CA2004987A1 - Preparation of a multicoat coating, water-thinnable paint, preparation of crosslinked polymeric microparticles and crosslinked polymeric microparticles - Google Patents
Preparation of a multicoat coating, water-thinnable paint, preparation of crosslinked polymeric microparticles and crosslinked polymeric microparticlesInfo
- Publication number
- CA2004987A1 CA2004987A1 CA002004987A CA2004987A CA2004987A1 CA 2004987 A1 CA2004987 A1 CA 2004987A1 CA 002004987 A CA002004987 A CA 002004987A CA 2004987 A CA2004987 A CA 2004987A CA 2004987 A1 CA2004987 A1 CA 2004987A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- component
- mixture
- ethylenically unsaturated
- 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.)
- Abandoned
Links
- 239000011859 microparticle Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 title claims abstract description 7
- 239000003973 paint Substances 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims abstract description 6
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 40
- 150000002148 esters Chemical class 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 31
- 101000620894 Homo sapiens Lysophosphatidic acid phosphatase type 6 Proteins 0.000 description 28
- 101001135804 Homo sapiens Protein tyrosine phosphatase receptor type C-associated protein Proteins 0.000 description 28
- 102100022916 Lysophosphatidic acid phosphatase type 6 Human genes 0.000 description 28
- -1 alkalimetal salts Chemical class 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 125000005442 diisocyanate group Chemical group 0.000 description 16
- 150000002009 diols Chemical class 0.000 description 15
- 150000007513 acids Chemical class 0.000 description 14
- 229920005862 polyol Polymers 0.000 description 13
- 150000003077 polyols Chemical class 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 229940048053 acrylate Drugs 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 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 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940012017 ethylenediamine Drugs 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
- 239000003960 organic solvent Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 2
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-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
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
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- 229960002887 deanol Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
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- WVWYODXLKONLEM-UHFFFAOYSA-N 1,2-diisocyanatobutane Chemical compound O=C=NC(CC)CN=C=O WVWYODXLKONLEM-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
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- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 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
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical group C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-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
- 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
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Abstract The invention relates to a process for the preparation of a multicoat coating, in which process a pigmented basecoat is used which comprises crosslinked polymeric microparticles obtainable by emulsion polymeri-zation. In this process the crosslinked polymeric microparticles comprised in the basecoat are obtainable by using 0.5 to 2.4% by weight of allyl methacrylate or 1.5 to 8.0% by weight of ethylene glycol di(meth)acrylate or 1.5 to 8.0% by weight of butanediol di(meth)acrylate or 1.5 to 10.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0% by weight of divinylbenzene, the weight percentages referring to the total amount of the monomer used.
Description
~ 198~
. ,. : : ., 21.10.1988/fe LPAP - 0812z PAT 88 184 :
BASF Lacke + Farben AG, Munster Preparation of a multicoat coating, water-thinnable Paint, ~preparatio~ f crosslinked polymeric micro-particles and crosslinked pol~neric microparticles :: :
': :," ' The invention relates to a process for the preparation of a multicoat coating on a substrate sur-face, in which process (1) a pigmented aqueous basecoat which comprises cross-linked polymeric microparticles, obtainable by ~ :
emulsion polymerization of ;
(A) ethylenically unsaturated monomers which contain one ethylenically unsaturated group in the molecule, or a mixture of such monomers, .;
and of :
(B) an ethylenically un~aturated monomer which co.ntains ~wo ethylenically unsaturated groups in the molecule, i~ applied to the substrate ~urface (2) a polymeric film is formed from the compo~ition ~ :
! 20 ! applied in 3tage (1) (3) a clear topcoat i~ applied to the basecoat obtained in thi~ manner, and subsequently (4) the basecoat and the topcoat are baked together.
The invention also relates to a water-thinnable paint which comprises crosslinked polymeri~
2~4g~7 - 2 - 21.10.1988/fe LPAP - 0812z PAT as 184 microparticles, obtainable by emulsion polymerization of (A) ethylenically unsatuxated monomers which contain one ethylenically unsaturated group in the molecule, or a mixture of such monomers, and of S (B) an ethylenically unsaturated monomer which contains two ethylenically unsaturated groups in the molecule The invention further relates to a process for the prep~ration of cxos~linked polymeric microparticles and to the crosslinked polymeric microparticles prepared by this process.
The process, described above, for the preparation of multicoated coatings is known from EP-B 38,127 and is particularly employed for producin~ metallic finishes on automotive bodies.
Nhen, in the process under discu~sion, aqueous basecoats a~e u~ed which compri~e crosslinked polymeric microparticles obtainable by emulsion polymerization of ethylanically unsaturated monomer~ (cf. EP-B 38,127, ~column 4, lines 51 to 60, column 20, line 40 to column 25, line 50), coatings are obtained which are in need of improvement in respect of gloss and adhesion.
The ob~ect forming the basis of the present invention i~ to prepare pigmented aqueous basecoats which comprise cros31inked polymeric microparticles, obtainable 2S by emulsion polymerization of (A) ethylenically unsaturated monomers which contain one ethylenically unsaturated group in the molecule, or zo~ 3a~
.:
- 3 - 21.10.1988/fe LPAP - 0812z a mixture of such monomers, and of (B) an ethylenically unsaturated monomer which contains two ethylenically unsatur~ted groups in the molecule, and which basecoats give rise t;o multicoat coatings with improved gloss and Lmproved adhesion.
Surprisingly, this object is achieved via the preparation of basecoats which comprise crosslinked polymeric particles; these microparticles can be obtained by using as component (B) 0.5 to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5% by weight of allyl methacrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferably 4.0% by weight of ethylene glycol di~meth)acrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly prsferably 4.0~ by weight of butanediol dL(meth)acrylate or 1.5 to 10.0, preferably 3.0 to 7.0, particulaxly preferably 5.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0, preferably 1.0 to 4.0, particularly preferably 2.0% by weight of divinylbenzene, the weight percQntages referring to the total amounts of component (A) u~ed and of component (B) used (the weight percentage of component (A) used + the weight percentage of component (B) u~ed = 100~ by weight).
The c:rosslinked polymeric microparticles used according to the invention can be prepared by emulsion polymerization of the components ~A) and (B) in an aqueous medium in kno~n equipment, eg. a stirred reaction .. :: .; . - - . . - : - . . - . . .
2~)04~8~7 - 4 - 21.10.1988/fe LPAP - 0812z vessel provided with means of heating and cooling. The addition of the monomers can be effected by first placing a solution comprising ~he total water, the emulsifier and some of the initiator in the reaction vessel and then slowly adding, at the polymerization temperature, the monomer or the mixture of monomers and, separately but side by side, the remaining initiator. Howevex, it is also possible first to introduce in the reaction vessel some of the water and emulsifier and to form from the remaining water and emulsifier and from the monomer or mixture of monomers a pre-emulsion which is then slowly added at the polymerizatlon temperature, the initiator being again added separately.
The emulsion polymerization proces~ i a process known for a long time ~cf., for example, ~Chemie, Physik und Technologie der Kunststoffe in Einzeldarstellungen, DLspersionen synthetischer Hochpolymerer" ["Chemistry, Physics and Technology of Plastics in Individual Product~, Disper~ions of Synthetic High Polymers"], Part I, by F. H~lscher, Springer Verlag, Berlin, Heidelberg, New York, i969).
If the emulsion polymerization to be carried out to prepare the crosslinked polymeric microparticles to be usad according to the invention is initiated by a redox initiator system consisting of H2O2 and a non-ionic, water-solublQ reducing agent (as disclosed in EP-A 107,-iO0), basecoats are obtained which are suitable ~ ~ 7 . . . .
. ,. : : ., 21.10.1988/fe LPAP - 0812z PAT 88 184 :
BASF Lacke + Farben AG, Munster Preparation of a multicoat coating, water-thinnable Paint, ~preparatio~ f crosslinked polymeric micro-particles and crosslinked pol~neric microparticles :: :
': :," ' The invention relates to a process for the preparation of a multicoat coating on a substrate sur-face, in which process (1) a pigmented aqueous basecoat which comprises cross-linked polymeric microparticles, obtainable by ~ :
emulsion polymerization of ;
(A) ethylenically unsaturated monomers which contain one ethylenically unsaturated group in the molecule, or a mixture of such monomers, .;
and of :
(B) an ethylenically un~aturated monomer which co.ntains ~wo ethylenically unsaturated groups in the molecule, i~ applied to the substrate ~urface (2) a polymeric film is formed from the compo~ition ~ :
! 20 ! applied in 3tage (1) (3) a clear topcoat i~ applied to the basecoat obtained in thi~ manner, and subsequently (4) the basecoat and the topcoat are baked together.
The invention also relates to a water-thinnable paint which comprises crosslinked polymeri~
2~4g~7 - 2 - 21.10.1988/fe LPAP - 0812z PAT as 184 microparticles, obtainable by emulsion polymerization of (A) ethylenically unsatuxated monomers which contain one ethylenically unsaturated group in the molecule, or a mixture of such monomers, and of S (B) an ethylenically unsaturated monomer which contains two ethylenically unsaturated groups in the molecule The invention further relates to a process for the prep~ration of cxos~linked polymeric microparticles and to the crosslinked polymeric microparticles prepared by this process.
The process, described above, for the preparation of multicoated coatings is known from EP-B 38,127 and is particularly employed for producin~ metallic finishes on automotive bodies.
Nhen, in the process under discu~sion, aqueous basecoats a~e u~ed which compri~e crosslinked polymeric microparticles obtainable by emulsion polymerization of ethylanically unsaturated monomer~ (cf. EP-B 38,127, ~column 4, lines 51 to 60, column 20, line 40 to column 25, line 50), coatings are obtained which are in need of improvement in respect of gloss and adhesion.
The ob~ect forming the basis of the present invention i~ to prepare pigmented aqueous basecoats which comprise cros31inked polymeric microparticles, obtainable 2S by emulsion polymerization of (A) ethylenically unsaturated monomers which contain one ethylenically unsaturated group in the molecule, or zo~ 3a~
.:
- 3 - 21.10.1988/fe LPAP - 0812z a mixture of such monomers, and of (B) an ethylenically unsaturated monomer which contains two ethylenically unsatur~ted groups in the molecule, and which basecoats give rise t;o multicoat coatings with improved gloss and Lmproved adhesion.
