TWI510584B - 光學薄膜用黏著劑組成物及表面保護薄膜 - Google Patents
光學薄膜用黏著劑組成物及表面保護薄膜 Download PDFInfo
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- TWI510584B TWI510584B TW102138465A TW102138465A TWI510584B TW I510584 B TWI510584 B TW I510584B TW 102138465 A TW102138465 A TW 102138465A TW 102138465 A TW102138465 A TW 102138465A TW I510584 B TWI510584 B TW I510584B
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- Prior art keywords
- meth
- acrylate
- optical film
- adhesive composition
- mass
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims description 53
- 230000001070 adhesive effect Effects 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 37
- 239000010408 film Substances 0.000 title claims description 32
- 239000012788 optical film Substances 0.000 title claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 58
- -1 alkali metal salt Chemical class 0.000 claims description 47
- 239000004925 Acrylic resin Substances 0.000 claims description 37
- 229920000178 Acrylic resin Polymers 0.000 claims description 36
- 229920005862 polyol Polymers 0.000 claims description 20
- 150000003077 polyols Chemical class 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 150000008040 ionic compounds Chemical class 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 15
- 239000005056 polyisocyanate Substances 0.000 description 14
- 229920001228 polyisocyanate Polymers 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000008096 xylene Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OTMBZPVYOQYPBE-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclododecane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCCCCCCCC1 OTMBZPVYOQYPBE-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- JFHKCZFPXJVELF-UHFFFAOYSA-L