JP6635613B2 - Surface protection film - Google Patents
Surface protection film Download PDFInfo
- Publication number
- JP6635613B2 JP6635613B2 JP2018120711A JP2018120711A JP6635613B2 JP 6635613 B2 JP6635613 B2 JP 6635613B2 JP 2018120711 A JP2018120711 A JP 2018120711A JP 2018120711 A JP2018120711 A JP 2018120711A JP 6635613 B2 JP6635613 B2 JP 6635613B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- sensitive adhesive
- pressure
- cation
- 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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- 239000010408 film Substances 0.000 claims description 87
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 74
- -1 isooctyl Chemical group 0.000 claims description 62
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 37
- 239000010410 layer Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 35
- 230000001681 protective effect Effects 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 27
- 230000001070 adhesive effect Effects 0.000 claims description 27
- 239000002216 antistatic agent Substances 0.000 claims description 24
- 229920000058 polyacrylate Polymers 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 150000008040 ionic compounds Chemical group 0.000 claims description 17
- 239000012788 optical film Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- 238000011109 contamination Methods 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 229920000642 polymer Polymers 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
- 230000005611 electricity Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 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
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000005058 Isophorone 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 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
- 150000002513 isocyanates Chemical class 0.000 description 2
- 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 2
- 238000004898 kneading Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 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
- 238000012546 transfer Methods 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001244373 Carex spissa Species 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 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 group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 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 class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 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
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate 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
- DQPBABKTKYNPMH-UHFFFAOYSA-M amino sulfate Chemical compound NOS([O-])(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-M 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000008901 benefit 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
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 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
- 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 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
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000007689 inspection Methods 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical class [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 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
- 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
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000012545 processing Methods 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 class 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
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、帯電防止性能を有する粘着剤組成物を用いて、樹脂フィルムの少なくとも片面に帯電防止性能を有する粘着剤層を形成した表面保護フィルムを提供することに関する。本発明に係わる表面保護フィルムは、特に優れた帯電防止性能を有している。このため、静電気が発生し易いプラスチックフィルムが構成部材として使用されている偏光板、位相差板、反射防止フィルム等の、光学フィルムの表面を保護する目的で使用される。 The present invention relates to providing a surface protective film in which a pressure-sensitive adhesive layer having antistatic performance is formed on at least one surface of a resin film using a pressure-sensitive adhesive composition having antistatic performance. The surface protective film according to the present invention has particularly excellent antistatic performance. For this reason, it is used for the purpose of protecting the surface of an optical film such as a polarizing plate, a retardation plate, an anti-reflection film or the like in which a plastic film in which static electricity is easily generated is used as a component.
従来から、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、反射防止フィルムなどの、光学フィルムの製造工程においては、光学フィルムの表面を一時的に保護するための表面保護フィルムが貼着される。このような表面保護フィルムは、光学フィルムを製造する工程のみに使用され、光学フィルムを液晶ディスプレイに組み込む時点で、光学フィルムから剥離して除去される。このような光学フィルムの表面を保護するための表面保護フィルムは、製造工程においてのみに使用されるため、一般には、工程フィルムと呼ばれることもある。 Conventionally, in the process of manufacturing an optical film, such as a polarizing plate, a retardation plate, and an anti-reflection film, which are members of a liquid crystal display, a surface protection film for temporarily protecting the surface of the optical film is attached. Is done. Such a surface protection film is used only in a process of manufacturing an optical film, and is peeled off from the optical film when the optical film is incorporated into a liquid crystal display. Such a surface protection film for protecting the surface of the optical film is used only in a manufacturing process, and is generally called a process film.
このように、光学フィルム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。表面保護フィルムが、光学フィルム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。
また、偏光板、位相差板、反射防止フィルムなどの光学フィルムは、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、反射防止フィルムなどの光学フィルム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るため、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、反射防止フィルムなどの光学フィルムを、金属性の被着体、例えば、ベゼルなどに貼り合わせても腐食が起こらない、耐腐食性を有する粘着剤組成物が求められている。
また、最終的に偏光板、位相差板、反射防止フィルムなどの光学フィルムから表面保護フィルムを剥がすときには、被着体を汚染しないこと、いわゆる糊残りが起こらないことが求められている。
As described above, the surface protective film used in the process of manufacturing the optical film has the optically transparent polyethylene terephthalate (PET) resin film with the pressure-sensitive adhesive layer formed on one surface. Until the surface protection film is bonded to the optical film, a release film that has been subjected to a release treatment for protecting the pressure-sensitive adhesive layer is bonded on the pressure-sensitive adhesive layer.
In addition, optical films such as polarizing plates, retardation plates, and anti-reflection films, with surface protective films attached, are used for product inspections involving optical evaluations such as display performance, hue, contrast, and contamination of liquid crystal display panels. Therefore, as a required performance for the surface protective film, it is required that no bubbles or foreign matter adhere to the pressure-sensitive adhesive layer.
In recent years, when a surface protective film is peeled from an optical film such as a polarizing plate, a retardation plate, or an anti-reflection film, a peeling charge caused by static electricity generated when an adherend is peeled off an adhesive layer is a liquid crystal. Since there is a concern that this may affect the failure of the electric control circuit of the display, the adhesive layer is required to have excellent antistatic performance.
In addition, a pressure-sensitive adhesive composition that does not corrode even when an optical film such as a polarizing plate, a retardation film, or an antireflection film is bonded to a metal adherend, for example, a bezel, is required. Have been.
Further, when the surface protective film is finally peeled off from an optical film such as a polarizing plate, a retardation plate or an anti-reflection film, it is required that the adherend is not contaminated, that is, so-called adhesive residue does not occur.
