JP4682299B2 - Pressure sensitive adhesive for protective sheet - Google Patents
Pressure sensitive adhesive for protective sheet Download PDFInfo
- Publication number
- JP4682299B2 JP4682299B2 JP2003387105A JP2003387105A JP4682299B2 JP 4682299 B2 JP4682299 B2 JP 4682299B2 JP 2003387105 A JP2003387105 A JP 2003387105A JP 2003387105 A JP2003387105 A JP 2003387105A JP 4682299 B2 JP4682299 B2 JP 4682299B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- meth
- sensitive adhesive
- peeling
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000001681 protective effect Effects 0.000 title claims description 57
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 36
- 239000000178 monomer Substances 0.000 claims description 29
- 230000009477 glass transition Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 125000000524 functional group Chemical group 0.000 claims description 21
- 229920000058 polyacrylate Polymers 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- -1 polyethylene terephthalate Polymers 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002799 BoPET Polymers 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 150000001541 aziridines Chemical class 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 229940048053 acrylate Drugs 0.000 description 28
- 239000010408 film Substances 0.000 description 20
- 238000007334 copolymerization reaction Methods 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000012788 optical film Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DKJBREHOVWISMR-UHFFFAOYSA-N 1-chloro-2,3-diisocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1N=C=O DKJBREHOVWISMR-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- PJKZIJHEVDPKBZ-UHFFFAOYSA-N 2-(triaziridinyl)-1,3,5-triazine Chemical compound C1=NC=NC(N2NN2)=N1 PJKZIJHEVDPKBZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-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
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 description 1
- XXGJJYJASLTCBM-UHFFFAOYSA-N CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CCC(CO)(CO)CO Chemical compound CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CCC(CO)(CO)CO XXGJJYJASLTCBM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229940114077 acrylic acid Drugs 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 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
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、高速剥離性に優れた保護シート用感圧接着剤に関し、さらに詳細には高速剥離においても剥離に要する力が小さく、かつ剥離速度による剥離力の変化の小さい保護シート用感圧接着剤及びこれを用いた光学フィルム用表面保護シートに関するものである。 The present invention relates to a pressure-sensitive adhesive for protective sheets excellent in high-speed peelability. More specifically, the pressure-sensitive adhesive for protective sheets has a small force required for peeling even during high-speed peeling and a small change in peeling force depending on the peeling speed. The present invention relates to an agent and a surface protective sheet for an optical film using the same.
近年、ディスプレイ分野の発展に伴い、特殊な光学部材が増えてきている。その中でも、光学フィルムについては、液晶ディスプレイに使用される偏光板、位相差板、輝度向上フィルムや、プラズマディスプレイに使用されるARフィルム、電磁波シールドフィルム、IRカットフィルム等、非常に多くのものが知られており、これらは積層され使用されることが多い。 In recent years, with the development of the display field, special optical members are increasing. Among them, there are a great many optical films such as polarizing plates, retardation plates, brightness enhancement films used for liquid crystal displays, AR films, electromagnetic wave shielding films, IR cut films used for plasma displays. These are known and are often laminated and used.
そして、ディスプレイが組み立てられるまでに、これらの光学フィルムは通常、打ち抜き加工、輸送、検査等の工程を経るが、その工程中に、傷、汚れ等が付かないように、その表面には通常、表面保護シートが貼り付けられている。 And until the display is assembled, these optical films usually go through processes such as punching, transportation, inspection, etc., but the surface is usually free from scratches, dirt, etc. A surface protection sheet is attached.
これら表面保護シートは、各工程終了後、不要になった時点で剥がされ廃棄されるが、かかる剥離作業は、手作業が主であるため、その剥離速度は比較的高速であり、またその速度を剥離開始時から終了時まで一定とすることは困難であった。 These surface protective sheets are peeled off and discarded when they are no longer needed after each process. However, since such peeling work is mainly manual work, the peeling speed is relatively high and the speed is also high. It was difficult to maintain a constant from the start to the end of peeling.
一般的に剥離速度が速くなるほど、剥離に要する力(以下、「剥離力」と略記する)が大きくなるため、表面保護シート剥離の作業効率が悪くなったり、剥離時に光学フィルムを損傷、汚染してしまう等の問題があった。また、滑らかに剥離することなくバリバリという音を発するいわゆるジッピングと呼ばれる現象が起こるという問題もあった。さらに、剥離力を充分小さくしようとすると、作業工程中に浮きやハガレといった問題が起こる場合があった。そのため、高速剥離においても低速剥離においても、剥離力が小さく、かつ浮きやハガレといった問題を生じない表面保護シートの要求が高まっている。 In general, the faster the peeling speed, the greater the force required for peeling (hereinafter abbreviated as “peeling force”), and therefore the work efficiency of surface protection sheet peeling deteriorates, and the optical film is damaged or contaminated during peeling. There was a problem such as. In addition, there is a problem that a phenomenon called so-called zipping, which produces a crisp sound without peeling off smoothly, occurs. Furthermore, if the peeling force is made sufficiently small, problems such as floating and peeling may occur during the work process. For this reason, there is an increasing demand for a surface protection sheet that has a small peeling force and does not cause problems such as floating and peeling even in high-speed peeling or low-speed peeling.
一般に、プラスチック板、ステンレス等の金属板、ガラス板等の表面を保護するためのシート用の感圧接着剤としては、(メタ)アクリル酸エステルと側鎖に官能基を有する単量体とを共重合させて得られたポリマーに、架橋剤を加えたものが知られている。しかし、これらの保護シートは、剥離することなく基板に粘着させたまま使用するものであり、当然にその剥離性を改良しようとしたものではなかった。 In general, as a pressure-sensitive adhesive for a sheet for protecting the surface of a plastic plate, a metal plate such as stainless steel, a glass plate, etc., a (meth) acrylic acid ester and a monomer having a functional group in the side chain are used. A polymer obtained by adding a crosslinking agent to a polymer obtained by copolymerization is known. However, these protective sheets are used while being adhered to the substrate without being peeled off, and of course they were not intended to improve the peelability.
