JP6618038B2 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP6618038B2 JP6618038B2 JP2016128451A JP2016128451A JP6618038B2 JP 6618038 B2 JP6618038 B2 JP 6618038B2 JP 2016128451 A JP2016128451 A JP 2016128451A JP 2016128451 A JP2016128451 A JP 2016128451A JP 6618038 B2 JP6618038 B2 JP 6618038B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- component
- adhesive composition
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 62
- 239000000853 adhesive Substances 0.000 title claims description 53
- 230000001070 adhesive effect Effects 0.000 title claims description 53
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 86
- -1 acrylate compound Chemical class 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 27
- 239000005056 polyisocyanate Substances 0.000 claims description 26
- 229920001228 polyisocyanate Polymers 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229920002635 polyurethane Polymers 0.000 claims description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 13
- 239000012790 adhesive layer Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229950000688 phenothiazine Drugs 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 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 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000008096 xylene 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
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- ZEOVXNVKXIPWMS-UHFFFAOYSA-N 2,2-dichloropropane Chemical compound CC(C)(Cl)Cl ZEOVXNVKXIPWMS-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-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
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical compound C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、新規な粘着剤組成物であって、熱硬化後にはその塗膜に各種基材を貼り合わせることができ、該塗膜に紫外線を照射した後にはその粘着力が低下し前記基材を剥離する時に糊残りが発生しない（即ち優れた剥離性を奏する）という特徴を備える組成物に関する。 The present invention is a novel pressure-sensitive adhesive composition, and various substrates can be bonded to the coating film after thermosetting, and the adhesive strength decreases after the coating film is irradiated with ultraviolet rays. The present invention relates to a composition having a feature that no adhesive residue is generated when a material is peeled (that is, excellent peelability is exhibited).
粘着剤は様々な部材同士の接着に用いられている。中でも、透明性がある粘着剤層は光学部品同士の接着、例えば、タッチパネルを製造する際のタッチセンサーと前面板との接着に用いられている。また、タッチセンサーと画像表示装置との接着にもそうした粘着剤が使用されている。 The pressure-sensitive adhesive is used for bonding various members. Among these, a transparent pressure-sensitive adhesive layer is used for adhesion between optical components, for example, adhesion between a touch sensor and a front plate when manufacturing a touch panel. Such a pressure-sensitive adhesive is also used for bonding the touch sensor and the image display device.
しかしながら、従来の粘着剤は、例えば両面粘着シート態様で光学部材同士を貼り合わせる際に、気泡や異物を巻き込む等作業ミスを生じることがあるため、剥離する必要があった。即ち、貼り合わせ時に作業ミスが生じても、光学部材を再利用するため光学部材から粘着シートを糊残りなく剥がすことができる、いわゆる剥離性が求められていた。 However, the conventional pressure-sensitive adhesive has to be peeled off because, for example, when the optical members are bonded to each other in a double-sided pressure-sensitive adhesive sheet form, an operation error such as entrapment of bubbles or foreign matters may occur. That is, even if an operation error occurs at the time of bonding, there is a need for so-called releasability that allows the adhesive sheet to be peeled off from the optical member without adhesive residue in order to reuse the optical member.
特許文献１では、貼り合わせ後、活性エネルギー線を照射することで粘着力が低下し、被着体から糊残りなく剥離することができる多層両面粘着シートが提案されている。このものは、最外粘着剤層が、アクリルポリマーと熱硬化型架橋剤と重合性不飽和基含有単量体とを含有する。この最外粘着剤層は、熱硬化により作製され、タッチパネルと画像表示装置と貼り合わせた後、活性エネルギー線を照射することにより、粘着力が低下する。しかしながら、該多層両面粘着シートは、作製方法が複雑であり、活性エネルギー線を照射後の粘着力の低下率も不十分である。 Patent Document 1 proposes a multilayer double-sided pressure-sensitive adhesive sheet that can be peeled off from an adherend without adhesive residue by irradiating active energy rays after bonding. In this, the outermost pressure-sensitive adhesive layer contains an acrylic polymer, a thermosetting crosslinking agent, and a polymerizable unsaturated group-containing monomer. This outermost pressure-sensitive adhesive layer is produced by thermosetting, and after being bonded to the touch panel and the image display device, the adhesive force is reduced by irradiating active energy rays. However, the multilayer double-sided PSA sheet has a complicated production method, and the rate of decrease in adhesive strength after irradiation with active energy rays is insufficient.
一方、半導体ウエハのダイシング工程では、一時的接着等の目的で粘着シートが用いられている。また、近年は、導体チップを損傷させることなくピックアップできる方法が提案されており、この方法では、粘着剤層に紫外線を照射することでその粘着力が低下し、半導体チップを損傷させることなく容易に粘着シートを剥離できる。 On the other hand, in the dicing process of a semiconductor wafer, an adhesive sheet is used for the purpose of temporary adhesion or the like. In recent years, a method has been proposed that can pick up without damaging the conductor chip. In this method, the adhesive force is reduced by irradiating the adhesive layer with ultraviolet rays, and the semiconductor chip is not easily damaged. The adhesive sheet can be peeled off.
特許文献２では、アクリルポリマー、ポリイソシアネート、多官能モノマー・オリゴマー、及び光重合開始剤を有するダイシングテープ用粘着剤が提案されている。このものは、貼り合わせ後、活性エネルギー線を照射することで粘着力が低下し、被着体からダイシングテープを剥離することが可能になる。しかしながら、剥離後に被着面に粘着剤が残存する恐れがあり、基材に対する剥離性は十分とは言いがたい。 Patent Document 2 proposes a dicing tape pressure-sensitive adhesive having an acrylic polymer, a polyisocyanate, a polyfunctional monomer / oligomer, and a photopolymerization initiator. In this case, the adhesive strength is reduced by irradiating active energy rays after bonding, and the dicing tape can be peeled off from the adherend. However, there is a possibility that the pressure-sensitive adhesive remains on the adherend surface after peeling, and it is difficult to say that the peelability from the substrate is sufficient.
本発明は、熱及び紫外線で硬化する粘着剤組成物であって、その粘着層が、熱硬化後には適度な粘着力を呈するため各種基材を貼り合わせることができ、かつ、紫外線照射後にはその粘着力が低下して糊残りを生じずに優れた剥離性を奏するものである、新規な組成物を提供することを主たる目的とする。 The present invention is a pressure-sensitive adhesive composition that is cured by heat and ultraviolet light, and the pressure-sensitive adhesive layer exhibits an appropriate pressure-sensitive adhesive force after heat curing so that various substrates can be bonded together, and after ultraviolet light irradiation. The main object is to provide a novel composition that exhibits excellent peelability without lowering its adhesive strength and leaving no adhesive residue.
本発明者は、前記課題を解決すべく鋭意検討した結果、特定の粘着剤組成物により課題を解決できることを見出し、本発明を完成するに至った。即ち本発明は、以下の粘着剤組成物に関する。 As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by a specific pressure-sensitive adhesive composition, and have completed the present invention. That is, this invention relates to the following adhesive compositions.
１．主剤、硬化剤、光重合開始剤及び有機溶剤を含む粘着剤組成物であって、前記主剤は、ポリカーボネートポリオール（а−１）及び脂肪族ポリイソシアネート（а−２）を反応させて得られる末端水酸基含有ポリウレタン（Ａ）であり、前記硬化剤は、多官能ポリイソシアネート（ｂ−１）及び水酸基を（メタ）アクリレート化合物（ｂ−２）を反応させ、イソシアネート基と（メタ）アクリロイル基の両反応基を持つ（メタ）アクリル変性ポリイソシアネート（Ｂ）であることを特徴とする粘着剤組成物。 1. A pressure-sensitive adhesive composition comprising a main agent, a curing agent, a photopolymerization initiator and an organic solvent, wherein the main agent is a terminal obtained by reacting a polycarbonate polyol (а-1) and an aliphatic polyisocyanate (а-2). It is a hydroxyl group-containing polyurethane (A), and the curing agent reacts the polyfunctional polyisocyanate (b-1) and the hydroxyl group with the (meth) acrylate compound (b-2), and both the isocyanate group and the (meth) acryloyl group. A pressure-sensitive adhesive composition, which is a (meth) acryl-modified polyisocyanate (B) having a reactive group.
２．前記末端水酸基を有するポリウレタン（Ａ）の重量平均分子量（ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値）が４０，０００〜１１０，０００である、前記項１記載の粘着剤組成物。 2. Item 2. The pressure-sensitive adhesive composition according to item 1, wherein the polyurethane (A) having a terminal hydroxyl group has a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of 40,000 to 110,000.
３．前記多官能ポリイソシアネート（ｂ−１）の全イソシアネート基モル数に対する水酸基含有（メタ）アクリル化合物（ｂ−２）の全水酸基モル数が０．１〜１である、前記項１又は２記載の粘着剤組成物。 3. Item 3. The item 1 or 2, wherein the hydroxyl group-containing (meth) acrylic compound (b-2) has a total hydroxyl group mole number of 0.1 to 1 with respect to the total isocyanate group mole number of the polyfunctional polyisocyanate (b-1). Adhesive composition.
