JPH06346038A - Aqueous re-stripping type pressure-sensitive adhesive - Google Patents
Aqueous re-stripping type pressure-sensitive adhesiveInfo
- Publication number
- JPH06346038A JPH06346038A JP29347593A JP29347593A JPH06346038A JP H06346038 A JPH06346038 A JP H06346038A JP 29347593 A JP29347593 A JP 29347593A JP 29347593 A JP29347593 A JP 29347593A JP H06346038 A JPH06346038 A JP H06346038A
- Authority
- JP
- Japan
- Prior art keywords
- group
- parts
- sensitive adhesive
- weight
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 66
- 239000000178 monomer Substances 0.000 claims abstract description 77
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- -1 methylol group Chemical group 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000002560 nitrile group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 18
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000877 Melamine resin Polymers 0.000 abstract description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229910001873 dinitrogen Inorganic materials 0.000 description 34
- 239000006185 dispersion Substances 0.000 description 27
- 239000012452 mother liquor Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 238000001816 cooling Methods 0.000 description 23
- 239000011521 glass Substances 0.000 description 22
- 239000003995 emulsifying agent Substances 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 19
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000007664 blowing Methods 0.000 description 11
- 229920006267 polyester film Polymers 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 208000028659 discharge Diseases 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 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 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 229940065472 octyl acrylate Drugs 0.000 description 7
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000006017 1-propenyl group Chemical group 0.000 description 3
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002347 octyl 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])[H] 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- JTXUVYOABGUBMX-UHFFFAOYSA-N didodecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCC JTXUVYOABGUBMX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- KFSQJVOLYQRELE-HWKANZROSA-N (e)-2-ethylbut-2-enoic acid Chemical compound CC\C(=C/C)C(O)=O KFSQJVOLYQRELE-HWKANZROSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-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
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101150000971 SUS3 gene Proteins 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere 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
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- KSDGSKVLUHKDAL-UHFFFAOYSA-L disodium;3-[2-carboxylatoethyl(dodecyl)amino]propanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCN(CCC([O-])=O)CCC([O-])=O KSDGSKVLUHKDAL-UHFFFAOYSA-L 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- YHGNXQAFNHCBTK-OWOJBTEDSA-N trans-3-hexenedioic acid Chemical compound OC(=O)C\C=C\CC(O)=O YHGNXQAFNHCBTK-OWOJBTEDSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、粘着テープ用、ラベル
用、シート用などの水系再剥離型感圧接着剤に関し、さ
らに詳しくは、自動車の焼付け塗装時など、高温下にお
いても使用でき再剥離性に優れている水系再剥離型感圧
接着剤に関する。TECHNICAL FIELD The present invention relates to a water-based re-peelable pressure-sensitive adhesive for adhesive tapes, labels, sheets, etc. More specifically, it can be used under high temperature such as during baking of automobiles and re-peelable. The present invention relates to a water-based removable pressure-sensitive adhesive having excellent properties.
【０００２】[0002]
【発明の技術的背景】再剥離型感圧接着剤は、例えば、
粘着テープ用、ラベル用、シート用などの粘着剤として
用いられており、このような粘着剤層が設けられた粘着
テープは、自動車の外装の焼付け塗装などの高温条件下
でもマスキング材として使用されることがある。BACKGROUND OF THE INVENTION Removable pressure-sensitive adhesives are, for example,
It is used as an adhesive for adhesive tapes, labels, sheets, etc.The adhesive tape provided with such an adhesive layer is used as a masking material even under high temperature conditions such as baking coating on the exterior of automobiles. Sometimes.
【０００３】このような再剥離型感圧接着剤としては、
例えば、特開平１-２６３１７６号公報には、（ａ）６
０〜１００重量％のビニルモノマーが、各アルキル基が
その炭素原子の少なくとも半分を単一鎖中に有し、該ア
ルキル鎖の平均長さが少なくとも４そして１２より多く
ない非第三アルキルアクリレートの部類から選ばれる少
なくとも１種の末端不飽和ビニルモノマー９５〜９９.
９重量部と、（ｂ）疎水性および親水性部分の両者を有
し、少なくとも５個、但し、４０個より多くない炭素原
子を含有し、かつ、水−分散性の界面活性剤である少な
くとも１種のビニル不飽和単独重合性モノマー０.１〜
５重量部［（ａ）＋（ｂ）の合計重量部は１００であ
る］からなるモノマーとを共重合させてなるコポリマー
からなる感圧接着剤であって、特定の式で表わされるポ
リオキシエチレンホスフェート（i）およびその塩（i
i）の少なくとも１種から選ばれるホスフェート乳化剤
を該接着剤の約０.２〜約５重量部の量で含む、速い乾
燥性を有する感圧接着剤が開示されている。As such a removable pressure-sensitive adhesive,
For example, JP-A-1-263176 discloses (a) 6
0 to 100% by weight of vinyl monomer is of a non-tertiary alkyl acrylate in which each alkyl group has at least half of its carbon atoms in a single chain and the average length of said alkyl chain is at least 4 and not more than 12. At least one terminally unsaturated vinyl monomer 95-99 selected from the class.
At least 5 parts by weight, and (b) at least 5 but not more than 40 carbon atoms, having both hydrophobic and hydrophilic moieties, and being a water-dispersible surfactant. One vinyl unsaturated homopolymerizable monomer 0.1-
A pressure-sensitive adhesive comprising a copolymer obtained by copolymerizing 5 parts by weight [the total part by weight of (a) + (b) is 100], which is a polyoxyethylene represented by a specific formula. Phosphate (i) and its salt (i
A fast-drying pressure-sensitive adhesive is disclosed which comprises a phosphate emulsifier selected from at least one of i) in an amount of from about 0.2 to about 5 parts by weight of the adhesive.
【０００４】しかしながら、この公報の各実施例に具体
的に開示されている接着剤は、各種の被着体（例えば、
ＳＵＳ板、塩ビ等）からの再剥離性に劣り、特に高温条
件下で使用しようとすると著しく再剥離性に劣り、低温
から高温までの広い温度範囲にわたっては良好な再剥離
性を示さない。However, the adhesives specifically disclosed in the respective examples of this publication are not suitable for various adherends (for example,
It is inferior in removability from a SUS plate, vinyl chloride, etc.), particularly when used under high temperature conditions, and removability in remarkably inferior removability over a wide temperature range from low temperature to high temperature.
【０００５】また、特開平４-２９８５８５号公報に
は、アルキル基の炭素数が４〜１２の（メタ）アクリル
酸アルキルエステルと一般式（Ｉ） ＣＨ2＝Ｃ（Ｒ1）-ＣＯＯ（ＣＨ2-ＣＨ（Ｒ2）-Ｏ）n-Ｈ （Ｉ） （式中、Ｒ1，Ｒ2は水素原子またはメチル基、ｎは２〜
３０の数である。）で表わされる水酸基含有モノマーを
含むビニル系モノマー混合物であり、かつ該モノマー混
合物中の水酸基含有モノマーの含有量が２〜５０重量％
であるビニル系モノマー混合物を共重合して得られる合
成樹脂エマルジョン（固形分換算）に対してイソシアネ
ート系化合物を０．１〜２０重量％配合してなる転写塗
工が可能な再剥離型粘着剤組成物が開示されている。Further, in Japanese Patent Laid-Open No. 4-298585, a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms and a general formula (I) CH 2 ═C (R 1 ) —COO (CH 2 -CH (R 2) -O) n -H (I) ( wherein, R 1, R 2 is a hydrogen atom or a methyl radical, n is 2
The number is 30. ) Is a vinyl-based monomer mixture containing a hydroxyl group-containing monomer, and the content of the hydroxyl group-containing monomer in the monomer mixture is 2 to 50% by weight.
A re-peelable pressure-sensitive adhesive capable of transfer coating, which is obtained by blending 0.1 to 20% by weight of an isocyanate compound with a synthetic resin emulsion (solid content conversion) obtained by copolymerizing a vinyl monomer mixture Compositions are disclosed.
【０００６】しかしながら、この公報に記載された水酸
基含有モノマー（Ｉ）が配合された再剥離型粘着剤組成
物は、上記のような被着体に対して特に高温条件下で使
用しようとすると、著しく再剥離性に劣り、良好な再剥
離性を示さない。However, when the removable pressure-sensitive adhesive composition containing the hydroxyl group-containing monomer (I) described in this publication is used for an adherend such as the above under particularly high temperature conditions, Removability is remarkably inferior and good removability is not exhibited.
【０００７】このような問題点を解決すべく鋭意研究し
たところ、本発明者らは、特定の（メタ）アクリル酸ア
ルキルエステルと、特定のカルボキシル基含有単量体
と、特定の官能基含有単量体と、特定の反応性界面活性
剤とを、特定量用いて乳化重合してなる感圧接着剤は、
各種の被着体からの再剥離性に優れ、高温条件下で使用
されても優れた再剥離性を示すことなどを見い出し本発
明を完成するに至った。As a result of intensive studies aimed at solving such problems, the present inventors have found that a specific (meth) acrylic acid alkyl ester, a specific carboxyl group-containing monomer, and a specific functional group-containing monomer. A pressure-sensitive adhesive obtained by emulsion polymerization of a monomer and a specific reactive surfactant using a specific amount,
The inventors have found that they are excellent in removability from various adherends and exhibit excellent removability even when used under high temperature conditions, and have completed the present invention.
