JP5712706B2 - Adhesive, adhesive sheet and display - Google Patents
Adhesive, adhesive sheet and display Download PDFInfo
- Publication number
- JP5712706B2 JP5712706B2 JP2011056983A JP2011056983A JP5712706B2 JP 5712706 B2 JP5712706 B2 JP 5712706B2 JP 2011056983 A JP2011056983 A JP 2011056983A JP 2011056983 A JP2011056983 A JP 2011056983A JP 5712706 B2 JP5712706 B2 JP 5712706B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- monomer
- sensitive adhesive
- weight
- meth
- 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.)
- Active
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- 230000001070 adhesive effect Effects 0.000 title claims description 45
- 239000000853 adhesive Substances 0.000 title claims description 44
- 239000000178 monomer Substances 0.000 claims description 90
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 80
- 239000005056 polyisocyanate Substances 0.000 claims description 37
- 229920001228 polyisocyanate Polymers 0.000 claims description 37
- 229920001577 copolymer Polymers 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 239000010408 film Substances 0.000 description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- -1 alkoxyalkyl acrylate Chemical compound 0.000 description 31
- 239000010410 layer Substances 0.000 description 28
- 239000002390 adhesive tape Substances 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 230000002087 whitening effect Effects 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229920000515 polycarbonate Polymers 0.000 description 11
- 239000004417 polycarbonate Substances 0.000 description 11
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 8
- 238000005187 foaming Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- UFXYYTWJETZVHG-UHFFFAOYSA-N 1,3-diisocyanatobutane Chemical compound O=C=NC(C)CCN=C=O UFXYYTWJETZVHG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-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
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 1
- ROYRUMBLNWJMGV-UHFFFAOYSA-N 10-trimethoxysilyldecane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCCCCCCCS ROYRUMBLNWJMGV-UHFFFAOYSA-N 0.000 description 1
- LHNAURKRXGPVDW-UHFFFAOYSA-N 2,3-diisocyanatobutane Chemical compound O=C=NC(C)C(C)N=C=O LHNAURKRXGPVDW-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
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- IFUWIYGOBMUJSU-UHFFFAOYSA-N 2-phenyl-3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CC(CS)C1=CC=CC=C1 IFUWIYGOBMUJSU-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- YFISHOAHNLGUEL-UHFFFAOYSA-N 3-tributoxysilylpropyl prop-2-enoate Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCOC(=O)C=C YFISHOAHNLGUEL-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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
- PPISUJHKYIZSRI-UHFFFAOYSA-N 6-trimethoxysilylhexane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCCCS PPISUJHKYIZSRI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 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
- IIMISJTWARSKOJ-UHFFFAOYSA-N dec-9-enyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCCCCCC=C IIMISJTWARSKOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- CGQIJXYITMTOBI-UHFFFAOYSA-N hex-5-enyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCC=C CGQIJXYITMTOBI-UHFFFAOYSA-N 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 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
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- YPQKTLPPOXNDMC-UHFFFAOYSA-N isocyanic acid;methylcyclohexane Chemical compound N=C=O.CC1CCCCC1 YPQKTLPPOXNDMC-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Position Input By Displaying (AREA)
Description
本発明は、透明導電膜を備えたディスプレイに好適に用いることができる透明導電膜用粘着剤に関する。 The present invention relates to a pressure-sensitive adhesive for a transparent conductive film that can be suitably used for a display having a transparent conductive film.
近年のエレクトロニクスの飛躍的な進歩により、液晶ディスプレイ（ＬＣＤ）、プラズ
マディスプレイ（ＰＤＰ）、リアプロジェクションディスプレイ（ＲＰＪ）、ＥＬディス
プレイ、発光ダイオ−ドディスプレイなどの様々なフラットパネルディスプレイ（ＦＰＤ
）が、表示装置として広く使用されようになってきた。このような表示装置には、通常、
外部光源からの反射を防ぐための反射防止フィルムや、表示装置の表面の傷付き防止のた
めの保護フィルム（プロテクトフィルム）など、用途に応じて様々なフィルムが使用され
ており、例えば、ＬＣＤを構成する液晶セル用部材においては、偏光フィルムや位相差フ
ィルムが積層されている。また、ＦＰＤは、表示装置として利用するだけではなく、その
表面にタッチパネルの機能を設けて、入力装置として利用されることもある。タッチパネ
ルにも、保護フィルム、反射防止フィルムやＩＴＯ蒸着樹脂フィルムなどが使用されてい
る。このようなフィルムは、粘着剤（感圧式接着剤）を介して被着体に貼着して積層させ
ることにより表示装置に使用されている。これらの用途において、粘着剤には、粘着性、
透明性に加え、高温環境や高温高湿環境下等で発泡や剥がれおよび白化を生じない性質（耐発泡・剥がれ性、耐湿熱白化性）、金属薄膜（金属酸化物薄膜を含む）を腐食させない性質（耐腐食性）などの優れた信頼性が求められる。
Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal displays (LCD), plasma displays (PDP), rear projection displays (RPJ), EL displays, light emitting diode displays, etc.
) Has been widely used as a display device. Such display devices typically include
Various films are used depending on the application, such as an antireflection film to prevent reflection from an external light source and a protective film (protection film) to prevent the surface of the display device from being scratched. In the liquid crystal cell member to be configured, a polarizing film and a retardation film are laminated. Further, the FPD is not only used as a display device, but may be used as an input device by providing a touch panel function on the surface thereof. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel. Such a film is used in a display device by being attached to an adherend via an adhesive (pressure-sensitive adhesive) and laminated. In these applications, the adhesive is adhesive,
In addition to transparency, it does not corrode metal thin films (including metal oxide thin films), properties that do not cause foaming, peeling, and whitening under high temperature and high temperature / humidity environments. Excellent reliability such as properties (corrosion resistance) is required.
従来これに対して、高温・高湿環境下での耐発泡・剥がれ性を改良する手法としては、
ホモポリマーのガラス転移温度（Ｔｇ）の高いモノマー（高Ｔｇモノマー）やカルボキシ
ル基などの官能基を含有するモノマーを共重合する手法や、高Ｔｇのオリゴマー（低分子
量ポリマー）を添加するなどの手法が知られている。また、耐腐食性能を付与するために
カルボキシル基以外の架橋可能な官能性アクリレートおよびアルコキシアルキルアクリレ
ートを共重合する手法が知られている。
On the other hand, as a technique to improve foam resistance and peeling resistance under high temperature and high humidity environment,
Techniques such as copolymerization of homopolymer monomers with high glass transition temperature (Tg) (high Tg monomers) and monomers containing functional groups such as carboxyl groups, and addition of high Tg oligomers (low molecular weight polymers) It has been known. In addition, a technique is known in which a crosslinkable functional acrylate other than a carboxyl group and an alkoxyalkyl acrylate are copolymerized in order to impart corrosion resistance.
例えば、（メタ）アクリル酸アルコキシアルキルエステルを主成分とし、これにカルボ
キシル基含有モノマーを共重合させて得られる粘着性ポリマー１００重量部と、メタクリ
ル酸アルキルエステル、メタクリル酸シクロアルキルエステル、メタクリル酸ベンジルま
たはスチレンから選ばれる１種または２種以上のモノマーを主成分とし、これにアミノ基
又はアミド基含有モノマーを共重合させて得られる低分子量ポリマー５〜４０重量部及び
架橋剤０．００１〜２．０重量部を含有する粘着剤組成物及びそれを用いた粘着シートが
知られている（特許文献１参照）。
For example, 100 parts by weight of a sticky polymer obtained by copolymerizing an alkoxyalkyl ester of (meth) acrylic acid and a carboxyl group-containing monomer thereto, an alkyl methacrylate, a cycloalkyl methacrylate, a benzyl methacrylate Alternatively, 5 to 40 parts by weight of a low molecular weight polymer obtained by copolymerizing one or more monomers selected from styrene as a main component and an amino group or amide group-containing monomer, and a crosslinking agent 0.001 to 2 A pressure-sensitive adhesive composition containing 0.0 part by weight and a pressure-sensitive adhesive sheet using the same are known (see Patent Document 1).
また、カルボキシル基含有モノマーを構成成分とし、かつ実質的に水酸基含有モノマー
が含まれないアクリル系共重合体と、ベンゾトリアゾールやその誘導体とを特定重量比で混合してなる粘着剤組成物と、 前記アクリル系共重合体中のカルボキシル基Ｘと反応し得る官能基Ｚを有するエポキシ架橋剤とを、特定重量比で配合して架橋して得られる粘着剤を用いた金属貼着用粘着シートが知られている（特許文献２参照）。
Further, an adhesive composition comprising a carboxyl group-containing monomer as a constituent component, and an acrylic copolymer substantially free of a hydroxyl group-containing monomer and benzotriazole or a derivative thereof mixed at a specific weight ratio, There is known a pressure-sensitive adhesive sheet for metal sticking using a pressure-sensitive adhesive obtained by blending and crosslinking an epoxy crosslinking agent having a functional group Z capable of reacting with a carboxyl group X in the acrylic copolymer at a specific weight ratio. (See Patent Document 2).
