JP2017527634A - Acrylic emulsion pressure-sensitive adhesive having excellent low-temperature adhesive strength and holding power and method for producing the same - Google Patents
Acrylic emulsion pressure-sensitive adhesive having excellent low-temperature adhesive strength and holding power and method for producing the same Download PDFInfo
- Publication number
- JP2017527634A JP2017527634A JP2016573475A JP2016573475A JP2017527634A JP 2017527634 A JP2017527634 A JP 2017527634A JP 2016573475 A JP2016573475 A JP 2016573475A JP 2016573475 A JP2016573475 A JP 2016573475A JP 2017527634 A JP2017527634 A JP 2017527634A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic emulsion
- sensitive adhesive
- group
- pressure
- acrylate
- 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
- 239000000839 emulsion Substances 0.000 title claims abstract description 106
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 83
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 76
- 239000000853 adhesive Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 37
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 35
- -1 allyl ester Chemical class 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001242 acetic acid derivatives Chemical class 0.000 claims abstract description 6
- 150000002825 nitriles Chemical class 0.000 claims abstract description 6
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 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 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- JJYWRQLLQAKNAD-UHFFFAOYSA-N 2-methylpent-2-enoic acid Chemical compound CCC=C(C)C(O)=O JJYWRQLLQAKNAD-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 239000004971 Cross linker Substances 0.000 claims 1
- 150000005215 alkyl ethers Chemical class 0.000 claims 1
- 150000002432 hydroperoxides Chemical class 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 235000011008 sodium phosphates Nutrition 0.000 claims 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 23
- 238000010998 test method Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OYKPJMYWPYIXGG-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(C)(C)C OYKPJMYWPYIXGG-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-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
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 206010013496 Disturbance in attention Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 206010043521 Throat irritation Diseases 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 201000010235 heart cancer Diseases 0.000 description 1
- 208000019622 heart disease Diseases 0.000 description 1
- 208000024348 heart neoplasm Diseases 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000479 mixture part Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- AIDWMELCBZUXNK-UHFFFAOYSA-M sodium;but-2-ene-1-sulfonate Chemical compound [Na+].CC=CCS([O-])(=O)=O AIDWMELCBZUXNK-UHFFFAOYSA-M 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/18—Homopolymers or copolymers of nitriles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本発明は、低温粘着力及び保持力に優れたアクリル系エマルジョン粘着剤及びその製造方法であって、i)(メタ)アクリル酸エステル単量体、ii)アリルエステル、ビニルエステル、不飽和アセテート及び不飽和ニトリルからなる群から選択される1つ以上の単量体、iii)不飽和カルボン酸単量体、iv)架橋剤、及びv)ヒドロキシエチルアクリレート単量体を含む混合物の重合で生成されたアクリル系エマルジョン樹脂を含み、前記混合物は、混合物の全重量を基準として、iii)不飽和カルボン酸単量体を0.6〜1.5重量%、及びv)ヒドロキシエチルアクリレート単量体を2.5〜10重量%含む、アクリル系エマルジョン粘着剤及びその製造方法に関する。The present invention relates to an acrylic emulsion pressure-sensitive adhesive having excellent low-temperature adhesive strength and holding power and a method for producing the same, comprising i) (meth) acrylic acid ester monomer, ii) allyl ester, vinyl ester, unsaturated acetate, and Produced by polymerization of a mixture comprising one or more monomers selected from the group consisting of unsaturated nitriles, iii) unsaturated carboxylic acid monomers, iv) cross-linking agents, and v) hydroxyethyl acrylate monomers. Acrylic emulsion resin, wherein the mixture is based on the total weight of the mixture, iii) 0.6 to 1.5 wt% of unsaturated carboxylic acid monomer, and v) hydroxyethyl acrylate monomer. The present invention relates to an acrylic emulsion pressure-sensitive adhesive containing 2.5 to 10% by weight and a method for producing the same.
Description
本出願は、2014年08月12日付けの韓国特許出願第2014−0104185号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。 This application claims the benefit of priority based on Korean Patent Application No. 2014-0104185 dated August 12, 2014, and all the contents disclosed in the Korean patent application literature are part of this specification. Included as
本発明は、低温粘着力及び保持力に優れたアクリル系エマルジョン粘着剤及びその製造方法に関する。 The present invention relates to an acrylic emulsion pressure-sensitive adhesive having excellent low-temperature adhesive strength and holding power and a method for producing the same.
最近、粘着剤が適用された建築物の内/外装材、インテリア材料及び広告材など、ステッカータイプの表面仕上げ材の使用が大きく増加している。前記粘着剤として、既存の油性粘着剤は、施工後、長期間の間残存溶媒が空気中に排出されるため、建築物の内部に居住する人に頭痛、眼・鼻・のどの刺激、咳、かゆみ、目まい、疲労感、集中力低下などの症状を発生させ、長期間露出時に呼吸器疾患、心臓病、癌などを誘発するシックハウス症候群(Sick House Syndrome)の問題を発生させる。 Recently, the use of sticker-type surface finishing materials such as interior / exterior materials, interior materials and advertising materials for buildings to which adhesives have been applied has increased significantly. As the above-mentioned adhesive, existing oil-based adhesives have a residual solvent discharged into the air for a long period of time after construction, which may cause headaches, eye / nose / throat irritation, cough, etc. It causes symptoms such as itching, dizziness, fatigue, and poor concentration, and causes a problem of sick house syndrome that induces respiratory disease, heart disease, cancer and the like when exposed for a long time.
このような理由から、水を分散媒として用いることで環境に優しく且つ人体に有害な物質の排出がない水性エマルジョン粘着剤に対する関心が高まり、急速に代替化が進んでいる。水性エマルジョン粘着剤は、粘着剤の粘度と分散体ポリマーの分子量とが無関係であるので、溶剤系ポリマーに比べて高分子量を有するポリマーを用いることができ、固形分の濃度範囲を広範囲に得ることができ、耐老化性が小さく、低粘度、低固形分領域での粘着性が良好であり、他のポリマーとの相溶性が良いという利点を有している。 For these reasons, the use of water as a dispersion medium has increased interest in an aqueous emulsion adhesive that is environmentally friendly and does not emit substances harmful to the human body, and is rapidly being replaced. In the case of aqueous emulsion adhesives, the viscosity of the adhesive and the molecular weight of the dispersion polymer are irrelevant, so polymers having a higher molecular weight than solvent-based polymers can be used, and a solid content concentration range can be obtained over a wide range. It has the advantages of low aging resistance, low viscosity, good adhesion in the low solid content region, and good compatibility with other polymers.
しかし、水を溶剤として用いるため、乾燥速度が遅く、疎水性の粘着面、非多孔質の被着剤に対する粘着性が低く、硬化剤の選択範囲が狭く、初期粘着力が低下するという問題を有するだけでなく、乳化剤及び分散剤を含んでいるため耐水性が低いなど、油性粘着剤ほどの物性に至ることができないなどの問題を有している。 However, since water is used as a solvent, the drying speed is slow, the adhesiveness to the hydrophobic adhesive surface and the nonporous adherent is low, the selection range of the curing agent is narrow, and the initial adhesiveness is reduced. In addition to having an emulsifier and a dispersant, it has problems such as low water resistance and physical properties that are not as good as those of an oil-based adhesive.
一方、感圧粘着剤(Pressure sensitive adhesive:PSA)は、一般に、初期粘着力、粘着力及び凝集力に優れ、これらの間の均衡が良く、長期間付着後に除去のために剥離する場合に被着体の表面損傷及び汚染を誘発してはならないなどの特性が要求される。 On the other hand, a pressure sensitive adhesive (PSA) is generally excellent in initial adhesive strength, adhesive strength and cohesive strength, and has a good balance between them. Characteristics such as the surface damage and contamination of the kimono should not be induced.
また、最近、粘着剤の使用環境の多様化に伴い、前記の一般的な粘着物性以外に、低温粘着力及び保持力に優れた粘着剤に対する需要が高まっている。例えば、環境問題と関連して環境に優しいハイブリッド自動車などが多くの関心を集めており、ハイブリッド自動車に内蔵されたバッテリーなどに使用される粘着剤は、過酷な環境でも許容可能な水準の粘着力及び保持力を確保することができなければならない。 Recently, with the diversification of the use environment of pressure-sensitive adhesives, demand for pressure-sensitive adhesives having excellent low-temperature adhesive strength and holding power in addition to the above general pressure-sensitive adhesive properties is increasing. For example, environmentally friendly hybrid vehicles are attracting a lot of attention in relation to environmental issues, and adhesives used in batteries built in hybrid vehicles have an acceptable level of adhesive strength even in harsh environments. And it must be possible to ensure holding power.
