JPH0489808A - Aqueous resin composition - Google Patents
Aqueous resin compositionInfo
- Publication number
- JPH0489808A JPH0489808A JP20597490A JP20597490A JPH0489808A JP H0489808 A JPH0489808 A JP H0489808A JP 20597490 A JP20597490 A JP 20597490A JP 20597490 A JP20597490 A JP 20597490A JP H0489808 A JPH0489808 A JP H0489808A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- water
- azo group
- resin
- urethane
- 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
- 239000011342 resin composition Substances 0.000 title claims description 8
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims abstract description 19
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000002576 diazepinyl group Chemical class N1N=C(C=CC=C1)* 0.000 claims description 2
- 150000003230 pyrimidines Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 19
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001294 propane Substances 0.000 abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000379 polymerizing effect Effects 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 4
- 239000004970 Chain extender Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- -1 aminosulfonic acid Chemical class 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- PGUIOHNOYADLMU-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-[3-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)C1=CC=CC(C(O)(C(F)(F)F)C(F)(F)F)=C1 PGUIOHNOYADLMU-UHFFFAOYSA-N 0.000 description 1
- YTJDSANDEZLYOU-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-[4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)C1=CC=C(C(O)(C(F)(F)F)C(F)(F)F)C=C1 YTJDSANDEZLYOU-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- JZVIGYINCGLMQW-UHFFFAOYSA-N 1-(oxiran-2-yl)ethyl prop-2-enoate Chemical compound C=CC(=O)OC(C)C1CO1 JZVIGYINCGLMQW-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- BUVLLMREBRZNHQ-UHFFFAOYSA-N 2-(diethylamino)ethanol;hexanedioic acid Chemical compound CCN(CC)CCO.CCN(CC)CCO.OC(=O)CCCCC(O)=O BUVLLMREBRZNHQ-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
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- GPDWNEFHGANACG-UHFFFAOYSA-L [dibutyl(2-ethylhexanoyloxy)stannyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CC)CCCC GPDWNEFHGANACG-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling 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
- 150000003946 cyclohexylamines Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 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 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の目的）
（産業上の利用範囲）
最近、グラフトブロックポリマーが産業上広く使用され
るようになってきている。特にポリマーアロイの分野で
は積極的に展開されている。塗料分野においてもポリマ
ーの機能性を付与させるためにグラフトブロックポリマ
ーの研究が活発である。本発明は、ウレタン樹脂の水性
化においてアゾ基を含む活性水素含有複素環化合物とジ
イソシアネートとを反応させてなる高分子ウレタン系重
合開始剤を用いてα、β不飽和二重結合を有する水溶性
モノマーを重合させてなる水性樹脂組成物に関するもの
で、プラスチック基材、金属、紙、布、木工、無機基材
などに塗工、印刷等により、幅広い用途に通用でき産業
上極めて有用な素材を提供するものである。DETAILED DESCRIPTION OF THE INVENTION (Objective of the invention) (Scope of industrial use) Graft block polymers have recently come to be widely used industrially. In particular, it is being actively developed in the field of polymer alloys. In the field of paints, research on graft block polymers is active in order to impart functionality to polymers. The present invention uses a polymer urethane polymerization initiator made by reacting an active hydrogen-containing heterocyclic compound containing an azo group with a diisocyanate to make a water-soluble urethane resin containing α, β unsaturated double bonds. This relates to aqueous resin compositions made by polymerizing monomers, and can be applied to plastic substrates, metals, paper, cloth, wood, inorganic substrates, etc. by coating and printing, to create materials that can be used in a wide range of applications and are extremely useful in industry. This is what we provide.
（従来の技術）
従来ウレタン樹脂の水性化には、ウレタン樹脂のポリオ
ール成分に水溶性原料を使用する方法が用いられていた
。例えば原料ポリオールにポリエチレングリコールのよ
うな水溶性オリゴマーを使用する方法、またアミノスル
ホン酸なとのスルホン酸基含有化合物を使用する方法、
ポリヒドロキシカルボン酸などのようなカルボン酸基含
有化合物を使用する方法、第三級アミノ基を導入し酸で
中和するか、または四級化剤で第四級アンモニウム塩に
してなる化合物を使用する方法などがあるが、ウレタン
のポリオル成分に水溶性原料を使用する方法であるため
樹脂設計上制限される欠点があった。また末端イソシア
２−ト基を有するウレタンプレポリマーを重亜硫酸塩で
ブロックする方法や、高分子量のウレタンを溶剤系で製
造し、これを適当な乳化剤で強制的にエマルジョン化し
て溶剤を適宜回収する方法が知られている。しかしこれ
らの方法において重亜硫酸塩方法では安定性が悪く、ま
た乳化する方法では乳化剤などによる耐水性の極端な低
下を招くなどの欠点を有していた。(Prior Art) Conventionally, to make urethane resin water-based, a method has been used in which a water-soluble raw material is used as the polyol component of the urethane resin. For example, a method using a water-soluble oligomer such as polyethylene glycol as a raw material polyol, a method using a sulfonic acid group-containing compound such as aminosulfonic acid,
Method using a compound containing a carboxylic acid group such as polyhydroxycarboxylic acid, introducing a tertiary amino group and neutralizing it with acid, or using a compound formed by converting it into a quaternary ammonium salt with a quaternizing agent. However, this method uses a water-soluble raw material for the polyol component of the urethane, which has the disadvantage of being limited in terms of resin design. In addition, there is a method in which a urethane prepolymer having a terminal isocyanate group is blocked with bisulfite, or a method in which high molecular weight urethane is produced in a solvent system, forcibly emulsified with a suitable emulsifier, and the solvent is appropriately recovered. method is known. However, among these methods, the bisulfite method has poor stability, and the emulsification method has drawbacks such as an extreme decrease in water resistance due to emulsifiers.