このような例として例えば、特許文献1には、ガラス転移温度が異なる2種類の(メタ)アクリル系ポリマーを用いた粘着剤が記載されてはいるが、この先行技術では、ガラス転移温度が高いポリマーは、単に接着性を上げるために添加しているため、得られた粘着フィルムは、高速剥離時において極めて大きい剥離力を必要とし、剥離工程のある分野には全く適用できるものではなかった。 As such an example, for example, Patent Document 1 describes a pressure-sensitive adhesive using two types of (meth) acrylic polymers having different glass transition temperatures, but in this prior art, the glass transition temperature is high. Since the polymer is simply added to increase the adhesiveness, the obtained pressure-sensitive adhesive film requires an extremely large peeling force at the time of high-speed peeling, and cannot be applied at all in a field having a peeling process.
剥離工程がある分野で使用される保護シートにおいて、その剥離性を向上させようとする技術としては、アクリル系ポリマーと架橋剤よりなる粘着剤に、ポリエステル等の可塑剤を少量添加したものが知られている(特許文献2参照)。しかしながら、これでも高速剥離における剥離力が一般に大きく、また高速剥離での剥離力が小さくなるような組成にすると、浮きやハガレが生じる表面保護シートしかできなかった。 As a technology for improving the peelability of a protective sheet used in a field having a peeling process, a technique in which a small amount of a plasticizer such as polyester is added to an adhesive made of an acrylic polymer and a crosslinking agent is known. (See Patent Document 2). However, even in this case, when the composition is such that the peeling force in high-speed peeling is generally large and the peeling force in high-speed peeling is small, only a surface protective sheet that causes floating or peeling can be obtained.
従って、高速剥離性が良好で、ジッピングを起こさず、剥離速度による剥離力の変化が少なく、また熱時に浮きやハガレ等が起こらない耐久性のある表面保護シート用感圧接着剤の提供が求められており、本発明はこのような接着剤の提供をその課題とするものである。 Therefore, there is a need to provide a pressure-sensitive adhesive for surface protection sheets that has good high-speed peelability, does not cause zipping, has little change in peel force due to the peel speed, and does not cause floating or peeling when heated. Therefore, the present invention aims to provide such an adhesive.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、ガラス転移温度が一定値以下の(メタ)アクリル系ポリマーに、ガラス転移温度が一定値以上の(メタ)アクリル系ポリマーを併用し、かつゲル分率が一定値以上になるように架橋反応をさせた保護シート用感圧接着剤が上記課題を解決することを見出し本発明に至った。 As a result of intensive studies in order to solve the above problems, the present inventors have found that a (meth) acrylic polymer having a glass transition temperature of a certain value or less and a (meth) acrylic polymer having a glass transition temperature of a certain value or more. The pressure-sensitive adhesive for a protective sheet, which is used in combination and is subjected to a crosslinking reaction so that the gel fraction becomes a certain value or more, has found that the above problems can be solved, and has led to the present invention.
すなわち、本発明は、次の成分(A)、成分(B)及び成分(C)、
(A)少なくとも(メタ)アクリル酸アルキルエステル及び官能基含有モノマーが共重
合してなるガラス転移温度が−40℃以下の(メタ)アクリル系ポリマー
(B)(メタ)アクリル酸アルキルエステルを主成分とするガラス転移温度80℃以上
の(メタ)アクリル系ポリマー
(C)架橋剤
を含有し、成分(A)100重量部に対して、成分(B)を5〜20重量部で配合する架橋性組成物を、ゲル分率80%以上となるように架橋反応せしめてなる保護シート用感圧接着剤を提供するものである。
That is, the present invention includes the following components (A), (B) and (C),
(A) A (meth) acrylic polymer having a glass transition temperature of −40 ° C. or lower formed by copolymerization of at least a (meth) acrylic acid alkyl ester and a functional group-containing monomer. (Meth) acrylic polymer having a glass transition temperature of 80 ° C. or higher as a component (C) Crosslinking containing a crosslinking agent and blending component (B) at 5 to 20 parts by weight with respect to 100 parts by weight of component (A) The pressure-sensitive adhesive for protective sheets is obtained by crosslinking the adhesive composition so that the gel fraction becomes 80% or more.
また本発明は、上記保護シート用感圧接着剤を支持体上に塗工してなる表面保護シートを提供するものである。 Moreover, this invention provides the surface protection sheet formed by coating the said pressure sensitive adhesive for protective sheets on a support body.
ガラス転移温度の異なる2種類の(メタ)アクリル系ポリマーを限定された配合比で用い、かつ架橋剤による架橋の程度を調整してゲル分率を一定値以上とすることにより得られた本発明の保護シート用感圧接着剤は、これを表面保護シート用粘着剤としたときに、高速剥離性が良好であり、ジッピングを起こさず、剥離後に被着体が汚染されず、また剥離速度による剥離力の変化が少ない表面保護シートを提供することができる。さらには、貼り付け後、加熱しても浮きやハガレ等が起こらない耐久性のある表面保護シートを提供することができる。 The present invention obtained by using two types of (meth) acrylic polymers having different glass transition temperatures in a limited blending ratio and adjusting the degree of crosslinking with a crosslinking agent to bring the gel fraction to a certain value or more. When the pressure-sensitive adhesive for protective sheet is used as a pressure-sensitive adhesive for surface protective sheet, it has good high-speed peelability, does not cause zipping, does not contaminate the adherend after peeling, and depends on the peeling speed. It is possible to provide a surface protective sheet with little change in peeling force. Furthermore, it is possible to provide a durable surface protective sheet that does not float or peel off even if it is heated after being attached.
また、ガラス転移温度の異なる2種類の(メタ)アクリル系ポリマーの分子量範囲をそれぞれ限定することによって、剥離速度による剥離力の変化がさらに少ない表面保護シートを提供することができる。 In addition, by limiting the molecular weight ranges of the two types of (meth) acrylic polymers having different glass transition temperatures, it is possible to provide a surface protective sheet in which the change in peeling force due to the peeling speed is further reduced.
