JPH0257110B2 - - Google Patents
Info
- Publication number
- JPH0257110B2 JPH0257110B2 JP17675586A JP17675586A JPH0257110B2 JP H0257110 B2 JPH0257110 B2 JP H0257110B2 JP 17675586 A JP17675586 A JP 17675586A JP 17675586 A JP17675586 A JP 17675586A JP H0257110 B2 JPH0257110 B2 JP H0257110B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- pressure
- sensitive adhesive
- meth
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- -1 2-ethylhexyl Chemical group 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229960005070 ascorbic acid Drugs 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 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
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
〔産業上の利用分野〕
本発明は、新規な感圧接着剤組成物に関するも
のである。更に詳しくは、特定の水性樹脂分散体
を主成分とし、初期粘着力（以下、タツクと称
す。）、粘着力および凝集力に優れた、感圧接着テ
ープ、感圧接着シートおよび感圧接着ラベル等の
用途に有用でかつ新規な感圧接着剤組成物に関す
るものである。
〔従来の技術〕
現在、感圧接着剤には天然ゴム系、合成ゴム系
およびアクリル系等のものがあり、テープやシー
トおよびラベル等の形で多くの用途に使用されて
いる。なかでも、その優れた接着性や耐久性から
アクリル系の感圧接着剤が近年広く普及してきて
いる。アクリル系の感圧接着剤には有機溶剤溶液
型のものや水分散型のもの等があるが、環境衛生
や省資源の観点から水分散型のものが好ましい。
アクリル系の感圧接着剤の主成分をなすものは、
常温で粘着性を有するアクリル酸エステルの重合
体であるが、かかる重合体単独では凝集力が不充
分であり、感圧接着剤としては不満足なものしか
得られない。このため、常温では特に粘着性を有
しないが凝集力の高い重合体が得られる不飽和単
量体、例えば不飽和カルボン酸、酢酸ビニル、ス
チレン、アクリロニトリル、メタクリル酸エステ
ル類あるいは常温で粘着性を有する重合体を与え
るアクリル酸エステル以外のアクリル酸エステル
類等を、常温で粘着性を有する重合体が得られる
アクリル酸エステルと共重合することが行なわれ
ている。そして、水分散型のアクリル系感圧接着
剤を得る際には通常かかる共重合を乳化重合によ
つて行うため、有機溶剤等を用いる溶液重合によ
る場合に比べて高い分子量の重合体が得られ、従
つて高い凝集力を有する感圧接着剤となし得るこ
とが知られている。しかし、このようにして得ら
れるアクリル系の水分散型感圧接着剤を用いて得
られる感圧接着剤でも、感圧接着テープ等のよう
に、より高い凝集力を必要とする用途においては
まだ不充分である。
そこで、感圧接着剤の凝集力をより高めるため
に、例えば上記したような不飽和単量体を乳化重
合させる際に、多価アルコールのジあるいはトリ
（メタ）アクリレートやジビニルベンゼン等の内
部架橋剤を共重合させたり、乳化重合によつて得
た水性樹脂分散体に、メラミン化合物、エポキシ
化合物あるいは多価金属塩等の外部架橋剤を添加
する試みがなされている。しかし、従来公知のか
かる方法によつて凝集力自体は高めることができ
るものの、タツクおよび粘着力が大きく低下し、
それぞれが充分に高いタツク、粘着力および凝集
力の感圧接着剤を得ることは困難である。
〔本発明が解決しようとする問題点〕
従来の技術におけるかかる困難さの故に、水分
散型感圧接着剤は特に高い凝集力を必要としない
感圧接着シートや感圧接着剤ラベル等のみにその
使用が限定されており、優れたタツク、粘着力お
よび凝集力を併せ有していることが必要な感圧接
着テープ等には殆んど用いられていないのが現状
である。かかる現状に鑑み、本発明者らは、タツ
ク、粘着力および凝集力がそれぞれ充分に高い水
分散型感圧接着剤組成物を得ることにより、従来
限定されていた水分散型感圧接着剤の用途を拡げ
るべく鋭意検討の結果、本発明を完成するに到つ
た。
〔問題点を解決するための手段〕
即ち、本発明は一般式
（但し、R1およびR2は同一でも異つていてもよ
い水素またはメチル基、R3はｎが０のとき、炭
素数が４〜12個のアルキル基、ｎが１〜５のと
き、炭素数が１〜５個のアルキル基であり、ｎは
０または１〜５の整数である）で示される（メ
タ）アクリル酸エステル系単量体(A)40〜99.3重量
％、水酸基および／またはエポキシ基含有不飽和
単量体(B)0.5〜10重量％、スルホン酸基含有不飽
和単量体(C)0.1〜10重量％、その他の不飽和単量
体(D)０〜30重量％ならびにベンゾグアナミン樹脂
(E)0.1〜10重量％（但し、(A)、(B)、(C)、(D)および
(E)の合計は100重量％であつる。）からなる単量体
混合物を乳化重合して得られる水性樹脂分散体を
必須成分として含む感圧接着剤組成物に関するも
のである。
本発明において用いられる（メタ）アクリル酸
エステル系単量体(A)は前記一般式（）で表わさ
れるものである。使用できる単量体(A)としては、
例えば（メタ）アクリル酸ブチル、（メタ）アク
リル酸イソブチル、（メタ）アクリル酸sec−ブチ
ル、（メタ）アクリル酸tert−ブチル、（メタ）ア
クリル酸アミル、（メタ）アクリル酸イソアミル、
（メタ）アクリル酸ヘキシル、（メタ）アクリル酸
シクロヘキシル、（メタ）アクリル酸ヘプチル、