【０００８】[0008]
【発明の目的】本発明の目的は、低温から高温までの広
い温度範囲において各種の被着体に対して良好な再剥離
性を示す水系再剥離型感圧接着剤を提供することを目的
としている。OBJECT OF THE INVENTION The object of the present invention is to provide a water-based removable pressure-sensitive adhesive which exhibits good removability to various adherends in a wide temperature range from low temperature to high temperature. There is.
【０００９】[0009]
【発明の概要】本発明に係る水系再剥離型感圧接着剤
は、（ａ）炭素数１〜１２のアルキル基を有する（メ
タ）アクリル酸アルキルエステル４０〜９９.９重量部
と、（ｂ）該（メタ）アクリル酸アルキルエステルと共
重合可能なカルボキシル基含有単量体０.１〜１０重量
部と、（ｃ）該（メタ）アクリル酸アルキルエステル
（ａ）および該カルボキシル基含有単量体（ｂ）のいず
れとも共重合可能であって、ニトリル基、アミド基、水
酸基、Ｎ-メチロール基、Ｎ-メトキシアルキル基、フェ
ニル基、ハロゲン基、アルコキシ基およびグリシジル基
からなる群から選ばれる官能基を含有する単量体０．１
〜１０重量部［但し、上記カルボキシル基含有単量体
（ｂ）とこの官能基含有単量体（ｃ）とは合計で０．２
〜２０重量部である］と、上記（ａ）＋（ｂ）＋（ｃ）
の合計１００重量部に対して、（ｄ）ポリオキシアルキ
レン基[i]と、アルキルフェニルオキシ基、アルキルフ
ェニル基およびアルキル基から選ばれる親油性基[ii]
と、エチレン性二重結合を有するラジカル重合性官能基
[iii]とを有し、かつ、上記ポリオキシアルキレン基[i]
と、上記アルキルフェニルオキシ基、アルキルフェニル
基およびアルキル基から選ばれる親油性基[ii]とが、置
換または未置換の炭化水素基を介して結合しているか、
または直接結合している、反応性界面活性剤０.１〜７
０重量部とを、乳化重合してなることを特徴としてい
る。SUMMARY OF THE INVENTION The water-based removable pressure-sensitive adhesive according to the present invention comprises (a) 40 to 99.9 parts by weight of (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, and (b) ) 0.1 to 10 parts by weight of a carboxyl group-containing monomer copolymerizable with the (meth) acrylic acid alkyl ester, (c) the (meth) acrylic acid alkyl ester (a) and the carboxyl group-containing unit amount It is copolymerizable with any of the form (b) and is selected from the group consisting of nitrile group, amide group, hydroxyl group, N-methylol group, N-methoxyalkyl group, phenyl group, halogen group, alkoxy group and glycidyl group. Monomers containing functional groups 0.1
-10 parts by weight (however, the total amount of the carboxyl group-containing monomer (b) and the functional group-containing monomer (c) is 0.2
Is about 20 parts by weight], and the above (a) + (b) + (c)
(D) a polyoxyalkylene group [i] and a lipophilic group [ii] selected from an alkylphenyloxy group, an alkylphenyl group and an alkyl group, relative to 100 parts by weight of
And a radically polymerizable functional group having an ethylenic double bond
[iii] and has the above polyoxyalkylene group [i]
And the above-mentioned alkylphenyloxy group, an alkylphenyl group and a lipophilic group [ii] selected from an alkyl group, are bonded via a substituted or unsubstituted hydrocarbon group,
Or directly bound reactive surfactants 0.1 to 7
It is characterized by being emulsion-polymerized with 0 part by weight.
【００１０】上記のような本発明に係る水系再剥離型感
圧接着剤は、低温から高温までの広い温度範囲において
各種の被着体、例えばステンレス（ＳＵＳ）板、塩ビ
板、メラミン塗装板等に対して良好な再剥離性を示す。The water-based removable pressure-sensitive adhesive according to the present invention as described above is used for various adherends in a wide temperature range from low temperature to high temperature, such as stainless (SUS) plate, vinyl chloride plate, melamine coated plate, etc. Shows good removability.
【００１１】[0011]
【発明の具体的説明】以下、本発明に係る水系再剥離型
感圧接着剤について、具体的に説明する。本発明に係る
水系再剥離型感圧接着剤は、（ａ）炭素数１〜１２のア
ルキル基を有する（メタ）アクリル酸アルキルエステル
と、（ｂ）該（メタ）アクリル酸アルキルエステルと共
重合可能なカルボキシル基含有単量体と、（ｃ）該（メ
タ）アクリル酸アルキルエステル（ａ）および該カルボ
キシル基含有単量体（ｂ）のいずれとも共重合可能であ
って、ニトリル基、アミド基、水酸基、Ｎ-メチロール
基、Ｎ-メトキシアルキル基、フェニル基、ハロゲン
基、アルコキシ基およびグリシジル基からなる群から選
ばれる官能基を含有する単量体と、（ｄ）ポリオキシア
ルキレン基[i]と、アルキルフェニルオキシ基、アルキ
ルフェニル基およびアルキル基から選ばれる親油性基[i
i]と、エチレン性二重結合を有するラジカル重合性官能
基[iii]とを有し、かつ、上記ポリオキシアルキレン基
[i]と、上記アルキルフェニルオキシ基、アルキルフェ
ニル基およびアルキル基から選ばれる親油性基[ii]と
が、置換または未置換の炭化水素基を介して結合してい
るか、または直接結合している反応性界面活性剤とを、
乳化重合して得られる。DETAILED DESCRIPTION OF THE INVENTION The water-based removable pressure-sensitive adhesive according to the present invention will be specifically described below. The water-based removable pressure-sensitive adhesive according to the present invention is copolymerized with (a) a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, and (b) a (meth) acrylic acid alkyl ester. A copolymerizable carboxylic group-containing monomer, (c) the (meth) acrylic acid alkyl ester (a) and the carboxyl group-containing monomer (b) are copolymerizable with a nitrile group or an amide group. A hydroxyl group, an N-methylol group, an N-methoxyalkyl group, a phenyl group, a halogen group, an alkoxy group and a glycidyl group, and a monomer containing a functional group selected from the group consisting of (d) a polyoxyalkylene group [i ] And a lipophilic group selected from an alkylphenyloxy group, an alkylphenyl group and an alkyl group [i
i] and a radically polymerizable functional group [iii] having an ethylenic double bond, and the above polyoxyalkylene group
[i] and the above-mentioned alkylphenyloxy group, an alkylphenyl group and a lipophilic group selected from an alkyl group [ii] are bonded via a substituted or unsubstituted hydrocarbon group, or directly bonded to each other. With a reactive surfactant
Obtained by emulsion polymerization.
【００１２】なお、反応性界面活性剤（ｄ）を構成して
いるアルキルフェニルオキシ基、アルキルフェニル基、
アルキル基などの親油性基[ii]は、イソプロペニル基等
のラジカル重合性の置換基を有していてもよい。An alkylphenyloxy group, an alkylphenyl group, which constitutes the reactive surfactant (d),
The lipophilic group [ii] such as an alkyl group may have a radically polymerizable substituent such as an isopropenyl group.
【００１３】また、上記ポリオキシアルキレン基[i]
と、親油性基[ii]とが、置換または未置換の炭化水素基
を介して結合している場合、このような炭化水素基とし
ては、エチレン基など炭素数が１〜５程度のアルキレン
基が挙げられ、これらのアルキレン基の水素原子は、ビ
ニル結合を有する置換基（例：ＣＨ2＝ＣＨ-ＣＨ2Ｏ-Ｃ
Ｈ2-等）などラジカル重合性の置換基で置換されていて
もよい。Further, the above polyoxyalkylene group [i]
And the lipophilic group [ii] are bonded via a substituted or unsubstituted hydrocarbon group, such a hydrocarbon group may be an alkylene group having about 1 to 5 carbon atoms such as ethylene group. The hydrogen atom of these alkylene groups is a substituent having a vinyl bond (eg, CH 2 ═CH—CH 2 O—C
H 2-, etc.) may be substituted with a radically polymerizable substituent.
【００１４】エチレン性二重結合（Ｃ＝Ｃ）を有するラ
ジカル重合性官能基[iii]としては、具体的には、例え
ば、ビニル基、アクリロイル基、１-プロペニル基、イ
ソプロペニル基、アリル基等が挙げられる。Specific examples of the radically polymerizable functional group [iii] having an ethylenic double bond (C = C) include, for example, vinyl group, acryloyl group, 1-propenyl group, isopropenyl group and allyl group. Etc.
