CN1753965A - Emulsion-type pressure sensitive adhesive and process for producing the same - Google Patents
Emulsion-type pressure sensitive adhesive and process for producing the same Download PDFInfo
- Publication number
- CN1753965A CN1753965A CN 200480005491 CN200480005491A CN1753965A CN 1753965 A CN1753965 A CN 1753965A CN 200480005491 CN200480005491 CN 200480005491 CN 200480005491 A CN200480005491 A CN 200480005491A CN 1753965 A CN1753965 A CN 1753965A
- Authority
- CN
- China
- Prior art keywords
- methyl
- monomer
- alkyl acrylate
- sensitive adhesive
- pressure sensitive
- 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 103
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 180
- 239000000084 colloidal system Substances 0.000 claims abstract description 106
- 230000001681 protective effect Effects 0.000 claims abstract description 100
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 45
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 93
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 92
- 239000012736 aqueous medium Substances 0.000 claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 27
- 230000007704 transition Effects 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 10
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 abstract 1
- -1 vinyl halide Chemical class 0.000 description 43
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 40
- 239000000839 emulsion Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 33
- 239000013543 active substance Substances 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 239000002390 adhesive tape Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 239000004821 Contact adhesive Substances 0.000 description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 235000019394 potassium persulphate Nutrition 0.000 description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 230000035807 sensation Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229940065472 octyl acrylate Drugs 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006886 vinylation reaction Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229950007687 macrogol ester Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PWYYERNADDIMJR-UHFFFAOYSA-N pentyl but-2-enoate Chemical compound CCCCCOC(=O)C=CC PWYYERNADDIMJR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- YCBKMWAUQKGKBB-UHFFFAOYSA-N 1-(aziridin-1-yl)-2-methylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CC1 YCBKMWAUQKGKBB-UHFFFAOYSA-N 0.000 description 1
- SCMVPOVMOHQFKU-UHFFFAOYSA-N 1-(aziridin-1-yl)prop-2-en-1-one Chemical compound C=CC(=O)N1CC1 SCMVPOVMOHQFKU-UHFFFAOYSA-N 0.000 description 1
- 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 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- JFZBUNLOTDDXNY-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OCC(C)OC(=O)C(C)=C JFZBUNLOTDDXNY-UHFFFAOYSA-N 0.000 description 1
- DGZIMLVEXGVYDW-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(=O)C=C DGZIMLVEXGVYDW-UHFFFAOYSA-N 0.000 description 1
- PDSHPFREJVIDNV-UHFFFAOYSA-N 2-methoxyethyl trimethyl silicate Chemical compound COCCO[Si](OC)(OC)OC PDSHPFREJVIDNV-UHFFFAOYSA-N 0.000 description 1
- NSIWGZFZGMIPEC-UHFFFAOYSA-N 2-propoxyethyl 2-methylprop-2-enoate Chemical compound CCCOCCOC(=O)C(C)=C NSIWGZFZGMIPEC-UHFFFAOYSA-N 0.000 description 1
- ACHWNFGWACZQHU-UHFFFAOYSA-N 2-propoxyethyl prop-2-enoate Chemical compound CCCOCCOC(=O)C=C ACHWNFGWACZQHU-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- VGIIKDXZZPQRQL-UHFFFAOYSA-N C(C=CC)(=O)OCCCCCCCCCCCCCCC Chemical compound C(C=CC)(=O)OCCCCCCCCCCCCCCC VGIIKDXZZPQRQL-UHFFFAOYSA-N 0.000 description 1
- BDJVEBUABHVBJH-UHFFFAOYSA-N C(CCCCCCCCCC)OC(=O)C=CC Chemical compound C(CCCCCCCCCC)OC(=O)C=CC BDJVEBUABHVBJH-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 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
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DXSOPPVDQKAVFB-UHFFFAOYSA-N heptadecyl but-2-enoate Chemical compound C(CCCCCCCCCCCCCCCC)OC(=O)C=CC DXSOPPVDQKAVFB-UHFFFAOYSA-N 0.000 description 1
- LAAFBFYXEJYWMQ-UHFFFAOYSA-N hexadecyl but-2-enoate Chemical compound C(CCCCCCCCCCCCCCC)OC(=O)C=CC LAAFBFYXEJYWMQ-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid 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
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- UNBDCVXGGDKSCP-UHFFFAOYSA-N methyl 2-methylidenetetradecanoate Chemical compound CCCCCCCCCCCCC(=C)C(=O)OC UNBDCVXGGDKSCP-UHFFFAOYSA-N 0.000 description 1
- ZYASLVDNDXUOMI-UHFFFAOYSA-N n,n-dimethylmethanamine;prop-2-enoic acid Chemical compound C[NH+](C)C.[O-]C(=O)C=C ZYASLVDNDXUOMI-UHFFFAOYSA-N 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- FXQLMXPTQYAUPK-UHFFFAOYSA-N n-ethyl-n-methoxy-2-methylprop-2-enamide Chemical compound CCN(OC)C(=O)C(C)=C FXQLMXPTQYAUPK-UHFFFAOYSA-N 0.000 description 1
- UBVMBXTYMSRUDX-UHFFFAOYSA-N n-prop-2-enyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC=C UBVMBXTYMSRUDX-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- LYJZNXAVZMEXDH-UHFFFAOYSA-N octadecan-8-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCC LYJZNXAVZMEXDH-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- QHSPZGZEUDEIQM-UHFFFAOYSA-N tert-butyl but-2-enoate Chemical compound CC=CC(=O)OC(C)(C)C QHSPZGZEUDEIQM-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- NCYNWQDLQJUTIY-UHFFFAOYSA-N tetradecyl but-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=CC NCYNWQDLQJUTIY-UHFFFAOYSA-N 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
An emulsion-type pressure sensitive adhesive characterized in that it is one obtained by (co)polymerization of main monomers with the use of, as a protective colloid, an acrylic copolymer of 500 to 50,000 weight average molecular weight, the acrylic copolymer obtained by copolymerization of at least one hydrophilic monomer (A) selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate and (meth)acrylic acid and a (meth)acrylic acid alkyl ester (B) whose alkyl has 4 to 18 carbon atoms used in a weight ratio of 40 to 70 : 60 to 30, or obtained by copolymerization of monomer (A), monomer (B) and a third monomer (C) of acrylonitrile and/or styrene used in a weight ratio of (A) : [(B)+(C)] of 40 to 70 : 60 to 30 and further a weight ratio of (B) : (C) of 99.9 to 20 : 0.1 to 80. There is further provided a process for producing this emulsion-type pressure sensitive adhesive.
Description
Technical field
The present invention relates to a kind of method and emulsion-type pressure sensitive adhesive that uses protective colloid to produce emulsion-type pressure sensitive adhesive.More particularly, the present invention relates to a kind of method of emulsion-type pressure sensitive adhesive and emulsion-type pressure sensitive adhesive that obtains by this method of in the presence of the protective colloid that comprises specific hydrophilic monomer, stably preparing.
Background technology
The polymerization of dispersive such as vinyl acetate, (methyl) acrylate, methacrylic acid and cinnamic unsaturated compound makes unsaturated compound utilize tensio-active agent and/or water-soluble high-molecular compound to be scattered in the emulsion fully, to carry out continuously with the mode of afterreaction with this in water solvent.
For the wetting ability unsaturated compound that stably is dispersed in the aqueous medium, used tensio-active agent or water-soluble high-molecular compound must have high-hydrophilic in forming emulsion.Be used to disperse the tensio-active agent of unsaturated compound or thin polymkeric substance that water-soluble high-molecular compound adheres to unsaturated compound around.And, residual adhere to the water tolerance that tensio-active agent around the polymer beads or water-soluble high-molecular compound cause low product polymkeric substance.