特に高速剥離における剥離力を小さくすることにより、光学フィルムが関係する種々の生産工程の効率化を図ることのできる表面保護シートを提供することができる。 In particular, by reducing the peeling force in high-speed peeling, it is possible to provide a surface protective sheet that can improve the efficiency of various production processes related to the optical film.
本発明の保護シート用感圧接着剤の必須成分である成分(A)は、少なくとも、(メタ)アクリル酸アルキルエステル及び官能基含有モノマーが共重合してなるガラス転移温度が−40℃以下の(メタ)アクリル系ポリマーである。 Component (A), which is an essential component of the pressure-sensitive adhesive for protective sheets of the present invention, has a glass transition temperature of at least −40 ° C. formed by copolymerization of at least a (meth) acrylic acid alkyl ester and a functional group-containing monomer. It is a (meth) acrylic polymer.
成分(A)の共重合成分として用いられる、(メタ)アクリル酸アルキルエステルとしては、共重合後の(メタ)アクリル系ポリマーのガラス転移温度を−40℃以下にできるものであれば特に限定はされない。さらに、アルキルエステルのアルキル基はフェニル基等の有機置換基を有していてもよい。その具体例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸ベヘニル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸フェニルエチル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸フェノキシジエチレングリコールエステル等が挙げられる。これらは1種又は2種以上混合して用いられる。 The (meth) acrylic acid alkyl ester used as the copolymerization component of component (A) is not particularly limited as long as the glass transition temperature of the (meth) acrylic polymer after copolymerization can be made -40 ° C. or lower. Not. Furthermore, the alkyl group of the alkyl ester may have an organic substituent such as a phenyl group. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Cyclohexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, (meth) Examples include benzyl acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ester (meth) acrylate, and the like. These are used alone or in combination.
上記成分(A)は、そのガラス転移温度が−40℃以下とする必要があるため、アクリル酸アルキルエステルの使用が好ましく、特に好ましくは、アルキル基の炭素数が4〜12個のアクリル酸アルキルエステルであり、さらに中でもアクリル酸2−エチルヘキシルが最も好ましい。 Since the component (A) needs to have a glass transition temperature of −40 ° C. or lower, it is preferable to use an alkyl acrylate ester, and particularly preferably an alkyl acrylate having 4 to 12 carbon atoms in the alkyl group. Among them, 2-ethylhexyl acrylate is most preferable.
また、成分(A)の他の必須共重合成分である官能基含有モノマーは、後述する架橋剤と化学反応又は相互作用をする官能基、例えばエポキシ基、カルボキシル基、酸無水物残基、イソシアネート基、水酸基等を分子中に有する(共)重合可能なモノマーであれば特に限定はされないが、特に好ましいものとしては、官能基として、カルボキシル基又は水酸基を有するものが挙げられる。 In addition, the functional group-containing monomer which is another essential copolymerization component of the component (A) is a functional group that chemically reacts or interacts with a crosslinking agent described later, such as an epoxy group, a carboxyl group, an acid anhydride residue, an isocyanate. Although it will not specifically limit if it is a (co) polymerizable monomer which has group, a hydroxyl group, etc. in a molecule | numerator, Especially, what has a carboxyl group or a hydroxyl group as a functional group is mentioned.
上記のような官能基含有モノマーの具体的な例としては、(メタ)アクリル酸グリシジル等のエポキシ基含有モノマー;(メタ)アクリル酸、イタコン酸、クロトン酸、フマル酸等のカルボキシル基含有モノマー;無水マレイン酸等の酸無水物残基含有モノマー;(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸3−ヒドロキシプロピル、(メタ)アクリル酸4−ヒドロキシブチル等の水酸基含有モノマー;(メタ)アクリル酸ジメチルアミノエチル等のアミノ基含有モノマー等が挙げられる。 Specific examples of the functional group-containing monomer as described above include epoxy group-containing monomers such as glycidyl (meth) acrylate; carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, and fumaric acid; Acid anhydride residue-containing monomers such as maleic anhydride; hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; ) Amino group-containing monomers such as dimethylaminoethyl acrylate.
このうち、特に好ましいものとしては、官能基としてカルボキシル基を有する(メタ)アクリル酸及び官能基として水酸基を有する(メタ)アクリル酸2−ヒドロキシエチルが挙げられる。 Among these, particularly preferred are (meth) acrylic acid having a carboxyl group as a functional group and 2-hydroxyethyl (meth) acrylate having a hydroxyl group as a functional group.
成分(A)は、上記必須共重合成分だけが共重合されたものであってもよいが、その他に酢酸ビニルが共重合されていることが、保護シートに浮き、ハガレが発生しにくい点で特に好ましい。 Component (A) may be a copolymer obtained by copolymerizing only the above essential copolymerization component, but in addition to that vinyl acetate is copolymerized, it floats on the protective sheet and is less likely to cause peeling. Particularly preferred.
さらに、成分(A)の製造に当たっては、上記以外の重合性モノマーを使用することもできる。このような重合性モノマーの例としては、スチレン、ビニルトルエン、α−メチルスチレン、酢酸アリル等のビニル基含有化合物が挙げられる。 Furthermore, in the production of the component (A), polymerizable monomers other than those described above can also be used. Examples of such polymerizable monomers include vinyl group-containing compounds such as styrene, vinyl toluene, α-methyl styrene, and allyl acetate.
成分(A)を製造するにあたっての各モノマーの共重合比については特に限定はないが、好ましくは、(メタ)アクリル酸アルキルエステル50〜99質量%(以下、「質量%」を単に「%」と略記する)、官能基含有モノマー1〜10%及び酢酸ビニル0〜40%の共重合比である。共重合比の特に好ましい範囲等は以下の通りである。 The copolymerization ratio of each monomer in producing the component (A) is not particularly limited, but preferably 50 to 99% by mass of (meth) acrylic acid alkyl ester (hereinafter, “% by mass” is simply “%”). And a copolymerization ratio of 1 to 10% of a functional group-containing monomer and 0 to 40% of vinyl acetate. Particularly preferable ranges of the copolymerization ratio are as follows.