４．前記項１〜３のいずれかの粘着剤組成物であって、該粘着剤組成物の熱硬化物である粘着剤層の粘着力をＦ１（Ｎ／２５ｍｍ）、及び該粘着剤層１に紫外線を照射して得られる粘着剤層２の粘着力をＦ２（Ｎ／２５ｍｍ）とした場合において、粘着力の低下率（Ｆ２／Ｆ１）が０．５以下であることを特徴とする、粘着剤組成物。 4). Item 4. The pressure-sensitive adhesive composition according to any one of items 1 to 3, wherein the pressure-sensitive adhesive layer, which is a thermoset of the pressure-sensitive adhesive composition, has an adhesive force of F1 (N / 25 mm) and ultraviolet light applied to the pressure-sensitive adhesive layer 1. When the adhesive strength of the adhesive layer 2 obtained by irradiating is F2 (N / 25 mm), the adhesive strength reduction rate (F2 / F1) is 0.5 or less. Composition.
本発明の粘着剤組成物は、粘着シートや粘着テープの粘着剤層として利用できる。該粘着剤組成物は、熱硬化後の粘着剤層が適度な粘着力を有しており、各種被着体、例えば光学部品や導体チップ等に対して良好な粘着性を示す。一方、該粘着剤層は、紫外線を照射することでその粘着力が低下し剥離性を帯びる。そのため、本発明の粘着剤組成物を粘着剤層とする粘着シートや粘着テープは、剥離時に被着体に糊残りを発生し難い。該粘着シート及び該粘着テープは、例えば、タッチパネルの液晶部材の回収や半導体ウエハのダイシング工程の一時的接着用途での剥離性を求める分野にて非常に有用である。 The pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive layer for pressure-sensitive adhesive sheets and pressure-sensitive adhesive tapes. In the pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer after heat curing has an appropriate pressure-sensitive adhesive force, and exhibits good adhesion to various adherends such as optical components and conductor chips. On the other hand, when the adhesive layer is irradiated with ultraviolet rays, the adhesive strength is reduced and the adhesive layer is peelable. Therefore, the pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape having the pressure-sensitive adhesive composition of the present invention as a pressure-sensitive adhesive layer hardly causes adhesive residue on the adherend during peeling. The pressure-sensitive adhesive sheet and the pressure-sensitive adhesive tape are very useful, for example, in the field of demanding releasability in the application of temporary adhesion in the recovery of the liquid crystal member of the touch panel or the dicing process of the semiconductor wafer.
本発明の粘着剤組成物は、主剤、硬化剤、光重合開始剤及び有機溶剤を含む。 The pressure-sensitive adhesive composition of the present invention contains a main agent, a curing agent, a photopolymerization initiator, and an organic solvent.
前記主剤は、ポリカーボネートポリオール（а−１）（以下、（а−１）成分）及び脂肪族ポリイソシアネート（а−２）（以下、（а−２）成分）の反応物としての末端水酸基含有ポリウレタン（Ａ）（以下、（Ａ）成分）を含む。 The main agent is a terminal hydroxyl group-containing polyurethane as a reaction product of polycarbonate polyol (а-1) (hereinafter referred to as (а-1) component) and aliphatic polyisocyanate (а-2) (hereinafter referred to as (а-2) component). (A) (hereinafter referred to as component (A)).
上記（ａ−１）成分としては、例えば、１，５−ペンタンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、１，４−シクロヘキサンジメタノール、１，９−ノナンジオール、又は２−メチル−１，８−オクタンジオール等のジオールの一種又は二種以上をベースにしたポリカーボネートポリオールが挙げられる。市販品としては、例えば、宇部興産（株）製のエタナコールＵＨ−１００、ＵＨ−２００、ＵＨ−３００、ＵＨＣ５０−２００、ＵＨＣ５０−１００、及びＵＣ−１００等；（株）クラレ社製のクラレポリオールＣ−１０９０、２０９０、Ｃ−２０９０Ｒ、及びＣ−３０９０等；（株）ダイセル製のプラクセルＣＤ２１０、ＣＤ２１０ＰＬ、ＣＤ２２０、及びＣＤ２２０ＰＬ等；旭化成（株）製のポリカーボネートジオールデュラノールＴ６００２、Ｔ６００１、Ｔ５６５１、Ｔ５６５０Ｊ、Ｔ４６７１、Ｔ４６７２、Ｔ４６９２、及びＴ４６９１等；が挙げられ、二種以上を併用できる。これらの中でも、本発明に係る粘着剤組成物の粘着力及びその硬化層の柔軟性等の点より、３−メチル−１，５−ペンタンジオールを構成成分とするポリカーボネートポリオールが好ましく、特に、３−メチル−１，５−ペンタンジオールを構成成分とし且つ常温で液状の非結晶性ポリカーボネートポリオールが好ましい。そのようなポリカーボネートポリオールの市販品としては、例えば、前記クラレポリオールＣ−１０９０、２０９０、Ｃ−２０９０Ｒ、及びＣ−３０９０等が挙げられる。 Examples of the component (a-1) include 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, and 1,9-nonane. Polycarbonate polyols based on one or more diols such as diol or 2-methyl-1,8-octanediol. Examples of commercially available products include, for example, Etanacol UH-100, UH-200, UH-300, UHC50-200, UHC50-100, and UC-100 manufactured by Ube Industries, Ltd .; Kuraray polyol manufactured by Kuraray Co., Ltd. C-1090, 2090, C-2090R, C-3090, etc .; Placel CD210, CD210PL, CD220, CD220PL, etc. manufactured by Daicel Corporation; polycarbonate diol duranol T6002, T6001, T5651, T5650J manufactured by Asahi Kasei Corporation , T4671, T4672, T4692 and T4691; and two or more of them can be used in combination. Among these, polycarbonate polyols having 3-methyl-1,5-pentanediol as a constituent component are preferable from the viewpoint of the adhesive strength of the pressure-sensitive adhesive composition according to the present invention and the flexibility of the cured layer, and particularly, 3 A non-crystalline polycarbonate polyol having methyl-1,5-pentanediol as a constituent component and liquid at normal temperature is preferred. Examples of such a commercially available polycarbonate polyol include Kuraray polyol C-1090, 2090, C-2090R, and C-3090.
上記（ａ−１）成分の分子量は、特に限定されないが、粘着力及び柔軟性の点より７００〜４，０００程度であるのが好ましい。かかる範囲であると、粘着剤層が、粘着力、柔軟性及び剥離性がバランスよく発揮するようになる。この観点より、分子量は、１,０００〜３,０００程度であるのがより好ましい。 Although the molecular weight of the said (a-1) component is not specifically limited, It is preferable that it is about 700-4,000 from the point of adhesive force and a softness | flexibility. Within such a range, the pressure-sensitive adhesive layer exhibits a good balance of adhesive strength, flexibility and peelability. From this viewpoint, the molecular weight is more preferably about 1,000 to 3,000.
上記（ａ−２）成分としては、例えば、ジシクロヘキシルメタン−４，４´−ジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネートや、これらの２〜６量体等が挙げられ、二種以上を併用できる。中でも、剥離性を向上させる目的で、ジシクロヘキシルメタン−４，４´−ジイソシアネート、イソホロンジイソシアネートの環構造を有するポリイソシアネートを用いることが好ましい。 Examples of the component (a-2) include dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimers and hexamers thereof. Can be used together. Among these, for the purpose of improving the peelability, it is preferable to use polyisocyanate having a ring structure of dicyclohexylmethane-4,4′-diisocyanate or isophorone diisocyanate.
（ａ−１）成分と（ａ−２）成分とを反応させることにより、（Ａ）成分である水酸基末端ポリウレタンが得られる。（Ａ）成分の製造法は、特に限定されないが、例えば、合成時間短縮のための一括仕込み法（方法１）や、重量平均分子量を大きくするための分割仕込み法（方法２）が挙げられる。 By reacting the component (a-1) and the component (a-2), a hydroxyl group-terminated polyurethane as the component (A) is obtained. Although the manufacturing method of (A) component is not specifically limited, For example, the batch preparation method (method 1) for synthetic | combination time shortening and the division | segmentation preparation method (method 2) for enlarging a weight average molecular weight are mentioned.
方法１：（ａ−１）成分及び（ａ−２）成分を一括反応させ、短時間で（Ａ）成分を合成できる。
方法２：（ａ−１）成分の一部と（ａ−２）成分全量とを仕込み、一定時間反応させた後、残りの（ａ−１）成分を数回に分けて、一定の時間を開けて仕込み、反応させる。（Ａ）成分の重量平均分子量を大きくする場合は、この合成法が好ましい。
Method 1: The (a-1) component and the (a-2) component can be reacted together to synthesize the (A) component in a short time.
Method 2: A part of the component (a-1) and the total amount of the component (a-2) are charged and reacted for a predetermined time, and then the remaining component (a-1) is divided into several times, Open, charge and react. This synthesis method is preferred when the weight average molecular weight of the component (A) is increased.
