JP5734754B2 - Adhesive composition containing antistatic agent and adhesive film - Google Patents
Adhesive composition containing antistatic agent and adhesive film Download PDFInfo
- Publication number
- JP5734754B2 JP5734754B2 JP2011130157A JP2011130157A JP5734754B2 JP 5734754 B2 JP5734754 B2 JP 5734754B2 JP 2011130157 A JP2011130157 A JP 2011130157A JP 2011130157 A JP2011130157 A JP 2011130157A JP 5734754 B2 JP5734754 B2 JP 5734754B2
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- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- cation
- group
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 44
- 239000002216 antistatic agent Substances 0.000 title claims description 29
- 239000000853 adhesive Substances 0.000 title claims description 27
- 230000001070 adhesive effect Effects 0.000 title claims description 27
- 239000002313 adhesive film Substances 0.000 title claims description 9
- -1 pentafluorobenzenecarboxylate anion Chemical class 0.000 claims description 105
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 74
- 239000010408 film Substances 0.000 claims description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 230000001681 protective effect Effects 0.000 claims description 31
- 239000010410 layer Substances 0.000 claims description 27
- 150000001450 anions Chemical class 0.000 claims description 26
- 150000008040 ionic compounds Chemical class 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 13
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- 239000012790 adhesive layer Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000012788 optical film Substances 0.000 claims description 7
- 239000002998 adhesive polymer Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 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
- 238000004132 cross linking Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical group FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 3
- IKMBXKGUMLSBOT-UHFFFAOYSA-M 2,3,4,5,6-pentafluorobenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=C(F)C(F)=C(F)C(F)=C1F IKMBXKGUMLSBOT-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- NDTLNLAKGMRTFS-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCC)[N+]1=CN(C=C1)C NDTLNLAKGMRTFS-UHFFFAOYSA-M 0.000 description 2
- ZPIJNWKFPFKVBP-UHFFFAOYSA-M 1-octylpyridin-1-ium 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CC=CC=C1 ZPIJNWKFPFKVBP-UHFFFAOYSA-M 0.000 description 2
- 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
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 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
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects 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
- 239000012948 isocyanate Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 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
- ISOHBLZSJDMWHM-UHFFFAOYSA-M 1,1-dibutylpyrrolidin-1-ium 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCC)[N+]1(CCCC1)CCCC ISOHBLZSJDMWHM-UHFFFAOYSA-M 0.000 description 1
- CHRBKZSUZNROQX-UHFFFAOYSA-M 1,1-dioctylpyrrolidin-1-ium 2,3,4,5,6-pentafluorobenzenesulfonate Chemical compound FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1(CCCC1)CCCCCCCC CHRBKZSUZNROQX-UHFFFAOYSA-M 0.000 description 1
- XHEQWOXHRGASQY-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium 2,3,4,5,6-pentafluorobenzenesulfonate Chemical compound FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.C(CCC)[N+]1=CN(C=C1)C XHEQWOXHRGASQY-UHFFFAOYSA-M 0.000 description 1
- HUNSTASQUCBWCF-UHFFFAOYSA-M 1-butyl-4-methylpyridin-1-ium 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCC)[N+]1=CC=C(C=C1)C HUNSTASQUCBWCF-UHFFFAOYSA-M 0.000 description 1
- MSNUSNMPCULXKH-UHFFFAOYSA-M 1-butylpyridin-1-ium 2,3,4,5,6-pentafluorobenzenesulfonate Chemical compound FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.C(CCC)[N+]1=CC=CC=C1 MSNUSNMPCULXKH-UHFFFAOYSA-M 0.000 description 1
- OMPLFUALYIEKNF-UHFFFAOYSA-N 1-dodecyl-2-methylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1C OMPLFUALYIEKNF-UHFFFAOYSA-N 0.000 description 1
- HCCSYZCWVRVTKX-UHFFFAOYSA-M 1-dodecylpyridin-1-ium 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCCCCCC)[N+]1=CC=CC=C1 HCCSYZCWVRVTKX-UHFFFAOYSA-M 0.000 description 1
- HURXAIVQWRINFD-UHFFFAOYSA-M 1-hexyl-4-methylpyridin-1-ium 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCC)[N+]1=CC=C(C=C1)C HURXAIVQWRINFD-UHFFFAOYSA-M 0.000 description 1
- ADTIJBWKGHXBQM-UHFFFAOYSA-M 1-methyl-3-nonylimidazol-1-ium 2,3,4,5,6-pentafluorobenzoate Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCCC)[N+]1=CN(C=C1)C ADTIJBWKGHXBQM-UHFFFAOYSA-M 0.000 description 1
- DTKXBEGAVFHEIC-UHFFFAOYSA-M 1-nonylpyridin-1-ium 2,3,4,5,6-pentafluorobenzenesulfonate Chemical compound FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.C(CCCCCCCC)[N+]1=CC=CC=C1 DTKXBEGAVFHEIC-UHFFFAOYSA-M 0.000 description 1
- IKMBXKGUMLSBOT-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(F)C(F)=C(F)C(F)=C1F IKMBXKGUMLSBOT-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
- NXANBWOMRJUNJH-UHFFFAOYSA-M 3,5-dimethyl-1-octylpyridin-1-ium 2,3,4,5,6-pentafluorobenzenesulfonate Chemical compound FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CC(=CC(=C1)C)C NXANBWOMRJUNJH-UHFFFAOYSA-M 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- OSCFFOTZWZZXPR-UHFFFAOYSA-N 4-methyl-1-octylpyridin-1-ium Chemical compound CCCCCCCC[N+]1=CC=C(C)C=C1 OSCFFOTZWZZXPR-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
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OHHMXOLNJFRWFR-UHFFFAOYSA-M FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCC)[N+]1=CC=CC=C1 Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCC)[N+]1=CC=CC=C1 OHHMXOLNJFRWFR-UHFFFAOYSA-M 0.000 description 1
- SXCKCKRTJGJGBD-UHFFFAOYSA-M FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1(CCCC1)CCCCCCCC Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1(CCCC1)CCCCCCCC SXCKCKRTJGJGBD-UHFFFAOYSA-M 0.000 description 1
- GOKQERRVHUWNMJ-UHFFFAOYSA-L FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CC(=CC(=C1)C)C.FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.C(CCCCCCCCCCC)[N+]1=CC=CC=C1 Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CC(=CC(=C1)C)C.FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.C(CCCCCCCCCCC)[N+]1=CC=CC=C1 GOKQERRVHUWNMJ-UHFFFAOYSA-L 0.000 description 1
- VUQGTHHVNMFURF-UHFFFAOYSA-M FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CC=C(C=C1)C Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CC=C(C=C1)C VUQGTHHVNMFURF-UHFFFAOYSA-M 0.000 description 1
- YEFVIBULZXVOSI-UHFFFAOYSA-M FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CN(C=C1)C Chemical compound FC1=C(C(=C(C(=C1C(=O)[O-])F)F)F)F.C(CCCCCCC)[N+]1=CN(C=C1)C YEFVIBULZXVOSI-UHFFFAOYSA-M 0.000 description 1
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- RJKLQJUWKIDBCS-UHFFFAOYSA-L FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.FC1(C(C([N+](C1)(CCCC)CCCC)(OC1=CC=CC=C1)F)(F)F)F.C(CCC)[N+]1(CCCC1)CCCC.FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F Chemical compound FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.FC1(C(C([N+](C1)(CCCC)CCCC)(OC1=CC=CC=C1)F)(F)F)F.C(CCC)[N+]1(CCCC1)CCCC.FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F RJKLQJUWKIDBCS-UHFFFAOYSA-L 0.000 description 1
- ZDVZAXFBLPXVEQ-UHFFFAOYSA-N FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.[NH+]1=CNC=C1 Chemical compound FC1=C(C(=C(C(=C1S(=O)(=O)[O-])F)F)F)F.[NH+]1=CNC=C1 ZDVZAXFBLPXVEQ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 210000002858 crystal cell Anatomy 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
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying 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
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001678 irradiating effect Effects 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
- 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 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
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 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
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-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
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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Description
本発明は、帯電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、帯電防止剤として、ペンタフルオロフェニル基（Ｃ６Ｆ５基）を有する化合物（以下、「ペンタフルオロベンゼン化合物」という。）を含有する粘着剤組成物に関し、粘着性能を損なわずに帯電防止性に優れ、さらにリワーク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に関するものである。 The present invention relates to a pressure-sensitive adhesive composition containing an antistatic agent, and a pressure-sensitive adhesive film. More specifically, the present invention relates to a pressure-sensitive adhesive composition containing a compound having a pentafluorophenyl group (C 6 F 5 group) (hereinafter referred to as “pentafluorobenzene compound”) as an antistatic agent, without impairing the pressure-sensitive adhesive performance. The present invention relates to a pressure-sensitive adhesive composition excellent in antistatic property and reworkability, and a pressure-sensitive adhesive film using the same.