dibutyltin(2+);2,2-diethylhexanoate Chemical compound CCCC[Sn+2]CCCC.CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O JFHKCZFPXJVELF-UHFFFAOYSA-L 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- UYLUJGRCKKSWHS-UHFFFAOYSA-N prop-1-en-1-one Chemical compound CC=C=O UYLUJGRCKKSWHS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C08G18/24—Catalysts containing metal compounds of tin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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Description
本發明係關於一種光學薄膜用黏著劑組成物及表面保護薄膜。
近年來,在光學零件.電子零件領域為了達到表面保護之目的,常使用聚乙烯、聚酯、聚丙烯等的透明保護薄片(透明基材薄片)與黏著劑層合而成的表面保護薄膜。若此表面保護薄膜在由黏著薄片將脫模薄膜剝離時,以及將黏著薄片由被著體剝離時帶靜電,則會有周圍的灰塵附著而污染光學零件.電子零件的問題。
於是開發出賦予抗靜電性的黏著劑,例如在專利文獻1及2之中,揭示了在丙烯酸系共聚物中添加聚醚多元醇作為抗靜電劑的黏著劑。然而,添加聚醚多元醇作為抗靜電劑的黏著劑,在透明性方面會有問題,從品質保證的觀點看來,無法使用於要求具有透明性的表面保護薄膜。
另外,在專利文獻3之中揭示了藉由使聚醚多元醇接枝在丙烯酸聚合物,且兼具抗靜電性與透明性的黏著劑。
然而,由於此黏著劑的酸價高,因此會有難以使用於如ITO薄膜般的怕腐蝕的光學構件的問題。
專利文獻1:日本特開平6-128539號公報
專利文獻2:日本特開2005-325255號公報
專利文獻3:日本特開2010-6980號公報
本發明鑑於上述先前技術所具有的問題,目的為提供一種抗靜電性及透明性優異、對被著體的污染性及腐蝕性低的光學薄膜用黏著劑組成物、及表面保護薄膜。
本發明人等以光學薄膜用黏著劑組成物所具有的前述問題點為背景反覆潛心檢討的結果,發現了以特定重量比例含有特定重量平均分子量的(甲基)丙烯酸系樹脂,特定數量平均分子量的聚氧伸烷基多元醇、聚異氰酸酯、離子性化合物及錫系觸媒的光學薄膜用黏著劑組成物,會展現良好的抗靜電性及透明性、對被著體的低污染性及腐蝕性,本發明基於此見解而完成。
本發明如以下的(1)~(10)所示。
(1)一種光學薄膜用黏著劑組成物,其係含有(A)(甲基)丙
烯酸系樹脂65~85質量%、與(B)聚氧伸烷基多元醇10~30質量%、與(C)聚異氰酸酯1.0~5.0質量%、與(D)離子性化合物0.2~1.0質量%、及(E)錫系觸媒0.005~0.1質量%之光學薄膜用黏著劑組成物,其特徵為(A)(甲基)丙烯酸系樹脂的重量平均分子量為10萬~60萬,且(B)聚氧伸烷基多元醇的數量平均分子量為500~1500。
(2)如第(1)項之光學薄膜用黏著劑組成物,其中前述(A)(甲基)丙烯酸系樹脂包含含有羥基的(甲基)丙烯酸系單體0.5~10mol%作為共聚合成分。
(3)如第(2)項之光學薄膜用黏著劑組成物,其中前述含羥基的(甲基)丙烯酸系單體為(甲基)丙烯酸2-羥乙酯。
(4)如第(1)~(3)項中任一項之光學薄膜用黏著劑組成物,其中前述(A)(甲基)丙烯酸系樹脂含有(甲基)丙烯酸甲酯15~50mol%作為共聚合成分。
(5)如第(1)~(4)項中任一項之光學薄膜用黏著劑組成物,其中酸價為0~5mgKOH/g。
(6)如第(1)~(5)項中任一項之光學薄膜用黏著劑組成物,其中前述(D)離子性化合物為鹼金屬鹽。
