JP2012001584A - Aqueous resin composition, method for manufacturing the same, and metallic coating material - Google Patents
Aqueous resin composition, method for manufacturing the same, and metallic coating material Download PDFInfo
- Publication number
- JP2012001584A JP2012001584A JP2010135827A JP2010135827A JP2012001584A JP 2012001584 A JP2012001584 A JP 2012001584A JP 2010135827 A JP2010135827 A JP 2010135827A JP 2010135827 A JP2010135827 A JP 2010135827A JP 2012001584 A JP2012001584 A JP 2012001584A
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- JP
- Japan
- Prior art keywords
- weight
- parts
- polymerizable monomer
- unsaturated polymerizable
- resin 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000011248 coating agent Substances 0.000 title abstract description 8
- 238000000576 coating method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 title abstract 3
- 239000000178 monomer Substances 0.000 claims abstract description 81
- 125000002091 cationic group Chemical group 0.000 claims abstract description 48
- 239000012948 isocyanate Substances 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000002513 isocyanates Chemical group 0.000 claims abstract description 38
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 14
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 abstract description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 99
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000006185 dispersion Substances 0.000 description 32
- -1 vinyl compound Chemical class 0.000 description 31
- 229920005862 polyol Polymers 0.000 description 30
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 30
- 150000003077 polyols Chemical class 0.000 description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 17
- 238000007664 blowing Methods 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 16
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 16
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 235000010265 sodium sulphite Nutrition 0.000 description 15
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 14
- 239000005056 polyisocyanate Substances 0.000 description 13
- 229920001228 polyisocyanate Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000004359 castor oil Substances 0.000 description 10
- 235000019438 castor oil Nutrition 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 10
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 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 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-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
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
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- 239000004472 Lysine Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-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
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PZXSLFQJOZPCJG-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 PZXSLFQJOZPCJG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant 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
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LKWKEGNBDKESQJ-UHFFFAOYSA-N n,n-diaminoethanamine Chemical compound CCN(N)N LKWKEGNBDKESQJ-UHFFFAOYSA-N 0.000 description 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 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 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
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder 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
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012719 thermal polymerization Methods 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
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、水性樹脂組成物およびその製造方法、さらに水性樹脂組成物を含有する金属塗料に関するものである。 The present invention relates to an aqueous resin composition and a method for producing the same, and further to a metal paint containing the aqueous resin composition.
水性樹脂組成物の中でも、カチオン性基を含有するポリウレタン樹脂水性分散体は、従来から建築内装、皮革、金属、木材などの水性被覆組成物として広く使用されている（特許文献１）。
かかるカチオン性基含有ポリウレタン樹脂水性分散体は、一般的に、黄変が起こりやすく外観に影響があった。特に塗装後に高温条件下におくとにごりや黄変が目立つため、塗布後に高温乾燥ができず、塗膜形成時間を短縮することが困難である。
Among aqueous resin compositions, aqueous polyurethane resin dispersions containing cationic groups have been widely used as aqueous coating compositions for architectural interiors, leather, metals, wood, and the like (Patent Document 1).
Such a cationic group-containing polyurethane resin aqueous dispersion generally tends to yellow and has an influence on the appearance. In particular, dusting and yellowing are conspicuous when placed under high-temperature conditions after coating, so that high-temperature drying cannot be performed after coating, and it is difficult to shorten the coating film formation time.
また、耐候性や強靭性が要求される用途においては、カチオン性基含有ポリウレタン樹脂水性分散体と不飽和重合性モノマー重合体水性分散体を混合して使用する場合があるが、混合時の配合安定性が悪いためにゲル化や沈降が起こりやすく、界面活性剤などの乳化剤を添加する必要がある。 In applications where weather resistance and toughness are required, a cationic group-containing polyurethane resin aqueous dispersion and an unsaturated polymerizable monomer polymer aqueous dispersion may be used in combination. Since the stability is poor, gelation and sedimentation are likely to occur, and it is necessary to add an emulsifier such as a surfactant.
上記従来の問題点に鑑み、本発明は、塗布膜の外観が良好で且つ不飽和重合性モノマー重合体との配合安定性に優れた水性樹脂組成物、その製造方法および金属塗料を提供することを課題とする。 In view of the above-mentioned conventional problems, the present invention provides an aqueous resin composition having a good appearance of a coating film and excellent blending stability with an unsaturated polymerizable monomer polymer, a method for producing the same, and a metal paint. Is an issue.
不飽和重合性モノマー重合体（Ａ）が、カチオン性基含有ポリウレタン樹脂（Ｂ）で乳化されていることを特徴としている。 The unsaturated polymerizable monomer polymer (A) is emulsified with a cationic group-containing polyurethane resin (B).
また、本発明の水性樹脂組成物は、不飽和重合性モノマー（ａ）とカチオン性基含有イソシアネート基末端ウレタンプレポリマー（ｂ）とを含有する溶液を水に分散し、水及び／又はポリアミンで前記カチオン性基含有イソシアネート基末端ウレタンプレポリマー（ｂ）を鎖伸長してカチオン性基含有ポリウレタン樹脂（Ｂ）を乳化し、該乳化と同時に、または乳化後に、前記不飽和重合性モノマー（ａ）を重合して前記不飽和重合性モノマー重合体（Ａ）とすることにより得られることが好ましい。 Further, the aqueous resin composition of the present invention is obtained by dispersing a solution containing an unsaturated polymerizable monomer (a) and a cationic group-containing isocyanate group-terminated urethane prepolymer (b) in water, and using water and / or polyamine. The cationic group-containing isocyanate group-terminated urethane prepolymer (b) is chain-extended to emulsify the cationic group-containing polyurethane resin (B), and the unsaturated polymerizable monomer (a) is simultaneously or after emulsification. Is preferably obtained by polymerizing the unsaturated polymerizable monomer polymer (A).
本発明の水性樹脂組成物の製造方法は、 不飽和重合性モノマー（ａ）とカチオン性基含有イソシアネート基末端ウレタンプレポリマー（ｂ）とを含有する溶液を水に分散する工程と、
前記カチオン性基含有イソシアネート基末端ウレタンプレポリマー（ｂ）を水及び／又はポリアミンで鎖伸長することによりカチオン性基含有ポリウレタン樹脂（Ｂ）を乳化する工程と、前記不飽和重合性モノマー（ａ）を重合して不飽和重合性モノマー重合体（Ａ）を生成する工程とを含むことを特徴としている。
The method for producing an aqueous resin composition of the present invention comprises a step of dispersing a solution containing an unsaturated polymerizable monomer (a) and a cationic group-containing isocyanate group-terminated urethane prepolymer (b) in water;
Emulsifying the cationic group-containing polyurethane resin (B) by chain-extending the cationic group-containing isocyanate group-terminated urethane prepolymer (b) with water and / or polyamine, and the unsaturated polymerizable monomer (a). And a step of producing an unsaturated polymerizable monomer polymer (A).
本発明の金属塗料としては、前記の水性樹脂組成物を含有することを特徴としている。
The metal paint of the present invention is characterized by containing the above aqueous resin composition.
本発明の水性樹脂組成物は、不飽和重合性モノマー重合体（Ａ）が、カチオン性基含有ポリウレタン樹脂（Ｂ）で乳化されているため、塗布後の皮膜に黄変や濁りが生じにくい。
また、不飽和重合性モノマー重合体との相溶性にすぐれているため、不飽和重合性モノマー重合体水性分散体と混合する場合に、乳化剤や分散剤を用いることなく、安定して分散させることができる。
尚、本発明の水性樹脂組成物は、前記のように塗布後の皮膜に黄変や濁りが生じにくいことから、特に、金属表面処理剤などの金属塗料として用いることに適している。
In the aqueous resin composition of the present invention, since the unsaturated polymerizable monomer polymer (A) is emulsified with the cationic group-containing polyurethane resin (B), yellowing and turbidity do not easily occur in the coated film.
