JP2013057077A - Re-peelable antistatic acrylic adhesive - Google Patents
Re-peelable antistatic acrylic adhesive Download PDFInfo
- Publication number
- JP2013057077A JP2013057077A JP2012254381A JP2012254381A JP2013057077A JP 2013057077 A JP2013057077 A JP 2013057077A JP 2012254381 A JP2012254381 A JP 2012254381A JP 2012254381 A JP2012254381 A JP 2012254381A JP 2013057077 A JP2013057077 A JP 2013057077A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- weight
- antistatic
- pressure
- acrylic
- 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.)
- Granted
Links
- 239000003522 acrylic cement Substances 0.000 title claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 74
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 69
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 26
- -1 quaternary ammonium cations Chemical class 0.000 claims abstract description 25
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 230000003287 optical effect Effects 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 101
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 44
- 230000001681 protective effect Effects 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 7
- 230000003068 static effect Effects 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 87
- 239000010410 layer Substances 0.000 description 39
- 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 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000004925 Acrylic resin Substances 0.000 description 16
- 229920000178 Acrylic resin Polymers 0.000 description 16
- 239000002585 base Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000003999 initiator Substances 0.000 description 11
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 11
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000002313 adhesive film Substances 0.000 description 9
- 239000002216 antistatic agent Substances 0.000 description 9
- 229920002799 BoPET Polymers 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- YPQKTLPPOXNDMC-UHFFFAOYSA-N isocyanic acid;methylcyclohexane Chemical compound N=C=O.CC1CCCCC1 YPQKTLPPOXNDMC-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- UFXYYTWJETZVHG-UHFFFAOYSA-N 1,3-diisocyanatobutane Chemical compound O=C=NC(C)CCN=C=O UFXYYTWJETZVHG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- LHNAURKRXGPVDW-UHFFFAOYSA-N 2,3-diisocyanatobutane Chemical compound O=C=NC(C)C(C)N=C=O LHNAURKRXGPVDW-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
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000010348 incorporation Methods 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 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
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000003505 polymerization initiator Substances 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
- Inorganic Chemistry (AREA)
Abstract
Description
本発明は、帯電防止粘着剤及び該粘着剤の製造方法に関する。詳しくは、本発明は、被着体表面を所定の期間、機械的及び電気的に保護するための表面保護フィルムに好適な粘着剤に関する。より詳しくは、本発明の粘着剤は、液晶パネル、プラズマディスプレイ、偏光板、ＣＲＴ（ブラウン管）等の光学部品の再剥離性帯電防止粘着フィルム形成に好適に用いられる。 The present invention relates to an antistatic pressure-sensitive adhesive and a method for producing the pressure-sensitive adhesive. In detail, this invention relates to the adhesive suitable for the surface protection film for protecting the to-be-adhered body surface mechanically and electrically for a predetermined period. More specifically, the pressure-sensitive adhesive of the present invention is suitably used for forming a releasable antistatic pressure-sensitive adhesive film for optical parts such as liquid crystal panels, plasma displays, polarizing plates, CRTs (CRTs).
従来、ワープロ、コンピュータ、携帯電話、テレビ等の各種ディスプレイや、または偏光板やそれに準ずる積層体等の光学部品、電子基板等の表面には、通常、表面保護及び機能性付与の目的でポリエチレン、ポリエステル、ポリプロピレン等の透明な表面保護フィルム（基材フィルム）が粘着剤を介して積層される。 Conventionally, the surface of various displays such as word processors, computers, mobile phones, TVs, or optical components such as polarizing plates and laminates equivalent thereto, electronic substrates, and the like, usually for the purpose of surface protection and imparting functionality, A transparent surface protective film (base film) such as polyester or polypropylene is laminated via an adhesive.
これら表面保護粘着フィルムは、例えば液晶ディスプレイ等の組み込みが完了した後に、表面保護の役割を終え、剥離除去される場合が多い。しかし、表面保護粘着フィルム剥離時に静電気が発生して周囲のゴミを巻き込むという問題を抱えている。更に表面保護粘着フィルムを剥離する際に生じた剥離帯電により液晶や電子回路が破壊される、というトラブルが発生することがある。 In many cases, these surface protective pressure-sensitive adhesive films are peeled and removed after finishing the role of surface protection, for example, after the incorporation of a liquid crystal display or the like is completed. However, there is a problem that static electricity is generated when the surface protective adhesive film is peeled off and entraps surrounding dust. Furthermore, there may be a problem that the liquid crystal and the electronic circuit are destroyed due to peeling electrification generated when the surface protective adhesive film is peeled off.
そこで、表面保護粘着フィルムに帯電防止性を付与する手段として、以下に示すような
種々の方策が提案されている。
例えば、
（１） 表面保護粘着フィルムを構成する基材フィルム自体に帯電防止性を付与する、
（２） 表面保護粘着フィルムを構成する基材フィルムと粘着剤層との間に、又は基材フィルムの粘着剤層が積層されていない方の面に、あるいは基材フィルムと粘着剤層との間に、帯電防止性能を有する層を設ける、
（３） 表面保護粘着フィルムを構成する粘着剤層に帯電防止性を付与する、等。
Therefore, various measures as described below have been proposed as means for imparting antistatic properties to the surface protective adhesive film.
For example,
(1) imparting antistatic properties to the substrate film itself constituting the surface protective adhesive film;
(2) Between the base film and the pressure-sensitive adhesive layer constituting the surface protective pressure-sensitive adhesive film, on the side where the pressure-sensitive adhesive layer of the base film is not laminated, or between the base film and the pressure-sensitive adhesive layer In between, provide a layer having antistatic performance,
(3) Giving antistatic properties to the pressure-sensitive adhesive layer constituting the surface protective pressure-sensitive adhesive film, and the like.
（１）の方法は、基材フィルムの原料たるポリエステルやポリエチレン等の熱可塑性樹脂に有機スルホン酸塩基等のアニオン性化合物、金属粉、カーボンブラック等の導電性フィラーを練り混んで導電性基材フィルムを得る方法であり、この場合基材フィルムの透明性が低下したり、フィルムが着色したりする。
ところで、被着体に表面保護粘着フィルムを貼着している間も、被着体の表面保護外観が粘着フィルムを介して絶えず検査され得るようになっている必要がある。そのため、表面保護粘着フィルム粘着シート自体も、透明性に優れ、かつ光学的にも欠陥を有していないことが必要とされる。
従って、帯電防止剤含有基材フィルムを用いてなる表面保護粘着フィルムを被着体に貼着した場合、被着面が見えにくくなるという問題がある。また、基材フィルムが高価格になるという問題もある。
The method (1) is a method in which a conductive base material is prepared by kneading an anionic compound such as an organic sulfonate group, a metal powder, or a conductive filler such as carbon black with a thermoplastic resin such as polyester or polyethylene as a raw material for the base film. In this case, the transparency of the base film is lowered or the film is colored.
By the way, while the surface protective adhesive film is stuck on the adherend, the surface protective appearance of the adherend needs to be continuously inspected through the adhesive film. Therefore, the surface protective pressure-sensitive adhesive film pressure-sensitive adhesive sheet itself is required to be excellent in transparency and optically free from defects.
Therefore, when the surface protection adhesive film using an antistatic agent containing base film is stuck on a to-be-adhered body, there exists a problem that an adherend surface becomes difficult to see. There is also a problem that the base film becomes expensive.
（２）の方法は、以下に示すようにさらに様々なバリエーションがある（特開平７−２６２２３号公報、特開平１１−２５６１１６号公報、特開平２００１−２１９５２０号公報、特開２００２−０６０７０７号公報、特開２００２−２７５２９６号公報等参照）。
(２−１) 基材フィルムの少なくとも一方の面に金属化合物を蒸着する、
(２−２) 基材フィルムの少なくとも一方の面に、４級アンモニウム塩、スルホン酸塩基を有する長鎖アルキル化合物等のようなアニオン型界面活性剤、チオフェン誘導体、主鎖にイオン化された窒素元素を有するポリマーや、スルホン酸塩基変性ポリスチレン等の種々の帯電防止剤を含有する層を設ける、等。
しかし、例えばスルホン酸塩基を有する長鎖アルキル化合物等のようなアニオン型界面活性剤は比較的低分子量であるので、帯電防止剤の一部が帯電防止塗膜中を移動して基材フィルムとの界面に集積し基材フィルムの反対面等に移行する問題や、帯電防止性が経時的に低下するという問題がある。
また、主鎖にイオン化された窒素元素を有するポリマーや、スルホン酸塩基変性ポリスチレン等は比較的高分子量であるので、上記のような問題は生じない。しかし、良好な帯電防止性能を得るためには多量の帯電防止剤の配合が必要であり、帯電防止層の膜厚を厚くする必要があるため経済的でない。さらに、製品にならなかった屑フィルム（例えば、製造工程で切断除去したフィルム端部等）を回収し、フィルム製造用の再生材料として使用すると、溶融製膜の際に該再生材料中に含まれる帯電防止剤成分が熱劣化し、再生されるフィルムが著しく着色し実用性に欠ける（回収性が劣る）ものとなる等の問題が生じる。そのうえ、フィルム同士が剥離し難い（ブロッキングする）、塗膜が削れ易い等の欠点が生じ、その解決が望まれている。
The method (2) has various variations as described below (Japanese Patent Laid-Open Nos. 7-26223, 11-256116, 2001-219520, 2002-060707). JP, 2002-275296, A, etc.).
(2-1) depositing a metal compound on at least one surface of the substrate film;
(2-2) Anionic surfactants such as quaternary ammonium salts, long-chain alkyl compounds having a sulfonate group, thiophene derivatives, and nitrogen elements ionized in the main chain on at least one surface of the base film And a layer containing various antistatic agents such as sulfonate group-modified polystyrene.
However, since an anionic surfactant such as a long-chain alkyl compound having a sulfonate group has a relatively low molecular weight, a part of the antistatic agent moves through the antistatic coating film to form a base film. There is a problem of accumulating at the interface and transferring to the opposite surface of the base film, and a problem that the antistatic property decreases with time.
In addition, since the polymer having nitrogen element ionized in the main chain, sulfonate group-modified polystyrene, and the like have a relatively high molecular weight, the above-described problems do not occur. However, in order to obtain good antistatic performance, it is necessary to add a large amount of antistatic agent, and it is not economical because it is necessary to increase the thickness of the antistatic layer. Furthermore, when scrap film that has not been turned into a product (for example, film edges cut and removed in the manufacturing process) is collected and used as a recycled material for film production, it is included in the recycled material during melt film formation. There arises a problem that the antistatic agent component is thermally deteriorated, and the film to be regenerated is extremely colored and lacks practicality (recoverability is poor). In addition, there are disadvantages that the films are difficult to peel (block) and the coating film is easily scraped, and the solution is desired.
