TWI842958B - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- TWI842958B TWI842958B TW109134024A TW109134024A TWI842958B TW I842958 B TWI842958 B TW I842958B TW 109134024 A TW109134024 A TW 109134024A TW 109134024 A TW109134024 A TW 109134024A TW I842958 B TWI842958 B TW I842958B
- Authority
- TW
- Taiwan
- Prior art keywords
- meth
- adhesive sheet
- acrylic polymer
- acrylic
- mass
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 202
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 202
- 239000000178 monomer Substances 0.000 claims abstract description 151
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 33
- 230000009477 glass transition Effects 0.000 claims abstract description 29
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 161
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 25
- 229920001519 homopolymer Polymers 0.000 claims description 19
- 125000002723 alicyclic group Chemical group 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 11
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical group CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 78
- 229920002125 Sokalan® Polymers 0.000 abstract description 55
- 238000004383 yellowing Methods 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
- -1 polyethylene Polymers 0.000 description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000002002 slurry Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 239000012790 adhesive layer Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 229920001296 polysiloxane Polymers 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 229920006267 polyester film Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 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 10
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000004386 diacrylate group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OSJIQLQSJBXTOH-UHFFFAOYSA-N 8-tricyclo[5.2.1.02,6]decanylmethyl prop-2-enoate Chemical compound C12CCCC2C2CC(COC(=O)C=C)C1C2 OSJIQLQSJBXTOH-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 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
- 239000004593 Epoxy Substances 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
- 239000004419 Panlite Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-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
- 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 2
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 2
- KYTNZWVKKKJXFS-UHFFFAOYSA-N cycloundecane Chemical compound C1CCCCCCCCCC1 KYTNZWVKKKJXFS-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
- 238000010894 electron beam technology Methods 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 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
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- BXSPZNVFEYWSLZ-UHFFFAOYSA-N (3-phenoxyphenyl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 BXSPZNVFEYWSLZ-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明的課題在於提供一種對被黏物顯示出優異的密接性、且可抑制黃變的黏著片。本發明是有關於一種黏著片，其具有：(甲基)丙烯酸聚合體A，含有具有羥基的(甲基)丙烯酸單體單元與具有環結構的(甲基)丙烯酸單體單元，且重量平均分子量大於10000；以及(甲基)丙烯酸聚合體B，重量平均分子量為3000～10000，且玻璃轉移溫度為20℃～120℃，所述黏著片中，相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸聚合體A中具有羥基的(甲基)丙烯酸單體單元的含量為20質量%以上，具有環結構的(甲基)丙烯酸單體單元不具有氮原子作為環結構原子，相對於(甲基)丙烯酸聚合體A 100質量份，(甲基)丙烯酸聚合體B的含量為1質量份以上。The object of the present invention is to provide an adhesive sheet which exhibits excellent adhesion to an adherend and can suppress yellowing. The present invention relates to an adhesive sheet, which comprises: a (meth)acrylic acid polymer A, which contains (meth)acrylic acid monomer units having a hydroxyl group and (meth)acrylic acid monomer units having a ring structure, and has a weight average molecular weight greater than 10,000; and a (meth)acrylic acid polymer B, which has a weight average molecular weight of 3,000 to 10,000 and a glass transition temperature of 20° C. to 120° C. In the adhesive sheet, relative to the total mass of the (meth)acrylic acid polymer A, the content of the (meth)acrylic acid monomer units having a hydroxyl group in the (meth)acrylic acid polymer A is 20% by mass or more, the (meth)acrylic acid monomer units having a ring structure do not have nitrogen atoms as ring structure atoms, and relative to 100 parts by mass of the (meth)acrylic acid polymer A, the content of the (meth)acrylic acid polymer B is 1 part by mass or more.
Description
本發明是有關於一種黏著片。 The present invention relates to an adhesive sheet.
先前，液晶顯示器(liquid crystal display，LCD)等顯示裝置、或觸控面板等與顯示裝置組合使用的輸入裝置得到廣泛使用。於該些顯示裝置或輸入裝置中，於貼合光學構件的用途中使用透明的黏著片，於顯示裝置與輸入裝置的貼合中亦使用透明的黏著片。 Previously, display devices such as liquid crystal displays (LCDs) or input devices such as touch panels used in combination with display devices have been widely used. In these display devices or input devices, transparent adhesive sheets are used for bonding optical components, and transparent adhesive sheets are also used for bonding display devices and input devices.
例如，專利文獻1~專利文獻5中揭示了光學構件貼合用黏著片。此處，藉由使各種單體聚合而獲得丙烯酸系共聚物，由調配此種丙烯酸系共聚物而成的黏著劑組成物形成丙烯酸系黏著片。此種黏著片可為雙面黏著片，例如亦存在用於透明樹脂層與玻璃層的貼合的情況(例如，專利文獻4)。另外，為了貼合至具有凹凸的被黏物，亦正在研究使用具有後固化性的黏著片(例如，專利文獻5)。 For example, Patent Documents 1 to 5 disclose adhesive sheets for bonding optical components. Here, acrylic copolymers are obtained by polymerizing various monomers, and an acrylic adhesive sheet is formed by preparing an adhesive composition prepared from such acrylic copolymers. Such adhesive sheets can be double-sided adhesive sheets, for example, there are also cases where they are used for bonding transparent resin layers and glass layers (for example, Patent Document 4). In addition, in order to bond to an adherend with uneven surfaces, the use of post-curing adhesive sheets is also being studied (for example, Patent Document 5).
[現有技術文獻] [Prior art literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2012-233060號公報 [Patent document 1] Japanese Patent Publication No. 2012-233060
[專利文獻2]國際公開第2010/147047號 [Patent Document 2] International Publication No. 2010/147047
[專利文獻3]日本專利特開2016-186618號公報 [Patent document 3] Japanese Patent Publication No. 2016-186618
[專利文獻4]日本專利特開2018-001615號公報 [Patent Document 4] Japanese Patent Publication No. 2018-001615
[專利文獻5]國際公開第2015/080120號 [Patent Document 5] International Publication No. 2015/080120
對貼合至光學構件的黏著片要求高的透明性與密接性。近年來，貼合有黏著片的光學構件亦有時於高溫或高濕環境等嚴酷環境下使用，要求於此種條件下亦發揮高的透明性與密接性。 Adhesive sheets bonded to optical components require high transparency and adhesion. In recent years, optical components bonded with adhesive sheets are sometimes used in harsh environments such as high temperature or high humidity environments, and are required to exhibit high transparency and adhesion even under such conditions.
因此，本發明者等人為了解決此種先前技術的課題，以提供對被黏物顯示出優異的密接性、且可抑制黃變的黏著片為目的而進行了研究。 Therefore, in order to solve the problems of the prior art, the inventors of the present invention conducted research with the goal of providing an adhesive sheet that exhibits excellent adhesion to the adherend and can inhibit yellowing.
本發明者等人為了解決所述課題而進行了努力研究，結果發現：藉由在黏著片中調配不同種類的丙烯酸聚合體，可獲得對被黏物顯示出優異的密接性、且可抑制黃變的黏著片。 The inventors of the present invention have conducted intensive research to solve the above-mentioned problem and found that by mixing different types of acrylic polymers in an adhesive sheet, an adhesive sheet can be obtained that exhibits excellent adhesion to the adherend and can suppress yellowing.
具體而言，本發明具有以下的結構。 Specifically, the present invention has the following structure.
[1]一種黏著片，具有：(甲基)丙烯酸聚合體A，含有具有羥基的(甲基)丙烯酸單體單元與具有環結構的(甲基)丙烯酸單體單元，且重量平均分子量大於10000；以及(甲基)丙烯酸聚合體B，重量平均分子量為3000~10000，且玻璃轉移溫度為20℃~120℃，所述黏著片中，相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸聚合 體A中具有羥基的(甲基)丙烯酸單體單元的含量為20質量%以上，具有環結構的(甲基)丙烯酸單體單元不具有氮原子作為環結構原子，相對於(甲基)丙烯酸聚合體A 100質量份，(甲基)丙烯酸聚合體B的含量為1質量份以上。 [1] An adhesive sheet comprising: a (meth)acrylic polymer A, containing (meth)acrylic monomer units having a hydroxyl group and (meth)acrylic monomer units having a ring structure, and having a weight average molecular weight greater than 10,000; and a (meth)acrylic polymer B, having a weight average molecular weight of 3,000 to 10,000 and a glass transition temperature of 20°C to 120°C, wherein the content of the (meth)acrylic monomer units having a hydroxyl group in the (meth)acrylic polymer A is 20% by mass or more relative to the total mass of the (meth)acrylic polymer A, the (meth)acrylic monomer units having a ring structure do not have a nitrogen atom as a ring structure atom, and the content of the (meth)acrylic polymer B is 1 part by mass or more relative to 100 parts by mass of the (meth)acrylic polymer A.
[2]如[1]所述的黏著片，其中(甲基)丙烯酸聚合體A的羥基價為80mgKOH/g以上，且玻璃轉移溫度為-50℃以上。 [2] The adhesive sheet as described in [1], wherein the hydroxyl value of the (meth)acrylic polymer A is 80 mgKOH/g or more, and the glass transition temperature is -50°C or more.
[3]如[1]或[2]所述的黏著片，其中於將(甲基)丙烯酸聚合體B的表面自由能分散成分設為γdb 0.5(mJ/m2)0.5、將表面自由能極性成分設為γpb 0.5(mJ/m2)0.5的情況下，(甲基)丙烯酸聚合體A包含1質量%以上的製成均聚物時表面自由能分散成分(γda 0.5)成為γdb 0.5±1.0(mJ/m2)0.5、且表面自由能極性成分(γpa 0.5)成為γpb 0.5±1.2(mJ/m2)0.5的具有環結構的(甲基)丙烯酸單體單元。 [3] The adhesive sheet according to [1] or [2], wherein, when the surface free energy dispersive component of the (meth)acrylic polymer B is set to γd b 0.5 (mJ/m 2 ) 0.5 and the surface free energy polar component is set to γp b 0.5 (mJ/m 2 ) 0.5 , the (meth)acrylic polymer A contains 1 mass % or more of a (meth)acrylic monomer unit having a ring structure, wherein the surface free energy dispersive component (γd a 0.5 ) is γd b 0.5 ± 1.0 (mJ/m 2 ) 0.5 and the surface free energy polar component (γp a 0.5 ) is γp b 0.5 ± 1.2 (mJ/m 2 ) 0.5 when the homopolymer is prepared.
[4]如[1]至[3]中任一項所述的黏著片，其用於被黏物貼合，於將(甲基)丙烯酸聚合體B的表面自由能分散成分設為γdb 0.5(mJ/m2)0.5、將表面自由能極性成分設為γpb 0.5(mJ/m2)0.5、將被黏物的表面自由能分散成分設為γdc 0.5(mJ/m2)0.5、將表面自由能極性成分設為γpc 0.5(mJ/m2)0.5的情況下，被黏物的表面自由能分散成分(γdc 0.5)、與被黏物的表面自由能極性成分(γpc 0.5)滿足以下的條件(1)及條件(2)。 [4] The adhesive sheet according to any one of [1] to [3], which is used for bonding adherends, wherein the surface free energy dispersion component of the (meth)acrylic polymer B is γd b 0.5 (mJ/m 2 ) 0.5 , the surface free energy polar component is γp b 0.5 (mJ/m 2 ) 0.5 , the surface free energy dispersion component of the adherend is γd c 0.5 (mJ/m 2 ) 0.5 , and the surface free energy polar component is γp c 0.5 (mJ/m 2 ) 0.5 , the surface free energy dispersion component (γd c 0.5 ) of the adherend and the surface free energy polar component (γp c 0.5 ) of the adherend satisfy the following conditions (1) and (2).
(條件(1))：γdb 0.5=γdc 0.5±1.0 (Condition (1)): γd b 0.5 = γd c 0.5 ± 1.0
(條件(2))：γpb 0.5=γpc 0.5±2.0 (Condition (2)): γp b 0.5 =γp c 0.5 ±2.0
[5]如[1]至[4]中任一項所述的黏著片，其用於被黏物貼合，被黏物包含樹脂。 [5] The adhesive sheet as described in any one of [1] to [4], which is used for bonding an adherend, and the adherend contains a resin.
[6]如[1]至[5]中任一項所述的黏著片，其中相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸聚合體A中具有環結構的(甲基)丙烯酸單體單元的含量為5質量%以上。 [6] An adhesive sheet as described in any one of [1] to [5], wherein the content of the (meth)acrylic acid monomer unit having a ring structure in the (meth)acrylic acid polymer A is 5% by mass or more relative to the total mass of the (meth)acrylic acid polymer A.
[7]如[1]至[6]中任一項所述的黏著片，其中(甲基)丙烯酸聚合體B包含具有脂環的單體單元。 [7] The adhesive sheet as described in any one of [1] to [6], wherein the (meth)acrylic polymer B contains a monomer unit having an aliphatic ring.
[8]如[1]至[7]中任一項所述的黏著片，其中(甲基)丙烯酸聚合體B包含具有脂環的單體單元，構成脂環的碳數為6以上。 [8] An adhesive sheet as described in any one of [1] to [7], wherein the (meth)acrylic polymer B contains a monomer unit having an alicyclic ring, and the number of carbon atoms constituting the alicyclic ring is 6 or more.
[9]如[1]至[8]中任一項所述的黏著片，其中(甲基)丙烯酸聚合體B實質上不具有官能基。 [9] The adhesive sheet as described in any one of [1] to [8], wherein the (meth)acrylic polymer B does not substantially have a functional group.
[10]如[1]至[9]中任一項所述的黏著片，進而包含選自多官能單體及交聯劑中的至少一種。 [10] The adhesive sheet as described in any one of [1] to [9], further comprising at least one selected from a multifunctional monomer and a crosslinking agent.
[11]如[1]至[10]中任一項所述的黏著片，進而包含光聚合起始劑，光聚合起始劑為苯乙酮系光聚合起始劑或醯基氧化膦系光聚合起始劑。 [11] The adhesive sheet as described in any one of [1] to [10] further comprises a photopolymerization initiator, wherein the photopolymerization initiator is an acetophenone-based photopolymerization initiator or an acylphosphine oxide-based photopolymerization initiator.
根據本發明，可獲得一種對被黏物顯示出優異的密接性、且可抑制黃變的黏著片。 According to the present invention, an adhesive sheet can be obtained which exhibits excellent adhesion to an adherend and can suppress yellowing.
10:帶剝離片的黏著片 10: Adhesive sheet with peeling sheet
11:黏著劑層 11: Adhesive layer
12a:剝離片 12a: Peeling film
12b:剝離片 12b: Peeling film
圖1是表示具有剝離片的黏著片的剖面的概略圖。 FIG1 is a schematic diagram showing a cross section of an adhesive sheet having a peeling sheet.
以下，對本發明進行詳細說明。以下記載的結構要件的說明有時基於代表性的實施形態或具體例來進行，但本發明並不限定於此種實施形態。再者，本說明書中使用「~」表示的數值範圍是指包含「~」前後記載的數值作為下限值及上限值的範圍。 The present invention is described in detail below. The description of the structural elements described below is sometimes based on representative implementation forms or specific examples, but the present invention is not limited to such implementation forms. Furthermore, the numerical range represented by "~" in this specification refers to the range that includes the numerical values described before and after "~" as the lower limit and upper limit.
再者，本說明書中，「(甲基)丙烯酸」表示丙烯酸及甲基丙烯酸兩者或任一者。另外，本說明書中，「單量體」與「單體」含義相同，「聚合體」與「聚合物」含義相同。 Furthermore, in this specification, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid. In addition, in this specification, "monomer" and "monomer" have the same meaning, and "polymer" and "polymer" have the same meaning.
<黏著片> <Adhesive sheet>
本發明是有關於一種黏著片，其具有：(甲基)丙烯酸聚合體A，所述(甲基)丙烯酸聚合體A含有具有羥基的(甲基)丙烯酸單體單元與具有環結構的(甲基)丙烯酸單體單元，且重量平均分子量大於10000；以及(甲基)丙烯酸聚合體B，所述(甲基)丙烯酸聚合體B的重量平均分子量為3000~10000，且玻璃轉移溫度為20℃~120℃。此處，相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸聚合體A中具有羥基的(甲基)丙烯酸單體單元的含量為20質量%以上，具有環結構的(甲基)丙烯酸單體單元不具有氮原子作為環結構原子。另外，相對於(甲基)丙烯酸聚合體A 100質量份，(甲基)丙烯酸聚合體B的含量為1質量份以上。 The present invention relates to an adhesive sheet, which has: a (meth)acrylic polymer A, which contains a (meth)acrylic monomer unit having a hydroxyl group and a (meth)acrylic monomer unit having a ring structure, and has a weight average molecular weight greater than 10,000; and a (meth)acrylic polymer B, which has a weight average molecular weight of 3,000 to 10,000 and a glass transition temperature of 20°C to 120°C. Here, relative to the total mass of the (meth)acrylic polymer A, the content of the (meth)acrylic monomer unit having a hydroxyl group in the (meth)acrylic polymer A is 20% by mass or more, and the (meth)acrylic monomer unit having a ring structure does not have a nitrogen atom as a ring structure atom. In addition, relative to 100 parts by mass of the (meth)acrylic polymer A, the content of the (meth)acrylic polymer B is 1 part by mass or more.