（課題を解決するための手段）
本発明は上記の欠点を改良し、アゾ基を含む活性水素含
有複素環化合物とジイソシア名−トとを反応させてなる
高分子ウレタン系重合開始側を用いてαβ不飽和二重結
合を有する水溶性上ツマ−を重合させてなることを特徴
とする水性樹脂組成物に関するものである。(Means for Solving the Problems) The present invention improves the above-mentioned drawbacks by using a polymer urethane-based polymerization initiator formed by reacting an active hydrogen-containing heterocyclic compound containing an azo group with a diisocyanate. The present invention relates to an aqueous resin composition characterized by polymerizing a water-soluble polymer having an αβ unsaturated double bond.
本発明は、非常に反応性に冨むジイソンア２、−トを用
いているためにアゾ基を含む活性水素含有複素環化合物
と確実に反応させることにより高分子化できることにあ
る。即ちアクリルモノマーを重合する前に、先に高分子
ウレタン系重合開始剤を製造することが特徴でアゾ基を
含む活性水素含有複素環化合物をウレタン樹脂の鎖延長
剤成分として用いることにある。導入の仕方はジイソシ
ア名−トとアゾ基を含む活性水素含有複素環化合物とを
反応させて、その後、ジオール成分と反応させて鎖延長
させても良く、同時に仕込んで反応させても良い。さら
に予め一般のジオールとジイソシア名−トからウレタン
プレポリマーを製造して後、アゾ基を含む活性水素含有
複素環化合物を反応させても良い。そして本発明はこれ
らの高分子ウレタン系重合開始剤を用いてαβ不飽和二
重結合を有する水溶性モノマーを重合させてなる水性樹
脂組成物であって、これらの方法で得られる樹脂塗膜は
塗膜硬度か硬いにもかかわらす可撓性が得られるなどの
特徴を備えた新規な水性樹脂を提供するものである。The present invention uses diisonate, which is highly reactive, so that it can be polymerized by reliably reacting with an active hydrogen-containing heterocyclic compound containing an azo group. That is, before polymerizing the acrylic monomer, a polymer urethane polymerization initiator is first produced, and an active hydrogen-containing heterocyclic compound containing an azo group is used as a chain extender component of the urethane resin. The introduction may be carried out by reacting the diisocyanate with an active hydrogen-containing heterocyclic compound containing an azo group, and then reacting with a diol component to extend the chain, or it may be introduced at the same time and reacted. Furthermore, a urethane prepolymer may be produced in advance from a general diol and a diisocyanate, and then reacted with an active hydrogen-containing heterocyclic compound containing an azo group. The present invention is an aqueous resin composition obtained by polymerizing a water-soluble monomer having αβ unsaturated double bonds using these polymeric urethane polymerization initiators, and the resin coating film obtained by these methods is The purpose of the present invention is to provide a new water-based resin that has the characteristics of being flexible despite the hardness of the coating film.
本発明におけるジイソシアネートとしては、脂肪族、芳
香族、脂環式、ジイソシアネ一トが埜げられるが、例え
ば４．４′−ジフェニルメタンジイソシアネート（ＭＤ
Ｉ）、トリレンジイソシアネート（ＴＤ＋）、ナフタレ
ンジイソシアネート、ｐ−フェニレンジイソシア２−ト
、トランス−１，４−シクロヘキサンジイソシア不−）
（ＣＨＤＩ）、１３−ビス−（イソシアナトメチル−
ベンゼン、４゜４゛−ジシクロへキシルメタンジイソシ
アネート（Ｈ，、ＭＤ Ｉ ）、１，３−ビス−（イソ
シアナトメチル）−シクロヘキサン（Ｈ６ＸＤＩ）、ヘ
キサメチレンジイソシアネート（ＨＤＴ）、３−イソシ
アナトメチル−３，５，５”−トリメチルシクロヘキシ
ルイソシア不一ト（ＩＰＤＩ）、メタ−テトラメチルキ
シレンジイソシアネート又はパラ−テトラメチルキシレ
ンジイソシアネート（ｍ−ＴＭＸＤＩ、Ｔ）−ＴＭＸＤ
Ｉ）などが挙げられるがこれらに限定されるものではな
い。また硬化した重合体の耐候性が重要である用途に対
しては、例えばＣＨＤＩ、Ｈ、。ＭＤ ｉ Ｈ６ＸＤ
ｌ、ＨＤＩ、ＩＰＤＩ、ｍ−ＴＭＸＤＩまたは、Ｐ−Ｔ
ＭＸＤＩのような脂肪族又は脂環式ジイソシアネートを
使用する方が望ましい。Diisocyanates in the present invention include aliphatic, aromatic, alicyclic, and diisocyanates, such as 4,4'-diphenylmethane diisocyanate (MD
I), tolylene diisocyanate (TD+), naphthalene diisocyanate, p-phenylene diisocyanate, trans-1,4-cyclohexane diisocyanate)
(CHDI), 13-bis-(isocyanatomethyl-
Benzene, 4゜4゛-dicyclohexylmethane diisocyanate (H,, MD I ), 1,3-bis-(isocyanatomethyl)-cyclohexane (H6XDI), hexamethylene diisocyanate (HDT), 3-isocyanatomethyl- 3,5,5”-trimethylcyclohexyl isocyanate (IPDI), meta-tetramethylxylene diisocyanate or para-tetramethylxylene diisocyanate (m-TMXDI, T)-TMXD
Examples include, but are not limited to, I). Also, for applications where weather resistance of the cured polymer is important, for example CHDI, H. MD i H6XD
l, HDI, IPDI, m-TMXDI or PT
It is preferred to use aliphatic or cycloaliphatic diisocyanates such as MXDI.