(1)酢酸ビニルを共重合成分として含まない場合
特に好ましい範囲 更に特に好ましい範囲
(メタ)アクリル酸アルキルエステル 90〜99% 93〜97%
官能基含有モノマー 1〜10% 3〜 7%
(1) When vinyl acetate is not included as a copolymerization component
Particularly preferred range More particularly preferred range (Meth) acrylic acid alkyl ester 90-99% 93-97%
Functional group-containing monomer 1-10% 3-7%
(2)酢酸ビニルを共重合成分として含む場合
特に好ましい範囲 更に特に好ましい範囲
(メタ)アクリル酸アルキルエステル 50〜80% 60〜75%
官能基含有モノマー 1〜10% 3〜 7%酢酸ビニル 10〜40% 20〜35%
(2) When vinyl acetate is included as a copolymerization component
Particularly preferred range More particularly preferred range (meth) acrylic acid alkyl ester 50-80% 60-75%
Functional group-containing monomer 1-10% 3-7% Vinyl acetate 10-40% 20-35%
上記各成分を用いる成分(A)の製造方法は特に限定はされず、公知の方法を用いることができるが、ラジカル重合法が好ましく、溶液重合法が、分子量を調節しやすく、また不純物も少なくできるために好ましい。 The production method of the component (A) using each of the above components is not particularly limited, and a known method can be used, but a radical polymerization method is preferable, a solution polymerization method is easy to adjust the molecular weight, and there are few impurities. It is preferable because it is possible.
上記のようにして得られる成分(A)のガラス転移温度(Tg)は、−40℃以下であることが、高速剥離力が小さい良好な表面保護シートを与えるために必要である。より好ましい範囲は、−70℃〜−50℃である。本発明におけるガラス転移温度は、実際のポリマーの測定値を用いてもよいが、ホモポリマーのガラス転移温度が分かっているときには、以下のFOXの式によって算出することもできる。
1/Tg=Wa/Tga+Wb/Tgb
Tg :共重合体のガラス転移温度
Tga,Tgb,・・・:単量体a、単量体b・・・のホモポリマーのガラス転移温度
Wa,Wb・・・ :単量体a、単量体b・・・の重量分率
It is necessary for the glass transition temperature (Tg) of the component (A) obtained as described above to be −40 ° C. or less in order to provide a good surface protective sheet having a small high-speed peeling force. A more preferable range is -70 ° C to -50 ° C. As the glass transition temperature in the present invention, an actual polymer measurement value may be used. However, when the glass transition temperature of the homopolymer is known, it can also be calculated by the following FOX equation.
1 / Tg = Wa / Tga + Wb / Tgb
Tg: Glass transition temperature of copolymer Tga, Tgb,...: Glass transition temperature Wa, Wb of homopolymer of monomer a, monomer b...: Monomer a, single amount Weight fraction of body b ...
また、成分(A)の分子量は、特に限定はないが、重量平均分子量で、10万以上が好ましく、20万以上が特に好ましい。分子量が小さすぎると、ゲル分率を調整するために多量の架橋剤を配合させる必要があり、性能のバランスがとりにくくなる場合がある。さらに好ましい重量平均分子量の範囲は、30万〜100万である。 The molecular weight of component (A) is not particularly limited, but is preferably 100,000 or more and particularly preferably 200,000 or more in terms of weight average molecular weight. If the molecular weight is too small, it is necessary to add a large amount of a crosslinking agent in order to adjust the gel fraction, which may make it difficult to balance the performance. A more preferable range of weight average molecular weight is 300,000 to 1,000,000.
一方、本発明の保護シート用感圧接着剤の必須含有成分である成分(B)は、ガラス転移温度80℃以上の(メタ)アクリル系ポリマーである。(メタ)アクリル系ポリマーとは、少なくとも(メタ)アクリル酸アルキルエステルのホモポリマー又はコポリマーをいう。 On the other hand, the component (B) which is an essential component of the pressure-sensitive adhesive for protective sheets of the present invention is a (meth) acrylic polymer having a glass transition temperature of 80 ° C. or higher. The (meth) acrylic polymer refers to a homopolymer or copolymer of at least a (meth) acrylic acid alkyl ester.
成分(B)の原料である(メタ)アクリル酸アルキルエステルとしては、成分(B)のガラス転移温度を80℃以上にし得るものなら特に限定はないが、その例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸フェニルエチル、(メタ)アクリル酸フェノキシエチル等が挙げられ、これらは1種又は2種以上混合して用いられる。 The (meth) acrylic acid alkyl ester that is the raw material of the component (B) is not particularly limited as long as the glass transition temperature of the component (B) can be 80 ° C. or higher, and examples thereof include (meth) acrylic acid. Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate Examples thereof include ethyl and phenoxyethyl (meth) acrylate, and these are used alone or in combination.
上記(メタ)アクリル酸アルキルエステルとしては、成分(B)のガラス転移温度を80℃以上にするため、メタクリル酸アルキルエステルが好ましく、より好ましくは、アルキル基の炭素数が1〜4のメタクリル酸アルキルエステルであり、特にメタクリル酸メチルが最も好ましい。 As said (meth) acrylic-acid alkylester, in order to make the glass transition temperature of a component (B) 80 degreeC or more, a methacrylic acid alkylester is preferable, More preferably, the C1-C4 methacrylic acid of an alkyl group is preferable. Alkyl esters, particularly methyl methacrylate is most preferred.
また、成分(B)の必須共重合成分ではないが、成分(A)と成分(B)の相溶性を良好にするので、官能基含有モノマーが共重合されていることが好ましい。成分(B)における官能基含有モノマーとして好ましいもの及びその具体例は、成分(A)で挙げた官能基含有モノマーを挙げることができる。 Moreover, although it is not an essential copolymerization component of a component (B), since the compatibility of a component (A) and a component (B) is made favorable, it is preferable that the functional group containing monomer is copolymerized. The thing preferable as a functional group containing monomer in a component (B) and its specific example can mention the functional group containing monomer quoted by the component (A).