（３）の方法は、静電気の発生する剥離界面に帯電防止性能を付与する方法であり、帯電防止性能を有する樹脂を用いて粘着剤を構成する方法と、帯電防止剤含有粘着剤で粘着剤層を形成する方法とがある（特許文献１：特開平１−２５３４８２号公報）。
前者の場合、導電性と換言することもできる樹脂自体の帯電防止性能が不十分である。
後者の場合、用いられる帯電防止剤としては、各種界面活性剤やカーボンブラック等の導電性粉末が挙げられる。しかし、界面活性剤含有粘着剤を用いた場合、一般に界面活性剤が粘着剤層表面、即ち被着体との貼着界面に濃縮される傾向にあり、その界面活性剤故に粘着性能が湿度の影響を極めて受けやすい。つまり、水分が粘着剤層の凝集力を低下させ、表面保護粘着フィルムを剥離する際、被着体に粘着剤層が一部残りやすい（いわゆる「糊残り」し易い）。他方、カーボンブラック等の導電性粉末を含有する導電性粘着剤を用いた場合には、粘着剤層及び表面保護粘着フィルムの透明性が低下したり、フィルムが着色したりするという問題を生じる。
The method (3) is a method of imparting antistatic performance to the peeling interface where static electricity is generated, and a method of forming a pressure sensitive adhesive using a resin having antistatic performance, and a pressure sensitive adhesive containing an antistatic agent-containing pressure sensitive adhesive. There is a method of forming a layer (Patent Document 1: JP-A-1-253482).
In the former case, the antistatic performance of the resin itself, which can be paraphrased as electrical conductivity, is insufficient.
In the latter case, examples of the antistatic agent used include various surfactants and conductive powders such as carbon black. However, when a surfactant-containing pressure-sensitive adhesive is used, the surfactant generally tends to be concentrated on the surface of the pressure-sensitive adhesive layer, i.e., the bonding interface with the adherend, and the pressure-sensitive adhesive performance is low due to the surfactant. Very sensitive. That is, when moisture reduces the cohesive force of the pressure-sensitive adhesive layer and peels off the surface protective pressure-sensitive adhesive film, a part of the pressure-sensitive adhesive layer tends to remain on the adherend (so-called “glue residue”). On the other hand, when a conductive pressure-sensitive adhesive containing conductive powder such as carbon black is used, there arises a problem that transparency of the pressure-sensitive adhesive layer and the surface protective pressure-sensitive adhesive film is lowered or the film is colored.
透明性に優れ着色の問題がほとんど生じない帯電防止剤の利用が、特許文献２：特許第２７１８５１９号に開示されている。
しかし、特許文献２記載の発明は、導電性粘着剤に関するとはいうものの生体に貼り付けて使用する電極パッド用のものであり、特許文献２記載の導電性粘着剤は表面保護粘着フィルム用には到底使用し得るものではなかった。
However, the invention described in
本発明の目的は、各種ディスプレイ、偏光板等の光学部材の表面保護粘着フィルム用の粘着剤として好適な透明性に優れ着色もほとんどなく、再剥離性に優れ、剥離時の剥離帯電が少ない帯電防止粘着剤を提供することを目的とする。 The object of the present invention is to provide excellent transparency and little coloration suitable as a pressure-sensitive adhesive for surface protective adhesive films of optical members such as various displays and polarizing plates. An object is to provide a pressure-sensitive adhesive.
本発明者は鋭意検討の結果、側鎖に水酸基及びアルキレンオキサイド鎖を有するアクリル系共重合体（Ａ）にイオン化合物（Ｂ）及び硬化剤（Ｃ）を含有させることにより、適度な導電性を有する帯電防止粘着剤が得られることを見出し、本発明を完成した。 As a result of intensive studies, the present inventor has appropriate conductivity by adding an ionic compound (B) and a curing agent (C) to the acrylic copolymer (A) having a hydroxyl group and an alkylene oxide chain in the side chain. The present invention was completed by finding that an antistatic pressure-sensitive adhesive can be obtained.
即ち、本発明は、側鎖に水酸基及びアルキレンオキサイド鎖を有する、水酸基を有するモノマー１〜３０重量％を含むモノマーを溶液重合してなるアクリル系共重合体（Ａ）（ただし、カルボキシル基を有するものを除く）、リチウム、鉄、銅、ナトリウム、カリウムおよび４級アンモニウムからなる群より選択される１種の陽イオンを含むイオン化合物（Ｂ）及び３官能イソシアネート化合物である硬化剤（Ｃ）を含有し、２３℃−６５％ＲＨ雰囲気でのガラス板に対する１８０度ピール、引っ張り速度３００ｍｍ／分での粘着力が２００ｇ／２５ｍｍ以下であることを特徴とする光学部材用の再剥離性帯電防止アクリル粘着剤。 That is, the present invention relates to an acrylic copolymer (A) having a hydroxyl group and an alkylene oxide chain in the side chain and a solution polymerized monomer containing a monomer having a hydroxyl group in an amount of 1 to 30% by weight (however, having a carboxyl group). An ionic compound (B) containing one kind of cation selected from the group consisting of lithium, iron, copper, sodium, potassium and quaternary ammonium, and a curing agent (C) which is a trifunctional isocyanate compound A releasable antistatic acrylic for optical members containing 180 ° peel to a glass plate in a 23 ° C.-65% RH atmosphere and having an adhesive strength of 200 g / 25 mm or less at a pulling speed of 300 mm / min. Adhesive.
本発明により、適度な表面抵抗値を有し、透明性、再剥離性に優れる帯電防止粘着剤が得られるようになった。 According to the present invention, an antistatic pressure-sensitive adhesive having an appropriate surface resistance value and excellent in transparency and removability can be obtained.
本発明に用いられる、アクリル系共重合体（Ａ）は、水酸基とアルキレンオキサイド鎖を有するものであり、水酸基を有するアクリル系モノマーとアルキレンオキサイド鎖を有するアクリル系モノマーと、必要に応じてこれらと共重合可能な他のアクリル系モノマーから合成することができる。 The acrylic copolymer (A) used in the present invention has a hydroxyl group and an alkylene oxide chain, and if necessary, an acrylic monomer having a hydroxyl group and an acrylic monomer having an alkylene oxide chain. It can be synthesized from other acrylic monomers that can be copolymerized.
本発明に用いられる、水酸基を有するアクリル系モノマーとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート等が挙げられる。本発明では、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）アクリレートが好ましい。 Examples of the acrylic monomer having a hydroxyl group used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate and the like. Can be mentioned. In the present invention, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.
本発明において、水酸基を有するアクリル系モノマーを使用する目的は、被着体に対する粘着力を確保しつつ再剥離性を確保するためである。さらに詳しく説明すると、粘着剤層を形成する際に使用する後述のイソシアネート系硬化剤等の硬化剤（Ｃ）とこれらの水酸基との反応を利用して架橋構造を形成し、他方後述するようにアクリル系共重合体（Ａ）の分子量を制御することにより、粘着力と再剥離性とのバランスをとることができる。 In the present invention, the purpose of using the acrylic monomer having a hydroxyl group is to ensure the removability while ensuring the adhesive force to the adherend. More specifically, a cross-linked structure is formed by utilizing the reaction between a curing agent (C) such as an isocyanate curing agent described later used in forming the pressure-sensitive adhesive layer and these hydroxyl groups, and as described later. By controlling the molecular weight of the acrylic copolymer (A), it is possible to balance the adhesive strength and the removability.
よって、アクリル系共重合体（Ａ）及び後述するアルキレンオキサイド鎖を有しないアクリル系共重合体（Ｄ）を併用する場合には共重合に供される全モノマーを１００重量％とした場合、水酸基を有するアクリル系モノマーは１〜３０重量％であることが好ましい。さらに好ましくは、３〜１０重量％である。水酸基を有するアクリルモノマーが１重量％未満だと、粘着剤層としての架橋度及び凝集力が不足し、粘着力が大きくなりすぎたり、糊残りが発生しやすいので好ましくない。３０重量％を超えると、架橋度が高くなりすぎて粘着性が乏しくなるので好ましくない。 Therefore, when the acrylic copolymer (A) and the acrylic copolymer (D) having no alkylene oxide chain, which will be described later, are used in combination, the total monomer used for the copolymerization is 100% by weight. It is preferable that the acrylic monomer which has 1-30 weight%. More preferably, it is 3 to 10% by weight. If the acrylic monomer having a hydroxyl group is less than 1% by weight, the degree of cross-linking and cohesion as the pressure-sensitive adhesive layer are insufficient, and the pressure-sensitive adhesive force becomes excessively large or adhesive residue is liable to occur. If it exceeds 30% by weight, the degree of crosslinking becomes too high and the tackiness becomes poor.
本発明に用いられる、アルキレンオキサイド鎖を有するアクリルモノマーとしては、エチレンオキサイド鎖を有するモノマー、プロピレンオキサイド鎖を有するモノマー、およびその両者を有するモノマーが挙げられる。 Examples of the acrylic monomer having an alkylene oxide chain used in the present invention include a monomer having an ethylene oxide chain, a monomer having a propylene oxide chain, and a monomer having both.
エチレンオキサイド鎖を有するモノマーとしては、メトキシポリエチレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート等が挙げられる。
プロピレンオキサイド鎖を有するモノマーとしては、メトキシポリプロピレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート等を挙げることができる。
本発明では、後述のイオン化合物との相溶性を考慮して、エチレンオキサイド鎖を有するモノマーが好ましく、メトキシポリエチレングリコール（メタ）アクリレートが特に好ましい。
Examples of the monomer having an ethylene oxide chain include methoxypolyethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate.
Examples of the monomer having a propylene oxide chain include methoxypolypropylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate.
In the present invention, a monomer having an ethylene oxide chain is preferable in consideration of compatibility with an ionic compound described later, and methoxypolyethylene glycol (meth) acrylate is particularly preferable.