高分子ウレタン系重合開始剤を製造するのに本発明で使
用されるアゾ基を含む活性水素含有複素環化合物として
は、アゾ基を含むイミダシリン誘導体及びまたはその塩
としては２．２゛−アゾビス（２（２−イミダプリン−
２−イル）プロパン）、２゜２” −アゾビス（２−（
２−イミダシリン−２〜イル）プロパン）ジヒドロクロ
リド、２，２−アゾビス（２−（５−メチル−２−イミ
ダシリン−２イル）プロパン）ジヒドロクロリドなど、
アゾ基を含むピリミジン誘導体及びまたはその塩として
は２２゛−アゾビス（２−（３，４，５，６−テトラヒ
ドロビリミジン−２−イル）プロパン）ジしドロクロリ
ドなど、アゾ基を含むジアゼピン誘導体及びまたはその
塩としては２，２゛−アゾビス（２−（４５，６，７−
チトラヒドローＩＨ−１，３−ジアゼピン−２−イル）
プロパン）ジヒドロクロリドなどが挙げられるがこれら
に限定されるものではなく基本的に熱分解によりラジカ
ルを発注するアゾ基を含む活性水素台を複素環化合物で
あれば使用できる。Examples of the active hydrogen-containing heterocyclic compound containing an azo group used in the present invention to produce a polymeric urethane polymerization initiator include imidacillin derivatives containing an azo group and/or salts thereof, such as 2.2゛-azobis( 2 (2-imidapurine-
2-yl)propane), 2゜2''-azobis(2-(
2-imidacillin-2-yl)propane) dihydrochloride, 2,2-azobis(2-(5-methyl-2-imidacillin-2yl)propane) dihydrochloride, etc.
Examples of pyrimidine derivatives containing an azo group and/or salts thereof include diazepine derivatives containing an azo group such as 22'-azobis(2-(3,4,5,6-tetrahydrobyrimidin-2-yl)propane)dihydrochloride; Or its salt is 2,2゛-azobis(2-(45,6,7-
titrahydro IH-1,3-diazepin-2-yl)
Examples include, but are not limited to, dihydrochloride (propane), etc. Basically, any heterocyclic compound containing an active hydrogen group containing an azo group that generates radicals by thermal decomposition can be used.
また鎖延長剤として一般のジオールを併用することも可
能である。それらのジオールはイソシアネトと反応し得
る水素原子を少なくとも２個有し、般に分子量１０００
０までの組成物である。例えば、エチレングリコール、
プロピレングリコール、ブチレングリコール、１，６−
ヘキサンジオール、１８−オクタンジオール、ネオペン
チルグリコール、シクロヘキサンジメタツール、ペンタ
エリスリトル、ジエチレングリコール、トリエチレング
リコル、テトラエチレングリコール、ポリエーテルグリ
コール、ポリエステルグリコール、両末端水酸基を有す
る液状ポリオレフィンなどのジオール類など、また耐候
性を上げるにはシリコンジオール、フルオロジオールな
ども使用できる。例えば、１．３−ビス（２−ヒドロキ
シへキサフルオロイソプロピル）ベンゼン、１．４−ビ
ス（２−ヒドロキシへキサフルオロイソプロピル）ベン
ゼン、１，１，２，３゜３、ペンタヒドロパーフルオロ
ウンデカン−１，２ジオール、１，１，２，３．３−ペ
ンタヒトロバフルオロノナン−１，２−ジオール、ヘキ
サフルオロビスフェノールＡ、末端反応性シリコーンジ
オルとしては、Ｘ−２２−１６０ＡＳ、Ｘ−２２１６０
Ａ、Ｘ−２２−１６０Ｂ、Ｘ−２２−１６００（以上、
信越化学（株）製）、ＰＳ１９７、ＰＸｌｏｌ（以上、
チッソ（株）製）などが挙げられるがこれらに限定され
るものではない。It is also possible to use a general diol as a chain extender. These diols have at least two hydrogen atoms capable of reacting with isocyanates and generally have a molecular weight of 1000.
The composition is up to 0. For example, ethylene glycol,
Propylene glycol, butylene glycol, 1,6-
Diols such as hexanediol, 18-octanediol, neopentyl glycol, cyclohexane dimetatool, pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyether glycol, polyester glycol, and liquid polyolefins having hydroxyl groups at both ends. Silicon diols, fluorodiols, etc. can also be used to increase weather resistance. For example, 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzene, 1,1,2,3°3, pentahydroperfluoroundecane- 1,2 diol, 1,1,2,3.3-pentahydrofluorononane-1,2-diol, hexafluorobisphenol A, terminal-reactive silicone diol such as X-22-160AS, X-22160
A, X-22-160B, X-22-1600 (and above,
Shin-Etsu Chemical Co., Ltd.), PS197, PXlol (manufactured by Shin-Etsu Chemical Co., Ltd.),
(manufactured by Chisso Corporation), but is not limited to these.
高分子ウレタン系重合開始剤を製造する際に必要とあれ
ば触媒を用いることができる。例えば、三級アミン、有
機金属化合物などが使用される。三級アミンとしてトリ
エチルアミン、トリエチレンジアミン、トリメチルアミ
ンのようなトリアルキルアミン、テトラメチレンジアミ
ン、Ｎ、Ｎ、Ｎ’ 、Ｎ’ −テトラメチル−１，３−
ブタンジアミンのようなテトラアルキルジアミン、ビス
（ジエチルエタノールアミン）アジペートのようなエス
テルアミン、Ｎ、 Ｎジメチルシクロヘキシルアミンの
よ、うなシクロへキシルアミン誘導体、Ｎ−メチルモル
ホリンのようなモルホリン誘導体；Ｎ、Ｎ”−ジエチル
−２−メチルピペラジンのようなピペラジン誘導体があ
げられるがこれらに限定されるものではない。さらに有
機金属化合物としてはジブチル錫ジラウレート、ジブチ
ル錫ジ（２−エチルヘキソエート）などのジアルキル錫
化合物が挙げられるがこれらに限定されるものではない
。またこれらのジアルキル錫化合物と三級アミンとの併
用も可能である。A catalyst can be used if necessary when producing a polymer urethane polymerization initiator. For example, tertiary amines, organometallic compounds, etc. are used. Tertiary amines include triethylamine, triethylenediamine, trialkylamines such as trimethylamine, tetramethylenediamine, N,N,N',N'-tetramethyl-1,3-
Tetraalkyl diamines such as butanediamine, ester amines such as bis(diethylethanolamine) adipate, cyclohexylamine derivatives such as N,N dimethylcyclohexylamine, morpholine derivatives such as N-methylmorpholine; Examples include, but are not limited to, piperazine derivatives such as "-diethyl-2-methylpiperazine.Further, examples of organometallic compounds include dialkyl compounds such as dibutyltin dilaurate and dibutyltin di(2-ethylhexoate). Examples include, but are not limited to, tin compounds. It is also possible to use these dialkyltin compounds in combination with tertiary amines.
