JP2020083909A - Adhesive sheet and laminate sheet - Google Patents
Adhesive sheet and laminate sheet Download PDFInfo
- Publication number
- JP2020083909A JP2020083909A JP2018214562A JP2018214562A JP2020083909A JP 2020083909 A JP2020083909 A JP 2020083909A JP 2018214562 A JP2018214562 A JP 2018214562A JP 2018214562 A JP2018214562 A JP 2018214562A JP 2020083909 A JP2020083909 A JP 2020083909A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- mass
- meth
- film
- 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.)
- Pending
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 21
- 239000000853 adhesive Substances 0.000 title claims abstract description 20
- 238000004132 cross linking Methods 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 239000012790 adhesive layer Substances 0.000 claims abstract description 11
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 144
- 239000010410 layer Substances 0.000 claims description 70
- -1 isocyanate compound Chemical class 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 37
- 229920006243 acrylic copolymer Polymers 0.000 claims description 33
- 150000003606 tin compounds Chemical class 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 28
- 229920001577 copolymer Polymers 0.000 abstract 2
- 239000010408 film Substances 0.000 description 122
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000178 monomer Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 238000004804 winding Methods 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 241000951471 Citrus junos Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 2
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 2
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 2
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 2
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 2
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
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- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 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
- 239000008096 xylene Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
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- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KCHWKBCUPLJWJA-UHFFFAOYSA-N dodecyl 3-oxobutanoate Chemical compound CCCCCCCCCCCCOC(=O)CC(C)=O KCHWKBCUPLJWJA-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
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- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- BMOMBHKAYGMGCR-UHFFFAOYSA-N octadecyl 3-oxobutanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC(C)=O BMOMBHKAYGMGCR-UHFFFAOYSA-N 0.000 description 1
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- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
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- 238000011417 postcuring Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- OECBPUHKHTYFET-UHFFFAOYSA-J tris(decanoyloxy)stannyl decanoate Chemical compound [Sn+4].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O OECBPUHKHTYFET-UHFFFAOYSA-J 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、粘着シート及び積層シートに関する。具体的には、本発明は、粘着シート及び該粘着シートを介して、フィルム基材と剥離フィルムが貼合された積層シートに関する。 The present invention relates to an adhesive sheet and a laminated sheet. Specifically, the present invention relates to a pressure-sensitive adhesive sheet and a laminated sheet in which a film substrate and a release film are bonded together via the pressure-sensitive adhesive sheet.
近年、携帯電話、携帯ゲーム機、デジタルカメラ等の電子機器が急速に普及している。電子機器や各種装置を構成する部品の固定には、粘着シートが用いられている。また、液晶ディスプレイ（ＬＣＤ）などの表示装置には、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、表示装置表面の傷付き防止の為の保護フィルム（プロテクトフィルム）、落下時などに光学部材が飛散することを防止する飛散防止フィルムなど、用途に応じて様々な粘着シート付きフィルムが使用されている。このように、各種光学部品の固定には粘着シートが用いられており、粘着シートとしては、基材の片面又は両面に粘着剤層が設けられた粘着シートが多用されている。 2. Description of the Related Art In recent years, electronic devices such as mobile phones, portable game machines, and digital cameras have rapidly become popular. BACKGROUND ART Adhesive sheets are used to fix components that make up electronic devices and various devices. In addition, a display device such as a liquid crystal display (LCD) is usually provided with an antireflection film for preventing reflection from an external light source, a protective film (protective film) for preventing scratches on the display device surface, a drop film, etc. In addition, various films with adhesive sheets are used depending on the application, such as a shatterproof film that prevents the optical members from scattering. As described above, the pressure-sensitive adhesive sheet is used for fixing various optical components, and as the pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is provided on one surface or both surfaces of a substrate is often used.
例えば、特許文献１には、フィルム基材に粘着剤層が設けられ、粘着剤層に剥離シートが積層された保護粘着フィルムであって、剥離シートの表面粗さＲａが１０〜１００ｎｍであり、粘着剤層の２３℃における貯蔵弾性率Ｇ'が２．０×１０5Ｐａ以上の保護粘着フィルムが開示されている。 For example, in Patent Document 1, a pressure-sensitive adhesive layer is provided on a film base material, which is a protective pressure-sensitive adhesive film in which a release sheet is laminated on the pressure-sensitive adhesive layer, the release sheet having a surface roughness Ra of 10 to 100 nm. A protective pressure-sensitive adhesive film having a storage elastic modulus G′ of the pressure-sensitive adhesive layer at 23° C. of 2.0×10 5 Pa or more is disclosed.
ところで、上述したような粘着シートは、剥離フィルム上に粘着剤を塗布することで粘着剤層を形成し、さらにその粘着剤層上にフィルム基材や剥離フィルム等を積層することで製造される。このような粘着シートは、ロール状に巻き取られて保管や運搬がなされている。このような粘着シートの巻回体においては、製造時や保管時に巻締りが生じることで粘着剤層に微細な凹凸が多数発生し、いわゆるゆず肌が発生する場合がある。 By the way, the pressure-sensitive adhesive sheet as described above is manufactured by forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive on the release film, and further laminating a film substrate or a release film on the pressure-sensitive adhesive layer. .. Such an adhesive sheet is wound in a roll shape and stored or transported. In such a wound body of the pressure-sensitive adhesive sheet, a large number of fine irregularities are generated in the pressure-sensitive adhesive layer due to the tightening of the winding during the production or storage, and so-called sore skin may occur.
特許文献２には、第１の面と第２の面とを備える粘着剤層と、第１の剥離フィルムと、第２の剥離フィルムとを有する両面粘着シートが開示されている。また、特許文献２では、第１の剥離フィルムと第２の剥離フィルムの粘着剤層と接する面とは反対側の面の算術平均粗さＲａを５〜３５ｎｍとし、最大突起高さＲｐを５０〜４００ｎｍとすることにより、ゆず肌の発生を抑制することが検討されている。 Patent Document 2 discloses a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a first surface and a second surface, a first release film, and a second release film. In Patent Document 2, the arithmetic mean roughness Ra of the surface of the first release film and the surface of the second release film opposite to the surface in contact with the pressure-sensitive adhesive layer is 5 to 35 nm, and the maximum protrusion height Rp is 50. It has been studied to suppress the occurrence of orange peel skin by setting the thickness to 400 nm.
上述したように、剥離フィルムと粘着剤層を有する粘着シートが知られており、ゆず肌の発生について検討がなされている。しかしながら、従来の粘着シートにおいても、ゆず肌が発生する場合があり、その改善が求められていた。 As described above, a pressure-sensitive adhesive sheet having a release film and a pressure-sensitive adhesive layer is known, and the occurrence of orange peel has been studied. However, even in the conventional pressure-sensitive adhesive sheet, there is a case where an orange peel skin occurs, and improvement thereof has been demanded.
そこで本発明者らは、このような従来技術の課題を解決するために、ゆず肌の発生が抑制され、表面性状が良好な粘着シートを提供することを目的として検討を進めた。 Therefore, in order to solve such a problem of the conventional technique, the present inventors have proceeded with a study for the purpose of providing a pressure-sensitive adhesive sheet that suppresses the generation of orange peel and has good surface properties.
上記の課題を解決するために鋭意検討を行った結果、本発明者らは、粘着剤層を形成する粘着剤組成物において、架橋促進剤の含有量を所定範囲内とすることにより、ゆず肌の発生が抑制された積層シートが得られることを見出した。
具体的に、本発明は、以下の構成を有する。
As a result of intensive studies to solve the above problems, the present inventors have found that in the pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive layer, the content of the crosslinking accelerator is within the predetermined range to give yuzu skin. It has been found that a laminated sheet in which the occurrence of is suppressed can be obtained.
Specifically, the present invention has the following configurations.
［１］ 粘着剤組成物を硬化させてなる粘着シートであって、
粘着剤組成物は、（メタ）アクリル共重合体、架橋剤及び架橋促進剤を含み、
架橋促進剤の含有量は（メタ）アクリル共重合体１００質量部に対して０．４５〜１．０質量部である、粘着シート。
［２］ 架橋剤がイソシアネート化合物である［１］に記載の粘着シート。
［３］ 架橋剤の含有量が（メタ）アクリル共重合体１００質量部に対して０．１〜０．８質量部である［１］又は［２］に記載の粘着シート。
［４］ 架橋促進剤が有機スズ化合物である［１］〜［３］のいずれかに記載の粘着シート。
［５］ フィルム基材、粘着剤層及び剥離フィルムがこの順で積層された積層シートであって、
粘着剤層は（メタ）アクリル共重合体、架橋剤に由来する構造及び架橋促進剤を含み、
架橋促進剤の含有量は、（メタ）アクリル共重合体１００質量部に対して０．４５〜１．０質量部である積層シート。
［６］ 粘着剤層のゲル分率が４０％以上である［５］に記載の積層シート。
［７］ 架橋促進剤が有機スズ化合物である［５］又は［６］に記載の積層シート。
［８］ 剥離フィルムの露出面の算術平均粗さが３５ｎｍ以上である［５］〜［７］のいずれかに記載の積層シート。
［９］ 剥離フィルムの露出面を、ウェーブスキャン装置を用いて波長０．３〜１．０ｍｍの波長域の反射強度（Ｗｂ）を測定した場合、反射強度（Ｗｂ）が１０以上である［５］〜［８］のいずれかに記載の積層シート。
[1] A pressure-sensitive adhesive sheet obtained by curing a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition contains a (meth)acrylic copolymer, a crosslinking agent and a crosslinking accelerator,
Content of a crosslinking accelerator is 0.45-1.0 mass part with respect to 100 mass parts of (meth)acrylic copolymers, an adhesive sheet.