In addition, because it is highly compatible with the unsaturated polymerizable monomer polymer, it can be stably dispersed without using an emulsifier or a dispersant when mixed with the unsaturated polymerizable monomer polymer aqueous dispersion. Can do.
In addition, the aqueous resin composition of the present invention is particularly suitable for use as a metal paint such as a metal surface treatment agent because yellowing and turbidity do not easily occur in the coated film as described above.
本発明は、不飽和重合性モノマー重合体（Ａ）が、カチオン性基含有ポリウレタン樹脂（Ｂ）で乳化されている水性樹脂組成物に関するものである。 The present invention relates to an aqueous resin composition in which an unsaturated polymerizable monomer polymer (A) is emulsified with a cationic group-containing polyurethane resin (B).
＜不飽和重合性モノマー重合体（Ａ）＞
本発明の不飽和重合性モノマー重合体（Ａ）は不飽和重合性モノマー（ａ）から構成される。
本発明の不飽和重合性モノマー重合体（Ａ）を構成する不飽和重合性モノマー（ａ）としては、カルボン酸基含有不飽和重合性モノマー、カルボン酸基含有不飽和重合性モノマーのアルキルエステル、ビニル化合物などが挙げられる。
<Unsaturated polymerizable monomer polymer (A)>
The unsaturated polymerizable monomer polymer (A) of the present invention is composed of an unsaturated polymerizable monomer (a).
As the unsaturated polymerizable monomer (a) constituting the unsaturated polymerizable monomer polymer (A) of the present invention, a carboxylic acid group-containing unsaturated polymerizable monomer, an alkyl ester of a carboxylic acid group-containing unsaturated polymerizable monomer, A vinyl compound etc. are mentioned.
カルボン酸基含有不飽和重合性モノマーとしては、メタクリル酸を含む（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸などが挙げられる。 Examples of the carboxylic acid group-containing unsaturated polymerizable monomer include (meth) acrylic acid containing methacrylic acid, crotonic acid, maleic acid, itaconic acid and the like.
カルボン酸基含有不飽和重合性モノマーのアルキルエステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ｎ-ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸イソステアリル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｔ−ブチルシクロヘキシル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸ビシクロ［３，３，１］ノニル、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸アリル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸４−ヒドロキシブチル、メトキシエチレングリコール（メタ） アクリレート、メトキシポリエチレングリコール（メタ） アクリレート、エトキシエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、プロポキシエチレングリコール（メタ） アクリレート、プロポキシポリエチレングリコール（メタ） アクリレート、メトキシプロピレングリコール（メタ） アクリレート、メトキシポリプロピレングリコール（メタ） アクリレート、エトキシプロピレングリコール（メタ）アクリレート、エトキシポリプロピレングリコール（メタ）アクリレート、プロポキシプロピレングリコール（メタ） アクリレート、プロポキシポリプロピレングリコール（メタ） アクリレートなどのモノ（メタ）アクリル酸エステル、エチレングリコールジ（メタ） アクリレート、ポリエチレングリコールジ（メタ） アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（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、などのジ（メタ）アクリレート化合物、トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレートなどのトリ（メタ）アクリレート化合物、ペンタエリスルトールテトラ（メタ）アクリレートなどのテトラ（メタ）アクリレート化合物、ソルビトールヘキサ（メタ）アクリレートなどのヘキサ（メタ）アクリレート化合物などが挙げられる。 Examples of alkyl esters of carboxylic acid group-containing unsaturated polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic Decyl acid, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ( (Meth) acrylic acid adamantyl, (meth) acrylic acid bicyclo [3, 3, 1] nonyl, 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, methoxyethylene glycol (meth) acrylate, methoxypolyethylene Glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, Mono, such as methoxypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, propoxypropylene glycol (meth) acrylate, propoxy polypropylene glycol (meth) acrylate (Meth) acrylic acid ester, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, etc. Di (meth) acrylate compound, trimethylolpropane tri (meth) acrylate, Examples include tri (meth) acrylate compounds such as lysine tri (meth) acrylate, tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, and hexa (meth) acrylate compounds such as sorbitol hexa (meth) acrylate. .
カルボン酸基含有不飽和重合性モノマーのビニル化合物としては、酢酸ビニル、プロピオン酸ビニル、スチレン、α−メチルスチレン、ビニルトルエン、アクリロニトリル、メタクリロニトリル、ブタジエン、イソプレンが挙げられる。 Examples of the vinyl compound of the carboxylic acid group-containing unsaturated polymerizable monomer include vinyl acetate, vinyl propionate, styrene, α-methylstyrene, vinyl toluene, acrylonitrile, methacrylonitrile, butadiene, and isoprene.
尚、各不飽和重合性モノマー（ａ）は、単独または２種以上を併用して用いることができる。 Each unsaturated polymerizable monomer (a) can be used alone or in combination of two or more.
前記不飽和重合性モノマー（ａ）を重合する際には、熱重合の他、公知の重合開始剤（ｃ）を添加して重合反応をさせることができる。
重合開始剤（ｃ）としては、例えば、２，２’−アゾビスイソブチロニトリル、
２，２’−アゾビス（２−メチルプロピオンアミジン）二硫酸塩、２，２’−アゾビス（２−アミジノプロパン）ジヒドロクロライド、２，２’−アゾビス［２−（５−メチル−２−イミダゾリン−２−イル）プロパン］ジヒドロクロライド、２，２’−アゾビス（Ｎ，Ｎ’−ジメチレンイソブチルアミジン）などのアゾ系開始剤；フェニル置換エタンなどの置換エタン系開始剤などが使用できる。
または、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムなどの過硫酸塩；、
過酸化水素、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイドなどの過酸化物などの過酸化物系開始剤と、亜硫酸ナトリウムなどの亜硫酸塩；硫酸水素ナトリウムなどの亜酸水素塩；硫酸第一銅、硫酸第一鉄などの金属塩；Ｌ−アスコルビン酸などの有機還元剤などの還元剤との組み合わせによるレドックス開始剤も利用できる。
また、重合方法としては、乳化重合などの公知の方法が用いられる。
重合温度は、前記重合開始剤の種類によって調整されるが、例えば２０℃〜１００℃が好ましい。
前記重合開始剤（ｃ）の使用量は、通常、不飽和重合性モノマー（ａ）１００重量部に対して、例えば０．００５〜１％が適当である。
When the unsaturated polymerizable monomer (a) is polymerized, a known polymerization initiator (c) can be added to cause a polymerization reaction in addition to thermal polymerization.
Examples of the polymerization initiator (c) include 2,2′-azobisisobutyronitrile,
2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazoline- 2-yl) propane] dihydrochloride, azo initiators such as 2,2′-azobis (N, N′-dimethyleneisobutylamidine); substituted ethane initiators such as phenyl substituted ethane, and the like can be used.
Or persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate;
Peroxide initiators such as peroxides such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and sulfites such as sodium sulfite; bisulfites such as sodium hydrogen sulfate; Metal salts such as copper and ferrous sulfate; redox initiators in combination with a reducing agent such as an organic reducing agent such as L-ascorbic acid can also be used.