またα、β不飽和二重結合を有する水溶性モノマとして
はアクリル酸、メタクリル酸、マレイン酸、無水マレイ
ン酸、イタコン酸、フマル酸、クロトン酸などが挙げら
れるが必ずしもこれらに限定されるものではなく、アン
モニア、有機アミン、水酸化ナトリウムなどのアルカリ
により容易に水性化可能なモノマーであればよい。Water-soluble monomers having α,β unsaturated double bonds include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, crotonic acid, etc., but are not necessarily limited to these. Any monomer that can be easily made aqueous with an alkali such as ammonia, organic amine, or sodium hydroxide may be used.
アミノ基を有する水溶性モノマーとしてはアリルアミン
、Ｎ、Ｎ−ジメチルアミノエチルメタクリレト、Ｎ、Ｎ
−ジエチルアミノエチルメタクリレトなどが挙げられる
が必ずしもこれらに限定されるものではなく、四級化し
て水性化できるものであればよい。例えば、ビニルピリ
ジンや、グリシジルメタクリレートに有機アミンを反応
させて四級化できるものでもよい。Water-soluble monomers having an amino group include allylamine, N,N-dimethylaminoethyl methacrylate, N,N
-diethylaminoethyl methacrylate, etc., but are not necessarily limited to these, and any material that can be quaternized and made aqueous may be used. For example, vinylpyridine or glycidyl methacrylate that can be quaternized by reacting with an organic amine may be used.
またα、β不飽和二重結合を有する七ツマ−としては、
アクリル酸アルキル（炭素数１−２２）エステル類：例
えばメチルアクリレート、エチルアクリレート、ｎ−ブ
チルアクリレート、１ｓｏ−ブチルアクリレート、ｔｅ
ｒｔ−ブチルアクリレート、２エチルへキシルアクリレ
ート、グリシジルアクリレート、メチルグリシジルアク
リレートなど。メタクリル酸アルキル（炭素数１−２２
）エステル類：例えばメチルメタクリレート、エチルア
クリレー、ｎ−ブチルメタクリレート、１ｓｏ−ブチル
メタクリレート、ｔｅｒｔ−ブチルメタクリレート、２
−エチルへキシルメタクリレート、グリシジルメタクリ
レートなど。水酸基含有ビニル単量体類：例えばヒドロ
キシエチルアクリレート、ヒドロキシエチルメタクリレ
ート、ヒドロキシプロピルアクリレト、ヒドロキシプロ
ピルメタクリレートなど。その他の単量体類：例えばス
チレン、ビニルトルエン、アクリロニトリル、塩化ビニ
ル、酢酸ビニル、塩化ビニリデン、ビニルピロリドンな
ど。以上のα、β不飽和二重結合を有する七ツマ−が挙
げられるが基本的にラジカルにより重合するものであれ
ばよくこれらに限定されるものではない。そして、使用
に際しては、これらの１種または２種以上を前記α、β
不飽和二重結合を有する水溶性上ツマ−と共重合させで
水性化できれば何ら問題はない。In addition, as a heptadmer with α and β unsaturated double bonds,
Alkyl acrylate (1-22 carbon atoms) esters: e.g. methyl acrylate, ethyl acrylate, n-butyl acrylate, 1so-butyl acrylate, te
rt-butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, methylglycidyl acrylate, etc. Alkyl methacrylate (1-22 carbon atoms)
) Esters: For example, methyl methacrylate, ethyl acrylate, n-butyl methacrylate, 1so-butyl methacrylate, tert-butyl methacrylate, 2
-Ethylhexyl methacrylate, glycidyl methacrylate, etc. Hydroxyl group-containing vinyl monomers: for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc. Other monomers such as styrene, vinyltoluene, acrylonitrile, vinyl chloride, vinyl acetate, vinylidene chloride, vinylpyrrolidone, etc. Examples include the above-mentioned heptamers having α,β unsaturated double bonds, but the invention is not limited to these as long as they can basically be polymerized by radicals. When using, one or more of these may be added to the α, β
There will be no problem if it can be made water-soluble by copolymerizing with a water-soluble polymer having an unsaturated double bond.
本発明組成物が水性化できる理由は必ずしも明確ではな
いが、高分子ウレタン系開始剤により生成したアクリル
ウレタンブロック共重合体がアクリル樹脂とウレタン樹
脂の相溶性を向上させ、さらに水溶性アクリル樹脂が乳
化剤として作用するものと推察される。The reason why the composition of the present invention can be made water-based is not necessarily clear, but the acrylic urethane block copolymer produced by the polymeric urethane initiator improves the compatibility between the acrylic resin and the urethane resin, and the water-soluble acrylic resin It is presumed that it acts as an emulsifier.
