JP4776272B2 - Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and surface protective film - Google Patents
Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and surface protective film Download PDFInfo
- Publication number
- JP4776272B2 JP4776272B2 JP2005135658A JP2005135658A JP4776272B2 JP 4776272 B2 JP4776272 B2 JP 4776272B2 JP 2005135658 A JP2005135658 A JP 2005135658A JP 2005135658 A JP2005135658 A JP 2005135658A JP 4776272 B2 JP4776272 B2 JP 4776272B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- perchlorate
- composition
- protective 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.)
- Expired - Fee Related
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 144
- 239000000203 mixture Substances 0.000 title claims description 142
- 230000001681 protective effect Effects 0.000 title claims description 75
- 229920000642 polymer Polymers 0.000 title claims description 30
- 230000001070 adhesive effect Effects 0.000 claims description 58
- 239000000853 adhesive Substances 0.000 claims description 55
- 239000000178 monomer Substances 0.000 claims description 50
- 239000010410 layer Substances 0.000 claims description 49
- 239000003093 cationic surfactant Substances 0.000 claims description 35
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 30
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- -1 isocyanate compound Chemical class 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 229920006243 acrylic copolymer Polymers 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 8
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 8
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 8
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 8
- 125000001033 ether group Chemical group 0.000 claims description 7
- 239000002985 plastic film Substances 0.000 claims description 6
- 229920006255 plastic film Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 239000002998 adhesive polymer Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 description 31
- 239000003431 cross linking reagent Substances 0.000 description 30
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 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 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000005058 Isophorone diisocyanate Chemical class 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- LKAWQFHWVVSFTR-UHFFFAOYSA-N 2-(methylamino)ethanol;hydrochloride Chemical compound [Cl-].C[NH2+]CCO LKAWQFHWVVSFTR-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 3
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000003419 tautomerization reaction Methods 0.000 description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000003756 stirring Methods 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
- 230000005641 tunneling Effects 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- QNRSQFWYPSFVPW-UHFFFAOYSA-N 5-(4-cyanobutyldiazenyl)pentanenitrile Chemical compound N#CCCCCN=NCCCCC#N QNRSQFWYPSFVPW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 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
- 239000013522 chelant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 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
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 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
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-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
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、粘着剤用重合体組成物、表面保護フィルム用粘着剤組成物および表面保護フィルムに関し、さらに詳しくは、プラスチック製品や金属製品の保護に適した適度な粘着力と剥離性に優れ、かつ帯電防止性を有する表面保護フィルム用粘着剤組成物の製造に有用な粘着剤用重合体組成物、表面保護フィルム用粘着剤組成物、および該組成物からなる粘着剤層を有する表面保護フィルムに関する。 The present invention relates to a polymer composition for pressure-sensitive adhesive, a pressure-sensitive adhesive composition for surface protective film, and a surface protective film, and more specifically, excellent in suitable adhesive force and peelability suitable for protection of plastic products and metal products, Polymer composition for pressure-sensitive adhesive useful for production of pressure-sensitive adhesive composition for surface protective film having antistatic property, pressure-sensitive adhesive composition for surface protective film, and surface protective film having a pressure-sensitive adhesive layer comprising the composition About.
一般に、プラスチック板や金属製品などの表面を保護するために表面保護フィルムが広く使用されている。該表面保護フィルム用粘着剤としては、耐候性や透明性の点からアクリル系粘着剤が多く使用されている。アクリル系粘着剤としては、（メタ）アクリル酸アルキルエステル単量体とカルボキシル基、水酸基またはエポキシ基などの官能基を含有する単量体とを共重合させた重合体を、ポリイソシアネート化合物、メラミン樹脂、エポキシ樹脂あるいは金属キレート化合物などで架橋させたものが使用されている。これらの表面保護フィルムの被着体である偏光フィルム、プラスチック板、家電製品、自動車、さらに電子機器などは、静電気対策、埃などの汚れの付着防止という観点から帯電防止性が必要とされていることから、表面保護フィルムにも同様に帯電防止性が要求されている。 In general, a surface protective film is widely used to protect the surface of a plastic plate or a metal product. As the pressure-sensitive adhesive for the surface protective film, many acrylic pressure-sensitive adhesives are used from the viewpoint of weather resistance and transparency. As the acrylic pressure-sensitive adhesive, a polymer obtained by copolymerizing a (meth) acrylic acid alkyl ester monomer and a monomer containing a functional group such as a carboxyl group, a hydroxyl group or an epoxy group, a polyisocyanate compound, a melamine Those crosslinked with a resin, an epoxy resin, a metal chelate compound or the like are used. Polarizing films, plastic plates, home appliances, automobiles, and electronic devices that are adherents to these surface protective films are required to have antistatic properties from the standpoint of countermeasures against static electricity and the prevention of adhesion of dirt such as dust. For this reason, the surface protection film is also required to have antistatic properties.
しかしながら、従来のゴム系粘着剤やアクリル系粘着剤は帯電防止性を有していないため、これらの粘着剤からなる粘着剤層を有する表面保護フィルムは、被着体からの剥離時において、静電気による電子機器などへの影響や、埃などの汚れが付着しやすいなどの問題がある。 However, since conventional rubber-based adhesives and acrylic-based adhesives do not have antistatic properties, surface protective films having an adhesive layer made of these adhesives are electrostatically charged when peeled off from the adherend. There are problems such as the effects on the electronic devices and the like, and dirt such as dust tends to adhere.
上記の問題を解決するために多くの手段が検討されてきた。例えば、特許文献１では第４級アンモニウム塩と層状珪酸塩を含有する熱可塑性樹脂もしくはゴムからなる粘着剤組成物が開示されている。しかし、このような粘着剤組成物では、様々なプラスチックフィルム基材に塗布して表面保護フィルムを得ることはできない。また、特許文献２ではプラスチックフィルム基材に第４級アンモニウム塩を含む帯電防止剤層を形成し、その上に粘着剤層を形成した帯電防止性粘着シートが開示されている。しかし、この帯電防止性粘着シートの場合には、上記の２層を個々に形成させなくてはならず実用的ではない。 Many means have been investigated to solve the above problems. For example, Patent Document 1 discloses a pressure-sensitive adhesive composition made of a thermoplastic resin or rubber containing a quaternary ammonium salt and a layered silicate. However, such a pressure-sensitive adhesive composition cannot be applied to various plastic film substrates to obtain a surface protective film. Patent Document 2 discloses an antistatic pressure-sensitive adhesive sheet in which an antistatic agent layer containing a quaternary ammonium salt is formed on a plastic film substrate, and an adhesive layer is formed thereon. However, in the case of this antistatic pressure-sensitive adhesive sheet, the above two layers must be formed individually, which is not practical.
さらに、特許文献３ではエーテル結合および／またはエステル結合を含む化合物、およびエーテル結合および／またはエステル結合を含む（共）重合体の群から選ばれた少なくとも１種、ならびにアルカリ金属またはアルカリ土類金属塩類を、アニオン吸着能を有する化合物でアニオンを吸着して得られる成分を含有することを特徴とする制電性組成物が開示されている。しかし、この特許文献３には、粘着剤用重合体組成物、表面保護フィルム用粘着剤組成物としての言及がなされていない。
本発明の目的は、優れた帯電防止性を有し、ポットライフが長く作業性が良好で、適度な粘着力を有し、経時的粘着力変化が少なく、被着体から剥離後に被着体表面が汚染されない表面保護フィルムであって、さらに加熱処理時のフクレやトンネリングの現象のない表面保護フィルム用粘着剤組成物に適した粘着剤用重合体組成物、表面保護フィルム用粘着剤組成物および該組成物からなる粘着剤層を有する表面保護フィルムを提供することである。 The object of the present invention is to provide an excellent antistatic property, a long pot life, good workability, a suitable adhesive force, little change in adhesive force over time, and adherend after peeling from the adherend. A surface protective film whose surface is not contaminated, and further a polymer composition for pressure-sensitive adhesives suitable for a pressure-sensitive adhesive composition for surface protective films which does not cause swelling or tunneling during heat treatment, and a pressure-sensitive adhesive composition for surface protective films And a surface protective film having a pressure-sensitive adhesive layer made of the composition.
以上の課題を解決するために、本発明者らは鋭意研究を重ねた結果、カチオン系界面活性剤と過塩素酸塩との両方を含有させた粘着剤組成物、またさらにリチウム塩を含有させた粘着剤組成物を用いることにより、今までに得られなかった良好な帯電防止性を有する表面保護フィルムが得られることを見出し、さらに、特定の架橋剤とケト−エノール互変異性を生じる化合物を添加することにより、ポットライフが長いにもかかわらず架橋速度が速く、養生期間を短縮でき、また、貼付初期と経時の粘着力の差が少なく、さらに、透明性が良好で剥離後の被着体表面への汚染がない表面保護フィルムを与える粘着剤組成物が得られることを見出し、本発明に至った。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, the pressure-sensitive adhesive composition containing both a cationic surfactant and a perchlorate, and further containing a lithium salt. It has been found that a surface protective film having a good antistatic property that has not been obtained so far can be obtained by using a pressure-sensitive adhesive composition, and a compound that causes keto-enol tautomerism with a specific crosslinking agent In addition, the crosslinking speed is fast despite the pot life being long, the curing period can be shortened, the difference in adhesive strength between the initial stage of application and time is small, and the transparency is good and the coating after peeling is good. The present inventors have found that a pressure-sensitive adhesive composition that gives a surface protective film free from contamination on the surface of the adherend can be obtained, and have led to the present invention.
