EP0447428B1 - Verfahren zur herstellung eines mehrschichtigen überzuges, wasserverdünnbare beschichtungszusammensetzungen, wasserverdünnbare emulsionspolymere und verfahren zur herstellung von wasserverdünnbaren emulsionspolymeren - Google Patents
Verfahren zur herstellung eines mehrschichtigen überzuges, wasserverdünnbare beschichtungszusammensetzungen, wasserverdünnbare emulsionspolymere und verfahren zur herstellung von wasserverdünnbaren emulsionspolymeren Download PDFInfo
- Publication number
- EP0447428B1 EP0447428B1 EP90900099A EP90900099A EP0447428B1 EP 0447428 B1 EP0447428 B1 EP 0447428B1 EP 90900099 A EP90900099 A EP 90900099A EP 90900099 A EP90900099 A EP 90900099A EP 0447428 B1 EP0447428 B1 EP 0447428B1
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- EP
- European Patent Office
- Prior art keywords
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- monomer
- monomers
- 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.)
- Expired - Lifetime
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- 239000004908 Emulsion polymer Substances 0.000 title claims abstract description 49
- 239000008199 coating composition Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 135
- 239000000203 mixture Substances 0.000 claims abstract description 126
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- 230000009477 glass transition Effects 0.000 claims abstract description 24
- -1 aliphatic ester Chemical class 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 30
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 29
- 239000003995 emulsifying agent Substances 0.000 claims description 27
- 150000002148 esters Chemical class 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- 239000000049 pigment Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 229920005749 polyurethane resin Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 37
- 239000002585 base Substances 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 31
- 239000002253 acid Substances 0.000 description 30
- 239000000839 emulsion Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 20
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 150000002009 diols Chemical class 0.000 description 16
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- 150000003077 polyols Chemical class 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 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 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000002596 lactones Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- OVLGNUHSJCCFPG-UHFFFAOYSA-N nonoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCOC1=CC=CC=C1 OVLGNUHSJCCFPG-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 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 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 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 4
- 238000003756 stirring Methods 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 229960002887 deanol Drugs 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
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- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 3
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- 238000003860 storage Methods 0.000 description 3
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- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
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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 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 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 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 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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- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2451/00—Type of carrier, type of coating (Multilayers)
Definitions
- the invention also relates to water-thinnable coating compositions, water-thinnable emulsion polymers and a process for the preparation of water-thinnable emulsion polymers.
- aqueous base coating compositions used are composed such that they can be applied to the substrate in relatively thin, fast-drying layers, in particular with the aid of automatic painting systems, and after carrying out process steps (3) and (4), the metal pigment particles in parallel alignment to the substrate surface.
- the aqueous base coating compositions must be composed in such a way that the base layer of the baked metal effect coating adheres well to the substrate and the transparent cover layer adheres well to the base layer. Furthermore, the aqueous base coating compositions must be composed in such a way that the baked-on metallic effect coating shows no matting, delamination phenomena or even bubbles after exposure to a constant temperature of condensed water.
- aqueous basecoat compositions exhibit high storage stability.
- DE-A-36 28 124 discloses aqueous base coating compositions which contain, as film-forming material, a mixture of a water-dilutable emulsification polymer and a water-dilutable polyurethane resin. These basecoat compositions do not optimally meet the requirements set out above.
- the object on which the present invention is based is to provide aqueous base coating compositions which are suitable for the process in question and which optimally meet the requirements set out above.
- aqueous coating compositions which can be used as wood lacquers and which contain a water-thinnable emulsion polymer which is free of hydroxyl groups and can be obtained via a two-stage emulsion polymerization process.
- U.S. Patent 4,150,005 discloses aqueous coating compositions containing a water-thinnable emulsion polymer which can be obtained by preparing a highly hydrophilic polymer with a low glass transition temperature in a first emulsion polymerization stage and in its presence in a second emulsion polymerization stage a hydrophobic polymer with a high glass transition temperature is produced.
- Multi-layer protective and / or decorative coatings of the type described above and the problems encountered in the manufacture of these coatings are not addressed in U.S. Patent No. 4,150,005.
- GB-A-2,034,334 describes aqueous coating compositions which contain a water-thinnable emulsion polymer which can be obtained via a two-stage emulsion polymerisation process and which must have N-methylol groups.
- GB-A-2,034,334 is not indicative of the fact that the two polymer stages have to differ in their glass transition temperatures in the manner according to the invention.
- Multilayer protective and / or decorative coatings of the type described above and the problems encountered in the manufacture of these coatings are not addressed in GB-A-2,034,334.
- EP-A-287 144 describes a process for producing a multilayer coating of the type described above, in which aqueous base coating compositions are used which contain a water-dilutable emulsification polymer which can be obtained via a two-stage emulsion polymerization process and which in the second stage ("shell" ) has a very high proportion of acid groups and in which the first and second polymer stages differ in their glass transition temperatures in such a way that the first stage has a lower glass transition temperature than the second stage.
- aqueous base coating compositions which contain a water-dilutable emulsification polymer which can be obtained via a two-stage emulsion polymerization process and which in the second stage (“shell" ) has a very high proportion of acid groups and in which the first and second polymer stages differ in their glass transition temperatures in such a way that the first stage has a lower glass transition temperature than the second stage.
- the water-dilutable emulsion polymers used according to the invention are, in a known manner, for example in a stirred tank, by a two-stage emulsion polymerization in an aqueous medium with heating and cooling device, producible.
- the monomers can be added in such a way that a solution of all of the water, the emulsifier and part of the initiator is introduced and the monomer or monomer mixture and separately therefrom, but in parallel the rest of the initiator is slowly added at the polymerization temperature.
- the water and the emulsifier it is also possible to introduce some of the water and the emulsifier and to prepare a pre-emulsion from the rest of the water and the emulsifier and from the monomer or monomer mixture, which is added slowly at the polymerization temperature, the initiator again being added separately. It is preferred in the first stage to add the monomer or monomer mixture in the form of a pre-emulsion and in the second stage to add the monomer or monomer mixture in bulk, ie without water and emulsifier, and to add the initiator separately but in parallel.
- the polymerization temperature is generally in the range from 20 to 100 ° C., preferably 40 to 90 ° C.
- the quantitative ratio between the monomers and the water can be selected so that the resulting dispersion has a solids content of 30 to 60% by weight, preferably 35 to 50% by weight.
- An anionic emulsifier is preferably used alone or in a mixture as the emulsifier.
- anionic emulsifiers are the alkali metal salts of sulfuric acid half-esters of alkylphenols or alcohols, furthermore the sulfuric acid half-esters of oxethylated alkylphenols or oxethylated alcohols, preferably the alkali metal salts of sulfuric acid half-esters of a nonylphenol, alkyl or with 4-5 moles of ethylene oxide per mole Aryl sulfonate, sodium lauryl sulfate, sodium lauryl ethoxylate sulfate and secondary sodium alkane sulfonates, the carbon chain of which contains 8-20 carbon atoms.
- the amount of the anionic emulsifier is 0.1-5.0% by weight, based on the monomers, preferably 0.5-3.0% by weight.
- a nonionic emulsifier of the ethoxylated alkylphenol or fatty alcohol type for example an addition product of 1 mol of nonylphenol and 4-30 mol of ethylene oxide, can be used in a mixture with the anionic emulsifier.
- a peroxide compound is preferably used as the radical-forming initiator.
- the initiator is water-soluble or monomer-soluble.
- a water-soluble initiator is preferably used.
- Suitable initiators are the customary inorganic per compounds, such as ammonium persulfate, potassium persulfate, ammonium or alkali metal peroxydiphosphate and organic peroxides, such as e.g. Benzoyl peroxide, organic peresters, such as perisopivalate, partly in combination with reducing agents, such as sodium disulfite, hydrazine, hydroxylamine and catalytic amounts of accelerators, such as iron, cobalt, cerium and vanadyl salts, preferably alkali metal or ammonium peroxydisulfates.
- reducing agents such as sodium disulfite, hydrazine, hydroxylamine
- accelerators such as iron, cobalt, cerium and vanadyl salts, preferably alkali metal or ammonium peroxydisulfates.
- the redox initiator systems disclosed in EP-A-107300 can also be used.
- the first stage 10 to 90, preferably 35 to 65 parts by weight of an ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers are emulsion polymerized.
- the monomer or monomer mixture used in the first stage is selected so that when the monomer or monomer mixture used in the first stage is completely polymerized out, a polymer with a glass transition temperature (T G1 ) of + 30 ° C. to + 110 ° C, preferably 60 to 95 ° C is obtained. Since the glass transition temperature of emulsion polymers according to the equation
- Examples of monomers which can be used in the first stage are: vinylaromatic hydrocarbons, such as styrene, ⁇ -alkylstyrene and vinyltoluene, esters of acrylic acid or methacrylic acid, in particular aliphatic and cycloaliphatic acrylates or methacrylates with up to 20 carbon atoms in the alcohol radical, such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl, lauryl and cyclohexyl acrylate or methacrylate, acrylic and / or methacrylic acid, acrylic and / or methacrylamide, N-methylolacrylamide and / or N-methylol methacrylamide, hydroxyalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl
- ethylenically unsaturated monomers or mixtures of ethylenically unsaturated monomers which are essentially free of hydroxyl and carboxyl groups preference is given to using ethylenically unsaturated monomers or mixtures of ethylenically unsaturated monomers which are essentially free of hydroxyl and carboxyl groups.
- substantially free is intended to mean that it is preferred to use monomers or monomer mixtures which are free from hydroxyl and carboxyl groups, but that the monomers or monomer mixtures used also contain small amounts (for example as a result of impurities) of hydroxyl and / or may contain carboxyl groups.
- the content of hydroxyl and carboxyl groups should preferably be at most so high that a polymer prepared from the monomer or monomer mixture used in the first stage has an OH number of at most 5 and an acid number of at most 3.
- component (a1) can be used, for example: cyclohexyl acrylate, cyclohexyl methacrylate, alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical, such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
- alkyl radical such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
- component (a2) e.g. vinylaromatic hydrocarbons such as styrene, ⁇ -alkylstyrene and vinyltoluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile or mixtures of these monomers are used.
- vinylaromatic hydrocarbons such as styrene, ⁇ -alkylstyrene and vinyltoluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile or mixtures of these monomers are used.
- the monomer or monomer mixture used in the first stage and the monomer or monomer mixture used in the second stage are selected in such a way that the emulsion polymer obtained has a hydroxyl number of 2 to 100, preferably 10 to 50 and the difference T G1 - T G2 is 10 to 170, preferably 80 to 150 ° C.
- Examples of monomers which can be used in the second stage are: vinylaromatic hydrocarbons, such as styrene, ⁇ -alkylstyrene and vinyltoluene, Esters of acrylic acid or methacrylic acid, in particular aliphatic and cycloaliphatic acrylates or methacrylates with up to 20 carbon atoms in the alcohol radical, such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl, lauryl and cyclohexyl acrylate or - methacrylate, acrylic and / or methacrylic acid, acrylic and / or methacrylamide, N-methylolacrylamide and / or N-methylolmethacrylamide, hydroxyalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxypropy
- component (b1) e.g. are used: cyclohexyl acrylate, cyclohexyl methacrylate, alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical, such as e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
- alkyl radical such as e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
- hydroxyalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid can be derived from an alkylene glycol esterified with the acid, or can be obtained by reacting the acid with an alkylene oxide.
- Hydroxyalkyl esters of acrylic acid and methacrylic acid, in which the hydroxyalkyl group contains up to 4 carbon atoms, or mixtures of these hydroxyalkyl esters are preferably used as component (b2).
- hydroxyalkyl esters examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate.
- esters of other unsaturated acids such as ethacrylic acid, crotonic acid and similar acids with up to about 6 carbon atoms per molecule, can also be used.
- Acrylic acid and / or methacrylic acid and / or acrylamidomethylpropanesulfonic acid are preferably used as component (b3).
- ethylenically unsaturated acids with up to 6 carbon atoms in the molecule can also be used.
- examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
- component (b4) e.g. are used: vinyl aromatic hydrocarbons, such as styrene, ⁇ -alkylstyrene and vinyl toluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile, or mixtures of these monomers.
- vinyl aromatic hydrocarbons such as styrene, ⁇ -alkylstyrene and vinyl toluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile, or mixtures of these monomers.
- the emulsion polymer used according to the invention should have a number average molar mass (determination: gel permeation chromatography using polystyrene as the standard) of 200,000 to 2,000,000, preferably 300,000 to 1,500,000.
- aqueous base coating compositions according to the invention contain, in addition to the emulsion polymer described above, a water-dilutable polyurethane resin as the film-forming material.
- the base coating compositions according to the invention preferably contain water-thinnable, urea-containing polyurethane resins which have a number average molecular weight (determination: gel permeation chromatography using polystyrene as the standard) of 1000 to 60,000, preferably 1500 to 50,000 and an acid number of 5 to 70, preferably 10 to 30 and by reaction, preferably chain extension of prepolymers containing isocyanate groups with polyamines and / or hydrazine can be produced.
- a number average molecular weight determination: gel permeation chromatography using polystyrene as the standard
- the prepolymer containing isocyanate groups can be prepared by reacting polyalcohols having a hydroxyl number from 10 to 1800, preferably 50 to 500, with excess polyisocyanates at temperatures up to 150 ° C., preferably 50 to 130 ° C., in organic solvents which do not react with isocyanates can, succeed.
- the equivalence ratio of NCO to OH groups is between 1.5 and 1.0 to 1.0, preferably between 1.4 and 1.2 to 1.
- the polyols used to prepare the prepolymer can be low molecular weight and / or high molecular weight and they can contain inert anionic groups.
- Low molecular weight polyols can be used to increase the hardness of the polyurethane. They have a molecular weight from 60 to about 400 and can contain aliphatic, alicyclic or aromatic groups. Amounts of up to 30% by weight of the total polyol constituents, preferably about 2 to 20% by weight, are used.
- the low molecular weight polyols with up to about 20 carbon atoms per molecule such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butylene glycol, 1,6-hexanediol, are advantageous , Trimethylolpropane, castor oil or hydrogenated castor oil, di-trimethylolpropane ether, pentaerythritol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, neopentylglycol, hydroxypivalic acid-neopentylglycol ester, hydroxyethylated or hydroxypropylated bisphenol A, bisphenol A, mixtures thereof .
- a high proportion of a predominantly linear polyol with a preferred hydroxyl number of 30 to 150 should be added.
- Up to 97% by weight of the total polyol can consist of saturated and unsaturated polyesters and / or polyethers with a molecular weight Mn exist from 400 to 5000.
- polyether diols such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and / or poly (oxybutylene) glycols.
- the selected polyether diols should not introduce excessive amounts of ether groups, otherwise the polymers formed will swell in water.
- the preferred polyether diols are poly (oxypropylene) glycols in the molecular weight range Mn from 400 to 3000.
- Polyester diols are produced by esterification of organic dicarboxylic acids or their anhydrides with organic diols or are derived from a hydroxycarboxylic acid or a lactone.
- polyols or polycarboxylic acids with a higher valency can be used to a small extent.
- the dicarboxylic acids and diols can be linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acids or diols.
- the diols used to prepare the polyesters consist, for example, of alkylene glycols, such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and other diols, such as dimethylcyclohexane.
- the acid component of the polyester consists primarily of low molecular weight dicarboxylic acids or their anhydrides with 2 to 30, preferably 4 to 18, carbon atoms in the molecule.
- Suitable acids are, for example, o-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaric acid, hexachlorheptanedicarboxylic acid, tetrachlorophthalic acid and / or.
- their anhydrides if they exist, can also be used.
- polyester polyols smaller ones can also be used Amounts of carboxylic acids with 3 or more carboxyl groups, for example trimellitic anhydride or the adduct of maleic anhydride with unsaturated fatty acids, are present.
- polyester diols are also used which are obtained by reacting a lactone with a diol. They are characterized by the presence of a terminal hydroxyl group and recurring polyester content of the formula - (- CO- (CHR) n -CH2-0 -) -.
- n is preferably 4 to 6 and the substituent R is hydrogen, an alkyl, cycloalkyl or alkoxy radical.
- No substituent contains more than 12 carbon atoms. The total number of carbon atoms in the substituent does not exceed 12 per lactone ring. Examples include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.
- the lactone used as a raw material can be represented by the following general formula in which n and R have the meaning already given.
- Unsubstituted -caprolactone in which n has the value 4 and all R substituents are hydrogen, is preferred for the preparation of the polyester diols.
- the reaction with lactone is started by low molecular weight polyols, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, dimethylolcyclohexane.
- other reaction components such as ethylenediamine, alkyldiacanolamines or urea, can also be reacted with caprolactone.
- polylactam diols which are produced by reacting, for example, ⁇ -caprolactam with low molecular weight diols.
- Aliphatic, cycloaliphatic and / or aromatic poly are used as typical multifunctional isocyanates isocyanates with at least two isocyanate groups per molecule.
- the isomers or isomer mixtures of organic diisocyanates are preferred.
- Suitable aromatic diisocyanates are phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, biphenylene diisocyanate, naphthylene diisocyanate and diphenylmethane diisocyanate. Due to their good resistance to ultraviolet light, (cyclo) aliphatic diisocyanates produce products with a low tendency to yellowing.
- Examples include isophorone diisocyanate, cyclopentylene diisocyanate and the hydrogenation products of aromatic diisocyanates, such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate and dicyclohexylmethane diisocyanate.
- aromatic diisocyanates such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate and dicyclohexylmethane diisocyanate.
- aliphatic diisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, dimethylethylene diisocyanate, methyltrimethylene diisocyanate and trimethylhexane diisocyanate.
- Isophorone diisocyanate and dicyclohexyl methane diisocyanate are particularly preferred as diisocyanates.
- the polyisocyanate component used to form the prepolymer can also contain a proportion of higher-quality polyisocyanates, provided that this does not cause gel formation.
- Products which have been found to be suitable as triisocyanates are those which are formed by trimerization or oligomerization of diisocyanates or by reaction of diisocyanates with compounds containing polyfunctional OH or NH groups.
- the average functionality can optionally be reduced by adding monoisocyanates.
- chain terminating monoisocyanates are phenyl isocyanate, cyclohexyl isocyanate and stearyl isocyanate.
- Polyurethanes are generally not compatible with water Lich, if special components are not incorporated in their synthesis and / or special manufacturing steps are carried out. So large an acid number is built in that the neutralized product can be dispersed stably in water.
- compounds which contain two H-active groups reacting with isocyanate groups and at least one group capable of forming anions.
- Suitable groups which react with isocyanate groups are, in particular, hydroxyl groups and primary and / or secondary amino groups.
- Groups which are capable of forming anions are carboxyl, sulfonic acid and / or phosphonic acid groups.
- Carboxylic acid or carboxylate groups are preferably used. They should be so inert that the isocyanate groups of the diisocyanate preferably react with the other groups of the molecule that are reactive toward isocyanate groups.
- alkanoic acids with two substituents on the carbon atom are used.
- the substituent can be a hydroxyl group, an alkyl group or an alkylol group.
- These polyols have at least one, generally 1 to 3 carboxyl groups in the molecule. They have two to about 25, preferably 3 to 10, carbon atoms. Examples of such compounds are dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid.
- Examples of such compounds are 2,2-dimethylol acetic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid and 2,2-dimethylol pentanoic acid.
- the preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid.
- Compounds containing amino groups are, for example, -diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid and 2,4-diaminodiphenyl ether sulfonic acid.
- the polyol containing carboxyl groups can be 3 to Make up 100% by weight, preferably 5 to 50% by weight, of the total polyol component in the NCO prepolymer.
- the amount of ionizable carboxyl groups available through the carboxyl group neutralization in salt form is generally at least 0.4% by weight, preferably at least 0.7% by weight, based on the solid.
- the upper limit is about 6% by weight.
- the amount of dihydroxyalkanoic acids in the unneutralized prepolymer gives an acid number of at least 5, preferably at least 10.
- the upper limit of the acid number is 70, preferably 40, based on the solids.
- this dihydroxyalkanoic acid is advantageously at least partially neutralized with a tertiary amine in order to avoid a reaction with the isocyanates.
- the NCO prepolymers used according to the invention can be prepared by simultaneously reacting the polyol or polyol mixture with an excess of diisocyanate.
- the implementation can also be carried out in stages in the prescribed order. Examples are described in DE 26 24 442 and DE 32 10 051.
- the reaction temperature is up to 150 ° C, with a temperature in the range of 50 to 130 ° C being preferred. The reaction continues until practically all of the hydroxyl functions have been converted.
- the NCO prepolymer contains at least about 0.5% by weight of isocyanate groups, preferably at least 1% by weight of NCO, based on the solid.
- the upper limit is approximately 15% by weight, preferably 10% by weight, particularly preferably 5% by weight.
- the reaction can optionally be carried out in the presence of a catalyst such as organotin compounds and / or tertiary amines.
- a catalyst such as organotin compounds and / or tertiary amines.
- organic that do not contain Zerewitinoff active hydrogen are possible.
- Usable solvents are, for example, dimethylformamide, esters, ethers, such as diethylene glycol dimethyl ether, keto esters, ketones, such as methyl ethyl ketone and acetone, ketones substituted with methoxy groups, such as methoxy hexanone, glycol ether esters, chlorinated hydrocarbons, aliphatic and alicyclic hydrocarbon pyrrolidones, such as N-methylpyrrolidone Furans, aromatic hydrocarbons and their mixtures.
- the amount of solvent can vary within wide limits and should be sufficient to form a prepolymer solution with a suitable viscosity.
- Suitable tertiary amines are, for example, trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, N-methylmorpholine.
- the NCO prepolymer is diluted with water and then results in a finely divided dispersion.
- the isocyanate groups still present are included Di- and / or polyamines reacted with primary and / or secondary amino groups as chain extenders. This reaction leads to a further linkage and increase in the molecular weight.
- the competitive reaction between amine and water with the isocyanate must be well coordinated (time, temperature, concentration) in order to obtain optimum properties and well monitored for reproducible production.
- Water-soluble compounds are preferred as chain extenders because they increase the dispersibility of the polymeric end product in water.
- Hydrazine and organic diamines are preferred because they usually build up the highest molecular weight without gelling the resin.
- the prerequisite for this is that the ratio of the amino groups to the isocyanate groups is selected appropriately.
- the amount of chain extender is determined by its functionality, the NCO content of the prepolymer and the duration of the reaction.
- the ratio of the active hydrogen atoms in the chain extender to the NCO groups in the prepolymer should generally be less than 2: 1 and preferably in the range from 1.0: 1 to 1.75: 1.
- the presence of excess active hydrogen, especially in the form of primary amino groups, can result in polymers with undesirably low molecular weights.
- Polyamines are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They can carry substituents that have no hydrogen atoms that are reactive with isocyanate groups. Examples are polyamines with a linear or branched aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups.
- the diamines include ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethylamine, 1,6-hexamethylenediamine, trimethylhexamethylenediamine, methanediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane and aminoethylethanolamine.
- Preferred diamines are alkyl or cycloalkyl diamines, such as propylenediamine and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.
- the chain can be extended at least partially with a polyamine that has at least three amine groups with a reactive hydrogen.
- This type of polyamine can be used in such an amount that unreacted amine nitrogen atoms with 1 or 2 reactive hydrogen atoms are present after the polymer has been extended.
- useful polyamines are diethylenetriamine, triethylenetetraamine, dipropylenetriamine and dibutylenetriamine.
- Preferred polyamines are the alkyl or cycloalkyl triamines, such as diethylenetriamine.
- monoamines such as ethylhexylamine, can also be added.
- the mixture of emulsion polymer and polyurethane resin contained in the preferred aqueous base coating compositions as a film-forming material consists of 95 to 40% by weight of emulsion polymer and 5 to 60% by weight of polyurethane resin, the proportions each referring to the solids content and their total always 100% by weight .-%.
- the aqueous base coating compositions according to the invention advantageously also contain further compatible water-dilutable synthetic resins, such as, for example, aminoplast resins, polyesters and polyethers, which generally serve as grind resins for the pigments.
- the aqueous base coating compositions according to the invention preferably contain 5 to 20, particularly preferably 10 to 16% by weight, based on the total solids content of the base coating compositions, of a water-dilutable aminoplast resin, preferably melamine resin and 5 to 20, preferably 8 to 15% by weight, of a water-dilutable polyether (eg polypropylene glycol with a number average molecular weight of 400 to 900).
- a water-dilutable aminoplast resin preferably melamine resin and 5 to 20, preferably 8 to 15% by weight
- a water-dilutable polyether eg polypropylene glycol with a number average molecular weight of 400 to 900.
- the base coating compositions according to the invention can contain coloring pigments on an inorganic basis, such as e.g. Titanium dioxide, iron oxide, soot, etc., coloring pigments on an organic basis as well as common metal pigments (e.g. commercially available aluminum bronzes, stainless steel bronzes ...) and non-metallic effect pigments (e.g. pearlescent or interference pigments).
- the base coating compositions according to the invention preferably contain metal pigments and / or effect pigments.
- the pigmentation level is in the usual ranges.
- crosslinked polymeric microparticles such as are disclosed in EP-A-38 127 and / or customary rheological inorganic or organic additives, can be added to the base coating compositions according to the invention.
- water-soluble cellulose ethers such as hydroxyethyl cellulose, methyl cellulose or carboxymethyl cellulose
- synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride, act as thickeners Copolymers and their derivatives or also hydrophobically modified ethoxylated urethanes or polyacrylates.
- Carboxyl group-containing polyacrylate copolymers are particularly preferred with an acid number of 60 to 780, preferably 200 to 500.
- the base coating compositions according to the invention generally have a solids content of about 15 to 50% by weight.
- the solids content varies with the intended use of the coating compositions.
- metallic paints for example, it is preferably 17 to 25% by weight.
- plain-colored paints it is higher, for example 30 to 45% by weight.
- the coating compositions according to the invention can additionally contain customary organic solvents. Their share is kept as low as possible. For example, it is below 15% by weight.
- the base coating compositions according to the invention are generally adjusted to a pH between 6.5 and 9.0.
- the pH can be adjusted with conventional amines, e.g. Ammonia, triethylamine, dimethylaminoethanol and N-methylmorpholine can be adjusted.
- the task explained at the outset is solved.
- the base coating compositions according to the invention high-quality coatings can be produced even without overcoating with a transparent top coating composition.
- the coating compositions according to the invention can be applied to any substrates, such as metal, wood, plastic or paper.
- Emulsion polymer dispersion 1 Emulsion polymer dispersion 1
- Emulsion polymer dispersion 2 Emulsion polymer dispersion 2
- An emulsion is prepared in the stirrable feed vessel from 720 g deionized water, 24 g emulsifier 1, 10.8 g acrylamide, 518 g methyl methacrylate, 292 g n-butyl methacrylate and 205 g styrene. 30% by weight of this emulsion are added for presentation. A solution of 0.9 g of ammonium peroxodisulfate APS in 55 g of deionized water is then added dropwise in the course of 5 minutes. An exothermic reaction occurs. The reaction temperature is kept between 80 and 85 ° C.
- a mixture of 700 g of n-butyl acrylate, 89.8 g of hydroxypropyl methacrylate, 35.9 g of methyl methacrylate, 35.9 g of methacrylic acid, 26.9 g of acrylamide and 4.5 g is then added within 2 hours Eikosa (ethylene glycol) nonylphenyl ether (Antarox®CO 850 from GAF Corp., emulsifier 2) was added. After the addition has ended, the reaction mixture is kept at 82 ° C. for a further 1.5 hours. It is then cooled and the dispersion is spread over a fabric 30 ⁇ m mesh size given. A finely divided dispersion with a non-volatile content of 45% by weight, a pH of 2.5, an acid number of 14 and an OH number of 20 is obtained.
- Emulsion polymer dispersion 5 Emulsion polymer dispersion 5
- stirrable feed vessel 720 g of deionized water 24 g of emulsifier 1, 43.2 g of acrylamide, 907 g of methyl methacrylate and 216 g of n-butyl methacrylate, 842 g of n-butyl acrylate, 108 g of hydroxypropyl methacrylate, 43.2 g of methacrylic acid and 5.4 g emulsifier 2 an emulsion is prepared. 10% by weight of this emulsion are added for presentation. A solution of 0.87 g of ammonium peroxodisulfate in 53 g of deionized water is then added dropwise in the course of 5 minutes. An exothermic reaction occurs.
- reaction temperature is kept between 82 and 88 ° C. 15 minutes after the addition of the APS solution has ended, the remaining 90% by weight of the emulsion are added within 3 hours and a solution of 2.23 g of APS in 478 g of deionized water is added within 3.5 hours, the temperature being at Is held at 82 ° C.
- reaction mixture is kept at 82 ° C. for a further 1.5 hours. It is then cooled and the dispersion is passed over a 30 ⁇ m mesh. A finely divided dispersion with a non-volatile content of 45% by weight, a pH of 5.8, an acid number of 13 and an OH number of 20 is obtained.
- the mass obtained is poured into 1840 g of cold deionized water with vigorous stirring. 86 g of a 15% hydrazine solution are added to the dispersion obtained within 20 minutes, with vigorous stirring. The resulting, very finely divided dispersion has a solids content of 35% and a run-out time of 27 seconds in the DIN cup 4.
- the mixture is adjusted to a pH value of 7.7 with a 5% aqueous dimethylethanolamine solution and with 9.4 g of a 3.5% solution of a commercially available polyacrylic acid thickener (Viscalex®HV 30 from Allied Colloids, pH value: 8 , 0) offset.
- Mixture 2 is obtained.
- Mixtures 1 and 2 are produced at 800-1000 rpm for 30 minutes to produce the basecoats of the invention. mixed and then adjusted to a pH of 7.7 with a 5% aqueous solution of dimethylethanolamine. The viscosity is then adjusted to an outflow time of 25 seconds in a DIN 4 cup by adding deionized water.
- the base coating compositions BB1, BB2, BB3 and BB4 according to the invention are obtained.
- the base coating composition BB5 is obtained by incorporating 36.2 g of the emulsion polymer dispersion 1 into the mixture 2. BB5 does not contain a polyurethane resin dispersion.
- the base coating compositions thus obtained show excellent storage stability.
- the base coating compositions are sprayed onto well-known methods onto phosphated steel sheets (Bonder 132) coated with a commercially available electrodeposition coating and a commercially available filler, overcoated with a commercially available clearcoat after a flash-off time of 10 minutes and baked at 140 ° C. for 20 minutes.
- the metallic effect coatings obtained in this way show a good metallic effect, good adhesion to the filler, good adhesion between the basecoat and topcoat, good gloss and good resistance in a condensed water constant climate according to DIN 50 017.
- BB1, BB2, BB3 and BB4 show a better metallic effect than BB5.
- a part of the painted sheets is coated again with the base coating compositions BB1, BB2, BB3, BB4 and BB5 and overcoated with a commercially available clear coat.
- the coatings obtained in this way are baked at 80 ° C. for 40 minutes.
- the coatings baked at 80 ° C adhere well to the coatings baked at 140 ° C.
- a basecoat composition prepared as described above using the emulsion polymer dispersion 5 shows insufficient storage stability.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT90900099T ATE91923T1 (de) | 1988-12-09 | 1989-11-27 | Verfahren zur herstellung eines mehrschichtigen ueberzuges, wasserverduennbare beschichtungszusammensetzungen, wasserverduennbare emulsionspolymere und verfahren zur herstellung von wasserverduennbaren emulsionspolymeren. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3841540 | 1988-12-09 | ||
DE3841540A DE3841540A1 (de) | 1988-12-09 | 1988-12-09 | Verfahren zur herstellung eines mehrschichtigen ueberzuges, wasserverduennbare beschichtungszusammensetzungen, wasserverduennbare emulsionspolymere und verfahren zur herstellung von wasserverduennbaren emulsionspolymeren |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0447428A1 EP0447428A1 (de) | 1991-09-25 |
EP0447428B1 true EP0447428B1 (de) | 1993-07-28 |
Family
ID=6368825
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90900099A Expired - Lifetime EP0447428B1 (de) | 1988-12-09 | 1989-11-27 | Verfahren zur herstellung eines mehrschichtigen überzuges, wasserverdünnbare beschichtungszusammensetzungen, wasserverdünnbare emulsionspolymere und verfahren zur herstellung von wasserverdünnbaren emulsionspolymeren |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0447428B1 (ja) |
JP (1) | JPH075860B2 (ja) |
AU (1) | AU630645B2 (ja) |
BR (1) | BR8907816A (ja) |
CA (1) | CA2004988C (ja) |
DE (2) | DE3841540A1 (ja) |
ES (1) | ES2060136T3 (ja) |
WO (1) | WO1990006186A1 (ja) |
ZA (1) | ZA899023B (ja) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3942804A1 (de) * | 1989-12-23 | 1991-06-27 | Basf Lacke & Farben | Verfahren zur herstellung eines mehrschichtigen ueberzuges |
DE4009000A1 (de) * | 1990-03-21 | 1991-09-26 | Basf Lacke & Farben | Verfahren zur herstellung einer mehrschichtigen reparaturlackierung |
DE4143688B4 (de) | 1991-03-30 | 2007-03-29 | Basf Coatings Ag | Verwendung eines Mischsystems sowie Verfahren zur Herstellung von Wasserbasislacken und von wasserverdünnbaren Überzugsmitteln |
DE4216613A1 (de) * | 1992-05-20 | 1993-11-25 | Basf Lacke & Farben | Verfahren zur Herstellung einer zweischichtigen Lackierung und für dieses Verfahren geeignete wäßrige Lacke |
AT400440B (de) * | 1993-12-06 | 1995-12-27 | Vianova Kunstharz Ag | Verfahren zur herstellung von wasserverdünnbaren lackbindemitteln und deren verwendung |
ES2191756T3 (es) * | 1995-06-07 | 2003-09-16 | Sherwin Williams Co | Composiciones acuosas de primera capa para usar en aplicaciones de primera capa/capa transparente. |
DE19904330A1 (de) | 1999-01-28 | 2000-08-10 | Basf Coatings Ag | Wäßriger Beschichtungsstoff und Modulsystem zu seiner Herstellung |
DE19930066A1 (de) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Farb- und/oder effektgebende Mehrschichtlackierung, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE19930067A1 (de) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Beschichtungsstoff und seine Verwendung zur Herstellung von Füllerschichten und Steinschlagschutzgrundierungen |
DE19930664A1 (de) | 1999-07-02 | 2001-01-11 | Basf Coatings Ag | Klarlack und seine Verwendung zur Herstellung von Klarlackierungen und farb- und/oder effektgebenden Mehrschichtlackierungen |
DE19930665A1 (de) | 1999-07-02 | 2001-01-11 | Basf Coatings Ag | Basislack und seine Verwendung zur Herstellung von farb- und/oder effektgebenden Basislackierungen und Mehrschichtlackierung |
DE19938759A1 (de) | 1999-08-16 | 2001-02-22 | Basf Coatings Ag | Beschichtungsstoff und seine Verwendung zur Herstellung hochkratzfester mehrschichtiger Klarlackierungen |
US6437036B1 (en) * | 1999-11-17 | 2002-08-20 | Basf Corporation | Waterborne primer with improved chip resistance |
DE19959923A1 (de) | 1999-12-11 | 2001-06-28 | Basf Coatings Ag | Wäßrige Primärdispersionen und Beschichtungsstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10005819A1 (de) | 2000-02-10 | 2001-08-23 | Basf Coatings Ag | Wäßrige Primärdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10018078A1 (de) | 2000-04-12 | 2001-11-08 | Basf Coatings Ag | Formmassen und Verfahren zur Herstellung von Formkörpern |
DE10018601A1 (de) | 2000-04-14 | 2001-10-25 | Basf Coatings Ag | Wäßrige Primärdispersionen und Beschichtungsstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10029802A1 (de) | 2000-06-16 | 2002-01-03 | Basf Coatings Ag | Farb- und/oder effektgebende wäßrige Beschichtungsstoffe und ihre Verwendung zur Herstellung farb- und/oder effektgebender, verformbarer Laminate |
DE10106566A1 (de) | 2001-02-13 | 2002-08-22 | Basf Coatings Ag | Von flüchtigen organischen Stoffen im wesentlichen oder völlig freier wäßriger Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung |
DE10106567A1 (de) | 2001-02-13 | 2002-08-22 | Basf Coatings Ag | Von flüchtigen organischen Stoffen im wesentlichen oder völlig freie wäßrige Primärdispersion, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10126651A1 (de) | 2001-06-01 | 2002-12-12 | Basf Coatings Ag | Pulverlacksuspensionen (Pulverslurries) und Pulverlacke, Verfahren zu ihrer Herstellung und ihre Verwendung |
US6822040B2 (en) | 2001-09-25 | 2004-11-23 | Basf Corporation | Basecoat composition with improved repair properties |
EP3009248A1 (en) | 2014-10-13 | 2016-04-20 | RECTICEL Automobilsysteme GmbH | Method for producing an elastomeric skin having a grained surface |
RU2746776C2 (ru) * | 2016-07-15 | 2021-04-20 | БАСФ Коатингс ГмбХ | Водное базовое покрытие и получение многослойных красочных систем посредством применения базового покрытия |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4150005A (en) * | 1977-03-17 | 1979-04-17 | Rohm And Haas Company | Internally plasticized polymer latex |
GB1598419A (en) * | 1978-05-17 | 1981-09-23 | Ici Ltd | Coating process |
GB2034334B (en) * | 1978-10-24 | 1983-03-02 | Canadian Ind | Process for preparing emulsions of copolymers containing n-methylol or n-methylol ether groups |
US4973621A (en) * | 1987-04-07 | 1990-11-27 | Akzo N.V. | Aqueous coating composition based on a dispersion of an addition polymer, especially suited to be used in an aqueous base coat |
DE3807531A1 (de) * | 1988-03-08 | 1989-09-21 | Basf Ag | Herstellung von waessrigen polyalkylmethacrylat-dispersionen durch emulsionspolymerisation in zwei stufen und deren verwendung in holzlacken |
-
1988
- 1988-12-09 DE DE3841540A patent/DE3841540A1/de not_active Withdrawn
-
1989
- 1989-11-27 EP EP90900099A patent/EP0447428B1/de not_active Expired - Lifetime
- 1989-11-27 BR BR898907816A patent/BR8907816A/pt not_active IP Right Cessation
- 1989-11-27 DE DE9090900099T patent/DE58905068D1/de not_active Expired - Fee Related
- 1989-11-27 WO PCT/EP1989/001434 patent/WO1990006186A1/de active IP Right Grant
- 1989-11-27 JP JP2500544A patent/JPH075860B2/ja not_active Expired - Fee Related
- 1989-11-27 ES ES90900099T patent/ES2060136T3/es not_active Expired - Lifetime
- 1989-11-27 ZA ZA899023A patent/ZA899023B/xx unknown
- 1989-11-27 AU AU46550/89A patent/AU630645B2/en not_active Ceased
- 1989-12-08 CA CA002004988A patent/CA2004988C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CA2004988A1 (en) | 1990-06-09 |
DE3841540A1 (de) | 1990-06-13 |
AU630645B2 (en) | 1992-11-05 |
BR8907816A (pt) | 1991-10-22 |
DE58905068D1 (de) | 1993-09-02 |
CA2004988C (en) | 1999-08-24 |
WO1990006186A1 (de) | 1990-06-14 |
ES2060136T3 (es) | 1994-11-16 |
EP0447428A1 (de) | 1991-09-25 |
JPH075860B2 (ja) | 1995-01-25 |
ZA899023B (en) | 1990-08-29 |
AU4655089A (en) | 1990-06-26 |
JPH04501737A (ja) | 1992-03-26 |
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