JPH08183935A - Re-releasable pressure-sensitive adhesive sheet - Google Patents
Re-releasable pressure-sensitive adhesive sheetInfo
- Publication number
- JPH08183935A JPH08183935A JP6328395A JP32839594A JPH08183935A JP H08183935 A JPH08183935 A JP H08183935A JP 6328395 A JP6328395 A JP 6328395A JP 32839594 A JP32839594 A JP 32839594A JP H08183935 A JPH08183935 A JP H08183935A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- weight
- adhesive sheet
- paper
- 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.)
- Pending
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 111
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 37
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 19
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical group 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 7
- 230000009477 glass transition Effects 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 235000007586 terpenes Nutrition 0.000 claims description 9
- 150000003505 terpenes Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 125000002298 terpene group Chemical group 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 15
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 abstract description 5
- 239000000123 paper Substances 0.000 description 60
- 239000000853 adhesive Substances 0.000 description 53
- 230000001070 adhesive effect Effects 0.000 description 53
- 239000002585 base Substances 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 238000004873 anchoring Methods 0.000 description 16
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- -1 polyethylene Polymers 0.000 description 12
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 8
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000001771 impaired effect Effects 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000740 bleeding effect Effects 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 229910052570 clay Inorganic materials 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- 239000003505 polymerization initiator Substances 0.000 description 3
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- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SZPUDSQPVUIVKC-UHFFFAOYSA-N ethoxymethyl prop-2-enoate Chemical compound CCOCOC(=O)C=C SZPUDSQPVUIVKC-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WYOXPIKARMAQFM-UHFFFAOYSA-N n,n,n',n'-tetrakis(oxiran-2-ylmethyl)ethane-1,2-diamine Chemical compound C1OC1CN(CC1OC1)CCN(CC1OC1)CC1CO1 WYOXPIKARMAQFM-UHFFFAOYSA-N 0.000 description 1
- JZQJBERPOZBRKD-UHFFFAOYSA-N n-(4-methoxybutyl)prop-2-enamide Chemical compound COCCCCNC(=O)C=C JZQJBERPOZBRKD-UHFFFAOYSA-N 0.000 description 1
- FSJNAJKLBMNIKF-UHFFFAOYSA-N n-[2-[bis(oxiran-2-ylmethyl)amino]ethyl]-n,n',n'-tris(oxiran-2-ylmethyl)ethane-1,2-diamine Chemical compound C1OC1CN(CC1OC1)CCN(CC1OC1)CCN(CC1OC1)CC1CO1 FSJNAJKLBMNIKF-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は値札、工程管理用のラベ
ル等に使用される再剥離性粘着シートに関し、特にビデ
オカセット、オーディオカセット、フロッピーディスク
等のインデックスラベル用として好適な再剥離性粘着シ
ートに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a removable pressure-sensitive adhesive sheet used for price tags, process control labels, etc., and particularly suitable for use as index labels for video cassettes, audio cassettes, floppy disks, etc. Regarding the seat.
【０００２】[0002]
【従来の技術】粘着シートは商業用、事務用、家庭用等
非常に広範囲にわたってラベル、シール、ステッカー、
ワッペン等に加工して使用されている。粘着シートの一
般的な構成は、表面基材と剥離シートとの間に粘着剤層
を形成したものであり、表面基材には紙、フィルム、金
属フォイル等が用いられ、剥離シートとしてはグラシン
紙のような高密度原紙、クレーコート紙、ポリエチレン
ラミネート原紙等にシリコーン化合物や弗素化合物の如
き剥離剤を塗布したものが用いられる。また、粘着剤と
しては、ゴム系、アクリル系、ビニルエーテル系等のエ
マルジョン、溶剤又は無溶剤型の各種粘着剤が使用され
る。かかる粘着シートは、商品等の被着体に貼付けされ
た後は被着体に貼りついたまま永続的に利用される永久
接着タイプのものと、商品の用途等に応じて表示の目的
を達成した後は剥離され破棄される再剥離タイプのもの
とがある。この後者のタイプのものが再剥離性粘着シー
トである。2. Description of the Related Art Adhesive sheets are used for labels, stickers, stickers, etc.
It is used after being processed into patches. The general structure of the pressure-sensitive adhesive sheet is one in which a pressure-sensitive adhesive layer is formed between a surface base material and a release sheet, and paper, film, metal foil or the like is used for the surface base material, and the release sheet is glassine. High-density base paper such as paper, clay-coated paper, polyethylene laminated base paper, etc. coated with a release agent such as a silicone compound or a fluorine compound is used. As the pressure-sensitive adhesive, various types of rubber-based, acrylic-based, vinyl ether-based emulsion, solvent or solventless pressure-sensitive adhesives are used. Such an adhesive sheet achieves the purpose of display, depending on the intended use of the product, and a permanent adhesive type that is permanently used while being attached to the adherend after being adhered to the adherend such as a product. There is a re-peeling type that is peeled off and discarded after doing. This latter type is a removable pressure sensitive adhesive sheet.
【０００３】[0003]
【発明が解決しようとする課題】再剥離性粘着シートは
値段の貼り替えの多い値札や工程管理用のラベル等に使
用されているが、それらのラベルが最終的に剥離される
際に、破れた表面基材の一部や粘着剤が商品である被着
体に残存しない状態で容易に剥離できること、つまり被
着体の外観を損ねる被着体汚染を起こさない優れた再剥
離性を持つことが基本的に要求される。尚、このように
粘着剤が被着体に残存することを簡単に糊残りと称して
いる。また、再剥離性粘着シートの一種としてビデオカ
セット、オーディオカセット、フロッピーディスク等に
使用されるインデックス用ラベルがある。これらのラベ
ルも、テープ、ディスク内の情報を新たに記録しなおし
た場合に古いラベルを剥離し破棄し、新しいラベルを貼
って使用するので、その際に上記と同様の優れた再剥離
性を持つことが必要になる。更に、これらのインデック
ス用ラベルは、ビデオカセットデッキ等の機器内で温度
変化等によりラベルの浮き、めくれが生じやすく、この
ような現象は、カセットの排出不能等の機械の故障の原
因に直接的につながるので大きな問題となっている。Removable pressure-sensitive adhesive sheets are used for price tags whose prices are often replaced and labels for process control, but when those labels are finally peeled off, they are torn. It can be easily peeled off without leaving part of the surface substrate or adhesive on the adherend that is the product, that is, it has excellent removability that does not cause contamination of the adherend that damages the appearance of the adherend. Is basically required. It should be noted that the fact that the pressure-sensitive adhesive remains on the adherend in this way is simply referred to as adhesive residue. In addition, there is an index label used for video cassettes, audio cassettes, floppy disks, etc. as one type of removable adhesive sheet. With these labels, when new information is recorded on the tape or disc, the old label is peeled off and discarded, and a new label is applied. You need to have it. Furthermore, these index labels are liable to be lifted or flipped due to temperature changes in equipment such as video cassette decks, and such a phenomenon is directly related to the cause of mechanical failure such as cassette ejection failure. It is a big problem because it leads to.
【０００４】本発明は以上の問題を解決し、被着体から
剥がす際には表面基材の破れや糊残りにより被着体の外
観を損ねて被着体汚染を生ずることが無い優れた再剥離
性を示し、かつ被着体に接着された時には浮き、めくれ
が無い再剥離性粘着シートを得ることを目的とする。The present invention solves the above problems, and when peeled off from an adherend, the appearance of the adherend is not spoiled by the breakage of the surface base material or the adhesive residue, and the excellent recontamination does not occur. An object of the present invention is to obtain a re-peelable pressure-sensitive adhesive sheet which exhibits releasability, floats when adhered to an adherend, and has no curl.
【０００５】[0005]
【課題を解決するための手段】本発明に係る再剥離性粘
着シートは、剥離シート、粘着剤層、表面基材を積層し
て有する再剥離性粘着シートにおいて、粘着剤層を形成
する粘着剤として、下記（ａ），（ｂ），（ｃ）及び必
要に応じて加えられる（ｄ）からなる単量体組成物を乳
化重合して得られ、かつポリスチレン換算数平均分子量
（Ｍｎ）が０．１×１０4以上であって５．０×１０4未
満であり、かつポリスチレン換算重量平均分子量（Ｍ
ｗ）とポリスチレン換算数平均分子量（Ｍｎ）の比（Ｍ
ｗ／Ｍｎ）が４０〜８００、平均粒子径が１００〜５０
０ｎｍ、ガラス転移温度が−５０℃以下である共重合体
の水系エマルジョンを主成分とし、粘着付与剤としてロ
ジン系樹脂及びテルペン系樹脂の中から選択される樹脂
を添加し、かつ、該共重合体のカルボキシル基１当量当
たりエポキシ基が０．５〜２当量となるように、２個以
上のエポキシ基を持つポリグリシジル化合物を添加した
粘着剤を用いることを特徴とする。 （ａ）アルキル基の炭素数が８〜１２の（メタ）アクリ
ル酸アルキルエステル単量体を８０〜９９重量％ （ｂ）（メタ）アクリロニトリルを０．３〜１０重量％ （ｃ）α，β−不飽和カルボン酸を０．１〜５重量％ （ｄ）その他の共重合可能な単量体を０〜５重量％ また、粘着付与剤としては、テルペンフェノール樹脂が
特に好ましい。A removable pressure-sensitive adhesive sheet according to the present invention is a removable pressure-sensitive adhesive sheet having a release sheet, a pressure-sensitive adhesive layer, and a surface base material laminated on each other. Is obtained by emulsion polymerization of a monomer composition consisting of (a), (b), (c) below and (d) optionally added, and has a polystyrene reduced number average molecular weight (Mn) of 0. 1 × 10 4 or more and less than 5.0 × 10 4 and polystyrene-equivalent weight average molecular weight (M
w) and polystyrene equivalent number average molecular weight (Mn) ratio (M
w / Mn) is 40 to 800, and the average particle size is 100 to 50.
The main component is an aqueous emulsion of a copolymer having 0 nm and a glass transition temperature of −50 ° C. or lower, and a resin selected from rosin-based resins and terpene-based resins is added as a tackifier, and the copolymerization It is characterized by using a pressure-sensitive adhesive to which a polyglycidyl compound having two or more epoxy groups is added so that the epoxy groups are 0.5 to 2 equivalents per equivalent of carboxyl groups of the combined polymer. (A) 80 to 99% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group with 8 to 12 carbon atoms (b) 0.3 to 10% by weight of (meth) acrylonitrile (c) α, β -0.1 to 5% by weight of unsaturated carboxylic acid (d) 0 to 5% by weight of other copolymerizable monomer Further, as the tackifier, a terpene phenol resin is particularly preferable.