さらに、アルコキシアルキルアクリレート（成分Ａ）及び架橋可能な官能基を有するア
クリル系モノマー（成分Ｂ）を必須の単量体成分として構成される重量平均分子量４０万
〜１６０万のアクリル系ポリマーおよび架橋剤を含む粘着剤組成物であって、アクリル系
ポリマーを構成する全モノマー成分１００重量部に対する成分Ａの含有量が４５〜９９．
５重量部、成分Ｂの含有量が０．５〜４．５重量部であり、アクリル系ポリマーを構成す
るモノマー成分中にカルボキシル基含有モノマーを実質的に含まない粘着剤組成物が知ら
れている（特許文献３参照）。
Furthermore, an acrylic polymer having a weight average molecular weight of 400,000 to 1,600,000 and a crosslinking agent comprising an alkoxyalkyl acrylate (component A) and an acrylic monomer having a crosslinkable functional group (component B) as essential monomer components The content of component A is 45 to 99. with respect to 100 parts by weight of all monomer components constituting the acrylic polymer.
A pressure-sensitive adhesive composition containing 5 parts by weight and containing 0.5 to 4.5 parts by weight of component B and substantially free of carboxyl group-containing monomers in the monomer component constituting the acrylic polymer is known. (See Patent Document 3).
しかし、Ｔｇを高くした粘着剤では、回路などの段差を埋め込む性能が劣るという問題
を有していた。またカルボキシル基含有モノマーを必須としている粘着剤では、透明導電膜、特に金属薄膜（金属酸化物薄膜を含む）に貼付した際の耐腐食性が不十分である等の問題を有していた。カルボキシル基以外の架橋可能な官能性アクリレートおよびアルコキシアルキルアクリレートを共重合した粘着剤では、湿熱白化が十分抑えられないという問題を有していた。すなわち、塗工性、透明性、耐発泡・剥がれ性に優れ、なおかつ耐腐食性能、粘着性能に優れさらに回路などの段差を埋め込む性能にも優れた粘着剤が強く望まれていた。
However, the pressure-sensitive adhesive having a high Tg has a problem that the performance of embedding a step such as a circuit is inferior. In addition, the pressure sensitive adhesive in which the carboxyl group-containing monomer is essential has problems such as insufficient corrosion resistance when applied to a transparent conductive film, particularly a metal thin film (including a metal oxide thin film). The pressure-sensitive adhesive obtained by copolymerizing a crosslinkable functional acrylate other than a carboxyl group and an alkoxyalkyl acrylate has a problem that wet heat whitening cannot be sufficiently suppressed. That is, there has been a strong demand for an adhesive that has excellent coating properties, transparency, foam resistance / peeling resistance, and excellent corrosion resistance and adhesive performance, as well as excellent performance for embedding steps such as circuits.
本発明は、塗工性、透明性、耐発泡・剥がれ性に優れ、なおかつ耐腐食性能、粘着性能に優れさらに回路などの段差を埋め込む性能にも優れた透明導電膜用粘着剤を提供することを目的とする。さらに、透明導電膜用粘着剤を用いた粘着シートおよびタッチパネル等のディスプレイを提供することを目的とする。 The present invention provides a pressure-sensitive adhesive for a transparent conductive film, which is excellent in coating property, transparency, foam resistance / peeling resistance, excellent in corrosion resistance performance, adhesive performance, and in performance of embedding steps such as circuits. With the goal. Furthermore, it aims at providing displays, such as an adhesive sheet and a touch panel using the adhesive for transparent conductive films.
本発明者らは、上記課題を解決するために鋭意検討した結果、カルボキシル基含有単量体を用いずに、少なくとも、イソシアネート基との反応可能な官能基を有する単量体と、アミノ基を含有する単量体と、アミド結合を含有する単量体とを共重合した共重合体と、
ポリイソシアネート系硬化剤とを含む粘着剤により上記課題を解決するに至った。
As a result of intensive studies to solve the above problems, the present inventors have found that at least a monomer having a functional group capable of reacting with an isocyanate group and an amino group, without using a carboxyl group-containing monomer. A copolymer obtained by copolymerizing a monomer containing and a monomer containing an amide bond;
The pressure-sensitive adhesive containing the polyisocyanate curing agent has led to the solution of the above problems.
すなわち、本発明は、共重合体（Ｘ）と、ポリイソシアネート系硬化剤（Ｙ）とを含む透明導電膜用粘着剤であって、
前記共重合体（Ｘ）が、少なくとも、カルボキシル基以外のイソシアネート基と反応可能な官能基を含有する単量体（Ａ）０．１〜１０重量％と、アミノ基を含有する単量体（Ｂ）０．１〜１０重量％と、アミド結合を含有する単量体（Ｃ）１〜５０重量％とを含む単量体を共重合してなることを特徴とする透明導電膜用粘着剤に関する。
That is, the present invention is a transparent conductive film pressure-sensitive adhesive containing a copolymer (X) and a polyisocyanate curing agent (Y),
The copolymer (X) contains at least 0.1 to 10% by weight of a monomer (A) containing a functional group capable of reacting with an isocyanate group other than a carboxyl group, and a monomer containing an amino group ( B) A pressure-sensitive adhesive for transparent conductive films obtained by copolymerizing a monomer containing 0.1 to 10% by weight and a monomer (C) containing 1 to 50% by weight containing an amide bond About.
また、前記ポリイソシアネート系硬化剤（Ｙ）は、芳香脂肪族系ポリイソシアネート、脂肪族系ポリイソシアネートおよび脂環族ポリイソシアネートからなる群より選択される１種以上の化合物、またはこれらの化合物の変性体であることが好ましい。 The polyisocyanate curing agent (Y) is one or more compounds selected from the group consisting of araliphatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates, or modifications of these compounds. It is preferable that it is a body.
また、本発明の透明導電膜用粘着剤は、基材等へ塗工して粘着剤層を有する粘着シートとして使用することが好ましい。 Moreover, it is preferable that the adhesive for transparent conductive films of this invention is applied to a base material etc. and used as an adhesive sheet which has an adhesive layer.
また、前記粘着シートはディスプレイに使用することが好ましい。 Moreover, it is preferable to use the said adhesive sheet for a display.
本発明の粘着剤は、塗工性、透明性、耐発泡・剥がれ性、耐湿熱白化性、段差埋め込み
性に優れ、また適度な粘着力を有している。そのため、これらの特性を備えた粘着シート
を提供でき、ディスプレイなどの光学部材の接着に好適に用いることができる。また、透明導電膜、特に金属薄膜（金属酸化物薄膜を含む）に貼付した際の耐腐食性に優れることから、ＩＴＯ（インジウム・スズ）フィルムなどの金属薄膜フィルムに回路形成された部分にも直接貼付できる。また、段差を埋め込む性能に優れるため、タッチパネルなどの回路の段差や加飾による段差のある部材の接着にも用いることができる。
The pressure-sensitive adhesive of the present invention is excellent in coating property, transparency, foaming / peeling resistance, wet heat whitening resistance, step embedding property, and has an appropriate pressure-sensitive adhesive force. Therefore, a pressure-sensitive adhesive sheet having these characteristics can be provided, and can be suitably used for bonding an optical member such as a display. In addition, since it has excellent corrosion resistance when applied to transparent conductive films, especially metal thin films (including metal oxide thin films), it is also applied to portions where circuits are formed on metal thin films such as ITO (indium tin) films. Can be attached directly. Moreover, since it is excellent in the performance of embedding a step, it can be used for bonding a step of a circuit such as a touch panel or a member having a step by decoration.
なお、本発明において耐湿熱白化性とは、加熱加湿後に粘着シートの粘着剤層が白く変色し難いことである。 In the present invention, the term “moisture and heat whitening resistance” means that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet does not easily turn white after heating and humidification.
まず、本発明を実施するための形態を挙げてさらに詳しく説明する。 First, the embodiment for carrying out the present invention will be described in further detail.
本発明の透明導電膜用粘着剤は、少なくとも、カルボキシル基以外のイソシアネート基と反応可能な官能基を含有する単量体（Ａ）［以下、単に単量体（Ａ）と記述することがある］０．１〜１０重量％と、アミノ基を含有する単量体（Ｂ）［以下、単に単量体（Ｂ）と記述することがある］０．１〜１０重量％と、アミド結合を含有する単量体（Ｃ）［以下、単に単量体（Ｃ）と記述することがある］１〜５０重量％とを含む単量体を共重合してなる共重合体（Ｘ）と、ポリイソシアネート系硬化剤（Ｙ）とを含むことが重要である。 The pressure-sensitive adhesive for transparent conductive film of the present invention contains at least a monomer (A) containing a functional group capable of reacting with an isocyanate group other than a carboxyl group [hereinafter sometimes simply referred to as a monomer (A). ] 0.1 to 10% by weight and an amino group-containing monomer (B) [hereinafter sometimes simply referred to as monomer (B)] 0.1 to 10% by weight and an amide bond A copolymer (X) obtained by copolymerizing a monomer containing 1 to 50% by weight of the monomer (C) [hereinafter sometimes simply referred to as the monomer (C)], It is important to contain a polyisocyanate curing agent (Y).