本発明にアルキレンオキサイド鎖を有するアクリルモノマーを使用する目的は、イオン化合物（Ｂ）とアルキレンオキサイドで錯体を形成させ、導電性を発現させるためである。よって、アルキレンオキサイド鎖の役割は非常に大きく、単に錯体形成の場を与えるだけでなく、イオン化合物（Ｂ）の移動媒体としての働きも同時に担っている。言い換えると、本発明における導電性は、イオン化合物（Ｂ）の量とアルキレンオキサイド鎖を有するモノマーの含有量によって大きく変動する。 The purpose of using the acrylic monomer having an alkylene oxide chain in the present invention is to form a complex with the ionic compound (B) and the alkylene oxide to develop conductivity. Therefore, the role of the alkylene oxide chain is very large and not only provides a field for complex formation, but also serves as a transfer medium for the ionic compound (B). In other words, the conductivity in the present invention varies greatly depending on the amount of the ionic compound (B) and the content of the monomer having an alkylene oxide chain.
よって、アクリル系共重合体（Ａ）及び後述するアルキレンオキサイド鎖を有しないアクリル系共重合体（Ｄ）を併用する場合には共重合に供される全モノマーを１００重量％とした場合、アルキレンオキサイド鎖を有するアクリル系モノマーは、１〜６０重量％が好ましい。さらに好ましくは５〜５０重量％である。 Therefore, when the acrylic copolymer (A) and the acrylic copolymer (D) having no alkylene oxide chain described later are used in combination, the total monomer used for copolymerization is 100% by weight. The acrylic monomer having an oxide chain is preferably 1 to 60% by weight. More preferably, it is 5 to 50% by weight.
本発明に用いられる、上記のアクリルモノマーと共重合可能なモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、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、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ノナデシル（メタ）アクリレート、イコシル（メタ）アクリレート、ヘンイコシル（メタ）アクリレート、ドコシル（メタ）アクリレート等を挙げることができる。本発明においては、粘着物性を確保するという点で、炭素数が４〜１２のアクリル系モノマーを共重合に供することが好ましい。さらに好ましくは、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレートである。 Examples of the monomer that can be copolymerized with the acrylic monomer used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (Meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate Nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate and docosyl (meth) acrylate. In the present invention, it is preferable to use an acrylic monomer having 4 to 12 carbon atoms for copolymerization from the viewpoint of securing adhesive properties. More preferred are butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
上述の水酸基を有するアクリル系モノマー、アルキレンオキサイド鎖を有するアクリル系モノマー、及びその他のモノマー等を共重合してなるアクリル系共重合体（Ａ）の重量平均分子量（Ｍｗ）は５万〜１００万であることが好ましく、５万〜２０万の低分子量アクリル系共重合体（Ａ１）であることがより好ましい。 The weight average molecular weight (Mw) of the acrylic copolymer (A) obtained by copolymerizing the above acrylic monomer having a hydroxyl group, an acrylic monomer having an alkylene oxide chain, and other monomers is 50,000 to 1,000,000. Preferably, it is a low molecular weight acrylic copolymer (A1) having a molecular weight of 50,000 to 200,000.
背景技術の項でも述べたように光学部材用保護フィルム用の粘着剤には、帯電防止機能と再剥離性と透明性が要求される。従って、帯電防止機能の観点からはアクリル系共重合体（Ａ）がより多くのアルキレンオキサイド鎖を含むことが好ましい。
ところで、光学部材の中には非常に薄く、壊れやすいものがある一方、比較的丈夫なものもあり、保護フィルムをどのような被着体に貼着するかによって、保護フィルムそして粘着剤に要求される剥離力の大きさは異なる。
即ち、壊れやすい光学部材を被着体とする場合には、貼着後保護フィルムを剥離する際に被着体を損傷しないようにするために、剥離力は２００ｇ／２５ｍｍ以下であることが好ましく、さらに好ましくは１００ｇ／２５ｍｍ以下である。
一方、比較的強い光学部材を被着体とする場合には、剥離力は１０００ｇ／２５ｍｍ程度まで許容され得る。
尚、剥離時に粘着剤が被着体に残らないことは被着体がどのようなものであっても常に要求される。
As described in the background art section, the adhesive for the protective film for optical members is required to have an antistatic function, removability and transparency. Therefore, from the viewpoint of the antistatic function, it is preferable that the acrylic copolymer (A) contains more alkylene oxide chains.
By the way, some optical members are very thin and fragile, while others are relatively strong. Depending on the type of adherend to which the protective film is attached, the protective film and adhesive are required. The magnitude of the peel force applied is different.
That is, when the fragile optical member is used as an adherend, the peeling force is preferably 200 g / 25 mm or less so as not to damage the adherend when the protective film is peeled off after sticking. More preferably, it is 100 g / 25 mm or less.
On the other hand, when a relatively strong optical member is used as the adherend, the peeling force can be allowed to be about 1000 g / 25 mm.
It should be noted that it is always required that the pressure-sensitive adhesive does not remain on the adherend when it is peeled regardless of the adherend.
粘着剤の剥離力は、粘着剤を構成する主たる成分自体の有する凝集力と、該主成分と後述する硬化剤（Ｃ）との架橋の状況によって大きく影響を受ける。一般に主成分に対して硬化剤（Ｃ）を多量に用いることによって、剥離力を低下することができる。また、一般に主成分の分子量を大きくすることによって、主成分自体の凝集力を大きくすることができる。 The peel strength of the pressure sensitive adhesive is greatly influenced by the cohesive strength of the main component itself constituting the pressure sensitive adhesive and the state of crosslinking between the main component and the curing agent (C) described later. In general, the peeling force can be reduced by using a large amount of the curing agent (C) with respect to the main component. In general, the cohesive force of the main component itself can be increased by increasing the molecular weight of the main component.
本発明の粘着剤において、剥離時の２００ｇ／２５ｍｍ以下の低剥離力が要求される場合には、主成分、即ちアクリル系共重合体（Ａ）１００重量部に対して硬化剤（Ｃ）を１０〜４０重量部用いることが好ましく、１２．５〜３７．５重量部用いることがより好ましく、１５〜３０重量部用いることがさらに好ましい。尚、低剥離力発現の観点からは硬化剤（Ｃ）は多い方が好ましい。しかし、多すぎると架橋が過度になり、滑らかには剥離できず、きしみながら剥離する。
本発明で使用するアルキレンオキサイド鎖を有するアクリル系モノマーは、一般に他のアクリル系モノマーと容易に共重合することが可能ではあるが、その反面連鎖移動効果が大きい。従って、導電性向上の観点からアルキレンオキサイド鎖の含有量を多くしようとすると、得られるアクリル系共重合体（Ａ）の分子量が低下し易く、分子量が低下するとアクリル系共重合体（Ａ）自体の凝集力が低下し易くなり、剥離時に被着体に粘着剤が残存し易くなる。
しかし、低剥離力確保のために上記したようにアクリル系共重合体（Ａ）に対して相対的に多量の硬化剤（Ｃ）を用いると、密な架橋の粘着剤層を得ることができるので、比較的低分子量のアクリル系共重合体（Ａ１）を用いても剥離時に被着体に粘着剤が残存することがなくなる。
従って、低抵抗かつ上記のような低剥離力が要求される場合には、アクリル系共重合体（Ａ）として、アルキレンオキサイド鎖を有するアクリル系モノマーをより多く共重合してなるＭｗが５万〜２０万の低分子量アクリル系共重合体（Ａ１）を用いることが好ましい態様の１つである。
In the pressure-sensitive adhesive of the present invention, when a low peeling force of 200 g / 25 mm or less at the time of peeling is required, the curing agent (C) is added to 100 parts by weight of the main component, that is, the acrylic copolymer (A). It is preferable to use 10 to 40 parts by weight, more preferably 12.5 to 37.5 parts by weight, and still more preferably 15 to 30 parts by weight. In addition, it is preferable that there are many hardening | curing agents (C) from a viewpoint of low peeling force expression. However, if it is too much, crosslinking will be excessive, and it will not be able to peel off smoothly, but will peel off with squeaking.
The acrylic monomer having an alkylene oxide chain used in the present invention can generally be easily copolymerized with other acrylic monomers, but has a large chain transfer effect. Therefore, if the content of the alkylene oxide chain is increased from the viewpoint of improving conductivity, the molecular weight of the resulting acrylic copolymer (A) tends to decrease, and if the molecular weight decreases, the acrylic copolymer (A) itself The cohesive force tends to decrease, and the pressure-sensitive adhesive tends to remain on the adherend during peeling.
However, when a relatively large amount of the curing agent (C) is used with respect to the acrylic copolymer (A) in order to secure a low peeling force, a densely crosslinked pressure-sensitive adhesive layer can be obtained. Therefore, even if a relatively low molecular weight acrylic copolymer (A1) is used, the adhesive does not remain on the adherend during peeling.
Therefore, when the low resistance and the low peeling force as described above are required, the acrylic copolymer (A) has an Mw obtained by copolymerizing more acrylic monomers having an alkylene oxide chain of 50,000. It is one of the preferred embodiments to use ˜200,000 low molecular weight acrylic copolymer (A1).
また、本発明においては、アクリル系共重合体（Ａ）として、Ｍｗが２０万〜１００万の高分子量アクリル系共重合体（Ａ２）を用いることもできる。アルキレンオキサイド鎖を有するアクリル系モノマーの連鎖移動効果を制御しながら共重合することによって、比較的高分子量でありながら、導電性に優れるアクリル系共重合体（Ａ２）を得ることができる。
例えば、重合の工程を複数にしたり（多段重合反応）、開始剤の量を少なくしたり、モノマー濃度を制御したりすることによって得ることができる。より具体的には、共重合に供するアルキレンオキサイド鎖を有するアクリル系モノマーを重合の初期には全く若しくはほとんど用いずに、重合を進行させ、ある程度高分子量化した後に、アルキレンオキサイド鎖を有するアクリル系モノマーの全部若しくは大部分を重合に供することによって得ることができる。このようないわゆる二段重合法を利用する場合、アルキレンオキサイド鎖を有するアクリル系モノマーの主たる量を重合する際には、重合開始剤もさらに用いることができる。
In the present invention, a high molecular weight acrylic copolymer (A2) having an Mw of 200,000 to 1,000,000 can also be used as the acrylic copolymer (A). By copolymerizing while controlling the chain transfer effect of the acrylic monomer having an alkylene oxide chain, it is possible to obtain an acrylic copolymer (A2) having a relatively high molecular weight and excellent conductivity.
