JP2006176562A - Water-based adhesive composition - Google Patents
Water-based adhesive composition Download PDFInfo
- Publication number
- JP2006176562A JP2006176562A JP2004368877A JP2004368877A JP2006176562A JP 2006176562 A JP2006176562 A JP 2006176562A JP 2004368877 A JP2004368877 A JP 2004368877A JP 2004368877 A JP2004368877 A JP 2004368877A JP 2006176562 A JP2006176562 A JP 2006176562A
- Authority
- JP
- Japan
- Prior art keywords
- water
- group
- weight
- parts
- adhesive composition
- 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
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 50
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 23
- -1 N-substituted amide group Chemical group 0.000 claims abstract description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000126 latex Polymers 0.000 claims abstract description 11
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 7
- 239000000057 synthetic resin Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 229920005601 base polymer Polymers 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000003827 glycol group Chemical group 0.000 claims description 9
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 208000008842 sick building syndrome Diseases 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011120 plywood Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920006322 acrylamide copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- 229920006173 natural rubber latex Polymers 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000000243 solution 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
- 235000019698 starch Nutrition 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 1
- XOQMWEWYWXJOAN-UHFFFAOYSA-N 3-methyl-3-(prop-2-enoylamino)butanoic acid Chemical compound OC(=O)CC(C)(C)NC(=O)C=C XOQMWEWYWXJOAN-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- CJKWEXMFQPNNTL-UHFFFAOYSA-N bis(prop-2-enyl) 1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylate Chemical compound C=CCOC(=O)C1C(C(=O)OCC=C)C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl CJKWEXMFQPNNTL-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- HJWBBBADPXPUPA-UHFFFAOYSA-N ethyl 3-(4-chlorophenyl)-5-methyl-1,2-oxazole-4-carboxylate Chemical compound CCOC(=O)C1=C(C)ON=C1C1=CC=C(Cl)C=C1 HJWBBBADPXPUPA-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011534 incubation Methods 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
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- WYRJQOPVEMCABI-UHFFFAOYSA-N n,n,n',n'-tetrakis(prop-2-enyl)butane-1,4-diamine Chemical compound C=CCN(CC=C)CCCCN(CC=C)CC=C WYRJQOPVEMCABI-UHFFFAOYSA-N 0.000 description 1
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、水系接着剤組成物、詳しくは、分岐構造を有するポリアクリルアミド系水溶性樹脂を水性ベースポリマーに配合してなる水系接着剤組成物に関する。 The present invention relates to an aqueous adhesive composition, and more particularly to an aqueous adhesive composition obtained by blending a polyacrylamide water-soluble resin having a branched structure with an aqueous base polymer.
従来は、接着剤として、溶剤型のものが汎用されていたが、火災、爆発、大気汚染、作業環境、人体への安全性等で問題があるため、近年では酢酸ビニルエマルジョンやアクリルエマルジョン等の合成樹脂エマルジョンや、スチレン−ブタジエン共重合体ラテックス、天然ゴムラテックス、クロロプレンラテックス等のゴム系ラテックスというような水性ベースポリマーを主成分とする水系接着剤が多く使用されている。 Conventionally, solvent type adhesives have been widely used as adhesives, but in recent years there are problems with fire, explosion, air pollution, work environment, safety to the human body, etc. Recently, vinyl acetate emulsion, acrylic emulsion, etc. Aqueous adhesives based on aqueous base polymers such as synthetic resin emulsions, rubber-based latexes such as styrene-butadiene copolymer latex, natural rubber latex, and chloroprene latex are often used.
水系接着剤としては、前記の水性ベースポリマーに、接着力などの粘・接着特性を付与するため、ロジン類、ロジン誘導体、石油系樹脂、テルペン系樹脂などの粘着付与樹脂エマルジョンや、ユリア(尿素)樹脂、メラミン樹脂等のアミノ樹脂を配合してなる水系接着剤組成物が知られている。 Water-based adhesives include tackifier resin emulsions such as rosins, rosin derivatives, petroleum-based resins, and terpene-based resins, urea (urea), and the like to impart adhesive and adhesive properties to the aqueous base polymer. ) Aqueous adhesive compositions obtained by blending amino resins such as resins and melamine resins are known.
但し、これら粘着付与樹脂エマルジョンは、比較的高価である上に、調製の際に可塑剤や有機溶剤を用いる場合があり、この場合には可塑剤や有機溶剤が製品中に残存するという問題があった。また、調製時に乳化剤を使用するため、耐水性などの接着特性が不充分な場合もあった。更にアミノ樹脂は、原料にホルムアルデヒドを使用しているため、ホルムアルデヒドを放散するといった問題があった。最近では、環境ホルモンやシックハウス症候群などの環境問題から、可塑剤や揮発性有機溶剤、特にホルムアルデヒドの使用や放散が制限されるようになってきており、これら粘着付与樹脂エマルジョンやアミノ樹脂に代わる安価で環境問題に懸念のない添加剤が望まれている。 However, these tackifying resin emulsions are relatively expensive, and in some cases, a plasticizer or an organic solvent is used in the preparation. In this case, there is a problem that the plasticizer or the organic solvent remains in the product. there were. In addition, since an emulsifier is used during preparation, there are cases where adhesive properties such as water resistance are insufficient. Furthermore, since amino resins use formaldehyde as a raw material, there is a problem that formaldehyde is diffused. Recently, due to environmental problems such as environmental hormones and sick house syndrome, the use and release of plasticizers and volatile organic solvents, especially formaldehyde, has been limited. Inexpensive alternatives to these tackifying resin emulsions and amino resins. Therefore, an additive that is not concerned about environmental problems is desired.
そこで、合板などの基材と紙とを張り合わせて出来る化粧合板用の接着剤組成物に、ホルムアルデヒドを放散しない材料として、ポリアクリルアミド樹脂のようなアミド基を有する水溶性樹脂を配合する方法が提案されている(特許文献1参照)が、一般のポリアクリルアミド樹脂水溶液では、比較的低分子量にも関わらず、固形分が低く高粘度のため、作業性や乾燥性に問題があり、かつ接着力や凝集力も満足できるものではなかった。 Therefore, a method is proposed in which a water-soluble resin having an amide group, such as polyacrylamide resin, is used as a material that does not disperse formaldehyde in an adhesive composition for decorative plywood, which is made by bonding a base material such as plywood and paper. However, a general polyacrylamide resin aqueous solution has a problem of workability and drying property due to its low solid content and high viscosity despite its relatively low molecular weight, and adhesion strength. Also, the cohesive strength was not satisfactory.