【０００６】[0006]
【作用】本発明者等は先に説明した課題を解決するため
に以下のような検討、解析を行った。通常、再剥離性粘
着シートは粘着剤を剥離紙に塗布、乾燥後、得られた粘
着剤層を表面基材と張り合わせ加圧することにより転写
して製造される。この際、粘着剤層を形成する粘着剤の
表面基材に対する投錨性が悪いと被着体から剥がすとき
に粘着剤が被着体から剥離しないで表面基材のみが剥が
れ糊残りを発生する。また、逆に粘着剤の表面基材への
投錨性が高すぎるとラベルの不透明度が低下して所謂ブ
リードを起こし表面基材の外観を損なってしまう。尚、
このブリードは被着体に貼っている状態であるか否かに
かかわらず、粘着剤層を表面基材と張り合わせてシート
を作成した時から起こりうる状態になるものである。一
方、ラベルの再剥離性を向上させるために粘着剤の被着
体に対する接着力を低下させると、表面基材との接着力
も低下するため糊残りを生じたり、温度変化等によるラ
ベルの浮き、めくれを生じる。又、ラベルの浮き、めく
れを向上させるために粘着剤の塗布量を多くすると、粘
着シートの断面から粘着剤がはみ出す現象（以下「ウー
ズ」という）を生じる。このように、再剥離性粘着シー
トにおいては、粘着剤の被着体に対する接着力、ラベル
の被着体からの再剥離性、粘着剤の表面基材に対する適
当な浸透性等をバランスよく有し、粘着剤の塗布量を少
なくすることが要求される。The present inventors conducted the following studies and analyzes in order to solve the above-mentioned problems. Usually, a removable pressure-sensitive adhesive sheet is manufactured by applying a pressure-sensitive adhesive to a release paper, drying it, and then transferring the pressure-sensitive adhesive layer obtained by laminating the pressure-sensitive adhesive layer to a surface base material and applying pressure. At this time, if the tackiness of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer on the surface substrate is poor, the pressure-sensitive adhesive does not peel off from the adherend when peeled off from the adherend, and only the surface substrate peels off to cause an adhesive residue. On the contrary, if the anchoring property of the pressure-sensitive adhesive to the surface base material is too high, the opacity of the label lowers, so-called bleeding occurs, and the appearance of the surface base material is impaired. still,
This bleeding is a state that can occur from the time when a sheet is produced by laminating the pressure-sensitive adhesive layer with the surface base material, regardless of whether or not the bleeding is attached to the adherend. On the other hand, when the adhesive strength of the pressure-sensitive adhesive to the adherend is reduced in order to improve the removability of the label, the adhesive strength with the surface base material is also reduced to cause adhesive residue, or the label floats due to temperature change, etc. Causes curling. Further, when the amount of the adhesive applied is increased in order to improve the floating and turning of the label, a phenomenon (hereinafter referred to as "wooze") of the adhesive protruding from the cross section of the adhesive sheet occurs. As described above, the releasable pressure-sensitive adhesive sheet has a well-balanced adhesive force of the pressure-sensitive adhesive to the adherend, removability of the label from the adherend, and appropriate permeability of the pressure-sensitive adhesive to the surface substrate. It is required to reduce the amount of adhesive applied.
【０００７】本発明者等は以上の検討、解析の上に種々
の試行を繰り返して、貼り付ける前の巻取り状態や積層
状態、シートを断裁した際に、ウーズが無く、被着体に
貼り付けた時にはラベルの浮き、めくれが無く、剥離時
には優れた再剥離性を有し、かつブリードにより表面基
材を損なうこともない製造しやすい再剥離性粘着シート
を得ることを見いだし本発明に至ったものである。本発
明で使用する（メタ）アクリル酸の表現はアクリル酸お
よび／またはメタクリル酸を意味するもので、（メタ）
アクリロニトリル等の表現も同様である。本発明で使用
するアルキル基の炭素数が８〜１２の（メタ）アクリル
酸アルキルエステル単量体の具体例としては、アクリル
酸２−エチルヘキシル、メタクリル酸２−エチルヘキシ
ル、アクリル酸ｎ−オクチル、メタクリル酸ｎ−オクチ
ル、アクリル酸イソノニル、メタクリル酸イソノニル、
アクリル酸ラウリル、メタクリル酸ラウリルなどを挙げ
ることができる。好ましくはアクリル酸２−エチルヘキ
シル、アクリル酸イソノニル、メタクリル酸ラウリルが
挙げられる。又、これら（メタ）アクリル酸エステルは
単独でも、２種類以上組み合わせても使用することがで
きる。アルキル基の炭素数が８〜１２の（メタ）アクリ
ル酸アルキルエステル単量体の使用量は、単量体混合物
の全重量基準で８０〜９９重量％、好ましくは８５〜９
９重量％、さらに好ましくは９０〜９８重量％である。
８０重量％未満では得られる粘着剤の被着体に対する粘
着力が弱すぎて、ラベルの浮き、めくれの問題が起こ
る。また、９９％を越える場合、得られる粘着剤の被着
体に対する粘着力が強すぎて紙破れ等が起こり、紙等の
一部が被着体に貼りついたままになって被着体汚染の問
題が生じる。また、炭素数が８〜１２以外の（メタ）ア
クリル酸アルキルエステル単量体を、単量体混合物の全
重量基準で８０〜９９重量％用いた場合、例えば、ブチ
ルアクリレートを用いた場合は、粘着剤の表面基材に対
する投錨性が高すぎて表面基材の外観を損なったり、被
着体に対する接着力が強すぎて再剥離性が劣る。The present inventors repeated various trials based on the above-mentioned examination and analysis and found that there was no ooze when the sheet was cut in a wound state or a laminated state before being attached, and a sheet was cut. The present invention has been found to obtain a removable pressure-sensitive adhesive sheet which is free from label floating and curling when attached, has excellent removability at the time of peeling, and does not damage the surface substrate by bleeding and is easy to manufacture. It is a thing. The expression (meth) acrylic acid used in the present invention means acrylic acid and / or methacrylic acid, and
The same applies to expressions such as acrylonitrile. Specific examples of the (meth) acrylic acid alkyl ester monomer having an alkyl group with 8 to 12 carbon atoms used in the present invention include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, and methacryl. Acid n-octyl, isononyl acrylate, isononyl methacrylate,
Examples thereof include lauryl acrylate and lauryl methacrylate. Preferred are 2-ethylhexyl acrylate, isononyl acrylate, and lauryl methacrylate. Further, these (meth) acrylic acid esters can be used alone or in combination of two or more kinds. The amount of the (meth) acrylic acid alkyl ester monomer whose alkyl group has 8 to 12 carbon atoms is 80 to 99% by weight, preferably 85 to 9% by weight based on the total weight of the monomer mixture.
It is 9% by weight, more preferably 90 to 98% by weight.
If it is less than 80% by weight, the adhesive force of the obtained adhesive to the adherend is too weak, causing problems such as label floating and curling. On the other hand, when it exceeds 99%, the adhesive force of the obtained adhesive to the adherend is too strong and paper tear occurs, and a part of the paper or the like remains attached to the adherend and the adherend is contaminated. Problem arises. When the (meth) acrylic acid alkyl ester monomer having a carbon number other than 8 to 12 is used in an amount of 80 to 99% by weight based on the total weight of the monomer mixture, for example, when butyl acrylate is used, The anchoring property of the pressure-sensitive adhesive to the surface base material is too high and the appearance of the surface base material is impaired, or the adhesive force to the adherend is too strong and the removability is poor.
【０００８】本発明で使用するα，β−不飽和カルボン
酸の具体例としては、アクリル酸、メタクリル酸、イタ
コン酸、マレイン酸、フマル酸などを挙げることができ
る。好ましくはアクリル酸、メタクリル酸を挙げること
ができる。また、これらα，β−不飽和カルボン酸は単
独でも、２種類以上組み合わせても使用できる。α，β
−不飽和カルボン酸の使用量は特に重要であり、単量体
混合物の全重量基準で０．１〜５重量％、好ましくは
０．２〜４重量％、さらに好ましくは０．３〜３重量％
である。０．１重量％未満では、粘着剤の表面基材に対
する投錨性が高すぎて表面基材の外観を損なう。また、
５重量％を越えると投錨性が低すぎて再剥離性が劣った
り、粘着剤が湿度劣化等を受けやすくなる。Specific examples of the α, β-unsaturated carboxylic acid used in the present invention include acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid. Acrylic acid and methacrylic acid are preferred. Further, these α, β-unsaturated carboxylic acids can be used alone or in combination of two or more kinds. α, β
The amount of unsaturated carboxylic acid used is of particular importance, 0.1-5% by weight, preferably 0.2-4% by weight, more preferably 0.3-3% by weight, based on the total weight of the monomer mixture. %
Is. If it is less than 0.1% by weight, the anchoring property of the adhesive to the surface base material is too high and the appearance of the surface base material is impaired. Also,
If it exceeds 5% by weight, the anchoring property is too low and the removability is inferior, and the pressure sensitive adhesive is susceptible to humidity deterioration and the like.
【０００９】本発明においては、（メタ）アクリロニト
リルを特定の割合で使用することによって被着体汚染を
起こさない接着剤を得ることができる。（メタ）アクリ
ロニトリルの使用量は、０．３〜１０重量％、好ましく
は０．５〜７重量％、さらに好ましくは０．７〜５重量
％である。この範囲外では上記被着体汚染の防止効果が
少なく、紙破れあるいは糊残りによる被着体汚染が起こ
りやすい。In the present invention, by using (meth) acrylonitrile in a specific ratio, it is possible to obtain an adhesive which does not cause contamination of the adherend. The amount of (meth) acrylonitrile used is 0.3 to 10% by weight, preferably 0.5 to 7% by weight, and more preferably 0.7 to 5% by weight. Outside this range, the effect of preventing contamination of the adherend is small, and the adherend is likely to be contaminated due to paper breakage or adhesive residue.