上記（Ａ）成分の重量平均分子量（ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値）は、特に限定されないが、粘着力及び剥離性の点から、４０，０００〜１１０，０００程度であるのが好ましく、５０，０００〜９０，０００程度であるのがより好ましい。 The weight average molecular weight of the component (A) (polystyrene conversion value by gel permeation chromatography) is not particularly limited, but is preferably about 40,000 to 110,000 in terms of adhesive strength and peelability. More preferably, it is about 50,000 to 90,000.
なお、上記（Ａ）成分一分子中の平均水酸基数は、格別限定されないが、粘着力及び剥離性の点から、１．５〜３程度であるのが好ましく、より好ましくは１．８〜２．２程度である。 The average number of hydroxyl groups in one molecule of the component (A) is not particularly limited, but is preferably about 1.5 to 3, more preferably 1.8 to 2 from the viewpoint of adhesive strength and peelability. .2 or so.
前記硬化剤は、多官能ポリイソシアネート（ｂ−１）（以下、（ｂ−１）成分）及び水酸基含有（メタ）アクリレート化合物（ｂ−２）（以下、（ｂ−２）成分）の反応物であって、分子内にイソシアネート基と（メタ）アクリロイル基を併有する（メタ）アクリル変性ポリイソシアネート（Ｂ）（以下、（Ｂ）成分）を含む。 The curing agent is a reaction product of polyfunctional polyisocyanate (b-1) (hereinafter referred to as (b-1) component) and a hydroxyl group-containing (meth) acrylate compound (b-2) (hereinafter referred to as (b-2) component). And (meth) acryl-modified polyisocyanate (B) (hereinafter referred to as component (B)) having both an isocyanate group and a (meth) acryloyl group in the molecule.
上記（ｂ−１）成分としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート又は脂環式ポリイソシアネートが用いられる。芳香族ポリイソシアネートの具体例としては、４，４’−ジフェニルメタンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ナフタレン−１，５−ジイソシアネート、ｏ−キシリレンジイソシアネート、ｍ−キシリレンジイソシアネート、２，４−トリレンダイマー等が挙げられる。脂肪族ポリイソシアネートの具体例としては、テトラメチ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、メチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、４，４−メチレンビス（シクロヘキシルイソシアネート）、イソホロンジイソシアネート等が挙げられる。脂環式ポリイソシアネートの具体例としては、ビシクロヘプタントリイソシアネート等が挙げられる。また、上記に列挙したイソシアネート化合物のアダクト体、ビューレット体及びイソシアヌレート体等が挙げられる。これらは二種以上を併用できる。 As said (b-1) component, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Moreover, the adduct body of the isocyanate compound enumerated above, a burette body, an isocyanurate body, etc. are mentioned. Two or more of these can be used in combination.
上記（ｂ−１）成分としては、粘着力及び剥離性を向上させる目的で、脂肪族ポリイソシアネートのイソシアヌレート体と脂肪族ポリイソシアネートのアダクト体を用いることが好ましい。例えば、ヘキサメチレンジイソシアネートの多量体（イソシアヌレート体）とヘキサメチレンジイソシアネートの多量体（アダクト体）等が挙げられ、二種以上を併用できる。 As said (b-1) component, it is preferable to use the isocyanurate body of aliphatic polyisocyanate and the adduct body of aliphatic polyisocyanate for the purpose of improving adhesive force and peelability. For example, a hexamethylene diisocyanate multimer (isocyanurate) and a hexamethylene diisocyanate multimer (adduct) can be used, and two or more can be used in combination.
上記（ｂ−２）成分としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、テトラヒドロフルフリルアクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート、４−ヒドロキシブチル（メタ）アクリレート、１０−ジエチレングリコールアクリレート、ポリエチレングリコールアクリレート、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、グリシドールジメタクリレート、２−アクリロイルオキシエチルアシッドフォスフェート、ヒドロキシプロピル化トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールテトラアクリレート、テトラメチロールメタントリアクリレート等の水酸基含有の（メタ）アクリレート化合物等が挙げられ、二種以上を併用できる。 Examples of the component (b-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl ( (Meth) acrylate, 10-diethylene glycol acrylate, polyethylene glycol acrylate, N-methylol acrylamide, N-methylol methacrylamide, glycidol dimethacrylate, 2-acryloyloxyethyl acid phosphate, hydroxypropylated trimethylolpropane triacrylate, pentaerythritol triacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, tetramethylo Methane triacrylate of the hydroxyl group-containing (meth) acrylate compounds, and the like, can be used in combination of two or more.
上記（ｂ−２）成分の中でも、剥離性を向上させる目的で、多官能アクリレート化合物を用いることが好ましい。例えば、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールテトラアクリレート等が挙げられ、二種以上を併用できる。 Among the components (b-2), it is preferable to use a polyfunctional acrylate compound for the purpose of improving peelability. Examples thereof include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, and the like, and two or more kinds can be used in combination.
上記（ｂ−２）成分の使用量は特に限定されないが、（ｂ−１）成分のイソシアネート基の合計モル数と、（ｂ−２）成分の水酸基の合計モル数との比率が通常０．１〜１程度であるのがよい。かかる範囲であると、熱硬化後の粘着層の粘着層と、紫外線照射後の粘着層の剥離性とがバランスよく発現する傾向にある。この観点より、該比率は好ましくは０．２〜０．７程度である。 Although the usage-amount of the said (b-2) component is not specifically limited, The ratio of the total mole number of the isocyanate group of (b-1) component and the total mole number of the hydroxyl group of (b-2) component is usually 0.1. It is good that it is about 1-1. Within such a range, the adhesive layer of the adhesive layer after thermosetting and the peelability of the adhesive layer after ultraviolet irradiation tend to be well-balanced. From this viewpoint, the ratio is preferably about 0.2 to 0.7.
前記（Ｂ）成分の使用量は特に限定されないが、（Ａ）成分１００部に対して通常０．１〜２０程度、好ましくは１〜１０程度となる範囲であればよい。 Although the usage-amount of the said (B) component is not specifically limited, About 0.1-20 normally with respect to 100 parts of (A) component, Preferably it should just be the range used as about 1-10.
光重合開始剤は、紫外線照射により分解しラジカルを発生するものであれば、各種公知のものを格別限定なく使用できる。例えばベンゾイン化合物、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、チタノセン化合物、チオキサントン化合物、オキシムエステル化合物等の光重合開始剤、アミンやキノン等の光増感剤等が挙げられる。具体的には、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−１−［４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］フェニル］−２−メチル−プロパン−１−オン、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン、２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウム、１，２−オクタンジオン１−［４−（フェニルチオ）−２−（ｏ−ベンゾイルオキシム）］、エタノン１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（ｏ−アセチルオキシム）等が挙げられ、二種以上を併用できる。光重合開始剤の使用量は特に限定されないが、通常、（Ａ）成分１００質量部に対して、０．１〜２０程度、好ましくは１〜１０程度となる範囲であればよい。 As the photopolymerization initiator, various known ones can be used without any particular limitation as long as they are decomposed by ultraviolet irradiation to generate radicals. Examples thereof include photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and oxime ester compounds, and photosensitizers such as amines and quinones. Specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl- Propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (dimethylamino) -2- [(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxy Id, bis (2,4,6-trimethylbenzoyl) - phenylphosphine oxide, bis (eta 5-2,4-cyclopentadiene-1-yl) - bis (2,6-difluoro-3-(1H-pyrrol - 1-yl) -phenyl) titanium, 1,2-octanedione 1- [4- (phenylthio) -2- (o-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime) and the like, and two or more kinds can be used in combination. Although the usage-amount of a photoinitiator is not specifically limited, Usually, what is necessary is just about 0.1-20 with respect to 100 mass parts of (A) component, Preferably it is the range used as about 1-10.
有機溶剤は、本発明の粘着剤組成物の希釈溶媒である。具体例としては、ブタン、ペンタン、ヘキサン、イソペンタン、ヘプタン、オクタン、イソオクタン等の脂肪族炭化水素、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式炭化水素、或いはベンゼン、トルエン、エチルベンゼン、キシレン等の芳香族炭化水素の炭化水素系溶媒、ジエチルエーテル、テトラヒドロフラン等の鎖状・環状エーテル系溶媒、クロロホルム、ジクロクジメチルメタン等のハロゲン系溶媒等が挙げられ、二種以上を併用できる。本発明においては、粘着剤組成物を溶解させる溶媒が好ましい。これらの有機溶剤の使用量は特に限定されないが、通常、（Ａ）成分１００質量部に対して、４０〜１０００質量部程度、好ましくは１００〜４００質量部程度である。 The organic solvent is a dilution solvent for the pressure-sensitive adhesive composition of the present invention. Specific examples include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane and isooctane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, or benzene, Aromatic hydrocarbon hydrocarbon solvents such as toluene, ethylbenzene and xylene, chain and cyclic ether solvents such as diethyl ether and tetrahydrofuran, halogen solvents such as chloroform and dichlorodimethylmethane, and the like. Can be used together. In the present invention, a solvent that dissolves the pressure-sensitive adhesive composition is preferable. Although the usage-amount of these organic solvents is not specifically limited, Usually, it is about 40-1000 mass parts with respect to 100 mass parts of (A) component, Preferably it is about 100-400 mass parts.
