性之脫模膜之情形時,在上述硬化步驟結束後且上述支持體貼附步驟之前,剝離上述脫模膜。In the manufacturing method of the electronic component of the present invention, the support body attaching step is then performed: attaching the support body on the non-ultraviolet curing adhesive layer. In the manufacturing method of the electronic component of the present invention, since the adhesive layer of the adhesive tape is divided into an ultraviolet curing adhesive layer and a non-ultraviolet curing adhesive layer, even when the curing step is performed before the support body is attached, the non-ultraviolet curing adhesive layer will not be cured. Therefore, the adhesive tape can be attached to the support body with sufficient adhesive force. Furthermore, in the case where the adhesive tape has the above-mentioned ultraviolet-transmissive release film, the above-mentioned release film is peeled off after the above-mentioned curing step is completed and before the above-mentioned support body attaching step.
於本發明之電子零件之製造方法中,繼而進行熱處理步驟:將被黏著體於150℃以上之高溫進行處理。 作為上述熱處理步驟,可列舉基板製造步驟或晶片安裝步驟等。於上述基板製造步驟中通常進行150℃以上之熱處理,於上述晶片安裝步驟中通常進行200℃以上之熱處理。於本發明之電子零件之製造方法中,由於已在熱處理步驟之前使紫外線硬化型黏著劑層硬化,故而即便於在熱處理步驟中進行伴隨150℃以上高溫之處理之情形時,亦可抑制接著亢進,於處理結束後容易地剝離被黏著體。又,由於紫外線硬化型黏著劑層中含有聚矽氧化合物,故而可進一步抑制接著亢進。In the manufacturing method of the electronic component of the present invention, a heat treatment step is then performed: the adherend is treated at a high temperature of 150°C or above. As the above-mentioned heat treatment step, a substrate manufacturing step or a chip mounting step can be listed. In the above-mentioned substrate manufacturing step, a heat treatment of 150°C or above is usually performed, and in the above-mentioned chip mounting step, a heat treatment of 200°C or above is usually performed. In the manufacturing method of the electronic component of the present invention, since the ultraviolet curing adhesive layer has been cured before the heat treatment step, even if the heat treatment step is accompanied by a high temperature of 150°C or above, the hyperadhesion can be suppressed, and the adherend can be easily peeled off after the treatment is completed. Furthermore, since the UV-curable adhesive layer contains polysilicone, it is possible to further suppress hyperadhesion.
本發明之電子零件之製造方法進而具有自上述黏著帶剝離上述被黏著體之剝離步驟。由於在上述硬化步驟中紫外線硬化型黏著劑層交聯、硬化,故而可抑制糊劑殘留,容易自黏著帶剝離被黏著體。又,由於黏著帶之非紫外線硬化型黏著劑層之釋氣量為10000 ppm以下,故而於上述熱處理步驟中,非紫外線硬化型黏著劑層不易因釋氣而發泡。其結果為,於支持體與非紫外線硬化型黏著劑層之間,黏著帶不易剝離,因此亦可抑制於剝離時在被黏著體側殘留黏著帶。進而,由於上述非紫外線硬化型黏著劑層之拉伸強度處於一定範圍內,故而於剝離時黏著帶不易拉斷。 發明之效果The manufacturing method of the electronic component of the present invention further has a peeling step of peeling the adherend from the adhesive tape. Since the UV-curing adhesive layer is crosslinked and cured in the curing step, the adhesive residue can be suppressed and the adherend can be easily peeled from the adhesive tape. In addition, since the gas release amount of the non-UV-curing adhesive layer of the adhesive tape is less than 10,000 ppm, the non-UV-curing adhesive layer is not easy to bubble due to gas release in the heat treatment step. As a result, the adhesive tape is not easy to peel off between the support and the non-UV-curing adhesive layer, so it can also be suppressed that the adhesive tape remains on the adherend side during peeling. Furthermore, since the tensile strength of the non-UV curing adhesive layer is within a certain range, the adhesive tape is not easily torn when peeling. Effect of the invention
根據本發明,可提供一種黏著帶及使用該黏著帶之電子零件之製造方法,該黏著帶於電子零件之製造中亦可用於不透光之支持體,且即便於進行高溫處理之情形時亦可抑制自被黏著體及支持體之剝離或糊劑殘留。According to the present invention, an adhesive tape and a method for manufacturing electronic components using the adhesive tape can be provided. The adhesive tape can also be used for an opaque support in the manufacture of electronic components, and can suppress peeling from the adherend and the support or paste residue even when a high temperature treatment is performed.
