JP5733672B2 - Water-based emulsion pressure sensitive adhesive - Google Patents
Water-based emulsion pressure sensitive adhesive Download PDFInfo
- Publication number
- JP5733672B2 JP5733672B2 JP2013002256A JP2013002256A JP5733672B2 JP 5733672 B2 JP5733672 B2 JP 5733672B2 JP 2013002256 A JP2013002256 A JP 2013002256A JP 2013002256 A JP2013002256 A JP 2013002256A JP 5733672 B2 JP5733672 B2 JP 5733672B2
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- Prior art keywords
- weight
- sensitive adhesive
- meth
- emulsion
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 38
- 239000000839 emulsion Substances 0.000 title claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 29
- 239000000178 monomer Substances 0.000 claims description 52
- -1 phosphate ester compound Chemical class 0.000 claims description 40
- 229920001567 vinyl ester resin Polymers 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 20
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 description 34
- 239000000853 adhesive Substances 0.000 description 32
- 230000001070 adhesive effect Effects 0.000 description 32
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 26
- 239000003995 emulsifying agent Substances 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 229940048053 acrylate Drugs 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 239000004908 Emulsion polymer Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Natural products CCC(CC)C(O)=O OXQGTIUCKGYOAA-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
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- ZAPBLOWGJNQWBJ-UHFFFAOYSA-N ethenyl 2-methylpentanoate Chemical compound CCCC(C)C(=O)OC=C ZAPBLOWGJNQWBJ-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- BTFFUEGVQBZTMY-UHFFFAOYSA-N ethenyl 3-methylbutanoate Chemical compound CC(C)CC(=O)OC=C BTFFUEGVQBZTMY-UHFFFAOYSA-N 0.000 description 1
- ZYYVTDQWKWHSOP-UHFFFAOYSA-N ethenyl 3-methylpentanoate Chemical compound CCC(C)CC(=O)OC=C ZYYVTDQWKWHSOP-UHFFFAOYSA-N 0.000 description 1
- HAKBVZWOUUNFLW-UHFFFAOYSA-N ethenyl 4-methylpentanoate Chemical compound CC(C)CCC(=O)OC=C HAKBVZWOUUNFLW-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-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
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
この発明は、粘着テープ、粘着ラベル、粘着シート等の粘着シート状体に使用されるエマルジョン状の感圧接着剤に関する。 The present invention relates to an emulsion-type pressure-sensitive adhesive used for pressure-sensitive adhesive sheets such as pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, and pressure-sensitive adhesive sheets.
粘着テープ、粘着ラベル、粘着シート等の粘着シート状体に用いられる感圧接着剤は、おもに天然ゴム系を中心としたゴム系のものとアクリル系のものに分類される。ゴム系のものはタックに富み、常温および低温での粘着バランスに優れているが、耐熱性や耐候性が十分でないため、アクリル系接着剤が主流になりつつある。アクリル系接着剤の利点としては、耐熱性、耐候性に優れ、また様々な要求物性に応じて、共重合モノマーを選択できることがあげられる。 Pressure-sensitive adhesives used for pressure-sensitive adhesive sheets such as pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, and pressure-sensitive adhesive sheets are mainly classified into rubber-based ones centering on natural rubber and acrylic ones. Rubber-based materials are rich in tack and have excellent adhesion balance at normal and low temperatures, but acrylic adhesives are becoming mainstream because of insufficient heat resistance and weather resistance. Advantages of the acrylic adhesive include excellent heat resistance and weather resistance, and the ability to select a copolymerization monomer according to various required physical properties.
しかし、前記のアクリル系感圧接着剤は、貼り付けた後、加熱したり、長期間放置したりすることにより、接着力が増大し、これにより再剥離の際の糊残りや基材切れ等が生じるため、作業性が悪くなるという問題点を有する。 However, the above-mentioned acrylic pressure-sensitive adhesive is heated, or left for a long period of time after being applied, thereby increasing the adhesive force. Therefore, there is a problem that workability is deteriorated.
また、アクリル系接着剤は、溶剤型とエマルジョン型に分類される。溶剤型においては、前記の問題に対して様々な試みがなされているが、その重合方法のため、凝集力のある高重合度のポリマーが得られにくいという欠点がある。さらに、凝集力のないポリマーからなる感圧接着剤を用いると、特に高温時、被着体への糊残り、汚染の問題が生じやすく、更に塗布乾燥時に揮発する溶剤の回収が困難となりやすく、作業性、設備のコスト、環境上の立場から問題を有する。 Acrylic adhesives are classified into a solvent type and an emulsion type. In the solvent type, various attempts have been made to solve the above problem, but due to the polymerization method, there is a drawback that it is difficult to obtain a polymer having a high polymerization degree with cohesive strength. Furthermore, when a pressure-sensitive adhesive made of a polymer having no cohesive force is used, adhesive residue on the adherend and contamination are likely to occur, particularly at high temperatures, and it is difficult to recover the solvent that volatilizes during application drying. There are problems from the viewpoint of workability, equipment cost, and environment.
一方、特許文献1に、エチレン−酢酸ビニル樹脂とアクリル系単量体との共重合体を有するエマルジョンからなる感圧接着剤が開示されている。この感圧接着剤は、長期間放置しても、接着力を一定範囲内に保持することができ、再剥離の際、糊残り等の問題を解消することができる。 On the other hand, Patent Document 1 discloses a pressure-sensitive adhesive comprising an emulsion having a copolymer of an ethylene-vinyl acetate resin and an acrylic monomer. This pressure-sensitive adhesive can maintain the adhesive strength within a certain range even when left for a long period of time, and can solve problems such as adhesive residue at the time of re-peeling.
特許文献1に記載の感圧接着剤は、常温での初期接着性や、長期間放置後の接着性に優れる。ただ、最近、低温条件下での初期接着性の向上についても求められるようになってきている。また、ポリオレフィン等の難接着性基材に対しても、接着性の向上が求められている。さらに、長期間貼付した後に剥離した際に生じやすい糊残り等の汚染を抑制することも求められている。 The pressure-sensitive adhesive described in Patent Document 1 is excellent in initial adhesiveness at room temperature and adhesiveness after standing for a long time. However, recently, an improvement in initial adhesiveness under low temperature conditions has been demanded. Moreover, the improvement of adhesiveness is calculated | required also with respect to hard-to-adhere base materials, such as polyolefin. Furthermore, it is also required to suppress contamination such as adhesive residue that is likely to occur when peeled after being applied for a long time.
そこで、この発明は、常温での初期接着性や、長期間放置後の接着性に加えて、低温条件下での初期接着性にも優れた、水系エマルジョン型の感圧接着剤を得ることを目的とする。 Therefore, the present invention provides a water-based emulsion-type pressure-sensitive adhesive that is excellent in initial adhesiveness at room temperature, adhesiveness after standing for a long time, and initial adhesiveness under low temperature conditions. Objective.
この発明は、水系エマルジョン型感圧接着剤として、エチレン2〜35重量部、炭素原子数8〜15の脂肪族カルボン酸のビニルエステル1〜97重量部、(メタ)アクリル酸アルキルエステル1〜97重量部を含む単量体混合物(全体を100重量部とする。)を、乳化重合して得られる共重合体を含有させることにより、前記課題を解決したのである。 This invention is a water-based emulsion type pressure sensitive adhesive having 2 to 35 parts by weight of ethylene, 1 to 97 parts by weight of a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms, and 1 to 97 (meth) acrylic acid alkyl ester. The said subject was solved by including the copolymer obtained by emulsion-polymerizing the monomer mixture (The whole shall be 100 weight part) containing a weight part.
また、他の水系エマルジョン型感圧接着剤として、構成成分として、エチレン2〜35重量%、炭素原子数8〜15の脂肪族カルボン酸のビニルエステル1〜97重量%、及び(メタ)アクリル酸アルキルエステルと共重合可能なその他の単量体2〜96重量%(合計量を100重量%とする。)を含有するエチレン−ビニルエステル系共重合体の存在下、このエチレン−ビニルエステル系共重合体100重量部に対して、(メタ)アクリル酸アルキルエステル1〜2000重量部を乳化重合して得られる重合体を含有させたものを用いてもよい。 In addition, as other water-based emulsion type pressure-sensitive adhesives, the constituent components are 2 to 35% by weight of ethylene, 1 to 97% by weight of vinyl ester of aliphatic carboxylic acid having 8 to 15 carbon atoms, and (meth) acrylic acid. This ethylene-vinyl ester copolymer is present in the presence of an ethylene-vinyl ester copolymer containing 2 to 96% by weight of other monomers copolymerizable with the alkyl ester (the total amount is 100% by weight). You may use what contained the polymer obtained by emulsion-polymerizing 1-2000 weight part of (meth) acrylic-acid alkylester with respect to 100 weight part of polymers.
さらに、他の水系エマルジョン型感圧接着剤として、構成成分として、エチレン2〜35重量%、炭素原子数8〜15の脂肪族カルボン酸のビニルエステル1〜97重量%及び(メタ)アクリル酸アルキルエステルと共重合可能なその他の単量体0〜96重量%(合計量を100重量%とする。)を含有するエチレン−ビニルエステル系共重合体と、(メタ)アクリル酸アルキルエステル、及びこの(メタ)アクリル酸アルキルエステルと共重合可能なその他の単量体とを、前記(メタ)アクリル酸アルキルエステルに対して、前記共重合可能な単量体を等量以下の割合で乳化重合して得られる共重合体を含有させたものを用いてもよい。 Further, as other water-based emulsion type pressure-sensitive adhesives, the constituents are 2 to 35% by weight of ethylene, 1 to 97% by weight of an aliphatic carboxylic acid vinyl ester having 8 to 15 carbon atoms, and alkyl (meth) acrylate. An ethylene-vinyl ester copolymer containing 0 to 96% by weight of other monomers copolymerizable with the ester (the total amount is 100% by weight), an alkyl (meth) acrylate, and this (Meth) acrylic acid alkyl ester and other monomer copolymerizable with the above (meth) acrylic acid alkyl ester by emulsion polymerization of the copolymerizable monomer at a ratio equal to or less than the equivalent amount. A copolymer containing a copolymer obtained in this manner may be used.
さらにまた、前記の各水系エマルジョン型感圧接着剤の構成成分である炭素数8〜15の脂肪族カルボン酸のビニルエステルとして、バーサチック酸ビニルを用いるのがよい。 Furthermore, it is preferable to use vinyl versatate as a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms, which is a constituent component of each water-based emulsion type pressure-sensitive adhesive.
この発明にかかる感圧接着剤は、エチレン、炭素原子数8〜15の脂肪族カルボン酸のビニルエステル、(メタ)アクリル酸アルキルエステルから得られる共重合体を含有するエマルジョン、所定の割合のその他の単量体成分を、エチレン−ビニルエステル系共重合体の存在下で、(メタ)アクリル酸アルキルエステルを乳化重合して得られる重合体を含有するエマルジョン、又は所定の割合のその他の単量体成分を含有するエチレン−ビニルエステル系共重合体と、(メタ)アクリル酸アルキルエステル、及びこの(メタ)アクリル酸アルキルエステルと共重合可能な単量体との共重合体との混合樹脂を含有するエマルジョンを用いるので、常温での初期接着性や、長期間放置後の接着性に加えて、低温条件下での初期接着性にも優れた、水系エマルジョン型の感圧接着剤を得ることができる。 The pressure-sensitive adhesive according to the present invention includes an emulsion containing a copolymer obtained from ethylene, a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms, and a (meth) acrylic acid alkyl ester, and other components in a predetermined ratio. An emulsion containing a polymer obtained by emulsion polymerization of a (meth) acrylic acid alkyl ester in the presence of an ethylene-vinyl ester copolymer, or other monomer in a predetermined proportion A mixed resin of an ethylene-vinyl ester copolymer containing a body component, a copolymer of (meth) acrylic acid alkyl ester, and a monomer copolymerizable with this (meth) acrylic acid alkyl ester Because the emulsion is used, in addition to the initial adhesiveness at room temperature and the adhesiveness after standing for a long period of time, excellent initial adhesiveness under low temperature conditions, It is possible to obtain a system emulsion type pressure sensitive adhesive.
また、炭素原子数8〜15の脂肪族カルボン酸のビニルエステルとして、バーサチック酸ビニルを用いることにより、低温条件下での初期接着性をさらに向上させることができる。 Further, by using vinyl versatate as a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms, initial adhesiveness under a low temperature condition can be further improved.
以下、この発明の実施形態を説明する。
この発明にかかる感圧接着剤は、構成樹脂の構成成分として、エチレン、炭素原子数8〜15の脂肪族カルボン酸のビニルエステル、及び(メタ)アクリル酸アルキルエステルを少なくとも用いた重合体であり、この重合体には、前記3つの単量体を含む単量体混合物を乳化重合して得られる共重合体(A)を含む水系エマルジョン型の接着剤、前記のエチレン、炭素原子数8〜15の脂肪族カルボン酸のビニルエステルからなる共重合体をシード樹脂とし、このシード樹脂の存在下で前記(メタ)アクリル酸アルキルエステル、及び必要に応じてこの(メタ)アクリル酸アルキルエステルと共重合可能なその他の単量体を乳化重合して得られる乳化重合体(B)を含む水系エマルジョン型の接着剤、及び、エチレン及び炭素原子数8〜15の脂肪族カルボン酸のビニルエステルからなる共重合体と、前記(メタ)アクリル酸アルキルエステル、及び必要に応じてこの(メタ)アクリル酸アルキルエステルと共重合可能なその他の単量体を乳化重合して得られる重合体(又は共
重合体)との樹脂混合体(C)を含む水系エマルジョン型の接着剤である。以下、それぞれについて説明する。
Embodiments of the present invention will be described below.
The pressure-sensitive adhesive according to the present invention is a polymer using at least ethylene, a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms, and a (meth) acrylic acid alkyl ester as a constituent component of the constituent resin. The polymer includes an aqueous emulsion-type adhesive containing a copolymer (A) obtained by emulsion polymerization of a monomer mixture containing the three monomers, the ethylene, and a carbon atom number of 8 to A copolymer of 15 aliphatic carboxylic acid vinyl esters is used as a seed resin, and in the presence of the seed resin, the (meth) acrylic acid alkyl ester and, if necessary, the (meth) acrylic acid alkyl ester are copolymerized. A water-based emulsion adhesive containing an emulsion polymer (B) obtained by emulsion polymerization of other polymerizable monomers, and ethylene and carbon atoms of 8 to 15 Emulsion polymerization of a copolymer comprising a vinyl ester of an aliphatic carboxylic acid, the (meth) acrylic acid alkyl ester, and if necessary, other monomers copolymerizable with the (meth) acrylic acid alkyl ester It is an aqueous emulsion type adhesive containing the resin mixture (C) with the polymer (or copolymer) obtained in this way. Each will be described below.
[共重合体(A)]
前記共重合体(A)は、構成樹脂の構成成分として、エチレン、炭素原子数8〜15の脂肪族カルボン酸のビニルエステル、及び(メタ)アクリル酸アルキルエステルを含む単量体混合物を乳化重合して得られる共重合体である。
[Copolymer (A)]
The copolymer (A) is an emulsion polymerization of a monomer mixture containing ethylene, a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms, and a (meth) acrylic acid alkyl ester as a constituent component of the constituent resin. It is a copolymer obtained by doing this.
前記炭素原子数8〜15の脂肪族カルボン酸のビニルエステル(以下、「特定の脂肪族カルボン酸ビニルエステル」と称する。)としては、カプリル酸ビニル、カプリン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル等があげられる。これらの中でも、バーサチック酸ビニルを用いると、得られる接着剤の低温初期接着性をより向上させることができるので、好ましい。 Examples of the vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms (hereinafter referred to as “specific aliphatic carboxylic acid vinyl ester”) include vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate. Etc. Among these, it is preferable to use vinyl versatate because the low-temperature initial adhesiveness of the obtained adhesive can be further improved.
前記(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸アミル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n−オクチル、(メタ)アクリル酸n−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)アクリル酸ラウリル等があげられる。なお、この発明において、「(メタ)アクリル」は、「アクリル」又は「メタクリル」のいずれかを意味する。 Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, and (meth) acrylic. 2-ethylhexyl acid, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate Etc. In the present invention, “(meth) acryl” means either “acryl” or “methacryl”.
前記の各単量体以外に、必要に応じて、前記のその他の単量体成分である、(メタ)アクリル酸アルキルエステルと共重合可能なその他の単量体(以下、単に「その他の単量体」と称する。)を用いることができる。このようなその他の単量体として、(メタ)アクリロニトリル、(メタ)アクリルアミド、ヒドロキシアルキル基の炭素数が1〜4の(メタ)アクリル酸ヒドロキシアルキルエステル等や、酪酸ビニル、イソ酪酸ビニル、吉草酸ビニル、イソ吉草酸ビニル、ピバル酸ビニル、ヒドロアンゲリカ酸ビニル、カプロン酸ビニル、2−メチルペンタン酸ビニル、3−メチルペンタン酸ビニル、4−メチルペンタン酸ビニル、2,2−ジメチルブタン酸ビニル、2,3−ジメチルブタン酸ビニル、3,3−ジメチルブタン酸ビニル、2−エチルブタン酸ビニルがあげられる。 In addition to the above-mentioned monomers, other monomers that are copolymerizable with the (meth) acrylic acid alkyl ester, which are other monomer components as required (hereinafter simply referred to as “other monomers”). Can be used.). Examples of such other monomers include (meth) acrylonitrile, (meth) acrylamide, hydroxyalkyl group (meth) acrylic acid hydroxyalkyl ester having 1 to 4 carbon atoms, vinyl butyrate, vinyl isobutyrate, Vinyl herbate, vinyl isovalerate, vinyl pivalate, vinyl hydroangelate, vinyl caproate, vinyl 2-methylpentanoate, vinyl 3-methylpentanoate, vinyl 4-methylpentanoate, vinyl 2,2-dimethylbutanoate 2,3-dimethylbutanoic acid vinyl, 3,3-dimethylbutanoic acid vinyl, and 2-ethylbutanoic acid vinyl.
前記エチレン含有量は、前記単量体混合物全体を100重量部としたとき、2重量部以上が必要であり、5重量部以上が好ましい。2重量部未満だと、粘着剤として用いた場合に糊残り等が起こるおそれがある。一方、上限は、35重量部がよく、20重量部が好ましい。35重量部より多いと、重合反応性が低下するそれがある。 The ethylene content needs to be 2 parts by weight or more, preferably 5 parts by weight or more, when the whole monomer mixture is 100 parts by weight. If it is less than 2 parts by weight, adhesive residue or the like may occur when used as an adhesive. On the other hand, the upper limit is preferably 35 parts by weight, and preferably 20 parts by weight. When the amount is more than 35 parts by weight, the polymerization reactivity may decrease.
前記特定の脂肪族カルボン酸ビニルエステルは、前記単量体混合物全体を100重量部としたとき、1重量部以上が必要であり、30重量部以上が好ましく、50重量部以上がさらに好ましい。1重量部未満だと、凝集力が不足して、耐汚染性が悪化する傾向があるという問題点を生ずる場合がある。一方、上限は、97重量部であり、80重量部が好ましい。97重量部より多いと、低温時に粘着力が低下するおそれがある。 The specific aliphatic carboxylic acid vinyl ester is required to be 1 part by weight or more, preferably 30 parts by weight or more, and more preferably 50 parts by weight or more, based on 100 parts by weight of the whole monomer mixture. If the amount is less than 1 part by weight, the cohesive force may be insufficient, which may cause a problem that the stain resistance tends to deteriorate. On the other hand, the upper limit is 97 parts by weight, preferably 80 parts by weight. When the amount is more than 97 parts by weight, the adhesive strength may decrease at low temperatures.
前記(メタ)アクリル酸アルキルエステル含有量は、前記単量体混合物全体を100重量部としたとき、1重量部以上であり、5重量部以上がよく、10重量部以上が好ましい。1重量部未満だと、低温での粘着力が不足するおそれがある。一方、上限は、97重量部であり、50重量部が好ましい。97重量部より多いと、凝集力が不足して、耐汚染性が低下するおそれがある。 The content of the (meth) acrylic acid alkyl ester is 1 part by weight or more, preferably 5 parts by weight or more, and preferably 10 parts by weight or more, based on 100 parts by weight of the whole monomer mixture. If it is less than 1 part by weight, the adhesive strength at low temperatures may be insufficient. On the other hand, the upper limit is 97 parts by weight, preferably 50 parts by weight. When the amount is more than 97 parts by weight, the cohesive force is insufficient, and the stain resistance may be lowered.
前記のその他の単量体の含有量は、前記単量体混合物全体を100重量部としたとき、
0重量部以上がよく、2重量部以上が好ましい。この単量体は用いなくてもよいので、下限は0重量部となる。一方、上限は、96重量部がよく、70重量部が好ましい。96重量部より多いと、粘着力が不足するおそれがある。
When the content of the other monomer is 100 parts by weight of the whole monomer mixture,
The amount is preferably 0 part by weight or more, and preferably 2 parts by weight or more. Since this monomer may not be used, the lower limit is 0 part by weight. On the other hand, the upper limit is preferably 96 parts by weight, and preferably 70 parts by weight. If it is more than 96 parts by weight, the adhesive strength may be insufficient.
前記共重合体(A)は、エマルジョンとして用いるのが好ましい。このようなエマルジョンは、重合体(A)を構成する前記の各単量体を乳化剤の下で、水又は水を主成分とし、これに水と相溶性のあるメタノール、エタノール等のアルコール等の溶媒を加えた混合溶液等の水系媒体中で乳化重合させて得ることができる。 The copolymer (A) is preferably used as an emulsion. Such an emulsion is composed of water or water as a main component under the emulsifier for each of the above-mentioned monomers constituting the polymer (A), and is compatible with water such as alcohols such as methanol and ethanol. It can be obtained by emulsion polymerization in an aqueous medium such as a mixed solution with a solvent added.
[乳化重合体(B)]
前記乳化重合体(B)は、エチレン、炭素原子数8〜15の脂肪族カルボン酸のビニルエステルからなる共重合体をシード樹脂とし、このシード樹脂の存在下で前記(メタ)アクリル酸アルキルエステル、及び必要に応じて、前記その他の単量体を乳化重合して得られる。
[Emulsion polymer (B)]
In the emulsion polymer (B), a copolymer of ethylene and a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms is used as a seed resin, and the (meth) acrylic acid alkyl ester in the presence of the seed resin. And, if necessary, obtained by emulsion polymerization of the other monomers.
前記の炭素原子数8〜15の脂肪族カルボン酸のビニルエステル(特定の脂肪族カルボン酸ビニルエステル)、(メタ)アクリル酸アルキルエステル、及び前記その他の単量体は、前記した共重合体(A)で用いられるものと同様である。 The vinyl ester of the aliphatic carboxylic acid having 8 to 15 carbon atoms (specific aliphatic vinyl carboxylic acid vinyl ester), the (meth) acrylic acid alkyl ester, and the other monomer are the above-described copolymer ( The same as that used in A).
前記エチレン含有量は、前記シード樹脂を構成する構造単位全体を100重量%としたとき、2重量%以上が必要であり、5重量%以上が好ましい。2重量%未満だと、粘着剤として用いた場合に糊残り等が起こるおそれがあるという問題点を生ずる場合がある。一方、上限は、35重量%がよく、20重量%が好ましい。35重量%より多いと、重合反応性が低下するそれがあるという問題点を生ずる場合がある。 The ethylene content is required to be 2% by weight or more, preferably 5% by weight or more, assuming that the entire structural unit constituting the seed resin is 100% by weight. If it is less than 2% by weight, there may be a problem that adhesive residue may occur when used as an adhesive. On the other hand, the upper limit is preferably 35% by weight, and preferably 20% by weight. If it is more than 35% by weight, there may be a problem that the polymerization reactivity may decrease.
前記特定の脂肪族カルボン酸ビニルエステルは、前記シード樹脂を構成する構造単位全体を100重量%としたとき、1重量%以上が必要であり、30重量%以上が好ましく、50重量%以上がさらに好ましい。1重量%未満だと、凝集力が不足して、耐汚染性が悪化する傾向があるという問題点を生ずる場合がある。一方、上限は、97重量%であり、80重量%が好ましい。97重量%より多いと低温時に粘着力が低下するおそれがある。 The specific aliphatic carboxylic acid vinyl ester needs to be 1% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight or more, assuming that the entire structural unit constituting the seed resin is 100% by weight. preferable. If it is less than 1% by weight, the cohesive force may be insufficient, which may cause a problem that the stain resistance tends to deteriorate. On the other hand, the upper limit is 97% by weight, preferably 80% by weight. If it exceeds 97% by weight, the adhesive strength may be lowered at low temperatures.
前記のその他の単量体の含有量は、前記単量体混合物全体を100重量%としたとき、0重量%以上がよく、2重量%以上が好ましい。この単量体は用いなくてもよいので、下限は0重量%となる。一方、上限は、96重量%がよく、70重量%が好ましい。96重量%より多いと、粘着力が不足するおそれがある。 The content of the other monomer is preferably 0% by weight or more, and preferably 2% by weight or more, when the entire monomer mixture is 100% by weight. Since this monomer may not be used, the lower limit is 0% by weight. On the other hand, the upper limit is preferably 96% by weight, and preferably 70% by weight. If it exceeds 96% by weight, the adhesive strength may be insufficient.
前記(メタ)アクリル酸アルキルエステル含有量は、前記シード樹脂100重量部に対して、1重量部以上がよく、10重量部以上が好ましい。1重量部未満だと、粘着力が不足するおそれがある。一方、上限は、2000重量部がよく、1000重量部が好ましい。2000重量部より多いと、ポリオレフィンに対する粘着力が不十分となるおそれがある。 The content of the (meth) acrylic acid alkyl ester is preferably 1 part by weight or more and preferably 10 parts by weight or more with respect to 100 parts by weight of the seed resin. If it is less than 1 part by weight, the adhesive strength may be insufficient. On the other hand, the upper limit is preferably 2000 parts by weight, and preferably 1000 parts by weight. When the amount is more than 2000 parts by weight, the adhesive strength to polyolefin may be insufficient.
前記その他の単量体含有量は、前記(メタ)アクリル酸アルキルエステルの使用量に対し、等量以下、すなわち100重量%以下がよく、30重量%以下が好ましい。等量より多いと、粘着力が不足するという問題点を生ずる場合がある。なお、この単量体は用いなくてもよいので、下限は0重量%となる。 The content of the other monomer is preferably equal to or less than that of the (meth) acrylic acid alkyl ester, that is, 100% by weight or less, and preferably 30% by weight or less. If the amount is more than the same amount, the problem of insufficient adhesive strength may occur. Since this monomer does not need to be used, the lower limit is 0% by weight.
前記シード樹脂は、エマルジョンとして用いるのが好ましい。このようなエマルジョンは、シード樹脂を構成する前記の各単量体を乳化剤の下で、水又は水を主成分とし、これに水と相溶性のあるメタノール、エタノール等のアルコール等の溶媒を加えた混合溶液等
の水系媒体中で乳化重合させて得ることができる。
The seed resin is preferably used as an emulsion. In such an emulsion, the above-mentioned monomers constituting the seed resin are mixed with water or water as a main component under an emulsifier, and a solvent such as alcohol such as methanol or ethanol having compatibility with water is added thereto. It can be obtained by emulsion polymerization in an aqueous medium such as a mixed solution.
そして、前記乳化重合体(B)は、エマルジョンとして用いられる。このようなエマルジョンは、前記シード樹脂の存在下で、前記の(メタ)アクリル酸アルキルエステル、及び必要に応じて前記その他の単量体を、乳化剤の下で、水又は水を主成分とし、これに水と相溶性のあるメタノール、エタノール等のアルコール等の溶媒を加えた混合溶液等の水系媒体中で乳化重合させることにより得られる。 And the said emulsion polymer (B) is used as an emulsion. In such an emulsion, in the presence of the seed resin, the (meth) acrylic acid alkyl ester and, if necessary, the other monomer, water or water as a main component under an emulsifier, It can be obtained by emulsion polymerization in an aqueous medium such as a mixed solution obtained by adding a solvent such as methanol or ethanol having compatibility with water.
[樹脂混合体(C)]
樹脂混合体(C)は、特定のエチレン−ビニルエステルからなる共重合体と、(メタ)アクリル酸アルキルエステルを主構成成分とする重合体又は共重合体との混合体である。
[Resin mixture (C)]
The resin mixture (C) is a mixture of a copolymer composed of a specific ethylene-vinyl ester and a polymer or copolymer having (meth) acrylic acid alkyl ester as a main constituent.
前記特定のエチレン−ビニルエステルからなる共重合体とは、エチレンと炭素原子数8〜15の脂肪族カルボン酸のビニルエステルからなる共重合体をいう。 The copolymer comprising the specific ethylene-vinyl ester refers to a copolymer comprising ethylene and a vinyl ester of an aliphatic carboxylic acid having 8 to 15 carbon atoms.
前記のエチレンの含有量、炭素原子数8〜15の脂肪族カルボン酸のビニルエステルの含有量及び種類、その他の単量体、並びに乳化重合方法は、前記の[乳化重合体(B)]の欄で示した内容と同様である。 The content of ethylene, the content and type of vinyl esters of aliphatic carboxylic acids having 8 to 15 carbon atoms, other monomers, and the emulsion polymerization method are the same as those in [Emulsion polymer (B)]. The contents are the same as those shown in the column.
また、前記(メタ)アクリル酸アルキルエステルを主構成成分とする重合体又は共重合体とは、前記(メタ)アクリル酸アルキルエステル、及び必要に応じて前記その他の単量体を乳化重合して得られる重合体又は共重合体をいう。前記(メタ)アクリル酸アルキルエステル、及び前記その他の単量体は、前記した共重合体(A)で用いられるものと同様である。 The polymer or copolymer having the (meth) acrylic acid alkyl ester as a main constituent component is obtained by emulsion polymerization of the (meth) acrylic acid alkyl ester and, if necessary, the other monomer. It refers to the resulting polymer or copolymer. The (meth) acrylic acid alkyl ester and the other monomers are the same as those used in the copolymer (A).
前記(メタ)アクリル酸アルキルエステルを主構成成分とする重合体又は共重合体における前記(メタ)アクリル酸アルキルエステル含有量は、この(メタ)アクリル酸アルキルエステルを主構成成分とする重合体又は共重合体の構成単位全体を100重量%としたとき、50重量%以上がよく、80重量%以上が好ましい。50重量%未満だと、粘着力が不足するおそれがある。なお、この重合体又は共重合体は、前記(メタ)アクリル酸アルキルエステルの単独重合体でもよいので、含有量の上限は、100重量%である。 The content of the (meth) acrylic acid alkyl ester in the polymer or copolymer containing the (meth) acrylic acid alkyl ester as a main constituent component is a polymer containing the (meth) acrylic acid alkyl ester as a main constituent component. When the total constitutional unit of the copolymer is 100% by weight, it is preferably 50% by weight or more, and preferably 80% by weight or more. If it is less than 50% by weight, the adhesive strength may be insufficient. In addition, since the homopolymer of the said (meth) acrylic acid alkyl ester may be sufficient as this polymer or copolymer, the upper limit of content is 100 weight%.
前記(メタ)アクリル酸アルキルエステルを主構成成分とする重合体又は共重合体における前記その他の単量体の含有量は、前記(メタ)アクリル酸アルキルエステルの使用量に対し、等量以下、すなわち100重量%以下がよく、70重量%以下が好ましい。等量より多いと、粘着力が不足するおそれがあるという問題点を生ずる場合がある。なお、この単量体は用いなくてもよいので、下限は0重量%となる。 The content of the other monomer in the polymer or copolymer having the (meth) acrylic acid alkyl ester as a main component is equal to or less than the amount of the (meth) acrylic acid alkyl ester used, That is, it is preferably 100% by weight or less, and preferably 70% by weight or less. If the amount is more than the same amount, there may be a problem that the adhesive strength may be insufficient. Since this monomer does not need to be used, the lower limit is 0% by weight.
前記の特定のエチレン−ビニルエステルからなる共重合体と、(メタ)アクリル酸アルキルエステルを主構成成分とする重合体又は共重合体との混合比(重量比)は、固形分で、5/95以上がよく、10/90以上が好ましい。5/95より小さいと、低温時の粘着力が不十分となることがある。一方、上限は、90/10がよく、80/20が好ましい。90/10より大きいと、粘着力が不足するおそれがある。 The mixing ratio (weight ratio) of the copolymer composed of the specific ethylene-vinyl ester and the polymer or copolymer having (meth) acrylic acid alkyl ester as a main constituent component is 5 / 95 or more is preferable, and 10/90 or more is preferable. If it is less than 5/95, the adhesive strength at low temperatures may be insufficient. On the other hand, the upper limit is preferably 90/10, and preferably 80/20. If it is larger than 90/10, the adhesive strength may be insufficient.
前記の特定のエチレン−ビニルエステルからなる共重合体や、(メタ)アクリル酸アルキルエステルを主構成成分とする重合体又は共重合体は、エマルジョンとして用いるのが好ましい。このようなエマルジョンは、各樹脂を構成する前記の各単量体を乳化剤の下で、水又は水を主成分とし、これに水と相溶性のあるメタノール、エタノール等のアルコール等の溶媒を加えた混合溶液等の水系媒体中で乳化重合させて得ることができる。 The copolymer made of the specific ethylene-vinyl ester and the polymer or copolymer having a (meth) acrylic acid alkyl ester as a main constituent component are preferably used as an emulsion. In such an emulsion, each of the above-mentioned monomers constituting each resin is mixed with water or water as a main component under an emulsifier, and a solvent such as methanol or ethanol having compatibility with water is added thereto. It can be obtained by emulsion polymerization in an aqueous medium such as a mixed solution.
[乳化重合]
前記の各乳化重合は、前記の各成分に、乳化剤、重合開始剤、重合調整剤(分子量調整剤)等を加え、重合することにより行われる。なお、この乳化重合には、必要に応じて、その他の添加剤をこの発明の目的・効果を損なわない範囲で加えることができる。
[Emulsion polymerization]
Each said emulsion polymerization is performed by adding an emulsifier, a polymerization initiator, a polymerization regulator (molecular weight regulator) etc. to each said component, and superposing | polymerizing. It should be noted that other additives can be added to the emulsion polymerization as necessary within a range that does not impair the object and effect of the present invention.
前記乳化剤としては、アニオン性、ノニオン性、カチオン性、両イオン性の乳化剤があげられる。前記アニオン性乳化剤しては、オレイン酸カリウム、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、アルカンスルホン酸ナトリウム、アルキルナフタレンスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルアリールエーテル硫酸ナトリウム等があげられる。 Examples of the emulsifier include anionic, nonionic, cationic and amphoteric emulsifiers. Examples of the anionic emulsifier include potassium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkanesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl Examples thereof include sodium aryl ether sulfate.
前記ノニオン性乳化剤としては、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オキシプロピレンブロックポリマー、ポリオキシエチレングリコール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ヒドロキシエチルセルロース等があげられる。 Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block polymer, polyoxyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and hydroxyethyl cellulose.
前記カチオン性乳化剤としては、ステアリルアミン塩酸塩、ラウリルトリメチルアンモニウムクロライド、トリメチルオクタデシルアンモニウムクロライド等があげられる。
両イオン性のものとして、ラウリルベタイン、ラウリルジメチルアミンオキサイド等があげられる。
Examples of the cationic emulsifier include stearylamine hydrochloride, lauryltrimethylammonium chloride, and trimethyloctadecylammonium chloride.
Examples of amphoteric ones include lauryl betaine and lauryl dimethylamine oxide.
これらの乳化剤の使用量は、使用する全単量体成分に対して5.0重量%以下であることが好ましく、3.0重量%以下であることがより好ましい。5.0重量%よりも多い場合、耐汚染性を低下させる傾向がある。 The amount of these emulsifiers to be used is preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on all monomer components used. When it is more than 5.0% by weight, the stain resistance tends to be lowered.
前記重合開始剤としては、過酸化物系開始剤、アゾ系開始剤や過硫酸塩系開始剤があげられる。この過酸化物系開始剤としては、例えば、ベンゾイルペルオキシド、ラウロイルペルオキシド、メチルエチルケトンペルオキシド、ジクミルペルオキシド、t−ブチルヒドロペルオキシド、過酸化水素等があげられる。 Examples of the polymerization initiator include peroxide initiators, azo initiators, and persulfate initiators. Examples of the peroxide initiator include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide.
前記アゾ系開始剤としては、例えばアゾビスイソブチロニトリル、アゾビスシアノバレリアン酸、アゾビスシアノペンタン酸、アゾビス−2−アミジノプロパン塩酸塩等があげられる。
前記過硫酸塩系開始剤としては、例えば過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等があげられる。
Examples of the azo initiator include azobisisobutyronitrile, azobiscyanovaleric acid, azobiscyanopentanoic acid, azobis-2-amidinopropane hydrochloride, and the like.
Examples of the persulfate-based initiator include ammonium persulfate, potassium persulfate, and sodium persulfate.
前記重合調整剤(分子量調整剤)としては、例えばチオグリコール酸、ブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、ラウリルメルカプタン、2−エチルヘキシルチオグリコレート、2−メルカプトエタノール等があげられる。 Examples of the polymerization regulator (molecular weight regulator) include thioglycolic acid, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, lauryl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol and the like.
前記乳化重合は、好適には、乳化剤水溶液、重合開始剤、及び乳化重合体(B)の製造においては、シード樹脂の存在下、各単量体成分、乳化剤及び水からなるモノマーエマルジョンを加えることによって行なわれる。より好ましくは、前記乳化剤水溶液に重合開始剤、及び乳化重合体(B)の製造においては、シード樹脂を加え、これにモノマーエマルジョンを滴下することによって行なわれる。この際、重合温度は40〜90℃であることが好ましく、60〜80℃であることがより好ましい。また、モノマーエマルジョンの添加終了後、熟成反応を行なわせることが好ましい。その際の反応温度は好ましくは60〜90℃、より好ましくは60〜80℃であり、反応時間は好ましくは2〜5時間、より好ましくは3〜4時間である。 In the emulsion polymerization, preferably, in the production of an aqueous emulsifier solution, a polymerization initiator, and an emulsion polymer (B), a monomer emulsion comprising each monomer component, an emulsifier and water is added in the presence of a seed resin. Is done by. More preferably, in the production of the polymerization initiator and the emulsion polymer (B) in the emulsifier aqueous solution, a seed resin is added and a monomer emulsion is added dropwise thereto. At this time, the polymerization temperature is preferably 40 to 90 ° C, and more preferably 60 to 80 ° C. Moreover, it is preferable to carry out a ripening reaction after the addition of the monomer emulsion is completed. The reaction temperature at that time is preferably 60 to 90 ° C., more preferably 60 to 80 ° C., and the reaction time is preferably 2 to 5 hours, more preferably 3 to 4 hours.
[添加剤]
前記の共重合体(A)、乳化重合体(B)、及び樹脂混合体(C)には、必要に応じて、その他の添加剤として、リン酸エステル化合物を添加してもよい。このリン酸エステル化合物の例としては、ポリオキシエチレンアルキルエーテルリン酸エステル塩、ポリオキシエチレンアルキルアリールエーテルリン酸エステル塩、アルキルエーテルリン酸エステル等があげられる。
[Additive]
As necessary, a phosphate ester compound may be added to the copolymer (A), the emulsion polymer (B), and the resin mixture (C). Examples of the phosphoric acid ester compound include polyoxyethylene alkyl ether phosphoric acid ester salts, polyoxyethylene alkyl aryl ether phosphoric acid ester salts, alkyl ether phosphoric acid esters and the like.
前記リン酸エステル化合物を使用する場合、その添加量は、樹脂成分100重量部あたり、0.05重量部以上が好ましく、1重量部以上がより好ましい。0.05重量部より少ないと、耐汚染性が十分に得られないおそれがある。一方、上限は、20重量部が好ましく、10重量部がより好ましい。20重量部より多いと、十分な粘着力が得られないおそれがある。 When the phosphoric acid ester compound is used, the amount added is preferably 0.05 parts by weight or more and more preferably 1 part by weight or more per 100 parts by weight of the resin component. If the amount is less than 0.05 parts by weight, there is a possibility that sufficient stain resistance cannot be obtained. On the other hand, the upper limit is preferably 20 parts by weight, and more preferably 10 parts by weight. When the amount is more than 20 parts by weight, there is a possibility that sufficient adhesive strength cannot be obtained.
前記リン酸エステル化合物以外のその他の添加剤として、前記の乳化重合時に、必要に応じて、防腐剤、防カビ剤、増粘剤、濡れ剤、消泡剤、粘着付与樹脂、可塑剤などを配合することができる。また、pH調整剤として、アンモニア水、苛性ソーダ、苛性カリ、炭酸ナトリウムなどを用いることもできる。なお、これらその他の添加剤は、乳化重合時だけでなく、乳化重合終了後に添加することもできる。 As other additives other than the phosphoric acid ester compound, at the time of the emulsion polymerization, an antiseptic, an antifungal agent, a thickener, a wetting agent, an antifoaming agent, a tackifier resin, a plasticizer, etc. Can be blended. Moreover, ammonia water, caustic soda, caustic potash, sodium carbonate, etc. can also be used as a pH adjuster. These other additives can be added not only at the time of emulsion polymerization but also after the completion of emulsion polymerization.
[用途]
前記の共重合体(A)、乳化重合体(B)、又は樹脂混合体(C)からなる乳化重合体を、基材の少なくとも一方の面に塗工して、水系エマルジョン型感圧接着剤から形成される層を得ることができる。そのような層を有する積層体は、粘着テープ、粘着ラベル、粘着シート等の粘着シート状体として使用することができる。
[Usage]
An aqueous emulsion-type pressure-sensitive adhesive is prepared by coating the emulsion polymer comprising the copolymer (A), the emulsion polymer (B), or the resin mixture (C) on at least one surface of the substrate. A layer formed from can be obtained. A laminate having such a layer can be used as a pressure-sensitive adhesive sheet, such as a pressure-sensitive adhesive tape, a pressure-sensitive adhesive label, or a pressure-sensitive adhesive sheet.
以下に実施例を用いてさらに詳細に説明する。なお、下記実施例及び比較例における測定方法について説明する。 This will be described in more detail with reference to examples. The measurement methods in the following examples and comparative examples will be described.
<特性の測定又は評価>
[初期粘着力の測定]
常温(25℃)下において、被着体をステンレス(SUS)板とし、JIS Z 0237に準じて180°引き剥がし接着力の測定を行った。
<Measurement or evaluation of characteristics>
[Measurement of initial adhesive strength]
Under normal temperature (25 ° C.), the adherend was a stainless steel (SUS) plate and peeled 180 ° according to JIS Z 0237, and the adhesive strength was measured.
[5℃における初期粘着力の測定]
被着体をポリエチレン(PE)板(日本テストパネル(株)製:幅2cm)に変更し、かつ、試験片を5℃に冷却し、次いで、この5℃の条件下で、前記の初期粘着力の測定を行った。
[Measurement of initial adhesive strength at 5 ° C]
The adherend was changed to a polyethylene (PE) plate (manufactured by Nippon Test Panel Co., Ltd .: width 2 cm), and the test piece was cooled to 5 ° C. Force measurements were taken.
[経時促進試験]
被着体をSUS板とし、東洋精機(株)製耐候促進試験機;アトラス・ユーブンコンにおいて、60℃雰囲気、紫外線照射下で4時間、40℃雰囲気、湿度90%下で4時間の1サイクル8時間を、9サイクル、合計72時間放置した後、JIS Z 0237に準じて180°引き剥がし接着力の測定を行った。また、このときの汚染の状態を確認し、下記の基準で判断した。
○:汚染なし
△:わずかに汚染あり
×:全面に汚染あり
[Aging acceleration test]
One cycle 8 in which the adherend is a SUS plate and the weathering acceleration tester manufactured by Toyo Seiki Co., Ltd .; Atlas Ubunkon, 60 ° C. atmosphere, 4 hours under UV irradiation, 40 ° C. atmosphere, 90% humidity 4 hours The time was left for 9 cycles for a total of 72 hours, and then peeled off by 180 ° according to JIS Z 0237, and the adhesive strength was measured. Moreover, the state of contamination at this time was confirmed and judged according to the following criteria.
○: No contamination △: Slightly contaminated ×: Fully contaminated
<原材料>
[エチレン]
・エチレン…三菱化学(株)製、以下、「Et」と称する。
<Raw materials>
[ethylene]
-Ethylene: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as "Et".
[ビニルエステル]
・酢酸ビニル…日本合成化学(株)製、以下、「VAC」と称する。
・バーサチック酸ビニル…シェル化学(株)製、以下、「VV」と称する。
[Vinyl ester]
Vinyl acetate: manufactured by Nippon Synthetic Chemical Co., Ltd., hereinafter referred to as “VAC”.
-Vinyl versatate: manufactured by Shell Chemical Co., Ltd., hereinafter referred to as "VV".
[アクリル系単量体]
・アクリル酸2−エチルヘキシル…三菱化学(株)製、以下、「2EHA」と称する。
・アクリル酸ブチル…三菱化学(株)製、以下、「BA」と称する。
・メタクリル酸メチル…三菱レイヨン(株)製、以下、「MMA」と称する。
・メタクリル酸…三菱レイヨン(株)製、以下、「MAA」と称する。
[Acrylic monomer]
・ 2-ethylhexyl acrylate: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as “2EHA”.
・ Butyl acrylate: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as “BA”.
-Methyl methacrylate: Mitsubishi Rayon Co., Ltd., hereinafter referred to as "MMA".
Methacrylic acid: manufactured by Mitsubishi Rayon Co., Ltd., hereinafter referred to as “MAA”.
[エチレン−酢酸ビニル系共重合体]
・エチレン−酢酸ビニル−バーサチック酸ビニル共重合体…住友化学(株)製:スミカフレックス950HQ、固形分:53重量%、以下、「S−950」と称する。
・エチレン−酢酸ビニル共重合体…住友化学(株)製:スミカフレックス401HQ、固形分:55重量%、以下、「S−401」と称する。
[Ethylene-vinyl acetate copolymer]
-Ethylene-vinyl acetate-vinyl versatate copolymer: Sumitomo Chemical Co., Ltd. product: Sumikaflex 950HQ, solid content: 53% by weight, hereinafter referred to as "S-950".
-Ethylene-vinyl acetate copolymer: manufactured by Sumitomo Chemical Co., Ltd .: Sumikaflex 401HQ, solid content: 55% by weight, hereinafter referred to as "S-401".
[リン酸エステル化合物]
・アルキルエーテルリン酸エステル…東邦化学工業(株)製:フォスファノールRD−720、以下、「RD−720」と称する。
[Phosphate compound]
-Alkyl ether phosphate ester: Toho Chemical Co., Ltd .: Phosphanol RD-720, hereinafter referred to as “RD-720”.
[乳化剤]
・ヒドロキシエチルセルロース…ダイセル化学(株)製、以下、「HEC」と称する。
・ドデシルベンゼンスルホン酸ナトリウム…(株)花王製:ネオペレックスG−65、以下、「G−65」と称する。
・ポリオキシエチレンアルキルエーテル…(株)花王製:エマルゲン1118S−70、以下、「1118S−70」と称する。
[emulsifier]
Hydroxyethyl cellulose: manufactured by Daicel Chemical Industries, Ltd., hereinafter referred to as “HEC”.
-Sodium dodecylbenzenesulfonate: manufactured by Kao Corporation: Neoperex G-65, hereinafter referred to as "G-65".
Polyoxyethylene alkyl ether: manufactured by Kao Corporation: Emulgen 1118S-70, hereinafter referred to as “1118S-70”.
[共重合体(A)を含む水系エマルジョンの製造]
(参考例1〜2、参考比較例1〜2)
耐圧容器に、水80重量部、及び表1に示す量のビニルエステル、アクリル系単量体、及び表1に示す量の各乳化剤を添加した。また、硫酸第一鉄七水和物0.002重量部、酢酸ナトリウム0.06重量部及び酢酸0.1重量部を溶解した溶液を添加した。
次に、耐圧容器内を窒素ガスで置換し、容器内を50℃まで昇温した後、エチレンで5.0MPaまで加圧し、2.5%過硫酸ナトリウム水溶液を1.1重量部/h、及び9%ロンガリット水溶液0.8重量部/hを耐圧容器に添加して重合を開始させた。続いて、耐圧容器内の液温が上昇したことを確認した後、表1に示す量のアクリル系単量体、表1に示す量の各乳化剤、表1に示す量のリン酸エステル化合物、及び水80重量部を混合した調整液を、3時間かけて滴下した。このとき、容器内の液温を50℃に維持した。
次いで、重合開始後5時間経過した時点で酸化剤を3%過硫酸ナトリウム及び2%tert−ブチルハイドロパーオキサイド水溶液に切り替え、6重量部/hの速度で耐圧容器に添加し、残留ビニルエステルが1%未満になった時点で耐圧容器を冷却し、未反応のエチレンガスを除去した後、エマルジョン組成物を得た。
次いで、得られたエマルジョン組成物を、アプリケーターを用いて紙基材に、乾燥後の塗膜の厚さが30μmになるように塗工し、乾燥したのち、10mm×150mmに切断して、試験片を作製した。
[Production of aqueous emulsion containing copolymer (A)]
(Reference Examples 1-2, Reference Comparative Examples 1-2)
To the pressure vessel, 80 parts by weight of water, vinyl ester in the amount shown in Table 1, acrylic monomer, and each emulsifier in the amount shown in Table 1 were added. Moreover, the solution which melt | dissolved 0.002 weight part of ferrous sulfate heptahydrate, 0.06 weight part of sodium acetate, and 0.1 weight part of acetic acid was added.
Next, the inside of the pressure vessel was replaced with nitrogen gas, the temperature inside the vessel was raised to 50 ° C., and then pressurized to 5.0 MPa with ethylene, and a 2.5% sodium persulfate aqueous solution was added at 1.1 parts by weight / h, Then, 0.8 parts by weight / h of 9% Rongalite aqueous solution was added to the pressure vessel to initiate the polymerization. Subsequently, after confirming that the liquid temperature in the pressure vessel had risen, the acrylic monomer in the amount shown in Table 1, each emulsifier in the amount shown in Table 1, the phosphate compound in the amount shown in Table 1, And the adjustment liquid which mixed 80 weight part of water was dripped over 3 hours. At this time, the liquid temperature in the container was maintained at 50 ° C.
Next, when 5 hours have elapsed after the start of polymerization, the oxidant was switched to 3% sodium persulfate and 2% tert-butyl hydroperoxide aqueous solution and added to the pressure vessel at a rate of 6 parts by weight / h, and the residual vinyl ester was removed. When the pressure became less than 1%, the pressure-resistant vessel was cooled to remove unreacted ethylene gas, and an emulsion composition was obtained.
Next, the obtained emulsion composition was applied to a paper substrate using an applicator so that the thickness of the coating film after drying was 30 μm, dried, and then cut into 10 mm × 150 mm, and tested. A piece was made.
[乳化重合体(B)を含む水系エマルジョンの製造]
(参考例3〜4、実施例1〜2、比較例1〜2)
温度計、還流冷却器、撹拌装置及び滴下ロートを備えた反応容器に、表2に示す量のシード樹脂(表2には、固形分量を記載)と水20重量部を仕込み、70℃に昇温した。次に、表2に示す量のアクリル系単量体、表2に示す量の各乳化剤、表2に示す量のリン酸エステル化合物、及び水27重量部を混合した調整液を、アゾビス−2−アミジノプロパン塩酸塩(和光純薬(株)製;V−50)0.3gを反応容器に加えた後、2時間かけて滴下した。その後、80℃で2時間熟成して、感圧接着性樹脂組成物となるエマルジョン組成物を得た。
次いで、得られたエマルジョン組成物を、アプリケーターを用いて紙基材に、乾燥後の塗膜の厚さが30μmになるように塗工し、乾燥したのち、10mm×150mmに切断して、試験片を作製した。
得られた試験片を用いて、前記の方法に従って、諸特性を測定又は評価した。その結果を表2に示す。
[Production of aqueous emulsion containing emulsion polymer (B)]
(Reference Example 3-4, Example 1-2, Comparative Example 1-2)
Into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, the amount of seed resin shown in Table 2 (the solid content is shown in Table 2) and 20 parts by weight of water are charged and the temperature is raised to 70 ° C. Warm up. Next, an azobis-2 mixture prepared by mixing the acrylic monomer in the amount shown in Table 2, each emulsifier in the amount shown in Table 2, the phosphate ester compound in the amount shown in Table 2, and 27 parts by weight of water was mixed. -Amidinopropane hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd .; V-50) (0.3 g) was added to the reaction vessel, and then added dropwise over 2 hours. Thereafter, the mixture was aged at 80 ° C. for 2 hours to obtain an emulsion composition to be a pressure-sensitive adhesive resin composition.
Next, the obtained emulsion composition was applied to a paper substrate using an applicator so that the thickness of the coating film after drying was 30 μm, dried, and then cut into 10 mm × 150 mm, and tested. A piece was made.
Using the obtained test piece, various properties were measured or evaluated according to the method described above. The results are shown in Table 2.
[樹脂混合体(C)を含む水系エマルジョンの製造]
(参考例5)
温度計、還流冷却器、撹拌装置及び滴下ロートを備えた反応容器に、水40重量部を仕込み、70℃に昇温し、V−50の0.3gを反応容器に加えた。次に、表3に示す量のアクリル系単量体、表3に示す量の各乳化剤、表3に示す量のリン酸エステル化合物、及び水40重量部を混合した調整液を、2時間かけて滴下した。その後、80℃で2時間熟成して、アクリル系共重合体エマルジョン組成物を得た。
得られたアクリル系共重合体エマルジョン組成物(固形分量:100重量部)に、エチレン−酢酸ビニル共重合体50重量部(固形分)を加え、混合して樹脂混合体を得た。
次いで、得られた樹脂混合体を、アプリケーターを用いて紙基材に、乾燥後の塗膜の厚さが30μmになるように塗工し、乾燥したのち、10mm×150mmに切断して、試験片を作製した。
得られた試験片を用いて、前記の方法に従って、諸特性を測定又は評価した。その結果を表3に示す。
[Production of aqueous emulsion containing resin mixture (C)]
(Reference Example 5 )
A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 40 parts by weight of water, heated to 70 ° C., and 0.3 g of V-50 was added to the reaction vessel. Next, the adjustment liquid which mixed the acrylic monomer of the quantity shown in Table 3, each emulsifier of the quantity shown in Table 3, the phosphate compound of the quantity shown in Table 3, and 40 weight part of water over 2 hours. And dripped. Thereafter, the mixture was aged at 80 ° C. for 2 hours to obtain an acrylic copolymer emulsion composition.
To the obtained acrylic copolymer emulsion composition (solid content: 100 parts by weight), 50 parts by weight (solid content) of ethylene-vinyl acetate copolymer was added and mixed to obtain a resin mixture.
Next, the obtained resin mixture was applied to a paper substrate using an applicator so that the thickness of the coating film after drying was 30 μm, dried, and then cut to 10 mm × 150 mm, and tested. A piece was made.
Using the obtained test piece, various properties were measured or evaluated according to the method described above. The results are shown in Table 3.
Claims (4)
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