本発明の粘着剤組成物には、必要に応じて、各種公知の粘着付与樹脂を添加してもよい。粘着付与樹脂の例としては、ロジンやロジンのエステル化物等のロジン系樹脂；ジテルペン重合体やα−ピネン−フェノール共重合体等のテルペン系樹脂；脂肪族系（Ｃ５系）や芳香族系（Ｃ９系）等の石油樹脂；その他、スチレン系樹脂、フェノール系樹脂、キシレン樹脂等が挙げられ、二種以上を併用できる。該粘着付与樹脂の使用量は特に限定されないが、通常、本発明に係る粘着剤組成物の固形分（該粘着付与樹脂を除く）１００質量部に対して、０．１〜２０質量部程度である。 You may add various well-known tackifying resin to the adhesive composition of this invention as needed. Examples of tackifying resins include rosin resins such as rosin and rosin esterified products; terpene resins such as diterpene polymers and α-pinene-phenol copolymers; aliphatic (C5) and aromatic ( Petroleum resins such as C9); other examples include styrene resins, phenol resins, xylene resins, and the like, and two or more types can be used in combination. Although the usage-amount of this tackifying resin is not specifically limited, Usually, it is about 0.1-20 mass parts with respect to 100 mass parts of solid content (except this tackifying resin) of the adhesive composition which concerns on this invention. is there.
本発明の粘着剤組成物には、必要に応じて、各種公知の重合性多官能モノマーを添加してもよい。具体的には、例えば、ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート等が挙げられ、二種以上を併用できる。その使用量は特に限定されないが、通常、本発明に係る粘着剤組成物の固形分（該重合性多官能モノマーを除く）１００質量部に対して、０〜２０質量％程度である。 You may add various well-known polymerizable polyfunctional monomers to the adhesive composition of this invention as needed. Specifically, for example, hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, etc. Two or more types can be used in combination. Although the usage-amount is not specifically limited, Usually, it is about 0-20 mass% with respect to 100 mass parts of solid content (except this polymerizable polyfunctional monomer) of the adhesive composition which concerns on this invention.
本発明の粘着剤組成物には、必要に応じて、シランカップリング剤、レベリング剤、消泡剤等の添加剤を含めてよい。 The pressure-sensitive adhesive composition of the present invention may contain additives such as a silane coupling agent, a leveling agent, and an antifoaming agent as necessary.
シランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシランのビニル基を有するトリアルコキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルトリメトキシシランのアミノ基を有するトリアルコキシシラン；３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシランのグリシジル基を有するトリアルコキシシラン等が挙げられ、二種以上を併用できる。その使用量は特に限定されないが、通常、（Ａ）成分１００質量部に対して０．１〜５質量部程度である。 Examples of the silane coupling agent include vinyltrimethoxysilane, trialkoxysilane having a vinyl group of vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane. Trialkoxysilanes having amino groups of: 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane having a glycidyl group Silane etc. are mentioned and 2 or more types can be used together. Although the usage-amount is not specifically limited, Usually, it is about 0.1-5 mass parts with respect to 100 mass parts of (A) component.
レベリング剤としては、例えば、ポリエーテル変性ポリジメチルシロキサン、ポリエステル変性ポリジメチルシロキサン、アラルキル変性ポリメチルアルキルシロキサン、ポリエステル変性水酸基含有ポリジメチルシロキサン、ポリエーテルエステル変性水酸基含有ポリジメチルシロキサン、アクリル系共重合物、メタクリル系共重合物、ポリエーテル変性ポリメチルアルキルシロキサン、アクリル酸アルキルエステル共重合物、メタクリル酸アルキルエステル共重合物、レシチン等が挙げられ、二種以上を併用できる。その使用量は特に限定されないが、通常、（Ａ）成分１００質量部に対して０．０〜２質量部程度である。 Examples of leveling agents include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, and acrylic copolymers. Methacrylic copolymer, polyether-modified polymethylalkylsiloxane, acrylic acid alkyl ester copolymer, methacrylic acid alkyl ester copolymer, lecithin and the like, and two or more kinds can be used in combination. Although the usage-amount is not specifically limited, Usually, it is about 0.0-2 mass parts with respect to 100 mass parts of (A) component.
消泡剤としては、シリコーン樹脂、アルキルビニルエーテル・アクリル酸アルキルエステル・メタクリル酸アルキルエステルとの共重合物等が挙げられ、二種以上を併用できる。その使用量は特に限定されないが、通常、（Ａ）成分の固形分１００質量部に対して０．０５〜２質量部程度である。 Examples of antifoaming agents include silicone resins, copolymers of alkyl vinyl ethers, alkyl acrylates and alkyl methacrylates, and two or more types can be used in combination. Although the usage-amount is not specifically limited, Usually, it is about 0.05-2 mass parts with respect to 100 mass parts of solid content of (A) component.
添加剤には、他にも、可塑剤、表面潤滑剤、軟化剤、酸化防止剤、界面活性剤、帯電防止剤及び染料等が含まれる。 Other additives include plasticizers, surface lubricants, softeners, antioxidants, surfactants, antistatic agents, dyes, and the like.
本発明の粘着剤組成物の製造法は特に限定されず、前記主剤、硬化剤、光重合開始剤及び有機溶剤、並びに必要に応じて前記添加剤を所定の量で混合すればよい。各成分の混合方法及び添加順序は特段限定されない。 The production method of the pressure-sensitive adhesive composition of the present invention is not particularly limited, and the main agent, curing agent, photopolymerization initiator, organic solvent, and, if necessary, the additive may be mixed in a predetermined amount. The mixing method and addition order of each component are not particularly limited.
また、本発明の粘着剤組成物には、保管安定性を向上させるため、二液態様で利用できる。具体的には、前記主剤、光重合開始剤及び有機溶剤を含む主剤液と、前記硬化剤及び有機溶剤を含む硬化剤液を基材に塗布する直前で混合することができる。 In addition, the pressure-sensitive adhesive composition of the present invention can be used in a two-part form in order to improve storage stability. Specifically, the main agent liquid containing the main agent, the photopolymerization initiator and the organic solvent, and the curing agent liquid containing the curing agent and the organic solvent can be mixed immediately before being applied to the substrate.
本発明の粘着剤組成物の粘度は特に限定されないが、塗布適性等の観点より、通常、Ｅ型粘度が１００〜１００００ｍＰａ・ｓ（２５℃）程度、好ましくは３００〜３０００ｍＰａ・ｓ（２５℃）程度である。 The viscosity of the pressure-sensitive adhesive composition of the present invention is not particularly limited, but from the viewpoint of coating suitability and the like, the E-type viscosity is usually about 100 to 10,000 mPa · s (25 ° C.), preferably 300 to 3000 mPa · s (25 ° C.). Degree.
本発明の粘着剤組成物は、通常基材シート等に塗布されて粘着シートや粘着テープ等として実用に供されることが多い。かかる粘着シートや粘着テープ等を製造するには、まず本発明の粘着剤組成物を、シリコン処理等が施された基材の処理面に塗工したり、或いは直接基材に塗工して、加熱処理等により乾燥させて粘着剤層を形成させたりすることができる。粘着剤層の厚さは、用途によって様々であるが、通常は１〜２００μｍ程度、好ましくは５〜１００μｍ程度である。 The pressure-sensitive adhesive composition of the present invention is usually applied to a base sheet or the like and is practically used as a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape. In order to produce such an adhesive sheet, an adhesive tape, etc., first, the adhesive composition of the present invention is applied to the treated surface of a substrate subjected to silicon treatment or the like, or directly applied to the substrate. The pressure-sensitive adhesive layer can be formed by drying by heat treatment or the like. The thickness of the pressure-sensitive adhesive layer varies depending on the application, but is usually about 1 to 200 μm, preferably about 5 to 100 μm.
基材シートとしては、紫外線等が透過するフィルムが使用でき、例えば、ポリ塩化ビニル、ポリブテン、ポリブタジエン、ポリウレタン、エチレン−酢酸ビニル共重合体、ポリエチレンテレフタレート、ポリエチレン、ポリピロピレン、エチレン−プロピレン共重合体、ポリメチルペンテン、ポリブチレンテレフタレート等の透明フィルムが挙げられ、特に半導体ウエハのダイシング工程で、エキスパンドが必要な用途に用いる場合には、エキスパンド時の延伸性に優れるポリ塩化ビニル、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体等の透明或いは紫外線透過が可能な着色フィルムが好適に用いられる。基材の厚みは特に限定されないが、通常５０〜５００μｍ程度、好ましくは１００〜３００μｍ程度である。 As the base sheet, a film that transmits ultraviolet rays or the like can be used. For example, polyvinyl chloride, polybutene, polybutadiene, polyurethane, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyethylene, polypyropylene, ethylene-propylene copolymer, Examples include transparent films such as polymethylpentene and polybutylene terephthalate. Especially when used in applications that require expansion in the dicing process of semiconductor wafers, polyvinyl chloride, polyethylene, polypropylene, and ethylene that have excellent stretchability during expansion. -A colored film capable of being transparent or transmitting ultraviolet rays, such as a propylene copolymer and an ethylene-vinyl acetate copolymer, is preferably used. Although the thickness of a base material is not specifically limited, Usually, it is about 50-500 micrometers, Preferably it is about 100-300 micrometers.