従来の技術は、水性エマルジョン粘着剤の初期粘着力、粘着力及び凝集力はある程度解決しているが、これと同時に低温粘着力及び保持力も優れた粘着剤は提供していない。 The conventional technology has solved the initial adhesive force, adhesive force and cohesive force of the aqueous emulsion adhesive to some extent, but at the same time, it does not provide an adhesive having excellent low-temperature adhesive force and holding force.
したがって、環境に配慮しながらも、低温粘着力及び保持力に優れた粘着剤の技術に対する必要性が高い実情である。 Therefore, there is a high need for an adhesive technology that is excellent in low-temperature adhesive strength and holding power while considering the environment.
本発明は、上記のような従来技術の問題点及び過去から要請されてきた技術的課題を解決することを目的とする。 An object of the present invention is to solve the above-described problems of the prior art and technical problems that have been requested from the past.
本出願の発明者らは、鋭意研究と様々な実験を重ねた結果、アクリル系エマルジョン粘着剤が、混合物の全重量を基準として不飽和カルボン酸単量体を0.6〜1.5重量%、及びヒドロキシエチルアクリレート単量体を2.5〜10重量%含む場合、低温粘着力及び保持力が向上することを見出し、本発明を完成するに至った。 The inventors of the present application have conducted extensive research and various experiments. As a result, the acrylic emulsion pressure-sensitive adhesive contains 0.6 to 1.5% by weight of the unsaturated carboxylic acid monomer based on the total weight of the mixture. And when the hydroxyethyl acrylate monomer is contained in an amount of 2.5 to 10% by weight, it has been found that low-temperature adhesive strength and holding power are improved, and the present invention has been completed.
したがって、本発明に係るアクリル系エマルジョン粘着剤は、i)炭素数1〜14のアルキル基を有する(メタ)アクリル酸エステル単量体、ii)アリルエステル、ビニルエステル、不飽和アセテート及び不飽和ニトリルからなる群から選択される1つ以上の単量体、iii)不飽和カルボン酸からなる群から選択される1つ以上の単量体、iv)架橋剤、及びv)ヒドロキシエチルアクリレート単量体を含む混合物の重合で生成されたアクリル系エマルジョン樹脂を含み、前記混合物は、混合物の全重量を基準として、iii)不飽和カルボン酸からなる群から選択される1つ以上の単量体を0.6〜1.5重量%、及びv)ヒドロキシエチルアクリレート単量体を2.5〜10重量%含むことを特徴とする。 Accordingly, the acrylic emulsion pressure-sensitive adhesive according to the present invention includes i) a (meth) acrylic acid ester monomer having an alkyl group having 1 to 14 carbon atoms, ii) an allyl ester, a vinyl ester, an unsaturated acetate, and an unsaturated nitrile. One or more monomers selected from the group consisting of: iii) one or more monomers selected from the group consisting of unsaturated carboxylic acids, iv) a crosslinking agent, and v) a hydroxyethyl acrylate monomer And iii) one or more monomers selected from the group consisting of unsaturated carboxylic acids based on the total weight of the mixture. 6 to 1.5% by weight, and v) 2.5 to 10% by weight of hydroxyethyl acrylate monomer.
本明細書において使用された用語、“混合物”は、アクリル系単量体をベースとして、以下で説明する単量体及び架橋剤などが共に混合された状態で投入されて製造されてもよく、前記単量体及び架橋剤などが順次投入されて製造されてもよいなどの多様性を含む。 The term “mixture” used in the present specification may be manufactured based on an acrylic monomer and charged with a monomer and a crosslinking agent described below mixed together, It includes a variety of such that the monomer and the crosslinking agent may be sequentially added and manufactured.
前記iii)の不飽和カルボン酸からなる群から選択される1つ以上の単量体は、混合物の全重量を基準として0.8〜1.3重量%含まれてもよく、詳細には0.9〜1.2重量%含まれてもよい。 One or more monomers selected from the group consisting of the unsaturated carboxylic acid of iii) may be included in an amount of 0.8 to 1.3% by weight based on the total weight of the mixture. .9 to 1.2 wt% may be included.
前記v)のヒドロキシエチルアクリレート単量体は、混合物の全重量を基準として2.5〜8重量%含まれてもよく、詳細には2.5〜6重量%含まれてもよい。 The hydroxyethyl acrylate monomer v) may be included in an amount of 2.5 to 8% by weight based on the total weight of the mixture, and more specifically 2.5 to 6% by weight.
このように、不飽和カルボン酸単量体及びヒドロキシエチルアクリレート単量体を適正量含む場合、低温粘着力及び保持力が増加する効果があり、特に、このような効果は、ヒドロキシエチルアクリレート単量体に存在する水酸基の水素結合及び双極子−双極子引力(dipole−dipole attraction)などを通じた分子間引力の増加、及び高分子内で水酸基と水酸基又は水酸基と極性作用基の自己架橋(self cross−linking)を通じた凝集力の増加によるものと推定される。 Thus, when an appropriate amount of unsaturated carboxylic acid monomer and hydroxyethyl acrylate monomer is included, there is an effect of increasing the low-temperature adhesive strength and holding power. Increase of intermolecular attractive force through hydrogen bonding of a hydroxyl group existing in the body and dipole-dipole attraction, and self-crosslinking of hydroxyl group and hydroxyl group or hydroxyl group and polar functional group in the polymer (self cross) It is presumed to be due to an increase in cohesive force through -linking).
ヒドロキシエチルアクリレート単量体の含量が前記範囲を外れ、2.5重量%未満である場合は、高分子内に自己架橋があまり形成されないため、保持力が大きく減少し、10重量%を超える場合は、高分子内に自己架橋が過度に多く形成されてしまい、粘着剤が必要以上に硬くなるため、被粘着剤との引力が相対的に弱くなって低温粘着力が減少するため、所望の効果を得ることができないという問題がある。 When the content of the hydroxyethyl acrylate monomer is outside the above range and is less than 2.5% by weight, since the self-crosslinking is not formed so much in the polymer, the holding power is greatly reduced and the content exceeds 10% by weight. In the polymer, self-crosslinking is formed excessively in the polymer, and the pressure-sensitive adhesive becomes harder than necessary, so that the attractive force with the pressure-sensitive adhesive becomes relatively weak and the low-temperature pressure-sensitive adhesive force decreases. There is a problem that the effect cannot be obtained.
また、極性単量体であるヒドロキシエチルアクリレートと同様に、極性単量体である不飽和カルボン酸との反応性が物性に大きな影響を及ぼす。特に、粘着剤の架橋度及び安定性に大きな影響を及ぼし、これは、極性単量体間の強い相互作用によるものと推定される。 Similarly to hydroxyethyl acrylate, which is a polar monomer, the reactivity with unsaturated carboxylic acid, which is a polar monomer, greatly affects the physical properties. In particular, it has a great influence on the degree of crosslinking and stability of the pressure-sensitive adhesive, which is presumed to be due to strong interaction between polar monomers.
前記不飽和カルボン酸単量体の含量が前記範囲を外れ、0.6重量%未満である場合、極性基材であるガラスに対する初期低温粘着力、初期粘着力及び保持力が減少し、1.5重量%を超える場合、高分子内の架橋結合が強くなってガラス転移温度が上昇し、結局、このような理由で、保持力は一部上昇できるが、低温での初期粘着力が大幅に低下するという問題がある。 When the content of the unsaturated carboxylic acid monomer is out of the above range and is less than 0.6% by weight, the initial low-temperature adhesive force, initial adhesive force and holding force with respect to the glass which is a polar substrate are decreased. When it exceeds 5% by weight, the cross-linking bond in the polymer becomes strong and the glass transition temperature rises. As a result, the holding power can be partially increased for this reason, but the initial adhesive strength at low temperature is greatly increased. There is a problem of lowering.