【００１０】上記アルキル基の炭素数が８〜１２の（メ
タ）アクリル酸アルキルエステル単量体、（メタ）アク
リロニトリルおよびα，β−不飽和カルボン酸と共重合
可能な単量体の具体例としては、アクリル酸メチル、メ
タクリル酸メチル、アクリル酸エチル、メタクリル酸エ
チル、アクリル酸イソプロピル、メタクリル酸イソプロ
ピル、アクリル酸ブチル、メタクリル酸ブチルなどのア
ルキル基の炭素数が７以下のアクリル酸アルキルエステ
ルおよびメタクリル酸アルキルエステル、アクリル酸ヒ
ドロキシエチル、メタクリル酸ヒドロキシエチルなどの
アクリル酸ヒドロキシアルキルエステルおよびメタクリ
ル酸ヒドロキシアルキルエステル、アクリル酸メトキシ
エチル、アクリル酸エトキシメチルなどのアクリル酸ア
ルコキシアルキルエステルおよびメタクリル酸アルコキ
シアルキルエステル、アクリル酸グリシジル、メタクリ
ル酸グリシジルなどのアクリル酸グリシジルエステル及
びメタクリル酸グリシジルエステル、アクリルアミド、
メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ
−メトキシメチルアクリルアミド、Ｎ−メトキシブチル
アクリルアミドなどのアミド類、スチレン、α−メチル
スチレンなどの芳香族不飽和炭化水素などを挙げること
ができる。これらアルキル基の炭素数が８〜１２の（メ
タ）アクリル酸アルキルエステル単量体、（メタ）アク
リロニトリルおよびα，β−不飽和カルボン酸と共重合
可能な単量体の使用量は、単量体混合物の全重量基準で
０〜５重量％である。５重量％以上では得られる粘着剤
の被着体に対する粘着力が弱すぎてラベルの浮き、めく
れの問題が生じる。Specific examples of the (meth) acrylic acid alkyl ester monomer having an alkyl group having 8 to 12 carbon atoms, the monomer copolymerizable with (meth) acrylonitrile and α, β-unsaturated carboxylic acid are given below. Is an acrylic acid alkyl ester having an alkyl group having 7 or less carbon atoms such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, and butyl methacrylate, and methacrylic acid. Acid alkyl esters, hydroxyethyl acrylates such as hydroxyethyl acrylate and hydroxyethyl methacrylate, and hydroxyalkyl methacrylates such as methacrylic acid hydroxyalkyl esters, methoxyethyl acrylate, ethoxymethyl acrylate, and alkoxyalkyl acrylates. Stell and methacrylic acid alkoxyalkyl esters, glycidyl acrylate, glycidyl acrylate such as glycidyl methacrylate and glycidyl methacrylate, acrylamide,
Methacrylamide, N-methylolacrylamide, N
Examples thereof include amides such as -methoxymethylacrylamide and N-methoxybutylacrylamide, and aromatic unsaturated hydrocarbons such as styrene and α-methylstyrene. The amount of the (meth) acrylic acid alkyl ester monomer having 8 to 12 carbon atoms of the alkyl group, the (meth) acrylonitrile and the monomer copolymerizable with the α, β-unsaturated carboxylic acid is a single amount. 0-5% by weight, based on the total weight of the body mixture. If it is 5% by weight or more, the adhesive force of the obtained adhesive to the adherend is too weak, and the problem of label floating and flipping occurs.
【００１１】本発明は上記単量体混合物を水中で乳化重
合させて共重合体エマルジョンを調製する。その際、エ
マルジョン中の共重合体のポリスチレン換算数平均分子
量は特に重要であり、０．１×１０4以上５．０×１０4
未満、好ましくは０．３×１０4以上４．５×１０4未
満、さらに好ましくは０．５×１０4以上４．０×１０4
未満である。０．１×１０4未満では粘着剤の表面基材
に対する投錨性が高すぎて表面基材の外観を損なった
り、被着体に対する接着力が強すぎて、紙破れのため再
剥離性が劣る。一方、５．０×１０4を越えると投錨性
が低くなりすぎて、糊残りのため再剥離性が劣ったり、
接着力が低下してラベルの浮き、めくれを生じる。In the present invention, the above monomer mixture is emulsion polymerized in water to prepare a copolymer emulsion. At that time, the polystyrene-equivalent number average molecular weight of the copolymer in the emulsion is particularly important, and is 0.1 × 10 4 or more and 5.0 × 10 4 or more.
Less, preferably 0.3 × 10 4 or more and less than 4.5 × 10 4 , more preferably 0.5 × 10 4 or more and 4.0 × 10 4.
Is less than. If it is less than 0.1 × 10 4 , the anchoring property of the pressure-sensitive adhesive to the surface base material is too high, and the appearance of the surface base material is impaired, or the adhesive strength to the adherend is too strong, and the removability is poor due to paper breakage. . On the other hand, if it exceeds 5.0 × 10 4 , the anchoring property becomes too low, and the removability is poor due to adhesive residue,
The adhesive strength is reduced and the label floats and is turned up.
【００１２】ポリスチレン換算重量平均分子量（Ｍｗ）
とポリスチレン換算数平均分子量（Ｍｎ）の比（Ｍｗ／
Ｍｎ）は４０〜８００、好ましくは５０〜７００、さら
に好ましくは６０〜６００である。この範囲外ではラベ
ルの浮き、めくれを生じたり、表面基材に対する投錨性
が高くなり表面基材の外観を損なう。また、エマルジョ
ン中のポリマー粒子としての共重合体の平均粒子径も重
要であり、１００〜５００ｎｍ、好ましくは１５０〜４
５０ｎｍ、さらに好ましくは１８０〜４００ｎｍであ
る。１００ｎｍ未満では粘着剤の表面基材に対する投錨
性が高すぎて表面基材の外観を損なう。また、５００ｎ
ｍを越えると投錨性が低すぎて、糊残りのため再剥離性
が劣る。本発明においては、共重合体の重量平均分子量
と平均粒子径のバランスが重要であり上記範囲内になる
ように調製することにより再剥離性、表面基材の外観、
接着力の優れた再剥離性粘着シートが得られる。本発明
に使用する粘着剤を構成する共重合体のガラス転移温度
は−５０℃以下、好ましくは−９０℃〜−５０℃であ
る。ガラス転移温度が−５０℃を超えると、粘着剤の接
着力が低下してラベルの浮き、めくれを生じる。本発明
において、共重合体のガラス転移温度Ｔｇは、下記の数
式に基いて計算される。Polystyrene-equivalent weight average molecular weight (Mw)
And the polystyrene equivalent number average molecular weight (Mn) ratio (Mw /
Mn) is 40 to 800, preferably 50 to 700, and more preferably 60 to 600. Outside of this range, the label may be lifted or turned over, or the anchorage to the surface base material may be increased and the appearance of the surface base material may be impaired. The average particle size of the copolymer as the polymer particles in the emulsion is also important, and is 100 to 500 nm, preferably 150 to 4 nm.
The thickness is 50 nm, more preferably 180 to 400 nm. If it is less than 100 nm, the anchoring property of the pressure-sensitive adhesive to the surface base material is too high and the appearance of the surface base material is impaired. Also, 500n
If it exceeds m, the anchoring property is too low and the removability is poor due to adhesive residue. In the present invention, the balance between the weight average molecular weight and the average particle size of the copolymer is important, and the removability and appearance of the surface base material are adjusted by adjusting the weight ratio to fall within the above range.
A releasable pressure-sensitive adhesive sheet having excellent adhesive strength can be obtained. The glass transition temperature of the copolymer constituting the pressure-sensitive adhesive used in the present invention is -50 ° C or lower, preferably -90 ° C to -50 ° C. If the glass transition temperature exceeds −50 ° C., the adhesive strength of the pressure-sensitive adhesive will be reduced, causing the label to float and turn over. In the present invention, the glass transition temperature Tg of the copolymer is calculated based on the following mathematical formula.
【００１３】[0013]
【数１】 Ｔｇ ：共重合体のガラス転移温度（絶対温度表示） Ｔｇi ：第ｉ単量体ホモポリマーのガラス転移温度（絶
対温度表示） Ｗi ：第ｉ単量体の重量分率[Equation 1] Tg: glass transition temperature of copolymer (absolute temperature display) Tgi: glass transition temperature of i-th monomer homopolymer (absolute temperature display) Wi: weight fraction of i-th monomer
【００１４】本発明においては上記単量体混合物を水中
で乳化重合によって共重合させるが、他の重合方法、例
えば、溶液重合によって単量体混合物の重合を行うと、
粘着剤の表面基材に対する投錨性が高すぎて表面基材の
外観を損なったり、被着体に対する接着力が強すぎて再
剥離性が劣る。乳化重合であればその重合処理の方法は
特に限定するものではなく、例えばポリオキシエチレン
ノニルフェニルエーテル、ラウリル硫酸ナトリウム、ド
デシルベンゼンスルホン酸ナトリウムの如き乳化剤と、
過硫酸塩、アゾビスイソブチルニトリル、過酸化物類な
どの重合開始剤、ブチルメルカプタン、ドデシルメルカ
プタン、イソプロピルアルコール、メタノール、チオグ
リコール酸オクチル、四塩化炭素の如き分子量調節剤を
含む水溶液中に、上記単量体混合物を乳化した後、反応
器に連続的にまたは間欠的に供給しながら単量体混合物
の重合反応を完結させる方法が挙げられる。また、この
共重合体エマルジョンには、必要に応じて、充填剤、可
塑剤、増粘剤、湿潤剤、消泡剤、アルカリ剤、安定剤等
の添加剤を併用して粘着剤とすることもできるが、その
場合でも良好な再剥離性を得て、ラベル浮きが生じない
ために粘着剤中の共重合体成分は６０重量％以上含有す
ることが好ましい。また、再剥離性粘着シートの不透明
度を上げるために充填剤として顔料を０．５〜２０重量
％含有させることが好ましい。これは表面基材として米
坪１００ｇ／ｍ2 以下の紙を使用した場合に特に有効で
ある。充填剤として使用される顔料としては、カオリ
ン、タルク、クレー、酸化チタン、酸化カルシウム、水
酸化カルシウム、炭酸カルシウム、水酸化マグネシウ
ム、炭酸マグネシウム、酸化亜鉛、炭酸亜鉛、酸化アル
ミニウム、水酸化アルミニウム等が挙げられる。In the present invention, the above-mentioned monomer mixture is copolymerized in water by emulsion polymerization. When the monomer mixture is polymerized by another polymerization method, for example, solution polymerization,
The anchoring property of the pressure-sensitive adhesive to the surface base material is too high and the appearance of the surface base material is impaired, or the adhesive force to the adherend is too strong and the removability is poor. The method of the polymerization treatment is not particularly limited as long as it is emulsion polymerization, for example, polyoxyethylene nonylphenyl ether, sodium lauryl sulfate, and an emulsifier such as sodium dodecylbenzenesulfonate,
Persulfate, azobisisobutylnitrile, a polymerization initiator such as peroxides, butyl mercaptan, dodecyl mercaptan, isopropyl alcohol, methanol, octyl thioglycolate, in an aqueous solution containing a molecular weight modifier such as carbon tetrachloride, the above After emulsifying the monomer mixture, a method of completing the polymerization reaction of the monomer mixture while continuously or intermittently supplying the monomer mixture can be mentioned. If necessary, the copolymer emulsion may also be used with a filler, a plasticizer, a thickener, a wetting agent, a defoaming agent, an alkali agent, a stabilizer, and the like to form an adhesive. However, it is preferable that the copolymer component in the pressure-sensitive adhesive is contained in an amount of 60% by weight or more in order to obtain good removability and prevent label floating even in that case. Further, in order to increase the opacity of the removable pressure-sensitive adhesive sheet, it is preferable to add a pigment in an amount of 0.5 to 20% by weight as a filler. This is particularly effective when paper having a weight of 100 g / m 2 or less is used as the surface base material. Examples of the pigment used as a filler include kaolin, talc, clay, titanium oxide, calcium oxide, calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium carbonate, zinc oxide, zinc carbonate, aluminum oxide, aluminum hydroxide and the like. Can be mentioned.