すなわち、本発明は、カチオン系界面活性剤と過塩素酸塩とを粘着剤用重合体中に含有してなることを特徴とする粘着剤用重合体組成物を提供する。該組成物においては、さらにリチウム塩を含有してなること；カチオン系界面活性剤の含有量が、組成物の固形分の０．２〜７質量％を占める量であり、過塩素酸塩の含有量が、組成物の固形分の０．１〜５質量％を占める量であること；リチウム塩の含有量が、組成物の固形分の０．１〜２質量％を占める量であることが好ましい。 That is, this invention provides the polymer composition for adhesives characterized by including a cationic surfactant and a perchlorate in the polymer for adhesives. The composition further comprises a lithium salt; the content of the cationic surfactant is an amount that occupies 0.2 to 7% by mass of the solid content of the composition, and is a perchlorate salt. The content is an amount occupying 0.1 to 5% by mass of the solid content of the composition; the lithium salt content is an amount occupying 0.1 to 2% by mass of the solid content of the composition Is preferred.
また、本発明の粘着剤用重合体組成物においては、前記粘着剤用重合体が、水酸基を含有する共重合可能な単量体を全単量体中において０．１〜８質量％を占める量、およびエーテル基を含有する共重合可能な単量体を全単量体中において０．５〜１０質量％を占める量で含む（メタ）アクリル酸アルキルエステル単量体を主成分とする単量体組成物からなるアクリル系共重合体であることが好ましい。 Moreover, in the polymer composition for adhesives of this invention, the said polymer for adhesives occupies 0.1-8 mass% in all the monomers which can copolymerize the monomer containing a hydroxyl group. And a monomer comprising a (meth) acrylic acid alkyl ester monomer as a main component, containing a copolymerizable monomer containing an ether group in an amount of 0.5 to 10% by mass in all monomers. An acrylic copolymer made of a monomer composition is preferred.
また、本発明は、カチオン系界面活性剤と過塩素酸塩とを粘着剤成分中に含有してなることを特徴とする表面保護フィルム用粘着剤組成物を提供する。該組成物においては、さらにリチウム塩を含有してなること；粘着剤成分が、アクリル系共重合体（Ａ）と、脂肪族系および／または脂環族系の多官能イソシアネート系化合物および／または多官能イソシアヌレート系化合物（Ｂ）と、ケト−エノール互変異性を生じる化合物（Ｃ）とからなり、カチオン系界面活性剤の含有量が、カチオン系界面活性剤と過塩素酸塩と上記重合体（Ａ）の合計量の０．２〜７質量％を占める量であり、過塩素酸塩の含有量が、カチオン系界面活性剤と過塩素酸塩と上記重合体（Ａ）の合計量の０．１〜５質量％を占める量であること；およびリチウム塩の含有量が、カチオン系界面活性剤と過塩素酸塩と上記重合体（Ａ）の合計量の０．１〜２質量％を占める量であることが好ましい。 Moreover, this invention provides the adhesive composition for surface protection films characterized by including a cationic surfactant and perchlorate in an adhesive component. The composition further comprises a lithium salt; the pressure-sensitive adhesive component is an acrylic copolymer (A), an aliphatic and / or alicyclic polyfunctional isocyanate compound, and / or It consists of a polyfunctional isocyanurate compound (B) and a compound (C) that produces keto-enol tautomerism, and the content of the cationic surfactant is such that the cationic surfactant, perchlorate, It is an amount that occupies 0.2 to 7% by mass of the total amount of the union (A), and the content of perchlorate is the total amount of the cationic surfactant, perchlorate, and the polymer (A). And the lithium salt content is 0.1 to 2 mass of the total amount of the cationic surfactant, perchlorate and the polymer (A). % Is preferred.
また、上記本発明の表面保護フィルム用粘着剤組成物においては、アクリル系共重合体（Ａ）が、水酸基を含有する共重合可能な単量体を全単量体中において０．１〜８質量％を占める量、およびエーテル基を含有する共重合可能な単量体を全単量体中において０．５〜１０質量％を占める量で含む（メタ）アクリル酸アルキルエステル単量体を主成分とする単量体組成物からなるアクリル系共重合体であることが好ましい。 In the pressure-sensitive adhesive composition for a surface protective film of the present invention, the acrylic copolymer (A) contains 0.1 to 8 copolymerizable monomers containing a hydroxyl group in all monomers. The main component is a (meth) acrylic acid alkyl ester monomer containing an amount accounting for 0.5% by mass and a copolymerizable monomer containing an ether group in an amount accounting for 0.5 to 10% by mass in all monomers. An acrylic copolymer comprising a monomer composition as a component is preferred.
また、本発明は、プラスチックフィルム基材の表面に前記本発明の粘着剤組成物からなる粘着剤層を有することを特徴とする表面保護フィルムを提供する。 Moreover, this invention provides the surface protection film characterized by having the adhesive layer which consists of an adhesive composition of the said this invention on the surface of a plastic film base material.
本発明の粘着剤組成物は、適度な粘着力を有し、基材に対する密着性が良く、優れた帯電防止性を有し、再剥離性やポットライフも良好であることから、偏光フィルム、プラスチック板、家電製品、自動車および電子機器などの物品の表面保護フィルム用として有利に使用することができる。また、本発明の粘着剤組成物は、架橋速度が早いことから、表面保護フィルムの製造に際し加熱熟成したり、室温で長期間養生する必要がなく、表面保護フィルムの生産性を向上させることができる。 The pressure-sensitive adhesive composition of the present invention has a suitable pressure-sensitive adhesive force, has good adhesion to a substrate, has excellent antistatic properties, has good removability and pot life, a polarizing film, It can be advantageously used as a surface protective film for articles such as plastic plates, home appliances, automobiles and electronic devices. In addition, since the pressure-sensitive adhesive composition of the present invention has a high crosslinking rate, there is no need for heat aging in the production of the surface protective film or curing for a long time at room temperature, thereby improving the productivity of the surface protective film. it can.
次に発明を実施するための最良の形態を挙げて本発明をさらに詳しく説明する。本発明の粘着剤用重合体組成物は、カチオン系界面活性剤と過塩素酸塩とを粘着剤用重合体中に含有してなることを特徴としている。該粘着剤用重合体組成物は、これに架橋剤などの必要な添加剤を添加して、後述する本発明の粘着剤組成物を製造する原料もしくは中間体として有用である。 Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention. The polymer composition for pressure-sensitive adhesives of the present invention is characterized by containing a cationic surfactant and a perchlorate in a polymer for pressure-sensitive adhesives. The polymer composition for pressure-sensitive adhesives is useful as a raw material or an intermediate for producing the pressure-sensitive adhesive composition of the present invention to be described later by adding necessary additives such as a crosslinking agent thereto.
本発明に使用するカチオン系界面活性剤は、表面保護フィルムに用いられる粘着剤組成物に帯電防止性を持たせるために必要である。該カチオン系界面活性剤は溶剤可溶なものが使用でき、例えば、アルキルアミン塩、第４級アンモニウム塩および構造式は不明であるがニューエレガンＡ（商品名、日本油脂（株）製）などが挙げられ、具体的にはステアリルアミンアセテート、塩化アルキルビス（２−ヒドロキシエチル）メチルアンモニウム、ラウリルトリメチルアンモニウムクロライドなどが挙げられる。 The cationic surfactant used in the present invention is necessary for imparting antistatic properties to the pressure-sensitive adhesive composition used for the surface protective film. As the cationic surfactant, a solvent-soluble one can be used. For example, alkylamine salt, quaternary ammonium salt and New Elegan A (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), whose structural formula is unknown. Specific examples include stearylamine acetate, alkylbis (2-hydroxyethyl) methylammonium chloride, lauryltrimethylammonium chloride, and the like.
カチオン系界面活性剤の使用量は、組成物の固形分の０．２〜７質量％を占める量であり、好ましくは１〜５質量％を占める量である。使用量が０．２〜７質量％の範囲内であれば、最終的に得られる粘着剤組成物の粘着物性を損なうことなく、また、粘着剤層の透明性を維持したまま良好な帯電防止性を有し、カチオン系界面活性剤が、得られる粘着剤組成物表面にブリードアウトすることはない。 The usage-amount of a cationic surfactant is the quantity which occupies 0.2-7 mass% of solid content of a composition, Preferably it is the quantity which occupies 1-5 mass%. If the amount used is in the range of 0.2 to 7% by mass, good antistatic properties can be obtained while maintaining the transparency of the pressure-sensitive adhesive layer without impairing the physical properties of the pressure-sensitive adhesive composition finally obtained. The cationic surfactant does not bleed out on the surface of the resulting pressure-sensitive adhesive composition.
本発明に使用する過塩素酸塩は、上記のカチオン系界面活性剤を単独で使用した場合、充分な帯電防止性を得られないが、過塩素酸塩を使用することにより帯電防止効果を向上させることができる。これに対して上記カチオン系界面活性剤を必要以上に多く使用しても帯電防止性の向上効果はなく、むしろ粘着剤組成物の粘着物性に悪影響をもたらすが、過塩素酸塩を併用することによりこのような悪影響は解消される。該過塩素酸塩としては、過塩素酸ナトリウム、過塩素酸カリウム、過塩素酸リチウムなどが挙げられる。その使用量は組成物の固形分の０．１〜５質量％を占める量である。添加量が０．１〜５質量％の範囲内であれば、粘着剤組成物の粘着物性を損なうことなく、また、表面保護フィルムにおける粘着剤層の透明性を維持することができる。 The perchlorate used in the present invention cannot obtain sufficient antistatic properties when the above cationic surfactant is used alone, but the antistatic effect is improved by using perchlorate. Can be made. On the other hand, even if the above cationic surfactant is used more than necessary, there is no effect of improving the antistatic property, but rather adversely affects the adhesive properties of the adhesive composition. This eliminates such adverse effects. Examples of the perchlorate include sodium perchlorate, potassium perchlorate, and lithium perchlorate. The amount used is an amount occupying 0.1 to 5% by mass of the solid content of the composition. If the addition amount is within the range of 0.1 to 5% by mass, the transparency of the pressure-sensitive adhesive layer in the surface protective film can be maintained without impairing the physical properties of the pressure-sensitive adhesive composition.