(7)如第(1)~(6)項中任一項之光學薄膜用黏著劑組成物,其中前述(E)錫系觸媒為二月桂酸二辛基錫。
(8)一種表面保護薄膜,其特徵為:在透明基材上的單面形成使如第(1)~(7)項中任一項之光學薄膜用黏著劑組成物硬化所得到的黏著劑層。
(9)如第(8)項之表面保護薄膜,其中表面固有電阻值為1.0
×1010
Ω/□以下,且霧度為1.2以下。
(10)如第(8)或(9)項之表面保護薄膜,其中前述透明基材為厚度5~200μm的聚對苯二甲酸乙二酯、聚乙烯、聚丙烯、聚苯乙烯、聚醯亞胺、聚乙烯醇、聚氯乙烯或纖維素。
依據本發明可提供一種抗靜電性及透明性優異、對被著體的污染性及腐蝕性較低的光學薄膜用黏著劑組成物、及表面保護薄膜。
以下對本發明作詳細說明。
本發明之光學薄膜用黏著劑組成物係含有(A)(甲基)丙烯酸系樹脂、與(B)聚氧伸烷基多元醇、與(C)聚異氰酸酯、與(D)離子性化合物、及(E)錫系觸媒。
本發明中的(甲基)丙烯酸系樹脂,是指丙烯酸系樹脂或甲基丙烯酸系樹脂,另外,(甲基)丙烯酸酯,是指丙烯酸酯或甲基丙烯酸酯。並且,(甲基)丙烯酸酯系樹脂,是指全構成單體的80mol%以上為(甲基)丙烯酸酯系單體的聚合物。
本發明中之(A)(甲基)丙烯酸系樹脂的聚合所使用的
(甲基)丙烯酸系單體並無特別限定,而以不含羧基(化學式:-COOH)為佳。(甲基)丙烯酸系單體的例子可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸異硬脂酯等的(甲基)丙烯酸烷酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸降莰酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸降莰烷酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊氧基乙酯、三環癸烷二羥甲基二(甲基)丙烯酸酯等的(甲基)丙烯酸環烷酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸2-甲氧基乙氧基乙酯、(甲基)丙烯酸2-乙氧基乙氧基乙酯等的(甲基)丙烯酸烷氧基烷酯、甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯等的烷氧基(聚)伸烷二醇(甲基)丙烯酸酯、(甲基)丙烯酸八氟戊酯等的(甲基)丙烯酸氟烷酯、(甲基)丙烯酸N,N-二甲基胺乙酯、(甲基)丙烯酸N,N-二乙基胺乙酯等的(甲基)丙烯酸二烷基胺基烷酯、(甲基)丙烯醯胺、二丙酮(甲基)丙烯醯胺等的含醯胺基的(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯等的含環氧基的(甲基)丙烯
酸酯、聚矽氧變性(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等的多官能性(甲基)丙烯酸酯等。該等可單獨使用,或可組合兩種以上來使用。
若考慮(A)(甲基)丙烯酸系樹脂與(B)聚氧伸烷基多元醇的相溶性,亦即使光學薄膜用黏著劑組成物硬化所得到的黏著劑層的透明性,則以含有丙烯酸甲酯或甲基丙烯酸甲酯15~50mol%作為(A)(甲基)丙烯酸系樹脂的共聚合成分為佳,含有25~45mol%為較佳。
另外,本發明中之(A)(甲基)丙烯酸系樹脂,從可介由聚異氰酸酯與聚氧伸烷基多元醇發生反應而一體化(提升透明性)的觀點看來,以包含含有羥基的(甲基)丙烯酸系單體作為共聚合成分為佳。含羥基的(甲基)丙烯酸系單體的例子可列舉(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯、1,3-丁二醇(甲基)丙烯酸酯、1,4-丁二醇(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯、3-甲基戊二醇(甲基)丙烯酸酯等的含羥基的(甲基)丙烯酸酯等。其中,從共聚合性及反應性這點看來,以(甲基)丙烯酸2-羥乙酯為佳。含羥基的(甲基)丙烯酸系單體以含有0.5~10mol%以作為(A)(甲基)丙烯酸系樹脂的共聚合成分為佳,含有0.6~8.0mol%為較佳。
另外,在本發明中之(A)(甲基)丙烯酸系樹脂中,在不損及聚合性的範圍,可使用其他聚合性單體作為共聚合成
分。這種聚合性單體的例子可列舉丙烯腈、甲基丙烯腈、苯乙烯、α-甲基苯乙烯、醋酸乙烯酯、丙酸乙烯酯、硬脂酸乙烯酯、氯乙烯、偏二氯乙烯、烷基乙烯基醚、乙烯基甲苯、乙烯基吡啶、乙烯基吡咯烷酮、伊康酸二烷酯、富馬酸二烷酯、烯丙醇、丙烯酸氯化物、甲基乙烯酮、N-丙烯醯胺甲基三甲基氯化銨、烯丙基三甲基氯化銨、二甲基烯丙基乙烯酮等。
本發明中之(A)(甲基)丙烯酸系樹脂的重量平均分子量必須在10萬~60萬,宜為15萬~50萬,較佳為20萬~40萬。在重量平均分子量小於10萬的情況,由於凝集力變小,會產生殘膠。另一方面,在重量平均分子量大於60萬的情況,(A)(甲基)丙烯酸系樹脂與(B)聚氧伸烷基多元醇的相溶性變差,所得到的黏著劑層的透明性變差。
此處重量平均分子量是使用凝膠滲透層析(昭和電工股份有限公司製,Shodex(註冊商標)GPC-101),以下述條件在常溫下作測定,並以聚苯乙烯換算所算出之值。
管柱:昭和電工股份有限公司製,Shodex(註冊商標)LF-804
管柱溫度:40℃
試樣:共聚物的0.2質量%四氫呋喃溶液
流量:1ml/分鐘
溶離液:四氫呋喃
另外,本發明中之(A)(甲基)丙烯酸系樹脂的玻璃轉移溫度(Tg)係以-80~0℃為佳,較佳為-70~-10℃。在Tg高於0℃的情況,對被著體的潤濕變差,而為不佳。另一方
面,在Tg低於-80℃的情況,由於凝集力變小,可能會產生殘膠,而為不佳。此外,(A)(甲基)丙烯酸系樹脂的Tg,可藉由適當地改變所使用的單體成分或組成比來調整。
此處,Tg是指由以下的方法所求得的值。由(A)(甲基)丙烯酸系樹脂採取10mg的試樣,使用示差掃描熱量計(DSC),以10℃/分鐘的昇溫速度由-80℃至200℃改變溫度,進行示差掃描熱量測定,將玻璃轉移造成的吸熱開始溫度定為Tg。此外,在觀察到兩個Tg的情況,取兩個Tg的平均值。
本發明中之(A)(甲基)丙烯酸系樹脂的聚合方法並不受特別限制,可藉由溶液聚合、乳化聚合、塊狀聚合、懸浮聚合、交替共聚合等的周知的方法來進行聚合。其中以溶液聚合為特別適合。
另外,所得到的共聚物可為隨機共聚物、嵌段共聚物等的任一者。
(A)(甲基)丙烯酸系樹脂的聚合時所使用的聚合起始劑並不受特別限定,可由周知者之中適當地選擇使用。可適當地例示例如2,2’-偶氮雙(異丁腈)、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-羰腈)、2,2’-偶氮雙(2,4,4-三甲基戊烷)、二甲基-2,2’-偶氮雙(2-甲基丙酸酯)等的偶氮系聚合起始劑;過氧化苯甲醯、第三丁基過氧化氫、過氧化二第三丁基、第三丁基過氧苯甲酸酯、
過氧化二異丙苯、1,1-雙(第三丁基過氧)3,3,5-三甲基環己烷、1,1-雙(第三丁基過氧)環十二烷等的過氧化物系聚合起始劑等的油溶性聚合起始劑。這些聚合起始劑可單獨使用,或可組合兩種以上來使用。聚合起始劑的使用量只要是通常的使用量則即可,例如可在相對於單體100質量份為0.01~5質量份左右的範圍來作選擇,以0.02~4質量份的範圍為佳,0.03~3質量份為較佳。
此外,在溶液聚合中可使用各種一般的溶劑。這種溶劑可列舉醋酸乙酯、醋酸正丙酯、醋酸正丁酯等的酯類、甲苯、苯等的芳香族烴類、正己烷、正庚烷等的脂肪族烴類、環己烷、甲基環己烷等的脂環式烴類、甲基乙基酮、甲基異丁基酮等的酮類等的有機溶劑。這些溶劑可單獨使用,或可組合兩種以上來使用。
另外,本發明中之(A)(甲基)丙烯酸系樹脂的摻合量必須在65~85質量%,較佳為70~85質量%。在摻合量少於65質量%的情況,會污染被著體,另一方面,在摻合量超過85質量%的情況,無法得到足夠的帶電特性。
本發明中之(B)聚氧伸烷基多元醇只要是具有醚基的聚合物多元醇,則不受特別限定,可適當地使用周知的聚合物多元醇。(B)聚氧伸烷基多元醇的例子可列舉聚乙二醇、聚丙二醇、聚四亞甲基醚二醇及該等的衍生物或共聚物等。其中,從容易調整與(甲基)丙烯酸系樹脂的相溶性
的理由來考量,以聚丙二醇為佳。該等可單獨使用,或可混合兩種以上來使用。
本發明中之(B)聚氧伸烷基多元醇的數量平均分子量必須在500~1500,宜為800~1200。在數量平均分子量超過1500的情況,黏著劑層的透明性變差。另一方面,在數量平均分子量小於500的情況,可能會產生殘膠,而為不佳。數量平均分子量是指藉由GPC(凝膠滲透層析)作測定所得到的值。
另外,本發明中之(B)聚氧伸烷基多元醇的摻合量必須在10~30質量%,較佳為15~25質量%。在摻合量少於10質量%的情況,無法得到足夠的帶電特性,另一方面,在摻合量超過30質量%的情況,會污染被著體。
本發明中的(C)聚異氰酸酯可列舉芳香族系、脂肪族系、脂環式系等的聚異氰酸酯。(C)聚異氰酸酯的例子可列舉1,4-四亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯(HDI)、2-甲基-1,5-戊烷二異氰酸酯、3-甲基-1,5-戊烷二異氰酸酯、三甲基六亞甲基二異氰酸酯、異佛酮二異氰酸酯、環己基二異氰酸酯、甲苯二異氰酸酯(TDI)、氫化甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、聚苯基甲烷聚異氰酸酯、二甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、四甲基二甲苯二異氰酸酯、降莰烯二異氰酸酯、萘二異氰酸酯、三羥甲基丙烷/甲苯
二異氰酸酯三聚物加成物、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物、六亞甲基二異氰酸酯之異氰尿酸酯體等的異氰酸酯加成物、聚醚聚異氰酸酯、聚酯聚異氰酸酯等。該等可單獨使用,或可組合兩種以上來使用。
另外,本發明中之(C)聚異氰酸酯的摻合量必須在1.0~5.0質量%,較佳為2.0~4.0質量%。在摻合量少於1.0質量%的情況,無法得到足夠的凝集力,另一方面,在摻合量超過5.0質量%的情況,黏著層變得過硬,對被著體的潤濕性變差。
本發明所使用的(D)離子性化合物,可列舉由陰離子與陽離子所構成,且在25℃為液態或固態的離子性化合物。具體而言,可列舉鹼金屬鹽、離子性液體(在25℃為液態)、界面活性劑等。其中,從不易污染被著體的理由來考量,以鹼金屬鹽為佳。
鹼金屬鹽可列舉由鋰、鈉、鉀等的鹼金屬陽離子與陰離子所構成之化合物,具體而言,可列舉氯化鈉、氯化鉀、氯化鋰、過氯酸鋰、氯酸鉀、硝酸鉀、硝酸鈉、碳酸鈉、硫氰酸鈉、LiBr、LiI、LiBF4
、LiPF6
、LiSCN、醋酸鈉、海藻酸鈉、木質素磺酸鈉、甲苯磺酸鈉、LiCF3
SO3
、Li(CF3
SO2
)2
N、Li(C2
F5
SO2
)2
N、Li(CF3
SO2
)3
C等。這些鹼金屬鹽可單獨使用,或可組合兩種以上來使用。
另外,本發明中之(D)離子性化合物的摻合量必須在
0.2~1.0質量%,較佳為0.3~0.8質量%。在摻合量少於0.2質量%的情況,無法得到足夠的帶電特性,另一方面,在摻合量超過1.0質量%的情況,會污染被著體。
本發明中的(E)錫系觸媒,可列舉二丁基錫二月桂酸酯、二丁基錫二乙基己酸酯、二月桂酸二辛基錫等。其中,從(C)聚異氰酸酯的硬化性良好且安全性高的理由來考量,以二月桂酸二辛基錫為佳。
另外,本發明中的(E)錫系觸媒的摻合量必須在0.005~0.1質量%,較佳為0.01~0.05質量%。在摻合量少於0.005質量%的情況,無法得到足夠的凝集力,另一方面,在摻合量超過0.1質量%的情況,(甲基)丙烯酸系樹脂的安定性變差,使用期限變短。
本發明之光學薄膜用黏著劑組成物係以酸價為0~5mgKOH/g為佳,0~1mgKOH/g為較佳,0~0.3mgKOH/g為更佳,0~0.1mgKOH/g為最佳。若酸價高於5mgKOH/g,則對於ITO薄膜等的怕腐蝕的材料而言難以使用。此外,組成物的酸價是依據JIS K0070所測得的值。例如藉由以下所述的方式作測定。
以精密天秤在100ml三角燒瓶中精秤試樣約2g左右,於其中加入乙醇/二乙醚=1/1(質量比)的混合溶劑10ml並使其溶解。進一步在此容器中添加1~3滴作為指示劑的酚酞乙醇溶液,充分攪拌至試樣成為均勻。將其以
0.1N氫氧化鉀-乙醇溶液滴定,指示劑的淺紅色持續30秒鐘時,定為中和的終點。將此結果代入下述一般式(1),所得到之值定為組成物的酸價。
[數1]酸價(mgKOH/g)=[B×f×5.611]/S (1)
上式中,B為0.1N氫氧化鉀-乙醇溶液的使用量(ml),f為0.1N氫氧化鉀-乙醇溶液的因子,S為試樣的採取量(g)。
另外,在本發明之光學薄膜用黏著劑組成物中,在不損及透明性的範圍,亦可因應必要添加周知的各種添加劑。添加劑可列舉可塑劑、表面潤滑劑、整平劑、軟化劑、抗氧化劑、抗老化劑、光安定劑、紫外線吸收劑、聚合禁止劑、苯并三唑系等的光安定劑、磷酸酯系及其他阻燃劑、如界面活性劑般的抗靜電劑等。
另外,本發明之光學薄膜用黏著劑組成物,亦可為了調整塗佈時的黏度之目地而使用有機溶劑來稀釋。可使用有機溶劑可列舉例如甲基乙基酮、丙酮、醋酸乙酯、四氫呋喃、二噁烷、環己酮、正己烷、甲苯、二甲苯、正丙醇、異丙醇、醋酸正丙酯等。這些有機溶劑可單獨使用,或可混合兩種以上來使用。
本發明的表面保護薄膜是在透明基材上的單面形成使上述光學薄膜用黏著劑組成物硬化所得到的黏著劑層者。黏著劑層的厚度通常為3~100μm,宜為5~50μm。
透明基材可列舉例如聚對苯二甲酸乙二酯、聚乙烯、
聚丙烯、聚苯乙烯、聚醯亞胺、聚乙烯醇、聚氯乙烯、纖維素等。透明基材的厚度通常為5~200μm,宜為10~100μm左右。
此外還可在透明基材的單面因應必要實施利用聚矽氧系、氟系、長鏈烷基系等的脫模劑的脫模處理及防污處理、酸處理、鹼處理、底漆處理、電暈處理、電漿處理、紫外線處理等的易接著處理。
另外,透明基材較適合採用經過抗靜電處理者。對透明基材實施的抗靜電處理不受特別限定,而可採用在一般所使用的透明基材的至少單面設置抗靜電層之方法或將抗靜電劑混練至透明基材之方法。
此外,為了在本發明的表面保護薄膜形成黏著劑層,可使用周知的塗佈法(coating)並可使用慣用的塗佈機,例如凹版輥式塗佈機、逆輥式塗佈機、吻輥塗佈機、浸漬輥塗佈機、棒式塗佈機、刀片塗佈機、噴霧塗佈機、逗號形刮刀塗佈機、直接塗佈機等進行塗佈。
本發明的表面保護薄膜,可因應必要為了保護黏著面之目的而在黏著劑層表面貼合間隔物。構成間隔物的基材已知有紙或塑膠薄膜,然而從表面平滑性優異這點看來,適合使用塑膠薄膜。該薄膜只要是可保護上述黏著劑層的薄膜,則不受特別限定,可列舉例如聚乙烯薄膜、聚丙烯薄膜、聚對苯二甲酸乙二酯薄膜、聚丁烯薄膜等。
如上述般構成的本發明的表面保護薄膜,其黏著面的表面固有電阻值為1.0×1010
Ω/□以下且霧度為1.2以下,
因此可使用於容易產生靜電的塑膠製品等。其中,適合使用作為為了保護液晶顯示器等所使用的偏光板、波長板、位相差板、光學補償薄膜、反射薄片、亮度提升薄膜等的光學構件表面之目的所使用的表面保護薄膜。
以下藉由實施例及比較例對本發明作較具體的說明,然而本發明完全不受這些例子限定。
在具備冷凝管、氮氣導入管、溫度計及攪拌裝置的反應容器中,加入醋酸正丙酯500質量份、丙烯酸2-乙基己酯265質量份(0.53mol)、丙烯酸異莰酯41質量份(0.07mol)、甲基丙烯酸甲酯105質量份(0.39mol)、丙烯酸2-羥乙酯2質量份(0.007mol)及2,2’-偶氮雙(異丁腈)0.4質量份,在氮氣流中並在95℃下進行聚合8小時,得到玻璃轉移溫度-30℃、重量平均分子量25萬的(甲基)丙烯酸系樹脂(A-1)。此外,(甲基)丙烯酸系樹脂的玻璃轉移溫度及重量平均分子量的測定是藉由先前敘述的方法來進行。
另外,(甲基)丙烯酸系樹脂(A-2)及(甲基)丙烯酸系樹脂(A-3)所使用的單體如表1般作變更,除此之外,以與(甲基)丙烯酸系樹脂(A-1)同樣的方式合成。亦對(甲基)丙烯酸系樹脂(A-2)~(A-3)進行玻璃轉移溫度及重量平均分子量的測定。將結果揭示於表1。
以表2所示的組成摻合(甲基)丙烯酸系樹脂、聚氧伸烷基多元醇、聚異氰酸酯、離子性化合物及錫系觸媒,進一步以醋酸乙酯將固體成分濃度調節在50質量%,在室溫下使用分散機混合,而得到光學薄膜用黏著劑組成物溶液。將此溶液流延塗佈在對厚度38μm的聚對苯二甲酸乙二酯(PET)薄膜的單面實施剝離處理而成的間隔物的剝離處理面上,使乾燥後的厚度成為50μm,在50℃加熱乾燥5分鐘及在110℃加熱乾燥3分鐘,進一步貼合厚度50μm的PET薄膜,而製作出黏著薄片。
以前述方法測定各組成物的酸價。將結果揭示於表2。
將所得到的黏著薄片切成40×40mm的大小之後,將其放置在溫度23℃及相對濕度65%的環境下3小時來調濕之後,將間隔物撕開,依據JIS K6911所記載之方法測定黏著面的表面固有電阻。將結果揭示於表2。此外,意味著若表面固有電阻值愈小,則代表抗靜電性能愈高。
將所得到的黏著薄片切取30mm×30mm的大小,將黏著薄片的間隔物撕開,貼合在玻璃板,以此作為測定用樣品。對於測定用樣品使用村上色彩技術研究所股份有限公司製「HR-100型」,並使用霧度計NM-150(村上色彩技術研究所股份有限公司製)來進行霧度的測定。霧度(%)是將擴散透過率除以全光線透過率,並且乘以100來計算。此外,n數定為3次,採用其平均值。測定全光線透過率(%)。將結果揭示於表2。此外,霧度值愈小,則代表透明性愈高。
將所得到的黏著薄片切取25mm×100mm的大小,將黏著薄片的間隔物撕開,將黏著面(測定面)貼附在測試板,以2kg的橡膠輥(寬度:約50mm)往返滾壓1次而製作出測定用樣品。測試板是採用玻璃板。將所得到的測定用樣品在溫度23℃及相對濕度50%的環境下放置24小時之後,依據JIS Z0237,以剝離速度300mm/分鐘進行180°方向的拉伸測試,測定黏著薄片對玻璃板的黏著力(N/25mm)。將所得到的測定值定為黏著力。將結果揭示於表2。
將以上所得到的黏著薄片切取50mm×50mm的大小,將間隔物撕開並黏貼在玻璃板。將此樣品在70℃下放置5
天之後,將黏著薄片撕開,以目視確認對玻璃表面的污染性,依照下述基準作評估。將結果揭示於表2。
○:與貼合前的玻璃表面相比,沒有變化。
×:在玻璃表面觀察到殘膠。
Claims (10)
- 一種光學薄膜用黏著劑組成物,其係含有(A)(甲基)丙烯酸系樹脂65~85質量%、與(B)聚氧伸烷基多元醇10~30質量%、與(C)聚異氰酸酯1.0~5.0質量%、與(D)離子性化合物0.2~1.0質量%、以及(E)錫系觸媒0.005~0.1質量%之光學薄膜用黏著劑組成物,其特徵為(A)(甲基)丙烯酸系樹脂的重量平均分子量為10萬~60萬,且(B)聚氧伸烷基多元醇的數量平均分子量為500~1500。
- 如申請專利範圍第1項之光學薄膜用黏著劑組成物,其中前述(A)(甲基)丙烯酸系樹脂包含含有羥基的(甲基)丙烯酸系單體0.5~10mol%作為共聚合成分。
- 如申請專利範圍第2項之光學薄膜用黏著劑組成物,其中前述含羥基的(甲基)丙烯酸系單體為(甲基)丙烯酸2-羥乙酯。
- 如申請專利範圍第1~3項中任一項之光學薄膜用黏著劑組成物,其中前述(A)(甲基)丙烯酸系樹脂含有(甲基)丙烯酸甲酯15~50mol%作為共聚合成分。
- 如申請專利範圍第1~3項中任一項之光學薄膜用黏著劑組成物,其中酸價為0~5mgKOH/g。
- 如申請專利範圍第1~3項中任一項之光學薄膜用黏著劑組成物,其中前述(D)離子性化合物為鹼金屬鹽。
- 如申請專利範圍第1~3項中任一項之光學薄膜用黏著劑組成物,其中前述(E)錫系觸媒為二月桂酸二辛基錫。
- 一種表面保護薄膜,其特徵為:在透明基材上的單面形成使如申請專利範圍第1~3項中任一項之光學薄膜用黏著劑組成物硬化所得到的黏著劑層。
- 如申請專利範圍第8項之表面保護薄膜,其中表面固有電阻值為1.0×1010 Ω/□以下,且霧度為1.2以下。
- 如申請專利範圍第8或9項之表面保護薄膜,其中前述透明基材為厚度5~200μm的聚對苯二甲酸乙二酯、聚乙烯、聚丙烯、聚苯乙烯、聚醯亞胺、聚乙烯醇、聚氯乙烯或纖維素。
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