一具体例において、前記アクリル系エマルジョン粘着剤は、初期低温粘着力が12N/inch以上であってもよく、また、試験法FINAT TEST METHOD NO.8に準拠した保持力試験において、アクリル系エマルジョン粘着剤の粘着試片のステンレススチールの表面(SUS 304)に対する接着時間が100min以上であってもよく、前記初期低温粘着力及び保持力についての詳細は後述する。 In one specific example, the acrylic emulsion pressure-sensitive adhesive may have an initial low-temperature adhesive strength of 12 N / inch or more, and a test method FINAT TEST METHOD NO. In the holding power test according to No. 8, the adhesion time of the acrylic emulsion pressure-sensitive adhesive specimen to the stainless steel surface (SUS 304) may be 100 min or more. Details of the initial low-temperature adhesive force and holding power Will be described later.
以下、本発明に係るアクリル系エマルジョン粘着剤について詳細に説明する。 Hereinafter, the acrylic emulsion adhesive according to the present invention will be described in detail.
一具体例において、前記i)の単量体は、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチルアクリレート、t−ブチルメタクリレート、ペンチルメタクリレート、ヘキシルメタクリレート、ヘプチルアクリレート、イソオクチルアクリレート、オクチルメタクリレート、2−エチルヘキシル(メタ)アクリレート、イソデシルアクリレート、デシルメタクリレート、ドデシルメタクリレート、イソボルニルメタクリレート、及びラウリル(メタ)アクリレートからなる群から選択される1つ以上であってもよく、詳細には、混合物の全重量を基準として60〜90重量%含まれてもよい。 In one specific example, the monomer of i) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, t-butyl. The group consisting of methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl acrylate, isooctyl acrylate, octyl methacrylate, 2-ethylhexyl (meth) acrylate, isodecyl acrylate, decyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, and lauryl (meth) acrylate One or more selected from the above may be used, and in particular, 60 to 90% by weight based on the total weight of the mixture may be included.
前記i)の単量体は、前記のように、エマルジョン樹脂の全重量を基準として60〜90重量%含まれてもよい。60重量%未満含まれる場合には、アクリル系エマルジョン粘着剤の初期粘着力を確保することができず、90重量%を超えて含まれる場合には、使用後、除去時に被着物に対する粘着剤の転写が大きく発生するため、好ましくない。 As described above, the monomer i) may be included in an amount of 60 to 90% by weight based on the total weight of the emulsion resin. When the content is less than 60% by weight, the initial adhesive strength of the acrylic emulsion pressure-sensitive adhesive cannot be ensured. When the content exceeds 90% by weight, the pressure-sensitive adhesive on the adherend is removed at the time of removal after use. Since transfer is greatly generated, it is not preferable.
また、前記i)のアルキル基の炭素数は、詳細には1〜14個であってもよく、より詳細には2〜14個であってもよい。1個未満である場合には、アクリル系エマルジョン粘着剤の凝集力が低下し、14個を超える場合には、アクリル系エマルジョン粘着剤が柔軟になりすぎて粘着物性が低下するため、好ましくない。 Moreover, 1-14 may be sufficient as the carbon number of the alkyl group of said i), and 2-14 may be sufficient as it in detail. When the number is less than 1, the cohesive force of the acrylic emulsion pressure-sensitive adhesive decreases, and when it exceeds 14, the acrylic emulsion pressure-sensitive adhesive becomes too soft and the physical properties of the pressure-sensitive adhesive deteriorate, which is not preferable.
一具体例において、前記ii)の単量体は、酢酸ビニル、ブタン酸ビニル、プロピオン酸ビニル、ラウリン酸ビニル、ビニルピロリドン、アクリロニトリル及びメタクリロニトリルからなる群から選択される1つ以上であってもよく、詳細には、酢酸ビニル、ブタン酸ビニルまたはアクリロニトリルであってもよい。 In one embodiment, the monomer of ii) is one or more selected from the group consisting of vinyl acetate, vinyl butanoate, vinyl propionate, vinyl laurate, vinyl pyrrolidone, acrylonitrile and methacrylonitrile. In particular, it may be vinyl acetate, vinyl butanoate or acrylonitrile.
前記ii)の単量体は、混合物の全重量を基準として1〜35重量%含まれてもよく、詳細には、7〜25重量%含まれてもよい。1重量%未満含まれる場合には、アクリル系エマルジョン粘着剤が柔軟になりすぎて十分な粘着物性を確保することができず、35重量%を超えて含まれる場合には、アクリル系エマルジョン粘着剤が硬くなりすぎて著しい粘着力の低下が発生するため、好ましくない。 The monomer ii) may be included in an amount of 1 to 35% by weight based on the total weight of the mixture, and more specifically 7 to 25% by weight. When the content is less than 1% by weight, the acrylic emulsion pressure-sensitive adhesive becomes too soft to secure sufficient adhesive properties. When the content exceeds 35% by weight, the acrylic emulsion pressure-sensitive adhesive Is not preferable because it becomes too hard and a significant decrease in adhesive strength occurs.
一具体例において、前記iii)の単量体は、アクリル酸、イタコン酸、無水マレイン酸、フマル酸、クロトン酸、メタクリル酸、及びエチルメタクリル酸からなる群から選択される1つ以上であってもよく、詳細にはアクリル酸であってもよい。 In one embodiment, the monomer of iii) is one or more selected from the group consisting of acrylic acid, itaconic acid, maleic anhydride, fumaric acid, crotonic acid, methacrylic acid, and ethyl methacrylic acid. In particular, acrylic acid may be used.
前記iii)の単量体は、混合物の全重量を基準として0.6〜1.5重量%含まれてもよい。0.6重量%未満含まれる場合には、アクリル系エマルジョン粘着剤が柔軟になりすぎて十分な粘着物性を確保することができず、1.5重量%を超えて含まれる場合には、アクリル系エマルジョン粘着剤が硬くなりすぎて著しい粘着力の低下が発生するため、好ましくない。 The monomer of iii) may be included in an amount of 0.6 to 1.5% by weight based on the total weight of the mixture. If it is contained less than 0.6% by weight, the acrylic emulsion pressure-sensitive adhesive becomes too soft to ensure sufficient adhesive properties, and if it contains more than 1.5% by weight, acrylic This is not preferable because the system emulsion pressure-sensitive adhesive becomes too hard and a significant decrease in adhesive strength occurs.
一具体例において、凝集力を補強するための前記vi)の架橋剤は、混合物の全重量を基準として0.1〜3重量%含まれてもよく、前記範囲内で、アクリル系エマルジョン粘着剤が十分な凝集力を有する。 In one embodiment, the crosslinking agent of vi) for reinforcing the cohesive force may be included in an amount of 0.1 to 3% by weight based on the total weight of the mixture. Has sufficient cohesive strength.
前記架橋剤は、凝集力を補強するために添加されるものであって、一具体例において、アルキレンオキシド基を5〜15個含み、アクリレート基又はビニル基を有する化合物であってもよい。詳細には、アルキレンオキシド基を6〜12個含み、アクリレート基又はビニル基を有する化合物であってもよく、前記範囲内で、常温及び老化粘着性、安定性がいずれも優れるという効果がある。 The crosslinking agent is added to reinforce the cohesive force. In one specific example, the crosslinking agent may be a compound containing 5 to 15 alkylene oxide groups and having an acrylate group or a vinyl group. Specifically, it may be a compound containing 6 to 12 alkylene oxide groups and having an acrylate group or a vinyl group, and within the above range, there is an effect that the room temperature, aging tackiness and stability are all excellent.
参考に、前記アルキレンオキシド基の個数は、使用された架橋剤内に含まれたアルキレンオキシド基の平均数を意味し、架橋剤内にアルキレンオキシド基が5個未満である場合、製造される粘着剤が必要以上に硬くなって初期粘着力が低下し、アルキレンオキシド基が15個を超える場合には、製造される粘着剤が必要以上に柔軟になって粘着物性が低下するため、好ましくない。 For reference, the number of alkylene oxide groups means the average number of alkylene oxide groups contained in the used crosslinking agent, and the pressure-sensitive adhesive produced when the number of alkylene oxide groups is less than 5 in the crosslinking agent. When the agent becomes harder than necessary and the initial adhesive strength is reduced, and the number of alkylene oxide groups exceeds 15, the produced adhesive becomes more flexible than necessary and the adhesive physical properties are lowered, which is not preferable.