（メタ）アクリル酸オクチル、（メタ）アクリル酸
２−エチルヘキシル、（メタ）アクリル酸ノニル、
（メタ）アクリル酸イソノニル、（メタ）アクリル
酸デシル、（メタ）アクリル酸ドデシル、（メタ）
アクリル酸ブトキシエチル、（メタ）アクリル酸
エチルカルビトールエステル、（メタ）アクリル
酸メチルトリグリコールエステル、（メタ）アク
リル酸ジプロピレングリコールメチルエーテルエ
ステル等を挙げることができ、これらの１種また
は２種以上を用いることができる（メタ）アクリ
ル酸エステル系単量体(A)は感圧接着剤組成物にタ
ツクおよび粘着力を付与するための必須成分で、
単量体混合物中40〜98.5重量％の範囲で使用す
る。該単量体(A)が40重量％未満の量では充分なタ
ツク、粘着力が発現せず、逆に98.5重量％を超え
る量では充分に高い凝集力が発現しないので好ま
しくない。
本発明に用いられる水酸基および／またはエポ
キシ基含有不飽和単量体(B)としては、例えば（メ
タ）アクリル酸２−ヒドロキシエチル、（メタ）
アクリル酸３−ヒドロキシプロピル、Ｎ−メチロ
ール（メタ）アクリルアミド、（メタ）アクリル
酸グリシジル、アリルグリシジルエーテル、ポリ
エチレングリコールモノアリルエーテル、ポリエ
チレングリコールモノ（メタ）アクリレート等を
挙げることができ、これらの１種または２種以上
を用いることができる。該単量体(B)はベンゾグア
ナミン樹脂(E)との反応に必須の成分で、単量体混
合物中0.5〜10重量％の範囲で使用する。該単量
体(B)が0.5重量％未満の量ではベンゾグアナミン
樹脂(E)との反応のための実質有効量となり得ず、
従つて感圧接着剤組成物に充分な凝集力を付与し
難く、逆に10重量％を超える量ではタツクおよび
粘着力が低下するので好ましくない。
本発明において用いられるスルホン酸基含有不
飽和単量体(C)としては、例えばビニルスルホン
酸、アリルスルホン酸、スチレンスルホン酸、２
−アクリルアミド−２−メチルプロパンスルホン
酸、３−アリロキシ−２−ヒドロキシプロパンス
ルホン酸、（メタ）アクリル酸２−スルホエチル、
（メタ）アクリル酸３−スルホプロピル等の不飽
和スルホン酸やそれらのアルカリ金属塩、アルカ
リ土類金属塩、アンモニウム塩もしくは置換アン
モニウム塩を挙げることができ、これらの１種ま
たは２種以上を用いることができる。該単量体(C)
は前記単量体(B)に含まれる水酸基および／または
エポキシ基とベンゾグアナミン樹脂(E)とが反応す
る際に、内部触媒として作用する。水酸基およ
び／またはエポキシ基とベンゾグアナミン樹脂(E)
との反応の際の触媒作用に限つて言えば、必ずし
も該単量体(C)を使用する必要はなく、スルホン酸
基を有する一般的な化合物、例えばパラトルエン
スルホン酸等でも充分にその効果を達し得るが、
このような化合物の使用は感圧接着剤組成物の耐
水性の低下を招くので好ましくない。従つて、本
発明においてはスルホン酸基含有不飽和単量体(C)
を必須成分として用いるものである。該単量体(C)
は単量体混合物中0.1〜10重量％の範囲で使用す
る。該単量体(C)が0.1重量％未満の量では充分な
触媒作用が発揮されにくく、逆に10重量％を超え
る量では耐水性が低下するので好ましくない。
本発明において用いられるその他の不飽和単量
体(D)としては、例えば（メタ）アクリル酸、クロ
トン酸等の不飽和一塩基カルボン酸；マレイン
酸、イタコン酸等の不飽和二塩基カルボン酸また
はこれらのモノエステル；エチレン、ブタジエン
等の脂肪族不飽和炭化水素；塩化ビニル等の脂肪
族不飽和炭化水素類のハロゲン置換体；スチレ
ン、α−メチルスチレン、ジビニルベンゼン等の
芳香族不飽和炭化水素類；酢酸ビニル等のビニル
エステル類；ビニルエーテル類；アリルアルコー
ルと各種有機酸とのエステル類や各種アルコール
とのエーテル類；アクリロニトリル等の不飽和シ
アン化化合物；（メタ）アクリルアミド等の不飽
和アミド化合物；アルキル基の炭素数が４〜12以
外の（メタ）アクリル酸アルキルエステルおよび
（メタ）アクリル酸アリールエステル；クロトン
酸等の不飽和一塩基カルボン酸の各種エステル
類；マレイン酸、フマル酸等の不飽和二塩基カル
ボン酸の各種ジエステル類を挙げることができ、
これらのうち１種または２種以上を使用すること
ができる。該単量体(D)は必要に応じて、単量体混
合物中30重量％以下の量で使用することができ
る。該単量体(D)が30重量％を超える量では充分に
高いタツクおよび粘着力が発現しないので好まし
くない。
本発明において用いられるベンゾグアナミン樹
脂(E)としては、特公昭54−7314号明細書に示す方
法によつて製造される脱水ベンゾグアナミン；メ
チルエーテル化ベンゾグアナミン；ブチルエーテ
ル化ベンゾグアナミン等が挙げられる。ベンゾグ
アナミン樹脂(E)は前記単量体(B)に含まれる水酸基
および／またはエポキシ基と反応し感圧接着剤組
成物に凝集力を付与するためのもので、単量体混
合物中0.1〜10重量％の範囲で使用する。ベンゾ
グアナミン樹脂(E)が0.1重量％未満の量では充分
に高い凝集力が発現せず、10重量％を超える量で
は充分に高いタツクおよび粘着力が発現しないの
で好ましくない。
本発明の感圧接着剤組成物の必須成分である水
性樹脂分散体は、前記単量体(A)、(B)、(C)、(D)およ
び(E)からなる単量体混合物を従来公知の方法で乳
化重合してできる。例えば、乳化剤の存在下ある
いは不存在下に重合開始剤を用いて、前記単量体
混合物を乳化重合すればよい。
この際、必要により用いられる乳化剤として
は、従来公知のいかなる乳化剤も用いることがで
きる。例えば陰イオン性乳化剤として脂肪酸塩、
高級アルコール硫酸エステル塩、アルキルベンゼ
ンスルホン酸塩、アルキルナフタレンスルホン酸
塩、ナフタレンスルホン酸ホルマリン縮合物、ジ
アルキルスルホコハク酸エステル塩、ポリオキシ
エチレンアルキルスルホコハク酸モノエステル
塩、ポリオキシエチレンアルキル硫酸エステル
塩、ポリオキシエチレンアルキルアリール硫酸エ
ステル塩、ポリオキシエチレンアルキルリン酸エ
ステル塩等；非イオン性乳化剤としてポリオキシ
エチレンアルキルエーテル、ポリオキシエチレン