For example, it can be obtained by using a plurality of polymerization steps (multistage polymerization reaction), reducing the amount of the initiator, or controlling the monomer concentration. More specifically, an acrylic monomer having an alkylene oxide chain is used after the polymerization is advanced to a certain degree of high molecular weight with little or no use of an acrylic monomer having an alkylene oxide chain for copolymerization at the initial stage of the polymerization. It can be obtained by subjecting all or most of the monomers to polymerization. When such a so-called two-stage polymerization method is used, a polymerization initiator can be further used when the main amount of the acrylic monomer having an alkylene oxide chain is polymerized.
尚、高分子量アクリル系共重合体（Ａ２）は上記低分子量アクリル系共重合体（Ａ１）に比して、それ自体の凝集力が大きいので硬化剤（Ｃ）の量を減らしても剥離時に糊残りは生じ難い。しかし、剥離力が１００ｇ／２５ｍｍ以下、好ましくは５０ｇ／２５ｍｍ以下というような微粘着が要求されるような場合には、粘着剤中に密な架橋構造を形成することが好ましい。従って、硬化剤（Ｃ）は、上記低分子量アクリル系共重合体（Ａ１）の場合と同様に高分子量アクリル系共重合体（Ａ２）１００重量部に対して１０〜４０重量部程度用いることが好ましい。 The high molecular weight acrylic copolymer (A2) has a higher cohesive strength than the low molecular weight acrylic copolymer (A1). Therefore, even when the amount of the curing agent (C) is reduced, the high molecular weight acrylic copolymer (A2) No adhesive residue is likely to occur. However, when fine adhesion such as a peel strength of 100 g / 25 mm or less, preferably 50 g / 25 mm or less is required, it is preferable to form a dense cross-linked structure in the adhesive. Accordingly, the curing agent (C) is used in an amount of about 10 to 40 parts by weight with respect to 100 parts by weight of the high molecular weight acrylic copolymer (A2) as in the case of the low molecular weight acrylic copolymer (A1). preferable.
さらに、本発明においては、アルキレンオキサイド鎖を有しないアクリル系共重合体（Ｄ）を併用することもでき、Ｍｗが２０万以上１００万以下のアルキレンオキサイド鎖を有しない高分子量アクリル系共重合体（Ｄ１）を、Ｍｗが５万〜２０万のアルキレンオキサイド鎖を有する低分子量アクリル系共重合体（Ａ１）と併用することも本発明の態様の１つである。
高分子量アクリル系共重合体（Ｄ１）を併用する場合は、低分子量アクリル系共重合体（Ａ１）／高分子量アクリル系共重合体（Ｄ１）＝５〜８０／２０〜９５（重量比）であることが好ましく、１０〜６０／４０〜９０（重量比）であることがより好ましい。
上記したように低分子量アクリル系共重合体（Ａ１）は、多くの場合導電性には優れるが、凝集力の小ささ故に糊残りの抑制・防止の観点から硬化剤（Ｃ）を多量に使用する必要がある。このような低分子量アクリル系共重合体（Ａ１）に対し、高分子量アクリル系共重合体（Ｄ１）を併用することによって、硬化剤（Ｃ）の使用量を減らすことができる。例えば、低分子量アクリル系共重合体（Ａ１）と高分子量アクリル系共重合体（Ｄ１）の合計１００重量部に対し、硬化剤（Ｃ）を１〜８重量部用いることができ、２〜５重量部用いることができる。剥離時に１０００ｇ／２５ｍｍ程度までの剥離力が許容され得る場合には、このように、高分子量アクリル系共重合体（Ｄ１）を併用しつつ、硬化剤（Ｃ）を減らすことによって、様々なレベルの帯電防止性、再剥離性に対する要求に応えることができる。
また、低分子量アクリル系共重合体（Ａ１）と高分子量アクリル系共重合体（Ｄ１）の合計１００重量部に対し、硬化剤（Ｃ）を１０〜４０重量部用いれば、低剥離力の粘着剤を得ることもできる。
Furthermore, in the present invention, an acrylic copolymer (D) having no alkylene oxide chain can be used in combination, and a high molecular weight acrylic copolymer having no alkylene oxide chain having an Mw of 200,000 to 1,000,000. It is also one aspect of the present invention to use (D1) in combination with a low molecular weight acrylic copolymer (A1) having an alkylene oxide chain having an Mw of 50,000 to 200,000.
When the high molecular weight acrylic copolymer (D1) is used in combination, the low molecular weight acrylic copolymer (A1) / high molecular weight acrylic copolymer (D1) = 5 to 80/20 to 95 (weight ratio). It is preferably 10 to 60/40 to 90 (weight ratio).
As described above, the low molecular weight acrylic copolymer (A1) is excellent in conductivity in many cases, but uses a large amount of the curing agent (C) from the viewpoint of suppressing or preventing adhesive residue because of its small cohesive force. There is a need to. By using the high molecular weight acrylic copolymer (D1) in combination with such a low molecular weight acrylic copolymer (A1), the amount of the curing agent (C) used can be reduced. For example, 1 to 8 parts by weight of the curing agent (C) can be used with respect to a total of 100 parts by weight of the low molecular weight acrylic copolymer (A1) and the high molecular weight acrylic copolymer (D1). Part by weight can be used. In the case where a peeling force of up to about 1000 g / 25 mm can be tolerated at the time of peeling, various levels can be obtained by reducing the curing agent (C) while using the high molecular weight acrylic copolymer (D1) in this way. It is possible to meet the demand for antistatic property and removability.
Further, when 10 to 40 parts by weight of the curing agent (C) is used with respect to 100 parts by weight of the total of the low molecular weight acrylic copolymer (A1) and the high molecular weight acrylic copolymer (D1), the adhesive with low peeling force is used. An agent can also be obtained.
本発明において用いられるアルキレンオキサイド鎖を有しない高分子量アクリル系共重合体（Ｄ）は、アルキレンオキサイド鎖を有するアクリル系モノマーを重合に供しない以外、アクリル系共重合体（Ａ）と同様に得ることができる。 The high molecular weight acrylic copolymer (D) having no alkylene oxide chain used in the present invention is obtained in the same manner as the acrylic copolymer (A) except that an acrylic monomer having an alkylene oxide chain is not subjected to polymerization. be able to.
本発明においては、アクリル系共重合体（Ａ）と高分子量アクリル系共重合体（Ｄ）とをそれぞれ得ておき、両者を混合してもよいし、あるいは高分子量アクリル系共重合体（Ｄ）を得、該高分子量アクリル系共重合体（Ｄ）の存在下にアクリル系共重合体（Ａ）用のモノマーを重合してもよい。後者の方法は、先に述べたアクリル系共重合体（Ａ）を得る際の多段重合法にやや似ている。両者の相違点は、アクリル系共重合体（Ａ）を得る際の多段重合法は、アルキレンオキサイド鎖を有するアクリル系モノマーの主たる量を重合する二段目以降の重合の際には、アルキレンオキサイド鎖を有するアクリル系モノマーのみを重合に供するのに対し、高分子量アクリル系共重合体（Ｄ）の存在下にアクリル系共重合体（Ａ）用のモノマーを重合する場合、２段目以降の重合の際にはアルキレンオキサイド鎖を有するアクリル系モノマー及び他のモノマーを重合に供する点である。 In the present invention, the acrylic copolymer (A) and the high molecular weight acrylic copolymer (D) are obtained in advance, and both may be mixed, or the high molecular weight acrylic copolymer (D And the monomer for the acrylic copolymer (A) may be polymerized in the presence of the high molecular weight acrylic copolymer (D). The latter method is somewhat similar to the multistage polymerization method for obtaining the acrylic copolymer (A) described above. The difference between the two is that in the multistage polymerization method for obtaining the acrylic copolymer (A), in the second and subsequent polymerizations in which the main amount of the acrylic monomer having an alkylene oxide chain is polymerized, the alkylene oxide is used. Where only the acrylic monomer having a chain is subjected to polymerization, whereas the monomer for the acrylic copolymer (A) is polymerized in the presence of the high molecular weight acrylic copolymer (D), the second and subsequent stages are polymerized. In the polymerization, an acrylic monomer having an alkylene oxide chain and other monomers are used for the polymerization.
本発明に用いるイオン化合物（Ｂ）としては、塩化ナトリウム、塩化カリウム、塩化リチウム、過塩素酸リチウム、塩化アンモニウム、塩素酸カリウム、塩化アルミニウム、塩化銅、塩化第一鉄、塩化第二鉄、硫酸アンモニウム、硝酸カリウム、硝酸ナトリウム、炭酸ナトリウム、チオシアン酸ナトリウム等の無機塩類、
酢酸ナトリウム、アルギン酸ソーダ、リグニンスルホン酸ソーダ、トルエンスルホン酸ソーダ等の有機塩類が挙げられる。
これらは単独もしくは混合して使用することができる。導電性及び安全性等の観点から、塩化ナトリウム、塩化カリウム、過塩素酸リチウム等が好ましい。
Examples of the ionic compound (B) used in the present invention include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate. , Inorganic salts such as potassium nitrate, sodium nitrate, sodium carbonate, sodium thiocyanate,
Organic salts such as sodium acetate, sodium alginate, sodium lignin sulfonate, and sodium toluene sulfonate are listed.
These can be used alone or in combination. From the viewpoints of conductivity and safety, sodium chloride, potassium chloride, lithium perchlorate and the like are preferable.
また、その含有量は、アクリル系共重合体（Ａ）１００重量部に対して、またはアクリル系共重合体（Ｄ）を併用する場合には両者共重合体の合計１００重量部に対して、０．１〜５０重量部であることが好ましい。さらに好ましくは１〜３０重量部である。０．１重量部未満では十分なイオン導電性が得られず、５０重量部よりも多くイオン化合物（Ｂ）を含有しても導電性向上の効果がほとんど期待できなくなり、さらに粘着物性の低下、及び樹脂との相溶性の低下により塗膜の白化が起こりやすくなるので好ましくない。 Moreover, the content is 100 parts by weight of the acrylic copolymer (A), or in the case where the acrylic copolymer (D) is used in combination, with respect to a total of 100 parts by weight of both copolymers, It is preferable that it is 0.1-50 weight part. More preferably, it is 1-30 weight part. If it is less than 0.1 parts by weight, sufficient ionic conductivity cannot be obtained, and even if it contains more than 50 parts by weight of the ionic compound (B), the effect of improving the conductivity can hardly be expected. And, since the whitening of the coating film tends to occur due to a decrease in compatibility with the resin, it is not preferable.