なお、成分(B)の製造に当たっては、上記以外の重合性モノマーを使用することもできる。この共重合され得る重合性モノマーの例としては、酢酸ビニル、スチレン、ビニルトルエン、α−メチルスチレン、酢酸アリル等のビニル基含有化合物が挙げられる。 In the production of component (B), polymerizable monomers other than those described above can also be used. Examples of the polymerizable monomer that can be copolymerized include vinyl group-containing compounds such as vinyl acetate, styrene, vinyl toluene, α-methylstyrene, and allyl acetate.
上記した各成分を使用する成分(B)の製造方法は特に限定はされず、公知の方法を用いることができるが、ラジカル重合法が好ましく、その中でも溶液重合法が特に好ましい。 The production method of the component (B) using each of the components described above is not particularly limited, and a known method can be used, but a radical polymerization method is preferable, and among them, a solution polymerization method is particularly preferable.
かくして得られる成分(B)のガラス転移温度は、80℃以上であることが、高速剥離力を抑制し、さらに、浮き、ハガレの防止のために必要である。好ましくは、90℃以上である。 The glass transition temperature of the component (B) thus obtained is 80 ° C. or higher, which is necessary for suppressing high-speed peeling force and for preventing floating and peeling. Preferably, it is 90 ° C. or higher.
また、成分(B)の分子量は、特に限定はないが、重量平均分子量で、1000〜5万が好ましく、特に好ましくは、3000〜3万である。分子量が大きすぎると、成分(A)との相溶性が悪くなる場合がある。 The molecular weight of the component (B) is not particularly limited, but is preferably 1000 to 50,000, and particularly preferably 3000 to 30,000 in terms of weight average molecular weight. If the molecular weight is too large, the compatibility with the component (A) may deteriorate.
本発明の保護シート用感圧接着剤の必須含有成分である成分(C)架橋剤は、少なくとも成分(A)の有する官能基と化学反応又は相互作用をして成分(A)を架橋させる物質である。成分(C)としては、かかる条件を満たせば特に限定されるものではないが、エポキシ基を有する化合物、イソシアネート基を有する化合物、アジリジン誘導体、金属キレート化合物等が好ましい。 The component (C) cross-linking agent that is an essential component of the pressure-sensitive adhesive for protective sheets of the present invention is a substance that cross-links the component (A) through chemical reaction or interaction with at least the functional group of the component (A). It is. The component (C) is not particularly limited as long as such conditions are satisfied, but a compound having an epoxy group, a compound having an isocyanate group, an aziridine derivative, a metal chelate compound, and the like are preferable.
このうち、エポキシ基を有する化合物としては、特に限定はないが、具体的には、ビスフェノールAエピクロルヒドリン型のエポキシ系樹脂、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、1,6−ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、N,N,N',N'−テトラグリシジル−m−キシリレンジアミン、1,3−ビス(N,N'−ジアミングリシジルアミノメチル)シクロヘキサン等の分子中に2個以上のエポキシ基を有する化合物が挙げられる。 Among them, the compound having an epoxy group is not particularly limited, and specifically, bisphenol A epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether. 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis ( N, N′-diamine glycidylaminomethyl) cyclohexane and the like include compounds having two or more epoxy groups in the molecule.
また、イソシアネート基を有する化合物としては、特に限定はないが、具体的には、トリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネート等の分子中に2個のイソシアネート基を有する化合物;それらをトリメチロールプロパン、ペンタエリスリトール、等の多価アルコールと付加反応させた化合物、イソシアネート化合物やイソシアヌレート化合物、ビュレット型化合物、さらには公知のポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール等と付加反応させたウレタンプレポリマー型の分子内に2個以上のイソシアネート基を有する化合物等を挙げることができる。これらは1種又は2種以上用いられる。 Further, the compound having an isocyanate group is not particularly limited, and specifically, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. A compound having two isocyanate groups in the molecule; a compound obtained by subjecting them to addition reaction with a polyhydric alcohol such as trimethylolpropane or pentaerythritol, an isocyanate compound, an isocyanurate compound, a burette type compound, or a known poly Addition reaction with ether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc. The urethane prepolymer type in the molecule can be exemplified compounds having two or more isocyanate groups. These are used alone or in combination of two or more.
このうち好ましいものとしては、具体的にはトリレンジイソシアネート、キシリレンジイソシアネート若しくはヘキサメチレンジイソシアネート又はそれらのトリメチロールプロパン等の多価アルコール付加体が挙げられる。 Among these, preferred are polyhydric alcohol adducts such as tolylene diisocyanate, xylylene diisocyanate or hexamethylene diisocyanate or trimethylolpropane thereof.
さらに、アジリジン誘導体としては、1,1'−(メチレン−ジp−フェニレン)ビス−3,3−アジリジル尿素、1,1'−(ヘキサメチレン)ビス−3,3−アジリジル尿素、2,4,6−トリアジリジニル−1,3,5−トリアジン、トリメチロールプロパン−トリス−(2−アジリジニルプロピオネート)等が挙げられる。 Furthermore, as the aziridine derivative, 1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridylurea, 1,1 ′-(hexamethylene) bis-3,3-aziridylurea, 2,4 , 6-triaziridinyl-1,3,5-triazine, trimethylolpropane-tris- (2-aziridinylpropionate), and the like.
さらに金属キレート化合物としては、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロム、ジルコニウム等の多価金属にアセチルアセトン、アセト酢酸エチル等が配位した化合物等が挙げられる。 Furthermore, examples of the metal chelate compound include compounds in which acetylacetone, ethyl acetoacetate, and the like are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. It is done.