When the water tolerance of the polymkeric substance of strengthening being produced, the stability of reaction system is worsened, thereby the unsaturated compound in water medium demonstrates the dispersion stabilization of decline, and in reaction process the polymer beads precipitation.
In other words, the reaction that is in the unsaturated compound of emulsion state requires this unsaturated compound to disperse with being stabilized, although and tensio-active agent or water-soluble high-molecular compound after reaction is finished, adhere to aggregated particles around, this tensio-active agent or water-soluble high-molecular compound also can not reduce the water tolerance of polymer beads.But, the requirement that conventional tensio-active agent or water-soluble high-molecular compound are difficult to satisfy this contradiction.
The problem that is run in the polymerization unsaturated compound process in aqueous medium; JP-A-H08-239408 discloses the monomer polymerization in having the water miscible liquid of the polymer protection colloid that is not less than 20000 weight average molecular weight when existing, and wherein the polymer protection colloid comprises that (I) has (methyl) acrylate, (III) principal monomer that the unsaturated monomer of the vinylation of acidic group or anhydride group, (II) have a fatty alcohol of 10 or more carbon atoms and be selected from (methyl) vinylformic acid C
1～9Alkyl ester, have 20 or still less vinyl esters of carboxylic acids, the vinylation of carbon atom unsaturated nitrile, vinyl halide and have 2～8 carbon atoms and the aliphatic hydrocrbon of 1 or 2 two key and (IV) other monomer.
JP-A-2001-122911 discloses a kind of method of emulsion polymerization of unsaturated compound of the unsaturated group with vinylation unsaturated group, and wherein this method has been used the protective colloid as the water solubility copolymer of the homopolymer of the N-vinyl carboxyl amine of N-vinyl acetamide or N-vinyl carboxyl amine and the compound that can close with this N-vinyl carboxyl amine copolymer.
The use of protective colloid can improve the dispersion stabilization of polymkeric substance, but the product polymkeric substance that existence use protective colloid obtains is to the insufficient problem of adhesion characteristics on wet surface.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing emulsion-type pressure sensitive adhesive, can obtain the good dispersion of monomer and polymkeric substance thus, and resulting polymkeric substance can form the pressure sensitive adhesive that demonstrates good adhesion characteristics to wet surface.
Although another object of the present invention provide a kind of for emulsion-type but still demonstrate good to wet surface adhesion characteristics and utilize monomer and emulsion-type pressure sensitive adhesive that the good dispersion of polymkeric substance is produced.
First kind of method according to production emulsion-type pressure sensitive adhesive of the present invention is included in protective colloid and has (being total to) polymerization principal monomer down, and described protective colloid is the acrylic copolymer that comprises following component:
At least a hydrophilic monomer (A-1) that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate; With
(methyl) alkyl acrylate (B-1) should have 4～18 carbon atoms with (A-1) hydrophilic monomer copolymerization and its alkyl by (methyl) alkyl acrylate;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the copolymerization weight ratio in 60～30 scopes closes;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
Second kind of method according to production emulsion-type pressure sensitive adhesive of the present invention is included in protective colloid and has (being total to) polymerization principal monomer down, and described protective colloid is the acrylic copolymer that comprises following component:
At least a wetting ability (A-1) monomer that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate; With
(methyl) alkyl acrylate (B-1), should (methyl) alkyl acrylate be can with the copolymerization of (A-1) hydrophilic monomer and its alkyl have 4～18 carbon atoms; With
Be vinyl cyanide and/or cinnamic the 3rd monomer (C);
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-1) in 60～30 scopes: [(B-1)+(C)] weight ratio and 99.9～20: (B-1) in 0.1～80 scope: (C) weight ratio is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
The third method according to production emulsion-type pressure sensitive adhesive of the present invention is included in protective colloid and has (being total to) polymerization principal monomer down, and described protective colloid is the acrylic copolymer that comprises following component:
Vinylformic acid and/or methacrylic acid hydrophilic monomer (A-2); With
(methyl) alkyl acrylate (B-2), should (methyl) alkyl acrylate be can with the copolymerization of (A-2) hydrophilic monomer and its alkyl have 4～9 carbon atoms;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the weight ratio in 60～30 scopes is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
The 4th kind of method according to production emulsion-type pressure sensitive adhesive of the present invention is included in protective colloid and has (being total to) polymerization principal monomer down, and described protective colloid is the acrylic copolymer that comprises following component:
Vinylformic acid and/or methacrylic acid hydrophilic monomer (A-2);
(methyl) alkyl acrylate (B-2), should (methyl) alkyl acrylate be can with the copolymerization of (A-2) hydrophilic monomer and its alkyl have 4～9 carbon atoms; With
Be vinyl cyanide and/or cinnamic the 3rd monomer (C);
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-2) in 60～30 scopes: [(B-2)+(C)] weight ratio and 99.9～20: (B-2) in 0.1～80 scope: (C) weight ratio is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
First kind of emulsion-type pressure sensitive adhesive according to the present invention comprises aqueous medium and (being total to) polymkeric substance that is scattered in this aqueous medium; should obtain by (be total to) the polymerization principal monomer in the presence of protective colloid by (being total to) polymkeric substance, described protective colloid is the acrylic acid series that comprises following component:
At least a hydrophilic monomer (A-1) that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate; With
(methyl) alkyl acrylate (B-1), should (methyl) alkyl acrylate be can with the copolymerization of (A-1) hydrophilic monomer and its alkyl have 4～18 carbon atoms;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the weight ratio in 60～30 scopes is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
Second kind of emulsion-type pressure sensitive adhesive according to the present invention comprises aqueous medium and (being total to) polymkeric substance that is scattered in the aqueous medium; should obtain by (be total to) the polymerization principal monomer in the presence of protective colloid by (being total to) polymkeric substance, described protective colloid is the acrylic copolymer that comprises following component:
At least a hydrophilic monomer (A-1) that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate;
(methyl) alkyl acrylate (B-1) should (methyl) alkyl acrylate be to have 4～18 carbon atoms with (A-1) hydrophilic monomer copolymerization and its alkyl; With
Be vinyl cyanide and/or cinnamic the 3rd monomer (C);
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-1) in 60～30 scopes: [(B-1)+(C)] weight ratio and 99.9～20: (B-1) in 0.1～80 scope: (C) weight ratio is carried out copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
The third emulsion-type pressure sensitive adhesive according to the present invention comprises aqueous medium and (being total to) polymkeric substance that is scattered in this aqueous medium; should obtain by (be total to) the polymerization principal monomer in the presence of protective colloid by (being total to) polymkeric substance, described protective colloid is the acrylic copolymer that comprises following component:
Vinylformic acid and/or methacrylic acid hydrophilic monomer (A-2); With
(methyl) alkyl acrylate (B-2), should (methyl) alkyl acrylate be can with the copolymerization of (A-2) hydrophilic monomer and its alkyl have 4～9 carbon atoms;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the weight in 60～30 scopes is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
The 4th kind of emulsion-type pressure sensitive adhesive according to the present invention comprises aqueous medium and (being total to) polymkeric substance that is scattered in this aqueous medium; should obtain by (be total to) the polymerization principal monomer in the presence of protective colloid by (being total to) polymkeric substance, described protective colloid is the acrylic copolymer that comprises following component:
Vinylformic acid and/or methacrylic acid hydrophilic monomer (A-2);
(methyl) alkyl acrylate (B-2), should (methyl) alkyl acrylate be can with the copolymerization of (A-2) hydrophilic monomer and its alkyl have 4～9 carbon atoms; With
Be vinyl cyanide and/or cinnamic the 3rd monomer (C);
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-2) in 60～30 scopes: [(B-2)+(C)] weight ratio and 99.9～20: (B-2) in 0.1～80 scope: (C) weight ratio is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
In producing first kind to the 4th kind method of emulsion-type pressure sensitive adhesive, deposit the pressure sensitive adhesive that principal monomer obtains and have the second-order transition temperature (Tg) that is not higher than 0 ℃ by in the presence of protective colloid, (being total to) polymerization.