本発明は、通常条件下での接着力や凝集力に優れるのは勿論のこと、特に初期接着性や作業性に優れ、シックハウス症候群等の環境問題につき懸念の少ない水系接着剤組成物を提供することを目的とする。 The present invention provides a water-based adhesive composition that is excellent in adhesive strength and cohesive strength under normal conditions, particularly excellent in initial adhesiveness and workability, and less concerned about environmental problems such as sick house syndrome. For the purpose.
本発明者は、前記課題を解決すべく、ポリアクリルアミド系水溶性樹脂の構造に着目して鋭意検討を重ねた結果、従来のホルムアルデヒドを放散するアミノ樹脂や粘着付与樹脂エマルジョンなどの代わりに、特定の分岐構造を有するポリアクリルアミド系水溶性樹脂を、水性ベースポリマーに配合することにより、通常条件下での接着力や凝集力に優れるのは勿論のこと、初期接着性や作業性に優れ、しかも環境問題の懸念が少ない優れた水系接着剤組成物が得られることを見出した。 As a result of intensive studies focusing on the structure of the polyacrylamide water-soluble resin in order to solve the above-mentioned problems, the present inventor has identified a specific formaldehyde instead of an amino resin or tackifying resin emulsion that emits formaldehyde. By blending a polyacrylamide water-soluble resin having a branched structure with an aqueous base polymer, it has excellent initial adhesion and workability as well as excellent adhesion and cohesion under normal conditions. It has been found that an excellent aqueous adhesive composition with less concern about environmental problems can be obtained.
すなわち、本発明は、(a)(メタ)アクリルアミド40〜98重量部、(b)イオン性ビニルモノマーであって、アリル基、ポリアルキレングリコール基または一般式(1):−CONR1R2(式中、R1
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す)で表されるN−置換アミド基を側鎖に有しないものの少なくとも1種1〜50重量部、(c)アリル基、ポリアルキレングリコール基または一般式(1):−CONR1R2(式中、R1
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す)で表されるN−置換アミド基を側鎖に有するビニルモノマーの少なくとも1種0.01〜20重量部を含有してなるビニルモノマーの混合物を、水中で共重合させて得られる分岐構造を有するポリアクリルアミド系水溶性樹脂(A)、ならびに合成樹脂エマルジョンおよびゴム系ラテックスから選ばれる少なくとも一種の水性ベースポリマー(B)を含有する水系接着剤組成物に関する。
That is, the present invention is, (a) (meth) acrylamide 40-98 parts by weight, (b) an ionic vinyl monomer, an allyl group, a polyalkylene glycol group or a group represented by formula (1): - CONR 1 R 2 ( In which R 1
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. 1 to 50 parts by weight of at least one of those having no N-substituted amide group in the side chain, represented by the following formula: Allyl group, polyalkylene glycol group or general formula (1): —CONR 1 R 2 (wherein R 1
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. 0.01 to 20 parts by weight of at least one vinyl monomer having a side chain having an N-substituted amide group represented by the following formula: Polyacrylamide-based water-soluble resin (A) having a branched structure obtained by copolymerizing a mixture of vinyl monomers contained in water, and at least one aqueous base polymer selected from synthetic resin emulsion and rubber-based latex ( The present invention relates to an aqueous adhesive composition containing B).
本発明の特定の分岐構造を有するポリアクリルアミド系水溶性樹脂を水性ベースポリマーに配合して得られる水系接着剤組成物は、通常条件下での接着力や凝集力に優れるのは勿論のこと、初期接着性や作業性に優れ、しかもホルムアルデヒドを放散するなどの懸念が少なく、特に化粧合板などの建材、木工、紙加工などの用途に最適である。なお、本発明の水系接着剤がこのように各種性能に優れるのは定かでないが、ポリアクリルアミド系水溶性樹脂が、連鎖移動性置換基の作用により分岐構造が導入された構造となっていることから、特に木や紙などの基材との接点が多く親和性、密着性が向上し、優れた接着性能を発現するものと考えられる。また比較的高分子量にもかかわらず、分岐構造であるがゆえに、製品は高固形分かつ低粘度で作業性や乾燥性に優れ、凝集力を落とすことなく種々の特徴ある性能を示すものと考えられる。 The water-based adhesive composition obtained by blending the polyacrylamide-based water-soluble resin having a specific branched structure of the present invention with an aqueous base polymer is of course excellent in adhesive strength and cohesive strength under normal conditions, It has excellent initial adhesiveness and workability, and has few concerns such as formaldehyde diffusion, and is particularly suitable for building materials such as decorative plywood, woodworking, and paper processing. Although it is not certain that the aqueous adhesive of the present invention is excellent in various performances as described above, the polyacrylamide water-soluble resin has a structure in which a branched structure is introduced by the action of a chain transfer substituent. Therefore, it is considered that there are many contacts with a base material such as wood or paper, and the affinity and adhesion are improved, and excellent adhesion performance is exhibited. In addition, despite the relatively high molecular weight, because of the branched structure, the product is considered to exhibit various characteristic performances without reducing cohesive strength, with high solid content and low viscosity, excellent workability and drying properties. .
本発明において、(a)(メタ)アクリルアミド(以下、(a)成分という)とは、アクリルアミドおよび/またはメタクリルアミドをいう(以下、(メタ)とは同意である)。これらのなかでも経済性の面からはアクリルアミドを単独使用するのがよい。 In the present invention, (a) (meth) acrylamide (hereinafter referred to as component (a)) refers to acrylamide and / or methacrylamide (hereinafter referred to as (meth) is an agreement). Among these, it is preferable to use acrylamide alone from the viewpoint of economy.