本発明で使用する架橋性組成物は、成分(A)、成分(B)及び成分(C)を含有するものであるが、このうち成分(B)の配合量は、成分(A)100重量部に対して、5〜20重量部である。成分(B)の配合量が5重量部未満の場合には、剥離力の剥離速度依存性が大きく、高速剥離時の粘着力が大きくなりすぎる場合があり、20重量部より多い場合には、ジッピングが生じる場合がある。好ましくは、8〜15重量部である。一方、成分(C)の配合量は特に限定はないが、成分(A)100重量部に対して、0.5〜10重量部程度が好ましく、特に好ましくは、1〜5重量部である。 The crosslinkable composition used in the present invention contains the component (A), the component (B), and the component (C). Among these, the amount of the component (B) is 100% by weight of the component (A). 5 to 20 parts by weight with respect to parts. When the blending amount of the component (B) is less than 5 parts by weight, the peeling speed is greatly dependent on the peeling speed, and the adhesive force at the time of high-speed peeling may be too large. Zipping may occur. Preferably, it is 8-15 weight part. On the other hand, the amount of the component (C) is not particularly limited, but is preferably about 0.5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight with respect to 100 parts by weight of the component (A).
上記の成分(A)ないし成分(C)を必須成分として含有する架橋性組成物は、常法に従って支持体上に塗布し、溶剤を留去し、熟成を行い架橋させることにより保護シート用感圧接着剤となるが、本発明の保護シート用感圧接着剤は、ゲル分率80%以上であることが必須である。ここで、本発明におけるゲル分率とは、実施例中に記載した測定方法で求めたものと定義される。ゲル分率が80%未満の場合は、粘着力が大きくなりすぎる 場合がある。 The crosslinkable composition containing the component (A) to the component (C) as an essential component is coated on a support according to a conventional method, the solvent is distilled off, aging is performed, and crosslinking is performed to form a protective sheet feeling. Although it becomes a pressure adhesive, it is essential that the pressure sensitive adhesive for protective sheets of the present invention has a gel fraction of 80% or more. Here, the gel fraction in this invention is defined as what was calculated | required with the measuring method described in the Example. When the gel fraction is less than 80%, the adhesive strength may become too large.
以上のようにして得られる、本発明の保護シート用感圧接着剤は、その高速剥離力が100gf/24mm(1inch)以下であることが好ましい。ここで本発明における「保護シート用感圧接着剤の高速剥離力」とは、実施例1に記載した製造方法と同様の方法で製造した当該保護シート用感圧接着剤を支持体上に有する表面保護フィルムを、実施例中に記載した高速剥離力測定方法に従って測定したものと定義される。 The pressure sensitive adhesive for protective sheet of the present invention obtained as described above preferably has a high speed peeling force of 100 gf / 24 mm (1 inch) or less. Here, “the high-speed peeling force of the pressure-sensitive adhesive for protective sheet” in the present invention has the pressure-sensitive adhesive for protective sheet produced by the same method as the production method described in Example 1 on the support. It is defined that the surface protective film was measured according to the high speed peel force measuring method described in the examples.
また、本発明の保護シート用感圧接着剤は、その低速剥離力が20gf/24mm以下であることが好ましい。ここで本発明における「保護シート用感圧接着剤の低速剥離力」とは、実施例1に記載した製造方法と同様の方法で製造した当該保護シート用感圧接着剤を支持体上に有する表面保護フィルムを、実施例中に記載した低速剥離力測定方法に従って測定したものと定義される。 Moreover, it is preferable that the low pressure peeling force is 20 gf / 24 mm or less as for the pressure sensitive adhesive for protective sheets of this invention. Here, “the low-speed peeling force of the pressure-sensitive adhesive for protective sheet” in the present invention has the pressure-sensitive adhesive for protective sheet produced by the same method as the production method described in Example 1 on the support. The surface protective film is defined as measured according to the low speed peel force measuring method described in the examples.
少なくとも成分(A)、成分(B)及び成分(C)を含有する架橋性組成物を支持体上に塗工して、塗布溶剤留去、熟成等を行うことにより、本発明の保護シート用感圧接着剤が、支持体上に塗工されてなる表面保護シートを得ることができる。ここで使用される支持体としては、特に限定はされないが、ポリエチレンテレフタレート(PET)等のポリエステル、ポリエチレン、ポリプロピレン、エチレン酢ビ共重合体等のプラスチック製フィルムが好適に使用できる。 By coating the crosslinkable composition containing at least component (A), component (B) and component (C) on a support, and performing coating solvent distillation, aging, etc., the protective sheet of the present invention A surface protective sheet in which a pressure sensitive adhesive is coated on a support can be obtained. Although it does not specifically limit as a support body used here, Plastic films, such as polyester, such as a polyethylene terephthalate (PET), polyethylene, a polypropylene, and an ethylene vinyl acetate copolymer, can be used conveniently.
また塗工に当たっては、溶剤を使用しても良く、使用される溶剤としては、特に限定はするものではないが、例えば、酢酸エチル、トルエン、メチルエチルケトン等が挙げられる。 In the coating, a solvent may be used, and the solvent to be used is not particularly limited, and examples thereof include ethyl acetate, toluene, methyl ethyl ketone and the like.
さらに、塗工の方法も、従来公知の方法を使用することができ、得られた表面保護シートの粘着面に剥離シートを貼り合わせても良い。 Furthermore, as a coating method, a conventionally known method can be used, and a release sheet may be bonded to the adhesive surface of the obtained surface protective sheet.
次に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれら実施例に何ら制約されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.
実 施 例 1
成分(A)として、表1に示した共重合組成、ガラス転移温度及び重量平均分子量を有する(メタ)アクリル系ポリマー(A−1)100重量部、成分(B)として、表2に示した共重合組成、ガラス転移温度及び重量平均分子量を有する(メタ)アクリル系ポリマー(B−1)10重量部及び架橋剤としてテトラッドCを3重量部を用い、これらを酢酸エチルに溶解させ架橋性組成物溶液を得た。得られた溶液を、厚さ38μmのポリエチレンテレフタレート(以下「PET」と略記する)フィルム上に、乾燥後の厚みが20μmになるように塗布し、80℃で溶媒を除去した。次いで、乾燥面に38μm厚みのシリコーンコートされたカバー用PETフィルムを貼り合わせて、23℃、湿度65%の雰囲気下で、7日間熟成させ表面保護フィルムを得た。
Example 1
As component (A), the copolymer composition shown in Table 1, the glass transition temperature and 100 parts by weight of (meth) acrylic polymer (A-1) having a weight average molecular weight, and as component (B) are shown in Table 2. Using 10 parts by weight of (meth) acrylic polymer (B-1) having a copolymer composition, glass transition temperature and weight average molecular weight, and 3 parts by weight of tetrad C as a crosslinking agent, these are dissolved in ethyl acetate to form a crosslinkable composition. A product solution was obtained. The obtained solution was applied onto a polyethylene terephthalate (hereinafter abbreviated as “PET”) film having a thickness of 38 μm so that the thickness after drying was 20 μm, and the solvent was removed at 80 ° C. Next, a 38 μm-thick silicone-coated PET film for cover was bonded to the dry surface and aged for 7 days in an atmosphere of 23 ° C. and 65% humidity to obtain a surface protective film.