Use (being total to) polymerization of the principal monomer of above-mentioned protective colloid can make dispersive monomer and the very high dispersion stabilization of polymkeric substance acquisition that obtains in water medium.And, although the pressure sensitive adhesive of the present invention that obtains as mentioned above is emulsion-type but still demonstrates the good adhesion characteristics to wet surface.
Embodiment
Hereinafter, will the method for emulsion-type pressure sensitive adhesive produced according to the invention be described in detail.
The production method of emulsion-type pressure sensitive adhesive is used specific protective colloid and is carried out (being total to) polymerization of principal monomer.
As described below, first kind and second kind method of producing emulsion-type pressure sensitive adhesive is to carrying out (being total to) polymerization of principal monomer in the presence of protective colloid.
Protective colloid used herein is the acrylic copolymer that comprises specific hydrophilic monomer (A-1) and specific (methyl) alkyl acrylate (B-1).
Hydrophilic monomer (A-1) is at least a monomer that is selected from the group that comprises acrylamide (AM), Methacrylamide, Hydroxyethyl acrylate (HEA) and hydroxyethyl methylacrylate (HEMA).These hydrophilic monomers can use individually or use in combination arbitrarily.
With hydrophilic monomer (A-1) copolymerization with (methyl) alkyl acrylate (B-1) of forming protective colloid for can with the copolymerization of (A-1) hydrophilic monomer and its alkyl have 4～18, (methyl) alkyl acrylates (B-1) of preferred 4～8 carbon atoms.The example of these (methyl) alkyl acrylates (B-1) comprises (methyl) alkyl acrylate with straight chained alkyl, as (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl; And (methyl) alkyl acrylate with branched-chain alkyl, as (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid t-butyl ester.These (methyl) alkyl acrylates (B-1) can use individually or use in combination.Especially, the present invention preferably uses (methyl) alkyl acrylate with branched-chain alkyl, particularly (methyl) ethyl acrylate, Isooctyl acrylate monomer.
And the protective colloid that the present invention uses can be by copolymerization hydrophilic monomer (A-1), its alkyl has (methyl) alkyl acrylate (B-1) of 4～18 carbon atoms and the acrylic copolymer that obtains as vinyl cyanide and/or cinnamic the 3rd monomer (C).
Use as the multipolymer that is made of hydrophilic monomer (A-1) and (methyl) alkyl acrylate (B-1) of protective colloid makes the pressure sensitive adhesive that is used to prepare the monomer of pressure sensitive adhesive and obtains demonstrate dispersiveness, and also makes the pressure sensitive adhesive that obtains give play to the good adhesion characteristics to wet surface.
When protective colloid was the acrylic copolymer of being made up of hydrophilic monomer (A-1) and (methyl) alkyl acrylate (B-1), the preparation of multipolymer related to by 40～70: 60～30, preferred 60～70: the hydrophilic monomer of the weight ratio in 40～30 scopes (A-1) and (methyl) alkyl acrylate (B-1) (gross weight is 100 weight parts).Use as the multipolymer of the hydrophilic monomer with above-mentioned weight ratio (A-1)/(methyl) alkyl acrylate (B-1) of protective colloid makes the pressure sensitive adhesive that is used to form the principal monomer of pressure sensitive adhesive and obtains stably disperse in aqueous medium, and also makes the pressure sensitive adhesive that utilizes protective colloid to obtain give play to the good adhesion characteristics to wet surface.Hydrophilic monomer (A-1) and (methyl) alkyl acrylate (B-1) of being used to form protective colloid are the monomer of hyperergy, and the monomeric amount that wherein is loaded into is approximately consistent with the composition of the multipolymer that obtains.For example, when the preferred monomer acrylamide of the present invention (AM) and (methyl) acrylic acid-2-ethyl polyhexamethylene (2EHA) are loaded into 60: 40 weight ratio, the product multipolymer will have the composition of 60: 40 (weight ratio) according to the weight ratio of being packed into.
When protective colloid is by hydrophilic monomer (A-1); during (methyl) alkyl acrylate (B-1) and the 3rd monomer (C) constitute specific acrylic copolymer; the acrylic copolymer that uses has 40～70: 60～30; preferred 60～70: the weight ratio [(hydrophilic monomer (A-1)): (specific (methyl) alkyl acrylate (B-1)+the 3rd monomer (C))] (gross weight is 100 weight parts) in 40～30 scopes and: 0.1～80 99.9～20; preferred 99.9～40: the weight ratio [specific (methyl) alkyl acrylate (B-1): the 3rd monomer (C)] (gross weight is 100 weight parts) in 0.1～60 scope.The 3rd monomer (C) that uses with above-mentioned amount has improved the polymerization stability that forms the acrylic copolymer of protective colloid.Any (C) that surpasses the amount of 80wt% with respect to (B-1) and (C) summation can cause the polymerization stability of difference, and this is worthless.
The third and the 4th kind of method of being used to produce emulsion-type pressure sensitive adhesive are carried out (being total to) polymerization of principal monomer in the presence of specific protective colloid.
The protective colloid of Shi Yonging is the acrylic copolymer that is made of specific hydrophilic monomer (A-2) and specific (methyl) acrylic acid alkyl (B-2) herein.
Hydrophilic monomer (A-2) is vinylformic acid (AA) and/or methacrylic acid (MA).Just, hydrophilic monomer (A-2) can only be a kind of in vinylformic acid (AA) and the methacrylic acid (MA), maybe can be the combination of vinylformic acid (AA) and methacrylic acid (MA).When hydrophilic monomer (A-2) be vinylformic acid (AA) and methacrylic acid (MA) in conjunction with the time, vinylformic acid (AA) and methacrylic acid (MA) can be arbitrarily than being used.
With hydrophilic monomer (A-2) copolymerization with (methyl) alkyl acrylate (B-2) that forms protective colloid can be with hydrophilic monomer (A-2) copolymerization and its alkyl have 4～9, (methyl) alkyl acrylates (B-2) of preferred 4～8 carbon atoms.The example of these (methyl) alkyl acrylates (B-2) comprises (methyl) alkyl acrylate with alkyl, as (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems; (methyl) alkyl acrylate with branched-chain alkyl is as (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid-t-butyl ester.These (methyl) alkyl acrylates (B-1) can use individually or use in combination arbitrarily.Especially, the present invention preferably uses (methyl) alkyl acrylate with branched-chain alkyl, particularly (methyl) ethyl acrylate, vinylformic acid-t-butyl ester, Isooctyl acrylate monomer.
The protective colloid that the present invention uses can be by copolymerization hydrophilic monomer (A-2), its alkyl has (methyl) alkyl acrylate (B-2) of 4～9 carbon atoms and the acrylic copolymer that obtains as vinyl cyanide and/or cinnamic the 3rd monomer (C).
The use by hydrophilic monomer (A-2) and (methyl) alkyl acrylate (B-2) formation multipolymer as protective colloid makes the pressure sensitive adhesive that is used to prepare the monomer of pressure sensitive adhesive and obtains demonstrate dispersiveness, and also makes the pressure sensitive adhesive that obtains give play to the good adhesion characteristics to wet surface.