本発明の粘着剤組成物は、特にタッチパネルの液晶部材の回収や半導体ウエハのダイシング工程の一時的接着用途での剥離を求める分野に非常に有用である。 The pressure-sensitive adhesive composition of the present invention is very useful particularly in the field of demanding the separation of the liquid crystal member of the touch panel and the temporary bonding for the semiconductor wafer dicing process.
本発明の粘着剤組成物は、熱硬化後には粘着性を奏する粘着剤を形成し、その後紫外線を照射すると粘着性を失う点に大きな特徴がある。具体的には、該粘着剤組成物の熱硬化物である粘着剤層１の粘着力をＦ１（Ｎ／２５ｍｍ）、及び該粘着剤層１に紫外線を照射して得られる粘着剤層２の粘着力をＦ２（Ｎ／２５ｍｍ）とした場合において、粘着力の低下率（Ｆ２/Ｆ１）が０．５以下であることを特徴とする。 The pressure-sensitive adhesive composition of the present invention is greatly characterized in that it forms a pressure-sensitive adhesive that exhibits adhesiveness after thermosetting and loses its adhesiveness when irradiated with ultraviolet rays thereafter. Specifically, the pressure-sensitive adhesive layer 1 that is a thermoset of the pressure-sensitive adhesive composition has an adhesive force F1 (N / 25 mm), and the pressure-sensitive adhesive layer 2 obtained by irradiating the pressure-sensitive adhesive layer 1 with ultraviolet rays. When the adhesive strength is F2 (N / 25 mm), the rate of decrease in adhesive strength (F2 / F1) is 0.5 or less.
Ｆ１は、ＪＩＳ Ｚ ０２３７による１８０度ピール強度を意味する。その値は、基材シートの種類によっても変わるが、通常５Ｎ／２５ｍｍ以上、好ましくは５〜３０Ｎ／２５ｍｍ程度である。また、Ｆ２もＪＩＳ Ｚ ０２３７による１８０度ピール強度を意味しており、その値は通常２Ｎ／２５ｍｍ以下、好ましくは０．０１〜１Ｎ／２５ｍｍ程度である。 F1 means 180 degree peel strength according to JIS Z 0237. The value varies depending on the type of the base sheet, but is usually 5 N / 25 mm or more, preferably about 5 to 30 N / 25 mm. F2 also means 180 degree peel strength according to JIS Z 0237, and the value is usually 2 N / 25 mm or less, preferably about 0.01 to 1 N / 25 mm.
粘着剤層１を得るための熱硬化の条件は特に限定されないが、通常、６０℃〜２００℃程度、０．１分〜１０分程度である。（Ａ）成分の水酸基と（Ｂ）成分のイソシアネート基を十分反応させると基材が熱による劣化を抑えるために、加熱温度は８０℃〜１５０℃程度が好ましい。また、加熱時間は、同様の観点より、０．５分〜５分程度が好ましい。 The conditions of thermosetting for obtaining the pressure-sensitive adhesive layer 1 are not particularly limited, but are usually about 60 ° C. to 200 ° C. and about 0.1 minutes to 10 minutes. When the hydroxyl group of component (A) and the isocyanate group of component (B) are sufficiently reacted, the heating temperature is preferably about 80 ° C. to 150 ° C. in order to suppress deterioration due to heat. The heating time is preferably about 0.5 to 5 minutes from the same viewpoint.
粘着剤層１の厚みは特に限定されないが、通常１〜１０００μｍ程度、好ましくは１〜１００μｍ程度である。粘着剤層１は、１０μｍ以下でも十分な粘着力を奏し、かつ紫外線照射後は優れた剥離性を示す。 Although the thickness of the adhesive layer 1 is not specifically limited, Usually, about 1-1000 micrometers, Preferably it is about 1-100 micrometers. The pressure-sensitive adhesive layer 1 exhibits a sufficient adhesive force even at 10 μm or less, and exhibits excellent peelability after irradiation with ultraviolet rays.
粘着剤層２を得るための紫外線光源としては、例えば、高圧水銀灯、超高圧水銀灯カーボンアーク灯、キセノン灯、メタルハライドランプ、ケミカルランプ、ブラックライトが用いられる。紫外線照射条件は、高圧水銀ランプの場合は５〜３０００ｍＪ／ｃｍ2 、好ましくは１００〜１０００ｍＪ／ｃｍ2 の条件で行われる。照射時間は、光源の種類、光源と塗布面との距離、塗工厚、その他の条件によっても異なるが、通常は数秒、場合によっては数分の１秒でもよい。 As the ultraviolet light source for obtaining the pressure-sensitive adhesive layer 2, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or a black light is used. Ultraviolet irradiation conditions, in the case of high-pressure mercury lamp 5~3000mJ / cm 2, preferably at the conditions of 100~1000mJ / cm 2. The irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, the coating thickness, and other conditions, but it is usually several seconds, and may be a fraction of a second in some cases.
以下に本発明を、実施例及び比較例を通じて具体的に説明するが、それらによって本発明の範囲が限定されることはない。また実施例中、「％」及び「部」は特に断りのない限り「質量％」を意味する。 Hereinafter, the present invention will be described in detail through examples and comparative examples, but the scope of the present invention is not limited thereby. In the examples, “%” and “part” mean “% by mass” unless otherwise specified.
＜（Ａ）成分の合成＞
合成例１
冷却菅と撹拌機を備える反応装置に、重量平均分子量２０００のポリカーボネートポリオール（クラレ（株）製、商品名「クラレポリオール Ｃ−２０９０」）２６７部、ジシクロヘキシルメタン４，４´−ジイソシアネート３３部、トルエン７００部及びオクチル酸スズ０．２部を加え、８０℃まで昇温して３時間保温した後、ＮＣＯ測定にて反応完結を確認し、重量平均分子量６７，０００、平均水酸基数２．０のポリウレタン（以下、（Ａ−１）成分という）のトルエン溶液を得た。
<Synthesis of component (A)>
Synthesis example 1
In a reactor equipped with a cooling tank and a stirrer, 267 parts of polycarbonate polyol having a weight average molecular weight of 2000 (Kuraray Co., Ltd., trade name “Kuraray polyol C-2090”), 33 parts of dicyclohexylmethane 4,4′-diisocyanate, toluene 700 parts and 0.2 part of tin octylate were added, heated to 80 ° C. and kept for 3 hours, and the completion of the reaction was confirmed by NCO measurement. The weight average molecular weight was 67,000 and the average number of hydroxyl groups was 2.0. A toluene solution of polyurethane (hereinafter referred to as component (A-1)) was obtained.
比較合成例１
合成例１と同様の反応装置に、重量平均分子量４，０００の水素添加ポリブタジエンポリオール（日本曹達（株）製、商品名「ＮＩＳＳＯ−ＰＢ ＧＩ−３０００」）３７７部、ジシクロヘキシルメタン４，４´−ジイソシアネート２３部、希釈溶剤トルエン６００部及びオクチル酸スズ０．３部を加え、８０℃まで昇温して３時間保温した後、ＮＣＯ測定にて反応完結を確認することにより、重量平均分子量６８，０００、平均水酸基数２．０のポリウレタン（以下、（Ａ−２）成分という）のトルエン溶液を得た。
Comparative Synthesis Example 1
In the same reactor as in Synthesis Example 1, 377 parts of a hydrogenated polybutadiene polyol having a weight average molecular weight of 4,000 (manufactured by Nippon Soda Co., Ltd., trade name “NISSO-PB GI-3000”), dicyclohexylmethane 4,4′- After adding 23 parts of diisocyanate, 600 parts of diluting solvent toluene and 0.3 part of tin octylate, raising the temperature to 80 ° C. and keeping it warm for 3 hours, confirming the completion of the reaction by NCO measurement, the weight average molecular weight 68, 000 and a toluene solution of polyurethane having an average number of hydroxyl groups of 2.0 (hereinafter referred to as component (A-2)).
比較合成例２
合成例１と同様の反応装置に、重量平均分子量２，０００のポリエステルポリオール（ダイセル（株）製、商品名「ＰＬＡＣＣＥＬ−Ｌ２２０ＡＬ）２６７部、ジシクロヘキシルメタン４，４´−ジイソシアネート３３部、希釈溶剤トルエン７００部及びオクチル酸スズ０．２部を加え、８０℃まで昇温して３時間保温した後、ＮＣＯ測定にて反応完結を確認することにより、重量平均分子量７４，０００、平均水酸基数２．０のポリウレタン（以下、（Ａ−３）成分という）のトルエン溶液を得た。
Comparative Synthesis Example 2
In the same reactor as in Synthesis Example 1, 267 parts of a polyester polyol having a weight average molecular weight of 2,000 (manufactured by Daicel Corp., trade name “PLACCEL-L220AL), 33 parts of dicyclohexylmethane 4,4′-diisocyanate, and toluene as a diluent solvent 700 parts and 0.2 parts of tin octylate were added, heated to 80 ° C. and kept for 3 hours, and then the completion of the reaction was confirmed by NCO measurement, whereby a weight average molecular weight of 74,000 and an average number of hydroxyl groups of 2. A toluene solution of 0 polyurethane (hereinafter referred to as component (A-3)) was obtained.