【００１５】本発明においては、粘着付与剤としてロジ
ン系樹脂及びテルペン系樹脂から選択される少なくとも
一つの樹脂を特定の割合で使用することによって、少な
い粘着剤の塗布量でラベルの浮き、めくれの無い粘着剤
を得ることができる。一般に、粘着付与剤を使用すると
接着力が強くなるが、ラベルの浮き、めくれの様な長い
時間を要して起こる現象には必ずしも効果は無い。しか
し、前記の水系エマルジョンにロジン系樹脂及びテルペ
ン系樹脂から選択される少なくとも一つの樹脂を添加し
た粘着剤を使用することによって、少ない粘着剤の塗布
量でラベルの浮き、めくれが無く、ウーズの良い粘着シ
ートを得ることができる。粘着付与剤の使用量は、乳化
重合して得られた共重合体の水系エマルジョンに対して
３〜３０重量％、好ましくは５〜２０重量％である。３
重量％未満では、得られる粘着剤の接着力が弱すぎてラ
ベルの浮き、めくれが生じる。また、３０重量％を超え
る場合は、粘着剤の被着体に対する接着力が強すぎて剥
離時に紙破れが発生する。本発明で使用する粘着付与剤
のロジン系樹脂の具体例としては、ガム系，トール油
系，ウッド系などのロジン、ロジンに水素化，不均化，
重合，マレイン化，エステル化などの処理を施したロジ
ン誘導体がある。また、テルペン系樹脂の具体例として
は、α−又はβ−ピネン系，ジペンテン系，テルペンフ
ェノール系などが挙げられる。これらの中でも、好まし
くはテルペンフェノール樹脂を用いることができる。ま
た、これら粘着付与剤は単独でも、２種類以上組み合わ
せても使用できる。In the present invention, at least one resin selected from rosin-based resins and terpene-based resins is used as a tackifier in a specific ratio, so that a label can be floated and turned over with a small amount of adhesive applied. It is possible to obtain a non-adhesive. Generally, when a tackifier is used, the adhesive strength is increased, but it is not always effective for the phenomenon that takes a long time, such as the label floating or curling. However, by using an adhesive obtained by adding at least one resin selected from rosin-based resins and terpene-based resins to the above-mentioned water-based emulsion, there is no label floating, curling, and ooze with a small coating amount of the adhesive. A good adhesive sheet can be obtained. The tackifier is used in an amount of 3 to 30% by weight, preferably 5 to 20% by weight, based on the aqueous emulsion of the copolymer obtained by emulsion polymerization. Three
If the content is less than 10% by weight, the adhesive strength of the obtained pressure-sensitive adhesive is too weak to cause label floating and curling. If it exceeds 30% by weight, the adhesive strength of the pressure-sensitive adhesive to the adherend is too strong and paper tearing occurs at the time of peeling. Specific examples of the rosin-based resin of the tackifier used in the present invention include gum-based, tall oil-based, wood-based rosin, hydrogenation and disproportionation of rosin,
There are rosin derivatives that have undergone treatments such as polymerization, maleation, and esterification. Specific examples of the terpene-based resin include α- or β-pinene-based resin, dipentene-based resin, terpene-phenol-based resin and the like. Among these, the terpene phenol resin can be preferably used. These tackifiers can be used alone or in combination of two or more.
【００１６】本発明に使用される粘着剤は、上記共重合
体エマルジョンに架橋剤として２個以上のエポキシ基を
含有するポリグリシジル化合物を、このポリグリシジル
化合物中のエポキシ基が上記共重合体中のカルボキシル
基１当量当たり０．５〜２当量となる割合で添加して調
製される。ポリグリシジル化合物の配合量が０．５当量
未満では、得られる粘着剤の被着体に対する粘着力が強
すぎて、糊残りが生じて被着体の汚染が生じる。一方、
２当量を越えると、得られる粘着剤の基材に対する投錨
性が悪くなる。本発明で使用するポリグリシジル化合物
の具体例としては、エチレングリコールまたはポリエチ
レングリコールジグリシジルエーテル、プロピレングリ
コールまたはポリプロピレングリコールジグリシジルエ
ーテル、ネオペンチル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、
ジブロモネオペンチルグリコールジグリシジルエーテ
ル、ｏ−フタル酸ジグリシジルエステル、グリセリンポ
リグリシジルエーテル、トリメチロールプロパンポリグ
リシジルエーテル、ジグリセロールポリグリシジルエー
テル、ポリグリセロールポリグリシジルエーテル、ソル
ビトールポリグリシジルエーテルなどを挙げることがで
きる。その他、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル
−ｍ−キシレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ' ’，Ｎ'
’−ペンタグリシジルジエチレントリアミン、Ｎ，
Ｎ，Ｎ’，Ｎ’−テトラグリシジルエチレンジアミンな
ども使用することができる。The pressure-sensitive adhesive used in the present invention comprises a polyglycidyl compound containing two or more epoxy groups as a cross-linking agent in the copolymer emulsion, wherein the epoxy groups in the polyglycidyl compound are in the copolymer. It is prepared by adding 0.5 to 2 equivalents per equivalent of the carboxyl group. If the blending amount of the polyglycidyl compound is less than 0.5 equivalent, the adhesive force of the obtained pressure-sensitive adhesive to the adherend is too strong, resulting in adhesive residue and contamination of the adherend. on the other hand,
If it exceeds 2 equivalents, the anchoring property of the obtained pressure-sensitive adhesive to the substrate becomes poor. Specific examples of the polyglycidyl compound used in the present invention include ethylene glycol or polyethylene glycol diglycidyl ether, propylene glycol or polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Dibromoneopentyl glycol diglycidyl ether, o-phthalic acid diglycidyl ester, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like can be mentioned. . Others, N, N, N ', N'-tetraglycidyl-m-xylenediamine, N, N, N', N '', N '
'-Pentaglycidyldiethylenetriamine, N,
N, N ', N'-tetraglycidyl ethylenediamine etc. can also be used.
【００１７】本発明においては、表面基材としては特に
限定されるものではないが、例えば上質紙、クレープ
紙、耐水紙、中性紙等の紙類やポリエチレンフィルム、
ポリエステルフィルム、二軸延伸ポリエステルフィル
ム、ポリプロピレンフィルム、塩化ビニルフィルム、ポ
リカーボネイトフィルム、ポリスチロールフィルム、合
成紙、不織布等のフィルム類、さらにこれらに各種塗被
層を設けてなるアート紙、コート紙、キャストコート
紙、各種記録層を設けた感熱記録紙、インクジェット記
録用紙、熱転写記録受像紙等の塗被シートが挙げられ
る。中でも、価格、粘着剤の表面基材への投錨性の点か
ら支持体に紙を使用したものが好ましい。尚、粘着剤の
投錨性がこのように適度にコントロールされているの
で、支持体に紙を使用した場合でも投錨性が強くなりす
ぎることに起因する外観不良が極めて起こりにくい。従
って、シートを製造後すぐに、大きな圧力がかかる巻取
り状態や積層状態で一時保管等することに制約を受けに
くいので本発明の再剥離性粘着シートは極めて製造しや
すいという長所を有する。又、感熱紙に関しては、粘着
剤の投錨性が過度であると、発色濃度の低下（減感）な
どの弊害を生じるが、本発明で使用する粘着剤では同様
の理由でそのような弊害を発生しにくい。In the present invention, the surface base material is not particularly limited, but for example, papers such as high-quality paper, crepe paper, water resistant paper, neutral paper and polyethylene films,
Films such as polyester film, biaxially oriented polyester film, polypropylene film, vinyl chloride film, polycarbonate film, polystyrene film, synthetic paper, non-woven fabric, etc., and art paper, coated paper, cast with various coating layers Examples thereof include coated sheets such as coated paper, heat-sensitive recording paper provided with various recording layers, ink jet recording paper, and thermal transfer recording image-receiving paper. Among them, the one using paper as the support is preferable from the viewpoints of cost and anchoring property of the adhesive to the surface substrate. Since the anchoring property of the pressure-sensitive adhesive is appropriately controlled in this way, even when paper is used as the support, it is extremely unlikely that the appearance defect due to the excessive anchoring property is caused. Therefore, the removable pressure-sensitive adhesive sheet of the present invention has an advantage that it is extremely easy to manufacture since it is less likely to be temporarily stored in a wound state or a laminated state where a large pressure is applied immediately after the sheet is manufactured. Regarding thermal paper, when the anchoring property of the pressure-sensitive adhesive is excessive, it causes a harmful effect such as a decrease in color density (desensitization), but the pressure-sensitive adhesive used in the present invention has such a bad effect for the same reason. Hard to occur.