When protective colloid was the acrylic copolymer of being made up of hydrophilic monomer (A-2) and (methyl) alkyl acrylate (B-2), the preparation of multipolymer related to 40～70: 60～30, preferred 60～70: hydrophilic monomer (A-2) and (methyl) alkyl acrylate (B-2) (gross weight is 100 weight parts) of the weight ratio in 40～30 scopes.Use as the multipolymer of the hydrophilic monomer with above-mentioned weight ratio (A-2)/(methyl) alkyl acrylate (B-2) of protective colloid makes the pressure sensitive adhesive that is used to form the principal monomer of pressure sensitive adhesive and obtains disperse in aqueous medium with being stabilized, and it is good in wet surperficial adhesion characteristics that the pressure sensitive adhesive that utilizes protective colloid to obtain has been given play to.Hydrophilic monomer (A-2) and (methyl) alkyl acrylate (B-2) of being used to form protective colloid are the monomer of hyperergy, and the monomeric amount of wherein packing into is approximately consistent with the composition of the multipolymer that obtains.For example, when the preferred monomer vinylformic acid of the present invention (AA) and (methyl) 2-ethylhexyl acrylate (2EHA) are loaded into 60: 40 weight ratio, the product multipolymer will have the composition of 60: 40 (weight ratio) according to the weight ratio of being packed into.
When protective colloid is by hydrophilic monomer (A-2); during special acrylic copolymer that specific (methyl) alkyl acrylate (B-2) and the 3rd monomer (C) constitute, the acrylic copolymer of use has 40～70: 60～30; preferred 60～70: the weight ratio [(hydrophilic monomer (A-2)): (specific (methyl) alkyl acrylate (B-2)+the 3rd monomer (C))] in 40～30 scopes; with 99.9～20: 0.1～80; preferred 99.9～40: the weight ratio [specific (methyl) alkyl acrylate (B-2): the 3rd monomer (C)] (gross weight is 100 weight parts) in 0.1～60 scope.The 3rd monomer (C) that uses with above-mentioned amount has improved the polymerization stability that forms the acrylic copolymer of protective colloid.Any (C) that surpasses the amount of 80wt% can cause the polymerization stability of difference, and this is worthless.
The multipolymer that is formed on protective colloid used in the production method of emulsion-type pressure sensitive adhesive of the present invention has the weight average molecular weight of 500～50000 scopes, preferred 500～10000 scopes.Use as the multipolymer with this weight average molecular weight of protective colloid makes the pressure sensitive adhesive that is used for the principal monomer of pressure sensitive adhesive and obtains advantageously disperse at aqueous medium.
The multipolymer that forms protective colloid can be by disperseing in aqueous medium and copolymerization hydrophilic monomer (A-1) or (A-2) produced with (methyl) alkyl acrylate (B-1) or (B-2).Tensio-active agent is used in and disperses hydrophilic monomer (A-1) or (A-2) and (methyl) alkyl acrylate (B-1) or (B-2).Tensio-active agent used herein can be any negatively charged ion, positively charged ion, nonionic or zwitterionics.The present invention preferably uses anionic or non-ionic tensio-active agent.Tensio-active agent can or use in combination by single ground.Based on the hydrophilic monomer (A-1) of per 100 weight parts or (A-2) and (methyl) alkyl acrylate (B-1) or gross weight (B-2), the amount of tensio-active agent is generally in 30～100 weight parts, preferred 50～80 weight part scopes.
The present invention can use dispersion agent together or do not use tensio-active agent and only use dispersion agent with tensio-active agent.The example that is used in dispersion agent of the present invention comprises water-soluble high-molecular compound such as polyvinyl alcohol.Based on the hydrophilic monomer (A-1) of per 100 weight parts or (A-2) and (methyl) alkyl acrylate (B-1) or gross weight (B-2), the amount of dispersion agent generally be not more than 200 weight parts, preferably in 50～150 weight part scopes.
Polymerization starter is used in the formation of protective colloid.The example that is used in the polymerization starter of protective colloid production comprises as ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide, the two compounds (azobis compound) of azo and organo-peroxide.Based on the hydrophilic monomer (A-1) of per 100 weight parts or (A-2) and (methyl) alkyl acrylate (B-1) or gross weight (B-2), the amount of reaction initiator generally be not more than 5 weight parts, preferably in 2～4 weight part scopes.
In addition, the production of protective colloid preferably relates to the use of chain-transfer agent.The example that is used for chain-transfer agent of the present invention comprises n-lauryl mercaptan, butanethiol, 3-thiohydracrylic acid, Thiovanic acid and mercaptoacetate.Based on the hydrophilic monomer (A-1) of per 100 weight parts or (A-2) and (methyl) alkyl acrylate (B-1) or gross weight (B-2), the amount of chain-transfer agent generally be not more than 10 weight parts, preferably in 0.01～2 weight part scope.
Protective colloid can be by disperseing in aqueous medium and copolymerization hydrophilic monomer (A-1) or (A-2) produce with (methyl) alkyl acrylate (B-1) or (B-2).Temperature of reaction generally in 60～90 ℃, preferred 70～85 ℃ of scopes, and the reaction times under these conditions be generally 5～30 minutes, preferred 10～20 minutes.
Above-mentioned reaction produces the dispersion of protective colloid in water Jie character.Protective colloid can be used at after separating from aqueous medium, or can be used as the dispersion in the aqueous medium and be used.
In the production method of emulsion-type pressure sensitive adhesive of the present invention, principal monomer is to use any protective colloid as described above and (being total to) polymeric.
The principal monomer of Shi Yonging is a kind ofly can be dispersed in monomer in the water medium by protective colloid in the present invention.Spendable in the present invention monomeric example comprises the monomer with polymerisable unsaturated link(age).Monomer with polymerisable unsaturated link(age) is based on alkyl acrylate, and these monomeric examples with polymerisable unsaturated link(age) comprise following compound:
Alkyl acrylate is as methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, 2-EHA, Octyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, dodecylacrylate;
The vinylformic acid aryl ester is as phenyl acrylate, benzyl acrylate;
Vinylformic acid alcoxyl base alkane ester is as vinylformic acid methoxyl group ethyl ester, vinylformic acid ethoxy ethyl ester, vinylformic acid propoxy-ethyl ester, vinylformic acid butoxy ethyl ester, vinylformic acid oxyethyl group propyl ester;
Vinylformic acid and salt thereof are as acrylic acid an alkali metal salt;
Methacrylic acid and salt thereof are as an alkali metal salt of methacrylic acid;
Alkyl methacrylate is as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic acid 2-ethylhexyl, Octyl methacrylate, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate;
Aryl methacrylate is as phenyl methacrylate, benzyl methacrylate;
Methacrylic acid alkoxyl group alkane ester is as methacrylic acid methoxy base ethyl ester, methacrylic acid ethoxy ethyl ester, methacrylic acid propoxy-ethyl ester, methacrylic acid butoxy ethyl ester, methacrylic acid oxyethyl group propyl ester;
Diacrylate (gathering) alkylene glycol ester is as ethylene glycol diacrylate, diacrylate binaryglycol ester, diacrylate triglycol ester, diacrylate macrogol ester, diacrylate propylene glycol ester, dipropylene glycol diacrylate and diacrylate tripropylene glycol ester.
Dimethacrylate (gathering) alkylene glycol ester is as Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), dimethacrylate triglycol ester, dimethacrylate macrogol ester, dimethyl allene acid propylene glycol ester, dipropyleneglycol dimethacrylate and dimethacrylate tripropylene glycol ester.
Polyacrylic ester is as three vinylformic acid trishydroxymethyl propyl ester;
Polymethacrylate is as trimethylammonium vinylformic acid trishydroxymethyl propyl ester;
Vinyl cyanide;
Methacrylonitrile;
Vinyl acetate;
Vinylidene chloride;
The ethylene halide based compound is as vinylformic acid 2-monochloroethane ester and methacrylic acid 2-monochloroethane ester;
The acrylate of alicyclic alcohol is as the vinylformic acid cyclohexyl ester;
The methacrylic ester of alicyclic alcohol is as the methacrylic acid cyclohexyl ester;
The polymerisable compound that contains azoles quinoline base is as 2-vinyl-2-azoles quinoline, 2-vinyl-5-methyl-2-azoles quinoline and 2-pseudoallyl-2-azoles quinoline.