アルキルアリールエーテル、ポリオキシエチレン
脂肪酸エステル、ソルビタン脂肪酸エステル、ポ
リオキシエチレンソルビタン脂肪酸エステル、オ
キシエチレンオキシプロピレンブロツク共重合
体、脂肪酸モノグリセライド等を挙げることがで
きる。そしてかかる乳化剤の群から選ばれた１種
または２種以上を使用することができ、その使用
量は前記単量体混合物に対して10重量％以下とす
るのが好ましい。尚、必要に応じ保護コロイド類
を単独または乳化剤と共に使用することもでき
る。
前記単量体混合物を乳化重合させるための重合
触媒としては、過硫酸アンモニウムや過酸化水素
等の無機の過酸化物；ｔ−ブチルハイドロパーオ
キシド等の有機の過酸化物；その他のラジカル生
成性重合開始剤を使用することができ、その使用
量は前記単量体混合物100重量部に対して0.01〜
３重量部、好ましくは0.1〜１重量部の範囲であ
る。過酸化物を使用する場合に、重合速度を増大
させたり反応温度を低下させる必要があれば、可
溶性亜硫酸塩やアスコルビン酸等の還元剤あるい
は硫酸第１鉄等の水中で重金属イオンを発生する
金属化合物を過酸化物と組合せてレドツクス系と
することができる。更に、必要により分子量を調
節するために公知の分子量調節剤、例えば各種メ
ルカプタン類等を使用することもできる。
乳化重合の温度は、前記単量体混合物の種類や
組成および重合触媒の種類等により適宜選択され
るが、通常０〜100℃の範囲である。
乳化重合の水の量は、通常、前記単量体混合物
100重量部に対し300〜40重量部の範囲である。
このようにして得られる水性樹脂分散体のPHは
通常酸性であるが、本発明においては必要に応じ
て例えばアンモニア等の塩基性物質を添加して中
性またはアルカリ性にして使用することができ
る。
本発明の感圧接着剤組成物は、前記方法により
得た水性樹脂分散体を必須成分として含んでなる
ものであり、該水性樹脂分散体をそのまま感圧接
着剤として用いても充分な性能を発揮し得るが、
更に必要に応じて以下に示すような各種添加剤を
添加することができる。
まず、本発明の感圧接着剤組成物の粘着力を更
に高める必要がある場合には、軟化点が60℃程度
以上の粘着性付与樹脂、例えばロジン系樹脂、石
油樹脂系樹脂、クマロンインデン系樹脂、フエノ
ール系樹脂等を水性樹脂分散体中の重合体100重
量部に対して200重量部以下、好ましくは５〜60
重量部の範囲で添加することができる。タツクを
高める必要がある場合には液状粘着付与樹脂、平
均分子量が8000〜20000の低分子量重合体、可塑
剤等を添加することができる。
また、本発明の感圧接着剤組成物の凝集力を更
に高める必要がある場合には、水性樹脂分散体中
の重合体100重量部に対して0.005〜２重量部の範
囲内で、外部架橋剤として作用し得るエポキシ化
合物、メラミン化合物、イソシアネート化合物等
を水溶液、水性分散液あるいは有機溶剤溶液の形
で添加することもできる。
本発明の感圧接着剤組成物には、さらに必要に
応じて、消泡剤、増粘剤、粘性調節剤、着色剤、
充填剤、老化防止剤等の公知の添加剤を添加する
こともできる。
〔発明の効果〕
このようにして得られる本発明の感圧接着剤組
成物はタツク、粘着力および凝集力のそれぞれが
充分に高いために、剪断力に対しても高い抵抗力
を示すものである。よつて、従来の水分散型感圧
接着剤組成物では適用できなかつた感圧接着テー
プ等に使用することができる。また、感圧接着テ
ープのみでなく、感圧接着シートや感圧接着ラベ
ル等に使用した場合でも高い凝集力のために、ス
リツト加工あるいは打抜き加工時の粘着剤のはみ
出しによる問題が生じず、かつ、高いタツクのた
めに、一般にタツクが低下する低温時においてあ
るいは粗面への接着に際して優れた粘着力を発揮
するものである。更には、一般に接着が困難とさ
れるポリエチレンやポリプロピレン等の非極性基
材に対しても良好な粘着力およびこれらの曲面に
接着した際の耐反撥性を示し、上記した効果と併
せて、巾広い用途に応用できるものである。
本発明の感圧接着剤組成物によつて得られるか
かる効果がいかなる理由に基づくものであるかに
ついては未だ明確ではないが、次のように考えら
れる。
即ち、それ自体凝集力の高いベンゾグアナミン
樹脂(E)が粒子内に相溶して均一に存在しかつ、主
として乳化重合中、ベンゾグアナミン樹脂(E)自体
の硬化反応も伴いながら、前記単量体(A)〜(D)の共
重合により生成した共重合体と、水酸基および／
またはエポキシ基との反応を介して架橋反応する
か、あるいは部分的にはグラフトすることによ
り、結果として、高いタツクや粘着力の発現に必
要な該共重合体のミクロな動きを拘束することな
く、マクロな流動を抑制することができるために
高い凝集力を発現し得るものと考えられる。しか
し、かかる理由だけで本発明は何ら制限を受ける
ものではない。
〔実施例〕
次に実施例および比較例をあげて本発明を更に
具体的に説明するが、本発明はこれらの実施例に
限定されるものではない。尚、特にことわりがな
い限り例中の部は重量部を、また％は重量％を意
味するものとする。
実施例 １
アクリル酸ブチル250部、メタクリル酸２−ヒ
ドロキシエチル30部、メタクリル酸２−スルホエ
チル10部および脱水ベンゾグアナミン樹脂（メチ
ロール化ベンゾグアナミンの初期縮合物、日本触
媒化学工業(株)製）10部を混合し脱水ベンゾグアナ
ミン樹脂を溶解させた後、この混合物にアクリル
酸２−エチルヘキシル700部およびターシヤリー
ドデシルメルカプタン0.1部を加えて単量体混合
物を調製した。“ハイテノールＮ−08”（三洋化成
工業(株)製、乳化剤）15部を脱イオン水285部に溶
解させ乳化剤水溶液を調製した。この水溶液と上
記単量体混合物とを混合撹拌し、単量体水性分散
液を得た。
還流冷却器、温度計、窒素ガス吹込口、滴下ロ
ートおよび撹拌機を備えた２のガラス製フラス
コに210部の脱イオン水を仕込み、75℃に昇温し
た。窒素気流中、撹拌しながら過硫酸アンモニウ
ムの10％水溶液５部および重亜硫酸ナトリウムの
５％水溶液５部を添加した後すみやかに、上記単
量体水性分散液の10％に相当する量を添加した。