【００１８】表面基材の支持体として紙が使用される場
合、一般的に紙層間の強度となる内部結合強度が弱い
と、剥がすときに上紙破れが生じ易い。従って、JAPAN
TAPPI紙パルプ試験方法 No.54 -93に従って求めた内部
結合強度が０．３１５ kJ/ｍ2(１５０ ft ・Lb／in2)程
度以上の紙を従来は使用する必要があった。しかし、本
発明で使用する粘着剤は、被着体に対する接着力が弱い
にもかかわらずラベル浮きが発生しにくいので、例えば
古紙再生パルプを多量に使用した比較的内部結合強度の
弱い紙も使用できる。即ち、従来のものに比べて内部結
合強度が低い紙、具体的には、０．１４７ kJ/ｍ2 （７
０ft・Lb／in2 ）程度の紙でも使用することができる。
尚、この内部結合強度が強くなるほど、再剥離性の点で
は問題は無いが、紙腰が強くなりすぎてラベル浮きを生
じたり、印刷適性が悪化したりするので内部結合強度は
０．８４１ kJ/ｍ2 （４００ ft ・Lb／in2 ）未満にす
ることが好ましい。このような内部結合強度の調整は紙
を抄紙するときに使用する紙料中のパルプ繊維や内添助
剤の選択、組合せ等によって行うことができる。なお、
紙料中にはパルプ繊維の他に、従来から使用されている
填料、各種のアニオン性、ノニオン性、カチオン性或い
は両性の歩留向上剤、濾水性向上剤、紙力増強剤や内添
サイズ剤等の抄紙用内添助剤を適宜添加することがで
き、さらに必要に応じて表面サイズ剤を併用することも
できる。また、抄紙方法については特に限定されず、例
えば抄紙ｐＨが４. ５付近である酸性抄紙法、抄紙ｐＨ
を約６の弱酸性〜約９の弱アルカリ性とする所謂中性抄
紙法等全ての抄紙方法に適用することができ、抄紙機も
長網抄紙機、ツインワイヤー抄紙機、丸網抄紙機、ヤン
キー抄紙機等を適宜使用できる。When paper is used as the support for the surface base material, generally, if the internal bond strength, which is the strength between the paper layers, is weak, the top paper is likely to tear when peeled. Therefore, JAPAN
Conventionally, it was necessary to use paper having an internal bond strength of about 0.315 kJ / m 2 (150 ft · Lb / in 2 ) or more determined according to TAPPI paper pulp test method No. 54-93. However, since the pressure-sensitive adhesive used in the present invention is unlikely to cause label floating even though the adhesive strength to the adherend is weak, for example, paper with a relatively weak internal bond strength using a large amount of recycled pulp of waste paper is also used. it can. That is, paper with lower internal bond strength than the conventional one, specifically 0.147 kJ / m 2 (7
It can also be used with paper of about 0ft · Lb / in 2 ).
It should be noted that, as the internal bond strength becomes stronger, there is no problem in terms of removability, but since the paper stiffness becomes too strong and label floating occurs or the printability deteriorates, the internal bond strength becomes 0.841 kJ. It is preferably less than / m 2 (400 ft · Lb / in 2 ). Such adjustment of the internal bond strength can be performed by selecting, combining, and the like of pulp fibers and internal addition aids in the paper stock used when making paper. In addition,
In addition to pulp fibers, the stock contains fillers that have been used in the past, various anionic, nonionic, cationic or amphoteric retention improvers, drainage improvers, paper strength enhancers and internal addition sizes. An internal additive for papermaking, such as an agent, can be appropriately added, and a surface sizing agent can be used in combination, if necessary. Further, the papermaking method is not particularly limited, and for example, an acidic papermaking method in which the papermaking pH is around 4.5, a papermaking pH
It can be applied to all papermaking methods, such as the so-called neutral papermaking method in which is made to have a weak acidity of about 6 to a weak alkalinity of about 9, and the paper machine is also a Fourdrinier paper machine, a twin wire paper machine, a round wire paper machine, a Yankee. A paper machine or the like can be used as appropriate.
【００１９】本発明においては、必要に応じて表面基材
と粘着剤層の間にプライマー層を設けることができる。
特に、表面基材の支持体としてフィルム等の投錨性の低
い支持体を用いる場合は、プライマー層を設けることが
好ましい。プライマー層としては、例えば、水酸化マグ
ネシウム、炭酸マグネシウム、硫酸マグネシウム、酸化
カルシウム、水酸化カルシウム、炭酸カルシウム、サチ
ンホワイト、珪酸カルシウム、酸化亜鉛、酸化チタン、
酸化アルミニウム、水酸化アルミニウム、タルク、カオ
リンなどの顔料と、澱粉、ポリビニルアルコール、カル
ボキシメチルセルロース、スチレン・ブタジエン共重合
体、アクリル共重合体、酢酸ビニル共重合体などのバイ
ンダーを用いたものが挙げられる。また、塗被層や記録
層として顔料塗被層を設けた塗被シートは印刷適性、熱
転写適性、インクジェット適性等の記録適性が向上する
と共に、粘着剤の投錨による外観不良も起こり難くなる
ため、支持体として紙を用いた場合は特に好ましい。In the present invention, a primer layer may be provided between the surface base material and the pressure-sensitive adhesive layer, if necessary.
In particular, when a support having a low anchoring property such as a film is used as the support for the surface base material, it is preferable to provide a primer layer. Examples of the primer layer include magnesium hydroxide, magnesium carbonate, magnesium sulfate, calcium oxide, calcium hydroxide, calcium carbonate, satin white, calcium silicate, zinc oxide, titanium oxide,
Examples include pigments such as aluminum oxide, aluminum hydroxide, talc, and kaolin, and binders such as starch, polyvinyl alcohol, carboxymethyl cellulose, styrene / butadiene copolymer, acrylic copolymer, and vinyl acetate copolymer. . Further, a coated sheet provided with a pigment coating layer as a coating layer or a recording layer has improved printability such as printability, heat transfer suitability, and ink jet suitability, and an appearance defect due to anchoring of an adhesive is less likely to occur. It is particularly preferable to use paper as the support.
【００２０】顔料塗被層に用いられる顔料は特に限定さ
れるものではないが、例えば、カオリン、タルク、クレ
ー、焼成クレー、シリカ、酸化チタン、酸化カルシウ
ム、水酸化カルシウム、炭酸カルシウム、硫酸カルシウ
ム、サチンホワイト、珪酸カルシウム、水酸化マグネシ
ウム、炭酸マグネシウム、硫酸マグネシウム、珪酸マグ
ネシウム、酸化亜鉛、炭酸亜鉛、硫酸亜鉛、酸化アルミ
ニウム、水酸化アルミニウム、珪酸アルミニウム等が挙
げられる。また、顔料塗被層に用いられるバインダーも
特に限定されるものではないが、例えば、澱粉、ポリビ
ニルアルコール、カゼイン、カルボキシメチルセルロー
ス、デキストリン、メチルセルロース、スチレン・ブタ
ジエン共重合体、メチルメタクリレート・ブタジエン共
重合体、塩化ビニル共重合体、エチレン・塩化ビニル共
重合体、塩化ビニリデン共重合体、エチレン・塩化ビニ
リデン共重合体、アクリル共重合体、酢酸ビニル共重合
体、エチレン・酢酸ビニル共重合体等が挙げられる。顔
料塗被層には、必要に応じて増粘剤、染料や消泡剤、分
散剤、湿潤剤などの助剤を添加することもできる。The pigment used in the pigment coating layer is not particularly limited, but examples thereof include kaolin, talc, clay, calcined clay, silica, titanium oxide, calcium oxide, calcium hydroxide, calcium carbonate and calcium sulfate. Examples include satin white, calcium silicate, magnesium hydroxide, magnesium carbonate, magnesium sulfate, magnesium silicate, zinc oxide, zinc carbonate, zinc sulfate, aluminum oxide, aluminum hydroxide, aluminum silicate and the like. Further, the binder used in the pigment coating layer is not particularly limited, and examples thereof include starch, polyvinyl alcohol, casein, carboxymethyl cellulose, dextrin, methyl cellulose, styrene / butadiene copolymer, and methyl methacrylate / butadiene copolymer. , Vinyl chloride copolymer, ethylene / vinyl chloride copolymer, vinylidene chloride copolymer, ethylene / vinylidene chloride copolymer, acrylic copolymer, vinyl acetate copolymer, ethylene / vinyl acetate copolymer and the like. To be If necessary, an auxiliary agent such as a thickener, a dye, a defoaming agent, a dispersant or a wetting agent may be added to the pigment coated layer.
【００２１】本発明において再剥離性粘着シートを構成
する方法については格別の限定は無く、剥離シートの剥
離剤層面上に粘着剤を塗布、乾燥することにより粘着剤
層を形成し、表面基材を貼り合わせて仕上げられる。該
剥離シートとしては、グラシン紙のような高密度原紙、
クレーコート紙、又はクラフト紙、上質紙にポリエチレ
ン等をラミネートしたポリラミ紙、フィルム等に、フッ
素樹脂やシリコーン樹脂を乾燥重量で０．０５〜３ｇ／
ｍ2 程度塗布し熱硬化、電離放射線硬化等によって剥離
剤層を形成したものが使用される。この場合の塗布装置
としては、例えば多段ロールコーター、エアーナイフコ
ーター、バーコーター、オフセットグラビアコーター、
ダイレクトグラビアコーター等が使用される。また粘着
剤は剥離シートに塗被される場合の塗被装置としては、
例えばリバースロールコーター、ナイフコーター、エア
ーナイフコーター、バーコーター、スロットダイコータ
ー、リップコーター、リバースグラビアコーター等が使
用され、塗被量は乾燥重量で５〜３０ｇ／ｍ2 程度の範
囲が好ましい。There is no particular limitation on the method of constructing the removable pressure-sensitive adhesive sheet in the present invention, and the pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive on the surface of the release agent layer of the release sheet and drying it. Can be finished by pasting. As the release sheet, high-density base paper such as glassine paper,
Clay-coated paper, kraft paper, poly-laminated paper laminated with polyethylene, etc. on high-quality paper, film, etc., with fluororesin or silicone resin in a dry weight of 0.05 to 3 g /
A release agent layer formed by applying about m 2 and forming a release agent layer by heat curing, ionizing radiation curing or the like is used. As the coating device in this case, for example, multi-stage roll coater, air knife coater, bar coater, offset gravure coater,
A direct gravure coater is used. Further, the pressure-sensitive adhesive, as a coating device when coated on the release sheet,
For example, a reverse roll coater, a knife coater, an air knife coater, a bar coater, a slot die coater, a lip coater, a reverse gravure coater and the like are used, and the coating amount is preferably in the range of about 5 to 30 g / m 2 in dry weight.
【００２２】[0022]
【実施例】以下、実施例をあげて本発明をより具体的に
説明するが、勿論本発明はこれらに限定されるものでは
ない。また例中の部、割合、塗布量等は特に断わらない
かぎり、全て固形分重量で示すものである。EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these. Unless otherwise specified, all parts, proportions, coating amounts and the like in the examples are shown by solid content weight.
【００２３】各実施例、比較例の再剥離性粘着シートを
作成する上で基本的に使用される（粘着剤の製造方法）
と（再剥離性粘着シートの作成方法）について以下に説
明する。 （粘着剤の製造方法）撹拌機、温度調節器及び還流式冷
却器を備えたオートクレーブに水と重合開始剤を仕込
み、７０℃に昇温した。ついで、単量体混合物、分子量
調節剤、乳化剤を添加した後、撹拌、乳化してプレエマ
ルジョンを調製した。このプレエマルジョン全量を３時
間かけて連続的に添加しながら８０℃で撹拌して乳化重
合させた。その後、さらに８０℃で２時間撹拌を続けて
共重合を完結させた。このエマルジョンに粘着付与剤を
添加し、さらに顔料として酸化チタンの５０％分散液を
６重量％添加し、アンモニアによりｐＨ８．５に調整し
た後、ポリアクリル酸ナトリウム「ＡＳＥ−６０（ロー
ム＆ハース社製）」を添加して、粘度（Ｂ形粘度計、Ｎ
ｏ．４ロータ、６０ｒ．ｐ．ｍで測定）を４０００ｃｐ
ｓに調整した。次に、架橋剤としてジグリセロールポリ
グリシジルエーテル「デナコールＥＸ−４２１（ナガセ
化成工業社製）」を、当該エマルジョン中の共重合体中
のカルボキシル基とジグリセロールポリグリシジルエー
テル中のエポキシ基が同当量となる割合で添加すること
により粘着剤を製造した。It is basically used in producing the removable pressure-sensitive adhesive sheets of Examples and Comparative Examples (method of producing pressure-sensitive adhesive).
And (a method for producing a removable pressure-sensitive adhesive sheet) will be described below. (Method for producing pressure-sensitive adhesive) Water and a polymerization initiator were charged into an autoclave equipped with a stirrer, a temperature controller and a reflux condenser, and the temperature was raised to 70 ° C. Next, a monomer mixture, a molecular weight modifier and an emulsifier were added, followed by stirring and emulsifying to prepare a pre-emulsion. The whole amount of this pre-emulsion was continuously added over 3 hours while stirring at 80 ° C. for emulsion polymerization. Then, stirring was further continued at 80 ° C. for 2 hours to complete the copolymerization. A tackifier was added to this emulsion, 6% by weight of a 50% titanium oxide dispersion was added as a pigment, and the pH was adjusted to 8.5 with ammonia. Then, sodium polyacrylate "ASE-60 (Rohm & Haas Co. Made), and the viscosity (B type viscometer, N
o. 4 rotor, 60r. p. (measured in m) is 4000 cp
It was adjusted to s. Next, as a cross-linking agent, diglycerol polyglycidyl ether "Denacol EX-421 (manufactured by Nagase Kasei Co., Ltd.)" was used, and the carboxyl group in the copolymer in the emulsion and the epoxy group in diglycerol polyglycidyl ether had the same equivalent amount. A pressure-sensitive adhesive was produced by adding it in a ratio such that
【００２４】（再剥離性粘着シートの作成方法）上記の
粘着剤と表面基材とを使用し、別途、市販のポリエチレ
ンラミネート剥離紙に前記粘着剤を、乾燥重量で２０ｇ
／ｍ2 となるように塗布、乾燥させた後、この粘着剤層
面と前記表面基材の裏面とを貼り合わせて再剥離性粘着
シートを作成した。(Preparation Method of Removable Adhesive Sheet) Using the above-mentioned adhesive and the surface substrate, the above adhesive is separately added to a commercially available polyethylene laminate release paper, and the dry weight is 20 g.
After coating and drying so as to be / m 2 , the pressure-sensitive adhesive layer surface and the back surface of the front surface substrate were attached to each other to prepare a removable pressure-sensitive adhesive sheet.
【００２５】実施例１ 単量体混合物としてアクリル酸２−エチルヘキシル９
４．３部、アクリロニトリル５．０部、アクリル酸０．
７部、重合開始剤として過硫酸ナトリウム０．４部、分
子量調節剤としてｎ−ブチルメルカプタン０．０２部
と、乳化剤としてドデシルベンゼンスルホン酸ナトリウ
ム１．０部、ポリオキシエチレンノニルフェニルエーテ
ル１．０部、粘着付与剤としてテルペンフェノール樹脂
「タマノルＥ−１００（荒川化学工業社製）」１０部及
び水４０部を用いて上記方法により粘着剤を製造した。
その粘着剤を使用し、表面基材として５０μｍのポリエ
ステルフィルムを用いて再剥離性粘着シートを得た。 実施例２ 表面基材として米坪７５ｇ／ｍ2 の上質紙を用いた以外
は実施例１と同様にして再剥離性粘着シートを得た。Example 1 2-Ethylhexyl acrylate 9 as a monomer mixture
4.3 parts, acrylonitrile 5.0 parts, acrylic acid 0.
7 parts, 0.4 parts of sodium persulfate as a polymerization initiator, 0.02 parts of n-butyl mercaptan as a molecular weight modifier, 1.0 part of sodium dodecylbenzenesulfonate as an emulsifier, and 1.0 of polyoxyethylene nonylphenyl ether. Parts, 10 parts of a terpene phenol resin "Tamanor E-100 (manufactured by Arakawa Chemical Industry Co., Ltd.)" as a tackifier, and 40 parts of water were used to produce an adhesive by the above method.
Using the pressure-sensitive adhesive, a removable pressure-sensitive adhesive sheet was obtained using a 50 μm polyester film as the surface substrate. Example 2 A re-peelable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that high-quality paper having a surface area of 75 g / m 2 was used as the surface substrate.
【００２６】実施例３ 実施例２において使用したと同一の米坪７５ｇ／ｍ2 の
上質紙にさらに、カオリン４０部、炭酸カルシウム４０
部、スチレン・ブタジエン共重合体エマルジョン２０部
からなる顔料塗被層を、乾燥重量で１０ｇ／ｍ2 となる
ように塗布後、４段スーパーキャレンダーで処理して得
た紙厚８６μｍの塗被紙を表面基材として使用した他は
実施例１と同様にして再剥離性粘着シートを得た。尚、
この表面基材の顔料塗被面の反対面に粘着剤層が形成さ
れるようにした。Example 3 On the same high-quality paper of 75 g / m 2 as used in Example 2, 40 parts of kaolin and 40 parts of calcium carbonate were further added.
Part, and a pigment coating layer consisting of 20 parts of a styrene / butadiene copolymer emulsion are coated so that the dry weight is 10 g / m 2, and then treated with a 4-stage super calender to obtain a coating having a paper thickness of 86 μm. A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that paper was used as the surface substrate. still,
The pressure-sensitive adhesive layer was formed on the surface of the surface base material opposite to the surface coated with the pigment.
【００２７】実施例４ 表面基材として、中性抄紙した米坪７５ｇ／ｍ2 の上質
紙を用いた以外は実施例１と同様にして再剥離性粘着シ
ートを得た。 実施例５ 粘着付与剤として重合ロジン系樹脂「スーパーエステル
Ｅ−６５０（荒川化学工業社製）」１０部を用いた以外
は実施例３と同様にして再剥離性粘着シートを得た。 実施例６ 粘着付与剤として重合ロジン系樹脂「スーパーエステル
Ｅ−６５０（荒川化学工業社製）」２５部を用いた以外
は実施例３と同様にして再剥離性粘着シートを得た。 実施例７ 単量体混合物としてアクリル酸２−エチルヘキシル９
４．３部、アクリロニトリル３．０部、アクリル酸０．
７部、Ｎ−メチロールアクリルアミド２．０部を使用し
た以外は実施例３と同様にして再剥離性粘着シートを得
た。Example 4 A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that, as the surface base material, high-quality paper having a weight of 75 g / m 2 and having a weight of neutral paper was used. Example 5 A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 10 parts of a polymerized rosin-based resin "Super Ester E-650 (manufactured by Arakawa Chemical Industry Co., Ltd.)" was used as a tackifier. Example 6 A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 25 parts of a polymerized rosin-based resin "Super Ester E-650 (manufactured by Arakawa Chemical Industry Co., Ltd.)" was used as a tackifier. Example 7 2-Ethylhexyl Acrylate 9 as Monomer Mixture
4.3 parts, acrylonitrile 3.0 parts, acrylic acid 0.
A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 7 parts and 2.0 parts of N-methylolacrylamide were used.
【００２８】実施例８ 単量体混合物としてアクリル酸イソノニル８６．３部、
アクリロニトリル５．０部、メタクリル酸０．７部、ア
クリル酸ブチル８．０部を使用した以外は実施例３と同
様にして再剥離性粘着シートを得た。 実施例９ 単量体混合物としてアクリル酸イソノニル１８．３部、
メタクリル酸ラウリル７４．０部、アクリロニトリル
５．０部、アクリル酸０．７部、メタクリル酸メチル
２．０部を使用した以外は実施例３と同様にして再剥離
性粘着シートを得た。 実施例１０ 単量体混合物としてアクリル酸２−エチルヘキシル９
２．５部、アクリロニトリル３．３部、メタクリル酸
０．７部、Ｎ−メチロールアクリルアミド３．０部、メ
タクリル酸ジメチルアミノエチル０．５部を使用した以
外は実施例３と同様にして再剥離性粘着シートを得た。 実施例１１ 先に説明した（粘着剤の製造方法）の中で使用した。酸
化チタンを用いなかった以外は実施例３と同様にして再
剥離性粘着シートを得た。Example 8 86.3 parts of isononyl acrylate as a monomer mixture,
A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 5.0 parts of acrylonitrile, 0.7 parts of methacrylic acid, and 8.0 parts of butyl acrylate were used. Example 9 18.3 parts isononyl acrylate as a monomer mixture,
A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 74.0 parts of lauryl methacrylate, 5.0 parts of acrylonitrile, 0.7 parts of acrylic acid, and 2.0 parts of methyl methacrylate were used. Example 10 2-Ethylhexyl acrylate 9 as a monomer mixture
Re-peel in the same manner as in Example 3 except that 2.5 parts, 3.3 parts of acrylonitrile, 0.7 parts of methacrylic acid, 3.0 parts of N-methylol acrylamide, and 0.5 parts of dimethylaminoethyl methacrylate were used. A pressure-sensitive adhesive sheet was obtained. Example 11 Used in (Preparation Method of Adhesive) described above. A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that titanium oxide was not used.
【００２９】比較例１ 分子量調節剤としてｎ−ブチルメルカプタンの添加量を
０．００１部に変更した以外は実施例１と同様にして再
剥離性粘着シートを得た。 比較例２ 分子量調節剤としてｎ−ブチルメルカプタンの添加量を
０．００１部に変更した以外は実施例３と同様にして再
剥離性粘着シートを得た。 比較例３ 分子量調節剤としてｎ−ブチルメルカプタンの添加量を
０．５部に変更した以外は実施例３と同様にして再剥離
性粘着シートを得た。 比較例４ 乳化剤としてドデシルベンゼンスルホン酸ナトリウムの
添加量を０．２部に変更した以外は実施例３と同様にし
て再剥離性粘着シートを得た。Comparative Example 1 A removable pressure sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the amount of n-butyl mercaptan added as a molecular weight modifier was changed to 0.001 part. Comparative Example 2 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that the amount of n-butyl mercaptan added as a molecular weight modifier was changed to 0.001 part. Comparative Example 3 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that the addition amount of n-butyl mercaptan as a molecular weight modifier was changed to 0.5 part. Comparative Example 4 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that the addition amount of sodium dodecylbenzenesulfonate as an emulsifier was changed to 0.2 part.
【００３０】比較例５ 乳化剤としてドデシルベンゼンスルホン酸ナトリウムの
添加量を３．０部に変更した以外は実施例３と同様にし
て再剥離性粘着シートを得た。 比較例６ 分子量調節剤としてｎ−ブチルメルカプタンの代わりに
チオグリコール酸オクチル０．２部を使用した以外は実
施例３と同様にして再剥離性粘着シートを得た。 比較例７ 分子量調節剤としてｎ−ブチルメルカプタンの代わりに
チオグリコール酸オクチル０．０２部を使用した以外は
実施例３と同様にして再剥離性粘着シートを得た。 比較例８ 架橋剤としてジグリセロールポリグリシジルエーテル
を、エマルジョン中の共重合体中のカルボキシル基に対
してジグリセロールポリグリシジルエーテル中のエポキ
シ基が６．０当量となる割合で添加した以外は実施例３
と同様にして再剥離性粘着シートを得た。Comparative Example 5 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that the amount of sodium dodecylbenzenesulfonate used as an emulsifier was changed to 3.0 parts. Comparative Example 6 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 0.2 part of octyl thioglycolate was used as the molecular weight modifier instead of n-butyl mercaptan. Comparative Example 7 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 0.02 part of octyl thioglycolate was used instead of n-butyl mercaptan as a molecular weight modifier. Comparative Example 8 Example except that diglycerol polyglycidyl ether was added as a cross-linking agent at a ratio of 6.0 equivalent of epoxy groups in diglycerol polyglycidyl ether to carboxyl groups in the copolymer in emulsion. Three
A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in.
【００３１】比較例９ 架橋剤としてジグリセロールポリグリシジルエーテル
を、エマルジョン中の共重合体中のカルボキシル基に対
してジグリセロールポリグリシジルエーテル中のエポキ
シ基が０．１当量となる割合で添加した以外は実施例３
と同様にして再剥離性粘着シートを得た。 比較例１０ 架橋剤としてジグリセロールポリグリシジルエーテルの
代わりにアリルグリシジルエーテルを用いた以外は実施
例３と同様にして再剥離性粘着シートを得た。 比較例１１ 単量体混合物としてアクリル酸２−エチルヘキシル９
７．２部、アクリロニトリル０．１部、アクリル酸０．
７部、Ｎ−メチロールアクリルアミド２．０部を使用し
た以外は実施例３と同様にして再剥離性粘着シートを得
た。 比較例１２ 単量体混合物としてアクリル酸２−エチルヘキシル８
２．３部、アクリロニトリル１５．０部、アクリル酸
０．７部、Ｎ−メチロールアクリルアミド２．０部を使
用した以外は実施例３と同様にして再剥離性粘着シート
を得た。Comparative Example 9 Except that diglycerol polyglycidyl ether was added as a cross-linking agent in such a ratio that the epoxy groups in diglycerol polyglycidyl ether were 0.1 equivalent to the carboxyl groups in the copolymer in the emulsion. Is Example 3
A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in. Comparative Example 10 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that allyl glycidyl ether was used as the crosslinking agent instead of diglycerol polyglycidyl ether. Comparative Example 11 2-Ethylhexyl acrylate 9 as a monomer mixture
7.2 parts, acrylonitrile 0.1 part, acrylic acid 0.
A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 7 parts and 2.0 parts of N-methylolacrylamide were used. Comparative Example 12 2-Ethylhexyl Acrylate 8 as Monomer Mixture
A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 2.3 parts, 15.0 parts of acrylonitrile, 0.7 parts of acrylic acid, and 2.0 parts of N-methylolacrylamide were used.
【００３２】比較例１３ 単量体混合物としてアクリル酸２−エチルヘキシル３
０．０部、アクリロニトリル５．０部、アクリル酸０．
７部、アクリル酸ブチル６４．３部を使用した以外は実
施例３と同様にして再剥離性粘着シートを得た。 比較例１４ 単量体混合物としてアクリル酸２−エチルヘキシル９
４．９５部、アクリロニトリル３．０部、アクリル酸
０．０５部、Ｎ−メチロールアクリルアミド２．０部を
使用した以外は実施例３と同様にして再剥離性粘着シー
トを得た。 比較例１５ 単量体混合物としてアクリル酸２−エチルヘキシル８
８．０部、アクリロニトリル３．０部、アクリル酸７．
０部、Ｎ−メチロールアクリルアミド２．０部を使用し
た以外は実施例３と同様にして再剥離性粘着シートを得
た。 比較例１６ 単量体混合物としてアクリル酸２−エチルヘキシル６
４．０部、アクリロニトリル４．０部、アクリル酸０．
７部、アクリル酸ブチル２９．３部、Ｎ−メチロールア
クリルアミド２．０部を使用した以外は実施例３と同様
にして再剥離性粘着シートを得た。Comparative Example 13 2-Ethylhexyl Acrylate 3 as a monomer mixture
0.0 parts, acrylonitrile 5.0 parts, acrylic acid 0.
A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 7 parts and 64.3 parts of butyl acrylate were used. Comparative Example 14 2-Ethylhexyl acrylate 9 as a monomer mixture
A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 4.95 parts, acrylonitrile 3.0 parts, acrylic acid 0.05 part, and N-methylolacrylamide 2.0 parts were used. Comparative Example 15 2-Ethylhexyl Acrylate 8 as a monomer mixture
8.0 parts, acrylonitrile 3.0 parts, acrylic acid 7.
A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3, except that 0 part and 2.0 parts of N-methylolacrylamide were used. Comparative Example 16 2-Ethylhexyl acrylate 6 as a monomer mixture
4.0 parts, acrylonitrile 4.0 parts, acrylic acid 0.
A releasable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 7 parts, 29.3 parts of butyl acrylate and 2.0 parts of N-methylol acrylamide were used.
【００３３】比較例１７ 粘着付与剤として石油樹脂「ＫＥ−７５６Ｂ（荒川化学
工業社製）」１０部を使用した以外は実施例３と同様に
して再剥離性粘着シートを得た。 比較例１８ 粘着付与剤として重合ロジン系樹脂「スーパーエステル
Ｅ−６５０」４５部を使用した以外は実施例３と同様に
して再剥離性粘着シートを得た。 比較例１９ 実施例３において粘着付与剤を使用せずに再剥離性粘着
シートを得た。 比較例２０ 粘着剤を乾燥重量で２６ｇ／ｍ2 塗布した以外は比較例
１９と同様にして再剥離性粘着シートを得た。Comparative Example 17 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 10 parts of petroleum resin "KE-756B (manufactured by Arakawa Chemical Industry Co., Ltd.)" was used as a tackifier. Comparative Example 18 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that 45 parts of the polymerized rosin-based resin "Super Ester E-650" was used as the tackifier. Comparative Example 19 A removable pressure-sensitive adhesive sheet was obtained without using the tackifier in Example 3. Comparative Example 20 A removable pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 19 except that the pressure-sensitive adhesive was applied in a dry weight of 26 g / m 2 .
【００３４】実施例１〜１１及び比較例１〜２０で使用
した粘着剤について、そのプレエマルジョンの共重合完
結時のポリスチレン換算数平均分子量、ポリスチレン換
算重量平均分子量とポリスチレン換算数平均分子量の
比、平均粒子径及びガラス転移温度を下記の方法で求め
た。その結果を表１及び２に示す。 〔ポリスチレン換算数平均分子量、ポリスチレン換算重
量平均分子量とポリスチレン換算数平均分子量の比〕ゲ
ルパーミエーションクロマトグラフィー装置「ＨＣＬ−
８０２０（東ソー社製）」を用いて測定した。 〔平均粒子径〕ナノサイザー（コールター社製）を用い
て測定した。 〔ガラス転移温度〕各単量体ホモポリマーのガラス転移
温度より、先に説明した数式に基いて計算した。Regarding the pressure-sensitive adhesives used in Examples 1 to 11 and Comparative Examples 1 to 20, the polystyrene-equivalent number average molecular weight, the ratio of the polystyrene-equivalent weight average molecular weight to the polystyrene-equivalent number average molecular weight at the completion of the copolymerization of the pre-emulsion, The average particle diameter and the glass transition temperature were determined by the following methods. The results are shown in Tables 1 and 2. [Ratio of polystyrene reduced number average molecular weight, polystyrene reduced weight average molecular weight and polystyrene reduced number average molecular weight] Gel permeation chromatography device "HCL-"
8020 (manufactured by Tosoh Corporation) ". [Average particle diameter] It was measured using Nanosizer (manufactured by Coulter Co.). [Glass transition temperature] The glass transition temperature was calculated from the glass transition temperature of each monomer homopolymer based on the above-described mathematical formula.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】実施例１〜実施例１１及び比較例１〜比較
例２０で得られた再剥離性粘着シートについて、ラベル
浮き、再剥離性、ブリード及びウーズを下記の方法で評
価した。ラベル浮きと再剥離性は、再剥離性粘着シート
を２３℃６５％ＲＨの雰囲気下で２週間エージングした
後評価した。その結果を表３及び４に示す。With respect to the removable pressure-sensitive adhesive sheets obtained in Examples 1 to 11 and Comparative Examples 1 to 20, label floating, removability, bleed and ooze were evaluated by the following methods. Label floating and removability were evaluated after aging the removable pressure-sensitive adhesive sheet in an atmosphere of 23 ° C. and 65% RH for 2 weeks. The results are shown in Tables 3 and 4.