帯電防止アクリル粘着剤を用いてなる粘着フィルム、即ち光学部材用保護フイルムの経時安定性には、含まれるイオン化合物（Ｂ）の量と、アクリル共重合体（Ａ）に含まれるアルキレンオキサイド鎖の量が大きく影響する。
アルキレンオキサイド鎖の量が多い場合は、イオン化合物（Ｂ）と効率よく錯体を形成することができるが、アルキレンオキサイド鎖の量が少なく、イオン化合物の量が多いと、錯体を形成し得ない過剰のイオン化合物が粘着剤層表面に移行し、上記のような白化現象が起こりやすくなる。また、経時での表面抵抗値も上昇しやすくなってしまう。
これらの観点から、粘着剤層中に含まれるアルキレンオキサイド鎖の量をできるだけ多くし、要求される導電性を発現し得る最低限のイオン化合物（Ｂ）を添加することが好ましい。
The stability over time of the pressure-sensitive adhesive film using an antistatic acrylic pressure-sensitive adhesive, that is, the protective film for optical members, includes the amount of the ionic compound (B) contained and the amount of alkylene oxide chain contained in the acrylic copolymer (A). The amount is greatly affected.
When the amount of the alkylene oxide chain is large, a complex can be formed efficiently with the ionic compound (B), but when the amount of the alkylene oxide chain is small and the amount of the ionic compound is large, an excess that cannot form a complex is formed. The ionic compound moves to the surface of the pressure-sensitive adhesive layer, and the whitening phenomenon as described above tends to occur. In addition, the surface resistance value with time tends to increase.
From these viewpoints, it is preferable to increase the amount of alkylene oxide chains contained in the pressure-sensitive adhesive layer as much as possible and to add the minimum ionic compound (B) capable of expressing the required conductivity.
本発明の帯電防止アクリル粘着剤においては、凝集力及び架橋度を上げるために、好適に硬化剤（Ｃ）を使用することができる。
本発明の硬化剤（Ｃ）としては、アクリル系共重合体（Ａ）及び（Ｄ）中に含まれる水酸基等の官能基と反応し得る官能基を有する好ましくは１分子中に２個以上有するものが好ましい。例えば、公知の３官能イソシアネート化合物、公知の多官能エポキシ化合物を好適に使用することができる。これらは併用することもできる。
In the antistatic acrylic pressure-sensitive adhesive of the present invention, a curing agent (C) can be suitably used in order to increase the cohesive strength and the degree of crosslinking.
The curing agent (C) of the present invention preferably has two or more functional groups that can react with functional groups such as hydroxyl groups contained in the acrylic copolymers (A) and (D). Those are preferred. For example, a known trifunctional isocyanate compound or a known polyfunctional epoxy compound can be suitably used. These can also be used in combination.
公知の３官能イソシアネート化合物としては、公知のジイソシアネート化合物を３官能ポリオール成分で変性したいわゆるアダクト体、ジイソシアネート化合物が水と反応したビュレット体、ジイソシアネート化合物３分子から形成されるイソシアヌレート環を有する３量体（イソシアヌレート体）を使用することができる。 The known trifunctional isocyanate compound includes a so-called adduct obtained by modifying a known diisocyanate compound with a trifunctional polyol component, a burette obtained by reacting the diisocyanate compound with water, and a 3 amount having an isocyanurate ring formed from three molecules of the diisocyanate compound. The body (isocyanurate body) can be used.
公知のジイソシアネート化合物としては、芳香族ジイソシアネート、脂肪族ジイソシアネート、芳香脂肪族ジイソシアネート、脂環族ジイソシアネート等が挙げられる。 Known diisocyanate compounds include aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and the like.
芳香族ジイソシアネートとしては、１，３−フェニレンジイソシアネート、４，４'−ジフェニルジイソシアネート、１，４−フェニレンジイソシアネート、４，４'−ジフェニルメタンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４'−トルイジンジイソシアネート、ジアニシジンジイソシアネート、４，４'−ジフェニルエーテルジイソシアネート等を挙げることができる。 As aromatic diisocyanates, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Examples thereof include isocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, and 4,4′-diphenyl ether diisocyanate.
脂肪族ジイソシアネートとしては、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２−プロピレンジイソシアネート、２，３−ブチレンジイソシアネート、１，３−ブチレンジイソシアネート、ドデカメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート等を挙げることができる。 Aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4 , 4-trimethylhexamethylene diisocyanate and the like.
芳香脂肪族ジイソシアネートとしては、ω，ω'−ジイソシアネート−１，３−ジメチルベンゼン、ω，ω'−ジイソシアネート−１，４−ジメチルベンゼン、ω，ω'−ジイソシアネート−１，４−ジエチルベンゼン、１，４−テトラメチルキシリレンジイソシアネート、１，３−テトラメチルキシリレンジイソシアネート等を挙げることができる。 Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.
脂環族ジイソシアネートとしては、３−イソシアネートメチル−３，５，５−トリメチルシクロヘキシルイソシアネート、１，３−シクロペンタンジイソシアネート、１，３−シクロヘキサンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチル−２，４−シクロヘキサンジイソシアネート、メチル−２，６−シクロヘキサンジイソシアネート、４，４'−メチレンビス（シクロヘキシルイソシアネート）、１，４−ビス（イソシアネートメチル）シクロヘキサン、１，４−ビス（イソシアネートメチル）シクロヘキサン等を挙げることができる。 Examples of alicyclic diisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4- Examples include cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, and the like. .
本発明に用いられるジイソシアネート化合物としては、４，４'−ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、３−イソシアネートメチル−３，５，５−トリメチルシクロヘキシルイソシアネート（イソホロンジイソシアネート）を使用することが好ましい。 As the diisocyanate compound used in the present invention, it is preferable to use 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate).
公知の多官能エポキシ化合物としては、エポキシ基を分子内に複数個有する化合物であればよく、特に限定されるものではない。該多官能エポキシ化合物としては、具体できには、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、ビスフェノールＡ・エピクロロヒドリン型エポキシ樹脂、Ｎ，Ｎ，Ｎ'Ｎ'−テトラグリシジル−ｍ−キシレンジアミン、１，３−ビス（Ｎ，Ｎ−ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ−ジグリシジルアニリン、Ｎ，Ｎ−ジグリシジルトルイジン等が挙げられる。 The known polyfunctional epoxy compound is not particularly limited as long as it is a compound having a plurality of epoxy groups in the molecule. Specific examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, N, N, N′N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, etc. It is done.
上述の硬化剤（Ｃ）については、３官能イソシアネート化合物および多官能エポキシ化合物をそれぞれ単独および併用して使用することができる。柔軟性を重視する用途で使用する場合は、３官能イソシアネート化合物を使用することが好ましく、耐熱性を要求される場合、多官能エポキシ化合物を使用することが好ましい。
上記したように２００ｇ／２５ｍｍ以下、好ましくは１００ｇ／２５ｍｍ以下の低剥離力が求められる場合には、アクリル系共重合体（Ａ）１００重量部に対して硬化剤（Ｃ）を１０〜４０重量部用いることが好ましく、１２．５〜３７．５重量部用いることがより好ましく、１５〜３０重量部用いることがさらに好ましい。
また、多官能エポキシ化合物を使用する場合は、より効果的に架橋剤として作用するために、アクリル系共重合体（Ａ）にアクリル酸またはメタクリル酸が含まれていることが好ましい。その含有量については、全アクリルモノマー中、重量比で０．５〜５％であることが好ましい。０．５％未満では、架橋剤として十分に作用せず、５％を超えると、硬化剤（Ｃ）を添加後のポットライフが短くなりやすいので好ましくない。
About the above-mentioned hardening | curing agent (C), a trifunctional isocyanate compound and a polyfunctional epoxy compound can be used individually and in combination, respectively. When used in applications that place importance on flexibility, it is preferable to use a trifunctional isocyanate compound. When heat resistance is required, it is preferable to use a polyfunctional epoxy compound.
As described above, when a low peeling force of 200 g / 25 mm or less, preferably 100 g / 25 mm or less is required, the curing agent (C) is used in an amount of 10 to 40 weights per 100 parts by weight of the acrylic copolymer (A). Part is preferably used, more preferably 12.5 to 37.5 parts by weight, and still more preferably 15 to 30 parts by weight.
Moreover, when using a polyfunctional epoxy compound, in order to act as a crosslinking agent more effectively, it is preferable that acrylic acid or methacrylic acid is contained in the acrylic copolymer (A). About the content, it is preferable that it is 0.5 to 5% by weight ratio in all the acrylic monomers. If it is less than 0.5%, it does not sufficiently act as a crosslinking agent, and if it exceeds 5%, the pot life after the addition of the curing agent (C) tends to be short, such being undesirable.
本発明の帯電防止粘着剤には、さらに必要に応じて、他の樹脂、例えばアクリル樹脂、ポリエステル樹脂、アミノ樹脂、エポキシ樹脂、ポリウレタン樹脂を併用することもできる。また、用途に応じて、粘着付与剤、タルク、炭酸カルシウム、酸化チタン等の充填剤、着色剤、紫外線吸収剤、酸化防止剤、消泡剤、光安定剤等の添加剤を配合しても良い。 If necessary, the antistatic pressure-sensitive adhesive of the present invention may be used in combination with other resins such as acrylic resins, polyester resins, amino resins, epoxy resins, and polyurethane resins. Depending on the application, additives such as tackifiers, talc, calcium carbonate, titanium oxide, etc., colorants, ultraviolet absorbers, antioxidants, antifoaming agents, light stabilizers, etc. may be blended. good.
本発明の帯電防止粘着剤を用いて、該粘着剤から形成される粘着剤層と、プラスチックフィルム、紙、布、発泡体等の基材とが積層された粘着シートを得ることができ、粘着剤層の表面を剥離シートで被覆しておくことができる。
粘着シートは、各種基材に粘着剤を塗布したり含浸したりし、これを乾燥・硬化することによって得ることができる。あるいは、剥離シート上に粘着剤を塗布し、これを乾燥し、形成されつつある粘着剤層表面に各種基材を積層し、粘着剤中の水酸基と硬化剤（Ｃ）中のイソシアネート基、あるいは粘着剤中のカルボキシル基と硬化剤（Ｃ）中のエポキシ基との反応を進行させることによっても得ることができる。
By using the antistatic pressure-sensitive adhesive of the present invention, it is possible to obtain a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive and a substrate such as a plastic film, paper, cloth, and foam are laminated. The surface of the agent layer can be covered with a release sheet.