[2] The pressure-sensitive adhesive sheet according to [1], wherein the crosslinking agent is an isocyanate compound.
[3] The pressure-sensitive adhesive sheet according to [1] or [2], wherein the content of the crosslinking agent is 0.1 to 0.8 parts by mass with respect to 100 parts by mass of the (meth)acrylic copolymer.
[4] The pressure-sensitive adhesive sheet according to any one of [1] to [3], wherein the crosslinking accelerator is an organotin compound.
[5] A laminated sheet in which a film substrate, an adhesive layer and a release film are laminated in this order,
The pressure-sensitive adhesive layer contains a (meth)acrylic copolymer, a structure derived from a crosslinking agent, and a crosslinking accelerator,
The content of the crosslinking accelerator is 0.45 to 1.0 part by mass based on 100 parts by mass of the (meth)acrylic copolymer.
[6] The laminated sheet according to [5], wherein the adhesive layer has a gel fraction of 40% or more.
[7] The laminated sheet according to [5] or [6], wherein the crosslinking accelerator is an organotin compound.
[8] The laminated sheet according to any one of [5] to [7], wherein the exposed surface of the release film has an arithmetic average roughness of 35 nm or more.
[9] When the reflection intensity (Wb) of the exposed surface of the release film is measured in a wavelength range of 0.3 to 1.0 mm using a wave scan device, the reflection intensity (Wb) is 10 or more [5. ]-The laminated sheet in any one of [8].
本発明によれば、ゆず肌の発生が抑制され、表面性状が良好な粘着シート及び積層シートを得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, generation|occurrence|production of a yuzu skin is suppressed and the adhesive sheet and laminated sheet with favorable surface property can be obtained.
以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。なお、本明細書において「〜」を用いて表される数値範囲は「〜」前後に記載される数値を下限値及び上限値として含む範囲を意味する。 Hereinafter, the present invention will be described in detail. The description of the constituent requirements described below may be made based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
（積層シート）
本発明は、図１に示されるように、フィルム基材１０、粘着剤層２０及び剥離フィルム３０がこの順で積層された積層シート１００に関する。すなわち、フィルム基材１０と剥離フィルム３０は、粘着剤層２０を介して貼合されている。なお、本発明は、積層シートをロール状に巻き取った巻回体に関するものであってもよい。
(Laminated sheet)
The present invention relates to a laminated
本発明の積層シートに含まれる粘着剤層は（メタ）アクリル共重合体、架橋剤に由来する構造及び架橋促進剤を含む。そして、架橋促進剤の含有量は、（メタ）アクリル共重合体１００質量部に対して０．４５〜１．０質量部である。本発明の積層シートは、粘着剤層が上記構成を有するシートであるため、積層シートを巻回体とした場合であっても、積層シートの粘着剤層に微細な凹凸構造が形成されることを抑制することができ、その結果、フィルム基材表面がゆず肌状となることを抑制することができる。フィルム基材表面の面性状については、目視評価を行うことができる。例えば、フィルム基材表面に蛍光灯の光を反射させて観察し、フィルム基材に写り込んだ蛍光灯の像が歪まずに見える場合にはゆず肌の発生がなく、外観（面性状）が良好であると判定できる。本発明においては、積層シートを３インチの紙管に張力６０Ｎで１００ｍ分巻き取って巻回体とし、その巻回体を２３℃、相対湿度５０％の条件下で１週間保管した場合であってもフィルム基材表面のゆず肌の発生が抑制されている。 The pressure-sensitive adhesive layer contained in the laminated sheet of the present invention contains a (meth)acrylic copolymer, a structure derived from a crosslinking agent, and a crosslinking accelerator. The content of the crosslinking accelerator is 0.45 to 1.0 part by mass with respect to 100 parts by mass of the (meth)acrylic copolymer. Since the pressure-sensitive adhesive layer of the laminated sheet of the present invention is a sheet having the above-mentioned constitution, even when the laminated sheet is a wound body, a fine uneven structure is formed in the pressure-sensitive adhesive layer of the laminated sheet. Can be suppressed, and as a result, it is possible to prevent the surface of the film substrate from becoming orange peel. The surface quality of the film substrate surface can be visually evaluated. For example, when the light of a fluorescent lamp is reflected on the surface of the film substrate and observed, and when the image of the fluorescent lamp reflected on the film substrate looks undistorted, there is no orange peel and the appearance (texture) is It can be determined to be good. In the present invention, the laminated sheet is wound around a 3-inch paper tube with a tension of 60 N for 100 m to form a wound body, and the wound body is stored for one week under the conditions of 23° C. and 50% relative humidity. However, the occurrence of orange peel on the surface of the film substrate is suppressed.
なお、フィルム基材表面のゆず肌の発生については、目視評価の他に、フィルム基材表面の反射強度（Ｗｂ）の値や、反射強度（Ｗｃ）の値によっても評価できる。具体的には、積層シートの剥離フィルムを剥離し、露出した粘着剤層を黒アクリル板に貼合した後に、フィルム基材面の反射光の量をＢＹＫ Ｇａｒｄｎｅｒ社製のウェーブ−スキャン デュアルを用いて測定する。ウェーブスキャン装置では、シート表面のうねりや波打ちによる光の拡散反射が明暗領域の波長パターンとして測定される。具体的には、シート表面にレーザー（点光源）をシート表面に対して６０°で照射させ、反射光の量をセンサーにて読み取る。このような反射光は所定間隔で測定され、これにより表面の光学的プロファイルを検出する。そして、得られた光学的プロファイルをフィルター関数変換を用いて分類した後に、波長０．３〜１．０ｍｍの波長域の反射強度（Ｗｂ）と波長１．０〜３．０ｍｍ領域の反射強度Ｗｃを取得する。フィルム基材表面の反射強度（Ｗｂ）は、４．０未満であることが好ましく、３．０以下であることがより好ましく、２．０以下であることがさらに好ましく、１．０以下であることが特に好ましい。また、フィルム基材表面の反射強度（Ｗｃ）は、２．４未満であることが好ましく、２．０以下であることがより好ましく、１．５以下であることがさらに好ましく、１．３以下であることが特に好ましい。 The occurrence of orange peel on the surface of the film substrate can be evaluated not only by visual evaluation but also by the value of the reflection intensity (Wb) or the value of the reflection intensity (Wc) on the surface of the film substrate. Specifically, after peeling off the release film of the laminated sheet and pasting the exposed adhesive layer on a black acrylic plate, the amount of reflected light on the film substrate surface was measured by using a wave-scan dual manufactured by BYK Gardner. To measure. In the wave scanning device, the undulation of the sheet surface or the diffuse reflection of light due to waviness is measured as a wavelength pattern in the light and dark regions. Specifically, the sheet surface is irradiated with a laser (point light source) at 60° with respect to the sheet surface, and the amount of reflected light is read by a sensor. Such reflected light is measured at predetermined intervals to detect the optical profile of the surface. Then, after classifying the obtained optical profiles using the filter function conversion, the reflection intensity (Wb) in the wavelength region of 0.3 to 1.0 mm and the reflection intensity Wc in the wavelength region of 1.0 to 3.0 mm are obtained. To get. The reflection intensity (Wb) on the surface of the film substrate is preferably less than 4.0, more preferably 3.0 or less, further preferably 2.0 or less, and 1.0 or less. Is particularly preferable. The reflection intensity (Wc) of the surface of the film substrate is preferably less than 2.4, more preferably 2.0 or less, further preferably 1.5 or less, and 1.3 or less. Is particularly preferable.
（粘着剤層）
積層シートに含まれる粘着剤層は、粘着剤組成物を硬化させてなる粘着シートからなる層である。本発明は、粘着剤組成物を硬化させてなる粘着シートに関するものでもある。ここで、粘着剤層（粘着シート）を形成する粘着剤組成物は、（メタ）アクリル共重合体、架橋剤及び架橋促進剤を含み、架橋促進剤の含有量は（メタ）アクリル共重合体１００質量部に対して０．４５〜１．０質量部である。なお、本明細書において、“（メタ）アクリル”とは、アクリルおよびメタクリルの双方、または、いずれかを表す。
(Adhesive layer)
The pressure-sensitive adhesive layer included in the laminated sheet is a layer formed of a pressure-sensitive adhesive sheet obtained by curing the pressure-sensitive adhesive composition. The present invention also relates to a pressure-sensitive adhesive sheet obtained by curing the pressure-sensitive adhesive composition. Here, the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) contains a (meth)acrylic copolymer, a crosslinking agent and a crosslinking accelerator, and the content of the crosslinking accelerator is (meth)acrylic copolymer. It is 0.45 to 1.0 part by mass with respect to 100 parts by mass. In addition, in this specification, "(meth)acryl" represents both acryl and methacryl, or either.
粘着剤層（粘着シート）のゲル分率は、２０％以上であることが好ましく、３０％以上であることがより好ましく、４０％以上であることがさらに好ましく、４５％以上であることが特に好ましい。なお、上記ゲル分率は、粘着剤層を形成した直後のゲル分率であるが、経時後の粘着剤層のゲル分率も上記下限値以上であることが好ましい。粘着剤層を形成した直後のゲル分率を上記下限値以上とすることで、粘着剤層が変形し難くなり、巻回時におけるゆず肌の発生が抑制されやすくなる。
ゲル分率を測定する際には、まず、粘着剤組成物を剥離フィルム上に塗工した後
３時間以内の粘着剤層を金属メッシュ（１５０メッシュ）に包んだ状態で酢酸エチルに浸し、４０℃で２４時間放置する。そして、取り出した粘着剤層を１００℃で１時間乾燥させ、酢酸エチル浸漬前後の重量比率を算出し、下記式からゲル分率を算出する。
ゲル分率（％）＝酢酸エチル浸漬後の粘着剤層の重量／酢酸エチル浸漬前の粘着剤層の重量×１００
The gel fraction of the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and particularly preferably 45% or more. preferable. The gel fraction is the gel fraction immediately after forming the pressure-sensitive adhesive layer, but the gel fraction of the pressure-sensitive adhesive layer after aging is also preferably the above lower limit or more. By setting the gel fraction immediately after forming the pressure-sensitive adhesive layer to the above lower limit value or more, the pressure-sensitive adhesive layer is less likely to be deformed, and the occurrence of orange peel during winding is easily suppressed.
When measuring the gel fraction, first, after coating the pressure-sensitive adhesive composition on a release film, the pressure-sensitive adhesive layer within 3 hours is wrapped in a metal mesh (150 mesh) and immersed in ethyl acetate, Leave at 24°C for 24 hours. Then, the taken out pressure-sensitive adhesive layer is dried at 100° C. for 1 hour, the weight ratio before and after the immersion in ethyl acetate is calculated, and the gel fraction is calculated from the following formula.
Gel fraction (%)=weight of pressure-sensitive adhesive layer after immersion in ethyl acetate/weight of pressure-sensitive adhesive layer before immersion in ethyl acetate×100
粘着剤層（粘着シート）の厚みは、３μｍ以上であることが好ましく、５μｍ以上であることがより好ましく、１５μｍ以上であることがさらに好ましい。また、粘着剤層の厚みの上限値は特に限定されるものではないが、本発明においては、例えば、５０μｍ以下であってもゆず肌の発生を抑制することができる。粘着剤層は、その厚みが大きい方がゆず肌の影響が出にくいが、本発明においては、例えば、粘着剤層の厚みが５０μｍ以下といった薄膜の場合であってもゆず肌の発生を抑制することができる。 The thickness of the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 15 μm or more. In addition, although the upper limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, in the present invention, even if it is 50 μm or less, the occurrence of orange peel can be suppressed. The larger the thickness of the pressure-sensitive adhesive layer, the less likely it is that the skin will be affected, but in the present invention, for example, even if the pressure-sensitive adhesive layer is a thin film having a thickness of 50 μm or less, the occurrence of orange skin is suppressed. be able to.
＜（メタ）アクリル共重合体＞
（メタ）アクリル共重合体は、架橋性官能基を有する（メタ）アクリレートに由来する単位を含むものであることが好ましい。なお、本明細書および特許請求の範囲において、「単位」は重合体を構成する繰り返し単位（単量体単位）である。
<(Meth)acrylic copolymer>
The (meth)acrylic copolymer preferably contains a unit derived from (meth)acrylate having a crosslinkable functional group. In addition, in the present specification and claims, the “unit” is a repeating unit (monomer unit) constituting a polymer.
架橋性官能基は、カルボキシ基、ヒドロキシ基、アミノ基、アミド基、エポキシ基及びイソシアネート基から選択される少なくとも１種であることが好ましく、カルボキシ基、ヒドロキシ基、アミノ基およびエポキシ基から選択される少なくとも１種であることがより好ましい。
カルボキシ基含有単量体単位としては、アクリル酸、メタクリル酸が挙げられる。
ヒドロキシ基含有単量体単位は、ヒドロキシ基含有単量体に由来する繰り返し単位である。ヒドロキシ基含有単量体としては、例えば、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸２−ヒドロキシプロピルなどの（メタ）アクリル酸ヒドロキシアルキル、（メタ）アクリル酸モノ（ジエチレングリコール）などの（メタ）アクリル酸［（モノ、ジ又はポリ）アルキレングリコール］、（メタ）アクリル酸モノカプロラクトンなどの（メタ）アクリル酸ラクトンが挙げられる。
アミノ基含有単量体単位としては、例えば、（メタ）アクリルアミド、アリルアミン等のアミノ基含有単量体に由来する繰り返し単位が挙げられる。
エポキシ基含有単量体単位としては、（メタ）アクリル酸グリシジル等のグリシジル基含有単量体に由来する繰り返し単位が挙げられる。
The crosslinkable functional group is preferably at least one selected from a carboxy group, a hydroxy group, an amino group, an amide group, an epoxy group and an isocyanate group, and is selected from a carboxy group, a hydroxy group, an amino group and an epoxy group. More preferably, it is at least one kind.
Examples of the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
The hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer. Examples of the hydroxy group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; Examples thereof include (meth)acrylic acid [(mono-, di- or poly)alkylene glycol] such as (meth)acrylic acid mono(diethylene glycol), and (meth)acrylic acid lactone such as (meth)acrylic acid monocaprolactone.
Examples of the amino group-containing monomer unit include repeating units derived from amino group-containing monomers such as (meth)acrylamide and allylamine.
Examples of the epoxy group-containing monomer unit include a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth)acrylate.
（メタ）アクリル共重合体は、さらに、非架橋性（メタ）アクリル酸エステル単位を含むものであることが好ましい。非架橋性（メタ）アクリル酸エステル単位は、（メタ）アクリル酸アルキルエステルに由来する繰り返し単位であることが好ましい。（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ｎ−ペンチル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ−ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ｎ−デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ−ウンデシル、（メタ）アクリル酸ｎ−ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル等が挙げられる。これらは１種類を単独で使用してもよいし、２種類以上を併用してもよい。 The (meth)acrylic copolymer preferably further contains a non-crosslinkable (meth)acrylic acid ester unit. The non-crosslinkable (meth)acrylic acid ester unit is preferably a repeating unit derived from a (meth)acrylic acid alkyl ester. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth). Isobutyl acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-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-undecyl (meth)acrylate, (meth) Examples thereof include n-dodecyl acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate. These may be used alone or in combination of two or more.
（メタ）アクリル共重合体は、必要に応じて、上述した単量体単位以外に、他の単量体単位を有してもよい。他の単量体は、上述したアクリル単量体と共重合可能なものであればよく、例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニルのようなカルボン酸ビニルエステル類やスチレン等が挙げられる。 The (meth)acrylic copolymer may have other monomer units in addition to the above-mentioned monomer units, if necessary. The other monomer may be one that can be copolymerized with the above-mentioned acrylic monomer, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, lauric acid. Examples thereof include carboxylic acid vinyl esters such as vinyl, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate and vinyl benzoate, and styrene.
（メタ）アクリル共重合体の重量平均分子量は、１０万〜２００万が好ましく、２０万〜１５０万がより好ましい。重量平均分子量は、サイズ排除クロマトグラフィー（ＳＥＣ）により測定し、ポリスチレン基準で求めた値である。（メタ）アクリル共重合体としては、市販のものを用いてもよく、公知の方法により合成したものを用いてもよい。 The weight average molecular weight of the (meth)acrylic copolymer is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,500,000. The weight average molecular weight is a value measured by size exclusion chromatography (SEC) and determined based on polystyrene. As the (meth)acrylic copolymer, a commercially available one may be used, or one synthesized by a known method may be used.
＜架橋剤＞
粘着剤層を形成する粘着剤組成物は、架橋剤を含む。架橋剤は、例えば熱により（メタ）アクリル共重合体と反応する架橋剤であることが好ましい。
<Crosslinking agent>
The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer contains a crosslinking agent. The cross-linking agent is preferably a cross-linking agent that reacts with the (meth)acrylic copolymer by heat, for example.
架橋剤としては、例えば、イソシアネート化合物、エポキシ化合物、オキサゾリン化合物、アジリジン化合物、金属キレート化合物、ブチル化メラミン化合物などの公知の架橋剤の中から、（メタ）アクリル共重合体が有する架橋性官能基との反応性を考慮して適宜選択できる。中でも、架橋剤はイソシアネート化合物であることが好ましい。 As the cross-linking agent, for example, among known cross-linking agents such as an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound, and a butylated melamine compound, a cross-linkable functional group contained in a (meth)acrylic copolymer is included. It can be appropriately selected in consideration of the reactivity with. Among them, the crosslinking agent is preferably an isocyanate compound.
イソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート等が挙げられる。ジイシアネートは２官能のまま用いてもよいし、アダクト、ヌレート、ビュレットなどの３官能誘導体にして用いても良い。 Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like. The diisocyanate may be used as it is, or may be used as a trifunctional derivative such as adduct, nurate, or buret.
架橋剤としては１種類を単独で用いても２種類以上を併用してもよい。粘着剤組成物中の架橋剤の含有量は、（メタ）アクリル共重合体１００質量部に対し、０．０１質量部以上であることが好ましく、０．１質量部以上であることがより好ましい。また、架橋剤の含有量は、（メタ）アクリル共重合体１００質量部に対し、３質量部以下であることが好ましく、１質量部以下であることがより好ましく、０．８質量部以下であることがさらに好ましい。 As the crosslinking agent, one type may be used alone, or two or more types may be used in combination. The content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the (meth)acrylic copolymer. .. The content of the cross-linking agent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and 0.8 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic copolymer. It is more preferable that there is.
＜架橋促進剤＞
粘着剤層を形成する粘着剤組成物は、架橋促進剤を含む。粘着剤組成物中の架橋促進剤の含有量はアクリル共重合体１００質量部に対して０．４５〜１．０質量部である。本発明においては、架橋促進剤の添加量を上記範囲内とすることにより、粘着剤層に微細な凹凸構造が形成されることを抑制することができ、その結果、フィルム基材表面がゆず肌状となることを抑制することができる。
<Crosslinking accelerator>
The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer contains a crosslinking accelerator. The content of the crosslinking accelerator in the pressure-sensitive adhesive composition is 0.45 to 1.0 part by mass with respect to 100 parts by mass of the acrylic copolymer. In the present invention, by setting the addition amount of the crosslinking accelerator within the above range, it is possible to suppress the formation of a fine uneven structure in the pressure-sensitive adhesive layer, and as a result, the film base material surface has an orange peel surface. Can be suppressed.
架橋促進剤としては架橋反応系に適したものが用いられればよく、例えば、有機スズ化合物；Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサンジアミン、トリエチルアミン、イミダゾール等のアミノ化合物；アルミニウム錯体等の金属錯体；パラトルエンスルホン酸、リン酸、塩酸、塩化アンモニウム等の酸触媒などが挙げられる。これらの中でも、触媒作用の観点から、有機スズ化合物が好ましい。 As the crosslinking accelerator, those suitable for the crosslinking reaction system may be used, and examples thereof include organic tin compounds; amino compounds such as N,N,N′,N′-tetramethylhexanediamine, triethylamine and imidazole; aluminum complexes and the like. A metal complex of; an acid catalyst such as paratoluenesulfonic acid, phosphoric acid, hydrochloric acid, ammonium chloride, and the like. Among these, organotin compounds are preferable from the viewpoint of catalytic action.
有機スズ化合物としては、例えば、ジメチルスズジクロライド等の有機スズ化合物；ジメチルスズジラウレート、ジメチルスズジ（２−エチルヘキサノエート）、ジメチルスズジアセテート、ジブチルスズジラウレート、ジヘキシルスズジアセテート、ジオクチルスズジラウレート等の有機スズ化合物の脂肪酸塩；ジメチルスズビス（イソオクチルチオグリコール酸エステル）塩、ジオクチルスズビス（イソオクチルチオグリコール酸エステル）塩等の有機スズ化合物のチオグリコール酸エステル塩；オクチル酸スズ、デカン酸スズ等の金属石鹸などが挙げられる。上記の中でも、触媒作用の観点から、有機スズ化合物の脂肪酸塩が好ましく、特にジブチルスズジラウレートが好ましい。 Examples of the organotin compound include organotin compounds such as dimethyltin dichloride; dimethyltin dilaurate, dimethyltin di(2-ethylhexanoate), dimethyltin diacetate, dibutyltin dilaurate, dihexyltin diacetate, dioctyltin dilaurate, and the like. Fatty acid salt of tin compound; thioglycolic acid ester salt of organic tin compound such as dimethyltin bis (isooctyl thioglycolic acid ester) salt and dioctyl tin bis (isooctyl thioglycolic acid ester) salt; tin octylate, tin decanoate And the like, such as metal soap. Among the above, fatty acid salts of organic tin compounds are preferable, and dibutyltin dilaurate is particularly preferable, from the viewpoint of catalytic action.
＜架橋遅延剤＞
粘着剤層を形成する粘着剤組成物は、架橋遅延剤を含んでもよい。架橋遅延剤としては、例えば、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸オクチル、アセト酢酸オレイル、アセト酢酸ラウリル、アセト酢酸ステアリル等のβ−ケトエステルや、アセチルアセトン、２，４−ヘキサンジオン、ベンゾイルアセトン等のβ−ジケトンが挙げられる。これらの中でも、ポットライフと硬化性のバランスの点から、架橋遅延剤としてアセチルアセトンを用いることが好ましい。
<Crosslink retarder>
The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer may contain a crosslinking retarder. Examples of the crosslinking retarder include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate and stearyl acetoacetate, acetylacetone, 2,4-hexanedione, and benzoylacetone. .Beta.-diketone. Among these, acetylacetone is preferably used as the crosslinking retarder from the viewpoint of the balance between pot life and curability.
架橋遅延剤としては１種類を単独で用いても２種類以上を併用してもよい。粘着剤組成物中の架橋剤の含有量は、所望とする接着物性等に応じて適宜選択され、特に限定されないが、（メタ）アクリル共重合体１００質量部に対し、０．０００１質量部以上であることが好ましく、０．００１質量部以上であることがより好ましい。また、架橋遅延剤の含有量は、（メタ）アクリル共重合体１００質量部に対し、５質量部以下であることが好ましく、３質量部以下であることがより好ましい。粘着剤組成物が架橋遅延剤を含有することにより、粘着剤組成物の過剰な粘度上昇やゲル化を抑制し、粘着剤組成物のポットライフを延長することができる。 As the crosslinking retarder, one kind may be used alone, or two or more kinds may be used in combination. The content of the crosslinking agent in the pressure-sensitive adhesive composition is appropriately selected according to the desired adhesive properties and the like, and is not particularly limited, but 0.0001 parts by mass or more relative to 100 parts by mass of the (meth)acrylic copolymer. Is preferable, and 0.001 parts by mass or more is more preferable. Further, the content of the crosslinking retarder is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, relative to 100 parts by mass of the (meth)acrylic copolymer. When the pressure-sensitive adhesive composition contains the crosslinking retarder, it is possible to suppress an excessive increase in viscosity and gelation of the pressure-sensitive adhesive composition and to extend the pot life of the pressure-sensitive adhesive composition.
＜溶剤＞
粘着剤層を形成する粘着剤組成物は、溶剤を含んでいてもよい。この場合、溶剤は、粘着剤組成物の塗工適性の向上のために用いられる。溶剤としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の炭化水素類；ジクロロメタン、トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、ジクロロプロパン等のハロゲン化炭化水素類；メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、イソブチルアルコール、ジアセトンアルコール等のアルコール類；ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、イソホロン、シクロヘキサノン等のケトン類；酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸アミル、酪酸エチル等のエステル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテルアセタート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセタート等のポリオール及びその誘導体が挙げられる。
<Solvent>
The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer may contain a solvent. In this case, the solvent is used for improving the coating suitability of the pressure-sensitive adhesive composition. Examples of the solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichloropropane; methanol, ethanol, Alcohols such as propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone; methyl acetate , Ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl butyrate and other esters; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Examples thereof include polyols such as glycol monomethyl ether acetate and derivatives thereof.
溶剤は１種類を単独で使用してもよいし、２種類以上を併用してもよい。粘着剤組成物中の溶剤の含有量は、特に限定されないが、（メタ）アクリル共重合体１００質量部に対し、２５質量部以上５００質量部以下とすることが好ましく、３０質量部以上４００質量部以下とすることがより好ましい。 As the solvent, one type may be used alone, or two or more types may be used in combination. The content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but is preferably 25 parts by mass or more and 500 parts by mass or less, and 30 parts by mass or more and 400 parts by mass with respect to 100 parts by mass of the (meth)acrylic copolymer. It is more preferable that the amount is not more than part.
＜他の成分＞
粘着剤層は、本発明の効果を損なわない範囲で、上記以外の他の成分を含有してもよい。他の成分としては、粘着剤用の添加剤として公知の成分を挙げることができる。例えば可塑剤、酸化防止剤、金属腐食防止剤、粘着付与剤、シランカップリング剤、紫外線吸収剤、ヒンダードアミン系化合物等の光安定剤等の中から必要に応じて選択できる。また、着色を目的に染料や顔料を添加してもよい。
可塑剤としては、例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニルのようなカルボン酸ビニルエステル類やスチレン等が挙げられる。
酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。これら酸化防止剤は１種類を単独で使用してもよいし、２種類以上を併用してもよい。
金属腐食防止剤としては、粘着剤の相溶性や効果の高さから、ベンゾリアゾール系樹脂を好ましい例として挙げることができる。
粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。
シランカップリング剤としては、例えば、メルカプトアルコキシシラン化合物（例えば、メルカプト基置換アルコキシオリゴマー等）などが挙げられる。
紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。ただし、後硬化時の活性エネルギー線に紫外線を用いる場合は、重合反応を阻害しない範囲で添加することが好ましい。
<Other ingredients>
The pressure-sensitive adhesive layer may contain components other than the above components as long as the effects of the present invention are not impaired. Examples of other components include components known as additives for pressure-sensitive adhesives. For example, a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, and a light stabilizer such as a hindered amine compound can be selected as necessary. Further, a dye or a pigment may be added for the purpose of coloring.
Examples of the plasticizer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, and benzoic acid. Examples thereof include carboxylic acid vinyl esters such as vinyl acid salt and styrene.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like. These antioxidants may be used alone or in combination of two or more.
As the metal corrosion inhibitor, a benzotriazole resin can be mentioned as a preferable example because of the compatibility of the pressure-sensitive adhesive and the high effect.
Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, petroleum resin and the like.
Examples of the silane coupling agent include a mercaptoalkoxysilane compound (eg, a mercapto group-substituted alkoxy oligomer).
Examples of the ultraviolet absorber include benzotriazole compounds and benzophenone compounds. However, when ultraviolet rays are used as the active energy rays at the time of post-curing, it is preferable to add them in a range that does not inhibit the polymerization reaction.
（剥離フィルム）
本発明の積層シートに用いられる剥離フィルムは、剥離フィルム用基材と剥離剤層とを有する積層剥離フィルムであってもよく、合成樹脂等からなる単層剥離フィルムであってもよい。この場合、単層剥離フィルムとしては、例えば、低極性基材としてポリエチレンフィルムやポリプロピレンフィルム等のポリオレフィンフィルム等が挙げられる。積層剥離フィルムにおける剥離フィルム用基材には、紙類、樹脂フィルムが使用される。剥離フィルム用基材が樹脂フィルムである場合、ポリエチレンフィルムやポリプロピレンフィルム等のポリオレフィンフィルム等が挙げられる。剥離剤層を構成する剥離剤としては、例えば、汎用の付加型もしくは縮合型のシリコーン系剥離剤や長鎖アルキル基含有化合物等が用いられる。特に、反応性が高い付加型シリコーン系剥離剤が好ましく用いられる。
(Peeling film)
The release film used in the laminated sheet of the present invention may be a laminated release film having a release film substrate and a release agent layer, or may be a single layer release film made of a synthetic resin or the like. In this case, examples of the single-layer release film include polyolefin films such as polyethylene film and polypropylene film as the low-polarity base material. Papers and resin films are used as the release film substrate in the laminated release film. When the base material for the release film is a resin film, a polyolefin film such as a polyethylene film or a polypropylene film can be used. As the release agent constituting the release agent layer, for example, a general-purpose addition type or condensation type silicone type release agent, a long chain alkyl group-containing compound, or the like is used. In particular, an addition type silicone release agent having high reactivity is preferably used.
剥離フィルムの露出面（粘着剤層と接する面とは反対側の面）の算術平均粗さ（Ｒａ）は、１０ｎｍ以上であってもよく、２０ｎｍ以上であってもよく、３０ｎｍ以上であってもよく、３５ｎｍ以上であってもよい。また、剥離フィルムの露出面（粘着剤層と接する面とは反対側の面）の最大突起高さ（Ｒｐ）は、５０ｎｍ以上であってもよく、１００ｎｍ以上であってもよい。このように、本発明においては、算術平均粗さ（Ｒａ）や最大突起高さ（Ｒｐ）の値がある程度大きい場合においてもゆず肌の発生を抑制することができる。なお、剥離フィルムの算術平均粗さ（Ｒａ）は、１０ｎｍ未満であってもよく、剥離フィルムの最大突起高さ（Ｒｐ）は、５０ｎｍ未満であってもよい。
なお、剥離フィルムにおいて、算術平均粗さＲａ及び最大突起高さＲｐを測定する際には、ＪＩＳ Ｂ ０６０１−１９９４に準拠して測定する。剥離フィルムが、剥離剤層を有している場合には、剥離剤層が設けられた面とは反対側の面の測定を行う。測定機器としては、ミツトヨ社製の表面粗さ測定機ＳＶ３２００（触針式）等を用いることができる。
The exposed surface of the release film (the surface opposite to the surface in contact with the pressure-sensitive adhesive layer) has an arithmetic average roughness (Ra) of 10 nm or more, 20 nm or more, or 30 nm or more. May be 35 nm or more. The maximum protrusion height (Rp) of the exposed surface (the surface opposite to the surface in contact with the pressure-sensitive adhesive layer) of the release film may be 50 nm or more, or 100 nm or more. As described above, in the present invention, it is possible to suppress the occurrence of orange peel skin even when the values of the arithmetic mean roughness (Ra) and the maximum protrusion height (Rp) are large to some extent. The arithmetic mean roughness (Ra) of the release film may be less than 10 nm, and the maximum protrusion height (Rp) of the release film may be less than 50 nm.
In the release film, the arithmetic mean roughness Ra and the maximum protrusion height Rp are measured in accordance with JIS B 0601-1994. When the release film has a release agent layer, the surface opposite to the surface provided with the release agent layer is measured. As a measuring instrument, a surface roughness measuring instrument SV3200 (stylus type) manufactured by Mitutoyo can be used.
また、剥離フィルムの露出面（粘着剤層と接する面とは反対側の面）を、ウェーブスキャン装置を用いて波長０．３〜１．０ｍｍの波長域の反射強度（Ｗｂ）を測定した場合、反射強度（Ｗｂ）は、１０以上であってもよく、１２以上であってもよく、１５以上であってもよい。なお、剥離フィルムの反射強度（Ｗｂ）は、１０未満であってもよい。 When the exposed surface of the release film (the surface opposite to the surface in contact with the pressure-sensitive adhesive layer) was measured for reflection intensity (Wb) in the wavelength range of 0.3 to 1.0 mm using a wave scan device. The reflection intensity (Wb) may be 10 or more, 12 or more, or 15 or more. The reflection strength (Wb) of the release film may be less than 10.
剥離フィルムの反射強度を測定する際には、ガラス板上に剥離フィルムの剥離処理面（積層シートにおいて粘着剤層に貼合される側の面）を下にして置いた後、剥離フィルムの剥離処理面とは反対側の面（積層シートにおいて粘着剤層とは反対側の露出面）の反射光の量ＢＹＫ Ｇａｒｄｎｅｒ社製のウェーブ−スキャン デュアルを用いて測定する。そして、得られた光学的プロファイルをフィルター関数変換を用いて分類した後に、波長０．３〜１．０ｍｍの波長域の反射強度を取得する。なお、剥離フィルムの反射強度（Ｗｂ）を測定する際には、積層前の剥離フィルムについて測定を行うことが好ましいが、積層シートから剥離フィルムを剥離した後に、剥離フィルムについて測定を行ってもよく、積層シートの剥離フィルムの露出面（粘着剤層と接する面とは反対側の面）について測定を行ってもよい。 When measuring the reflection strength of the release film, put it on a glass plate with the release-treated surface of the release film (the surface of the laminated sheet that is to be attached to the adhesive layer) facing down, and then remove the release film. Amount of reflected light on the surface opposite to the treated surface (exposed surface on the opposite side of the pressure-sensitive adhesive layer in the laminated sheet) It is measured using a wave-scan dual manufactured by BYK Gardner. Then, after classifying the obtained optical profile by using the filter function conversion, the reflection intensity in the wavelength range of 0.3 to 1.0 mm is acquired. When measuring the reflection strength (Wb) of the release film, it is preferable to measure the release film before lamination, but it is also possible to measure the release film after releasing the release film from the laminated sheet. The measurement may be performed on the exposed surface of the release film of the laminated sheet (the surface opposite to the surface in contact with the pressure-sensitive adhesive layer).
剥離フィルムの厚みは、１０μｍ以上であることが好ましく、２０μｍ以上であることがより好ましく、３０μｍ以上であることがさらに好ましい。また、剥離フィルムの厚みは、１５０μｍ以下であることが好ましく、１２０μｍ以下であることがより好ましく、１００μｍ以下であることがさらに好ましい。 The thickness of the release film is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more. The thickness of the release film is preferably 150 μm or less, more preferably 120 μm or less, and further preferably 100 μm or less.
（フィルム基材）
フィルム基材としては、一般に粘着シートの基材として使用される各種の樹脂フィルム基材を挙げることができる。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレン、ポリプロピレン、セロファン、ジアセチルセルロース、トリアセチルセルロース、アセチルセルロースブチレート、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、エチレン−酢酸ビニル共重合体、ポリスチレン、ポリカーボネート、ポリメチルペンテン、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリエーテルイミド、ポリイミド、シクロオレフィン、フッソ樹脂、ナイロン、アクリル樹脂等の樹脂フィルムを挙げることができる。
(Film base material)
Examples of the film base material include various resin film base materials generally used as a base material of an adhesive sheet. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, Resin films of polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, cycloolefin, fluorine resin, nylon, acrylic resin and the like can be mentioned.
フィルム基材は、上記樹脂フィルムのみからなる基材であっても良いが、他の層を設けた積層フィルム基材であってもよい。この場合、他の層としては、例えば、ハードコート層、反射防止層、低屈折率層、高屈折率層、防眩層、帯電防止層、紫外線吸収層、ガスバリア層、ブロッキング防止層等を挙げることができる。 The film substrate may be a substrate composed only of the above resin film, or may be a laminated film substrate provided with other layers. In this case, examples of the other layer include a hard coat layer, an antireflection layer, a low refractive index layer, a high refractive index layer, an antiglare layer, an antistatic layer, an ultraviolet absorbing layer, a gas barrier layer, and an antiblocking layer. be able to.
フィルム基材の厚みは、特に限定されるものではないが、１０μｍ以上２００μｍ以下であることが好ましい。フィルム基材は、その厚みが大きい方がゆず肌の影響が出にくいが、本発明においては、例えば、フィルム基材の厚みが３８μｍ以下や２５μｍ以下といった薄膜の場合であってもゆず肌の発生を抑制することができる。 The thickness of the film substrate is not particularly limited, but is preferably 10 μm or more and 200 μm or less. The greater the thickness of the film substrate, the less likely it is that the skin will be affected, but in the present invention, even if the thickness of the film substrate is a thin film of 38 μm or less or 25 μm or less, the occurrence of orange skin occurs. Can be suppressed.
（積層シートの製造方法）
積層シートの製造方法は、特に限定されるものではないが、例えば、剥離フィルム上に粘着剤組成物を塗工して塗膜を形成する工程と、この塗膜を加熱することにより粘着剤層を得る工程と、この粘着剤層上にフィルム基材を貼合する工程と、を含むことが好ましい。本発明においては、上述した工程の後に、さらに、積層シートを巻回する工程を設け、積層シートの巻回体を得る工程を含むことが好ましい。
(Method for manufacturing laminated sheet)
The method for producing the laminated sheet is not particularly limited, for example, a step of applying a pressure-sensitive adhesive composition on a release film to form a coating film, and heating the coating film to form a pressure-sensitive adhesive layer. It is preferable to include a step of obtaining and a step of laminating a film base material on the pressure-sensitive adhesive layer. In the present invention, it is preferable to further include a step of winding the laminated sheet after the above-mentioned step to obtain a wound body of the laminated sheet.
塗膜を形成する工程では、公知の塗工装置を用いて粘着剤組成物塗工することが好ましい。塗工装置としては、例えば、ブレードコーター、エアナイフコーター、ロールコーター、バーコーター、グラビアコーター、マイクログラビアコーター、ロッドブレードコーター、リップコーター、ダイコーター、カーテンコーター等が挙げられる。 In the step of forming a coating film, it is preferable to apply the pressure-sensitive adhesive composition using a known coating device. Examples of the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, and a curtain coater.
塗膜の加熱は、加熱炉、赤外線ランプ等の公知の加熱装置を用いて実施できる。加熱温度は、６０℃以上２００℃以下であることが好ましい。 The coating film can be heated using a known heating device such as a heating furnace or an infrared lamp. The heating temperature is preferably 60° C. or higher and 200° C. or lower.
このようにして得られた積層シートを巻回体とする場合には、積層シートを紙管等の管状体に巻回する。巻回時の積層シートの張力は、２０Ｎ以上であることが好ましく、３０Ｎ以上であることがより好ましい。巻回時の積層シートの張力の上限値は特に限定されるものではないが、張力が大きいほど、ゆず肌の発生が促進される傾向にあるため、巻回時の積層シートの張力は、１００Ｎ以下であることが好ましい。 When the laminated sheet thus obtained is used as a wound body, the laminated sheet is wound around a tubular body such as a paper tube. The tension of the laminated sheet during winding is preferably 20 N or more, and more preferably 30 N or more. The upper limit of the tension of the laminated sheet at the time of winding is not particularly limited, but the higher the tension is, the more the tendency of the generation of tanned skin is promoted. Therefore, the tension of the laminated sheet at the time of winding is 100 N. The following is preferable.
積層シートを巻回体とする場合には、巻取り長さは、５０ｍ以上であってもよく、６０ｍ以上であってもよく、１００ｍ以上であってもよい。巻取り長さの上限値は特に限定されるものではなく、積層シートの用途に応じて適宜変更できる。 When the laminated sheet is used as a wound body, the winding length may be 50 m or more, 60 m or more, and 100 m or more. The upper limit of the winding length is not particularly limited and can be appropriately changed depending on the application of the laminated sheet.
上述した工程では、塗膜の加熱により、（メタ）アクリル共重合体及び架橋剤等の反応が進行して硬化物（粘着剤層）が形成される。粘着剤組成物を硬化状態とするためには、塗工後溶剤を除去した後に、一定温度で一定期間粘着シートを静置するエージング処理を施してもよい。エージング処理は、巻回体とした後に施されてもよく、例えば、２３℃で７日間静置して行うことができる。 In the above-mentioned steps, the reaction of the (meth)acrylic copolymer and the cross-linking agent proceeds by heating the coating film to form a cured product (adhesive layer). In order to bring the pressure-sensitive adhesive composition into a cured state, the solvent may be removed after coating, and then the pressure-sensitive adhesive sheet may be allowed to stand for a certain period of time at a certain temperature. The aging treatment may be performed after forming the wound body, and for example, the aging treatment can be performed by leaving it at 23° C. for 7 days.
（用途）
本発明の積層シートは、光学部材貼合用の積層シートであることが好ましい。積層シートを光学部材に貼合する際には、剥離フィルムを剥離し、露出した粘着剤層を光学部材に貼合する。本発明の積層シートは、剥離フィルムを剥離することで、例えば、反射防止フィルム、飛散防止フィルム、表面保護フィルム、配向フィルム、偏光フィルム、位相差フィルム、輝度向上フィルムとして用いられる。
(Use)
The laminated sheet of the present invention is preferably a laminated sheet for bonding optical members. When the laminated sheet is attached to the optical member, the release film is peeled off and the exposed pressure-sensitive adhesive layer is attached to the optical member. By peeling off the release film, the laminated sheet of the present invention is used as, for example, an antireflection film, an anti-scattering film, a surface protection film, an alignment film, a polarizing film, a retardation film, or a brightness enhancement film.
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The features of the present invention will be described more specifically below with reference to Examples and Comparative Examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.
（実施例１）
[粘着剤組成物の調製]
攪拌機、還流冷却器、逐次滴下装置、温度計を備えた反応装置に、酢酸エチル１５０質量部及び２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．０５質量部を仕込んだ。次いで、別の容器にアクリル酸２−エチルヘキシル（２ＥＨＡ）２７６質量部、アクリル酸２−ヒドロキシエチル（２ＨＥＡ）２１６質量部、メタクリル酸２−エチルヘキシル（２ＥＨＭＡ）１０８質量部からなる単量体混合液６００質量部を準備し、このうち１５０質量部を反応装置に仕込み、加熱し、還流温度で３０分間還流を行った。次いで、還流温度条件下で単量体混合液の残り４５０質量部と酢酸エチル３５質量部及び２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．０３質量部を１２０分間にわたって逐次滴下し、滴下終了後更に１２０分間の重合反応を行った。その後、酢酸エチル１５質量部とｔ−ブチルパーオキシピバレート１．０質量部の混合液を４０分にわたって逐次滴下し、更に２００分間重合反応を行った。反応終了後、酢酸エチルにて固形分５０質量％に希釈し、（メタ）アクリル共重合体（Ｘ）の溶液を得た。（メタ）アクリル共重合体（Ｘ）の重量平均分子量は４５０，０００であった。なお、（メタ）アクリル共重合体（Ｘ）の重量平均分子量（Ｍｗ）は、ＴＨＦ（テトラヒドロフラン）に溶解した試料をＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定した。
上記の通り得られたアクリル共重合体（Ｘ）の固形分１００質量部に対して、架橋剤（日本カーバイド社製：ニッセツ ＣＫ−１２１）を０．１１質量部、架橋促進剤（トーヨーケム社製：ＢＸＸ−３７７８−１０）を０．４５質量部、架橋遅延剤（トーヨーケム社製：ＢＸＸ５６３８）を０．０６３質量部加え、酢酸エチルにて固形分濃度が３９質量％の溶液となるように希釈攪拌し、粘着剤組成物Ａを調製した。
(Example 1)
[Preparation of adhesive composition]
A reactor equipped with a stirrer, a reflux condenser, a sequential dropping device, and a thermometer was charged with 150 parts by mass of ethyl acetate and 0.05 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile). Then, in another container, a monomer mixture liquid 600 containing 276 parts by mass of 2-ethylhexyl acrylate (2EHA), 216 parts by mass of 2-hydroxyethyl acrylate (2HEA), and 108 parts by mass of 2-ethylhexyl methacrylate (2EHMA). Part by mass was prepared, and 150 parts by mass were charged into a reactor, heated, and refluxed at a reflux temperature for 30 minutes. Next, the remaining 450 parts by mass of the monomer mixture, 35 parts by mass of ethyl acetate, and 0.03 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile) were successively added dropwise under a reflux temperature condition over 120 minutes. Then, after the dropping was completed, the polymerization reaction was further performed for 120 minutes. Then, a mixed solution of 15 parts by mass of ethyl acetate and 1.0 part by mass of t-butylperoxypivalate was successively added dropwise over 40 minutes, and a polymerization reaction was further performed for 200 minutes. After completion of the reaction, the solid content was diluted to 50% by mass with ethyl acetate to obtain a solution of (meth)acrylic copolymer (X). The weight average molecular weight of the (meth)acrylic copolymer (X) was 450,000. The weight average molecular weight (Mw) of the (meth)acrylic copolymer (X) was measured by GPC (gel permeation chromatography) using a sample dissolved in THF (tetrahydrofuran).
With respect to 100 parts by mass of the solid content of the acrylic copolymer (X) obtained as described above, 0.11 parts by mass of a crosslinking agent (manufactured by Nippon Carbide Co.: Nisetsu CK-121) and a crosslinking accelerator (manufactured by Toyochem Co., Ltd.) : BXX-3778-10) in an amount of 0.45 part by mass, a cross-linking retarder (manufactured by Toyochem Co., Ltd.: BXX5638) in an amount of 0.063 part by mass, and diluted with ethyl acetate to a solution having a solid content concentration of 39% by mass. The pressure-sensitive adhesive composition A was prepared by stirring.
［基材付粘着シート（積層シート）の作製］
ロール状に巻回されている厚み７５μｍの剥離フィルム（東洋紡社製：Ｅ７００２）を繰り出し、その剥離フィルムの剥離処理面上に、上記粘着剤組成物Ａをリップコーターにより塗布し、１００℃で１．５分間乾燥させ、剥離フィルムの上に厚さが１５μｍの粘着剤層を形成した。次いで、ロール状に巻回されている厚み２３μｍのフィルム基材（東レ社製：Ｕ４０３）を繰り出し、上記粘着剤層上に貼り合わせ、３インチの紙管に張力６０Ｎで１００ｍ巻き取って基材付粘着シート（積層シート）の巻回体を作製した。次に、上記巻回体を２３℃、相対湿度５０％で１週間保管した後、８０ｍ巻き出した位置で基材付粘着シートを５ｍ採取した。
別途、ゲル分率等の測定用サンプルとして、基材レス粘着シートを作製した。上述した基材付粘着シートの作製において、剥離フィルム（東洋紡社製：Ｅ７００２）を、厚み７５μｍの（帝人フィルムソリューション社製：Ａ７１）に変更し、フィルム基材（東レ社製：Ｕ４０３）を、厚み７５μｍの剥離フィルム（帝人フィルムソリューション社製：Ａ３８ＳＴ）に変更した以外は上記基材付粘着シートと同様にして、基材レス粘着シートの巻回体を得た。
[Production of adhesive sheet with base material (laminated sheet)]
A 75 μm-thick release film (E7002, manufactured by Toyobo Co., Ltd.) wound in a roll is unwound, and the pressure-sensitive adhesive composition A is applied onto the release-treated surface of the release film with a lip coater, and the temperature is 1° C. at 1° C. After drying for 5 minutes, a pressure-sensitive adhesive layer having a thickness of 15 μm was formed on the release film. Then, a film base material having a thickness of 23 μm (manufactured by Toray Industries: U403) wound in a roll shape is unrolled, adhered onto the pressure-sensitive adhesive layer, and wound onto a 3-inch paper tube at a tension of 60 N for 100 m to form a base material. A wound body of the attached pressure-sensitive adhesive sheet (laminated sheet) was produced. Next, the wound body was stored at 23° C. and a relative humidity of 50% for 1 week, and then the adhesive sheet with a substrate was sampled for 5 m at a position where it was rolled out by 80 m.
Separately, a substrateless pressure-sensitive adhesive sheet was prepared as a sample for measuring the gel fraction and the like. In the production of the pressure-sensitive adhesive sheet with a base material described above, the release film (manufactured by Toyobo Co., Ltd.: E7002) was changed to a thickness of 75 μm (made by Teijin Film Solutions: A71), and the film base material (manufactured by Toray Co.: U403) was changed to A roll of a substrate-less pressure-sensitive adhesive sheet was obtained in the same manner as the pressure-sensitive adhesive sheet with a substrate, except that the release film having a thickness of 75 μm (A38ST manufactured by Teijin Film Solutions, Ltd.) was used.
（実施例２）
粘着剤組成物Ａの調製において、架橋促進剤の添加部数を０．４５質量部から０．６質量部に変更した以外は実施例１と同様にして実施例２の基材付粘着シートと基材レス粘着シートを得た。
(Example 2)
In the preparation of the pressure-sensitive adhesive composition A, the pressure-sensitive adhesive sheet with a base material and the base material of Example 2 were used in the same manner as in Example 1 except that the addition number of the crosslinking accelerator was changed from 0.45 part by mass to 0.6 part by mass. A material-less pressure-sensitive adhesive sheet was obtained.
（実施例３）
粘着剤組成物Ａの調製において、架橋促進剤の添加部数を０．４５質量部から１．０質量部に変更した以外は実施例１と同様にして実施例３の基材付粘着シートと基材レス粘着シートを得た。
(Example 3)
In the preparation of the pressure-sensitive adhesive composition A, the pressure-sensitive adhesive sheet with the substrate of Example 3 and the base were prepared in the same manner as in Example 1 except that the addition number of the crosslinking accelerator was changed from 0.45 parts by mass to 1.0 part by mass. A material-less pressure-sensitive adhesive sheet was obtained.
（実施例４）
アクリル重合体溶液（トーヨーケム社製：ＢＰＳ６３７７−ＯＰ）の固形分１００質量部に対して、架橋剤（東洋インキ社製：ＢＸＸ５６２７）を０．７５質量部、架橋促進剤（トーヨーケム社製：ＢＸＸ−３７７８−１０）を０．６質量部、架橋遅延剤（トーヨーケム社製：ＢＸＸ５６３８）を０．０１３質量部加え、酢酸エチルにて固形分濃度が３９質量％の溶液となるように希釈攪拌し、粘着剤組成物Ｂを調製した。
粘着剤組成物Ａを粘着剤組成物Ｂに変更し、さらに剥離フィルム（東洋紡社製：Ｅ７００２）を、厚み７５μｍの（帝人フィルムソリューション社製：Ａ３８ＳＴ）に変更した以外は実施例１と同様にして実施例４の基材付粘着シートと基材レス粘着シートを得た。
(Example 4)
To 100 parts by mass of the solid content of the acrylic polymer solution (BPS6377-OP manufactured by Toyochem Co., Ltd.), 0.75 parts by mass of a crosslinking agent (BXX5627 manufactured by Toyo Ink Co., Ltd.) and a crosslinking accelerator (BXX-manufactured by Toyochem Co., Ltd.) are used. 3778-10) in an amount of 0.6 part by mass, a crosslinking retarder (manufactured by Toyochem Co., Ltd.: BXX5638) in an amount of 0.013 part by mass, and diluted with ethyl acetate so that the solid content concentration is 39% by mass, and the mixture is stirred. Adhesive composition B was prepared.
Same as Example 1 except that the pressure-sensitive adhesive composition A was changed to the pressure-sensitive adhesive composition B, and the release film (Toyobo Co., Ltd.: E7002) was changed to a thickness of 75 μm (Teijin Film Solution Co., Ltd.: A38ST). Thus, a pressure-sensitive adhesive sheet with a base material and a pressure-sensitive adhesive sheet without a base material of Example 4 were obtained.
（実施例５）
粘着剤組成物Ｂの調製において、架橋促進剤の添加部数を０．６質量部から０．８質量部に変更した以外は実施例４と同様にして実施例５の基材付粘着シートと基材レス粘着シートを得た。
(Example 5)
In the preparation of the pressure-sensitive adhesive composition B, the pressure-sensitive adhesive sheet with the substrate of Example 5 and the base were prepared in the same manner as in Example 4 except that the addition number of the crosslinking accelerator was changed from 0.6 parts by mass to 0.8 parts by mass. A material-less pressure-sensitive adhesive sheet was obtained.
（比較例１）
粘着剤組成物Ａの調製において、架橋促進剤の添加部数を０．４５質量部から０質量部に、架橋遅延剤の添加部数を０．０６３質量部から０質量部に変更した以外は実施例１と同様にして比較例１の基材付粘着シートと基材レス粘着シートを得た。
(Comparative Example 1)
In the preparation of the pressure-sensitive adhesive composition A, except that the addition amount of the crosslinking accelerator was changed from 0.45 parts by mass to 0 parts by mass and the addition amount of the crosslinking retarder was changed from 0.063 parts by mass to 0 parts by mass. In the same manner as in Example 1, a pressure-sensitive adhesive sheet with a substrate and a pressure-sensitive adhesive sheet without a substrate of Comparative Example 1 were obtained.
（比較例２）
粘着剤組成物Ａの調製において、架橋促進剤の添加部数を０．４５質量部から０．４質量部に、架橋遅延剤の添加部数を０．０６３質量部から０質量部に変更した以外は実施例１と同様にして比較例２の基材付粘着シートと基材レス粘着シートを得た。
(Comparative example 2)
In the preparation of the pressure-sensitive adhesive composition A, except that the addition amount of the crosslinking accelerator was changed from 0.45 parts by mass to 0.4 parts by mass and the addition amount of the crosslinking retarder was changed from 0.063 parts by mass to 0 parts by mass. In the same manner as in Example 1, a pressure-sensitive adhesive sheet with a substrate and a pressure-sensitive adhesive sheet without a substrate of Comparative Example 2 were obtained.
（比較例３）
粘着剤組成物Ｂの調製において、架橋促進剤の添加部数を０．６質量部から０．００３質量部に、架橋遅延剤の添加部数を０．０１３質量部から０．００１３質量部に変更した以外は実施例４と同様にして比較例３の基材付粘着シートと基材レス粘着シートを得た。
(Comparative example 3)
In the preparation of the pressure-sensitive adhesive composition B, the number of added parts of the crosslinking accelerator was changed from 0.6 parts by mass to 0.003 parts by mass, and the number of added parts of the crosslinking retarder was changed from 0.013 parts by mass to 0.0013 parts by mass. Except for this, the pressure-sensitive adhesive sheet with a substrate and the pressure-sensitive adhesive sheet without a substrate of Comparative Example 3 were obtained in the same manner as in Example 4.
（比較例４）
架橋促進剤の添加部数を０．００３質量部から０．１５質量部に変更した以外は比較例３と同様にして比較例４の基材付粘着シートと基材レス粘着シートを得た。
(Comparative example 4)
A pressure-sensitive adhesive sheet with a base material and a pressure-sensitive adhesive sheet without a base material of Comparative Example 4 were obtained in the same manner as Comparative Example 3 except that the addition amount of the crosslinking accelerator was changed from 0.003 parts by mass to 0.15 parts by mass.
（比較例５）
架橋促進剤の添加部数を０．００３質量部から０．３質量部に変更した以外は比較例３と同様にして比較例５の基材付粘着シートと基材レス粘着シートを得た。
(Comparative example 5)
A pressure-sensitive adhesive sheet with a base material and a pressure-sensitive adhesive sheet without a base material of Comparative Example 5 were obtained in the same manner as in Comparative Example 3 except that the addition number of the crosslinking accelerator was changed from 0.003 parts by mass to 0.3 part by mass.
（測定）
＜反射強度＞
粉塵除去用粘着ローラーを用いて３０×４０ｃｍのガラス板表面の粉塵を除去した。次いで、実施例及び比較例の剥離フィルムを１５×２０ｃｍにカットした後、剥離処理面を下にしてガラス板上に置いた。剥離処理面の反対面の反射光の量をウェーブ−スキャン デュアル（ＢＹＫ Ｇａｒｄｎｅｒ社製）を用いて測定した。表示される波長０．３〜１．０ｍｍ領域の反射強度Ｗｂの値を表１に記載した。
(Measurement)
<Reflection intensity>
The dust on the surface of the glass plate of 30×40 cm was removed using an adhesive roller for removing dust. Then, the release films of Examples and Comparative Examples were cut into a size of 15×20 cm and placed on a glass plate with the release-treated surface facing down. The amount of reflected light on the surface opposite to the release treated surface was measured using a wave-scan dual (manufactured by BYK Gardner). Table 1 shows the value of the reflection intensity Wb in the displayed wavelength range of 0.3 to 1.0 mm.
＜算術平均粗さ（Ｒａ）および最大突起高さ（Ｒｐ）＞
実施例および比較例で用いた剥離フィルムにおいて、剥離処理面とは反対面の算術平均粗さＲａ及び最大突起高さＲｐを、ミツトヨ社製の表面粗さ測定機ＳＶ３２００（触針式）を使用して、ＪＩＳ Ｂ ０６０１−１９９４に準拠して測定した。
<Arithmetic mean roughness (Ra) and maximum protrusion height (Rp)>
In the release films used in Examples and Comparative Examples, the arithmetic mean roughness Ra and the maximum protrusion height Rp on the surface opposite to the release-treated surface were measured using a surface roughness measuring machine SV3200 (stylus type) manufactured by Mitutoyo Corporation. Then, it was measured according to JIS B 0601-1994.
＜ゲル分率＞
実施例及び比較例の基材レス粘着シートの巻回体から、塗工乾燥直後に基材レス粘着シートを６０×１００ｍｍにカットした後、両面の剥離フィルムを剥がし、粘着剤層を金属メッシュ（１５０メッシュ）に包んだ。メッシュに包まれたサンプルを酢酸エチルに浸し、４０℃で２４時間放置した。取り出した粘着剤層を１００℃で１時間乾燥させ、酢酸エチル浸漬前後の重量比率を算出し、下記式から塗工乾燥直後の粘着剤層のゲル分率を求めた。
ゲル分率（％）＝酢酸エチル浸漬後の粘着剤層の重量／酢酸エチル浸漬前の粘着剤層の重量×１００
<Gel fraction>
From the wound body of the substrate-less pressure-sensitive adhesive sheet of each of Examples and Comparative Examples, the substrate-less pressure-sensitive adhesive sheet was cut into 60×100 mm immediately after coating and drying, and then the release films on both sides were peeled off to separate the pressure-sensitive adhesive layer from the metal mesh ( 150 mesh). The sample wrapped in the mesh was dipped in ethyl acetate and left at 40° C. for 24 hours. The pressure-sensitive adhesive layer taken out was dried at 100° C. for 1 hour, the weight ratio before and after dipping in ethyl acetate was calculated, and the gel fraction of the pressure-sensitive adhesive layer immediately after coating and drying was calculated from the following formula.
Gel fraction (%)=weight of pressure-sensitive adhesive layer after immersion in ethyl acetate/weight of pressure-sensitive adhesive layer before immersion in ethyl acetate×100
（評価）
＜ゆず肌評価＞
実施例及び比較例の基材付粘着シートの剥離フィルムを剥がし、露出した粘着剤層を黒アクリル板（三菱ケミカル社製）に貼合した。その後、蛍光灯の光を反射させて観察し、フィルム基材に写り込んだ蛍光灯の像の歪を以下の基準で評価した。
◎：フィルム基材に写り込んだ蛍光灯の像の歪がなく、ゆず肌の発生が完全に抑制されている。
○：フィルム基材に写り込んだ蛍光灯の像が僅かに歪んで見え、若干のゆず肌の発生があるが問題のないレベルである。
×：フィルム基材に写り込んだ蛍光灯の像が歪んで見え、ゆず肌が発生している。
(Evaluation)
<Yuzu skin evaluation>
The release films of the pressure-sensitive adhesive sheets with substrates of Examples and Comparative Examples were peeled off, and the exposed pressure-sensitive adhesive layer was attached to a black acrylic plate (manufactured by Mitsubishi Chemical Corporation). Then, the light of the fluorescent lamp was reflected and observed, and the distortion of the image of the fluorescent lamp reflected on the film substrate was evaluated according to the following criteria.
⊚: The image of the fluorescent lamp reflected on the film base material is not distorted, and the occurrence of orange peel skin is completely suppressed.
◯: The image of the fluorescent lamp reflected on the film substrate looks slightly distorted, and some discolored skin is generated, but there is no problem.
X: The image of the fluorescent lamp reflected on the film base material appears distorted, and the skin is discolored.
実施例で得られた積層シートにおいては、外観が良好であり、いわゆるゆず肌の発生が見られなかった。一方、比較例で得られた積層シートにおいては、外観不良が発生しており、ゆず肌の発生が見られた。 In the laminated sheets obtained in the examples, the appearance was good and so-called orange peel was not observed. On the other hand, in the laminated sheets obtained in Comparative Examples, defective appearance was observed and orange peel was observed.
１０ フィルム基材
２０ 粘着剤層
３０ 剥離フィルム
１００ 積層シート
10
Claims (9)
前記粘着剤組成物は、（メタ）アクリル共重合体、架橋剤及び架橋促進剤を含み、
前記架橋促進剤の含有量は前記（メタ）アクリル共重合体１００質量部に対して０．４５〜１．０質量部である、粘着シート。 A pressure-sensitive adhesive sheet obtained by curing a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition contains a (meth)acrylic copolymer, a crosslinking agent and a crosslinking accelerator,
Content of the said crosslinking accelerator is 0.45-1.0 mass part with respect to 100 mass parts of said (meth)acrylic copolymers, Adhesive sheet.
前記粘着剤層は（メタ）アクリル共重合体、架橋剤に由来する構造及び架橋促進剤を含み、
前記架橋促進剤の含有量は、前記（メタ）アクリル共重合体１００質量部に対して０．４５〜１．０質量部である積層シート。 A laminated sheet in which a film substrate, an adhesive layer and a release film are laminated in this order,
The pressure-sensitive adhesive layer contains a (meth)acrylic copolymer, a structure derived from a crosslinking agent, and a crosslinking accelerator,
The content of the crosslinking accelerator is 0.45 to 1.0 part by mass with respect to 100 parts by mass of the (meth)acrylic copolymer.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007138057A (en) * | 2005-11-21 | 2007-06-07 | Soken Chem & Eng Co Ltd | Adhesive composition for optical film and adhesive sheet, and optical member using the same |
| JP2012001647A (en) * | 2010-06-18 | 2012-01-05 | Teraoka Seisakusho:Kk | Adhesive for optical element |
| JP2013001733A (en) * | 2011-06-13 | 2013-01-07 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition, optical film using the same, and liquid crystal display device |
| JP2014508192A (en) * | 2010-12-31 | 2014-04-03 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition for polarizing plate and polarizing plate containing the same |
| JP2014084337A (en) * | 2012-10-19 | 2014-05-12 | Dic Corp | Protective adhesive film |
| WO2015145771A1 (en) * | 2014-03-28 | 2015-10-01 | リンテック株式会社 | Adhesive and adhesive sheet |
| JP2016190902A (en) * | 2015-03-30 | 2016-11-10 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive film |
| JP2016193612A (en) * | 2016-06-27 | 2016-11-17 | 藤森工業株式会社 | Peelable film for antistatic surface protective film |
| JP2017157809A (en) * | 2016-03-04 | 2017-09-07 | リンテック株式会社 | Semiconductor processing sheet, winding body thereof, and manufacturing method of winding body |
| JP2018090799A (en) * | 2016-12-06 | 2018-06-14 | 日本合成化学工業株式会社 | Adhesive composition, adhesive obtained by crosslinking the same, adhesive for masking film, masking film, adhesive film for transparent electrode layer formation step, tape for semiconductor manufacture step, and method for using masking film |
| JP2018127539A (en) * | 2017-02-08 | 2018-08-16 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive film |
-
2018
- 2018-11-15 JP JP2018214562A patent/JP2020083909A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007138057A (en) * | 2005-11-21 | 2007-06-07 | Soken Chem & Eng Co Ltd | Adhesive composition for optical film and adhesive sheet, and optical member using the same |
| JP2012001647A (en) * | 2010-06-18 | 2012-01-05 | Teraoka Seisakusho:Kk | Adhesive for optical element |
| JP2014508192A (en) * | 2010-12-31 | 2014-04-03 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition for polarizing plate and polarizing plate containing the same |
| JP2013001733A (en) * | 2011-06-13 | 2013-01-07 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition, optical film using the same, and liquid crystal display device |
| JP2014084337A (en) * | 2012-10-19 | 2014-05-12 | Dic Corp | Protective adhesive film |
| WO2015145771A1 (en) * | 2014-03-28 | 2015-10-01 | リンテック株式会社 | Adhesive and adhesive sheet |
| JP2016190902A (en) * | 2015-03-30 | 2016-11-10 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive film |
| JP2017157809A (en) * | 2016-03-04 | 2017-09-07 | リンテック株式会社 | Semiconductor processing sheet, winding body thereof, and manufacturing method of winding body |
| JP2016193612A (en) * | 2016-06-27 | 2016-11-17 | 藤森工業株式会社 | Peelable film for antistatic surface protective film |
| JP2018090799A (en) * | 2016-12-06 | 2018-06-14 | 日本合成化学工業株式会社 | Adhesive composition, adhesive obtained by crosslinking the same, adhesive for masking film, masking film, adhesive film for transparent electrode layer formation step, tape for semiconductor manufacture step, and method for using masking film |
| JP2018127539A (en) * | 2017-02-08 | 2018-08-16 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive film |
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