【００３８】〔ラベル浮き〕３．５インチフロッピーデ
ィスクを用いて、１８０度の折り返し部を有するように
試験片を貼った。その状態で７０℃雰囲気下に７日間放
置、さらに２３℃６５％ＲＨの雰囲気下に２４時間放置
した後の試験片の状態を観察した。ラベル浮きを下記の
基準に基づいて評価した。 Ａ：全く浮きが見られない Ｂ：少し浮きが見られる Ｃ：かなり浮きが見られる Ｄ：折り返し部が完全に跳ね上がっている[Label Lifting] Using a 3.5-inch floppy disk, a test piece was attached so as to have a folded portion of 180 degrees. In that state, the state of the test piece was observed after being left in an atmosphere of 70 ° C. for 7 days and further in an atmosphere of 23 ° C. and 65% RH for 24 hours. Label floating was evaluated based on the following criteria. A: No lift is seen at all B: Some lift is seen C: A lot of lift is seen D: The folded part is completely flipped up
【００３９】〔再剥離性〕表面の平滑なＡＢＳ板及び
３．５インチフロッピーディスクに試験片を貼り、２３
℃６５％ＲＨの雰囲気下に７日間放置後、速さ３００ｍ
ｍ／分、角度１８０度で剥離し、被着体の状態を観察し
た。再剥離性は下記の基準で評価した。 Ａ：被着体に糊、表面基材とも全く残っていない Ｂ：糊が少し残っている Ｃ：かなり糊が残っている Ｄ：表面基材が破れて残っている[Removability] A test piece was attached to an ABS plate having a smooth surface and a 3.5-inch floppy disk,
After leaving for 7 days in an atmosphere of 65 ° C RH, 300m speed
Peeling was performed at m / min and an angle of 180 degrees, and the state of the adherend was observed. The removability was evaluated according to the following criteria. A: Neither glue nor surface material remains on the adherend B: Some glue remains C: Some glue remains D: The surface material is broken and remains
【００４０】〔ブリード〕試験片に１ｋｇ／ｍ2 の圧力
を加え、２５℃の雰囲気下に２４時間放置後、ブリード
の状態を観察した。ブリードは下記の基準で評価した。 Ａ：全くブリードしていない Ｂ：少しブリードしている Ｃ：かなりブリードしている[Bleed] A pressure of 1 kg / m 2 was applied to the test piece, and after leaving it in an atmosphere of 25 ° C. for 24 hours, the state of bleeding was observed. Bleed was evaluated according to the following criteria. A: No bleed at all B: Bleed a little C: Bleed quite a bit
【００４１】〔ウーズ〕５cm×５cmの試験片２０枚の上
に１kgの重りを乗せ、４０℃の雰囲気下に２４時間放置
後、試験片の切り口を手で触ってウーズを評価した。ウ
ーズは下記の基準で評価した。 Ａ：全く粘着性を感じない Ｂ：少し粘着性を感じる Ｃ：かなり粘着性を感じる[Wooze] A weight of 1 kg was placed on 20 test pieces of 5 cm × 5 cm, left for 24 hours in an atmosphere of 40 ° C., and the cuts of the test pieces were touched by hand to evaluate the ooze. The ooze was evaluated according to the following criteria. A: No stickiness is felt B: A little stickiness is felt C: A lot of stickiness is felt
【００４２】[0042]
【表３】 [Table 3]
【００４３】[0043]
【表４】 [Table 4]
【００４４】〔その他の評価〕尚、実施例２〜１１にお
いて、表面基材としては全て内部結合強度が１００ ft
・Lb／in2 程度の比較的紙層間の強度が弱い紙を使用し
たが、再剥離性は全て良好であった。また、上記実施例
以外に、表面基材にそれぞれ熱転写用紙、インクジェッ
ト用紙、感熱紙を用いた以外は実施例３と同様にして各
再剥離性粘着シートを得た。次いで、実施例３と同様に
各評価試験を行ったところ実施例３とほぼ同様の評価結
果が得られた。[Other Evaluations] In Examples 2 to 11, all the surface base materials had an internal bond strength of 100 ft.
・ Although paper with a relatively low strength between the paper layers, such as Lb / in 2, was used, the removability was all good. In addition, in addition to the above-described examples, each releasable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that thermal transfer paper, inkjet paper, and thermal paper were used for the surface base material. Then, when each evaluation test was performed in the same manner as in Example 3, substantially the same evaluation results as in Example 3 were obtained.
【００４５】[0045]
【効果】本発明の再剥離性粘着シートは、ウーズが無
く、被着体に粘着時には浮き、めくれが無く、被着体か
ら剥がす際には表面基材の破れや糊残りにより被着体の
外観を損ねて被着体汚染を生ずることも無い優れた再剥
離性を示し、かつブリードにより表面基材を損なうこと
もない。[Effect] The removable pressure-sensitive adhesive sheet of the present invention has no ooze, does not float when adhered to an adherend, does not curl, and is peeled off from the adherend due to tearing of the surface base material or adhesive residue It exhibits excellent removability without impairing the appearance and causing contamination of the adherend, and does not damage the surface substrate by bleeding.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 133/08 ＪＤＤ 193/00 ＪＡＫ // Ｃ０９Ｊ 163/00 ＪＦＭ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C09J 133/08 JDD 193/00 JAK // C09J 163/00 JFM
Claims (2)
て有する再剥離性粘着シートにおいて、粘着剤層を形成
する粘着剤として、下記（ａ），（ｂ），（ｃ）及び必
要に応じて加えられる（ｄ）からなる単量体組成物を乳
化重合して得られ、かつポリスチレン換算数平均分子量
（Ｍｎ）が０．１×１０4以上であって５．０×１０4未
満であり、かつポリスチレン換算重量平均分子量（Ｍ
ｗ）とポリスチレン換算数平均分子量（Ｍｎ）の比（Ｍ
ｗ／Ｍｎ）が４０〜８００、平均粒子径が１００〜５０
０ｎｍ、ガラス転移温度が−５０℃以下である共重合体
の水系エマルジョンを主成分とし、粘着付与剤としてロ
ジン系樹脂及びテルペン系樹脂の中から選択される樹脂
を添加し、かつ、該共重合体のカルボキシル基１当量当
たりエポキシ基が０．５〜２当量となるように、２個以
上のエポキシ基を持つポリグリシジル化合物を添加した
粘着剤を用いることを特徴とする再剥離性粘着シート。 （ａ）アルキル基の炭素数が８〜１２の（メタ）アクリ
ル酸アルキルエステル単量体を８０〜９９重量％ （ｂ）（メタ）アクリロニトリルを０．３〜１０重量％ （ｃ）α，β−不飽和カルボン酸を０．１〜５重量％ （ｄ）その他の共重合可能な単量体を０〜５重量％1. A releasable pressure-sensitive adhesive sheet comprising a release sheet, a pressure-sensitive adhesive layer, and a surface base material laminated together, and as the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, the following (a), (b), (c) and It is obtained by emulsion polymerization of a monomer composition comprising (d), which is added as necessary, and has a polystyrene reduced number average molecular weight (Mn) of 0.1 × 10 4 or more and 5.0 × 10 4 And a polystyrene equivalent weight average molecular weight (M
w) and polystyrene equivalent number average molecular weight (Mn) ratio (M
w / Mn) is 40 to 800, and the average particle size is 100 to 50.
The main component is an aqueous emulsion of a copolymer having 0 nm and a glass transition temperature of −50 ° C. or lower, and a resin selected from rosin-based resins and terpene-based resins is added as a tackifier, and the copolymerization A releasable pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive to which a polyglycidyl compound having two or more epoxy groups is added so that the amount of epoxy groups is 0.5 to 2 equivalents per equivalent of carboxyl groups in the combined product. (A) 80 to 99% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group with 8 to 12 carbon atoms (b) 0.3 to 10% by weight of (meth) acrylonitrile (c) α, β 0.1 to 5% by weight of unsaturated carboxylic acid (d) 0 to 5% by weight of other copolymerizable monomer
ール樹脂である請求項１記載の再剥離性粘着シート。2. The removable pressure-sensitive adhesive sheet according to claim 1, wherein the resin as the tackifier is a terpene phenol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6328395A JPH08183935A (en) | 1994-12-28 | 1994-12-28 | Re-releasable pressure-sensitive adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6328395A JPH08183935A (en) | 1994-12-28 | 1994-12-28 | Re-releasable pressure-sensitive adhesive sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08183935A true JPH08183935A (en) | 1996-07-16 |
Family
ID=18209780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6328395A Pending JPH08183935A (en) | 1994-12-28 | 1994-12-28 | Re-releasable pressure-sensitive adhesive sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08183935A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10298513A (en) * | 1997-04-25 | 1998-11-10 | Oji Paper Co Ltd | Repeelable adhesive label |
| JP2005023169A (en) * | 2003-06-30 | 2005-01-27 | Soken Chem & Eng Co Ltd | Acrylic blister-resistant adhesive resin composition, transfer filmy adhesive, blister-resistant adhesive sheet and use thereof |
| JP2008133482A (en) * | 2008-01-26 | 2008-06-12 | Nitto Denko Corp | Water-dispersed self-adhesive composition, self-adhesive sheet, and self-adhesive foamed rubber sheet using the same |
| JP2010235710A (en) * | 2009-03-30 | 2010-10-21 | Lintec Corp | Water-dispersed pressure-sensitive acrylic adhesive composition, pressure-sensitive adhesive sheet and method for using the same |
| JP2012062416A (en) * | 2010-09-16 | 2012-03-29 | Lintec Corp | Removable self-adhesive sheet |
| JP2013036011A (en) * | 2011-08-11 | 2013-02-21 | Lintec Corp | Removable adhesive sheet |
-
1994
- 1994-12-28 JP JP6328395A patent/JPH08183935A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10298513A (en) * | 1997-04-25 | 1998-11-10 | Oji Paper Co Ltd | Repeelable adhesive label |
| JP2005023169A (en) * | 2003-06-30 | 2005-01-27 | Soken Chem & Eng Co Ltd | Acrylic blister-resistant adhesive resin composition, transfer filmy adhesive, blister-resistant adhesive sheet and use thereof |
| JP4555921B2 (en) * | 2003-06-30 | 2010-10-06 | 綜研化学株式会社 | Acrylic-based blister-resistant adhesive resin composition, transfer-film-like adhesive using the same, blister-resistant adhesive sheet and uses thereof |
| JP2008133482A (en) * | 2008-01-26 | 2008-06-12 | Nitto Denko Corp | Water-dispersed self-adhesive composition, self-adhesive sheet, and self-adhesive foamed rubber sheet using the same |
| JP2010235710A (en) * | 2009-03-30 | 2010-10-21 | Lintec Corp | Water-dispersed pressure-sensitive acrylic adhesive composition, pressure-sensitive adhesive sheet and method for using the same |
| JP2012062416A (en) * | 2010-09-16 | 2012-03-29 | Lintec Corp | Removable self-adhesive sheet |
| JP2013036011A (en) * | 2011-08-11 | 2013-02-21 | Lintec Corp | Removable adhesive sheet |
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