比較合成例３
窒素置換可能な４ツ口フラスコに、アクリル酸ブチルエステル９５部、２−ヒドロキシエチルメタクリレート５部、酢酸エチル１３０部を仕込み窒素置換下で６３℃まで昇温し、開始剤ＡＩＢＮを０．０７５部投入、重合を開始し、重合開始４時間後に開始剤ＡＩＢＮを０．１５部追加投入しさらに４時間重合を行う。重合後酢酸エチルを４７０部投入し、重量平均分子量１３０万のアクリル系ポリマー（根上工業（株）製、商品名「パラクロンＫＡＲ−８」、以下、（Ａ−４）成分という）の酢酸エチル溶液を得た。
Comparative Synthesis Example 3
A 4-necked flask capable of nitrogen substitution was charged with 95 parts of butyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, and 130 parts of ethyl acetate. The temperature was raised to 63 ° C. under nitrogen substitution, and 0.075 part of initiator AIBN was added. Charge and polymerization are started, and after 4 hours from the start of polymerization, 0.15 part of initiator AIBN is added and polymerization is performed for another 4 hours. After polymerization, 470 parts of ethyl acetate was added and an ethyl acetate solution of an acrylic polymer having a weight average molecular weight of 1.3 million (manufactured by Negami Kogyo Co., Ltd., trade name “Paraklon KAR-8”, hereinafter referred to as component (A-4)) Got.
＜（Ｂ）成分の合成＞
合成例２
冷却菅と撹拌機がついた反応装置に、ＮＣＯ含有率２１．９％のヘキサメチレンジイソシアネートの３量体（イソシアヌレート体）（日本ポリウレタン社製、商品名「コロネートＨＸＲ」、以下（Ｂ−７）成分という）５０部、ペンタエリスリトールトリアクリレート（東亞合成（株）製、商品名「アロニックスＭ３０６」、水酸基価１５５ｍｇＫＯＨ／ｇ）３１部、トルエン３５部、重合禁止剤である４−メトキシフェノール０．０３部及びフェノチアジン０．０４部、並びにオクチル酸スズ０．０４部を加え、８０℃まで昇温して１時間保温した後、ＮＣＯ測定にて反応完結を確認することにより（理論ＮＣＯ価より低い場合は反応終了）、イソシアネート基とアクリロイル基の両反応基を持つアクリル変性ポリイソシアネート（以下、（Ｂ−１）成分という）のトルエン溶液を得た。
<Synthesis of component (B)>
Synthesis example 2
In a reactor equipped with a cooling tank and a stirrer, a trimer of hexamethylene diisocyanate having an NCO content of 21.9% (isocyanurate) (trade name “Coronate HXR” manufactured by Nippon Polyurethane Co., Ltd., below (B-7) ) Component) 50 parts, pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M306”, hydroxyl value 155 mg KOH / g) 31 parts, toluene 35 parts, 4-methoxyphenol as a polymerization inhibitor 03 parts, 0.04 part of phenothiazine and 0.04 part of tin octylate were added, and after heating to 80 ° C. and keeping the temperature for 1 hour, the completion of the reaction was confirmed by NCO measurement (lower than the theoretical NCO value) In the case, the reaction is completed), an acrylic-modified polyisocyanate having both reactive groups of isocyanate group and acryloyl group (hereinafter, B-1) was obtained a toluene solution of that component).
合成例３
合成例２と同様の反応装置に、ＮＣＯ含有率２１．９％のヘキサメチレンジイソシアネートの３量体（イソシアヌレート体）（日本ポリウレタン社製、商品名「コロネートＨＸＲ」）５０部、ペンタエリスリトールトリアクリレート（東亞合成（株）製、商品名「アロニックスＭ３０６」、水酸基価１５５ｍｇＫＯＨ／ｇ）４７部、トルエン４２部、重合禁止剤である４−メトキシフェノール０．０４部及びフェノチアジン０．０５部、並びにオクチル酸スズ０．０４部を加え、８０℃まで昇温して１時間保温した後、ＮＣＯ測定にて反応完結を確認することにより（理論ＮＣＯ価より低い場合は反応終了）、イソシアネート基とアクリロイル基の両反応基を持つアクリル変性ポリイソシアネート（以下、（Ｂ−２）成分という）のトルエン溶液を得た。
Synthesis example 3
In the same reactor as in Synthesis Example 2, 50 parts of hexamethylene diisocyanate trimer (isocyanurate) (product name “Coronate HXR” manufactured by Nippon Polyurethane Co., Ltd.) having an NCO content of 21.9%, pentaerythritol triacrylate (Toagosei Co., Ltd., trade name “Aronix M306”, hydroxyl value 155 mg KOH / g) 47 parts, toluene 42 parts, polymerization inhibitor 4-methoxyphenol 0.04 part and phenothiazine 0.05 part, and octyl Add 0.04 part of tin oxide, heat up to 80 ° C. and incubate for 1 hour, and confirm the completion of the reaction by NCO measurement (when the reaction is lower than the theoretical NCO value), isocyanate group and acryloyl group Toluene of acrylic modified polyisocyanate having both reactive groups (hereinafter referred to as component (B-2)) To obtain a liquid.
合成例３
合成例１と同様の反応装置に、ＮＣＯ含有率８．９％のヘキサメチレンジイソシアネートのアダクト体（旭化成社製、商品名「デュラネートＥ−４０２」）５０部、ペンタエリスリトールトリアクリレート（東亞合成（株）製、商品名「アロニックスＭ３０６」、水酸基価１５５ｍｇＫＯＨ／ｇ）１３部、トルエン２７部、重合禁止剤である４−メトキシフェノール０．０３部及びフェノチアジン０．０４部、並びにオクチル酸スズ０．０３部を加え、８０℃まで昇温して１時間保温した後、ＮＣＯ測定にて反応完結を確認することにより（理論ＮＣＯ価より低い場合は反応終了）、イソシアネート基とアクリロイル基の両反応基を持つアクリル変性ポリイソシアネート（以下、（Ｂ−３）成分という）のトルエン溶液を得た。
Synthesis example 3
In the same reactor as in Synthesis Example 1, 50 parts of hexamethylene diisocyanate adduct having a NCO content of 8.9% (product name “Duranate E-402” manufactured by Asahi Kasei Co., Ltd.), pentaerythritol triacrylate (Toagosei Co., Ltd.) ), Trade name “Aronix M306”, hydroxyl value 155 mg KOH / g) 13 parts, 27 parts of toluene, 0.03 part of 4-methoxyphenol and 0.04 part of phenothiazine as polymerization inhibitors, and 0.03 of tin octylate After the temperature was raised to 80 ° C. and kept warm for 1 hour, the reaction completion was confirmed by NCO measurement (when the reaction was lower than the theoretical NCO value, the reaction was completed), and both reactive groups of isocyanate group and acryloyl group were obtained. A toluene solution of acrylic modified polyisocyanate having (hereinafter referred to as (B-3) component) was obtained.
合成例４
合成例１と同様の反応装置に、ＮＣＯ含有率２１．９％のヘキサメチレンジイソシアネートの３量体（イソシアヌレート体）（日本ポリウレタン社製、商品名「コロネートＨＸＲ」）５０部、ジペンタエリスリトールテトラアクリレート（東亞合成（株）製、商品名「アロニックスＭ４０３」、水酸基価９２ｍｇＫＯＨ／ｇ）１４３部、トルエン３２２部、重合禁止剤である４−メトキシフェノール０．０８部及びフェノチアジン０．１２部、並びにオクチル酸スズ０．０８部を加え、８０℃まで昇温して１時間保温した後、ＮＣＯ測定にて反応完結を確認することにより（理論ＮＣＯ価より低い場合は反応終了）、イソシアネート基とアクリロイル基の両反応基を持つアクリル変性ポリイソシアネート（以下、（Ｂ−４）成分という）のトルエン溶液を得た。
Synthesis example 4
In the same reactor as in Synthesis Example 1, 50 parts of hexamethylene diisocyanate trimer (isocyanurate) (product name “Coronate HXR” manufactured by Nippon Polyurethane Co., Ltd.) with an NCO content of 21.9%, dipentaerythritol tetra Acrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M403”, hydroxyl value 92 mg KOH / g) 143 parts, toluene 322 parts, polymerization inhibitor 4-methoxyphenol 0.08 parts and phenothiazine 0.12 parts, and Add 0.08 parts of tin octylate, heat up to 80 ° C. and incubate for 1 hour, and confirm the completion of the reaction by NCO measurement (when the reaction is lower than the theoretical NCO value, the reaction is completed), isocyanate group and acryloyl Of acrylic modified polyisocyanate having both reactive groups (hereinafter referred to as component (B-4)) It was obtained ene solution.