藉由所述結構，本發明的黏著片對被黏物發揮優異的密接性。另外，本實施形態的黏著片對極性不同的各種被黏物亦可顯示出優異的密接性。具體而言，本發明的黏著片對樹脂板等被黏物 顯示出優異的密接性。另外，此種密接性即便於在濕熱環境下長時間放置的情況下亦可發揮。 By virtue of the above structure, the adhesive sheet of the present invention exhibits excellent adhesion to the adherend. In addition, the adhesive sheet of the present embodiment can also exhibit excellent adhesion to various adherends of different polarities. Specifically, the adhesive sheet of the present invention exhibits excellent adhesion to adherends such as resin boards. In addition, this adhesion can be exhibited even when placed in a humid and hot environment for a long time.
本說明書中，黏著片的密接性可藉由測定濕熱恆定負荷來評價。於測定濕熱恆定負荷時，首先，將聚酯膜貼合至黏著片的其中一面後，將聚碳酸酯片、聚甲基丙烯酸甲酯片或玻璃板貼合至黏著片的另一面。之後，利用高壓釜於溫度30℃、壓力0.5MPa的環境下處理30分鐘後，於大氣壓、室溫環境下靜置一天。繼而，將貼合至各被黏物的黏著片於調整為溫度85℃、相對濕度85%的恆溫恆濕機內部靜置30分鐘，此時於黏著片的未接著部分鉤掛100g的砝碼，測定黏著片自被黏物面剝離而砝碼落下為止的時間。此時，於黏著片自被黏物面剝離而砝碼落下為止的時間為15分鐘以上的情況下，可評價為對各被黏物的密接性良好。 In this specification, the adhesion of the adhesive sheet can be evaluated by measuring the wet heat constant load. When measuring the wet heat constant load, first, a polyester film is attached to one side of the adhesive sheet, and then a polycarbonate sheet, a polymethyl methacrylate sheet, or a glass plate is attached to the other side of the adhesive sheet. After that, the adhesive sheet is treated in an autoclave at a temperature of 30°C and a pressure of 0.5 MPa for 30 minutes, and then left at atmospheric pressure and room temperature for one day. Next, the adhesive sheet attached to each adherend was placed in a constant temperature and humidity chamber adjusted to 85°C and 85% relative humidity for 30 minutes. A 100g weight was hung on the unattached portion of the adhesive sheet, and the time from when the adhesive sheet peeled off from the adherend surface and the weight fell was measured. At this time, if the time from when the adhesive sheet peeled off from the adherend surface and the weight fell was more than 15 minutes, it was evaluated that the adhesion to each adherend was good.
進而，本實施形態的黏著片由於具有所述結構，故可抑制黃變。因此，即便於貼合至光學構件後亦可維持高透明的黏著片。黏著片的黃變性可藉由測定L*a*b*色空間中的色度b*值來評價。黏著片的b*值較佳為未滿3，更佳為未滿2。進而，本實施形態的黏著片中於供至耐候試驗後亦可抑制黃變。例如，對於黏著片，利用氙氣耐氣候機於相對濕度50%、黑色面板溫度63℃、照度180W/cm2的條件下照射300小時的光線的情況下，黏著片的b*值亦較佳為未滿3，更佳為未滿2。再者，黏著片的b*值例如可使用須賀試驗機器製造的測色計Coloer Cute i來測定。本說明書中相對於評價前b*值而言耐候性試驗後的b*值增加，試驗後的b* 值未滿3的情況下，可評價為可獲得黃變抑制效果。 Furthermore, the adhesive sheet of this embodiment can suppress yellowing due to the structure. Therefore, the adhesive sheet can maintain high transparency even after being attached to an optical component. The yellowing property of the adhesive sheet can be evaluated by measuring the chromaticity b * value in the L * a * b * color space. The b * value of the adhesive sheet is preferably less than 3, and more preferably less than 2. Furthermore, the adhesive sheet of this embodiment can suppress yellowing after being subjected to a weathering test. For example, when the adhesive sheet is irradiated with light for 300 hours using a xenon weathering machine under the conditions of a relative humidity of 50%, a black panel temperature of 63°C, and an illumination of 180W/ cm2 , the b * value of the adhesive sheet is also preferably less than 3, and more preferably less than 2. The b * value of the adhesive sheet can be measured, for example, using a colorimeter Coloer Cute i manufactured by Suga Test Instruments Co., Ltd. In this specification, the b * value after the weathering test increases relative to the b * value before the evaluation, and when the b * value after the test is less than 3, it can be evaluated that the yellowing suppression effect can be obtained.
本實施形態的黏著片較佳為僅包括黏著劑層的黏著片，更佳為雙面黏著片。作為雙面黏著片，可列舉：包含黏著劑層的單層黏著片、積層有多層黏著劑層的多層黏著片、於黏著劑層與黏著劑層之間積層有其他黏著劑層的多層黏著片。再者，本實施形態的黏著片可為於黏著劑層與黏著劑層之間積層有支撐體的多層黏著片。於雙面黏著片具有支撐體的情況下，較佳為使用透明的支撐體作為支撐體。作為支撐體，可使用與透明基材同樣地用於光學領域的一般的膜。此種雙面黏著片由於作為黏著片整體的透明性亦優異，故可較佳地用於光學構件彼此的接著。 The adhesive sheet of this embodiment is preferably an adhesive sheet including only an adhesive layer, and more preferably a double-sided adhesive sheet. As double-sided adhesive sheets, there can be listed: a single-layer adhesive sheet including an adhesive layer, a multi-layer adhesive sheet having multiple layers of adhesive layers, and a multi-layer adhesive sheet having other adhesive layers layered between adhesive layers. Furthermore, the adhesive sheet of this embodiment can be a multi-layer adhesive sheet having a support layer layered between adhesive layers. In the case where the double-sided adhesive sheet has a support, it is preferred to use a transparent support as the support. As a support, a general film used in the optical field can be used, similar to a transparent substrate. This double-sided adhesive sheet has excellent transparency as a whole, so it can be preferably used for bonding optical components.
本實施形態的黏著片中，於將(甲基)丙烯酸聚合體B的表面自由能分散成分設為γdb 0.5(mJ/m2)0.5、將表面自由能極性成分設為γpb 0.5(mJ/m2)0.5的情況下，(甲基)丙烯酸聚合體A較佳為包含1質量%以上的製成均聚物時表面自由能分散成分(γda 0.5)成為γdb 0.5±1.0(mJ/m2)0.5、且表面自由能極性成分(γpa 0.5)成為γpb 0.5±1.2(mJ/m2)0.5的具有環結構的(甲基)丙烯酸單體單元。藉由將(甲基)丙烯酸聚合體A設為所述結構，黏著片可對被黏物發揮更優異的密接性。另外，此種更優異的密接性即便於在濕熱環境下長時間放置的情況下亦可發揮。 In the adhesive sheet of the present embodiment, when the surface free energy dispersive component of the (meth)acrylic polymer B is set to γd b 0.5 (mJ/m 2 ) 0.5 and the surface free energy polar component is set to γp b 0.5 (mJ/m 2 ) 0.5 , the (meth)acrylic polymer A preferably contains 1 mass % or more of a (meth)acrylic monomer unit having a ring structure, wherein when a homopolymer is prepared, the surface free energy dispersive component (γd a 0.5 ) is γd b 0.5 ±1.0 (mJ/m 2 ) 0.5 and the surface free energy polar component (γp a 0.5 ) is γp b 0.5 ±1.2 (mJ/m 2 ) 0.5 . By setting the (meth)acrylic polymer A to the above structure, the adhesive sheet can exhibit better adhesion to the adherend. In addition, this better adhesion can be exhibited even when it is left in a humid and hot environment for a long time.
於將(甲基)丙烯酸聚合體B的表面自由能分散成分設為γdb 0.5(mJ/m2)0.5、將表面自由能極性成分設為γpb 0.5(mJ/m2)0.5的情況下，(甲基)丙烯酸聚合體A包含1質量%以上的製成均聚物時表 面自由能分散成分(γda 0.5)成為γdb 0.5±1.0(mJ/m2)0.5、且表面自由能極性成分(γpa 0.5)成為γpb 0.5±1.2(mJ/m2)0.5的具有環結構的(甲基)丙烯酸單體單元。即，(甲基)丙烯酸聚合體A含有的具有環結構的(甲基)丙烯酸單體為製成均聚物時的表面自由能分散成分(γda 0.5)成為γdb 0.5±1.0(mJ/m2)0.5的單體，且為製成均聚物時的表面自由能極性成分(γpa 0.5)成為γpb 0.5±1.2(mJ/m2)0.5的單體。於(甲基)丙烯酸聚合體A含有多種具有環結構的(甲基)丙烯酸單體單元的情況下，只要至少一種具有環結構的(甲基)丙烯酸單體滿足所述條件即可。 When the surface free energy dispersion component of the (meth)acrylic polymer B is γd b 0.5 (mJ/m 2 ) 0.5 and the surface free energy polar component is γp b 0.5 (mJ/m 2 ) 0.5 , the (meth)acrylic polymer A contains 1 mass% or more of a (meth)acrylic monomer unit having a ring structure, wherein the surface free energy dispersion component (γd a 0.5 ) is γd b 0.5 ±1.0 (mJ/m 2 ) 0.5 and the surface free energy polar component (γp a 0.5 ) is γp b 0.5 ±1.2 (mJ/m 2 ) 0.5 when the homopolymer is prepared. That is, the (meth)acrylic monomer having a ring structure contained in the (meth)acrylic polymer A is a monomer whose surface free energy dispersion component (γd a 0.5 ) when forming a homopolymer is γd b 0.5 ±1.0 (mJ/m 2 ) 0.5 , and whose surface free energy polar component (γp a 0.5 ) when forming a homopolymer is γp b 0.5 ±1.2 (mJ/m 2 ) 0.5 . When the (meth)acrylic polymer A contains a plurality of (meth)acrylic monomer units having a ring structure, it is sufficient that at least one of the (meth)acrylic monomers having a ring structure satisfies the above conditions.
丙烯酸聚合體A含有的具有環結構的(甲基)丙烯酸單體只要製成均聚物時的表面自由能分散成分(γda 0.5)為γdb 0.5±1.0(mJ/m2)0.5即可，較佳為γdb 0.5±0.5(mJ/m2)0.5。另外，丙烯酸聚合體A含有的具有環結構的(甲基)丙烯酸單體只要製成均聚物時的表面自由能極性成分(γpa 0.5)為γpb 0.5±1.2(mJ/m2)0.5即可，較佳為γpb 0.5±1.0(mJ/m2)0.5。如此，藉由使(甲基)丙烯酸聚合體B的表面自由能分散成分與表面自由能極性成分、及包含丙烯酸聚合體A含有的具有環結構的(甲基)丙烯酸單體的均聚物的表面自由能分散成分與表面自由能極性成分具有所述相關性，可提高(甲基)丙烯酸聚合體A與(甲基)丙烯酸聚合體B的相容性。藉此，由黏著劑組成物形成的黏著片可對被黏物發揮更優異的密接性。 The surface free energy dispersion component (γd a 0.5 ) of the (meth)acrylic monomer having a ring structure contained in the acrylic polymer A when forming a homopolymer is γd b 0.5 ± 1.0 (mJ/m 2 ) 0.5 , preferably γd b 0.5 ± 0.5 (mJ/m 2 ) 0.5 . In addition, the surface free energy polar component (γp a 0.5 ) of the (meth)acrylic monomer having a ring structure contained in the acrylic polymer A when forming a homopolymer is γp b 0.5 ± 1.2 (mJ/m 2 ) 0.5 , preferably γp b 0.5 ± 1.0 (mJ/m 2 ) 0.5 . Thus, by making the surface free energy dispersive component and the surface free energy polar component of the (meth)acrylic polymer B and the surface free energy dispersive component and the surface free energy polar component of the homopolymer of the (meth)acrylic monomer having a ring structure contained in the acrylic polymer A have the above correlation, the compatibility of the (meth)acrylic polymer A and the (meth)acrylic polymer B can be improved. Thereby, the adhesive sheet formed by the adhesive composition can exhibit better adhesion to the adherend.
此處，(甲基)丙烯酸聚合體B的表面自由能分散成分與表面自由能極性成分、及包含具有環結構的(甲基)丙烯酸單體的均 聚物的表面自由能分散成分與表面自由能極性成分為如以下般測定的值。首先，將構成(甲基)丙烯酸聚合體A的各環結構的(甲基)丙烯酸單體100g與乙酸乙酯200g放入500ml燒瓶中，進行氮氣置換後升溫至70℃並投入AIBN 0.2g，使其反應5小時，並加以冷卻，從而回收均聚物的聚合溶液。以塗敷厚度成為25μm的方式將構成(甲基)丙烯酸聚合體A的各環結構的(甲基)丙烯酸均聚物溶液、(甲基)丙烯酸聚合體B以成為50質量%的方式進行溶液聚合後的溶液分別塗敷至PET膜後，利用100℃的乾燥機乾燥3分鐘，藉此獲得表面接觸角測定用試樣。以所述方式分別獲得(甲基)丙烯酸聚合體B及環結構聚合物的表面接觸角測定用試樣。然後，測定所獲得的表面接觸角測定用試樣的接觸角。具體而言，使純水2μl以及二碘甲烷1μl的液滴落下至接觸角測定用試樣的表面，利用θ/2法算出接觸角。然後，將讀取的接觸角的值(θ)適用於以下的Young-Dupre公式，並算出表面自由能。再者，於接觸角的測定時例如可使用菲布羅(FIBRO)公司製造的DAT1100。 Here, the surface free energy dispersion component and surface free energy polar component of the (meth)acrylic acid polymer B, and the surface free energy dispersion component and surface free energy polar component of the homopolymer containing the (meth)acrylic acid monomer having a ring structure are values measured as follows. First, 100 g of each ring structure (meth)acrylic acid monomer constituting the (meth)acrylic acid polymer A and 200 g of ethyl acetate are placed in a 500 ml flask, and after nitrogen substitution, the temperature is raised to 70°C and 0.2 g of AIBN is added, and the reaction is allowed to proceed for 5 hours, followed by cooling to recover a polymerization solution of the homopolymer. A solution of a (meth)acrylic acid homopolymer constituting each ring structure of a (meth)acrylic acid polymer A and a solution obtained by solution polymerization of a (meth)acrylic acid polymer B in a manner of 50% by mass were applied to a PET film in a coating thickness of 25 μm, and then dried in a drier at 100°C for 3 minutes to obtain a sample for measuring a surface contact angle. Samples for measuring a surface contact angle of a (meth)acrylic acid polymer B and a ring structure polymer were obtained in the above manner. Then, the contact angle of the obtained sample for measuring a surface contact angle was measured. Specifically, 2 μl of pure water and 1 μl of diiodomethane were dropped onto the surface of the sample for measuring a contact angle, and the contact angle was calculated using the θ/2 method. Then, the read contact angle value (θ) is applied to the following Young-Dupre formula to calculate the surface free energy. In addition, when measuring the contact angle, for example, DAT1100 manufactured by FIBRO can be used.
所述式中，γd L為液體(水或二碘甲烷)的表面自由能分 散成分，γp L為液體(水或二碘甲烷)的表面自由能極性成分，γd s為固體(接觸角測定用試樣)的表面自由能分散成分，γp s為固體(接觸角測定用試樣)的表面自由能極性成分。另外，WLS為固體與液體的附著能量，γL為液體的表面能量。 In the above formula, γ d L is the surface free energy dispersion component of the liquid (water or diiodomethane), γ p L is the surface free energy polar component of the liquid (water or diiodomethane), γ d s is the surface free energy dispersion component of the solid (contact angle measurement sample), γ p s is the surface free energy polar component of the solid (contact angle measurement sample). In addition, W LS is the adhesion energy between the solid and the liquid, and γ L is the surface energy of the liquid.
本發明亦可有關於一種於黏著片的兩表面包括剝離片的帶剝離片的黏著片。於本實施形態的黏著片的兩表面包括剝離片的情況下，如圖1所示帶剝離片的黏著片10較佳為於黏著劑層11的兩表面具有剝離片12a及剝離片12b。 The present invention may also be related to an adhesive sheet with a release sheet including release sheets on both surfaces of the adhesive sheet. In the case where the adhesive sheet of the present embodiment includes release sheets on both surfaces, the adhesive sheet with a release sheet 10 preferably has a release sheet 12a and a release sheet 12b on both surfaces of the adhesive layer 11 as shown in FIG. 1 .