実 施 例 2〜7 及び 比 較 例 1〜11
表1及び表2に示した(メタ)アクリル系ポリマー並びに表3に示した成分(C)の架橋剤を、それぞれ表3に示した配合量で用いた以外は、実施例1と同様にして表面保護フィルムを得た。
Examples 2 to 7 and Comparative Examples 1 to 11
Except that the (meth) acrylic polymer shown in Tables 1 and 2 and the crosslinking agent of the component (C) shown in Table 3 were used in the amounts shown in Table 3, respectively, in the same manner as in Example 1. A surface protective film was obtained.
ここで、表中の記号は以下の通り。
2EHA :アクリル酸2−エチルヘキシル
AA :アクリル酸
2HEA :アクリル酸2−ヒドロキシエチル
VAc :酢酸ビニル
BA :アクリル酸ブチル
MA :アクリル酸メチル
MMA :メタクリル酸メチル
DM :アクリル酸ジメチルアミノエチル
2HEMA :メタクリル酸2−ヒドロキシエチル
IBMA :メタクリル酸イソブチル
テトラッドC :三菱瓦斯化学社製エポキシ系架橋剤
コロネートL :日本ポリウレタン工業社製イソシアネート系架橋剤
ケミタイトPZ-33 :日本触媒社製 アジリジン系架橋剤
アルミキレートA:川研ファインケミカル社製 金属キレート架橋剤
Tgは、ガラス転移温度を表す
Here, the symbols in the table are as follows.
2EHA: 2-ethylhexyl acrylate AA: acrylic acid 2HEA: 2-hydroxyethyl acrylate VAc: vinyl acetate BA: butyl acrylate MA: methyl acrylate MMA: methyl methacrylate DM: dimethylaminoethyl acrylate 2HEMA: methacrylic acid 2 -Hydroxyethyl IBMA: Isobutyl methacrylate
Tetrad C: Epoxy-based crosslinking agent Coronate L manufactured by Mitsubishi Gas Chemical Co., Ltd .: Isocyanate-based crosslinking agent Chemitite PZ-33 manufactured by Nippon Polyurethane Industry Co., Ltd. Tg represents the glass transition temperature
試 験 例
下記の方法で、上記実施例1〜7及び比較例1〜11の表面保護フィルムについてゲル分率、低速剥離力、高速剥離力及び熱時のハガレを試験した。表4に試験結果を示す。
Test Example The following methods were used to test the gel fraction, the low speed peel force, the high speed peel force, and the heat peeling when the surface protective films of Examples 1 to 7 and Comparative Examples 1 to 11 were used. Table 4 shows the test results.
(ゲ ル 分 率)
上記各表面保護フィルムを50mm×50mmに裁断し、その裁断した表面保護フィルムから粘着剤を剥がしとり、粘着剤の初期の重量を秤量した。その粘着剤を100gの酢酸エチルに浸漬し室温で24時間放置した。その後200メッシュ金網でろ過し、メッシュに残った残分を80℃で2時間乾燥し秤量した。初期の重量及び残分の重量から、下記式によってゲル分率を算出した。
ゲル分率(%)=100×(残分の重量)/(初期の重量)
(Gel fraction)
Each said surface protection film was cut | judged to 50 mm x 50 mm, the adhesive was peeled off from the cut surface protection film, and the initial weight of the adhesive was weighed. The adhesive was immersed in 100 g of ethyl acetate and allowed to stand at room temperature for 24 hours. Thereafter, the mixture was filtered through a 200 mesh wire mesh, and the residue remaining on the mesh was dried at 80 ° C. for 2 hours and weighed. From the initial weight and the remaining weight, the gel fraction was calculated by the following formula.
Gel fraction (%) = 100 × (weight of residual) / (initial weight)
( 低 速 剥 離 力 )
上記各表面保護フィルムを25mm×150mmに裁断し、カバー用PETフィルムを剥離後、偏光板(トリアセチルセルロース面)に貼り付け、室温で24時間放置した。その後、引き剥がし速度300mm/分で、180°方向(逆方法)に引っ張り、剥離を開始する力を低速剥離力とした。
(Low speed peeling force)
Each of the above surface protective films was cut into 25 mm × 150 mm, the cover PET film was peeled off, and then attached to a polarizing plate (triacetyl cellulose surface) and left at room temperature for 24 hours. Then, it pulled in 180 degree direction (reverse method) at a peeling speed of 300 mm / min, and the force which starts peeling was made into the low speed peeling force.
( 高 速 剥 離 力 )
上記各表面保護フィルムを25mm×150mmに裁断し、カバー用PETフィルムを剥離後、偏光板(トリアセチルセルロース面)に貼り付け、室温で24時間放置した。その後、引き剥がし速度10000mm/分で、180°方向(逆方法)に引っ張り、剥離を開始する力を高速剥離力とした。
(High speed peeling force)
Each of the above surface protective films was cut into 25 mm × 150 mm, the cover PET film was peeled off, and then attached to a polarizing plate (triacetyl cellulose surface) and left at room temperature for 24 hours. Thereafter, the pulling speed was 10,000 mm / min, and the film was pulled in the 180 ° direction (reverse method), and the force for starting peeling was defined as the high-speed peeling force.