合成例５
合成例１と同様の反応装置に、ＮＣＯ含有率２１．９％のヘキサメチレンジイソシアネートの３量体（イソシアヌレート体）（日本ポリウレタン社製、商品名「コロネートＨＸＲ」）５０部、２−ヒドロキシエチルアクリレート（大阪有機（株）製、商品名「ＨＥＡ」）１５部、トルエン２８部、重合禁止剤である４−メトキシフェノール０．０３部及びフェノチアジン０．０５部、並びにオクチル酸スズ０．０３部を加え、８０℃まで昇温して１時間保温した後、ＮＣＯ測定にて反応完結を確認することにより（理論ＮＣＯ価より低い場合は反応終了）、イソシアネート基とアクリロイル基の両反応基を持つアクリル変性ポリイソシアネート（以下、（Ｂ−５）成分という）のトルエン溶液を得た。
Synthesis example 5
In the same reactor as in Synthesis Example 1, 50 parts of hexamethylene diisocyanate trimer (isocyanurate) (trade name “Coronate HXR” manufactured by Nippon Polyurethane Co., Ltd.) having an NCO content of 21.9%, 2-hydroxyethyl 15 parts of acrylate (Osaka Organic Co., Ltd., trade name “HEA”), 28 parts of toluene, 0.03 part of 4-methoxyphenol and 0.05 part of phenothiazine as a polymerization inhibitor, and 0.03 part of tin octylate After heating up to 80 ° C. and keeping the temperature for 1 hour, by confirming the completion of the reaction by NCO measurement (when the reaction is lower than the theoretical NCO value, the reaction is completed), both the isocyanate group and the acryloyl group are present. A toluene solution of acrylic-modified polyisocyanate (hereinafter referred to as component (B-5)) was obtained.
比較合成例１
合成例１と同様の反応装置に、ＮＣＯ含有率２１．９％のヘキサメチレンジイソシアネートの３量体（イソシアヌレート体）（日本ポリウレタン社製、商品名「コロネート ＨＸＲ」）５０部、ペンタエリスリトールトリアクリレート（東亞合成（株）製、商品名「アロニックス Ｍ３０６」、水酸基価１５５ｍｇＫＯＨ／ｇ）９４部、希釈溶剤トルエン６２部、重合禁止剤である４−メトキシフェノール０．０５部及びフェノチアジン０．０８部、並びにオクチル酸スズ０．０５部を加え、８０℃まで昇温して１時間保温した後、ＮＣＯ測定にて反応完結を確認することにより（理論ＮＣＯ価より低い場合は反応終了）、（Ｂ−１）成分のＮＣＯ基と（Ｂ−２）成分の水酸基を完全に反応し、ＮＣＯ基が残らない多官能アクリレート化合物（以下、（Ｂ−６）成分という）のトルエン溶液を得た。
Comparative Synthesis Example 1
In the same reactor as in Synthesis Example 1, 50 parts of hexamethylene diisocyanate trimer (isocyanurate) (trade name “Coronate HXR” manufactured by Nippon Polyurethane Co., Ltd.) with an NCO content of 21.9%, pentaerythritol triacrylate (Manufactured by Toagosei Co., Ltd., trade name “Aronix M306”, hydroxyl value 155 mg KOH / g) 94 parts, diluent solvent toluene 62 parts, polymerization inhibitor 4-methoxyphenol 0.05 parts and phenothiazine 0.08 parts, In addition, 0.05 part of tin octylate was added, the temperature was raised to 80 ° C. and kept for 1 hour, and then the completion of the reaction was confirmed by NCO measurement (when the reaction was lower than the theoretical NCO value, the reaction was completed), (B− 1) A polyfunctional acrylate compound in which the NCO group of the component and the hydroxyl group of the component (B-2) are completely reacted to leave no NCO group ( Lower, to obtain a toluene solution of that (B-6) component).
＜粘着剤組成物の調製＞
実施例１
（Ａ−１）成分１００部、（Ｂ−１）成分４部、（Ｃ）成分として１−ヒドロキシ−シクロヘキシルフェニルケトン（ＢＡＳＦ社製、商品名「ＩＲＧＡＣＵＲＥ １８４」、以下（Ｃ）成分という）５部、希釈溶剤（Ｄ）成分として、トルエン（以下（Ｄ−１）成分という）２５４部を、いずれも純分換算で配合し、粘着剤組成物を調製した（表１参照）。
<Preparation of pressure-sensitive adhesive composition>
Example 1
(A-1) component 100 parts, (B-1) component 4 parts, (C) component 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF, trade name “IRGACURE 184”, hereinafter referred to as component (C)) 5 As a diluent solvent (D) component, 254 parts of toluene (hereinafter referred to as component (D-1)) were blended in terms of pure matter to prepare an adhesive composition (see Table 1).
実施例２
実施例１において、（Ｂ−１）成分を（Ｂ−２）成分に変更した以外は同様にして、粘着剤組成物を調製した。
Example 2
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the component (B-1) was changed to the component (B-2).
実施例３
実施例２において、（Ｂ−２）成分を６部に変更し、かつ（Ｄ−１）成分を２５９部に変更した以外は同様にして、粘着剤組成物を調製した。
Example 3
In Example 2, a pressure-sensitive adhesive composition was prepared in the same manner except that the component (B-2) was changed to 6 parts and the component (D-1) was changed to 259 parts.
実施例４
実施例３において、（Ｂ−２）成分を（Ｂ−３）成分に変更した以外は同様にして、粘着剤組成物を調製した。
Example 4
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 3, except that the component (B-2) was changed to the component (B-3).
実施例５
実施例１において、（Ｂ−１）成分を（Ｂ−４）成分に変更した以外は同様にして、粘着剤組成物を調製した。
Example 5
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the component (B-1) was changed to the component (B-4).
実施例６
実施例１において、（Ｂ−１）成分を（Ｂ−５）成分に変更した以外は同様にして、粘着剤組成物を調製した。
Example 6
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the component (B-1) was changed to the component (B-5).
比較例１
実施例１において、（Ｃ）成分を配合しなかった以外は同様にして粘着剤組成物を調製した。
Comparative Example 1
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the component (C) was not blended.
比較例２
実施例２において、（Ｂ−１）成分を（Ｂ−６）成分に変更した以外は同様にして、粘着剤組成物を調製した。
Comparative Example 2
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 2, except that the component (B-1) was changed to the component (B-6).
比較例３
実施例１において、（Ｂ−１）成分を（Ｂ−７）成分を１部に、（Ｃ）成分を５部に、（Ｄ−１）成分を２４７部にした以外は同様にして、粘着剤組成物を調製した。
Comparative Example 3
In Example 1, the same applies except that the component (B-1) was changed to 1 part of the component (B-7), the component (C) was changed to 5 parts, and the component (D-1) was changed to 247 parts. An agent composition was prepared.
比較例４
比較例３において、（Ｄ−１）成分を２５４部に変更し、かつ、トリメチロールプロパントリアクリレート（大阪有機（株）社製、商品名（ビスコート#２９５）以下（Ｅ）成分という）を３部加えた以外は同様にして、粘着剤組成物を調製した。
Comparative Example 4
In Comparative Example 3, the component (D-1) was changed to 254 parts, and trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name (Biscoat # 295) or less, referred to as component (E)) was 3 A pressure-sensitive adhesive composition was prepared in the same manner except that parts were added.
比較例５
実施例２において、（Ａ−１）成分を（Ａ−２）成分に変更した以外は同様にして、粘着剤組成物を調製した。
Comparative Example 5
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 2, except that the component (A-1) was changed to the component (A-2).
比較例６
実施例２において、（Ａ−１）成分を（Ａ−３）成分に変更した以外は同様にして、粘着剤組成物を調製した。
Comparative Example 6
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 2, except that the component (A-1) was changed to the component (A-3).
比較例７
実施例１において、（Ａ−１）成分を（Ａ−４）成分に変更し、かつ（Ｄ−１）成分を酢酸エチル（（Ｄ−２）成分）９８１部に変更した以外同様にして、粘着剤組成物を調製した。
Comparative Example 7
In Example 1, the same procedure was performed except that the component (A-1) was changed to the component (A-4) and the component (D-1) was changed to 981 parts of ethyl acetate (component (D-2)). A pressure-sensitive adhesive composition was prepared.
（Ｂ−７）：ヘキサメチレンジイソシアネートの多量体（イソシアヌレート体）
（日本ポリウレタン社製、商品名「コロネートＨＸＲ」）
（Ｄ−２）：酢酸エチル
（Ｅ）：トリメチロールプロパントリアクリレート（大阪有機（株）社製、商品名（ビスコート＃２９５））
(B-7): Hexamethylene diisocyanate multimer (isocyanurate)
(Product name “Coronate HXR” manufactured by Nippon Polyurethanes)
(D-2): Ethyl acetate (E): Trimethylolpropane triacrylate (manufactured by Osaka Organic Chemicals Co., Ltd., trade name (Biscoat # 295))
各実施例及び比較例の粘着剤組成物の粘度、固形分及び相溶性を以下の基準で評価した（表２）。 The viscosity, solid content, and compatibility of the pressure-sensitive adhesive compositions of each Example and Comparative Example were evaluated according to the following criteria (Table 2).
＜固形分質量＞
実施例１に係る粘着剤組成物のサンプル１ｇを金属軟膏缶に入れ、１０５℃３時間で乾燥させた後の質量を％で表示した。
<Mass of solid content>
1 g of the pressure-sensitive adhesive composition sample according to Example 1 was put in a metal ointment can and dried at 105 ° C. for 3 hours.