Surprisingly, this object is achieved via the preparation of basecoats which comprise crosslinked polymeric particles; these microparticles can be obtained by using as component (B) 0.5 to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5% by weight of allyl methacrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferably 4.0% by weight of ethylene glycol di~meth)acrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly prsferably 4.0~ by weight of butanediol dL(meth)acrylate or 1.5 to 10.0, preferably 3.0 to 7.0, particulaxly preferably 5.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0, preferably 1.0 to 4.0, particularly preferably 2.0% by weight of divinylbenzene, the weight percQntages referring to the total amounts of component (A) u~ed and of component (B) used (the weight percentage of component (A) used + the weight percentage of component (B) u~ed = 100~ by weight).
The c:rosslinked polymeric microparticles used according to the invention can be prepared by emulsion polymerization of the components ~A) and (B) in an aqueous medium in kno~n equipment, eg. a stirred reaction .. :: .; . - - . . - : - . . - . . .
2~)04~8~7 - 4 - 21.10.1988/fe LPAP - 0812z vessel provided with means of heating and cooling. The addition of the monomers can be effected by first placing a solution comprising ~he total water, the emulsifier and some of the initiator in the reaction vessel and then slowly adding, at the polymerization temperature, the monomer or the mixture of monomers and, separately but side by side, the remaining initiator. Howevex, it is also possible first to introduce in the reaction vessel some of the water and emulsifier and to form from the remaining water and emulsifier and from the monomer or mixture of monomers a pre-emulsion which is then slowly added at the polymerizatlon temperature, the initiator being again added separately.
The emulsion polymerization proces~ i a process known for a long time ~cf., for example, ~Chemie, Physik und Technologie der Kunststoffe in Einzeldarstellungen, DLspersionen synthetischer Hochpolymerer" ["Chemistry, Physics and Technology of Plastics in Individual Product~, Disper~ions of Synthetic High Polymers"], Part I, by F. H~lscher, Springer Verlag, Berlin, Heidelberg, New York, i969).
If the emulsion polymerization to be carried out to prepare the crosslinked polymeric microparticles to be usad according to the invention is initiated by a redox initiator system consisting of H2O2 and a non-ionic, water-solublQ reducing agent (as disclosed in EP-A 107,-iO0), basecoats are obtained which are suitable ~ ~ 7 . . . .
- 5 -21.10.1988/fe LPAP - 0812z for producing multicoat coatings with high resistance in the condensed water steady conditions test.
Examples of suitable non-ionic, water-soluble reducing agents are: ascorbic ac:id, sulfur compounds such as thiourea and mercaptans, amines such as hydroxylamine, triethylamine and ethanolamine, reducing acids such as glycolic acid~ tartaric acid and diphenylglycolic acid, and benzyl alcohol. Ascorbic acid is used in preference.
The emulsion polymerization under discussion may also be initiated by conventional initiators, eg. per-compounds such as ammonium persulfate, potassium per-sulfate, ammonium peroxydiphosphate or alkali metal peroxydiphosphate, and organic peroxides, eg. benzoyl peroxide, organic peresters such as perisopivolate, 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.
An anionic emulsifier may be used as the emul-sifier, either alone or in admixture.
Examples of anionic emulsifiers are the alkalimetal salts of sulfuric acid hemi~esters of alkylphenols or alcohols, also the sulfuric acid hemi-esters of oxyethylated alkylphenols or oxyethylated alcohols, preferably the alkali metal salts of the sulfuric acid hemi-ester of a nonylphenol, alkylsulfonate or arylsul-fonata which has reacted with 4 - 5 mol of ethylene oxide ;20~49~7 .
Examples of suitable non-ionic, water-soluble reducing agents are: ascorbic ac:id, sulfur compounds such as thiourea and mercaptans, amines such as hydroxylamine, triethylamine and ethanolamine, reducing acids such as glycolic acid~ tartaric acid and diphenylglycolic acid, and benzyl alcohol. Ascorbic acid is used in preference.
The emulsion polymerization under discussion may also be initiated by conventional initiators, eg. per-compounds such as ammonium persulfate, potassium per-sulfate, ammonium peroxydiphosphate or alkali metal peroxydiphosphate, and organic peroxides, eg. benzoyl peroxide, organic peresters such as perisopivolate, 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.
An anionic emulsifier may be used as the emul-sifier, either alone or in admixture.
Examples of anionic emulsifiers are the alkalimetal salts of sulfuric acid hemi~esters of alkylphenols or alcohols, also the sulfuric acid hemi-esters of oxyethylated alkylphenols or oxyethylated alcohols, preferably the alkali metal salts of the sulfuric acid hemi-ester of a nonylphenol, alkylsulfonate or arylsul-fonata which has reacted with 4 - 5 mol of ethylene oxide ;20~49~7 .
- 6 - 21.10.1988/fe LPAP - OB12z per mole, sodium lauryl sulfate, sodium lauryl ethoxylate sulfate and secondary sodium alkane sulfonates who~e carbon chain contains 8 - 20 carbon atoms. The amount of the anionic emulsifier is 0.1 - 5.0% by weight, based on S the monomers, preferably 0.5 - 3.0% by weight. Further- -more, in order to raise the ~tability of the aqueous ~ ~ -dispersions, it is possible to use additionally a non-ionic emulsifier of the typè of an ethoxylated alkyl-phenol or fatty alcohol, eg. an adduct of 1 mol of ~ ~ ;
nonylphenol and 4 - 30 mol of ethylene oxide in admixture with the anionic emulsifier. ;
It is pref~rred to keep the amount of ionic emulsifier used as low as possible.
The emulsion polymerization is generally carried out at temperature~ of 20 to 100C, preferably 40 to 90C. ` `
A mixture whLch consists of (al) 60 to g9, preferably 70 to 90% by weight of an aliphatic or cycloaliphatic ester of acrylic acid or methacrylic acid or a mixture of such esters (a2) 0 to 5, preferably 2 to 4~ by weight of an ethyleni~
cally unsaturated monomer which carries at least one carboxyl group in the molecule and is copolymeriz-able with (al), (a3) and (a4), or a mixture of such monomer~
(a3) 1 to 40, preferably 2 to 15% by weight of an ethy~
lenically unsaturated monomer which carries at least ..,~
,'.': '.,, ',` ' "',"~,"" "~',' '' ,- 2~)~)4~318~i;
- _ 7 - 21.10.1988/fe - LPAP - 0812z one hydroxyl group in the molecule and is copolymerizable with (al), (a2) and (a4), or a mixture of such monomers, and (a4) 0 to 30, preferably 5 to 20~ by weight of a further ethylenically unsaturated monomer which is copoly-merizable with (al), (a2) and (a3), or a mixture of such monomers, is preferably used as component (A), the to~al of the weight percentages of (al), (a2~, (a3) and (a4) being always 100% by weight.
The following can be used, for example, as component (al): cyclohexyl acrylate, cyclohexyl methacry-late, alkyl acrylates and alkyl methacrylates having up to 20 carbon atoms in the alkyl radical, eg. methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylates and methacrylate~ or mixtures of these monomers.
Acrylic acid and/or methacrylic acid are pre-ferably USQCI as component (a2). However, other ethyl~
enically un~aturated acids having up to 6 carbon atoms in the mo1ecule may be also used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
The following may be used, for example, as component (~3): hydroxyalkyl e~ters of acrylic acid, methacrylic acid or any other ~ et~ylenically unsatura-ted carboxylic acid. These esters may be derived from an . . ~. ~ . - .
.~ .... ` . . . . . . . .. . . . .. .. . . . .
- 8 - 21.10.1988/fe LPAP - 0812z alkylene glycol which is esterified with the acid, or they can be obtained by reacting the acid with an alky-lene oxide. Hydroxyalkyl esters of acrylic acid and methacrylic acid in which the hydroxyalkyl group contains up to 4 car~on atoms, or a mixture of these hydroxyalkyl ester , are preferably used as component (a3~. Examples of such hydroxyalkyl esters are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropoxypropyl acry-late, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxybutyl acrylate or 4-hydroxybutyl (meth)acrylate. The corresponding esters of other un-saturated acids, eg. ethacrylic acid, crotonic acid and similar acids having up to about 6 carbon atom~ pex lS molecule may be al~o used.
The following may be used, for example, as component (a4~: vinylaromatic hydrocarbons such as ~tyrene, ~-~lkyl~tyrene and vinyltoluene, ac~ylamide, methacrylamide, acrylonitrile and methacrylonitrile, or mixture3 of the3e monomers. -It is an e~ential part of the invention that 0.5to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5~ by weight of allyl methacrylate or 1.5 to 8.0, prsferably 2.0 to 5.0, particularly preferably 4.0~ by weight of ethylene glycol di(meth)acrylate or 1.5 to 8.0, preferably 2 0 a to 5.0, particularly preferably 4.0% by weight of butanediol di(meth)acrylate or 1.5 to 10.0~
~, - 9 - 21.10.1988/fe LPAP - 0812z preferably ~.0 to 7.0, particularly preferably 5.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0, preferably 1.0 to 4.0, particularly preferably 2.0~ by weight of divinylbenzene are used as component (B), the weight percentages referring to the total amounts of the component (A) used and of the component (~) used (the weight percentage of the component (A) used + the weight percentage of the component (B) used = 100~ by weight).
The crosslinked polymeric microparticles used according to the invention must have a diameter of 0.01 to 10 ~m.
Basecoats which comprise, in addition to the crosslinked polymeric microparticles described above, also a water-thinnable polyurethane resin, furnish multicoat coating~ with a particularly good effect and are preerred. The preferred basecoats preferably comprise a~ the polyurethane resins water-thinnable poly-urethane re ins containing urea groups having a number average molecular weight of 1,000 to 60,000, preferably 1,500 to 50,000 (dete~mined by gel permeation chromato-graphy using polystyrene as standard) and an acid value of 5 to 70, preferably 10 to 30. Such polyurethane resins may be prepaxed by reacting isocyanate-containing pre-polymer~ with organic polyamines and/or hydrazine.
~he preparation of the isocyanate-containing prepolymer~ may be carried out by reacting polyalcohols having a hydroxyl value of 10 to 1,800, preferably 50 to -: : .. . .
'';.''" , ,: ........ . ' ' '. ' ' , '.~: ~.: '- - -. . . :
; ~ . : . ~ .
- 10 - 21.10.1988/fe LPAP - 0812z 500, with an excess of polyisocyanates at temperatures up to 150C, preferably 50 to 130C, in organic solvents which are inert to isocyanates. 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 l;o 1. The polyols used for the preparation of the prepolymers may be low-molecular and/or high-molecular and they may contain anionic groups which axe slow to react.