本発明組成物には必要に応じて、さらにアミノ樹脂、エ
ポキシ樹脂またはイソシアネート樹脂等を配合すること
ができる。このような添加樹脂は架橋剤として作用し、
より強固な皮膜を形成し、耐水性、耐アルカリ性、耐酸
性、耐溶剤性を付与することができる。かかるアミノ樹
脂としては、メタノールあるいはブタノールなど一価の
アルコールでそれぞれ変性された従来からの公知の尿素
−ホルムアルデヒド縮重合物、モノメリック及びポリメ
リックのメラミン樹脂、ヘンゾグアナミン樹脂などが挙
げられる。The composition of the present invention may further contain an amino resin, an epoxy resin, an isocyanate resin, or the like, if necessary. Such additive resin acts as a crosslinking agent,
It can form a stronger film and provide water resistance, alkali resistance, acid resistance, and solvent resistance. Examples of such amino resins include conventionally known urea-formaldehyde condensation products modified with monohydric alcohols such as methanol or butanol, monomeric and polymeric melamine resins, and henzoguanamine resins.
またエポキシ樹脂はその分子中のエポキシ基と樹脂中の
水酸基あるいはアミン基の付加反応によって架橋し、よ
り強固な皮膜を形成することができる。かかるエポキシ
樹脂としては平均分子量が少なくとも約３５０以上、好
適には約３５０〜３０００及びエポキシ当量が１５０〜
３０００、好適には２００〜２０００の範囲のポリフェ
ノールグリシジルエーテル類等である。またイソシアネ
ート樹脂としては、トリメチロールプロパンなどの多価
アルコールによりそれぞれ変性された従来からの公知の
多官能インシアネート樹脂、イソシアヌレート結合、ビ
ューレット結合によりそれぞれ変性された多官能イソシ
アネート樹脂などが挙げられる。前記したアミノ樹脂及
びまたはエポキシ樹脂及びまたはイソシアネート樹脂と
水性樹脂との割合は重量百分率比で４０／６０〜５／９
５、好ましくは３０／７０〜１０／９０である。前記ア
ミノ樹脂及びまたはエポキシ樹脂の使用量が前記範囲を
越えるとかえって物性が低下する傾向がある。また前記
範囲より少ないと架橋剤としての効果が充分でない。In addition, epoxy resin can be crosslinked by an addition reaction between the epoxy group in its molecule and the hydroxyl group or amine group in the resin to form a stronger film. Such epoxy resins have an average molecular weight of at least about 350 or more, preferably about 350-3000, and an epoxy equivalent weight of 150-3000.
3,000, preferably polyphenol glycidyl ethers in the range of 200 to 2,000. Examples of the isocyanate resin include conventionally known polyfunctional incyanate resins modified with polyhydric alcohols such as trimethylolpropane, polyfunctional isocyanate resins modified with isocyanurate bonds, biuret bonds, etc. . The ratio of the above-mentioned amino resin and/or epoxy resin and/or isocyanate resin and aqueous resin is 40/60 to 5/9 in weight percentage ratio.
5, preferably 30/70 to 10/90. If the amount of the amino resin and/or epoxy resin used exceeds the above range, the physical properties tend to deteriorate on the contrary. Moreover, if it is less than the above range, the effect as a crosslinking agent will not be sufficient.
さらに、顔料、充填剤、可塑剤、顔料分散剤、増粘剤、
消泡剤、レベリング剤なとの添加剤も併用することがで
きる。In addition, pigments, fillers, plasticizers, pigment dispersants, thickeners,
Additives such as antifoaming agents and leveling agents can also be used in combination.
以下に実施例を示す。但しいずれも数字は重量部を示す
。Examples are shown below. However, all numbers indicate parts by weight.
実施例１
１）デュラネートＤ−１０１（注１） １０部２）
ブチレングリコール １．５部３）ジブ
チル錫ジラウレート ０．０１部４）ジオキサ
ン ３０部５）２．２“−ア
ゾビス（２−（２−イミダプリン−２−イル）プロパン
）０．５部
６）イソプロピルアルコール ９０部７）
メタクリル酸 １０部８）メチ
ルメタクリレート ５部９）アンモニ
ア水（２８％） １０部１０）水
１００部１）〜４）を還流凝縮器、撹
拌機、内部温度計、気体導入管を備えた四つロフラスコ
にいれ、窒素気流中で６０°Ｃにて１時間反応させる。Example 1 1) Duranate D-101 (Note 1) 10 parts 2)
Butylene glycol 1.5 parts 3) Dibutyltin dilaurate 0.01 part 4) Dioxane 30 parts 5) 2.2"-azobis(2-(2-imidaprin-2-yl)propane) 0.5 part 6) Isopropyl alcohol 90 copies 7)
Methacrylic acid 10 parts 8) Methyl methacrylate 5 parts 9) Aqueous ammonia (28%) 10 parts 10) Water
100 parts 1) to 4) are placed in a four-loaf flask equipped with a reflux condenser, a stirrer, an internal thermometer, and a gas inlet tube, and reacted for 1 hour at 60°C in a nitrogen stream.