( 熱 時 の ハ ガ レ)
上記各表面保護フィルムをそれぞれ60mm×120mmに裁断し、カバー用PETフィルムを剥離後、ガラス基板上に貼り付け、85℃、ドライで500時間及び60℃、95%RHで500時間放置し、表面保護フィルムに発生する浮きやハガレの状態を目視で観察した。以下の基準で評価した。
○:粘着シートに剥がれが起こらなかった
△:粘着シートに剥がれがわずかに起こった
×:粘着シートに剥がれが起こった
(Hagare in the heat)
Each of the above surface protective films is cut into 60 mm × 120 mm, the cover PET film is peeled off, and then attached to a glass substrate, and left at 85 ° C., dry for 500 hours, and at 60 ° C., 95% RH for 500 hours. The state of float and peeling generated on the protective film was visually observed. Evaluation was made according to the following criteria.
○: Peeling did not occur on the pressure-sensitive adhesive sheet Δ: Slight peeling occurred on the pressure-sensitive adhesive sheet ×: Peeling occurred on the pressure-sensitive adhesive sheet
表4に示すように、実施例1〜7の保護シート用感圧接着剤を使用した表面保護フィルムは、低速剥離力がすべて20g/24mm以下、高速剥離力が100g/24mm以下であり、高速剥離性に優れるとともに、剥離速度変化による剥離力の変動が少ないものであった。さらに、高速剥離時にジッピングも起こらず、また熱時の浮きやハガレも見られず耐久性に優れたものであった。 As shown in Table 4, the surface protective films using the pressure-sensitive adhesives for protective sheets of Examples 1 to 7 all have a low-speed peel force of 20 g / 24 mm or less and a high-speed peel force of 100 g / 24 mm or less. In addition to excellent peelability, there was little variation in peel force due to changes in peel speed. Furthermore, no zipping occurred at the time of high-speed peeling, and no heat float or peeling occurred, and the durability was excellent.
本発明の保護シート用感圧接着剤は、高速剥離性が良好であり、ジッピングを起こさず、また剥離速度による剥離力の変化が少ない表面保護シートを提供することができるものである。従って、本発明の保護シート用感圧接着剤を使用した表面保護シートは、貼り付け後、加熱しても浮きやハガレ等が起こらず耐久性のあるものであり、ディスプレイ分野で使用される光学フィルムや、各種プラスチック板、ステンレス等の金属板、ガラス板等の表面保護にも有利に使用することができるものである。
以上
The pressure-sensitive adhesive for protective sheets of the present invention can provide a surface protective sheet that has good high-speed peelability, does not cause zipping, and has little change in peel force depending on the peel speed. Therefore, the surface protective sheet using the pressure-sensitive adhesive for protective sheet of the present invention is durable and does not cause floating or peeling even if heated after being applied, and is used in the display field. It can be advantageously used for surface protection of films, various plastic plates, metal plates such as stainless steel, and glass plates.
more than
Claims (7)
(A)少なくともアクリル酸2−エチルヘキシル及び官能基含有モノマーが共重合して
なる重量平均分子量が10万〜100万であり、ガラス転移温度が−40℃以下
の(メタ)アクリル系ポリマー
(B)(メタ)アクリル酸アルキルエステルを主成分とする重量平均分子量が1000
〜5万であり、ガラス転移温度80℃以上の(メタ)アクリル系ポリマー
(C)架橋剤
を含有し、成分(A)100重量部に対して、成分(B)を5〜20重量部で配合する架橋性組成物を、ゲル分率80%以上となるように架橋反応せしめてなり、これを酢酸エチルに溶解させた溶液を、厚さ38μmのポリエチレンテレフタレート(PET)フィルム上に、乾燥後の厚みが20μmになるように塗布して80℃で溶媒を除去し、次いで、乾燥面に38μm厚みのシリコーンコートされたカバー用PETフィルムを貼り合わせて、23℃、湿度65%の雰囲気下で、7日間熟成させて得られる表面保護フィルムを、25mm×150mmに裁断し、カバー用PETフィルムを剥離後、偏光板(トリアセチルセルロース面)に貼り付け、室温で24時間放置した後、引き剥がし速度10000mm/分で180°方向(逆方法)に引っ張った時、剥離を開始する力(高速剥離力)が100gf/24mm(1inch)以下であり、引き剥がし速度300mm/分で180°方向(逆方法)に引っ張った時、剥離を開始する力(低速剥離力)が20gf/24mm以下である保護シート用感圧接着剤。 Next component (A), component (B) and component (C),
(A) A (meth) acrylic polymer having a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of −40 ° C. or less (B) , which is obtained by copolymerizing at least 2-ethylhexyl acrylate and a functional group-containing monomer. The weight average molecular weight mainly composed of (meth) acrylic acid alkyl ester is 1000.
(Meth) acrylic polymer having a glass transition temperature of 80 ° C. or higher (C) containing a crosslinking agent, and the component (B) is 5 to 20 parts by weight with respect to 100 parts by weight of the component (A). The crosslinkable composition to be blended is subjected to a crosslinking reaction so that the gel fraction is 80% or more, and a solution in which this is dissolved in ethyl acetate is dried on a polyethylene terephthalate (PET) film having a thickness of 38 μm. The film was applied to a thickness of 20 μm, the solvent was removed at 80 ° C., and then a 38 μm-thick silicone-coated cover PET film was bonded to the dry surface, and the atmosphere was 23 ° C. and humidity 65%. The surface protective film obtained by aging for 7 days was cut to 25 mm × 150 mm, the cover PET film was peeled off, and then attached to the polarizing plate (triacetyl cellulose surface). After standing times, when Tsu pulling the peeling speed of 10000 mm / min at 180 ° direction (reverse process), the force to initiate peeling (fast peel strength) of not more than 100 gf / 24 mm (1inch), peeling speed 300mm / when Tsu pulling direction of 180 ° (reverse process) in minutes, the force to initiate peeling (slow peel force) pressure sensitive adhesive protective sheet is not more than 20 gf / 24 mm.
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