重合反応の開始を確認した後上記単量体水性分散
液の残量、過硫酸アンモニウムの10％水溶液95部
および重亜硫酸ナトリウムの５％水溶液95部を
150分間かけて平行して滴下し、この間75℃に保
ち上記単量体混合物を重合させた。滴下終了後80
℃に昇温し、30分間保つた後ターシヤリーブチル
ハイドロパーオキサイド1.4部およびＬ−アスコ
ルビン酸の10％水溶液２部を添加し、更に30分間
保つてから冷却し、不揮発分60℃の水性分散体を
得た。この水性分散体に25％のアンモニア水を添
加してPHを7.5に調整し感圧接着剤組成物(1)を得
た。
得られた感圧接着剤組成物(1)を、厚さ25μのポ
リエステルフイルムの片面に、乾燥後の厚みが
45μとなるように塗布し、80℃で２分間乾燥して
感圧接着テープを作成した。得られた感圧接着テ
ープについて下記に示す方法でタツク、粘着力お
よび凝集力の尺度となる保持力を測定した。結果
を第１表に示す。
〈タツク〉 JIS Ｚ 0237に定められた球転法に
よるタツクを測定した。
〈粘着力〉 JIS Ｚ 0237に定められた180゜引き
はがし粘着力（被着体：ステンレス板、ｇ／
25mm）を測定した。また同様の方法でポリエ
チレン板を被着体とした場合の粘着力も測定
した。
〈保持力〉 JIS Ｚ 0237に定められた方法に準
じて、貼り付け面積20mm×20mmで40℃および
80℃で１Kgの荷重をかけて保持時間または一
定時間後のズレ巾を測定した。
比較例 １
実施例１で使用した脱水ベンゾグアナミン樹脂
を全く使用しない以外は実施例１と全く同様の方
法で比較感圧接着剤組成物(1)を得て、実施例１と
同様の測定を行つた。結果を第１表に示す。
比較例 ２
比較例１で得られた比較感圧接着剤組成物(1)
100部に“スミテツクスレジンＭ−３”10％水溶
液（住友化学工業(株)製、メチロール化メラミン樹
脂）６部およびスミテツクスアクセラレーター
ACX1％水溶液（住友化学工業(株)製）６部を添加
混合した比較感圧接着剤組成物(2)を調製し、実施
例１と同様の測定を行つた。
結果を第１表に示す。
比較例 ３
実施例１で使用したメタクリル酸２−ヒドロキ
シエチルを全く使用しない以外は実施例１と全く
同様の方法で比較感圧接着剤組成物(3)を得て、実
施例１と同様の測定を行つた。
結果を第１表に示す。
比較例 ４
実施例１で使用したメタクリル酸２−スルホエ
チルを全く使用しない以外は実施例１と全く同様
の方法で比較感圧接着剤組成物(4)を得て、実施例
１と同様の測定を行つた。結果を第１表に示す。
比較例 ５
実施例１で使用した脱水ベンゾグアナミン樹脂
10部のかわりにジビニルベンゼン３部を使用して
実施例１と全く同様の方法で比較感圧接着剤組成
物(5)を得て、実施例１と同様の測定を行つた。結
果を第１表に示す。
実施例 ２
実施例１で得られた感圧接着剤組成物100部に
“スタロン＃2130”（安原油脂工業(株)製、乳化テル
ペンフエノール樹脂、40％濃度）44部を添加混合
して粘着付与剤を含有する感圧接着剤組成物(2)を
調製し、実施例１と同様の測定を行つた。結果を
第１表に示す。
実施例 ３
実施例１において単量体混合物をアクリル酸メ
チルトリグリコールエステル（CH2＝CHCOO−
（−CH2CH2O−）−oCH3）830部、酢酸ビニル100
部、メタクリル酸２−ヒドロキシエチル20部、ス
チレンスルホン酸20部、脱水ベンゾグアナミン樹
脂30部、およびターシヤリードデシルメルカプタ
ン0.1部からなる組成の単量体混合物とする以外
は実施例１と全く同様の方法で感圧接着剤組成物
(3)を得て実施例１と同様の測定を行つた。結果を
第１表に示す。
[Industrial Field of Application] The present invention relates to a novel pressure-sensitive adhesive composition. More specifically, pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, and pressure-sensitive adhesive labels that contain a specific aqueous resin dispersion as a main component and have excellent initial adhesive strength (hereinafter referred to as tack), adhesive strength, and cohesive strength. The present invention relates to a novel pressure-sensitive adhesive composition useful for applications such as the above. [Prior Art] Currently, pressure sensitive adhesives include natural rubber, synthetic rubber, and acrylic adhesives, and are used in many applications in the form of tapes, sheets, labels, and the like. Among these, acrylic pressure-sensitive adhesives have become widely popular in recent years due to their excellent adhesiveness and durability. Acrylic pressure-sensitive adhesives include organic solvent solution type and water dispersion type, but water dispersion type is preferred from the viewpoint of environmental hygiene and resource saving.