The polymerisable compound that contains '-aziridino is as acryloyl aziridine, methacryloyl aziridine, vinylformic acid-2-'-aziridino ethyl ester and methacrylic acid-2-'-aziridino ethyl ester;
The vinyl monomer that contains epoxy group(ing) is as glycidyl allyl ether, glycidyl acrylate, glycidyl methacrylate, acrylic acid-2-ethyl glycidyl ester and methacrylic acid 2-ethyl glycidyl ester.
The vinyl compound of hydroxyl is as vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacrylate, vinylformic acid-2-hydroxypropyl acrylate, acrylic or methacrylic acid and polypropylene glycol or the monoesters of polyoxyethylene glycol and the adducts of (methyl) vinylformic acid-2-hydroxyl ethyl ester and lactone;
Fluorine-containing vinyl monomer is as the alkyl methacrylate of fluorine replacement and the alkyl acrylate of fluorine replacement;
Undersaturated carboxylic acid is as compound and its acid anhydride of methylene-succinic acid (itaconicacid), Ba Dousuan (crotonic acid), toxilic acid and fumaric acid (not comprising (methyl) vinylformic acid) and salt and (part) esterification thereof;
The vinyl monomer that contains the halogen that responds is as 2-chloroethyl vinyl ether and vinyl monochloroacetate;
The vinyl monomer of amide-containing is as Methacrylamide, N-methylol methacrylamide, N-methoxy ethyl Methacrylamide and N-butoxymethyl Methacrylamide.
The vinyl monomer that contains organic silicon group is as vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane, allyltrimethoxysilanis, trimethoxy-silylpropyl allylamine and 2-methoxy ethoxy Trimethoxy silane; With
Be the macromonomer that has the vinyl polymer of complete polymerisable vinyl at its end (for example, the macromonomer of fluoro-type, contain the macromonomer of silicone and the macromonomer of styrene type).
These monomers can separately or be used in combination.
In the present invention, especially, be used in combination monomer, thereby gained (being total to) polymkeric substance has and is not higher than 0 ℃, the preferred second-order transition temperature (Tg) in-85～0 ℃ of scope.For example, preferably combination comprises 2-EHA (2EHA), vinylformic acid (AA) and vinyl cyanide (AN) (for example being 96: 2: 2).
Principal monomer is dispersed in the aqueous medium that contains low quantity of surfactant so that monomer emulsion to be provided.Tensio-active agent used herein can be any negatively charged ion, positively charged ion, nonionic, zwitter-ion and reactive tensio-active agent.The present invention preferably uses negatively charged ion or non-ionic tensio-active agent.These tensio-active agents can separately or be used in combination.Based on the blended principal monomer of per 100 weight parts, the amount of tensio-active agent is generally in the scope of 0.1～5 weight part, preferred 0.5～1.5 weight part.Aqueous medium used herein generally is a water, and based on the principal monomer of per 100 weight parts, the amount of aqueous medium is generally in the scope of 10～100 weight parts, preferred 25～50 weight parts.
The monomer emulsion that obtains as mentioned above is added drop-wise in the protective colloid dispersion while stirring lentamente, and reaction liquid generally be heated to 60～90 ℃, preferred 70～85 ℃ with the reaction principal monomer.Under this temperature, the reaction of principal monomer will need 2～6 hours, preferred 2～4 hours.
Principal monomer reacts under these conditions to form the pressure sensitive adhesive particle.Especially, the pressure sensitive adhesive that obtains of the reaction by under these conditions be distributed in 200000～1200000, the GPC weight average molecular weight in preferred 500000～800000 scopes.Protective colloid adheres to pressure sensitive adhesive particulate outside surface, and with pressure sensitive adhesive particle integrator, thereby be dispersed in the aqueous medium particle stabilizedly.
Pressure sensitive adhesive particle in aqueous medium generally has the average particulate diameter of 0.3～2.0 μ m, the median size in preferred 0.5～1.0 mu m range, and they stably are dispersed in the water medium.
Contain pressure sensitive adhesive particulate reaction liquid and be cooled to room temperature.Although disperse and can be used, a spot of tensio-active agent of preferred adding is in pressure sensitive adhesive particulate aqueous dispersion.Tensio-active agent used herein comprises that anion surfactant is as based on phosphatic tensio-active agent.Based on the resulting pressure sensitive adhesive particle of per 100 weight parts, the amount of tensio-active agent generally is not more than 5 weight parts, preferably in the scope of 1.0～3.0 weight parts.Use tensio-active agent that the pressure sensitive adhesive particle of formation more stably is dispersed in the aqueous medium with this consumption, can't worsen the adhesion characteristics of gained pressure sensitive adhesive wet surface.
In the pressure sensitive adhesive particle that so obtains, the multipolymer of protective colloid adheres to around the pressure sensitive adhesive particulate of principal monomer; The pressure sensitive adhesive particle integrator of multipolymer and principal monomer, and mainly be present on the pressure sensitive adhesive particulate surface.The Action of Surfactant that is present in the multipolymer of lip-deep protective colloid and randomly adds, thus pressure sensitive adhesive is dispersed in the aqueous medium particle stabilizedly.Simultaneously, the deep under the pressure sensitive adhesive particle surface by have good adhesive property, and the pressure sensitive adhesive that preferably has a second-order transition temperature (Tg) that is not higher than 0 ℃ form, and the deep provides good adhesion characteristic.In addition, when pressure sensitive adhesive of the present invention was applied to wet surface, the multipolymer of the protective colloid on the pressure sensitive adhesive particle surface absorbed the water on the adherend, to stop the negative impact of water to the adhesion characteristic of pressure sensitive adhesive.Therefore, pressure sensitive adhesive obtained by the method for the present invention demonstrates the good adhesion characteristics to wet surface.
Pressure sensitive adhesive can advantageously be administered to adherend and can be stripped from and be applied to again adherend, and promptly pressure sensitive adhesive is very excellent aspect adhesion characteristics (repeating bonding or the repetition peel property).It is impossible peeling off the pollution that causes being produced by remaining pressure sensitive adhesive on the adherend adherend surface.
The pressure sensitive adhesive that the inventive method obtains is generally the aqueous emulsion form.This aqueous emulsion can directly be used on the upholder that maybe can be administered to as polyester film, and dehydrated as the pressure sensitive adhesive band.Aqueous emulsion is administered to subsequent dewatering on the two sides of upholder application as double-sided pressure-sensitive adhesive agent band is provided.In addition, suitably select pressure sensitive adhesive to be applied on thereon the upholder and can be used as adhesive agent transition zone (adhesive transfer tape), wherein on upholder, form pressure sensitive adhesive layer, the lamination that is made of upholder and pressure sensitive adhesive layer is adhered on the adherend, the pressure sensitive adhesive layer of lamination is transferred on the surface of adherend then, and upholder is stripped from.
Embodiment
According to the following examples will present invention is described, but should think that the present invention is in no way limited to embodiment.
[embodiment 1]
In the flask of being furnished with agitator, reflux exchanger and dropping funnel, pack into based on the tensio-active agent of 1 weight part of the water of 40 weight parts, acrylamide (AM), 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA), the Potassium Persulphate as initiator (KPS) of 0.1 weight part and the n-lauryl mercaptan as chain-transfer agent of 0.04 weight part of 1.5 weight parts, replace air in the flask with nitrogen subsequently.
In an independent container, pack into the water of 40 weight parts, and the surfactant dissolves of 0.5 weight part is in wherein.Subsequently, the vinyl cyanide of 93.5 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA), 2 parts by weight of acrylic (AA) and 2 weight parts is added into solution with the preparation monomer emulsion.
Contents in the flask are heated to 75 ℃ and stirring, 15 minutes multipolymer (weight average molecular weights: 1000) with formation acrylamide (AM) and acrylic acid-2-ethyl polyhexamethylene (2EHA) of heating under this temperature.Afterwards, as above prepared monomer emulsion is under 75 ℃, dripped in 3 hours.