(b)イオン性ビニルモノマー(以下、(b)成分という。)としては、アニオン性ビニルモノマー(b−1)(以下、(b−1)成分という。)およびカチオン性ビニルモノマー(b−2)(以下、(b−2)成分という。)であってアリル基、ポリアルキレングリコール基または一般式(1):−CONR1R2(式中、R1
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す。)で表されるN−置換アミド基を側鎖(以下、アリル基、ポリアルキレングリコール基または一般式(1):−CONR1R2(式中、R1
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す。)で表されるN−置換アミド基を連鎖移動性置換基ということもある。)に有しないものから選ばれるいずれか少なくとも一種を用いる。(b−1)成分の具体例としては、例えば(メタ)アクリル酸、クロトン酸等のモノカルボン酸;マレイン酸、フマル酸、イタコン酸、ムコン酸、シトラコン酸等のジカルボン酸;ビニルスルホン酸、スチレンスルホン酸、2−アクリルアミド−2−メチルプロパンスルホン酸などの有機スルホン酸;またはこれら各種有機酸のナトリウム塩、カリウム塩等があげられる。これらのなかでも重合性や価格面から、アクリル酸が好ましい。また、(b−2)成分の具体例としては、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリルアミド、ジエチルアミノプロピル(メタ)アクリルアミド、ビニルピリジンなどの第三級アミノ基を有するビニルモノマーまたはそれらの塩酸、硫酸、酢酸などの無機酸もしくは有機酸の塩類、または該第三級アミノ基含有ビニルモノマ−とメチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリンなどの四級化剤との反応によって得られる第四級アンモニウム塩を含有するビニルモノマー等があげられる。これらのなかでも重合性や価格面から、ジメチルアミノエチル(メタ)アクリレートが好ましい。これら(b)成分は、(b−1)成分または(b−2)成分を単独で使用してもよく、(b−1)成分およびカチオン性ビニルモノマー(b−2)成分を併用して使用してもよい。
(B) As an ionic vinyl monomer (hereinafter referred to as component (b)), an anionic vinyl monomer (b-1) (hereinafter referred to as component (b-1)) and a cationic vinyl monomer (b-2). ) (Hereinafter referred to as component (b-2)), which is an allyl group, a polyalkylene glycol group, or a general formula (1): —CONR 1 R 2 (wherein R 1
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. Represents a group represented by a formula 1-4 alkyl ester or acetyl group). ) Represented by a side chain (hereinafter, allyl group, polyalkylene glycol group or general formula (1): —CONR 1 R 2 (wherein R 1
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. Represents a group represented by a formula 1-4 alkyl ester or acetyl group). The N-substituted amide group represented by) is sometimes referred to as a chain transfer substituent. At least one selected from those not possessed in (1) is used. Specific examples of the component (b-1) include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, muconic acid and citraconic acid; vinyl sulfonic acid, Examples thereof include organic sulfonic acids such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid; and sodium salts and potassium salts of these various organic acids. Among these, acrylic acid is preferable from the viewpoint of polymerizability and price. Specific examples of the component (b-2) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, and vinylpyridine. Vinyl monomers having a quaternary amino group or salts of inorganic or organic acids such as hydrochloric acid, sulfuric acid and acetic acid, or quaternary compounds such as the tertiary amino group-containing vinyl monomers and methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc. And vinyl monomers containing a quaternary ammonium salt obtained by reaction with an agent. Among these, dimethylaminoethyl (meth) acrylate is preferable from the viewpoint of polymerizability and price. As these (b) components, the (b-1) component or the (b-2) component may be used alone, or the (b-1) component and the cationic vinyl monomer (b-2) component are used in combination. May be used.
(c)アリル基、ポリアルキレングリコール基または一般式(1):−CONR1R2(式中、R1
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す)で表されるN−置換アミド基を側鎖に有するビニルモノマー(以下、(c)成分という。)とは、重合に際し連鎖移動点として作用するアリル基、ポリアルキレングリコール基または一般式(1):−CONR1R2(式中、R1
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す)で表されるN−置換アミド基を側鎖に有し、得られる共重合体に多くの分岐構造を導入できるビニルモノマーをいう。本発明はかかる連鎖移動性の置換基の作用により、高分子量化した場合にも比較的低粘度で、かつ各種基材への密着性に優れた分岐構造を有するポリアクリルアミド系水溶性樹脂を得ようとするものである。
(C) Allyl group, polyalkylene glycol group or general formula (1): -CONR 1 R 2 (wherein R 1
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. A vinyl monomer having an N-substituted amide group in the side chain (hereinafter referred to as component (c)). An allyl group, a polyalkylene glycol group or general formula (1): -CONR 1 R 2 (wherein R 1 represents a chain transfer point during polymerization)
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. N-substituted amide group represented by the formula (1) represents an alkyl ester represented by formulas 1 to 4 or an acetyl group) in the side chain, and many branched structures are introduced into the resulting copolymer. A vinyl monomer that can be used. The present invention provides a polyacrylamide-based water-soluble resin having a branched structure that has a relatively low viscosity even when the molecular weight is increased and has excellent adhesion to various substrates by the action of such a chain transfer substituent. It is about to try.
(c)成分の具体例としては、アリル(メタ)アクリレート、N−
アリル(メタ)アクリルアミド、N−ジアリル(メタ)アクリルアミドなどがあげられる。また、連鎖移動性置換基としてポリアルキレングリコール基を有するビニルモノマーとしては、少なくとも2個のオキシアルキレン基の繰り返し単位を有するものがあげられる。通常はオキシアルキレン基の繰り返し単位10個程度までのものを使用するのが好ましい。具体例としては、ジエチレングリコールモノ(メタ)アクリレート、トリエチレングリコールモノ(メタ)アクリレート、テトラエチレングリコールモノ(メタ)アクリレート等のポリエチレングリコールモノ(メタ)アクリレート、前記同様のポリプロピレングリコールモノ(メタ)アクリレート、メトキシポリエチレングリコールモノ(メタ)アクリレート、ポリトリメチレングリコールモノ(メタ)アクリレート、ポリテトラメチレングリコールモノ(メタ)アクリレート、ポリエチレングリコールプロピレングリコールモノ(メタ)アクリレート等があげられる。また、連鎖移動性置換基として前記一般式(1)で表されるN−置換アミド基を有するビニルモノマーの具体例としては、ジメチルアクリルアミド、ダイアセトンアクリルアミド、イソプロピルアクリルアミド、2−アクリルアミド−2−メチルプロパンスルホン酸、2−アクリルアミド−2−メチルプロパンカルボン酸およびこれらの炭素数1〜4のアルキルエステルがあげられる。これら(c)成分のなかでも、重合性がよく共重合体に多くの分岐構造を導入できることから、ポリエチレンメタクリレートや、ジメチルアクリルアミドが好ましい。
Specific examples of the component (c) include allyl (meth) acrylate, N-
Examples include allyl (meth) acrylamide and N-diallyl (meth) acrylamide. Examples of the vinyl monomer having a polyalkylene glycol group as a chain transfer substituent include those having a repeating unit of at least two oxyalkylene groups. Usually, it is preferable to use up to about 10 repeating units of an oxyalkylene group. Specific examples include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and the same polypropylene glycol mono (meth) acrylate as described above, Examples include methoxypolyethylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol propylene glycol mono (meth) acrylate, and the like. Specific examples of the vinyl monomer having an N-substituted amide group represented by the general formula (1) as a chain transfer substituent include dimethylacrylamide, diacetone acrylamide, isopropylacrylamide, and 2-acrylamido-2-methyl. Examples thereof include propanesulfonic acid, 2-acrylamido-2-methylpropanecarboxylic acid, and alkyl esters having 1 to 4 carbon atoms. Among these (c) components, polyethylene methacrylate and dimethylacrylamide are preferred because they have good polymerizability and can introduce many branched structures into the copolymer.