The main components of acrylic pressure sensitive adhesives are:
Although this is a polymer of acrylic acid ester that has tackiness at room temperature, such a polymer alone has insufficient cohesive force and can only be used as an unsatisfactory pressure-sensitive adhesive. For this reason, unsaturated monomers such as unsaturated carboxylic acids, vinyl acetate, styrene, acrylonitrile, methacrylic acid esters, etc., which do not have particular tackiness at room temperature but have high cohesive strength, or which have tackiness at room temperature. It has been carried out to copolymerize acrylic esters other than the acrylic esters that yield polymers with acrylic esters that yield polymers that are sticky at room temperature. When obtaining a water-dispersed acrylic pressure-sensitive adhesive, such copolymerization is usually carried out by emulsion polymerization, which makes it possible to obtain a polymer with a higher molecular weight than by solution polymerization using an organic solvent. Therefore, it is known that pressure-sensitive adhesives having high cohesive strength can be obtained. However, even pressure-sensitive adhesives obtained using acrylic water-dispersed pressure-sensitive adhesives obtained in this way are still not suitable for applications that require higher cohesive strength, such as pressure-sensitive adhesive tapes. It is insufficient. Therefore, in order to further increase the cohesive force of pressure-sensitive adhesives, for example, when emulsion polymerizing unsaturated monomers such as those mentioned above, internal crosslinking of di- or tri(meth)acrylates of polyhydric alcohols, divinylbenzene, etc. Attempts have been made to copolymerize agents or add external crosslinking agents such as melamine compounds, epoxy compounds, or polyvalent metal salts to aqueous resin dispersions obtained by emulsion polymerization. However, although the cohesive force itself can be increased by such conventionally known methods, the tack and adhesive force are greatly reduced.
It is difficult to obtain pressure sensitive adhesives of sufficiently high tack, tack and cohesion, respectively. [Problems to be solved by the present invention] Due to such difficulties in the conventional technology, water-dispersed pressure-sensitive adhesives are only suitable for pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels, etc. that do not require particularly high cohesive strength. Currently, its use is limited, and it is hardly used in pressure-sensitive adhesive tapes, etc., which require excellent tack, adhesive strength, and cohesive strength. In view of the current situation, the present inventors have developed a water-dispersed pressure-sensitive adhesive composition that has sufficiently high tack, adhesive force, and cohesive force, thereby improving the ability of water-dispersed pressure-sensitive adhesives that have been limited in the past. As a result of intensive study to expand the applications, we have completed the present invention. [Means for solving the problem] That is, the present invention solves the general formula (However, R 1 and R 2 may be the same or different hydrogen or methyl group, R 3 is an alkyl group having 4 to 12 carbon atoms when n is 0, and when n is 1 to 5, 40 to 99.3% by weight of a (meth)acrylic acid ester monomer (A) represented by an alkyl group having 1 to 5 carbon atoms, where n is an integer of 0 or 1 to 5, a hydroxyl group and/or Or epoxy group-containing unsaturated monomer (B) 0.5-10% by weight, sulfonic acid group-containing unsaturated monomer (C) 0.1-10% by weight, other unsaturated monomer (D) 0-30% by weight % and benzoguanamine resin
(E) 0.1 to 10% by weight (however, (A), (B), (C), (D) and
The sum of (E) is 100% by weight. ) The present invention relates to a pressure-sensitive adhesive composition containing as an essential component an aqueous resin dispersion obtained by emulsion polymerization of a monomer mixture consisting of: The (meth)acrylic acid ester monomer (A) used in the present invention is represented by the above general formula (). Monomers (A) that can be used include:
For example, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate,
Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate,
(meth)octyl acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate,
Isononyl (meth)acrylate, Decyl (meth)acrylate, Dodecyl (meth)acrylate, (meth)
Examples include butoxyethyl acrylate, ethyl (meth)acrylate carbitol ester, methyl triglycol (meth)acrylate, dipropylene glycol methyl ether (meth)acrylate, and one or two of these. The (meth)acrylic acid ester monomer (A), which can be used as described above, is an essential component for imparting tack and adhesive strength to the pressure-sensitive adhesive composition.
It is used in a range of 40 to 98.5% by weight in the monomer mixture. If the amount of the monomer (A) is less than 40% by weight, sufficient tack and adhesive strength will not be developed, and if the amount exceeds 98.5% by weight, a sufficiently high cohesive force will not be developed, which is not preferred. Examples of the hydroxyl group- and/or epoxy group-containing unsaturated monomer (B) used in the present invention include 2-hydroxyethyl (meth)acrylate, (meth)
Examples include 3-hydroxypropyl acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, allyl glycidyl ether, polyethylene glycol monoallyl ether, polyethylene glycol mono(meth)acrylate, and one type thereof. Or two or more types can be used. The monomer (B) is an essential component for the reaction with the benzoguanamine resin (E), and is used in an amount of 0.5 to 10% by weight in the monomer mixture. If the amount of the monomer (B) is less than 0.5% by weight, it cannot be a substantially effective amount for the reaction with the benzoguanamine resin (E),
Therefore, it is difficult to impart sufficient cohesive force to the pressure-sensitive adhesive composition, and conversely, if the amount exceeds 10% by weight, the tack and adhesive strength will decrease, which is not preferable. Examples of the sulfonic acid group-containing unsaturated monomer (C) used in the present invention include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid,
-acrylamide-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, 2-sulfoethyl (meth)acrylate,
Examples include unsaturated sulfonic acids such as 3-sulfopropyl (meth)acrylate, alkali metal salts, alkaline earth metal salts, ammonium salts, or substituted ammonium salts thereof, and one or more of these may be used. be able to. The monomer (C)
acts as an internal catalyst when the hydroxyl group and/or epoxy group contained in the monomer (B) reacts with the benzoguanamine resin (E). Hydroxyl group and/or epoxy group and benzoguanamine resin (E)
As far as the catalytic action in the reaction with the monomer (C) is concerned, it is not necessarily necessary to use the monomer (C), and common compounds having a sulfonic acid group, such as para-toluenesulfonic acid, can also have sufficient effects. can be achieved, but
The use of such compounds is undesirable because it leads to a decrease in the water resistance of the pressure sensitive adhesive composition. Therefore, in the present invention, the sulfonic acid group-containing unsaturated monomer (C)
is used as an essential component. The monomer (C)
is used in a range of 0.1 to 10% by weight in the monomer mixture. If the amount of the monomer (C) is less than 0.1% by weight, sufficient catalytic action will not be exhibited easily, while if the amount exceeds 10% by weight, the water resistance will decrease, which is not preferable. Other unsaturated monomers (D) used in the present invention include, for example, unsaturated monobasic carboxylic acids such as (meth)acrylic acid and crotonic acid; unsaturated dibasic carboxylic acids such as maleic acid and itaconic acid; These monoesters; aliphatic unsaturated hydrocarbons such as ethylene and butadiene; halogen-substituted aliphatic unsaturated hydrocarbons such as vinyl chloride; aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene, and divinylbenzene Vinyl esters such as vinyl acetate; Vinyl ethers; Esters of allyl alcohol and various organic acids and ethers of various alcohols; Unsaturated cyanide compounds such as acrylonitrile; Unsaturated amide compounds such as (meth)acrylamide ; (meth)acrylic acid alkyl esters and (meth)acrylic acid aryl esters in which the alkyl group has a carbon number other than 4 to 12; various esters of unsaturated monobasic carboxylic acids such as crotonic acid; maleic acid, fumaric acid, etc. Various diesters of unsaturated dibasic carboxylic acids can be mentioned,
One or more of these can be used. The monomer (D) can be used in an amount of 30% by weight or less in the monomer mixture, if necessary. If the amount of monomer (D) exceeds 30% by weight, sufficiently high tack and adhesive strength will not be achieved, which is not preferable. Examples of the benzoguanamine resin (E) used in the present invention include dehydrated benzoguanamine produced by the method shown in Japanese Patent Publication No. 54-7314; methyl etherified benzoguanamine; butyl etherified benzoguanamine. The benzoguanamine resin (E) reacts with the hydroxyl group and/or epoxy group contained in the monomer (B) to impart cohesive force to the pressure-sensitive adhesive composition, and has a content of 0.1 to 10% in the monomer mixture. Use within a range of % by weight. If the amount of benzoguanamine resin (E) is less than 0.1% by weight, sufficiently high cohesive force will not be exhibited, and if the amount exceeds 10% by weight, sufficiently high tack and adhesive strength will not be exhibited, which is not preferable. The aqueous resin dispersion, which is an essential component of the pressure-sensitive adhesive composition of the present invention, contains a monomer mixture consisting of the monomers (A), (B), (C), (D) and (E). It can be made by emulsion polymerization using a conventionally known method. For example, the monomer mixture may be emulsion polymerized using a polymerization initiator in the presence or absence of an emulsifier. At this time, any conventionally known emulsifier can be used as the emulsifier used if necessary. For example, fatty acid salts as anionic emulsifiers,
Higher alcohol sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, naphthalene sulfonic acid formalin condensate, dialkyl sulfosuccinate ester salt, polyoxyethylene alkyl sulfosuccinate monoester salt, polyoxyethylene alkyl sulfate ester salt, polyoxy Ethylene alkylaryl sulfate salt, polyoxyethylene alkyl phosphate salt, etc.; as a nonionic emulsifier, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Examples include esters, oxyethylene oxypropylene block copolymers, fatty acid monoglycerides, and the like. One or more emulsifiers selected from the group of such emulsifiers can be used, and the amount used is preferably 10% by weight or less based on the monomer mixture. In addition, protective colloids can be used alone or together with an emulsifier, if necessary. Examples of polymerization catalysts for emulsion polymerization of the monomer mixture include inorganic peroxides such as ammonium persulfate and hydrogen peroxide; organic peroxides such as t-butyl hydroperoxide; and other radical-generating polymerization catalysts. An initiator can be used in an amount of 0.01 to 100 parts by weight of the monomer mixture.
3 parts by weight, preferably in the range of 0.1 to 1 part by weight. When using peroxides, if it is necessary to increase the polymerization rate or lower the reaction temperature, reducing agents such as soluble sulfites and ascorbic acid or metals that generate heavy metal ions in water such as ferrous sulfate may be used. The compounds can be combined with peroxides to form redox systems. Furthermore, if necessary, known molecular weight regulators such as various mercaptans can be used to adjust the molecular weight. The emulsion polymerization temperature is appropriately selected depending on the type and composition of the monomer mixture, the type of polymerization catalyst, etc., and is usually in the range of 0 to 100°C. The amount of water in emulsion polymerization is usually determined by the amount of water in the monomer mixture.
The amount ranges from 300 to 40 parts by weight per 100 parts by weight. The pH of the aqueous resin dispersion thus obtained is usually acidic, but in the present invention, it can be made neutral or alkaline by adding a basic substance such as ammonia, if necessary. The pressure-sensitive adhesive composition of the present invention contains the aqueous resin dispersion obtained by the above method as an essential component, and even if the aqueous resin dispersion is used as it is as a pressure-sensitive adhesive, it exhibits sufficient performance. Although it can be demonstrated,
Furthermore, various additives as shown below can be added as necessary. First, if it is necessary to further increase the adhesive strength of the pressure-sensitive adhesive composition of the present invention, use a tackifier resin with a softening point of about 60°C or higher, such as rosin resin, petroleum resin resin, coumaron indensine, etc. 200 parts by weight or less, preferably 5 to 60 parts by weight of the resin, phenolic resin, etc., per 100 parts by weight of the polymer in the aqueous resin dispersion.
It can be added within a range of parts by weight. If it is necessary to increase the toughness, a liquid tackifying resin, a low molecular weight polymer having an average molecular weight of 8,000 to 20,000, a plasticizer, etc. can be added. In addition, if it is necessary to further increase the cohesive force of the pressure-sensitive adhesive composition of the present invention, external crosslinking may be added within the range of 0.005 to 2 parts by weight based on 100 parts by weight of the polymer in the aqueous resin dispersion. Epoxy compounds, melamine compounds, isocyanate compounds, etc. that can act as agents can also be added in the form of aqueous solutions, aqueous dispersions, or organic solvent solutions. The pressure-sensitive adhesive composition of the present invention may further contain an antifoaming agent, a thickener, a viscosity modifier, a coloring agent,
Known additives such as fillers and anti-aging agents may also be added. [Effects of the Invention] The pressure-sensitive adhesive composition of the present invention thus obtained has sufficiently high tack, adhesive force and cohesive force, and thus exhibits high resistance to shearing force. be. Therefore, it can be used in pressure-sensitive adhesive tapes, etc., which cannot be applied with conventional water-dispersed pressure-sensitive adhesive compositions. In addition, when used not only for pressure-sensitive adhesive tapes but also for pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels, etc., the high cohesive strength prevents problems caused by adhesive extrusion during slitting or punching. Because of its high tack, it exhibits excellent adhesive strength at low temperatures, where tack generally decreases, or when adhering to rough surfaces. Furthermore, it exhibits good adhesion to non-polar substrates such as polyethylene and polypropylene, which are generally difficult to adhere to, as well as repulsion resistance when bonded to curved surfaces. It can be applied to a wide range of applications. Although it is not yet clear what the reason for this effect obtained by the pressure-sensitive adhesive composition of the present invention is based on, it is thought to be as follows. That is, the benzoguanamine resin (E), which itself has a high cohesive force, exists uniformly and compatibly within the particles, and mainly during emulsion polymerization, the monomer (E) is mixed with the curing reaction of the benzoguanamine resin (E) itself. The copolymer produced by the copolymerization of A) to (D) and the hydroxyl group and/or
or by crosslinking through reaction with epoxy groups, or by partial grafting, without restricting the microscopic movements of the copolymer necessary for the development of high tack and adhesive strength. It is thought that high cohesive force can be developed because macroscopic flow can be suppressed. However, the present invention is not limited in any way solely by this reason. [Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "part" in the examples means parts by weight, and "%" means weight %. Example 1 250 parts of butyl acrylate, 30 parts of 2-hydroxyethyl methacrylate, 10 parts of 2-sulfoethyl methacrylate, and 10 parts of dehydrated benzoguanamine resin (initial condensate of methylolated benzoguanamine, manufactured by Nippon Shokubai Chemical Co., Ltd.) After mixing and dissolving the dehydrated benzoguanamine resin, 700 parts of 2-ethylhexyl acrylate and 0.1 part of tertiarydecyl mercaptan were added to the mixture to prepare a monomer mixture. An aqueous emulsifier solution was prepared by dissolving 15 parts of "Hitenol N-08" (manufactured by Sanyo Chemical Industries, Ltd., emulsifier) in 285 parts of deionized water. This aqueous solution and the above monomer mixture were mixed and stirred to obtain a monomer aqueous dispersion. Two glass flasks equipped with a reflux condenser, a thermometer, a nitrogen gas inlet, a dropping funnel, and a stirrer were charged with 210 parts of deionized water, and the temperature was raised to 75°C. Immediately after adding 5 parts of a 10% aqueous solution of ammonium persulfate and 5 parts of a 5% aqueous solution of sodium bisulfite with stirring in a nitrogen stream, an amount corresponding to 10% of the above monomer aqueous dispersion was added.
After confirming the start of the polymerization reaction, add the remaining amount of the above monomer aqueous dispersion, 95 parts of a 10% aqueous solution of ammonium persulfate, and 95 parts of a 5% aqueous solution of sodium bisulfite.
The monomer mixture was added dropwise in parallel over 150 minutes while being kept at 75° C. to polymerize the monomer mixture. 80 minutes after completion of dripping
After raising the temperature to 30°C and keeping it for 30 minutes, 1.4 parts of tert-butyl hydroperoxide and 2 parts of a 10% aqueous solution of L-ascorbic acid were added, and after keeping it for another 30 minutes, it was cooled to form an aqueous dispersion with a non-volatile content of 60°C. I got a body. 25% ammonia water was added to this aqueous dispersion to adjust the pH to 7.5 to obtain a pressure sensitive adhesive composition (1). The obtained pressure-sensitive adhesive composition (1) was applied to one side of a 25μ thick polyester film so that the thickness after drying was
It was applied to a thickness of 45 μm and dried at 80° C. for 2 minutes to prepare a pressure-sensitive adhesive tape. The holding power, which is a measure of tack, adhesive force, and cohesive force, of the obtained pressure-sensitive adhesive tape was measured by the method shown below. The results are shown in Table 1. <Tack> Tack was measured using the ball rolling method specified in JIS Z 0237. <Adhesive strength> 180° peeling adhesive strength specified in JIS Z 0237 (adherent: stainless steel plate, g/
25mm) was measured. In addition, the adhesive strength was also measured using a polyethylene plate as an adherend using the same method. <Holding force> According to the method specified in JIS Z 0237, the pasting area is 20mm x 20mm at 40℃ and
A load of 1 kg was applied at 80° C., and the holding time or the width of deviation after a certain period of time was measured. Comparative Example 1 A comparative pressure-sensitive adhesive composition (1) was obtained in exactly the same manner as in Example 1, except that the dehydrated benzoguanamine resin used in Example 1 was not used at all, and the same measurements as in Example 1 were carried out. Ivy. The results are shown in Table 1. Comparative Example 2 Comparative pressure-sensitive adhesive composition obtained in Comparative Example 1 (1)
100 parts, 6 parts of "Sumitex Resin M-3" 10% aqueous solution (manufactured by Sumitomo Chemical Co., Ltd., methylolated melamine resin) and Sumitex Accelerator
A comparative pressure-sensitive adhesive composition (2) was prepared by adding and mixing 6 parts of a 1% ACX aqueous solution (manufactured by Sumitomo Chemical Co., Ltd.), and the same measurements as in Example 1 were performed. The results are shown in Table 1. Comparative Example 3 A comparative pressure-sensitive adhesive composition (3) was obtained in exactly the same manner as in Example 1, except that 2-hydroxyethyl methacrylate used in Example 1 was not used at all, and a comparative pressure-sensitive adhesive composition (3) was obtained in the same manner as in Example 1. I took measurements. The results are shown in Table 1. Comparative Example 4 A comparative pressure-sensitive adhesive composition (4) was obtained in exactly the same manner as in Example 1, except that 2-sulfoethyl methacrylate used in Example 1 was not used at all, and the same measurements as in Example 1 were carried out. I went there. The results are shown in Table 1. Comparative Example 5 Dehydrated benzoguanamine resin used in Example 1
A comparative pressure-sensitive adhesive composition (5) was obtained in exactly the same manner as in Example 1 using 3 parts of divinylbenzene instead of 10 parts, and the same measurements as in Example 1 were carried out. The results are shown in Table 1. Example 2 44 parts of "Staron #2130" (manufactured by Yasushi Oil Industries Co., Ltd., emulsified terpene phenol resin, 40% concentration) was added to 100 parts of the pressure-sensitive adhesive composition obtained in Example 1 and mixed to form an adhesive. A pressure-sensitive adhesive composition (2) containing the imparting agent was prepared, and the same measurements as in Example 1 were performed. The results are shown in Table 1. Example 3 In Example 1, the monomer mixture was converted into acrylic acid methyl triglycol ester (CH 2 =CHCOO-
(−CH 2 CH 2 O−) − o CH 3 ) 830 parts, vinyl acetate 100
The same method as in Example 1 was used, except that the monomer mixture was made of: pressure sensitive adhesive composition
(3) was obtained and the same measurements as in Example 1 were performed. The results are shown in Table 1.
【表】
実施例 ４
実施例２で得られた感圧接着剤組成物(1)を、乾
燥後の厚みが60μとなるように、離型紙に塗布
し、80℃で２分間乾燥し、このものをレーヨン不
織布（14ｇ/m2）の両面に転写してテープ厚130μ
の両面粘着テープを作製した。この両面粘着テー
プの片面に厚さ25μのポリエステルフイルムを貼
り付けたものについて実施例１に記載した方法に
よるタツク、粘着力および保持力を測定した。ま
た、この両面粘着テープを25mm×25mmのサイズに
裁断したものの両側に厚さ0.5mmのアルミニウム
板を貼り付け23℃で24時間放置後、一方のアルミ
ニウム板を面方向に10mm／分の速度で引つ張つて
破断するまでの最高抗張力（剪断強度）を測定し
た。これらの結果をまとめて第２表に示す。[Table] Example 4 The pressure-sensitive adhesive composition (1) obtained in Example 2 was applied to release paper so that the thickness after drying was 60μ, dried at 80°C for 2 minutes, and Transfer the material to both sides of rayon non-woven fabric (14g/m 2 ) and tape thickness 130μ
A double-sided adhesive tape was prepared. A polyester film having a thickness of 25 μm was attached to one side of this double-sided adhesive tape, and the tack, adhesion and holding power were measured by the method described in Example 1. In addition, this double-sided adhesive tape was cut into a size of 25 mm x 25 mm, an aluminum plate with a thickness of 0.5 mm was pasted on both sides, and after being left at 23°C for 24 hours, one aluminum plate was cut in the surface direction at a speed of 10 mm/min. The maximum tensile strength (shear strength) until it broke when pulled was measured. These results are summarized in Table 2.
Claims (1)
い水素またはメチル基、R3はｎが０のとき、炭
素数が４〜12個のアルキル基、ｎが１〜５のと
き、炭素数が１〜５個のアルキル基であり、ｎは
０または１〜５の正の整数である。） で示される（メタ）アクリル酸エステル系単量体
(A)40〜99.3重量％、 水酸基および／またはエポキシ基含有不飽和単
量体(B)0.5〜10重量％、 スルホン酸基含有不飽和単量体(C)0.1〜10重量
％、 その他の不飽和単量体(D)０〜30重量％ならびに ベンゾグアナミン樹脂(E)0.1〜10重量％ （但し、(A)、(B)、(C)、(D)および(E)成分の合計は
100重量％である。） からなる単量体混合物を乳化重合して得られる水
性樹脂分散体を必須成分として含む感圧接着剤組
成物。[Claims] 1. General formula (However, R 1 and R 2 may be the same or different hydrogen or methyl group, R 3 is an alkyl group having 4 to 12 carbon atoms when n is 0, and when n is 1 to 5, An alkyl group having 1 to 5 carbon atoms, and n is 0 or a positive integer of 1 to 5.) (Meth)acrylic acid ester monomer represented by
(A) 40-99.3% by weight, unsaturated monomer containing hydroxyl group and/or epoxy group (B) 0.5-10% by weight, unsaturated monomer containing sulfonic acid group (C) 0.1-10% by weight, other Unsaturated monomer (D) 0-30% by weight and benzoguanamine resin (E) 0.1-10% by weight (However, the total of components (A), (B), (C), (D) and (E) is
It is 100% by weight. ) A pressure-sensitive adhesive composition containing as an essential component an aqueous resin dispersion obtained by emulsion polymerization of a monomer mixture consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17675586A JPS6335676A (en) | 1986-07-29 | 1986-07-29 | Pressure-sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17675586A JPS6335676A (en) | 1986-07-29 | 1986-07-29 | Pressure-sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6335676A JPS6335676A (en) | 1988-02-16 |
| JPH0257110B2 true JPH0257110B2 (en) | 1990-12-04 |
Family
ID=16019243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17675586A Granted JPS6335676A (en) | 1986-07-29 | 1986-07-29 | Pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6335676A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2624820B2 (en) * | 1989-03-09 | 1997-06-25 | 日東電工株式会社 | Identification tag for dry cleaning and fixing method |
| DE4024192A1 (en) * | 1990-07-30 | 1992-02-06 | Uhu Gmbh | Solvent-free adhesive |
| JPH0778313B2 (en) * | 1991-06-04 | 1995-08-23 | 日華化学株式会社 | Dyeing aid for hydrophobic synthetic fibers |
| JP2007217594A (en) * | 2006-02-17 | 2007-08-30 | Dainippon Ink & Chem Inc | Acrylic water-based adhesive |
-
1986
- 1986-07-29 JP JP17675586A patent/JPS6335676A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6335676A (en) | 1988-02-16 |
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