作為剝離片，可列舉：具有剝離片用基材與設置於該剝離片用基材的單面的剝離劑層的剝離性積層片、或者作為極性基材的聚乙烯膜或聚丙烯膜等聚烯烴膜。 As the peeling sheet, there can be cited: a peeling laminate sheet having a peeling sheet substrate and a peeling agent layer provided on one side of the peeling sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a polar substrate.
剝離性積層片中的剝離片用基材可使用紙類、高分子膜。作為構成剝離劑層的剝離劑，例如可使用通用的加成型或縮合型的矽酮系剝離劑或含長鏈烷基的化合物。特別是可較佳地使用反應性高的加成型矽酮系剝離劑。 The peeling sheet substrate in the peelable laminate can be made of paper or polymer film. As the peeling agent constituting the peeling agent layer, for example, a general-purpose addition-type or condensation-type silicone-based peeling agent or a compound containing a long-chain alkyl group can be used. In particular, a highly reactive addition-type silicone-based peeling agent can be preferably used.
作為矽酮系剝離劑，具體而言可列舉東麗道康寧矽酮(Toray Dow Corning Silicone)公司製造的BY24-4527、SD-7220等或信越化學工業(股)製造的KS-3600、KS-774、X62-2600等。另外，較佳為於矽酮系剝離劑中含有具有SiO2單元與(CH3)3SiO1/2單元或CH2=CH(CH3)SiO1/2單元的有機矽化合物即矽酮樹脂。作為矽酮樹脂的具體例，可列舉東麗道康寧矽酮(Toray Dow Corning Silicone)公司製造的BY24-843、SD-7292、SHR-1404等或信越化 學工業(股)製造的KS-3800、X92-183等。 Specific examples of silicone-based stripping agents include BY24-4527 and SD-7220 manufactured by Toray Dow Corning Silicone Co., Ltd. and KS-3600, KS-774, and X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. In addition, it is preferred that the silicone-based stripping agent contains an organic silicon compound having a SiO 2 unit and a (CH 3 ) 3 SiO 1/2 unit or a CH 2 =CH(CH 3 )SiO 1/2 unit, that is, a silicone resin. Specific examples of silicone resins include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., and KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.
作為剝離性積層片，亦可使用市售品。例如可列舉帝人杜邦薄膜(Teijin Dupont Film)(股)製造的作為經脫模處理的聚對苯二甲酸乙二酯膜的重隔離膜A71、或帝人杜邦薄膜(Teijin Dupont Film)(股)製造的作為經脫模處理的聚對苯二甲酸乙二酯膜的輕隔離膜A38ST。 As the release laminate, commercial products may be used. For example, heavy release film A71 manufactured by Teijin Dupont Film (Co., Ltd.) as a polyethylene terephthalate film subjected to mold release treatment, or light release film A38ST manufactured by Teijin Dupont Film (Co., Ltd.) as a polyethylene terephthalate film subjected to mold release treatment.
帶剝離片的黏著片較佳為於黏著片的兩表面具有剝離力互不相同的一對剝離片。即，為了容易剝離，剝離片較佳為設為使剝離片12a與剝離片12b的剝離性不同。若自其中一者的剝離性與自另一者的剝離性不同，則容易僅先剝離剝離性高的剝離片。該情況下，只要根據貼合方法或貼合順序調整剝離片12a與剝離片12b的剝離性即可。 The adhesive sheet with a release sheet is preferably a pair of release sheets having different release forces on both surfaces of the adhesive sheet. That is, in order to facilitate peeling, the release sheet is preferably set to make the release properties of the release sheet 12a and the release sheet 12b different. If the release property from one of them is different from the release property from the other, it is easy to peel only the release sheet with high release property first. In this case, it is sufficient to adjust the release properties of the release sheet 12a and the release sheet 12b according to the bonding method or bonding sequence.
黏著片的厚度可根據用途適宜設定，並無特別限定，較佳為5μm~1000μm，更佳為8μm~500μm，特佳為10μm~300μm。藉由將黏著片的厚度設為所述範圍內，可維持黏著性能同時抑制黏著劑的溢出或黏連，因此可提高加工性。進而，藉由將黏著劑層的厚度設為所述範圍內，容易製造雙面黏著片。 The thickness of the adhesive sheet can be appropriately set according to the purpose, and there is no particular limitation. It is preferably 5μm~1000μm, more preferably 8μm~500μm, and particularly preferably 10μm~300μm. By setting the thickness of the adhesive sheet within the above range, the adhesive performance can be maintained while suppressing the overflow or adhesion of the adhesive, thereby improving the processability. Furthermore, by setting the thickness of the adhesive layer within the above range, it is easy to manufacture a double-sided adhesive sheet.
<(甲基)丙烯酸聚合體A> <(Meth)acrylic acid polymer A>
黏著片含有包含具有羥基的(甲基)丙烯酸單體單元與具有環結構的(甲基)丙烯酸單體單元、且重量平均分子量大於10000的(甲基)丙烯酸聚合體A。相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸聚合體A中具有羥基的(甲基)丙烯酸單體單元的含 量為20質量%以上。另外，(甲基)丙烯酸聚合體A中具有環結構的(甲基)丙烯酸單體單元不具有氮原子作為環結構原子。 The adhesive sheet contains a (meth)acrylic acid polymer A having a hydroxyl group and a (meth)acrylic acid monomer unit having a ring structure and having a weight average molecular weight greater than 10,000. The content of the (meth)acrylic acid monomer unit having a hydroxyl group in the (meth)acrylic acid polymer A is 20% by mass or more relative to the total mass of the (meth)acrylic acid polymer A. In addition, the (meth)acrylic acid monomer unit having a ring structure in the (meth)acrylic acid polymer A does not have a nitrogen atom as a ring structure atom.
較佳為(甲基)丙烯酸聚合體A的羥基價為80mgKOH/g以上，且玻璃轉移溫度為-50℃以上。 It is preferred that the hydroxyl value of the (meth)acrylic polymer A is above 80 mgKOH/g and the glass transition temperature is above -50°C.
(甲基)丙烯酸聚合體A的羥基價較佳為80mgKOH/g以上，更佳為90mgKOH/g以上，進而佳為100mgKOH/g以上。另外，(甲基)丙烯酸聚合體A的羥基價較佳為200mgKOH/g以下。此處，(甲基)丙烯酸聚合體A的羥基價是根據具有羥基的(甲基)丙烯酸單體的分子量與濃度來算出mol濃度，將相對於每單位重量而成為當量的氫氧化鉀濃度設為重量，以mgKOH/g的形式算出的值。藉由將(甲基)丙烯酸聚合體A的羥基價設為所述範圍內，可賦予耐濕熱白化性，更有效果地提高黏著片相對於被黏物的密接性。 The hydroxyl value of the (meth)acrylic polymer A is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, and further preferably 100 mgKOH/g or more. In addition, the hydroxyl value of the (meth)acrylic polymer A is preferably 200 mgKOH/g or less. Here, the hydroxyl value of the (meth)acrylic polymer A is a value calculated in the form of mgKOH/g by calculating the mol concentration based on the molecular weight and concentration of the (meth)acrylic monomer having a hydroxyl group, setting the potassium hydroxide concentration that is equivalent per unit weight as weight. By setting the hydroxyl value of the (meth)acrylic polymer A within the above range, wet heat whitening resistance can be imparted, and the adhesion of the adhesive sheet to the adherend can be more effectively improved.
(甲基)丙烯酸聚合體A的玻璃轉移溫度較佳為-50℃以上，更佳為-47℃以上，進而佳為-45℃以上。另外，(甲基)丙烯酸聚合體A的玻璃轉移溫度較佳為-30℃以下。藉由將(甲基)丙烯酸聚合體A的玻璃轉移溫度設為所述範圍內，可更有效果地提高黏著片相對於被黏物的密接性。 The glass transition temperature of the (meth)acrylic polymer A is preferably above -50°C, more preferably above -47°C, and further preferably above -45°C. In addition, the glass transition temperature of the (meth)acrylic polymer A is preferably below -30°C. By setting the glass transition temperature of the (meth)acrylic polymer A within the above range, the adhesion of the adhesive sheet to the adherend can be more effectively improved.
作為具有羥基的(甲基)丙烯酸單體，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯及(甲基)丙烯酸8-羥基辛酯、聚烷二醇單(甲基)丙烯酸酯等。其中可較佳地使用選自(甲基)丙烯酸2-羥 基乙酯及(甲基)丙烯酸4-羥基丁酯中的至少一種。 Examples of (meth)acrylic monomers having a hydroxyl group include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, polyalkylene glycol mono(meth)acrylate, etc. Among them, at least one selected from 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate can be preferably used.
(甲基)丙烯酸聚合體A中具有羥基的(甲基)丙烯酸單體單元的含量只要相對於(甲基)丙烯酸聚合體A的總質量而為20質量%以上即可，較佳為25質量%以上。另外，(甲基)丙烯酸聚合體A中具有羥基的(甲基)丙烯酸單體單元的含量較佳為50質量%以下。藉由將具有羥基的(甲基)丙烯酸單體單元的含量設為所述範圍內，可賦予親水性，藉此可更有效果地提高黏著片與被黏物的密接性及耐濕熱白化性。 The content of the (meth)acrylic monomer unit having a hydroxyl group in the (meth)acrylic polymer A can be 20% by mass or more relative to the total mass of the (meth)acrylic polymer A, preferably 25% by mass or more. In addition, the content of the (meth)acrylic monomer unit having a hydroxyl group in the (meth)acrylic polymer A is preferably 50% by mass or less. By setting the content of the (meth)acrylic monomer unit having a hydroxyl group within the above range, hydrophilicity can be imparted, thereby more effectively improving the adhesion between the adhesive sheet and the adherend and the resistance to wet heat whitening.
(甲基)丙烯酸聚合體A含有具有環結構的(甲基)丙烯酸單體單元。具有環結構的(甲基)丙烯酸單體較佳為具有脂環或芳香族環的(甲基)丙烯酸單體。作為脂環，例如可列舉：環丙烷、環丁烷、環戊烷、環己烷、環庚烷、環辛烷、環壬烷、環癸烷、環十一烷、環十二烷、降冰片烯、降冰片二烯、二環戊二烯、異冰片基、四氫呋喃、四氫吡喃等。再者，脂環亦可具有螺環結構。作為芳香族環，例如可列舉：苯、萘、蒽、吡啶、呋喃、苯並呋喃、吡咯、噻吩、咪唑、噁唑。其中，環結構特佳為選自環己烷、苯、二環戊二烯及異冰片基中的至少一種。再者，所述環結構可進而具有取代基。作為取代基，例如可列舉選自鹵素原子、鹵化烷基、烷基、烯基、醯基、羥基、羥基烷基、烷氧基、芳基、雜芳基、脂環基、氰基、環氧基、氧雜環丁基、巰基、胺基、(甲基)丙烯醯基等中的能夠取代的取代基。其中，環結構不具有氮原子作為環結構原子。 The (meth)acrylic polymer A contains a (meth)acrylic monomer unit having a ring structure. The (meth)acrylic monomer having a ring structure is preferably a (meth)acrylic monomer having an alicyclic ring or an aromatic ring. Examples of the alicyclic ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, norbornene, norbornadiene, dicyclopentadiene, isobornyl, tetrahydrofuran, tetrahydropyran, etc. Furthermore, the alicyclic ring may also have a spirocyclic structure. Examples of the aromatic ring include benzene, naphthalene, anthracene, pyridine, furan, benzofuran, pyrrole, thiophene, imidazole, and oxazole. Among them, the ring structure is particularly preferably at least one selected from cyclohexane, benzene, dicyclopentadiene and isobornyl. Furthermore, the ring structure may further have a substituent. As the substituent, for example, a substituent selected from a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an aryl group, a heteroaryl group, an alicyclic group, a cyano group, an epoxide group, an oxyheterocyclobutyl group, an amine group, a (meth)acryloyl group, etc. can be listed. Among them, the ring structure does not have a nitrogen atom as a ring structure atom.
作為具有環結構的(甲基)丙烯酸單體，例如可較佳地使 用(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸3-苯氧基苄酯、(甲基)丙烯酸O-苯基苯氧基乙酯等。 As the (meth)acrylic acid monomer having a ring structure, for example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, O-phenylphenoxyethyl (meth)acrylate, etc. can be preferably used.
相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸聚合體A中具有環結構的(甲基)丙烯酸單體單元的含量較佳為1質量%以上，更佳為3質量%以上，進而佳為5質量%以上，特佳為9質量%以上。另外，(甲基)丙烯酸聚合體A中具有環結構的(甲基)丙烯酸單體單元的含量較佳為30質量%以下。藉由將具有環結構的(甲基)丙烯酸單體單元的含量設為所述範圍內，可提高(甲基)丙烯酸聚合體A與(甲基)丙烯酸聚合體B的相容性，藉此可更有效果地提高黏著片與被黏物的密接性。 Relative to the total mass of the (meth)acrylic polymer A, the content of the (meth)acrylic monomer unit having a ring structure in the (meth)acrylic polymer A is preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more, and particularly preferably 9 mass % or more. In addition, the content of the (meth)acrylic monomer unit having a ring structure in the (meth)acrylic polymer A is preferably 30 mass % or less. By setting the content of the (meth)acrylic monomer unit having a ring structure within the above range, the compatibility of the (meth)acrylic polymer A and the (meth)acrylic polymer B can be improved, thereby more effectively improving the adhesion between the adhesive sheet and the adherend.
具有環結構的(甲基)丙烯酸單體較佳為於製成均聚物時，表面自由能分散成分(γda 0.5)成為γdb 0.5±1.0(mJ/m2)0.5，且表面自由能極性成分(γpa 0.5)成為γpb 0.5±1.2(mJ/m2)0.5。於(甲基)丙烯酸聚合體A含有多種具有環結構的(甲基)丙烯酸單體單元的情況下，只要至少一種具有環結構的(甲基)丙烯酸單體滿足所述條件即可。再者，γdb 0.5為(甲基)丙烯酸聚合體B的表面自由能分散成分，γpb 0.5為(甲基)丙烯酸聚合體B的表面自由能極性成分。 The (meth)acrylic monomer having a ring structure preferably has a surface free energy dispersion component (γd a 0.5 ) of γd b 0.5 ±1.0 (mJ/m 2 ) 0.5 and a surface free energy polar component (γp a 0.5 ) of γp b 0.5 ±1.2 (mJ/m 2 ) 0.5 when a homopolymer is prepared. In the case where the (meth)acrylic polymer A contains a plurality of (meth)acrylic monomer units having a ring structure, it is sufficient that at least one (meth)acrylic monomer having a ring structure satisfies the above conditions. In addition, γd b 0.5 is the surface free energy dispersion component of the (meth)acrylic polymer B, and γp b 0.5 is the surface free energy polar component of the (meth)acrylic polymer B.
相對於(甲基)丙烯酸聚合體A的總質量，構成具有所述表面自由能的均聚物的具有環結構的(甲基)丙烯酸單體單元的含量較佳為1質量%以上，更佳為3質量%以上，進而佳為5質量%以上。另外，相對於(甲基)丙烯酸聚合體A的總質量，具有環結構 的(甲基)丙烯酸單體單元的含量較佳為30質量%以下。藉由將構成具有所述表面自由能的均聚物的具有環結構的(甲基)丙烯酸單體單元的含量設為所述範圍內，可提高(甲基)丙烯酸聚合體A與(甲基)丙烯酸聚合體B的相容性，可更有效果地提高黏著片與被黏物的密接性。 Relative to the total mass of the (meth)acrylic polymer A, the content of the (meth)acrylic monomer unit with a ring structure constituting the homopolymer having the surface free energy is preferably 1 mass % or more, more preferably 3 mass % or more, and further preferably 5 mass % or more. In addition, relative to the total mass of the (meth)acrylic polymer A, the content of the (meth)acrylic monomer unit with a ring structure is preferably 30 mass % or less. By setting the content of the (meth)acrylic monomer unit with a ring structure constituting the homopolymer having the surface free energy within the above range, the compatibility of the (meth)acrylic polymer A and the (meth)acrylic polymer B can be improved, and the adhesion between the adhesive sheet and the adherend can be more effectively improved.
(甲基)丙烯酸聚合體A除了含有具有羥基的(甲基)丙烯酸單體單元、與具有環結構的(甲基)丙烯酸單體單元以外，亦可含有(甲基)丙烯酸烷基酯單元。作為(甲基)丙烯酸烷基酯的例子，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸山萮酯等(甲基)丙烯酸烷基酯等。相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸烷基酯單元的含量較佳為30質量%以上，更佳為40質量%以上。另外，相對於(甲基)丙烯酸聚合體A的總質量，(甲基)丙烯酸烷基酯單元的含量較佳為80質量%以下，更佳為75質量%以下。藉由將(甲基)丙烯酸烷基酯單元的含量設為所述範圍內，可提高對被黏物的黏著力。 The (meth)acrylic polymer A may contain (meth)acrylic acid alkyl ester units in addition to (meth)acrylic acid monomer units having a hydroxyl group and (meth)acrylic acid monomer units having a ring structure. Examples of (meth)acrylic acid alkyl esters include (meth)acrylic acid methyl esters, (meth)acrylic acid ethyl esters, (meth)acrylic acid butyl esters, (meth)acrylic acid isobutyl esters, (meth)acrylic acid 2-ethylhexyl esters, (meth)acrylic acid nonyl esters, (meth)acrylic acid decyl esters, (meth)acrylic acid lauryl esters, (meth)acrylic acid cetyl esters, (meth)acrylic acid stearyl esters, (meth)acrylic acid behenyl esters, and the like. The content of the (meth)acrylic acid alkyl ester units is preferably 30% by mass or more, and more preferably 40% by mass or more, relative to the total mass of the (meth)acrylic polymer A. In addition, relative to the total mass of the (meth)acrylic polymer A, the content of the (meth)acrylic acid alkyl ester unit is preferably 80 mass % or less, and more preferably 75 mass % or less. By setting the content of the (meth)acrylic acid alkyl ester unit within the above range, the adhesion to the adherend can be improved.
(甲基)丙烯酸聚合體A除了含有具有羥基的(甲基)丙烯酸單體單元、與具有環結構的(甲基)丙烯酸單體單元以外，亦可含有具有交聯性官能基的(甲基)丙烯酸單體單元。作為具有交聯性官能基的(甲基)丙烯酸單體具有的交聯性官能基，可列舉：羧基、醯 胺基、胺基、硫醇基、異氰酸酯基、環氧基、矽烷醇基。(甲基)丙烯酸聚合體A中具有交聯性官能基的(甲基)丙烯酸單體單元的含量較佳為10質量%以下，更佳為5質量%以下。 In addition to the (meth)acrylic monomer units having a hydroxyl group and the (meth)acrylic monomer units having a ring structure, the (meth)acrylic monomer units having a crosslinking functional group may also be contained in the (meth)acrylic monomer units. Examples of the crosslinking functional groups in the (meth)acrylic monomer units having a crosslinking functional group include: carboxyl group, amide group, amino group, thiol group, isocyanate group, epoxy group, and silanol group. The content of the (meth)acrylic monomer units having a crosslinking functional group in the (meth)acrylic polymer A is preferably 10% by mass or less, and more preferably 5% by mass or less.
(甲基)丙烯酸聚合體A視需要可具有其他單量體單元。其他單量體只要能夠與所述單體成分共聚即可，例如可列舉：(甲基)丙烯腈、乙酸乙烯酯、氯乙烯、乙基乙烯基醚。(甲基)丙烯酸聚合體A中的其他單量體單元的含量較佳為10質量%以下，更佳為5質量%以下。 The (meth)acrylic polymer A may have other monomer units as needed. As long as the other monomers can be copolymerized with the monomer components, for example: (meth)acrylonitrile, vinyl acetate, vinyl chloride, ethyl vinyl ether. The content of other monomer units in the (meth)acrylic polymer A is preferably 10% by mass or less, and more preferably 5% by mass or less.
(甲基)丙烯酸聚合體A的重量平均分子量只要大於10000即可，較佳為10萬以上，更佳為20萬以上。另外，(甲基)丙烯酸聚合體A的重量平均分子量較佳為200萬以下，更佳為150萬以下，進而佳為120萬以下，特佳為100萬以下。再者，(甲基)丙烯酸聚合體A的重量平均分子量是藉由凝膠滲透層析法(gel permeation chromatography，GPC)進行測定，並使用利用分子量已知的標準聚苯乙烯製成的校準曲線換算而求出的值。作為(甲基)丙烯酸聚合體A，可使用市售者，亦可使用利用公知的方法而合成者。 The weight average molecular weight of the (meth)acrylic polymer A only needs to be greater than 10,000, preferably greater than 100,000, and more preferably greater than 200,000. In addition, the weight average molecular weight of the (meth)acrylic polymer A is preferably less than 2 million, more preferably less than 1.5 million, further preferably less than 1.2 million, and particularly preferably less than 1 million. Furthermore, the weight average molecular weight of the (meth)acrylic polymer A is measured by gel permeation chromatography (GPC) and is calculated using a calibration curve made of standard polystyrene with a known molecular weight. As the (meth)acrylic polymer A, a commercially available one may be used, or one synthesized by a known method may be used.
<(甲基)丙烯酸聚合體B> <(Meth)acrylic acid polymer B>
黏著片含有重量平均分子量為3000~10000、且玻璃轉移溫度為20℃~120℃的(甲基)丙烯酸聚合體B。與(甲基)丙烯酸聚合體A相比，(甲基)丙烯酸聚合體B為低分子量成分，具有作為丙烯酸系黏著賦予劑的功能。(甲基)丙烯酸聚合體B較佳為實質上 不具有官能基，於該情況下，(甲基)丙烯酸聚合體B不與所述(甲基)丙烯酸聚合體A形成交聯結構。 The adhesive sheet contains a (meth)acrylic polymer B having a weight average molecular weight of 3000 to 10000 and a glass transition temperature of 20°C to 120°C. Compared with the (meth)acrylic polymer A, the (meth)acrylic polymer B is a low molecular weight component and has the function of an acrylic adhesive agent. The (meth)acrylic polymer B preferably has substantially no functional group, in which case the (meth)acrylic polymer B does not form a cross-linked structure with the (meth)acrylic polymer A.
再者，於將(甲基)丙烯酸聚合體B的表面自由能分散成分設為γdb 0.5(mJ/m2)0.5、將表面自由能極性成分設為γpb 0.5(mJ/m2)0.5的情況下，所述(甲基)丙烯酸聚合體A較佳為包含1質量%以上的製成均聚物時表面自由能分散成分(γda 0.5)成為γdb 0.5±1.0(mJ/m2)0.5、且表面自由能極性成分(γpa 0.5)成為γpb 0.5±1.2(mJ/m2)0.5的具有環結構的(甲基)丙烯酸單體單元。 Furthermore, when the surface free energy dispersion component of the (meth)acrylic polymer B is set to γd b 0.5 (mJ/m 2 ) 0.5 and the surface free energy polar component is set to γp b 0.5 (mJ/m 2 ) 0.5 , the (meth)acrylic polymer A preferably contains 1 mass % or more of a (meth)acrylic monomer unit having a ring structure, wherein when a homopolymer is prepared, the surface free energy dispersion component (γd a 0.5 ) is γd b 0.5 ±1.0 (mJ/m 2 ) 0.5 and the surface free energy polar component (γp a 0.5 ) is γp b 0.5 ±1.2 (mJ/m 2 ) 0.5 .
本實施形態的黏著片除了含有(甲基)丙烯酸聚合體A以外，含有(甲基)丙烯酸聚合體B，藉此黏著片可對被黏物顯示出優異的密接性。進而，本實施形態的黏著片由於使用不含有氮原子作為環結構原子的(甲基)丙烯酸聚合體A，故耐黃變性優異。如此，於本發明中藉由含有具有規定結構且種類不同的(甲基)丙烯酸聚合體，可以高水準兼顧黏著片的密接性與耐黃變性。 The adhesive sheet of this embodiment contains (meth)acrylic polymer B in addition to (meth)acrylic polymer A, so that the adhesive sheet can show excellent adhesion to the adherend. Furthermore, the adhesive sheet of this embodiment has excellent yellowing resistance because it uses (meth)acrylic polymer A that does not contain nitrogen atoms as ring structure atoms. In this way, in the present invention, by containing (meth)acrylic polymers with a predetermined structure and different types, the adhesive sheet can have both high adhesion and yellowing resistance.
(甲基)丙烯酸聚合體B較佳為包含具有脂環的單體單元。另外，於(甲基)丙烯酸聚合體B包含具有脂環的單體單元的情況下，構成脂環的碳數較佳為6以上。作為碳數為6以上的脂環，例如可列舉：環己烷、環庚烷、環辛烷、環壬烷、環癸烷、環十一烷、環十二烷、降冰片烯、降冰片二烯、二環戊二烯、異冰片基等。再者，脂環亦可具有螺環結構。 The (meth)acrylic polymer B preferably contains monomer units having an alicyclic ring. In addition, when the (meth)acrylic polymer B contains monomer units having an alicyclic ring, the carbon number constituting the alicyclic ring is preferably 6 or more. Examples of the alicyclic ring having 6 or more carbon numbers include: cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, norbornene, norbornadiene, dicyclopentadiene, isobornyl, etc. Furthermore, the alicyclic ring may also have a spirocyclic structure.
作為具有脂環的單體，例如可較佳地使用(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯氧基乙 酯等。 As monomers having an alicyclic ring, for example, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. can be preferably used.
於(甲基)丙烯酸聚合體B包含具有環結構的單體單元的情況下，相對於(甲基)丙烯酸聚合體B的總質量，具有環結構的單體單元的含量較佳為10質量%以上，更佳為20質量%以上。另外，相對於(甲基)丙烯酸聚合體B的總質量，具有環結構的單體單元的含量較佳為60質量%以下，更佳為50質量%以下。藉由將具有環結構的單體單元的含量設為所述範圍內，可提高丙烯酸聚合體A與丙烯酸聚合體B的相容性，提高黏著片與被黏物的密接性。 When the (meth)acrylic polymer B contains a monomer unit having a ring structure, the content of the monomer unit having a ring structure is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the (meth)acrylic polymer B. In addition, the content of the monomer unit having a ring structure is preferably 60% by mass or less, and more preferably 50% by mass or less, relative to the total mass of the (meth)acrylic polymer B. By setting the content of the monomer unit having a ring structure within the above range, the compatibility of the acrylic polymer A and the acrylic polymer B can be improved, and the adhesion between the adhesive sheet and the adherend can be improved.
(甲基)丙烯酸聚合體B除了含有具有環結構的單體單元以外，亦可進而含有(甲基)丙烯酸烷基酯單元。作為(甲基)丙烯酸烷基酯的例子，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸山萮酯等(甲基)丙烯酸烷基酯等。其中，(甲基)丙烯酸聚合體B較佳為包含(甲基)丙烯酸甲酯。相對於(甲基)丙烯酸聚合體B的總質量，(甲基)丙烯酸烷基酯單元的含量較佳為40質量%以上，更佳為50質量%以上。另外，相對於(甲基)丙烯酸聚合體B的總質量，(甲基)丙烯酸烷基酯單元的含量較佳為95質量%以下，更佳為90質量%以下。藉由將(甲基)丙烯酸烷基酯單元的含量設為所述範圍內，可提高丙烯酸聚合體A與丙烯酸聚合體B的相容性，提高黏著片與被黏物的密接性。 In addition to the monomer unit having a ring structure, the (meth)acrylic polymer B may further contain an alkyl (meth)acrylate unit. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate and the like. Among them, the (meth)acrylic polymer B preferably contains methyl (meth)acrylate. The content of the alkyl (meth)acrylate unit is preferably 40% by mass or more, and more preferably 50% by mass or more, relative to the total mass of the (meth)acrylic polymer B. In addition, relative to the total mass of the (meth)acrylic polymer B, the content of the (meth)acrylic alkyl ester unit is preferably 95 mass % or less, and more preferably 90 mass % or less. By setting the content of the (meth)acrylic alkyl ester unit within the above range, the compatibility of the acrylic polymer A and the acrylic polymer B can be improved, and the adhesion between the adhesive sheet and the adherend can be improved.
(甲基)丙烯酸聚合體B視需要可具有其他單量體單元。其他單量體只要能夠與所述單體成分共聚即可，例如可列舉：(甲基)丙烯腈、乙酸乙烯酯、氯乙烯、乙基乙烯基醚等。(甲基)丙烯酸聚合體B中的其他單量體單元的含量較佳為10質量%以下，更佳為5質量%以下。 The (meth)acrylic polymer B may have other monomer units as needed. As long as the other monomers can be copolymerized with the monomer components, for example, (meth)acrylonitrile, vinyl acetate, vinyl chloride, ethyl vinyl ether, etc. The content of other monomer units in the (meth)acrylic polymer B is preferably 10% by mass or less, and more preferably 5% by mass or less.
(甲基)丙烯酸聚合體B的重量平均分子量只要為3000以上即可，較佳為3200以上，更佳為3500以上。另外，(甲基)丙烯酸聚合體B的重量平均分子量只要為10000以下即可，較佳為9500以下，更佳為9000以下，進而佳為8000以下，特佳為6000以下。(甲基)丙烯酸聚合體B的重量平均分子量是藉由凝膠滲透層析法(GPC)進行測定，並使用利用分子量已知的標準聚苯乙烯製成的校準曲線換算而求出的值。作為(甲基)丙烯酸聚合體B，可使用市售者，亦可使用利用公知的方法而合成者。 The weight average molecular weight of (meth)acrylic polymer B can be 3000 or more, preferably 3200 or more, and more preferably 3500 or more. In addition, the weight average molecular weight of (meth)acrylic polymer B can be 10000 or less, preferably 9500 or less, more preferably 9000 or less, further preferably 8000 or less, and particularly preferably 6000 or less. The weight average molecular weight of (meth)acrylic polymer B is measured by gel permeation chromatography (GPC) and is calculated using a calibration curve made of standard polystyrene with known molecular weight. As (meth)acrylic polymer B, a commercially available one can be used, or one synthesized by a known method can be used.
(甲基)丙烯酸聚合體B的玻璃轉移溫度只要為20℃以上即可，較佳為30℃以上，更佳為40℃以上。另外，(甲基)丙烯酸聚合體B的玻璃轉移溫度只要為120℃以下即可，較佳為110℃以下，更佳為100℃以下，進而佳為80℃以下。藉由將(甲基)丙烯酸聚合體B的玻璃轉移溫度設為所述範圍內，可更有效果地提高黏著片相對於被黏物的密接性。 The glass transition temperature of the (meth)acrylic polymer B only needs to be above 20°C, preferably above 30°C, and more preferably above 40°C. In addition, the glass transition temperature of the (meth)acrylic polymer B only needs to be below 120°C, preferably below 110°C, more preferably below 100°C, and further preferably below 80°C. By setting the glass transition temperature of the (meth)acrylic polymer B within the above range, the adhesion of the adhesive sheet to the adherend can be more effectively improved.
黏著片中的(甲基)丙烯酸聚合體B的含量只要相對於(甲基)丙烯酸聚合體A 100質量份而為1質量份以上即可，較佳為1.5質量份以上，更佳為2質量份以上。另外，相對於(甲基)丙烯酸聚 合體A 100質量份，黏著片中的(甲基)丙烯酸聚合體B的含量較佳為20質量份以下。藉由將(甲基)丙烯酸聚合體B的含量設為所述範圍內，可更有效果地提高黏著片相對於被黏物的密接性。 The content of (meth)acrylic polymer B in the adhesive sheet can be 1 part by mass or more relative to 100 parts by mass of (meth)acrylic polymer A, preferably 1.5 parts by mass or more, and more preferably 2 parts by mass or more. In addition, the content of (meth)acrylic polymer B in the adhesive sheet is preferably 20 parts by mass or less relative to 100 parts by mass of (meth)acrylic polymer A. By setting the content of (meth)acrylic polymer B within the above range, the adhesion of the adhesive sheet to the adherend can be more effectively improved.
<多官能單體> <Multifunctional monomer>
本實施形態的黏著片可含有於分子內具有兩個以上反應性雙鍵的多官能單體。多官能單體為具有兩個以上反應性雙鍵者，其中多官能單體較佳為具有兩個以上且未滿五個的反應性雙鍵，更佳為具有兩個以上且未滿四個的反應性雙鍵。 The adhesive sheet of this embodiment may contain a multifunctional monomer having two or more reactive double bonds in the molecule. A multifunctional monomer is one having two or more reactive double bonds, wherein the multifunctional monomer preferably has two or more but less than five reactive double bonds, and more preferably has two or more but less than four reactive double bonds.
作為多官能單體，例如作為二官能單體，可列舉：聚乙二醇二丙烯酸酯、聚丙烯二丙烯酸酯、烷基二丙烯酸酯、聚四亞甲基二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、二噁烷二丙烯酸酯、三環癸醇二丙烯酸酯、芴二丙烯酸酯。另外，作為三官能以上的單體，可列舉：烷氧基化三羥甲基丙烷三丙烯酸酯、烷氧基化甘油三丙烯酸酯、己內酯改質異三聚氰酸三丙烯酸酯、季戊四醇丙烯酸酯、烷氧基化季戊四醇丙烯酸酯、(烷氧基化)季戊四醇丙烯酸酯、(烷氧基化)二-三羥甲基丙烷丙烯酸酯、(烷氧基化)二季戊四醇丙烯酸酯、(乙氧基化)聚甘油丙烯酸酯等。 As a multifunctional monomer, for example, as a difunctional monomer, there can be listed: polyethylene glycol diacrylate, polypropylene diacrylate, alkyl diacrylate, polytetramethylene glycol diacrylate, polypropylene glycol diacrylate, dioxane diacrylate, tricyclodecanol diacrylate, fluorene diacrylate. In addition, as a trifunctional or higher monomer, there can be listed: alkoxylated trihydroxymethylpropane triacrylate, alkoxylated glycerol triacrylate, caprolactone-modified isocyanuric acid triacrylate, pentaerythritol acrylate, alkoxylated pentaerythritol acrylate, (alkoxylated) pentaerythritol acrylate, (alkoxylated) di-trihydroxymethylpropane acrylate, (alkoxylated) dipentaerythritol acrylate, (ethoxylated) polyglycerol acrylate, etc.
多官能單體較佳為於一分子內具有烷二醇基的多官能單體。於該情況下，一分子中的烷二醇基的數量較佳為1~20。作為此種多官能單體，例如可列舉：聚乙二醇二丙烯酸酯、三羥甲基丙烷環氧丙烷改質三丙烯酸酯等。 The polyfunctional monomer is preferably a polyfunctional monomer having an alkanediol group in one molecule. In this case, the number of alkanediol groups in one molecule is preferably 1 to 20. Examples of such polyfunctional monomers include polyethylene glycol diacrylate, trihydroxymethylpropane propylene oxide modified triacrylate, etc.
作為多官能單體，可使用市售品。作為市售品的例子， 可列舉新中村化學工業公司製造的二官能單體A-400(聚乙二醇#400二丙烯酸酯)、三官能單體A-TMPT((烷氧基化)三羥甲基丙烷丙烯酸酯)、東亞合成公司製造的二官能單體M240(聚乙二醇二丙烯酸酯)、四官能單體M-408(二-三羥甲基丙烷四丙烯酸酯)等。 As the multifunctional monomer, commercial products can be used. Examples of commercial products include the difunctional monomer A-400 (polyethylene glycol #400 diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., the trifunctional monomer A-TMPT ((alkoxylated) trihydroxymethylpropane acrylate), the difunctional monomer M240 (polyethylene glycol diacrylate) manufactured by Toagosei Co., Ltd., and the tetrafunctional monomer M-408 (di-trihydroxymethylpropane tetraacrylate).
多官能單體於黏著片中與所述(甲基)丙烯酸聚合體構成交聯結構。再者，相對於黏著劑組成物的總質量，後述的黏著劑組成物中的多官能單體的含量較佳為0.01質量%~10質量%，更佳為0.05質量%~5質量%。藉由將多官能單體的含量設為所述範圍內，可提高黏著片的硬度，可提高黏著片的耐久性或加工性。 The multifunctional monomer forms a cross-linked structure with the (meth) acrylic polymer in the adhesive sheet. Furthermore, relative to the total mass of the adhesive composition, the content of the multifunctional monomer in the adhesive composition described below is preferably 0.01 mass% to 10 mass%, and more preferably 0.05 mass% to 5 mass%. By setting the content of the multifunctional monomer within the above range, the hardness of the adhesive sheet can be increased, and the durability or processability of the adhesive sheet can be improved.
<交聯劑> <Crosslinking agent>
本實施形態的黏著片可含有交聯劑。交聯劑可考慮與(甲基)丙烯酸聚合體具有的交聯性官能基的反應性來適宜選擇。例如可自異氰酸酯化合物、環氧化合物、噁唑啉化合物、氮丙啶化合物、金屬螯合物化合物、丁基化三聚氰胺化合物等公知的交聯劑中選擇。其中，交聯劑較佳為包含自異氰酸酯化合物、環氧化合物及金屬螯合物化合物中選擇的至少一種。 The adhesive sheet of this embodiment may contain a crosslinking agent. The crosslinking agent may be appropriately selected in consideration of the reactivity with the crosslinking functional group of the (meth)acrylic polymer. For example, it may be selected from known crosslinking agents such as isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, and butylated melamine compounds. Among them, the crosslinking agent preferably includes at least one selected from isocyanate compounds, epoxy compounds, and metal chelate compounds.
作為異氰酸酯化合物，例如可列舉：甲苯二異氰酸酯、苯二甲基二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯等。作為市售品的例子，可列舉甲苯二異氰酸酯化合物(東曹(股)製造，考牢奈特(Coronate)L)、苯二甲基二異氰酸酯化合物(三井化學(股)製造，塔克奈特(Takenate)D-110N)等。作為環氧 化合物，例如可列舉泰特拉德(TETRAD)-C(三菱瓦斯化學(Mitsubishi Gas Chemical)公司製造)、泰特拉德(TETRAD)-X(三菱瓦斯化學(Mitsubishi Gas Chemical)公司製造)等。作為金屬螯合物化合物，例如可列舉鋁螯合物(Alumichelate)A(川研精化(Kawaken Fine Chemicals)公司製造)等。 Examples of isocyanate compounds include toluene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of commercially available products include toluene diisocyanate compounds (Coronate L manufactured by Tosoh Co., Ltd.) and xylene diisocyanate compounds (Takenate D-110N manufactured by Mitsui Chemicals Co., Ltd.). Examples of epoxy compounds include TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Examples of metal chelate compounds include aluminum chelate A (manufactured by Kawaken Fine Chemicals).
交聯劑於黏著片中與所述(甲基)丙烯酸聚合體構成交聯結構。相對於黏著劑組成物的總質量，後述的黏著劑組成物中的交聯劑的含量較佳為0.01質量%~10質量%，更佳為0.05質量%~5質量%。藉由將交聯劑的含量設為所述範圍內，可提高黏著片的硬度，可提高黏著片的耐久性或加工性。 The crosslinking agent forms a crosslinking structure with the (meth) acrylic polymer in the adhesive sheet. The content of the crosslinking agent in the adhesive composition described below is preferably 0.01% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass, relative to the total mass of the adhesive composition. By setting the content of the crosslinking agent within the above range, the hardness of the adhesive sheet can be increased, and the durability or processability of the adhesive sheet can be improved.
<光聚合起始劑> <Photopolymerization initiator>
本實施形態的黏著片可含有光聚合起始劑。光聚合起始劑為藉由活性能量線的照射而引發多官能單體的聚合者。此處，所謂「活性能量線」是指電磁波或帶電粒子束中具有能量子(energy quantum)者，可列舉：紫外線、電子束、可見光線、X射線、離子束等。其中，就通用性的方面而言，較佳為紫外線或電子束，特佳為紫外線。 The adhesive sheet of this embodiment may contain a photopolymerization initiator. The photopolymerization initiator is a substance that initiates polymerization of multifunctional monomers by irradiation with active energy rays. Here, the so-called "active energy rays" refers to electromagnetic waves or charged particle beams that have energy quanta, and can be listed as: ultraviolet rays, electron beams, visible light, X-rays, ion beams, etc. Among them, ultraviolet rays or electron beams are preferred in terms of versatility, and ultraviolet rays are particularly preferred.
作為光聚合起始劑，並無特別限定，例如除了2,2-二甲氧基-2-苯基苯乙酮、1-羥基環己基-苯基酮、2-羥基-2-甲基-1-苯基丙酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-甲基丙酮、2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)苄基)苯基)-2-甲基-1-丙酮等苯乙酮系光聚合起始劑、2,4,6-三甲基苯甲醯基-二苯基氧化膦或2,4,6-三甲基 苯甲醯基苯基氧化膦等醯基氧化膦系光聚合起始劑、苯甲醯基甲酸甲酯或4-甲基二苯甲酮等分子內脫氫型光聚合起始劑以外，可列舉肟酯系光聚合起始劑或陽離子系光聚合起始劑等油溶性聚合起始劑。其中，光聚合起始劑較佳為苯乙酮系光聚合起始劑或醯基氧化膦系光聚合起始劑。 The photopolymerization initiator is not particularly limited, and for example, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl-1 In addition to acetophenone-based photopolymerization initiators such as acetone, acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzyl-diphenylphosphine oxide or 2,4,6-trimethyl benzylphenylphosphine oxide, and intramolecular dehydrogenation-type photopolymerization initiators such as methyl benzoylformate or 4-methylbenzophenone, oil-soluble polymerization initiators such as oxime ester-based photopolymerization initiators or cationic-based photopolymerization initiators can be listed. Among them, the photopolymerization initiator is preferably an acetophenone-based photopolymerization initiator or an acylphosphine oxide-based photopolymerization initiator.
作為此種苯乙酮系光聚合起始劑的市售品，可列舉：艾薩固萬(EsacureOne)(寡聚(2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基丙酮]、IGM樹脂(IGM RESINS B.V.)公司製造的光起始劑)、奧姆尼拉德(Omnirad)651(2,2-二甲氧基-2-苯基苯乙酮、IGM樹脂(IGM RESINS B.V.)公司製造)、奧姆尼拉德(Omnirad)184(1-羥基環己基-苯基酮、IGM樹脂(IGM RESINS B.V.)公司製造)、奧姆尼拉德(Omnirad)1173(2-羥基-2-甲基-1-苯基丙酮、IGM樹脂(IGM RESINS B.V.)公司製造)等。另外，作為醯基氧化膦系光聚合起始劑的市售品，可列舉奧姆尼拉德(Omnirad)819(雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、IGM樹脂(IGM RESINS B.V.)公司製造)或奧姆尼拉德(Omnirad)TPO(2,4,6-三甲基苯甲醯基-二苯基氧化膦、IGM樹脂(IGM RESINS B.V.)公司製造)等。 Examples of commercially available acetophenone-based photopolymerization initiators include EsacureOne (oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenylacetone], a photoinitiator manufactured by IGM Resins B.V.), Omnirad 651 (2,2-dimethoxy-2-phenylacetophenone, manufactured by IGM Resins B.V.), Omnirad 184 (1-hydroxycyclohexyl-phenylketone, manufactured by IGM Resins B.V.), Omnirad 1173 (2-hydroxy-2-methyl-1-phenylacetone, manufactured by IGM Resins B.V.), and Omnirad 184 (1-hydroxycyclohexyl-phenylketone, manufactured by IGM Resins B.V.). B.V.) etc. In addition, commercially available products of acylphosphine oxide-based photopolymerization initiators include Omnirad 819 (bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, manufactured by IGM Resins B.V.) or Omnirad TPO (2,4,6-trimethylbenzyl-diphenylphosphine oxide, manufactured by IGM Resins B.V.) etc.
相對於黏著劑組成物的總質量，構成黏著片的黏著劑組成物中的光聚合起始劑的含量較佳為0.01質量%~10質量%，更佳為0.1質量%~5質量%。藉由將光聚合起始劑的含量設為所述範圍內，可提高黏著片的硬度，可提高黏著片的耐久性或加工性。 The content of the photopolymerization initiator in the adhesive composition constituting the adhesive sheet is preferably 0.01% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the adhesive composition. By setting the content of the photopolymerization initiator within the above range, the hardness of the adhesive sheet can be increased, and the durability or processability of the adhesive sheet can be improved.
<其他成分> <Other ingredients>
於不損害本發明的效果的範圍內，黏著片可含有所述以外的其他成分。作為其他成分，可列舉作為黏著劑用的添加劑而公知的成分。例如可自塑化劑、抗氧化劑、金屬腐蝕抑制劑、矽烷偶合劑、紫外線吸收劑、受阻胺系化合物等光穩定劑等中視需要進行選擇。另外，亦可以著色為目的而添加染料或顏料。 The adhesive sheet may contain other ingredients other than those mentioned above within the scope that does not impair the effect of the present invention. As other ingredients, known ingredients as additives for adhesives can be listed. For example, it can be selected from plasticizers, antioxidants, metal corrosion inhibitors, silane coupling agents, ultraviolet absorbers, hindered amine compounds and other light stabilizers as needed. In addition, dyes or pigments can also be added for the purpose of coloring.
作為塑化劑，例如可使用無官能基丙烯酸聚合體。作為無官能基丙烯酸聚合體，可列舉僅包含不具有丙烯酸酯基以外的官能基的丙烯酸單量體單元的聚合體、或包含不具有丙烯酸酯基以外的官能基的丙烯酸單量體單元與不具有官能基的非丙烯酸單量體單元的聚合體。由於無官能基丙烯酸聚合體不交聯，因此可不對黏著性產生影響而提高貼合至被黏物時的階差追隨性。 As a plasticizer, for example, a non-functional acrylic polymer can be used. Examples of non-functional acrylic polymers include polymers containing only acrylic monomer units that do not have functional groups other than acrylate groups, or polymers containing acrylic monomer units that do not have functional groups other than acrylate groups and non-acrylic monomer units that do not have functional groups. Since non-functional acrylic polymers do not crosslink, they can improve the step tracking property when attached to the adherend without affecting the adhesiveness.
作為抗氧化劑，可列舉：酚系抗氧化劑、胺系抗氧化劑、內酯系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑等。該些抗氧化劑可單獨使用一種，亦可併用兩種以上。 As antioxidants, there are phenolic antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. These antioxidants can be used alone or in combination of two or more.
作為金屬腐蝕抑制劑，就黏著劑的相容性或效果的高度而言，可列舉苯並***系樹脂作為較佳例。 As a metal corrosion inhibitor, benzotriazole resins can be cited as a better example in terms of compatibility with adhesives or high effectiveness.
作為矽烷偶合劑，例如可列舉巰基烷氧基矽烷化合物(例如，巰基取代烷氧基寡聚物等)、(甲基)丙烯醯氧基丙基甲氧基矽烷等。 Examples of silane coupling agents include alkyl alkoxysilane compounds (e.g., alkyl substituted alkoxy oligomers, etc.), (meth)acryloxypropylmethoxysilane, etc.
作為紫外線吸收劑，例如可列舉苯並***系化合物、二苯甲酮系化合物、三嗪系化合物等。 Examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, etc.
<黏著劑組成物> <Adhesive composition>
本實施形態的黏著片較佳為包含使黏著劑組成物(塗敷液)硬化而成的黏著劑層的片。黏著劑組成物中至少包含(甲基)丙烯酸聚合體A與(甲基)丙烯酸聚合體B。另外，黏著劑組成物中亦可包含所述多官能單體、交聯劑、光聚合起始劑、其他成分。 The adhesive sheet of this embodiment is preferably a sheet comprising an adhesive layer formed by hardening an adhesive composition (coating liquid). The adhesive composition contains at least (meth)acrylic polymer A and (meth)acrylic polymer B. In addition, the adhesive composition may also contain the multifunctional monomer, crosslinking agent, photopolymerization initiator, and other components.
黏著劑組成物可含有包含(甲基)丙烯酸聚合體A的丙烯酸漿A。此處，丙烯酸漿A中至少包含(甲基)丙烯酸聚合體A與構成(甲基)丙烯酸聚合體A的單體。因此，黏著劑組成物亦可除了包含(甲基)丙烯酸聚合體A以外，包含構成(甲基)丙烯酸聚合體A的單體。再者，於丙烯酸漿A含有構成(甲基)丙烯酸聚合體A的單體的情況下，該些單體於製造黏著片的步驟中聚合，形成(甲基)丙烯酸聚合體A。 The adhesive composition may contain acrylic syrup A containing (meth)acrylic polymer A. Here, acrylic syrup A contains at least (meth)acrylic polymer A and monomers constituting (meth)acrylic polymer A. Therefore, the adhesive composition may also contain monomers constituting (meth)acrylic polymer A in addition to (meth)acrylic polymer A. Furthermore, when acrylic syrup A contains monomers constituting (meth)acrylic polymer A, these monomers are polymerized in the step of manufacturing the adhesive sheet to form (meth)acrylic polymer A.
另外，黏著劑組成物中可包含溶劑。於該情況下，溶劑用於提高黏著劑組成物的塗敷適應性。作為溶劑，例如可列舉：己烷、庚烷、辛烷、甲苯、二甲苯、乙基苯、環己烷、甲基環己烷等烴類；二氯甲烷、三氯乙烷、三氯乙烯、四氯乙烯、二氯丙烷等鹵化烴類；甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、二丙酮醇等醇類；二***、二異丙醚、二噁烷、四氫呋喃等醚類；丙酮、甲基乙基酮、甲基異丁基酮、異佛爾酮、環己酮等酮類；乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、丁酸乙酯等酯類；乙二醇單甲醚、乙二醇單***、乙二醇單甲醚乙酸酯、丙二醇單甲醚、丙二醇單***、丙二醇單甲醚乙酸酯等多元醇及其衍生物。 In addition, the adhesive composition may contain a solvent. In this case, the solvent is used to improve the coating compatibility of the adhesive composition. Examples of solvents include: hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichloropropane; alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, and diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, and ethyl butyrate; polyols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate, and their derivatives.
<黏著片的製造方法> <Method for manufacturing adhesive sheet>
本實施形態的黏著片的製造方法較佳為包括將黏著劑組成物塗敷於剝離片上而形成塗膜的步驟、以及對該塗膜照射活性能量線的步驟。再者，於黏著劑組成物中包含溶劑的情況下，亦較佳為包括加熱步驟。加熱步驟中可於去除溶劑的同時，藉由塗膜的加熱來形成黏著劑層。 The manufacturing method of the adhesive sheet of this embodiment preferably includes the steps of applying the adhesive composition on the peeling sheet to form a coating film, and irradiating the coating film with active energy rays. Furthermore, when the adhesive composition contains a solvent, it is also preferably included in the heating step. In the heating step, the adhesive layer can be formed by heating the coating film while removing the solvent.
黏著劑組成物的塗敷可使用公知的塗敷裝置來實施。作為塗敷裝置，例如可列舉：刮板塗佈機、氣刀塗佈機、輥塗機、棒塗機、凹版塗佈機、微型凹版塗佈機、棒式刮板塗佈機、唇塗佈機、模塗機、簾式塗佈機等。 The adhesive composition can be applied using a known coating device. Examples of coating devices include: scraper coater, air knife coater, roller coater, rod coater, gravure coater, micro gravure coater, rod-type scraper coater, lip coater, die coater, curtain coater, etc.
於對塗膜照射活性能量線的步驟中，較佳為以累計光量為100mJ/cm2~10000mJ/cm2的方式照射活性能量線，更佳為以累計光量為500mJ/cm2~5000mJ/cm2的方式照射活性能量線。於對塗膜照射活性能量線的步驟中，可分兩階段照射活性能量線。例如，與第一階段相比，亦可提高第二階段的照射強度。藉由進行此種兩階段照射，可容易地調整所獲得的黏著片中包含的聚合物的分子量，或者抑制隔離膜等的熱收縮等。 In the step of irradiating the coating film with active energy rays, it is preferred to irradiate the coating film with active energy rays in a manner of cumulative light intensity of 100 mJ/cm 2 to 10000 mJ/cm 2 , and more preferably, to irradiate the coating film with active energy rays in a manner of cumulative light intensity of 500 mJ/cm 2 to 5000 mJ/cm 2. In the step of irradiating the coating film with active energy rays, the active energy rays may be irradiated in two stages. For example, the irradiation intensity in the second stage may be increased compared to the first stage. By performing such two-stage irradiation, it is easy to adjust the molecular weight of the polymer contained in the obtained adhesive sheet, or to suppress thermal shrinkage of the isolation film, etc.
<黏著片的用途> <Application of adhesive sheet>
本實施形態的黏著片用於被黏物貼合。此處，於將(甲基)丙烯酸聚合體B的表面自由能分散成分設為γdb 0.5(mJ/m2)0.5、將表面自由能極性成分設為γpb 0.5(mJ/m2)0.5的情況下，貼合黏著片的被黏物的表面自由能分散成分(γdc 0.5)與被黏物的表面自由能極性成分(γpc 0.5)較佳為滿足以下的條件(1)及條件(2)。 The adhesive sheet of this embodiment is used for bonding adherends. Here, when the surface free energy dispersion component of the (meth)acrylic polymer B is set to γd b 0.5 (mJ/m 2 ) 0.5 and the surface free energy polar component is set to γp b 0.5 (mJ/m 2 ) 0.5 , the surface free energy dispersion component (γd c 0.5 ) and the surface free energy polar component (γp c 0.5 ) of the adherend to which the adhesive sheet is bonded preferably satisfy the following conditions (1) and (2).
(條件(1))：γdb 0.5=γdc 0.5±1.0 (Condition (1)): γd b 0.5 = γd c 0.5 ± 1.0
(條件(2))：γpb 0.5=γpc 0.5±2.0 (Condition (2)): γp b 0.5 =γp c 0.5 ±2.0
藉由使黏著片中包含的(甲基)丙烯酸聚合體B的表面自由能分散成分與表面自由能極性成分、及被黏物的表面自由能分散成分與表面自由能極性成分具有所述相關性，本實施形態的黏著片可對被黏物顯示出更優異的密接性。因此，本實施形態的黏著片特佳為用於貼合至滿足所述條件(1)與條件(2)的被黏物的用途。 By making the surface free energy dispersive component and the surface free energy polar component of the (meth)acrylic polymer B contained in the adhesive sheet, and the surface free energy dispersive component and the surface free energy polar component of the adherend have the above correlation, the adhesive sheet of this embodiment can show better adhesion to the adherend. Therefore, the adhesive sheet of this embodiment is particularly preferably used for bonding to the adherend that meets the above conditions (1) and (2).
滿足所述條件(1)與條件(2)的被黏物較佳為包含樹脂。作為樹脂種類，例如可列舉：聚碳酸酯、聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚萘二甲酸乙二酯、三乙醯纖維素、聚醯亞胺、醯化纖維素等。再者，聚碳酸酯的表面自由能分散成分(γdc 0.5)為6.85，表面自由能極性成分(γpc 0.5)為0.65。另外，聚甲基丙烯酸甲酯的表面自由能分散成分(γdc 0.5)為6.50，表面自由能極性成分(γpc 0.5)為1.75。進而聚對苯二甲酸乙二酯的表面自由能分散成分(γdc 0.5)為5.81，表面自由能極性成分(γpc 0.5)為3.59。三乙醯纖維素的表面自由能分散成分(γdc 0.5)為5.59，表面自由能極性成分(γpc 0.5)為3.99。該些被黏物的表面自由能分散成分(γdc 0.5)與表面自由能極性成分(γpc 0.5)可利用與所述方法相同的方法來測定。 The adherend satisfying the above conditions (1) and (2) preferably comprises a resin. Examples of the resin include polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, triacetyl cellulose, polyimide, acylated cellulose, etc. The surface free energy dispersion component (γd c 0.5 ) of polycarbonate is 6.85, and the surface free energy polar component (γp c 0.5 ) is 0.65. In addition, the surface free energy dispersion component (γd c 0.5 ) of polymethyl methacrylate is 6.50, and the surface free energy polar component (γp c 0.5 ) is 1.75. Furthermore, the surface free energy dispersion component (γd c 0.5 ) of polyethylene terephthalate is 5.81, and the surface free energy polar component (γp c 0.5 ) is 3.59. The surface free energy dispersion component (γd c 0.5 ) of triacetyl cellulose is 5.59, and the surface free energy polar component (γp c 0.5 ) is 3.99. The surface free energy dispersion component (γd c 0.5 ) and the surface free energy polar component (γp c 0.5 ) of these adherends can be measured by the same method as described above.
其中，被黏物較佳為用於光學構件貼合。作為光學構件，可列舉觸控面板或圖像顯示裝置等光學製品中的各結構構件。作為觸控面板的結構構件，例如可列舉：於透明樹脂膜設置有ITO膜 的ITO膜、於玻璃板的表面設置有ITO膜的ITO玻璃、於透明樹脂膜塗佈導電性聚合物而成的透明導電性膜、硬塗膜、耐指紋性膜等。作為圖像顯示裝置的結構構件，例如可列舉：液晶顯示裝置中所使用的抗反射膜、配向膜、偏光膜、相位差膜、亮度提高膜等。另外，本實施形態的黏著片亦可用於液晶模組與觸控面板模組等模組彼此的貼合。 Among them, the adherend is preferably used for bonding optical components. As optical components, various structural components in optical products such as touch panels or image display devices can be listed. As structural components of touch panels, for example, ITO film with ITO film provided on transparent resin film, ITO glass with ITO film provided on the surface of glass plate, transparent conductive film formed by coating conductive polymer on transparent resin film, hard coating film, fingerprint-resistant film, etc. can be listed. As structural components of image display devices, for example, anti-reflection film, alignment film, polarizing film, phase difference film, brightness enhancement film, etc. used in liquid crystal display devices can be listed. In addition, the adhesive sheet of this embodiment can also be used for bonding modules such as liquid crystal module and touch panel module.
該些構件中所使用的材料亦可為玻璃、聚碳酸酯、聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚萘二甲酸乙二酯、環烯烴聚合物、三乙醯纖維素、聚醯亞胺、醯化纖維素等。 The materials used in these components may also be glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymer, triacetyl cellulose, polyimide, acylated cellulose, etc.
[實施例] [Implementation example]
以下列舉實施例與比較例來更具體地說明本發明的特徵。以下的實施例所示的材料、使用量、比例、處理內容、處理程序等只要不脫離本發明的主旨，則可適宜變更。因此，本發明的範圍不應由以下所示的具體例來限定地進行解釋。 The following examples and comparative examples are used to more specifically illustrate the features of the present invention. The materials, usage amounts, proportions, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the main purpose of the present invention. Therefore, the scope of the present invention should not be interpreted as limited by the specific examples shown below.
(實施例1) (Implementation Example 1)
(包含(甲基)丙烯酸聚合體的漿A的製作) (Preparation of slurry A containing (meth)acrylic acid polymer)
向包括攪拌機、氮氣導入管、冷卻管、溫度計的2L燒瓶中投入丙烯酸丁酯450g、丙烯酸4-羥基丁酯360g、丙烯酸環己酯100g、甲基丙烯酸異丁酯90g、正十二烷基硫醇0.4g，以氮氣流量300ml/min進行60分鐘氮氣置換後，將氮氣流量降低至100ml/min為止，利用水浴升溫並加熱至60℃為止。繼而，投入AIBN 0.15g，於控制發熱的同時反應30分鐘，之後加以冷卻，藉此合 成(甲基)丙烯酸聚合體。之後，以45：36：10：9的比率將所述丙烯酸單體投入至燒瓶中，獲得固體成分濃度為30質量%的丙烯酸漿A。 Into a 2L flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer, 450g of butyl acrylate, 360g of 4-hydroxybutyl acrylate, 100g of cyclohexyl acrylate, 90g of isobutyl methacrylate, and 0.4g of n-dodecyl mercaptan were added. After nitrogen replacement at a nitrogen flow rate of 300ml/min for 60 minutes, the nitrogen flow rate was reduced to 100ml/min, and the temperature was raised to 60°C using a water bath. Subsequently, 0.15g of AIBN was added, and the reaction was carried out for 30 minutes while controlling the heat, and then cooled to synthesize a (meth)acrylic acid polymer. Thereafter, the acrylic acid monomer was added to the flask at a ratio of 45:36:10:9 to obtain acrylic acid slurry A with a solid content concentration of 30% by mass.
((甲基)丙烯酸聚合體A的分子量測定) (Determination of molecular weight of (meth)acrylic acid polymer A)
向丙烯酸漿A 100g中添加IGM樹脂(IGM RESINS B.V.)公司製造的光起始劑(艾薩固萬(EsacureOne))0.5g並加以攪拌及脫泡，將所得者以厚度成為100μm的方式塗敷於塗佈了矽酮脫模劑的50μm聚酯膜上，進而於其上重疊塗佈了矽酮脫模劑的50μm聚酯膜。之後，利用化學燈以7mW/cm2的光強度照射2分鐘，從而獲得包含(甲基)丙烯酸聚合體A的層。採集該層並溶解於乙酸乙酯中，對所得者進行GPC測定，結果(甲基)丙烯酸聚合體A的重量平均分子量為40萬。 0.5 g of a photoinitiator (EsacureOne) manufactured by IGM Resins BV was added to 100 g of acrylic slurry A, stirred and defoamed, and the resulting mixture was applied to a 50 μm polyester film coated with a silicone release agent in a thickness of 100 μm, and a 50 μm polyester film coated with a silicone release agent was stacked thereon. Thereafter, the mixture was irradiated with a light intensity of 7 mW/cm 2 for 2 minutes using a chemical lamp to obtain a layer containing (meth)acrylic polymer A. The layer was collected and dissolved in ethyl acetate, and the obtained mixture was subjected to GPC measurement, and the weight average molecular weight of (meth)acrylic polymer A was 400,000.
((甲基)丙烯酸聚合體B的合成) (Synthesis of (meth)acrylic acid polymer B)
向包括攪拌機、氮氣導入管、冷卻管、溫度計的2L燒瓶中投入甲基丙烯酸甲酯300g、甲基丙烯酸二環戊酯200g、正十二烷基硫醇35g、乙酸乙酯300g、甲基乙基酮200g，以氮氣流量300ml/min進行60分鐘氮氣置換後，將氮氣流量降低至100ml/min為止，利用水浴升溫並加熱至70℃為止。繼而，投入AIBN 0.4g，於控制發熱的同時反應3小時後，進而追加0.6g的AIBN並反應4小時。如此獲得包含(甲基)丙烯酸聚合體B的樹脂溶液B。對樹脂溶液B進行GPC測定的結果為(甲基)丙烯酸聚合體B的重量平均分子量為3,600。 Into a 2L flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer, 300g of methyl methacrylate, 200g of dicyclopentyl methacrylate, 35g of n-dodecyl mercaptan, 300g of ethyl acetate, and 200g of methyl ethyl ketone were added. After nitrogen replacement at a nitrogen flow rate of 300ml/min for 60 minutes, the nitrogen flow rate was reduced to 100ml/min, and the temperature was raised in a water bath to 70°C. Subsequently, 0.4g of AIBN was added, and after reacting for 3 hours while controlling the heat, 0.6g of AIBN was further added and reacted for 4 hours. In this way, a resin solution B containing a (meth)acrylic polymer B was obtained. The result of GPC measurement of the resin solution B was that the weight average molecular weight of the (meth)acrylic polymer B was 3,600.
(黏著片的製作) (Adhesive sheet production)
準備如下者作為黏著劑組成物：將樹脂溶液B流入金屬球棒，於乾燥機溫度120℃下乾燥2小時，並去除溶媒，使所得者以10g溶解於丙烯酸漿A 100g中後，添加IGM樹脂(IGM RESINS B.V.)公司製造的光起始劑(艾薩固萬(EsacureOne))0.5g、新中村化學工業公司製造的多官能單體(A-400)0.4g並加以攪拌脫泡。以黏著劑層的厚度成為100μm的方式將塗敷液塗敷於塗佈了矽酮脫模劑的50μm聚酯膜上，進而於其上重疊塗佈了矽酮脫模劑的50μm聚酯膜。之後，利用化學燈以7mW/cm2的光強度照射2分鐘後，利用高壓水銀燈以累計光量為1500mJ/cm2的方式照射，藉此獲得實施例1的黏著片。 The following was prepared as an adhesive composition: Resin solution B was poured into a metal ball rod, dried at a dryer temperature of 120°C for 2 hours, and the solvent was removed, and 10 g of the obtained solution was dissolved in 100 g of acrylic slurry A, and 0.5 g of a photoinitiator (EsacureOne) manufactured by IGM Resins BV and 0.4 g of a multifunctional monomer (A-400) manufactured by Shin-Nakamura Chemical Industries were added and stirred for defoaming. The coating liquid was applied to a 50 μm polyester film coated with a silicone release agent so that the thickness of the adhesive layer became 100 μm, and a 50 μm polyester film coated with a silicone release agent was further overlapped thereon. Thereafter, the film was irradiated with a chemical lamp at a light intensity of 7 mW/cm 2 for 2 minutes, and then irradiated with a high-pressure mercury lamp at a cumulative light intensity of 1500 mJ/cm 2 , thereby obtaining the adhesive sheet of Example 1.
(實施例2) (Example 2)
如表1般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成。將((甲基)丙烯酸聚合體B的合成)中的正十二烷基硫醇的添加量變更為30g，獲得重量平均分子量為4,900的聚合體B。進而將相對於丙烯酸漿A的(甲基)丙烯酸聚合體B的混合量變更為表1中記載的比例，將添加量設為5g。除了所述事項以外，與實施例1同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (Preparation of (meth)acrylic acid polymer slurry A) was changed as shown in Table 1. The amount of n-dodecyl mercaptan added in (Synthesis of (meth)acrylic acid polymer B) was changed to 30 g, and polymer B with a weight average molecular weight of 4,900 was obtained. Furthermore, the mixing amount of (meth)acrylic acid polymer B relative to acrylic acid slurry A was changed to the ratio described in Table 1, and the addition amount was set to 5 g. Except for the above matters, the adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(實施例3) (Implementation Example 3)
如表1般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成，並如表1般變更((甲基)丙烯酸聚合體B的合成)中的單體的組成，除此以外與實施例1同樣地獲得黏著劑組成物 及黏著片。 The adhesive composition and adhesive sheet were obtained in the same manner as in Example 1 except that the monomer composition in (Preparation of (meth)acrylic acid polymer slurry A) was changed as in Table 1 and the monomer composition in (Synthesis of (meth)acrylic acid polymer B) was changed as in Table 1.
(實施例4) (Implementation Example 4)
如表1般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成，進而將相對於丙烯酸漿A的(甲基)丙烯酸聚合體B的添加量設為5g，除此以外與實施例1同樣地獲得黏著劑組成物及黏著片。 The composition of the monomers in (Preparation of (meth)acrylic acid polymer slurry A) was changed as shown in Table 1, and the amount of (meth)acrylic acid polymer B added to acrylic acid slurry A was set to 5 g. The adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(實施例5) (Example 5)
如表1般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成。如表1般變更((甲基)丙烯酸聚合體B的合成)中的單體的組成。進而將相對於丙烯酸漿A的(甲基)丙烯酸聚合體B的添加量變更為5g。除了所述事項以外，與實施例1同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (Preparation of (meth)acrylic acid polymer slurry A) was changed as shown in Table 1. The monomer composition in (Synthesis of (meth)acrylic acid polymer B) was changed as shown in Table 1. Furthermore, the amount of (meth)acrylic acid polymer B added to acrylic acid slurry A was changed to 5g. Except for the above matters, the adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(實施例6) (Implementation Example 6)
向包括攪拌機、氮氣導入管、冷卻管、溫度計的2L燒瓶中投入丙烯酸丁酯310g、丙烯酸4-羥基丁酯145g、丙烯酸環己酯45g、乙酸乙酯500g、正十二烷基硫醇0.4g，以氮氣流量300ml/min進行60分鐘氮氣置換後，將氮氣流量降低至100ml/min為止，利用水浴升溫並加熱至70℃為止。繼而，投入AIBN 0.25g，於控制發熱的同時反應2小時後，追加投入0.5g的AIBN並於75℃下反應5小時。之後投入200g的乙酸乙酯並加以冷卻，藉此獲得固體成分濃度為40質量%的(甲基)丙烯酸聚合體A溶液。再者，GPC測定的結果為(甲基)丙烯酸聚合體A的重量平均分子量為40 萬。 In a 2L flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer, 310 g of butyl acrylate, 145 g of 4-hydroxybutyl acrylate, 45 g of cyclohexyl acrylate, 500 g of ethyl acetate, and 0.4 g of n-dodecyl mercaptan were added, and nitrogen replacement was performed at a nitrogen flow rate of 300 ml/min for 60 minutes. The nitrogen flow rate was reduced to 100 ml/min, and the temperature was raised to 70°C using a water bath. Subsequently, 0.25 g of AIBN was added, and the reaction was carried out for 2 hours while controlling the heat. After that, 0.5 g of AIBN was added and the reaction was carried out at 75°C for 5 hours. Thereafter, 200 g of ethyl acetate was added and the mixture was cooled to obtain a (meth)acrylic acid polymer A solution having a solid content concentration of 40% by mass. Furthermore, the results of GPC measurement showed that the weight average molecular weight of (meth)acrylic acid polymer A was 400,000.
相對於所獲得的丙烯酸聚合體A溶液100g，添加4g的實施例1中使用的(甲基)丙烯酸聚合體B，添加0.67g的東曹製造的考牢奈特(Coronate)L-75作為交聯劑，進行攪拌混合而製成黏著劑組成物。 To 100 g of the obtained acrylic polymer A solution, 4 g of the (meth)acrylic polymer B used in Example 1 and 0.67 g of Coronate L-75 manufactured by Tosoh were added as a crosslinking agent, and the mixture was stirred and mixed to prepare an adhesive composition.
以乾燥後的黏著劑層的厚度成為100μm的方式將所述黏著劑組成物塗敷於塗佈了矽酮脫模劑的50μm聚酯膜上，利用90℃的乾燥機乾燥3分鐘，藉此獲得實施例6的黏著片。 The adhesive composition was applied to a 50 μm polyester film coated with a silicone release agent in such a way that the thickness of the adhesive layer after drying became 100 μm, and dried in a dryer at 90°C for 3 minutes to obtain the adhesive sheet of Example 6.
(比較例1) (Comparison Example 1)
如表2般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成，不添加(甲基)丙烯酸聚合體B，除此以外與實施例1同樣地獲得黏著劑組成物及黏著片。 The composition of the monomers in (preparation of slurry A containing (meth)acrylic acid polymer) was changed as shown in Table 2, and (meth)acrylic acid polymer B was not added. The adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(比較例2) (Comparison Example 2)
如表2般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成，將多官能單體(A-400)的添加量設為0.3g，除此以外與實施例1同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (Preparation of (meth)acrylic acid polymer slurry A) was changed as shown in Table 2, and the amount of multifunctional monomer (A-400) added was set to 0.3 g. The adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(比較例3) (Comparison Example 3)
如表2般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成，將多官能單體(A-400)的添加量設為0.3g，除此以外與實施例1同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (Preparation of (meth)acrylic acid polymer slurry A) was changed as shown in Table 2, and the amount of multifunctional monomer (A-400) added was set to 0.3 g. The adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(比較例4) (Comparison Example 4)
如表2般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中 的單體的組成，將多官能單體(A-400)的添加量設為0.3g，除此以外與實施例1同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (Preparation of (meth)acrylic acid polymer slurry A) was changed as shown in Table 2, and the amount of the multifunctional monomer (A-400) added was set to 0.3 g. The adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(比較例5) (Comparison Example 5)
如表2般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成。進而使(甲基)丙烯酸聚合體B的組成如表2般，將正十二烷基硫醇變更為1g，從而獲得重量平均分子量為14,000的聚合體B。除了所述事項以外，與實施例1同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (preparation of slurry A containing (meth)acrylic acid polymer) was changed as shown in Table 2. The composition of (meth)acrylic acid polymer B was changed to 1g as shown in Table 2, thereby obtaining polymer B with a weight average molecular weight of 14,000. Except for the above matters, the adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(比較例6) (Comparison Example 6)
如表2般變更(包含(甲基)丙烯酸聚合體的漿A的製作)中的單體的組成，代替聚合體B，添加氫化萜烯酚樹脂(安原化工(Yasuhara Chemical)公司製造UH-115平均分子量700、玻璃轉移溫度113℃)，除此以外與實施例1同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (preparation of slurry A containing (meth) acrylic polymer) was changed as shown in Table 2, and hydrogenated terpene phenol resin (UH-115 manufactured by Yasuhara Chemical Co., Ltd., average molecular weight 700, glass transition temperature 113°C) was added instead of polymer B. The adhesive composition and adhesive sheet were obtained in the same manner as in Example 1.
(測定) (Measurement)
((甲基)丙烯酸聚合體A的玻璃轉移溫度的算出) (Calculation of glass transition temperature of (meth)acrylic polymer A)
(甲基)丙烯酸聚合體A的玻璃轉移溫度利用以下的FOX式來求出。 The glass transition temperature of (meth)acrylic polymer A is calculated using the following FOX formula.
1/Tgp=W1/Tg1+W2/Tg2+…+Wn/Tgn 1/Tgp=W1/Tg1+W2/Tg2+…+Wn/Tgn
Tgp為聚合體A的玻璃轉移溫度，Wn為各單體的重量分率，Tgn為將各單體製成均聚物時的玻璃轉移溫度。 Tgp is the glass transition temperature of polymer A, Wn is the weight fraction of each monomer, and Tgn is the glass transition temperature when each monomer is made into a homopolymer.
((甲基)丙烯酸聚合體B的玻璃轉移溫度的測定) (Determination of glass transition temperature of (meth)acrylic polymer B)
(甲基)丙烯酸聚合體B的玻璃轉移溫度的測定是使用精工儀器(Seiko Instruments)製造的DSC6200。參考設為氧化鋁10mg，於直徑5mm的樣品用鋁盤中放入10mg左右的樹脂溶液B的溶媒去除品，於氮氣流量50ml/min的環境下以升溫速度10℃/min於0℃~150℃內升溫。此時，讀取比熱變化的拐點作為(甲基)丙烯酸聚合體B的玻璃轉移溫度。 The glass transition temperature of (meth)acrylic polymer B was measured using DSC6200 manufactured by Seiko Instruments. The reference was set to 10 mg of aluminum oxide, and about 10 mg of the solvent-removed product of resin solution B was placed in a 5 mm diameter sample aluminum pan, and the temperature was raised from 0°C to 150°C at a heating rate of 10°C/min in an environment with a nitrogen flow rate of 50 ml/min. At this time, the inflection point of the specific heat change was read as the glass transition temperature of (meth)acrylic polymer B.
((甲基)丙烯酸聚合體A的羥基價的算出) (Calculation of the hydroxyl value of (meth)acrylic acid polymer A)
羥基價是根據含羥基的單體的分子量與濃度算出mol濃度，將相對於每單位重量而成為當量的氫氧化鉀濃度設為重量，以mgKOH/g的形式來算出。 The hydroxyl value is calculated based on the molecular weight and concentration of the monomer containing the hydroxyl group, and the molar concentration is calculated by setting the concentration of potassium hydroxide that becomes equivalent per unit weight as the weight, and calculating it in the form of mgKOH/g.
(評價) (Evaluation)
(濕熱恆定負荷) (Wet heat constant load)
將實施例及比較例中所獲得的黏著片單面的隔離膜去除，貼合至易接著處理的100μm的聚酯膜(東洋紡製造的A4300)上。繼而，以對於被黏物的貼附部成為寬度25mm、長度75mm的方式進行切割。使該樣品於1mm厚度、寬度115mm、長度250mm的浮法玻璃、或1mm厚度、寬度115mm、長度250mm的聚碳酸酯(帝人製造的龐拉伊特(Panlite)1151)分別距被黏物端部20mm以上，將樣品全長75mm的內50mm貼附於被黏物後，利用2kg的輥往返壓接兩次。之後利用高壓釜於溫度30℃、壓力0.5MPa的環境下處理30分鐘後，在大氣壓、室溫環境下靜置一天。繼而，將包含各被黏物的樣品於調整為溫度85℃、相對濕度85% 的恆溫恆濕機內部靜置30分鐘。此時，各被黏物設置於上方。繼而，將100g的砝碼鉤掛在樣品的未接著部分即長度25mm的端部，測定黏著片自被黏物面剝離而砝碼落下為止的時間，按照以下的基準進行評價。 The separator film on one side of the adhesive sheet obtained in the embodiment and the comparative example was removed, and the sheet was bonded to a 100 μm polyester film (A4300 manufactured by Toyobo) that is easy to connect. Then, the sheet was cut so that the bonding portion to the adherend would be 25 mm wide and 75 mm long. The sample was placed more than 20 mm away from the end of the adherend on a float glass with a thickness of 1 mm, a width of 115 mm, and a length of 250 mm, or a polycarbonate with a thickness of 1 mm, a width of 115 mm, and a length of 250 mm (Panlite 1151 manufactured by Teijin), and the inner 50 mm of the total length of 75 mm of the sample was bonded to the adherend, and then pressed back and forth twice using a 2 kg roller. After that, the samples were treated in an autoclave at a temperature of 30°C and a pressure of 0.5 MPa for 30 minutes, and then left at atmospheric pressure and room temperature for one day. Then, the samples containing each adherend were left in a constant temperature and humidity machine adjusted to a temperature of 85°C and a relative humidity of 85% for 30 minutes. At this time, each adherend was placed on top. Then, a 100g weight was hooked on the unattached part of the sample, i.e., the end with a length of 25 mm, and the time from the adhesive sheet peeling off from the adherend surface and the weight falling was measured, and the evaluation was performed according to the following criteria.
○：黏著片自被黏物面剝離而砝碼落下為止的時間為15分鐘以上 ○: The time from the adhesive sheet peeling off from the adherend surface to the weight falling off is more than 15 minutes
×：黏著片自被黏物面剝離而砝碼落下為止的時間未滿15分鐘 ×: The time from the adhesive sheet peeling off from the adherend surface to the weight falling is less than 15 minutes
(黃變性) (Xanthochromia)
於實施例及比較例中所獲得的黏著片的兩面貼合寬度52mm、長度76mm、1mm厚度的玻璃(松浪硝子(Matsunami)製造)後，利用高壓釜於溫度30℃、壓力0.5MPa的環境下處理30分鐘，於大氣壓、室溫環境下靜置一天。繼而，將包含各被黏物的樣品設置於須賀試驗機器製造的氙氣耐氣候機SX75，於相對濕度50%、黑色面板溫度63℃、照度180W/cm2的條件下照射300小時的光線後，利用須賀試驗機器製造的測色計Coloer Cute i來測定色度的b*值，按照以下的基準進行評價。 After the adhesive sheets obtained in the examples and comparative examples were bonded to glass (Matsunami) with a width of 52 mm, a length of 76 mm, and a thickness of 1 mm, the two sides were treated in an autoclave at a temperature of 30°C and a pressure of 0.5 MPa for 30 minutes, and then left to stand for one day in an atmosphere at room temperature. Subsequently, the samples including the adherends were placed in a xenon weathering chamber SX75 manufactured by Suga Testing Instruments and irradiated for 300 hours under the conditions of a relative humidity of 50%, a black panel temperature of 63°C, and an illumination of 180 W/cm 2. The b * value of the chromaticity was measured using a colorimeter Coloer Cute i manufactured by Suga Testing Instruments, and the evaluation was performed according to the following criteria.
○：相對於評價前b*值而言耐候性試驗後的b*值增加，b*值未滿2 ○: The b * value after the weathering test increases compared to the b * value before evaluation, and the b * value is less than 2
△：相對於評價前b*值而言耐候性試驗後的b*值增加，b*值為2以上且未滿3 △: The b * value after the weathering test increases compared to the b * value before evaluation, and the b * value is 2 or more and less than 3
×：相對於評價前b*值而言耐候性試驗後的b*值增加，b*值為 3以上 ×: The b * value after the weathering test increases compared to the b * value before evaluation, and the b * value is 3 or more
<(甲基)丙烯酸烷基酯> <(Meth) acrylate alkyl ester>
BA：丙烯酸丁酯 BA: Butyl acrylate
2EHA：丙烯酸2-乙基己酯 2EHA: 2-ethylhexyl acrylate
iBMA：甲基丙烯酸異丁酯 iBMA: isobutyl methacrylate
MMA：甲基丙烯酸甲酯 MMA: Methyl methacrylate
<具有羥基的(甲基)丙烯酸單體> <(Meth)acrylic acid monomer having hydroxyl group>
4HBA：丙烯酸4-羥基丁酯 4HBA: 4-Hydroxybutyl acrylate
<具有環結構的單體> <Monomer with ring structure>
CHA：丙烯酸環己酯 CHA: Cyclohexyl acrylate
CHMA：甲基丙烯酸環己酯 CHMA: Cyclohexyl methacrylate
DCPA：丙烯酸二環戊酯 DCPA: dicyclopentyl acrylate
PO-A：丙烯酸苯氧基乙酯 PO-A: Phenoxyethyl acrylate
NVP：正乙烯基吡咯啶酮 NVP: n-vinylpyrrolidone
DCPMA：甲基丙烯酸二環戊酯 DCPMA: dicyclopentyl methacrylate
IBXMA：甲基丙烯酸異冰片酯 IBXMA: Isobornyl methacrylate
St：苯乙烯 St: Styrene
實施例中所獲得的黏著片對任一被黏物亦均顯示出優異的密接性。另外，實施例中所獲得的黏著片可抑制黃變。比較例中表示對聚碳酸酯或玻璃的密接性差，根據被黏物的種類的不同而無法獲得優異的密接性。另外，比較例4中黏著片發生黃變。 The adhesive sheet obtained in the embodiment also showed excellent adhesion to any adherend. In addition, the adhesive sheet obtained in the embodiment can suppress yellowing. The comparative example showed poor adhesion to polycarbonate or glass, and excellent adhesion could not be obtained depending on the type of adherend. In addition, the adhesive sheet in comparative example 4 yellowed.
(實施例11) (Implementation Example 11)
((甲基)丙烯酸聚合體A的合成) (Synthesis of (meth)acrylic acid polymer A)
向包括攪拌機、氮氣導入管、冷卻管、溫度計的2L燒瓶中投入丙烯酸丁酯640g、甲基丙烯酸環己酯90g、丙烯酸4-羥基丁酯270g、正十二烷基硫醇0.4g，以氮氣流量300ml/min進行60 分鐘氮氣置換後，將氮氣流量降低至100ml/min為止，利用水浴升溫並加熱至60℃為止。繼而，投入AIBN 0.15g，於控制發熱的同時反應30分鐘，之後加以冷卻，藉此合成(甲基)丙烯酸聚合體A。之後，以64：9：27的比率將所述丙烯酸單體投入至燒瓶中，獲得(甲基)丙烯酸聚合體A為30質量%的丙烯酸漿A。再者，GPC測定的結果為(甲基)丙烯酸聚合體A的重量平均分子量為40萬。 Into a 2L flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer, 640 g of butyl acrylate, 90 g of cyclohexyl methacrylate, 270 g of 4-hydroxybutyl acrylate, and 0.4 g of n-dodecyl mercaptan were added, and nitrogen replacement was performed at a nitrogen flow rate of 300 ml/min for 60 minutes. The nitrogen flow rate was then reduced to 100 ml/min, and the temperature was raised to 60°C using a water bath. Subsequently, 0.15 g of AIBN was added, and the reaction was carried out for 30 minutes while controlling the heat, and then cooled to synthesize (meth)acrylic acid polymer A. Thereafter, the acrylic acid monomer was added to the flask at a ratio of 64:9:27 to obtain acrylic acid slurry A containing 30% by mass of (meth)acrylic acid polymer A. Furthermore, the results of GPC measurement showed that the weight average molecular weight of (meth)acrylic acid polymer A was 400,000.
((甲基)丙烯酸聚合體B的合成) (Synthesis of (meth)acrylic acid polymer B)
向包括攪拌機、氮氣導入管、冷卻管、溫度計的2L燒瓶中投入甲基丙烯酸甲酯300g、甲基丙烯酸二環戊酯200g、正十二烷基硫醇35g、乙酸乙酯300g、甲基乙基酮200g，以氮氣流量300ml/min進行60分鐘氮氣置換後，將氮氣流量降低至100ml/min為止，利用水浴升溫並加熱至70℃為止。繼而，投入AIBN 0.4g，於控制發熱的同時反應3小時後，進而追加0.6g的AIBN並反應4小時。如此獲得包含(甲基)丙烯酸聚合體B的樹脂溶液B。對樹脂溶液B進行GPC測定的結果為(甲基)丙烯酸聚合體B的重量平均分子量為3,600。 Into a 2L flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer, 300g of methyl methacrylate, 200g of dicyclopentyl methacrylate, 35g of n-dodecyl mercaptan, 300g of ethyl acetate, and 200g of methyl ethyl ketone were added. After nitrogen replacement at a nitrogen flow rate of 300ml/min for 60 minutes, the nitrogen flow rate was reduced to 100ml/min, and the temperature was raised in a water bath to 70°C. Subsequently, 0.4g of AIBN was added, and after reacting for 3 hours while controlling the heat, 0.6g of AIBN was further added and reacted for 4 hours. In this way, a resin solution B containing a (meth)acrylic polymer B was obtained. The result of GPC measurement of the resin solution B was that the weight average molecular weight of the (meth)acrylic polymer B was 3,600.
(黏著片的製作) (Adhesive sheet production)
準備如下者作為黏著劑組成物(塗敷液)：將樹脂溶液B流入金屬球棒，於乾燥機溫度120℃下乾燥2小時，並去除溶媒，使所得者以10g溶解於丙烯酸漿A 100g中後，添加IGM樹脂(IGM RESINS B.V.)公司製造的光起始劑(艾薩固萬(EsacureOne))0.5g、新中村化學工業製造的多官能單體(A-400)0.4g並加以攪拌 脫泡。以黏著劑層的厚度成為100μm的方式將塗敷液塗敷於塗佈了矽酮脫模劑的50μm聚酯膜上，進而於其上重疊塗佈了矽酮脫模劑的50μm聚酯膜。之後，利用化學燈以7mW/cm2的光強度照射2分鐘後，利用高壓水銀燈以累計光量為1500mJ/cm2的方式照射，藉此獲得實施例11的黏著片。 The following was prepared as an adhesive composition (coating liquid): Resin solution B was poured into a metal ball rod, dried in a dryer at 120°C for 2 hours, and the solvent was removed. 10 g of the resulting solution was dissolved in 100 g of acrylic slurry A, and 0.5 g of a photoinitiator (EsacureOne) manufactured by IGM Resins BV and 0.4 g of a multifunctional monomer (A-400) manufactured by Shin-Nakamura Chemical Industry were added and stirred for defoaming. The coating liquid was applied to a 50 μm polyester film coated with a silicone release agent so that the thickness of the adhesive layer was 100 μm, and a 50 μm polyester film coated with a silicone release agent was stacked thereon. After that, the film was irradiated with a chemical lamp at a light intensity of 7 mW/cm 2 for 2 minutes, and then irradiated with a high-pressure mercury lamp at a cumulative light intensity of 1500 mJ/cm 2 , thereby obtaining an adhesive sheet of Example 11.
(實施例12) (Example 12)
如表4般變更((甲基)丙烯酸聚合體A的合成)中的單體的組成，除此以外與實施例11同樣地獲得黏著劑組成物及黏著片。 The composition of the monomers in (Synthesis of (meth)acrylic acid polymer A) was changed as shown in Table 4, and the adhesive composition and adhesive sheet were obtained in the same manner as in Example 11.
(實施例13) (Implementation Example 13)
如表4般變更((甲基)丙烯酸聚合體A的合成)中的單體的組成，並如表4般變更((甲基)丙烯酸聚合體B的合成)中的單體的組成，除此以外與實施例11同樣地獲得黏著劑組成物及黏著片。 The adhesive composition and adhesive sheet were obtained in the same manner as in Example 11 except that the monomer composition in (Synthesis of (meth)acrylic acid polymer A) was changed as shown in Table 4 and the monomer composition in (Synthesis of (meth)acrylic acid polymer B) was changed as shown in Table 4.
(實施例14) (Example 14)
如表4般變更((甲基)丙烯酸聚合體A的合成)中的單體的組成。如表4般變更((甲基)丙烯酸聚合體B的合成)中的單體的組成。進而將相對於丙烯酸漿A的(甲基)丙烯酸聚合體B的混合量變更為表4中記載的比例，將添加量設為5g。除了所述事項以外，與實施例11同樣地獲得黏著劑組成物及黏著片。 The monomer composition in (Synthesis of (meth)acrylic polymer A) was changed as shown in Table 4. The monomer composition in (Synthesis of (meth)acrylic polymer B) was changed as shown in Table 4. Furthermore, the mixing amount of (meth)acrylic polymer B relative to acrylic syrup A was changed to the ratio shown in Table 4, and the addition amount was set to 5g. Except for the above matters, the adhesive composition and adhesive sheet were obtained in the same manner as in Example 11.
(比較例11) (Comparison Example 11)
不混合(甲基)丙烯酸聚合體B，除此以外與實施例11同樣地獲得黏著劑組成物及黏著片。 The adhesive composition and adhesive sheet were obtained in the same manner as in Example 11 except that the (meth)acrylic acid polymer B was not mixed.
(比較例12) (Comparison Example 12)
如表4般變更((甲基)丙烯酸聚合體A的合成)中的單體的組成，除此以外與實施例11同樣地獲得黏著劑組成物及黏著片。 The composition of the monomers in (Synthesis of (meth)acrylic acid polymer A) was changed as shown in Table 4, and the adhesive composition and adhesive sheet were obtained in the same manner as in Example 11.
(試算及測定) (Calculation and measurement)
((甲基)丙烯酸聚合體A的玻璃轉移溫度的算出) (Calculation of glass transition temperature of (meth)acrylic polymer A)
(甲基)丙烯酸聚合體A的玻璃轉移溫度利用以下的FOX式來求出。 The glass transition temperature of (meth)acrylic polymer A is calculated using the following FOX formula.
1/Tgp=W1/Tgl+W2/Tg2+…+Wn/Tgn 1/Tgp=W1/Tgl+W2/Tg2+…+Wn/Tgn
Tgp為聚合體A的玻璃轉移溫度，Wn為各單體的重量分率，Tgn為將各單體製成均聚物時的玻璃轉移溫度。 Tgp is the glass transition temperature of polymer A, Wn is the weight fraction of each monomer, and Tgn is the glass transition temperature when each monomer is made into a homopolymer.
((甲基)丙烯酸聚合體B的玻璃轉移溫度的測定) (Determination of glass transition temperature of (meth)acrylic polymer B)
(甲基)丙烯酸聚合體B的玻璃轉移溫度的測定是使用精工儀器(Seiko Instruments)製造的DSC6200。參考設為氧化鋁10mg，於直徑5mm的樣品用鋁盤中放入10mg左右的樹脂溶液B的溶媒去除品，於氮氣流量50ml/min的環境下以升溫速度10℃/min於0℃~150℃內升溫。此時，讀取比熱變化的拐點作為(甲基)丙烯酸聚合體B的玻璃轉移溫度。 The glass transition temperature of (meth)acrylic polymer B was measured using DSC6200 manufactured by Seiko Instruments. The reference was set to 10 mg of aluminum oxide, and about 10 mg of the solvent-removed product of resin solution B was placed in a 5 mm diameter sample aluminum pan, and the temperature was raised from 0°C to 150°C at a heating rate of 10°C/min in an environment with a nitrogen flow rate of 50 ml/min. At this time, the inflection point of the specific heat change was read as the glass transition temperature of (meth)acrylic polymer B.
((甲基)丙烯酸聚合體A的羥基價的算出) (Calculation of the hydroxyl value of (meth)acrylic acid polymer A)
羥基價是根據含羥基的單體的分子量與濃度算出mol濃度，將相對於每單位重量而成為當量的氫氧化鉀濃度設為重量，以mgKOH/g的形式來算出。 The hydroxyl value is calculated based on the molecular weight and concentration of the monomer containing the hydroxyl group, and the molar concentration is calculated by setting the concentration of potassium hydroxide that becomes equivalent per unit weight as the weight, and calculating it in the form of mgKOH/g.
(表面自由能的測定) (Determination of surface free energy)
將構成(甲基)丙烯酸聚合體A的各環結構的(甲基)丙烯酸單 體100g與乙酸乙酯200g放入500ml燒瓶中，進行氮氣置換後升溫至70℃並投入AIBN 0.2g。反應5小時後，並加以冷卻而回收樹脂溶液。以塗敷厚度成為25μm的方式將環結構丙烯酸均聚物樹脂溶液塗敷至PET膜後，利用100℃的乾燥機乾燥3分鐘，藉此獲得表面接觸角測定用試樣。 100g of each ring structure (meth)acrylic acid monomer constituting (meth)acrylic acid polymer A and 200g of ethyl acetate were placed in a 500ml flask, replaced with nitrogen, heated to 70°C and added with 0.2g of AIBN. After reacting for 5 hours, the resin solution was recovered by cooling. After applying the ring structure acrylic acid homopolymer resin solution to a PET film in a coating thickness of 25μm, it was dried in a dryer at 100°C for 3 minutes to obtain a sample for surface contact angle measurement.
樹脂溶液B亦同樣地進行塗敷、乾燥，從而獲得接觸角測定用試樣。 Resin solution B was applied and dried in the same manner to obtain a sample for contact angle measurement.
另外，用作被黏物的聚碳酸酯板(帝人製造的龐拉伊特(Panlite)1151)與PMMA板(三菱化學製造的亞克力萊特(Acrylite))亦同樣地作為接觸角測定用試樣而準備。 In addition, a polycarbonate plate (Panlite 1151 manufactured by Teijin) and a PMMA plate (Acrylite manufactured by Mitsubishi Chemical) used as adherends were also prepared as samples for contact angle measurement.
接觸角是使用菲布羅(FIBRO)公司製造的DAT1100，使純水2μl以及二碘甲烷1μl的液滴落下至接觸角測定用試樣的表面，利用θ/2法來算出。將讀取的接觸角的值(θ)適用於以下的Young-Dupre公式，並算出表面自由能。 The contact angle is calculated using the θ/2 method by using DAT1100 manufactured by FIBRO, dropping 2μl of pure water and 1μl of diiodomethane onto the surface of the contact angle measurement sample. The read contact angle value (θ) is applied to the following Young-Dupre formula to calculate the surface free energy.
所述式中，γd L為液體(水或二碘甲烷)的表面自由能分散成分，γp L為液體(水或二碘甲烷)的表面自由能極性成分，γd s 為固體(接觸角測定用試樣)的表面自由能分散成分，γp s為固體(接觸角測定用試樣)的表面自由能極性成分。另外，WLS為固體與液體的附著能量，γL為液體的表面能量。 In the above formula, γ d L is the surface free energy dispersion component of the liquid (water or diiodomethane), γ p L is the surface free energy polar component of the liquid (water or diiodomethane), γ d s is the surface free energy dispersion component of the solid (contact angle measurement sample), γ p s is the surface free energy polar component of the solid (contact angle measurement sample). In addition, W LS is the adhesion energy between the solid and the liquid, and γ L is the surface energy of the liquid.
(評價) (Evaluation)
(濕熱恆定負荷) (Wet heat constant load)
將實施例及比較例中所獲得的黏著片單面的隔離膜去除，貼合至易接著處理的100μm的聚酯膜(東洋紡製造的A4300)上，以對於被黏物的貼附部成為寬度25mm、長度75mm的方式進行切割。使該樣品分別以寬度25mm、50mm的面積貼附於1mm厚度的PMMA、或聚碳酸酯(帝人製造的龐拉伊特(Panlite)1151)後，利用2kg的輥往返壓接兩次。之後利用高壓釜於溫度30℃、壓力0.5MPa的環境下處理30分鐘後，在大氣壓、室溫環境下靜置一天。繼而，將包含各被黏物的樣品於調整為溫度85℃、相對濕度85%的恆溫恆濕機內部靜置30分鐘。此時，各被黏物設置於上方。繼而，將100g的砝碼鉤掛在聚酯膜長度25mm的端部，測定黏著片自被黏物面剝離而砝碼落下為止的時間，按照以下的基準進行評價。 The separator film on one side of the adhesive sheet obtained in the embodiment and the comparative example was removed, and the sheet was attached to a 100μm polyester film (A4300 manufactured by Toyobo) that is easy to process, and cut so that the attached part to the adherend has a width of 25mm and a length of 75mm. The sample was attached to a 1mm thick PMMA or polycarbonate (Panlite 1151 manufactured by Teijin) with a width of 25mm and 50mm, respectively, and then pressed twice with a 2kg roller. After that, it was treated in an autoclave at a temperature of 30°C and a pressure of 0.5MPa for 30 minutes, and then left at atmospheric pressure and room temperature for one day. Next, the samples containing each adherend were placed in a constant temperature and humidity chamber at 85°C and 85% relative humidity for 30 minutes. At this time, each adherend was placed on top. Next, a 100g weight was hooked on the end of the polyester film with a length of 25mm, and the time from when the adhesive sheet was peeled off from the adherend surface and the weight fell was measured, and the evaluation was performed according to the following criteria.
○：黏著片自被黏物面剝離而砝碼落下為止的時間為15分鐘以上 ○: The time from the adhesive sheet peeling off from the adherend surface to the weight falling off is more than 15 minutes
×：黏著片自被黏物面剝離而砝碼落下為止的時間未滿15分鐘 ×: The time from the adhesive sheet peeling off from the adherend surface to the weight falling is less than 15 minutes
<(甲基)丙烯酸烷基酯> <(Meth) acrylate alkyl ester>
BA：丙烯酸丁酯 BA: Butyl acrylate
MMA：甲基丙烯酸甲酯 MMA: Methyl methacrylate
DMAA：丙烯酸二甲基醯胺 DMAA: dimethyl acrylate
<具有羥基的(甲基)丙烯酸單體> <(Meth)acrylic acid monomer having hydroxyl group>
4HBA：丙烯酸4-羥基丁酯 4HBA: 4-Hydroxybutyl acrylate
<具有環結構的單體> <Monomer with ring structure>
CHMA：甲基丙烯酸環己酯 CHMA: Cyclohexyl methacrylate
DCPA：丙烯酸二環戊酯 DCPA: dicyclopentyl acrylate
PO-A：丙烯酸苯氧基乙酯 PO-A: Phenoxyethyl acrylate
POB-A：丙烯酸3-苯氧基苄酯 POB-A: 3-phenoxybenzyl acrylate
DCPMA：甲基丙烯酸二環戊酯 DCPMA: dicyclopentyl methacrylate
IBXMA：甲基丙烯酸異冰片酯 IBXMA: Isobornyl methacrylate
實施例中所獲得的黏著片對任一被黏物亦均顯示出優異的密接性。另外，實施例中所獲得的黏著片可抑制黃變。 The adhesive sheet obtained in the embodiment also shows excellent adhesion to any adherend. In addition, the adhesive sheet obtained in the embodiment can suppress yellowing.
10:帶剝離片的黏著片 10: Adhesive sheet with peeling sheet
11:黏著劑層 11: Adhesive layer
12a:剝離片 12a: Peeling film
12b:剝離片 12b: Peeling film
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| Application Number | Priority Date | Filing Date | Title |
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| JP2019182626A JP6705543B1 (en) | 2019-10-03 | 2019-10-03 | Adhesive composition and adhesive sheet |
| JP2019-182626 | 2019-10-03 | ||
| JP2019-182625 | 2019-10-03 | ||
| JP2019182625A JP6705542B1 (en) | 2019-10-03 | 2019-10-03 | Adhesive sheet |
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| Publication Number | Publication Date |
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| TW202116945A TW202116945A (en) | 2021-05-01 |
| TWI842958B true TWI842958B (en) | 2024-05-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093806A (en) | 2011-11-18 | 2014-10-08 | 3M创新有限公司 | Pressure-sensitive adhesive composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093806A (en) | 2011-11-18 | 2014-10-08 | 3M创新有限公司 | Pressure-sensitive adhesive composition |
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