In addition, reaction is carried out finishing in 2 hours under 80 ℃, with postcooling.Subsequently, 1.5 weight parts is added into the preparation polymer emulsion based on phosphatic tensio-active agent.The pressure sensitive adhesive that so obtains has-67 ℃ second-order transition temperature (Tg), and weight average molecular weight is 750000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 1.
[embodiment 2]
(weight average molecular weight: 1100) use 1.5 parts by weight of acrylic hydroxyethyl esters (HEA) to replace the acrylamide (AM) of 1.5 weight parts is produced, polymer emulsion obtains with the method identical with embodiment 1 except the multipolymer of protective colloid.The pressure sensitive adhesive that obtains has-68 ℃ second-order transition temperature (Tg), and weight average molecular weight is 800000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 1.
[embodiment 3]
(weight average molecular weight: 900) use vinylbenzene (St) the replacement 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) of 0.5 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) and 0.5 weight part is produced, polymer emulsion obtains with the method identical with embodiment 1 except the multipolymer of protective colloid.The pressure sensitive adhesive that obtains has-66 ℃ second-order transition temperature (Tg), and weight average molecular weight is 800000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 1.
[comparative example 1]
(weight average molecular weight: 1200) use the acrylamide (AM) of the acrylamide (AM) of 0.75 weight part and 1.75 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) replacement 1.5 weight parts and 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) be produced, polymer emulsion obtains with the method identical with embodiment 1 except the multipolymer of protective colloid.The pressure sensitive adhesive that obtains has-68 ℃ second-order transition temperature (Tg), and weight average molecular weight is 800000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 1.
[comparative example 2]
(weight average molecular weight: 1200) use the acrylamide (AM) of the acrylamide (AM) of 2 weight parts and 0.5 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) replacement 1.5 weight parts and 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) be produced, polymer emulsion obtains with the method identical with embodiment 1 except the multipolymer of protective colloid.The pressure sensitive adhesive that obtains has-68 ℃ second-order transition temperature (Tg), and weight average molecular weight is 850000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 1.
[comparative example 3]
(weight average molecular weight: 700) use the vinylbenzene of 0.1 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) and 0.9 weight part to replace 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) is produced, trial obtains polymer emulsion with the method identical with embodiment 1 except the multipolymer of protective colloid.This test is owing to the polymerization stability difference causes unsettled polymer emulsion.
The composition of the protective colloid that uses provides in table 1.
Table 1
| The composition of protective colloid (weight ratio) | The composition of polymer emulsion (weight ratio) | |
| Embodiment 1 | AM/2EHA＝60/40 | 2EHA/AA/AN＝93.5/2/2 |
| Embodiment 2 | HEA/2EHA＝60/40 | 2EHA/AA/AN＝93.5/2/2 |
| Embodiment 3 | AM/2EHA/St＝60/20/20 | 2EHA/AA/AN＝93.5/2/2 |
| The comparative example 1 | AM/2EHA＝30/70 | 2EHA/AA/AN＝93.5/2/2 |
| The comparative example 2 | AM/2EHA＝80/20 | 2EHA/AA/AN＝93.5/2/2 |
| The comparative example 3 | AM/2EHA/St＝60/4/36 | - |
[embodiment 4～6 and comparative example 4～6]
Use each polymer emulsion (embodiment 1～3 and comparative example 1～3) that obtains as mentioned above to make adhesive tape with following method.
Thick PET (polyethyleneterephthalate) film of 25 μ m uses scraper to apply the emulsion of the coat-thickness of 50 μ m, subsequently at 100 ℃ with dry 3 minutes of fan.From moisture eliminator, take out adhesive tape, and the pressure sensitive adhesive layer that interleaving paper is administered to adhesive tape is with preparation adhesive tape sample.
According to the bond strength of JIS-Z-0237 specimen to SUS.
In addition, adhesive tape adhered to 7 days 40 ℃ of down non-placements, and was stripped to estimate repetition peel property and adherend contaminative.
The result provides in table 2.
Table 2
| Pressure sensitive adhesive | Bond strength | Repeat peel property | Adherend pollutes | |
| Embodiment 4 | Embodiment 1 | 400g/25mm | Good | No |
| Embodiment 5 | Embodiment 2 | 300g/25mm | Good | No |
| Embodiment 6 | Embodiment 3 | 300g/25mm | Good | No |
| The comparative example 4 | The comparative example 1 | 200g/25mm | Difference | Have |
| The comparative example 5 | The comparative example 2 | 450g/25mm | Difference | Have |
| The comparative example 6 | The comparative example 3 | - | - | - |
[embodiment 7]
(to the test of the surperficial adhesion characteristics that wets)
The pressure sensitive adhesive tape sample that is obtained by embodiment 4 and comparative example 4 by following method evaluation is to the adhesion characteristics on wet surface.
The sheet glass of A50mm * 70mm was 5 ℃ of refrigerator internal cooling 1 hour.
Sheet glass takes out from refrigerator, and at room temperature places.When the surface became wet, the adhesive tape sample was applied and uses the hand stripping tape by each personnel who selects randomly from five personnel.Adhesion characteristics to wet surface is estimated by assignment as described below.
1: sensation does not have adhesion.
2: feel slight adhesion.
3: sensation significantly adheres to.
4: feel stronger adhesion.
Table 3
| The adhesive tape sample of embodiment 4 | Comparative example 4 adhesive tape sample | |
| Personnel 1 | 3 | 1 |
| Personnel 2 | 3 | 1 |
| Personnel 3 | 2 | 1 |
| Personnel 4 | 4 | 2 |
| Personnel 5 | 3 | 1 |
Above-mentioned evaluation result is handled by statistics ground by the t-check.The adhesive tape of the embodiment 4 of the pressure sensitive adhesive of the embodiment 1 that this processing proof use method of the present invention obtains has above the significance of comparative example's 4 adhesive tapes of use comparative example's 1 pressure sensitive adhesive, has 1% risk (risk).
Table 4
| Variable 1 | Variable 2 | |
| On average | 3 | 1.2 |
| Variance | 0.5 | 0.2 |
| The project of observing | 5 | 5 |
| Theoretical mean number summation | 0 | |
| Degree of freedom | 7 | |
| T | 4.810702 | |
| P (T＜=t) (side) | 0.000971 | |
| T cut off value (side) | 1.894578 | |
| P (T＜=t) (both sides) | 0.001942 | |
| T cut off value (both sides) | 2.364623 | |
[embodiment 8]
In the flask of being furnished with agitator, reflux exchanger and dropping funnel, pack into based on the tensio-active agent of 1 weight part of the water of 40 weight parts, 1.5 parts by weight of acrylic (AA), 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA), the Potassium Persulphate as initiator (KPS) of 0.1 weight part, the n-lauryl mercaptan as chain-transfer agent of 0.04 weight part, replace air in the flask with nitrogen subsequently.
In an independent container, pack into the water of 40 weight parts, and the surfactant dissolves of 0.5 weight part is in wherein.Subsequently, the vinyl cyanide (AN) of 93.5 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA), 2 parts by weight of acrylic (AA) and 2 weight parts joins solution with the preparation monomer emulsion.
Contents in the flask are heated to 75 ℃ and stirring, 15 minutes multipolymer (weight average molecular weights: 800) with formation vinylformic acid (AA) and 2-ethylhexyl acrylate (2EHA) of heating under this temperature.Afterwards, as above prepared monomer emulsion was being dripped in 3 hours under 75 ℃.
In addition, under 80 ℃, carry out finishing reaction in 2 hours, with postcooling.Subsequently, 1.5 weight parts is added into the preparation polymer emulsion based on phosphatic tensio-active agent.
The pressure sensitive adhesive that so obtains has-67 ℃ second-order transition temperature (Tg), and weight average molecular weight is 720000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 5.
[embodiment 9]
(weight average molecular weight: 700) use vinylbenzene (St) the replacement 1.0 parts by weight of acrylic 2-(ethyl hexyl) esters (2EHA) of 0.5 parts by weight of acrylic 2-(ethyl hexyl) ester (2EHA) and 0.5 weight part are produced, polymer emulsion obtains with the method identical with embodiment 8 except the multipolymer of protective colloid.
The pressure sensitive adhesive that obtains has-66 ℃ second-order transition temperature (Tg), and weight average molecular weight is 820000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 5.
[comparative example 7]
(weight average molecular weight: 800) use 1 parts by weight of acrylic (AA), 1 parts by weight of acrylic-n-butyl ester (BA) and 0.5 parts by weight of acrylic dodecyl ester (LA) replacement 1.5 parts by weight of acrylic (AA) and 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) be produced, polymer emulsion obtains with the method identical with embodiment 8 except the multipolymer of protective colloid.
The pressure sensitive adhesive that obtains has-68 ℃ second-order transition temperature (Tg), and weight average molecular weight is 550000.
The composition of the polymer emulsion that uses and the composition of protective colloid provide in table 5.
[comparative example 8]
(weight average molecular weight: 600) use the vinylbenzene (St) of 0.1 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) and 0.9 weight part to replace 1.0 parts by weight of acrylic-2-(ethyl hexyl) ester (2EHA) is produced, trial obtains polymer emulsion with the method identical with embodiment 8 except the multipolymer of protective colloid.This test is because the polymerization stability difference causes unsettled polymer emulsion.
The composition of the protective colloid that uses provides in table 5.
Table 5
| The composition of protective colloid (weight ratio) | The composition of pressure sensitive adhesive (weight ratio) | |
| Embodiment 8 | AA/2EHA＝60/40 | 2EHA/AA/AN＝93.5/2/2 |
| Embodiment 9 | AA/2EHA/St＝60/20/20 | 2EHA/AA/AN＝93.5/2/2 |
| The comparative example 7 | AA/BA/LA＝40/40/20 | 2EHA/AA/AN＝93.5/2/2 |
| The comparative example 8 | AA/2EHA/St＝60/4/36 | - |
[embodiment 10 and 11 and comparative example 9 and 10]
Use as above-mentioned each polymer emulsion that obtains (embodiment 8 and 9 and comparative example 7 and 8) is made adhesive tape with following method.
Thick PET (polyethyleneterephthalate) film of 25 μ m uses scraper to apply the emulsion of 50 μ m coat-thicknesses, subsequently at 100 ℃ with dry 3 minutes of fan.From moisture eliminator, take out adhesive tape, and the pressure sensitive adhesive layer that interleaving paper is administered to adhesive tape is with preparation adhesive tape sample.
According to the bond strength of JIS-Z-0237 specimen to SUS.
In addition, adhesive tape was placed 7 days down at 40 ℃, and was stripped to estimate repetition peel property and adherend contaminative.
The result provides in table 6.
Table 6
| Pressure sensitive adhesive | Bond strength | Repeat peel property | Adherend pollutes | |
| Embodiment 10 | Embodiment 8 | 400g/25mm | Good | No |
| Embodiment 11 | Embodiment 9 | 300g/25mm | Good | A little |
| The comparative example 9 | The comparative example 7 | 200g/25mm | Difference | Have |
| The comparative example 10 | The comparative example 8 | - | - | - |
[embodiment 12]
(to the test of the surperficial adhesion characteristics that wets)
Estimate respectively wet surperficial adhesion characteristics by following method by the embodiment 10 of the pressure sensitive adhesive that uses embodiment 8 and comparative example 7 and the pressure sensitive adhesive tape sample that comparative example 9 obtains.
The sheet glass of A50mm * 70mm was 5 ℃ of refrigerator internal cooling 1 hour.
Sheet glass takes out from refrigerator, and at room temperature places.When the surface became wet, the adhesive tape sample was applied and uses the hand stripping tape by each personnel who selects randomly from five personnel.Adhesion characteristics to wet surface is estimated by assignment as described below.
1: sensation does not have adhesion.
2: feel slight adhesion.
3: sensation significantly adheres to.
4: feel stronger adhesion.
Table 7
| The adhesive tape sample of embodiment 10 | Comparative example 9 adhesive tape sample | |
| Personnel 1 | 3 | 1 |
| Personnel 2 | 3 | 1 |
| Personnel 3 | 2 | 2 |
| Personnel 4 | 4 | 2 |
| Personnel 5 | 3 | 1 |
Above-mentioned evaluation result is handled by statistics ground by the t-check.This processing proves that the adhesive tape of the embodiment 10 of the pressure sensitive adhesive that uses the embodiment 8 that obtains by the inventive method has the significance of the comparative example's 9 who surpasses the pressure sensitive adhesive that uses comparative example 7 adhesive tape, has 1% risk.
Table 4
| Variable 1 | Variable 2 | |
| On average | 3 | 1.4 |
| Variance | 0.5 | 0.3 |
| The project of observing | 5 | 5 |
| Theoretical mean number summation | 0 | |
| Degree of freedom | 8 | |
| t | 4 | |
| P (T＜=t) (side) | 0.001975 | |
| T cut off value (side) | 1.859548 | |
| P (T＜=t) (both sides) | 0.00395 |
| T cut off value (both sides) | 2.306006 |
Industrial applicibility
Method according to production contact adhesive of the present invention exists at the preparation contact adhesive at specific protecting colloid; this specific protecting colloid is to comprise the particular hydrophilic monomer (A-1) of special ratios or (A-2) and specific (methyl) alkyl acrylate (B-1) or specific copolymer (B-2); thereby monomer and the contact adhesive that obtains obtain good dispersion stabilization, and so that contact adhesive stably produced.
In addition, the contact adhesive that is obtained by this method demonstrates the good adhesion characteristic to adherend. And contact adhesive can advantageously be applied to adherend and be stripped from and be applied to again adherend. And it is impossible peeling off the pollution that causes being produced by the residue contact adhesive on the adherend adherend surface.
In addition, the method according to this invention, contact adhesive is in the presence of specific protecting colloid, be produced in aqueous medium. The copolymer of protecting colloid adheres to the surface of product contact adhesive particle, and absorbs the water on adherend surface. Therefore, the contact adhesive that obtains according to the present invention demonstrates good even to the adhesion characteristics on wet surface. In other words, although contact adhesive of the present invention is the emulsion-type of property of water-bearing medium, show good even to the adhesion characteristics on wet surface.
Claims (10)
1, a kind of method of producing emulsion-type pressure sensitive adhesive, this method are included in protective colloid and have (being total to) polymerization principal monomer down, and protective colloid is the acrylic copolymer that comprises following component:
(A-1) at least a hydrophilic monomer that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate and hydroxyethyl methylacrylate; With
(B-1) (methyl) alkyl acrylate should can have 4～18 carbon atoms with hydrophilic monomer (A-1) copolymerization and its alkyl by (methyl) alkyl acrylate;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the weight ratio in 60～30 scopes is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
2, a kind of method of producing emulsion-type pressure sensitive adhesive, this method are included in protective colloid and have (being total to) polymerization principal monomer down, and protective colloid is the acrylic copolymer that comprises following component:
(A-1) at least a hydrophilic monomer that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate and hydroxyethyl methylacrylate;
(B-1) (methyl) alkyl acrylate should can have 4～18 carbon atoms with hydrophilic monomer (A-1) copolymerization and its alkyl by (methyl) alkyl acrylate; With
(C) vinyl cyanide and/or cinnamic the 3rd monomer;
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-1) in 60～30 scopes: [(B-1)+(C)] weight ratio and 99.9～20: (B-1) in 0.1～80 scope: (C) weight ratio is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
3, a kind of method of producing emulsion-type pressure sensitive adhesive, this method are included in protective colloid and have (being total to) polymerization principal monomer down, and protective colloid is the acrylic copolymer that comprises following component:
(A-2) vinylformic acid and/or methacrylic acid hydrophilic monomer; With
(B-2) (methyl) alkyl acrylate should can have 4～9 carbon atoms with hydrophilic monomer (A-2) copolymerization and its alkyl by (methyl) alkyl acrylate;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the copolymerization weight ratio in 60～30 scopes closes;
This acrylic copolymer have in 500～50000 scopes weight average molecular weight.