その後室温まで冷却して５）、６）を加え、撹拌しなが
ら２時間重付加を行なう。その後、７）、８）を加えて
窒素気流下、７５°Ｃに昇温しでて撹拌しながら４時間
反応させる。その後９）、１０）を添加して水性化し脱
溶媒を行う。このようにして得られた水性樹脂は、室温
で安定であり分子量はＭｗ＝３５０００であった。得ら
れたフィルムは、耐衝撃性に優れ、可撓性がありかつ透
明性に優れるフィルムであった。（注１）デュラネート
Ｄ−２０１（２官能）ＩＤＩ系ウレタンオリゴマー 旭
化成工業（株）製）実施例２
１）３−イソソアナトメチル−３，５，５−トリメチル
シクロヘキシルイソシアネート ４部２）Ｐｏｌ
ｙ ｂｄ Ｒ−１５ＨＴ（？！２） ５部３）１
．６−ヘキサンジオール １部４）トリエ
チルアミン ３．０部５）ジオキサ
ン ３０部６）２．２ −ア
ゾビス（２−（−２−イミダプリン２−イル）プロパン
）ジヒドロクロリド０．８部
７）エタノール ３０部８
）Ｎ、Ｎ−ジメチルアミノエチルメタクリレート２０部
９）エチルアクリレート １０部１
０）酢Ｍ ８部１１）
水 １００部１）〜５）を実施
例１と同様な装置で、６０°Ｃ１時間反応させる。それ
を室温まで冷却した後、６）、７）を加え、８時間撹拌
しながら反応させる。さらに８）、９）を加えて７０°
Ｃ１６時間反応させる。Thereafter, the mixture was cooled to room temperature, 5) and 6) were added, and polyaddition was carried out for 2 hours while stirring. Thereafter, 7) and 8) were added, the temperature was raised to 75°C under a nitrogen stream, and the mixture was reacted for 4 hours with stirring. Thereafter, 9) and 10) are added to make the mixture aqueous, and the solvent is removed. The aqueous resin thus obtained was stable at room temperature and had a molecular weight of Mw=35,000. The obtained film had excellent impact resistance, flexibility, and transparency. (Note 1) Duranate D-201 (bifunctional) IDI urethane oligomer manufactured by Asahi Kasei Industries, Ltd.) Example 2 1) 3-isosoanatomethyl-3,5,5-trimethylcyclohexyl isocyanate 4 parts 2) Pol
y bd R-15HT (?!2) 5 parts 3) 1
．． 6-Hexanediol 1 part 4) Triethylamine 3.0 parts 5) Dioxane 30 parts 6) 2.2-Azobis(2-(-2-imidapurin-2-yl)propane)dihydrochloride 0.8 part 7) Ethanol 30 parts 8
) N,N-dimethylaminoethyl methacrylate 20 parts 9) Ethyl acrylate 10 parts 1
0) Vinegar M 8 parts 11)
100 parts of water 1) to 5) are reacted at 60°C for 1 hour in the same apparatus as in Example 1. After cooling it to room temperature, 6) and 7) are added, and the mixture is allowed to react with stirring for 8 hours. Furthermore, add 8) and 9) to 70°
React for 16 hours.
その後１０）、１１）を添加して水性化し脱溶媒を行う
。このようにして得られた水性樹脂は、室温で安定であ
り分子量はＭｗ＝４２０００であった。得られたフィル
ムは、耐衝撃性に優れ、可撓性がありかつ透明性に優れ
るフィルムであった。Thereafter, 10) and 11) are added to make the mixture aqueous, and the solvent is removed. The aqueous resin thus obtained was stable at room temperature and had a molecular weight of Mw=42,000. The obtained film had excellent impact resistance, flexibility, and transparency.
（注２）Ｐｏｌｙ ｂｄ Ｒ−１５ＨＴ（両末端水
酸基ポリブタジェン 出光石油化学（株）製）実施例３
１）４．４−ジフェニルメタンジイソシアネート５部
２）χ−２１−１６０Ａ３ ９部３）１．
６−ヘキサンジオール ０．５部４）ジブチル
錫ジラウレート ０．０１部５）ジオキサン
８０部６）２．２°−アゾビ
ス（２−（５−メチル−２イミダシリン−２−イル）プ
ロパン）ジヒドロクロリ ト
０ 、 ７ 部
７）イソプロピルアルコール ５０部３）
Ｎ、Ｎ−ジエチルアミノエチルメタクリレート２０部
９）ブチルメタクリレート １０部１０
）酢酸 ７部１１）水
１００部１）〜５）を実施例
１と同様な装置で５０°Ｃ１時間反応させ、その後室温
まで冷却し、６）、７）を加えて室温で８時間撹拌する
。さらに８）、９）を加えて７０°Ｃ６時間重合する。(Note 2) Poly bd R-15HT (polybutadiene with hydroxyl groups at both ends, manufactured by Idemitsu Petrochemical Co., Ltd.) Example 3 1) 4.4-diphenylmethane diisocyanate 5 parts 2) χ-21-160A3 9 parts 3) 1.
6-Hexanediol 0.5 part 4) Dibutyltin dilaurate 0.01 part 5) Dioxane
80 parts 6) 2.2°-Azobis(2-(5-methyl-2imidacylin-2-yl)propane)dihydrochloride
0, 7 parts 7) Isopropyl alcohol 50 parts 3)
N,N-diethylaminoethyl methacrylate 20 parts 9) Butyl methacrylate 10 parts 10
) 7 parts of acetic acid 11) 100 parts of water 1) to 5) are reacted at 50°C for 1 hour in the same apparatus as in Example 1, then cooled to room temperature, 6) and 7) are added and stirred at room temperature for 8 hours. . Furthermore, 8) and 9) were added and polymerized at 70°C for 6 hours.
その後１０）、１１）を添加して水性化し脱溶媒を行う
。このようにして得られた水性樹脂は、室温で安定であ
り分子量はＭｗ＝３２０００であった。得られたフィル
ムは、耐衝撃性に優れ、可撓性がありかつ透明性に優れ
るフィルムであった。Thereafter, 10) and 11) are added to make the mixture aqueous, and the solvent is removed. The aqueous resin thus obtained was stable at room temperature and had a molecular weight of Mw=32,000. The obtained film had excellent impact resistance, flexibility, and transparency.