上記本発明の粘着剤用重合体組成物は、さらに過塩素酸リチウム以外のリチウム塩を含有することが好ましい。ここで使用するリチウム塩は、上記のカチオン系界面活性剤と過塩素酸塩とを併用した場合より、最終的に得られる表面保護フィルムにさらなる優れた帯電防止効果を与えることができる。このようなリチウム塩としては、例えば、トリフルオロメタンスルホン酸リチウムやリチウムビストリフルオロメタンスルホンイミドなどが挙げられる。その使用量は、組成物の固形分の０．１〜２質量％を占める量である。使用量が０．１〜２質量％の範囲内であれば、粘着剤組成物の粘着物性を損なうことなく、また、表面保護フィルムにおける粘着剤層の透明性を維持することができ、経済的にも良好な範囲である。 The polymer composition for pressure-sensitive adhesives of the present invention preferably further contains a lithium salt other than lithium perchlorate. The lithium salt used here can give a further excellent antistatic effect to the finally obtained surface protective film, compared with the case where the above cationic surfactant and perchlorate are used in combination. Examples of such a lithium salt include lithium trifluoromethanesulfonate and lithium bistrifluoromethanesulfonimide. The amount used is an amount occupying 0.1 to 2% by mass of the solid content of the composition. If the amount used is in the range of 0.1 to 2% by mass, the transparency of the pressure-sensitive adhesive layer in the surface protective film can be maintained without impairing the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition. It is also a good range.
従来、帯電防止剤を含有しないアクリル粘着剤からなる粘着剤層の表面抵抗は１０15〜１０16Ωであり、帯電防止剤と言われる各種界面活性剤をアクリル粘着剤に添加した場合、両者が混合しなかったり、粘着剤の粘着物性に悪影響を与えたり、与えないまでもその表面抵抗は１０13〜１０14Ωと帯電防止効果が少なかった。カチオン系界面活性剤と過塩素酸塩と、あるいはさらにリチウム塩を用いる本発明により、粘着剤層の表面抵抗は１０7〜１０11Ωとなり、粘着剤層が優れた帯電防止性を有するようになる。 Conventionally, the surface resistance of the pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive containing no antistatic agent is 10 15 to 10 16 Ω, and when various surfactants called antistatic agents are added to the acrylic pressure-sensitive adhesive, The surface resistance was 10 13 to 10 14 Ω and the antistatic effect was small even when the mixture was not mixed or the adhesive properties of the adhesive were adversely affected or not given. According to the present invention using a cationic surfactant and perchlorate, or further a lithium salt, the surface resistance of the pressure-sensitive adhesive layer is 10 7 to 10 11 Ω so that the pressure-sensitive adhesive layer has excellent antistatic properties. Become.
以上のカチオン系界面活性剤、過塩素酸塩およびリチウム塩は、粘着剤用重合体の製造時の単量体中に存在させてもよいし、重合反応媒体中に存在させてもよいし、得られる重合体中に添加してもよく、何れにしても帯電防止効果には全く差異はなく、上記添加時期は適宜に選択することができる。 The above cationic surfactant, perchlorate and lithium salt may be present in the monomer during the production of the adhesive polymer, or may be present in the polymerization reaction medium, It may be added to the resulting polymer, and in any case, there is no difference in the antistatic effect, and the addition timing can be appropriately selected.
上記カチオン系界面活性剤および過塩素酸塩、あるいはさらにリチウム塩が添加される粘着剤用重合体は、ゴム系、アクリル系およびウレタン系粘着剤などが挙げられるが、好ましくはアクリル系共重合体である。好ましいアクリル系共重合体（Ａ）は、（メタ）アクリル酸アルキルエステル単量体を主成分とし、水酸基を含有する共重合可能な単量体組成物およびエーテル基を含有する共重合可能な単量体組成物を共重合してなる共重合体であり、必要に応じてカルボキシル基を含有する共重合可能な単量体組成物を共重合することができる。なお、本発明の特許請求の範囲および明細書における「（メタ）アクリル」という用語は、「アクリル」および「メタクリル」の双方を意味する。 Examples of the polymer for pressure-sensitive adhesive to which the cationic surfactant and perchlorate or further lithium salt are added include rubber-based, acrylic-based and urethane-based pressure-sensitive adhesives, preferably acrylic-based copolymers. It is. A preferred acrylic copolymer (A) is composed of a (meth) acrylic acid alkyl ester monomer as a main component, a copolymerizable monomer composition containing a hydroxyl group, and a copolymerizable monomer containing an ether group. It is a copolymer obtained by copolymerizing a monomer composition, and a copolymerizable monomer composition containing a carboxyl group can be copolymerized as necessary. The term “(meth) acryl” in the claims and the specification of the present invention means both “acryl” and “methacryl”.
上記（メタ）アクリル酸アルキルエステル単量体としては、アルキル基の炭素数が４以上のものが好ましく、より好ましくは４〜１４のものであり、具体的には、ブチル基、ペンチル基、ヘキシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基を有する炭素数４〜１４のアルキルアルコールと（メタ）アクリル酸のエステル化合物からなる単量体であり、これらより選ばれる少なくとも１種を使用することができる。なお、アルキル基は直鎖でも分岐鎖でも使用することができる。該（メタ）アクリル酸アルキルエステル単量体の使用量は、全単量体中において６７．７〜９９．０質量％を占める量である。使用量が６７．７質量％より少ない場合は、最終的に得られる粘着剤組成物の粘着力が低くなり、表面保護フィルムとした場合に被着体からの浮きや剥れを生じやすい。 The (meth) acrylic acid alkyl ester monomer preferably has an alkyl group having 4 or more carbon atoms, more preferably 4 to 14 carbon atoms, specifically, a butyl group, a pentyl group, or a hexyl group. It is a monomer comprising an alkyl alcohol having 4 to 14 carbon atoms having a group, undecyl group, dodecyl group, tridecyl group or tetradecyl group and an ester compound of (meth) acrylic acid, and at least one selected from these is used. be able to. The alkyl group can be used as a straight chain or a branched chain. The amount of the (meth) acrylic acid alkyl ester monomer used is an amount occupying 67.7 to 99.0% by mass in all monomers. When the amount used is less than 67.7% by mass, the adhesive strength of the finally obtained pressure-sensitive adhesive composition becomes low, and when it is used as a surface protective film, it tends to float or peel off from the adherend.
本発明に使用する水酸基を含有する共重合可能な単量体としては、具体的には、２−ヒドロキシエチル（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−ヒドロキシプロピル（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレートおよびポリプロピレングリコール（メタ）アクリレートなどが挙げられ、これらの群より選ばれる少なくとも１種を使用することができる。水酸基を含有する共重合可能な単量体の使用量は、全単量体中において０．１〜８質量％を占める量であることが必要である。好ましくは０．５〜６質量％、より好ましくは１〜５質量％を占める量である。その使用量が０．１質量％より少ない場合、後述する架橋剤（Ｂ）を添加した場合に架橋点が少なく十分な凝集力が得られず、表面保護フィルムを作成した場合には、該表面保護フィルムを物品表面に貼着しその剥離後に粘着剤層の凝集破壊により被着体へ粘着剤の転着が起こる。一方、その使用量が８質量％より多い場合は、粘着剤組成物の製造時にゲル化を起こしやすい。また、粘着剤組成物を調製する際に架橋剤（Ｂ）を添加したときには、ポットライフが短く作業性に問題があり、また、共重合体（Ａ）の凝集力が高くなり過ぎて粘着力が低下して、粘着剤層の基材に対する密着性が悪くなる。 Specific examples of the copolymerizable monomer containing a hydroxyl group used in the present invention include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Caprolactone-modified (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and the like, and at least one selected from these groups can be used. The use amount of the copolymerizable monomer containing a hydroxyl group needs to be an amount occupying 0.1 to 8% by mass in all monomers. Preferably it is 0.5-6 mass%, More preferably, it is the quantity which occupies 1-5 mass%. When the amount used is less than 0.1% by mass, when a crosslinking agent (B) described later is added, there are few crosslinking points and sufficient cohesive force cannot be obtained, and when a surface protective film is produced, After the protective film is attached to the surface of the article and peeled off, the adhesive is transferred to the adherend due to cohesive failure of the adhesive layer. On the other hand, when the usage-amount is more than 8 mass%, it gelatinizes easily at the time of manufacture of an adhesive composition. In addition, when the crosslinking agent (B) is added when preparing the pressure-sensitive adhesive composition, the pot life is short and there is a problem in workability, and the cohesive force of the copolymer (A) becomes too high, and the pressure-sensitive adhesive force. Decreases, and the adhesiveness of the pressure-sensitive adhesive layer to the substrate deteriorates.
本発明に使用するエーテル基を含有する共重合可能な単量体としては、具体的には２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレートおよびアクリロイルモルフォリンなどが挙げられ、これらの群から選ばれる少なくとも１種を使用することができる。エーテル基を含有する共重合可能な単量体の使用量は、全単量体中において０．５〜１０質量％を占める量であることが必要である。好ましくは０．８〜８質量％、より好ましくは１〜５質量％を占める量である。その使用量が０．５質量％より少ない場合、粘着剤層の帯電防止効果が経時で低下する。使用量が０．５〜１０質量％の範囲内であれば粘着剤層の帯電防止効果は維持され、経済的にも良好な範囲である。 Specific examples of the copolymerizable monomer containing an ether group used in the present invention include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and phenoxy. Examples include ethyl (meth) acrylate and acryloylmorpholine, and at least one selected from these groups can be used. The amount of the copolymerizable monomer containing an ether group needs to be an amount occupying 0.5 to 10% by mass in all monomers. Preferably it is the quantity which occupies 0.8-8 mass%, More preferably, it is 1-5 mass%. When the amount used is less than 0.5% by mass, the antistatic effect of the pressure-sensitive adhesive layer decreases with time. When the amount used is in the range of 0.5 to 10% by mass, the antistatic effect of the pressure-sensitive adhesive layer is maintained, which is economically favorable.
本発明において必要に応じて使用するカルボキシル基を含有する共重合可能な単量体としては、具体的には、（メタ）アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸；およびマレイン酸、イタコン酸の炭素数１〜１２の直鎖または分岐鎖を有するアルコールとのハーフエステルなどが挙げられ、これらの群より選ばれる少なくとも１種を使用することができる。カルボキシル基を含有する共重合可能な単量体の使用量は全単量体中において０〜０．３質量％を占める量であることが好ましい。その使用量が０．３質量％を超える場合、最終的に得られる粘着剤組成物のポットライフが短くなり、表面保護フィルムの製造時における作業性に問題が生じる。 Specific examples of the copolymerizable monomer containing a carboxyl group used in the present invention include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride; and A half ester of maleic acid, itaconic acid with a C1-C12 linear or branched alcohol, and the like can be used, and at least one selected from these groups can be used. The amount of the copolymerizable monomer containing a carboxyl group is preferably an amount occupying 0 to 0.3% by mass in all monomers. When the amount of use exceeds 0.3% by mass, the pot life of the finally obtained pressure-sensitive adhesive composition is shortened, resulting in a problem in workability during the production of the surface protective film.
上記の単量体組成物からなる共重合体は、通常の塊状重合、溶液重合、懸濁重合または乳化重合などで製造することができるが、好ましくは溶液重合である。溶液重合における溶剤としては、酢酸エチル、トルエン、ヘキサン、アセトンなどの通常の有機溶剤を使用することができる。また、重合に使用する重合開始剤は、ベンゾイルパーオキサイド、ラウロイルパーオキサイドなどの過酸化物、アゾビスイソブチロニトリル、アゾビスバレロニトリルなどのアゾビス化合物などの油溶性の開始剤を使用することができる。 The copolymer comprising the above monomer composition can be produced by ordinary bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like, preferably solution polymerization. As a solvent in the solution polymerization, an ordinary organic solvent such as ethyl acetate, toluene, hexane, acetone or the like can be used. The polymerization initiator used for the polymerization should be an oil-soluble initiator such as peroxides such as benzoyl peroxide and lauroyl peroxide, and azobis compounds such as azobisisobutyronitrile and azobisvaleronitrile. Can do.
共重合を溶液重合で行なう場合には、共重合体は有機溶剤の溶液として得られるので、該溶液をそのまま粘着剤組成物の製造に使用できるので有利である。この際の共重合体溶液の共重合体濃度は約３５〜７０質量％であることが、引き続く粘着剤組成物の製造に有利である。なお、前記の通り、前記カチオン系界面活性剤、過塩素酸塩およびリチウム塩は、上記共重合体の製造時の単量体中に存在させてもよいし、重合反応媒体中に存在させてもよいし、得られる共重合体溶液中に添加してもよい。また、本発明の粘着剤用重合体組成物は、固体状でも、分散状態でも、溶液状態でもよいが、上記の理由から有機溶剤の溶液状態であることが好ましい。 When the copolymerization is performed by solution polymerization, the copolymer is obtained as an organic solvent solution, which is advantageous because the solution can be used as it is for the production of the pressure-sensitive adhesive composition. In this case, the copolymer concentration of the copolymer solution is about 35 to 70% by mass, which is advantageous for the subsequent production of the pressure-sensitive adhesive composition. As described above, the cationic surfactant, perchlorate and lithium salt may be present in the monomer during the production of the copolymer or in the polymerization reaction medium. Alternatively, it may be added to the resulting copolymer solution. Moreover, the polymer composition for pressure-sensitive adhesives of the present invention may be in a solid state, a dispersed state or a solution state, but for the above reasons, it is preferably a solution state of an organic solvent.
次に本発明の表面保護フィルム用粘着剤組成物について説明する。本発明の表面保護フィルム用粘着剤組成物は、前記カチオン系界面活性剤と前記過塩素酸塩（またはさらにリチウム塩）とを粘着剤成分中に含有してなることを特徴としている。粘着剤成分はゴム系、アクリル系およびウレタン系粘着剤などが挙げられるが、好ましい粘着剤成分は上記した本発明の粘着剤用重合体組成物に使用するアクリル系共重合体（Ａ）からなる。 Next, the pressure-sensitive adhesive composition for a surface protective film of the present invention will be described. The pressure-sensitive adhesive composition for a surface protective film of the present invention is characterized in that the pressure-sensitive adhesive component contains the cationic surfactant and the perchlorate (or lithium salt). Examples of the pressure-sensitive adhesive component include rubber-based, acrylic-based and urethane-based pressure-sensitive adhesives. A preferable pressure-sensitive adhesive component is composed of the acrylic copolymer (A) used in the above-described polymer composition for pressure-sensitive adhesives of the present invention. .
本発明の粘着剤組成物は、前記のカチオン系界面活性剤と過塩素酸塩（またはさらにリチウム塩）に加えて、架橋剤（Ｂ）を含むことが好ましい。架橋剤（Ｂ）としては、脂肪族系および／または脂環族系の多官能イソシアネート系化合物および／または多官能イソシアヌレート系化合物が挙げられ、具体的には、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、それらのアダクト体などのポリイソシアネート系化合物、水素添加キシレンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどが挙げられ、これらの群から選ばれる少なくとも１種を使用することができる。好ましくはヘキサメチレンジイソシアネート系、イソホロンジイソシアネート系化合物およびこれらから変性されたプレポリマーである。より好ましくはヘキサメチレンジイソシアネート化合物／イソホロンジイソシアネート系化合物の割合が１００／０〜５０／５０の混合物およびこれらから変性されたプレポリマーである。 The pressure-sensitive adhesive composition of the present invention preferably contains a crosslinking agent (B) in addition to the cationic surfactant and perchlorate (or lithium salt). Examples of the crosslinking agent (B) include aliphatic and / or alicyclic polyfunctional isocyanate compounds and / or polyfunctional isocyanurate compounds. Specific examples include hexamethylene diisocyanate, isophorone diisocyanate, And polyisocyanate compounds such as adducts, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like, and at least one selected from these groups can be used. Preferred are hexamethylene diisocyanate type, isophorone diisocyanate type compounds and prepolymers modified from these. More preferred are mixtures of hexamethylene diisocyanate compound / isophorone diisocyanate compound of 100/0 to 50/50 and prepolymers modified from these.
架橋剤（Ｂ）の添加量は、前記共重合体（Ａ）（共重合体が溶液である場合にはその固形分、以下同様）１００質量部に対して０．５〜７質量部（架橋剤が溶液である場合にはその固形分、以下同様）である。好ましくは１〜５質量部である。添加量が０．５質量部より少ないと、加熱後の表面保護フィルムの粘着剤層の粘着力や高温多湿時の凝集力が低下し、一方、７質量部を超えると粘着剤組成物のポットライフが短く、該組成物の使用時の作業性に問題があり、また、架橋が進みすぎて粘着力が低下して表面保護フィルムにおいてフクレやトンネリング現象が発生する。 The addition amount of the crosslinking agent (B) is 0.5 to 7 parts by mass (cross-linking with respect to 100 parts by mass of the copolymer (A) (when the copolymer is a solution, the solid content thereof). If the agent is a solution, its solid content, and so on). Preferably it is 1-5 mass parts. When the addition amount is less than 0.5 parts by mass, the adhesive force of the pressure-sensitive adhesive layer of the surface protective film after heating and the cohesive force at high temperature and high humidity decrease, while when it exceeds 7 parts by mass, the pot of the adhesive composition The life is short, there is a problem in workability when using the composition, and the cross-linking proceeds so much that the adhesive strength is lowered, causing a bulge or tunneling phenomenon in the surface protective film.
また、本発明の粘着剤組成物は、ケト−エノール互変異性を生じる化合物（Ｃ）を含有することが好ましい。該化合物（Ｃ）は、前記架橋剤（Ｂ）単独で使用された場合、粘着剤組成物のポットライフが短く作業性に問題があったが、化合物（Ｃ）を添加することにより、粘着剤組成物の粘度上昇およびゲル化を抑え、粘着剤組成物のポットライフを長くすることができる。 Moreover, it is preferable that the adhesive composition of this invention contains the compound (C) which produces keto-enol tautomerism. When the compound (C) is used alone as the crosslinking agent (B), the pot life of the pressure-sensitive adhesive composition is short and there is a problem in workability. However, by adding the compound (C), the pressure-sensitive adhesive The viscosity increase and gelation of the composition can be suppressed, and the pot life of the pressure-sensitive adhesive composition can be extended.
化合物（Ｃ）としては、具体的にはアセチルアセトン、アセト酢酸エステルおよびマロン酸エステルから選ばれる少なくとも１種を使用することができる。該化合物（Ｃ）の添加量は共重合体１００質量部あたり固形分で０．１〜１５質量部である。好ましくは０．５〜１０質量部であり、より好ましくは１〜７質量部である。添加量が０．１〜１５質量部の範囲内であれば、粘着剤組成物の粘度上昇およびゲル化を抑える効果が得られ、経済的にも良好な範囲である。 As the compound (C), specifically, at least one selected from acetylacetone, acetoacetate and malonate can be used. The addition amount of this compound (C) is 0.1-15 mass parts in solid content per 100 mass parts of copolymers. Preferably it is 0.5-10 mass parts, More preferably, it is 1-7 mass parts. If the addition amount is in the range of 0.1 to 15 parts by mass, the effect of suppressing the increase in viscosity and gelation of the pressure-sensitive adhesive composition can be obtained, which is also in an economically favorable range.