【００１５】（メタ）アクリル酸アルキルエステル（ａ） このような水系再剥離型感圧接着剤を乳化重合にて調製
する際に用いられる、アルキル基の炭素数が１〜１２の
（メタ）アクリル酸アルキルエステル（ａ）としては、
具体的には、（メタ）アクリル酸メチル、（メタ）アク
リル酸エチル、（メタ）アクリル酸ノルマルブチル、
（メタ）アクリル酸イソプロピル、（メタ）アクリル酸
-２-エチルヘキシル、（メタ）アクリル酸ノルマルオク
チル、（メタ）アクリル酸イソノニル、（メタ）アクリ
ル酸ラウリルなどが挙げられる。これらの内では、（メ
タ）アクリル酸ノルマルオクチル、（メタ）アクリル酸
イソノニル、（メタ）アクリル酸ラウリル、（メタ）ア
クリル酸ノルマルブチルが好ましく用いられる。 (Meth) acrylic acid alkyl ester (a) (meth) acryl having an alkyl group having 1 to 12 carbon atoms, which is used when such an aqueous removable pressure-sensitive adhesive is prepared by emulsion polymerization. As the acid alkyl ester (a),
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate,
Isopropyl (meth) acrylate, (meth) acrylic acid
Examples thereof include 2-ethylhexyl, normal octyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate. Among these, normal octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, and normal butyl (meth) acrylate are preferably used.
【００１６】これらの（メタ）アクリル酸アルキルエス
テルは、単独あるいは２種以上組み合わせて用いること
ができる。カルボキシル基含有単量体（ｂ） 上記（メタ）アクリル酸アルキルエステル（ａ）と共重
合可能なカルボキシル基含有単量体（ｂ）としては、具
体的には、アクリル酸、メタクリル酸、α-エチルアク
リル酸、クロトン酸、α-メチルクロトン酸、α-エチル
クロトン酸、イソクロトン酸、チグリン酸、アンゲリカ
酸、マレイン酸、フマル酸、イタコン酸、シトラコン
酸、メサコン酸、グルタコン酸、ジヒドロムコン酸な
ど、１〜２個程度のカルボキシル基を有する単量体が挙
げられる。これらの内では、アクリル酸、メタクリル酸
が好ましく用いられる。These (meth) acrylic acid alkyl esters can be used alone or in combination of two or more kinds. Carboxyl group-containing monomer (b) Specific examples of the carboxyl group-containing monomer (b) copolymerizable with the (meth) acrylic acid alkyl ester (a) include acrylic acid, methacrylic acid, α- Ethyl acrylic acid, crotonic acid, α-methyl crotonic acid, α-ethyl crotonic acid, isocrotonic acid, tiglic acid, angelic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, dihydromuconic acid, etc. Examples thereof include monomers having about 1 to 2 carboxyl groups. Among these, acrylic acid and methacrylic acid are preferably used.
【００１７】これらのカルボキシル基含有単量体は、単
独あるいは２種以上組み合わせて用いることができる。官能基含有単量体（ｃ） 該（メタ）アクリル酸アルキルエステル（ａ）および該
カルボキシル基含有単量体（ｂ）のいずれとも共重合可
能であって、上述したような特定の官能基を含有する単
量体（ｃ）として、具体的には、ニトリル基を有する
（メタ）アクリロニトリル等、アミド基を有する（メ
タ）アクリル酸アミド等、水酸基を有する（メタ）アク
リル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキ
シプロピル、（メタ）アクリル酸ヒドロキシブチル等、
Ｎ-メチロール基を有するＮ-メチロール（メタ）アクリ
ルアミド等、Ｎ-メトキシアルキル基を有するＮ-メトキ
シメチル（メタ）アクリルアミド、Ｎ-メトキシエチル
（メタ）アクリルアミド、Ｎ-メトキシプロピル（メ
タ）アクリルアミド、Ｎ-メトキシブチル（メタ）アク
リルアミド等、フェニル基を有するスチレン、α-メチ
ルスチレン、（メタ）アクリル酸フェニル、（メタ）ア
クリル酸ベンジル等、ハロゲン基を有する塩化ビニル、
臭化ビニル、フッ化ビニル等、アルコキシ基を有する
（メタ）アクリル酸メトキシエチル、（メタ）アクリル
酸エトキシエチル等、グリシジル基を有する（メタ）ア
クリル酸グリシジル等、が挙げられる。These carboxyl group-containing monomers may be used alone or in combination of two or more. Functional group-containing monomer (c) Copolymerizable with both the (meth) acrylic acid alkyl ester (a) and the carboxyl group-containing monomer (b) and having a specific functional group as described above. Specific examples of the monomer (c) to be contained include (meth) acrylonitrile having a nitrile group, (meth) acrylic acid amide having an amide group, hydroxyethyl (meth) acrylate having a hydroxyl group, (meth ) Hydroxypropyl acrylate, hydroxybutyl (meth) acrylate, etc.
N-methylol (meth) acrylamide having N-methylol group, N-methoxymethyl (meth) acrylamide having N-methoxyalkyl group, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N -Styrene having a phenyl group such as methoxybutyl (meth) acrylamide, α-methylstyrene, phenyl (meth) acrylate, benzyl (meth) acrylate, etc., vinyl chloride having a halogen group,
Examples thereof include vinyl bromide, vinyl fluoride and the like, methoxyethyl (meth) acrylate having an alkoxy group, ethoxyethyl (meth) acrylate and the like, glycidyl (meth) acrylate having a glycidyl group and the like.
【００１８】これらの内では、アミド基を有する（メ
タ）アクリル酸アミド、エトキシ基を有する（メタ）ア
クリル酸エトキシエチル、ニトリル基を有する（メタ）
アクリロニトリルが好ましく用いられる。Among them, (meth) acrylic acid amide having an amide group, ethoxyethyl (meth) acrylate having an ethoxy group, and (meth) having a nitrile group.
Acrylonitrile is preferably used.
【００１９】なお、上記官能基含有単量体（ｃ）の内
で、ニトリル基、アミド基、水酸基あるいはアルコキシ
基を有する単量体は親水性を有し、乳化重合を容易に
し、重合中にはエマルジョンの分散安定性を高め、しか
も重合後のエマルジョンの分散安定性を向上させること
ができる。Among the above functional group-containing monomers (c), the monomer having a nitrile group, an amide group, a hydroxyl group or an alkoxy group has hydrophilicity, facilitates emulsion polymerization, and Can improve the dispersion stability of the emulsion and further improve the dispersion stability of the emulsion after polymerization.
【００２０】また、Ｎ-メチロール基、Ｎ-メトキシアル
キル基あるいはグリシジル基を有する単量体は自己架橋
性を有し、粘着剤としての凝集力を高めることができ、
その添加量を変えることにより、粘着力と凝集力のバラ
ンスを調整することができる。Further, the monomer having an N-methylol group, an N-methoxyalkyl group or a glycidyl group has self-crosslinking property and can enhance the cohesive force as an adhesive,
By changing the addition amount, the balance between the adhesive force and the cohesive force can be adjusted.
【００２１】また、フェニル基、ニトリル基あるいは、
ハロゲン基を有する単量体は、ガラス転移温度（Ｔｇ）
が高く、粘着剤としての弾力性を変化させ、その添加量
を変えることによって、粘着力と凝集力のバランスを調
整することができる。Further, a phenyl group, a nitrile group, or
The monomer having a halogen group has a glass transition temperature (Tg)
Therefore, the balance between the adhesive force and the cohesive force can be adjusted by changing the elasticity as an adhesive and changing the addition amount.
【００２２】反応性界面活性剤（ｄ） 反応性界面活性剤（ｄ）としては、下記［イ］〜［ホ］に
記載するような化合物が挙げられる。 Reactive Surfactant (d) Examples of the reactive surfactant (d) include the compounds described in [a] to [e] below.