実施例４
１ デュラネートＤ−２０１
２エチレングリコール
３ ジブチル錫ジラウレート
４ ジオキサン
５２．２’−アゾビス（２−（２
２−イル）プロパン）
１０部
０．７部
０．０１部
３０部
イミダシリン
０．５部
６）イソプロピルアルコール ９０部７）
メタクリル酸 １５部８）メチ
ルメタクリレート ３部９）２−ヒド
ロキシエチルメタクリレート ２部１０）アンモニア
水（２８％） １５部１１）水
１００部１２）エポン８２Ｂ
１０部１）〜４〕を還流凝縮器、撹ｆｆ
機、内部温度計、気体導入管を備えた四つロフラスコに
いれ、窒素気流中で６０°Ｃにて１時間反応させる。そ
の後室温まで冷却して５）、６）を加え、撹拌しながら
２時間重付加を行なう。その後、７）〜９）を加えて窒
素気流下、７５℃に昇温しでで撹拌しながら４時間反応
させる。その後１０）、１１）を添加して水性化し脱溶
媒を行う。このようにして得られた水性樹脂は、室温で
安定であり分子量はＭｗ＝３６０００であった。得られ
た水性樹脂５０部に対して１２）を添加して５０°Ｃの
雰囲気中で皮膜を形成させた。得られたフィルムは、可
撓性がありかつ透明性に優れるフィルムであった。Example 4 1 Duranate D-201 2 Ethylene glycol 3 Dibutyltin dilaurate 4 Dioxane 52. 2'-Azobis(2-(2 2-yl)propane) 10 parts 0.7 parts 0.01 parts 30 parts Imidacillin 0.5 Part 6) Isopropyl alcohol 90 parts 7)
Methacrylic acid 15 parts 8) Methyl methacrylate 3 parts 9) 2-hydroxyethyl methacrylate 2 parts 10) Aqueous ammonia (28%) 15 parts 11) Water
100 copies 12) Epon 82B
10 parts 1) to 4] in a reflux condenser, stirring ff
The mixture was placed in a four-bottle flask equipped with an internal thermometer, an internal thermometer, and a gas inlet tube, and reacted for 1 hour at 60°C in a nitrogen stream. Thereafter, the mixture was cooled to room temperature, 5) and 6) were added, and polyaddition was carried out for 2 hours while stirring. Thereafter, 7) to 9) were added, the temperature was raised to 75°C under a nitrogen stream, and the mixture was reacted for 4 hours with stirring. Thereafter, 10) and 11) are added to make the mixture aqueous, and the solvent is removed. The aqueous resin thus obtained was stable at room temperature and had a molecular weight of Mw=36,000. 12) was added to 50 parts of the obtained aqueous resin to form a film in an atmosphere at 50°C. The obtained film was flexible and had excellent transparency.
比較例１
１）デュラネートＤ−１０１１５部
２）エチレングリコール １．６部３）
ジブチル錫ジラウレート ０．０１部４）ジオ
キサン ５０部５）ｎ−ブタ
ノール ０．８部６）Ｎ、Ｎ−ジメ
チルアミノエチルメタクリレート２０部
７）エチルアクリレート １０部Ｂ
）２．２’ −アゾビスイソブチロニトリル０．４部
９）酢酸 ８部１０
）水 １００部ｌ）〜４）を還
流凝縮器、撹拌機、内部温度計、気体導入管を備えた四
つロフラスコにいれ、窒素気流中で６０°Ｃにて１時間
反応させる。その後５）〜８）を加えて窒素気流下、７
５°Ｃに昇温しでで撹拌しながら４時間反応させる。そ
の後９）、１０）を添加して水性化し脱溶媒を行う。こ
のものはすくに二層に分離した。この樹脂の分子量はＭ
Ｗ＝３８０００であった。得られたフィルムは可撓性が
あったが、不透明なフィルムであった。Comparative Example 1 1) Duranate D-10115 parts 2) Ethylene glycol 1.6 parts 3)
Dibutyltin dilaurate 0.01 parts 4) Dioxane 50 parts 5) n-Butanol 0.8 parts 6) N,N-dimethylaminoethyl methacrylate 20 parts 7) Ethyl acrylate 10 parts B
) 2.2'-Azobisisobutyronitrile 0.4 parts 9) Acetic acid 8 parts 10
) 100 parts of water 1) to 4) are placed in a four-hole flask equipped with a reflux condenser, a stirrer, an internal thermometer, and a gas inlet tube, and reacted for 1 hour at 60°C in a nitrogen stream. After that, add 5) to 8) and add 7) under nitrogen stream.
The temperature was raised to 5°C and the mixture was allowed to react for 4 hours with stirring. Thereafter, 9) and 10) are added to make the mixture aqueous, and the solvent is removed. This product easily separated into two layers. The molecular weight of this resin is M
W=38,000. The resulting film was flexible, but opaque.
比較例２
１）デュラネートＤ−２０１１０部
２）エチレングリコール ０．５部３）
ジブチル錫ジラウレート 、 ０．０１部４）
ジオキサン ５０部５）イソ
プロピルアルコール ９０部６）メタクリ
ル酸 １５部７）メチルメタク
リレート ５部Ｂ）２．２’ −アゾ
ビスイソブチロニトリル０．４部
９）アンモニア水（２８％） １５部１０
）水 １００部１）〜４）を還
流凝縮器、撹拌機、内部温度計、気体導入管を備えた四
つロフラスコにいれ、窒素気流中で６０°Ｃにて１時間
反応させる。その後５）〜８）を加えて窒素気流下、７
５°Ｃに昇温しでで撹拌しながら４時間反応させる。そ
の後９）、１０）を添加して水性化したところすぐに凝
集して水性化できなかった。Comparative Example 2 1) Duranate D-20110 parts 2) Ethylene glycol 0.5 parts 3)
Dibutyltin dilaurate, 0.01 part 4)
Dioxane 50 parts 5) Isopropyl alcohol 90 parts 6) Methacrylic acid 15 parts 7) Methyl methacrylate 5 parts B) 2.2'-azobisisobutyronitrile 0.4 parts 9) Aqueous ammonia (28%) 15 parts 10
) 100 parts of water 1) to 4) are placed in a four-hole flask equipped with a reflux condenser, a stirrer, an internal thermometer, and a gas inlet tube, and reacted for 1 hour at 60°C in a nitrogen stream. After that, add 5) to 8) and add 7) under nitrogen stream.