本発明の粘着剤組成物は、その粘着剤成分として、前記の本発明の粘着剤用重合体組成物を使用することが好ましいが、前記帯電防止剤を含まない共重合体（またはその溶液）に、上記架橋剤（Ｂ）および化合物（Ｃ）を加えると同時に、または架橋剤（Ｂ）および化合物（Ｃ）に添加の前後に前記カチオン系界面活性剤と過塩素酸塩とを添加してもよい。その添加量は前記と同様である。カチオン系界面活性剤、過塩素酸塩あるいはリチウム塩の添加時期は、本発明の粘着剤組成物の帯電防止効果には全く差異はなく、適宜に選択することができる。 The pressure-sensitive adhesive composition of the present invention preferably uses the above-described polymer composition for pressure-sensitive adhesives of the present invention as the pressure-sensitive adhesive component, but does not contain the antistatic agent (or a solution thereof). The cationic surfactant and perchlorate are added simultaneously with the addition of the crosslinking agent (B) and the compound (C) or before and after the addition to the crosslinking agent (B) and the compound (C). Also good. The amount added is the same as described above. The timing of addition of the cationic surfactant, perchlorate or lithium salt is not different at all in the antistatic effect of the pressure-sensitive adhesive composition of the present invention, and can be appropriately selected.
また、本発明の粘着剤組成物は、その使用の容易性の点から有機溶剤の溶液形態であることが好ましい。かかる観点からして粘着剤成分としては、前記本発明の共重合体の有機溶剤溶液を使用し、該溶液中に前記架橋剤（Ｂ）および化合物（Ｃ）を前記の割合で添加し、必要に応じて溶剤で希釈することが好ましい。溶液状態である場合の本発明の粘着剤組成物の濃度は、固形分として３０〜５０質量％であることが、表面保護フィルムの製造工程上好ましい。 Moreover, it is preferable that the adhesive composition of this invention is a solution form of the organic solvent from the point of the ease of the use. From this point of view, as the adhesive component, an organic solvent solution of the copolymer of the present invention is used, and the cross-linking agent (B) and the compound (C) are added to the solution in the above proportions. Depending on the case, it is preferable to dilute with a solvent. The concentration of the pressure-sensitive adhesive composition of the present invention in a solution state is preferably 30 to 50% by mass as a solid content in the production process of the surface protective film.
以上の如くして得られる本発明の粘着剤組成物は、該粘着剤組成物の溶液をポリエステルフィルム（２５μｍ厚）に乾燥後粘着剤層厚が２５μｍになるように直接塗工して、９０℃で６０秒間乾燥させた後、粘着剤層面をシリコーン処理されたポリエステルフィルムセパレーター（３８μｍ厚）で被覆して、２３℃、５０％ＲＨ中に３日間養生した後の試料シート（表面保護フィルム）をステンレス板に貼り合わせた時の０．３ｍ／分の剥離速度における粘着力が０．０５〜０．５Ｎ／２５ｍｍ（ＪＩＳ Ｚ０２３７粘着テープ・粘着シート試験方法に準じて測定）を有することが好ましい。粘着剤層の粘着力が０．０５Ｎ／２５ｍｍより低い場合は、表面保護フィルムの被着体からの浮きや剥れを生じやすい。０．５Ｎ／２５ｍｍを超える場合は、表面保護フィルムを剥がす際に被着体を汚染するなど、再剥離性が悪くなる。 The pressure-sensitive adhesive composition of the present invention obtained as described above was applied directly to a polyester film (25 μm thickness) so that the pressure-sensitive adhesive layer thickness was 25 μm after drying the solution of the pressure-sensitive adhesive composition. After drying at 60 ° C. for 60 seconds, the pressure-sensitive adhesive layer surface was coated with a silicone-treated polyester film separator (38 μm thickness) and cured in 23 ° C. and 50% RH for 3 days (surface protective film) It is preferable that the adhesive strength at a peeling speed of 0.3 m / min when bonded to a stainless steel plate is 0.05 to 0.5 N / 25 mm (measured according to JIS Z0237 adhesive tape / adhesive sheet test method). . When the adhesive strength of the pressure-sensitive adhesive layer is lower than 0.05 N / 25 mm, the surface protective film tends to float or peel from the adherend. When it exceeds 0.5 N / 25 mm, the removability deteriorates, for example, the adherend is contaminated when the surface protective film is peeled off.
また、本発明の粘着剤組成物の粘着性を調整する目的で必要に応じ種々のものを本発明の効果を損なわない範囲で配合してもよい。配合に使用される具体例としては、テルペン系、テルペン−フェノール系、クマロンインデン系、スチレン系、ロジン系、キシレン系、フェノール系、石油系などの粘着付与剤、メラミン樹脂、アミン−エポキシ樹脂、酸化防止剤、紫外線吸収剤、充填剤、顔料、可塑剤、界面活性剤などが挙げられる。 Moreover, you may mix | blend various things in the range which does not impair the effect of this invention as needed in order to adjust the adhesiveness of the adhesive composition of this invention. Specific examples used for blending include terpene, terpene-phenol, coumarone indene, styrene, rosin, xylene, phenol, petroleum, and other tackifiers, melamine resins, and amine-epoxy resins. , Antioxidants, ultraviolet absorbers, fillers, pigments, plasticizers, surfactants and the like.
本発明の表面保護フィルムは、プラスチックフィルム基材の表面に前記本発明の粘着剤組成物からなる粘着剤層を有することを特徴としている。上記基材としては、例えば、ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体、ポリエステル、ポリ塩化ビニル、ポリカーボネート、ポリアミド、ポリスチレンなどのフィルムあるいはこれらの複合フィルムなどが使用できる。該基材に粘着剤組成物を塗布するに先立ち、粘着剤層の基材に対する密着性を向上させるために基材表面にコロナ処理などを行って使用することができる。また、シリコン剥離剤、ウレタン、シリコンアクリル樹脂などで背面処理されたプラスチックフィルムを基材として使用することができる。さらに、形成された粘着剤層の表面に汎用のシリコン剥離紙、シリコン剥離フィルムなどで貼着して、粘着剤層を保護することもできる。 The surface protective film of the present invention has a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of the present invention on the surface of a plastic film substrate. Examples of the substrate include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyester, polyvinyl chloride, polycarbonate, polyamide, polystyrene, and composite films thereof. Prior to application of the pressure-sensitive adhesive composition to the substrate, the surface of the substrate can be subjected to corona treatment or the like in order to improve the adhesion of the pressure-sensitive adhesive layer to the substrate. Also, a plastic film that has been back-treated with a silicon release agent, urethane, silicon acrylic resin, or the like can be used as a substrate. Further, the pressure-sensitive adhesive layer can be protected by sticking to the surface of the formed pressure-sensitive adhesive layer with a general-purpose silicon release paper, a silicon release film or the like.
本発明の粘着剤組成物の基材に対する塗布は、通常使用されている塗布装置、例えば、ロール塗布装置などで行なうことができる。塗布量は、使用される用途により異なるが乾燥後粘着剤層厚として通常５〜３００μｍである。乾燥は通常７０〜１５０℃、３０〜１２０秒間で行われる。 Application | coating with respect to the base material of the adhesive composition of this invention can be performed with the normally used coating device, for example, a roll coating device. The coating amount varies depending on the intended use, but is usually 5 to 300 μm as the pressure-sensitive adhesive layer thickness after drying. Drying is usually performed at 70 to 150 ° C. for 30 to 120 seconds.
次に実施例および比較例を挙げて本発明をさらに詳しく説明するが、本発明はこれらによって制限されるものではない。なお、実施例および比較例において「部」および「％」とあるのは、特に断りのない限り質量基準である。 EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not restrict | limited by these. In Examples and Comparative Examples, “parts” and “%” are based on mass unless otherwise specified.
［実施例１（共重合体組成物溶液Ａ−１）］
攪拌機、温度計、還流冷却器および窒素導入管を備えた反応装置に、窒素ガスを封入後、酢酸エチル７５部、アセトン１５部、ブチルアクリレート５５部、２−エチルヘキシルアクリレート２５部、２−ヒドロキシエチルアクリレート５部、２−メトキシエチルアクリレート１０部および重合開始剤（アゾビスイソブチロニトリル）０．２部を仕込む。攪拌しながら溶剤の還流温度で７時間反応する。反応終了後、カチオン系界面活性剤（塩化アルキルビス（２−ヒドロキシルエチル）メチルアンモニウム）３部、過塩素酸ナトリウム２部およびトルエン９５部を添加して室温まで冷却する。粘度３，５００ｍＰａ・ｓ、固形分３５％である共重合体組成物溶液Ａ−１を得た。
[Example 1 (Copolymer composition solution A-1)]
Nitrogen gas is sealed in a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and then 75 parts of ethyl acetate, 15 parts of acetone, 55 parts of butyl acrylate, 25 parts of 2-ethylhexyl acrylate, 2-hydroxyethyl Charge 5 parts of acrylate, 10 parts of 2-methoxyethyl acrylate, and 0.2 part of a polymerization initiator (azobisisobutyronitrile). The reaction is carried out for 7 hours at the reflux temperature of the solvent with stirring. After completion of the reaction, 3 parts of a cationic surfactant (alkylbis (2-hydroxylethyl) methylammonium chloride), 2 parts of sodium perchlorate and 95 parts of toluene are added and cooled to room temperature. A copolymer composition solution A-1 having a viscosity of 3,500 mPa · s and a solid content of 35% was obtained.