なお、本発明において単量体（Ａ）は、単量体（Ｂ）および単量体（Ｃ）以外の単量体である。また、単量体（Ｂ）は、単量体（Ａ）および単量体（Ｃ）以外の単量体である。また、単量体（Ｃ）は、単量体（Ａ）および単量体（Ａ）以外の単量体である。 In the present invention, the monomer (A) is a monomer other than the monomer (B) and the monomer (C). The monomer (B) is a monomer other than the monomer (A) and the monomer (C). The monomer (C) is a monomer other than the monomer (A) and the monomer (A).
本発明において共重合体（Ｘ）は、単量体を溶液重合、乳化重合、懸濁重合、または塊状重合等で共重合できるが、透明性や粘着性の観点から溶液重合が好ましい。また、共重合体（Ｘ）の重量平均分子量は、粘着性能のバランスの観点から２０万〜１５０万が好ましい。また、共重合体（Ｘ）のガラス転移温度は、タックと凝集力の観点から−４０〜３０℃が好ましい。 In the present invention, the copolymer (X) can be copolymerized with monomers by solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization or the like, but solution polymerization is preferable from the viewpoint of transparency and adhesiveness. In addition, the weight average molecular weight of the copolymer (X) is preferably 200,000 to 1,500,000 from the viewpoint of the balance of adhesive performance. The glass transition temperature of the copolymer (X) is preferably -40 to 30 ° C from the viewpoint of tack and cohesive strength.
一般的にタッチパネル等のディスプレイには、透明導電膜の周辺部に銀ペースト等で形成した数十μｍの段差の導電回路を有する場合が多い。そして、本発明の透明導電膜用粘着剤を用いた粘着テープをその導電回路に貼り付けた場合、共重合体（Ｘ）とポリイソシアネート系硬化剤（Ｙ）との組み合わせの効果により、段差の角等に気泡が残存しない優れた段差埋め込み性を実現できる。ここで、透明導電膜とはＩＴＯ（インジウム・スズ）フィルムなどの金属薄膜フィルム、ポリチオフェンやポリアニリン等の導電性高分子薄膜などが挙げられる。なお、本発明において段差埋め込み性は、４０℃〜５０℃程度の低温熱ラミネートでの段差埋め込み性を意味するものであり、プリント配線板の技術分野で実施されている、ドライフィルム状の接着シートを８０℃〜２００℃程度で配線回路上へラミネートすることで段差を埋め込む、高温熱ラミネートとは区別すべきものである。 In general, a display such as a touch panel often has a conductive circuit with a step of several tens of μm formed with a silver paste or the like around a transparent conductive film. And when the adhesive tape using the adhesive for transparent conductive films of this invention is affixed on the conductive circuit, the effect of the combination of the copolymer (X) and the polyisocyanate curing agent (Y) An excellent step embedding property in which bubbles do not remain at corners or the like can be realized. Here, examples of the transparent conductive film include a metal thin film such as an ITO (indium tin) film, and a conductive polymer thin film such as polythiophene and polyaniline. In the present invention, the step embedding property means the step embedding property in a low-temperature thermal laminate of about 40 ° C. to 50 ° C., and is a dry film-like adhesive sheet implemented in the technical field of printed wiring boards. It should be distinguished from high temperature thermal lamination, in which a step is embedded by laminating a film on a wiring circuit at about 80 ° C. to 200 ° C.
本発明において単量体に、アミド結合を含有する単量体（Ｃ）を用いることが重要である。単量体（Ｃ）は、分子内にアミド結合を有するため水分に対する親和性が高い。そのため単量体（Ｃ）を用いた共重合体（Ｘ）は、水分に対する親和性が高い。そして、共重合体（Ｘ）を含む粘着剤は、粘着テープの粘着剤層として用いることが好ましい。次に、その粘着シートをガラスへ貼り付けた後、高温高湿環境下へ放置した場合、一般的に水分が粘着剤層に浸入する傾向にある。しかし当該粘着剤層は、水分に対する親和性の高いアミド基を有する共重合体（Ｘ）を含むため、水分と共重合体（Ｘ）の親和性が良好である。そのため、透明な粘着剤層は白色に変化せずに透明を維持することができる。本願では粘着剤層へあえて水分を浸入させているということができる。一方、単量体（Ｃ）を用いない共重合体を含む粘着剤層は、水分に対する親和性が劣るため、粘着テープをガラスへ貼り付けた後に高温高湿環境下へ放置したとき、粘着剤層へ浸入した水分は共重合体と親和せず、微粒子状になることで透明な粘着剤層が、白色に変化すると考えられる。 In the present invention, it is important to use a monomer (C) containing an amide bond as the monomer. Since the monomer (C) has an amide bond in the molecule, it has a high affinity for moisture. Therefore, the copolymer (X) using the monomer (C) has a high affinity for moisture. And it is preferable to use the adhesive containing copolymer (X) as an adhesive layer of an adhesive tape. Next, when the pressure-sensitive adhesive sheet is attached to glass and then left in a high-temperature and high-humidity environment, moisture generally tends to enter the pressure-sensitive adhesive layer. However, since the said adhesive layer contains the copolymer (X) which has an amide group with high affinity with respect to a water | moisture content, the affinity of a water | moisture content and a copolymer (X) is favorable. Therefore, the transparent pressure-sensitive adhesive layer can maintain transparency without changing to white. In the present application, it can be said that moisture is intruded into the adhesive layer. On the other hand, since the pressure-sensitive adhesive layer containing the copolymer not using the monomer (C) has poor affinity for moisture, when the pressure-sensitive adhesive tape is attached to glass and left in a high-temperature and high-humidity environment, the pressure-sensitive adhesive layer Moisture that has penetrated into the layer does not have an affinity for the copolymer, and it is considered that the transparent pressure-sensitive adhesive layer turns white by forming fine particles.
本発明において単量体（Ｃ）を用いた共重合体を含む粘着テープは、アミド結合の存在により、高温高湿環境下においても、粘着力の低下が少なく、粘着剤層に気泡の発生が少なく、粘着テープが被着体から浮きや剥離が発生しにくい特徴を有する（以下、耐湿熱性ということがある）。 In the present invention, the pressure-sensitive adhesive tape containing the copolymer using the monomer (C) has little decrease in adhesive force even in a high-temperature and high-humidity environment due to the presence of an amide bond, and bubbles are generated in the pressure-sensitive adhesive layer. The adhesive tape has a characteristic that the adhesive tape hardly floats or peels off from the adherend (hereinafter sometimes referred to as “moisture and heat resistance”).
アミド結合を含有する単量体（Ｃ）としては、例えば（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニルピロリドンなどが挙げられる。単量体（Ｃ）は単独で使用してもよく、２種類以上併用してもよい。 Examples of the monomer (C) containing an amide bond include (meth) acrylamide, N-methylolacrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, N-vinylacetamide, and N-vinyl. Examples include pyrrolidone. A monomer (C) may be used independently and may be used together 2 or more types.
単量体（Ｃ）は、全単量体１００重量％中、１〜５０重量％であることが重要であり、１０〜４０重量％が好ましい。単量体（Ｃ）が１重量％に満たない場合、高温高湿環境下へ放置したとき、粘着剤層は白色に変色しやすい傾向にある。また、単量体（Ｃ）が５０重量％を超えると粘着力の低下が大きく、粘着テープが被着体から浮きや剥がれが発生しやすい傾向にある。 It is important that the monomer (C) is 1 to 50% by weight in 100% by weight of all monomers, and 10 to 40% by weight is preferable. When the monomer (C) is less than 1% by weight, the pressure-sensitive adhesive layer tends to turn white when left in a high temperature and high humidity environment. On the other hand, when the monomer (C) exceeds 50% by weight, the adhesive force is greatly reduced, and the adhesive tape tends to easily float or peel off from the adherend.
本発明において単量体（Ａ）は、カルボキシル基以外の、イソシアネート基との反応可能な官能基を有する単量体であることが重要である。共重合体（Ｘ）がカルボキシル基を有すると、共重合体（Ｘ）含む粘着剤を粘着テープに用いた場合、その粘着テープを透明導電膜に貼り付けたときに透明導電膜が腐食する恐れがある。そのため、単量体（Ａ）の官能基は、たとえば、ヒドロキシル基などが好ましい。In the present invention, it is important that the monomer (A) is a monomer having a functional group capable of reacting with an isocyanate group other than a carboxyl group. If the copolymer (X) has a carboxyl group, when the adhesive containing the copolymer (X) is used for an adhesive tape, the transparent conductive film may corrode when the adhesive tape is attached to the transparent conductive film. There is. Therefore, the functional groups of the monomer (A) is, for example, human Dorokishiru group.
ヒドロキシル基を含有する単量体としては、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、８−ヒドロキシオクチル（メタ）アクリレート、１０−ヒドロキシデシル（メタ）アクリレート、１２−ヒドロキシラウリル（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート類、ビニルアルコール、アリルアルコールなどが挙げられる。 Examples of the monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, Examples include caprolactone-modified (meth) acrylates, vinyl alcohol, and allyl alcohol.