一具体例において、前記架橋剤は、有機架橋剤であるポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、1,6−ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、エトキシ化トリメチルプロパントリアクリレート、トリプロピレングリコールジアクリレート、1,3−ブタンジオールジアクリレート、ペンタエリスリトールトリアクリレート、3−トリメトキシシリルプロピルメタクリレート、ビニルトリメトキシシラン及びジビニルベンゼンなどと、無機架橋剤であるアルミニウムアセチルアセトネート、酢酸亜鉛、炭酸ジルコニウムなどからなる群から選択された1つ以上であってもよく、詳細には、ポリエチレングリコールジアクリレート及びポリプロピレングリコールジアクリレートからなる群から選択される1つ以上であってもよい。 In one specific example, the crosslinking agent is an organic crosslinking agent such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylpropane triacrylate, tripropylene glycol. Diacrylate, 1,3-butanediol diacrylate, pentaerythritol triacrylate, 3-trimethoxysilylpropyl methacrylate, vinyltrimethoxysilane, divinylbenzene, etc. and aluminum acetylacetonate, zinc acetate, zirconium carbonate as inorganic crosslinking agents One or more selected from the group consisting of, for example, polyethylene glycol diacrylate and polypropylene glycol It may be one or more selected from the group consisting of diacrylates.
一方、一具体例において、前記混合物にはエポキシ基含有不飽和単量体がさらに含まれてもよく、前記エポキシ基含有不飽和単量体は、詳細には、グリシジル(メタ)アクリレート、α−メチルグリシジル(メタ)アクリレート、アリルグリシジルエーテル、オキソシクロヘキシル(メタ)アクリレート、3,4−エポキシシクロヘキシルメチル(メタ)アクリレートからなる群から選択される1つ以上であってもよく、より詳細には、グリシジル(メタ)アクリレート又はアリルグリシジルエーテルであってもよい。 On the other hand, in one specific example, the mixture may further include an epoxy group-containing unsaturated monomer, and the epoxy group-containing unsaturated monomer may be glycidyl (meth) acrylate, α- It may be one or more selected from the group consisting of methyl glycidyl (meth) acrylate, allyl glycidyl ether, oxocyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and more specifically, It may be glycidyl (meth) acrylate or allyl glycidyl ether.
前記エポキシ基含有不飽和単量体は、混合物の全重量を基準として0.1〜3重量%含まれてもよく、前記範囲内で、粘着剤組成物が十分な凝集力を有する。 The epoxy group-containing unsaturated monomer may be included in an amount of 0.1 to 3% by weight based on the total weight of the mixture, and the pressure-sensitive adhesive composition has sufficient cohesive strength within the above range.
本発明はまた、前記アクリル系エマルジョン粘着剤の製造方法を開示する。 The present invention also discloses a method for producing the acrylic emulsion pressure-sensitive adhesive.
前記アクリル系エマルジョン粘着剤の製造方法は、乳化重合による場合、特に制限されるものではないが、反応熱の制御が容易な単量体添加法又はシード重合法を用いることができる。 The method for producing the acrylic emulsion pressure-sensitive adhesive is not particularly limited in the case of emulsion polymerization, but a monomer addition method or a seed polymerization method that can easily control the reaction heat can be used.
具体的に、前記アクリル系エマルジョン粘着剤の製造方法は、 Specifically, the manufacturing method of the acrylic emulsion adhesive is:
(A)i)炭素数1〜14のアルキル基を有する(メタ)アクリル酸エステル単量体、ii)アリルエステル、ビニルエステル、不飽和アセテート及び不飽和ニトリルからなる群から選択される1つ以上の単量体、iii)不飽和カルボン酸からなる群から選択される1つ以上の単量体を混合物の全重量を基準として0.6〜1.5重量%、iv)架橋剤、及びv)ヒドロキシエチルアクリレート単量体を混合物の全重量を基準として2.5〜10重量%含む混合物を製造する過程; (A) i) (meth) acrylic acid ester monomer having an alkyl group having 1 to 14 carbon atoms, ii) one or more selected from the group consisting of allyl ester, vinyl ester, unsaturated acetate and unsaturated nitrile Iii) 0.6 to 1.5% by weight based on the total weight of the mixture of one or more monomers selected from the group consisting of unsaturated carboxylic acids, iv) a crosslinking agent, and v ) Producing a mixture comprising 2.5 to 10% by weight of hydroxyethyl acrylate monomer, based on the total weight of the mixture;
(B)前記混合物に界面活性剤、電解質、及び水を投入して乳化液を製造する過程; (B) A process of producing an emulsion by adding a surfactant, an electrolyte, and water to the mixture;
(C)前記乳化液に開始剤を添加した後、乳化重合する過程; (C) A process of emulsion polymerization after adding an initiator to the emulsion;
を含むことを特徴とする。 It is characterized by including.
前記アクリル系エマルジョン粘着剤の製造方法は、 The method for producing the acrylic emulsion adhesive is:
(D)前記アクリル系エマルジョン粘着剤に酸度(pH)調節剤を添加し、アクリル系エマルジョン粘着剤の酸度を6〜9に調節する過程をさらに含むことができる。 (D) An acidity (pH) adjuster may be added to the acrylic emulsion pressure-sensitive adhesive to further adjust the acidity of the acrylic emulsion pressure-sensitive adhesive to 6-9.
前記(B)の界面活性剤は、前記乳化重合時の初期粒子生成、生成された粒子の大きさの調節及び粒子の安定性などのために用いられ、親水性基と親油性基で構成されており、アニオン、カチオン及び非イオン界面活性剤などに分けられる。主にアニオン及び非イオン界面活性剤を用い、機械的安定性及び化学的安定性などを補完するために互いに混ぜて用いることもある。 The surfactant (B) is used for the initial particle generation at the time of the emulsion polymerization, the adjustment of the size of the generated particles, the stability of the particles, etc., and is composed of a hydrophilic group and a lipophilic group. It is divided into anionic, cationic and nonionic surfactants. Anionic and nonionic surfactants are mainly used, and they may be mixed with each other to supplement mechanical stability and chemical stability.
このような界面活性剤は、アニオン界面活性剤及び/又は非イオン界面活性剤であってもよく、具体的に、アニオン界面活性剤は、ソジウムアルキルジフェニルオキシドジスルホネート、ソジウムポリオキシエチレンアルキルエーテルサルフェート、ソジウムポリオキシエチレンラウリルエーテルサルフェート、及びソジウムジアルキルスルホサクシネートからなる群から選択される1つ以上であってもよく、非イオン界面活性剤は、ポリエチレンオキシドアルキルアリールエーテル、ポリエチレンオキシドアルキルアミン、及びポリエチレンオキシドアルキルエステルからなる群から選択される1つ以上であってもよい。 Such surfactants may be anionic surfactants and / or nonionic surfactants, specifically, anionic surfactants include sodium alkyl diphenyl oxide disulfonate, sodium polyoxyethylene alkyl. The nonionic surfactant may be one or more selected from the group consisting of ether sulfate, sodium polyoxyethylene lauryl ether sulfate, and sodium dialkyl sulfosuccinate, and the nonionic surfactant may be polyethylene oxide alkyl aryl ether, polyethylene oxide It may be one or more selected from the group consisting of alkylamines and polyethylene oxide alkyl esters.
前記重合反応に使用される電解質は、pHを調節し、重合されるアクリル系エマルジョン樹脂に安定性を付与するものであり、具体的には、ソジウムバイカーボネート、ソジウムカーボネート、ソジウムホスフェート、ソジウムサルフェート及びソジウムクロライドなどからなる群から選択される1種以上であってもよく、詳細にはソジウムカーボネートであってもよく、前記混合物100重量部を基準として0.1〜2重量部であってもよく、詳細には0.3〜1重量部であってもよい。 The electrolyte used for the polymerization reaction adjusts pH and imparts stability to the polymerized acrylic emulsion resin. Specifically, sodium bicarbonate, sodium carbonate, sodium phosphate, It may be one or more selected from the group consisting of sodium sulfate and sodium chloride, and more specifically may be sodium carbonate, 0.1 to 2 weights based on 100 parts by weight of the mixture Part or more specifically 0.3 to 1 part by weight.