［実施例２〜４および比較例１〜４（共重合体組成物溶液Ａ−２〜Ａ−４およびＡ−６〜Ａ−９）］
表１に示すように単量体と添加物の種類および量を変える以外は実施例１と全く同様にして実施例および比較例の共重合体組成物溶液Ａ−２〜Ａ−４およびＡ−６〜Ａ−９を得た。
[Examples 2 to 4 and Comparative Examples 1 to 4 (Copolymer composition solutions A-2 to A-4 and A-6 to A-9)]
As shown in Table 1, the copolymer composition solutions A-2 to A-4 and A- of Examples and Comparative Examples were exactly the same as Example 1 except that the types and amounts of monomers and additives were changed. 6-A-9 were obtained.
［実施例５（共重合体組成物溶液Ａ−５）］
攪拌機、温度計、還流冷却器および窒素導入管を備えた反応装置に、窒素ガスを封入後、酢酸エチル７５部、アセトン１５部、ブチルアクリレート６０部、２−エチルヘキシルアクリレート２６部、２−ヒドロキシエチルアクリレート１部、２−メトキシエチルアクリレート８部、リチウム塩（トリフルオロメタンスルホン酸リチウム）０．３部および重合開始剤（アゾビスイソブチロニトリル）０．２部を仕込む。撹拌しながら溶剤の還流温度で７時間反応する。反応終了後、カチオン系界面活性剤（ニューエレガンＡ）４部、過塩素酸ナトリウム０．７部、トルエン９５部を添加して室温まで冷却する。粘度４，５００ｍＰａ・ｓ、固形分３５％である共重合体組成物溶液Ａ−５を得た。
[Example 5 (Copolymer composition solution A-5)]
Nitrogen gas is sealed in a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and then 75 parts of ethyl acetate, 15 parts of acetone, 60 parts of butyl acrylate, 26 parts of 2-ethylhexyl acrylate, 2-hydroxyethyl 1 part of acrylate, 8 parts of 2-methoxyethyl acrylate, 0.3 part of lithium salt (lithium trifluoromethanesulfonate) and 0.2 part of polymerization initiator (azobisisobutyronitrile) are charged. The reaction is carried out for 7 hours at the reflux temperature of the solvent with stirring. After completion of the reaction, 4 parts of a cationic surfactant (New Elegan A), 0.7 part of sodium perchlorate and 95 parts of toluene are added and cooled to room temperature. A copolymer composition solution A-5 having a viscosity of 4,500 mPa · s and a solid content of 35% was obtained.
表１中、単量体組成物、界面活性剤およびリチウム塩の種類を下記の略号で示した。
ＢＡ：ブチルアクリレート
２ＥＨＡ：２−エチルヘキシルアクリレート
２ＨＥＡ：２−ヒドロキシエチルアクリレート
ＡＡｃ：アクリル酸
２ＭＥＡ：２−メトキシエチルアクリレート
ＡＣＭＯ：アクリロイルモルフォリン
カチオン−１：塩化アルキルビス（２−ヒドロキシルエチル）メチルアンモニウム（ライオン（株）製、商品名エソカードＣ／１２）
カチオン−２：日本油脂（株）製、商品名ニューエレガンＡ
リチウム塩：トリフルオロメタンスルホン酸リチウム（三光化学工業（株）製、商品名サンコウノールＥＡｃ−３０Ｔ）
In Table 1, the types of monomer composition, surfactant and lithium salt are indicated by the following abbreviations.
BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate 2HEA: 2-hydroxyethyl acrylate AAc: acrylic acid 2 MEA: 2-methoxyethyl acrylate ACMO: acryloylmorpholine cation-1: alkylbis (2-hydroxylethyl) methylammonium chloride (Lion) (Product name, ESO Card C / 12)
Cation-2: Nippon Oil & Fats Co., Ltd., trade name New Elegan A
Lithium salt: Lithium trifluoromethanesulfonate (manufactured by Sanko Chemical Co., Ltd., trade name Sankounol EAc-30T)
［実施例６］
実施例６は、実施例１で得られた共重合体組成物溶液Ａ−１の固形分１００部に対して、架橋剤としてＢ−１であるヘキサメチレンジイソシアネート・イソシアヌレート型架橋剤（旭化成ケミカルズ（株）製、商品名デュラネートＴＰＡ−１００）２部およびアセチルアセトン２部を添加して充分に混合して粘着剤組成物を得た。この粘着剤組成物のポットライフは良好であった。該粘着剤組成物を粘着剤層厚が２５μｍになるように、基材である２５μｍ厚のポリエステルフィルムに直接塗工して、９０℃で６０秒乾燥させて粘着剤層を形成した後、粘着剤層面にシリコーンコートされた３８μｍ厚のポリエステルフィルムセパレーターを被覆して表面保護フィルムを作製した。この表面保護フィルムは、２３℃、５０％ＲＨ中で３日間養生後の粘着剤層の粘着力（０．３ｍ／分の剥離速度で、ＪＩＳ Ｚ０２３７粘着テープ・粘着シート試験方法に準じて測定）は、０．１２Ｎ／２５ｍｍで適度な強度であった。また、上記粘着剤層の表面抵抗は１０10Ωと有用な帯電防止性を示した。さらに粘着剤層の基材に対する密着性、粘着剤層の透明性、粘着剤層の再剥離性ともに良好であった。結果を表２に示す。
[Example 6]
Example 6 is a hexamethylene diisocyanate isocyanurate type crosslinking agent (Asahi Kasei Chemicals Co., Ltd.) which is B-1 as a crosslinking agent with respect to 100 parts of the solid content of the copolymer composition solution A-1 obtained in Example 1. 2 parts by Co., Ltd., trade name Duranate TPA-100) and 2 parts of acetylacetone were added and mixed well to obtain an adhesive composition. The pot life of this pressure-sensitive adhesive composition was good. The pressure-sensitive adhesive composition was directly applied to a 25 μm-thick polyester film as a substrate so that the pressure-sensitive adhesive layer thickness was 25 μm, and dried at 90 ° C. for 60 seconds to form a pressure-sensitive adhesive layer. A surface protective film was prepared by covering the surface of the agent layer with a 38 μm thick polyester film separator coated with silicone. This surface protective film has an adhesive strength of an adhesive layer after curing for 3 days at 23 ° C. and 50% RH (measured in accordance with JIS Z0237 adhesive tape / adhesive sheet test method at a peeling speed of 0.3 m / min). Was moderate strength at 0.12 N / 25 mm. Further, the surface resistance of the pressure-sensitive adhesive layer was 10 10 Ω, showing useful antistatic properties. Furthermore, the adhesiveness of the adhesive layer to the substrate, the transparency of the adhesive layer, and the removability of the adhesive layer were good. The results are shown in Table 2.
［実施例７］
実施例７は、実施例６の架橋剤をＢ−２であるヘキサメチレンジイソシアネート・ビュレット型架橋剤（旭化成ケミカルズ（株）製、商品名デュラネート２１Ｓ−７５Ｅに変更する以外は、実施例６と全く同様にして、粘着剤組成物および表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤組成物、表面保護フィルムまたは粘着剤層に関し、ポットライフ、３日間養生後の粘着力、表面抵抗、基材に対する密着性、透明性、再剥離性の全てにおいて良好であった。結果を表２に示す。
[Example 7]
Example 7 is exactly the same as Example 6 except that the cross-linking agent of Example 6 is B-2 hexamethylene diisocyanate burette type cross-linking agent (Asahi Kasei Chemicals Co., Ltd., trade name Duranate 21S-75E). Similarly, the pressure-sensitive adhesive composition and the surface protective film were obtained and tested in the same manner as in Example 6. The results were as follows for the pressure-sensitive adhesive composition, the surface protective film or the pressure-sensitive adhesive layer, after pot life, after 3 days of curing. The adhesive strength, surface resistance, adhesion to the substrate, transparency, and removability were all good, and the results are shown in Table 2.
［実施例８］
実施例８は、実施例６の架橋剤をＢ−３であるヘキサメチレンジイソシアネート・ビュレット型架橋剤（旭化成ケミカルズ（株）製、商品名デュラネートＷ３３３０−７５Ｅ）、およびアセチルアセトンを４部に変更する以外は、実施例６と全く同様にして粘着剤組成物および表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤組成物、表面保護フィルムまたは粘着剤層に関し、ポットライフ、３日間養生後の粘着力、表面抵抗、基材に対する密着性、粘着剤層の透明性、再剥離性の全てにおいて良好であった。結果を表２に示す。
[Example 8]
In Example 8, the cross-linking agent of Example 6 is B-3, except that the hexamethylene diisocyanate buret type cross-linking agent (Asahi Kasei Chemicals Co., Ltd., trade name Duranate W3330-75E) and acetylacetone are changed to 4 parts. Were the same as in Example 6 to obtain a pressure-sensitive adhesive composition and a surface protective film, and were tested in the same manner as in Example 6. The results relate to the pressure-sensitive adhesive composition, the surface protective film or the pressure-sensitive adhesive layer, and all of pot life, adhesive strength after curing for 3 days, surface resistance, adhesion to the substrate, transparency of the pressure-sensitive adhesive layer, and removability It was good. The results are shown in Table 2.