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、（１）優れた帯電防止性能、（２）耐腐食性、（３）糊残りの発生防止などが、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（１）〜（３）のそれぞれ、個々の要求性能を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（１）〜（３）の全ての要求性能を、同時に満たすことは非常に困難な課題であった。
As described above, in recent years, the performance requirements for the pressure-sensitive adhesive layer constituting the surface protective film include (1) excellent antistatic performance, (2) corrosion resistance, and (3) prevention of generation of adhesive residue. There is a demand for ease of use when using a protective film.
However, even if each of these requirements (1) to (3), which is the required performance for the pressure-sensitive adhesive layer constituting the surface protective film, can be satisfied, the pressure-sensitive adhesive layer of the surface protective film is required. It has been a very difficult task to satisfy all the required performances of (1) to (3) at the same time.
例えば、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能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ている。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１）。
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。
For example, as for excellent antistatic performance, a method of kneading an antistatic agent into a base film and the like are disclosed as methods for imparting antistatic performance to a surface protective film. Examples of the antistatic agent include (a) various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt and a tertiary to tertiary amino group, (b) a sulfonate group, and sulfuric acid. Anionic antistatic agents having anionic groups such as ester bases, phosphate ester bases and phosphonate groups, (c) amphoteric antistatic agents such as amino acid-based and aminosulfate-based, (d) amino alcohol-based and glycerin-based And nonionic antistatic agents such as polyethylene glycol, and (e) a high molecular weight antistatic agent obtained by increasing the molecular weight of the above antistatic agent (Patent Document 1).
In recent years, it has been proposed that such an antistatic agent be contained in a base film or directly contained in a pressure-sensitive adhesive layer instead of being applied to the surface of a base film.
また、従来の帯電防止剤としてアルカリ金属塩を用いたものは、例えば、特許文献２において、（メタ）アクリル系ポリマーにイオン性物質として、過塩素酸のアルカリ金属塩、過塩素酸のアルカリ土類金属塩、有機ホウ素錯体のアルカリ金属塩、および有機ホウ素錯体のアルカリ土類金属塩からなる群から選ばれる１種を用いることが開示されている。しかし、アルカリ金属塩からなる帯電防止剤を含む粘着剤組成物は、金属腐食性を有するため、被着体が金属である場合には、腐食が生じるという問題があった。このため、優れた帯電防止性能と同時に、耐腐食性を有する粘着剤組成物が求められている。 Further, in the case where a conventional antistatic agent using an alkali metal salt is used, for example, in Patent Document 2, an alkali metal salt of perchloric acid or an alkaline earth perchlorate is used as an ionic substance in a (meth) acrylic polymer. It is disclosed to use one selected from the group consisting of a metal salt, an alkali metal salt of an organic boron complex, and an alkaline earth metal salt of an organic boron complex. However, since the pressure-sensitive adhesive composition containing an antistatic agent composed of an alkali metal salt has metal corrosiveness, there is a problem that corrosion occurs when the adherend is a metal. Therefore, a pressure-sensitive adhesive composition having excellent antistatic performance and corrosion resistance is required.
また、糊残りの発生防止については、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３）。
特許文献３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３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し、また、粘着剤の発泡や剥離を起こさないとしている。
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る。すなわち、誤って貼合したときに剥離が難しく、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、糊残リの発生防止には必要と考えられる。
Further, for the prevention of the generation of adhesive residue, for example, in an acrylic resin, a curing agent of an isocyanate compound and a specific silicate oligomer blended in an amount of 0.0001 to 10 parts by weight with respect to 100 parts by weight of the acrylic resin. An agent composition has been proposed (Patent Document 3).
In Patent Document 3, an alkyl acrylate having about 2 to 12 carbon atoms in an alkyl group or an alkyl methacrylate having about 4 to 12 carbon atoms in an alkyl group is used as a main monomer component. It is stated that the functional group-containing monomer component can be contained. In general, it is preferable to contain the main monomer 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 desired that the content be 0.01 to 25% by weight. The pressure-sensitive adhesive composition described in Patent Literature 3 has a small change over time in cohesive force and adhesive force even under high temperature or high temperature and high humidity, and has an excellent effect on curved surface adhesive force. It does not cause foaming or peeling of the agent.
In general, when the pressure-sensitive adhesive layer has a soft property, adhesive residue easily occurs. That is, when they are bonded by mistake, peeling is difficult, and re-bonding tends to be difficult. From this, it is considered necessary to crosslink the monomer having a functional group such as a carboxyl group to the main agent to make the pressure-sensitive adhesive layer a certain hardness in order to prevent the generation of adhesive residue.
また、糊残りの発生防止については、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４）。
また、上記と同様の共重合体に（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。しかし、これらは、表面張力が低くて表面が平滑なプラスチック板などの表面保護に使用すると、加工時や保存時の加熱により浮きなどの剥離現象を生じる問題があった。
The following proposals are known for preventing the generation of adhesive residue. Acrylic pressure-sensitive adhesive containing 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, which is subjected to a crosslinking treatment with a crosslinking agent. The layer has a problem that the adhesive is transferred to the adherend when adhered for a long period of time, and that the adhesive strength to the adherend is largely increased with time. In order to avoid this, a copolymer of an alkyl (meth) acrylate having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group is used, and this is cross-linked with a cross-linking agent. There is known a device provided with a pressure-sensitive adhesive layer (Patent Document 4).
In addition, a small amount of a copolymer of an alkyl (meth) acrylate and a carboxyl group-containing copolymerizable compound is blended with the same copolymer as described above, and a pressure-sensitive adhesive layer obtained by subjecting this to a crosslinking treatment with a crosslinking agent is provided. And so on. However, when these are used for protecting a surface of a plastic plate or the like having a low surface tension and a smooth surface, there is a problem that a peeling phenomenon such as floating occurs due to heating during processing or storage.
従来の帯電防止性能を有する粘着剤組成物は、優れた帯電防止性能が求められる用途において、帯電防止剤としてアルカリ金属塩が用いられてきた。しかし、アルカリ金属塩を用いると、被着体が金属の場合には腐食が生じることが問題であった。さらには、従来の表面保護フィルムは、被着体に対する汚染性を有していることから、表面保護フィルムに使用される粘着剤層に求められる要求性能を満たすことはできなかった。 In a conventional pressure-sensitive adhesive composition having antistatic performance, an alkali metal salt has been used as an antistatic agent in applications requiring excellent antistatic performance. However, when an alkali metal salt is used, corrosion occurs when the adherend is metal. Furthermore, since the conventional surface protective film has a property of contaminating an adherend, the performance required for the pressure-sensitive adhesive layer used for the surface protective film cannot be satisfied.
本発明は、上記の事情に鑑みてなされたものであり、優れた帯電防止性能を備え、さらには、耐腐食性を有し、汚染性が低い粘着剤組成物を用いた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, and provides a surface protection film using an adhesive composition having excellent antistatic performance, corrosion resistance, and low contamination. The task is to
本発明における粘着剤組成物は、融点が３０℃以上のイオン性化合物を含むことで、耐腐食性を有し、優れた帯電防止性能を得ることを技術思想としている。さらに、ヒドロキシル基を有する（メタ）アクリル系モノマーを含むことで、糊残りが少なく、汚染性が低い粘着剤組成物を得ることができる。このような粘着剤組成物を用いることにより、優れた帯電防止性能を備え、さらには、耐腐食性を有し、汚染性が低い粘着剤組成物、それを用いた粘着フィルム及び表面保護フィルムを提供することができる。 The technical idea of the pressure-sensitive adhesive composition of the present invention is to include an ionic compound having a melting point of 30 ° C. or higher to have corrosion resistance and to obtain excellent antistatic performance. Furthermore, by containing a (meth) acrylic monomer having a hydroxyl group, it is possible to obtain a pressure-sensitive adhesive composition having a small amount of adhesive residue and low contamination. By using such a pressure-sensitive adhesive composition, it has excellent antistatic performance, and further, has a corrosion resistance, a low-contamination pressure-sensitive adhesive composition, a pressure-sensitive adhesive film and a surface protection film using the same. Can be provided.
前記課題を解決するため、本発明は、アクリル系ポリマーと、帯電防止剤と、架橋剤とを含有する粘着剤組成物を架橋してなる粘着剤層が、樹脂フィルムの片面に形成してなる表面保護フィルムであって、前記アクリル系ポリマーが、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーの少なくとも１種と、（Ｂ）ヒドロキシル基を有する（メタ）アクリル系モノマーと、を共重合させた（メタ）アクリル系ポリマーであり、前記アクリル系ポリマーの１００重量部に対して、前記（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーの少なくとも１種以上のうち、イソオクチル（メタ）アクリレート、又は２−エチルヘキシル（メタ）アクリレートを５０重量部以上の割合で含有してなり、前記アクリル系ポリマーの酸価が３０以下であり、前記帯電防止剤が、融点が３０℃超かつ８０℃以下の温度３０℃で固体であるイオン性化合物であって、アルカリ金属塩でないイオン性化合物であり、前記粘着剤層を、樹脂フィルムの片面に形成した２５ｍｍ幅の表面保護フィルムを偏光板に貼り合せた測定試料を、引張試験機を用いて３０ｍ／ｍｉｎの引張速度で１８０°剥離して測定した剥離強度を粘着力とし、前記粘着剤層の粘着力が０．５〜１．２Ｎ／２５ｍｍであることを特徴とする表面保護フィルムを提供する。 In order to solve the above-mentioned problem, the present invention provides an acrylic polymer, an antistatic agent, and a pressure-sensitive adhesive layer formed by cross-linking a pressure-sensitive adhesive composition containing a cross-linking agent, which is formed on one surface of a resin film. A surface protection film, wherein the acrylic polymer has (A) at least one kind of a (meth) acrylate monomer having a C1 to C14 alkyl group and (B) a (meth) acryl having a hydroxyl group. A (meth) acrylic polymer obtained by copolymerizing a (meth) acrylic polymer with a (meth) acrylic ester having 100 to 100 parts by weight of the acrylic polymer. Isooctyl (meth) acrylate or 2-ethylhexyl (meth) acrylate is contained in at least 50 parts by weight of at least one kind of monomer. Te becomes, the and an acid value of the acrylic polymer is 30 or less, the antistatic agent, a melting point ionic compound is 30 ° C. Ultra and 80 ° C. temperature below 30 ° C. in a solid, an alkali metal salt Is a non- ionic compound , and a pressure-sensitive adhesive layer, a 25-mm-wide surface protection film formed on one side of a resin film, and a measurement sample obtained by laminating the same to a polarizing plate, were subjected to a tensile tester at a tensile speed of 30 m / min. Provided is a surface protection film characterized in that the peel strength measured by 180 ° peeling is defined as adhesive strength, and the adhesive strength of the adhesive layer is 0.5 to 1.2 N / 25 mm .
前記イオン性化合物が、カチオンとアニオンを有するイオン性化合物であって、前記カチオンが、ピリジニウムカチオン、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、ホスホニウムカチオン、スルホニウムカチオンからなる群から選択した１種であり、前記アニオンが、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 −）からなる群から選択した１種であることが好ましい。
前記粘着剤層のゲル分率が、９５〜１００％であることが好ましい。
前記表面保護フィルムは、偏光板の表面保護フィルムの用途として使用することが好ましい。また、前記樹脂フィルムの前記粘着剤層が形成された側とは反対面に、帯電防止および汚染防止処理がされていることが好ましい。
また、本発明は、前記表面保護フィルムが貼合された光学フィルムを提供する。
The ionic compound is an ionic compound having a cation and an anion, wherein the cation is selected from the group consisting of a pyridinium cation, a pyrimidinium cation, a pyrazolium cation, a pyrrolidinium cation, a phosphonium cation, and a sulfonium cation. And the anions are hexafluorophosphate (PF 6 − ), thiocyanate (SCN − ), alkylbenzene sulfonate (RC 6 H 4 SO 3 − ), perchlorate (ClO 2 − ). 4 - is preferably one selected from the group consisting of) -), tetrafluoroborate (BF 4.
The pressure-sensitive adhesive layer preferably has a gel fraction of 95 to 100%.
The surface protective film is preferably used as a surface protective film for a polarizing plate. Further, it is preferable that an antistatic and antifouling treatment is performed on a surface of the resin film opposite to a side on which the adhesive layer is formed.
Further, the present invention provides an optical film to which the surface protective film is attached.
本発明によれば、優れた帯電防止性能を備え、さらには、被着体に対する耐腐食性を有し、汚染性の低い粘着剤組成物、それを用いてなる粘着フィルム及び表面保護フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it has excellent antistatic performance, furthermore, it has corrosion resistance with respect to an adherend, and provides a low-contamination adhesive composition, an adhesive film and a surface protective film using the same. can do.
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、アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーを主成分とする、（メタ）アクリル系ポリマーを含む粘着剤組成物において、融点が３０℃以上のイオン性化合物を含むことを特徴とする。
また、本発明の粘着剤組成物は、アルキル基の炭素数が、Ｃ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーを主成分とする（メタ）アクリル系ポリマーを含む粘着剤組成物において、（メタ）アクリル系ポリマーの酸価が３０以下であり、融点が３０℃以上のイオン性化合物を含むことを特徴とする。
Hereinafter, the present invention will be described based on preferred embodiments.
The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a (meth) acrylic polymer whose main component is a (meth) acrylic acid ester monomer having a C1 to C14 alkyl group, and has a melting point of 30 ° C. It is characterized by containing the above ionic compound.
Further, the pressure-sensitive adhesive composition of the present invention includes a (meth) acryl-based polymer having a (meth) acrylic acid ester monomer having an alkyl group having a carbon number of C1 to C14 as a main component. ) The acrylic polymer has an acid value of 30 or less and contains an ionic compound having a melting point of 30 ° C. or more.
アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸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、イソプロピル（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、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（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。アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーは、（メタ）アクリル系ポリマーに対する重量比が、５０〜１００％であることが好ましい。 Examples of the (meth) acrylic acid ester monomer having a carbon number of an alkyl group of C1 to C14 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (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 (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate Cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched, or cyclic. The weight ratio of the (meth) acrylic acid ester monomer having a C1 to C14 alkyl group to the (meth) acrylic polymer is preferably 50 to 100%.
（メタ）アクリル系ポリマーは、ヒドロキシル基を有する（メタ）アクリル系モノマーを含むことが好ましい。ヒドロキシル基を有する（メタ）アクリル系モノマーとしては、８−ヒドロキシオクチル（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、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類や、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る。 The (meth) acrylic polymer preferably contains a (meth) acrylic monomer having a hydroxyl group. Examples of the (meth) acrylic monomer having a hydroxyl group include 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Examples include hydroxyalkyl (meth) acrylates, and hydroxyl group-containing (meth) acrylamides such as N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.
（メタ）アクリル系ポリマーは、カルボキシル基を含有する共重合可能なモノマーを含むことができる。カルボキシル基を含有する共重合可能なモノマーとしては、（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）アクリレートなどが挙げられる。
さらに、（メタ）アクリル系ポリマーは、上記以外の共重合性ビニルモノマーを含むことができる。他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。
ただし、カルボキシル基を含有するモノマー等の、酸性を示すモノマー（以下、酸性モノマーと呼ぶ）は、過度に添加されるとその酸により腐食性が大きくなるおそれがある。このため、（メタ）アクリル系ポリマーの酸価が、３０以下であることが好ましい。
ここで、「酸価」とは、酸の含有量を表す指標の一つであり、酸性成分を有しているポリマー１ｇを中和するのに要する、水酸化カリウムのｍｇ数で表される。
The (meth) acrylic polymer can include a copolymerizable monomer having a carboxyl group. Examples of the copolymerizable monomer having a carboxyl group include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate.
Further, the (meth) acryl-based polymer may contain a copolymerizable vinyl monomer other than the above. Other copolymerizable vinyl monomers include, besides aromatic group-containing (meth) acrylates such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, styrene, acrylamide, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, Various vinyl monomers such as vinyl acetate and vinyl chloride are exemplified.
However, a monomer showing an acidity (hereinafter, referred to as an acidic monomer) such as a monomer containing a carboxyl group may have an increased corrosiveness due to the acid if added excessively. For this reason, the (meth) acrylic polymer preferably has an acid value of 30 or less.
Here, the “acid value” is one of indexes indicating the content of an acid, and is represented by the number of mg of potassium hydroxide required to neutralize 1 g of a polymer having an acidic component. .
本発明の粘着剤組成物は、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、融点が３０℃以上のイオン性化合物である。このような帯電防止剤は、アルカリ金属塩に比べると融点が低いため、また、長鎖のアルキル基を有するため、アクリル共重合体との親和性は高いと推測される。 The pressure-sensitive adhesive composition of the present invention preferably contains an antistatic agent in order to impart antistatic performance. The antistatic agent is preferably a solid at ordinary temperature (for example, 30 ° C.), and more specifically, an ionic compound having a melting point of 30 ° C. or higher. Such an antistatic agent has a lower melting point than an alkali metal salt, and has a long-chain alkyl group, so that it is presumed that the affinity for the acrylic copolymer is high.
融点が３０℃以上のイオン性化合物としては、カチオンとアニオンを有するイオン性化合物であって、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℃以上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。イオン性化合物の融点は、３０〜８０℃が好ましい。カチオンが有してもよい置換基としては、アルキル基、アリール基などが挙げられる。前記イオン性化合物は、アルカリ金属塩ではないため、従来のアルカリ金属塩における金属腐食性を有するという問題を解決することができる。 As the ionic compound having a melting point of 30 ° C. or higher, an ionic compound having a cation and an anion, wherein the cation is a pyridinium cation, an imidazolium cation, a pyrimidinium cation, a pyrazolium cation, a pyrrolidinium cation, or ammonium A nitrogen-containing onium cation such as a cation, a phosphonium cation, a sulfonium cation, or the like, wherein the anions are hexafluorophosphate (PF 6 − ), thiocyanate (SCN − ), or alkylbenzene sulfonate (RC 6 H 4) Compounds that are inorganic or organic anions such as SO 3 − ), perchlorate (ClO 4 − ), and tetrafluoroborate (BF 4 − ) are exemplified. A resin having a melting point of 30 ° C. or more can be obtained by selecting the chain length of the alkyl group, the position and the number of the substituents, and the like. The cation is preferably a quaternary nitrogen-containing onium cation, and a quaternary pyridinium cation such as 1-alkylpyridinium (the carbon atoms at positions 2 to 6 may have a substituent or may be unsubstituted); Quaternary imidazolium cations such as 3-dialkylimidazolium (the carbon atoms at positions 2, 4, and 5 may have a substituent or unsubstituted), and quaternary ammonium cations such as tetraalkylammonium. . The melting point of the ionic compound is preferably from 30 to 80C. Examples of the substituent that the cation may have include an alkyl group and an aryl group. Since the ionic compound is not an alkali metal salt, it is possible to solve the problem of the conventional alkali metal salt having metal corrosiveness.
本発明の粘着剤組成物に用いられる主剤の（メタ）アクリル系ポリマーは、アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーの１種または２種以上を主成分とし、必要に応じて他のモノマーを添加して、重合させることで合成することができる。（メタ）アクリル系ポリマーの重合方法は特に限定されるものではなく、溶液重合、乳化重合等、適宜の重合方法が使用可能である。 The (meth) acryl-based polymer as a main component used in the pressure-sensitive adhesive composition of the present invention contains one or more (meth) acrylic acid ester monomers having a C1 to C14 alkyl group as a main component, and Can be synthesized by adding another monomer according to the above and polymerizing. The polymerization method of the (meth) acrylic polymer is not particularly limited, and an appropriate polymerization method such as solution polymerization and emulsion polymerization can be used.
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。架橋反応をさせるための方法としては、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官能または３官能以上のイソシアネート化合物、２官能または３官能以上のエポキシ化合物、２官能または３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、架橋促進剤、可塑剤、充填剤、硬化促進剤、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. As a method for causing a cross-linking reaction, the pressure-sensitive adhesive composition may include a known cross-linking agent, or may be cross-linked by photocross-linking such as ultraviolet (UV). Examples of the crosslinking agent include difunctional or trifunctional or more isocyanate compounds, difunctional or trifunctional or more functional epoxy compounds, difunctional or trifunctional or more acrylate compounds, and metal chelate compounds.
Furthermore, known additives such as a silane coupling agent, an antioxidant, a surfactant, a crosslinking accelerator, a plasticizer, a filler, a curing accelerator, a curing retarder, a processing aid, and an antioxidant are appropriately used as other components. Can be blended. These can be used alone or in combination of two or more.
前記粘着剤組成物を架橋させてなる粘着剤層の表面抵抗値は、５．０×１０＋１０Ω／□以下であることが好ましい。また、該粘着剤層の剥離帯電圧は、±０〜１ｋＶであることが好ましい。なお、本発明において、「±０〜１ｋＶ」とは、０〜−１ｋＶ及び０〜＋１ｋＶ、すなわち、−１〜＋１ｋＶを意味する。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 pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition preferably has a surface resistance of 5.0 × 10 +10 Ω / □ or less. The peeling voltage of the pressure-sensitive adhesive layer is preferably ± 0 to 1 kV. In the present invention, “± 0 to 1 kV” means 0 to −1 kV and 0 to +1 kV, that is, −1 to +1 kV. If the surface resistance value is large, the performance of releasing static electricity generated by charging at the time of peeling is inferior, so the peeling band caused by the static electricity generated when the adherend is peeled off the adhesive layer by reducing the surface resistance value sufficiently 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を架橋してなる粘着剤層（架橋後の粘着剤）のゲル分率は、９５〜１００％であることが好ましい。このようにゲル分率が高いことにより、低速度剥離領域における粘着力が過大にならず、共重合体からの未重合モノマーあるいはオリゴマーの溶出が低減して、汚染防止性や高温・高湿度における耐久性が改善され、被着体の汚染を抑制することができる。 The gel fraction of the pressure-sensitive adhesive layer (cross-linked pressure-sensitive adhesive) obtained by cross-linking the pressure-sensitive adhesive composition of the present invention is preferably 95 to 100%. With such a high gel fraction, the adhesive force in the low-speed peeling region does not become excessive, the elution of unpolymerized monomers or oligomers from the copolymer is reduced, and the anti-staining property and the high temperature and high humidity The durability is improved, and contamination of the adherend can be suppressed.
本発明の粘着フィルムは、本発明の粘着剤組成物を架橋してなる粘着剤層が、樹脂フィルムの片面または両面に形成してなる粘着フィルムである。また、本発明の表面保護フィルムは、本発明の粘着剤組成物を架橋してなる粘着剤層が、樹脂フィルムの片面に形成してなる表面保護フィルムである。本発明の粘着剤組成物は、優れた帯電防止性能を備え、さらには、被着体に対する耐腐食性を有し、汚染性が低いため、本発明の表面保護フィルムを被着体に貼り合わせ、粘着剤層を介して表面保護フィルムの上をボールペンでなぞった後に、被着体から剥がしても、被着体に汚染移行が無い。このため、偏光板の表面保護フィルムの用途として好適に使用することができる。 The pressure-sensitive adhesive film of the present invention is a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition of the present invention is formed on one or both sides of a resin film. Further, the surface protective film of the present invention is a surface protective film in which a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition of the present invention is formed on one surface of a resin film. The pressure-sensitive adhesive composition of the present invention has excellent antistatic performance, and further has corrosion resistance to the adherend and low contamination, so that the surface protective film of the present invention is bonded to the adherend. Even if the surface protective film is traced with a ballpoint pen through the pressure-sensitive adhesive layer and then peeled off from the adherend, there is no transfer of contamination to the adherend. Therefore, it can be suitably used as a surface protective film for a polarizing plate.
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汚染防止処理、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。
As the base film of the pressure-sensitive adhesive layer or 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 on which the pressure-sensitive adhesive layer of the resin film is formed, a silicone-based, fluorine-based release agent or coating agent, anti-contamination treatment with silica fine particles, etc. 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 fitted with the adhesive surface.
In the case of an optical surface protection film such as a polarizing plate surface protection 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 described specifically with reference to Examples.
＜粘着剤組成物の製造＞
［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、２−ヒドロキシエチルアクリレート５．０重量部とともに溶剤（酢酸エチル）を１００重量部加えた。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、アクリル共重合体溶液を得た。アクリル共重合体の一部を採取し、後述する酸価の測定試料として用いた。
このアクリル共重合体溶液に対して、１−オクチルピリジニウム 六フッ化リン酸塩１．５重量部、コロネートＨＸ（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）１．５重量部、ジオクチル錫ジラウレート０．０２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。
［実施例２〜４及び比較例１〜３］
モノマー及び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の粘着剤組成物と同様にして、実施例２〜４及び比較例１〜３の粘着剤組成物を得た。
ここで、（Ａ）アクリルモノマー、（Ｂ）水酸基モノマー、（Ｃ）酸性モノマーは、アクリル共重合体溶液の重合前に反応装置に加え、（Ｄ）イソシアネート（ＮＣＯ）架橋剤、（Ｅ）架橋促進剤、（Ｆ）帯電防止剤は、添加剤として、重合後のアクリル共重合体溶液に加えた。
<Production of pressure-sensitive adhesive composition>
[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 by weight of a solvent (ethyl acetate) was added to the reactor with 100 parts by weight of 2-ethylhexyl acrylate and 5.0 parts by weight of 2-hydroxyethyl acrylate. Thereafter, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours and reacted at 65 ° C. for 8 hours to obtain an acrylic copolymer solution. A part of the acrylic copolymer was collected and used as a sample for measuring an acid value described later.
1.5 parts by weight of 1-octylpyridinium hexafluorophosphate, 1.5 parts by weight of coronate HX (isocyanurate of hexamethylene diisocyanate compound) and 0.02 parts of dioctyltin dilaurate were added to this acrylic copolymer solution. The pressure-sensitive adhesive composition of Example 1 was obtained by adding parts by weight and stirring and mixing.
[Examples 2 to 4 and Comparative Examples 1 to 3]
Except that each of the composition of the monomer and the additive was as described in Table 1, the pressure-sensitive adhesive compositions of Examples 2 to 4 and Comparative Examples 1 to 3 were the same as in the pressure-sensitive adhesive composition of Example 1 described above. I got something.
Here, (A) an acrylic monomer, (B) a hydroxyl group monomer, and (C) an acidic monomer are added to a reaction apparatus before polymerization of an acrylic copolymer solution, and (D) an isocyanate (NCO) crosslinking agent, (E) a crosslinking agent. The accelerator and the antistatic agent (F) were added to the acrylic copolymer solution after polymerization as additives.
表１において、各成分の配合比は、（Ａ）群の合計を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、タケネート（登録商標）Ｄ−１４０Ｎは三井化学株式会社の商品名である。表２のイソシアネート（ＮＣＯ）架橋剤の化合物名において、ＨＤＩ、ＩＰＤＩ、ＴＭＰは、それぞれ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、トリメチロールプロパンを意味する。 In Table 1, the compounding ratio of each component is shown in parentheses by the numerical value of parts by weight obtained by assuming that the total of the group (A) is 100 parts by weight. Table 2 shows the compound names of the abbreviations of the components used in Table 1. Incidentally, Coronate (registered trademark) HX, HL and L-45 are trade names of Nippon Polyurethane Industry Co., Ltd., and Takenate (registered trademark) D-140N is a trade name of Mitsui Chemicals, Inc. In the compound names of the isocyanate (NCO) crosslinking agent in Table 2, HDI, IPDI, and TMP mean hexamethylene diisocyanate, isophorone diisocyanate, and trimethylolpropane, respectively.
＜表面保護フィルムの製造＞
実施例１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汚染防止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汚染防止処理された面とは反対の面に粘着シートを転写させ、「帯電防止及び汚染防止処理された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２〜４及び比較例１〜３］
実施例１の粘着剤組成物に代えて、それぞれ実施例２〜４及び比較例１〜３の粘着剤組成物を用いるほかは、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２〜４及び比較例１〜３の表面保護フィルムを得た。
<Manufacture of surface protection film>
After applying the pressure-sensitive adhesive composition of Example 1 on a release film composed of a silicone resin-coated polyethylene terephthalate (PET) film, the solvent was removed by drying at 90 ° C. to reduce the thickness of the pressure-sensitive adhesive layer. An adhesive sheet having a thickness of 25 μm was obtained. Then, an adhesive sheet is transferred to one side of the polyethylene terephthalate (PET) film which has been subjected to the antistatic and antifouling treatment, and the adhesive sheet is transferred to the surface opposite to the antistatic and antifouling treatment surface. The surface protection film of Example 1 having a laminated structure of “PET film / adhesive layer / peeling film (PET film coated with silicone resin)” was obtained.
[Examples 2 to 4 and Comparative Examples 1 to 3]
Except that the pressure-sensitive adhesive compositions of Examples 2 to 4 and Comparative Examples 1 to 3 are used instead of the pressure-sensitive adhesive composition of Example 1, the same procedures as in the surface protective film of Example 1 described above are performed. Surface protective films of Nos. 2 to 4 and Comparative Examples 1 to 3 were obtained.
＜試験方法及び評価＞
実施例１〜４及び比較例１〜３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、アルミ箔上に貼り合わせた後、６０℃、９０％ＲＨの高温高湿の雰囲気下で４８時間放置した後、腐食性の測定試料とした。
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、剥離帯電圧の測定試料とした。
<Test method and evaluation>
After aging the surface protective films in Examples 1 to 4 and Comparative Examples 1 to 3 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 pressure-sensitive adhesive layer was removed. Was bonded on an aluminum foil, and left in a high-temperature and high-humidity atmosphere of 60 ° C. and 90% RH for 48 hours to obtain a corrosive measurement sample.
Further, the surface protective film on which the pressure-sensitive adhesive layer was exposed was adhered to the surface of the polarizing plate pasted on the liquid crystal cell via the pressure-sensitive adhesive layer, and was left for 1 day. What was autoclaved and left at room temperature for further 12 hours was used as a sample for measuring adhesive strength and peeling voltage.
＜酸価の測定方法＞
アクリル共重合体の酸価は、試料を溶剤（ジエチルエーテルとエタノールを体積比２：１で混合したもの）に溶かし、電位差自動滴定装置（京都電子工業製、ＡＴ−６１０）を用いて、０．１上記電位差滴定装置を用い、濃度が約０．１ｍｏｌ／ｌの水酸化カリウムエタノール溶液で電位差滴定を行い、試料を中和するために必要な水酸化カリウムエタノール溶液の量を測定した。そして、下記式より、酸価を求めた。
酸価＝（Ｂ×ｆ×５．６１１）／Ｓ
Ｂ＝滴定に用いた０．１ｍｏｌ／ｌ水酸化カリウムエタノール溶液の量（ｍｌ）
ｆ＝０．１ｍｏｌ／ｌ水酸化カリウムエタノール溶液のファクター
Ｓ＝試料の固形分の質量（ｇ）
<Method of measuring acid value>
The acid value of the acrylic copolymer was determined by dissolving the sample in a solvent (diethyl ether and ethanol mixed at a volume ratio of 2: 1), and using an automatic potentiometric titrator (AT-610, manufactured by Kyoto Electronics Industry). Using the above potentiometric titrator, potentiometric titration was performed with a potassium hydroxide ethanol solution having a concentration of about 0.1 mol / l, and the amount of the potassium hydroxide ethanol solution necessary for neutralizing the sample was measured. Then, the acid value was determined from the following formula.
Acid value = (B × f × 5.611) / S
B = Amount (ml) of 0.1 mol / l potassium hydroxide ethanol solution used for titration
f = factor of 0.1 mol / l potassium hydroxide ethanol solution S = mass (g) of solid content of sample
＜粘着力の測定＞
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、引張速度３０ｍ／ｍｉｎにおいて剥がして測定した剥離強度（Ｎ／２５ｍｍ）を粘着力とした。
<Measurement of adhesive strength>
Peel strength obtained by peeling the measurement sample obtained above (a 25 mm wide surface protective film bonded to the surface of a polarizing plate) in a 180 ° direction using a tensile tester at a tensile speed of 30 m / min. (N / 25 mm) was defined as the adhesive strength.
＜剥離帯電圧の測定方法＞
上記で得られた測定試料を、３０ｍ／ｍｉｎの引張速度で１８０°剥離した際に、偏光板が帯電して発生する電圧（帯電圧）を、高精度静電気センサＳＫ−０３５、ＳＫ−２００（株式会社キーエンス製）を用いて測定し、測定値の最大値を剥離帯電圧（ｋＶ）とした。
<Method of measuring peeling voltage>
When the measurement sample obtained above was peeled at 180 ° at a tensile speed of 30 m / min, the voltage (charge voltage) generated by charging the polarizing plate was measured by the high-precision electrostatic sensors SK-035 and SK-200 ( (Manufactured by Keyence Corporation), and the maximum value of the measured values was taken as the peeling charge voltage (kV).
＜腐食性の評価方法＞
試料をアルミ箔上に貼り合わせた後、６０℃×９０％ＲＨの高温高湿条件下に４８ｈｒ放置した。その後、試料をアルミ箔から剥がし、アルミ箔表面を目視にて確認し、下記の基準で評価した。
○：アルミ箔表面に変色が確認されなかった。
△：アルミ箔表面に一部変色が確認された。
×：アルミ箔表面に変色が確認された。
<Evaluation method for corrosiveness>
After bonding the sample on an aluminum foil, the sample was left for 48 hours under a high temperature and high humidity condition of 60 ° C. × 90% RH. Thereafter, the sample was peeled off from the aluminum foil, the surface of the aluminum foil was visually checked, and evaluated according to the following criteria.
：: No discoloration was observed on the aluminum foil surface.
Δ: Discoloration was partially observed on the aluminum foil surface.
X: Discoloration was confirmed on the aluminum foil surface.
＜汚染性の評価方法＞
上記で得られた測定試料の表面保護フィルムの上を、ボールペンで（荷重５００ｇ、３往復）なぞった後、７０℃×２４ｈｒ放置した。偏光板から表面保護フィルムを剥離して偏光板の表面を観察し、偏光板に汚染移行の無いことを確認し、下記の基準で評価した。
○：偏光板に汚染移行が無かった。
△：ボールペンでなぞった軌跡に沿って、少なくとも一部に汚染移行が確認された。
×：ボールペンでなぞった軌跡に沿って、汚染移行が確認され、粘着剤表面からも粘着剤の離脱が確認された。
<Contamination evaluation method>
After tracing the surface protection film of the measurement sample obtained above with a ballpoint pen (load 500 g, 3 reciprocations), the sample was allowed to stand at 70 ° C. for 24 hours. The surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed. It was confirmed that the polarizing plate had no migration of contamination, and evaluated according to the following criteria.
：: No contamination was transferred to the polarizing plate.
Δ: Contamination transfer was confirmed at least partially along the locus traced with a ballpoint pen.
×: Contamination migration was confirmed along the locus traced by a ballpoint pen, and detachment of the pressure-sensitive adhesive was also confirmed from the surface of the pressure-sensitive adhesive.
試験及び評価の結果を、表３に示す。
融点が３０℃以上のイオン性化合物を帯電防止剤とした実施例１〜４では、帯電防止性能が優れ、さらに、被着体に対する耐腐食性を有し、汚染性も低いものとなった。
帯電防止剤に過塩素酸リチウム塩を用いた比較例１では、腐食性が大きく、汚染性もやや高いものとなった。
帯電防止剤にビス（トリフルオロメタンスルホニル）イミドリチウム塩を用い、粘着剤のアクリル系ポリマーの酸価が高い比較例２では、剥離帯電圧が高くて帯電防止性能が劣り、汚染性が高く、腐食性もやや大きいものとなった。
帯電防止剤にトリフルオロメタンスルホン酸リチウム塩を用いた比較例３では、腐食性がやや大きく、汚染性がやや高いものとなった。
このように、比較例１〜３の表面保護フィルムでは、（１）優れた帯電防止性能、（２）耐腐食性、（３）糊残りの発生防止を、同時に満たすことができなかった。
Table 3 shows the results of the test and the evaluation.
In Examples 1 to 4 in which an ionic compound having a melting point of 30 ° C. or more was used as an antistatic agent, the antistatic performance was excellent, the corrosion resistance to an adherend was low, and the contamination was low.
In Comparative Example 1 in which lithium perchlorate was used as the antistatic agent, the corrosiveness was large and the contamination was somewhat high.
Comparative Example 2 in which bis (trifluoromethanesulfonyl) imide lithium salt was used as the antistatic agent and the acid value of the acrylic polymer of the adhesive was high, the peeling voltage was high, the antistatic performance was poor, the contamination was high, and the corrosion was high. The sex has also become somewhat large.
In Comparative Example 3 in which lithium trifluoromethanesulfonate was used as the antistatic agent, the corrosiveness was slightly large and the contamination was slightly high.
As described above, the surface protective films of Comparative Examples 1 to 3 could not simultaneously satisfy (1) excellent antistatic performance, (2) corrosion resistance, and (3) prevention of adhesive residue.
Claims (4)
前記アクリル系ポリマーが、
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーの少なくとも１種と、（Ｂ）ヒドロキシル基を有する（メタ）アクリル系モノマーと、
を共重合させた（メタ）アクリル系ポリマーであり、
前記アクリル系ポリマーの１００重量部に対して、前記（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーの少なくとも１種以上のうち、イソオクチル（メタ）アクリレート、又は２−エチルヘキシル（メタ）アクリレートを５０重量部以上の割合で含有してなり、
前記アクリル系ポリマーの酸価が３０以下であり、
前記帯電防止剤が、融点が３０℃超かつ８０℃以下の温度３０℃で固体であるイオン性化合物であって、アルカリ金属塩でないイオン性化合物であり、
前記粘着剤層を、樹脂フィルムの片面に形成した２５ｍｍ幅の表面保護フィルムを偏光板に貼り合せた測定試料を、引張試験機を用いて３０ｍ／ｍｉｎの引張速度で１８０°剥離して測定した剥離強度を粘着力とし、前記粘着剤層の粘着力が０．５〜１．２Ｎ／２５ｍｍであることを特徴とする表面保護フィルム。 An acrylic polymer, an antistatic agent, and a pressure-sensitive adhesive layer formed by cross-linking a pressure-sensitive adhesive composition containing a cross-linking agent, a surface protective film formed on one surface of the resin film,
The acrylic polymer,
(A) at least one kind of (meth) acrylate monomer having a carbon number of C1 to C14 of an alkyl group, and (B) a (meth) acrylic monomer having a hydroxyl group;
Is a (meth) acrylic polymer obtained by copolymerizing
Of at least one kind of (meth) acrylic acid ester monomer in which the alkyl group (A) has C1 to C14, based on 100 parts by weight of the acrylic polymer, isooctyl (meth) acrylate or 2- Containing ethylhexyl (meth) acrylate in a proportion of 50 parts by weight or more,
The acid value of the acrylic polymer is 30 or less,
The antistatic agent is an ionic compound that has a melting point of more than 30 ° C. and is a solid at a temperature of 30 ° C. that is 80 ° C. or less, and is an ionic compound that is not an alkali metal salt;
The pressure-sensitive adhesive layer was bonded to a polarizing plate with a surface protection film having a width of 25 mm formed on one side of a resin film, and the measurement was performed by peeling 180 ° at a tensile speed of 30 m / min using a tensile tester. A surface protection film, wherein the peel strength is defined as adhesive strength, and the adhesive strength of the adhesive layer is 0.5 to 1.2 N / 25 mm.
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