一具体例において、前記開始剤は、水溶性開始剤であって、アンモニウム又はアルカリ金属の過硫酸塩、過酸化水素、ペルオキシド、ヒドロペルオキシドなどの水溶性重合開始剤であってもよく、低温下で乳化重合反応を行うために、還元剤1種以上と共に使用することもできる。前記還元剤は、ソジウムバイサルファイト、ソジウムメタバイサルファイト、ソジウムハイドロサルファイト、ソジウムチオサルフェート、ソジウムホルムアルデヒドスルホキシレート、アスコルビン酸などであってもよい。 In one embodiment, the initiator may be a water-soluble initiator, and may be a water-soluble polymerization initiator such as ammonium or alkali metal persulfate, hydrogen peroxide, peroxide, hydroperoxide, etc. In order to carry out the emulsion polymerization reaction, it can be used together with one or more reducing agents. The reducing agent may be sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and the like.
前記乳化重合反応の温度は、詳細には0〜100℃であってもよく、より詳細には40〜90℃であってもよく、前記開始剤を単独、又は前記開始剤と前記還元剤のうち1種以上を混合して使用する方法などで調節することができる。 The temperature of the emulsion polymerization reaction may be specifically 0 to 100 ° C., more specifically 40 to 90 ° C., the initiator alone, or the initiator and the reducing agent. It can adjust by the method etc. which mix and use 1 or more types among them.
前記アクリル系エマルジョン粘着剤に酸度(pH)調節剤を添加して酸度を調節することができ、このとき、アクリル系エマルジョン粘着剤の酸度は、詳細には6〜9に調節されてもよく、より詳細には7〜8に調節されてもよく、前記酸度調節剤は、アルカリ性物質であって、1価金属又は2価金属の水酸化物、塩化物、炭酸塩などの無機物、アンモニアまたは有機アミンなどであってもよい。 The acidity can be adjusted by adding an acidity (pH) regulator to the acrylic emulsion pressure-sensitive adhesive. At this time, the acidity of the acrylic emulsion pressure-sensitive adhesive may be specifically adjusted to 6 to 9, More specifically, the acidity adjusting agent may be adjusted to 7 to 8, and the acidity adjusting agent is an alkaline substance, and is an inorganic substance such as a monovalent metal or divalent metal hydroxide, chloride or carbonate, ammonia or organic. It may be an amine.
さらに、本発明に係るアクリル系エマルジョン粘着剤は、シリコン離型紙の表面にコーティングするときに発生するアクリル系エマルジョン粘着剤の収縮現象を防止するために、増粘剤及び湿潤剤(wetting agent)をさらに含むことができる。 Furthermore, the acrylic emulsion pressure-sensitive adhesive according to the present invention includes a thickener and a wetting agent in order to prevent the shrinkage phenomenon of the acrylic emulsion pressure-sensitive adhesive that occurs when coating the surface of the silicon release paper. Further can be included.
前記増粘剤は、CMC(Carboxyl Methyl Cellulose)、アクリルゾル、ポリビニルアルコール、スターチ、アルジネート、デキストリンなどであってもよく、詳細には、ポリビニルアルコールであってもよい。 The thickener may be CMC (Carboxyl Methyl Cellulose), acrylic sol, polyvinyl alcohol, starch, alginate, dextrin, or the like, and specifically, polyvinyl alcohol.
前記湿潤剤(wetting agent)は、親水性の粘着剤を疎水性に変化させて、疎水性のシリコーン離型紙の表面に粘着剤が良好に密着するようにするもので、通常、界面活性剤混合物であり、グリコール又はアルコールがさらに含まれてもよい。 The wetting agent is used to change the hydrophilic pressure-sensitive adhesive to hydrophobic so that the pressure-sensitive adhesive adheres well to the surface of the hydrophobic silicone release paper. And may further contain glycols or alcohols.
本発明はまた、アクリル系エマルジョン粘着剤を粘着用フィルム又はシート上に適用して粘着剤層を形成する粘着シートを提供する。 The present invention also provides an adhesive sheet in which an acrylic emulsion adhesive is applied on an adhesive film or sheet to form an adhesive layer.
前記粘着シートは、建築内外装材、インテリア材料、広告用フィルム、またはラベルの粘着用フィルムやシートであってもよく、前記粘着剤層は、厚さが10〜100μm、詳細には20〜30μmであってもよく、コーティング性に優れているため、十分な粘着物性を有する。 The pressure-sensitive adhesive sheet may be a building interior / exterior material, an interior material, an advertising film, or a label pressure-sensitive adhesive film or sheet, and the pressure-sensitive adhesive layer has a thickness of 10 to 100 μm, specifically 20 to 30 μm. Since it is excellent in coating properties, it has sufficient adhesive properties.
以下、本発明の実施例を参照して説明するが、以下の実施例は、本発明を例示するためのものであり、本発明の範疇がこれらのみに限定されるものではない。 Hereinafter, the present invention will be described with reference to examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
<実施例1>
温度計、撹拌機、滴下漏斗、窒素導入管及び還流冷却器を備えた2L容量のガラス反応器に、水175gと30%ソジウムポリオキシエチレンアルキルエーテルサルフェート1gを入れ、攪拌しながら、反応器の内部を窒素で置換した後、窒素雰囲気下で80℃に昇温させ、これを60分間維持した。
<Example 1>
Into a 2 L glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, 175 g of water and 1 g of 30% sodium polyoxyethylene alkyl ether sulfate were added, and the reactor was stirred. After replacing the inside with nitrogen, the temperature was raised to 80 ° C. in a nitrogen atmosphere, and this was maintained for 60 minutes.
別途に、プレエマルジョンの製造のために、ビーカーに2−エチルヘキシルアクリレート645g、ヒドロキシエチルアクリレート20g、酢酸ビニル15g、メタメチルアクリレート15g、アクリル酸8g、ポリエチレングリコールジアクリレート1g、及びn-ドデシルメルカプタン0.3gを投入した後、30分間混合して混合物を製造した。 Separately, for the preparation of the pre-emulsion, 645 g of 2-ethylhexyl acrylate, 20 g of hydroxyethyl acrylate, 15 g of vinyl acetate, 15 g of metamethyl acrylate, 8 g of acrylic acid, 1 g of polyethylene glycol diacrylate, and n-dodecyl mercaptan. After charging 3 g, the mixture was mixed for 30 minutes to produce a mixture.
前記混合物に30%ソジウムポリオキシエチレンアルキルエーテルサルフェート13g、50%アルキルジフェニルオキシドジスルホネート7g、ソジウムカーボネート2g、ソジウムメチルアリルスルホネート2g及び水175gを投入し、攪拌機で10分間攪拌して、白濁の乳化液を製造した。 To the mixture, 13 g of 30% sodium polyoxyethylene alkyl ether sulfate, 7 g of 50% alkyl diphenyl oxide disulfonate, 2 g of sodium carbonate, 2 g of sodium methylallyl sulfonate and 175 g of water and stirred for 10 minutes with a stirrer, A cloudy emulsion was produced.
前記ガラス反応器に、10%過硫酸アンモニウム溶液3.5gを投入し、10分間攪拌して溶解させた。 The glass reactor was charged with 3.5 g of a 10% ammonium persulfate solution and stirred for 10 minutes to dissolve.
前記ガラス反応器に、前記乳化液と10%過硫酸アンモニウム溶液90gを4時間の間均等に連続投入した。その後、10%過硫酸アンモニウム溶液2gをさらに投入した後、30分間、80℃に昇温し、この温度を1時間の間維持させた後、常温に冷却して、アクリル系エマルジョン粘着剤を製造した。 The emulsion and 90 g of 10% ammonium persulfate solution were uniformly and continuously charged into the glass reactor for 4 hours. Thereafter, 2 g of 10% ammonium persulfate solution was further added, and then the temperature was raised to 80 ° C. for 30 minutes. This temperature was maintained for 1 hour, and then cooled to room temperature to produce an acrylic emulsion adhesive. .
前記アクリル系エマルジョン粘着剤に28%アンモニア水溶液を添加して、pHを7〜8に調節した。 A 28% aqueous ammonia solution was added to the acrylic emulsion adhesive to adjust the pH to 7-8.
<実施例2>
前記実施例1において、プレエマルジョンの製造時にヒドロキシエチルアクリレートを40g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Example 2>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 40 g of hydroxyethyl acrylate was added during the production of the pre-emulsion.
<実施例3>
前記実施例1において、プレエマルジョンの製造時にヒドロキシエチルアクリレートを55g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Example 3>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 55 g of hydroxyethyl acrylate was added during the production of the pre-emulsion.