本発明では、任意のビニルモノマー成分として(d)前記(a)成分および(c)成分を除く非架橋性ノニオン性ビニルモノマー(以下、(d)成分という)を使用できる。かかる(d)成分としては、前記(b−1)成分のアルキルエステルや、アクリロニトリル、スチレン、酢酸ビニル、メチルビニルエーテルなどがあげられる。 In the present invention, as the optional vinyl monomer component, (d) a non-crosslinkable nonionic vinyl monomer (hereinafter referred to as component (d)) excluding the components (a) and (c) can be used. Examples of the component (d) include the alkyl ester of the component (b-1), acrylonitrile, styrene, vinyl acetate, methyl vinyl ether and the like.
さらに本発明では、任意のビニルモノマー成分として(e)(a)〜(d)成分を除く架橋性ビニルモノマー(以下、(e)成分という)を使用することもできる。(e)成分としては、前記(a)〜(d)成分に含まれず、ビニル基を少なくとも2つ以上有するものを用いることができる。具合的には、たとえば、2官能性ビニルモノマーとして、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート等のジ(メタ)アクリレート類、メチレンビス(メタ)アクリルアミド、エチレンビス(メタ)アクリルアミド、ヘキサメチレンビス(メタ)アクリルアミド等のビス(メタ)アクリルアミド類、アジピン酸ジビニル、セバシン酸ジビニル等のジビニルエステル類、アリルメタクリレート、エポキシアクリレート類、ウレタンアクリレート類、N−メチロールアクリルアミド、ジアリルアミン、ジアリルジメチルアンモニウム、ジアリルフタレート、ジアリルクロレンデート、ジビニルベンゼン等があられる。また、3官能性モノマーとして、1,3,5−トリアクリロイルヘキサヒドロ−S−トリアジン、トリアリルイソシアヌレート、トリアリルアミン、トリアリルトリメリテート、N,N−ジアリルアクリルアミド等があげられる。4官能性ビニルモノマーとして、テトラメチロールメタンテトラアクリレート、テトラアリルピロメリテート、N,N,N’,N’−テトラアリル−1,4−ジアミノブタン、テトラアリルアミン塩、テトラアリルオキシエタン等があげられる。なお、これらのなかでは、製造時の反応性御が容易なことから、官能基がすべてビニル系二重結合のものが好ましい。
Furthermore, in this invention, the crosslinkable vinyl monomer (henceforth (e) component) except (e) (a)-(d) component can also be used as arbitrary vinyl monomer components. (E) As a component, what is not contained in said (a)-(d) component and has at least 2 or more vinyl groups can be used. Specifically, for example, as a bifunctional vinyl monomer, di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, methylene bis (meth) Bis (meth) acrylamides such as acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth) acrylamide, divinyl esters such as divinyl adipate and divinyl sebacate, allyl methacrylate, epoxy acrylates, urethane acrylates, N -Methylolacrylamide, diallylamine, diallyldimethylammonium, diallyl phthalate, diallyl chlorendate, divinylbenzene and the like. Examples of the trifunctional monomer include 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, triallyl trimellitate, N, N-diallylacrylamide and the like. Examples of tetrafunctional vinyl monomers include tetramethylolmethane tetraacrylate, tetraallyl pyromellitate, N, N, N ′, N′-tetraallyl-1,4-diaminobutane, tetraallylamine salts, tetraallyloxyethane, and the like. . Of these, the functional groups are preferably all vinyl-based double bonds since the reactivity during production is easy.
本発明の前記(a)〜(e)成分の各使用量は、得られる水溶性樹脂の水系接着剤組成物としての性能を十分考慮して決定しなければならない。すなわち、(a)〜(e)成分の各使用量は、以下の通りである。 The amount of each of the components (a) to (e) used in the present invention must be determined in consideration of the performance of the resulting water-soluble resin as an aqueous adhesive composition. That is, each usage-amount of (a)-(e) component is as follows.
すなわち、(a)成分は、40〜98重量部、好ましくは70〜96重量部である。(a)成分が40重量部に満たない場合には、水系接着剤組成物の接着力が不十分であり、98重量部を越える場合には水溶性樹脂のイオン量が不足し、水性ベースポリマーとの相溶性や基材への密着性が不十分であり、いずれの場合にも好ましくない。 That is, the component (a) is 40 to 98 parts by weight, preferably 70 to 96 parts by weight. When the component (a) is less than 40 parts by weight, the adhesive strength of the aqueous adhesive composition is insufficient, and when it exceeds 98 parts by weight, the ion amount of the water-soluble resin is insufficient, and the aqueous base polymer And inadequate compatibility and adhesion to a substrate are not preferable in any case.
(b)成分は、1〜50重量部程度、好ましくは1〜8重量部である。(b)成分が1重量部に満たない場合にはイオン量が不足し基材への密着性が不十分であり、50重量部を越える場合にはイオン量過多になり過凝集するため、いずれの場合にも好ましくない。なお、(b)成分として、(b−1)成分および(b−2)成分の両者を使用する場合の割合は、接着剤配合物の安定性や接着力を向上させる目的で、配合する水性ベースポリマーのイオン性や、接着剤を塗布する基材表面のイオン性などを考慮して適宜に調整すればよい。 (B) A component is about 1-50 weight part, Preferably it is 1-8 weight part. When component (b) is less than 1 part by weight, the amount of ions is insufficient and the adhesion to the substrate is insufficient, and when it exceeds 50 parts by weight, the amount of ions is excessive and agglomerates. This is also not preferable. In addition, the ratio in the case of using both the component (b-1) and the component (b-2) as the component (b) is an aqueous composition added for the purpose of improving the stability and adhesive strength of the adhesive composition. What is necessary is just to adjust suitably considering the ionicity of a base polymer, the ionicity of the base-material surface which apply | coats an adhesive agent, etc.
(c)成分も同様に通常0.01〜20重量部、好ましくは0.1〜10重量部である。(c)成分が0.01重量部に満たない場合には、水溶性樹脂に多くの分岐構造を導入できないため基材への密着性が不十分であり、20重量部を越える場合には分岐が進みすぎてゲル化するため、いずれの場合にも好ましくない。なお、(c)成分であって、アニオン性基、カチオン性基を有するものを用いる場合には、(c)成分中に含まれる連鎖移動性置換基とアニオン性基、カチオン性基の含有量を考慮に入れて、使用量を決定すればよいが、基本的には、(c)成分の使用量が当該範囲となるように調整すればよい。 The component (c) is also usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight. When the component (c) is less than 0.01 part by weight, the adhesiveness to the base material is insufficient because many branched structures cannot be introduced into the water-soluble resin. Is not preferable in any case because the gelation proceeds too much. In addition, when (c) component which has an anionic group and a cationic group is used, the content of the chain transfer substituent, the anionic group and the cationic group contained in the component (c) In consideration of the above, the amount of use may be determined, but basically, the amount of use of component (c) may be adjusted to fall within this range.
(d)成分を使用する場合には、1〜20重量部、好ましくは1〜15重量部である。(d)成分を、1重量部以上使用することにより、接着剤組成物の接着力を向上させることができる。(d)成分が20重量部を越える場合には、水への溶解性が悪くなる傾向があり好ましくない。 (D) When using a component, it is 1-20 weight part, Preferably it is 1-15 weight part. By using 1 part by weight or more of component (d), the adhesive strength of the adhesive composition can be improved. When the component (d) exceeds 20 parts by weight, the solubility in water tends to deteriorate, which is not preferable.
(e)成分を使用する場合には、0.01〜1重量部、好ましくは0.01〜0.5重量部である。(e)成分を、0.01重量部以上使用することにより、接着剤組成物の凝集力を向上させることができる。(e)成分が1重量部を越える場合には、架橋が進みすぎてゲル化する傾向があるため好ましくない。 (E) When using a component, it is 0.01-1 weight part, Preferably it is 0.01-0.5 weight part. By using 0.01 part by weight or more of component (e), the cohesive force of the adhesive composition can be improved. When the component (e) exceeds 1 part by weight, it is not preferable because the crosslinking tends to gel too much.
本発明に用いる(A)成分は、前記(a)〜(c)成分(必要に応じて(d)、(e)成分を含む)からなるビニルモノマーの混合物を、水中で共重合させて得られるが、その製造は同時重合、連続滴下重合等の従来公知の各種方法により行うことができる。例えば、所定の反応容器に前記ビニルモノマーの混合物および水を仕込み、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、またはこれらと亜硫酸水素ナトリウムのごとき還元剤とを組み合わせた形のレドックス系重合開始剤等の通常のラジカル重合開始剤を加え、攪拌下、加温することにより目的物を製造できる。そのほか、前記(a)〜(c)成分を共重合して主鎖を製造後、前記(a)および(b)成分を主成分とする側鎖をグラフト重合させることにより高分子量でグラフト構造の主鎖と側鎖のイオン成分に偏りを持たせたアクリルアミド系共重合体を製造する方法や、前記(a)〜(e)成分からなるビニルモノマーの混合物を、澱粉類やセルロース類、およびそれらの誘導体に代表される水分散性多糖類水溶液の存在下に共重合してグラフト構造の多糖類−アクリルアミド系共重合体を製造する方法などが挙げられる。なお、反応温度は通常50〜100℃程度であり、反応時間は通常0.1〜5時間である。 The component (A) used in the present invention is obtained by copolymerizing a mixture of vinyl monomers composed of the components (a) to (c) (including (d) and (e) components as necessary) in water. However, the production can be performed by various conventionally known methods such as simultaneous polymerization and continuous dropping polymerization. For example, a redox polymerization initiator in the form of a mixture of the vinyl monomers and water in a predetermined reaction vessel and a combination of a persulfate such as potassium persulfate and ammonium persulfate, or a reducing agent such as sodium bisulfite. The desired product can be produced by adding a normal radical polymerization initiator such as the above and heating under stirring. In addition, after the main chain is produced by copolymerizing the components (a) to (c), the side chain mainly composed of the components (a) and (b) is graft-polymerized to obtain a high molecular weight graft structure. A method for producing an acrylamide copolymer in which the ionic components of the main chain and side chain are biased, a mixture of vinyl monomers comprising the components (a) to (e), starches and celluloses, and And a method of producing a polysaccharide-acrylamide copolymer having a graft structure by copolymerization in the presence of a water-dispersible polysaccharide aqueous solution typified by the above derivative. In addition, reaction temperature is about 50-100 degreeC normally, and reaction time is 0.1 to 5 hours normally.
かくして得られた本発明の分岐構造を有するポリアクリルアミド系水溶性樹脂のpHは通常3〜9程度、粘度は10重量%の水溶液において100〜10000mPa・s(25℃)程度である。 The thus obtained polyacrylamide-based water-soluble resin having a branched structure of the present invention has a pH of usually about 3 to 9 and a viscosity of about 100 to 10,000 mPa · s (25 ° C.) in a 10% by weight aqueous solution.
本発明の水系接着剤組成物は、前記(A)成分を、合成樹脂系エマルジョンおよびゴム系ラテックスからなる群より選ばれる少なくとも一種の水性ベースポリマー(B)(以下、(B)成分という。)に、配合してなるものである。 In the aqueous adhesive composition of the present invention, the component (A) is at least one aqueous base polymer (B) selected from the group consisting of a synthetic resin emulsion and a rubber latex (hereinafter referred to as component (B)). And blended.
(B)成分として用いられる合成樹脂系エマルジョンとしては、酢酸ビニル樹脂エマルジョン、エチレン−酢酸ビニル樹脂エマルジョン、エチレン−酢酸ビニル−塩化ビニル樹脂エマルジョン、エチレン−塩化ビニル樹脂エマルジョン、酢酸ビニル−アクリル樹脂エマルジョン、アクリル樹脂エマルジョン、エチレン−アクリル樹脂エマルジョン、スチレン−アクリル樹脂エマルジョン、ウレタン樹脂エマルジョン、ウレタン−アクリル樹脂エマルジョン、塩化ビニリデン樹脂エマルジョンなどが例示できる。 As the synthetic resin emulsion used as the component (B), vinyl acetate resin emulsion, ethylene-vinyl acetate resin emulsion, ethylene-vinyl acetate-vinyl chloride resin emulsion, ethylene-vinyl chloride resin emulsion, vinyl acetate-acrylic resin emulsion, Examples thereof include an acrylic resin emulsion, an ethylene-acrylic resin emulsion, a styrene-acrylic resin emulsion, a urethane resin emulsion, a urethane-acrylic resin emulsion, and a vinylidene chloride resin emulsion.
また、ゴム系ラテックスとしては、例えば天然ゴムラテックス、ブタジエンラテックス、スチレン−ブタジエン共重合体ラテックス、アクリロニトリル−ブタジエン共重合体ラテックス、クロロプレンラテックス等の、各種公知のものを使用できる。 As the rubber latex, various known materials such as natural rubber latex, butadiene latex, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, and chloroprene latex can be used.
これら合成樹脂系エマルジョンやゴム系ラテックスは、カルボキシル基、N−メチロール基、グリシジル基、アミノ基、アミド基、水酸基などの官能基を導入したものを使用しても良く、上記合成樹脂系エマルジョンおよびゴム系ラテックスから選ばれる水性ベースポリマーのうち、1種を単独で、または2種以上を混合して使用できる。 These synthetic resin-based emulsions and rubber-based latexes may be those having functional groups such as carboxyl group, N-methylol group, glycidyl group, amino group, amide group and hydroxyl group introduced therein. Among the aqueous base polymers selected from rubber-based latexes, one kind can be used alone, or two or more kinds can be mixed and used.
(A)成分と(B)成分との配合割合は、(B)成分100重量部(固形分換算)に対し、(A)成分を、1〜60重量部程度(固形分換算)、好ましくは3〜40重量部程度(固形分換算)の範囲とする。(A)成分の合計量が1重量部に満たない場合は、水溶性樹脂を添加することによる改質効果がほとんど認められない場合があり、また60重量部を越える場合には接着剤組成物の凝集力や耐水性が低下する傾向にある。 The blending ratio of the component (A) and the component (B) is about 1 to 60 parts by weight (in terms of solid content) of the component (A), preferably 100 parts by weight (in terms of solid content) of the component (B). The range is about 3 to 40 parts by weight (in terms of solid content). When the total amount of the component (A) is less than 1 part by weight, the modification effect by adding the water-soluble resin may be hardly observed, and when it exceeds 60 parts by weight, the adhesive composition There is a tendency for the cohesive strength and water resistance of the to decrease.
本発明の水系接着剤組成物は、(A)成分、(B)成分を必須成分として構成されるが、これらのほかに必要に応じて、充填剤、消泡剤、増粘剤、酸化防止剤、防腐剤などを添加することができ、更に環境問題に懸念の無い範囲で、高沸点の溶剤や可塑剤、保水剤、成膜助剤などを添加することもできる。例えば、本発明で使用される充填剤としては、特に制限されないが、好ましいものとして、重質炭酸カルシウムや珪砂などが挙げられ、これらを単独でも併用してもよい。充填剤の配合割合は、(B)成分100重量部(固形分換算)に対して、通常は200〜500重量部程度である。 The aqueous adhesive composition of the present invention is composed of the component (A) and the component (B) as essential components, but in addition to these, a filler, an antifoaming agent, a thickener, and an antioxidant can be used. Additives, preservatives, and the like can be added, and high-boiling solvents, plasticizers, water retention agents, film-forming aids, and the like can be added as long as there is no concern about environmental problems. For example, although it does not restrict | limit especially as a filler used by this invention, Heavy calcium carbonate, silica sand, etc. are mentioned as a preferable thing, These may be used individually or in combination. The blending ratio of the filler is usually about 200 to 500 parts by weight with respect to 100 parts by weight of component (B) (in terms of solid content).
本発明の水系接着剤組成物は、(A)成分と(B)成分とがあらかじめ混合された一液型接着剤組成物として使用してもよく、また、(A)成分と(B)成分とを使用時に混合する二液型接着剤組成物として使用しても良い。通常は作業性の観点から一液型とすることが好ましい。 The aqueous adhesive composition of the present invention may be used as a one-component adhesive composition in which the component (A) and the component (B) are mixed in advance, and the component (A) and the component (B). May be used as a two-component adhesive composition that is mixed at the time of use. Usually, it is preferable to use a one-pack type from the viewpoint of workability.
以下、実施例および比較例を挙げて本発明をより具体的に説明する。なお、部および%はいずれも重量基準による。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. All parts and% are based on weight.
製造例1
撹拌機、温度計、還流冷却管および窒素ガス導入管を備えた四つ口フラスコに、アクリルアミド76部、アクリル酸2部、ジメチルアミノエチルメタクリレ−ト4部、ポリエチレングリコールメタクリレート(日本油脂(株)製、PE350)18部およびイオン交換水400部を仕込み、窒素ガスを通じて反応系内の酸素を除去した。次に、系内を40℃にし撹拌下に重合開始剤として過硫酸アンモニウム0.5部および亜硫酸水素ナトリウム0.3部を投入した。85℃まで昇温し、2時間保温した後、冷却して、pH=4.6、固形分20%、粘度(25℃、B型粘度計)9600mPa・sの分岐構造を有するポリアクリルアミド系水溶性樹脂(A−1)を得た。
Production Example 1
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 76 parts of acrylamide, 2 parts of acrylic acid, 4 parts of dimethylaminoethyl methacrylate, polyethylene glycol methacrylate (Nippon Yushi Co., Ltd.) ), PE350) 18 parts and ion-exchanged water 400 parts, and oxygen in the reaction system was removed through nitrogen gas. Next, the system was heated to 40 ° C., and 0.5 parts of ammonium persulfate and 0.3 part of sodium hydrogen sulfite were added as a polymerization initiator with stirring. The temperature was raised to 85 ° C., kept for 2 hours, and then cooled, and the polyacrylamide water solution having a branched structure of pH = 4.6, solid content 20%, viscosity (25 ° C., B-type viscometer) 9600 mPa · s Resin (A-1) was obtained.
製造例2
攪拌機、温度計、還流冷却管、滴下ロートを2つおよび窒素ガス導入管を備えた六つ口フラスコに、アクリルアミド18部、アクリル酸3部、ジメチルアミノエチルメタクリレ−ト2部、PE-
350(日本油脂(株)製、ポリエチレングリコールメタクリレート)23部およびイオン交換水300部を仕込み、窒素ガスを通じて反応系内の酸素を除去した。次に、系内を40℃にし攪拌下に重合開始剤として過硫酸アンモニウム0.25部および亜硫酸水素ナトリウム0.15部を投入した。85℃まで昇温した後、2時間保温し、主鎖となる共重合体を得た。保温終了後、該共重合体にアクリルアミド48部、アクリル酸1部、ジメチルアミノエチルメタクリレ−ト5部およびイオン交換水250部と、過硫酸カリウム0.5部およびイオン交換水15部を同時にそれぞれ別の滴下ロートより1時間かけて滴下し、1時間保温後、冷却し、pH4.5、固形分15%、粘度(25℃)が8400mPa・sの分岐構造を有するポリアクリルアミド系水溶性樹脂(A−2)を得た。
Production Example 2
In a six-necked flask equipped with a stirrer, thermometer, reflux condenser, two dropping funnels and a nitrogen gas inlet tube, 18 parts of acrylamide, 3 parts of acrylic acid, 2 parts of dimethylaminoethyl methacrylate, PE-
350 parts (manufactured by NOF Corporation, polyethylene glycol methacrylate) and 300 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. Next, the system was heated to 40 ° C., and 0.25 parts of ammonium persulfate and 0.15 part of sodium hydrogen sulfite were added as a polymerization initiator with stirring. After raising the temperature to 85 ° C., the temperature was kept for 2 hours to obtain a copolymer to be the main chain. After the incubation, 48 parts of acrylamide, 1 part of acrylic acid, 5 parts of dimethylaminoethyl methacrylate and 250 parts of ion-exchanged water, 0.5 part of potassium persulfate and 15 parts of ion-exchanged water were simultaneously added to the copolymer. Dropped from another dropping funnel over 1 hour, kept warm for 1 hour, cooled, polyacrylamide water-soluble resin having a branched structure of pH 4.5, solid content 15%, viscosity (25 ° C.) of 8400 mPa · s (A-2) was obtained.
製造例3
攪拌機、温度計、還流冷却管および窒素ガス導入管を備えた四つ口フラスコに、アクリルアミド74部、アクリル酸2部、ジメチルアミノエチルメタクリレート4部、PE-
350(日本油脂(株)製、ポリエチレングリコールメタクリレート)20部からなるビニルモノマーの混合物100部および陽イオン性タピオカ澱粉(日澱化学(株)製)81部を含有する糊液(5%水溶液)1620部を仕込み、窒素ガスを通じて反応系内の酸素を除去した。次に、系内を40℃にし攪拌下に重合開始剤として過硫酸アンモニウム0.5部および亜硫酸水素ナトリウム0.3部を投入した。85℃まで昇温し、2時間保温後、冷却し、pH4.5、固形分10%、粘度(25℃)が8500mPa・sの分岐構造を有する多糖類−ポリアクリルアミド系水溶性樹脂(A−3)を得た。
Production Example 3
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 74 parts of acrylamide, 2 parts of acrylic acid, 4 parts of dimethylaminoethyl methacrylate, PE-
350 (Nippon Yushi Co., Ltd., polyethylene glycol methacrylate) 20 parts of vinyl monomer mixture 100 parts and cationic tapioca starch (Nissho Chemical Co., Ltd.) 81 parts paste liquid (5% aqueous solution) 1620 parts were charged and oxygen in the reaction system was removed through nitrogen gas. Next, the system was heated to 40 ° C., and 0.5 parts of ammonium persulfate and 0.3 part of sodium hydrogen sulfite were added as a polymerization initiator with stirring. The temperature was raised to 85 ° C., kept for 2 hours, then cooled, and the polysaccharide-polyacrylamide water-soluble resin (A-) having a branched structure with a pH of 4.5, a solid content of 10%, and a viscosity (25 ° C.) of 8500 mPa · s. 3) was obtained.
製造例4〜5、比較製造例1〜3
実施例1において、(a)〜(e)成分の種類またはその使用量のうちいずれか少なくとも1種を表1のように変えたほかは、実施例1と同様の操作を行いポリアクリルアミド系水溶性樹脂(A)を得た。得られたポリアクリルアミド系水溶性樹脂(A)の性状値を表2に示す。
Production Examples 4-5, Comparative Production Examples 1-3
In Example 1, the same operation as in Example 1 was carried out except that at least one of the types of the components (a) to (e) or the amount used thereof was changed as shown in Table 1, and the polyacrylamide water solution Resin (A) was obtained. Table 2 shows the property values of the obtained polyacrylamide-based water-soluble resin (A).
表1中、ビニルモノマーの混合物の各成分は、AM:アクリルアミド、AA:アクリル酸、IA:イタコン酸、DM:ジメチルアミノエチルメタクリレート、DMAA:ジメチルアクリルアミド、PE90:ポリエチレングリコールモノメタクリレート(日本油脂(株)製)、PE350:ポリエチレングリコールモノメタクリレート(日本油脂(株)製)、AN:アクリロニトリル、MBAM:メチレンビスアクリルアミドを示す。また、その他成分の使用量は、ビニルモノマーの混合物100重量部に対する使用量(重量部)である。 In Table 1, each component of the mixture of vinyl monomers is AM: acrylamide, AA: acrylic acid, IA: itaconic acid, DM: dimethylaminoethyl methacrylate, DMAA: dimethylacrylamide, PE90: polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd.) )), PE350: polyethylene glycol monomethacrylate (manufactured by NOF Corporation), AN: acrylonitrile, MBAM: methylenebisacrylamide. Moreover, the usage-amount of another component is the usage-amount (weight part) with respect to 100 weight part of mixtures of a vinyl monomer.
実施例1
エチレン−酢酸ビニル系共重合体エマルジョン(住化ケムテックス(株)製、商品名「スミカフレックス400HQ」、不揮発分55%)182重量部(固形分換算で100重量部)に対し、製造例1の分岐構造を有するポリアクリルアミド系樹脂水溶液(A−1)を50重量部(固形分換算で10重量部)を混合し、水系接着剤組成物を得た。
Example 1
With respect to 182 parts by weight (100 parts by weight in terms of solid content) of Production Example 1 with respect to the ethylene-vinyl acetate copolymer emulsion (manufactured by Sumika Chemtex Co., Ltd., trade name “Sumikaflex 400HQ”, nonvolatile content 55%) 50 parts by weight (10 parts by weight in terms of solid content) of a polyacrylamide-based resin aqueous solution (A-1) having a branched structure was mixed to obtain an aqueous adhesive composition.
実施例2〜7、比較例1〜3
実施例1において、ポリアクリルアミド系樹脂水溶液(A)の種類またはその使用量を表3のように変えた他は、実施例1と同様に水系接着剤組成物を得た。
Examples 2-7, Comparative Examples 1-3
In Example 1, a water-based adhesive composition was obtained in the same manner as in Example 1 except that the type of polyacrylamide resin aqueous solution (A) or the amount thereof used was changed as shown in Table 3.
比較例4
実施例1において、エチレン−酢酸ビニル系共重合体エマルジョン(住化ケムテックス(株)製、商品名「スミカフレックス400HQ」、不揮発分55%)100重量部(固形分換算で55重量部)に対し、ポリアクリルアミド系樹脂水溶液(A)の代わりに、軟化点100℃のロジンエステル樹脂エマルジョン(荒川化学工業(株)製、商品名「スーパーエステルE−720」、固形分50%)10部(固形分換算で5重量部)を配合して水系接着剤組成物を得た。
Comparative Example 4
In Example 1, for an ethylene-vinyl acetate copolymer emulsion (manufactured by Sumika Chemtex Co., Ltd., trade name “Sumikaflex 400HQ”, nonvolatile content 55%) 100 parts by weight (55 parts by weight in terms of solid content) In place of the polyacrylamide-based resin aqueous solution (A), 10 parts of a rosin ester resin emulsion having a softening point of 100 ° C. (trade name “Superester E-720”, solid content 50%, manufactured by Arakawa Chemical Industries, Ltd.) An aqueous adhesive composition was obtained by blending 5 parts by weight).
表3中の各成分は、S−400HQ:エチレン−酢酸ビニル系共重合体エマルジョン(住化ケムテックス(株)製、商品名「スミカフレックス400HQ」、不揮発分55%)、E−720:軟化点100℃のロジンエステル樹脂エマルジョン(荒川化学工業(株)製、商品名「スーパーエステルE−720」、固形分50%)を示す。また、表中の各成分量は、全て固形換算重量部である。 Each component in Table 3 is S-400HQ: ethylene-vinyl acetate copolymer emulsion (manufactured by Sumika Chemtex Co., Ltd., trade name “Sumikaflex 400HQ”, non-volatile content 55%), E-720: softening point A rosin ester resin emulsion at 100 ° C. (trade name “Superester E-720”, solid content 50%, manufactured by Arakawa Chemical Industries, Ltd.) is shown. Moreover, each component amount in a table | surface is all solid conversion weight part.
(水系接着剤組成物の性能評価)
実施例1〜7および比較例1〜4で得られた水系接着剤組成物を、以下の性能評価方法にて各種試験を行った。
(Performance evaluation of aqueous adhesive composition)
Various tests were performed on the aqueous adhesive compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 by the following performance evaluation methods.
(接着性能試験)
以下の試験方法により接着特性を評価した。
(1)初期接着性
ダンボール原紙(坪量280g/m2)に、上記水系接着剤組成物を、アプリケーターを用いてWETで3ml塗布する。直ちに幅25mmの短冊状にカットした上質紙(坪量70g/m2)を張り合わせ、その後一定時間毎に剥離して、紙が全面材破した時間で表示した。結果を表4に示す。
(2)接着強度
綿帆布(#9)に、上記水系接着剤組成物をDRYで100g/m2塗布し、各種基材と張り合わせる。23℃×65%RHにて4日間以上乾燥後、引張り速度300mm/minで180°剥離を行った。結果を表4に示す。表中、SUSはステンレス板、PEはポリエチレン板、板紙は坪量280g/m2で、「材破」は板紙が全面破壊したことを示す。
(3)保持力
綿帆布(#9)に、上記水系接着剤組成物をDRYで100g/m2塗布し、ステンレス板と張り合わせる(接着面積25×25mm)。23℃×65%RHにて4日間以上乾燥後、クリープテスターにセットして荷重を1kg掛け、2℃/minで150℃まで昇温し、その後150℃で保持してずれ落ちるまでの時間を測定した。評価結果を表4に示す。
(4)残存溶剤量
上記水系接着剤配合物において、環境問題を勘案し、配合物中のトルエンの残存量をガスクロマトグラフにより測定した。測定結果を表4に示す。尚、表中のNDは検出限界(10ppm)以下であることを示す。
(Adhesion performance test)
The adhesive properties were evaluated by the following test method.
(1) Initial adhesiveness 3 ml of the aqueous adhesive composition is applied to cardboard base paper (basis weight 280 g / m 2 ) by WET using an applicator. Immediately, high-quality paper (basis weight 70 g / m 2 ) cut into a strip shape with a width of 25 mm was pasted, peeled off at regular intervals, and displayed as the time when the paper broke the entire surface. The results are shown in Table 4.
(2) Adhesive strength The above-mentioned aqueous adhesive composition is applied to cotton canvas (# 9) at 100 g / m 2 by DRY and bonded to various substrates. After drying at 23 ° C. × 65% RH for 4 days or longer, 180 ° peeling was performed at a pulling speed of 300 mm / min. The results are shown in Table 4. In the table, SUS is a stainless steel plate, PE is a polyethylene plate, paperboard has a basis weight of 280 g / m 2 , and “material breakage” indicates that the paperboard is completely destroyed.
(3) Holding power 100 g / m 2 of the aqueous adhesive composition is applied to cotton canvas (# 9) by DRY and bonded to a stainless steel plate (adhesive area 25 × 25 mm). After drying for 4 days or more at 23 ° C x 65% RH, set it on a creep tester, apply a load of 1 kg, raise the temperature to 150 ° C at 2 ° C / min, and then hold it at 150 ° C until it slips off. It was measured. The evaluation results are shown in Table 4.
(4) Residual solvent amount In consideration of environmental problems, the residual amount of toluene in the blend was measured by a gas chromatograph. Table 4 shows the measurement results. In addition, ND in a table | surface shows that it is below a detection limit (10 ppm).
Claims (4)
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す)で表されるN−置換アミド基を側鎖に有しないものの少なくとも1種1〜50重量部、(c)アリル基、ポリアルキレングリコール基または一般式(1):−CONR1R2(式中、R1
は水素原子またはメチル基を表し、R2はメチル基、イソプロピル基または一般式(2):−C(CH3)2−CH2−R3(R3はカルボキシル基、スルホニル基もしくはこれらの炭素数1〜4のアルキルエステル、またはアセチル基を表す)で表される基を表す)で表されるN−置換アミド基を側鎖に有するビニルモノマーの少なくとも1種0.01〜20重量部を含有してなるビニルモノマーの混合物を、水中で共重合させて得られる分岐構造を有するポリアクリルアミド系水溶性樹脂(A)、ならびに合成樹脂系エマルジョンおよびゴム系ラテックスから選ばれる少なくとも一種の水性ベースポリマー(B)を含有する水系接着剤組成物。 (A) 40 to 98 parts by weight of (meth) acrylamide, (b) an ionic vinyl monomer, which is an allyl group, a polyalkylene glycol group, or a general formula (1): —CONR 1 R 2 (wherein R 1
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. 1 to 50 parts by weight of at least one of those having no N-substituted amide group in the side chain, represented by the following formula: Allyl group, polyalkylene glycol group or general formula (1): —CONR 1 R 2 (wherein R 1
Represents a hydrogen atom or a methyl group, R 2 represents a methyl group, an isopropyl group, or a general formula (2): —C (CH 3 ) 2 —CH 2 —R 3 (R 3 represents a carboxyl group, a sulfonyl group, or a carbon thereof. 0.01 to 20 parts by weight of at least one vinyl monomer having a side chain having an N-substituted amide group represented by the following formula: Polyacrylamide water-soluble resin (A) having a branched structure obtained by copolymerizing a mixture of vinyl monomers in water, and at least one aqueous base polymer selected from synthetic resin emulsions and rubber latex A water-based adhesive composition containing (B).
Claims 1 to 3 obtained by blending 1 to 60 parts by weight (in terms of solid content) of polyacrylamide-based water-soluble resin (A) having a branched structure with respect to 100 parts by weight (in terms of solid content) of the aqueous base polymer (B). The water-based adhesive composition according to any one of the above.
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US7672385B2 (en) | 2005-07-15 | 2010-03-02 | Sanyo Electric Co., Ltd. | Radio apparatus |
WO2015060553A1 (en) * | 2013-10-23 | 2015-04-30 | 동우화인켐 주식회사 | Adhesive composition and composite polarizing plate using same |
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CN118284675A (en) | 2021-11-17 | 2024-07-02 | 株式会社普利司通 | Adhesive composition, organic fiber-rubber composite material, rubber article, and tire |
EP4434763A1 (en) | 2021-11-17 | 2024-09-25 | Bridgestone Corporation | Adhesive composition, organic fibrous material, rubber article, organic fiber/rubber composite, and tire |
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