WO1998023681A1 - Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom - Google Patents
Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom Download PDFInfo
- Publication number
- WO1998023681A1 WO1998023681A1 PCT/US1997/020543 US9720543W WO9823681A1 WO 1998023681 A1 WO1998023681 A1 WO 1998023681A1 US 9720543 W US9720543 W US 9720543W WO 9823681 A1 WO9823681 A1 WO 9823681A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- epoxy
- polyol
- self
- epoxy resin
- Prior art date
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 124
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 239000006185 dispersion Substances 0.000 title claims abstract description 56
- 239000008199 coating composition Substances 0.000 title claims abstract description 15
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 title description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 49
- -1 aliphatic alcohols Chemical class 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 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 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000002118 epoxides Chemical group 0.000 claims description 23
- 229920003986 novolac Polymers 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003085 diluting agent Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 239000006184 cosolvent Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 31
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 150000002989 phenols Chemical class 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 229920000768 polyamine Polymers 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 229920003180 amino resin Polymers 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 125000000466 oxiranyl group Chemical group 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 239000004533 oil dispersion Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 235000019693 cherries Nutrition 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
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- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
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- CMHRXXDBSMGASP-UHFFFAOYSA-N 1-dodecoxydodecane;potassium Chemical compound [K].CCCCCCCCCCCCOCCCCCCCCCCCC CMHRXXDBSMGASP-UHFFFAOYSA-N 0.000 description 1
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
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- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004089 sulfido group Chemical group [S-]* 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
Definitions
- the present invention relates to coating compositions made from aqueous epoxy dispersions. More specifically, this invention relates to self-
- Epoxy resins have long been in widespread use as components in coating compositions. Coatings which comprise cured epoxy resins are
- epoxy resins which may be applied to a substrate with either minimal or no release of volatile organic components.
- This invention relates to a method of preparing a self-dispersing epoxy
- resin composition comprising reacting a polyepoxide with a polyoxyalkylene polyol wherein the equivalent ratio of epoxide groups of said polyepoxide to hydroxyl groups of said polyoxyalkylene polyol is greater than 10: 1 , to form
- the self-dispersing epoxy resin of the invention forms an aqueous
- films of the self-dispersing curable epoxy resin are useful as a coating composition.
- the self-dispersing curable epoxy resin formulation of the invention is prepared by first reacting a polyepoxide with a polyoxyalkylene polyol.
- the ratio of epoxide groups of said polyepoxide to hydroxyl groups of said polyoxyalkylene polyol is greater than 10: 1 , typically from about 1 1 : 1 to about 50: 1 , more typically from about 1 5: 1 to about 25: 1 .
- the reaction should be conducted under conditions which promote substantial completion of the reaction as evidenced by consumption of the polyoxyalkylene polyol, but which typically is incomplete with respect to the consumption of the
- polyepoxide typically, at the termination of the reaction, at least about 1 50% of the equivalents of epoxy groups based on the equivalents of the hydroxyl groups initially present in the polyoxyalkylene polyol will have
- the polyoxyalkylene polyol reactant comprises one or more polyol compounds where the polyol compound comprises both at least 2 hydroxyl
- the polyol will typically be a mixture of compounds and should have an average
- the polyol will typically have a molecular weight of from about 200 to about 20,000, more typically from about 1 ,000 to about
- the polyoxyalkylene polyol reactant is soluble or at least partially
- molecular weight (e.g. weight average) ranges from about 4,000 to about
- ethylene oxide ranges from about 60% to about 90%, more typically from about 65 % to about 85% . These copolymers are described in the Encyclopedia of Polvmer Science and Engineering, vol. 6, pp. 254-259 (John
- preferred polyoxyalkylene polyols are block copolymers of propylene oxide and ethylene oxide having from about 75% to about 85% polyoxyethylene
- suitable polyoxyalkylene polyol reactants include reacting a hydroxyl group containing initiator, e.g. water, or a diol,
- the Polyepoxide reactant comprises one or more compounds each
- the polyepoxide reactant has an average of about 2 epoxide groups present in the molecule, e.g. an average epoxy functionality of from about 1 .5 to about 2.5, more typically from about 1 .8 to about 2.2.
- polyepoxides are comprised of one or more polyglycidyl ethers of polyhydric phenols having two (2) or more epoxide groups and one (1 ) or more six-carbon aromatized rings present in the molecule.
- Techniques to prepare such epoxy resins are known in the art, and include reacting compounds having 2 or more hydroxyl groups with epichlorohydrin in the presence of a suitable catalyst. Suitable epoxy resins
- EPON (Reg.
- aromatic polycarboxylic acids which may be used include, for example, phthaiic acid, isophthalic acid or terephthalic acid.
- the epoxy compounds of this type may be derived from mononuclear phenols, such as, for example, resorcinol or hydroquinone; or they are based on polynuclear phenols, such as, for example, bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone, 1 , 1 ,2,2-tetrakis(4- hydroxyphenyDethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-
- dibromo-4-hydroxyphenyl propane and from novolacs obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or
- furfuraldehyde with phenols, such as phenol, or with phenols that are substituted in the nucleus by halide atoms or C,-C 18 (preferably C ⁇ C 9 ) alkyl groups, such as, for example, 4-chlorophenol, 2-methylphenol or 4-tert- butylphenol, or by condensation with bisphenols, in the manner described
- epoxy resins that have an epoxy content of from 2 to 10 equivalents/mole and that are giycidyl ethers or glycidyl esters of aromatic or alkylaromatic compounds. Especially preferred epoxy resins
- polyglycidyl ethers of bisphenols such as, for example, of 2,2-bis(4- hydroxyphenyUpropane (bisphenol A) or bis(4-hydroxyphenyl)methane
- epoxy resins are polyglycidyl ethers based on bisphenol A.
- Preferred epoxy resins are liquids at room temperature and typically
- epoxide equivalent weight of less than about 400 grams/equivalent, e.g. from about 100 grams/equivalent to about 350 grams/equivalent, more
- the polyhydric phenol reactant comprises one or more compounds
- the polyhydric phenol reactant may contain substituents such as alkyl, aryl, sulfido, sulfonyl, halo, and the like.
- the polyhydric phenol is represented by the structural formula:
- R 9 represents an 'h' valent C 6 -C 50 organic radical comprising at least one six-carbon aromatized ring, and 'h' represents a number of phenolic
- Suitable polyhydric phenol compounds are commercially available from Dow Chemical Company, Midland, Michigan, and Shell
- Suitable polyhydric phenols are 2,2-bis(4- hydroxyphenyDpropane, 2,2-bis(3-bromo-4-hydroxyphenyl)-propane, 2,2-
- dihydric phenols are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and bis(4-hydroxyphenyl)methane (bisphenol F) for reasons of cost and
- an alkyl-phenol-formaldehyde novolac resin is also used in a small amount, e.g. from about 0.015 to about 0.060 moles, more typically from about 0.025 moles to about 0.040 moles, per mole of
- Alkyl- phenol-formaldehyde novolac resins are made from alkyl phenols and
- alkyl group contains 4 to 1 2 carbon atoms.
- alkyl phenols include tertiary-butyl phenol, hexyl phenol, octyl phenol, nonyl phenol and dodecyl phenol.
- a preferred alkyl phenol is nonyl phenol.
- Novolac resins are made by reacting the phenol with formaldehyde under acid conditions. In novolac resins the phenol moieties are linked together
- Novolac resins contain no reactive methylol groups.
- Novolac resins useful in this invention have molecular weights within the range of about 1000 to about 5000 and melting points of about 50° to
- the preparation of the self-dispersing curable epoxy resins of the invention proceed through a polyol-epoxy adduct, where the polyol-epoxy
- adduct is subsequently reacted with a polyhydric phenol and an epoxy resin.
- the polyol-epoxy adduct is prepared by condensation of the
- polyoxyalkylene polyols mentioned with the polyepoxy compound in the presence of suitable catalysts typically at 50° to 250°C, preferably at 90° to 200°C, the equivalent ratio of the epoxy groups to the OH groups being
- polyol-epoxy adduct is meant the mixture that results from the condensation reaction.
- Suitable catalysts for preparing the dispersing agent are strong
- inorganic and organic bases such as, for example, sodium hydroxide,
- potassium hydroxide lithium hydroxide, barium hydroxide, strontium hydroxide, alkali metal alcholates, such as sodium methoxide, lithium methoxide, sodium ethoxide and potassium dodecyloxide, and the alkali metal salts of carboxylic acids, such as, for example, sodium stearate and
- lithium stearate strong inorganic and organic protic acids, for example phosphoric acid, tetrafluoroboric acid and benzenesulfonic acid, are also suitable.
- the catalysts used can be Lewis acids. Examples include tin(IV) chloride, titanium(IV) chloride, titanium(IV) isopropoxide,
- Catalysts which are preferably used are boron trifluoride-diethyl ether, boron trifluoride-amine complexes and aqueous tetrafluoroboric acid.
- the amount of catalyst is in general 0.1 to 5, preferably 0.1 to 1 % by weight, relative to the reaction mixture.
- the catalyst can be diluted in a solvent, such as diethyl ether, a glycol ether or cyclic ether, ketones, and the like.
- the mixtures of hydroxyl- and epoxy-containing compounds to be reacted are heated to the temperature at which condensation proceeds at a sufficient rate, e.g., within about 30
- reaction is monitored by the increase of the epoxy equivalent, which indicates a decrease in the epoxy group content.
- the reaction can be stopped by cooling below the reaction
- the structure of the polyol-epoxy adduct is dependant on the
- polyoxyalkylene polyol reacts with an epoxy group of the polyepoxide.
- reaction creates an intermediate that has a hydroxyl functionality as a result of the opening of the oxirane ring of the epoxy group of the polyepoxide that reacted with the hydroxyl group of the polyoxyalkylene polyol.
- polyepoxide has additional epoxy functionality
- the intermediate will also have at least one residual epoxy functionality for each of the hydroxyl
- the hydroxyl groups of the intermediate can then react with the oxirane ring of an additional polyepoxide and will most probably do so because of the high ratio of polyepoxide to polyoxyalkylene polyol.
- This resulting intermediate will also have a new hydroxyl group because of the opening of the oxirane ring of the additional molecule of polyepoxide which
- the resulting second intermediate will be a diol which also has four epoxide groups. If each of the hydroxyl groups of this second intermediate diol reacts with a diepoxide molecule, the
- polyol-epoxy adduct of this invention will have a high epoxy functionality, typically the average epoxy functionality of the adduct will be
- the Self-Dispersing Curable Epoxy Resin may be prepared by reacting a polyol-epoxy adduct with a polyhydric phenol and an epoxy resin, which epoxy resin may be the same or different from the polyepoxide used to form the polyol-epoxy adduct.
- an epoxy resin which epoxy resin may be the same or different from the polyepoxide used to form the polyol-epoxy adduct.
- polyepoxides is descriptive of the epoxy resins which are useful herein for preparing the self-dispersing epoxy resin.
- relative proportions of the reactants may vary broadly, but the epoxy resin is used in a stoichiometric excess to the polyhydric phenol. Typically, for each equivalent of epoxy resin, there will be from about 0.01 to 1 .0 reactive equivalents, preferably from about 0.4 to 0.6 reactive equivalents of a
- epoxy resin will be preferably from about 1 to 25, typically from about 1 .5 to 20 and more typically from about 2 to 1 5 weight percent of the self- dispersible resin.
- the self-dispersing epoxy resin is typically prepared by
- epoxy equivalent weight is obtained, e.g. from about 500 to about 700 g/eq., typically for about one hour and then cooled to about 1 20°C, whereupon a small amount of a water-soluble organic solvent is added prior
- the epoxy resin will be further comprised of a minor amount, on both a weight and equivalents basis as a percentage of the epoxy resin, of an epoxy novolac resin.
- the amount of the epoxy is not limited to a minor amount, on both a weight and equivalents basis as a percentage of the epoxy resin, of an epoxy novolac resin.
- novolac resin will typically be from about 0.01 5 to about 0.060 mole per mole of the polyepoxide, more typically from about 0.025 to about 0.040 mole per mole of the polyepoxide.
- An example of such an epoxy novolac resin will typically be from about 0.01 5 to about 0.060 mole per mole of the polyepoxide, more typically from about 0.025 to about 0.040 mole per mole of the polyepoxide.
- DEN 438 and 438 from Dow Chemical, which are a phenol- formaldehyde epoxy novolac with a nominal epoxy functionality of about 3.6
- the self-dispersing curable epoxy resin of the present invention may be any one of the present invention.
- organic cosolvents include the alkyl ethers of monohydric
- alkyl group comprises C r C 8 linear or branched aliphatic or alicyclic chains.
- cosolvent can affect the
- pot-life of the self-dispersing curable epoxy resin For example, for a given resin it may be possible to increase the pot-life by substituting for a cosolvent such as Ektasolve EP (Eastman Chemicals) with one of the cosolvent
- the preferred stable aqueous epoxy resin dispersions of the present invention are those which contain a monoepoxide reactive diluent, e.g. a
- the monoepoxide component can contain alicyclic and aromatic structures, as well as halogen,
- unsaturated hydrocarbons such as decene and cyclohexene; glycidyl ethers
- glycidyl esters of monocarboxylic acids such as hexanoic acid; acetals of glycidaldehyde; and the like.
- the preferred reactive diluent is glycidyl ether of monohydric C 8 -C 10 aliphatic alcohols.
- the resin dispersion has significant beneficial effects in addition to modifying the viscosity of the dispersion.
- the said water-immiscible reactive diluent appears to coat the particles of epoxy resin solids and thereby provide the aqueous dispersion with improved shear, freeze-thaw resistance,
- epoxide diluent in said aqueous dispersion may be sufficient to increase the pot- life of a coating composition prepared from said aqueous dispersion.
- the monoepoxide reactive diluent will be present in an amount of about 0.1 % to about 10%, more typically about 0.5% to about 7.5%, and most
- the reactive diluent is epoxy functional, it becomes chemically bonded into the film which is formed during the subsequent room
- reactive diluent contributes to the calculated proportion of non-volatiles in the dispersion composition.
- a multi-functional-epoxide can be present in the aqueous dispersion
- the amount of the multi-functional- epoxide will typically range from about 1 % to about 10%, more typically from about 2% to about 8%, by weight of the self-dispersing resin.
- epoxy novolac resins e.g. DEN 438 and 439 from Dow Chemical, which are a phenol-
- the aqueous epoxy dispersion of the invention is prepared by charging the self-dispersing curable epoxy resin to a reaction vessel, then heating the resin to about 50-100°C with stirring. Water is gradually added to the self- dispersing curable epoxy resin while the temperature is allowed to drop to about 50°C. During this period, the water in oil dispersion is formed and then inverts to an oil in water dispersion. After inversion, additional water
- the particle size of the oil phase in the aqueous dispersion can be modified by physical techniques to reduce the particle size.
- the particle size reduction is preferably accomplished by subjecting an aqueous dispersion of
- aqueous dispersion of self-dispersing resin will typically exhibit excellent chemical and physical stability over an extended shelf-life, e.g. of
- Epoxide equivalent weight can be determined by differential titration with perchloric acid using crystal violet as
- the resin should not display layer formation for a period of at least one month from the preparation of the
- aqueous dispersion i.e. there should be no formation of a macro-observable water phase as a layer separate from the dispersed resin phase.
- Coating Compositions Comprising an Aqueous Dispersion of the Self-
- the coating composition of the invention is prepared by combining the aqueous epoxy dispersion with a suitable hardening agent.
- the coatings are tack free after 45 minutes and have excellent film properties.
- An aqueous epoxy resin paint composition of the present invention may further contain additives conventionally employed in coating technology, such as organic
- pigments inorganic pigments, surfactants, thickeners, and the like.
- a room temperature curable water-borne coating composition is prepared by admixing a stable epoxy dispersion composition as described above with an epoxy-interacting curing vehicle, such as a polyamine curing agent.
- an epoxy-interacting curing vehicle such as a polyamine curing agent.
- admixture is in the range of from 0.5:1 to 2: 1 and, preferably, is in the range between about 0.8:1 to 1 .5:1.
- the amino hydrogens must be sufficiently reactive to effect crosslinking interaction with the epoxy groups at ambient temperatures.
- Suitable polyamine curing agents are those which are soluble or
- curing agents dispersible in water and which contain more than 2 active hydrogen atoms per molecule.
- curing agents are alkylene polyamines
- alkylene polyamines include ethylene diamine, diethylene triamine,
- polyamido amines which are reaction products of alkylene polyamines and fatty acids.
- polyamidoamines are well known in the art and are described in U.S. Pat. Nos. 2,705,223, 2,81 1 ,495 and 2,899,397, which patents are hereby incorporated by reference.
- Other polyamidoamines are well known in the art and are described in U.S. Pat. Nos. 2,705,223, 2,81 1 ,495 and 2,899,397, which patents are hereby incorporated by reference.
- polyamine curing agents are the adducts of polyamines and epoxy compounds such as those described in U.S. Pat. Nos. 2,651 ,589,
- Examples of useful curing agents also include those disclosed in U.S. patent application Serial No. 08/085,861 , filed June 30, 1 993, entitled
- epoxy curing agents comprise the reaction product of reactants consisting essentially of an alkylene polyamine having less than about 12 carbon atoms, an aromatic mono-glycidyl ether having less than about 18 carbon atoms, and a diglycidyl ether of an aromatic diol having an average degree of
- said aromatic glycidyl ether and said diglycidyl ether of an aromatic diol is not essentially less than one, and the ratio of epoxide equivalents of said aromatic mono-glycidyl ether to epoxide equivalents of said diglycidyl ether
- a curing accelerator in addition to the amine curing agent, can be any curing accelerator.
- Such an accelerator will serve to stabilize the coating composition.
- Useful accelerators for amine curing agents include tertiary amines, e.g. N,N'-bis(dimethyl-amino-
- Suitable aminoplast resins are the reaction products of ureas and melamines with aldehydes further etherified in some cases with
- aminoplast resin components are urea, ethylene
- aminoplast resins include formaldehyde, acetaldehyde and propionaldehyde.
- the aminoplast resins can be used in the alkylol form but, preferably, are utilized in the ether
- etherifying agent is a monohydric alcohol containing from 1 to 8 carbon atoms.
- suitable aminoplast resins are methylol urea, dimethoxymethylol urea, butylated polymeric urea-formaldehyde resins,
- Phenolplast resins are the reaction products of phenols and aldehydes which contain reactive methylol groups. These compositions can be monomeric or polymeric in nature depending on the molar ratio of phenol to
- aldehyde used in the initial condensation reaction examples include phenol, o, m or p-cresol, 2,4-xylenol, 3,4-xylenol, 2,5-xylenol,
- Useful aldehydes are formaldehyde, acetaldehyde and propionaldehyde.
- Particularly useful phenolplast resins are polymethylol phenols wherein the phenolic group is
- curing agents may also be useful, e.g. catalytic curing agents: Lewis bases (such as tertiary amines), Lewis acids (such as boron trifluoride), cationic curing agents (such as aryldiazonium salts, diaryliodinium salts, onium salts of Group Via elements, especially sulfur) and reactive curing agents:
- Lewis bases such as tertiary amines
- Lewis acids such as boron trifluoride
- cationic curing agents such as aryldiazonium salts, diaryliodinium salts, onium salts of Group Via elements, especially sulfur
- reactive curing agents such as aryldiazonium salts, diaryliodinium salts, onium salts of Group Via elements, especially sulfur
- a suitable laboratory apparatus consists of a reaction kettle, an electrical stirrer, a condenser, means for application of vacuum and inert atmosphere, heating mantle and means to control temperature.
- a general procedure used for the preparation of epoxy-polyols consisted of addition of polyoxyalkylene glycol (polyol) and the diglycidyl ether of bis-phenol A (liquid epoxy resin, LER) to the reaction kettle. The mixture was heated with stirring to 100°C under a nitrogen atmosphere. When reaction temperature reached 100°C, flow of nitrogen was discontinued and vacuum to 100-500 mbar was applied. The reaction vessel was held under vacuum for 10-15 minutes and then nitrogen atmosphere was reapplied. Catalyst was added and the reaction mixture heated to 180°C.
- EPON 828 Shell Chemical Company, Houston, TX.
- a suitable laboratory apparatus for the preparation of epoxy resins consists of a reaction kettle, an electrical stirrer, a condenser, means for application of inert atmosphere, heating mantle and means to control temperature, and fluid metering pumps.
- a general procedure used for the preparation of self-dispersing resin was by melting the epoxy-polyol (as is from Example 1-4) by heating in an oven kept at 80 ⁇ 20°C and then charge to the reactor.
- a liquid epoxy resin D.E.R.
- reaction mixture After completion of reaction as judged by determination of epoxy content the reaction mixture was cooled to 120°C and 2-propoxyethanol was added over 30-45 minutes with a fluid metering pump. The reaction mixture was then cooled to 95 °C and the first portion of deionized water was added over 20- 30 minutes with a fluid metering pump. This gave a water-in-oil dispersion which was cooled with good agitation to 45-60°C so that the water-in-oil dispersion inverted to an oil-in-water dispersion. A reactive diluent such as ERISYS GE-7 (CVC Specialty Chemicals, Cherry Hill, NJ) was added followed by addition of the second portion of water.
- ERISYS GE-7 CVC Specialty Chemicals, Cherry Hill, NJ
- the dispersion of epoxy resin obtained in this manner was heated to 60-75°C, mixed to attain a homogeneous dispersion, cooled to 35-45°C and discharged.
- Composition of the dispersions made according to this same or a similar general procedure are given in Table 2. Characteristics of dispersions were obtained as described below and are reported in Table 3. Particle size was determined by a Microtrac II model 7997- 10 & 20, mean value given in Table 3. Viscosity determined by a Brookfield model DVII+ viscometer. Solids were determined by heating about one gram of the sample in oven maintained at 150°C for one hour. Molecular weight was determined by Size Exclusion Chromatography using Phenogel columns calibrated with narrow molecular weight distribution standards. Table 2
- Example Composition weight %
- Example 2 Table 1. 5. With SP 1090 (nonylphenol novolac resin, Schenectady Chemicals, Inc., Schenectady, NY) added prior to molecular weight advancement.
- SP 1090 nonylphenol novolac resin, Schenectady Chemicals, Inc., Schenectady, NY
- Example 8 620 1.1 2,050 53.5 4,290 1,460 2.94
- Example 9 610 0.8 8,620 53.4 5,450 1,550 3.51
- Example 10 610 1.9 93,100 54.2 5,870 1 ,440 4.07
- a general procedure used for the preparation of coatings was by combining epoxy resin dispersions with EPI-CURE 8290 curing agent (Shell Chemical Co., Houston, TX) at 1:1 equivalent ratio and drawing down with wire-wound bar over metal panels.
- Formula of a red-oxide primer used for this purpose is given in Table 4.
- Coatings were baked at 82 °C and then evaluated for solvent resistance with methyl ethyl ketone (MEK). Solvent resistance was measured 1 and 24 hours after baking of coatings. Results for coatings made in accordance with the same or a similar general procedure are given in Table 5.
- Curing agent used was Epi-Cure (Reg TM) 8290-Y-60 available from Shell Chemical Company.
- Example 5 135 239 154 305
- Epoxy Resin MEK double rubs after 30 mm
- Sample ID MEK double rubs for coatings baked for 30 min @ 82°C
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CA002270965A CA2270965A1 (en) | 1996-11-26 | 1997-11-19 | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
AU74047/98A AU7404798A (en) | 1996-11-26 | 1997-11-19 | Self-dispersing curable epoxy resins, dispersions made therewith, and coat ing compositions made therefrom |
DE69728555T DE69728555T2 (en) | 1996-11-26 | 1997-11-19 | SELF-DISPERSING HARDENABLE EPOXY RESINS, DISPERSIONES AND COATING COMPOSITIONS THEREWITH MAKED |
EP97949396A EP0941286B1 (en) | 1996-11-26 | 1997-11-19 | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/757,030 | 1996-11-26 | ||
US08/757,030 US5719210A (en) | 1996-11-26 | 1996-11-26 | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
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WO1998023681A1 true WO1998023681A1 (en) | 1998-06-04 |
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PCT/US1997/020543 WO1998023681A1 (en) | 1996-11-26 | 1997-11-19 | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
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US (1) | US5719210A (en) |
EP (1) | EP0941286B1 (en) |
AU (1) | AU7404798A (en) |
CA (1) | CA2270965A1 (en) |
DE (1) | DE69728555T2 (en) |
WO (1) | WO1998023681A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19848113C2 (en) * | 1998-10-19 | 2001-08-02 | Ulf Pruemmer Polymer Chemie Gm | Hardening agent for aqueous epoxy resin dispersions |
US6344152B2 (en) | 1999-06-11 | 2002-02-05 | Prc-Desoto International, Inc. | Derivatives of cycloaliphatic diamines as cosolvents for aqueous hydrophobic amines |
US20020094945A1 (en) * | 2000-12-18 | 2002-07-18 | Gross Stephen F. | Reaction products of alkoxylated compounds and polyepoxides |
US20040204551A1 (en) * | 2003-03-04 | 2004-10-14 | L&L Products, Inc. | Epoxy/elastomer adduct, method of forming same and materials and articles formed therewith |
US8283403B2 (en) | 2006-03-31 | 2012-10-09 | Applied Nanotech Holdings, Inc. | Carbon nanotube-reinforced nanocomposites |
US8129463B2 (en) | 2006-03-31 | 2012-03-06 | Applied Nanotech Holdings, Inc. | Carbon nanotube-reinforced nanocomposites |
US8445587B2 (en) | 2006-04-05 | 2013-05-21 | Applied Nanotech Holdings, Inc. | Method for making reinforced polymer matrix composites |
WO2009036790A1 (en) * | 2007-09-21 | 2009-03-26 | Henkel Ag & Co. Kgaa | Primer compositions for adhesive bonding systems and coatings |
ES2379739T3 (en) | 2008-04-05 | 2012-05-03 | Cognis Ip Management Gmbh | Emulsifiers for epoxy resins |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE498918A (en) * | 1949-10-25 | 1900-01-01 | ||
BE518342A (en) * | 1952-03-11 | 1900-01-01 | ||
US2811495A (en) * | 1952-06-20 | 1957-10-29 | Gen Mills Inc | Mixed suspensoids of epoxy resins and polyamide resins |
NL210722A (en) * | 1955-09-20 | |||
LU37345A1 (en) * | 1959-06-30 | 1900-01-01 | ||
NL302868A (en) * | 1963-03-21 | |||
US3301804A (en) * | 1963-09-30 | 1967-01-31 | Koppers Co Inc | Aqueous emulsion comprising reaction product of liquid epoxy resin and amino boric acid ester |
US3366600A (en) * | 1964-06-02 | 1968-01-30 | Grace W R & Co | Process for preparing amine-phenol curing agent epoxy resin compositions |
NL137295C (en) * | 1965-11-03 | |||
CH470344A (en) * | 1966-12-02 | 1969-03-31 | Ciba Geigy | Process for the production of new adducts from polypoxides and polyamines |
US3515698A (en) * | 1967-05-24 | 1970-06-02 | Hercules Inc | High molecular weight polymers containing the reaction product of an aliphatic amine and a mono- or dioxirane as antistatic agent |
US3634348A (en) * | 1969-05-09 | 1972-01-11 | Shell Oil Co | Electrodepositable phosphate ester-polyepoxide emulsions |
US3639344A (en) * | 1969-08-21 | 1972-02-01 | Sika Chemical Corp | Coating compositions comprising an epoxy resin and aliphatic amine reaction products |
US3799854A (en) * | 1970-06-19 | 1974-03-26 | Ppg Industries Inc | Method of electrodepositing cationic compositions |
US3931109A (en) * | 1972-03-13 | 1976-01-06 | The Dow Chemical Company | Process for coating substrates with high molecular weight epoxy resins |
CH598404B5 (en) * | 1975-04-04 | 1978-04-28 | Ciba Geigy Ag | |
US4033917A (en) * | 1975-05-12 | 1977-07-05 | Desoto, Inc. | Electrodeposition of aqueous dispersions of copolymers of polyethylenically unsaturated epoxy-amine adducts |
US4177177A (en) * | 1976-03-26 | 1979-12-04 | El Aasser Mohamed S | Polymer emulsification process |
US4105634A (en) * | 1976-08-11 | 1978-08-08 | Celanese Corporation | Production of thermosetting resinous polyepoxides |
US4093594A (en) * | 1976-08-18 | 1978-06-06 | Celanese Polymer Specialties Company | Process for preparing cathodically depositable coating compositions |
BE857754A (en) * | 1976-08-18 | 1978-02-13 | Celanese Polymer Special Co | COMPOSITION OF RESIN FOR COATINGS, ESPECIALLY BY CATHODIC ELECTRODEPOSITION |
US4113684A (en) * | 1976-12-10 | 1978-09-12 | Westinghouse Electric Corp. | Low temperature cure epoxy-amine adhesive compositions |
US4197389A (en) * | 1977-07-18 | 1980-04-08 | Hoechst Aktiengesellschaft | Hardening agent for aqueous epoxy resin compositions |
US4182831A (en) * | 1977-12-07 | 1980-01-08 | Celanese Polymer Specialties Company | Cationic epoxide resinous composition |
US4246148A (en) * | 1979-08-27 | 1981-01-20 | Celanese Corporation | Two component aqueous coating composition based on an epoxy-polyamine adduct and a polyepoxide |
US4315044A (en) * | 1980-11-05 | 1982-02-09 | Celanese Corporation | Stable aqueous epoxy dispersions |
US4533254A (en) * | 1981-04-17 | 1985-08-06 | Biotechnology Development Corporation | Apparatus for forming emulsions |
US4423166A (en) * | 1981-07-20 | 1983-12-27 | Ppg Industries, Inc. | Ungelled polyepoxide-polyoxyalkylenepolyamine resins, aqueous dispersions thereof, and their use in cationic electrodeposition |
US4420574A (en) * | 1981-07-20 | 1983-12-13 | Ppg Industries, Inc. | Ungelled polyepoxide-polyoxyalkylenepolyamine resins, aqueous dispersions thereof, and their use in cationic electrodeposition |
DE3147458A1 (en) * | 1981-12-01 | 1983-07-14 | Hoechst Ag, 6230 Frankfurt | STABLE AQUEOUS EPOXY RESIN DISPERSION, METHOD FOR THE PRODUCTION AND USE THEREOF |
US4522851A (en) * | 1982-09-30 | 1985-06-11 | Mobay Chemical Corporation | Process for coating aqueous dispersion of epoxy resin and blocked polyisocyanate containing chemically incorporated anionic hydrophilic groups |
US4423170A (en) * | 1982-10-15 | 1983-12-27 | Texaco Inc. | One component water reduced epoxy adhesives |
US4420606A (en) * | 1982-10-15 | 1983-12-13 | Texaco Inc. | One component water reduced epoxy adhesives |
US4421906A (en) * | 1982-10-15 | 1983-12-20 | Texaco Inc. | Water-based epoxy resin coating composition |
GB8329881D0 (en) * | 1983-11-09 | 1983-12-14 | Shell Int Research | Preparation of binders for coatings |
JPS60181349A (en) * | 1984-02-24 | 1985-09-17 | 津田駒工業株式会社 | Wind-up control apparatus of loom |
GB8409670D0 (en) * | 1984-04-13 | 1984-05-23 | Dow Chemical Rheinwerk Gmbh | Coating |
GB2173802B (en) * | 1985-04-18 | 1989-12-28 | Ici Plc | Non-gelled amine-epoxide reaction products and coating compositions comprising acid salts thereof |
US4608406A (en) * | 1985-04-18 | 1986-08-26 | Celanese Corporation | Stable aqueous epoxy resin dispersions |
US4608405A (en) * | 1985-05-06 | 1986-08-26 | Celanese Corporation | Aqueous based epoxy resin curing agents |
DE3518732A1 (en) * | 1985-05-24 | 1986-11-27 | BASF Lacke + Farben AG, 4400 Münster | WATER-DISCOVERABLE BINDING AGENTS FOR CATIONIC ELECTRO-DIP COATINGS AND METHOD FOR THEIR PRODUCTION |
US4728384A (en) * | 1986-06-23 | 1988-03-01 | Ashland Oil, Inc. | Two component epoxy structural adhesives with improved flexibility |
US4769438A (en) * | 1987-06-29 | 1988-09-06 | Texaco Inc. | Aminated propoxylated 1,4-butanediol epoxy resin adducts as epoxy resin curatives |
CA1336029C (en) * | 1987-11-06 | 1995-06-20 | Michiharu Kitabatake | Coating resin composition containing an epoxy-polyamine resin |
US4835225A (en) * | 1988-01-13 | 1989-05-30 | The Dow Chemical Company | Modified advanced epoxy resins |
US4810535A (en) * | 1988-02-01 | 1989-03-07 | Ppg Industries, Inc. | Glycidol-modified polyepoxide-polyoxyalkylenepolyamine adducts |
AT391140B (en) * | 1988-08-18 | 1990-08-27 | Vianova Kunstharz Ag | METHOD FOR THE PRODUCTION OF CATHODICALLY DEPOSITABLE VARNISH BINDING AGENTS AND THE USE THEREOF |
US4886867A (en) * | 1988-11-14 | 1989-12-12 | Texaco Chemical Company | Novel compositions from polyoxyalkylene amines and epoxides |
US5059293A (en) * | 1988-12-13 | 1991-10-22 | Kansai Paint Co., Ltd. | Coating resin composition |
US5221700A (en) * | 1988-12-22 | 1993-06-22 | Basf Corporation | Pigment grind resin comprising the reaction product of epoxide resin, amine and monoepoxide |
DE3908085A1 (en) * | 1989-03-13 | 1990-09-20 | Ruetgerswerke Ag | CURING AGENT FOR EPOXY COMPOUNDS, THEIR PRODUCTION AND USE |
DE3918511A1 (en) * | 1989-06-07 | 1990-12-13 | Basf Lacke & Farben | METHOD OF COATING ELECTRICALLY CONDUCTIVE SUBSTRATES, WAFERRING PAINT, METHOD FOR PRODUCING A CATIONIC AMIN MODIFIED EPOXY RESIN AND CATIONIC AMIN MODIFIED EPOXY RESIN PRODUCED BY THIS PROCESS |
GB9000564D0 (en) * | 1990-01-10 | 1990-03-14 | Dow Rheinmuenster | Modified polyoxyethlene epoxy resin amphiphiles and stable aqueous epoxy dispersions thereof |
US5057557A (en) * | 1990-05-11 | 1991-10-15 | The Dow Chemical Company | Modified epoxy resin compositions |
US5246984A (en) * | 1992-06-03 | 1993-09-21 | Air Products And Chemicals, Inc. | Water dispersible polyamine-epoxy adduct and epoxy coating composition |
US5583167A (en) * | 1993-06-30 | 1996-12-10 | Henkel Corporation | Curing agents for aqueous epoxy resins |
US5565505A (en) * | 1993-06-30 | 1996-10-15 | Henkel Corporation | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
US5565506A (en) * | 1994-03-01 | 1996-10-15 | Henkel Corporation | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
-
1996
- 1996-11-26 US US08/757,030 patent/US5719210A/en not_active Expired - Lifetime
-
1997
- 1997-11-19 DE DE69728555T patent/DE69728555T2/en not_active Expired - Lifetime
- 1997-11-19 AU AU74047/98A patent/AU7404798A/en not_active Abandoned
- 1997-11-19 EP EP97949396A patent/EP0941286B1/en not_active Expired - Lifetime
- 1997-11-19 CA CA002270965A patent/CA2270965A1/en not_active Abandoned
- 1997-11-19 WO PCT/US1997/020543 patent/WO1998023681A1/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
DATABASE WPI WORLD PATENT INF 1 January 1900 (1900-01-01), "Prodn. of hydroxy- or epoxy-terminated material - comprises reacting di:epoxide with di:hydroxy cpd. using triplate salt catalyst", XP002905654, Database accession no. 1992-227503 * |
Also Published As
Publication number | Publication date |
---|---|
EP0941286A1 (en) | 1999-09-15 |
EP0941286B1 (en) | 2004-04-07 |
US5719210A (en) | 1998-02-17 |
CA2270965A1 (en) | 1998-06-04 |
EP0941286A4 (en) | 2001-10-04 |
DE69728555D1 (en) | 2004-05-13 |
AU7404798A (en) | 1998-06-22 |
DE69728555T2 (en) | 2005-03-24 |
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