従来から、電子機器部品、光学機器部品、画像表示パネルなどの精密部品及び部材の製造加工・組み立て工程においては、これらの精密部品及び部材の表面を一時的に保護して、作業環境雰囲気からのパーティクル・気体状の汚染物質の付着や、すりキズ・打痕の発生を防止するために表面保護フィルムが、精密部品及び部材の表面に貼着されている。
例えば、液晶ディスプレイを構成する部材である偏光板、位相差板などの光学部材を製造する工程において使用される表面保護フィルムは、光学的に透明性を有するポリエチレンテレフタレート（ＰＥＴ）樹脂フィルムの片面に粘着剤層が形成されているが、光学部材に貼り合わせるまで、その粘着剤層を保護するための剥離処理された剥離フィルムが、粘着剤層の上に貼り合わされている。
Conventionally, in the manufacturing process and assembly process of precision parts and components such as electronic equipment parts, optical equipment parts, and image display panels, the surfaces of these precision parts and parts are temporarily protected from the working environment atmosphere. A surface protective film is adhered to the surface of precision parts and members in order to prevent adhesion of particles and gaseous contaminants, as well as generation of scratches and dents.
For example, a surface protective film used in a process for producing an optical member such as a polarizing plate or a retardation plate, which is a member constituting a liquid crystal display, is provided on one side of an optically transparent polyethylene terephthalate (PET) resin film. Although the pressure-sensitive adhesive layer is formed, a release film subjected to release treatment for protecting the pressure-sensitive adhesive layer is bonded onto the pressure-sensitive adhesive layer until it is bonded to the optical member.
また、偏光板、位相差板などの光学部材は、表面保護フィルムを貼り合わされた状態で、液晶表示板の表示能力、色相、コントラスト、異物混入などの光学的評価を伴う製品検査を行うため、表面保護フィルムに対する要求性能としては、粘着剤層に気泡や異物が付着していないことが求められている。
また、近年では、偏光板、位相差板などの光学部材から表面保護フィルムを剥がすときに、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が、液晶ディスプレイの電気制御回路の故障に影響することが懸念され、粘着剤層に対して優れた帯電防止性能が求められている。
また、偏光板、位相差板などの光学部材に表面保護フィルムを貼り合わせるときに、各種の理由により、一旦、表面保護フィルムを剥がして、再度、表面保護フィルムを貼り直すことがあり、そのときに被着体の光学部材から剥がし易いこと（リワーク性）が求められている。
このように、近年においては、表面保護フィルムを構成する粘着剤層に対する要求性能として、粘着力の経時安定性、優れた帯電防止性能、及びリワーク性能などが、表面保護フィルムを使用するに当たっての使い易さの点から求められている。
しかし、表面保護フィルムを構成する粘着剤層に対する要求性能である、これらの、粘着力の経時安定性、優れた帯電防止性能、及びリワーク性能の、それぞれの要求性能を、別々に満たすことは出来ても、表面保護フィルムの粘着剤層に求められる要求性能を、同時に安価なコストで満たすことは困難な課題であった。
In addition, optical members such as polarizing plates and retardation plates are subjected to product inspection with optical evaluation such as display capability, hue, contrast, and foreign matter mixing of the liquid crystal display plate in a state where the surface protective film is bonded. As the required performance for the surface protective film, it is required that no bubbles or foreign substances adhere to the pressure-sensitive adhesive layer.
Also, in recent years, when the surface protective film is peeled off from an optical member such as a polarizing plate or a retardation plate, the peeling electrification caused by the static electricity generated when the adherend peels off the adhesive layer is electrically controlled by the liquid crystal display. There is a concern that it may affect circuit failure, and excellent antistatic performance is required for the pressure-sensitive adhesive layer.
In addition, when a surface protective film is bonded to an optical member such as a polarizing plate or a retardation plate, for various reasons, the surface protective film may be peeled off once, and then the surface protective film may be reattached. In addition, it is required to be easily peeled from the optical member of the adherend (reworkability).
As described above, in recent years, the required performance for the pressure-sensitive adhesive layer constituting the surface protective film includes the adhesive stability over time, excellent antistatic performance, rework performance, etc., when using the surface protective film. It is required from the point of ease.
However, these required performances for the pressure-sensitive adhesive layer that constitutes the surface protective film, such as adhesive stability with time, excellent antistatic performance, and rework performance, can be satisfied separately. However, it was a difficult task to satisfy the required performance required for the pressure-sensitive adhesive layer of the surface protective film at the same time at a low cost.
例えば、粘着力の経時安定性については、次のような提案が知られている。
炭素数が７以下のアルキル基を有する（メタ）アクリル酸アルキルエステルとカルボキシル基含有共重合性化合物との共重合体を主成分とし、これを架橋剤で架橋処理してなるアクリル系の粘着剤層では、長期間接着した場合に粘着剤が被着体側へ移着し、また被着体に対する接着力の経時上昇性が大きいという問題があった。これを回避するため、炭素数８〜１０のアルキル基を有する（メタ）アクリル酸アルキルエステルとアルコ―ル性水酸基を有する共重合性化合物との共重合体を用い、これを架橋剤で架橋処理した粘着剤層を設けたものが知られている（特許文献１）。
また、上記同様の共重合体に（メタ）アクリル酸アルキルエステルとカルボキシル基含有共重合性化合物との共重合体を少量配合し、これを架橋剤で架橋処理した粘着剤層を設けたものなどが提案されている。
For example, the following proposals are known for the stability of adhesive strength with time.
An acrylic pressure-sensitive adhesive comprising a copolymer of a (meth) acrylic acid alkyl ester having an alkyl group having 7 or less carbon atoms and a carboxyl group-containing copolymerizable compound as a main component and a crosslinking treatment with a crosslinking agent. In the layer, there is a problem that the adhesive is transferred to the adherend side when adhered for a long period of time, and the adhesive strength with respect to the adherend is highly increased over time. In order to avoid this, a copolymer of a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group is used, and this is crosslinked with a crosslinking agent. The thing which provided the adhesive layer which carried out is known (patent document 1).
In addition, a copolymer obtained by blending a small amount of a copolymer of (meth) acrylic acid alkyl ester and a carboxyl group-containing copolymerizable compound into the same copolymer as described above, and providing a pressure-sensitive adhesive layer obtained by crosslinking this with a crosslinking agent, etc. Has been proposed.
また、優れた帯電防止性能については、表面保護フィルムに帯電防止性を付与させための方法として、基材フィルムに帯電防止剤を練り込む方法などが示され、帯電防止剤としては、例えば、（ａ）第４級アンモニウム塩、ピリジニウム塩、第１〜３級アミノ基などのカチオン性基を有する各種のカチオン性帯電防止剤、（ｂ）スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基、ホスホン酸塩基などのアニオン性基を有するアニオン性帯電防止剤、（ｃ）アミノ酸系、アミノ硫酸エステル系などの両性帯電防止剤、（ｄ）アミノアルコール系、グリセリン系、ポリエチレングリコール系などのノニオン性帯電防止剤、（ｅ）上記の様な帯電防止剤を高分子量化した高分子型帯電防止剤、などが開示されている（特許文献２）。 As for the excellent antistatic performance, as a method for imparting antistatic properties to the surface protective film, a method of kneading an antistatic agent into the base film is shown, and examples of the antistatic agent include ( a) Various cationic antistatic agents having cationic groups such as quaternary ammonium salts, pyridinium salts, and primary to tertiary amino groups, (b) sulfonate groups, sulfate ester bases, phosphate ester bases, phosphones Anionic antistatic agent having an anionic group such as acid base, (c) Amphoteric antistatic agent such as amino acid type and amino sulfate ester type, (d) Nonionic charging such as amino alcohol type, glycerin type and polyethylene glycol type An antistatic agent, (e) a polymer antistatic agent obtained by increasing the molecular weight of the antistatic agent as described above, and the like are disclosed (Patent Document 2).