［実施例９］
実施例９は、実施例６の架橋剤をＢ−４であるイソシアヌレート型架橋剤（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＝７０／３０、旭化成ケミカルズ（株）製、商品名デュラネートＴ４３３０−７５Ｂ）を４部、およびアセチルアセトンを６部に変更する以外は、実施例６と全く同様にして粘着剤組成物および表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤組成物、表面保護フィルムまたは粘着剤層に関し、ポットライフ、３日間養生後の粘着力、表面抵抗、基材に対する密着性、粘着剤層の透明性、再剥離性の全てにおいて良好であった。結果を表２に示す。
[Example 9]
Example 9 is an isocyanurate type crosslinking agent (hexamethylene diisocyanate / isophorone diisocyanate = 70/30, manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate T4330-75B), which is B-4 as the crosslinking agent of Example 6. Parts and acetylacetone were changed to 6 parts, and a pressure-sensitive adhesive composition and a surface protective film were obtained in the same manner as in Example 6 and tested in the same manner as in Example 6. The results relate to the pressure-sensitive adhesive composition, the surface protective film or the pressure-sensitive adhesive layer, and all of pot life, adhesive strength after curing for 3 days, surface resistance, adhesion to the substrate, transparency of the pressure-sensitive adhesive layer, and removability It was good. The results are shown in Table 2.
［実施例１０］
実施例１０は、実施例２で得られた共重合体組成物溶液Ａ−２を使用して、架橋剤は実施例６で使用したＢ−１を３部、およびアセチルアセトンを４部使用する以外は、実施例６と全く同様にして粘着剤組成物および表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤組成物、表面保護フィルムまたは粘着剤層に関し、ポットライフ、３日間養生後の粘着力、表面抵抗、基材に対する密着性、粘着剤層の透明性、再剥離性の全てにおいて良好であった。結果を表２に示す。
[Example 10]
Example 10 uses the copolymer composition solution A-2 obtained in Example 2 except that the crosslinking agent uses 3 parts of B-1 used in Example 6 and 4 parts of acetylacetone. Were the same as in Example 6 to obtain a pressure-sensitive adhesive composition and a surface protective film, and were tested in the same manner as in Example 6. The results relate to the pressure-sensitive adhesive composition, the surface protective film or the pressure-sensitive adhesive layer, and all of pot life, adhesive strength after curing for 3 days, surface resistance, adhesion to the substrate, transparency of the pressure-sensitive adhesive layer, and removability It was good. The results are shown in Table 2.
［実施例１１］
実施例１１は、実施例３で得られた共重合体組成物溶液Ａ−３を使用して、架橋剤は実施例６で使用したＢ−１を５部、およびアセチルアセトンを２部使用する以外は、実施例６と全く同様にして粘着剤組成物および表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤組成物、表面保護フィルムまたは粘着剤層に関し、ポットライフ、３日間養生後の粘着力、表面抵抗、基材に対する密着性、粘着剤層の透明性、再剥離性の全てにおいて良好であった。結果を表２に示す。
[Example 11]
Example 11 uses the copolymer composition solution A-3 obtained in Example 3, except that the crosslinking agent uses 5 parts of B-1 used in Example 6 and 2 parts of acetylacetone. Were the same as in Example 6 to obtain a pressure-sensitive adhesive composition and a surface protective film, and were tested in the same manner as in Example 6. The results relate to the pressure-sensitive adhesive composition, the surface protective film or the pressure-sensitive adhesive layer, and all of pot life, adhesive strength after curing for 3 days, surface resistance, adhesion to the substrate, transparency of the pressure-sensitive adhesive layer, and removability It was good. The results are shown in Table 2.
［実施例１２］
実施例１２は、実施例４で得られた共重合体組成物溶液Ａ−４を使用して、架橋剤は実施例９で使用したＢ−４を２部、およびアセチルアセトンを３部使用する以外は、実施例６と全く同様にして粘着剤組成物および表面保護フィルムを得、実施例６と同様に試験した。結果は、粘着剤組成物、表面保護フィルムまたは粘着剤層に関し、ポットライフ、３日間養生後の粘着力、表面抵抗、基材に対する密着性、粘着剤層の透明性、再剥離性の全てにおいて良好だった。結果を表２に示す。
[Example 12]
Example 12 uses the copolymer composition solution A-4 obtained in Example 4, except that 2 parts of B-4 used in Example 9 and 3 parts of acetylacetone are used as the crosslinking agent. Were obtained in the same manner as in Example 6 to obtain an adhesive composition and a surface protective film, and were tested in the same manner as in Example 6. The results relate to the pressure-sensitive adhesive composition, the surface protective film or the pressure-sensitive adhesive layer, and all of pot life, adhesive strength after curing for 3 days, surface resistance, adhesion to the substrate, transparency of the pressure-sensitive adhesive layer, and removability It was good. The results are shown in Table 2.
［実施例１３］
実施例１３は、実施例５で得られた共重合体組成物溶液Ａ−５を使用して、架橋剤は実施例９で使用したＢ−４を２部、およびアセチルアセトンを３部使用する以外は、実施例６と全く同様にして粘着剤組成物および表面保護フィルムを得、実施例６と同様に試験した。結果は、粘着剤組成物、表面保護フィルムまたは粘着剤層に関し、ポットライフ、３日間養生後の粘着力、表面抵抗、基材に対する密着性、粘着剤層の透明性および再剥離性の全てにおいて良好だった。結果を表２に示す。
[Example 13]
Example 13 uses the copolymer composition solution A-5 obtained in Example 5, except that 2 parts of B-4 used in Example 9 and 3 parts of acetylacetone are used as the crosslinking agent. Were obtained in the same manner as in Example 6 to obtain an adhesive composition and a surface protective film, and were tested in the same manner as in Example 6. The results relate to the pressure-sensitive adhesive composition, the surface protective film or the pressure-sensitive adhesive layer, all in pot life, adhesive strength after curing for 3 days, surface resistance, adhesion to the substrate, transparency of the pressure-sensitive adhesive layer and removability. It was good. The results are shown in Table 2.
［比較例５］
比較例５は、比較例１で得られたカチオン系界面活性剤と過塩素酸ナトリウムを添加しない共重合体組成物溶液Ａ−６を使用した以外は、実施例６と全く同様にして表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤層の表面抵抗が１０15Ωであって有用な帯電防止性を示さなかった。結果を表３に示す。
[Comparative Example 5]
In Comparative Example 5, surface protection was carried out in the same manner as in Example 6 except that the cationic surfactant obtained in Comparative Example 1 and the copolymer composition solution A-6 to which sodium perchlorate was not added were used. Films were obtained and tested as in Example 6. As a result, the surface resistance of the pressure-sensitive adhesive layer was 10 15 Ω and did not show useful antistatic properties. The results are shown in Table 3.
［比較例６］
比較例６は、比較例２で得られた過塩素酸ナトリウムを添加しない共重合体組成物溶液Ａ−７を使用した以外は、実施例６と全く同様にして表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤層の表面抵抗が１０13Ωであって有用な帯電防止性を示さなかった。結果を表３に示す。
[Comparative Example 6]
In Comparative Example 6, a surface protective film was obtained in the same manner as in Example 6 except that the copolymer composition solution A-7 to which sodium perchlorate obtained in Comparative Example 2 was not added was used. The test was conducted in the same manner as in 6. As a result, the surface resistance of the pressure-sensitive adhesive layer was 10 13 Ω and did not show useful antistatic properties. The results are shown in Table 3.
［比較例７］
比較例７は、比較例３で得られたカチオン系界面活性剤の含有量が、本発明の範囲外であり、かつ過塩素酸ナトリウムを使用しない共重合体組成物溶液Ａ−８を使用した以外は、実施例６と全く同様にして表面保護フィルムを得ようとしたが、粘着剤層の透明性が悪く、また、粘着物性が損なわれていた。結果を表３に示す。
[Comparative Example 7]
Comparative Example 7 used a copolymer composition solution A-8 in which the content of the cationic surfactant obtained in Comparative Example 3 was outside the scope of the present invention and sodium perchlorate was not used. Except for the above, an attempt was made to obtain a surface protective film in exactly the same manner as in Example 6, but the transparency of the pressure-sensitive adhesive layer was poor, and the physical properties of the pressure-sensitive adhesive were impaired. The results are shown in Table 3.
［比較例８］
比較例８は、比較例４で得られたカチオン系界面活性剤を添加しない共重合体組成物溶液Ａ−９を使用した以外は、実施例６と全く同様にして表面保護フィルムを得、実施例６と同様に試験をした。結果は、粘着剤層の表面抵抗が１０13Ωであって有用な帯電防止性を示さなかった。結果を表３に示す。
[Comparative Example 8]
In Comparative Example 8, a surface protective film was obtained in the same manner as in Example 6 except that the copolymer composition solution A-9 to which the cationic surfactant obtained in Comparative Example 4 was not added was used. Test as in Example 6. As a result, the surface resistance of the pressure-sensitive adhesive layer was 10 13 Ω and did not show useful antistatic properties. The results are shown in Table 3.
表２および３中、架橋剤の種類を下記の略号で示した。
・Ｂ−１：ヘキサメチレンジイソシアネート・イソシアヌレート型架橋剤（旭化成ケミカルズ（株）製、商品名デュラネートＴＰＡ−１００）
・Ｂ−２：ヘキサメチレンジイソシアネート・ビュレット型架橋剤（旭化成ケ ミカルズ（株）製、商品名デュラネート２１Ｓ−７５Ｅ）
・Ｂ−３：ヘキサメチレンジイソシアネート・ビュレット型架橋剤（旭化成ケミカルズ（株）製、商品名デュラネートＷ３３３０−７５Ｅ）
・Ｂ−４：イソシアヌレート型架橋剤（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＝７０／３０、旭化成ケミカルズ（株）製、商品名デュラネートＴ４３３０−７５Ｂ）
In Tables 2 and 3, the types of crosslinking agents are indicated by the following abbreviations.