As the polymerization method, a known method such as emulsion polymerization is used.
Although superposition | polymerization temperature is adjusted with the kind of said polymerization initiator, 20 to 100 degreeC is preferable, for example.
The amount of the polymerization initiator (c) used is usually suitably 0.005 to 1% with respect to 100 parts by weight of the unsaturated polymerizable monomer (a).
本発明の水性樹脂組成物中に含まれるカチオン性基含有ポリウレタン樹脂（Ｂ）としては下記のものが使用される。 The following are used as the cationic group-containing polyurethane resin (B) contained in the aqueous resin composition of the present invention.
＜カチオン性基含有ポリウレタン樹脂（Ｂ）＞
本発明で使用されるカチオン性基含有ポリウレタン樹脂（Ｂ）は、従来公知の方法で製造することができ、例えば、ポリオール化合物（ｂ−１）、イソシアネート化合物（ｂ−２）およびカチオン性基含有化合物（ｂ−３）を反応させて得られるイソシアネート基末端ウレタンプレポリマー（ｂ）に含まれるカチオン性基を、酸で中和、または四級化剤で四級化し、水または/およびポリアミンで鎖伸長反応することにより得られる。
<Cationic group-containing polyurethane resin (B)>
The cationic group-containing polyurethane resin (B) used in the present invention can be produced by a conventionally known method, for example, a polyol compound (b-1), an isocyanate compound (b-2) and a cationic group-containing The cationic group contained in the isocyanate group-terminated urethane prepolymer (b) obtained by reacting the compound (b-3) is neutralized with an acid or quaternized with a quaternizing agent, and then with water or / and a polyamine. Obtained by chain extension reaction.
（ポリオール化合物（ｂ−１））
前記ポリオール化合物としては、分子量４００以下の低分子量ポリオール、ポリエステルポリオール、ポリエーテルポリオール、ひまし油系ポリオール、ポリカーボネートポリオール、又は炭化水素系ポリオールなどが挙げられる。
これらのポリオール化合物は、１種が単独で、又は２種以上が組み合わされて用いられ得る。
(Polyol compound (b-1))
Examples of the polyol compound include low molecular weight polyols having a molecular weight of 400 or less, polyester polyols, polyether polyols, castor oil-based polyols, polycarbonate polyols, and hydrocarbon-based polyols.
These polyol compounds may be used alone or in combination of two or more.
前記低分子量ポリオールは、分子量４００以下のものであり、前記低分子量ポリオールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、ネオペンチルグリコール、１，３−ブタンジオール、１，４−ブタンジオール、３−メチルペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、２−メチル−１，３−プロパンジオール、ビスフェノールＡ、水添ビスフェノールＡ、シクロヘキサンジメタノール、グリセリン、又はトリメチロールプロパンなどが挙げられる。 The low molecular weight polyol has a molecular weight of 400 or less, and examples of the low molecular weight polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 3-methylpentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated Bisphenol A, cyclohexanedimethanol, glycerin, or trimethylolpropane can be used.
前記ポリエステルポリオールとしては、前記低分子量ポリオールと多価カルボン酸とを反応させてなる水酸基末端エステル化縮合物が挙げられる。
前記多価カルボン酸としては、例えば、コハク酸、グルタル酸、アジピン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、テトラヒドロフラン酸、エンドメチンテトラヒドロフラン酸、又はヘキサヒドロフタル酸などが挙げられる。
Examples of the polyester polyol include a hydroxyl group-terminated esterified condensate obtained by reacting the low molecular weight polyol with a polyvalent carboxylic acid.
Examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuran acid, endomethine tetrahydrofuran acid, and hexahydrophthalic acid. Can be mentioned.
前記ポリエーテルポリオールとしては、ビスフェノールＡなどの前記低分子量ポリオール、ペンタエリスリトール、ソルビトール、又はショ糖などにアルキレンオキサイドを付加重合したものが挙げられる。
前記アルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどが挙げられる。
Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide to the low molecular weight polyol such as bisphenol A, pentaerythritol, sorbitol, or sucrose.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.
前記ひまし油系ポリオールとしては、ひまし油、ひまし油に水素付加した水添ひまし油、ひまし油脂肪酸又はこれに水素付加した水添ひまし油脂肪酸を用いて製造されたポリオールなどが挙げられる。また、ひまし油と他の天然油脂とのエステル交換物、ひまし油と多価アルコールとの反応物、ひまし油脂肪酸と多価アルコールとのエステル化反応物、又はこれらに前記アルキレンオキサイドを付加重合したポリオールなどが挙げられる。 Examples of the castor oil-based polyol include castor oil, hydrogenated castor oil hydrogenated to castor oil, castor oil fatty acid, or polyol produced using hydrogenated castor oil fatty acid hydrogenated thereto. Further, a transesterification product of castor oil and other natural fats and oils, a reaction product of castor oil and polyhydric alcohol, an esterification reaction product of castor oil fatty acid and polyhydric alcohol, or a polyol obtained by addition polymerization of the alkylene oxide to these Can be mentioned.
前記ポリカーボネートポリオールとしては、従来公知のものが挙げられ、該ポリカーボネートポリオールは、例えば、前記低分子量ポリオールとジフェニルカーボネートとの反応により、又は、前記低分子量ポリオールとホスゲンとの反応により得られる。 A conventionally well-known thing is mentioned as said polycarbonate polyol, This polycarbonate polyol is obtained by reaction of the said low molecular weight polyol and diphenyl carbonate, or by reaction of the said low molecular weight polyol and phosgene, for example.
前記炭化水素系ポリオールとしては、ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリブタジエンポリオール、又は水添ポリイソプレンポリオールなどが挙げられる。 Examples of the hydrocarbon polyol include polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.
（イソシアネート化合物（ｂ−２））
前記イソシアネート化合物としては、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、および芳香脂肪族ポリイソシアネート等のポリイソシアネートが挙げられる。
前記イソシアネート化合物は、単独で、又は２種以上を組み合わされて用いることができる。
(Isocyanate compound (b-2))
Examples of the isocyanate compound include polyisocyanates such as aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.
The said isocyanate compound can be used individually or in combination of 2 or more types.
前記脂肪族ポリイソシアネートとしては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２−メチルペンタン−１，５−ジイソシアネート、３−メチルペンタン−１，５−ジイソシアネート等が挙げられる。 Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane- Examples include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
前記脂環族ポリイソシアネートとしては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン等が挙げられる。 Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Is mentioned.
前記芳香族ポリイソシアネートとしては、トリレンジイソシアネート、２，２’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、４，４’−ジベンジルジイソシアネート、１，５−ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート等が挙げられる。 Examples of the aromatic polyisocyanate include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1, Examples include 5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.
前記芳香脂肪族ポリイソシアネートとしては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α，α−テトラメチルキシリレンジイソシアネート等が挙げられる。 Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α, α, α, α-tetramethylxylylene diisocyanate.
また、前記イソシアネート化合物は、前記ポリイソシアネートの２量体もしくは３量体、ビューレット化イソシアネート等の変性体、ポリメチレンポリフェニルポリイソシアネート（ポリメリックＭＤＩ）などを用いることができる。 In addition, as the isocyanate compound, a dimer or trimer of the polyisocyanate, a modified product such as a buret isocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), or the like can be used.
前記イソシアネート化合物の中でも、水性樹脂組成物の黄変をより抑制できるという点で、脂肪族ポリイソシアネートまたは脂環族ポリイソシアネートが特に好ましい。 Among the isocyanate compounds, aliphatic polyisocyanates or alicyclic polyisocyanates are particularly preferable in that yellowing of the aqueous resin composition can be further suppressed.
（カチオン性基含有化合物（ｂ−３））
前記カチオン性基含有化合物としては、例えば、Ｎ−メチルジエタノールアミン、Ｎ−メチルジエタノールアミンなどのアルキルジアルカノールアミン；Ｎ−メチルジアミノエチルアミン；Ｎ−エチルジアミノアミンなどのアルキルジアミノアルキルアミンなどが挙げられる。
また、これらを酸や四級化剤で四級化したものも使用することができる。
(Cationic group-containing compound (b-3))
Examples of the cationic group-containing compound include alkyl dialkanolamines such as N-methyldiethanolamine and N-methyldiethanolamine; N-methyldiaminoethylamines; alkyldiaminoalkylamines such as N-ethyldiaminoamine.
Moreover, what quaternized these with an acid or a quaternizing agent can also be used.
尚、本発明でいうカチオン性基としては、例えば、三級アミノ基を酸で中和した、または四級化剤で四級化した四級アンモニウム基が挙げられる。
また、カチオン性基含有化合物（ｂ−３）に関しては、四級アンモニウム基を形成しうる三級アミン基含有化合物であってもよい。
Examples of the cationic group in the present invention include a quaternary ammonium group obtained by neutralizing a tertiary amino group with an acid or quaternizing with a quaternizing agent.
Further, the cationic group-containing compound (b-3) may be a tertiary amine group-containing compound capable of forming a quaternary ammonium group.
前記ポリオール化合物（ｂ−１）、イソシアネート化合物（ｂ−２）およびカチオン性基含有化合物（ｂ−３）を反応させてイソシアネート基末端ウレタンプレポリマー（ｂ）を得るが、反応方法としては公知の方法で行うことができ、例えば、３０℃〜１３０℃で
０．５時間〜１０時間程度の反応条件で行うことができる。
The polyol compound (b-1), isocyanate compound (b-2) and cationic group-containing compound (b-3) are reacted to obtain an isocyanate group-terminated urethane prepolymer (b). For example, the reaction can be performed at 30 ° C. to 130 ° C. under reaction conditions of about 0.5 hours to 10 hours.
前記イソシアネート基末端ウレタンプレポリマー（ｂ）に含まれているカチオン性基を中和する酸としては、塩酸および硫酸などの無機酸、ギ酸、酢酸、プロピオン酸、酪酸、乳酸、リンゴ酸、マロン酸、アジピン酸などの有機酸が挙げられる。 Acids that neutralize the cationic groups contained in the isocyanate group-terminated urethane prepolymer (b) include inorganic acids such as hydrochloric acid and sulfuric acid, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, and malonic acid. And organic acids such as adipic acid.
前記イソシアネート基末端ウレタンプレポリマー（ｂ）に含まれるカチオン性基を四級化する四級化剤としては、塩化メチルおよび臭化メチルなどのハロゲン化アルキル、ジメチル硫酸およびジエチル硫酸などのジアルキル硫酸が挙げられる。 Examples of the quaternizing agent for quaternizing the cationic group contained in the isocyanate group-terminated urethane prepolymer (b) include alkyl halides such as methyl chloride and methyl bromide, and dialkyl sulfates such as dimethyl sulfate and diethyl sulfate. Can be mentioned.
前記のように、カチオン性基を中和または四級化されたイソシアネート基末端ウレタンプレポリマー（ｂ）を水、または水とポリアミンの混合物で鎖伸長してカチオン性基含有ポリウレタン樹脂（Ｂ）が形成される。
前記鎖伸長剤として水と混合されるポリアミンは、例えば、エチレンジアミン、トリメチレンジアミン、プロピレンジアミン、ジエチレントリアミン、トリエチレンテトラミンなどの脂肪族ポリアミン、メタキシレンジアミン、トリレンジアミン、ジアミノジフェニルメタン等の芳香族ポリアミン、ピペラジン、イソホロンジアミン等の脂環族ポリアミン、ヒドラジン、アジピン酸ジヒドラジドのようなポリヒドラジド等が使用できる。
前記ポリアミン化合物は単独で使用してもよく、２種以上を併用してもよい。
また、ポリマー化を大きく阻害しない程度に反応停止剤としてジブチルアミンなどのモノアミンやメチルエチルケトオキシムのような反応停止剤を使用してもよい。
また、前記ポリアミンと水の混合物を鎖伸長剤として使用することもできる。
As described above, the cationic group-containing polyurethane resin (B) is obtained by chain-extending the isocyanate group-terminated urethane prepolymer (b) neutralized or quaternized with a cationic group with water or a mixture of water and a polyamine. It is formed.
Polyamines mixed with water as the chain extender include, for example, aliphatic polyamines such as ethylenediamine, trimethylenediamine, propylenediamine, diethylenetriamine, and triethylenetetramine, aromatic polyamines such as metaxylenediamine, tolylenediamine, and diaminodiphenylmethane. An alicyclic polyamine such as piperazine and isophoronediamine, a polyhydrazide such as hydrazine and adipic acid dihydrazide, and the like can be used.
The said polyamine compound may be used independently and may use 2 or more types together.
Moreover, you may use reaction terminators, such as monoamines, such as a dibutylamine, and methyl ethyl ketoxime, as a reaction terminator to such an extent that polymerization is not inhibited greatly.
Also, a mixture of the polyamine and water can be used as a chain extender.
本発明の水性樹脂組成物は下記の方法で製造することができる。
前記ポリオール化合物（ｂ−１）、イソシアネート化合物（ｂ−２）およびカチオン性基含有化合物（ｂ−３）を反応させてイソシアネート基末端ウレタンプレポリマーとし、これを５℃〜４５℃に冷却して、酸または四級化剤を添加し、カチオン性基本含有イソシアネート基末ウレタンプレポリマー（ｂ）を製造する。
尚、溶媒として、アセトン、メチルエチルケトン、テトラヒドロフラン、ジオキサン、酢酸エチル、酢酸ブチルなどの任意の有機溶媒を使用することができる。
この場合、前記ポリオール化合物（ｂ−１）、イソシアネート化合物（ｂ−２）およびカチオン性基含有化合物（ｂ−３）の混合比率は、前記イソシアネート基末端ウレタンプレポリマーの遊離のイソシアネート基含有量が、カチオン性基本含有イソシアネート基末ウレタンプレポリマー（ｂ）に対して０．１〜１０重量％、好ましくは、０．５〜５重量％になるように混合することが好ましい。
また、前記カチオン性基含有化合物（ｂ−３）の混合比率は、イソシアネート基末端ウレタンプレポリマーのアミン価が５〜８０ｍｇＫＯＨ／ｇとなるようにすることが好ましい。
続いて、カチオン性基含有イソシアネート基末端ウレタンポリマー（ｂ）１００重量部に対して不飽和重合性モノマー（ａ）を１〜９００重量部添加し、均一溶液とした後、不飽和重合性モノマー（ａ）とカチオン性基含有イソシアネート基末端ウレタンポリマー（ｂ）の合計量１００重量部に対して水を１００〜９００重量部を添加することで乳化させ、必要によりポリアミンを添加して鎖伸長反応をすることによりポリウレタン樹脂（Ｂ）を得る。
さらに鎖伸長と同時または反応後に、不飽和重合性モノマー（ａ）を重合して不飽和重合性モノマー重合体（Ａ）を生成し、有機溶媒を減圧留去することにより、本発明の不飽和重合性モノマー重合体（Ａ）がカチオン性基含有イソシアネート基末端ウレタンプレポリマー（ｂ）で乳化されている水性樹脂組成物が製造される。
The aqueous resin composition of the present invention can be produced by the following method.
The polyol compound (b-1), the isocyanate compound (b-2) and the cationic group-containing compound (b-3) are reacted to form an isocyanate group-terminated urethane prepolymer, which is cooled to 5 ° C to 45 ° C. Then, an acid or a quaternizing agent is added to produce a cationic base-containing isocyanate group powder urethane prepolymer (b).
As the solvent, any organic solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate can be used.
In this case, the mixing ratio of the polyol compound (b-1), the isocyanate compound (b-2) and the cationic group-containing compound (b-3) is such that the free isocyanate group content of the isocyanate group-terminated urethane prepolymer is the same. The cationic base-containing isocyanate group urethane prepolymer (b) is preferably mixed in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.
The mixing ratio of the cationic group-containing compound (b-3) is preferably such that the amine value of the isocyanate group-terminated urethane prepolymer is 5 to 80 mgKOH / g.
Subsequently, 1 to 900 parts by weight of the unsaturated polymerizable monomer (a) is added to 100 parts by weight of the cationic group-containing isocyanate group-terminated urethane polymer (b) to obtain a uniform solution, and then the unsaturated polymerizable monomer ( a) and a cationic group-containing isocyanate group-terminated urethane polymer (b) are emulsified by adding 100 to 900 parts by weight of water with respect to 100 parts by weight of the total amount, and if necessary, a polyamine is added to carry out a chain extension reaction. By doing so, a polyurethane resin (B) is obtained.
Further, at the same time as chain extension or after reaction, the unsaturated polymerizable monomer (a) is polymerized to produce an unsaturated polymerizable monomer polymer (A). An aqueous resin composition is produced in which the polymerizable monomer polymer (A) is emulsified with the cationic group-containing isocyanate group-terminated urethane prepolymer (b).
本発明の水性樹脂組成物は、前記不飽和重合性モノマー重合体（Ａ）と前記カチオン性基含有ポリウレタン樹脂（Ｂ）成分とが、重量比でＡ／Ｂ＝９０／１０〜１／９９であることが好ましく、８０／２０〜１０／９０であることがより好ましい。上記範囲内とすることにより、水性樹脂組成物の分散安定性がより向上すると共に、得られる皮膜の黄変をより抑制することができる In the aqueous resin composition of the present invention, the unsaturated polymerizable monomer polymer (A) and the cationic group-containing polyurethane resin (B) component have a weight ratio of A / B = 90/10 to 1/99. It is preferable that the ratio is 80/20 to 10/90. By being within the above range, the dispersion stability of the aqueous resin composition can be further improved, and yellowing of the resulting film can be further suppressed.
さらに、本発明の水性樹脂組成物には、必要に応じて一般的に使用される各種添加剤を使用することができる。このような添加剤としては、例えば、耐候剤、抗菌剤、抗カビ剤、顔料、充填材、防錆剤、顔料、染料、造膜助剤、無機架橋剤、有機架橋剤（ 例えばブロックドイソシアネート系架橋剤、エポキシ系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、メラミン系架橋剤） 、シランカップリング剤、ブロッキング防止剤、粘度調整剤、レベリング剤、消泡剤、分散安定剤、光安定剤、酸化防止剤、紫外線吸収剤、無機、有機充填剤、可塑剤、滑剤、帯電防止剤等が挙げられる。
また、本発明の水性樹脂組成物は、一般の塗料として広く用いることができるが、特に金属表面処理剤などの金属塗料として使用するのに適している。
Furthermore, in the aqueous resin composition of the present invention, various commonly used additives can be used as necessary. Examples of such additives include weathering agents, antibacterial agents, antifungal agents, pigments, fillers, rust inhibitors, pigments, dyes, film-forming aids, inorganic crosslinking agents, organic crosslinking agents (for example, blocked isocyanates). -Based crosslinking agents, epoxy-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, melamine-based crosslinking agents), silane coupling agents, antiblocking agents, viscosity modifiers, leveling agents, antifoaming agents, dispersion stabilizers, light Stabilizers, antioxidants, ultraviolet absorbers, inorganic and organic fillers, plasticizers, lubricants, antistatic agents and the like can be mentioned.
The aqueous resin composition of the present invention can be widely used as a general paint, but is particularly suitable for use as a metal paint such as a metal surface treatment agent.
以下に実施例および比較例を挙げて本発明についてさらに詳細に説明する。
まず、下記実施例および比較例の各水性樹脂組成物を準備する。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
First, each aqueous resin composition of the following Examples and Comparative Examples is prepared.
（実施例１）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-3成分としてＮ−メチルジエタノールアミン３３ 重量部、ｂ-２成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（b）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２６０重量部を加えた。続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
Example 1
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube is adducted with 2 moles of bisphenol A ethylene oxide as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as b-3 component, 231 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone as b-2 component were added, and 75 ° C. For 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (b) having an amine value of 40 mgKOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 34.9 parts by weight of dimethyl sulfuric acid, and then 260 parts by weight of methyl methacrylate was added as a component. Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例２）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド４モル付加物（ニューポールＢＰＥ−４０、三洋化成工業株式会社製）７５．６重量部、トリメチロールプロパン７．３０重量部、ｂ-３成分としてＮ−メチルジエタノールアミン２ ８ ． ０ 重量部、ポリエチレングリコール（ＰＥＧ−６００Ｓ、第一工業製薬株式会社製）を５３．２重量部ｂ-２成分として４，４’−ジシクロヘキシルメタンジイソシアネートを１９０．８重量部およびメチルエチルケトン２６６重量部を加え、７５℃で４時間反応させてアミン価３７ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．２％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸１７．８重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル３７２．７重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝５０／５０であった。
(Example 2)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube is adducted with 4 moles of bisphenol A ethylene oxide as a b-1 component (New Pole BPE-40, manufactured by Sanyo Chemical Industries, Ltd.) 75.6 parts by weight, 7.30 parts by weight of trimethylolpropane, N-methyldiethanolamine 2 8 as b-3 component. 0 part by weight, polyethylene glycol (PEG-600S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as 53.2 parts by weight b-2 component, 190.8 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 266 parts by weight of methyl ethyl ketone In addition, the mixture was reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 37 mgKOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.2%.
Next, this solution was cooled to 45 ° C., added with 17.8 parts by weight of dimethylsulfuric acid, and then quaternized. Then, 372.7 parts by weight of methyl methacrylate was added as a component.
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) and the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 50/50.
（実施例３）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）４３．６重量部、ビスフェノールＡのエチレンオキサイド４モル付加物（ニューポールＢＰＥ−４０、三洋化成工業株式会社製）１８．７重量部、１，４−シクロヘキサンジメタノールを１．５重量部、トリメチロールプロパンを５．７重量部、ｂ-3成分としてＮ−メチルジエタノールアミン２３．７重量部、メトキシポリエチレングリコール（Ｍ−ＰＥＧ ＣＰ−２５００、第一工業製薬株式会社製）１．５重量部、ポリエチレングリコール（ＰＥＧ−６００Ｓ、第一工業製薬株式会社製）４５重量部、ｂ-2成分として４，４’−ジシクロヘキシルメタンジイソシアネート１９０．８重量部およびメチルエチルケトン２６６重量部を加え、７５℃で４時間反応させてアミン価３４ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．０％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸１７．８重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル３２５重量部を加えた。
続いて、水２０００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝５０／５０であった。
(Example 3)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube is adducted with 2 moles of bisphenol A ethylene oxide as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) 43.6 parts by weight, bisphenol A ethylene oxide 4 mol adduct (New Pole BPE-40, Sanyo Chemical Industries, Ltd.) 18.7 parts by weight, 1,4-cyclohexanedimethanol 1.5 parts by weight, tri 5.7 parts by weight of methylolpropane, 23.7 parts by weight of N-methyldiethanolamine as b-3 component, 1.5 parts by weight of methoxypolyethylene glycol (M-PEG CP-2500, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyethylene 45 parts by weight of glycol (PEG-600S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 4,4′-disi as b-2 component 190.8 parts by weight of cyclohexylmethane diisocyanate and 266 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 34 mg KOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.0%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 17.8 parts by weight of dimethyl sulfate, and then 325 parts by weight of methyl methacrylate was added as the component a.
Subsequently, the mixture was emulsified and dispersed using a homogenizer while gradually adding 2000 parts by weight of water, 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added, and the mixture was reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) and the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 50/50.
（実施例４）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-3成分としてＮ−メチルジエタノールアミン３３重量部、ｂ-2成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２０８重量部およびアクリル酸ｎ−ブチルを５２重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
Example 4
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube is adducted with 2 moles of bisphenol A ethylene oxide as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as b-3 component, 231 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone as b-2 component were added, and 75 ° C. For 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 40 mgKOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C. and quaternized by adding 34.9 parts by weight of dimethyl sulfate, and then 208 parts by weight of methyl methacrylate and 52 parts by weight of n-butyl acrylate were added as component a. .
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例５）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ−１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ−３成分としてＮ−メチルジエタノールアミン３３重量部、ｂ−２成分として４，４’−
ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２０８重量部およびアクリル酸２−エチルヘキシルを５２重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 5)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube, 2-mole addition product of ethylene oxide of bisphenol A as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as component b-3, 4,4′- as component b-2
231 parts by weight of dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 40 mg KOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C. and quaternized by adding 34.9 parts by weight of dimethyl sulfuric acid, and then 208 parts by weight of methyl methacrylate and 52 parts by weight of 2-ethylhexyl acrylate were added as component a. .
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例６）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-３成分としてＮ−メチルジエタノールアミン３３重量部、ｂ−２成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（b）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２４７重量部およびトリエチレングリコールジメタクリレート１３重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 6)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube is adducted with 2 moles of bisphenol A ethylene oxide as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as b-3 component, 231 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone as b-2 component were added at 75 ° C. For 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (b) having an amine value of 40 mgKOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C. and quaternized by adding 34.9 parts by weight of dimethyl sulfuric acid, and then 247 parts by weight of methyl methacrylate and 13 parts by weight of triethylene glycol dimethacrylate were added as component a.
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例７）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてポリエステルポリオール（クラレポリオールＰ−５２０、株式会社クラレ製）１２０重量部、トリメチロールプロパン６重量部、ｂ-３成分としてＮ−メチルジエタノールアミン３３重量部、ｂ−２成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２４７重量部およびトリエチレングリコールジメタクリレート１３重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 7)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 120 parts by weight of polyester polyol (Kuraray polyol P-520, manufactured by Kuraray Co., Ltd.) as b-1 component, 6 weight of trimethylolpropane Part, N-3 methyldiethanolamine 33 parts by weight as b-3 component, 231 parts by weight 4,4'-dicyclohexylmethane diisocyanate and 260 parts by weight methyl ethyl ketone as b-2 component, and reacted at 75 ° C. for 4 hours to give an amine value of 40 mgKOH / G of a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) was obtained.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C. and quaternized by adding 34.9 parts by weight of dimethyl sulfuric acid, and then 247 parts by weight of methyl methacrylate and 13 parts by weight of triethylene glycol dimethacrylate were added as component a.
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例８）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成品工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-３成分としてＮ−メチルジエタノールアミン３３重量部、ｂ−２成分として４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）１００重量部、４，４’−ジシクロヘキシルメタンジイソシアネート１３０重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２６０重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 8)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to ethylene oxide 2-mol adduct of bisphenol A as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) ) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as the b-3 component, 100 parts by weight of 4,4′-diphenylmethane diisocyanate (MDI) as the b-2 component, 4,4′-dicyclohexyl 130 parts by weight of methane diisocyanate and 260 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 40 mg KOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 34.9 parts by weight of dimethyl sulfuric acid, and then 260 parts by weight of methyl methacrylate was added as a component.
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例９）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成品工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-３成分としてＮ−メチルジエタノールアミン３３重量部、ｂ−２成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ギ酸１２．８重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２６０重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
Example 9
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to ethylene oxide 2-mol adduct of bisphenol A as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) ) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as the b-3 component, 231 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone as the b-2 component, The reaction was carried out at 4 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 40 mgKOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, after cooling this solution to 45 degreeC and adding 12.8 weight part of formic acid and making it quaternized, 260 weight part of methyl methacrylate was added as a component.
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例１０）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成品工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-３成分としてＮ−メチルジエタノールアミン３３重量部、ｂ−２成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２６０重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ジエチレントリアミン１０重量部を添加した後、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 10)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to ethylene oxide 2-mol adduct of bisphenol A as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) ) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as the b-3 component, 231 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone as the b-2 component, The reaction was carried out at 4 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 40 mgKOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 34.9 parts by weight of dimethyl sulfuric acid, and then 260 parts by weight of methyl methacrylate was added as a component.
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. After adding 10 parts by weight of diethylenetriamine, 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added. After reacting at 3 ° C. for 3 hours to polymerize the unsaturated polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例１１）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成品工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-３成分としてＮ−メチルジエタノールアミン３３重量部、ｂ−２成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３１重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３４．９重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２６０重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、過硫酸アンモニウム１重量部を添加し、７０℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 11)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to ethylene oxide 2-mol adduct of bisphenol A as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) ) 120 parts by weight, 6 parts by weight of trimethylolpropane, 33 parts by weight of N-methyldiethanolamine as the b-3 component, 231 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone as the b-2 component, The reaction was carried out at 4 ° C. for 4 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (B) having an amine value of 40 mgKOH / g.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 34.9 parts by weight of dimethyl sulfuric acid, and then 260 parts by weight of methyl methacrylate was added as a component.
Subsequently, 2300 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. After adding 1 part by weight of ammonium persulfate and reacting at 70 ° C. for 3 hours, the unsaturated polymerizable monomer was polymerized. The emulsified dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例１２）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド４モル付加物（ニューポールＢＰＥ−４０ＮＫ、三洋化成品工業株式会社製）７５．６重量部、トリメチロールプロパン７．３０重量部、ｂ-３成分としてＮ−メチルジエタノールアミン１３．０重量部、ｂ-１成分としてポリエチレングリコール（ＰＥＧ−６００Ｓ、第一工業製薬株式会社製）５３．２重量部、ｂ−２成分として４，４’−ジシクロヘキシルメタンジイソシアネート１５３．0重量部およびメチルエチルケトン２６６重量部を加え、７５℃で４時間反応させてアミン価２０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．２％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸１３．８重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル３０３．１重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、
ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝５０／５０であった。
(Example 12)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to ethylene oxide 4 mol adduct of bisphenol A as a b-1 component (New Pole BPE-40NK, manufactured by Sanyo Chemical Industries, Ltd.) ) 75.6 parts by weight, 7.30 parts by weight of trimethylolpropane, 13.0 parts by weight of N-methyldiethanolamine as the b-3 component, polyethylene glycol (PEG-600S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as the b-1 component ) 53.2 parts by weight, 153.0 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 266 parts by weight of methyl ethyl ketone as b-2 components were added and reacted at 75 ° C. for 4 hours to terminate the isocyanate group having an amine value of 20 mgKOH / g. A methyl ethyl ketone solution of urethane prepolymer (B) was obtained.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.2%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 13.8 parts by weight of dimethyl sulfuric acid, and then 303.1 parts by weight of methyl methacrylate was added as a component.
Subsequently, emulsifying and dispersing using a homogenizer while gradually adding 2300 parts by weight of water,
After adding 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite and reacting at 25 ° C. for 3 hours to polymerize the unsaturated polymerizable monomer, the emulsion dispersion is depressurized at 50 ° C. to remove it. Solvent was used to obtain an aqueous resin composition having a nonvolatile content of 25%.
The weight ratio of the polyurethane resin (B) and the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 50/50.
（実施例１３）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド４モル付加物（ニューポールＢＰＥ−４０ＮＫ、三洋化成品工業株式会社製）７５．６重量部、トリメチロールプロパン７．３０重量部、ｂ-３成分としてＮ−メチルジエタノールアミン４４．０重量部、ｂ-１成分としてポリエチレングリコール（ＰＥＧ−６００Ｓ、第一工業製薬株式会社製）５３．２重量部、ｂ−２成分として４，４’−ジシクロヘキシルメタンジイソシアネート２３３重量部およびメチルエチルケトン２６６重量部を加え、７５℃で４時間反応させてアミン価６０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（Ｂ）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．２％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸４３．４重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル４１３．１重量部を加えた。
続いて、水２３００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、
ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝５０／５０であった。
(Example 13)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to ethylene oxide 4 mol adduct of bisphenol A as a b-1 component (New Pole BPE-40NK, manufactured by Sanyo Chemical Industries, Ltd.) ) 75.6 parts by weight, 7.30 parts by weight of trimethylolpropane, 44.0 parts by weight of N-methyldiethanolamine as the b-3 component, polyethylene glycol (PEG-600S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as the b-1 component ) 53.2 parts by weight, 233 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 266 parts by weight of methyl ethyl ketone as b-2 components were reacted at 75 ° C. for 4 hours to react with an isocyanate group-terminated urethane prepolymer having an amine value of 60 mg KOH / g. A methyl ethyl ketone solution of polymer (B) was obtained.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.2%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 43.4 parts by weight of dimethyl sulfuric acid, and then 413.1 parts by weight of methyl methacrylate was added as the component a.
Subsequently, emulsifying and dispersing using a homogenizer while gradually adding 2300 parts by weight of water,
After adding 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite and reacting at 25 ° C. for 3 hours to polymerize the unsaturated polymerizable monomer, the emulsion dispersion is depressurized at 50 ° C. to remove it. Solvent was used to obtain an aqueous resin composition having a nonvolatile content of 25%.
The weight ratio of the polyurethane resin (B) and the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 50/50.
（実施例１４）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-3成分としてＮ−メチルジエタノールアミン３０ 重量部、ｂ-２成分としてイソホロンジイソシアネート１９２重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（b）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸３１．８重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル２３２重量部を加えた。続いて、水２２００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 14)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube is adducted with 2 moles of bisphenol A ethylene oxide as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) 120 parts by weight, 6 parts by weight of trimethylolpropane, 30 parts by weight of N-methyldiethanolamine as the b-3 component, 192 parts by weight of isophorone diisocyanate and 260 parts by weight of methyl ethyl ketone as the b-2 component were added and reacted at 75 ° C. for 4 hours. A methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (b) having an amine value of 40 mgKOH / g was obtained.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C., and quaternized by adding 31.8 parts by weight of dimethyl sulfate, and then 232 parts by weight of methyl methacrylate was added as a component. Subsequently, 2200 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（実施例１５）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ｂ-１成分としてビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）１２０重量部、トリメチロールプロパン６重量部、ｂ-3成分としてＮ−メチルジエタノールアミン２５ 重量部、ｂ-２成分としてヘキサメチレンジイソシアネート１３７重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマー（b）のメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸２６．５重量部を加えて四級化した後、ａ成分としてメタクリル酸メチル１９２重量部を加えた。続いて、水２１００重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、ｔ−ブチルヒドロパーオキサイド１重量部及び亜硫酸ナトリウム１重量部を添加し、２５℃で３時間反応させて不飽和重合性モノマーを重合させた後、この乳化分散液を５０℃で減圧して脱溶剤を行い、不揮発分２５％の水性樹脂組成物を得た。
得られた水性樹脂組成物中の、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比はＡ／Ｂ＝４０／６０であった。
(Example 15)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube is adducted with 2 moles of bisphenol A ethylene oxide as a b-1 component (New Pole BPE-20NK, manufactured by Sanyo Chemical Industries, Ltd.) 120 parts by weight, 6 parts by weight of trimethylolpropane, 25 parts by weight of N-methyldiethanolamine as the b-3 component, 137 parts by weight of hexamethylene diisocyanate and 260 parts by weight of methyl ethyl ketone as the b-2 component were added and reacted at 75 ° C. for 4 hours. Thus, a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer (b) having an amine value of 40 mgKOH / g was obtained.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C., 26.5 parts by weight of dimethyl sulfuric acid was added and quaternized, and then 192 parts by weight of methyl methacrylate was added as a component. Subsequently, 2100 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. 1 part by weight of t-butyl hydroperoxide and 1 part by weight of sodium sulfite were added and reacted at 25 ° C. for 3 hours to be unsaturated. After polymerizing the polymerizable monomer, the emulsion dispersion was depressurized at 50 ° C. to remove the solvent, and an aqueous resin composition having a nonvolatile content of 25% was obtained.
The weight ratio of the polyurethane resin (B) to the unsaturated polymerizable monomer polymer (A) in the obtained aqueous resin composition was A / B = 40/60.
（比較例１）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、ビスフェノールＡのエチレンオキサイド２モル付加物（ニューポールＢＰＥ−２０ＮＫ、三洋化成工業株式会社製）１００重量部、トリメチロールプロパン５重量部、Ｎ−メチルジエタノールアミン２７．５重量部、４，４’−ジシクロヘキシルメタンジイソシアネート１９２．５重量部およびメチルエチルケトン２６０重量部を加え、７５℃で４時間反応させてアミン価４０ｍｇＫＯＨ／ｇのイソシアネート基末端ウレタンプレポリマーのメチルエチルケトン溶液を得た。
この溶液の不揮発分に対する遊離のイソシアネート基含有量は３．６％であった。
次に、この溶液を４５℃まで冷却し、ジメチル硫酸２９．１重量部を加えて四級化した。 続いて、水１３８０重量部を徐々に加えながらホモジナイザーを使用して乳化分散し、５０℃で減圧して脱溶剤を行い、不揮発分２５％のカチオン性基含有ポリウレタン樹脂水性分散体を得た。
(Comparative Example 1)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube, 100 parts by weight of bisphenol A ethylene oxide 2-mol adduct (New Pole BPE-20NK, Sanyo Chemical Industries, Ltd.) 5 parts by weight of methylolpropane, 27.5 parts by weight of N-methyldiethanolamine, 192.5 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 260 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to give an amine value of 40 mgKOH / g A methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer was obtained.
The content of free isocyanate groups based on the nonvolatile content of this solution was 3.6%.
Next, this solution was cooled to 45 ° C. and quaternized by adding 29.1 parts by weight of dimethyl sulfate. Subsequently, the mixture was emulsified and dispersed using a homogenizer while gradually adding 1380 parts by weight of water, and the solvent was removed under reduced pressure at 50 ° C. to obtain a cationic group-containing polyurethane resin aqueous dispersion having a nonvolatile content of 25%.
（比較例２）
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコに、メタクリル酸メチルを２５０重量部及びノニオン性反応性界面活性剤（アクアロンＲＮ−３０、第一工業製薬株式会社製）を加え、水７５０ 重量部を徐々に加えながらホモジナイザーを使用して乳化分散を行った。得られた乳化分散体に過硫酸アンモニウムを添加し、８０℃で３時間反応させ、不揮発分２５％の不飽和重合性モノマー重合体水性分散体を得た。
(Comparative Example 2)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 250 parts by weight of methyl methacrylate and a nonionic reactive surfactant (Aqualon RN-30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The mixture was emulsified and dispersed using a homogenizer while gradually adding 750 parts by weight of water. Ammonium persulfate was added to the resulting emulsified dispersion and reacted at 80 ° C. for 3 hours to obtain an unsaturated polymerizable monomer polymer aqueous dispersion having a nonvolatile content of 25%.
（比較例３）
比較例１で得られたカチオン性基含有ポリウレタン樹脂水性分散体と、比較例２で得られた不飽和重合性モノマー重合体水性分散体とを、ポリウレタン樹脂（Ｂ）と、不飽和重合性モノマー重合体（Ａ）との重量比がＡ／Ｂ＝６０／４０となるように混合し、不飽和重合性モノマー重合体水性分散体を得た。
(Comparative Example 3)
The cationic group-containing polyurethane resin aqueous dispersion obtained in Comparative Example 1 and the unsaturated polymerizable monomer polymer aqueous dispersion obtained in Comparative Example 2 were converted into a polyurethane resin (B) and an unsaturated polymerizable monomer. The mixture was mixed so that the weight ratio with the polymer (A) was A / B = 60/40 to obtain an unsaturated polymerizable monomer polymer aqueous dispersion.
実施例１〜１５で得られた水性樹脂組成物および比較例１〜３で得られた水性分散体を用いて、下記の方法で試験片を作成し、外観（濁り、黄変）、物性（引張強度、伸度）、耐食性および不飽和重合性モノマー重合体水性分散体との配合安定性について評価した。 Using the aqueous resin compositions obtained in Examples 1 to 15 and the aqueous dispersion obtained in Comparative Examples 1 to 3, test pieces were prepared by the following method, and appearance (turbidity, yellowing), physical properties ( Tensile strength, elongation), corrosion resistance, and blending stability with an unsaturated polymerizable monomer polymer aqueous dispersion were evaluated.
（試験片の作成方法）
フッ素樹脂コーティングシャーレに乾燥膜厚２００μｍとなるように各実施例および比較例の水性樹脂組成物を入れ、８０℃で６時間、１２０℃で１時間加熱後、１５０℃で３０分乾燥することにより試験片を作製した。
(How to create a test piece)
By placing the aqueous resin composition of each example and comparative example in a fluororesin-coated petri dish to a dry film thickness of 200 μm, heating at 80 ° C. for 6 hours, 120 ° C. for 1 hour, and then drying at 150 ° C. for 30 minutes A test piece was prepared.
（外観）
前記各試験片の皮膜の外観を目視により観察し、濁りの有無および黄変の有無を評価した。
(appearance)
The appearance of the film of each test piece was visually observed to evaluate the presence or absence of turbidity and the presence or absence of yellowing.
（皮膜物性）
ＪＩＳ−Ｋ−６３０１に準じて、引張速度１００ｍｍ／ｍｉｎで引張強度（N/mm2）および伸度（％）を測定した。
(Film physical properties)
According to JIS-K-6301, tensile strength (N / mm 2 ) and elongation (%) were measured at a tensile speed of 100 mm / min.
（耐食性）
前記実施例１〜１５で得られた水性樹脂組成物および比較例１〜３で得られた水性分散体を、あらかじめ表面をイソプロパノールで脱脂した電気亜鉛メッキ鋼板（商品名：ノンクロメート処理 ユニジング、太佑機材株式会社製）に、乾燥膜厚み３μmになるように塗布し、８０℃で３０秒間焼き付けて耐食性評価用の試験片を作成した。
各試験片に５重量％食塩水を３５℃で７２時間噴霧し、白錆の発生の有無を目視にて確認した。
(Corrosion resistance)
Electro-galvanized steel sheet (trade name: non-chromate treatment unijing, Taiho) whose surface was degreased in advance with isopropanol from the aqueous resin compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 3 Co., Ltd.) was applied so as to have a dry film thickness of 3 μm, and baked at 80 ° C. for 30 seconds to prepare a test piece for corrosion resistance evaluation.
Each test piece was sprayed with 5% by weight saline at 35 ° C. for 72 hours, and the presence or absence of white rust was visually confirmed.
（配合安定性）
実施例１から１５で得られた水性樹脂組成物および比較例１および３で得られた水性樹脂組成物をそれぞれ５０重量部と、比較例２で得られた不飽和重合性モノマー重合体水性分散体５０重量部を混合した。
混合後１時間経過した時の混合液の状態を目視にて観察して、凝集物の有無を確認した。
(Compounding stability)
50 parts by weight of the aqueous resin composition obtained in Examples 1 to 15 and the aqueous resin composition obtained in Comparative Examples 1 and 3, respectively, and the aqueous dispersion of unsaturated polymerizable monomer polymer obtained in Comparative Example 2 50 parts by weight of the body was mixed.
The state of the liquid mixture when 1 hour passed after mixing was visually observed to confirm the presence or absence of aggregates.
それぞれの結果を表１に示した。 The results are shown in Table 1.
結果より、各実施例の水性樹脂組成物は、比較例１および３に比べて、濁り、変色もなく、且つ皮膜物性や耐食性にも優れていると同時に、不飽和重合性モノマー重合体水性分散体との混合時における配合安定性も優れていることが明らかである。比較例２については皮膜が形成できなかった。 From the results, the aqueous resin compositions of the respective examples were less turbid and discolored than Comparative Examples 1 and 3, and were excellent in film physical properties and corrosion resistance, and at the same time, an unsaturated polymerizable monomer polymer aqueous dispersion. It is clear that the compounding stability at the time of mixing with the body is also excellent. In Comparative Example 2, no film could be formed.
Claims (4)
前記カチオン性基含有イソシアネート基末端ウレタンプレポリマー（ｂ）を水及び／又はポリアミンで鎖伸長することによりカチオン性基含有ポリウレタン樹脂（Ｂ）を乳化する工程と、
前記不飽和重合性モノマー（ａ）を重合して不飽和重合性モノマー重合体（Ａ）を生成する工程とを含むことを特徴とする水性樹脂組成物の製造方法。 Dispersing a solution containing the unsaturated polymerizable monomer (a) and the cationic group-containing isocyanate group-terminated urethane prepolymer (b) in water;
Emulsifying the cationic group-containing polyurethane resin (B) by chain-extending the cationic group-containing isocyanate group-terminated urethane prepolymer (b) with water and / or a polyamine; and
A method for producing an unsaturated polymerizable monomer polymer (A) by polymerizing the unsaturated polymerizable monomer (a).
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