＜粘度＞
実施例１に係る粘着剤組成物のＥ型粘度を、市販の粘度計（製品名ＴＶＥ−１０、東機産業（株）製））を用い、２５℃及び５分の条件で測定した。
<Viscosity>
The E-type viscosity of the pressure-sensitive adhesive composition according to Example 1 was measured using a commercially available viscometer (product name TVE-10, manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. for 5 minutes.
＜相溶性＞
実施例１に係る粘着剤組成物の相溶性を以下の基準で目視評価した。
○：均一であり完全に透明である
△：微白濁ではあるが、沈降物、不溶解物もしくは液層分離はない
×：白濁、沈降物、不溶解物もしくは液層分離のいずれかが確認できる
<Compatibility>
The compatibility of the pressure-sensitive adhesive composition according to Example 1 was visually evaluated based on the following criteria.
○: Uniform and completely transparent Δ: Slightly cloudy but no precipitate, insoluble matter or liquid layer separation ×: Any of white turbidity, sediment, insoluble matter or liquid layer separation can be confirmed
＜粘着剤層及び積層体の作製＞
実施例１に係る粘着剤組成物を、コンマコーターで、１００μｍ厚の処理ポリエステルフィルム（東洋紡（株）製、商品名「コスモシャインＡ−４１００」）上に、５μｍの膜厚になるよう塗布し、順風乾燥機の中で１３０℃及び３分の条件で乾燥させることにより、熱硬化させた。次いで、この硬化塗膜面と３８μｍ厚の軽剥離処理ポリエステルフィルム（パナック（株）製、商品名「ＳＰ−ＰＥＴ−０１−３８ＢＵ」）を剥離処理面が接するよう貼り合わせることにより、ＰＥＴ／粘着剤層／剥離ＰＥＴのサンプルを作製した。他の実施例及び比較例に係る粘着剤組成物についても同様にしてサンプルを作製した。
［粘着剤層についての各種試験］
<Preparation of pressure-sensitive adhesive layer and laminate>
The pressure-sensitive adhesive composition according to Example 1 was applied on a treated polyester film (trade name “COSMO SHINE A-4100”, manufactured by Toyobo Co., Ltd.) having a thickness of 5 μm with a comma coater. Then, it was thermally cured by drying at 130 ° C. for 3 minutes in a smooth air dryer. Next, this cured coating film surface and a 38 μm-thick lightly release-treated polyester film (manufactured by Panac Corporation, trade name “SP-PET-01-38BU”) are bonded together so that the release-treated surface comes into contact with each other. An agent layer / exfoliated PET sample was prepared. Samples were similarly prepared for the pressure-sensitive adhesive compositions according to other examples and comparative examples.
[Various tests on the adhesive layer]
＜熱硬化後の粘着力Ｆ１の測定？＞
実施例１に係るサンプルから前記ポリエステルフィルムを剥離し、ガラス片（２ｍｍ厚、２５ｍｍ×１５ｍｍ）を、２ｋｇローラーで貼り合わせることによって、１００μｍＰＥＴ／粘着剤１層（５μｍ）／ガラス試験片からなるサンプルを作製した。次いで当該サンプルを２５℃及び５０％ＲＨの条件下で２４時間放置した後、ＰＥＴを１８０°方向に３００ｍｍ／ｍｉｎの速度で剥離させることにより、粘着力（Ｆ１）（Ｎ／２５ｍｍ）を測定した。なお、測定には市販の機器（製品名テンシロン万能材料試験機、ＡＮＤ株式会社製）を使用した。
<Measurement of adhesive strength F1 after thermosetting? >
Sample made of 100 μm PET / adhesive 1 layer (5 μm) / glass test piece by peeling the polyester film from the sample according to Example 1 and bonding glass pieces (2 mm thickness, 25 mm × 15 mm) with a 2 kg roller. Was made. Next, the sample was allowed to stand for 24 hours under conditions of 25 ° C. and 50% RH, and then the adhesive strength (F1) (N / 25 mm) was measured by peeling PET in the 180 ° direction at a speed of 300 mm / min. . For the measurement, a commercially available device (product name: Tensilon Universal Material Testing Machine, manufactured by AND Corporation) was used.
＜紫外線照射後の粘着力Ｆ２の測定＞
実施例１に係る、ＰＥＴ剥離後のサンプルの粘着剤層に、前記ガラス片を、２ｋｇローラーで貼り合わせることによって、１００μｍＰＥＴ／粘着剤１層（５μｍ）／ガラス試験片からなるサンプルを作製した。次いで当該サンプルを２５℃及び５０％ＲＨの条件下で２４時間放置した後、１２０ｗ/ｃｍの高圧水銀ランプ（岩崎電気株式会社製）を用いて、１００μｍＰＥＴ側から、９００ｍＪ/ｃｍ２の紫外線を照射し、１００μｍＰＥＴ／粘着剤２層（５μｍ）／ガラス試験片からなるサンプルを作製した。次いで当該サンプルを２５℃及び５０％ＲＨの条件下で２４時間放置した後、当該硬化粘着剤層に、ＰＥＴを１８０°方向に３００ｍｍ／ｍｉｎの速度で剥離させることにより、粘着力（Ｆ２）（Ｎ／２５ｍｍ）を、同一の機器を用いて測定した。次いで、粘着率の低下率（Ｆ２／Ｆ１）を算出したところ、０．３３であった。
<Measurement of adhesive strength F2 after UV irradiation>
A sample composed of 100 μm PET / adhesive 1 layer (5 μm) / glass test piece was prepared by pasting the glass piece on the adhesive layer of the sample after PET peeling according to Example 1 with a 2 kg roller. The sample was then allowed to stand for 24 hours at 25 ° C. and 50% RH, and then irradiated with 900 mJ / cm 2 of UV light from the 100 μm PET side using a 120 w / cm high-pressure mercury lamp (Iwasaki Electric Co., Ltd.). Then, a sample made of 100 μm PET / adhesive layer 2 (5 μm) / glass test piece was prepared. Next, the sample was allowed to stand at 25 ° C. and 50% RH for 24 hours, and then the cured adhesive layer was made to peel PET in the 180 ° direction at a speed of 300 mm / min, thereby causing an adhesive force (F2) ( N / 25 mm) was measured using the same instrument. Subsequently, when the rate of decrease in the adhesion rate (F2 / F1) was calculated, it was 0.33.
＜剥離性評価試験＞
Ｆ２測定後、ガラス表面に糊残りの状況を以下の基準で目視評価した。
○：ガラス表面に糊残りが全くない
△：ガラス表面に僅かに糊残り
×：ガラス表面全面糊残り
他の実施例及び比較例の粘着剤組成物についてもＦ１及びＦ２を測定し、剥離性を評価した。
<Peelability evaluation test>
After the F2 measurement, the state of adhesive residue on the glass surface was visually evaluated according to the following criteria.
○: There is no adhesive residue on the glass surface. Δ: Slight adhesive residue on the glass surface. ×: Adhesive residue on the entire glass surface. F1 and F2 were also measured for the adhesive compositions of other examples and comparative examples, and the peelability was determined. evaluated.
Claims (4)
前記主剤は、ポリカーボネートポリオール（а−１）及び脂肪族ポリイソシアネート（а−２）の反応物としての末端水酸基含有ポリウレタン（Ａ）であり、
前記硬化剤は、多官能ポリイソシアネート（ｂ−１）及び水酸基含有（メタ）アクリレート化合物（ｂ−２）の反応物であって、分子内にイソシアネート基と（メタ）アクリロイル基を併有する（メタ）アクリル変性ポリイソシアネート（Ｂ）であることを特徴とする、
粘着剤組成物。 A pressure-sensitive adhesive composition comprising a main agent, a curing agent, a photopolymerization initiator and an organic solvent,
The main agent is a terminal hydroxyl group-containing polyurethane (A) as a reaction product of polycarbonate polyol (а-1) and aliphatic polyisocyanate (а-2),
The curing agent is a reaction product of a polyfunctional polyisocyanate (b-1) and a hydroxyl group-containing (meth) acrylate compound (b-2), and has both an isocyanate group and a (meth) acryloyl group in the molecule (meta ) Acrylic modified polyisocyanate (B),
Adhesive composition.
該粘着剤組成物の熱硬化物である粘着剤層１の粘着力をＦ１（Ｎ／２５ｍｍ）、及び該粘着剤層１に紫外線を照射して得られる粘着剤層２の粘着力をＦ２（Ｎ／２５ｍｍ）とした場合において、粘着力の低下率（Ｆ２/Ｆ１）が０．５以下であることを特徴とする、
粘着剤組成物。
The pressure-sensitive adhesive composition according to any one of claims 1 to 3,
The pressure-sensitive adhesive strength of the pressure-sensitive adhesive composition 1 is F1 (N / 25 mm), and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer 2 obtained by irradiating the pressure-sensitive adhesive layer 1 with ultraviolet rays is F2 ( N / 25 mm), the rate of decrease in adhesive strength (F2 / F1) is 0.5 or less,
Adhesive composition.
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