In order to raise the hardness of the poly-urethane, low-molecular polyols may be used. They have a molecular weight of 60 up to about 400 and may comprise aliphatic, alicyclic or aromatic groups. Amounts of up to 30~ by weight of the total polyol components, preferably about 2 to 20% by weight, are usecl. The low-molecular polyols have advantageously up to about 20 carbon atoms per moleculs, such as ethylone glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butyleneglycol, 1,6-hexanediol trimethylolpropane, castor oil or hydrogenated castor oil, di(trimethylolpropane~ ether, pentaerythritol, 1,2-cyclohexanediol,1,4-cyclohexanedLmethanol,bisphenol A, bisphenol F, neopentyl glycol, neopentyl glycol hydroxypivalate, hydroxyethylated or hydroxypropylated bisphenol A, hydrogenated bisphenol A and mixtures thereof.
In orcler to obtain more flexible NCO prepolymers, .- . .: .
a high proportion of a predominantly linear polyol having ~
~ .
' .1 ;20~)~98 7 21.10.1988/fe LPAP - 0812z a preferred hydroxyl value 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 having a molecular mass Mn of 400 to 5,000. Suitable high-molecular polyols are aliphatic polyether diols of the general formula H-(-O-(-CHR-)n-)m-OH in which R is hydrogen or a low alkyl radical which may be unsubstitu-ted or substituted by various substituents, n being 2 to 6, preferably 3 to 4 and m being 2 to 100, preferably 5 to 50. Examples are linear or branched polyether diols such as polytoxyethylene) glycols, poly(oxypropylene) glycols and/or poly(oxybutylene) glycols. The chosen polyether diols should not introduce an excessive amount of ether groups, since otherwise the polymers formed swell in water. The preferred polyether diols are poly-(oxypropyleno) glycols in the molecular mass Mn range of 400 to 3,000. Polyester diols are prepared by esterifying organic dicarboxylic acids or their anhydrides with organic diols or they are derived from a hydroxycar-boxylic acid or a lactone. To prepare branched polyester polyols, polyols or polycarboxylic acids of high valency may be u~ed to a small extent. The dicarboxylic acids and diols may be linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acids or diols.
~he diols used for the preparation of the poly-e~ter~ con~ist, for example, of alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, . ~ .. . . . . .
~0~)4~ 7 - 12 - 21.10.1988/fe LPAP - 0812z 1,4-butanedi~l, 1,6-hexanediol, neopentyl glycol and other diol~ such as dimethylolcyClhexane- The acid com~
ponent of the polyester consists mainly of low molecular dicarboxylic acids or their anhydrideq having 2 to 30, S preferably 4 to 1~ carbon atoms in the molecule. Examples of æuitable acids are o-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, cyclohexane-dicarboxylic acid, quccinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaric acid, hexachloroheptanedicarboxylic acid, tetrachloro~
phthalic acid and/or dimerized fatty acids. The anhydride~ of thesa acids, whera they exist, may be used ~ `
instead of the acids. For the formation of polyester polyol , relatively small amounts of carboxylic acids with three or more carboxyl groups, for example tri-mellitic anhydride or the adduct of maleic anhydride and unsaturated Patty acids, may be also present.
According to the invention, it i~ also possible to use polye~ter diols which are obtained by reacting a lactone with a diol. They are distinguished by the pre~ence of a terminal hydroxyl group and recurring -:
polyester moieties of the formula -(C0-(CHR)n-CH2-0-), whers n is preferably 4 to 6 and the substituent R is hydrogen, alkyl, cycloalkyl or alkoxy. No sub~ti~uent contains more than 12 carbon atom~. The total numb~r of ~ -carbon atoms in tha substituent does not exceed 12 per ~-lac~ona ring. Appropriate example~ are hydro~ycaproic . .
- 13 - 21.10.1988/fe LPAP - 0812z PAT ~8 184 acid, hydroxybu~yric acid, hydroxydecanoic acid and~or hydroxystearic acid. The lactone used as starting mate-rial can be represented by the following general formula CH2~(CR2)n~ 1~ , O
in which n and R have the meaning already defined. For the prepara~ion of the polyester diols the unsubstituted -~-caprolactone, in which n has the value of 4 and all R
substituents are hydrogen, is preferred. The reaction with lactone is initiated by relatively low-molecular polyols, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol and dimethylolcyclohexane. However, other reactants such a~ ethylenediamine, alkyldialkanolamines or even urea may be reacted with caprolactone. -Suitable higher-molecular diols are also poly-lactam diols which are prepared by the reaction of, for example, 6 -caprolactam with relatively low-molecular diols.
Aliphatic, cycloaliphatic and/or aromatic poly-, isocyanates having at least two isocyanate groups per molecule are employed as typical multifunctional iso-cyanates. Isomar~ or isomeric mixtures of organic diisocyanate~ are preferred. Suitable aromatic diiso-cyanates are phenylene diisocyanate, toluylene diiso- ;
cyanate, xylylene dii~ocyanate, biphenylene diisocyanate, Z()04~
- 14 - 21.10.1988/fe LPAP - 0812z naphthylene diisocyanate and diphenylmethane diisocyanate.
Because of their good resistance to ultraviolet light, (cyclo)aliphatic diisocyanates give rise to products with a low tendency to yellowing. Example~ of these diisocyanates are isophorone diisocyanate, cyclo~
pentylene diisocyanate and hydrogenation products of aromatic diisocyanates such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate and dicyclohexylm~thane diisocyanate~ Examples of aliphatic diisocyanate~ are trimethylene diisocyanate, tetramethy-lene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, dimethylethylene diiso-cyanate, methyltrimethylene diisocyanate andtrimethylhexane diisocyanate. The diisocyanates particularly preferred are isophorone diisocyanate and dicyclohexylmethane diisocyanate. The polyisocyanate component u~ed for the formation of the prepolymer may also contain some polyisocyanates of higher valency, provided that these do not cause gelling. Suitable triisocyanates have been found to be products which are formed by trimerization or oligomerization of diisocya-nates or by the reaction of diisocyanates with -`-polyfunctional OH-containing or NH-containing compound~
Examples of thes3 are the biuret of hexamethylene diiso~
cyanate and water, the isocyanurate of hexamethylsne : .. -.. ... . . . .; .~ . . .. . .. . . . . . .. . . ..... ...... ... . .
98~
, - 15 - 21.10.1988/fe LPAP - 0812z diisocyanate or the adduct of i~ophorone diisocyanate and trLmethylolpropane. If desired, the average functionality can be reduced by the addition of monoisocyanates.
Examples of ~uch chain-terminating monoisocyanates are phenyl isocyanate~ cyclohexyl isocyanate and stearyl isocyanate.
Polyurethanes are generally not compatible with water, unless special components are incorporated during their synthesis and/or unless special preparative steps are undertaken. Such a high acid value is incorporated in thi manner that the neutralized product is disper-sible in water to give a stable dispQrsion. Compounds which are suitable for thi~ purpose contain two H-active groups which are reactive with isocyanate groups and at least one group capable of forming anions. Suitable groups wllich aro reactiva with isocyanate groups arQ
particularly hydroxyl groups as well as primary and/or secondary amino group-~. Groups which are capable of forming anions, are carboxyl, sulfonic acid and/or phosphonic acid groups. Carboxylic acid or carboxylate groups are preferred. They should be so slow to react that the isocyanate groups of the diisocyanate preferably react with the other groups in the molecule which are r~active toward isocyanate group~. Alkanoic acids having two ~ubstituents on the ~ carbon atom, are used for this purpose. Th~ substituent may be a hydroxyl group, an alkyl group or an alkylol group. These polyols have at 200~g8~
- 16 - 21.10.1988~fe - LPAP - 0812z 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 dihydroxy-propionic acid, dihydroxysuccinic acid and dihydroxyben-zoic acid. ~ group of dihydro:~yalkanoic acids which isparticularly preferred, are the ~ dimethylolalkanoic acids which are represented by the ~tructural formula ;-RC(CH2OH)2COOH, in which R is hydrogen or an alkyl group having up to 20 carbon atoms. Example~ of such compounds are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic -acid, 2,2-dimethylolbutyric acid and 2,2-dimethylol-pentanoic acid. The preferred dihydroxyalkanoic acid i~
2,2-dLmethylolpropionic acid. Examples of amino~con-taining compound~ are ~ diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluene sulfonic acid and 2,4-diaminodiphenyl ether sulfonic acid. The polyol containing carboxyl groups may form 3 to 100% by weight, preferably 5 to 50~ by weight, of the total polyol component in the NCO prepolymer.
The amount of ionizable carboxylic group~ avail-able in salt form by neutrali~a~ion of the carboxyl groups is generally at least 0.4~ by weight, prefera~ly at lea~t 0.7~ by weight, ba~ed on the solids content. The --upper limit i~ about 6% by weight. The amount of ;
dihydroxyalkanoic acids in the non-neutralized prepolymer give~ rise to an acid value of at leat 5, preferably at lea3t 10. The upper acid value limit is 70, preferably 21)0~9~3'7 - 17 - 21.10.1988/fe LPAP - 0812z 40, based on the solids content.
This dihydroxyalkanoic acid is advantageously at least partially neutrali2ed with a tertiary amine prior to the reaction with isocyanat~es in order to prevent a reaction with the isocyanates.
The NCO prepolymers used according to the inven-tion may be prepared by a simultaneous reaction of the polyol or polyol mixture with an excess of diisocyanate.
Otherwise the reaction may be carried out in stages in the prescribed sequence.
Examples are disclosed in DE 2,624,442 and DE 3,210,051. The reaction temperature is up to 150C, a temperature in the range of 50 to 130C being preferred.
The reaction is continued until virtually all the hydroxyl function~ have reacted.
The NCO prepolymer contains at least about 0.5%
by weight of i~ocyanste groups, preferably at least 1~ by weight of NCO, based on the solids content. The upper limit is about 15~ by weight, preferably 10% by weight, particularly preferably about 5% by weight. The reaction may be carried out in the pre~ence or ab3ence of a catalyst, such as organotin compounds and/or tertiary amines. In oxder to maintain the coreactants in a liquid state and to allow a bstter temperature control during the reaction, it is possible to add organic solvents which contain no active Zerewitinoff hydrogen. Examples of suitable solvents are dimethylformamide, e ters, ''.'.'. :'~
~ 20~)49~3~
- 18 - 21.10.1988/fe `
LP~P - 0812z ethers such as diethylene glyc:ol dimethyl ether, keto-.. ..
esters, ketones such as methyl ethyl ketone and acetone, ketones substituted by methoxy groups such as methoxyhexanone, glycol ether asters, chlorinated hydro-carbons, aliphatic and alicyclic hydrocarbon pyrrolidones such as N-methylpyrrolidone, hydxogenated furans, aroma- - -tic hydrocarbons and mixtures thereof. The amount of solvent can vary within a wide range and should be sufficient to allow the formation of a prepolymer solu-tion of suitable viscosity. 0.01 to 15% by weight of solvent~, preferably 0.02 to 8% by weight of solvents, -~
based on the solids content, is generally sufficient.
Should the boiling point of any water-insoluble solvents present be lower than water, such solvents may be care-fully distilled off by vacuum distillation or thin-layer evaporation after preparation of the polyurethane disper-sion containing urea groups. Higher-boiling ~olvents should be water-soluble and they remain in the aqueous polyurethane dispersion in order to facilitate the ;~
coalescence of the polymer particles during film forma- -tion. The solvent which is particularly preferred is N-mathylpyrrolidone, either alone or in admixture with ketones such as methyl ethyl ketone.
Tho anionic group of the NC0 prepolymer are at least partially neutralized with a tertiary amine. The increase in dispersibility in water caused thereby is sufficient to achieve infinite thinnability. It is also 2() 1)49~37 - 19 - 21.10.1988/fe sufficient to disperse the neutralized polyurethane containing urea groups to form a stable dispersion.
Examples of suitable tertiary amines are trimethylamine, triethylamine and N-methylmorphLoline. The NCO prepolymer is after neutralization thinned with water to give rise to a finely divided dispersion. Soon after that any isocyanate groups present are reacted with diamines and/or polyamines co~taining primary and/or secondary amino groups as chain lengtheners. This reaction leads to a further linking and to an increase of the molecular weight. In order to obtain optimum properties, the competing reaction between amiine and water wi~h the isocyanate must be carefully ad~usted (duration, tem-perature, concentration) and must be carefully controlled to be reproducible. Water-soluble compounds are preferred as chain lengtheners, since they increase the disper-sibility of the polymeric end product in water. Hydrazine and organic diamines are preferred, since they usually provide the highest molecular mass without the resin gelling. It is assumed, however, that for this purpose the ratio of the amino group~ to the isocyanate groups is expediently chosen. The amount of the chain lengkhener is determined by its functionality, the NCO content of ~he prepoiymer and by the reaction time. The ratio of the active hydrogen atoms in the chain leng~hener to the NC0 group~ in the prepolymer should usually be less than 2 s 1 and preferably in the region of 1.0 : 1 to 1.75 ~
'''' '' ' "
". :;,'`'~
~` Z~)0~ 37 '.~:`' ! , - - 20 - 21.10.1988/fe LPAP - 0812z The presence of excess active hydrogen, especially in the form of primary amino groups, may lead to polymers having undesirably low molecular mass. The polyamines are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They may carry subqtituents which are free from hydrogen atoms capable of reacting with isocyanate groups. Examples are polyamines with linear or branched alLphatic, cyclo~
aliphatic or aromatic structure and containing at least two primary amino groups. Suitable diamines are ethylene-diamine, propylenediamine, 1,4-butylenediamine, piper-azine, 1,4-cyclohexyldimethylamine, 1,6-hexamethylene-diamine, trimethylhexamethylenediamine, methanediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane and aminoethylethanolamine. Preferred diamines are alkyl-diamines or cycloalkyldiamine~ such as propylenediamine and l-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.
The chain lengthening may be achieved, at least partially, w:Lth a polyamine which contains at least three amine groups having a reactive hydrogen. This type of polyamine may be u~ed in such an amount that unreacted amine nitrogen atoms having 1 or 2 reactive hydrogen . , : .
atoms are present after the lengthening of the polymer.
Suitablo poly~mine~ of thi~ type are diethylenetriamine, triethylenetetramine, dipropylenetriamine and dibutylene-triamine. Preferred polyamines are the alkyltriamines or cycloalkyltri~mines such a~ diethylenetriamine. In order 20~87 - 21 - 21.10.1988/fe LPAP - 0812z to prevent gelling during the chain lengthening, a small amount of monoamines, such as ethylhexylamine, may be added.
The water thinnable polyurethane resins to be used according to the invention and their preparation are also disclosed in EP-A 89,497 and US-PS 4,719,132.
The preferred basecoats comprise a mixture of 90 to 40% by weight of the crosslinked polymeric micropar~
ticles described above and 10 to 60% by weight of the water thinnable polyurethane resin containing urea groups, described above, the weight percentages referring in each case to the solids content and their total being alway~ 100% by weight.
The aqueous basecoats according to the invention advantageously contain further water-thinnable synthetic resins, eg. aminoplast resins, polyesters and polyethers which ganerally serve as grinding resins for the :. :: ~:
pigments.
The aqueous basecoats according to the invention preferably compri e 5 to 20, particularly preferably 10 to 16% by wsight, based on the total solid~ content of the ba~ecoat, of a water-thinnable aminoplast resin, preferably melamine resin, and 5 to 20, preferably 8 to 15% by waight, of a water~thinnable polyether (eg.
polypropylene glycol having a number average molecular weight of 400 to 900).
The basecoats according to the invention may 2~104987 - 22 - 21.10.1988/fe LPAP - 0812z contain, as pigments, colored inorganic pigments, eg.
titanium dioxide, iron oxide, calrbon black etc., colored organic pigments as well as the usual metallic pigments ~eg. commarcial aluminum bronze~, alloy steel bron2es ...) and non-metallic effect pigments, eg. nacreous luster and interference pigments). The basecoats accord-ing to the invention preferably comprise metallic pigments and/or effect pigments. The degree of pigmenta-tion is within the usual ranges.
In addition, the ba~ecoats according to the invention may comprise the usual rheological inorganic or organic additive~. Thus, for example, water-soluble cellulose ethers such as hydroxyethyl cellulose, methyl cellulose or carboxymethyl cellulose as well as synthetic polymer~ containing ionic and/or associatively acting groups such a~ polyvinyl alcohol, poly(meth)acrylamide, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydrids copolymers or ethylene-maleic anhydride copolymers and derivatives thereo~, or hydrophobically modified ethoxylated urethanes or polyacrylates are example~ of thickeners. Carboxyl-containing polyacrylate copolymers having an acid value of 60 to 780, preferably 200 to 500, are particularly preferred.
The bacecoatc~ according to the invention general-ly have a solids content of about 15 to 50~ by weight.
The solids content varies, depending on the use of the basecoat. In metallic paintsy the ~olids content i8 ~0~ 87 ~ . ~
- 23 -21.10.1938/fe LPAP - 0812z PAT 88 1~4 preferably about 17 to 25% by weight. In solid-color paints it is higher, for example about 30 to 45% by weight. The basecoats according to the invention may additionally contain the usual organic solvents. The S amount of these is kept as low as possible, being for example below 15~ by weight. The pH of the basecoats according to the invention is generally adjusted to between 6.5 and 9Ø The pH may be adjusted with the usual amines, eg. ammonia, triethylamine, dimethylamino~
ethanol and N-methylmorpholine.
The object stated in greater detail at the outset is achieved by the preparation of the basecoats according ;`
to the invention.
The basecoats according to the invention provide high-~uality coatings even without being themselves coated with a clear topcoat. ;
The water-thinnable paints according to the invention may be applied to any substrate, eg. metal, wood, plastics or paper. Essentially any known app-lication methods, eg. spraying, blade-coating, dipping etc., may b~ used for this purpose. ~ -~
The invention is explained in greater detail in `~
the examples below. ~ ;~
A. Preparation of cros~linked polymeric microparticle~
57.01 parts by weight of deionized water and 0.08 parts by weight of a 30% aqueous solution of an emul~
fier (ammonium salt of penta(ethylene oxide) nonylphenyl . . - .- '' ~l~V9L~87 - 24 - 21 10.1988/fe LPAP - 0812z ether sulfate, Fenopon~ EP 110 from GAF Corp.) are intro-duced into a cylindrical glass double-walled container provided with a stirrer, reflux condenser and feed vessel~, and are warmed to 70C. Subsequently 10.94 parts by weight of methyl methacrylate, 2.74 parts by weight of styrene, 0.82 parts by weight of me~hacrylic acid, 0.39 parts by weight of the em~lsifier solution defined above, the amount of component (B) stated in Table 1 and the amount of n-butyl acrylate stated in Table 1 are thoroughly mlxed. 10% by weight of the mixture obtained in this manner are added to the mixture in the reaction ve~sel. 1.37 parts by weight of hydroxypropyl methacry-late are added to the remaining 90% by weight of the mixture. ~he mixture in the reaction vessel is heated to 70C and treated with 0.77 parts by weight of a 1.07%
~trength aqueou~ H202 solution and with 0.75 part~ by weight of a 1.23% ~trength aqueouc~ solution of ascorbic acid. An exothermic reaction sets in. After 20 minutes the mixture of monomers containing the hydroxypropyl methacrylate is added together with 6.90 part~ by weight of a 1.07% strength aqiueous HzOz solution and 6.74 parts by weight of a 1.23% strength aqueous solution o~ ascor-~bic acid at ~3uch a rate that the addition is completed after 4 hour~. The reaction temperature is kept at 70C
during the addition. When the addition has been com-plated, the reaction mixture i~ kept at 70C for a further 1 hour. It ic~ then cooled and any coagulate which " '`;'-/"' "" '` ~' '`"'" . '"' .' .. ' ' "' ~. '" ,, ' ' ' ,' i'; ,'. , ' " ' ' i , ' '' . '. ' "' ' ' 8~
- 2S - 21.10.1988/fe LPAP - 0812z PA~ 88 184 may have formed is removed by filtration. ;
. ~, , :, '' . :.' ,'. ' `':
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:. ~:~.::, . ~:,~ ~.,.
.:
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: ~
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- 26 - 21.10.1988/fe LPAP - 0812z ~;
-t .
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, ~ -~o, ~ .. _ ~, . ,;~-~ ~ ~ ~ X ..
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- 27 - 21.10.1988/fe LPAP - 0812z B. Preparati~n of water-thinnable polyurethane resins Polyurethane resin dispersion 1 ;-~
570 g of a commercial polyester prepared from caprolactone and ethylene glyco:L, having a hydroxyl value of 196, is dewatered at 100C for 1 hour under reduced pressure. 524 g of 4,4'-dicyclohexylmethane diisocyanate are added at 80C and the mixture is stirred at 90C
until the isocyanate content is 7.52% by weight, based on the total weight. The reaction mixture is cooled to 60C, treated with a solution of 67 g of dimethylolpro-pionic acid and 50 g of triathylamine in 400 g o~
N-methylpyrrolidone and is stirred for 1 hour at 90C.
The resultant mass is added to 1,840 g of cold deionized water with vigorous stirring. The di~persion obtained in thi~ manner is added with vigorou~ stirring to 86 g of a 15% strength hydrazine ~olution in the cour~e of ;~ ;
20 minutes. The resultant finely divided dispersion has a solid~ content of 35~ and an efflux ~ime of 27 second~
in DIN cup No. 4.
Polyurethane resin dispersion 2 83~ g of a polyester prepared from neopentyl glycol, 1,6-hexanediol and adipic acid, having a hydroxyl -value of 135 and an acid value of less than 3, are ~ ~ -dewatered at 100C for 1 hour under reduced pressure.
524 g of 4,4'-dicyclohexylmethane diisocyanate are added at 80C and tlle reaction mixture is stirred at 90C until ~ ~-the content of free isocyanate group~ is 6.18% by weight, L98~
, .
- 28 - 21.10.1988/fe - LPAP - 0812z based on the total weight. The reaction mixture is cooled to 60C and is then treated with a solution of 67 g of dimethylolpropionic acid and 50 g of triethylamine in 400 g of N-methylpyrrolidone and is stirred for 1 hour at 90C.
The resultant mass is added to 2,400 g of cold deionized water with vigorous stirring. A finely divided dispersion is obtained. This dispersion is treated, with vigorous stirring, with 80 g of a 30~ strength aqueous solution of ethylenediamine in the course of 20 minutes.
The resultant very finely divided dispersion has a solids content of 35% and an efflux time of 23 seconds in DIN
cup No. 4.
C. Preparation of_basecoats 17.0 g of butyl glycol, 3.5 g of a commercial melamine-formaldehyde resin ~Cymel~ 301), 2.9 g of poly-propylene glycol (a~erage molecular weight = 400) and 7.0 g of an aluminum bronze according to DE-OS 3,636,183 (aluminum content 60~ by weight) are stirred with the aid of a high-3pe~d stirrer for 15 minute~ at the rate of 300-500 rpm. A mixture 1 is obtained.
41 g of a dispersion of polymeric microparticles prepared by procedure A are mixed with 11.0 g of a polyurethane resin disper~ion prepared by procedure B.
The pH of the mixture is ad~usted to 7.7 with a 5%
strength aqueou~ solution of dimethylethanolamine and is treated with 17.6 g of a 3.5~ ~trength ~olution of a :.. :, . . . . . . .
149~37 ,;
- 29 - 21.10.1988/fe - LPAP - 0812z -:
commercial polyacrylic acid thickener (Viscalexa HV 30 from Allied Colloids, pH 8.0). The mix~ure 2 is obtained.
To prepare the basecoats, ~he mixtures 1 and 2 are mixed for 30 minutes at a rate of 800-1,000 rpm and the pH of the mixture is then adjusted to 7O7 with a 5%
strength aqueous solution of dimethylethanolamine. The viscosity i5 then ad~usted to an efflux tlme of 25 sec in DIN cup No. 4 by adding deionized water. -The basecoats are sprayed by well-known methods onto phosphated steel panels (Bonder 132) which have been coated with a commercial electrocoating paint and a `~
commercial filler; after a 10 minutes' flash-off period they are then coated with a commercial clearcoat and are -`
baked at 140C for 20 minutes. Some of the painted panels are recoated with the basecoats and by a commercial clearcoat. The resultant coatings are baked at 80C for 40 minutos. `~`
The coatings obtained were sub~ected to gloss measurement and to crosshatch tests. The results are summarized in Table 2.
.
.
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nonylphenol and 4 - 30 mol of ethylene oxide in admixture with the anionic emulsifier. ;
It is pref~rred to keep the amount of ionic emulsifier used as low as possible.
The emulsion polymerization is generally carried out at temperature~ of 20 to 100C, preferably 40 to 90C. ` `
A mixture whLch consists of (al) 60 to g9, preferably 70 to 90% by weight of an aliphatic or cycloaliphatic ester of acrylic acid or methacrylic acid or a mixture of such esters (a2) 0 to 5, preferably 2 to 4~ by weight of an ethyleni~
cally unsaturated monomer which carries at least one carboxyl group in the molecule and is copolymeriz-able with (al), (a3) and (a4), or a mixture of such monomer~
(a3) 1 to 40, preferably 2 to 15% by weight of an ethy~
lenically unsaturated monomer which carries at least ..,~
,'.': '.,, ',` ' "',"~,"" "~',' '' ,- 2~)~)4~318~i;
- _ 7 - 21.10.1988/fe - LPAP - 0812z one hydroxyl group in the molecule and is copolymerizable with (al), (a2) and (a4), or a mixture of such monomers, and (a4) 0 to 30, preferably 5 to 20~ by weight of a further ethylenically unsaturated monomer which is copoly-merizable with (al), (a2) and (a3), or a mixture of such monomers, is preferably used as component (A), the to~al of the weight percentages of (al), (a2~, (a3) and (a4) being always 100% by weight.
The following can be used, for example, as component (al): cyclohexyl acrylate, cyclohexyl methacry-late, alkyl acrylates and alkyl methacrylates having up to 20 carbon atoms in the alkyl radical, eg. methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylates and methacrylate~ or mixtures of these monomers.
Acrylic acid and/or methacrylic acid are pre-ferably USQCI as component (a2). However, other ethyl~
enically un~aturated acids having up to 6 carbon atoms in the mo1ecule may be also used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
The following may be used, for example, as component (~3): hydroxyalkyl e~ters of acrylic acid, methacrylic acid or any other ~ et~ylenically unsatura-ted carboxylic acid. These esters may be derived from an . . ~. ~ . - .
.~ .... ` . . . . . . . .. . . . .. .. . . . .
- 8 - 21.10.1988/fe LPAP - 0812z alkylene glycol which is esterified with the acid, or they can be obtained by reacting the acid with an alky-lene oxide. Hydroxyalkyl esters of acrylic acid and methacrylic acid in which the hydroxyalkyl group contains up to 4 car~on atoms, or a mixture of these hydroxyalkyl ester , are preferably used as component (a3~. Examples of such hydroxyalkyl esters are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropoxypropyl acry-late, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxybutyl acrylate or 4-hydroxybutyl (meth)acrylate. The corresponding esters of other un-saturated acids, eg. ethacrylic acid, crotonic acid and similar acids having up to about 6 carbon atom~ pex lS molecule may be al~o used.
The following may be used, for example, as component (a4~: vinylaromatic hydrocarbons such as ~tyrene, ~-~lkyl~tyrene and vinyltoluene, ac~ylamide, methacrylamide, acrylonitrile and methacrylonitrile, or mixture3 of the3e monomers. -It is an e~ential part of the invention that 0.5to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5~ by weight of allyl methacrylate or 1.5 to 8.0, prsferably 2.0 to 5.0, particularly preferably 4.0~ by weight of ethylene glycol di(meth)acrylate or 1.5 to 8.0, preferably 2 0 a to 5.0, particularly preferably 4.0% by weight of butanediol di(meth)acrylate or 1.5 to 10.0~
~, - 9 - 21.10.1988/fe LPAP - 0812z preferably ~.0 to 7.0, particularly preferably 5.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0, preferably 1.0 to 4.0, particularly preferably 2.0~ by weight of divinylbenzene are used as component (B), the weight percentages referring to the total amounts of the component (A) used and of the component (~) used (the weight percentage of the component (A) used + the weight percentage of the component (B) used = 100~ by weight).
The crosslinked polymeric microparticles used according to the invention must have a diameter of 0.01 to 10 ~m.
Basecoats which comprise, in addition to the crosslinked polymeric microparticles described above, also a water-thinnable polyurethane resin, furnish multicoat coating~ with a particularly good effect and are preerred. The preferred basecoats preferably comprise a~ the polyurethane resins water-thinnable poly-urethane re ins containing urea groups having a number average molecular weight of 1,000 to 60,000, preferably 1,500 to 50,000 (dete~mined by gel permeation chromato-graphy using polystyrene as standard) and an acid value of 5 to 70, preferably 10 to 30. Such polyurethane resins may be prepaxed by reacting isocyanate-containing pre-polymer~ with organic polyamines and/or hydrazine.
~he preparation of the isocyanate-containing prepolymer~ may be carried out by reacting polyalcohols having a hydroxyl value of 10 to 1,800, preferably 50 to -: : .. . .
'';.''" , ,: ........ . ' ' '. ' ' , '.~: ~.: '- - -. . . :
; ~ . : . ~ .
- 10 - 21.10.1988/fe LPAP - 0812z 500, with an excess of polyisocyanates at temperatures up to 150C, preferably 50 to 130C, in organic solvents which are inert to isocyanates. 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 l;o 1. The polyols used for the preparation of the prepolymers may be low-molecular and/or high-molecular and they may contain anionic groups which axe slow to react.
In order to raise the hardness of the poly-urethane, low-molecular polyols may be used. They have a molecular weight of 60 up to about 400 and may comprise aliphatic, alicyclic or aromatic groups. Amounts of up to 30~ by weight of the total polyol components, preferably about 2 to 20% by weight, are usecl. The low-molecular polyols have advantageously up to about 20 carbon atoms per moleculs, such as ethylone glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butyleneglycol, 1,6-hexanediol trimethylolpropane, castor oil or hydrogenated castor oil, di(trimethylolpropane~ ether, pentaerythritol, 1,2-cyclohexanediol,1,4-cyclohexanedLmethanol,bisphenol A, bisphenol F, neopentyl glycol, neopentyl glycol hydroxypivalate, hydroxyethylated or hydroxypropylated bisphenol A, hydrogenated bisphenol A and mixtures thereof.
In orcler to obtain more flexible NCO prepolymers, .- . .: .
a high proportion of a predominantly linear polyol having ~
~ .
' .1 ;20~)~98 7 21.10.1988/fe LPAP - 0812z a preferred hydroxyl value 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 having a molecular mass Mn of 400 to 5,000. Suitable high-molecular polyols are aliphatic polyether diols of the general formula H-(-O-(-CHR-)n-)m-OH in which R is hydrogen or a low alkyl radical which may be unsubstitu-ted or substituted by various substituents, n being 2 to 6, preferably 3 to 4 and m being 2 to 100, preferably 5 to 50. Examples are linear or branched polyether diols such as polytoxyethylene) glycols, poly(oxypropylene) glycols and/or poly(oxybutylene) glycols. The chosen polyether diols should not introduce an excessive amount of ether groups, since otherwise the polymers formed swell in water. The preferred polyether diols are poly-(oxypropyleno) glycols in the molecular mass Mn range of 400 to 3,000. Polyester diols are prepared by esterifying organic dicarboxylic acids or their anhydrides with organic diols or they are derived from a hydroxycar-boxylic acid or a lactone. To prepare branched polyester polyols, polyols or polycarboxylic acids of high valency may be u~ed to a small extent. The dicarboxylic acids and diols may be linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acids or diols.
~he diols used for the preparation of the poly-e~ter~ con~ist, for example, of alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, . ~ .. . . . . .
~0~)4~ 7 - 12 - 21.10.1988/fe LPAP - 0812z 1,4-butanedi~l, 1,6-hexanediol, neopentyl glycol and other diol~ such as dimethylolcyClhexane- The acid com~
ponent of the polyester consists mainly of low molecular dicarboxylic acids or their anhydrideq having 2 to 30, S preferably 4 to 1~ carbon atoms in the molecule. Examples of æuitable acids are o-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, cyclohexane-dicarboxylic acid, quccinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaric acid, hexachloroheptanedicarboxylic acid, tetrachloro~
phthalic acid and/or dimerized fatty acids. The anhydride~ of thesa acids, whera they exist, may be used ~ `
instead of the acids. For the formation of polyester polyol , relatively small amounts of carboxylic acids with three or more carboxyl groups, for example tri-mellitic anhydride or the adduct of maleic anhydride and unsaturated Patty acids, may be also present.
According to the invention, it i~ also possible to use polye~ter diols which are obtained by reacting a lactone with a diol. They are distinguished by the pre~ence of a terminal hydroxyl group and recurring -:
polyester moieties of the formula -(C0-(CHR)n-CH2-0-), whers n is preferably 4 to 6 and the substituent R is hydrogen, alkyl, cycloalkyl or alkoxy. No sub~ti~uent contains more than 12 carbon atom~. The total numb~r of ~ -carbon atoms in tha substituent does not exceed 12 per ~-lac~ona ring. Appropriate example~ are hydro~ycaproic . .
- 13 - 21.10.1988/fe LPAP - 0812z PAT ~8 184 acid, hydroxybu~yric acid, hydroxydecanoic acid and~or hydroxystearic acid. The lactone used as starting mate-rial can be represented by the following general formula CH2~(CR2)n~ 1~ , O
in which n and R have the meaning already defined. For the prepara~ion of the polyester diols the unsubstituted -~-caprolactone, in which n has the value of 4 and all R
substituents are hydrogen, is preferred. The reaction with lactone is initiated by relatively low-molecular polyols, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol and dimethylolcyclohexane. However, other reactants such a~ ethylenediamine, alkyldialkanolamines or even urea may be reacted with caprolactone. -Suitable higher-molecular diols are also poly-lactam diols which are prepared by the reaction of, for example, 6 -caprolactam with relatively low-molecular diols.
Aliphatic, cycloaliphatic and/or aromatic poly-, isocyanates having at least two isocyanate groups per molecule are employed as typical multifunctional iso-cyanates. Isomar~ or isomeric mixtures of organic diisocyanate~ are preferred. Suitable aromatic diiso-cyanates are phenylene diisocyanate, toluylene diiso- ;
cyanate, xylylene dii~ocyanate, biphenylene diisocyanate, Z()04~
- 14 - 21.10.1988/fe LPAP - 0812z naphthylene diisocyanate and diphenylmethane diisocyanate.
Because of their good resistance to ultraviolet light, (cyclo)aliphatic diisocyanates give rise to products with a low tendency to yellowing. Example~ of these diisocyanates are isophorone diisocyanate, cyclo~
pentylene diisocyanate and hydrogenation products of aromatic diisocyanates such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate and dicyclohexylm~thane diisocyanate~ Examples of aliphatic diisocyanate~ are trimethylene diisocyanate, tetramethy-lene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, dimethylethylene diiso-cyanate, methyltrimethylene diisocyanate andtrimethylhexane diisocyanate. The diisocyanates particularly preferred are isophorone diisocyanate and dicyclohexylmethane diisocyanate. The polyisocyanate component u~ed for the formation of the prepolymer may also contain some polyisocyanates of higher valency, provided that these do not cause gelling. Suitable triisocyanates have been found to be products which are formed by trimerization or oligomerization of diisocya-nates or by the reaction of diisocyanates with -`-polyfunctional OH-containing or NH-containing compound~
Examples of thes3 are the biuret of hexamethylene diiso~
cyanate and water, the isocyanurate of hexamethylsne : .. -.. ... . . . .; .~ . . .. . .. . . . . . .. . . ..... ...... ... . .
98~
, - 15 - 21.10.1988/fe LPAP - 0812z diisocyanate or the adduct of i~ophorone diisocyanate and trLmethylolpropane. If desired, the average functionality can be reduced by the addition of monoisocyanates.
Examples of ~uch chain-terminating monoisocyanates are phenyl isocyanate~ cyclohexyl isocyanate and stearyl isocyanate.
Polyurethanes are generally not compatible with water, unless special components are incorporated during their synthesis and/or unless special preparative steps are undertaken. Such a high acid value is incorporated in thi manner that the neutralized product is disper-sible in water to give a stable dispQrsion. Compounds which are suitable for thi~ purpose contain two H-active groups which are reactive with isocyanate groups and at least one group capable of forming anions. Suitable groups wllich aro reactiva with isocyanate groups arQ
particularly hydroxyl groups as well as primary and/or secondary amino group-~. Groups which are capable of forming anions, are carboxyl, sulfonic acid and/or phosphonic acid groups. Carboxylic acid or carboxylate groups are preferred. They should be so slow to react that the isocyanate groups of the diisocyanate preferably react with the other groups in the molecule which are r~active toward isocyanate group~. Alkanoic acids having two ~ubstituents on the ~ carbon atom, are used for this purpose. Th~ substituent may be a hydroxyl group, an alkyl group or an alkylol group. These polyols have at 200~g8~
- 16 - 21.10.1988~fe - LPAP - 0812z 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 dihydroxy-propionic acid, dihydroxysuccinic acid and dihydroxyben-zoic acid. ~ group of dihydro:~yalkanoic acids which isparticularly preferred, are the ~ dimethylolalkanoic acids which are represented by the ~tructural formula ;-RC(CH2OH)2COOH, in which R is hydrogen or an alkyl group having up to 20 carbon atoms. Example~ of such compounds are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic -acid, 2,2-dimethylolbutyric acid and 2,2-dimethylol-pentanoic acid. The preferred dihydroxyalkanoic acid i~
2,2-dLmethylolpropionic acid. Examples of amino~con-taining compound~ are ~ diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluene sulfonic acid and 2,4-diaminodiphenyl ether sulfonic acid. The polyol containing carboxyl groups may form 3 to 100% by weight, preferably 5 to 50~ by weight, of the total polyol component in the NCO prepolymer.
The amount of ionizable carboxylic group~ avail-able in salt form by neutrali~a~ion of the carboxyl groups is generally at least 0.4~ by weight, prefera~ly at lea~t 0.7~ by weight, ba~ed on the solids content. The --upper limit i~ about 6% by weight. The amount of ;
dihydroxyalkanoic acids in the non-neutralized prepolymer give~ rise to an acid value of at leat 5, preferably at lea3t 10. The upper acid value limit is 70, preferably 21)0~9~3'7 - 17 - 21.10.1988/fe LPAP - 0812z 40, based on the solids content.
This dihydroxyalkanoic acid is advantageously at least partially neutrali2ed with a tertiary amine prior to the reaction with isocyanat~es in order to prevent a reaction with the isocyanates.
The NCO prepolymers used according to the inven-tion may be prepared by a simultaneous reaction of the polyol or polyol mixture with an excess of diisocyanate.
Otherwise the reaction may be carried out in stages in the prescribed sequence.
Examples are disclosed in DE 2,624,442 and DE 3,210,051. The reaction temperature is up to 150C, a temperature in the range of 50 to 130C being preferred.
The reaction is continued until virtually all the hydroxyl function~ have reacted.
The NCO prepolymer contains at least about 0.5%
by weight of i~ocyanste groups, preferably at least 1~ by weight of NCO, based on the solids content. The upper limit is about 15~ by weight, preferably 10% by weight, particularly preferably about 5% by weight. The reaction may be carried out in the pre~ence or ab3ence of a catalyst, such as organotin compounds and/or tertiary amines. In oxder to maintain the coreactants in a liquid state and to allow a bstter temperature control during the reaction, it is possible to add organic solvents which contain no active Zerewitinoff hydrogen. Examples of suitable solvents are dimethylformamide, e ters, ''.'.'. :'~
~ 20~)49~3~
- 18 - 21.10.1988/fe `
LP~P - 0812z ethers such as diethylene glyc:ol dimethyl ether, keto-.. ..
esters, ketones such as methyl ethyl ketone and acetone, ketones substituted by methoxy groups such as methoxyhexanone, glycol ether asters, chlorinated hydro-carbons, aliphatic and alicyclic hydrocarbon pyrrolidones such as N-methylpyrrolidone, hydxogenated furans, aroma- - -tic hydrocarbons and mixtures thereof. The amount of solvent can vary within a wide range and should be sufficient to allow the formation of a prepolymer solu-tion of suitable viscosity. 0.01 to 15% by weight of solvent~, preferably 0.02 to 8% by weight of solvents, -~
based on the solids content, is generally sufficient.
Should the boiling point of any water-insoluble solvents present be lower than water, such solvents may be care-fully distilled off by vacuum distillation or thin-layer evaporation after preparation of the polyurethane disper-sion containing urea groups. Higher-boiling ~olvents should be water-soluble and they remain in the aqueous polyurethane dispersion in order to facilitate the ;~
coalescence of the polymer particles during film forma- -tion. The solvent which is particularly preferred is N-mathylpyrrolidone, either alone or in admixture with ketones such as methyl ethyl ketone.
Tho anionic group of the NC0 prepolymer are at least partially neutralized with a tertiary amine. The increase in dispersibility in water caused thereby is sufficient to achieve infinite thinnability. It is also 2() 1)49~37 - 19 - 21.10.1988/fe sufficient to disperse the neutralized polyurethane containing urea groups to form a stable dispersion.
Examples of suitable tertiary amines are trimethylamine, triethylamine and N-methylmorphLoline. The NCO prepolymer is after neutralization thinned with water to give rise to a finely divided dispersion. Soon after that any isocyanate groups present are reacted with diamines and/or polyamines co~taining primary and/or secondary amino groups as chain lengtheners. This reaction leads to a further linking and to an increase of the molecular weight. In order to obtain optimum properties, the competing reaction between amiine and water wi~h the isocyanate must be carefully ad~usted (duration, tem-perature, concentration) and must be carefully controlled to be reproducible. Water-soluble compounds are preferred as chain lengtheners, since they increase the disper-sibility of the polymeric end product in water. Hydrazine and organic diamines are preferred, since they usually provide the highest molecular mass without the resin gelling. It is assumed, however, that for this purpose the ratio of the amino group~ to the isocyanate groups is expediently chosen. The amount of the chain lengkhener is determined by its functionality, the NCO content of ~he prepoiymer and by the reaction time. The ratio of the active hydrogen atoms in the chain leng~hener to the NC0 group~ in the prepolymer should usually be less than 2 s 1 and preferably in the region of 1.0 : 1 to 1.75 ~
'''' '' ' "
". :;,'`'~
~` Z~)0~ 37 '.~:`' ! , - - 20 - 21.10.1988/fe LPAP - 0812z The presence of excess active hydrogen, especially in the form of primary amino groups, may lead to polymers having undesirably low molecular mass. The polyamines are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They may carry subqtituents which are free from hydrogen atoms capable of reacting with isocyanate groups. Examples are polyamines with linear or branched alLphatic, cyclo~
aliphatic or aromatic structure and containing at least two primary amino groups. Suitable diamines are ethylene-diamine, propylenediamine, 1,4-butylenediamine, piper-azine, 1,4-cyclohexyldimethylamine, 1,6-hexamethylene-diamine, trimethylhexamethylenediamine, methanediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane and aminoethylethanolamine. Preferred diamines are alkyl-diamines or cycloalkyldiamine~ such as propylenediamine and l-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.
The chain lengthening may be achieved, at least partially, w:Lth a polyamine which contains at least three amine groups having a reactive hydrogen. This type of polyamine may be u~ed in such an amount that unreacted amine nitrogen atoms having 1 or 2 reactive hydrogen . , : .
atoms are present after the lengthening of the polymer.
Suitablo poly~mine~ of thi~ type are diethylenetriamine, triethylenetetramine, dipropylenetriamine and dibutylene-triamine. Preferred polyamines are the alkyltriamines or cycloalkyltri~mines such a~ diethylenetriamine. In order 20~87 - 21 - 21.10.1988/fe LPAP - 0812z to prevent gelling during the chain lengthening, a small amount of monoamines, such as ethylhexylamine, may be added.
The water thinnable polyurethane resins to be used according to the invention and their preparation are also disclosed in EP-A 89,497 and US-PS 4,719,132.
The preferred basecoats comprise a mixture of 90 to 40% by weight of the crosslinked polymeric micropar~
ticles described above and 10 to 60% by weight of the water thinnable polyurethane resin containing urea groups, described above, the weight percentages referring in each case to the solids content and their total being alway~ 100% by weight.
The aqueous basecoats according to the invention advantageously contain further water-thinnable synthetic resins, eg. aminoplast resins, polyesters and polyethers which ganerally serve as grinding resins for the :. :: ~:
pigments.
The aqueous basecoats according to the invention preferably compri e 5 to 20, particularly preferably 10 to 16% by wsight, based on the total solid~ content of the ba~ecoat, of a water-thinnable aminoplast resin, preferably melamine resin, and 5 to 20, preferably 8 to 15% by waight, of a water~thinnable polyether (eg.
polypropylene glycol having a number average molecular weight of 400 to 900).
The basecoats according to the invention may 2~104987 - 22 - 21.10.1988/fe LPAP - 0812z contain, as pigments, colored inorganic pigments, eg.
titanium dioxide, iron oxide, calrbon black etc., colored organic pigments as well as the usual metallic pigments ~eg. commarcial aluminum bronze~, alloy steel bron2es ...) and non-metallic effect pigments, eg. nacreous luster and interference pigments). The basecoats accord-ing to the invention preferably comprise metallic pigments and/or effect pigments. The degree of pigmenta-tion is within the usual ranges.
In addition, the ba~ecoats according to the invention may comprise the usual rheological inorganic or organic additive~. Thus, for example, water-soluble cellulose ethers such as hydroxyethyl cellulose, methyl cellulose or carboxymethyl cellulose as well as synthetic polymer~ containing ionic and/or associatively acting groups such a~ polyvinyl alcohol, poly(meth)acrylamide, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydrids copolymers or ethylene-maleic anhydride copolymers and derivatives thereo~, or hydrophobically modified ethoxylated urethanes or polyacrylates are example~ of thickeners. Carboxyl-containing polyacrylate copolymers having an acid value of 60 to 780, preferably 200 to 500, are particularly preferred.
The bacecoatc~ according to the invention general-ly have a solids content of about 15 to 50~ by weight.
The solids content varies, depending on the use of the basecoat. In metallic paintsy the ~olids content i8 ~0~ 87 ~ . ~
- 23 -21.10.1938/fe LPAP - 0812z PAT 88 1~4 preferably about 17 to 25% by weight. In solid-color paints it is higher, for example about 30 to 45% by weight. The basecoats according to the invention may additionally contain the usual organic solvents. The S amount of these is kept as low as possible, being for example below 15~ by weight. The pH of the basecoats according to the invention is generally adjusted to between 6.5 and 9Ø The pH may be adjusted with the usual amines, eg. ammonia, triethylamine, dimethylamino~
ethanol and N-methylmorpholine.
The object stated in greater detail at the outset is achieved by the preparation of the basecoats according ;`
to the invention.
The basecoats according to the invention provide high-~uality coatings even without being themselves coated with a clear topcoat. ;
The water-thinnable paints according to the invention may be applied to any substrate, eg. metal, wood, plastics or paper. Essentially any known app-lication methods, eg. spraying, blade-coating, dipping etc., may b~ used for this purpose. ~ -~
The invention is explained in greater detail in `~
the examples below. ~ ;~
A. Preparation of cros~linked polymeric microparticle~
57.01 parts by weight of deionized water and 0.08 parts by weight of a 30% aqueous solution of an emul~
fier (ammonium salt of penta(ethylene oxide) nonylphenyl . . - .- '' ~l~V9L~87 - 24 - 21 10.1988/fe LPAP - 0812z ether sulfate, Fenopon~ EP 110 from GAF Corp.) are intro-duced into a cylindrical glass double-walled container provided with a stirrer, reflux condenser and feed vessel~, and are warmed to 70C. Subsequently 10.94 parts by weight of methyl methacrylate, 2.74 parts by weight of styrene, 0.82 parts by weight of me~hacrylic acid, 0.39 parts by weight of the em~lsifier solution defined above, the amount of component (B) stated in Table 1 and the amount of n-butyl acrylate stated in Table 1 are thoroughly mlxed. 10% by weight of the mixture obtained in this manner are added to the mixture in the reaction ve~sel. 1.37 parts by weight of hydroxypropyl methacry-late are added to the remaining 90% by weight of the mixture. ~he mixture in the reaction vessel is heated to 70C and treated with 0.77 parts by weight of a 1.07%
~trength aqueou~ H202 solution and with 0.75 part~ by weight of a 1.23% ~trength aqueouc~ solution of ascorbic acid. An exothermic reaction sets in. After 20 minutes the mixture of monomers containing the hydroxypropyl methacrylate is added together with 6.90 part~ by weight of a 1.07% strength aqiueous HzOz solution and 6.74 parts by weight of a 1.23% strength aqueous solution o~ ascor-~bic acid at ~3uch a rate that the addition is completed after 4 hour~. The reaction temperature is kept at 70C
during the addition. When the addition has been com-plated, the reaction mixture i~ kept at 70C for a further 1 hour. It ic~ then cooled and any coagulate which " '`;'-/"' "" '` ~' '`"'" . '"' .' .. ' ' "' ~. '" ,, ' ' ' ,' i'; ,'. , ' " ' ' i , ' '' . '. ' "' ' ' 8~
- 2S - 21.10.1988/fe LPAP - 0812z PA~ 88 184 may have formed is removed by filtration. ;
. ~, , :, '' . :.' ,'. ' `':
~ ~' ' " ,' ~"
:. ~:~.::, . ~:,~ ~.,.
.:
; . ;: .. :.~.
: ~
; ~, . ~:::
'` '',~' ~'`.'~'`' : ~
: ., .
,. ;'`'.``' .':;
,, ~,..:''' :~: ~: '' ', Z~)04!q~
...
- 26 - 21.10.1988/fe LPAP - 0812z ~;
-t .
o o o X
, ~ -~o, ~ .. _ ~, . ,;~-~ ~ ~ ~ X ..
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E~ C~_ ~ ~ ~ t P~ 7. ~1 :
- 27 - 21.10.1988/fe LPAP - 0812z B. Preparati~n of water-thinnable polyurethane resins Polyurethane resin dispersion 1 ;-~
570 g of a commercial polyester prepared from caprolactone and ethylene glyco:L, having a hydroxyl value of 196, is dewatered at 100C for 1 hour under reduced pressure. 524 g of 4,4'-dicyclohexylmethane diisocyanate are added at 80C and the mixture is stirred at 90C
until the isocyanate content is 7.52% by weight, based on the total weight. The reaction mixture is cooled to 60C, treated with a solution of 67 g of dimethylolpro-pionic acid and 50 g of triathylamine in 400 g o~
N-methylpyrrolidone and is stirred for 1 hour at 90C.
The resultant mass is added to 1,840 g of cold deionized water with vigorous stirring. The di~persion obtained in thi~ manner is added with vigorou~ stirring to 86 g of a 15% strength hydrazine ~olution in the cour~e of ;~ ;
20 minutes. The resultant finely divided dispersion has a solid~ content of 35~ and an efflux ~ime of 27 second~
in DIN cup No. 4.
Polyurethane resin dispersion 2 83~ g of a polyester prepared from neopentyl glycol, 1,6-hexanediol and adipic acid, having a hydroxyl -value of 135 and an acid value of less than 3, are ~ ~ -dewatered at 100C for 1 hour under reduced pressure.
524 g of 4,4'-dicyclohexylmethane diisocyanate are added at 80C and tlle reaction mixture is stirred at 90C until ~ ~-the content of free isocyanate group~ is 6.18% by weight, L98~
, .
- 28 - 21.10.1988/fe - LPAP - 0812z based on the total weight. The reaction mixture is cooled to 60C and is then treated with a solution of 67 g of dimethylolpropionic acid and 50 g of triethylamine in 400 g of N-methylpyrrolidone and is stirred for 1 hour at 90C.
The resultant mass is added to 2,400 g of cold deionized water with vigorous stirring. A finely divided dispersion is obtained. This dispersion is treated, with vigorous stirring, with 80 g of a 30~ strength aqueous solution of ethylenediamine in the course of 20 minutes.
The resultant very finely divided dispersion has a solids content of 35% and an efflux time of 23 seconds in DIN
cup No. 4.
C. Preparation of_basecoats 17.0 g of butyl glycol, 3.5 g of a commercial melamine-formaldehyde resin ~Cymel~ 301), 2.9 g of poly-propylene glycol (a~erage molecular weight = 400) and 7.0 g of an aluminum bronze according to DE-OS 3,636,183 (aluminum content 60~ by weight) are stirred with the aid of a high-3pe~d stirrer for 15 minute~ at the rate of 300-500 rpm. A mixture 1 is obtained.
41 g of a dispersion of polymeric microparticles prepared by procedure A are mixed with 11.0 g of a polyurethane resin disper~ion prepared by procedure B.
The pH of the mixture is ad~usted to 7.7 with a 5%
strength aqueou~ solution of dimethylethanolamine and is treated with 17.6 g of a 3.5~ ~trength ~olution of a :.. :, . . . . . . .
149~37 ,;
- 29 - 21.10.1988/fe - LPAP - 0812z -:
commercial polyacrylic acid thickener (Viscalexa HV 30 from Allied Colloids, pH 8.0). The mix~ure 2 is obtained.
To prepare the basecoats, ~he mixtures 1 and 2 are mixed for 30 minutes at a rate of 800-1,000 rpm and the pH of the mixture is then adjusted to 7O7 with a 5%
strength aqueous solution of dimethylethanolamine. The viscosity i5 then ad~usted to an efflux tlme of 25 sec in DIN cup No. 4 by adding deionized water. -The basecoats are sprayed by well-known methods onto phosphated steel panels (Bonder 132) which have been coated with a commercial electrocoating paint and a `~
commercial filler; after a 10 minutes' flash-off period they are then coated with a commercial clearcoat and are -`
baked at 140C for 20 minutes. Some of the painted panels are recoated with the basecoats and by a commercial clearcoat. The resultant coatings are baked at 80C for 40 minutos. `~`
The coatings obtained were sub~ected to gloss measurement and to crosshatch tests. The results are summarized in Table 2.
.
.
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Claims (8)
1. A process for the preparation of a multicoat coating on a substrate surface, in which process (1) a pigmented aqueous basecoat which comprises cross-linked polymeric microparticles, obtainable by emulsion polymerization of (A) ethylenically unsaturated monomers which contain one ethylenically unsaturated group per molecule, or a mixture of such monomers, and of (B) an ethylenically unsaturated monomer which contains two ethylenically unsaturated groups in the molecule, is applied to the substrate surface (2) a polymeric film is formed from the composition applied in stage (1) (3) a clear topcoat is applied to the basecoat obtained in this manner, and subsequently (4) the basecoat and the topcoat are baked together, wherein the crosslinked polymeric microparticles com-prised in the basecoat can be obtained by using as component (B) 0.5 to 2.4, preferably 1.0 to 2.0, particu-larly preferably 1.5% by weight of allyl methacrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferab-ly 4.0% by weight of ethylene glycol di(meth)acrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferab-ly 4.0% by weight of butanediol di(meth)acrylate or 1.5 to 10.0, preferably 3.0 to 7.0, particularly preferably 5.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0, preferably 1.0 to 4.0, particularly preferably 2.0%
by weight of divinylbenzene, the weight percentages referring to the total amounts of component (A) used and of component (B) used (the weight percentage of component (A) used + the weight percentage of component (B) used =
100% by weight).
by weight of divinylbenzene, the weight percentages referring to the total amounts of component (A) used and of component (B) used (the weight percentage of component (A) used + the weight percentage of component (B) used =
100% by weight).
2. A water-thinnable paint which comprises cross-linked polymeric microparticles, obtainable by emulsion polymerization of (A) ethylenically unsaturated monomers which contain one ethylenically unsaturated group in the molecule, or a mixture of such monomers, and (B) an ethylenically unsaturated monomer which contains two ethylenically unsaturated groups in the molecule wherein the crosslinked polymeric microparticles can be obtained by using as component (B) 0.5 to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5% by weight of allyl methacrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferably 4.0% by weight of ethylene glycol di(meth)acrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferably 4.0% by weight of butanediol di(meth)acrylate or 1.5 to 10.0, preferably 3.0 to 7.0, particularly preferably 5.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0, preferably 1.0 to 4.0, particularly preferably 2.0% by weight of divinylbenzene, the weight percentages referring to the total amounts of component (A) used and of component (B) used (the weight percentage of component (A) used + the weight percentage of component (B) used = 100% by weight).
3. The process or the paint as claimed in claim 1 or 2, wherein the emulsion polymerization of (A) and (B) is initiated by a redox initiator system consisting of H2O2 and a non-ionic, water-soluble reducing agent.
4. The process or the paint as claimed in any of claims 1 to 3, wherein a mixture which consists of (a1) 60 to 99, preferably 70 to 90% by weight of an aliphatic or cycloaliphatic ester of acrylic acid or methacrylic acid or a mixture of such esters (a2) 0 to 5, preferably 2 to 4% by weight of an ethyleni-cally unsaturated monomer which carries at least one carboxyl group in the molecule and is copolymeriz-able with (a1), (a3) and (a4), or a mixture of such monomers (a3) 1 to 40, preferably 2 to 15% by weight of an ethy-lenically unsaturated monomer which carries at least one hydroxyl group in the molecule and is copolymerizable with (a1), (a2) and (a4), or a mixture of such monomers, and (a4) 0 to 30, preferably 5 to 20% by weight of a further ethylenically unsaturated monomer which is copoly-merizable with (a1), (a2) and (a3), or a mixture of such monomers, is preferably used as component (A), the total of the weight percentages of (a1), (a2), (a3) and (a4) being always 100% by weight.
5. The process or the paint as claimed in any of claims 1 to 4, wherein the basecoat or the paint also comprises, in addition to the crosslinked polymeric microparticles, an aqueous dispersion of a water-thin-nable polyurethane resin.
6. A process for the preparation of crosslinked polymeric microparticles in which process (A) ethylenically unsaturated monomers which contain one ethylenically unsaturated group per molecule, together with (B) an ethylenically unsaturated monomer which contains two ethylenically unsaturated groups in the molecule, are subjected to an emulsion polymerization, wherein 0.5 to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5% by weight of allyl methacrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferably 4.0% by weight of ethylene glycol di(meth)acrylate or 1.5 to 8.0, preferably 2.0 to 5.0, particularly preferably 4.0% by weight of butanediol di(meth)acrylate or 1.5 to 10.0, preferably 3.0 to 7.0, particularly preferably 5.0% by weight of hexanediol di(meth)acrylate or 0.5 to 6.0, preferably 1.0 to 4.0, particularly preferably 2.0% by weight of divinylbenzene are used as component (B), the weight percentages referring to the total amounts of component (A) used and of component (B) used the weight percentage of component (A) used + the weight percentage of component (B) used = 100% by weight).
7. Crosslinked polymeric microparticles which are obtainable by the process as claimed in claim 6.
8. The process or the polymeric microparticles as claimed in claim 6 or 7, wherein a mixture which consists of (a1) 60 to 99, preferably 70 to 90% by weight of an aliphatic or cycloaliphatic ester of acrylic acid or methacrylic acid or a mixture of such esters (a2) 0 to 5, preferably 2 to 4% by weight of an ethyleni-cally unsaturated monomer which carries at least one carboxyl group in the molecule and is copolymeriz-able with (a1), (a3) and (a4), or a mixture of such monomers (a3) 1 to 40, preferably 2 to 15% by weight of an ethy-lenically unsaturated monomer which carries at least one hydroxyl group in the molecule and is copolymerizable with (a1), (a2) and (a4), or a mixture of such monomers, and (a4) 0 to 30, preferably 5 to 20% by weight of a further ethylenically unsaturated monomer which is copoly-merizable with (a1), (a2) and (a3), or a mixture of such monomers, is preferably used as component (A), the total of the weight percentages of (a1), (a2), (a3) and (a4) being always 100% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3841541.0 | 1988-12-09 | ||
| DE3841541A DE3841541A1 (en) | 1988-12-09 | 1988-12-09 | METHOD FOR PRODUCING A MULTILAYER LACQUERING, WATER-DUMBABILIZABLE VARNISH, METHOD FOR PRODUCING CROSSLINKED POLYMER MICROPARTICLES AND CROSSLINKED POLYMER MICROPARTICLES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2004987A1 true CA2004987A1 (en) | 1990-06-09 |
Family
ID=6368826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004987A Abandoned CA2004987A1 (en) | 1988-12-09 | 1989-12-08 | Preparation of a multicoat coating, water-thinnable paint, preparation of crosslinked polymeric microparticles and crosslinked polymeric microparticles |
Country Status (5)
| Country | Link |
|---|---|
| AU (1) | AU4644189A (en) |
| CA (1) | CA2004987A1 (en) |
| DE (1) | DE3841541A1 (en) |
| WO (1) | WO1990006187A1 (en) |
| ZA (1) | ZA899022B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6448326B1 (en) | 1991-03-03 | 2002-09-10 | Basf Coatings Ag | Mixer system for the preparation of water-thinnable coating compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4110520C5 (en) * | 1991-03-30 | 2005-10-20 | Basf Coatings Ag | Mixing system for the preparation of water-dilutable coating compositions |
| EP0525977A1 (en) * | 1991-06-28 | 1993-02-03 | Morton International, Inc. | Fast dry waterborne traffic marking paint |
| DE4338265C1 (en) * | 1993-11-10 | 1994-12-08 | Herberts Gmbh | Process for coil coating using coating compositions based on organic solvents |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0038127B1 (en) * | 1980-04-14 | 1984-10-17 | Imperial Chemical Industries Plc | Multi-layer coating process involving use of aqueous basecoat composition containing crosslinked polymer microparticles and having a pseudoplastic or thixotropic character |
| DE3378722D1 (en) * | 1982-03-18 | 1989-01-26 | Basf Corp | A process for preparing a multilayer coating on a substrate and a coated substrate prepared thereby |
| GB8613408D0 (en) * | 1986-06-03 | 1986-07-09 | Crown Decorative Prod Ltd | Thickeners |
-
1988
- 1988-12-09 DE DE3841541A patent/DE3841541A1/en not_active Withdrawn
-
1989
- 1989-11-27 AU AU46441/89A patent/AU4644189A/en not_active Abandoned
- 1989-11-27 WO PCT/EP1989/001435 patent/WO1990006187A1/en unknown
- 1989-11-27 ZA ZA899022A patent/ZA899022B/en unknown
- 1989-12-08 CA CA002004987A patent/CA2004987A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6448326B1 (en) | 1991-03-03 | 2002-09-10 | Basf Coatings Ag | Mixer system for the preparation of water-thinnable coating compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| AU4644189A (en) | 1990-06-26 |
| DE3841541A1 (en) | 1990-06-13 |
| ZA899022B (en) | 1990-08-29 |
| WO1990006187A1 (en) | 1990-06-14 |
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