単量体（Ａ）は、全単量体１００重量％中、０．１〜１０重量％であることが重要である。そして、０．３〜４重量％がより好ましく、０．５〜２重量％がさらに好ましい。単量体（Ａ）が０．１重量％に満たない場合、ポリイソシアネート系硬化剤（Ｙ）との間の架橋反応が不十分となり、高温高湿環境下へ放置したとき、粘着剤層に気泡が発生や、粘着剤層の凝集力不足による粘着テープの浮きや剥がれが生じやすい傾向にある。一方、１０重量％を超えると架橋反応が過剰になることで粘着力が不足し、粘着テープが被着体から浮きや剥がれが生じやすい傾向にある。単量体（Ａ）は単独で使用してもよく、２種類以上を併用してもよい。 It is important that the monomer (A) is 0.1 to 10% by weight in 100% by weight of all monomers. And 0.3 to 4 weight% is more preferable, and 0.5 to 2 weight% is further more preferable. When the monomer (A) is less than 0.1% by weight, the crosslinking reaction with the polyisocyanate curing agent (Y) becomes insufficient, and when left in a high temperature and high humidity environment, There is a tendency that bubbles are generated and the pressure-sensitive adhesive tape is easily lifted or peeled off due to insufficient cohesive strength of the pressure-sensitive adhesive layer. On the other hand, if it exceeds 10% by weight, the cross-linking reaction becomes excessive, resulting in insufficient adhesive strength, and the adhesive tape tends to be lifted or peeled off from the adherend. A monomer (A) may be used independently and may use 2 or more types together.
本発明において単量体に、アミノ基を含有する単量体（Ｂ）を用いることが重要である。共重合体（Ｘ）がアミノ基を有することで、当該共重合体を含む粘着剤を粘着テープに用いた場合、その粘着テープをポリカーボネートに貼り付けたときに、ポリカーボネートから発生する気泡（いわゆるアウトガス）を抑制することができる。なお、本発明のように共重合体（Ｘ）にアミノ基が組み込まれている以外に、粘着剤にアミノ基を含有する化合物を別途添加した場合、臭気の問題や前記アウトガス抑制効果が得にくい問題がある。 In the present invention, it is important to use a monomer (B) containing an amino group as the monomer. When copolymer (X) has an amino group, when a pressure-sensitive adhesive containing the copolymer is used for the pressure-sensitive adhesive tape, bubbles generated from the polycarbonate when the pressure-sensitive adhesive tape is attached to the polycarbonate (so-called outgassing) ) Can be suppressed. In addition to the case where an amino group is incorporated in the copolymer (X) as in the present invention, when a compound containing an amino group is separately added to the pressure-sensitive adhesive, it is difficult to obtain an odor problem and the outgas suppression effect. There's a problem.
アミノ基を含有する単量体（B）としては、例えばアミノメチル（メタ）アクリレート、ジメチルアミノメチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等が挙げられる。 Examples of the monomer (B) containing an amino group include aminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate.
単量体（B）は全単量体１００重量％中、０．１〜１０重量％であることが重要である。そして、０．２〜５重量％がより好ましい。単量体（B）が０．１重量％に満たない場合、ポリカーボネートから発生する気泡を抑制しにくい傾向にある。一方、１０重量％を越えると、粘着剤層が黄色に変色する傾向にある。 It is important that the monomer (B) is 0.1 to 10% by weight in 100% by weight of all monomers. And 0.2 to 5 weight% is more preferable. When the monomer (B) is less than 0.1% by weight, it tends to be difficult to suppress bubbles generated from the polycarbonate. On the other hand, when it exceeds 10% by weight, the pressure-sensitive adhesive layer tends to turn yellow.
本発明において単量体（Ａ）、単量体（Ｂ）および単量体（Ｃ）以外に用いることができる他の単量体としては、（メタ）アクリル酸アルキルエステル、アルキレンオキサイド含有単量体等が挙げられる。そして、粘着性能の面からカルボキシル基を有する単量体を用いないことが好ましい。
（メタ）アクリル酸アルキルエステルは、アルキル鎖の炭素数が１〜１４が好ましく、炭素数が４〜１４がより好ましい。具体的には、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、ｎ−トリデシル（メタ）アクリレート、ｎ−テトラデシル（メタ）アクリレート、さらにはシクロヘキシル（メタ）アクリレートなどの（メタ）アクリル酸環状アルキルエステルなどを挙げることができる。
Other monomers that can be used in addition to the monomer (A), monomer (B) and monomer (C) in the present invention include (meth) acrylic acid alkyl ester, alkylene oxide-containing monomer Examples include the body. And it is preferable not to use the monomer which has a carboxyl group from the surface of adhesive performance.
In the (meth) acrylic acid alkyl ester, the alkyl chain preferably has 1 to 14 carbon atoms, and more preferably 4 to 14 carbon atoms. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl ( Examples include (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and (meth) acrylic acid cyclic alkyl esters such as cyclohexyl (meth) acrylate.
アルキレンオキサイド含有単量体としては、例えばメトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート等を挙げることができる。 Examples of the alkylene oxide-containing monomer include methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, phenoxypolyethyleneglycol (meth) acrylate, and methoxypolypropyleneglycol (meth) acrylate.
また、スチレン、酢酸ビニルなどのビニル系単量体を使用することもできる。 Also, vinyl monomers such as styrene and vinyl acetate can be used.
本発明において単量体（Ａ）、単量体（Ｂ）、および単量体（Ｃ）以外に用いることができる他の単量体としては、アルキレンオキサイド含有単量体を使用することが好ましい。アルキレンオキサイド含有単量体は、1〜４５重量％使用することが好ましい。アルキレンオキサイドを有することにより粘着テープを被着体へ貼り付け高温雰囲気においた場合でも、粘着性を維持しつつ気泡の発生や、被着体からの剥がれをより抑制できる。 In the present invention, it is preferable to use an alkylene oxide-containing monomer as another monomer that can be used in addition to the monomer (A), the monomer (B), and the monomer (C). . The alkylene oxide-containing monomer is preferably used in an amount of 1 to 45% by weight. By having an alkylene oxide, even when the adhesive tape is attached to the adherend and placed in a high temperature atmosphere, the generation of bubbles and the peeling from the adherend can be further suppressed while maintaining the adhesiveness.
本発明において前記他の単量体を使用する場合は、全単量体１００重量％中、４０〜９８．９重量％であることが好ましい。 When using the said other monomer in this invention, it is preferable that it is 40-98.9 weight% in 100 weight% of all monomers.
本発明においてポリイソシアネート系硬化剤（Ｙ）は、公知のポリイソシアネート硬化剤を使用することができる。具体的には、芳香族系ポリイソシアネート、脂肪族系ポリイソシアネート、芳香脂肪族系ポリイソシアネート、脂環族系ポリイソシアネート等が挙げられる。 In the present invention, a known polyisocyanate curing agent can be used as the polyisocyanate curing agent (Y). Specific examples include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.
芳香族系ポリイソシアネートとしては、例えば１，３−フェニレンジイソシアネート、４，４’−ジフェニルジイソシアネート、１，４−フェニレンジイソシアネート、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、４，４’−トルイジンジイソシアネート、ジアニシジンジイソシアネート、４，４’−ジフェニルエーテルジイソシアネート等を挙げることができる。 Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate and the like.
脂肪族系ポリイソシアネートとしては、例えばトリ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、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２−プロピレンジイソシアネート、２，３−ブチレンジイソシアネート、１，３−ブチレンジイソシアネート、ドデカメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート等を挙げることができる。 Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like can be mentioned.
芳香脂肪族系ポリイソシアネートとしては、例えばω，ω’−ジイソシアネート−１，３−ジメチルベンゼン、ω，ω’−ジイソシアネート−１，４−ジメチルベンゼン、ω，ω‘−ジイソシアネート−１，４−ジエチルベンゼン、１，４−テトラメチルキシリレンジイソシアネート、１，３−テトラメチルキシリレンジイソシアネート、キシリレンジイソシアネート等を挙げることができる。 Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, xylylene diisocyanate and the like.
脂環族系ポリイソシアネートとしては、例えば３−イソシアネートメチル−３，５，５−トリメチルシクロヘキシルイソシアネート、１，３−シクロペンタンジイソシアネート、１，３−シクロヘキサンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチル−２，４−シクロヘキサンジイソシアネート、メチル−２，６−シクロヘキサ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）、１，４−ビス（イソシアネートメチル）シクロヘキサン等を挙げることができる。 Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2. , 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.
さらには、ポリフェニルメタンポリイソシアネート（ＰＡＰＩ）、ナフチレンジイソシ
アネート、及びこれらのポリイソシアネート変性物等を使用し得る。またポリイソシアネ
ート変性物としては、カルボジイミド基、ウレトジオン基、ウレトイミン基、水と反応し
たビュレット基、イソシアヌレート基のうちのいずれかの基、またはこれらの基の２種以
上を有する変性物を使用できる。そして、ポリオールとジイソシアネートとの反応生成物
もポリイソシアネートとして使用することができる。
Furthermore, polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and polyisocyanate modified products thereof can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group selected from isocyanurate groups, or a modified product having two or more of these groups can be used. . And the reaction product of a polyol and diisocyanate can also be used as polyisocyanate.
また、本発明においてポリイソシアネート系硬化剤（Ｙ）は、上記ポリイソシアネートの変性体を使用することも好ましい。当該変性体とは、上記ポリイソシアネートのビュレット体、アロハネート体、ヌレート体、トリメチロールプロパンアダクト体等が挙げられる。当該変性体は、３個〜６個程度のイソシアネート基を含有することが好ましく、ポットライフ等を考慮すると３個が好ましい。 In the present invention, it is also preferable to use a modified polyisocyanate as the polyisocyanate curing agent (Y). Examples of the modified body include a burette body, an allohanate body, a nurate body, and a trimethylolpropane adduct body of the polyisocyanate. The modified body preferably contains about 3 to 6 isocyanate groups, and 3 is preferable in consideration of pot life and the like.