また、近年では、このような帯電防止剤を基材フィルムに含有させたり、あるいは基材フィルムの表面に塗布するのではなく、直接に粘着剤層に含有させたりすることが提案されている（特許文献３）。
特許文献３では、（１）（ａ）ウレタンアクリレートと、（ｂ）ポリアルキレンオキサイド鎖を有する（メタ）アクリレートと、（ｃ）接着力付与性モノマーと、を主成分として含む重合性混合物を放射線重合することにより得られた共重合体、および、（２）イオン性化合物、を含む、帯電防止性粘着剤組成、及びそれを用いた粘着シートが開示されている。具体的な、粘着剤組成物の製造方法として、ポリエステルウレタンアクリレートのようなウレタンアクリレートと、メトキシポリエチレングリコールアクリレートのようなポリオキシアルキレン鎖を有する（メタ）アクリレートモノマーと、ヒドロキシプロピルアクリレートのような接着力付与性モノマーと、必要に応じてイソオクチルアクリレートのようなさらなるコモノマーとを含む重合性混合物に、過塩素酸リチウムのようなイオン性化合物を混合し、必要ならば光重合開始剤を添加し、完全に溶解するまで攪拌した後、紫外線などを照射して硬化することにより粘着剤組成物が得られるとしている。
しかし、イオン性化合物として使用している過塩素酸リチウムは、金属腐食性を有するため、得られた帯電防止性粘着剤組成の使用する場所が限られてしまうという問題があった。
Further, in recent years, it has been proposed that such an antistatic agent is contained in the base film or directly in the pressure-sensitive adhesive layer rather than being applied to the surface of the base film ( Patent Document 3).
In Patent Document 3, a polymerizable mixture containing (1) (a) urethane acrylate, (b) (meth) acrylate having a polyalkylene oxide chain, and (c) an adhesiveness-imparting monomer as radiation components is used as radiation. An antistatic pressure-sensitive adhesive composition containing a copolymer obtained by polymerization and (2) an ionic compound, and a pressure-sensitive adhesive sheet using the same are disclosed. As a specific method for producing a pressure-sensitive adhesive composition, urethane acrylate such as polyester urethane acrylate, (meth) acrylate monomer having a polyoxyalkylene chain such as methoxypolyethylene glycol acrylate, and adhesion such as hydroxypropyl acrylate An ionic compound such as lithium perchlorate is mixed in a polymerizable mixture containing a force-imparting monomer and optionally a further comonomer such as isooctyl acrylate, and a photoinitiator is added if necessary. It is said that a pressure-sensitive adhesive composition is obtained by stirring until it is completely dissolved and then irradiating with ultraviolet rays or the like to be cured.
However, since lithium perchlorate used as an ionic compound has metal corrosivity, there is a problem that the place where the obtained antistatic pressure-sensitive adhesive composition is used is limited.
また、リワーク性能については、例えば、アクリル樹脂中に、イソシアネート系化合物の硬化剤と、特定のシリケートオリゴマーをアクリル系樹脂１００重量部に対して０．０００１〜１０重量部で配合した粘着剤組成物が提案されている（特許文献４）。
特許文献４では、アルキル基の炭素数２〜１２程度のアクリル酸アルキルエステルやアルキル基の炭素数４〜１２程度のメタクリル酸アルキルエステル等を主モノマー成分とし、例えば、カルボキシル基含有モノマーなどの他の官能基含有モノマー成分を含むことができるとしている。一般的には上記主モノマーを５０重量％以上含有させることが好ましい、又、官能基含有モノマー成分の含有量は０．００１〜５０重量％、好ましくは０．００１〜２５重量％、更に好ましくは０．０１〜２５重量％であることが望まれる、としている。このような特許文献４に記載の粘着剤組成物は、高温下又は高温高湿下でも凝集力及び接着力の経時変化が小さく、かつ、曲面接着力にも優れた効果を示すことから、リワーク性を有するとしている。
一般に、粘着剤層を柔らかい性状のものにすると、糊残りが発生し易くなり、リワーク性が低下しやすい。すなわち、誤って貼合したときに剥離がし難く、貼り直しが困難となりやすい。このことから、カルボキシル基などの官能基を有するモノマーを主剤に架橋させて、粘着剤層を一定の硬さにすることが、リワーク性を持たせるためには必要と考えられる。
As for the rework performance, for example, an adhesive composition in which an isocyanate compound curing agent and a specific silicate oligomer are mixed in an acrylic resin in an amount of 0.0001 to 10 parts by weight with respect to 100 parts by weight of the acrylic resin. Has been proposed (Patent Document 4).
In Patent Literature 4, an alkyl group having about 2 to 12 carbon atoms in an alkyl group or an alkyl group having about 4 to 12 carbon atoms in an alkyl group has a main monomer component such as a carboxyl group-containing monomer. The functional group-containing monomer component can be included. In general, the main monomer is preferably contained in an amount of 50% by weight or more, and the content of the functional group-containing monomer component is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, more preferably It is said that it is desired to be 0.01 to 25% by weight. Such a pressure-sensitive adhesive composition described in Patent Document 4 has a small effect on cohesive force and adhesive force over time even under high temperature or high temperature and high humidity, and exhibits an excellent effect on curved surface adhesive force. It is said to have sex.
In general, when the pressure-sensitive adhesive layer has a soft property, adhesive residue tends to be generated, and the reworkability tends to be lowered. That is, it is difficult to peel off when pasted by mistake, and it is difficult to re-paste. From this, it is considered necessary to make the pressure-sensitive adhesive layer have a certain hardness by crosslinking a monomer having a functional group such as a carboxyl group to the main agent in order to have reworkability.
従来技術においては、表面保護フィルムを構成する粘着剤層に対する要求性能として、粘着力の経時安定性、優れた帯電防止性能、及びリワーク性能の、それぞれの要求性能を、別々に満たすことは出来ても、表面保護フィルムの粘着剤層に求められる要求性能を、同時に安価なコストで満たすことは困難な課題であった。
本発明は、上記事情に鑑みてなされたものであり、粘着性能を損なわずに帯電防止性に優れ、さらにリワーク性にも優れた、帯電防止剤を含有する粘着剤組成物、及びそれを用いた粘着フィルムを提供することを課題とする。
In the prior art, as the required performance for the pressure-sensitive adhesive layer constituting the surface protective film, it is possible to satisfy each required performance of the adhesive strength over time, excellent antistatic performance, and rework performance separately. However, it has been difficult to satisfy the required performance required for the pressure-sensitive adhesive layer of the surface protective film at the same time at a low cost.
The present invention has been made in view of the above circumstances, and is an adhesive composition containing an antistatic agent that is excellent in antistatic properties without impairing adhesive performance and also has excellent reworkability, and uses the same. It is an object to provide an adhesive film.
前記課題を解決するため、本発明は、粘着剤ポリマーと、架橋剤と、帯電防止剤とを含有する粘着剤組成物であって、前記粘着剤ポリマーがアクリル系ポリマーからなり、前記帯電防止剤として、アニオンとカチオンとからなり、前記アニオンが、ペンタフルオロベンゼンカルボン酸アニオン、ペンタフルオロベンゼンスルホン酸アニオン、ペンタフルオロフェノキシアニオンからなるアニオン群の中から選択された１種であるイオン性化合物を含有することを特徴とする粘着剤組成物を提供する。
前記粘着剤ポリマーが、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレート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、からなる共重合体であり、前記共重合体の１００重量部に対して、前記帯電防止剤が、（Ｃ）前記イオン性化合物を０．１〜１０重量部、を必須成分として含有することが好ましい。
前記粘着剤ポリマーが、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種と、（Ｂ′）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、からなる共重合体であり、前記共重合体の１００重量部に対して、前記帯電防止剤が、（Ｃ）前記イオン性化合物を０．１〜２０重量部、を必須成分として含有することが好ましい。
前記粘着剤ポリマーが、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも２種以上からなる共重合体であり、前記共重合体の１００重量部に対して、前記帯電防止剤が、（Ｃ）前記イオン性化合物を０．１〜２０重量部、を必須成分として含有することが好ましい。
前記粘着剤組成物からなる粘着剤層の表面抵抗値が１．０×１０＋１２Ω／□以下であることが好ましい。
前記イオン性化合物が、カチオン成分として、ピリジニウム、イミダゾリウム、スルホニウム、ホスホニウム、ピロリジニウム、グアニジニウム、アンモニウム、イソウロニウム、チオウロニウム、ピペリジニウム、ピラゾリウム、モルホリニウムからなるカチオン群から選択した一種であるイオン性化合物であることが好ましい。
To solve the above problems, the present invention includes a pressure-sensitive adhesive polymer, a crosslinking agent, a pressure-sensitive adhesive composition containing a antistatic agent, wherein becomes adhesive polymer of an acrylic polymer, said antistatic agent Containing an ionic compound consisting of an anion and a cation, wherein the anion is one selected from the group of anions consisting of a pentafluorobenzenecarboxylate anion, a pentafluorobenzenesulfonate anion, and a pentafluorophenoxy anion A pressure-sensitive adhesive composition is provided .
The pressure-sensitive adhesive polymer is (A) at least one alkyl (meth) acrylate monomer having an alkyl group with C1 to C14 carbon atoms and (B) at least a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group. and one is a copolymer comprising, per 100 parts by weight of the copolymer, the antistatic agent, (C) a said ionic compound 0.1 to 10 parts by weight, as essential components It is preferable to contain.
The pressure-sensitive adhesive polymer comprises (A) at least one alkyl (meth) acrylate monomer having a C1-C14 alkyl group, and (B ′) at least one copolymerizable vinyl monomer having a vinyl group, a copolymer comprising, per 100 parts by weight of the copolymer, the antistatic agent, it contains as an essential component from 0.1 to 20 parts by weight, the (C) the ionic compound preferable.
The adhesive polymer is a copolymer of at least two or more (A) an alkyl of carbon atoms in the alkyl group C1 to C14 (meth) acrylate monomer, per 100 parts by weight of the copolymer, the antistatic agent preferably contains as an essential component from 0.1 to 20 parts by weight, the (C) the ionic compound.
The surface resistance value of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is preferably 1.0 × 10 +12 Ω / □ or less.
The ionic compound is an ionic compound selected from the cation group consisting of pyridinium, imidazolium, sulfonium, phosphonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, and morpholinium as the cation component. Is preferred.
また、本発明は、基材の片面上に、前記粘着剤組成物からなる粘着剤層が積層されたことを特徴とする粘着フィルムを提供する。
また、本発明は、前記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。
また、本発明は、前記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。
また、本発明は、前記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。
また、本発明は、光学フィルムの少なくとも一方の面に、前記粘着剤組成物からなる粘着剤層が積層されている粘着剤付き光学フィルムを提供する。
また、本発明は、光学フィルムが偏光板である、前記記載の粘着剤付き光学フィルムを提供する。
また、本発明は、前記記載の粘着剤付き光学フィルムが、前記粘着剤層を介して貼り合わされてなる画像表示装置を提供する。
Moreover, this invention provides the adhesive film characterized by laminating | stacking the adhesive layer which consists of the said adhesive composition on the single side | surface of a base material.
Moreover, this invention provides the surface protection film using the said adhesive film.
Moreover, this invention provides the surface protection film for polarizing plates in which the said adhesive film was used.
Moreover, this invention provides the surface protection film for optics using the said adhesive film.
Moreover, this invention provides the optical film with an adhesive by which the adhesive layer which consists of the said adhesive composition is laminated | stacked on the at least one surface of the optical film.
Moreover, this invention provides the optical film with an adhesive of the said description whose optical film is a polarizing plate.
Moreover, this invention provides the image display apparatus by which the said optical film with an adhesive is bonded together through the said adhesive layer.
本発明によれば、ペンタフルオロベンゼン骨格を有する、比較的に安価な帯電防止剤を含有させた粘着剤を用いることで、粘着剤の全体コストを抑えることができ、帯電防止性やリワーク性などの欠点など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 having a pentafluorobenzene skeleton and containing a relatively inexpensive antistatic agent, the overall cost of the pressure-sensitive adhesive can be suppressed, and antistatic properties, reworkability, etc. It is possible to improve the problems such as the shortcomings.
以下、好適な実施の形態に基づいて本発明を説明する。
本発明の粘着剤組成物は、粘着剤の主剤となる粘着剤ポリマーと、帯電防止性能を付与する帯電防止剤を有し、この帯電防止剤として、ペンタフルオロフェニル基（Ｃ６Ｆ５基）を有する化合物であるペンタフルオロベンゼン化合物を含有することを特徴とする。
これにより、帯電防止性能に優れ、帯電防止性やリワーク性などの欠点などの課題を改善することが可能となる。
Hereinafter, the present invention will be described based on preferred embodiments.
The pressure-sensitive adhesive composition of the present invention has a pressure-sensitive adhesive polymer as a main component of a pressure-sensitive adhesive and an antistatic agent that imparts antistatic performance. As this antistatic agent, a pentafluorophenyl group (C 6 F 5 group). It contains the pentafluorobenzene compound which is a compound which has this.
Thereby, it is excellent in antistatic performance and it becomes possible to improve subjects, such as faults, such as antistatic property and rework property.
本発明に用いる粘着剤ポリマーとしては、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のアルキル（メタ）アクリレートモノマーの少なくとも１種を主成分とする共重合組成物が好ましい。
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーとしては、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）アクリレートなどが挙げられる。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。
The pressure-sensitive adhesive polymer used in the present invention is preferably an acrylic polymer, and in particular, (A) a copolymer composition mainly comprising at least one alkyl (meth) acrylate monomer having an alkyl group with C1 to C14 carbon atoms. Is preferred.
(A) Alkyl (meth) acrylate monomers having an alkyl group with C1 to C14 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 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 (meth) Examples include 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.
本発明に用いる粘着剤ポリマーとして、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレート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、（Ｂ′）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が挙げられる。
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。
上記以外の共重合性ビニルモノマーとしては、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、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。
As the pressure-sensitive adhesive polymer used in the present invention, a copolymer composition comprising (A) at least one alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 and at least one other copolymerizable monomer. You can also use things. In this case, examples of the other copolymerizable monomer include (B ′) a copolymerizable vinyl monomer having a vinyl group, and (B) a copolymerizable vinyl monomer having a hydroxyl group and / or a carboxyl group.
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.
Other copolymerizable vinyl monomers include aromatic group-containing (meth) acrylic esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, as well as styrene, acrylamide, acrylonitrile, methyl vinyl ether, ethyl vinyl ether And various vinyl monomers such as vinyl acetate and vinyl chloride.
また、本発明に用いる粘着剤ポリマーとして、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレート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のアルキル（メタ）アクリレート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 an adhesive polymer used for this invention, the copolymer composition which consists of at least 2 or more types of the alkyl (meth) acrylate monomer whose carbon number of (A) alkyl group is C1-C14 can also be employ | adopted. In this case, the copolymer composition can be obtained without using a copolymerizable vinyl monomer other than the alkyl (meth) acrylate monomer having (A) an alkyl group having C1 to C14 carbon atoms.
本発明の粘着剤組成物は、ペンタフルオロフェニル基（Ｃ６Ｆ５基）を有する化合物であるペンタフルオロベンゼン化合物を少なくとも１種以上、必須成分として含有する。このペンタフルオロベンゼン化合物は、帯電防止剤として、含有することが好ましい。下記（化１）の式に、ペンタフルオロベンゼン化合物の一般式を示す。式中、Ｙはアニオン性官能基や非イオン性ポリエーテル官能基などの帯電防止性能を有する官能基を含む部分構造を示す。 The pressure-sensitive adhesive composition of the present invention contains at least one pentafluorobenzene compound, which is a compound having a pentafluorophenyl group (C 6 F 5 group), as an essential component. This pentafluorobenzene compound is preferably contained as an antistatic agent. The general formula of the pentafluorobenzene compound is shown in the following formula (Chemical Formula 1). In formula, Y shows the partial structure containing the functional group which has antistatic performance, such as an anionic functional group and a nonionic polyether functional group.