4, a kind of method of producing emulsion-type pressure sensitive adhesive, this method are included in protective colloid and have (being total to) polymerization principal monomer down, and protective colloid is the acrylic copolymer that comprises following component:
(A-2) vinylformic acid and/or methacrylic acid hydrophilic monomer;
(B-2) (methyl) alkyl acrylate should can have 4～9 carbon atoms with hydrophilic monomer (A-2) copolymerization and its alkyl by (methyl) alkyl acrylate; With
(C) vinyl cyanide and/or cinnamic the 3rd monomer;
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-2) in 60～30 scopes: [(B-2)+(C)] weight ratio and 99.9～20: (B-2) in 0.1～80 scope: (C) weight ratio is by copolymerization;
This acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
5, according to the method for each described production emulsion-type pressure sensitive adhesive in the claim 1～4, wherein, (being total to) polymerization in the presence of protective colloid produces the pressure sensitive adhesive with the second-order transition temperature (Tg) that is not higher than 0 ℃.
6, a kind of emulsion-type pressure sensitive adhesive; it comprises aqueous medium and (being total to) polymkeric substance that is scattered in the aqueous medium; should obtain by (be total to) the polymerization principal monomer in the presence of protective colloid by (being total to) polymkeric substance, described protective colloid is the acrylic copolymer that comprises following component:
(A-1) at least a hydrophilic monomer that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate; With
(B-1) (methyl) alkyl acrylate should can have 4～18 carbon atoms with hydrophilic monomer (A-1) copolymerization and its alkyl by (methyl) alkyl acrylate;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the weight ratio in 60～30 scopes is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
7, a kind of emulsion-type pressure sensitive adhesive; it comprises aqueous medium and (being total to) polymkeric substance that is scattered in the aqueous medium; should obtain by (be total to) the polymerization principal monomer in the presence of protective colloid by (being total to) polymkeric substance, described protective colloid is an acrylic copolymer, comprising:
(A-1) at least a hydrophilic monomer that is selected from the group that comprises acrylamide, Methacrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate; With
(B-1) (methyl) alkyl acrylate should can have 4～18 carbon atoms with hydrophilic monomer (A-1) copolymerization and its alkyl by (methyl) alkyl acrylate; With
(C) vinyl cyanide and/or cinnamic the 3rd monomer;
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-1) in 60～30 scopes: [(B-1)+(C)] weight ratio and 99.9～20: (B-1) in 0.1～80 scope: (C) weight ratio is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
8, a kind of emulsion-type pressure sensitive adhesive, it comprises aqueous medium and (being total to) polymkeric substance that is scattered in the aqueous medium, should obtain by (be total to) the polymerization principal monomer in the presence of protective colloid by (being total to) polymkeric substance, protective colloid is an acrylic copolymer, comprising:
(A-2) vinylformic acid and/or methacrylic acid hydrophilic monomer; With
(B-2) (methyl) alkyl acrylate should can have 4～9 carbon atoms with hydrophilic monomer (A-2) copolymerization and its alkyl by (methyl) alkyl acrylate;
Hydrophilic monomer and (methyl) alkyl acrylate are with 40～70: the weight ratio in 60～30 scopes is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
9, a kind of emulsion-type pressure sensitive adhesive, it comprises aqueous medium and (being total to) polymkeric substance that is scattered in the aqueous medium, should obtain by there is (being total to) polymerization principal monomer at protective colloid by (being total to) polymkeric substance, protective colloid is an acrylic copolymer, comprising:
(A-2) vinylformic acid and/or methacrylic acid hydrophilic monomer;
(B-2) (methyl) alkyl acrylate should can have 4～9 carbon atoms with hydrophilic monomer (A-2) copolymerization and its alkyl by (methyl) alkyl acrylate; With
(C) vinyl cyanide and/or cinnamic the 3rd monomer;
Hydrophilic monomer, (methyl) alkyl acrylate and the 3rd monomer are with 40～70: (A-2) in 60～30 scopes: [(B-2)+(C)] weight ratio and 99.9～20: (B-2) in 0.1～80 scope: (C) weight ratio is by copolymerization;
Acrylic copolymer has the weight average molecular weight in 500～50000 scopes.
10,, wherein, comprise that the pressure sensitive adhesive of this (being total to) polymkeric substance has the second-order transition temperature (Tg) that is not higher than 0 ℃ according to each described production emulsion-type pressure sensitive adhesive in the claim 6～9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP054100/2003 | 2003-02-28 | ||
| JP054099/2003 | 2003-02-28 | ||
| JP2003054100A JP4250757B2 (en) | 2003-02-28 | 2003-02-28 | Method for producing emulsion-type adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1753965A true CN1753965A (en) | 2006-03-29 |
| CN100339455C CN100339455C (en) | 2007-09-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800054913A Expired - Lifetime CN100339455C (en) | 2003-02-28 | 2004-02-27 | Emulsion-type pressure sensitive adhesive and process for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4250757B2 (en) |
| CN (1) | CN100339455C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102933209A (en) * | 2010-04-13 | 2013-02-13 | 东亚合成株式会社 | Adhesive composition for medical use, adhesive patch for medical use, and method for producing the composition |
| CN101445575B (en) * | 2008-12-31 | 2013-06-26 | 九江世龙橡胶有限责任公司 | Heat-resistant acrylic ester rubber |
| CN104822710A (en) * | 2012-10-05 | 2015-08-05 | 巴斯夫欧洲公司 | Production of aqueous polymer dispersions with protective colloids in monomer feed method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4695411B2 (en) * | 2005-03-08 | 2011-06-08 | 大王製紙株式会社 | Concealment paper |
| CN104093807B (en) * | 2012-02-06 | 2017-09-12 | 巴斯夫欧洲公司 | The tackifier for adhesive and the aqueous polymer dispersions that can be prepared by the emulsion polymerization based on (methyl) acrylic acid C1 to C20 Arrcostabs can be used as |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721748A (en) * | 1985-08-05 | 1988-01-26 | National Starch And Chemical Corporation | Colloid stabilized latex adhesives |
| DE19505039A1 (en) * | 1995-02-15 | 1996-08-22 | Basf Ag | Process for the preparation of emulsifier-free aqueous polymer dispersions |
-
2003
- 2003-02-28 JP JP2003054100A patent/JP4250757B2/en not_active Expired - Fee Related
-
2004
- 2004-02-27 CN CNB2004800054913A patent/CN100339455C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445575B (en) * | 2008-12-31 | 2013-06-26 | 九江世龙橡胶有限责任公司 | Heat-resistant acrylic ester rubber |
| CN102933209A (en) * | 2010-04-13 | 2013-02-13 | 东亚合成株式会社 | Adhesive composition for medical use, adhesive patch for medical use, and method for producing the composition |
| CN102933209B (en) * | 2010-04-13 | 2015-06-17 | 东亚合成株式会社 | Adhesive composition for medical use, adhesive patch for medical use, and method for producing the composition |
| CN104822710A (en) * | 2012-10-05 | 2015-08-05 | 巴斯夫欧洲公司 | Production of aqueous polymer dispersions with protective colloids in monomer feed method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100339455C (en) | 2007-09-26 |
| JP2004263055A (en) | 2004-09-24 |
| JP4250757B2 (en) | 2009-04-08 |
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