本発明においてポリイソシアネート系硬化剤（Ｙ）は、粘着テープの高温環境下の耐熱性の観点、あるいは高温高湿環境下へ放置したときの粘着剤層の白色への変色を抑制する観点から芳香脂肪族系ポリイソシアネート、脂肪族系ポリイソシアネートおよび脂環族ポリイソシアネートからなる群より選択される１種以上の化合物、またはこれらの化合物の変性体であることが好ましい。具体的にはキシリレンジイソシアネートのトリメチロールプロパンアダクト体、ヘキサメチレンジイソシアネートのビュレット体、ヘキサメチレンジイソシアネートのヌレート体が好ましい。芳香族系ポリイソシアネートは、耐湿熱白化性が低下する恐れがある。 In the present invention, the polyisocyanate-based curing agent (Y) is a fragrance from the viewpoint of heat resistance of the pressure-sensitive adhesive tape in a high temperature environment, or from suppressing the discoloration of the pressure-sensitive adhesive layer to white when left in a high temperature and high humidity environment. One or more compounds selected from the group consisting of aliphatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates, or modified products of these compounds are preferred. Specifically, xylylene diisocyanate trimethylolpropane adduct, hexamethylene diisocyanate burette, and hexamethylene diisocyanate nurate are preferred. Aromatic polyisocyanates may have reduced heat and heat whitening resistance.
本発明においてポリイソシアネート系硬化剤（Ｙ）は、共重合体（Ｘ）１００重量部に対して０．０１〜５重量部用いることが好ましく、０．０５〜３重量部用いることがより好ましく、０．１〜３重量部用いることがさらに好ましい。 In the present invention, the polyisocyanate curing agent (Y) is preferably used in an amount of 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the copolymer (X). It is more preferable to use 0.1 to 3 parts by weight.
本発明において硬化剤は、本発明の効果を損なわない範囲において多官能エポキシ化合物を併用することもできる。多官能エポキシ化合物を併用することで、粘着剤層の耐熱性をより向上させることができる。多官能エポキシ化合物は、例えば、エチレングリコールジ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、１，６−ヘキサンジオールジグリシジルエーテル、ビスフェノールＡ・エピクロロヒドリン型エポキシ樹脂、Ｎ，Ｎ，Ｎ’Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、１，３−ビス（Ｎ，Ｎ−ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ−ジグリシジルアニリン、Ｎ，Ｎ−ジグリシジルトルイジン等が挙げられる。 In the present invention, the curing agent may be used in combination with a polyfunctional epoxy compound as long as the effects of the present invention are not impaired. By using a polyfunctional epoxy compound in combination, the heat resistance of the pressure-sensitive adhesive layer can be further improved. Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, N, N, N′N′— Examples include tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, and the like.
本発明において多官能エポキシ化合物は、共重合体１００重量部に対して０．１〜５重量部用いることが好ましい。 In the present invention, the polyfunctional epoxy compound is preferably used in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the copolymer.
本発明の透明導電膜用粘着剤は、シランカップリング剤を含むことが好ましい。シランカップリング剤を用いることで粘着剤層と被着体との密着性が良好となり、耐熱性、耐湿熱性を向上させることができる。さらに耐湿熱白化性、ポリカーボネート板へ貼り付け後のガス膨れ性および段差埋め込み性の物性をより向上できる。この目的で使用する場合、シランカップリング剤は、共重合体（Ｘ）１００重量部に対して、０．００１〜０．１重量部の範囲が好ましく、特に０．００５〜５重量部の範囲が好ましい。 It is preferable that the adhesive for transparent conductive films of this invention contains a silane coupling agent. By using a silane coupling agent, the adhesiveness between the pressure-sensitive adhesive layer and the adherend is improved, and heat resistance and heat-and-moisture resistance can be improved. Furthermore, the physical properties of heat-and-moisture whitening resistance, gas swellability after being attached to a polycarbonate plate, and step embedding properties can be further improved. When used for this purpose, the silane coupling agent is preferably in the range of 0.001 to 0.1 parts by weight, particularly in the range of 0.005 to 5 parts by weight, based on 100 parts by weight of the copolymer (X). Is preferred.
前記シランカップリング剤は、具体的には、例えば、γ−（メタ）アクリロキシメチルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリブトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシランなどの（メタ）アクリロキシ基を有するアルコキシシラン化合物；
ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシランなどのビニル基を有するアルコキシシラン化合物；
５−ヘキセニルトリメトキシシラン、９−デセニルトリメトキシシラン、スチリルトリメトキシシランなどのアルコキシシラン化合物；
γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシランなどのアミノアルキル基を有するアルコキシシラン化合物；
γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン、β−メルカプトメチルフェニルエチルトリメトキシシラン、メルカプトメチルトリメトキシシラン、６−メルカプトヘキシルトリメトキシシラン、１０−メルカプトデシルトリメトキシシランなどのメルカプト基を有するアルコキシシラン化合物；
テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどのテトラアルコキシシラン化合物；
３−グリシドキシプロピ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、３−グリシドキシプロピルメチルジメトキシシラン、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、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン、フェニルトリメトキシシラン、ヘキサメチルシラザン、ジフェニルジメトキシシラン、１，３，５−トリス（３−トリメトキシシリルプロピル）イソシアヌレート、ビニルトリス（２−メトキシエトキシ）シラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、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、３−イソシアネートプロピルトリエトキシシランなどが挙げられる。前記シランカップリング剤の中でも、３−グリシドキシプロピルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、が好ましい。
Specific examples of the silane coupling agent include γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, alkoxysilane compounds having a (meth) acryloxy group, such as γ- (meth) acryloxypropyltributoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane;
Alkoxysilane compounds having a vinyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane;
Alkoxysilane compounds such as 5-hexenyltrimethoxysilane, 9-decenyltrimethoxysilane, and styryltrimethoxysilane;
alkoxysilane compounds having an aminoalkyl group such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane;
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6 An alkoxysilane compound having a mercapto group, such as mercaptohexyltrimethoxysilane, 10-mercaptodecyltrimethoxysilane;
Tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane;
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, phenyltrimethoxysilane, hexamethylsilazane, diphenyldimethoxysilane, 1,3,5-tris (3-tri Methoxysilylpropyl) isocyanurate, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Such as 3-isocyanate propyl triethoxysilane and the like. Among the silane coupling agents, 3-glycidoxypropyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane are preferable.
本発明の透明導電膜用粘着剤には、上記共重合体（Ｘ）およびポリイソシアネート系硬化剤（Y）に加えて必要に応じて、他の樹脂、例えばアクリル樹脂、ポリエステル樹脂、アミノ樹脂、エポキシ樹脂、ポリウレタン樹脂を併用することもできる。また、用途に応じて、カップリング剤、粘着付与剤、タルク、炭酸カルシウム、酸化チタン等の充填剤、着色剤、軟化剤、紫外線吸収剤、酸化防止剤、消泡剤、光安定剤、耐候安定剤、硬化促進剤、硬化遅延剤、リン酸エステル等の添加剤を配合しても良い。 In addition to the copolymer (X) and the polyisocyanate curing agent (Y), the pressure-sensitive adhesive for transparent conductive film of the present invention, if necessary, other resins such as acrylic resin, polyester resin, amino resin, An epoxy resin and a polyurethane resin can be used in combination. Depending on the application, coupling agents, tackifiers, talc, calcium carbonate, titanium oxide and other fillers, colorants, softeners, UV absorbers, antioxidants, antifoaming agents, light stabilizers, weather resistance You may mix | blend additives, such as a stabilizer, a hardening accelerator, a hardening retarder, and phosphate ester.
本発明の粘着シートは、透明導電膜用粘着剤から形成してなる粘着剤層を含むことが重要である。粘着シートは、剥離ライナー上、または基材上へ粘着剤を塗工することによって得ることができる。 It is important that the pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive for transparent conductive films. The pressure-sensitive adhesive sheet can be obtained by applying a pressure-sensitive adhesive on a release liner or a substrate.
また、本発明の粘着シートは、基材の片面に粘着剤層が形成された片面粘着テープや、基材の両面に粘着剤層が形成された両面粘着テープでも良い。さらに２枚の剥離ライナー間に粘着剤層が形成されたいわゆるキャスト粘着テープであっても良い。なお、本発明において粘着テープと、粘着シートまたは粘着フィルムは同義語である。 Further, the pressure-sensitive adhesive sheet of the present invention may be a single-sided pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer is formed on one side of a base material, or a double-sided pressure-sensitive adhesive tape in which pressure-sensitive adhesive layers are formed on both sides of a base material. Furthermore, a so-called cast adhesive tape in which an adhesive layer is formed between two release liners may be used. In addition, in this invention, an adhesive tape and an adhesive sheet or an adhesive film are synonymous.
上記粘着剤層の厚みは、２〜１０００μｍが好ましく、５〜５００μｍがさらに好ましい。なお、粘着剤層は単層でも、２層以上の積層いずれの形態でもよい。そして粘着剤の塗工は、コンマコーターやダイコーターなどの公知の塗工機を用いることができる。 The thickness of the pressure-sensitive adhesive layer is preferably 2 to 1000 μm, and more preferably 5 to 500 μm. The pressure-sensitive adhesive layer may be a single layer or a laminate of two or more layers. The pressure-sensitive adhesive can be applied using a known coating machine such as a comma coater or a die coater.
本発明において基材は、特に制限されないが、例えばプラスチックフィルムや、反射防止（ＡＲ）フィルム、偏光板、位相差板などの各種光学フィルムが挙げられる。前記プラスチックフィルムとしては、ポリ塩化ビニルフィルム、ポリエチレンフィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリウレタンフィルム、ナイロンフィルム、ポリオレフィンフィルム、トリアセチルセルロースフィルム、シクロオレフィンフィルム等が挙げられる。上記記載の基材の厚さは特に制限されないが、１０〜２０００μｍが好ましい。 In the present invention, the substrate is not particularly limited, and examples thereof include various optical films such as a plastic film, an antireflection (AR) film, a polarizing plate, and a retardation plate. Examples of the plastic film include polyvinyl chloride film, polyethylene film, polyethylene terephthalate (PET) film, polyurethane film, nylon film, polyolefin film, triacetyl cellulose film, and cycloolefin film. The thickness of the substrate described above is not particularly limited, but is preferably 10 to 2000 μm.
本発明の粘着シートの被着体としては、特に制限されないが、透明導電膜を有するアクリル板、ポリカーボネート板、ガラス、ポリエチレンテレフタレートなどが挙げられる。また本発明の粘着シートは、液晶パネル、プラズマディスプレイパネル（ＰＤＰ），タッチパネルなどのディスプレイに用いることがより好ましい。特にタッチパネルの透明導電膜と導電回路が形成された面へ貼り付けることが好ましい。このような場合でも気泡の混入なく導電回路の段差を埋め込むことができる。さらに本発明において粘着剤層は、高温高湿環境下へ放置したときも、導電回路の腐食が抑制され、粘着剤層の透明性が維持できる。 The adherend of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and examples thereof include an acrylic plate having a transparent conductive film, a polycarbonate plate, glass, and polyethylene terephthalate. The pressure-sensitive adhesive sheet of the present invention is more preferably used for a display such as a liquid crystal panel, a plasma display panel (PDP), or a touch panel. It is particularly preferable that the touch panel is attached to the surface on which the transparent conductive film and the conductive circuit are formed. Even in such a case, the step of the conductive circuit can be embedded without mixing bubbles. Furthermore, in the present invention, even when the pressure-sensitive adhesive layer is left in a high-temperature and high-humidity environment, corrosion of the conductive circuit is suppressed and the transparency of the pressure-sensitive adhesive layer can be maintained.
本発明のディスプレイは、例えば、タッチパネルは、上記粘着シートの粘着剤層をＩＴＯによる透明導電膜や、銀ペーストによる回路が形成された基板へ貼付することにより製造できる。また、例えば、液晶パネルの形成は、上記粘着シートの粘着剤層を液晶セルの片側または両側に貼着することにより製造できる。 The display of the present invention can be produced, for example, by sticking the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to a substrate on which a transparent conductive film made of ITO or a circuit made of silver paste is formed. For example, the liquid crystal panel can be formed by sticking the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to one side or both sides of the liquid crystal cell.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例に限
定されない。なお、例中、「部」とは「重量部」を、「％」とは「重量％」をそれぞれ示
すものとする。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples. In the examples, “part” means “part by weight”, and “%” means “% by weight”.
＜合成例１＞
撹拌機、還流冷却管、窒素導入管、温度計、滴下管を備えた反応装置を使用して、表1の各単量体の合計量の５０重量％、開始剤としてアゾビスイソブチロニトリルを適量、溶剤として酢酸エチルを反応槽に仕込み、残りの単量体の全量、および酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を滴下管から約２時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却、酢酸エチルで希釈し、不揮発分４０％、粘度６０００ｍＰａ・ｓの共重合体溶液を得た。
<Synthesis Example 1>
Using a reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 50% by weight of the total amount of each monomer in Table 1, azobisisobutyronitrile as initiator Add the appropriate amount of ethyl acetate as a solvent to the reaction vessel, add the total amount of the remaining monomers, and add and mix the appropriate amounts of ethyl acetate and azobisisobutyronitrile over a period of about 2 hours. Polymerization was performed at about 80 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate to obtain a copolymer solution having a nonvolatile content of 40% and a viscosity of 6000 mPa · s.
＜合成例２〜３８＞
表１および表２の重量比率に従って各種原料を仕込み、合成例１と同様の方法でアクリル共重合体を合成した。又、得られたアクリル共重合体の不揮発分および、粘度を表１に示す。
<Synthesis Examples 2-38>
Various raw materials were charged according to the weight ratios in Table 1 and Table 2, and an acrylic copolymer was synthesized in the same manner as in Synthesis Example 1. In addition, Table 1 shows the nonvolatile content and viscosity of the obtained acrylic copolymer.
合成例１で得られた共重合体溶液１００部に対して、キシリレンジイソシアネートトリメチロールプロパンアダクト体の５０％酢酸エチル溶液１．０部を配合し粘着剤を得た。
To 100 parts of the copolymer solution obtained in Synthesis Example 1, 1.0 part of a 50% ethyl acetate solution of xylylene diisocyanate trimethylolpropane adduct was blended to obtain an adhesive.
得られた粘着剤をコンマコーターに使用して、剥離ライナー（厚さ３８μｍ）上に乾燥塗膜２５μｍになるように塗工し、１００℃で２分間乾燥させた後、粘着剤層に剥離ライナーを貼り合せ、この状態で室温にて７日間エージングさせ、基材レスの粘着シートを得た。なお、本願において実施例１は参考例である。
Using the resulting pressure-sensitive adhesive in a comma coater, a dry coating film (thickness 38 μm) was applied to a dry coating film of 25 μm, dried at 100 ° C. for 2 minutes, and then applied to the pressure-sensitive adhesive layer. In this state, the film was aged at room temperature for 7 days to obtain a baseless pressure-sensitive adhesive sheet. In the present application, Example 1 is a reference example.
＜実施例２〜３２、比較例１〜１３＞
表３〜表５に示すように、共重合体溶液の種類および硬化剤の種類、配合量を変更した以外は実施例１と同様にして、基材レスの粘着シートを得た。
<Examples 2-32 and Comparative Examples 1-13>
As shown in Tables 3 to 5, a baseless pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the type of copolymer solution, the type of curing agent, and the blending amount were changed.
そして実施例１〜３２および比較例１〜１３で得られた粘着剤と粘着シートを用いて、以下に示す方法に従って塗工性、粘着力、耐発泡・剥がれ性、透明性、耐腐食性、耐湿熱白化性、段差埋め込み性の評価を行った。結果を表３に示す。 And using the adhesives and adhesive sheets obtained in Examples 1 to 32 and Comparative Examples 1 to 13, according to the following methods, coating properties, adhesive strength, resistance to foaming / peeling, transparency, corrosion resistance, Wet and heat whitening resistance and level difference embedding were evaluated. The results are shown in Table 3.
＜塗工性＞
得られた粘着剤をコンマコーターを使用して、剥離ライナー上に３ｍ／分の塗工速度で塗工し、以下の基準で目視評価した。
○：スジ、はじき等がなく塗工面が平滑なもの
×：スジ、はじき等があり塗工面が平滑でないもの
<Coating property>
The obtained pressure-sensitive adhesive was coated on a release liner at a coating speed of 3 m / min using a comma coater, and visually evaluated according to the following criteria.
○: The coated surface is smooth without streaks, repellency, etc. ×: The coated surface is smooth with streaks, repellency, etc.
＜粘着力＞
得られた粘着シートを、ＰＥＴフィルム（東洋紡績（株）製、Ａ−４３００、厚さ１００μｍ）に貼り合わせ、幅２５ｍｍ×長さ１００ｍｍのサイズに切り出して試験用粘着シートを作製した。
この試験用粘着シートの剥離ライナーを剥がし、露出した粘着剤層を厚さ０．４ｍｍのガラス板に２３℃−５０％ＲＨにて貼着し、ＪＩＳ Ｚ−０２３７に準じてロール圧着した。圧着から２４時間経過後、万能引張試験機にて剥離強度（剥離角度１８０°、剥離速度３００ｍｍ／分；単位ｍＮ／２５ｍｍ幅）を測定した。
<Adhesive strength>
The obtained adhesive sheet was bonded to a PET film (A-4300, manufactured by Toyobo Co., Ltd., thickness: 100 μm) and cut into a size of 25 mm width × 100 mm length to prepare a test adhesive sheet.
The release liner of the pressure-sensitive adhesive sheet for test was peeled off, and the exposed pressure-sensitive adhesive layer was attached to a glass plate having a thickness of 0.4 mm at 23 ° C.-50% RH and roll-bonded according to JIS Z-0237. Peel strength (peeling angle 180 °, peeling rate 300 mm / min; unit mN / 25 mm width) was measured with a universal tensile tester 24 hours after the press bonding.
＜耐発泡・剥がれ性＞
得られた粘着シートを、ＰＥＴフィルム（東洋紡績（株）製、Ａ−４３００、厚さ１００μｍ）に貼り合わせ、幅１００ｍｍ×長さ１００ｍｍのサイズに切り出して試験用粘着シートを作製した。
この試験用粘着テープの剥離ライナーを剥がし、露出した粘着剤層をガラス板に貼着した後、８５℃の条件下に２４０時間放置し、２３℃−５０％ＲＨにて冷却した後、気泡の発生および粘着シートの浮きや剥がれを以下の条件で目視評価した。
○：気泡および浮き剥がれが全く見られないもの
×：気泡および浮き剥がれが見られたもの
<Foaming / peeling resistance>
The obtained pressure-sensitive adhesive sheet was bonded to a PET film (Toyobo Co., Ltd., A-4300, thickness 100 μm) and cut into a size of 100 mm width × 100 mm length to prepare a test pressure-sensitive adhesive sheet.
The release liner of this test adhesive tape was peeled off, and the exposed adhesive layer was attached to a glass plate. Then, the test was allowed to stand at 85 ° C. for 240 hours and cooled at 23 ° C.-50% RH. Generation | occurrence | production and the float and peeling of the adhesive sheet were visually evaluated on condition of the following.
○: No bubbles or lift-off observed X: Bubbles or lift-off observed
＜透明性＞
得られた粘着シートを、ＰＥＴフィルム（東洋紡績（株）製、Ａ−４３００、厚さ１００μｍ）に貼り合わせ、幅２５ｍｍ×長さ１００ｍｍのサイズに切り出して試験用粘着シートを作製した。
この試験用粘着テープの剥離ライナーを剥がし、２３℃−５０％ＲＨ雰囲気でガラス板にラミネーターを用いて貼着し、ＨＡＺＥを測定した。なお、ＨＡＺＥは日本電色工業（株）製Ｔｕｒｂｉｄｉｍｅｔｅｒ ＮＤＨ５０００Ｗを用いて測定した。評価基準は以下の通りである。
○：ＨＡＺＥが１．０未満であれば透明性良好
×：ＨＡＺＥが１．０以上では透明性不良
<Transparency>
The obtained adhesive sheet was bonded to a PET film (A-4300, manufactured by Toyobo Co., Ltd., thickness: 100 μm) and cut into a size of 25 mm width × 100 mm length to prepare a test adhesive sheet.
The release liner of the pressure-sensitive adhesive tape for test was peeled off and adhered to a glass plate in a 23 ° C.-50% RH atmosphere using a laminator, and HAZE was measured. In addition, HAZE was measured using Nippon Denshoku Industries Co., Ltd. Turbidimeter NDH5000W. The evaluation criteria are as follows.
○: Transparency is good if HAZE is less than 1.0 x: Transparency is poor if HAZE is 1.0 or more
＜耐腐食性＞
得られた粘着シートを、ＰＥＴフィルム（東洋紡績（株）製、Ａ−４３００、厚さ１００μｍ）に貼り合わせ、幅４０ｍｍ×長さ１００ｍｍのサイズに切り出して試験用粘着シートを作製した。
２３℃−５０％ＲＨにてＩＴＯによる透明導電膜が形成されたフィルム（サイズ４０ｍｍ×長さ１６０ｍｍ）のＩＴＯ膜形成面上に、試験用粘着テープの剥離ライナーを剥がし、ラミネーターを用いて貼着した。これを８５℃−９０％ＲＨ環境下で１０００時間放置し、貼付直後との抵抗値の変化率（％）を測定し、変化率により耐腐食性を評価した。なお、抵抗値は、三菱化学（株）製ローレスターＧＰ（型番ＭＣＰ−Ｔ６００）を用いて測定した。評価基準は以下の通りである。
○：抵抗値の変化率が１５０％未満。耐腐食性良好。
×：抵抗値の変化率が１５０％以上。耐腐食性不良。
<Corrosion resistance>
The obtained adhesive sheet was bonded to a PET film (A-4300, manufactured by Toyobo Co., Ltd., thickness: 100 μm) and cut into a size of 40 mm wide × 100 mm long to prepare a test adhesive sheet.
The release liner of the test adhesive tape is peeled off from the ITO film-forming surface of the film (size 40 mm x length 160 mm) on which the transparent conductive film made of ITO is formed at 23 ° C.-50% RH, and is adhered using a laminator. did. This was left to stand in an environment of 85 ° C.-90% RH for 1000 hours, the change rate (%) of the resistance value immediately after application was measured, and the corrosion resistance was evaluated by the change rate. In addition, resistance value was measured using Mitsubishi Chemical Corporation Lorester GP (model number MCP-T600). The evaluation criteria are as follows.
○: Resistance change rate is less than 150%. Good corrosion resistance.
X: The change rate of the resistance value is 150% or more. Poor corrosion resistance.
＜耐湿熱白化性＞
得られた粘着シートを、ＰＥＴフィルム（東洋紡績（株）製、Ａ−４３００、厚さ１００μｍ）に貼り合わせ、幅２５ｍｍ×長さ８０ｍｍのサイズに切り出して試験用粘着シートを作製した。
この試験用粘着テープの剥離ライナーを剥がし、２３℃−５０％ＲＨ雰囲気にてＩＴＯによる透明導電膜が形成されたフィルム（サイズ４０ｍｍ×長さ１６０ｍｍ）のＩＴＯ膜形成面上に、試験用粘着テープの剥離ライナーを剥がし、ラミネーターを用いて貼着した。これを８５℃−９０％ＲＨ環境下で１０００時間放置し、２３℃−５０％ＲＨにて３時間冷却した後のＨＡＺＥを測定した。なお、ＨＡＺＥは日本電色工業（株）製Ｔｕｒｂｉｄｉｍｅｔｅｒ ＮＤＨ５０００Ｗを用いて測定した。評価基準は以下の通りである。
◎：ＨＡＺＥが１．２未満であればほとんど白化が確認されず、耐湿熱白化性良好。
○：ＨＡＺＥが１．２以上８．０未満であれば、若干の白化があるが実用上問題ない。
×：ＨＡＺＥが８．０以上であると白化性不良で使用できない。
<Heat and heat whitening resistance>
The obtained adhesive sheet was bonded to a PET film (A-4300, manufactured by Toyobo Co., Ltd., thickness: 100 μm) and cut into a size of 25 mm width × 80 mm length to prepare a test adhesive sheet.
The release liner of the test adhesive tape is peeled off, and the test adhesive tape is formed on the ITO film-forming surface of the film (size 40 mm × length 160 mm) on which the transparent conductive film made of ITO is formed in an atmosphere of 23 ° C.-50% RH. The release liner was peeled off and stuck using a laminator. This was allowed to stand for 1000 hours in an environment of 85 ° C.-90% RH, and after cooling at 23 ° C.-50% RH for 3 hours, HAZE was measured. In addition, HAZE was measured using Nippon Denshoku Industries Co., Ltd. Turbidimeter NDH5000W. The evaluation criteria are as follows.
A: If HAZE is less than 1.2, almost no whitening is confirmed, and the moisture and heat whitening resistance is good.
○: If HAZE is 1.2 or more and less than 8.0, there is some whitening, but there is no practical problem.
X: When HAZE is 8.0 or more, it cannot be used due to poor whitening property.
＜耐ＰＣガス膨れ性の評価方法＞
耐発泡剥がれ性の評価として、試験用粘着テープを、幅１００ｍｍ×長さ１００ｍｍに裁断し、剥離フィルムを剥離して、ポリカーボネート（ＰＣ）板に貼り合わせて固定し、５０℃雰囲気下で０．５ＭＰａの圧力をかけて２０分間保持して、ＰＥＴフィルム／粘着剤層／ＰＣ板の層構造を有する試験片を作製した。上記試験片を８０℃のオーブン中で２４時間熱処理（耐熱性試験）を行った。
この耐熱性試験後、サンプル片の接着界面（感圧式接着剤層とＰＣ板との界面）を目視にて観察した。評価基準は以下の通りである。
○：「気泡」や「浮き」が全く見られなかった。良好。
△：「気泡」や「浮き」が僅かに認められる。実用上問題ない。
×：「気泡」や「浮き」が著しく認められる。実用不可。
<Method for evaluating PC gas swell resistance>
As an evaluation of the foaming peeling resistance, the test adhesive tape was cut into a width of 100 mm × a length of 100 mm, the release film was peeled off, and bonded and fixed to a polycarbonate (PC) plate. A test piece having a layer structure of PET film / adhesive layer / PC plate was produced by applying a pressure of 5 MPa and holding for 20 minutes. The test piece was subjected to heat treatment (heat resistance test) in an oven at 80 ° C. for 24 hours.
After this heat resistance test, the adhesion interface (the interface between the pressure-sensitive adhesive layer and the PC plate) of the sample piece was visually observed. The evaluation criteria are as follows.
○: “Bubble” and “Float” were not seen at all. Good.
Δ: “bubbles” and “floating” are slightly observed. There is no problem in practical use.
X: “Bubble” and “floating” are remarkably recognized. Not practical.