【００２３】すなわち、親水性に寄与するカルボキシル
基とポリオキシアルキレン基[i]とを有し、ポリオキシ
アルキレン基[i]が１〜１００モルの量のエチレンオキ
サイド基（ポリオキシエチレン基）であり、親油性基[i
i]がアルキルフェニル基であり、エチレン性二重結合を
有するラジカル重合性官能基[iii]がビニル基、アクリ
ロイル基、１-プロペニル基、イソプロペニル基または
アリル基であり、上記ポリオキシエチレン基[i]と、上
記アルキルフェニル基[ii]とが直接結合している下記の
ような非イオン性の化合物（反応性乳化剤）［イ］が挙
げられる。（但し、Ｐｈはフェニル基を表わす。以下同
様。） 化合物［イ］： ＣＨ2＝Ｃ（Ｈ）ＣＯＯ（Ｃ2Ｈ4Ｏ）6−Ｐｈ−Ｃ9Ｈ19
［日本乳化剤（株）製の改質剤、品番：５６０−Ａ］、 ＣＨ2＝Ｃ（Ｈ）ＣＯＯ（Ｃ2Ｈ4Ｏ）8−Ｐｈ−Ｃ9Ｈ19
［日本乳化剤（株）製の改質剤、品番：５６４−Ａ］、 ＣＨ2＝Ｃ（Ｈ）ＣＯＯ（Ｃ2Ｈ4Ｏ）16−Ｐｈ−Ｃ9Ｈ19
［日本乳化剤（株）製の改質剤、品番：５６８−Ａ］。That is, it has a carboxyl group that contributes to hydrophilicity and a polyoxyalkylene group [i], and the polyoxyalkylene group [i] is an ethylene oxide group (polyoxyethylene group) in an amount of 1 to 100 mol. Yes, lipophilic group [i
i] is an alkylphenyl group, the radical-polymerizable functional group having an ethylenic double bond [iii] is a vinyl group, an acryloyl group, a 1-propenyl group, an isopropenyl group or an allyl group, and the above polyoxyethylene group Examples include the following nonionic compounds (reactive emulsifiers) [a] in which [i] and the above-mentioned alkylphenyl group [ii] are directly bonded. (However, Ph represents forth phenyl group..) Compound [i]: CH 2 = C (H ) COO (C 2 H 4 O) 6 -Ph-C 9 H 19
[Nippon Emulsifier Co., Ltd. modifiers, No.: 560-A], CH 2 = C (H) COO (C 2 H 4 O) 8 -Ph-C 9 H 19
[Nippon Emulsifier Co., Ltd. modifiers, No.: 564-A], CH 2 = C (H) COO (C 2 H 4 O) 16 -Ph-C 9 H 19
[Modifier manufactured by Nippon Emulsifier Co., Ltd., product number: 568-A].
【００２４】上記化合物［イ］において、親油性基[ii]
をアルキルフェニル基に代えてアルキルフェニル基とし
た以外は上記化合物［イ］と同様な化合物である下記の
ような非イオン性の化合物［ロ］が挙げられる。In the above compound [a], the lipophilic group [ii]
The following nonionic compound [B], which is a compound similar to the above-mentioned compound [A], is used except that is replaced with an alkylphenyl group.
【００２５】化合物［ロ］： ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（Ｃ2Ｈ4Ｏ）15Ｃ12Ｈ25［日
本乳化剤（株）製の改質剤、品番：１１１５−ＭＡ］、 ＣＨ2＝Ｃ（Ｈ）ＣＯＯ（Ｃ2Ｈ4Ｏ）2Ｃ8Ｈ17［日本乳
化剤（株）製の改質剤、品番：ＥＨＤＧ−Ａ］。Compound [b]: CH 2 = C (CH 3 ) COO (C 2 H 4 O) 15 C 12 H 25 [Modifier manufactured by Nippon Emulsifier Co., Ltd., product number: 1115-MA], CH 2 = C (H) COO (C 2 H 4 O) 2 C 8 H 17 [ Japan emulsifier Co., Ltd. of the modifying agent, part number: EHDG-a].
【００２６】カルボキシル基とポリオキシアルキレン基
[i]とを有し、ポリオキシアルキレン基[i]が１〜１００
モルの量のエチレンオキサイド基（ポリオキシエチレン
基）であり、親油性基[ii]がアルキルフェニルオキシ基
であり、かつ、上記ポリオキシエチレン基[i]と、上記
置換アルキルフェニルオキシ基[ii]とが置換基（例：Ｃ
Ｈ2＝ＣＨ−ＣＨ2０−ＣＨ2-）を有する炭化水素基
（例：エチレン基）を介して結合している下記のような
非イオン性の化合物［ハ］が挙げられる。Carboxyl group and polyoxyalkylene group
[i] and has a polyoxyalkylene group [i] of 1 to 100
A molar amount of ethylene oxide group (polyoxyethylene group), the lipophilic group [ii] is an alkylphenyloxy group, and the polyoxyethylene group [i] and the substituted alkylphenyloxy group [ii] ] And are substituents (eg C
The following non-ionic compound [C] bonded via a hydrocarbon group (eg, ethylene group) having H 2 ═CH—CH 2 0-CH 2 —) may be mentioned.
【００２７】化合物［ハ］：Compound [C]:
【００２８】[0028]
【化１】 [Chemical 1]
【００２９】［旭電化工業（株）製：アデカリアソー
プ、品番：ＮＥ−１０（ｎ＝１０）、ＮＥ−２０（ｎ＝
２０）、ＮＥ−３０（ｎ＝３０）、ＮＥ−４０（ｎ＝４
０）］、ポリオキシアルキレン基[i]が１〜１００モル
の量のエチレンオキサイド基（ポリオキシエチレン基）
であり、親油性基[ii]が、ラジカル重合性の置換基
（例：イソプロペニル基）の結合したアルキルフェニル
オキシ基であり、かつ、上記ポリオキシエチレン基[i]
と、上記置換アルキルフェニルオキシ基[ii]とが直接結
合している下記のような非イオン性の化合物［ニ］が挙
げられる。[Asahi Denka Kogyo KK: ADEKA rear soap, product number: NE-10 (n = 10), NE-20 (n =
20), NE-30 (n = 30), NE-40 (n = 4)
0)], the polyoxyalkylene group [i] is an ethylene oxide group (polyoxyethylene group) in an amount of 1 to 100 mol.
And the lipophilic group [ii] is an alkylphenyloxy group to which a radically polymerizable substituent (eg, isopropenyl group) is bonded, and the above polyoxyethylene group [i]
And the following substituted alkylphenyloxy group [ii] is directly bonded to the following nonionic compound [d].
【００３０】化合物［ニ］：Compound [d]:
【００３１】[0031]
【化２】 [Chemical 2]
【００３２】［第一工業製薬（株）製：アクアロン、品
番：ＲＮ−２０（ｎ＝２０）、ＲＮ−５０（ｎ＝５
０）］ なお、上記のような反応性乳化剤において、付加してい
るエチレンオキサイド基の量が、１モル未満では、得ら
れる再剥離型感圧接着剤の再剥離性が低下し、また１０
０モルを超えると重合安定性が低下する傾向がある。[Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon, product numbers: RN-20 (n = 20), RN-50 (n = 5)
0)] In the reactive emulsifier as described above, if the amount of the added ethylene oxide group is less than 1 mol, the removability of the removable pressure-sensitive adhesive obtained is decreased, and
If it exceeds 0 mol, the polymerization stability tends to decrease.
【００３３】ポリオキシアルキレン基[i]が１〜１００
モルの量のプロピレンオキサイド基（ポリオキシプロピ
レン基）であり、親油性基[ii]がアルキルフェニルオキ
シ基であり、ラジカル重合性官能基[iii]がビニル基、
アクリロイル基、１-プロペニル基、イソプロペニル基
またはアリル基であり、かつ、上記ポリオキシプロピレ
ン基[i]と、上記アルキルフェニルオキシ基[ii]とが、
直接結合している下記のような非イオン性の化合物
［ホ］が挙げられる。The polyoxyalkylene group [i] is from 1 to 100
A molar amount of a propylene oxide group (polyoxypropylene group), a lipophilic group [ii] is an alkylphenyloxy group, a radically polymerizable functional group [iii] is a vinyl group,
An acryloyl group, a 1-propenyl group, an isopropenyl group or an allyl group, and the polyoxypropylene group [i] and the alkylphenyloxy group [ii] are
The following nonionic compounds [e] directly bonded are mentioned.
【００３４】ノニルフェノキシポリプロピレングリコー
ルアクリレート［ホ］： Ｃ9Ｈ19-Ｐｈ-Ｏ-（Ｒ）n-ＯＣＣＨ＝ＣＨ2 （Ｒ：ＣＨ2ＣＨ（ＣＨ3）Ｏ） ［新中村化学（株）製：ＮＫエステル、品番：ＮＰＡ−
５Ｐ（ｎ≒５）］ これらの内では、上記式（１）において、ｎが３０のア
デカリアソープ（ＮＥ−３０）、上記式（２）において
ｎが２０のアクアロン（ＲＮ−２０）、ｎが５０のアク
アロン（ＲＮ−５０）、 ＣＨ2＝Ｃ（Ｈ）ＣＯＯ（Ｃ2Ｈ4Ｏ）6−Ｐｈ−Ｃ9Ｈ19 ［日本乳化剤（株）製の改質剤、品番：５６０−Ａ］ が好ましく用いられる。Nonylphenoxy polypropylene glycol acrylate [e]: C 9 H 19 -Ph-O- (R) n -OCCH = CH 2 (R: CH 2 CH (CH 3 ) O) [manufactured by Shin-Nakamura Chemical Co., Ltd.] : NK ester, product number: NPA-
5P (n≈5)] Among these, in the above formula (1), n is 30 ADEKA rear soap (NE-30), and in the above formula (2), n is 20 aqualon (RN-20), n There 50 Aqualon (RN-50), CH 2 = C (H) COO (C 2 H 4 O) 6 -Ph-C 9 H 19 [ Nippon emulsifier Co., Ltd. modifiers, No.: 560-a ] Is preferably used.