The temperature was raised to 5°C and the mixture was allowed to react for 4 hours with stirring. Thereafter, when 9) and 10) were added to make the mixture aqueous, it immediately agglomerated and could not be made aqueous.
本発明組成物は水性であるため、火災の危険がなく、プ
ラスチック基材、金属、紙、布、木工、無機基材なと幅
広い用途に適用でき、産業上極めて有用な素材である。Since the composition of the present invention is water-based, there is no danger of fire, and it can be applied to a wide range of applications such as plastic substrates, metals, paper, cloth, woodworking, and inorganic substrates, making it an extremely useful material industrially.
Claims (1)
アネートとを反応させてなる高分子ウレタン系重合開始
剤を用いてα，β不飽和二重結合を有する水溶性モノマ
ーを重合させてなることを特徴とする水性樹脂組成物。 ２、アゾ基を含む活性水素含有複素環化合物としてアゾ
基を含むジイミダゾリン誘導体及びまたはその塩を用い
ることを特徴とする請求項１記載の水性樹脂組成物。 ３、アゾ基を含む活性水素含有複素環化合物としてアゾ
基を含むピリミジン誘導体及びまたはその塩を用いるこ
とを特徴とする請求項１記載の水性樹脂組成物。 ４、アゾ基を含む活性水素含有複素環化合物としてアゾ
基を含むジアゼピン誘導体及びまたはその塩を用いるこ
とを特徴とする請求項１記載の水性樹脂組成物。[Claims] 1. A water-soluble monomer having α,β unsaturated double bonds is produced using a polymer urethane polymerization initiator obtained by reacting an active hydrogen-containing heterocyclic compound containing an azo group with a diisocyanate. An aqueous resin composition characterized by being formed by polymerization. 2. The aqueous resin composition according to claim 1, wherein a diimidazoline derivative containing an azo group and/or a salt thereof is used as the active hydrogen-containing heterocyclic compound containing an azo group. 3. The aqueous resin composition according to claim 1, wherein a pyrimidine derivative containing an azo group and/or a salt thereof is used as the active hydrogen-containing heterocyclic compound containing an azo group. 4. The aqueous resin composition according to claim 1, wherein a diazepine derivative containing an azo group and/or a salt thereof is used as the active hydrogen-containing heterocyclic compound containing an azo group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20597490A JP2686353B2 (en) | 1990-08-03 | 1990-08-03 | Aqueous resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20597490A JP2686353B2 (en) | 1990-08-03 | 1990-08-03 | Aqueous resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0489808A true JPH0489808A (en) | 1992-03-24 |
| JP2686353B2 JP2686353B2 (en) | 1997-12-08 |
Family
ID=16515801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20597490A Expired - Fee Related JP2686353B2 (en) | 1990-08-03 | 1990-08-03 | Aqueous resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2686353B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020003754A1 (en) * | 2018-06-25 | 2020-01-02 | Dic株式会社 | Aqueous resin composition and method for producing same |
-
1990
- 1990-08-03 JP JP20597490A patent/JP2686353B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020003754A1 (en) * | 2018-06-25 | 2020-01-02 | Dic株式会社 | Aqueous resin composition and method for producing same |
| JPWO2020003754A1 (en) * | 2018-06-25 | 2021-03-11 | Dic株式会社 | Aqueous resin composition and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2686353B2 (en) | 1997-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3623263B2 (en) | Water-soluble or water-dispersible polyisocyanate composition, process for its production and its use in paints | |
| EP0350040B1 (en) | Aqueous dispersions of urethane-acrylic polymers and use thereof in paints | |
| CA2034857A1 (en) | Production of polyurethane polymers, the polymers so produced and compositions containing them | |
| MXPA05004674A (en) | Polyurethane dispersion and articles prepared therefrom. | |
| JP2006009019A (en) | Polyurethane dispersion prepared from high acid-functional polyester | |
| CA1191152A (en) | Process for the production of polymer-containing aromatic polyether polyamines | |
| US3294711A (en) | Graft polymers of vinyl acetate or vinyl chloride onto a saturated polyester backbone, and polyurethane foams therefrom | |
| AU747613B2 (en) | Low VOC, isocyanate based aqueous curable compositions | |
| WO1998038230A9 (en) | Low voc, isocyanate based aqueous curable compositions | |
| US6313218B1 (en) | Low VOC, isocyanate based aqueous curable compositions | |
| JP3629167B2 (en) | Two-component aqueous acrylic-urethane composition, adhesive and coating agent containing the composition | |
| JP2641955B2 (en) | Aqueous resin composition | |
| US5612406A (en) | Processes for production of azo macroinitiators for the synthesis of block copolymers and of aqueous block copolymer dispersions and emulsions and the use thereof | |
| JP2686353B2 (en) | Aqueous resin composition | |
| JPH08283310A (en) | Production of polymer | |
| JPS59138211A (en) | Production of water-based polyurethane-acrylate resin | |
| JP2656130B2 (en) | Aqueous resin composition | |
| JP2686347B2 (en) | Polymeric urethane polymerization initiator and resin obtained using the same | |
| JP3871386B2 (en) | Cross-linked aqueous emulsion composition | |
| JP2643493B2 (en) | Polymeric thiourethane polymerization initiator and use thereof | |
| US20040197481A1 (en) | Novel low viscosity prepolymers with low diisocyanate monomer content for moisture cure coatings | |
| JP3073201B2 (en) | Semicarbazide derivative and composition containing the semicarbazide derivative | |
| JP3555021B2 (en) | Semicarbazide derivative and composition containing the semicarbazide derivative | |
| JPH03160010A (en) | Resin of excellent weathering resistance | |
| JPH03143970A (en) | Binder for printing ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |