JP6028288B2 - Re-peelable water pressure sensitive adhesive - Google Patents
Re-peelable water pressure sensitive adhesive Download PDFInfo
- Publication number
- JP6028288B2 JP6028288B2 JP2013031814A JP2013031814A JP6028288B2 JP 6028288 B2 JP6028288 B2 JP 6028288B2 JP 2013031814 A JP2013031814 A JP 2013031814A JP 2013031814 A JP2013031814 A JP 2013031814A JP 6028288 B2 JP6028288 B2 JP 6028288B2
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- JP
- Japan
- Prior art keywords
- sensitive adhesive
- parts
- weight
- pressure
- meth
- 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 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 31
- -1 phosphate ester compound Chemical class 0.000 claims description 80
- 239000000178 monomer Substances 0.000 claims description 36
- 239000000839 emulsion Substances 0.000 claims description 34
- 229910019142 PO4 Inorganic materials 0.000 claims description 32
- 239000010452 phosphate Substances 0.000 claims description 32
- 229920000058 polyacrylate Polymers 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- 239000012298 atmosphere Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 8
- 229940001584 sodium metabisulfite Drugs 0.000 description 8
- 235000010262 sodium metabisulphite Nutrition 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 239000012874 anionic emulsifier Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 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 4
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 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
- 239000011787 zinc oxide Substances 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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 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
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 235000010352 sodium erythorbate Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- KATAXDCYPGGJNJ-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethoxy)propan-2-ol Chemical compound C1OC1COCC(O)COCC1CO1 KATAXDCYPGGJNJ-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- PBDXUGSZYRYWMI-UHFFFAOYSA-N 1-ethyl-3-heptylidenepyrrolidine-2,5-dione Chemical compound CCCCCCC=C1CC(=O)N(CC)C1=O PBDXUGSZYRYWMI-UHFFFAOYSA-N 0.000 description 1
- QSWFISOPXPJUCT-UHFFFAOYSA-N 1-methyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CN1C(=O)CC(=C)C1=O QSWFISOPXPJUCT-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- 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
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ZAYGISOXMIXWHX-UHFFFAOYSA-N 2-methylpropoxycarbonyloxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(=O)OCC(C)C ZAYGISOXMIXWHX-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 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 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 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
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003139 buffering effect Effects 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
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 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
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 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
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- ZFGUAQSDWQIVMM-UHFFFAOYSA-N n'-hydroxy-2-methylbutanimidamide Chemical compound CCC(C)C(N)=NO ZFGUAQSDWQIVMM-UHFFFAOYSA-N 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- GCTMVWJHICUMRV-UHFFFAOYSA-N octan-3-yl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC(CC)CCCCC)OC1=CC=CC=C1 GCTMVWJHICUMRV-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl 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])=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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WVSZBAHKLHXQFN-UHFFFAOYSA-N tetrahydrate;dihydrochloride Chemical compound O.O.O.O.Cl.Cl WVSZBAHKLHXQFN-UHFFFAOYSA-N 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical class OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、感圧式接着シート等に用いる再剥離型水性感圧接着剤に関する。 The present invention relates to a re-peelable water-based pressure-sensitive adhesive used for a pressure-sensitive adhesive sheet or the like.
近年、感圧式接着シートの再剥離性の向上及び再剥離時の耐汚染性の向上を目的として水性感圧接着剤の検討が種々行われており、例えば、 (A) 炭素数が2〜14のアルキル基を有するアクリル酸エステルおよびまたはメタクリル酸エステル80〜95重量%および脂肪族α,β−不飽和カルボン酸1〜5重量%を乳化重合して得られる水性エマルションを不揮 発分として100重量部、(B)リン酸およびまたはリン酸エステルを0.001重量部以上 0.1重量部未満および(C) 分子内に平均2個以上のグリシジル基を有するエポキシ化合物を前記(A) の水性樹脂エマルションの有するカルボキシル基1個に対してグリシジル基が 0.1〜2個の割合になるよう含有してなる再剥離型水性感圧接着剤組成物(例えば、特許文献1参照。)や、(a1)炭素数4〜12のアルキル基を含有する(メタ)アクリル酸アルキルエステル50〜99.89重量%、(a2)カルボキシル基含有不飽和単量体0.1〜10重量%、(a3)カルボニル基含有不飽和単量体0.01〜10重量%、および(a4)その他の不飽和単量体0〜49.89重量%を含む単量体混合物を、アニオン型反応性乳化剤の存在下に乳化重合させて得られる、ガラス転移温度が−50℃を越え−25℃以下のアクリル系樹脂からなるゲル分率が70重量%未満のエマルジョン、[B]ヒドラジン系化合物、ならびに[C]リン酸エステル系化合物を含有してなることを特徴とする再剥離型水性粘着剤(例えば、特許文献2参照。)が提案されている。 In recent years, various studies have been made on aqueous pressure-sensitive adhesives for the purpose of improving the removability of the pressure-sensitive adhesive sheet and improving the stain resistance at the time of re-peeling. For example, (A) the number of carbon atoms is 2 to 14 An aqueous emulsion obtained by emulsion polymerization of 80 to 95% by weight of an acrylic acid ester and / or methacrylic acid ester having an alkyl group of 1 to 5% by weight of an aliphatic α, β-unsaturated carboxylic acid is used as a non-volatile component. Parts by weight of (B) phosphoric acid and / or phosphate ester of 0.001 part by weight or more and less than 0.1 part by weight and (C) an epoxy compound having an average of 2 or more glycidyl groups in the molecule. Re-peelable water-based pressure-sensitive adhesive composition containing 0.1 to 2 glycidyl groups with respect to one carboxyl group of the aqueous resin emulsion (for example, see Patent Document 1). (A1) 50 to 99.89% by weight of (meth) acrylic acid alkyl ester containing an alkyl group having 4 to 12 carbon atoms, (a2) 0.1 to 10% by weight of a carboxyl group-containing unsaturated monomer, ( A monomer mixture containing 0.01 to 10% by weight of a3) carbonyl group-containing unsaturated monomer and (a4) 0 to 49.89% by weight of another unsaturated monomer is used as an anionic reactive emulsifier. An emulsion obtained by emulsion polymerization in the presence of an acrylic resin having a glass transition temperature of more than −50 ° C. and not more than −25 ° C. and having a gel fraction of less than 70% by weight, [B] a hydrazine compound, and [C A re-peelable water-based pressure-sensitive adhesive (for example, see Patent Document 2) characterized by containing a phosphate ester compound has been proposed.
しかし、従来の感圧式接着シートは、高温雰囲気で経時した後の再剥離性はある程度あったが、さらに高温雰囲気の場合の再剥離性、および高温雰囲気において感圧式接着シートが剥がれにくい耐久性の両立が難しい問題があった。 However, the conventional pressure-sensitive adhesive sheet had a certain degree of removability after aging in a high-temperature atmosphere, but the re-peelability in a high-temperature atmosphere and the durability that the pressure-sensitive adhesive sheet is difficult to peel off in a high-temperature atmosphere. There was a problem that was difficult to balance.
本発明は、被着体に長期間貼り付けた後に接着力の変化が少なく、被着体に貼り付けた後に高温雰囲気にて置かれた後の再剥離性が良好でありながら、浮き剥がれが生じ難い耐久性を有する感圧式接着テープを製造できる再剥離型水性感圧式接着剤の提供を目的とする。 The present invention has little change in adhesive force after being attached to an adherend for a long period of time, and has good re-peelability after being placed in a high-temperature atmosphere after being attached to an adherend, but does not float off. An object of the present invention is to provide a re-peelable water-based pressure-sensitive adhesive capable of producing a pressure-sensitive adhesive tape having durability that hardly occurs.
本発明は、炭素数2〜12のアルキル基を含有する(メタ)アクリル酸アルキルエステル50〜99重量%、カルボキシル基含有不飽和単量体0.5〜3重量%を含むエチレン性不飽和単量体を乳化重合して得られるアクリル系重合体のエマルジョン、および炭素数が8〜14のアルキル基を有するリン酸エステル系化合物を含み、前記リン酸エステル系化合物が、アルキレンオキサイド構造を有さず、かつアルキル基が分岐構造を有しており、アクリル系重合体100重量部に対してリン酸エステル系化合物が0.5〜5重量部であることを特徴とする再剥離型水性感圧式接着剤である。
The present invention relates to an ethylenically unsaturated monomer comprising 50 to 99 % by weight of a (meth) acrylic acid alkyl ester containing an alkyl group having 2 to 12 carbon atoms and 0.5 to 3% by weight of a carboxyl group-containing unsaturated monomer. An acrylic polymer emulsion obtained by emulsion polymerization of a monomer, and a phosphate ester compound having an alkyl group having 8 to 14 carbon atoms, wherein the phosphate ester compound has an alkylene oxide structure. In addition, the releasable water pressure-sensitive type , wherein the alkyl group has a branched structure, and the phosphoric ester compound is 0.5 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer. It is an adhesive.
上記の本発明によれば、再剥離型水性感圧式接着剤は、感圧式接着シートに加工して使用した場合、アクリル系重合体の合成に使用するモノマーの組合せ、および特定のリン酸エステル系化合物を特定量含むことで、前記アクリル系重合体と相溶性が悪い前記リン酸エステル系化合物は、感圧式接着層との界面に移行しやすいため、高温雰囲気において感圧式接着層の凝集力の低下を抑制できるため良好な接着力が得られる。さらに前記リン酸エステル系化合物は、前記界面に存在しやすいことで高温雰囲気において感圧式接着シートに浮きや剥がれが生じ難いのにも関わらず、再剥離が容易という効果を見出した。 According to the present invention, when the re-peelable water-based pressure sensitive adhesive is processed into a pressure sensitive adhesive sheet, the combination of monomers used for the synthesis of the acrylic polymer and the specific phosphate ester By including a specific amount of the compound, the phosphate ester compound having poor compatibility with the acrylic polymer is likely to move to the interface with the pressure-sensitive adhesive layer, so that the cohesive force of the pressure-sensitive adhesive layer is increased in a high-temperature atmosphere. Since the decrease can be suppressed, good adhesive force can be obtained. Further, the present inventors have found that the phosphoric acid ester compound is easy to be re-peeled even though the pressure-sensitive adhesive sheet hardly floats or peels off in a high-temperature atmosphere because it easily exists at the interface.
本発明により、被着体に長期間貼り付けた後に接着力の変化が少なく、被着体に貼り付けた後に高温雰囲気にて置かれた後の再剥離性が良好でありながら、浮き剥がれが生じ難い耐久性を有する感圧式接着テープを製造できる再剥離型水性感圧式接着剤を提供できた。 According to the present invention, there is little change in adhesive force after being applied to an adherend for a long period of time, and the removability after being placed in a high-temperature atmosphere after being attached to an adherend is good, but it does not float off. It was possible to provide a re-peelable water-based pressure sensitive adhesive capable of producing a pressure sensitive adhesive tape having durability that hardly occurs.
本発明の再剥離型水性感圧式接着剤は、炭素数2〜12のアルキル基を含有する(メタ)アクリル酸アルキルエステル50〜99重量%、カルボキシル基含有不飽和単量体0.5〜3重量%を含むエチレン性不飽和単量体を乳化重合して得られるアクリル系重合体のエマルジョン、および炭素数が8〜14のアルキル基を有するリン酸エステル系化合物を含み、前記リン酸エステル系化合物が、アルキレンオキサイド構造を有さず、かつアルキル基が分岐構造を有している。また、アクリル系重合体100重量部に対してリン酸エステル系化合物を0.5〜5重量部含む。前記再剥離型水性感圧式接着剤は、塗工・乾燥することで、形成した感圧式接着層と基材を有する感圧式接着シートとして使用することが好ましい。本発明の再剥離型水性感圧式接着剤は接着力、耐熱性および再剥離性が優れる。なお本発明で「シート」、「テープ」および「ラベル」は同義語である。また耐熱性とは80℃雰囲気での浮き剥がれが生じ難い性状を意味する。
The re-peelable water-based pressure-sensitive adhesive of the present invention has 50 to 99 % by weight of a (meth) acrylic acid alkyl ester containing an alkyl group having 2 to 12 carbon atoms and 0.5 to 3 carboxyl group-containing unsaturated monomer. emulsion of ethylenically unsaturated monomers emulsion polymerization obtained by acrylic polymer, and carbon atoms saw containing a phosphoric ester compound having 8 to 14 alkyl groups containing by weight%, the phosphoric acid ester The system compound does not have an alkylene oxide structure, and the alkyl group has a branched structure . Moreover, 0.5-5 weight part of phosphate ester compounds are contained with respect to 100 weight part of acrylic polymers. The re-peelable water-based pressure-sensitive adhesive is preferably used as a pressure-sensitive adhesive sheet having a formed pressure-sensitive adhesive layer and a substrate by coating and drying. The re-peelable water pressure-sensitive adhesive of the present invention is excellent in adhesive strength, heat resistance and re-peelability. In the present invention, “sheet”, “tape” and “label” are synonymous. Further, the heat resistance means a property that hardly causes floating in an 80 ° C. atmosphere .
前記アクリル系重合体は、炭素数2〜12のアルキル基を含有する(メタ)アクリル酸アルキルエステル50〜99.9重量%、カルボキシル基含有不飽和単量体0.5〜3重量%を含むエチレン性不飽和単量体を乳化重合して得る。なお、(メタ)は、例えばメチルアクリレートおよびメチルメタクリレートとのように2つの化合物を含むことを意味する。 The acrylic polymer contains 50 to 99.9% by weight of a (meth) acrylic acid alkyl ester containing an alkyl group having 2 to 12 carbon atoms and 0.5 to 3% by weight of a carboxyl group-containing unsaturated monomer. Obtained by emulsion polymerization of an ethylenically unsaturated monomer. In addition, (meth) means containing two compounds like methyl acrylate and methyl methacrylate, for example.
前記(メタ)アクリル酸アルキルエステルは、全不飽和単量体中に50〜99.9重量%含むことが好ましく、70〜99重量%がより好ましい。50〜99.9重量%含むことで接着力、耐熱性および再剥離性を得易くなる。 The (meth) acrylic acid alkyl ester is preferably contained in the total unsaturated monomer in an amount of 50 to 99.9% by weight, and more preferably 70 to 99% by weight. Inclusion of 50 to 99.9% by weight facilitates obtaining adhesive strength, heat resistance and removability.
前記(メタ)アクリル酸アルキルエステルは、具体的には、例えばエチル(メタ)アクリレート、プロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、iso−ブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、n−オクチル(メタ)アクリレート、iso−オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート、iso−ノニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート等が挙げられる。 Specific examples of the (meth) acrylic acid alkyl ester include ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and 2-ethylhexyl (meth). Examples include acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, iso-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate.
なお、前記(メタ)アクリル酸アルキルエステルは、アルキル基の水素原子の一部を、アルコキシ基などによって置換することも好ましい。具体的には2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート等が挙げられる。 In the (meth) acrylic acid alkyl ester, it is also preferable to substitute a part of the hydrogen atom of the alkyl group with an alkoxy group. Specific examples include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and the like.
前記カルボキシル基含有不飽和単量体は、全不飽和単量体中に0.5〜3重量%含むことが好ましく、1.0〜2.5重量%がより好ましい。0.5〜3重量%含むことで接着力、耐熱性および再剥離性を得易くなる。 The carboxyl group-containing unsaturated monomer is preferably included in the total unsaturated monomers in an amount of 0.5 to 3% by weight, more preferably 1.0 to 2.5% by weight. Inclusion of 0.5 to 3% by weight makes it easy to obtain adhesive strength, heat resistance and removability.
前記カルボキシル基含有不飽和単量体は、カルボキシル基以外にも酸無水物基含有化合物を含む。 The carboxyl group-containing unsaturated monomer includes an acid anhydride group-containing compound in addition to the carboxyl group.
前記カルボキシル基含有不飽和単量体は、具体的には、例えば(メタ)アクリル酸、β−カルボキシエチルアクリレート、イタコン酸、クロトン酸、フマル酸、無水フマル酸、マレイン酸、無水マレイン酸、マレイン酸ブチル等があげられる。 Specific examples of the carboxyl group-containing unsaturated monomer include (meth) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, maleic acid. Examples thereof include butyl acid.
本発明でアクリル系重合体の合成に使用できる他の不飽和単量体は、具体的には、例えばアミノメチル(メタ)アクリレート、ジメチルアミノメチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、(メタ)アクリルアミド、ダイアセトン(メタ)アクリルアミド、(メタ)アクリロニトリル、N−シクロヘキシルマレイミド、N−イソプロピルマレイミド、N−ラウリルマレイミド、N−フェニルマレイミド、N−メチルイタコンイミド、N−エチルイタコンイミド、N−ブチルイタコンイミド、N−オクチルイタコンイミド、N−2−エチルヘキシルイタコンイミド、N−シクロヘキシルイタコンイミド、N−ラウリルイタコンイミド、N−(メタ)アクリロイルオキシメチレンスクシンイミド、N−(メタ)アクリロイル−6−オキシヘキサメチレンスクシンイミド、N−(メタ)アクリロイル−8−オキシオクタメチレンスクシンイミド、グリシジル(メタ)アクリレート、酢酸ビニル、スチレン、メチルスチレン、ビニルトルエンなどが挙げられる。なお、ポリエチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールアジペートジ(メタ)アクリレートなどの公知の多官能(メタ)アクリレート化合物は、(メタ)アクリル酸アルキルエステル単量)およびカルボキシル基含有不飽和単量体以外の単量体に含まれる。 Specific examples of other unsaturated monomers that can be used in the synthesis of the acrylic polymer in the present invention include aminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Dimethylaminopropyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, (meth) acrylonitrile, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, N-methylitaconimide N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl leuconconimide, N-lauryl itaconimide, N- (meth) acryloylimide Simethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyoctamethylenesuccinimide, glycidyl (meth) acrylate, vinyl acetate, styrene, methylstyrene, vinyltoluene, etc. Can be mentioned. In addition, known polyfunctional (meth) acrylate compounds such as polyethylene glycol di (meth) acrylate and neopentyl glycol adipate di (meth) acrylate are (meth) acrylic acid alkyl ester single amount) and carboxyl group-containing unsaturated single amount. Included in monomers other than the body.
前記他の不飽和単量体のなかでもアセトアセトキシエチル(メタ)アクリレートは、再剥離性と耐熱性をさらに向上できるため好ましい。その使用量はアクリル系重合体を構成する不飽和単量体の0.01重量部以上1重量%未満であり、より好ましくは0.05重量部以上0.5重量部未満である。 Among the other unsaturated monomers, acetoacetoxyethyl (meth) acrylate is preferable because it can further improve removability and heat resistance. The amount used is 0.01 part by weight or more and less than 1 part by weight of the unsaturated monomer constituting the acrylic polymer, and more preferably 0.05 part by weight or more and less than 0.5 part by weight.
本発明でアクリル系重合体のエマルジョンは、上記の不飽和単量体を乳化重合することで得ることができる。乳化重合で使用する乳化剤は、アニオン性乳化剤およびノニオン性乳化剤を単独または、2種類以上使用することができる。 In the present invention, the acrylic polymer emulsion can be obtained by emulsion polymerization of the unsaturated monomer. As the emulsifier used in the emulsion polymerization, an anionic emulsifier and a nonionic emulsifier can be used alone or in combination of two or more.
前記アニオン系乳化剤は、ノニルフェニル骨格の旭電化工業株式会社製「アデカリアソープSE−10N」、第一工業製薬株式会社製「アクアロンHS−10、HS−20」等、長鎖アルキル骨格の第一工業製薬株式会社製「アクアロンKH−05、KH−10」、旭電化工業株式会社製「アデカリアソープSR−10N」等、燐酸エステル骨格の日本化薬株式会社製「KAYARAD」、ステアリン酸ナトリウム等の高級脂肪酸塩類、ドデシルベンゼンスルホン酸ナトリウム等のアルキルアリールスルホン酸塩類、ラウリル硫酸ナトリウム等のアルキル硫酸エステル塩類、ポリオキシエチレンラウリルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸エステル塩類、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類等が例示できる。 The anionic emulsifier is a long chain alkyl skeleton such as “Adekaria Soap SE-10N” manufactured by Asahi Denka Kogyo Co., Ltd., “Aqualon HS-10, HS-20” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. “AQUALON KH-05, KH-10” manufactured by Ichi Kogyo Seiyaku Co., Ltd., “Adekaria Soap SR-10N” manufactured by Asahi Denka Kogyo Co., Ltd., “KAYARAD” manufactured by Nippon Kayaku Co., Ltd. with a phosphate ester skeleton, sodium stearate Higher alkyl fatty acid salts such as sodium dodecylbenzene sulfonate, alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts such as sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene Nonylphenyl ether sulfate Polyoxyethylene alkylaryl ether sulfuric acid ester salts such as potassium can be exemplified.
前記ノニオン系乳化剤は、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ソルビタン高級脂肪酸エステル類、グリセリン高級脂肪酸エステル類等の分子末端あるいは中間部に不飽和二重結合を有し、単量体と共重合するものであり、旭電化工業株式会社製「アデカリアソープNE−10」、第一工業製薬株式会社製「アクアロンRN−10、RN−20、RN−50」、日本乳化剤株式会社製「アントックスNA−16」、ポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類、ソルビタンモノステアレート等のソルビタン高級脂肪酸エステル類、オレイン酸モノグリセライド等のグリセリン高級脂肪酸エステル類等が例示できる。 The nonionic emulsifier has an unsaturated double bond at the molecular terminal or middle part of polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, sorbitan higher fatty acid esters, glycerin higher fatty acid esters, etc. Asahi Denka Kogyo Co., Ltd. “Adekaria Soap NE-10”, Daiichi Kogyo Seiyaku Co., Ltd. “Aqualon RN-10, RN-20, RN-50”, Japan Emulsifier Stock "Antox NA-16" manufactured by the company, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether, and higher sorbitan fatty acid esters such as sorbitan monostearate Oleic acid monog Glycerine higher fatty acid esters such as celite and the like.
前記乳化剤のなかでも、良好な重合安定性が得られるためアニオン系乳化剤を使用するのが好ましく、特にポリオキシエチレンアルキルエーテル硫酸エステル塩類がより好ましく、ポリオキシエチレンジスチリルエーテルサルフェートアンモニウム塩がさらに好ましい。上記乳化剤の使用量は乳化重合に使用する全単量体100重量部に対して0.5〜3重量部使用するのが好ましい。前記範囲で使用することで重合安定性と再剥離性をより向上できる。 Among the emulsifiers, it is preferable to use an anionic emulsifier because good polymerization stability can be obtained. Particularly, polyoxyethylene alkyl ether sulfate ester salts are more preferable, and polyoxyethylene distyryl ether sulfate ammonium salt is more preferable. . The amount of the emulsifier used is preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the total monomers used for the emulsion polymerization. By using in the said range, superposition | polymerization stability and removability can be improved more.
乳化重合に使用する重合開始剤は、特に制限されず、水溶性重合開始剤、油溶性重合開始剤の両者を使用できる。具体的には、例えばアルキルパーオキサイド、t−ブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、p−メタンヒドロパーオキサイド、ラウロイルパーオキサイド、3,5,5−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、t−ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、ジクロルベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ−t−ブチルパーオキサイド、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、3,3,5−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、ジ−イソブチルパーオキシジカーボネート、ジ−2−エチルヘキシルパーオキシジカーボネート、t−ブチルパーオキシイソブチレート等の有機過酸化物、2,2’−アゾビスイソブチロニトリル、ジメチル−2,2’−アゾビスイソブチレート、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2−メチルブチロニトリル)、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、4,4’−アゾビス−4−シアノバレリックアシッドのアンモニウム(アミン)塩、2,2’−アゾビス(2−メチルアミドオキシム)ジヒドロクロライド、2,2’−アゾビス(2−メチルブタンアミドオキシム)ジヒドロクロライドテトラヒドレート、2,2’−アゾビス{2−メチル−N−〔1,1−ビス(ヒドロキシメチル)−2−ヒドロキシエチル〕−プロピオンアミド}、2,2’−アゾビス〔2−メチル−N−(2−ヒドロキシエチル)−プロピオンアミド〕、各種レドックス系触媒(この場合酸化剤としては、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム、過酸化水素、t−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、キュメンハイドロパーオキサイド、p−メタンハイドロパーオキサイド等が、還元剤としては亜硫酸ナトリウム、酸性亜硫酸ナトリウム、ロンガリット、アスコルビン酸等が用いられる。)等が挙げられる。これらの中でも重合安定性に優れ、かつ耐熱着色性に優れる点で、過硫酸カリウム、過硫酸ナトリウム、レドックス系触媒(酸化剤:過硫酸カリウム、過硫酸ナトリウム、還元剤:亜硫酸ナトリウム、酸性亜硫酸ナトリウム)等が好適である。 The polymerization initiator used for emulsion polymerization is not particularly limited, and both a water-soluble polymerization initiator and an oil-soluble polymerization initiator can be used. Specifically, for example, alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-Butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl Cyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butylperoxyisocarbonate Organic peroxides such as citrate, 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, ammonium (amine) salt of 4,4′-azobis-4-cyanovaleric acid, 2 , 2′-azobis (2-methylamidooxime) dihydrochloride, 2,2′-azobis (2-methylbutanamidoxime) dihydrochloride tetrahydrate, 2,2′-azobis {2-methyl-N- [1 , 1-bis (hydroxymethyl) -2-hydroxyethyl] -propionamide}, 2,2′-azobis [2-methyl-N- (2-H Roxyethyl) -propionamide], various redox catalysts (in this case, as an oxidizing agent, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-methane hydroperoxide and the like, and as a reducing agent, sodium sulfite, acidic sodium sulfite, Rongalite, ascorbic acid, etc. are used. Of these, potassium persulfate, sodium persulfate, redox catalyst (oxidizing agent: potassium persulfate, sodium persulfate, reducing agent: sodium sulfite, acidic sodium sulfite are excellent in polymerization stability and heat-resistant colorability. And the like are preferred.
重合開始剤の使用量は、乳化重合に使用する全単量体100重量部に対して、0.01〜2重量部が好ましく、0.03〜1.0重量部がより好ましい。0.01〜2重量部使用することで、共重合性と再剥離性をより向上できる。 The amount of the polymerization initiator used is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1.0 part by weight, based on 100 parts by weight of all monomers used for emulsion polymerization. By using 0.01 to 2 parts by weight, copolymerizability and removability can be further improved.
本発明では乳化重合の際、必要に応じてpHを調整するため、緩衝剤を使用できる。か前記緩衝剤としては、pH緩衝作用を有するものであれば特に制限されないが、具体的には、炭酸水素ナトリウム、炭酸水素カリウム、リン酸一ナトリウム、リン酸一カリウム、リン酸二ナトリウム、リン酸三ナトリウム、酢酸ナトリウム、酢酸アンモニウム、蟻酸ナトリウム、ギ酸アンモニウム、クエン酸三ナトリウム等が挙げられる。前記緩衝剤は、乳化重合に使用する全単量体100部に対して、5重量部未満使用することが好ましく、3重量部未満がより好ましい。 In the present invention, a buffer may be used to adjust the pH as necessary during emulsion polymerization. The buffering agent is not particularly limited as long as it has a pH buffering action. Specifically, sodium bicarbonate, potassium bicarbonate, monosodium phosphate, monopotassium phosphate, disodium phosphate, phosphorus Examples include trisodium acid, sodium acetate, ammonium acetate, sodium formate, ammonium formate, and trisodium citrate. The buffering agent is preferably used in an amount of less than 5 parts by weight, more preferably less than 3 parts by weight, based on 100 parts of all monomers used for emulsion polymerization.
本発明で乳化重合は、例えば単量体をエマルションに調製してから合成することが好ましい。乳化重合の方法は、単量体のエマルションの全量を予め反応容器中に仕込んでおいてもよく、その一部を反応容器中に仕込んでおき、残りを分割添加あるいは滴下してもよい。または、その全量を分割添加あるいは滴下しても良い。 In the present invention, the emulsion polymerization is preferably synthesized after, for example, preparing a monomer into an emulsion. In the emulsion polymerization method, the whole amount of the monomer emulsion may be charged in the reaction vessel in advance, or a part thereof may be charged in the reaction vessel, and the remainder may be added in portions or added dropwise. Alternatively, the entire amount may be added in portions or added dropwise.
本発明では乳化重合の際、連鎖移動剤を使用してアクリル系重合体の分子量を適宜調整できる。具体的には、例えばメルカプタン系化合物、チオグリコール系化合物、βメルカプトプロピオン酸などのチオール系化合物などが好ましい。 In the present invention, the molecular weight of the acrylic polymer can be appropriately adjusted using a chain transfer agent during emulsion polymerization. Specifically, for example, thiol compounds such as mercaptan compounds, thioglycol compounds, and β-mercaptopropionic acid are preferable.
本発明の再剥離型水性感圧接着剤は、炭素数が8〜14のアルキル基を有するリン酸エステル系化合物を含む。前記リン酸エステル系化合物を含むことで凝集力および再剥離性が良好になる。その理由として前記リン酸エステル系化合物は、アクリル系重合体と相溶性が悪いため感圧式接着層との界面に移行しやすい傾向にあるため、高温雰囲気において、感圧式接着層の凝集力を低下させず、また過度に感圧式接着層と被着体を密着させないことから良好な接着力が得られる。さらに前記リン酸エステル系化合物は、前記界面に存在しやすいことで高温雰囲気において感圧式接着シートに浮きや剥がれが生じ難いのにも関わらず、再剥離が容易という効果が得られる。 The re-peelable water-based pressure-sensitive adhesive of the present invention includes a phosphate ester compound having an alkyl group having 8 to 14 carbon atoms. By including the phosphate compound, the cohesive force and removability are improved. The reason for this is that the phosphate ester compound has a tendency to easily move to the interface with the pressure-sensitive adhesive layer because of its poor compatibility with the acrylic polymer. In addition, since the pressure-sensitive adhesive layer and the adherend are not brought into close contact with each other, a good adhesive force can be obtained. Further, since the phosphoric acid ester compound is likely to be present at the interface, it is easy to re-peel despite the fact that the pressure-sensitive adhesive sheet is unlikely to float or peel off in a high temperature atmosphere.
前記リン酸エステル系化合物は、アクリル系重合体100重量部に対して0.5〜5重量部使用することが好ましく、1〜3.5重量部がより好ましい。0.5〜5重量部使用することで凝集力および再剥離性を両立しやすくなる。 The phosphoric ester compound is preferably used in an amount of 0.5 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on 100 parts by weight of the acrylic polymer. By using 0.5 to 5 parts by weight, it becomes easy to achieve both cohesion and removability.
本発明において炭素数が8〜14のアルキル基を有するリン酸エステル系化合物は、具体的には、例えばとエチルヘキシルジフェニルフォスフェート、エチルヘキシルアシッドフォスフェート、ビス(2−エチルヘキシル)フォスフェート、イソデシルアシッドフォスフェート、トリデシルホスファイト、トリイソデシルアシッドフォスフェート、オレイルアシッドフォスフェートなどが挙げられる。 In the present invention, the phosphoric acid ester compound having an alkyl group having 8 to 14 carbon atoms specifically includes, for example, ethylhexyl diphenyl phosphate, ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, and isodecyl acid. Examples include phosphate, tridecyl phosphite, triisodecyl acid phosphate, oleyl acid phosphate, and the like.
また、前記リン酸エステル系化合物は、アルキレンオキサイド構造を有せず、かつアルキル基が分岐構造を有する化合物であることが好ましい。前記分岐構造により前記リン酸エステル系化合物は、再剥離性をより向上できる。このような化合物は、具体的には、例えばイソデシルアシッドフォスフェート、イソトリデシルアシッドフォスフェート等が好ましい。またこれら化合物は、乳化剤として機能しない。 Moreover, it is preferable that the said phosphate ester type compound is a compound which does not have an alkylene oxide structure and an alkyl group has a branched structure. Due to the branched structure, the phosphoric ester compound can further improve the removability. Specifically, such a compound is preferably, for example, isodecyl acid phosphate, isotridecyl acid phosphate, or the like. These compounds do not function as an emulsifier.
本発明で上記リン酸エステル系化合物を再剥離型水性感圧接着剤に導入する方法は以下に方法を例示できる。(1)アクリル系重合体を含むエマルションを合成した後、添加する手法。(2)リン酸エステル系化合物の存在下にアクリル系重合体を合成する手法。これらの方法の中でも(2)の方法は、再剥離性をより向上できるため好ましい。また(2)の具体的方法は、前記リン酸エステル系化合物と全単量体を配合した上で、単量体のエマルションを製造してから乳化重合することが好ましい Examples of the method for introducing the phosphate ester-based compound into the re-peelable water-based pressure-sensitive adhesive in the present invention include the following methods. (1) A method in which an emulsion containing an acrylic polymer is synthesized and then added. (2) A method of synthesizing an acrylic polymer in the presence of a phosphate ester compound. Among these methods, the method (2) is preferable because the removability can be further improved. Moreover, the specific method of (2) is preferably an emulsion polymerization after the emulsion of the monomer is produced after the phosphoric ester compound and all the monomers are blended.
本発明の再剥離型水性感圧式接着剤は、金属架橋剤を含むことが好ましい。前記金属架橋剤によって再剥離性がより向上し、さらに高温雰囲気で経時後に被着体に感圧式接着剤に由来する汚染が生じにくくなる。 The re-peelable water-based pressure sensitive adhesive of the present invention preferably contains a metal crosslinking agent. The releasability is further improved by the metal crosslinking agent, and further, contamination due to the pressure-sensitive adhesive is less likely to occur on the adherend after aging in a high temperature atmosphere.
前記金属架橋剤は、チタンキレート化合物、アルミキレート化合物、ジルコニウムキレート化合物、酸化亜鉛等が挙げられる。 Examples of the metal crosslinking agent include titanium chelate compounds, aluminum chelate compounds, zirconium chelate compounds, and zinc oxide.
前記金属架橋剤は、アクリル系重合体100重量部に対して、1重量部未満配合することが好ましい。前記配合により再剥離性がより向上する。 The metal crosslinking agent is preferably blended in an amount of less than 1 part by weight with respect to 100 parts by weight of the acrylic polymer. The re-peelability is further improved by the blending.
本発明の再剥離型水性感圧式接着剤は、前記金属架橋剤以外の架橋剤を併用することができる。具体的にはアジリジン系化合物、エポキシ系化合物、イソシアネート系化合物
カルボジイミド系化合物、ヒドラジド系化合物等が挙げられる。
The re-peelable water-based pressure sensitive adhesive of the present invention can be used in combination with a crosslinking agent other than the metal crosslinking agent. Specific examples include an aziridine compound, an epoxy compound, an isocyanate compound, a carbodiimide compound, and a hydrazide compound.
本発明の再剥離型水性感圧式接着剤は、上記以外にも任意成分としてレベリング剤、防腐剤、消泡剤、増粘剤、顔料分散体などの添加剤を添加する事が出来る。 In addition to the above, the re-peelable water-based pressure sensitive adhesive of the present invention may contain additives such as leveling agents, preservatives, antifoaming agents, thickeners, and pigment dispersions as optional components.
本発明の感圧式接着シートは、再剥離型水性感圧式接着剤から形成した感圧式接着層を有する。具体的な製造方法を例示すると(1)剥離性シートに再剥離型水性感圧式接着剤を塗工、乾燥することで感圧式接着層を形成し、さらに基材を貼り付ける。また(2)基材に再剥離型水性感圧式接着剤を工、乾燥することで感圧式接着層を形成し、さらに剥離性シートを貼り付ける。 The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer formed from a re-peelable aqueous pressure-sensitive adhesive. Specific examples of the production method are as follows: (1) A re-peelable water-type pressure-sensitive adhesive is applied to a peelable sheet and dried to form a pressure-sensitive adhesive layer, and a substrate is further attached. Further, (2) a pressure-sensitive adhesive layer is formed by applying a re-peelable water-based pressure-sensitive adhesive to the substrate and drying it, and further a peelable sheet is attached.
前記塗工方法は、例えばマイヤーバー、アプリケーター、刷毛、スプレー、ローラー、グラビアコーター、ダイコーター、リップコーター、コンマコーター、ナイフコーター、リバースコ−ター、スピンコーター等公知の方法が挙げられる。乾燥方法には特に制限はなく、熱風乾燥、赤外線や減圧法等が使用できる。乾燥温度は通常60〜180℃程度が好ましい。 Examples of the coating method include known methods such as Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, and spin coater. There is no restriction | limiting in particular in a drying method, Hot air drying, infrared rays, a pressure reduction method, etc. can be used. The drying temperature is usually preferably about 60 to 180 ° C.
前記感圧式接着層の厚さは、一般的に5μm〜100μmが好ましく、10μm〜50μmがより好ましい。 The thickness of the pressure-sensitive adhesive layer is generally preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.
本発明で基材は、紙、セロハン、プラスチックシート、ゴム、発泡体、布帛、ゴムびき布、樹脂含浸布、ガラス板、金属板、木材、偏光板などの光学フィルム等の板材またはシートが挙げられる。前記基材は、単独または積層体であっても良い。また、前記基材は、裏面(感圧式接着層を直接貼り合わせた面の反対面)に剥離処理、または帯電防止処理をすることができる。また前記基材は、公知のアンカー剤で塗工処理してもよい。 In the present invention, the base material is a plate material or sheet such as paper, cellophane, plastic sheet, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plate, metal plate, wood, polarizing plate, etc. It is done. The substrate may be a single body or a laminate. Moreover, the said base material can perform a peeling process or an antistatic process in the back surface (opposite surface which bonded the pressure-sensitive-type adhesive layer directly). The base material may be coated with a known anchor agent.
また本発明の「感圧式接着シート」が使用される被着体としては特に限定されず、金属、ガラス、プラスチック、ゴム、木材、塗料塗布面など広く適応される。 Further, the adherend on which the “pressure-sensitive adhesive sheet” of the present invention is used is not particularly limited, and can be widely applied to metals, glass, plastics, rubber, wood, paint coating surfaces, and the like.
また本発明の感圧式接着性シートの用途は特に限定されないが、各種ラベル用、マスキングテープ用途やプロテクトフィルム用途等に好適に使用できる。 The use of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but can be suitably used for various labels, masking tapes, protect films, and the like.
次に、実施例を示して本発明を更に詳細に説明するが、本発明はこれらによって限定されるものではない。尚、以下の説明において、部および%とあるのは、それぞれ重量部および重量%を意味する。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following description, parts and% mean parts by weight and% by weight, respectively.
(合成例1)
2−エチルヘキシルアクリレート94.9部、メチルメタクリレート3.0部、アクリル酸2.0部、アセトアセトキシエチルメタクリレート 0.1部、リン酸エステル化合物として大八化学工業(株)製「AP−10」(イソデシルアシッドフォスフェート)を2.7部添加し溶解した。さらにアニオン性乳化剤として第一工業製薬(株)製「ハイテノール NF−08」1.75部を脱イオン水7.0部に溶解したものを加え、さらに脱イオン水215部を加えて攪拌し乳化物を得た。これを滴下ロートに入れた。
撹拌機、冷却管、温度計および上記滴下ロートを取り付けた4つ口フラスコに、脱イオン水を425部、上記乳化物のうちの1.0部を仕込み、フラスコ内部を窒素ガスで置換し、撹拌しながら内温を70℃まで昇温した。10%過硫酸アンモニウム水溶液を30部、1%メタ重亜硫酸ナトリウム水溶液を3部添加した。10分後、上記滴下ロートから上記乳化物の残りを滴下開始し、これと同時に1%メタ重亜硫酸ナトリウム水溶液27部をそれぞれ滴下開始した。内温を70℃に保ったまま、上記乳化物および1%メタ重亜硫酸ナトリウム水溶液を210分かけて滴下した。さらに70℃で1時間反応を継続した後、内温を65℃に冷却し、日本油脂(株)製「パーブチルH−69」の10%水溶液0.1部、扶桑化学工業(株)製「エルビットN」の10%水溶液0.1部をそれぞれ10分おきに3回添加し、さらに60分反応を継続した。その後冷却し、30℃で25%アンモニア水を添加して中和することで不揮発分55%、pH7.5のアクリル系重合体のエマルションを得た。
(Synthesis Example 1)
“AP-10” manufactured by Daihachi Chemical Industry Co., Ltd. as 2-ethylhexyl acrylate 94.9 parts, methyl methacrylate 3.0 parts, acrylic acid 2.0 parts, acetoacetoxyethyl methacrylate 0.1 part, and phosphate ester compound 2.7 parts of (isodecyl acid phosphate) was added and dissolved. Further, 1.75 parts of “Haitenol NF-08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as an anionic emulsifier was added to 7.0 parts of deionized water, and 215 parts of deionized water was further added and stirred. An emulsion was obtained. This was placed in a dropping funnel.
A four-necked flask equipped with a stirrer, a condenser, a thermometer and the dropping funnel was charged with 425 parts of deionized water and 1.0 part of the emulsion, and the inside of the flask was replaced with nitrogen gas. The internal temperature was raised to 70 ° C. while stirring. 30 parts of 10% aqueous ammonium persulfate solution and 3 parts of 1% aqueous sodium metabisulfite solution were added. Ten minutes later, the dropping of the rest of the emulsion was started from the dropping funnel, and at the same time, 27 parts of a 1% sodium metabisulfite aqueous solution was started to drop. While maintaining the internal temperature at 70 ° C., the above emulsion and 1% aqueous sodium metabisulfite solution were added dropwise over 210 minutes. Furthermore, after continuing reaction at 70 degreeC for 1 hour, internal temperature was cooled to 65 degreeC, 0.1 part of 10% aqueous solution of "Perbutyl H-69" made by NOF Corporation, Fuso Chemical Industries Co., Ltd. " 0.1 part of a 10% aqueous solution of “Erbit N” was added three times every 10 minutes, and the reaction was continued for another 60 minutes. Thereafter, the mixture was cooled and neutralized by adding 25% aqueous ammonia at 30 ° C. to obtain an acrylic polymer emulsion having a nonvolatile content of 55% and a pH of 7.5.
表1に乳化重合に使用した不飽和単量体と、リン酸エステル化合物を重量比を示す。 Table 1 shows the weight ratio of the unsaturated monomer used in the emulsion polymerization and the phosphate ester compound.
(合成例2〜3、比較合成例1〜6)
単量体、リン酸エステル(B)、乳化剤を表1に記載した組成へ変更した以外は、合成例1と同様に重合を行いアクリル系共重合体を得た。
(Synthesis Examples 2-3, Comparative Synthesis Examples 1-6)
Polymerization was performed in the same manner as in Synthesis Example 1 except that the monomer, phosphate ester (B), and emulsifier were changed to the compositions shown in Table 1, to obtain an acrylic copolymer.
(合成例4)
2−エチルヘキシルアクリレート94.9部、メチルメタクリレート3.0部、アクリル酸2.0部、アセトアセトキシエチルメタクリレート 0.1部、さらにアニオン性乳化剤として第一工業製薬(株)製「ハイテノール NF−08」1.75部を脱イオン水7.0部に溶解したものを加え、さらに脱イオン水215部を加えて攪拌し乳化物を得た。これを滴下ロートに入れた。
撹拌機、冷却管、温度計および上記滴下ロートを取り付けた4つ口フラスコに、脱イオン水を425部、上記乳化物の1.0部を仕込み、フラスコ内部を窒素ガスで置換し、撹拌しながら内温を70℃まで昇温した。10%過硫酸アンモニウム水溶液を30部、1%メタ重亜硫酸ナトリウム水溶液を3部添加した。10分後、上記滴下ロートから上記乳化物の残を滴下開始し、同時に1%メタ重亜硫酸ナトリウム水溶液 27部をそれぞれ滴下開始した。内温を70℃に保ったまま、上記乳化物および1%メタ重亜硫酸ナトリウム水溶液を210分かけて滴下した。さらに70℃で1時間反応を継続した後、内温を65℃に冷却し、日本油脂(株)製「パーブチルH−69」の10%水溶液0.1部、扶桑化学工業(株)製「エルビットN」の10%水溶液0.1部をそれぞれ10分おきに3回添加し、さらに60分反応を継続した。さらにリン酸エステル化合物として大八化学工業(株)製「AP−10」(イソデシルアシッドフォスフェート)を2.7部添加した。その後冷却し、30℃で25%アンモニア水を添加して中和することで不揮発分55%、pH7.5のアクリル系重合体のエマルションを得た。
(Synthesis Example 4)
94.9 parts of 2-ethylhexyl acrylate, 3.0 parts of methyl methacrylate, 2.0 parts of acrylic acid, 0.1 part of acetoacetoxyethyl methacrylate, and “Hitenol NF-” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as an anionic emulsifier 08 "1.75 parts dissolved in 7.0 parts of deionized water was added, and further 215 parts of deionized water was added and stirred to obtain an emulsion. This was placed in a dropping funnel.
A four-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 425 parts of deionized water and 1.0 part of the above emulsion, and the inside of the flask was replaced with nitrogen gas and stirred. The internal temperature was raised to 70 ° C. 30 parts of 10% aqueous ammonium persulfate solution and 3 parts of 1% aqueous sodium metabisulfite solution were added. Ten minutes later, dropping of the residue of the emulsion was started from the dropping funnel, and at the same time, 27 parts of 1% aqueous sodium metabisulfite solution was added dropwise. While maintaining the internal temperature at 70 ° C., the above emulsion and 1% aqueous sodium metabisulfite solution were added dropwise over 210 minutes. Furthermore, after continuing reaction at 70 degreeC for 1 hour, internal temperature was cooled to 65 degreeC, 0.1 part of 10% aqueous solution of "Perbutyl H-69" made by NOF Corporation, Fuso Chemical Industries Co., Ltd. " 0.1 part of a 10% aqueous solution of “Erbit N” was added three times every 10 minutes, and the reaction was continued for another 60 minutes. Further, 2.7 parts of “AP-10” (isodecyl acid phosphate) manufactured by Daihachi Chemical Industry Co., Ltd. was added as a phosphate ester compound. Thereafter, the mixture was cooled and neutralized by adding 25% aqueous ammonia at 30 ° C. to obtain an acrylic polymer emulsion having a nonvolatile content of 55% and a pH of 7.5.
(合成例5)
合成例1の「AP−10」を東邦化学工業(株)製 フォスファノール「RS−710」に置き換えた以外は、同様に合成を行い不揮発分55%、pH7.5のアクリル系重合体のエマルションを得た。
(Synthesis Example 5)
Synthesis was performed in the same manner except that “AP-10” in Synthesis Example 1 was replaced with phosphanol “RS-710” manufactured by Toho Chemical Industry Co., Ltd. An acrylic polymer having a nonvolatile content of 55% and a pH of 7.5 An emulsion was obtained.
(比較合成例7)
2−エチルヘキシルアクリレート91.8部、メチルメタクリレート2.3部、アクリル酸3.5部、酢酸ビニル2.4部、さらにアニオン性乳化剤として花王(株)製「エマール10」3.5部、2.5%過硫酸カリウム水溶液 0.3部、クエン酸ナトリウム 0.02部さらに脱イオン水28.2部を加えて攪拌し乳化物を得、これを滴下ロートに入れた。撹拌機、冷却管、温度計および上記滴下ロートを取り付けた4つ口フラスコに、脱イオン水を40部、フラスコ内部を窒素ガスで置換し、撹拌しながら内温を70℃まで昇温した。2.5%過硫酸アンモニウム水溶液を0.3部、2.5%メタ重亜硫酸ナトリウム水溶液を1.0部添加した。10分後内温を70℃に保ったまま、上記滴下ロートから上記乳化物を3時間かけて滴下した。また上記乳化物の滴下中には2.5%メタ重亜硫酸ナトリウム水溶液0.2部を30分おきに4回添加した。滴下終了後さらに2時間反応行い、さらにリン酸エステル化合物としてオルトリン酸を0.04部添加した。その後冷却し、30℃で25%アンモニア水を添加して中和することで不揮発分55%、pH7.5のアクリル系重合体のエマルションを得た。
(Comparative Synthesis Example 7)
91.8 parts of 2-ethylhexyl acrylate, 2.3 parts of methyl methacrylate, 3.5 parts of acrylic acid, 2.4 parts of vinyl acetate, and 3.5 parts of “Emar 10” manufactured by Kao Corporation as an anionic emulsifier 0.3% aqueous solution of potassium persulfate 0.3 part, 0.02 part of sodium citrate and 28.2 parts of deionized water were added and stirred to obtain an emulsion, which was placed in a dropping funnel. In a four-necked flask equipped with a stirrer, a condenser, a thermometer and the dropping funnel, 40 parts of deionized water and the inside of the flask were replaced with nitrogen gas, and the internal temperature was raised to 70 ° C. while stirring. 0.3 parts of a 2.5% aqueous ammonium persulfate solution and 1.0 parts of a 2.5% aqueous sodium metabisulfite solution were added. After 10 minutes, the emulsion was dropped from the dropping funnel over 3 hours while maintaining the internal temperature at 70 ° C. During the dropwise addition of the emulsion, 0.2 part of a 2.5% aqueous sodium metabisulfite solution was added four times every 30 minutes. After completion of the dropwise addition, the reaction was further continued for 2 hours, and 0.04 part of orthophosphoric acid was added as a phosphate ester compound. Thereafter, the mixture was cooled and neutralized by adding 25% aqueous ammonia at 30 ° C. to obtain an acrylic polymer emulsion having a nonvolatile content of 55% and a pH of 7.5.
(比較合成例8)
n−ブチルアクリレート83.0部、アクリル酸2.0部、ダイアセトンアクリルアミド 0.5部、メチルメタクリレート 14.5部、連鎖移動剤として1−ドデカンチオール0.05部、さらにアニオン性乳化剤として三洋化成工業(株)製、「エレミノールJS−2」3.16部、水41.4部を混合撹拌し乳化物を得、これを滴下ロートに入れた。
撹拌機、冷却管、温度計および上記滴下ロートを取り付けた4つ口フラスコに、脱イオン水を31.7部、上記「エレミノールJS−2」0.26部、酢酸ナトリウム3水和物
0.41部を仕込み、撹拌下75℃に昇温した後、上記乳化液の5%(7.23部)を加した。さらに、80℃に昇温した後、3%過硫酸カリウム水溶液を0.8部添加し、その後15分後に、上記乳化液の残り95%(137.38部)と3%過硫酸カリウム水溶液3.2部を混合した混合液を3.5時間かけて滴下した。滴下終了後、80℃に保持したまま2時間反応を継続した後、内温を65℃に冷却し、10%アンモニア水溶液2.4部を添加して中和した。その後、55℃まで冷却し、日本油脂(株)製「パーブチルH−69」10%水溶液0.5部と10%L−アスコルビン酸水溶液0.5部をそれぞれ添加し、15分間反応させた後、再度、日本油脂(株)製「パーブチルH−69」の10%水溶液0.5部と10%L−アスコルビン酸水溶液0.5部をそれぞれ添加し、15分間反応させた。その後、30℃まで冷却した後、10%アンモニア水溶液を使用して、pHを8.0に調整し、リン酸エステル系化合物としてブチルアシッドフォスフェート(大八化学工業(株)製「AP−4」)0.5部を添加してエマルジョンを得た。尚、このエマルションの乾燥塗膜をトルエンに20℃で24時間浸漬し乾燥したときの、浸漬前の塗膜重量に対する浸漬後の残存塗膜重量の割合は50%であった。尚、特許文献2記載算出方法から計算した共重合体のガラス転移温度は−37.2℃であった。
(Comparative Synthesis Example 8)
83.0 parts of n-butyl acrylate, 2.0 parts of acrylic acid, 0.5 part of diacetone acrylamide, 14.5 parts of methyl methacrylate, 0.05 part of 1-dodecanethiol as a chain transfer agent, and Sanyo as an anionic emulsifier 3.16 parts of “Eleminol JS-2” manufactured by Kasei Kogyo Co., Ltd. and 41.4 parts of water were mixed and stirred to obtain an emulsion, which was put into a dropping funnel.
In a four-necked flask equipped with a stirrer, a condenser, a thermometer, and the dropping funnel, 31.7 parts of deionized water, 0.26 parts of the above-mentioned “Eleminol JS-2”, sodium acetate trihydrate After 41 parts were charged and heated to 75 ° C. with stirring, 5% (7.23 parts) of the above emulsion was added. Further, after raising the temperature to 80 ° C., 0.8 part of 3% potassium persulfate aqueous solution was added, and then 15 minutes later, the remaining 95% (137.38 parts) of the above emulsion and 3% potassium persulfate
(実施例1)
合成例1で得られたアクリル系重合体のエマルション100部に対し、消泡剤として株式会社ADEKA製 アデカネートB−940を 0.1部、防腐剤としてユニオンケミカル製 ユニケムフレックスBN−202を0.05部、濡れ剤として 花王(株)製 ペレックスOT−Pを0.1部、金属架橋剤としてBASFジャパン社(製)Zinc Oxide Solution No.1(炭酸、アンモニウム、亜鉛塩 2:2:1の水溶液)0.5部を添加し、さらにアルカリ増粘剤で増粘し、再剥離型水性感圧式接着剤を得た。これをコンマコーターで剥離性シート上に乾燥塗膜量が25g/m2になるように塗工し、100℃の乾燥オーブンで120秒間乾燥させ、市販の上質紙とラミネートして巻き取り、感圧式接着シートを得、後述する試験方法で性能を評価し、その結果を表2に示した。
Example 1
For 100 parts of the acrylic polymer emulsion obtained in Synthesis Example 1, 0.1 part of ADEKAATE B-940 manufactured by ADEKA Co., Ltd. is used as an antifoaming agent, and 0 part of Unichem Flex BN-202 manufactured by Union Chemical is used as an antiseptic. .05 parts, 0.1 part of Perex OT-P manufactured by Kao Corporation as a wetting agent, and Zinc Oxide Solution No. 0.5 part of 1 (aqueous solution of carbonic acid, ammonium, zinc salt 2: 2: 1) was added, and further thickened with an alkali thickener to obtain a re-peelable aqueous pressure-sensitive adhesive. This was coated on a peelable sheet with a comma coater so that the dry coating amount was 25 g / m 2 , dried in a drying oven at 100 ° C. for 120 seconds, laminated with commercially available high-quality paper, and wound up. A pressure-type adhesive sheet was obtained, and its performance was evaluated by the test method described later. The results are shown in Table 2.
(実施例2〜6、比較例1〜8)
アクリル系重合体のエマルションと架橋剤を表2記載のように変更した以外は、実施例1と同様に水性感圧式接着剤を得、感圧式接着シートを作成した。
ただし、実施例4、6は参考例である。
(Examples 2-6, Comparative Examples 1-8)
An aqueous pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the acrylic polymer emulsion and the crosslinking agent were changed as shown in Table 2, and a pressure-sensitive adhesive sheet was prepared.
However, Examples 4 and 6 are reference examples.
表1の略称は下記の通りである。
EHA:2−エチルヘキシルアクリレート
BA:ブチルアクリレート
AA:アクリル酸
MMA:メチルメタクリレート
AAEM:アセトアセトキシエチルメタクリレート
VAc:酢酸ビニル
DAAM:ダイアセトンアクリルアミド
AP−10:イソデシルアシッドフォスフェート
JP−513:イソトリデシルアシッドフォスフェート
JP−310:トリデシルホスファイト
AP−4:ブチルアシッドフォスフェート
RS−710:ポリオキシエチレンアルキル(C12〜15)エーテルリン酸(含有量90%)
Abbreviations in Table 1 are as follows.
EHA: 2-ethylhexyl acrylate BA: butyl acrylate AA: acrylic acid MMA: methyl methacrylate AAEM: acetoacetoxyethyl methacrylate VAc: vinyl acetate DAAM: diacetone acrylamide AP-10: isodecyl acid phosphate JP-513: isotridecyl acid Phosphate JP-310: Tridecyl phosphite AP-4: Butyl acid phosphate RS-710: Polyoxyethylene alkyl (C12-15) ether phosphate (content 90%)
[試験方法]
(1)接着力
23℃50%RH環境下にて感圧式接着シートを長さ100mm×幅25mmの形状に試料を準備した上で剥離性シートを剥がし、表面を研磨したステンレス鋼板に貼付け、2kgロールで1往復して、圧着直後の接着力を測定した。また、圧着後に測定試料を60℃雰囲気下で78時間放置した後、さらに23℃雰囲気下で1時間放置し熱経時後の接着力を測定した。なお接着力の測定は剥離速度:300mm/分で剥離角180゜で行った。また、下記の式より接着力の上昇率を算出した。
接着力上昇率(%)=[(熱経時後の接着力)/(圧着直後の接着力)−1]×100
[Test method]
(1) Adhesive strength After preparing a sample of a pressure-sensitive adhesive sheet in a shape of 100 mm length x 25 mm width in an environment of 23 ° C. and 50% RH, the peelable sheet is peeled off, and the surface is affixed to a polished stainless steel plate, 2 kg One reciprocation with a roll was performed to measure the adhesive force immediately after the press bonding. In addition, after pressure bonding, the measurement sample was allowed to stand for 78 hours in a 60 ° C. atmosphere, and then further left for 1 hour in a 23 ° C. atmosphere to measure the adhesive strength after heat aging. The adhesive force was measured at a peeling speed of 300 mm / min and a peeling angle of 180 °. Also, the rate of increase in adhesive strength was calculated from the following formula.
Adhesive strength increase rate (%) = [(Adhesive strength after thermal aging) / (Adhesive strength immediately after pressing) -1] × 100
(2)再剥離性
23℃50%RH環境下にて感圧式接着シートを長さ100mm×幅25mmの形状に試料を準備した上で剥離性シートを剥がし、表面を研磨したステンレス鋼板に貼付け、2kgロールで1往復して圧着した。さらに120℃雰囲気下24時間放置後さらに23℃雰囲気下で1時間放置した後、300mm/分の速さで180゜方向に剥離し、被着体の汚染を目視で確認し下記の基準で評した。
○:被着体に汚染がほとんど確認できない。
△:被着体にわずかに汚染が認められるが、実用上問題ない。
×:被着体に顕著に汚染が認められ、実用上問題がある。
(2) Removability After preparing a sample of a pressure-sensitive adhesive sheet in a shape of length 100 mm × width 25 mm in a 23 ° C. and 50% RH environment, the peelable sheet is peeled off and attached to a stainless steel plate whose surface is polished, One reciprocation with a 2 kg roll was performed for pressure bonding. Furthermore, after being left for 24 hours in a 120 ° C atmosphere and further left for 1 hour in a 23 ° C atmosphere, it was peeled off in a 180 ° direction at a speed of 300 mm / min. did.
○: Almost no contamination was observed on the adherend.
Δ: Slight contamination is observed on the adherend, but there is no practical problem.
X: Contamination was recognized remarkably on the adherend, and there was a problem in practical use.
(3)耐久性
23℃50%RH環境下にて感圧式接着シートを長さ100mm×幅10mmの形状に試料を準備した上で剥離性シートを80mm分剥がした。前記感圧式接着シート2の露出した感圧式接着層の長さ80mm部分を、表面を研磨したステンレス鋼板1に貼付け、2kgロールで1往復圧着した。その後80℃雰囲気に30分間放置し、剥離性シートを完全に剥がした上で、感圧式接着層がステンレス鋼板に接していない20mm部分に図1の通り、ひもで50gの錘3を下げることで感圧式接着シートの90°方向に荷重4をかけて高温雰囲気(80℃)での耐久性を評価した。評価は10分間行い感圧式接着シートが剥離して落下した場合は、落下時間を記録した。また、感圧式接着シートが落下しない場合は、感圧式接着シートが当初ステンレス鋼板と接着した長さ80mm部分についてステンレス鋼板から剥離した長さを記録した。
(3) Durability In a 23 ° C. 50% RH environment, a pressure-sensitive adhesive sheet was prepared in a shape of 100 mm long × 10 mm wide, and then the peelable sheet was peeled by 80 mm. The exposed 80 mm portion of the pressure-sensitive adhesive layer of the pressure-
表2の記号は下記の通りである。
・架橋剤
A:BASFジャパン社(製)Zinc Oxide Solution No.1
B:デナコール EX−313(ナガセケミテックス(株)製エポキシ硬化剤)
C:アジピン酸ジヒドラジドの5%水溶液
The symbols in Table 2 are as follows.
-Crosslinking agent A: BASF Japan (made) Zinc Oxide Solution No. 1
B: Denacol EX-313 (epoxy curing agent manufactured by Nagase Chemitex Corp.)
C: 5% aqueous solution of adipic acid dihydrazide
表2の結果から本発明の再剥離型水性感圧式接着剤である実施例1〜6は貼付経時後の粘着力変化が小さく、再剥離性・耐久性を満足するものであった。一方、比較例1〜8の感圧式接着剤は、貼付経時後の粘着力変化、再剥離性・耐久性のいずれかが不良であり、すべての特性を満足できなかった。 From the results shown in Table 2, Examples 1 to 6, which are the re-peelable water-based pressure-sensitive adhesives of the present invention, had a small change in adhesive strength after the lapse of time and satisfied re-peelability and durability. On the other hand, the pressure-sensitive adhesives of Comparative Examples 1 to 8 were inferior in any of adhesive force change, removability and durability after pasting, and could not satisfy all the characteristics.
1:ステンレス鋼板
2:感圧式接着シート
3:50gの錘
4:荷重の方向
1: Stainless steel plate 2: Pressure sensitive adhesive sheet 3: Weight of 50 g 4: Direction of load
Claims (5)
前記リン酸エステル系化合物が、アルキレンオキサイド構造を有さず、かつアルキル基が分岐構造を有しており、
アクリル系重合体100重量部に対してリン酸エステル系化合物が0.5〜5重量部であることを特徴とする再剥離型水性感圧式接着剤。 Emulsified ethylenically unsaturated monomer containing 50 to 99 wt% of (meth) acrylic acid alkyl ester containing alkyl group having 2 to 12 carbon atoms and 0.5 to 3 wt% of carboxyl group-containing unsaturated monomer An acrylic polymer emulsion obtained by polymerization, and a phosphate ester compound having an alkyl group having 8 to 14 carbon atoms,
The phosphate ester compound does not have an alkylene oxide structure, and the alkyl group has a branched structure,
A re-peelable water-based pressure sensitive adhesive, wherein the phosphoric ester compound is 0.5 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer.
アクリル系重合体100重量部に対してリン酸エステル系化合物が0.5〜5重量部である再剥離型水性感圧式接着剤の製造方法。
It possesses an alkyl group with a carbon number of 8-14, and a branched structure, in the presence of a phosphoric ester compound having no alkylene oxide structure, containing an alkyl group having 2 to 12 carbon atoms (meth) acrylate A process for producing an emulsion of an acrylic polymer by emulsion polymerization of an ethylenically unsaturated monomer containing 50 to 99% by weight of an acid alkyl ester and 0.5 to 3% by weight of a carboxyl group-containing unsaturated monomer. seen including,
A method for producing a releasable water-based pressure-sensitive adhesive, wherein the phosphoric ester compound is 0.5 to 5 parts by weight with respect to 100 parts by weight of an acrylic polymer .
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