<実施例4>
前記実施例1において、プレエマルジョンの製造時にヒドロキシエチルアクリレートを70g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Example 4>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 70 g of hydroxyethyl acrylate was added during the production of the pre-emulsion.
<比較例1>
前記実施例1において、プレエマルジョンの製造時にヒドロキシエチルアクリレートを投入しなかった以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 1>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that hydroxyethyl acrylate was not added during the production of the pre-emulsion.
<比較例2>
前記実施例1において、プレエマルジョンの製造時にヒドロキシエチルアクリレートを15g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative example 2>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 15 g of hydroxyethyl acrylate was added during the production of the pre-emulsion.
<比較例3>
前記実施例1において、プレエマルジョンの製造時にヒドロキシエチルアクリレートを90g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 3>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 90 g of hydroxyethyl acrylate was added during the production of the pre-emulsion.
<比較例4>
前記実施例1において、プレエマルジョンの製造時にヒドロキシエチルアクリレートを110g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 4>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 110 g of hydroxyethyl acrylate was added during the production of the pre-emulsion.
<比較例5>
前記実施例1において、プレエマルジョンの製造時にアクリル酸を4g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 5>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 4 g of acrylic acid was added during the production of the pre-emulsion.
<比較例6>
前記実施例1において、プレエマルジョンの製造時にアクリル酸を12g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 6>
In Example 1, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 12 g of acrylic acid was added during the production of the pre-emulsion.
<比較例7>
前記実施例2において、プレエマルジョンの製造時にアクリル酸を4g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 7>
In Example 2, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 4 g of acrylic acid was added during the production of the pre-emulsion.
<比較例8>
前記実施例3において、プレエマルジョンの製造時にアクリル酸を4g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 8>
In Example 3, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 4 g of acrylic acid was added during the production of the pre-emulsion.
<比較例9>
前記実施例4において、プレエマルジョンの製造時にアクリル酸を4g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 9>
In Example 4, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 4 g of acrylic acid was added during the production of the pre-emulsion.
<比較例10>
前記実施例4において、プレエマルジョンの製造時にアクリル酸を12g投入した以外は、同様の方法でアクリル系エマルジョン粘着剤を製造した。
<Comparative Example 10>
In Example 4, an acrylic emulsion pressure-sensitive adhesive was produced in the same manner except that 12 g of acrylic acid was added during the production of the pre-emulsion.
<実験例1>
粘着剤がコーティングされた粘着試片
前記実施例1〜4及び比較例1〜3から製造された粘着剤を39μmのPETフィルム上に塗布し、120℃のオーブンで1分間乾燥して、粘着層が20μmの厚さを有するようにした。厚さを測定した後、1inchx200mmの大きさに裁断して粘着試片を製造した。
<Experimental example 1>
Adhesive specimen coated with adhesive The adhesive prepared from Examples 1 to 4 and Comparative Examples 1 to 3 was coated on a 39 μm PET film, dried in an oven at 120 ° C. for 1 minute, and then an adhesive layer. Has a thickness of 20 μm. After measuring the thickness, an adhesive specimen was manufactured by cutting into a size of 1 inch × 200 mm.
前記実施例1〜4及び比較例1〜3から製造された粘着剤の粘着物性を、下記の方法で試験し、その結果を下記表1に示す。 The adhesive properties of the adhesives produced from Examples 1 to 4 and Comparative Examples 1 to 3 were tested by the following method, and the results are shown in Table 1 below.
*初期低温粘着力試験:試験法FINAT TEST METHOD NO.9に準拠して、−10℃のチャンバー内でアクリル系エマルジョン粘着剤の粘着試片を環状に作って10分間放置した後、ガラスの表面に圧力を加えずに貼り付ける。5秒後、TA Texture Analyzer機器を用いて300mm/minの速度で剥離しながら測定した。 * Initial low temperature adhesive strength test : Test method FINAT TEST METHOD NO. In accordance with No. 9, an acrylic emulsion pressure-sensitive adhesive test piece is formed in a ring shape in a chamber at −10 ° C. and allowed to stand for 10 minutes, and then applied to the glass surface without applying pressure. After 5 seconds, measurement was performed using a TA Texture Analyzer device while peeling at a speed of 300 mm / min.
*保持力試験:試験法FINAT TEST METHOD NO.8に準拠して、アクリル系エマルジョン粘着剤の粘着試片を、ステンレススチールの表面(SUS 304)に付着面が1inchx1inchになるように付着した後、シートの先端に1kgの錘をぶら下げ、錘が落ちる時間を測定した。 * Holding power test : Test method FINAT TEST METHOD NO. 8. After adhering the acrylic emulsion adhesive specimen to the stainless steel surface (SUS 304) so that the adhesion surface is 1 inch × 1 inch, a weight of 1 kg is hung from the front end of the sheet. The fall time was measured.
*初期粘着力試験:試験法FINAT TEST METHOD NO.9に準拠して、アクリル系エマルジョン粘着剤の粘着試片を環状に作って、ガラスの表面に圧力を加えずに貼り付け、5秒後、TA Texture Analyzer機器を用いて300mm/minの速度で剥離しながら測定した。 * Initial adhesion test : Test method FINAT TEST METHOD NO. In accordance with No. 9, an acrylic emulsion pressure-sensitive adhesive specimen was made into a ring shape, applied to the surface of the glass without applying pressure, and after 5 seconds, at a speed of 300 mm / min using a TA Texture Analyzer device. Measured while peeling.
*剥離力試験:試験法FINAT TEST METHOD NO.2に準拠して、アクリル系エマルジョン粘着剤の粘着試片を、2kgのローラーを300mm/minの速度で2回往復させてガラス板上に付着させ、20分間常温で熟成させた後、TA(Texture Analyzer)機器を用いて300mm/minの速度で90度剥離しながら測定した。 * Peel force test : Test method FINAT TEST METHOD NO. 2, an acrylic emulsion pressure-sensitive adhesive specimen was adhered to a glass plate by reciprocating a 2 kg roller twice at a speed of 300 mm / min, and aged at room temperature for 20 minutes. Measurement was performed using a Texture Analyzer instrument while peeling at 90 ° at a speed of 300 mm / min.
前記表1を参照すると、実施例1〜4のアクリル系エマルジョン粘着剤は、高分子内の不飽和カルボン酸であるアクリル酸単量体及びヒドロキシエチルアクリレート単量体の作用により、初期低温粘着力及び保持力が向上したことを確認できる一方、比較例1〜10のアクリル系エマルジョン粘着剤は、適正量のアクリル酸単量体又はヒドロキシエチルアクリレート単量体が含有されていないため、初期低温粘着力又は保持力が十分でないことを確認できる。 Referring to Table 1, the acrylic emulsion pressure-sensitive adhesives of Examples 1 to 4 have initial low-temperature adhesive strength due to the action of acrylic acid monomer and hydroxyethyl acrylate monomer which are unsaturated carboxylic acids in the polymer. On the other hand, the acrylic emulsion pressure-sensitive adhesives of Comparative Examples 1 to 10 do not contain an appropriate amount of acrylic acid monomer or hydroxyethyl acrylate monomer, so that the initial low-temperature pressure-sensitive adhesive can be confirmed. It can be confirmed that the force or holding force is not sufficient.
具体的に、実施例1〜4及び比較例1〜4を参照すると、アクリル酸の含量はいずれも約1〜1.2重量%でほぼ同様である一方、ヒドロキシエチルアクリレートの含量は、0〜14重量%の間で様々に分布している。比較例1及び比較例2を通じて、ヒドロキシエチルアクリレートが2.5重量%を境界にそれより少なく含まれる場合には、保持力が大幅に減少し、比較例3及び比較例4を通じて、ヒドロキシエチルアクリレートが10重量%を境界にそれより多く含まれる場合には、保持力は上昇するが、初期低温粘着力が大幅に減少することがわかる。 Specifically, referring to Examples 1 to 4 and Comparative Examples 1 to 4, the acrylic acid content is about 1 to 1.2% by weight, while the hydroxyethyl acrylate content is 0 to 0%. There are various distributions between 14% by weight. In Comparative Example 1 and Comparative Example 2, when the hydroxyethyl acrylate is less than 2.5% by weight as a boundary, the holding power is greatly reduced. Through Comparative Example 3 and Comparative Example 4, the hydroxyethyl acrylate is reduced. It can be seen that when 10% by weight is included more than that at the boundary, the holding power increases, but the initial low-temperature adhesive force is greatly reduced.