本発明で用いられるペンタフルオロベンゼン化合物が非イオン性の場合に用いられるポリエーテル官能基としては、ポリエチレンオキサイド基やポリプロピレンオキサイド基などのポリアルキレンオキサイド基が挙げられる。前記ポリエーテル官能基の末端基としては、水素原子、アルキル基、アシル基、アミノ基などが挙げられる。 Examples of the polyether functional group used when the pentafluorobenzene compound used in the present invention is nonionic include polyalkylene oxide groups such as a polyethylene oxide group and a polypropylene oxide group. Examples of the terminal group of the polyether functional group include a hydrogen atom, an alkyl group, an acyl group, and an amino group.
本発明で用いられるペンタフルオロベンゼン化合物は、アニオンとカチオンとをからなるイオン性化合物であることが好ましく、さらにこのイオン性化合物が、ペンタフルオロフェニル基（Ｃ６Ｆ５基）を有する各種アニオンからなるアニオン群の中から選択された１種をアニオンとして有することが好ましい。
ペンタフルオロフェニル基（Ｃ６Ｆ５基）を有するアニオンとしては、Ｃ６Ｆ５基を有するカルボン酸アニオン（上記ＹにＣＯＯ−を含むアニオン）、Ｃ６Ｆ５基を有するスルホン酸アニオン（上記ＹにＳＯ３ −を含むアニオン）、Ｃ６Ｆ５基を有するホスホン酸アニオン（上記ＹにＰＯ３ ２−を含むアニオン）、Ｃ６Ｆ５基を有するアルコキシドもしくはフェノキシアニオン（上記ＹにＯ−を含むアニオン）、Ｃ６Ｆ５基を有するイミドアニオン（上記ＹにＮ−を含むアニオン）、Ｃ６Ｆ５基を有するメチドアニオン（上記ＹにＣ−を含むアニオン）、Ｃ６Ｆ５基を有するボレートアニオン（上記ＹにＢ−を含むアニオン）などが挙げられる。
Ｃ６Ｆ５基を有するアニオンの具体例としては、特に限定されるものではないが、Ｃ６Ｆ５ＣＯＯ−、Ｃ６Ｆ５（ＣＨ２）ｎＣＯＯ−、Ｃ６Ｆ５（ＣＦ２）ｎＣＯＯ−、Ｃ６Ｆ５Ｏ（ＣＨ２）ｎＣＯＯ−、Ｃ６Ｆ５（ＣＨ＝ＣＨ）ｎＣＯＯ−、Ｃ６Ｆ５ＳＯ３ −、Ｃ６Ｆ５（ＣＨ２）ｎＳＯ３ −、Ｃ６Ｆ５（ＣＦ２）ｎＳＯ３ −、Ｃ６Ｆ５Ｏ（ＣＨ２）ｎＳＯ３ −、Ｃ６Ｆ５（ＣＨ＝ＣＨ）ｎＳＯ３ −、Ｃ６Ｆ５Ｏ−、Ｃ６Ｆ５（ＣＨ２）ｎＯ−、Ｃ６Ｆ５（ＣＦ２）ｎＯ−、Ｃ６Ｆ５Ｏ（ＣＨ２）ｎＯ−、（Ｃ６Ｆ５）２ＣＨＯ−、（Ｃ６Ｆ５）３ＣＯ−、Ｃ６Ｆ５ＯＳＯ３ −、Ｃ６Ｆ５Ｏ（ＣＨ２）ｎＳＯ３ −、Ｃ６Ｆ５Ｏ（ＣＦ２）ｎＳＯ３ −、（Ｃ６Ｆ５ＣＯ）２Ｎ−、（Ｃ６Ｆ５ＣＯ）３Ｃ−、（Ｃ６Ｆ５ＳＯ２）２Ｎ−、（Ｃ６Ｆ５ＳＯ２）３Ｃ−、（Ｃ６Ｆ５ＯＳＯ２）２Ｎ−、（Ｃ６Ｆ５ＯＳＯ２）３Ｃ−、Ｃ６Ｆ５ＰＯ３ ２−、（Ｃ６Ｆ５）４Ｂ−などが挙げられる（ただし、ｎは１以上の整数）。
本発明で用いられるペンタフルオロベンゼン化合物は、特に、ペンタフルオロベンゼンカルボン酸アニオン（上記ＹがＣＯＯ−であるアニオン。すなわち、Ｃ６Ｆ５ＣＯＯ−）、ペンタフルオロベンゼンスルホン酸アニオン（上記ＹがＳＯ３ −であるアニオン。すなわち、Ｃ６Ｆ５ＳＯ３ −）、ペンタフルオロフェノキシアニオン（上記ＹがＯ−であるアニオン。すなわち、Ｃ６Ｆ５Ｏ−）からなる化合物群の中から選択された少なくとも１種以上をアニオンとして含有するイオン性化合物であることが好ましい。
The pentafluorobenzene compound used in the present invention is preferably an ionic compound composed of an anion and a cation, and the ionic compound is selected from various anions having a pentafluorophenyl group (C 6 F 5 group). It is preferable to have as an anion one selected from the anion group.
Examples of the anion having a pentafluorophenyl group (C 6 F 5 group) include a carboxylic acid anion having a C 6 F 5 group (anion containing COO − in the above Y), and a sulfonic acid anion having a C 6 F 5 group (above. An anion containing SO 3 — in Y), a phosphonic acid anion having a C 6 F 5 group (anion containing PO 3 2− in Y), an alkoxide having a C 6 F 5 group or a phenoxy anion (O − in Y above) An anion containing C 6 F 5 group (anion containing N − in Y above), a methide anion containing C 6 F 5 group (an anion containing C − in Y above), and a C 6 F 5 group. borate anion having - like (B in the Y anion containing).
Specific examples of the anion having a C 6 F 5 group are not particularly limited, but C 6 F 5 COO − , C 6 F 5 (CH 2 ) n COO − , C 6 F 5 (CF 2 ) n COO -, C 6 F 5 O (CH 2) n COO -, C 6 F 5 (CH = CH) n COO -, C 6 F 5 SO 3 -, C 6 F 5 (CH 2) n SO 3 - C 6 F 5 (CF 2 ) n SO 3 − , C 6 F 5 O (CH 2 ) n SO 3 − , C 6 F 5 (CH═CH) n SO 3 − , C 6 F 5 O − , C 6 F 5 (CH 2) n O -, C 6 F 5 (CF 2) n O -, C 6 F 5 O (CH 2) n O -, (C 6 F 5) 2 CHO -, (C 6 F 5 ) 3 CO − , C 6 F 5 OSO 3 − , C 6 F 5 O (CH 2 ) n SO 3 − , C 6 F 5 O (CF 2) n SO 3 -, (C 6 F 5 CO) 2 N -, (C 6 F 5 CO) 3 C -, (C 6 F 5 SO 2) 2 N -, (C 6 F 5 SO 2) 3 C - , (C 6 F 5 OSO 2) 2 N -, (C 6 F 5 OSO 2) 3 C -, C 6 F 5 PO 3 2-, (C 6 F 5) 4 B - like (where, n is an integer of 1 or more).
Pentafluorobenzene compound used in the present invention, particularly, pentafluoro benzene carboxylate anion (the Y is COO - anion is i.e., C 6 F 5 COO -. ), Pentafluorobenzenesulfonic acid anion (the Y is SO 3 - is an anion in which, C 6 F 5 SO 3 - .), pentafluorophenoxy anions (above Y is O - anion i.e., C 6 F 5 O is -. selected from a) a group of compounds It is preferable that it is an ionic compound which contains at least 1 type or more as an anion.
本発明に用いる粘着剤ポリマーの共重合組成物の１００重量部に対して、帯電防止剤が、（Ｃ）前記のペンタフルオロベンゼン化合物群の中から選択された１種をアニオンとして有するイオン性化合物を０．１〜２０重量部、さらに好ましくは０．１〜１０重量部、含有することが好ましい。 An ionic compound in which the antistatic agent has (C) one selected from the group of pentafluorobenzene compounds as an anion with respect to 100 parts by weight of the copolymer composition of the pressure-sensitive adhesive polymer used in the present invention. 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight.
前記イオン性化合物が、カチオン成分として、ピリジニウム、イミダゾリウム、スルホニウム、ホスホニウム、ピロリジニウム、グアニジニウム、アンモニウム、イソウロニウム、チオウロニウム、ピペリジニウム、ピラゾリウム、モルホリニウム等からなるカチオン群から選択した一種であるイオン性化合物であることが好ましい。
ピリジニウムカチオンとしては、例えば、１−ヘキシル−４−メチルピリジニウムカチオン、１−オクチル−４−メチルピリジニウムカチオン、１−ブチル−４−メチルピリジニウムカチオン、２−メチル−１−ドデシルピリジニウムカチオン、１−メチルピリジニウムカチオン、１−エチルピリジニウムカチオン、１−ブチルピリジニウムカチオン、１−ヘキシルピリジニウムカチオン、１−オクチルピリジニウムカチオン、１−ノニルピリジニウムカチオン、１−ドデシルピリジニウムカチオンなどが挙げられる。
イミダゾリウムカチオンとしては、例えば、１，３−ジメチルイミダゾリウムカチオン、１−エチル−３−メチルイミダゾリウムカチオン、１−ブチル−３−メチルイミダゾリウムカチオン、１−オクチル−３−メチルイミダゾリウムカチオン、１−ノニル−３−メチルイミダゾリウムカチオン、１−ドデシル−３−メチルイミダゾリウムカチオンなどが挙げられる。
ピロリジニウムカチオンとしては、例えば、１−メチル−１−エチルピロリジニウムカチオン、１−メチル−１−ブチルピロリジニウムカチオン、１−ブチル−１−ブチルピロリジニウムカチオン、１−オクチル−１−オクチルピロリジニウムカチオン、１−ブチル−１−オクチルピロリジニウムカチオン、１−ノニル−１−ノニルピロリジニウムカチオン、１−ドデシル−１−ドデシルピロリジニウムカチオンなどが挙げられる。
アンモニウムカチオンとしては、例えば、テトラブチルアンモニウムカチオン、テトラペンチルアンモニウムカチオン、トリオクチルメチルアンモニウムカチオン、トリメチルヘキシルアンモニウムカチオン、トリメチルプロピルアンモニウムカチオン、Ｎ，Ｎ−ジメチル−Ｎ，Ｎ−ジデシルアンモニウムカチオン、Ｎ，Ｎ−ジアリル−Ｎ−ヘキシル−Ｎ−メチルアンモニウムカチオンおよびトリメチルエチルアンモニウムカチオンなどの脂肪族アンモニウムカチオン；フェニルトリメチルアンモニウムカチオン、ジメチルエチルフェニルアンモニウムカチオン、ジエチルメチルフェニルアンモニウムカチオンなどの芳香族アンモニウムカチオンなどが挙げられる。
ピペリジニウムカチオンとしては、例えば、１−メチル−１−エチルピペリジニウムカチオン、１−メチル−１−ブチルピペリジニウムカチオン、１−ブチル−１−ブチルピペリジニウムカチオン、１−オクル−１−オクチルピペリジニウムカチオン、１−ブチル−１−オクチルピペリジニウムカチオンなどが挙げられる。
モルホリニウムカチオンとしては、例えば、４−メチル−４−エチルモルホリニウムカチオン、４−メチル−４−ブチルモルホリニウムカチオン、４−メチル−４−ヘキシルモルホリニウムカチオン、４−オクチル−４−オクチルモルホリニウムカチオン、４−ブチル−４−オクチルモルホリニウムカチオン、４−ノニル−４−ノニルモルホリニウムカチオン、４−ドデシル−４−ドデシルモルホリニウムカチオンなどが挙げられる。
ホスホニウムカチオンとしては、例えば、テトラブチルホスホニウムカチオン、トリイソブチルメチルホスホニウムカチオン、テトラペンチルホスホニウムカチオンおよびテトラヘキシルホスホニウムカチオンなどが挙げられる。
The ionic compound is a kind of ionic compound selected from a cation group consisting of pyridinium, imidazolium, sulfonium, phosphonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, morpholinium, and the like as a cation component. It is preferable.
Examples of the pyridinium cation include 1-hexyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 2-methyl-1-dodecylpyridinium cation, and 1-methyl. Examples thereof include a pyridinium cation, a 1-ethylpyridinium cation, a 1-butylpyridinium cation, a 1-hexylpyridinium cation, a 1-octylpyridinium cation, a 1-nonylpyridinium cation, and a 1-dodecylpyridinium cation.
Examples of the imidazolium cation include 1,3-dimethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, Examples include 1-nonyl-3-methylimidazolium cation and 1-dodecyl-3-methylimidazolium cation.
Examples of the pyrrolidinium cation include 1-methyl-1-ethylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-butyl-1-butylpyrrolidinium cation, and 1-octyl-1. -Octylpyrrolidinium cation, 1-butyl-1-octylpyrrolidinium cation, 1-nonyl-1-nonylpyrrolidinium cation, 1-dodecyl-1-dodecylpyrrolidinium cation and the like.
Examples of ammonium cations include tetrabutylammonium cation, tetrapentylammonium cation, trioctylmethylammonium cation, trimethylhexylammonium cation, trimethylpropylammonium cation, N, N-dimethyl-N, N-didecylammonium cation, N, Aliphatic ammonium cations such as N-diallyl-N-hexyl-N-methylammonium cation and trimethylethylammonium cation; aromatic ammonium cations such as phenyltrimethylammonium cation, dimethylethylphenylammonium cation and diethylmethylphenylammonium cation It is done.
Examples of the piperidinium cation include 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-butyl-1-butylpiperidinium cation, and 1-octyl-1. -Octylpiperidinium cation, 1-butyl-1-octylpiperidinium cation and the like.
Examples of the morpholinium cation include 4-methyl-4-ethylmorpholinium cation, 4-methyl-4-butylmorpholinium cation, 4-methyl-4-hexylmorpholinium cation, and 4-octyl-4. -Octylmorpholinium cation, 4-butyl-4-octylmorpholinium cation, 4-nonyl-4-nonylmorpholinium cation, 4-dodecyl-4-dodecylmorpholinium cation and the like.
Examples of the phosphonium cation include a tetrabutylphosphonium cation, a triisobutylmethylphosphonium cation, a tetrapentylphosphonium cation, and a tetrahexylphosphonium cation.