以下列舉實施例更詳細地說明本發明之態樣,但本發明並非僅限定於該等實施例。The following embodiments are used to illustrate the present invention in more detail, but the present invention is not limited to these embodiments.
(實施例1) (非紫外線硬化型黏著劑之製造) 於具備溫度計、攪拌機、冷卻管之反應器內,添加作為(甲基)丙烯酸烷基酯之丙烯酸丁酯97重量份、作為含羧基之單體之丙烯酸3重量份及乙酸乙酯120重量份,進行氮氣置換後,對反應器進行加熱而開始回流。繼而,於上述反應器內添加作為聚合起始劑之偶氮二異丁腈0.1重量份。使於70℃回流5小時,獲得(甲基)丙烯酸系共聚物(基礎聚合物)之溶液。藉由GPC法對所獲得之(甲基)丙烯酸系共聚物測定聚苯乙烯換算之重量平均分子量及分子量分佈,結果分別為100萬、3。再者,測定機器及測定條件設為如下所述。 測定裝置:2690 Separations Model,Waters公司製造 管柱:GPC KF-806L,昭和電工公司製造 檢測器:示差折射計 樣品流量:1 mL/min 管柱溫度:40℃ 溶出液:乙酸乙酯(Example 1) (Manufacturing of non-UV curing adhesive) In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 97 parts by weight of butyl acrylate as a (meth)acrylic acid alkyl ester, 3 parts by weight of acrylic acid as a carboxyl group-containing monomer, and 120 parts by weight of ethyl acetate were added, and after nitrogen replacement, the reactor was heated and refluxed. Then, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was added to the above reactor. Refluxed at 70°C for 5 hours to obtain a solution of a (meth)acrylic acid copolymer (base polymer). The weight average molecular weight and molecular weight distribution of the obtained (meth)acrylic acid copolymer were measured by GPC method in terms of polystyrene, and the results were 1 million and 3, respectively. In addition, the measuring machine and measuring conditions were set as described below. Measuring device: 2690 Separations Model, manufactured by Waters Corporation Column: GPC KF-806L, manufactured by Showa Denko Co., Ltd. Detector: Differential refractometer Sample flow rate: 1 mL/min Column temperature: 40°C Eluent: Ethyl acetate
繼而,相對於所獲得之(甲基)丙烯酸系共聚物之溶液中所含之(甲基)丙烯酸系共聚物之固形物成分100重量份,添加以固形物成分比計0.35重量份之環氧系硬化劑、10重量份之二氧化矽填料,並進行攪拌而獲得非紫外線硬化型黏著劑之乙酸乙酯溶液。再者,環氧硬化劑與二氧化矽填料使用以下者。 環氧系硬化劑:Mitsubishi Gas Chemical公司製造,TETRAD-X,含三級胺基之環氧硬化劑 二氧化矽填料:Tokuyama公司製造,REOLOSIL MT-10Next, 0.35 parts by weight of epoxy curing agent and 10 parts by weight of silica filler were added to 100 parts by weight of the solid content of the (meth)acrylic copolymer solution obtained, and the mixture was stirred to obtain an ethyl acetate solution of a non-UV curing adhesive. The following epoxy curing agent and silica filler were used. Epoxy curing agent: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd., epoxy curing agent containing a tertiary amine group Silica filler: REOLOSIL MT-10, manufactured by Tokuyama Co., Ltd.
(紫外線硬化型黏著劑之製造) 準備具備溫度計、攪拌機、冷卻管之反應器,於該反應器內,添加作為(甲基)丙烯酸烷基酯之丙烯酸2-乙基己酯94重量份、作為含官能基之單體之甲基丙烯酸羥基乙酯6重量份、月桂硫醇0.01重量份、及乙酸乙酯80重量份後,對反應器進行加熱而開始回流。繼而,於上述反應器內添加作為聚合起始劑之1,1-雙(過氧化第三己基)-3,3,5-三甲基環己烷0.01重量份,於回流下開始聚合。繼而,於距聚合開始1小時後及2小時後,亦分別添加1,1-雙(過氧化第三己基)-3,3,5-三甲基環己烷0.01重量份,進而,於距聚合開始4小時後,添加過氧化三甲基乙酸第三己酯0.05重量份而使聚合反應繼續。進而,於距聚合開始8小時後,獲得固形物成分55重量%、重量平均分子量60萬之含官能基之(甲基)丙烯酸系聚合物之乙酸乙酯溶液。 相對於所獲得之包含含官能基之(甲基)丙烯酸系聚合物之乙酸乙酯溶液之樹脂固形物成分100重量份,添加作為含官能基之不飽和化合物之甲基丙烯酸2-異氰酸基乙酯3.5重量份而進行反應,獲得聚合性聚合物。其後,相對於所獲得之聚合性聚合物之乙酸乙酯溶液之樹脂固形物成分100重量份,混合作為聚矽氧化合物之矽二丙烯酸酯20重量份、二氧化矽填料3重量份、丙烯酸胺酯30重量份、異氰酸酯系交聯劑0.7重量份、及光聚合起始劑1重量份,獲得紫外線硬化型黏著劑之乙酸乙酯溶液。再者,矽二丙烯酸酯、二氧化矽填料、丙烯酸胺酯、異氰酸酯系交聯劑、光聚合起始劑使用以下者。 矽二丙烯酸酯:EBECRYL 350,DAICEL-ALLNEX公司製造,重量平均分子量1000 二氧化矽填料:REOLOSIL MT-10,Tokuyama公司製造 丙烯酸胺酯:UN-5500,根上工業公司製造 異氰酸酯系交聯劑:Coronate L,Nippon Urethane Industry公司製造 光聚合起始劑:Esacure One,Nihon SiberHegner公司製造(Production of UV-curable adhesive) Prepare a reactor equipped with a thermometer, a stirrer, and a cooling tube. Add 94 parts by weight of 2-ethylhexyl acrylate as an alkyl (meth)acrylate, 6 parts by weight of hydroxyethyl methacrylate as a functional group-containing monomer, 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate to the reactor, and then heat the reactor to start reflux. Then, add 0.01 parts by weight of 1,1-bis(tert-hexyl peroxide)-3,3,5-trimethylcyclohexane as a polymerization initiator to the reactor, and start polymerization under reflux. Then, 0.01 parts by weight of 1,1-bis(tert-hexyl peroxide)-3,3,5-trimethylcyclohexane was added 1 hour and 2 hours after the start of the polymerization, and 0.05 parts by weight of trimethylhexyl peroxide was added 4 hours after the start of the polymerization to continue the polymerization reaction. Furthermore, 8 hours after the start of the polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% by weight and a weight average molecular weight of 600,000 was obtained. 3.5 parts by weight of 2-isocyanatoethyl methacrylate as an unsaturated compound containing a functional group was added to 100 parts by weight of the resin solid content of the obtained ethyl acetate solution containing a functional group-containing (meth)acrylic polymer to react and obtain a polymerizable polymer. Then, 20 parts by weight of silicon diacrylate as a polysilicone compound, 3 parts by weight of silica filler, 30 parts by weight of acrylate amine, 0.7 parts by weight of isocyanate crosslinking agent, and 1 part by weight of photopolymerization initiator were mixed with 100 parts by weight of the resin solid content of the obtained ethyl acetate solution of the polymerizable polymer to obtain an ethyl acetate solution of a UV-curable adhesive. The silicon diacrylate, silica filler, acrylate amine, isocyanate crosslinking agent, and photopolymerization initiator used were as follows. Silicone diacrylate: EBECRYL 350, manufactured by DAICEL-ALLNEX, weight average molecular weight 1000 Silica filler: REOLOSIL MT-10, manufactured by Tokuyama Amine acrylate: UN-5500, manufactured by Negami Industries Isocyanate crosslinking agent: Coronate L, manufactured by Nippon Urethane Industry Photopolymerization initiator: Esacure One, manufactured by Nihon SiberHegner
(黏著帶之製造) 利用刮刀,於對單面實施過脫模處理之50 μm之聚對苯二甲酸乙二酯(PET)膜上以乾燥皮膜之厚度成為40 μm之方式塗佈所獲得之紫外線硬化型黏著劑溶液,於110℃加熱5分鐘使塗佈溶液乾燥,而獲得紫外線硬化型黏著劑層。 利用刮刀,於對單面實施過脫模處理之厚度50 μm之透明PET膜上以乾燥皮膜之厚度成為40 μm之方式塗佈所獲得之非紫外線硬化型黏著劑溶液,於110℃加熱5分鐘使塗佈溶液乾燥,而獲得非紫外線硬化型黏著劑層。 將所獲得之紫外線硬化型黏著劑層及非紫外線硬化型黏著劑層之未積層PET膜之面彼此貼合,而獲得黏著帶。(Manufacturing of adhesive tape) The obtained UV-curable adhesive solution was applied to a 50 μm thick polyethylene terephthalate (PET) film subjected to a mold release treatment on one side so that the dry film thickness was 40 μm, and the applied solution was dried by heating at 110°C for 5 minutes to obtain a UV-curable adhesive layer. The obtained non-UV-curable adhesive solution was applied to a 50 μm thick transparent PET film subjected to a mold release treatment on one side so that the dry film thickness was 40 μm, and the applied solution was dried by heating at 110°C for 5 minutes to obtain a non-UV-curable adhesive layer. The surfaces of the obtained UV-curing adhesive layer and the non-UV-curing adhesive layer on which the PET film was not laminated were bonded to each other to obtain an adhesive tape.
(拉伸強度之測定) 藉由上述方法製作僅由非紫外線硬化型黏著劑層構成之黏著帶。將所獲得之非紫外線硬化型黏著劑層切割成厚度200 μm、寬度10 mm作為樣品,於23℃、50%RH之條件,使用TENSILON UCE500(Orientec公司製造),以速度300 mm/分鐘、標線間距離40 mm測定拉伸強度。藉由相同之方法對所獲得之黏著帶測定硬化前之拉伸強度。(Determination of tensile strength) An adhesive tape consisting only of a non-UV curing adhesive layer was prepared by the above method. The non-UV curing adhesive layer was cut into pieces with a thickness of 200 μm and a width of 10 mm as a sample, and the tensile strength was measured at a speed of 300 mm/min and a distance between markings of 40 mm at 23°C and 50% RH using TENSILON UCE500 (manufactured by Orientec). The tensile strength of the obtained adhesive tape before curing was measured by the same method.
(釋氣量之測定) 藉由上述方法製作僅由非紫外線硬化型黏著劑層構成之黏著帶,將所獲得之僅由非紫外線硬化型黏著劑層構成之黏著帶切割成5 mm×5 mm而製作測定樣品。採用熱脫附GC-MS對所獲得之測定樣品進行測定,將所獲得之氣體量(甲苯換算ppm:μg/g)設為釋氣量。再者,所使用之測定工具或測定條件如下所述。 熱脫附裝置:TurboMatrix 350,PerkinElmer公司製造 GC-MS裝置:JMS Q1000,日本電子公司製造 樣品加熱條件:260℃,15 min(20 mL/min) 二次脫附:350℃,40 min 分流:入口25 mL/min,出口25 mL/min 注入量:2.5% 管柱:EQUITY-1(無極性,SIGMA-ALDRICH公司製造)0.32 mm×60 m×0.25 μm GC升溫:40℃(4 min)→以10℃/min之速度升溫→300℃(10 min) He流量:1.5 mL/min 離子化電壓:70 eV MS測定範圍:29〜600 amu(scan 500 ms) MS溫度:離子源溫度230℃,介面溫度250℃(Measurement of outgassing amount) The adhesive tape consisting only of a non-UV curing adhesive layer was prepared by the above method, and the obtained adhesive tape consisting only of a non-UV curing adhesive layer was cut into 5 mm × 5 mm to prepare a measurement sample. The obtained measurement sample was measured by thermal desorption GC-MS, and the obtained gas volume (toluene conversion ppm: μg/g) was set as the outgassing amount. In addition, the measurement tool or measurement conditions used are as follows. Thermal desorption device: TurboMatrix 350, manufactured by PerkinElmer GC-MS device: JMS Q1000, manufactured by NEC Corporation Sample heating conditions: 260℃, 15 min (20 mL/min) Secondary desorption: 350℃, 40 min Flow split: inlet 25 mL/min, outlet 25 mL/min Injection volume: 2.5% Column: EQUITY-1 (non-polar, manufactured by SIGMA-ALDRICH) 0.32 mm×60 m×0.25 μm GC temperature rise: 40℃ (4 min) → temperature rise at a rate of 10℃/min → 300℃ (10 min) He flow rate: 1.5 mL/min Ionization voltage: 70 eV MS measurement range: 29~600 amu (scan 500 ms) MS temperature: ion source temperature 230℃, interface temperature 250℃
(黏著強度之測定) 藉由上述方法製作僅由非紫外線硬化型黏著劑層構成之黏著帶,作為測定樣品。將所獲得之僅由非紫外線硬化型黏著劑層構成之黏著帶切割成10 mm×10 mm而製作測定樣品。對所獲得之測定樣品進行探針黏性測定。再者,所使用之測定工具或測定條件如下所述。 黏性試驗機:TAC1000,RHESCA公司製造 探針直徑:3 mmϕ 壓接負載:100 g 壓接時間:1秒 接觸速度:30 mm·min 剝離速度:600 mm/min(Measurement of adhesive strength) An adhesive tape consisting only of a non-UV curing adhesive layer was prepared by the above method as a test sample. The obtained adhesive tape consisting only of a non-UV curing adhesive layer was cut into 10 mm × 10 mm to prepare a test sample. The obtained test sample was subjected to a probe viscosity measurement. The measurement tool or measurement conditions used are as follows. Adhesion tester: TAC1000, manufactured by RHESCA Probe diameter: 3 mmφ Compression load: 100 g Compression time: 1 second Contact speed: 30 mm·min Peeling speed: 600 mm/min
(凝膠分率之測定) 僅刮取所獲得之黏著帶之非紫外線硬化型黏著劑層0.1 g,並浸漬於乙酸乙酯50 ml中,利用振動機,於溫度23度、120 rpm之條件振動24小時(以下將所刮取之非紫外線硬化型黏著劑層稱為黏著劑組成物)。振動後,使用金屬絲網(網眼#200目),將乙酸乙酯與吸收乙酸乙酯後膨潤之黏著劑組成物分離。將分離後之黏著劑組成物於110℃之條件乾燥1小時。測定乾燥後之連同金屬絲網在內之黏著劑組成物之重量,使用下述式算出非紫外線硬化型黏著劑層之凝膠分率。將結果示於表1、2。 凝膠分率(重量%)=100×(W1 -W2 )/W0 (W0 :初期黏著劑組成物重量,W1 :乾燥後之連同金屬絲網在內之黏著劑組成物重量,W2 :金屬絲網之初期重量)(Determination of gel fraction) Scrape only 0.1 g of the non-UV curing adhesive layer of the obtained adhesive tape, immerse it in 50 ml of ethyl acetate, and vibrate it for 24 hours at 23 degrees and 120 rpm using a vibrator (hereinafter referred to as the adhesive composition). After vibration, use a metal wire mesh (mesh #200) to separate the ethyl acetate from the adhesive composition that swells after absorbing ethyl acetate. Dry the separated adhesive composition at 110°C for 1 hour. The weight of the adhesive composition including the metal wire mesh after drying was measured, and the gel fraction of the non-UV curing adhesive layer was calculated using the following formula. The results are shown in Tables 1 and 2. Gel fraction (weight %) = 100 × (W 1 - W 2 ) / W 0 (W 0 : initial weight of the adhesive composition, W 1 : weight of the adhesive composition including the metal wire mesh after drying, W 2 : initial weight of the metal wire mesh)
(實施例2〜11、比較例1〜11) 將非紫外線硬化型黏著劑層之丙烯酸丁酯、丙烯酸、二氧化矽填料之調配量設為如表1、2所示,藉由變更聚合條件而使基礎聚合物之重量平均分子量及分子量分佈成為如表1、2所示,添加表1、2所示之量之黏著賦予劑,除此以外,藉由與實施例1相同之方式製造黏著帶,並測定各物性。再者,作為黏著賦予劑,使用根上工業公司製造之UN5500。作為異氰酸酯系硬化劑,使用Tosoh公司製造之Coronate L。(Examples 2 to 11, Comparative Examples 1 to 11) The amounts of butyl acrylate, acrylic acid, and silica filler in the non-UV curing adhesive layer were set as shown in Tables 1 and 2, and the weight average molecular weight and molecular weight distribution of the base polymer were changed by changing the polymerization conditions to be as shown in Tables 1 and 2. The adhesive agent was added in the amount shown in Tables 1 and 2. The adhesive tape was produced in the same manner as in Example 1, and the physical properties were measured. As the adhesive agent, UN5500 manufactured by Negami Industries was used. As the isocyanate curing agent, Coronate L manufactured by Tosoh Corporation was used.
<評價> 對實施例及比較例中獲得之黏著帶,藉由以下之方法進行評價。將結果示於表1、2。<Evaluation> The adhesive tapes obtained in the embodiments and comparative examples were evaluated by the following method. The results are shown in Tables 1 and 2.
(1)基板之熱處理後之評價 將黏著帶之紫外線硬化型黏著劑層側之面貼附於基板(TPWB-S02-READCUT,大昌電子公司製造)而獲得積層體。繼而,使用高壓水銀紫外線照射機,以向黏著帶表面之照射強度成為100 mW/cm2 之方式調節照度,自非紫外線硬化型黏著劑層側照射365 nm之紫外線30秒,而使紫外線硬化型黏著劑層交聯、硬化。其後,將積層體之非紫外線硬化型黏著劑層貼附於CCL支持體(覆銅積層板),進行260℃、6分鐘之熱處理合計3次。熱處理結束後,自基板剝離黏著帶。對於黏著帶之剝離、非紫外線硬化型黏著劑層之發泡、及基板之糊劑殘留,藉由下述方式進行評價。(1) Evaluation after heat treatment of substrate The UV-curable adhesive layer side of the adhesive tape was attached to a substrate (TPWB-S02-READCUT, manufactured by Dachang Electronics Co., Ltd.) to obtain a laminate. Then, using a high-pressure mercury UV irradiator, the irradiation intensity was adjusted so that the irradiation intensity on the adhesive tape surface became 100 mW/ cm2 , and 365 nm UV rays were irradiated from the non-UV-curable adhesive layer side for 30 seconds to crosslink and harden the UV-curable adhesive layer. Thereafter, the non-UV-curable adhesive layer of the laminate was attached to a CCL support (copper-clad laminate) and heat treated at 260°C for 6 minutes for a total of three times. After the heat treatment, the adhesive tape was peeled off from the substrate. The peeling of the adhesive tape, the bubbling of the non-UV curing adhesive layer, and the paste residue on the substrate were evaluated by the following method.
(黏著帶之剝離之評價) 目視觀察熱處理結束後之黏著帶,將於紫外線硬化型黏著劑層與基板之界面無剝離或空隙之情況設為「○」,將局部有剝離或空隙之情況設為「△」,將整個面有剝離或空隙之情況設為「×」,評價黏著帶之剝離。(Evaluation of adhesive tape peeling) The adhesive tape after heat treatment was visually observed, and the peeling of the adhesive tape was evaluated by setting "○" if there was no peeling or void at the interface between the UV-curing adhesive layer and the substrate, "△" if there was partial peeling or void, and "×" if there was peeling or void on the entire surface.
(非紫外線硬化型黏著劑層之發泡之評價) 目視觀察熱處理結束後之黏著帶之非紫外線硬化型黏著劑層,將無發泡之情況設為「◎」,將幾乎無發泡之情況設為「○」,將局部有發泡之情況設為「△」,將整個面有發泡之情況設為「×」,評價非紫外線硬化型黏著劑層之發泡。(Evaluation of the foaming of the non-UV curing adhesive layer) The non-UV curing adhesive layer of the adhesive tape after the heat treatment was visually observed, and the foaming of the non-UV curing adhesive layer was evaluated by setting "◎" for no foaming, "○" for almost no foaming, "△" for partial foaming, and "×" for foaming on the entire surface.
(基板之糊劑殘留之評價) 利用光學顯微鏡觀察剝離後之基板,將無糊劑殘留之情況設為「◎」,將幾乎無糊劑殘留之情況設為「○」,將局部有糊劑殘留之情況設為「△」,將整個面有糊劑殘留之情況設為「×」,評價基板之糊劑殘留。(Evaluation of paste residue on substrate) The substrate after peeling was observed under an optical microscope. No paste residue was marked as "◎", almost no paste residue was marked as "○", partial paste residue was marked as "△", and the entire surface was marked as "×" to evaluate the paste residue on the substrate.
(2)耐化學品性之評價 於所獲得之黏著帶之紫外線硬化型黏著劑層貼附聚醯亞胺膜,於非紫外線硬化型黏著劑層貼附CCL板(覆銅積層板),而製作測定樣品。將所獲得之測定樣品於70℃在PINEALPHA(荒川化學工業公司製造)中浸漬2h後,於110℃之烘箱中乾燥1小時。測定浸漬前後之重量減少率。 將於浸漬前後重量減少率為3.0%以下之情況設為「◎」,將大於3.0%且為5.0%以下之情況設為「○」,將大於5.0%且為8.0%以下之情況設為「△」,將大於8.0%、或者帶自被黏著體剝離之情況設為「×」,評價耐化學品性。(2) Evaluation of chemical resistance A polyimide film was attached to the UV-curing adhesive layer of the obtained adhesive tape, and a CCL board (copper clad laminate) was attached to the non-UV-curing adhesive layer to prepare a test sample. The obtained test sample was immersed in PINEALPHA (manufactured by Arakawa Chemical Industries, Ltd.) at 70°C for 2 hours and then dried in an oven at 110°C for 1 hour. The weight loss rate before and after immersion was measured. The chemical resistance was evaluated by setting the weight reduction rate before and after immersion to 3.0% or less as "◎", the weight reduction rate to 5.0% or less as "○", the weight reduction rate to 5.0% or less as "△", the weight reduction rate to 8.0% or more or less or less or less as "×".
[表1]
[表2]
根據本發明,可提供一種黏著帶及使用該黏著帶之電子零件之製造方法,該黏著帶於電子零件之製造中亦可用於不透光之支持體,且即便於進行高溫處理之情形時亦可抑制自被黏著體及支持體之剝離或糊劑殘留。According to the present invention, an adhesive tape and a method for manufacturing electronic components using the adhesive tape can be provided. The adhesive tape can also be used for an opaque support in the manufacture of electronic components, and can suppress peeling from the adherend and the support or paste residue even when a high temperature treatment is performed.
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