したがって、適正量のアクリル酸を含み、ヒドロキシエチルアクリレートを2.5〜10重量%含む場合、初期低温粘着力及び保持力が著しく上昇することがわかる。 Therefore, it can be seen that the initial low-temperature adhesive force and the holding power are remarkably increased when an appropriate amount of acrylic acid is contained and 2.5 to 10% by weight of hydroxyethyl acrylate is contained.
実施例1〜4及び比較例5〜10を参照すると、このような実施例及び比較例はいずれもヒドロキシエチルアクリレートを2.5〜10重量%で適正量含有している一方、アクリル酸は0.5〜1.7重量%の間で様々に含有している。実施例1と比較例5及び6、又は実施例4と比較例9及び10を比較すると、アクリル酸の含量が0.6重量%未満である場合、保持力が大きく減少し、1.5重量%を超える場合には、初期低温粘着力が大きく減少することがわかる。実施例2及び3と比較例7及び8を比較してみても、アクリル酸が0.6重量%未満含まれる場合、初期低温粘着力又は保持力が十分でないことを確認できる。 Referring to Examples 1 to 4 and Comparative Examples 5 to 10, each of these Examples and Comparative Examples contains an appropriate amount of hydroxyethyl acrylate at 2.5 to 10% by weight, while acrylic acid is 0. It is contained in various amounts between 5 and 1.7% by weight. When Example 1 and Comparative Examples 5 and 6 or Example 4 and Comparative Examples 9 and 10 are compared, when the acrylic acid content is less than 0.6% by weight, the holding power is greatly reduced to 1.5% by weight. When it exceeds%, it can be seen that the initial low-temperature adhesive strength is greatly reduced. Even when Examples 2 and 3 are compared with Comparative Examples 7 and 8, when acrylic acid is contained in an amount of less than 0.6% by weight, it can be confirmed that the initial low-temperature adhesive force or holding force is not sufficient.
これを通じて、適正量のヒドロキシエチルアクリレートを含み、アクリル酸を0.6〜1.5重量%含む場合、初期低温粘着力及び保持力が著しく上昇することがわかる。 From this, it can be seen that the initial low-temperature adhesive force and the holding power are remarkably increased when the appropriate amount of hydroxyethyl acrylate is contained and acrylic acid is contained in an amount of 0.6 to 1.5% by weight.
このような結果は、粘着剤内でヒドロキシエチルアクリレートとアクリル酸の極性作用基が強く相互作用し、微細な差でも粘着剤の物性に大きな影響を及ぼすものと推定される。 Such a result is presumed that the polar functional groups of hydroxyethyl acrylate and acrylic acid interact strongly in the pressure-sensitive adhesive, and even a small difference greatly affects the physical properties of the pressure-sensitive adhesive.
結論的に、混合物の全重量を基準として0.6〜1.5重量%の不飽和カルボン酸及び2.5〜10重量%のヒドロキシエチルアクリレート単量体を含むアクリル系エマルジョン粘着剤の場合、一般的な粘着物性が低下しないと共に、低温粘着力及び保持力が著しく上昇することを確認できる。 In conclusion, for acrylic emulsion adhesives containing 0.6 to 1.5 wt% unsaturated carboxylic acid and 2.5 to 10 wt% hydroxyethyl acrylate monomer, based on the total weight of the mixture, It can be confirmed that the general adhesive physical properties are not deteriorated and the low-temperature adhesive force and holding force are remarkably increased.
本発明の属する分野における通常の知識を有する者であれば、上記内容に基づいて本発明の範疇内で様々な応用及び変形を行うことが可能であろう。 A person having ordinary knowledge in the field to which the present invention belongs can make various applications and modifications within the scope of the present invention based on the above contents.
以上で説明したように、本発明によれば、アクリル系エマルジョン粘着剤が、混合物の全重量を基準として不飽和カルボン酸単量体を0.6〜1.5重量%及びヒドロキシエチルアクリレート単量体を2.5〜10重量%含む場合、低温粘着力及び保持力が著しく向上する。 As described above, according to the present invention, the acrylic emulsion pressure-sensitive adhesive contains 0.6 to 1.5% by weight of unsaturated carboxylic acid monomer and hydroxyethyl acrylate monomer based on the total weight of the mixture. When the body is contained in an amount of 2.5 to 10% by weight, the low-temperature adhesive force and the holding force are remarkably improved.
Claims (22)
前記混合物は、混合物の全重量を基準として、iii)不飽和カルボン酸からなる群から選択される1つ以上の単量体を0.6〜1.5重量%、及びv)ヒドロキシエチルアクリレート単量体を2.5〜10重量%含むことを特徴とする、アクリル系エマルジョン粘着剤。 i) a (meth) acrylic acid ester monomer having an alkyl group having 1 to 14 carbon atoms, ii) one or more monomers selected from the group consisting of allyl esters, vinyl esters, unsaturated acetates and unsaturated nitriles Iii) one or more monomers selected from the group consisting of unsaturated carboxylic acids, iv) a crosslinking agent, and v) an acrylic emulsion resin produced by polymerization of a mixture comprising hydroxyethyl acrylate monomers Including
The mixture comprises, based on the total weight of the mixture, iii) 0.6 to 1.5% by weight of one or more monomers selected from the group consisting of unsaturated carboxylic acids, and v) hydroxyethyl acrylate alone. An acrylic emulsion pressure-sensitive adhesive comprising 2.5 to 10% by weight of a monomer.
(A)i)炭素数1〜14のアルキル基を有する(メタ)アクリル酸エステル単量体、ii)アリルエステル、ビニルエステル、不飽和アセテート及び不飽和ニトリルからなる群から選択される1つ以上の単量体、iii)不飽和カルボン酸からなる群から選択される1つ以上の単量体を混合物の全重量を基準として0.6〜1.5重量%、iv)架橋剤、及びv)ヒドロキシエチルアクリレート単量体を混合物の全重量を基準として2.5〜10重量%含む混合物を製造する過程と、
(B)前記混合物に界面活性剤、電解質、及び水を投入して乳化液を製造する過程と、
(C)前記乳化液に開始剤を添加した後、乳化重合する過程と
を含むことを特徴とする、アクリル系エマルジョン粘着剤の製造方法。 It is a manufacturing method of the acrylic emulsion adhesive according to claim 1,
(A) i) (meth) acrylic acid ester monomer having an alkyl group having 1 to 14 carbon atoms, ii) one or more selected from the group consisting of allyl ester, vinyl ester, unsaturated acetate and unsaturated nitrile Iii) 0.6 to 1.5% by weight based on the total weight of the mixture of one or more monomers selected from the group consisting of unsaturated carboxylic acids, iv) a crosslinking agent, and v ) Producing a mixture comprising 2.5 to 10% by weight of hydroxyethyl acrylate monomer, based on the total weight of the mixture;
(B) A process of producing an emulsion by adding a surfactant, an electrolyte, and water to the mixture;
(C) A method for producing an acrylic emulsion pressure-sensitive adhesive, comprising the step of emulsion polymerization after adding an initiator to the emulsion.