B-1: Hexamethylene diisocyanate Isocyanurate type crosslinking agent (Asahi Kasei Chemicals Co., Ltd., trade name Duranate TPA-100)
B-2: Hexamethylene diisocyanate Burette type cross-linking agent (Asahi Kasei Chemicals Co., Ltd., trade name Duranate 21S-75E)
B-3: Hexamethylene diisocyanate Burette type crosslinking agent (Asahi Kasei Chemicals Co., Ltd., trade name Duranate W3330-75E)
B-4: Isocyanurate type crosslinking agent (hexamethylene diisocyanate / isophorone diisocyanate = 70/30, manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate T4330-75B)
試験方法
１．ポットライフ
共重合体組成物溶液に架橋剤およびアセチルアセトンを配合後の粘度、液状態を測定・観察する。
○：配合８時間後の粘度が、３０℃で５，０００ｍＰａ・ｓ未満のもの。
×：ゲル化するもの、または配合８時間後の粘度が、３０℃で５，０００ｍＰａ・ｓ以上のもの。
Test method 1. Measure and observe the viscosity and liquid state after blending the cross-linking agent and acetylacetone into the potlife copolymer composition solution.
○: The viscosity after 8 hours of blending is less than 5,000 mPa · s at 30 ° C.
X: Gelling or a viscosity after blending 8 hours at 5,000 mPa · s or more at 30 ° C.
２．粘着力
共重合体組成物溶液に架橋剤およびアセチルアセトンを添加して撹拌機にて約１０分間混合して粘着剤組成物を得、該粘着剤組成物を粘着剤層厚が２５μｍになるように２５μｍ厚のポリエステルフィルムに直接塗工して、９０℃で６０秒乾燥させた後、粘着剤層面にシリコーンコートされた３８μｍ厚のポリエステルフィルムセパレーターを被覆して表面保護フィルムを作製した。該表面保護フィルムを２３℃、５０％ＲＨ雰囲気中に３日間放置したものを、０．３ｍ／分の剥離速度で、ＪＩＳ Ｚ０２３７粘着テープ・粘着シート試験方法に準じて粘着力を測定した。
2. Adhesive strength A crosslinking agent and acetylacetone are added to the copolymer composition solution and mixed for about 10 minutes with a stirrer to obtain an adhesive composition, and the adhesive composition is adjusted so that the adhesive layer thickness is 25 μm. The film was directly applied to a 25 μm thick polyester film, dried at 90 ° C. for 60 seconds, and then coated with a 38 μm thick polyester film separator coated with silicone on the pressure-sensitive adhesive layer surface to prepare a surface protective film. The surface protection film was allowed to stand in an atmosphere of 23 ° C. and 50% RH for 3 days, and the adhesive strength was measured at a peeling rate of 0.3 m / min according to the JIS Z0237 adhesive tape / adhesive sheet test method.
３．表面抵抗
２３℃、５０％ＲＨ雰囲気中に３日間放置した表面保護フィルムの粘着剤層面の表面抵抗をハイレジスタンスメータで測定した。
3. Surface Resistance The surface resistance of the pressure-sensitive adhesive layer surface of the surface protective film left for 3 days in an atmosphere of 23 ° C. and 50% RH was measured with a high resistance meter.
４．基材に対する密着性
２３℃、５０％ＲＨ雰囲気中に３日間放置した表面保護フィルムの粘着剤層面を指で擦ったときの基材に対する密着性を評価した。
○：粘着剤が基材より全く剥がれない。
×：粘着剤が基材より剥がれる。
4). Adhesiveness to base material Adhesiveness to the base material when the surface of the pressure-sensitive adhesive layer of the surface protective film left in a 23 ° C., 50% RH atmosphere for 3 days was rubbed with a finger was evaluated.
○: The adhesive is not peeled off from the substrate at all.
X: The adhesive is peeled off from the substrate.
５．粘着剤層の透明性
２３℃、５０％ＲＨ雰囲気中に３日間放置した表面保護フィルムの粘着剤層の透明性を目視で観察した。
○：透明性良好。
×：白濁が見られる。
5. Transparency of the pressure-sensitive adhesive layer The transparency of the pressure-sensitive adhesive layer of the surface protective film that was left in an atmosphere of 23 ° C. and 50% RH for 3 days was visually observed.
○: Excellent transparency.
X: Cloudiness is seen.
６．再剥離性
２３℃、５０％ＲＨ雰囲気中に３日間放置した表面保護フィルムを偏光板に貼付した後、９０℃の恒温槽で２４時間放置した後、２３℃、５０％ＲＨ雰囲気中に取り出し、同雰囲気中で剥がしたときの再剥離の状態を目視で観察した。
○：粘着剤層残りや汚染性などなく良好。
×：粘着剤層残りや汚染性が見られる。
6). Re-peelability After a surface protective film left in a 23 ° C., 50% RH atmosphere for 3 days was attached to a polarizing plate, left in a 90 ° C. constant temperature bath for 24 hours, then taken out in a 23 ° C., 50% RH atmosphere, The state of re-peeling when peeled in the same atmosphere was visually observed.
○: Good with no adhesive layer residue or contamination.
X: Adhesive layer residue and contamination are seen.
本発明によれば、適度な粘着力を有し、基材に対する密着性が良く、優れた帯電防止性を有し、再剥離性やポットライフも良好である粘着剤組成物を提供できる。該粘着剤組成物を用いて形成した表面保護フィルムは、特に偏光フィルム、プラスチック板、家電製品、自動車、電子機器などの表面保護フィルムとして有用である。また、本発明の粘着剤組成物は架橋速度が早いことから、表面保護フィルムを製造する際に表面保護フィルムを加熱熟成したり、室温で長期間養生する必要がなく、表面保護フィルムの生産性を向上させることができる。
ADVANTAGE OF THE INVENTION According to this invention, it can provide the adhesive composition which has moderate adhesive force, the adhesiveness with respect to a base material, the outstanding antistatic property, and the re-peelability and pot life are also favorable. The surface protective film formed using the pressure-sensitive adhesive composition is particularly useful as a surface protective film for polarizing films, plastic plates, home appliances, automobiles, electronic devices and the like. Further, since the pressure-sensitive adhesive composition of the present invention has a high crosslinking rate, it is not necessary to heat and age the surface protective film or to cure at room temperature for a long time when producing the surface protective film. Can be improved.
Claims (10)
上記過塩素酸塩が、過塩素酸ナトリウム、過塩素酸カリウム及び過塩素酸リチウムの群から選択される少なくともいずれかであり、
上記粘着剤成分が、アクリル系共重合体（Ａ）と、脂肪族系および／または脂環族系の多官能イソシアネート系化合物および／または多官能イソシアヌレート系化合物（Ｂ）と、ケト−エノール互変異性を生じる化合物（Ｃ）とを含むことを特徴とする表面保護フィルム用粘着剤組成物。 Contained with both cationic surfactant and perchlorate, and an adhesive component,
The perchlorate is at least one selected from the group of sodium perchlorate, potassium perchlorate and lithium perchlorate;
The pressure-sensitive adhesive component comprises an acrylic copolymer (A), an aliphatic and / or alicyclic polyfunctional isocyanate compound and / or a polyfunctional isocyanurate compound (B), and a keto-enol mixture. A pressure-sensitive adhesive composition for a surface protective film , comprising a compound (C) that causes variability .
カチオン系界面活性剤と過塩素酸塩の両方と、粘着剤用重合体とを含有してなり、
上記過塩素酸塩が、過塩素酸ナトリウム、過塩素酸カリウム及び過塩素酸リチウムの群から選択される少なくともいずれかであり、
上記粘着剤用重合体が、水酸基を含有する共重合可能な単量体を全単量体中において０．１〜８質量％を占める量、およびエーテル基を含有する共重合可能な単量体を全単量体中において０．５〜１０質量％を占める量で含む（メタ）アクリル酸アルキルエステル単量体を主成分とする単量体組成物からなるアクリル系共重合体であることを特徴とする粘着剤用重合体組成物。 It is a polymer composition for adhesives used for manufacture of an adhesive composition for surface protection films given in any 1 paragraph of Claims 1-5,
With both cationic surfactant and perchlorate, Ri name contains an adhesive polymer for,
The perchlorate is at least one selected from the group of sodium perchlorate, potassium perchlorate and lithium perchlorate;
The above-mentioned polymer for pressure-sensitive adhesives contains 0.1 to 8% by mass of a copolymerizable monomer containing a hydroxyl group in all monomers, and a copolymerizable monomer containing an ether group the an amount which accounts for 0.5 to 10 mass% during Zentan mer (meth) acrylic copolymer der Rukoto made from a monomer composition mainly composed of an acrylic acid alkyl ester monomer A polymer composition for pressure-sensitive adhesives.
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| JP2001026772A (en) * | 1999-07-12 | 2001-01-30 | Mizusawa Ind Chem Ltd | Persistent antistatic agent |
| JP2001240830A (en) * | 2000-02-28 | 2001-09-04 | Saiden Chemical Industry Co Ltd | Adhesive composition and surface protective film |
| JP2002285134A (en) * | 2001-03-26 | 2002-10-03 | Sumitomo Bakelite Co Ltd | Adhesive sheet for processing semiconductor |
| JP2003282489A (en) * | 2002-03-26 | 2003-10-03 | Sumitomo Bakelite Co Ltd | Adhesive sheet used for processing semiconductor |
| JP4202685B2 (en) * | 2002-07-16 | 2008-12-24 | 大日本印刷株式会社 | Cover tape for paper carrier tape |
| JP4351834B2 (en) * | 2002-09-20 | 2009-10-28 | サイデン化学株式会社 | Aqueous pressure-sensitive adhesive composition for film substrate |
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2005
- 2005-05-09 JP JP2005135658A patent/JP4776272B2/en not_active Expired - Fee Related
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