【００３５】本発明に係る水系再剥離型感圧接着剤は、
上記原料モノマー（ａ）、（ｂ）、（ｃ）および（ｄ）
を乳化重合させることにより得られる。本発明に係る水
系再剥離型感圧接着剤を製造する際には、上記の（メ
タ）アクリル酸アルキルエステル（ａ）は、このエステ
ル（ａ）とカルボキシル基含有単量体（ｂ）と官能基含
有単量体（ｃ）との合計１００重量部中に、４０〜９
９.９重量部、カルボキシル基含有単量体（ｂ）は、０.
１〜１０重量部、好ましくは１〜４重量部の量で、官能
基含有単量体（ｃ）は、０．１〜１０重量部、好ましく
は１〜４重量部の量で用いられる。また、カルボキシル
基含有単量体（ｂ）と官能基含有単量体（ｃ）とは、こ
のエステル（ａ）とカルボキシル基含有単量体（ｂ）と
官能基含有単量体（ｃ）との合計１００重量部中に、合
計で０．２〜２０重量部、好ましくは２〜８重量部の量
で用いられる。The water-based removable pressure-sensitive adhesive according to the present invention is
The above raw material monomers (a), (b), (c) and (d)
Is obtained by emulsion polymerization. In the production of the water-based removable pressure-sensitive adhesive according to the present invention, the above-mentioned (meth) acrylic acid alkyl ester (a) is functionalized with the ester (a), the carboxyl group-containing monomer (b) and the functional group. 40 to 9 in 100 parts by weight in total with the group-containing monomer (c)
9.9 parts by weight, and the carboxyl group-containing monomer (b) is 0.
The functional group-containing monomer (c) is used in an amount of 1 to 10 parts by weight, preferably 1 to 4 parts by weight, and 0.1 to 10 parts by weight, preferably 1 to 4 parts by weight. The carboxyl group-containing monomer (b) and the functional group-containing monomer (c) are the ester (a), the carboxyl group-containing monomer (b) and the functional group-containing monomer (c). In a total of 100 parts by weight of 0.2 to 20 parts by weight, preferably 2 to 8 parts by weight.
【００３６】また、反応性界面活性剤（ｄ）は、（ａ）
と（ｂ）と（ｃ）との合計１００重量部に対して、０.
１〜７０.０重量部、好ましくは２.０〜２０.０重量部
の量で用いられる。Further, the reactive surfactant (d) is (a)
With respect to 100 parts by weight in total of (b) and (c),
It is used in an amount of 1 to 70.0 parts by weight, preferably 2.0 to 20.0 parts by weight.
【００３７】カルボキシル基含有単量体（ｂ）が、０.
１重量部未満でも、また１０重量部を超えても重合安定
性が低下する傾向がある。官能基含有単量体（ｃ）が、
１０重量部を超えると、重合安定性が低下してしまい、
得られる水系再剥離型感圧接着剤のタック、粘着力が低
下する傾向がある。The carboxyl group-containing monomer (b) contained 0.1.
If it is less than 1 part by weight or more than 10 parts by weight, the polymerization stability tends to decrease. The functional group-containing monomer (c) is
If it exceeds 10 parts by weight, the polymerization stability will decrease,
The tack and tackiness of the resulting water-based removable pressure-sensitive adhesive tend to decrease.
【００３８】なお、官能基含有単量体（ｃ）が、０.１
重量部未満では、凝集力と粘着力の良好なバランスが得
にくくなる傾向がある。また、カルボキシル基含有単量
体（ｂ）と官能基含有単量体（ｃ）とは、（ａ）と
（ｂ）と（ｃ）との合計１００重量部の中で、その合計
量が０．２重量部未満でも、また２０重量部を超えても
重合安定性が低下してしまい、得られる水系再剥離型感
圧接着剤のタック、粘着力が低下する傾向がある。The functional group-containing monomer (c) is 0.1
If it is less than part by weight, it tends to be difficult to obtain a good balance between cohesive strength and adhesive strength. The total amount of the carboxyl group-containing monomer (b) and the functional group-containing monomer (c) is 0 in 100 parts by weight of the total of (a), (b) and (c). If it is less than 0.2 parts by weight or more than 20 parts by weight, the polymerization stability tends to decrease, and the tack and tackiness of the resulting water-based removable pressure-sensitive adhesive tend to decrease.
【００３９】また、反応性界面活性剤（ｄ）が、（ａ）
と（ｂ）と（Ｃ）との合計１００重量部に対して、０.
１重量部未満では、再剥離性が低くなり、７０重量部を
超えると重合安定性が低下し、得られる水系再剥離型感
圧接着剤の基材に対する投錨性が低下する傾向がある。Further, the reactive surfactant (d) is (a)
With respect to a total of 100 parts by weight of (b) and (C),
If it is less than 1 part by weight, the removability tends to be low, and if it exceeds 70 parts by weight, the polymerization stability tends to be low and the anchorage of the resulting water-based removable pressure-sensitive adhesive to the substrate tends to be low.
【００４０】次に本発明に係る水系再剥離型感圧接着剤
の製造法を述べる。例えば、脱イオン水３０〜８０重量
部に、必要によりポリオキシエチレンラウリルエーテル
硫酸ナトリウムなどの外部乳化剤０.５〜５重量部を溶
解させてなる乳化剤水溶液に、（メタ）アクリル酸ノル
マルオクチルなどの（メタ）アクリル酸アルキルエステ
ル（ａ）４０〜９９.９重量部、（メタ）アクリル酸な
どのカルボキシル基含有単量体（ｂ）０.１〜１０重量
部、メタクリルアミドなどの官能基含有単量体（ｃ）
０．１〜１０重量部［但し、（ｂ）と（ｃ）の合計量
は、０．２〜２０重量部となるようにする］および、
（ａ）と（ｂ）と（ｃ）との合計１００重量部に対して
アデカリアソープ（品番：ＮＥ−３０）などの反応性界
面活性剤（ｄ）０.１〜７０.０重量部を攪拌下に分散さ
せて単量体水性分散液を調製する。Next, a method for producing the water-based removable pressure-sensitive adhesive according to the present invention will be described. For example, in an aqueous emulsifier solution prepared by dissolving 0.5 to 5 parts by weight of an external emulsifier such as sodium polyoxyethylene lauryl ether sulfate in 30 to 80 parts by weight of deionized water, normal octyl (meth) acrylate or the like is added. 40 to 99.9 parts by weight of (meth) acrylic acid alkyl ester (a), 0.1 to 10 parts by weight of a carboxyl group-containing monomer (b) such as (meth) acrylic acid, and a functional group-containing monomer such as methacrylamide. Quantum (c)
0.1 to 10 parts by weight [however, the total amount of (b) and (c) should be 0.2 to 20 parts by weight], and
To 100 parts by weight of the total of (a), (b) and (c), 0.1 to 70.0 parts by weight of a reactive surfactant (d) such as Adecaria soap (product number: NE-30) is added. Disperse with stirring to prepare an aqueous monomer dispersion.
【００４１】一方、脱イオン水３０〜８０重量部に、過
硫酸カリウムなど後述するような重合開始剤０.０５〜
２.０重量部、アクリル酸ノルマルブチルなどの重合性
モノマー２〜５重量部、必要により陰イオン活性剤の１
種であるドデシルベンゼンスルホン酸ナトリウムなどの
外部乳化剤０.５〜５重量部を加えて、水性反応母液を
調製する。On the other hand, in 30 to 80 parts by weight of deionized water, a polymerization initiator such as potassium persulfate in an amount of 0.05 to 5
2.0 parts by weight, 2 to 5 parts by weight of a polymerizable monomer such as normal butyl acrylate, and optionally 1 of an anion activator.
An aqueous reaction mother liquor is prepared by adding 0.5 to 5 parts by weight of an external emulsifier such as the seed sodium dodecylbenzene sulfonate.
【００４２】次いで、この水性反応母液を窒素ガス雰囲
気下で、６０〜８０℃程度の温度に加熱して反応を開始
させる。次いで、上記温度に保持された反応母液中に、
通常、反応開始直後より、１５０〜３００分程度の時間
をかけて上記単量体水性分散液を徐々に滴下し、乳化重
合を行う。このような単量体水性分散液の滴下終了後さ
らに６０〜１８０分間程度、反応液の温度を７５〜９０
℃程度の温度に保持すると、所望の水系再剥離型感圧接
着剤が得られる。なお、必要により、得られた乳化重合
体溶液を２０〜４０℃程度に冷却した後、該溶液のｐＨ
値を例えば７.０付近に調整してもよい。Then, this aqueous reaction mother liquor is heated to a temperature of about 60 to 80 ° C. in a nitrogen gas atmosphere to start the reaction. Then, in the reaction mother liquor maintained at the above temperature,
Usually, immediately after the start of the reaction, the above monomer aqueous dispersion is gradually added dropwise over about 150 to 300 minutes to carry out emulsion polymerization. After the dropping of the aqueous monomer dispersion is completed, the temperature of the reaction solution is adjusted to 75 to 90 minutes for about 60 to 180 minutes.
When kept at a temperature of about 0 ° C, the desired water-based removable pressure-sensitive adhesive is obtained. In addition, if necessary, after cooling the obtained emulsion polymer solution to about 20 to 40 ° C., the pH of the solution
The value may be adjusted to around 7.0, for example.
【００４３】重合開始剤としては、過硫酸カリウム、過
硫酸アンモニウムなどが挙げられる。感圧接着テープの製造 上記の水系再剥離型感圧接着剤層が基体の表面に設けら
れた感圧接着テープを製造するには、水系再剥離型感圧
接着剤を、乾燥後の膜厚が５〜４０μｍ程度となるよう
な量で、上質紙あるいは必要により予めコロナ放電処理
などの表面処理が施されたポリエステルフィルムなどの
基体上に塗布、吹付け等すればよい。このように水系再
剥離型感圧接着剤を基体上に塗布するには、例えばアプ
リケータなどが用いられる。Examples of the polymerization initiator include potassium persulfate and ammonium persulfate. Production of pressure-sensitive adhesive tape To produce a pressure-sensitive adhesive tape in which the above-mentioned water-based removable pressure-sensitive adhesive layer is provided on the surface of a substrate, the water-based removable pressure-sensitive adhesive is coated with a film thickness after drying. In an amount of about 5 to 40 μm may be applied, sprayed, or the like on a substrate such as high-quality paper or a polyester film which has been subjected to a surface treatment such as corona discharge treatment in advance if necessary. In order to apply the water-based removable pressure-sensitive adhesive to the substrate in this manner, an applicator or the like is used.
【００４４】本発明に係る水系再剥離型感圧接着剤を製
造する際には、上記（ａ）、（ｂ）、（ｃ）および
（ｄ）とともに、ホスフェート系乳化剤、その他の外部
乳化剤を用いてもよい。In producing the water-based removable pressure-sensitive adhesive according to the present invention, a phosphate-based emulsifier and other external emulsifiers are used together with the above (a), (b), (c) and (d). May be.
【００４５】ホスフェート系乳化剤として、例えば、下
記式（３）で表わされるポリオキシエチレンホスフェー
トおよびその塩を挙げることができる。Examples of the phosphate emulsifier include polyoxyethylene phosphate represented by the following formula (3) and salts thereof.
【００４６】[0046]
【化３】 [Chemical 3]
【００４７】（式中、Ｒ1、Ｒ2、およびＲ3の少なくと
も１つはＲ−Ｏ−（ＣＨ2ＣＨ2Ｏ）n−であり、他は、
−ＯＨであり、Ｒはアルキル基、アルケニル基、アリー
ル基、およびアルキルアリール基、アルコキシ基の内か
ら選ばれる。ｎは、正の整数である。）ホスフェート乳
化剤は、上記（ａ）と（ｂ）と（ｃ）と（ｄ）との合計
１００重量部当り、０.５〜１０重量部の量で用いられ
る。(In the formula, at least one of R 1 , R 2 and R 3 is R—O— (CH 2 CH 2 O) n —;
—OH, and R is selected from an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an alkoxy group. n is a positive integer. ) The phosphate emulsifier is used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the total of (a), (b), (c) and (d).
【００４８】その他の外部乳化剤としては、ドデシルベ
ンゼンスルホン酸ナトリウム、アルキルアリールポリエ
トキシスルホン酸ナトリウム、ｎ−ラウリル-β-イミノ
ジプロピオン酸ナトリウムなどを挙げることができる。Other external emulsifiers include sodium dodecylbenzene sulfonate, sodium alkylaryl polyethoxy sulfonate, sodium n-lauryl-β-iminodipropionate and the like.
【００４９】[0049]
【発明の効果】本発明に係る水系再剥離型感圧接着剤
は、低温から高温までの広い温度範囲で使用後、各種の
被着体、例えばステンレス（ＳＵＳ）板、塩ビ板、メラ
ミン塗装板等に対して良好な再剥離性を示す。EFFECTS OF THE INVENTION The water-based removable pressure-sensitive adhesive according to the present invention is used in a wide temperature range from low temperature to high temperature, and then various adherends such as stainless (SUS) plate, vinyl chloride plate and melamine coated plate are used. Good re-peelability is exhibited.
【００５０】[0050]
【実施例】以下、本発明を実施例に基づきより具体的に
説明するが、本発明はこれらの実施例に何ら限定される
ものではない。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.
【００５１】[0051]
【実施例１】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）アクリル酸ノルマルオクチル９６.０部、
（ｂ）アクリル酸１.０部、（ｃ）メタクリルアミド３.
０部、（ｄ）ＮＥ−３０ ２.０部を攪拌下に分散させ
て単量体水性分散液１５３部を調製した。Example 1 Synthesis of Pressure Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 96.0 parts of normal octyl acrylate,
(B) 1.0 part of acrylic acid, (c) methacrylamide 3.
0 part and 2.0 parts of (d) NE-30 were dispersed with stirring to prepare 153 parts of an aqueous monomer dispersion.
【００５２】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水５０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 50 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and further 0.2 parts of potassium persulfate and butyl acrylate were added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００５３】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１５３部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Next, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 153 parts of the above monomer aqueous dispersion was added dropwise from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００５４】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００５５】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25 μ. Applied to.
【００５６】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【００５７】[0057]
【実施例２】感圧接着剤の合成 脱イオン水５０部に、モノラウリルホスフェート１.０
部を溶解させた乳化剤水溶液に、（ａ）メタクリル酸イ
ソノニル９４.０部、（ｂ）メタクリル酸２.０部、
（ｃ）アクリル酸2-エトキシエチル４.０部、（ｄ）Ｒ
Ｎ−２０ ４.０部を攪拌下に分散させて単量体水性分
散液１５４部を調製した。Example 2 Synthesis of Pressure Sensitive Adhesive Monolauryl phosphate 1.0 in 50 parts deionized water.
(A) isononyl methacrylate 94.0 parts, (b) methacrylic acid 2.0 parts,
(C) 4.0 parts of 2-ethoxyethyl acrylate, (d) R
4.0 parts of N-20 were dispersed with stirring to prepare 154 parts of an aqueous monomer dispersion liquid.
【００５８】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水５０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 50 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and 0.2 parts of potassium persulfate and butyl acrylate were added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００５９】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１５４部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 154 parts of the above monomer aqueous dispersion was dropped from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００６０】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After the lapse of 180 minutes, the temperature of the reaction solution was kept at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００６１】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25 μ. Applied to.
【００６２】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【００６３】[0063]
【実施例３】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）アクリル酸ノルマルオクチル５０.０部、ア
クリル酸ノルマルブチル４６.０部、（ｂ）アクリル酸
２.０部、（ｃ）アクリロニトリル２.０部、（ｄ）ＲＮ
−５０ ４.０部を攪拌下に分散させて単量体水性分散
液１５４部を調製した。Example 3 Synthesis of Pressure Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 50.0 parts of normal octyl acrylate, acrylic Normal butyl acid 46.0 parts, (b) acrylic acid 2.0 parts, (c) acrylonitrile 2.0 parts, (d) RN
-50 parts of 4.0 parts were dispersed with stirring to prepare 154 parts of an aqueous monomer dispersion liquid.
【００６４】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水５０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 50 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and 0.2 parts of potassium persulfate and butyl acrylate were further added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００６５】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１５４部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Next, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 154 parts of the above monomer aqueous dispersion was dropped from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００６６】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００６７】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25μ. Applied to.
【００６８】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【００６９】[0069]
【実施例４】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）アクリル酸ノルマルオクチル５０.０部、ア
クリル酸ノルマルブチル４５.０部、（ｂ）メタクリル
酸４.０部、（ｃ）アクリルアミド１.０部、（ｄ）５６
０−Ａ １０.０部を攪拌下に分散させて単量体水性分
散液１１０部を調製した。Example 4 Synthesis of Pressure-Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 50.0 parts of normal octyl acrylate, acrylic Normal butyl acid 45.0 parts, (b) Methacrylic acid 4.0 parts, (c) Acrylamide 1.0 part, (d) 56
10 parts of 0-A was dispersed with stirring to prepare 110 parts of an aqueous monomer dispersion.
【００７０】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水６０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 60 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and further 0.2 parts of potassium persulfate and butyl acrylate were placed. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００７１】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１１０部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 110 parts of the above monomer aqueous dispersion was dropped from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００７２】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００７３】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25 μ. Applied to.
【００７４】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【００７５】[0075]
【実施例５】感圧接着剤の合成 脱イオン水５０部に、ジラウリルホスフェート１.０部
を溶解させた乳化剤水溶液に、（ａ）メタクリル酸ブチ
ル９０.０部、（ｂ）アクリル酸２.０部、（ｃ）メタク
リロニトリル８.０部、（ｄ）ＮＰＡ−５Ｐ ２.０部を
攪拌下に分散させて単量体水性分散液１０３部を調製し
た。Example 5 Synthesis of Pressure Sensitive Adhesive In an aqueous emulsifier solution prepared by dissolving 1.0 part of dilauryl phosphate in 50 parts of deionized water, (a) butyl methacrylate (90.0 parts), (b) acrylic acid (2) 0.0 parts, (c) methacrylonitrile 8.0 parts, and (d) NPA-5P 2.0 parts were dispersed with stirring to prepare 103 parts of an aqueous monomer dispersion.
【００７６】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水４０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 40 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and further 0.2 parts of potassium persulfate and butyl acrylate were added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００７７】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１０３部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 103 parts of the above monomer aqueous dispersion was added dropwise from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００７８】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００７９】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25μ polyester film and high-quality paper which had been corona-discharge treated using an applicator so that the coating film after drying had a thickness of 25μ. Applied to.
【００８０】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Next, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【００８１】[0081]
【比較例１】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）アクリル酸ノルマルオクチル９６.０部、
（ｂ）アクリル酸１.０部、（ｃ）メタクリルアミド３.
０部、（ｄ）スチレンスルホン酸ナトリウム２.０部を
攪拌下に分散させて単量体水性分散液１０３部を調製し
た。Comparative Example 1 Synthesis of Pressure Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 96.0 parts of normal octyl acrylate,
(B) 1.0 part of acrylic acid, (c) methacrylamide 3.
0 parts and (d) 2.0 parts of sodium styrenesulfonate were dispersed with stirring to prepare 103 parts of an aqueous monomer dispersion.
【００８２】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水４０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 40 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and further 0.2 parts of potassium persulfate and butyl acrylate were added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００８３】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１０３部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 103 parts of the above monomer aqueous dispersion was added dropwise from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００８４】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００８５】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying had a thickness of 25 μ. Applied to.
【００８６】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【００８７】[0087]
【比較例２】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）アクリル酸ノルマルオクチル６７.０部、
（ｂ）2-アクリロイルオキシエチルコハク酸３１.０
部、（ｃ）メタクリルアミド２.０部、（ｄ）ＲＮ−２
０ ２.０部を攪拌下に分散させて単量体水性分散液１
５２部を調製した。Comparative Example 2 Synthesis of Pressure Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 67.0 parts of normal octyl acrylate,
(B) 2-acryloyloxyethyl succinic acid 31.0
Parts, (c) methacrylamide 2.0 parts, (d) RN-2
0 2.0 parts was dispersed with stirring to prepare an aqueous monomer dispersion 1
52 parts were prepared.
【００８８】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水５０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 50 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and 0.2 parts of potassium persulfate and butyl acrylate were added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００８９】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１５２部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 152 parts of the above monomer aqueous dispersion was added dropwise from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００９０】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００９１】[0091]
【比較例３】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）メタクリル酸ラウリル６６.０部、（ｂ）ア
クリル酸３.０部、（ｃ）アクリル酸2-エトキシエチル
３１.０部、（ｄ）ＲＮ−５０ ４.０部を攪拌下に分散
させて単量体水性分散液１５４部を調製した。Comparative Example 3 Synthesis of Pressure-Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 66.0 parts of lauryl methacrylate, (b) ) 3.0 parts of acrylic acid, (c) 31.0 parts of 2-ethoxyethyl acrylate, and (d) 4.0 parts of RN-50 were dispersed with stirring to prepare 154 parts of an aqueous monomer dispersion. .
【００９２】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水５０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 50 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and 0.2 parts of potassium persulfate and butyl acrylate were added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【００９３】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１５４部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 154 parts of the above monomer aqueous dispersion was dropped from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００９４】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After the lapse of 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【００９５】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25 μ. Applied to.
【００９６】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【００９７】[0097]
【比較例４】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）アクリル酸ノルマルオクチル５０.０部、ア
クリル酸ノルマルブチル４５.０部、（ｂ）メタクリル
酸４.０部、（ｃ）アクリルアミド１.０部を攪拌下に分
散させて単量体水性分散液１５０部を調製した。別に攪
拌機、温度計、滴下ロート、窒素ガス吹き込み口、およ
び還流冷却装置を供えたガラス製反応器に、脱イオン水
４０部を入れ、さらに過硫酸カリウム０.２部、アクリ
ル酸ブチル２部、ドデシルベンゼンスルホン酸ナトリウ
ム１部を加えて、水性反応母液を調製した。Comparative Example 4 Synthesis of Pressure Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 50.0 parts of normal octyl acrylate, acrylic 45.0 parts of normal butyl acid acid, 4.0 parts of (b) methacrylic acid, and 1.0 part of (c) acrylamide were dispersed under stirring to prepare 150 parts of an aqueous monomer dispersion. Separately, 40 parts of deionized water was put into a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and further, 0.2 parts of potassium persulfate and 2 parts of butyl acrylate, An aqueous reaction mother liquor was prepared by adding 1 part of sodium dodecylbenzene sulfonate.
【００９８】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１５０部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 150 parts of the above monomer aqueous dispersion was dropped from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【００９９】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After the lapse of 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【０１００】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25 μ. Applied to.
【０１０１】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【０１０２】[0102]
【比較例５】感圧接着剤の合成 脱イオン水５０部に、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム１.０部を溶解させた乳化剤水溶液
に、（ａ）アクリル酸ノルマルオクチル５０.０部、ア
クリル酸ノルマルブチル４５.０部、（ｂ）メタクリル
酸４.０部、（ｄ）５６０−Ａ １０.０部を攪拌下に分
散させて単量体水性分散液１０９部を調製した。Comparative Example 5 Synthesis of Pressure Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of sodium polyoxyethylene lauryl ether sulfate in 50 parts of deionized water, (a) 50.0 parts of normal octyl acrylate, acrylic 45.0 parts of normal butyl acid, 4.0 parts of (b) methacrylic acid, and 10.0 parts of (d) 560-A were dispersed with stirring to prepare 109 parts of an aqueous monomer dispersion.
【０１０３】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水６０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 60 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and 0.2 parts of potassium persulfate and butyl acrylate were further added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【０１０４】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１０９部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 109 parts of the above monomer aqueous dispersion was added dropwise from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【０１０５】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【０１０６】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25 μ. Applied to.
【０１０７】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample.
【０１０８】[0108]
【比較例６】感圧接着剤の合成 脱イオン水５０部に、ジラウリルホスフェート１.０部
を溶解させた乳化剤水溶液に、（ａ）メタクリル酸ブチ
ル９０.０部、（ｂ）アクリル酸２.０部、（ｃ）メタク
リロニトリル８.０部、（ｄ）ＭＡ−１５０｛ＣＨ2＝Ｃ
（ＣＨ3）ＣＯＯ（Ｃ2Ｈ4Ｏ）15Ｈ［日本乳化剤（株）
製の改質剤、品番：ＭＡ−１５０］｝２.０部を攪拌下
に分散させて単量体水性分散液１０３部を調製した。Comparative Example 6 Synthesis of Pressure Sensitive Adhesive An aqueous emulsifier solution prepared by dissolving 1.0 part of dilauryl phosphate in 50 parts of deionized water, (a) butyl methacrylate (90.0 parts) and (b) acrylic acid (2) 0.0 parts, (c) methacrylonitrile 8.0 parts, (d) MA-150 {CH 2 = C
(CH 3 ) COO (C 2 H 4 O) 15 H [Japan Emulsifier Co., Ltd.
Produced modifier, product number: MA-150]} was dispersed under stirring to prepare 103 parts of an aqueous monomer dispersion.
【０１０９】別に攪拌機、温度計、滴下ロート、窒素ガ
ス吹き込み口、および還流冷却装置を供えたガラス製反
応器に、脱イオン水４０部を入れ、さらに過硫酸カリウ
ム０.２部、アクリル酸ブチル２部、ドデシルベンゼン
スルホン酸ナトリウム１部を加えて、水性反応母液を調
製した。Separately, 40 parts of deionized water was placed in a glass reactor equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas blowing port, and a reflux cooling device, and 0.2 parts of potassium persulfate and butyl acrylate were added. An aqueous reaction mother liquor was prepared by adding 2 parts and 1 part of sodium dodecylbenzenesulfonate.
【０１１０】次いで、このガラス製反応器内に窒素ガス
を導入して反応器内の空気を窒素ガスで置換した後、水
性反応母液を８２℃に加熱して反応を開始させた。反応
が開始した直後より、この滴下ロートから上記単量体水
性分散液１０３部を１８０分かけて滴下し、乳化重合を
行った。この間反応液の温度を、８２℃に保持した。Then, nitrogen gas was introduced into the glass reactor to replace the air in the reactor with nitrogen gas, and then the aqueous reaction mother liquor was heated to 82 ° C. to start the reaction. Immediately after the reaction was started, 103 parts of the above monomer aqueous dispersion was added dropwise from this dropping funnel over 180 minutes to carry out emulsion polymerization. During this time, the temperature of the reaction solution was maintained at 82 ° C.
【０１１１】１８０分経過後さらに１２０分間反応液の
温度を８２℃に維持して重合反応を完結させた、反応液
を２５℃に冷却した後、反応液のｐＨ値を７.０付近に
調整した。After the lapse of 180 minutes, the temperature of the reaction solution was maintained at 82 ° C. for another 120 minutes to complete the polymerization reaction. After cooling the reaction solution to 25 ° C., the pH value of the reaction solution was adjusted to around 7.0. did.
【０１１２】試料（感圧接着テープ）の作成 上記の感圧接着剤を、アプリケータを用いてコロナ放電
処理をした２５μのポリエステルフィルムおよび上質紙
に乾燥後の塗膜が２５μの厚みとなるように塗工した。Preparation of Sample (Pressure Sensitive Adhesive Tape) The above pressure sensitive adhesive was applied to a 25 μ polyester film and high-quality paper which had been corona-discharge treated using an applicator so that the coating film after drying would have a thickness of 25 μ. Applied to.
【０１１３】次いで、１０５℃で３分間乾燥して剥離紙
と貼合し、試料を作成した。次に、下記の方法で感圧接
着テープの性能評価を行った。試験方法： （１）重合安定性：重合安定性は、反応液を目視で観察
して、凝集物の存在が殆ど認められない場合を○とし、
若干の凝集物の存在が認められた場合を△とし、多くの
凝集物の存在が認められた場合を×とした。 （２）粘着力：ＪＩＳ Ｚ−０２３７に規定されている
試験板に対する１８０゜引きはがし粘着力をインストロ
ン型引張試験機を用いて測定した。試験板にはＳＵＳ３
０４を用いた。 （３）保持力：ＪＩＳ Ｚ−０２３７に規定されている
保持力の測定法に準じて４０℃で１kgの荷重をかけて落
下するまでの時間を測定した。試験板にはＳＵＳ３０４
を用いた。 （４）再剥離性：ＰＥＴフィルムおよび上質紙を各試験
板に貼着し、２kgのゴムロールで２往復して圧着し、５
℃、２３℃、１２０℃、１８０℃の各温度で６０分間保
存し、室温まで冷却してから再剥離性と同様にして評価
した。Then, it was dried at 105 ° C. for 3 minutes and laminated with release paper to prepare a sample. Next, the performance of the pressure-sensitive adhesive tape was evaluated by the following method. Test method: (1) Polymerization stability: Polymerization stability was evaluated as ○ when the presence of aggregates was hardly observed by visually observing the reaction solution.
When the presence of some agglomerates was observed, it was marked with Δ, and when the presence of many agglomerates was recognized, it was marked with x. (2) Adhesive force: 180 ° peeling adhesive force to a test plate specified in JIS Z-0237 was measured using an Instron type tensile tester. SUS3 for the test plate
04 was used. (3) Holding power: According to the measuring method of the holding power defined in JIS Z-0237, a load of 1 kg was applied at 40 ° C. and the time until falling was measured. SUS304 for the test plate
Was used. (4) Removability: PET film and high-quality paper were attached to each test plate, and then reciprocated twice with a rubber roll of 2 kg to perform pressure bonding.
It was stored for 60 minutes at each temperature of ° C, 23 ° C, 120 ° C, and 180 ° C, cooled to room temperature, and then evaluated in the same manner as the removability.
【０１１４】結果を表１に示す。The results are shown in Table 1.
【０１１５】[0115]
【表１】 [Table 1]
Claims (1)
る（メタ）アクリル酸アルキルエステル４０〜９９.９
重量部と、（ｂ）該（メタ）アクリル酸アルキルエステ
ルと共重合可能なカルボキシル基含有単量体０.１〜１
０重量部と、（ｃ）該（メタ）アクリル酸アルキルエス
テル（ａ）および該カルボキシル基含有単量体（ｂ）の
いずれとも共重合可能であって、ニトリル基、アミド
基、水酸基、Ｎ-メチロール基、Ｎ-メトキシアルキル
基、フェニル基、ハロゲン基、アルコキシ基およびグリ
シジル基からなる群から選ばれる官能基を含有する単量
体０．１〜１０重量部［但し、上記（ｂ）と（ｃ）との
合計は０．２〜２０重量部である］と、 上記（ａ）＋（ｂ）＋（ｃ）の合計１００重量部に対し
て、（ｄ）ポリオキシアルキレン基[i]と、 アルキルフェニルオキシ基、アルキルフェニル基および
アルキル基から選ばれる親油性基[ii]と、 エチレン性二重結合を有するラジカル重合性官能基[ii
i]とを有し、かつ、 上記ポリオキシアルキレン基[i]と、 上記アルキルフェニルオキシ基、アルキルフェニル基お
よびアルキル基から選ばれる親油性基[ii]とが、置換ま
たは未置換の炭化水素基を介して結合しているか、また
は直接結合している、反応性界面活性剤０.１〜７０重
量部とを、乳化重合してなることを特徴とする水系再剥
離型感圧接着剤。1. A (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms (40 to 99.9).
Parts by weight, and (b) a carboxyl group-containing monomer 0.1 to 1 copolymerizable with the (meth) acrylic acid alkyl ester.
0 part by weight, and (c) the (meth) acrylic acid alkyl ester (a) and the carboxyl group-containing monomer (b) can be copolymerized, and a nitrile group, an amide group, a hydroxyl group, N- 0.1 to 10 parts by weight of a monomer containing a functional group selected from the group consisting of a methylol group, an N-methoxyalkyl group, a phenyl group, a halogen group, an alkoxy group and a glycidyl group [provided that (b) and ( c) is 0.2 to 20 parts by weight], and (d) polyoxyalkylene group [i] is added to 100 parts by weight of (a) + (b) + (c). , A lipophilic group [ii] selected from an alkylphenyloxy group, an alkylphenyl group and an alkyl group, and a radically polymerizable functional group having an ethylenic double bond [ii]
i] and the above-mentioned polyoxyalkylene group [i] and the above-mentioned alkylphenyloxy group, an alkylphenyl group and a lipophilic group [ii] selected from an alkyl group are substituted or unsubstituted hydrocarbons. An aqueous re-peelable pressure-sensitive adhesive characterized by emulsion-polymerizing 0.1 to 70 parts by weight of a reactive surfactant, which is bonded via a group or is directly bonded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29347593A JP3748274B2 (en) | 1993-04-12 | 1993-11-24 | Water-based re-peelable pressure sensitive adhesive |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8458193 | 1993-04-12 | ||
| JP5-84581 | 1993-04-12 | ||
| JP29347593A JP3748274B2 (en) | 1993-04-12 | 1993-11-24 | Water-based re-peelable pressure sensitive adhesive |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004038729A Division JP2004263183A (en) | 1993-04-12 | 2004-02-16 | Water-based removable pressure-sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06346038A true JPH06346038A (en) | 1994-12-20 |
| JP3748274B2 JP3748274B2 (en) | 2006-02-22 |
Family
ID=26425597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29347593A Expired - Lifetime JP3748274B2 (en) | 1993-04-12 | 1993-11-24 | Water-based re-peelable pressure sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3748274B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10298513A (en) * | 1997-04-25 | 1998-11-10 | Oji Paper Co Ltd | Removable adhesive label |
| JP2001031938A (en) * | 1999-07-21 | 2001-02-06 | Nippon Zeon Co Ltd | Latex for removable pressure-sensitive adhesive, removable pressure-sensitive adhesive composition using the same, and recording material using the same |
| WO2008081755A1 (en) * | 2006-12-25 | 2008-07-10 | Nitto Denko Cs System Corporation | Adhesive tape and fixing method using the same |
| JP2021025407A (en) * | 2019-07-31 | 2021-02-22 | 旭化成建材株式会社 | Heat insulation method of architectural structure, heat insulation structure of architectural structure, adhesive and surface protective material |
-
1993
- 1993-11-24 JP JP29347593A patent/JP3748274B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10298513A (en) * | 1997-04-25 | 1998-11-10 | Oji Paper Co Ltd | Removable adhesive label |
| JP2001031938A (en) * | 1999-07-21 | 2001-02-06 | Nippon Zeon Co Ltd | Latex for removable pressure-sensitive adhesive, removable pressure-sensitive adhesive composition using the same, and recording material using the same |
| WO2008081755A1 (en) * | 2006-12-25 | 2008-07-10 | Nitto Denko Cs System Corporation | Adhesive tape and fixing method using the same |
| JP2021025407A (en) * | 2019-07-31 | 2021-02-22 | 旭化成建材株式会社 | Heat insulation method of architectural structure, heat insulation structure of architectural structure, adhesive and surface protective material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3748274B2 (en) | 2006-02-22 |
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