＜段差埋め込み性＞
得られた粘着シートを、ＰＥＴフィルム（東洋紡績（株）製、Ａ−４３００、厚さ１００μｍ）に貼り合わせ、幅２５ｍｍ×長さ１００ｍｍのサイズに切り出して試験用粘着シートを作製した。
一方、ＰＥＴフィルム上に、銀インキを用いてシルクスクリーンコーターにて幅１ｃｍで段差が１０μｍになるように印刷した。２３℃−５０％ＲＨ雰囲気でこの試験用粘着テープの剥離ライナーを剥がし、当該印刷フィルム（サイズ４０ｍｍ×長さ１００ｍｍ）の印刷面にラミネーターを用いて貼着した。これをオートクレーブ内で５０℃−０．５ＭＰａで２０分間処理した後、２３℃−５０％ＲＨ環境下にて２４時間放置した後、段差が埋まっているか以下の基準で目視評価した。
◎：ラミネーター貼着後に段差が埋まっている
○：オートクレーブ処理直後に段差が埋まっている
△：オートクレーブ処理２４時間後に段差が埋まっている
×：段差が埋まらない
<Step embedding>
The obtained adhesive sheet was bonded to a PET film (A-4300, manufactured by Toyobo Co., Ltd., thickness: 100 μm) and cut into a size of 25 mm width × 100 mm length to prepare a test adhesive sheet.
On the other hand, it printed on PET film so that a level | step difference might be set to 10 micrometers in width 1cm with a silk screen coater using silver ink. The release liner of this test adhesive tape was peeled off in a 23 ° C.-50% RH atmosphere, and adhered to the printing surface of the printing film (size 40 mm × length 100 mm) using a laminator. This was treated in an autoclave at 50 ° C.-0.5 MPa for 20 minutes, and then allowed to stand for 24 hours in an environment of 23 ° C.-50% RH.
◎: Step is buried after laminator is attached ○: Step is buried immediately after autoclave treatment △: Step is buried 24 hours after autoclave treatment ×: Step is not buried
表６に示すように、比較例１〜１３は、塗工性、粘着性、耐発泡・剥がれ性、透明性、耐腐食性、耐湿熱白化性、対ＰＣガス膨れ性、段差埋め込み性すべてを満足することはできなかった。一方、実施例１〜３２は優れた耐腐食性、耐湿熱白化性、段差埋め込み性を有し、かつ塗工性、粘着性、耐発泡・剥がれ性、耐ＰＣガス膨れ性、透明性に優れた結果であった。 As shown in Table 6, Comparative Examples 1 to 13 have all the coating properties, tackiness, resistance to foaming / peeling, transparency, corrosion resistance, resistance to moist heat whitening, resistance to PC gas expansion, and step embedding properties. I couldn't be satisfied. On the other hand, Examples 1 to 32 have excellent corrosion resistance, moisture and heat whitening resistance, step embedding property, and excellent coating property, adhesiveness, foaming / peeling resistance, PC gas swell resistance and transparency. It was the result.
本発明の粘着剤および粘着シートは、優れた塗工性、粘着性、耐発泡・剥がれ性、透明
性のみならず、高い耐腐食性、耐湿熱白化性、段差埋め込み性を併せ持ち、ディスプレイ
やタッチパネルなどの金属薄膜を直接貼り付け固定する用途などの光学部材の接着用途に
好適に用いることができる。
The pressure-sensitive adhesive and pressure-sensitive adhesive sheet of the present invention have not only excellent coating properties, pressure-sensitive adhesive properties, foaming / peeling resistance, and transparency, but also high corrosion resistance, moisture and heat whitening properties, step embedding properties, and displays and touch panels. It can use suitably for the adhesion | attachment use of optical members, such as a use which attaches and fixes metal thin films directly.
Claims (4)
前記共重合体（Ｘ）が、少なくとも、カルボキシル基以外のイソシアネート基と反応可能な官能基を含有する単量体（Ａ）０．１〜１０重量％と、アミノ基を含有する単量体（Ｂ）０．１〜１０重量％と、アミド結合を含有する単量体（Ｃ）１０〜５０重量％とを含む単量体を共重合してなることを特徴とする透明導電膜用粘着剤。A pressure-sensitive adhesive for transparent conductive film comprising a copolymer (X) and a polyisocyanate curing agent (Y),
The copolymer (X) contains at least 0.1 to 10% by weight of a monomer (A) containing a functional group capable of reacting with an isocyanate group other than a carboxyl group, and a monomer containing an amino group ( B) A pressure-sensitive adhesive for transparent conductive films obtained by copolymerizing a monomer containing 0.1 to 10% by weight and a monomer containing an amide bond (C) 10 to 50% by weight .
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|---|---|---|---|
| JP2011056983A JP5712706B2 (en) | 2011-03-15 | 2011-03-15 | Adhesive, adhesive sheet and display |
| TW101105237A TWI560255B (en) | 2011-03-15 | 2012-02-17 | Pressure sensitive adhesive, pressure sensitive adhesive sheet, and electronic device |
| KR1020120022728A KR101890713B1 (en) | 2011-03-15 | 2012-03-06 | Pressure sensitive adhesive, pressure sensitive adhesive sheet, and electronic device |
| CN201210058416.XA CN102676092B (en) | 2011-03-15 | 2012-03-06 | Tackiness agent, sheet adhesive and electronics |
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| JP2011056983A JP5712706B2 (en) | 2011-03-15 | 2011-03-15 | Adhesive, adhesive sheet and display |
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| JP5712706B2 true JP5712706B2 (en) | 2015-05-07 |
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| JP5790089B2 (en) * | 2011-03-31 | 2015-10-07 | Dic株式会社 | Double-sided adhesive tape |
| JP6057693B2 (en) * | 2012-12-17 | 2017-01-11 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| CN103087503B (en) * | 2013-01-14 | 2015-04-01 | 徐广敏 | Electronic pouring sealant and preparation method thereof |
| JP6325778B2 (en) * | 2013-06-28 | 2018-05-16 | リンテック株式会社 | Adhesive sheet and laminate |
| JP6130246B2 (en) * | 2013-06-28 | 2017-05-17 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| JP6442879B2 (en) * | 2013-06-28 | 2018-12-26 | 三菱ケミカル株式会社 | Laminated moisture barrier film |
| JP6130245B2 (en) * | 2013-06-28 | 2017-05-17 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| JP2015193706A (en) * | 2014-03-31 | 2015-11-05 | リンテック株式会社 | Method for producing surface protective film for conductive substrate |
| CN104175697B (en) * | 2014-07-04 | 2016-01-27 | 京东方科技集团股份有限公司 | The attaching method of polaroid, polaroid unit and display unit |
| WO2016111526A1 (en) | 2015-01-06 | 2016-07-14 | 엘지전자 주식회사 | Broadcast signal transmission device, broadcast signal reception device, broadcast signal transmission method, and broadcast signal reception method |
| KR101785198B1 (en) * | 2015-03-31 | 2017-10-12 | 스미또모 가가꾸 가부시키가이샤 | Optical laminate and liquid crystal display device |
| JP5956044B1 (en) * | 2015-10-07 | 2016-07-20 | 住友化学株式会社 | Optical laminate and liquid crystal display device |
| JP7112227B2 (en) * | 2017-03-31 | 2022-08-03 | 積水化学工業株式会社 | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
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| JP4788937B2 (en) | 2001-05-07 | 2011-10-05 | 綜研化学株式会社 | Adhesive composition and display adhesive sheet using the composition |
| JP4534431B2 (en) * | 2003-04-30 | 2010-09-01 | 東洋インキ製造株式会社 | Adhesive and optical member using the same |
| JP2005314595A (en) * | 2004-04-30 | 2005-11-10 | Sumitomo Chemical Co Ltd | Acrylic resin composition |
| JP5299804B2 (en) | 2004-08-03 | 2013-09-25 | 綜研化学株式会社 | Adhesive sheet for attaching metal |
| JP2007297452A (en) * | 2006-04-28 | 2007-11-15 | Daio Paper Corp | Adhesive sheet |
| JP4931197B2 (en) * | 2006-08-24 | 2012-05-16 | リケンテクノス株式会社 | Adhesive composition and adhesive sheet member using the same |
| JP4493643B2 (en) * | 2006-12-06 | 2010-06-30 | 日東電工株式会社 | Re-peelable pressure-sensitive adhesive composition, and pressure-sensitive adhesive tape or sheet |
| JP4531099B2 (en) | 2007-09-06 | 2010-08-25 | 日東電工株式会社 | Adhesive composition, and adhesive product and display using the same |
| WO2010013536A1 (en) * | 2008-07-31 | 2010-02-04 | リンテック株式会社 | Adhesive sheet |
| CN102482539A (en) * | 2009-08-28 | 2012-05-30 | 日东电工株式会社 | Adhesive tape or sheet, and base material therefor |
| KR20120060782A (en) * | 2009-09-01 | 2012-06-12 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Radiation-curable pressure-sensitive adhesive composition for optical members, and pressure-sensitive adhesion type optical members |
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| CN102676092B (en) | 2016-03-16 |
| KR20120105361A (en) | 2012-09-25 |
| CN102676092A (en) | 2012-09-19 |
| JP2012193248A (en) | 2012-10-11 |
| KR101890713B1 (en) | 2018-08-22 |
| TWI560255B (en) | 2016-12-01 |
| TW201237135A (en) | 2012-09-16 |
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