(D)前記乳化重合で合成されたアクリル系エマルジョン粘着剤に酸度(pH)調節剤を添加し、アクリル系エマルジョン粘着剤の酸度を6〜9に調節する過程をさらに含むことを特徴とする、請求項15に記載のアクリル系エマルジョン粘着剤の製造方法。 The manufacturing method includes:
(D) The method further comprises the step of adding an acidity (pH) adjuster to the acrylic emulsion pressure-sensitive adhesive synthesized by the emulsion polymerization, and adjusting the acidity of the acrylic emulsion pressure-sensitive adhesive to 6-9. The manufacturing method of the acrylic emulsion adhesive of Claim 15.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020140104185A KR101725869B1 (en) | 2014-08-12 | 2014-08-12 | Acrylic Emulsion Adhesive with Excellent Low Temperature Adhesion and Holding Power, and Preparation Method Thereof |
KR10-2014-0104185 | 2014-08-12 | ||
PCT/KR2015/007430 WO2016024729A1 (en) | 2014-08-12 | 2015-07-17 | Acrylic emulsion adhesive with excellent low-temperature adhesive strength and retention strength and manufacturing method therefor |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2017527634A true JP2017527634A (en) | 2017-09-21 |
JP6510567B2 JP6510567B2 (en) | 2019-05-08 |
Family
ID=55304320
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016573475A Active JP6510567B2 (en) | 2014-08-12 | 2015-07-17 | Acrylic emulsion pressure sensitive adhesive excellent in low temperature adhesion and holding power and method for producing the same |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6510567B2 (en) |
KR (1) | KR101725869B1 (en) |
CN (1) | CN106459711B (en) |
WO (1) | WO2016024729A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102179024B1 (en) | 2017-05-22 | 2020-11-16 | 주식회사 엘지화학 | Multilayer adhesive tape |
KR102470448B1 (en) * | 2017-12-15 | 2022-11-24 | 주식회사 엘지화학 | Aqueous acrylic adhesive for clothes and method for preparing the same |
KR102439756B1 (en) * | 2018-03-02 | 2022-09-01 | 주식회사 엘지화학 | Process for preparing aqueous acrylic adhesive composition |
KR102497140B1 (en) * | 2018-11-02 | 2023-02-06 | 주식회사 엘지화학 | Acrylic emulsion pressure snsitive adhesive composition |
KR102267592B1 (en) * | 2018-11-02 | 2021-06-21 | 주식회사 엘지화학 | Preparation method of aqueous adhesive composition for clothes |
KR102262503B1 (en) | 2018-12-17 | 2021-06-08 | 주식회사 엘지화학 | Preparation method of acrylic emusion resin |
KR102332742B1 (en) * | 2018-12-18 | 2021-11-30 | 주식회사 엘지화학 | Acrylic emulsion pressure sensitive adhesive composition |
KR102291556B1 (en) * | 2018-12-20 | 2021-08-20 | 주식회사 엘지화학 | Acrylic emulsion pressure snsitive adhesive composition |
US20220290015A1 (en) | 2019-09-17 | 2022-09-15 | Lg Chem, Ltd. | Acrylate-Based Emulsion Pressure-Sensitive Adhesive Composition |
CN111363492B (en) * | 2020-05-09 | 2022-02-11 | 永大(中山)有限公司 | Water purifier filter element adhesive tape and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001207146A (en) * | 2000-01-26 | 2001-07-31 | Saiden Chemical Industry Co Ltd | Water-based adhesive composition |
JP2002080804A (en) * | 2000-09-06 | 2002-03-22 | Mitsui Chemicals Inc | Adhesive film for grinding rear surface of semiconductor wafer and process for grinding rear surface of semiconductor wafer using this |
JP2010235710A (en) * | 2009-03-30 | 2010-10-21 | Lintec Corp | Water-dispersed pressure-sensitive acrylic adhesive composition, pressure-sensitive adhesive sheet and method for using the same |
JP2010254961A (en) * | 2009-03-30 | 2010-11-11 | Lintec Corp | Acrylic emulsion type adhesive composition, production method thereof, and adhesive sheet |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5276084A (en) * | 1988-04-27 | 1994-01-04 | Air Products And Chemicals, Inc. | High performance pressure sensitive adhesive emulsion |
KR20000059816A (en) * | 1999-03-09 | 2000-10-05 | 한형수 | Acrylic emulsion adhesive composition for album |
KR100568868B1 (en) * | 2003-07-11 | 2006-04-10 | (주)웨스텍코리아 | Method for guaranteeing an after service and a system for embodying the method |
KR100554952B1 (en) * | 2003-12-30 | 2006-03-03 | 김동수 | Acryl emulsion type pressure-sensitive adhesive compositions, preparing methods thereof, pressure-sensitive adhesive tape utilizing the same, and applied articles thereof |
US7652103B2 (en) * | 2008-02-14 | 2010-01-26 | 3M Innovative Properties Company | Acrylic pressure-sensitive adhesives with aziridine crosslinking agents |
KR101027854B1 (en) * | 2008-08-20 | 2011-04-07 | 주식회사 엘지화학 | Composition for acrylic pressure-sensitive adhesive and surface finishing material comprising the same |
WO2014058199A1 (en) * | 2012-10-09 | 2014-04-17 | 주식회사 엘지화학 | Acrylic emulsion adhesive composition comprising nano sized latex particles having a mono-modal particle size distribution, and production method for same |
TWI491693B (en) * | 2012-11-06 | 2015-07-11 | Lg Chemical Ltd | Acryl-silicone-based hybrid emulsion adhesive composition and method of preparing the same |
CN104945902A (en) * | 2015-06-03 | 2015-09-30 | 东南大学 | Polyimide composite material and preparation method and application thereof |
-
2014
- 2014-08-12 KR KR1020140104185A patent/KR101725869B1/en active IP Right Grant
-
2015
- 2015-07-17 CN CN201580032211.6A patent/CN106459711B/en active Active
- 2015-07-17 JP JP2016573475A patent/JP6510567B2/en active Active
- 2015-07-17 WO PCT/KR2015/007430 patent/WO2016024729A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001207146A (en) * | 2000-01-26 | 2001-07-31 | Saiden Chemical Industry Co Ltd | Water-based adhesive composition |
JP2002080804A (en) * | 2000-09-06 | 2002-03-22 | Mitsui Chemicals Inc | Adhesive film for grinding rear surface of semiconductor wafer and process for grinding rear surface of semiconductor wafer using this |
JP2010235710A (en) * | 2009-03-30 | 2010-10-21 | Lintec Corp | Water-dispersed pressure-sensitive acrylic adhesive composition, pressure-sensitive adhesive sheet and method for using the same |
JP2010254961A (en) * | 2009-03-30 | 2010-11-11 | Lintec Corp | Acrylic emulsion type adhesive composition, production method thereof, and adhesive sheet |
Also Published As
Publication number | Publication date |
---|---|
JP6510567B2 (en) | 2019-05-08 |
KR20160019652A (en) | 2016-02-22 |
WO2016024729A1 (en) | 2016-02-18 |
KR101725869B1 (en) | 2017-04-11 |
CN106459711A (en) | 2017-02-22 |
CN106459711B (en) | 2019-02-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6510567B2 (en) | Acrylic emulsion pressure sensitive adhesive excellent in low temperature adhesion and holding power and method for producing the same | |
JP5940221B2 (en) | Acrylic-silicone hybrid emulsion pressure-sensitive adhesive composition and method for producing the same | |
JP6194118B2 (en) | Acrylic emulsion adhesive and method for producing the same | |
KR101828931B1 (en) | Acrylic Emulsion Adhesive with Excellent Polyethylene Adhesion and Emulsion Polymerization Stability, and Preparation Method Thereof | |
JP6397058B2 (en) | Acrylic emulsion adhesive excellent in detergency and method for producing the same | |
KR101692805B1 (en) | Method of Producing Acrylic Emulsion Comprising Tackifier | |
JP6231693B2 (en) | Adhesive composition for polypropylene film and method for producing the same | |
TWI516508B (en) | Acrylic emulsion resin with excellent adhesiveness and method of preparing the same | |
KR102470448B1 (en) | Aqueous acrylic adhesive for clothes and method for preparing the same | |
KR102600008B1 (en) | Aqueous acrylic adhesive for pet film and method for preparing the same | |
JP6206137B2 (en) | Aqueous re-peelable pressure-sensitive adhesive and re-peelable pressure-sensitive adhesive sheet | |
KR20180076004A (en) | Acrylic emulsion adhesive and method for preparing the same | |
JP2016011414A (en) | Polymer emulsion, aqueous adhesive composition and pressure sensitive adhesive sheet | |
JP6044017B2 (en) | Aqueous re-peelable pressure-sensitive adhesive and re-peelable pressure-sensitive adhesive sheet | |
KR20140115166A (en) | Acrylic Emulsion Comprising Tackifier, Method of Producing the Same and Acrylic Emulsion Adhesive with the Same | |
KR20140117739A (en) | Acrylic Emulsion Adhesive with Excellent Coatability and Preparation Method Thereof | |
JP6554922B2 (en) | Re-peelable water pressure sensitive adhesive | |
JP6028288B2 (en) | Re-peelable water pressure sensitive adhesive | |
JP2020012017A (en) | Aqueous re-releasable adhesive and adhesive sheet | |
KR20190065078A (en) | Acrylic emulsion pressure snsitive adhesive composition | |
KR20210150874A (en) | Acrylic emulsion adhesive composition and adhesive comprising the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170922 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180614 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180730 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181024 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190311 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190404 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6510567 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |