JP6286703B2 - Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive film and surface protective film - Google Patents
Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive film and surface protective film Download PDFInfo
- Publication number
- JP6286703B2 JP6286703B2 JP2013062074A JP2013062074A JP6286703B2 JP 6286703 B2 JP6286703 B2 JP 6286703B2 JP 2013062074 A JP2013062074 A JP 2013062074A JP 2013062074 A JP2013062074 A JP 2013062074A JP 6286703 B2 JP6286703 B2 JP 6286703B2
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- JP
- Japan
- Prior art keywords
- sensitive adhesive
- tocopherol
- pressure
- film
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 95
- 230000003287 optical effect Effects 0.000 title claims description 64
- 239000000203 mixture Substances 0.000 title claims description 57
- 230000001681 protective effect Effects 0.000 title claims description 11
- -1 tocopherol compound Chemical class 0.000 claims description 63
- 229920006243 acrylic copolymer Polymers 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 37
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 33
- 239000003431 cross linking reagent Substances 0.000 claims description 31
- 239000003963 antioxidant agent Substances 0.000 claims description 29
- 235000006708 antioxidants Nutrition 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 27
- 230000003078 antioxidant effect Effects 0.000 claims description 25
- 239000011732 tocopherol Substances 0.000 claims description 23
- 229930003799 tocopherol Natural products 0.000 claims description 23
- 235000010384 tocopherol Nutrition 0.000 claims description 23
- 229960001295 tocopherol Drugs 0.000 claims description 23
- 150000008040 ionic compounds Chemical class 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 230000001588 bifunctional effect Effects 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229960000984 tocofersolan Drugs 0.000 claims description 7
- 150000003611 tocopherol derivatives Chemical class 0.000 claims description 7
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- GJJVAFUKOBZPCB-UHFFFAOYSA-N 2-methyl-2-(4,8,12-trimethyltrideca-3,7,11-trienyl)-3,4-dihydrochromen-6-ol Chemical compound OC1=CC=C2OC(CCC=C(C)CCC=C(C)CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-UHFFFAOYSA-N 0.000 claims description 4
- ODADKLYLWWCHNB-UHFFFAOYSA-N 2R-delta-tocotrienol Natural products OC1=CC(C)=C2OC(CCC=C(C)CCC=C(C)CCC=C(C)C)(C)CCC2=C1 ODADKLYLWWCHNB-UHFFFAOYSA-N 0.000 claims description 4
- OTXNTMVVOOBZCV-UHFFFAOYSA-N 2R-gamma-tocotrienol Natural products OC1=C(C)C(C)=C2OC(CCC=C(C)CCC=C(C)CCC=C(C)C)(C)CCC2=C1 OTXNTMVVOOBZCV-UHFFFAOYSA-N 0.000 claims description 4
- RZFHLOLGZPDCHJ-DLQZEEBKSA-N alpha-Tocotrienol Natural products Oc1c(C)c(C)c2O[C@@](CC/C=C(/CC/C=C(\CC/C=C(\C)/C)/C)\C)(C)CCc2c1C RZFHLOLGZPDCHJ-DLQZEEBKSA-N 0.000 claims description 4
- 239000011731 tocotrienol Substances 0.000 claims description 4
- 229930003802 tocotrienol Natural products 0.000 claims description 4
- 235000019148 tocotrienols Nutrition 0.000 claims description 4
- RZFHLOLGZPDCHJ-XZXLULOTSA-N α-Tocotrienol Chemical compound OC1=C(C)C(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1C RZFHLOLGZPDCHJ-XZXLULOTSA-N 0.000 claims description 4
- 239000002076 α-tocopherol Substances 0.000 claims description 4
- 235000004835 α-tocopherol Nutrition 0.000 claims description 4
- FGYKUFVNYVMTAM-WAZJVIJMSA-N β-tocotrienol Chemical compound OC1=CC(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1C FGYKUFVNYVMTAM-WAZJVIJMSA-N 0.000 claims description 4
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 claims description 4
- OTXNTMVVOOBZCV-WAZJVIJMSA-N γ-tocotrienol Chemical compound OC1=C(C)C(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 OTXNTMVVOOBZCV-WAZJVIJMSA-N 0.000 claims description 4
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 claims description 4
- ODADKLYLWWCHNB-LDYBVBFYSA-N δ-tocotrienol Chemical compound OC1=CC(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 ODADKLYLWWCHNB-LDYBVBFYSA-N 0.000 claims description 4
- RZFHLOLGZPDCHJ-KTWAZNHYSA-N 2,5,7,8-tetramethyl-2-[(3e,7e)-4,8,12-trimethyltrideca-3,7,11-trienyl]-3,4-dihydrochromen-6-ol Chemical compound OC1=C(C)C(C)=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1C RZFHLOLGZPDCHJ-KTWAZNHYSA-N 0.000 claims description 3
- 239000011627 DL-alpha-tocopherol Substances 0.000 claims description 3
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011723 β-tocotrienol Substances 0.000 claims description 3
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011722 γ-tocotrienol Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 65
- 239000002313 adhesive film Substances 0.000 description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 31
- 239000012788 optical film Substances 0.000 description 23
- 239000012790 adhesive layer Substances 0.000 description 18
- 239000002216 antistatic agent Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 229940093858 ethyl acetoacetate Drugs 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000002904 solvent 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
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229930003427 Vitamin E Natural products 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- 229940046009 vitamin E Drugs 0.000 description 2
- 235000019165 vitamin E Nutrition 0.000 description 2
- 239000011709 vitamin E Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- QHTSJPCQUQAHSQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium thiocyanate Chemical class [S-]C#N.C(CCCCCCCCCCC)[N+]1=CC=CC=C1 QHTSJPCQUQAHSQ-UHFFFAOYSA-M 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- 208000019901 Anxiety disease Diseases 0.000 description 1
- HMUXFMGHIBFLOV-UHFFFAOYSA-N C(CCCCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.C(CCCCCCC)[N+]1=CC=CC=C1 Chemical class C(CCCCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.C(CCCCCCC)[N+]1=CC=CC=C1 HMUXFMGHIBFLOV-UHFFFAOYSA-N 0.000 description 1
- TXPLBWYHZPZOES-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCC.C(CCCCCCCCCCC)[N+]1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCC.C(CCCCCCCCCCC)[N+]1=CC=CC=C1 TXPLBWYHZPZOES-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- JMUHMPKBGWVHNP-UHFFFAOYSA-L [ethyl(3-oxobutanoyloxy)alumanyl] 3-oxobutanoate Chemical compound C(CC(=O)C)(=O)[O-].C(C)[Al+2].C(CC(=O)C)(=O)[O-] JMUHMPKBGWVHNP-UHFFFAOYSA-L 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material 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
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical class FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000011729 δ-tocotrienol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
Description
本発明は、粘着剤組成物の酸化防止機能を発現させるために添加される酸化防止剤として、トコフェロール系酸化防止剤を含有する粘着剤組成物及び粘着フィルムに関する。さらに詳細には、酸化防止剤の成分として、トコフェロール系化合物を含有する粘着剤組成物に関し、従来のラクトン系酸化防止剤のような環境的不安要素も無く、さらに油溶性液体であるために、耐析出性にも優れた、粘着剤組成物及びそれを用いた粘着フィルムを提供することに関するものである。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive film containing a tocopherol-based antioxidant as an antioxidant to be added to develop the antioxidant function of the pressure-sensitive adhesive composition. More specifically, regarding the pressure-sensitive adhesive composition containing a tocopherol-based compound as an antioxidant component, there is no environmental anxiety factor like a conventional lactone-based antioxidant, and since it is an oil-soluble liquid, The present invention relates to providing a pressure-sensitive adhesive composition excellent in precipitation resistance and a pressure-sensitive adhesive film using the same.
粘着フィルムとして用いられる粘着剤は、ラジカル重合で生産されることが多い。重合後の粘着剤中に、ラジカルや重合開始剤が残存していると、フィルム化する前の粘着剤の保存安定性のみならず、フィルム化した後の粘着剤層についても、経時で変色するなどの不具合が生じる。特に、光学部材用粘着剤においては、粘着剤が無色透明であることが求められる。このため、色々な酸化防止剤を添加することで、そのラジカル捕捉作用や酸化防止作用等の機能を生かしてこれら不具合を克服していた。 An adhesive used as an adhesive film is often produced by radical polymerization. If radicals or polymerization initiators remain in the pressure-sensitive adhesive after polymerization, not only the storage stability of the pressure-sensitive adhesive before film formation but also the color of the pressure-sensitive adhesive layer after film formation changes over time. Such problems occur. In particular, the pressure-sensitive adhesive for optical members is required to be colorless and transparent. For this reason, by adding various antioxidants, these disadvantages have been overcome by making use of functions such as radical scavenging action and antioxidant action.
近年、粘着剤の分野においても環境対応を求められることが多い。従来の酸化防止剤ではラクトン系酸化防止剤のように環境面から使用できないなどの問題があり、その対策が必要とされてきた。例えば、特許文献１に記載されているような一般的な酸化防止剤は、一般的に、人体へ悪影響を及ぼすことから、取り扱いが法規制されている危険物質である。また、従来の酸化防止剤が、常温で粉末状であり、溶剤に溶解しても析出し易い。酸化防止剤の機能を追求した結果、添加量が必然と多くなると、粘着層からの析出等の欠点も発生していた。 In recent years, environmental measures are often required also in the field of adhesives. Conventional antioxidants have a problem that they cannot be used from the viewpoint of the environment like lactone antioxidants, and countermeasures have been required. For example, a general antioxidant as described in Patent Document 1 is a hazardous substance that is legally handled because it generally has an adverse effect on the human body. Further, conventional antioxidants are powdery at room temperature and are likely to precipitate even when dissolved in a solvent. As a result of pursuing the function of the antioxidant, if the amount added is inevitably increased, defects such as precipitation from the adhesive layer have also occurred.
本発明は、上記事情に鑑みてなされたものであり、光学部材用粘着剤の酸化や変色を防止でき、添加量が多くてもコストを抑えることができ、耐析出性にも優れる光学部材用粘着剤組成物、光学部材用粘着フィルム及び表面保護フィルムを提供することを課題とする。
また、本発明は、上記の課題の解決と併せて、剥離帯電圧を低減して表面保護フィルムを被着体から剥離し易くするために、粘着剤層の表面抵抗率を低下させる光学部材用粘着剤組成物、光学部材用粘着フィルム及び表面保護フィルムを提供することを課題とする。
The present invention has been made in view of the above circumstances, can prevent oxidation and discoloration of the pressure-sensitive adhesive for optical members, can reduce the cost even if the amount is large, and is excellent in precipitation resistance. An object is to provide a pressure-sensitive adhesive composition, a pressure-sensitive adhesive film for an optical member, and a surface protective film.
Further, the present invention is for an optical member that reduces the surface resistivity of the pressure-sensitive adhesive layer in order to reduce the peeling voltage and facilitate the peeling of the surface protective film from the adherend, in addition to solving the above-mentioned problems. An object is to provide a pressure-sensitive adhesive composition, a pressure-sensitive adhesive film for an optical member, and a surface protective film.
前記課題を解決するため、本発明は、（メタ）アクリル酸アルキルエステルを主成分とするアクリル系共重合体と、架橋剤と、酸化防止剤と、イオン化合物とを含有し、前記酸化防止剤として、油溶性であり常温で液体のトコフェロール系化合物を含有してなり、前記トコフェロール系化合物が、ｄ−α−トコフェロール、ｄｌ−α−トコフェロール、ｄ−β−トコフェロール、ｄｌ−β−トコフェロール、ｄ−γ−トコフェロール、ｄｌ−γ−トコフェロール、ｄ−δ−トコフェロール、ｄｌ−δ−トコフェロール、ｄ−α−トコトリエノール、ｄｌ−α−トコトリエノール、ｄ−β−トコトリエノール、ｄｌ−β−トコトリエノール、ｄ−γ−トコトリエノール、ｄｌ−γ−トコトリエノール、ｄ−δ−トコトリエノール、ｄｌ−δ−トコトリエノールからなる化合物群の中から選択された少なくとも１種であり、前記トコフェロール系化合物が、エステルに変化していないフェルール性水酸基を有する化合物であり、前記アクリル系共重合体の１００重量部に対して、前記トコフェロール系化合物の少なくとも１種以上の合計を０．０１〜１．５重量部、を必須成分として含有することを特徴とする光学部材用粘着剤組成物を提供する。 In order to solve the above-mentioned problems, the present invention comprises an acrylic copolymer mainly composed of (meth) acrylic acid alkyl ester, a crosslinking agent, an antioxidant, and an ionic compound, and the antioxidant And a tocopherol compound that is oil-soluble and liquid at room temperature, and the tocopherol compound is d-α-tocopherol, dl-α-tocopherol, d-β-tocopherol, dl-β-tocopherol, d -Γ-tocopherol, dl-γ-tocopherol, d-δ-tocopherol, dl-δ-tocopherol, d-α-tocotrienol, dl-α-tocotrienol, d-β-tocotrienol, dl-β-tocotrienol, d-γ -Tocotrienol, dl-γ-tocotrienol, d-δ-tocotrienol, dl-δ-tocotrieno And the tocopherol compound is a compound having a ferrule hydroxyl group that is not changed to an ester, and is 100 parts by weight of the acrylic copolymer. In addition, the present invention provides a pressure-sensitive adhesive composition for an optical member, containing 0.01 to 1.5 parts by weight of a total of at least one of the tocopherol compounds as an essential component.
前記イオン化合物が、温度３０℃で固体であり、融点が３０〜５０℃のイオン化合物であることが好ましい。 The ionic compound is preferably an ionic compound which is solid at a temperature of 30 ° C. and has a melting point of 30 to 50 ° C.
前記架橋剤が、２官能以上のイソシアネート系架橋剤、２官能以上のエポキシ系架橋剤、アルミニウムキレート系架橋剤からなる化合物群のうちから選択される１種以上の架橋剤であることが好ましい。 The cross-linking agent is preferably one or more cross-linking agents selected from the group consisting of a bifunctional or higher functional isocyanate cross-linking agent, a bifunctional or higher epoxy epoxy cross-linking agent, and an aluminum chelate cross-linking agent.
前記アクリル系共重合体が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、からなり、前記アクリル系共重合体の１００重量部に対して、（Ｃ）前記トコフェロール系化合物を０．０１〜１．５重量部、を必須成分として含有することが好ましい。 The acrylic copolymer contains (A) at least one (meth) acrylic acid alkyl ester monomer having a C1-C14 carbon number and (B) a hydroxyl group and / or a carboxyl group. It comprises at least one vinyl monomer, and contains 0.01 to 1.5 parts by weight of (C) the tocopherol compound as an essential component with respect to 100 parts by weight of the acrylic copolymer. Is preferred.
前記アクリル系共重合体が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、ビニル基を有する共重合性ビニルモノマーの少なくとも１種と、からなり、前記アクリル系共重合体の１００重量部に対して、（Ｃ）前記トコフェロール系化合物を０．０１〜１．５重量部、を必須成分として含有することが好ましい。 The acrylic copolymer is (A) at least one (meth) acrylic acid alkyl ester monomer having an alkyl group with C1-C14 carbon atoms, at least one copolymerizable vinyl monomer having a vinyl group, and It is preferable that 0.01 to 1.5 parts by weight of (C) the tocopherol compound is contained as an essential component with respect to 100 parts by weight of the acrylic copolymer.
前記アクリル系共重合体が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも２種以上からなり、前記アクリル系共重合体の１００重量部に対して、（Ｃ）前記トコフェロール系化合物を０．０１〜１．５重量部、を必須成分として含有することが好ましい。 The acrylic copolymer comprises (A) at least two kinds of (meth) acrylic acid alkyl ester monomers having an alkyl group with a C1-C14 carbon number, and relative to 100 parts by weight of the acrylic copolymer. (C) It is preferable to contain 0.01-1.5 weight part of the said tocopherol type compound as an essential component.
前記アクリル系共重合体が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、芳香族系モノマーの少なくとも１種と、からなり、前記アクリル系共重合体の１００重量部に対して、（Ｃ）前記トコフェロール系化合物を０．０１〜１．５重量部、を必須成分として含有することが好ましい。 The acrylic copolymer contains (A) at least one (meth) acrylic acid alkyl ester monomer having a C1-C14 carbon number and (B) a hydroxyl group and / or a carboxyl group. It consists of at least one vinyl monomer and at least one aromatic monomer, and (C) 0.01 to 1.5 tocopherol compound (C) with respect to 100 parts by weight of the acrylic copolymer. It is preferable to contain a weight part as an essential component.
また、本発明は、基材の片面上に、前記光学部材用粘着剤組成物が架橋された粘着剤層が積層されたことを特徴とする光学部材用粘着フィルムを提供する。 Moreover, this invention provides the adhesive film for optical members characterized by laminating | stacking the adhesive layer by which the said adhesive composition for optical members was bridge | crosslinked on the single side | surface of a base material.
また、本発明は、前記光学部材用粘着剤組成物が架橋された粘着剤層が用いられたことを特徴とする光学部材用粘着フィルムを提供する。 Moreover, this invention provides the adhesive film for optical members characterized by using the adhesive layer by which the said adhesive composition for optical members was bridge | crosslinked.
また、本発明は、前記光学部材用粘着フィルムが用いられた、表面保護フィルムを提供する。 Moreover, this invention provides the surface protection film in which the said adhesive film for optical members was used.
また、本発明は、前記光学部材用粘着フィルムが用いられた、偏光板用の表面保護フィルムを提供する。 Moreover, this invention provides the surface protection film for polarizing plates in which the said adhesive film for optical members was used.
また、本発明は、前記光学部材用粘着フィルムが用いられた、光学用の表面保護フィルムを提供する。 Moreover, this invention provides the surface protection film for optics using the said adhesive film for optical members.
また、本発明は、前記光学部材用粘着フィルムが用いられた、偏光板とディスプレイパネルの貼り合わせ用粘着フィルムを提供する。 Moreover, this invention provides the adhesive film for bonding of a polarizing plate and a display panel using the said adhesive film for optical members.
また、本発明は、前記光学部材用粘着フィルムが用いられた、偏光板を構成する材料の貼り合わせ用粘着フィルムを提供する。 Moreover, this invention provides the adhesive film for bonding of the material which comprises the polarizing plate using the said adhesive film for optical members.
また、本発明は、前記光学部材用粘着フィルムが用いられた、タッチパネル用粘着フィルムを提供する。 Moreover, this invention provides the adhesive film for touchscreens in which the said adhesive film for optical members was used.
また、本発明は、前記光学部材用粘着フィルムが用いられた、電子ペーパー用粘着フィルムを提供する。 Moreover, this invention provides the adhesive film for electronic papers using the said adhesive film for optical members.
本発明によれば、トコフェロール系化合物を酸化防止剤として含有する粘着剤組成物を用いることで、コストを抑えることができ、耐析出性など上記の課題を改善することが可能となる。 According to the present invention, by using a pressure-sensitive adhesive composition containing a tocopherol compound as an antioxidant, it is possible to reduce costs and improve the above-described problems such as precipitation resistance.
以下、好適な実施の形態に基づいて本発明を説明する。
本発明の光学部材用粘着剤組成物は、（メタ）アクリル酸アルキルエステルを主成分とするアクリル系共重合体と、架橋剤と、酸化防止剤とを含有し、前記酸化防止剤として、トコフェロール系化合物を含有する。トコフェロール系化合物は、一般にビタミンＥであり、天然由来の化学物質でもある。このことから、人体に対する悪影響も少なく、取り扱い上の安全性が高く、環境に対しても優しい。また、油溶性であり常温で液体であるため、粘着剤組成物との相溶性、及び、耐析出性にも優れている。
Hereinafter, the present invention will be described based on preferred embodiments.
The pressure-sensitive adhesive composition for an optical member of the present invention contains an acrylic copolymer mainly composed of (meth) acrylic acid alkyl ester, a crosslinking agent, and an antioxidant, and the tocopherol as the antioxidant. Contains system compounds. Tocopherol compounds are generally vitamin E and are naturally derived chemicals. For this reason, there is little adverse effect on the human body, the safety in handling is high, and it is friendly to the environment. Moreover, since it is oil-soluble and is liquid at normal temperature, it is excellent in compatibility with the pressure-sensitive adhesive composition and in precipitation resistance.
本発明の光学部材用粘着剤組成物に用いるアクリル系共重合体としては、アクリル系ポリマーが好ましく、特に、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種を主成分とする共重合体が好ましい。
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレートモノマーが挙げられる。アルキル（メタ）アクリレートモノマーのアルキル基は、直鎖、分枝状、環状のいずれでもよい。
As the acrylic copolymer used in the pressure-sensitive adhesive composition for an optical member of the present invention, an acrylic polymer is preferable, and in particular, the (A) alkyl (meth) acrylic acid alkyl ester monomer having a C1-C14 carbon number. A copolymer containing at least one kind as a main component is preferred.
(A) Alkyl group C1-C14 (meth) acrylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl ( Examples include alkyl (meth) acrylate monomers such as (meth) acrylate, decyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic.
本発明に用いるアクリル系共重合体として、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、他の共重合性モノマーの少なくとも１種とからなる共重合組成物を採用することもできる。この場合、他の共重合性モノマーとしては、ビニル基を有する共重合性ビニルモノマーや、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマー、芳香族系モノマーが挙げられる。 As the acrylic copolymer used in the present invention, (A) at least one (meth) acrylic acid alkyl ester monomer having an alkyl group with C1 to C14 carbon atoms and at least one other copolymerizable monomer. It is also possible to employ a copolymer composition. In this case, examples of the other copolymerizable monomer include a copolymerizable vinyl monomer having a vinyl group, (B) a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group, and an aromatic monomer.
水酸基を含有する共重合性ビニルモノマーとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、８−ヒドロキシオクチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル類や、Ｎ−ヒドロキシ（メタ）アクリルアミド、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミド等の水酸基含有（メタ）アクリルアミド類などが挙げられ、これらの化合物群の中から選択された、少なくとも１種以上であることが好ましい。
カルボキシル基を含有する共重合性ビニルモノマーとしては、（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレートからなどが挙げられ、これらの化合物群の中から選択された、少なくとも１種以上であることが好ましい。
芳香族系モノマーとしては、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の芳香族基含有（メタ）アクリル酸エステル類のほか、スチレン等が挙げられる。
上記以外の共重合性ビニルモノマーとしては、アクリルアミド、アクリロニトリル、メチルビニルエーテル、エチルビニルエーテル、酢酸ビニル、塩化ビニルなどの各種ビニルモノマーが挙げられる。
Examples of the copolymerizable vinyl monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Hydroxyl-containing (meth) acrylic esters such as hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl ( Examples include hydroxyl group-containing (meth) acrylamides such as (meth) acrylamide, and at least one selected from these compound groups is preferable.
Examples of the copolymerizable vinyl monomer containing a carboxyl group include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like. Preferably, at least one selected from these compound groups is used.
Examples of the aromatic monomer include styrene and the like in addition to aromatic group-containing (meth) acrylic esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
Examples of copolymerizable vinyl monomers other than the above include various vinyl monomers such as acrylamide, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, vinyl acetate, and vinyl chloride.
また、本発明に用いるアクリル系共重合体として、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも２種以上からなる共重合組成物を採用することもできる。この場合、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマー以外の共重合性ビニルモノマーを用いなくても共重合組成物とすることができる。 Moreover, as the acrylic copolymer used in the present invention, it is also possible to employ a copolymer composition comprising (A) at least two kinds of (meth) acrylic acid alkyl ester monomers having C1-C14 carbon atoms in the alkyl group. it can. In this case, the copolymer composition can be obtained without using a copolymerizable vinyl monomer other than the (meth) acrylic acid alkyl ester monomer having (A) an alkyl group having C1 to C14 carbon atoms.
アクリル系共重合体の重合方法は、特に限定されるものではなく、溶液重合法、乳化重合法等、適宜、公知の重合方法が使用可能である。アクリル系共重合体の重量平均分子量は、２０万〜２００万であることが好ましい。 The polymerization method of the acrylic copolymer is not particularly limited, and a known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used as appropriate. The weight average molecular weight of the acrylic copolymer is preferably 200,000 to 2,000,000.
本発明の光学部材用粘着剤組成物は、粘着剤層を形成する際に前記アクリル系共重合体を架橋することが好ましい。架橋をするため、光学部材用粘着剤組成物が既知の架橋剤を含んでも良く、紫外線（ＵＶ）など光架橋で架橋しても良い。架橋剤としては、２官能以上のイソシアネート系架橋剤、２官能以上のエポキシ系架橋剤、アルミニウムキレート系架橋剤からなる化合物群のうちから選択される１種以上の架橋剤が好ましい。架橋剤を用いる場合は、前記アクリル系共重合体の１００重量部に対して、０．１〜５重量部含有することが好ましい。 The pressure-sensitive adhesive composition for optical members of the present invention preferably crosslinks the acrylic copolymer when forming the pressure-sensitive adhesive layer. In order to perform crosslinking, the pressure-sensitive adhesive composition for optical members may contain a known crosslinking agent, or may be crosslinked by photocrosslinking such as ultraviolet (UV). As the crosslinking agent, one or more kinds of crosslinking agents selected from the group consisting of a bifunctional or higher functional isocyanate crosslinking agent, a bifunctional or higher epoxy crosslinking agent, and an aluminum chelate crosslinking agent are preferable. When using a crosslinking agent, it is preferable to contain 0.1-5 weight part with respect to 100 weight part of the said acrylic copolymer.
本発明の光学部材用粘着剤組成物に用いる酸化防止剤として、トコフェロール系化合物を含有する。トコフェロール系化合物は、一般にビタミンＥであり、天然由来の化学物質でもある。このことから、人体に対する悪影響も少なく、取り扱い上の安全性が高く、環境に対しても優しい。また、油溶性であり常温で液体であるため、粘着剤組成物との相溶性、及び、耐析出性にも優れている。
本発明に用いるトコフェロール系化合物としては、光学部材用粘着剤組成物に配合して用いる（人体内のように代謝を受けない）ことから、トコフェロールのフェルール性水酸基がエステル等に変化しておらず、フェルール性水酸基を有する化合物が好ましい。例えば、トコフェロールやトコトリエノールが挙げられる。トコフェロールやトコトリエノールには、天然型の化合物（ｄ−体）、非天然型の化合物（ｌ−体）、これらの等量混合物であるラセミ体（ｄｌ−体）などの区別があることが知られている。天然型の化合物（ｄ−体）やラセミ体（ｄｌ−体）は、食品添加物等として用いられるものもあることから、好ましい。
具体的なトコフェロール系化合物としては、ｄ−α−トコフェロール、ｄｌ−α−トコフェロール、ｄ−β−トコフェロール、ｄｌ−β−トコフェロール、ｄ−γ−トコフェロール、ｄｌ−γ−トコフェロール、ｄ−δ−トコフェロール、ｄｌ−δ−トコフェロール、ｄ−α−トコトリエノール、ｄｌ−α−トコトリエノール、ｄ−β−トコトリエノール、ｄｌ−β−トコトリエノール、ｄ−γ−トコトリエノール、ｄｌ−γ−トコトリエノール、ｄ−δ−トコトリエノール、ｄｌ−δ−トコトリエノールからなる化合物群の中から選択された少なくとも１種が挙げられる。２種以上のトコフェロール系化合物を併用してもよい。食品添加物として、「ミックストコフェロール」と呼ばれるものは、ｄ−α−トコフェロール、ｄ−β−トコフェロール、ｄ−γ−トコフェロール及びｄ−δ−トコフェロールを主成分とする混合物であり、「トコトリエノール」と呼ばれるものは、ｄ−α−トコトリエノール、ｄ−β−トコトリエノール、ｄ−γ−トコトリエノール及びｄ−δ−トコトリエノールを主成分とする混合物である。
本発明の光学部材用粘着剤組成物は、アクリル系共重合体の１００重量部に対して、トコフェロール系化合物を０．０１〜１．５重量部、含有することが好ましい。
As an antioxidant used in the pressure-sensitive adhesive composition for optical members of the present invention, a tocopherol compound is contained. Tocopherol compounds are generally vitamin E and are naturally derived chemicals. For this reason, there is little adverse effect on the human body, the safety in handling is high, and it is friendly to the environment. Moreover, since it is oil-soluble and is liquid at normal temperature, it is excellent in compatibility with the pressure-sensitive adhesive composition and in precipitation resistance.
As the tocopherol-based compound used in the present invention, it is blended and used in the pressure-sensitive adhesive composition for optical members (it does not undergo metabolism like the human body), so the ferruleic hydroxyl group of tocopherol is not changed to an ester or the like. A compound having a ferrule hydroxyl group is preferred. For example, tocopherol and tocotrienol are mentioned. It is known that tocopherol and tocotrienol have a distinction such as a natural type compound (d-form), a non-natural type compound (1-form), and a racemic form (dl-form) which is an equivalent mixture thereof. ing. Natural type compounds (d-form) and racemates (dl-form) are preferred because some are used as food additives and the like.
Specific tocopherol compounds include d-α-tocopherol, dl-α-tocopherol, d-β-tocopherol, dl-β-tocopherol, d-γ-tocopherol, dl-γ-tocopherol, d-δ-tocopherol. Dl-δ-tocopherol, d-α-tocotrienol, dl-α-tocotrienol, d-β-tocotrienol, dl-β-tocotrienol, d-γ-tocotrienol, dl-γ-tocotrienol, d-δ-tocotrienol, dl And at least one selected from the group of compounds consisting of -δ-tocotrienol. Two or more tocopherol compounds may be used in combination. What is called “mixed tocopherol” as a food additive is a mixture mainly composed of d-α-tocopherol, d-β-tocopherol, d-γ-tocopherol and d-δ-tocopherol, and “tocotrienol” What is called is a mixture based on d-α-tocotrienol, d-β-tocotrienol, d-γ-tocotrienol and d-δ-tocotrienol.
The pressure-sensitive adhesive composition for an optical member of the present invention preferably contains 0.01 to 1.5 parts by weight of a tocopherol compound with respect to 100 parts by weight of the acrylic copolymer.
本発明の光学部材用粘着剤組成物は、帯電防止性能を付与するため、帯電防止剤を含有することが好ましい。帯電防止剤は、常温（例えば３０℃）で固体であることが好ましく、より具体的には、帯電防止剤が融点３０〜５０℃のイオン化合物である。帯電防止剤は、アクリロイル基含有の４級アンモニウム塩型イオン化合物であってもよい。
これらの帯電防止剤は、融点が低いため、また、長鎖のアルキル基を有するため、アクリル系ポリマーとの親和性は高いと推測される。
The pressure-sensitive adhesive composition for optical members of the present invention preferably contains an antistatic agent in order to impart antistatic performance. The antistatic agent is preferably solid at room temperature (for example, 30 ° C.), and more specifically, the antistatic agent is an ionic compound having a melting point of 30 to 50 ° C. The antistatic agent may be an acryloyl group-containing quaternary ammonium salt type ionic compound.
Since these antistatic agents have a low melting point and have long-chain alkyl groups, it is presumed that they have a high affinity with acrylic polymers.
融点が３０〜５０℃のイオン化合物である帯電防止剤としては、カチオンとアニオンを有するイオン化合物であって、カチオンが、ピリジニウムカチオン、イミダゾリウムカチオン、ピリミジニウムカチオン、ピラゾリウムカチオン、ピロリジニウムカチオン、アンモニウムカチオン等の含窒素オニウムカチオンや、ホスホニウムカチオン、スルホニウムカチオン等であり、アニオンが、六フッ化リン酸塩（ＰＦ６ −）、チオシアン酸塩（ＳＣＮ−）、アルキルベンゼンスルホン酸塩（ＲＣ６Ｈ４ＳＯ３ −）、過塩素酸塩（ＣｌＯ４ −）、四フッ化ホウ酸塩（ＢＦ４ −）等の無機もしくは有機アニオンである化合物が挙げられる。アルキル基の鎖長や置換基の位置、個数等の選択により、融点が３０〜５０℃のものを得ることができる。カチオンは、好ましくは４級含窒素オニウムカチオンであり、１−アルキルピリジニウム（２〜６位の炭素原子は置換基を有しても無置換でもよい。）等の４級ピリジニウムカチオンや、１，３−ジアルキルイミダゾリウム（２，４，５位の炭素原子は置換基を有しても無置換でもよい。）等の４級イミダゾリウムカチオン、テトラアルキルアンモニウム等の４級アンモニウムカチオン等が挙げられる。 The antistatic agent which is an ionic compound having a melting point of 30 to 50 ° C. is an ionic compound having a cation and an anion, and the cation is pyridinium cation, imidazolium cation, pyrimidinium cation, pyrazolium cation, pyrrolidi A nitrogen-containing onium cation such as a nium cation or an ammonium cation, a phosphonium cation, or a sulfonium cation, and the anions include hexafluorophosphate (PF 6 − ), thiocyanate (SCN − ), alkylbenzene sulfonate ( RC 6 H 4 SO 3 − ), perchlorate (ClO 4 − ), tetrafluoroborate (BF 4 − ) and the like are compounds that are inorganic or organic anions. By selecting the chain length of the alkyl group, the position and number of substituents, etc., those having a melting point of 30-50 ° C. can be obtained. The cation is preferably a quaternary nitrogen-containing onium cation, such as a quaternary pyridinium cation such as 1-alkylpyridinium (the carbon atom at the 2-6 position may be substituted or unsubstituted), Quaternary imidazolium cations such as 3-dialkylimidazolium (the carbon atoms at 2, 4, and 5 positions may be substituted or unsubstituted), quaternary ammonium cations such as tetraalkylammonium, and the like. .
前記アクリロイル基含有の４級アンモニウム塩型イオン化合物としては、カチオンとアニオンを有するイオン化合物であって、カチオンが、（メタ）アクリロイルオキシアルキルトリアルキルアンモニウム〔Ｒ３Ｎ＋−ＣｎＨ２ｎ−ＯＣＯＣＱ＝ＣＨ２、ただし、Ｑ＝ＨまたはＣＨ３、Ｒ＝アルキル〕等の（メタ）アクリロイル基含有４級アンモニウムであり、アニオンが、六フッ化リン酸塩（ＰＦ６ −）、チオシアン酸塩（ＳＣＮ−）、有機スルホン酸塩（ＲＳＯ３ −）、過塩素酸塩（ＣｌＯ４ −）、四フッ化ホウ酸塩（ＢＦ４ −）、Ｆ含有イミド塩（ＲＦ ２Ｎ−）等の無機もしくは有機アニオンである化合物が挙げられる。Ｆ含有イミド塩（ＲＦ ２Ｎ−）のＲＦとしては、トリフルオロメタンスルホニル基、ペンタフルオロエタンスルホニル基等のパーフルオロアルカンスルホニル基やフルオロスルホニル基が挙げられる。Ｆ含有イミド塩としては、ビス（フルオロスルホニル）イミド塩〔（ＦＳＯ２）２Ｎ−〕、ビス（トリフルオロメタンスルホニル）イミド塩〔（ＣＦ３ＳＯ２）２Ｎ−〕、ビス（ペンタフルオロエタンスルホニル）イミド塩〔（Ｃ２Ｆ５ＳＯ２）２Ｎ−〕等のビススルホニルイミド塩が挙げられる。 The acryloyl group-containing quaternary ammonium salt type ionic compound is an ionic compound having a cation and an anion, and the cation is (meth) acryloyloxyalkyltrialkylammonium [R 3 N + —C n H 2n —OCOCQ = CH 2 , provided that (meth) acryloyl group-containing quaternary ammonium such as Q = H or CH 3 , R = alkyl] and the anion is hexafluorophosphate (PF 6 − ), thiocyanate ( SCN − ), organic sulfonate (RSO 3 − ), perchlorate (ClO 4 − ), tetrafluoroborate (BF 4 − ), F-containing imide salt (R F 2 N − ) and other inorganic materials Or the compound which is an organic anion is mentioned. F-containing imide salt (R F 2 N -) as the R F of, trifluoromethanesulfonyl group, and perfluoro alkane sulfonyl group or fluorosulfonyl group, such as pentafluoroethane sulfonyl group. Examples of the F-containing imide salt include bis (fluorosulfonyl) imide salt [(FSO 2 ) 2 N − ], bis (trifluoromethanesulfonyl) imide salt [(CF 3 SO 2 ) 2 N − ], and bis (pentafluoroethanesulfonyl). ) Bissulfonylimide salts such as imide salts [(C 2 F 5 SO 2 ) 2 N − ].
融点が３０〜５０℃のイオン化合物である帯電防止剤は、特に限定されるものでない。ピリジニウムカチオンを有する、融点が３０〜５０℃のイオン化合物の具体例としては、１−オクチルピリジニウム ドデシルベンゼンスルホン酸塩、１−ドデシルピリジニウム チオシアン酸塩、３−メチル−１−ドデシルピリジニウム 六フッ化リン酸塩、１−ドデシルピリジニウム ドデシルベンゼンスルホン酸塩、４−メチル−１−オクチルピリジニウム 六フッ化リン酸塩等が挙げられる。
また、前記アクリロイル基含有の４級アンモニウム塩型イオン化合物の具体例としては、ジメチルアミノメチル（メタ）アクリレート 六フッ化リン酸メチル塩〔（ＣＨ３）３Ｎ＋ＣＨ２ＯＣＯＣＱ＝ＣＨ２・ＰＦ６ −、ただし、Ｑ＝ＨまたはＣＨ３〕、ジメチルアミノエチル（メタ）アクリレート ビス（トリフルオロメタンスルホニル）イミドメチル塩〔（ＣＨ３）３Ｎ＋（ＣＨ２）２ＯＣＯＣＱ＝ＣＨ２・（ＣＦ３ＳＯ２）２Ｎ−、ただし、Ｑ＝ＨまたはＣＨ３〕、ジメチルアミノメチル（メタ）アクリレート ビス（フルオロスルホニル）イミドメチル塩〔（ＣＨ３）３Ｎ＋ＣＨ２ＯＣＯＣＱ＝ＣＨ２・（ＦＳＯ２）２Ｎ−、ただし、Ｑ＝ＨまたはＣＨ３〕等が挙げられる。
また、融点が３０〜５０℃のイオン化合物は、前記（Ａ）と前記（Ｂ）とを合わせた主成分の（メタ）アクリレートモノマーの１００重量部に対して、０．１〜５．０重量部の割合で含有されることが好ましい。
The antistatic agent which is an ionic compound having a melting point of 30 to 50 ° C. is not particularly limited. Specific examples of the ionic compound having a pyridinium cation and having a melting point of 30 to 50 ° C. include 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecylpyridinium thiocyanate, 3-methyl-1-dodecylpyridinium hexafluorophosphate And acid salts, 1-dodecylpyridinium dodecylbenzenesulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like.
Moreover, as a specific example of the acryloyl group-containing quaternary ammonium salt type ionic compound, dimethylaminomethyl (meth) acrylate hexafluorophosphate methyl salt [(CH 3 ) 3 N + CH 2 OCOCQ = CH 2 · PF 6 - with the proviso, Q = H or CH 3], dimethylaminoethyl (meth) acrylate bis (trifluoromethanesulfonyl) imidomethyl salt [(CH 3) 3 N + ( CH 2) 2 OCOCQ = CH 2 · (CF 3 SO 2 ) 2 N − , where Q═H or CH 3 ], dimethylaminomethyl (meth) acrylate bis (fluorosulfonyl) imidomethyl salt [(CH 3 ) 3 N + CH 2 OCOCQ═CH 2 · (FSO 2 ) 2 N -, however, Q = H or CH 3], and the like.
In addition, the ionic compound having a melting point of 30 to 50 ° C. is 0.1 to 5.0 weight with respect to 100 parts by weight of the main component (meth) acrylate monomer in which (A) and (B) are combined. It is preferably contained in a proportion of parts.
光学部材用粘着剤組成物に帯電防止剤を添加して帯電防止性能を持たせる場合、前記光学部材用粘着剤組成物からなる粘着剤層を積層した、光学部材用粘着フィルムの帯電防止性能として、前記粘着剤層の表面抵抗率が１．０×１０＋１２Ω／□以下であることが好ましく、５．０×１０＋１１Ω／□以下であることがより好ましい。表面抵抗率が大きいと、剥離時に帯電で発生した静電気を逃がす性能に劣る。そのため、表面抵抗率を十分に小さくすることにより、粘着剤層を被着体が剥がす時に発生する、静電気に伴って生じる剥離帯電圧が低減され、被着体の制御用電子回路等に影響することを抑制することができる。 When an antistatic agent is added to the pressure-sensitive adhesive composition for optical members to provide antistatic performance, the antistatic performance of the pressure-sensitive adhesive film for optical members in which the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members is laminated. The surface resistivity of the pressure-sensitive adhesive layer is preferably 1.0 × 10 +12 Ω / □ or less, and more preferably 5.0 × 10 +11 Ω / □ or less. When the surface resistivity is large, the performance of releasing static electricity generated by electrification at the time of peeling is inferior. Therefore, by making the surface resistivity sufficiently small, the stripping voltage generated due to static electricity that occurs when the adherend peels off the adhesive layer is reduced, affecting the electronic circuit for controlling the adherend, etc. This can be suppressed.
本発明の光学部材用粘着剤組成物は、粘着剤層を形成する際にアクリル系共重合体を架橋させることが好ましい。粘着剤層のアクリル系共重合体を架橋させるために、粘着剤組成物が既知の架橋剤を含んでいることが好ましい。本発明で使用される架橋剤は、２官能以上のイソシアネート系架橋剤、２官能以上のエポキシ系架橋剤、アルミニウムキレート系架橋剤からなる化合物群のうちから選択される１種以上の架橋剤であることが好ましい。架橋剤は、１種類を単独で使用してもよいし、２種類以上を組み合わせて併用してもよい。 The pressure-sensitive adhesive composition for optical members of the present invention preferably crosslinks the acrylic copolymer when forming the pressure-sensitive adhesive layer. In order to crosslink the acrylic copolymer of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition preferably contains a known crosslinking agent. The crosslinking agent used in the present invention is one or more kinds of crosslinking agents selected from the group consisting of a bifunctional or higher isocyanate crosslinking agent, a bifunctional or higher epoxy crosslinking agent, and an aluminum chelate crosslinking agent. Preferably there is. A crosslinking agent may be used individually by 1 type, and may be used together in combination of 2 or more types.
２官能以上のイソシアネート系化合物としては、１分子中に少なくとも２個以上のイソシアネート（ＮＣＯ）基を有するポリイソシアネート化合物であればよく、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート等のジイソシアネート類（１分子中に２個のＮＣＯ基を有する化合物）のビュレット変性体やイソシアヌレート変性体、トリメチロールプロパンやグリセリン等の３価以上のポリオール（１分子中に少なくとも３個以上のＯＨ基を有する化合物）とのアダクト体（ポリオール変性体）などが挙げられる。
また、３官能以上のイソシアネート化合物が、１分子中に少なくとも３個以上のイソシアネート（ＮＣＯ）基を有するポリイソシアネート化合物であり、特にヘキサメチレンジイソシアネート化合物のイソシアヌレート体、イソホロンジイソシアネート化合物のイソシアヌレート体、ヘキサメチレンジイソシアネート化合物のアダクト体、イソホロンジイソシアネート化合物のアダクト体、ヘキサメチレンジイソシアネート化合物のビュレット体、イソホロンジイソシアネート化合物のビュレット体からなる化合物群の中から選択された、少なくとも一種以上であることが好ましい。
２官能以上のイソシアネート系架橋剤は、アクリル系共重合体の１００重量部に対して、０．０１〜５．０重量部含まれることが好ましく、さらに好ましくは０．０２〜３．０重量部含まれるのがよい。
The bifunctional or higher isocyanate compound may be a polyisocyanate compound having at least two isocyanate (NCO) groups in one molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diene. A modified burette or isocyanurate of a diisocyanate such as isocyanate (compound having two NCO groups in one molecule) or a trivalent or higher polyol such as trimethylolpropane or glycerin (at least three or more in one molecule) And adduct bodies (polyol-modified bodies) with OH group compounds).
Further, the trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three isocyanate (NCO) groups in one molecule, in particular, an isocyanurate body of a hexamethylene diisocyanate compound, an isocyanurate body of an isophorone diisocyanate compound, At least one selected from the group consisting of adducts of hexamethylene diisocyanate compounds, adducts of isophorone diisocyanate compounds, burettes of hexamethylene diisocyanate compounds, and burettes of isophorone diisocyanate compounds is preferred.
The bifunctional or higher isocyanate crosslinking agent is preferably contained in an amount of 0.01 to 5.0 parts by weight, more preferably 0.02 to 3.0 parts by weight, based on 100 parts by weight of the acrylic copolymer. Should be included.
２官能以上のエポキシ系化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂等のなどのエポキシ樹脂が挙げられる。これらの中でも、２官能のビスフェノールＡ型およびビスフェノールＦ型等のビスフェノール型エポキシ樹脂が、低粘度の液状であり取り扱い易いことからより好ましい。
また、２官能以上のエポキシ系化合物は、具体的には、グリセリンポリ（例えばジ、トリ）グリシジルエーテル、ソルビトールポリグリシジルエーテル、ペンタエリスリトールポリ（例えばジ、トリ、テトラ）グリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル等が挙げられる。
２官能以上のエポキシ系化合物は、アクリル系共重合体の１００重量部に対して、０．０１〜５．０重量部含まれることが好ましく、さらに好ましくは０．０２〜３．０重量部含まれるのが良い。
Examples of the bifunctional or higher functional epoxy compound include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl ether type epoxy resins, and glycidyl amines. And epoxy resins such as type epoxy resins. Among these, bisphenol type epoxy resins such as bifunctional bisphenol A type and bisphenol F type are more preferable because they are liquids with low viscosity and are easy to handle.
In addition, the bifunctional or higher functional epoxy compounds are specifically glycerin poly (eg, di, tri) glycidyl ether, sorbitol polyglycidyl ether, pentaerythritol poly (eg, di, tri, tetra) glycidyl ether, trimethylolpropane poly. A glycidyl ether etc. are mentioned.
The bifunctional or higher functional epoxy compound is preferably contained in an amount of 0.01 to 5.0 parts by weight, more preferably 0.02 to 3.0 parts by weight, based on 100 parts by weight of the acrylic copolymer. It is good to be.
本発明の光学部材用粘着剤組成物は、（メタ）アクリル酸アルキルエステルを主成分とするアクリル系共重合体と、架橋剤と、酸化防止剤とを含有している。アクリル系共重合体がカルボキシル基または水酸基を有している場合には、これらの官能基とアルミニウムキレート系化合物との架橋を生じる。
本発明で使用できるアルミニウムキレート系化合物としては、アセチルアセトンアルミニウム塩、アセト酢酸エチルアルミニウム塩などのケトエノール互変異性体アルミニウム塩が好ましく、ケトエノール互変異性体アルミニウム塩の中でもアセチルアセトンアルミニウム塩は、架橋剤としての機能に優れるものとして好適に用いられる。
ケトエノール互変異性体アルミニウム塩に用いられる、ケトエノール互変異性体としては、アセチルアセトン等のβ−ジケトンや、アセト酢酸エチル、アセト酢酸メチル、アセト酢酸オレイル、アセト酢酸アルキル等のβ−ケトカルボン酸エステル等が挙げられる。
ケトエノール互変異性体アルミニウム塩としては、具体的には、アルミニウムトリス（アセチルアセトネート）、アルミニウムトリス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネートビス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネートビスオレイルアセトアセテート、エチルアセトアセテートアルミニウムジイソプロピレート、アルキルアセトアセテートアルミニウムジイソプロピレート等が挙げられる。
The pressure-sensitive adhesive composition for optical members of the present invention contains an acrylic copolymer mainly composed of (meth) acrylic acid alkyl ester, a crosslinking agent, and an antioxidant. When the acrylic copolymer has a carboxyl group or a hydroxyl group, crosslinking between these functional groups and the aluminum chelate compound occurs.
As the aluminum chelate compound that can be used in the present invention, ketoenol tautomeric aluminum salts such as acetylacetone aluminum salt and ethylaluminum acetoacetate are preferable, and among ketoenol tautomeric aluminum salts, acetylacetone aluminum salt is used as a crosslinking agent. It is preferably used as one having excellent functions.
Ketoenol tautomers used in aluminum salts include keto enol tautomers such as β-diketones such as acetylacetone, β-ketocarboxylates such as ethyl acetoacetate, methyl acetoacetate, oleyl acetoacetate, alkyl acetoacetate, etc. Is mentioned.
Specific examples of ketoenol tautomeric aluminum salts include aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), and aluminum monoacetylacetonate bisoleyl. Examples include acetoacetate, ethyl acetoacetate aluminum diisopropylate, alkyl acetoacetate aluminum diisopropylate, and the like.
さらにその他成分としてシランカップリング剤、酸化防止剤、界面活性剤、硬化促進剤、可塑剤、充填剤、硬化遅延剤、加工助剤、老化防止剤などの公知の添加剤を適宜に配合することができる。これらは、単独でもしくは２種以上併せて用いることができる。 Further, as other components, known additives such as silane coupling agents, antioxidants, surfactants, curing accelerators, plasticizers, fillers, curing retarders, processing aids, anti-aging agents, and the like are appropriately blended. Can do. These may be used alone or in combination of two or more.
本発明の光学部材用粘着フィルムは、本発明の光学部材用粘着剤組成物からなる粘着剤層を、基材又は離型フィルムの片面上に形成することで製造することができる。
粘着剤層の形成に用いる基材フィルムや、粘着面を保護する離型フィルム（セパレーター）としては、ポリエステルフィルムなどの樹脂フィルム等を用いることができる。
基材フィルムには、樹脂フィルムの粘着剤層が形成された側とは反対面に、シリコーン系、フッ素系の離型剤やコート剤、シリカ微粒子等による防汚処理、帯電防止剤の塗布や練り込み等による帯電防止処理を施すことができる。
剥離フィルムには、粘着剤層の粘着面と合わされる側の面に、シリコーン系、フッ素系の離型剤などにより離型処理が施される。
偏光板や位相差フィルムなどの各種光学フィルムを、液晶セルなどの光学部品及び他の光学フィルムに貼り合せる、粘着フィルムの粘着剤層は、十分な透明性を有することが好ましい。また、偏光板用の表面保護フィルムなどの光学用の表面保護フィルムの場合は、基材フィルム及び粘着剤層は、十分な透明性を有することが好ましい。
The pressure-sensitive adhesive film for optical members of the present invention can be produced by forming a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition for optical members of the present invention on one side of a substrate or a release film.
As the base film used for forming the pressure-sensitive adhesive layer and the release film (separator) for protecting the pressure-sensitive adhesive surface, a resin film such as a polyester film can be used.
On the base film, on the side opposite to the side where the adhesive layer of the resin film is formed, antifouling treatment with silicone-based, fluorine-based release agent or coating agent, silica fine particles, etc., application of antistatic agent, An antistatic treatment such as kneading can be performed.
The release film is subjected to a release treatment with a silicone-based or fluorine-based release agent or the like on the surface of the pressure-sensitive adhesive layer that is to be combined with the pressure-sensitive adhesive surface.
It is preferable that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film for bonding various optical films such as a polarizing plate and a retardation film to an optical component such as a liquid crystal cell and other optical films has sufficient transparency. In the case of an optical surface protective film such as a polarizing plate surface protective film, the base film and the pressure-sensitive adhesive layer preferably have sufficient transparency.
粘着フィルムが基材フィルムを有する場合、本発明の粘着フィルムは、例えば、表面保護フィルム、偏光板用の表面保護フィルム、光学用の表面保護フィルム、粘着剤付き光学フィルム、粘着剤付き偏光板などに好適に用いることができる。 When the adhesive film has a base film, the adhesive film of the present invention is, for example, a surface protective film, a surface protective film for a polarizing plate, an optical surface protective film, an optical film with an adhesive, a polarizing plate with an adhesive, etc. Can be suitably used.
粘着フィルムが基材フィルムを有しない場合、１つの粘着剤層の両面に、それぞれ離型フィルムの離型処理が施された面を合わせることで、「離型フィルム／粘着剤層／離型フィルム」の構成とすることもできる。この場合、両側の離型フィルムを、順次、あるいは同時に剥離して粘着面を露出することにより、光学フィルム等の光学部材と貼合可能になる。光学フィルムとしては、偏光フィルム、位相差フィルム、反射防止フィルム、防眩（アンチグレア）フィルム、紫外線吸収フィルム、赤外線吸収フィルム、光学補償フィルム、輝度向上フィルム等が挙げられる。
この場合、本発明の粘着フィルムは、偏光板とディスプレイパネルの貼り合わせに用いることができる。ディスプレイパネルとしては液晶表示装置や有機ＥＬ等が挙げられるが、これらに限定されるものではない。
また、本発明の光学部材用粘着フィルムは、偏光板を構成する材料の貼り合わせ用粘着フィルム、偏光板を主とする液晶表示装置の周辺部材用の各種光学フィルム、タッチパネル用粘着フィルム、電子ペーパー用粘着フィルム、有機ＥＬ用粘着フィルム等に用いることができる。
When the pressure-sensitive adhesive film does not have a base film, the surfaces of the pressure-sensitive adhesive layer that have been subjected to the release treatment of the release film are combined with each other to obtain “release film / pressure-sensitive adhesive layer / release film”. It is also possible to adopt a configuration of In this case, the release films on both sides are peeled sequentially or simultaneously to expose the adhesive surface, so that it can be bonded to an optical member such as an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an antiglare (antiglare) film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, and a brightness enhancement film.
In this case, the adhesive film of this invention can be used for bonding of a polarizing plate and a display panel. Examples of the display panel include a liquid crystal display device and an organic EL, but are not limited thereto.
The adhesive film for optical members of the present invention includes an adhesive film for bonding materials constituting the polarizing plate, various optical films for peripheral members of liquid crystal display devices mainly comprising a polarizing plate, an adhesive film for touch panels, and electronic paper. It can be used for adhesive films for organic and adhesive films for organic EL.
また、これらの光学フィルムの少なくとも一方の面に、前記粘着剤層が積層されてなる粘着剤層付き光学フィルムとすることができる。具体的には、「光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／離型フィルム」、「光学フィルム／粘着剤層」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」、「離型フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」等の構成が挙げられる。
例えば、「光学フィルム／粘着剤層／離型フィルム」のように、離型フィルムで保護された粘着剤層を有する場合、離型フィルムを剥がして、「光学フィルム／粘着剤層」のように粘着剤層を露出させ、他の光学フィルムと貼合することにより、粘着剤層が層間の貼合に用いられた「光学フィルム／粘着剤層／光学フィルム」のような構成が得られる。
Moreover, it can be set as the optical film with an adhesive layer formed by laminating | stacking the said adhesive layer on the at least one surface of these optical films. Specifically, “optical film / pressure-sensitive adhesive layer / optical film”, “optical film / pressure-sensitive adhesive layer / release film”, “optical film / pressure-sensitive adhesive layer”, “optical film / pressure-sensitive adhesive layer / optical film / “Adhesive layer / optical film”, “optical film / adhesive layer / optical film / adhesive layer / release film”, “release film / adhesive layer / optical film / adhesive layer / release film”, etc. A configuration is mentioned.
For example, when having a pressure-sensitive adhesive layer protected by a release film such as “optical film / pressure-sensitive adhesive layer / release film”, the release film is peeled off, and “optical film / pressure-sensitive adhesive layer” By exposing the pressure-sensitive adhesive layer and pasting with another optical film, a configuration such as “optical film / pressure-sensitive adhesive layer / optical film” in which the pressure-sensitive adhesive layer is used for bonding between layers is obtained.
以下、実施例をもって本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
＜アクリル系共重合体の製造＞
［実施例１］
撹拌機、温度計、還流冷却器及び窒素導入管を備えた反応装置に、窒素ガスを導入して、反応装置内の空気を窒素ガスで置換した。その後、反応装置に２−エチルヘキシルアクリレート１００重量部、６−ヒドロキシヘキシルアクリレート２．０重量部とともに溶剤（酢酸エチル）を１００部加えた。その後、重合開始剤としてアゾビスイソブチロニトリル０．１重量部を２時間かけて滴下させ、６５℃で８時間反応させ、重量平均分子量５０万の、実施例１のアクリル系共重合体溶液１を得た。
［実施例２〜７及び比較例１〜２］
単量体の組成を各々、表１の（Ａ）、（Ａ′）、及び（Ｂ）の記載のようにする以外は、上記の実施例１に用いるアクリル系共重合体溶液１と同様にして、実施例２〜７及び比較例１〜２に用いるアクリル系共重合体溶液を得た。
<Manufacture of acrylic copolymer>
[Example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, and the air in the reactor was replaced with nitrogen gas. Thereafter, 100 parts of 2-ethylhexyl acrylate and 2.0 parts by weight of 6-hydroxyhexyl acrylate and 100 parts of a solvent (ethyl acetate) were added to the reactor. Thereafter, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, reacted at 65 ° C. for 8 hours, and the acrylic copolymer solution of Example 1 having a weight average molecular weight of 500,000 was obtained. 1 was obtained.
[Examples 2-7 and Comparative Examples 1-2]
The monomer composition is the same as that of the acrylic copolymer solution 1 used in Example 1 except that the composition of each monomer is as described in (A), (A ′) and (B) of Table 1. Thus, acrylic copolymer solutions used in Examples 2 to 7 and Comparative Examples 1 and 2 were obtained.
＜光学部材用粘着剤組成物及び粘着フィルムの製造＞
［実施例１］
上記のとおり製造したアクリル系共重合体溶液１（そのうちアクリル系共重合体が１００重量部）に対して、コロネートＨＬ（ヘキサメチレンジイソシアネート（ＨＤＩ）化合物のアダクト体）２．０重量部を加えて撹拌混合して実施例１の光学部材用粘着剤組成物を得た。この光学部材用粘着剤組成物をシリコーン樹脂コートされたポリエチレンテレフタレート（ＰＥＴ）フィルムからなる剥離フィルムの上に塗布後、９０℃で乾燥することによって溶剤を除去し、粘着剤層の厚さが２５μｍである粘着フィルムを得た。
その後、一方の面に帯電防止及び防汚処理されたポリエチレンテレフタレート（ＰＥＴ）フィルムの帯電防止及び防汚処理された面とは反対の面に粘着フィルムを転写させ、「帯電防止及び防汚処理されたＰＥＴフィルム／粘着剤層／剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）」の積層構成を有する実施例１の粘着フィルムを得た。
［実施例２〜７及び比較例１〜２］
添加剤の組成を各々、表１の「架橋剤」、（Ｃ）及び（Ｄ）の記載のようにする以外は、上記の実施例１の粘着フィルムと同様にして、実施例２〜７及び比較例１〜２の粘着フィルムを得た。
<Manufacture of adhesive composition for optical members and adhesive film>
[Example 1]
Add 2.0 parts by weight of coronate HL (adduct of hexamethylene diisocyanate (HDI) compound) to the acrylic copolymer solution 1 (100 parts by weight of the acrylic copolymer) produced as described above. By stirring and mixing, the pressure-sensitive adhesive composition for optical member of Example 1 was obtained. After applying this pressure-sensitive adhesive composition for optical members onto a release film made of a polyethylene terephthalate (PET) film coated with silicone resin, the solvent is removed by drying at 90 ° C., and the thickness of the pressure-sensitive adhesive layer is 25 μm. An adhesive film was obtained.
Then, the adhesive film was transferred to the opposite side of the antistatic and antifouling surface of the polyethylene terephthalate (PET) film that had been antistatic and antifouling treated on one side. The pressure-sensitive adhesive film of Example 1 having a laminated structure of “PET film / pressure-sensitive adhesive layer / release film (PET film coated with silicone resin)” was obtained.
[Examples 2-7 and Comparative Examples 1-2]
Except that the composition of the additive is as described in “Crosslinking agent”, (C) and (D) in Table 1, Examples 2 to 7 and The adhesive film of Comparative Examples 1-2 was obtained.
表１において、各成分の配合比は、（Ａ）と（Ａ′）との合計量を１００重量部として求めた重量部の数値を括弧で囲んで示す。また、表１に用いた各成分の略記号の化合物名を、表２に示す。
なお、コロネート（登録商標）ＨＸ、同ＨＬ及び同Ｌ−４５は日本ポリウレタン工業株式会社の商品名であり、ＴＥＴＲＡＤ（登録商標）−Ｘは三菱ガス化学株式会社の商品名であり、デュラネート（登録商標）２４Ａ−１００は旭化成ケミカルズ株式会社の商品名である。デナコール（登録商標）ＥＸ−１２１は、ナガセケムテックス株式会社の単官能エポキシ化合物（２−エチルヘキシルグリシジルエーテル）の商品名である。ＩＲＧＡＮＯＸ（登録商標）１０１０は、ＢＡＳＦ社のヒンダードフェノール系酸化防止剤の商品名である。
In Table 1, the compounding ratio of each component is indicated by enclosing the numerical value of parts by weight enclosed in parentheses with the total amount of (A) and (A ′) as 100 parts by weight. In addition, Table 2 shows the names of the abbreviations of each component used in Table 1.
Coronate (registered trademark) HX, HL and L-45 are trade names of Nippon Polyurethane Industry Co., Ltd., and TETRAD (registered trademark) -X is a trade name of Mitsubishi Gas Chemical Co., Ltd. Trademark) 24A-100 is a trade name of Asahi Kasei Chemicals Corporation. Denacol (registered trademark) EX-121 is a trade name of a monofunctional epoxy compound (2-ethylhexyl glycidyl ether) manufactured by Nagase ChemteX Corporation. IRGANOX (registered trademark) 1010 is a trade name of a hindered phenol antioxidant from BASF.
＜試験方法及び評価＞
実施例１〜７及び比較例１〜２における粘着フィルムを２３℃、５０％ＲＨの雰囲気下で７日間エージングした後、剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）を剥がして、粘着剤層を露出させた粘着フィルムを、表面抵抗率の測定試料とした。
さらに、この粘着剤層を露出させた粘着フィルムを、粘着剤層を介して液晶セルに貼られた偏光板の表面に貼り合わせ、１日放置した後、５０℃、５気圧、２０分間オートクレーブ処理し、室温でさらに１２時間放置したものを、粘着力の測定試料とした。
<Test method and evaluation>
After aging the adhesive films in Examples 1 to 7 and Comparative Examples 1 and 2 in an atmosphere of 23 ° C. and 50% RH for 7 days, the release film (PET film coated with silicone resin) was peeled off, and the adhesive layer was removed. The exposed adhesive film was used as a sample for measuring surface resistivity.
Further, the pressure-sensitive adhesive film with the pressure-sensitive adhesive layer exposed is bonded to the surface of the polarizing plate attached to the liquid crystal cell via the pressure-sensitive adhesive layer, and left for 1 day, and then autoclaved at 50 ° C., 5 atm for 20 minutes. Then, the sample that was allowed to stand at room temperature for another 12 hours was used as a sample for measuring the adhesive strength.
＜粘着剤層の表面抵抗率＞
エージングした後、偏光板に貼り合わせる前に、剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）を剥がして粘着剤層を露出させ、抵抗率計ハイレスタＵＰ−ＨＴ４５０（三菱化学アナリテック製）を用いて粘着剤層の表面抵抗率を測定した。
<Surface resistivity of adhesive layer>
After aging, before bonding to the polarizing plate, peel off the release film (silicone resin-coated PET film) to expose the adhesive layer, and use a resistivity meter Hiresta UP-HT450 (manufactured by Mitsubishi Chemical Analytech) The surface resistivity of the pressure-sensitive adhesive layer was measured.
＜粘着力＞
上記で得られた粘着剤層を露出させた粘着フィルムを、２５ｍｍ幅の粘着フィルムに裁断し、偏光板の表面に貼り合わせた後、１８０°方向に引張試験機を用いて３０ｍ／ｍｉｎの剥離速度において剥がして測定した剥離強度を粘着力とした。
<Adhesive strength>
The pressure-sensitive adhesive film obtained by exposing the pressure-sensitive adhesive layer obtained above is cut into a 25 mm-wide pressure-sensitive adhesive film and bonded to the surface of the polarizing plate, and then peeled off at 30 ° using a tensile tester in the 180 ° direction. The peel strength measured by peeling off at a speed was defined as the adhesive strength.
＜光学部材用粘着剤組成物の貯蔵安定性＞
上記で得られた光学部材用粘着剤組成物を、５０℃雰囲気中に１ヶ月放置した後に、該光学部材用粘着剤組成物の粘度を測定し、粘度の上昇変化の有無により貯蔵安定性を確認する。評価基準は、粘度変化が２０％未満の場合を「○」、２０％以上５０％未満の場合を「△」、５０％以上の場合を「×」と評価した。
<Storage stability of the pressure-sensitive adhesive composition for optical members>
The pressure-sensitive adhesive composition for optical members obtained above is allowed to stand in a 50 ° C. atmosphere for 1 month, and then the viscosity of the pressure-sensitive adhesive composition for optical members is measured. Check. The evaluation criteria were evaluated as “◯” when the viscosity change was less than 20%, “Δ” when 20% or more and less than 50%, and “X” when 50% or more.
＜粘着フィルムの変色性＞
透明ＰＥＴに厚さ２５μｍの粘着剤層を積層した粘着フィルムを５０℃の雰囲気中に１ヶ月放置した後、粘着剤層の変色性を確認する。評価基準は、無色透明な場合を「○」、わずかに黄変している場合を「△」、黄変している場合を「×」と評価した。
<Discoloration of adhesive film>
An adhesive film obtained by laminating an adhesive layer having a thickness of 25 μm on transparent PET is left in an atmosphere at 50 ° C. for 1 month, and then the discoloration of the adhesive layer is confirmed. The evaluation criteria were “◯” when colorless and transparent, “Δ” when slightly yellowed, and “x” when yellowed.
＜粘着フィルムの耐析出性＞
透明ＰＥＴに厚さ２５μｍの粘着剤層を積層した粘着フィルムを５０℃の雰囲気中に２週間放置し、次いで、０℃雰囲気中に２週間放置した後、粘着フィルム上からの酸化防止剤の析出状態を確認する。評価基準は、酸化防止剤が全く析出していない場合を「○」、わずかに析出している場合を「△」、析出している場合を「×」とした。
<Precipitation resistance of adhesive film>
An adhesive film obtained by laminating an adhesive layer having a thickness of 25 μm on transparent PET is allowed to stand in an atmosphere of 50 ° C. for 2 weeks, then left in an atmosphere of 0 ° C. for 2 weeks, and then the antioxidant is deposited on the adhesive film. Check the status. The evaluation criteria were “◯” when no antioxidant was deposited, “Δ” when slightly deposited, and “X” when deposited.
表３に、評価結果を示す。なお、粘着剤層の表面抵抗率は、「ｍ×１０＋ｎ」を「ｍＥ＋ｎ」とする方式（ただし、ｍは任意の実数値、ｎは正の整数）により表記した。 Table 3 shows the evaluation results. The surface resistivity of the pressure-sensitive adhesive layer was expressed by a method in which “m × 10 + n ” is “mE + n” (where m is an arbitrary real value and n is a positive integer).
実施例１〜７の光学部材用粘着剤組成物及び粘着フィルムは、光学部材用粘着剤組成物の中に酸化防止剤としてトコフェロール系化合物を含有するため、光学部材用粘着剤組成物の貯蔵安定性、粘着フィルムの変色性、粘着フィルムの耐析出性がいずれも良好であった。
また、実施例２，５〜７の粘着フィルムについては、光学部材用粘着剤組成物の中に帯電防止剤としてイオン化合物を含有しているが、表３に示すとおり、表面抵抗率がいずれも、５．０×１０＋１１Ω／□以下となっており、剥離帯電圧の低減効果を有している。
このことから、本発明におけるイオン化合物による帯電防止性能が、酸化防止剤であるトコフェロール系化合物によって、阻害されないで有効であることが判明した。
また、比較例１の光学部材用粘着剤組成物及び粘着フィルムは、光学部材用粘着剤組成物の中に酸化防止剤を含まないため、光学部材用粘着剤組成物の貯蔵安定性と粘着フィルムの変色性に問題があった。
比較例２の光学部材用粘着剤組成物及び粘着フィルムは、光学部材用粘着剤組成物の中の酸化防止剤としてヒンダードフェノール系酸化防止剤を含有するため、粘着フィルムの耐析出性に問題があった。
Since the pressure-sensitive adhesive composition for optical members and the pressure-sensitive adhesive films of Examples 1 to 7 contain a tocopherol compound as an antioxidant in the pressure-sensitive adhesive composition for optical members, the storage stability of the pressure-sensitive adhesive composition for optical members is stable. , Discoloration of the adhesive film, and precipitation resistance of the adhesive film were all good.
Moreover, about the adhesive film of Example 2, 5-7, although the ionic compound is contained as an antistatic agent in the adhesive composition for optical members, as shown in Table 3, all have surface resistivity. 5.0 × 10 +11 Ω / □ or less, and has an effect of reducing the stripping voltage.
From this, it was found that the antistatic performance by the ionic compound in the present invention is effective without being inhibited by the tocopherol compound as an antioxidant.
Moreover, since the adhesive composition for optical members and the adhesive film of Comparative Example 1 do not contain an antioxidant in the adhesive composition for optical members, the storage stability and the adhesive film of the adhesive composition for optical members There was a problem with the discoloration.
Since the pressure-sensitive adhesive composition for optical members and the pressure-sensitive adhesive film of Comparative Example 2 contain a hindered phenolic antioxidant as an antioxidant in the pressure-sensitive adhesive composition for optical members, there is a problem with the precipitation resistance of the pressure-sensitive adhesive film. was there.
本発明の光学部材用粘着剤組成物は、人体へ悪影響を及ぼすことが少ないトコフェロール系化合物を酸化防止剤として使用していると共に、帯電防止性能、耐析出性にも優れることから、安全性と実用性に優れた光学部材用粘着フィルム及び表面保護フィルムを提供でき、産業上の利用価値が大である。 The pressure-sensitive adhesive composition for optical members of the present invention uses a tocopherol-based compound that has little adverse effect on the human body as an antioxidant, and is excellent in antistatic performance and precipitation resistance. An adhesive film for optical members and a surface protective film excellent in practicality can be provided, and the industrial utility value is great.
Claims (6)
前記トコフェロール系化合物が、ｄ−α−トコフェロール、ｄｌ−α−トコフェロール、ｄ−β−トコフェロール、ｄｌ−β−トコフェロール、ｄ−γ−トコフェロール、ｄｌ−γ−トコフェロール、ｄ−δ−トコフェロール、ｄｌ−δ−トコフェロール、ｄ−α−トコトリエノール、ｄｌ−α−トコトリエノール、ｄ−β−トコトリエノール、ｄｌ−β−トコトリエノール、ｄ−γ−トコトリエノール、ｄｌ−γ−トコトリエノール、ｄ−δ−トコトリエノール、ｄｌ−δ−トコトリエノールからなる化合物群の中から選択された少なくとも１種であり、
前記トコフェロール系化合物が、エステルに変化していないフェルール性水酸基を有する化合物であり、
前記アクリル系共重合体の１００重量部に対して、前記トコフェロール系化合物の少なくとも１種以上の合計を０．０１〜１．５重量部、を必須成分として含有することを特徴とする光学部材用粘着剤組成物。 Tocopherol containing an acrylic copolymer (meth) acrylic acid alkyl ester as a main component, a crosslinking agent, an antioxidant, and an ionic compound, and oil-soluble and liquid at room temperature as the antioxidant. Containing a compound,
The tocopherol compound is d-α-tocopherol, dl-α-tocopherol, d-β-tocopherol, dl-β-tocopherol, d-γ-tocopherol, dl-γ-tocopherol, d-δ-tocopherol, dl- δ-tocopherol, d-α-tocotrienol, dl-α-tocotrienol, d-β-tocotrienol, dl-β-tocotrienol, d-γ-tocotrienol, dl-γ-tocotrienol, d-δ-tocotrienol, dl-δ- At least one selected from the group of compounds consisting of tocotrienol,
The tocopherol compound is a compound having a ferrule hydroxyl group that is not changed to an ester,
For optical members, comprising 0.01 to 1.5 parts by weight of a total of at least one of the tocopherol compounds as an essential component with respect to 100 parts by weight of the acrylic copolymer Adhesive composition.
アクリル系共重合体（１）；（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、を共重合した共重合体、
アクリル系共重合体（２）；（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、ビニル基を有する共重合性ビニルモノマーの少なくとも１種と、を共重合した共重合体、
アクリル系共重合体（３）；（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも２種以上を共重合した共重合体、
アクリル系共重合体（４）；（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、芳香族系モノマーの少なくとも１種と、を共重合した共重合体、
のいずれかであることを特徴とする請求項１〜３のいずれかに記載の光学部材用粘着剤組成物。 The acrylic copolymer is the following acrylic copolymers (1) to (4),
Acrylic copolymer (1); (A) a copolymer containing at least one (meth) acrylic acid alkyl ester monomer having a C1-C14 alkyl group and (B) a hydroxyl group and / or a carboxyl group. A copolymer obtained by copolymerizing at least one kind of vinyl monomer;
Acrylic copolymer (2); (A) at least one (meth) acrylic acid alkyl ester monomer having a C1-C14 alkyl group, and at least one copolymerizable vinyl monomer having a vinyl group; A copolymer obtained by copolymerizing
Acrylic copolymer (3); (A) a copolymer obtained by copolymerizing at least two kinds of (meth) acrylic acid alkyl ester monomers having C1-C14 carbon atoms in the alkyl group;
Acrylic copolymer (4); (A) Copolymer containing at least one (meth) acrylic acid alkyl ester monomer having an alkyl group with C1 to C14 and (B) a hydroxyl group and / or a carboxyl group. A copolymer obtained by copolymerizing at least one kind of polymerizable vinyl monomer and at least one kind of aromatic monomer,
It is either of these, The adhesive composition for optical members in any one of Claims 1-3 characterized by the above-mentioned.
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| JP2013062074A JP6286703B2 (en) | 2013-03-25 | 2013-03-25 | Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive film and surface protective film |
| KR1020130161042A KR101603528B1 (en) | 2013-03-25 | 2013-12-23 | Adhesive composition for optical members, adhesive film for optical members, and surface-protective adhesive film |
| CN201310729400.1A CN104073194B (en) | 2013-03-25 | 2013-12-26 | Adhesive composition used for optical part, adhesive film used for optical part and surface protection film |
| TW104120470A TWI593767B (en) | 2013-03-25 | 2014-01-09 | Adhesive composition for optical members, adhesive film for optical members, and surface-protective adhesive film |
| TW103100825A TWI550049B (en) | 2013-03-25 | 2014-01-09 | Adhesive composition for optical members, adhesive film for optical members, and surface-protective adhesive film |
| KR1020160028049A KR101690020B1 (en) | 2013-03-25 | 2016-03-09 | Adhesive composition for optical members, adhesive film for optical members, and surface-protective adhesive film |
| KR1020160175206A KR101793994B1 (en) | 2013-03-25 | 2016-12-21 | Adhesive composition for optical members, adhesive film for optical members, and surface-protective adhesive film |
| KR1020170143102A KR101841979B1 (en) | 2013-03-25 | 2017-10-31 | Adhesive composition for optical members, adhesive film for optical members, and surface-protective adhesive film |
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| JP2021001354A (en) * | 2020-09-23 | 2021-01-07 | 藤森工業株式会社 | Adhesive composition for optical member, adhesive film for optical member and surface protective film |
| JP7309964B2 (en) | 2020-09-23 | 2023-07-18 | 藤森工業株式会社 | adhesive film |
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| JP6813643B2 (en) * | 2019-08-27 | 2021-01-13 | 藤森工業株式会社 | Optical film with adhesive |
| CN114945850B (en) * | 2020-01-09 | 2024-03-19 | Lg伊诺特有限公司 | Light path control member and display device including the same |
| JP7036895B2 (en) * | 2020-12-16 | 2022-03-15 | 藤森工業株式会社 | Optical film with adhesive |
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| JPH0561898A (en) | 1991-08-30 | 1993-03-12 | Oki Electric Ind Co Ltd | Automatic transaction system |
| JP2003105300A (en) * | 2001-09-28 | 2003-04-09 | Kanegafuchi Chem Ind Co Ltd | Adhesive composition |
| JP4412895B2 (en) * | 2002-12-05 | 2010-02-10 | 株式会社日本触媒 | Pressure sensitive adhesive composition |
| JP4542752B2 (en) * | 2003-05-30 | 2010-09-15 | 住化プラステック株式会社 | Waterproof tape |
| JP4969032B2 (en) * | 2004-09-08 | 2012-07-04 | 日東電工株式会社 | Adhesive tape and video sensor mounting method using the same |
| WO2006137559A1 (en) * | 2005-06-24 | 2006-12-28 | Toyo Ink Manufacturing Co., Ltd. | Antistatic acrylic pressure-sensitive adhesive |
| US20100092772A1 (en) * | 2007-05-07 | 2010-04-15 | Lintec Corporation | Pressure-sensitive adhesive sheet |
| JP5150176B2 (en) * | 2007-09-07 | 2013-02-20 | 富士フイルム株式会社 | Powder composition |
| JP5887046B2 (en) | 2009-10-07 | 2016-03-16 | 東亞合成株式会社 | Method for producing pressure-sensitive adhesive composition |
| JP5665116B2 (en) * | 2009-11-20 | 2015-02-04 | 日東電工株式会社 | Patches and patch preparations |
| JP2012180507A (en) * | 2011-02-10 | 2012-09-20 | Nitto Denko Corp | Adhesive |
| WO2012108348A1 (en) * | 2011-02-10 | 2012-08-16 | 日東電工株式会社 | Adhesive |
| JP5683369B2 (en) * | 2011-04-22 | 2015-03-11 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP6000697B2 (en) * | 2011-07-19 | 2016-10-05 | 日東電工株式会社 | Transparent adhesive |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021001354A (en) * | 2020-09-23 | 2021-01-07 | 藤森工業株式会社 | Adhesive composition for optical member, adhesive film for optical member and surface protective film |
| JP7071460B2 (en) | 2020-09-23 | 2022-05-19 | 藤森工業株式会社 | Adhesive composition for optical members, adhesive film for optical members and surface protection film |
| JP7309964B2 (en) | 2020-09-23 | 2023-07-18 | 藤森工業株式会社 | adhesive film |
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| Publication number | Publication date |
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| JP2014185280A (en) | 2014-10-02 |
| KR101793994B1 (en) | 2017-11-06 |
| TWI550049B (en) | 2016-09-21 |
| CN104073194A (en) | 2014-10-01 |
| CN104073194B (en) | 2016-08-17 |
| TW201439260A (en) | 2014-10-16 |
| KR20160030501A (en) | 2016-03-18 |
| KR101603528B1 (en) | 2016-03-15 |
| KR20160150094A (en) | 2016-12-28 |
| KR101841979B1 (en) | 2018-03-26 |
| TWI593767B (en) | 2017-08-01 |
| TW201536886A (en) | 2015-10-01 |
| KR101690020B1 (en) | 2016-12-27 |
| KR20140116781A (en) | 2014-10-06 |
| KR20170124994A (en) | 2017-11-13 |
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