The pressure-sensitive adhesive sheet can be obtained by applying or impregnating a pressure-sensitive adhesive to various substrates, and drying and curing it. Alternatively, a pressure-sensitive adhesive is applied on the release sheet, dried, and various substrates are laminated on the surface of the pressure-sensitive adhesive layer that is being formed, and a hydroxyl group in the pressure-sensitive adhesive and an isocyanate group in the curing agent (C), or It can also be obtained by advancing the reaction between the carboxyl group in the pressure-sensitive adhesive and the epoxy group in the curing agent (C).
本発明の粘着剤は、基材のうち透明なプラスチックフィルムに適用することによって、光学部材用の表面保護粘着フィルムを好適に得ることができる。 By applying the pressure-sensitive adhesive of the present invention to a transparent plastic film among the substrates, a surface protective pressure-sensitive adhesive film for an optical member can be suitably obtained.
プラスチックフィルムとしては、ポリ塩化ビニルフィルム、ポリエチレンフィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリウレタンフィルム、ナイロンフィルム、処理ポリオレフィンフィルム、未処理ポリオレフィンフィルム等が挙げられる。 Examples of the plastic film include polyvinyl chloride film, polyethylene film, polyethylene terephthalate (PET) film, polyurethane film, nylon film, treated polyolefin film, untreated polyolefin film, and the like.
本発明の帯電防止粘着剤は、乾燥・硬化した際に２〜２００μｍ程度の厚みになるように基材に塗布等することが好ましい。２μｍ未満だとイオン導電性が乏しくなり、２００μｍを越えると粘着シートの製造、取り扱いが難しくなる。
このようにして粘着剤層の表面抵抗値が１０11Ω／□以下の帯電防止粘着フィルムを得ることができる。
The antistatic pressure-sensitive adhesive of the present invention is preferably applied to a substrate so as to have a thickness of about 2 to 200 μm when dried and cured. If it is less than 2 μm, the ionic conductivity becomes poor, and if it exceeds 200 μm, the production and handling of the pressure-sensitive adhesive sheet becomes difficult.
In this manner, an antistatic pressure-sensitive adhesive film having a surface resistance value of the pressure-sensitive adhesive layer of 10 11 Ω / □ or less can be obtained.
本発明の帯電防止粘着剤を用い、その用途、要求性能等を考慮した上で、種々の態様の帯電防止粘着フィルムを得ることができる。
例えば、偏光板の保護フィルム用の帯電防止粘着フィルムについて、図面に基づいて説明する。
図１は、ＰＥＴフィルムの偏光板側に帯電防止アクリル粘着剤層が、
図２は、ＰＥＴフィルムの偏光板側、反対側の両面に帯電防止アクリル粘着剤層が、
図３は、ＰＥＴフィルムの偏光板側に帯電防止コーティング剤層、さらに帯電防止アクリル粘着剤層が、
図４は、ＰＥＴフィルムの偏光板側に帯電防止アクリル粘着剤層、その反対側に帯電防止コーティング剤層が、それぞれ位置する態様を示す。
光学部材、電子部材の表面保護用のフィルムに本発明の粘着剤を用いる場合、剥離帯電量をさらに低減するために、図３、４の様な形態をとることも可能である。
また、プラスチックフィルムに機能性を持たせる様な用途では、図２の様な形態をとり、機能性フィルムをさらに貼り合わせることもできる。
作業性及び製作コスト等を考慮すると、図１の場合が最も好ましい。
The antistatic pressure-sensitive adhesive film of various aspects can be obtained using the antistatic pressure-sensitive adhesive of the present invention in consideration of its use, required performance, and the like.
For example, an antistatic pressure-sensitive adhesive film for a protective film for a polarizing plate will be described with reference to the drawings.
FIG. 1 shows an antistatic acrylic adhesive layer on the polarizing plate side of a PET film.
FIG. 2 shows an antistatic acrylic pressure-sensitive adhesive layer on both the polarizing plate side and the opposite side of the PET film.
FIG. 3 shows an antistatic coating agent layer and further an antistatic acrylic adhesive layer on the polarizing plate side of the PET film.
FIG. 4 shows an embodiment in which an antistatic acrylic pressure-sensitive adhesive layer is located on the polarizing plate side of the PET film and an antistatic coating agent layer is located on the opposite side.
When the pressure-sensitive adhesive of the present invention is used for a film for protecting the surface of an optical member or an electronic member, it is possible to take a form as shown in FIGS. 3 and 4 in order to further reduce the peel charge amount.
Moreover, in the use which gives functionality to a plastic film, it takes the form as shown in FIG. 2 and the functional film can be further bonded.
In consideration of workability and production cost, the case of FIG. 1 is most preferable.
図３、図４に示すように粘着剤層とプラスチックフィルムとの間、またはプラスチックフィルムの粘着剤層側でない反対側（トップコート）に粘着性を有しない帯電防止性コーティング層を設ける場合に用いられる帯電防止剤としては、金属フィラー、４級アンモニウム塩誘導体、界面活性剤、導電性樹脂等を挙げることができる。 Used when an antistatic coating layer having no adhesiveness is provided between the adhesive layer and the plastic film or on the opposite side (top coat) of the plastic film that is not the adhesive layer side as shown in FIGS. Examples of the antistatic agent that can be used include metal fillers, quaternary ammonium salt derivatives, surfactants, and conductive resins.
金属フィラーとしては、酸化錫、酸化亜鉛、酸化鉄、酸化アンチモン等の金属酸化物、カーボン、銀、銅等の金属等が挙げられる。コーティング膜の透明性を考慮すると、酸化錫、酸化アンチモン等が好ましい。 Examples of the metal filler include metal oxides such as tin oxide, zinc oxide, iron oxide and antimony oxide, and metals such as carbon, silver and copper. In consideration of the transparency of the coating film, tin oxide, antimony oxide and the like are preferable.
４級アンモニウム塩誘導体としては、４級アンモニウム塩を有する（メタ）アクリレートモノマーの重合体、もしくは他の（メタ）アクリレートモノマーとの共重合体を使用することができる。 As the quaternary ammonium salt derivative, a polymer of a (meth) acrylate monomer having a quaternary ammonium salt or a copolymer with another (meth) acrylate monomer can be used.
帯電防止コーティング剤層は、塗膜として０．１μ〜５０μの厚さが好ましく、さらに好ましくは１μ〜２０μである。０．１μ以下では、帯電防止性能が十分に発揮できず、５０μ以上では、コスト、塗工性等に問題がある。 The antistatic coating agent layer preferably has a thickness of 0.1 μm to 50 μm as a coating film, more preferably 1 μm to 20 μm. If it is 0.1 μm or less, the antistatic performance cannot be sufficiently exhibited, and if it is 50 μm or more, there are problems in cost, coatability and the like.
合成例１
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの４６重量％、ＢＡの５０重量％、２ＨＥＡの５０重量％、ＡＭ９０Ｇの全量、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
残りのモノマー、酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却および酢酸エチルで希釈した。この反応溶液は、固形分４０％、粘度１３００ｃｐｓ、Ｍｗ（重量平均分子量）３１０，０００であった。
Synthesis example 1
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used, and the reaction kettle was 46% by weight of 2EHA, 50% by weight of BA, 50% by weight of 2HEA, and AM90G Total amount, ethyl acetate as solvent, azobisisobutyronitrile as initiator is charged in appropriate amount,
A solution prepared by adding appropriate amounts of the remaining monomer, ethyl acetate, and azobisisobutyronitrile was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 40%, a viscosity of 1300 cps, and Mw (weight average molecular weight) of 310,000.
合成例２
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの４４重量％、２ＨＥＡの５０重量％、Ｍ４０Ｇの全量、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
残りのモノマー、酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却および酢酸エチルで希釈した。この反応溶液は、固形分４１％、粘度１２００ｃｐｓ、Ｍｗ（重量平均分子量）３５０，０００であった。
Synthesis example 2
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 44% by weight of 2EHA, 2% by weight of HEA, the total amount of M40G, and ethyl acetate as a solvent. , Charge an appropriate amount of azobisisobutyronitrile as an initiator,
A solution prepared by adding appropriate amounts of the remaining monomer, ethyl acetate, and azobisisobutyronitrile was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 41%, a viscosity of 1200 cps, and a Mw (weight average molecular weight) of 350,000.
合成例３
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの３５重量％、ＢＡの３０重量％、２ＨＥＡの３０重量％、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
次に、２ＥＨＡの４２重量％、ＢＡの４０重量％、２ＨＥＡの４０重量％、Ｍ９０Ｇの３０重量％、酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて１時間重合させた。
さらにその後、残りのモノマー、酢酸エチル、アゾビスイソブチロにトリルを適量添加しで混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却および酢酸エチル、トルエンで希釈した。この反応溶液は、固形分４０％、粘度１５００ｃｐｓ、Ｍｗ（重量平均分子量）３３０，０００であった。
Synthesis example 3
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 35% by weight of 2EHA, 30% by weight of BA, 30% by weight of 2HEA, A suitable amount of ethyl acetate and azobisisobutyronitrile as an initiator is charged.
Next, an appropriate amount of 42% by weight of 2EHA, 40% by weight of BA, 40% by weight of 2HEA, 30% by weight of M90G, ethyl acetate, and azobisisobutyronitrile was added and mixed for about 1 hour. The solution was added dropwise and polymerized at about 80 ° C. for 1 hour in a nitrogen atmosphere.
Thereafter, a solution prepared by adding an appropriate amount of tolyl to the remaining monomers, ethyl acetate and azobisisobutyro was added dropwise over about 1 hour, and polymerization was performed at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate and toluene. This reaction solution had a solid content of 40%, a viscosity of 1500 cps, and Mw (weight average molecular weight) of 330,000.
合成例４
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの４０重量％、ＢＡの３０重量％、２ＨＥＡの３０重量％、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
次に、２ＥＨＡの４６重量％、ＢＡの４０重量％、２ＨＥＡの４０重量％、Ｍ９０Ｇの２０重量％、酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて１時間重合させた。
さらにその後、残りのモノマー、酢酸エチル、アゾビスイソブチロにトリルを適量添加しで混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却および酢酸エチル、トルエンで希釈した。この反応溶液は、固形分４０％、粘度３７００ｃｐｓ、Ｍｗ（重量平均分子量）２５０，０００であった。
Synthesis example 4
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 40% by weight of 2EHA, 30% by weight of BA, 30% by weight of 2HEA, A suitable amount of ethyl acetate and azobisisobutyronitrile as an initiator is charged.
Next, an appropriate amount of 46% by weight of 2EHA, 40% by weight of BA, 40% by weight of 2HEA, 20% by weight of M90G, ethyl acetate and azobisisobutyronitrile was added and mixed for about 1 hour. The solution was added dropwise and polymerized at about 80 ° C. for 1 hour in a nitrogen atmosphere.
Thereafter, a solution prepared by adding an appropriate amount of tolyl to the remaining monomers, ethyl acetate and azobisisobutyro was added dropwise over about 1 hour, and polymerization was performed at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate and toluene. This reaction solution had a solid content of 40%, a viscosity of 3700 cps, and Mw (weight average molecular weight) of 250,000.
合成例５
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの７４重量％、２ＨＥＡの５０重量％、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
残りのモノマー、酢酸エチル、トルエン、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却およびトルエンで希釈した。この反応溶液は、固形分４１％、粘度１０００ｃｐｓ、Ｍｗ（重量平均分子量）１１０，０００であった。
Synthesis example 5
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel was used. The reaction kettle was 74% by weight of 2EHA, 50% by weight of 2HEA, ethyl acetate as a solvent, and as an initiator. An appropriate amount of azobisisobutyronitrile is charged,
A solution prepared by adding appropriate amounts of the remaining monomers, ethyl acetate, toluene, and azobisisobutyronitrile was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with toluene. This reaction solution had a solid content of 41%, a viscosity of 1000 cps, and Mw (weight average molecular weight) of 110,000.
合成例６
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの４４重量％、ＢＡの５０重量％、２ＨＥＡの５０重量％、ＡＡの５０重量％、Ｍ４０Ｇの全量、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
残りのモノマー、酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却および酢酸エチルで希釈した。この反応溶液は、固形分４０％、粘度２０００ｃｐｓ、Ｍｗ（重量平均分子量）３２０，０００であった。
Synthesis Example 6
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used, and the reaction kettle was 44% by weight of 2EHA, 50% by weight of BA, 50% by weight of 2HEA, 50% by weight, total amount of M40G, ethyl acetate as solvent, azobisisobutyronitrile as initiator,
A solution prepared by adding appropriate amounts of the remaining monomer, ethyl acetate, and azobisisobutyronitrile was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 40%, a viscosity of 2000 cps, and Mw (weight average molecular weight) of 320,000.
合成例７
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの８８重量％、２ＨＥＡの５０重量％、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
残りのモノマー、酢酸エチル、トルエン、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却およびトルエンで希釈した。この反応溶液は、固形分４０％、粘度４００ｃｐｓ、Ｍｗ（重量平均分子量）１０５，０００であった。
Synthesis example 7
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 88% by weight of 2EHA, 50% by weight of 2HEA, ethyl acetate as a solvent, and as an initiator. An appropriate amount of azobisisobutyronitrile is charged,
A solution prepared by adding appropriate amounts of the remaining monomers, ethyl acetate, toluene, and azobisisobutyronitrile was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with toluene. This reaction solution had a solid content of 40%, a viscosity of 400 cps, and a Mw (weight average molecular weight) of 105,000.
合成例８
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの５０重量％、ＢＡの５０重量％、２ＨＥＡの５０重量％、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
残りのモノマー、酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却および酢酸エチルで希釈した。この反応溶液は、固形分４１％、粘度１７００ｃｐｓ、Ｍｗ（重量平均分子量）４００，０００であった。
Synthesis Example 8
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 50% by weight of 2EHA, 50% by weight of BA, 50% by weight of 2HEA, A suitable amount of ethyl acetate and azobisisobutyronitrile as an initiator is charged.
A solution prepared by adding appropriate amounts of the remaining monomer, ethyl acetate, and azobisisobutyronitrile was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 41%, a viscosity of 1700 cps, and Mw (weight average molecular weight) 400,000.
合成例９
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に２ＥＨＡの３５重量％、ＢＡの３０重量％、溶剤として酢酸エチル、開始剤としてアゾビスイソブチロニトリルを適量仕込み、
次に、２ＥＨＡの４２重量％、ＢＡの４０重量％、Ｍ９０Ｇの３０重量％、酢酸エチル、アゾビスイソブチロニトリルを適量添加して混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて１時間重合させた。
さらにその後、残りのモノマー、酢酸エチル、アゾビスイソブチロにトリルを適量添加しで混合した溶液を約１時間かけて滴下し、窒素雰囲気下約８０℃にて５時間重合させた。反応終了後、冷却および酢酸エチル、トルエンで希釈した。この反応溶液は、固形分４０％、粘度１３００ｃｐｓ、Ｍｗ（重量平均分子量）３５０，０００であった。
Synthesis Example 9
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 35% by weight of 2EHA, 30% by weight of BA, ethyl acetate as a solvent, and as an initiator. An appropriate amount of azobisisobutyronitrile is charged,
Next, a solution prepared by adding appropriate amounts of 42% by weight of 2EHA, 40% by weight of BA, 30% by weight of M90G, ethyl acetate and azobisisobutyronitrile was added dropwise over about 1 hour, Polymerization was performed at about 80 ° C. for 1 hour.
Thereafter, a solution prepared by adding an appropriate amount of tolyl to the remaining monomers, ethyl acetate and azobisisobutyro was added dropwise over about 1 hour, and polymerization was performed at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate and toluene. This reaction solution had a solid content of 40%, a viscosity of 1300 cps, and a Mw (weight average molecular weight) of 350,000.
合成例１０
表１に示す組成比のモノマーから構成される共重合体を以下の要領で得た。
即ち、撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコを用い、反応釜に全てのモノマー、溶剤としてベンゼン、開始剤としてアゾビスイソブチロニトリルを適量仕込み、窒素雰囲気下約８０℃にて５時間重合させ、固形分４０％の反応溶液を得た。
Synthesis Example 10
A copolymer composed of monomers having the composition ratio shown in Table 1 was obtained in the following manner.
That is, using a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, the reactor was charged with all the monomers, benzene as the solvent, and azobisisobutyronitrile as the initiator. Then, polymerization was carried out at about 80 ° C. for 5 hours under a nitrogen atmosphere to obtain a reaction solution having a solid content of 40%.
［実施例１］
合成例１で得られたアクリル樹脂溶液の固形分４０ｇに対して、過塩素酸リチウム３ｇ、硬化剤としてトリレンジイソシアネートトリメチロールプロパンアダクト体３７％酢酸エチル溶液を１０ｇ配合し粘着剤を得た。
得られた粘着剤を剥離紙に乾燥塗膜２５μになるように塗工し、１００℃−２分乾燥後、形成されつつある粘着剤層にポリエチレンテレフタレートフィルム（厚さ５０μ）を積層し、この状態で室温で２日間経過させ、試験用粘着テープを得た。
該粘着テープを用いて、以下に示す方法に従って、粘着力、表面抵抗値、再剥離性、透明性の評価を行った。
[Example 1]
To 40 g of the solid content of the acrylic resin solution obtained in Synthesis Example 1, 3 g of lithium perchlorate and 10 g of tolylene diisocyanate trimethylolpropane adduct 37% ethyl acetate solution as a curing agent were blended to obtain an adhesive.
The obtained pressure-sensitive adhesive was coated on a release paper so as to have a dry coating film thickness of 25 μm, dried at 100 ° C. for 2 minutes, and then a polyethylene terephthalate film (thickness 50 μm) was laminated on the pressure-sensitive adhesive layer being formed. In the state, it was allowed to pass at room temperature for 2 days to obtain a test adhesive tape.
Using the pressure-sensitive adhesive tape, the adhesive strength, surface resistance value, removability, and transparency were evaluated according to the following methods.
＜粘着力＞
試験用粘着テープの剥離紙を剥がし、露出した粘着剤層を厚さ０．４ｍｍのガラス板に２３℃−６５％ＲＨにて貼着し、ＪＩＳに準じてロール圧着した。圧着２４時間後、ショッパー型剥離試験器にて剥離強度（１８０度ピール、引っ張り速度３００ｍｍ／分；単位ｇ／２５ｍｍ幅）を測定した。
<Adhesive strength>
The release paper of the pressure-sensitive adhesive tape for test was peeled off, and the exposed pressure-sensitive adhesive layer was attached to a glass plate having a thickness of 0.4 mm at 23 ° C.-65% RH and roll-bonded according to JIS. After 24 hours, the peel strength (180 degree peel, pulling speed 300 mm / min; unit g / 25 mm width) was measured with a shopper type peel tester.
＜表面抵抗値＞
試験用粘着テープの剥離紙を剥がし、露出した粘着剤層表面を表面抵抗値測定装置（三菱化学株式会社製）を用いて測定した（Ω／□）。
<Surface resistance value>
The release paper of the pressure-sensitive adhesive tape for test was peeled off, and the exposed pressure-sensitive adhesive layer surface was measured using a surface resistance measuring device (manufactured by Mitsubishi Chemical Corporation) (Ω / □).
＜再剥離性＞
試験用粘着テープの剥離紙を剥がし、露出した粘着剤層をガラス板に貼着した後、６０℃−９５％ＲＨの条件下に放置し、２３℃−６５％ＲＨに冷却した後、剥離し、糊残り性を目視で評価した。剥離後、
被着体への糊移行の全くないもの ◎
ごくわずかにあるもの ○
部分的にあるもの △
完全に移行しているもの ×
として評価した。
<Removability>
After peeling off the release paper of the test adhesive tape and sticking the exposed adhesive layer to the glass plate, it was left under the condition of 60 ° C.-95% RH, cooled to 23 ° C.-65% RH, and then peeled off. The adhesive residue was visually evaluated. After peeling
No adhesive transfer to the adherend ◎
Very few ○
Partially △
Fully migrated ×
As evaluated.
＜透明性＞
試験用粘着テープの剥離紙を剥がし、露出した粘着剤層をガラス板に貼着した後、６０℃−９５％ＲＨの条件下に放置し、２３℃−６５％ＲＨに冷却した後、目視で評価した。
無色透明なもの ◎
ごく僅か曇っているもの ○
白濁、凝集物が見られるもの △
透明でないもの ×
<Transparency>
After peeling the release paper of the test adhesive tape and sticking the exposed adhesive layer to a glass plate, it was left under the condition of 60 ° C.-95% RH, cooled to 23 ° C.-65% RH, and then visually. evaluated.
Colorless and transparent ◎
Very slightly cloudy ○
Those that are cloudy or aggregated △
Not transparent ×
［実施例２、３、５］［比較例３］
合成例２、３、５、９で得られた各アクリル樹脂を用い、過塩素酸リチウムを５ｇ用いた以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Examples 2, 3, and 5] [Comparative Example 3]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that each acrylic resin obtained in Synthesis Examples 2, 3, 5, and 9 was used and 5 g of lithium perchlorate was used, and evaluation was performed in the same manner as in Example 1.
［実施例４］
合成例４で得られたアクリル樹脂を用い、塩化リチウムを３ｇ用いた以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Example 4]
Using the acrylic resin obtained in Synthesis Example 4 and using 3 g of lithium chloride, a pressure-sensitive adhesive was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
［実施例６］
合成例６で得られたアクリル樹脂を用い、硬化剤としてＮ，Ｎ，Ｎ'Ｎ'−テトラグリシジル−ｍ−キシレンジアミン５％トルエン溶液３ｇを用いた以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。なお、本願発明で実施例６は参考例である。
[Example 6]
Adhesive as in Example 1 except that the acrylic resin obtained in Synthesis Example 6 was used and 3 g of a 5% toluene solution of N, N, N′N′-tetraglycidyl-m-xylenediamine was used as a curing agent. And evaluated in the same manner as in Example 1. In the present invention, Example 6 is a reference example.
［実施例７］
合成例５で得られたアクリル樹脂溶液５０ｇと合成例８で得られたアクリル樹脂溶液５０ｇを混合し、過塩素酸リチウム５ｇを用いた以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Example 7]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 50 g of the acrylic resin solution obtained in Synthesis Example 5 and 50 g of the acrylic resin solution obtained in Synthesis Example 8 were mixed and 5 g of lithium perchlorate was used. Evaluation was performed in the same manner as in Example 1.
［実施例８］
合成例７で得られたアクリル樹脂を用い、過塩素酸リチウムを１ｇ用いた以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Example 8]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 1 g of lithium perchlorate was used using the acrylic resin obtained in Synthesis Example 7, and evaluation was performed in the same manner as in Example 1.
［実施例９］
合成例７で得られたアクリル樹脂を用い、過塩素酸リチウムを３ｇ用いた以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Example 9]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 3 g of lithium perchlorate was used, using the acrylic resin obtained in Synthesis Example 7, and evaluated in the same manner as in Example 1.
［実施例１０、１１］
合成例５、７で得られたアクリル樹脂を用い、過塩素酸リチウム１ｇを用い、さらに室温で７日間経過させて試験用粘着テープを得た、以外は実施例１と同様に評価した。
[Examples 10 and 11]
Evaluation was performed in the same manner as in Example 1 except that the acrylic resin obtained in Synthesis Examples 5 and 7 was used, 1 g of lithium perchlorate was used, and the test adhesive tape was obtained after 7 days at room temperature.
［比較例１、４］
合成例８、３で得られた各アクリル樹脂を用い、過塩素酸リチウムを用いない以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Comparative Examples 1 and 4]
Using each acrylic resin obtained in Synthesis Examples 8 and 3, a pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that lithium perchlorate was not used, and evaluation was performed in the same manner as in Example 1.
［比較例２］
合成例８で得られたアクリル樹脂を用いた以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Comparative Example 2]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the acrylic resin obtained in Synthesis Example 8 was used, and evaluated in the same manner as in Example 1.
［比較例５］
合成例２で得られたアクリル樹脂を用い、過塩素酸リチウム５ｇを用い、硬化剤を使用しない以外は実施例１と同様にして粘着剤を得、実施例１と同様に評価した。
[Comparative Example 5]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the acrylic resin obtained in Synthesis Example 2 was used, 5 g of lithium perchlorate was used, and no curing agent was used, and evaluation was performed in the same manner as in Example 1.
［比較例６］
合成例１０で得られたアクリル樹脂溶液を脱溶媒後、アセチルアセトンに溶解し、アクリル樹脂固形分に対して３％の重量の過塩素酸リチウムを添加して溶解させた。この均一粘調液体をアルミニウム箔上にキャストし、８０℃、約２日間の乾燥を行い、アセトンを完全に蒸散させた。得られた樹脂シートをポリエチレンテレフタレートフィルム（厚さ５０μ）に積層し、実施例１と同様に評価した。
[Comparative Example 6]
The acrylic resin solution obtained in Synthesis Example 10 was desolvated and then dissolved in acetylacetone, and 3% by weight of lithium perchlorate was added to the acrylic resin solid content and dissolved. This uniform viscous liquid was cast on an aluminum foil and dried at 80 ° C. for about 2 days to completely evaporate acetone. The obtained resin sheet was laminated on a polyethylene terephthalate film (thickness 50 μ) and evaluated in the same manner as in Example 1.
以上のように本発明の帯電防止粘着剤は、表面抵抗値（導電性）、透明性、再剥離性に優れていることが分かる。
これに対して、比較例１、４に示した粘着剤は、イオン化合物が含まれていないため、再剥離性、透明性は良好だが、導電性が全くない。比較例２に示した粘着剤は、アルキレンオキサイド鎖を有していないため、イオン化合物が溶解せずに凝集し、透明性、表面抵抗値が不良となっている。比較例３示したに粘着剤は、水酸基含有モノマーが含まれていないため、硬化剤による架橋効果が得られず、再剥離性が不良となった。比較例５示したに粘着剤は、硬化剤を全く使用していないため、凝集力が不足し、再剥離性が不良となった。
比較例６は、本発明のように予めアクリル系共重合体（Ａ）を得た後、剥離紙とポリエチレンテレフタレートフィルム間において該アクリル系共重合体（Ａ）をさらに硬化剤で架橋させて粘着剤層を形成しているわけではなく、単にアクリル樹脂をポリエチレンテレフタレートフィルムに積層し、硬化剤は使用していないので、粘着剤としての凝集力が不足し、再剥離性が不良となっている。
As described above, it can be seen that the antistatic pressure-sensitive adhesive of the present invention is excellent in surface resistance (conductivity), transparency and removability.
On the other hand, since the adhesive shown in Comparative Examples 1 and 4 does not contain an ionic compound, it has good removability and transparency, but has no conductivity. Since the pressure-sensitive adhesive shown in Comparative Example 2 does not have an alkylene oxide chain, the ionic compound does not dissolve and aggregates, resulting in poor transparency and surface resistance. Since the pressure-sensitive adhesive shown in Comparative Example 3 did not contain a hydroxyl group-containing monomer, the crosslinking effect by the curing agent was not obtained, and the removability was poor. Since the pressure-sensitive adhesive shown in Comparative Example 5 did not use a curing agent at all, the cohesive force was insufficient and the removability was poor.
In Comparative Example 6, after the acrylic copolymer (A) was obtained in advance as in the present invention, the acrylic copolymer (A) was further crosslinked with a curing agent between the release paper and the polyethylene terephthalate film. The adhesive layer is not formed, but the acrylic resin is simply laminated on the polyethylene terephthalate film, and the curing agent is not used. .
１：プラスチックフィルム基材（ＰＥＴ）
２：帯電防止アクリル粘着剤層
３：偏光板
４：帯電防止コーティング剤層
1: Plastic film substrate (PET)
2: Antistatic acrylic adhesive layer 3: Polarizing plate 4: Antistatic coating agent layer
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014058679A (en) * | 2003-12-26 | 2014-04-03 | Toyo Ink Sc Holdings Co Ltd | Antistatic acrylic adhesive |
| JP2019065089A (en) * | 2017-09-28 | 2019-04-25 | 藤森工業株式会社 | Adhesive composition, and surface protective film |
| JP2021036052A (en) * | 2020-11-19 | 2021-03-04 | 藤森工業株式会社 | Adhesive film |
| JP2022040328A (en) * | 2020-11-19 | 2022-03-10 | 藤森工業株式会社 | Adhesive agent composition, adhesive film, surface protective film and optical film with adhesive agent layer |
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| KR102141141B1 (en) * | 2016-09-13 | 2020-08-04 | 동우 화인켐 주식회사 | Optically Clear Adhesive Composition, and Optically Clear Adhesive Film comprising the Same, and Flat Panel Display |
| KR102125020B1 (en) * | 2018-09-05 | 2020-06-19 | (주)이녹스첨단소재 | Adhesive sheet for display and display comprising the same |
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| JP2000129235A (en) * | 1998-10-27 | 2000-05-09 | Minnesota Mining & Mfg Co <3M> | Antistatic pressure-sensitive adhesive composition |
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| JP4437632B2 (en) * | 2001-07-31 | 2010-03-24 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition for optical member surface protective film |
| JP4279118B2 (en) * | 2003-10-30 | 2009-06-17 | 藤森工業株式会社 | Surface protective film and optical component on which it is adhered |
| JP5582185B2 (en) * | 2003-12-26 | 2014-09-03 | 東洋インキＳｃホールディングス株式会社 | Removable antistatic acrylic adhesive |
| JP5422091B2 (en) * | 2003-12-26 | 2014-02-19 | 東洋インキＳｃホールディングス株式会社 | Antistatic acrylic adhesive |
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| JPH0280030A (en) * | 1988-09-19 | 1990-03-20 | Advance Co Ltd | Medical conducting adhesive |
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| JPH08155040A (en) * | 1994-12-08 | 1996-06-18 | Nitto Denko Corp | Conductive tacky adhesive and electrode pad formed by using the same |
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| JP2014058679A (en) * | 2003-12-26 | 2014-04-03 | Toyo Ink Sc Holdings Co Ltd | Antistatic acrylic adhesive |
| JP2019065089A (en) * | 2017-09-28 | 2019-04-25 | 藤森工業株式会社 | Adhesive composition, and surface protective film |
| JP2021036052A (en) * | 2020-11-19 | 2021-03-04 | 藤森工業株式会社 | Adhesive film |
| JP7014880B2 (en) | 2020-11-19 | 2022-02-01 | 藤森工業株式会社 | Adhesive film |
| JP2022040328A (en) * | 2020-11-19 | 2022-03-10 | 藤森工業株式会社 | Adhesive agent composition, adhesive film, surface protective film and optical film with adhesive agent layer |
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| JP2014058679A (en) | 2014-04-03 |
| JP5617987B2 (en) | 2014-11-05 |
| JP5582185B2 (en) | 2014-09-03 |
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