ピリジニウムカチオンとペンタフルオロベンゼン化合物のアニオンを有するイオン性化合物としては、例えば、１−ヘキシル−４−メチルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−ヘキシル−４−メチルピリジニウム ペンタフルオロフェノキシ塩、１−ヘキシル−４−メチルピリジニウム ペンタフルオロベンゼンスルホン酸塩、１−オクチル−４−メチルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−オクチル−４−メチルピリジニウム ペンタフルオロフェノキシ塩、１−オクチル−４−メチルピリジニウム ペンタフルオロベンゼンスルホン酸塩、１−ブチル−４−メチルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−ブチル−４−メチルピリジニウム ペンタフルオロフェノキシ塩、１−ブチル−４−メチルピリジニウム ペンタフルオロベンゼンスルホン酸塩、２−メチル−１−ドデシルピリジニウム ペンタフルオロベンゼンカルボン酸塩、２−メチル−１−ドデシルピリジニウム ペンタフルオロフェノキシ塩、２−メチル−１−ドデシルピリジニウム ペンタフルオロベンゼンスルホン酸塩、１−ブチルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−ブチルピリジニウム ペンタフルオロフェノキシ塩、１−ブチルピリジニウム ペンタフルオロベンゼンスルホン酸塩、１−オクチルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−オクチルピリジニウム ペンタフルオロフェノキシ塩、１−オクチルピリジニウム ペンタフルオロベンゼンスルホン酸塩、１−ノニルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−ノニルピリジニウム ペンタフルオロフェノキシ塩、１−ノニルピリジニウム ペンタフルオロベンゼンスルホン酸塩、１−ドデシルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−ドデシルピリジニウム ペンタフルオロフェノキシ塩、１−ドデシルピリジニウム ペンタフルオロベンゼンスルホン酸塩、１−オクチル−３，５ジメチルピリジニウム ペンタフルオロベンゼンカルボン酸塩、１−オクチル−３，５ジメチルピリジニウム ペンタフルオロフェノキシ塩、１−オクチル−３，５ジメチルピリジニウム ペンタフルオロベンゼンスルホン酸塩、などが挙げられる。
イミダゾリウムカチオンとペンタフルオロベンゼン化合物のアニオンを有するイオン性化合物としては、１−ブチル−３−メチルイミダゾリウム ペンタフルオロベンゼンカルボン酸塩、１−ブチル−３−メチルイミダゾリウム ペンタフルオロフェノキシ塩、１−ブチル−３−メチルイミダゾリウム ペンタフルオロベンゼンスルホン酸塩、１−オクチル−３−メチルイミダゾリウム ペンタフルオロベンゼンカルボン酸塩、１−オクチル−３−メチルイミダゾリウム ペンタフルオロフェノキシ塩、１−オクチル−３−メチルイミダゾリウム ペンタフルオロベンゼンスルホン酸塩、１−ノニル−３−メチルイミダゾリウム ペンタフルオロベンゼンカルボン酸塩、１−ノニル−３−メチルイミダゾリウム ペンタフルオロフェノキシ塩、１−ノニル−３−メチルイミダゾリウム ペンタフルオロベンゼンスルホン酸塩、１−ドデシル−３−メチルイミダゾリウム ペンタフルオロベンゼンカルボン酸塩、１−ドデシル−３−メチルイミダゾリウム ペンタフルオロフェノキシ塩、１−ドデシル−３−メチルイミダゾリウム ペンタフルオロベンゼンスルホン酸塩、などが挙げられる。
ピロリジニウムカチオンとペンタフルオロベンゼン化合物のアニオンを有するイオン性化合物としては、１−ブチル−１−ブチルピロリジニウム ペンタフルオロベンゼンカルボン酸塩、１−ブチル−１−ブチルピロリジニウム ペンタフルオロフェノキシ塩、１−ブチル−１−ブチルピロリジニウム ペンタフルオロベンゼンスルホン酸塩、１−オクチル−１−オクチルピロリジニウム ペンタフルオロベンゼンカルボン酸塩、１−オクチル−１−オクチルピロリジニウム ペンタフルオロフェノキシ塩、１−オクチル−１−オクチルピロリジニウム ペンタフルオロベンゼンスルホン酸塩、などが挙げられる。
Examples of the ionic compound having an anion of a pyridinium cation and a pentafluorobenzene compound include 1-hexyl-4-methylpyridinium pentafluorobenzenecarboxylate, 1-hexyl-4-methylpyridinium pentafluorophenoxy salt, and 1-hexyl. -4-methylpyridinium pentafluorobenzenesulfonate, 1-octyl-4-methylpyridinium pentafluorobenzenecarboxylate, 1-octyl-4-methylpyridinium pentafluorophenoxy salt, 1-octyl-4-methylpyridinium pentafluoro Benzenesulfonate, 1-butyl-4-methylpyridinium pentafluorobenzenecarboxylate, 1-butyl-4-methylpyridinium pentafluorophenoxy salt, 1-butyl- -Methylpyridinium pentafluorobenzenesulfonate, 2-methyl-1-dodecylpyridinium pentafluorobenzenecarboxylate, 2-methyl-1-dodecylpyridinium pentafluorophenoxy salt, 2-methyl-1-dodecylpyridinium pentafluorobenzenesulfone Acid salt, 1-butylpyridinium pentafluorobenzenecarboxylate, 1-butylpyridinium pentafluorophenoxy salt, 1-butylpyridinium pentafluorobenzenesulfonate, 1-octylpyridinium pentafluorobenzenecarboxylate, 1-octylpyridinium penta Fluorophenoxy salt, 1-octylpyridinium pentafluorobenzenesulfonate, 1-nonylpyridinium pentafluorobenzenecarboxylate 1-nonylpyridinium pentafluorophenoxy salt, 1-nonylpyridinium pentafluorobenzenesulfonate, 1-dodecylpyridinium pentafluorobenzenecarboxylate, 1-dodecylpyridinium pentafluorophenoxy salt, 1-dodecylpyridinium pentafluorobenzenesulfonate 1-octyl-3,5 dimethylpyridinium pentafluorobenzenecarboxylate, 1-octyl-3,5 dimethylpyridinium pentafluorophenoxy salt, 1-octyl-3,5 dimethylpyridinium pentafluorobenzenesulfonate, and the like It is done.
Examples of ionic compounds having an anion of an imidazolium cation and a pentafluorobenzene compound include 1-butyl-3-methylimidazolium pentafluorobenzenecarboxylate, 1-butyl-3-methylimidazolium pentafluorophenoxy salt, 1-butyl-3-methylimidazolium pentafluorobenzenecarboxylate, Butyl-3-methylimidazolium pentafluorobenzenesulfonate, 1-octyl-3-methylimidazolium pentafluorobenzenecarboxylate, 1-octyl-3-methylimidazolium pentafluorophenoxy salt, 1-octyl-3- Methyl imidazolium pentafluorobenzenesulfonate, 1-nonyl-3-methylimidazolium pentafluorobenzenecarboxylate, 1-nonyl-3-methylimidazolium pentafluorophenoxy salt, 1-noni -3-methylimidazolium pentafluorobenzenesulfonate, 1-dodecyl-3-methylimidazolium pentafluorobenzenecarboxylate, 1-dodecyl-3-methylimidazolium pentafluorophenoxy salt, 1-dodecyl-3-methyl And imidazolium pentafluorobenzene sulfonate.
Examples of ionic compounds having an anion of a pyrrolidinium cation and a pentafluorobenzene compound include 1-butyl-1-butylpyrrolidinium pentafluorobenzenecarboxylate, 1-butyl-1-butylpyrrolidinium pentafluorophenoxy salt 1-butyl-1-butylpyrrolidinium pentafluorobenzenesulfonate, 1-octyl-1-octylpyrrolidinium pentafluorobenzenecarboxylate, 1-octyl-1-octylpyrrolidinium pentafluorophenoxy salt, 1-octyl-1-octylpyrrolidinium pentafluorobenzenesulfonate, and the like.
前記粘着剤組成物からなる粘着剤層の表面抵抗値が１．０×１０＋１２Ω／□以下であることが好ましい。表面抵抗値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ため、表面抵抗値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、被着体の電気制御回路等に影響することを抑制することができる。 The surface resistance value of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is preferably 1.0 × 10 +12 Ω / □ or less. If the surface resistance value is large, the performance to release static electricity generated by electrification at the time of peeling is inferior. Therefore, by making the surface resistance value sufficiently small, the peeling band that occurs with the static electricity generated when the adherend peels off the adhesive layer The voltage is reduced, and it is possible to suppress the influence on the electric control circuit and the like of the adherend.
本発明の粘着剤組成物は、粘着剤層を形成する際に粘着剤ポリマーを架橋することが好ましい。架橋をするため、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化合物、２官能以上のエポキシ化合物、２官能以上のアクリレート化合物、金属キレート化合物などが挙げられる。
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。
The pressure-sensitive adhesive composition of the present invention preferably crosslinks the pressure-sensitive adhesive polymer when forming the pressure-sensitive adhesive layer. In order to perform crosslinking, the pressure-sensitive adhesive composition may contain a known crosslinking agent, or may be crosslinked by photocrosslinking such as ultraviolet (UV). Examples of the crosslinking agent include bifunctional or higher isocyanate compounds, bifunctional or higher epoxy compounds, bifunctional or higher acrylate compounds, and metal chelate compounds.
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.
本発明の粘着フィルムは、基材フィルムの片面上に、本発明の粘着剤組成物からなる粘着剤層が積層されたものである。本発明の粘着フィルムは、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に好適に用いることができる。
粘着剤層の基材フィルムや、粘着面を保護する剥離フィルム（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 of the present invention is obtained by laminating a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one side of a base film. The pressure-sensitive adhesive film of the present invention can be suitably used for a surface protective film, a surface protective film for polarizing plates, and an optical surface protective film.
As the base film of the pressure-sensitive adhesive layer and the release film (separator) that protects 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.
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.
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１．５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 a solvent (ethyl acetate) was added to the reaction apparatus together with 100 parts by weight of 2-ethylhexyl acrylate and 1.5 parts by weight of 6-hydroxyhexyl acrylate. 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 1 of Example 1 having a weight average molecular weight of 500,000 was obtained. Got.
[Examples 2-7 and Comparative Examples 1-2]
The monomer composition is used in Examples 2 to 7 and Comparative Examples 1 and 2 in the same manner as the acrylic copolymer solution 1 used in Example 1 except that the composition of each monomer is as shown in Table 1. An acrylic copolymer solution was obtained.
＜粘着剤組成物及び表面保護フィルムの製造＞
［実施例１］
上記のとおり製造したアクリル共重合体溶液１（そのうちアクリル共重合体が１００重量部）に対して、１−オクチルピリジニウム ペンタフルオロベンゼンカルボン酸塩１．０重量部、コロネートＨＸ（ヘキサメチレンジイソシアネート（ＨＤＩ）化合物のイソシアヌレート体）１．５重量部を加えて撹拌混合して実施例１の粘着剤組成物を得た。この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である粘着シートを得た。
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シートを転写させ、「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の表面保護フィルムを得た。
［実施例２〜７及び比較例１〜２］
添加剤の組成を各々、表１の記載のようにする以外は、上記の実施例１の表面保護フィルムと同様にして、実施例２〜７及び比較例１〜２の表面保護フィルムを得た。
<Production of pressure-sensitive adhesive composition and surface protective film>
[Example 1]
With respect to the acrylic copolymer solution 1 produced as described above (of which 100 parts by weight of the acrylic copolymer), 1.0 part by weight of 1-octylpyridinium pentafluorobenzenecarboxylate, coronate HX (hexamethylene diisocyanate (HDI ) Isocyanurate of compound) 1.5 parts by weight was added and mixed with stirring to obtain a pressure-sensitive adhesive composition of Example 1. After applying this adhesive composition on a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, the solvent is removed by drying at 90 ° C., and the adhesive layer has a thickness of 25 μm A sheet was obtained.
Then, the adhesive sheet 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. A surface protective film of Example 1 having a laminated structure of “PET film / adhesive layer / release film (silicone resin-coated PET film)” was obtained.
[Examples 2-7 and Comparative Examples 1-2]
The surface protective films of Examples 2 to 7 and Comparative Examples 1 and 2 were obtained in the same manner as the surface protective film of Example 1 except that the compositions of the additives were as described in Table 1. .
表１において、各成分の配合比は、アルキルアクリレートモノマーの合計（共重合性ビニルモノマーを用いた場合は、アルキルアクリレートモノマーと共重合性ビニルモノマーの合計）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。
In Table 1, the compounding ratio of each component is 100 parts by weight of the total of the alkyl acrylate monomers (when the copolymerizable vinyl monomer is used, the total of the alkyl acrylate monomer and the copolymerizable vinyl monomer). Numeric values are shown in parentheses. 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.
＜試験方法及び評価＞
実施例１〜７及び比較例１〜２における表面保護フィルムを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、粘着剤層を表出させたものを、表面抵抗値の測定試料とした。
さらに、この粘着剤層を表出させた表面保護フィルムを、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>
The surface protective films in Examples 1 to 7 and Comparative Examples 1 and 2 were aged in an atmosphere of 23 ° C. and 50% RH for 7 days, and then the release film (PET film coated with a silicone resin) was peeled off to form an adhesive layer. The surface resistance value was measured as a sample for measuring the surface resistance.
Further, the surface protective film on which the pressure-sensitive adhesive layer was exposed was bonded to the surface of the polarizing plate attached to the liquid crystal cell via the pressure-sensitive adhesive layer, and allowed to stand for 1 day, then at 50 ° C., 5 atm, 20 minutes. What was autoclaved and allowed to stand at room temperature for another 12 hours was used as a sample for measuring the adhesive strength.
＜粘着力＞
上記で得られた測定試料（２５ｍｍ幅の表面保護フィルムを偏光板の表面に貼り合わせたもの）を１８０°方向に引張試験機を用いて低速度（０．３ｍ／ｍｉｎ）及び高速度（３０ｍ／ｍｉｎ）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 measurement sample obtained above (a 25 mm wide surface protective film bonded to the surface of the polarizing plate) was rotated at a low speed (0.3 m / min) and a high speed (30 m) in a 180 ° direction using a tensile tester. / Min) was taken as the peel strength measured after peeling off.
＜表面抵抗＞
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表出し、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を測定した。
<Surface resistance>
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 resistance of the pressure-sensitive adhesive layer was measured.
上記の表１に、評価結果を示す。なお、表面抵抗値は、「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 1 shows the evaluation results. The surface resistance value 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の表面保護フィルムは、表面抵抗値が１．０×１０＋１２Ω／□以下であり、適度な粘着力を備えていた。すなわち、帯電防止性やリワーク性などの欠点などの課題を改善することができるものとなった。
比較例１〜２の表面保護フィルムは、表面抵抗値が１．０×１０＋１２Ω／□を超えており、帯電防止性に問題があるものとなった。さらに比較例１の表面保護フィルムは、粘着力が強すぎるため、リワーク性にも問題があるものとなった。
The surface protective films of Examples 1 to 7 had a surface resistance value of 1.0 × 10 +12 Ω / □ or less, and had appropriate adhesive strength. That is, problems such as defects such as antistatic properties and reworkability can be improved.
The surface protective films of Comparative Examples 1 and 2 had a surface resistance value exceeding 1.0 × 10 +12 Ω / □, and had problems with antistatic properties. Furthermore, the surface protective film of Comparative Example 1 has a problem in reworkability because the adhesive strength is too strong.
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| TW104115554A TWI510580B (en) | 2011-06-10 | 2012-05-07 | Adhesive composition containing an antistatic agent and adhesive film |
| CN201510257185.9A CN104861891A (en) | 2011-06-10 | 2012-06-05 | Adhesive composition containing anti-static agent and adhesion film |
| CN2012101828566A CN102816539A (en) | 2011-06-10 | 2012-06-05 | Antistatic agent-containing adhesive composition and adhesive film |
| KR1020120061694A KR20120137303A (en) | 2011-06-10 | 2012-06-08 | Adhesive composition containing antistatic agent and adhesive film |
| KR1020140183465A KR101636503B1 (en) | 2011-06-10 | 2014-12-18 | Adhesive composition containing antistatic agent, and adhesive film |
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| JP2020169338A (en) * | 2018-11-21 | 2020-10-15 | 藤森工業株式会社 | Adhesive layer including anti-static agent, and adhesive film |
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| JP2009126929A (en) * | 2007-11-22 | 2009-06-11 | Cheil Industries Inc | Adhesive composition, optical member and surface protective sheet |
| JP2009209257A (en) * | 2008-03-04 | 2009-09-17 | Toyo Ink Mfg Co Ltd | Resin for use in pressure-sensitive adhesive, and pressure-sensitive adhesive composition using it |
| JP5379168B2 (en) * | 2008-03-07 | 2013-12-25 | スリーエム イノベイティブ プロパティズ カンパニー | Antistatic lock copolymer pressure sensitive adhesive and article |
| JP5526645B2 (en) * | 2009-08-07 | 2014-06-18 | 東洋インキＳｃホールディングス株式会社 | Optical pressure-sensitive adhesive and optical pressure-sensitive adhesive sheet using the optical pressure-sensitive adhesive |
| JP5544800B2 (en) * | 2009-09-17 | 2014-07-09 | サイデン化学株式会社 | Surface protection film |
-
2011
- 2011-06-10 JP JP2011130157A patent/JP5734754B2/en active Active
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2012
- 2012-05-07 TW TW101116175A patent/TW201302949A/en unknown
- 2012-05-07 TW TW104115554A patent/TWI510580B/en active
- 2012-06-05 CN CN2012101828566A patent/CN102816539A/en active Pending
- 2012-06-05 CN CN201510257185.9A patent/CN104861891A/en active Pending
- 2012-06-08 KR KR1020120061694A patent/KR20120137303A/en active Application Filing
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020169338A (en) * | 2018-11-21 | 2020-10-15 | 藤森工業株式会社 | Adhesive layer including anti-static agent, and adhesive film |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201302949A (en) | 2013-01-16 |
| TWI510580B (en) | 2015-12-01 |
| KR20120137303A (en) | 2012-12-20 |
| JP2012255120A (en) | 2012-12-27 |
| KR20150013403A (en) | 2015-02-05 |
| KR101636503B1 (en) | 2016-07-06 |
| CN102816539A (en) | 2012-12-12 |
| KR20150023609A (en) | 2015-03-05 |
| TW201531541A (en) | 2015-08-16 |
| CN104861891A (en) | 2015-08-26 |
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