CA2102170A1 - Aqueous vehicle composition, coating media containing this composition, and their use - Google Patents
Aqueous vehicle composition, coating media containing this composition, and their useInfo
- Publication number
- CA2102170A1 CA2102170A1 CA002102170A CA2102170A CA2102170A1 CA 2102170 A1 CA2102170 A1 CA 2102170A1 CA 002102170 A CA002102170 A CA 002102170A CA 2102170 A CA2102170 A CA 2102170A CA 2102170 A1 CA2102170 A1 CA 2102170A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- aqueous
- lacquer
- acid
- groups
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 50
- 239000011248 coating agent Substances 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 239000008135 aqueous vehicle Substances 0.000 title claims abstract description 8
- 239000004922 lacquer Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000003981 vehicle Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004606 Fillers/Extenders Substances 0.000 claims abstract description 11
- 239000000049 pigment Substances 0.000 claims abstract description 11
- 150000007513 acids Chemical class 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 5
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 5
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000004132 cross linking Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 9
- 229920005862 polyol Polymers 0.000 description 38
- -1 ethanediol Chemical class 0.000 description 37
- 150000003077 polyols Chemical class 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 16
- 239000005056 polyisocyanate Substances 0.000 description 14
- 229920001228 polyisocyanate Polymers 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000004848 polyfunctional curative Substances 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 150000005846 sugar alcohols Polymers 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000003341 Bronsted base Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000002879 Lewis base Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 239000000243 solution Substances 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
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 3
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002118 epoxides Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229920002554 vinyl polymer Chemical class 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003055 poly(ester-imide) Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- QKOWXXDOHMJOMQ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)biuret Chemical compound O=C=NCCCCCCNC(=O)N(CCCCCCN=C=O)C(=O)NCCCCCCN=C=O QKOWXXDOHMJOMQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-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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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 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
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Herberts Gesellschaft mit beschr?nkter Haftung Abstract:
An aqueous vehicle composition is described, and also aqueous coating media which can be produced therefrom and their use in the production of multilayer coatings. The vehicle composition contains:
A) 10 - 90 weight % of one or more compounds acting as crosslinking agents with an average of at least two acidic CH hydrogen atoms and B) 10 - 90 weight % of one or more (meth)acrylic copolymers, polyesters or polyurethane resins suitable for the Michael addition, with at least two .alpha.,.beta.-unsaturated groups bonded via the carbonyl carbon atom of -?-, -?-O- and/or -?-?-, with a C=C equivalent weight of 85 - 1800 and a number average molecular weight (Mn) of 170 - 10,000 g/mole, wherein the equivalent ratio of A:B is 2:1 to 1:2;
C) 0.01 - 5 weight %, based on the sum of the weights of components A) and B), of a catalyst in the form of a Lewis or Br?nsted base, wherein the conjugate acids of the latter have a pKa value of at least 10, and also water and optionally solvents, pigments, extenders, the usual lacquer auxiliary process materials and/or additives.
An aqueous vehicle composition is described, and also aqueous coating media which can be produced therefrom and their use in the production of multilayer coatings. The vehicle composition contains:
A) 10 - 90 weight % of one or more compounds acting as crosslinking agents with an average of at least two acidic CH hydrogen atoms and B) 10 - 90 weight % of one or more (meth)acrylic copolymers, polyesters or polyurethane resins suitable for the Michael addition, with at least two .alpha.,.beta.-unsaturated groups bonded via the carbonyl carbon atom of -?-, -?-O- and/or -?-?-, with a C=C equivalent weight of 85 - 1800 and a number average molecular weight (Mn) of 170 - 10,000 g/mole, wherein the equivalent ratio of A:B is 2:1 to 1:2;
C) 0.01 - 5 weight %, based on the sum of the weights of components A) and B), of a catalyst in the form of a Lewis or Br?nsted base, wherein the conjugate acids of the latter have a pKa value of at least 10, and also water and optionally solvents, pigments, extenders, the usual lacquer auxiliary process materials and/or additives.
Description
-Herberts Gesellschaft mit beschr~nkter Haftung An aqueous vehicle composition coatina media containing this com~osition and their use This invention relates to an aqueous coating medium which is suitable for the production of base-, clear- and covering lacquer coatings, extender layers and primer coats, particularly in the production of multilayer coatings in the motor vehicle industry.
Coating media are known which are based on acidic CH compounds and olefinically unsaturated compounds. For example, EP-A-0 224 158 describes two-component lacquers which contain components of this type. These two-component lacquers can be thermally hardened; the hardening reaction is catalysed by Lewis and/or Bronsted bases. Acetoacetate polymers as crosslinking agents for acryloyl-unsaturated acrylates are described in EP-A-0 027 454. Systems of this type are suitable for the production of various coatings. These two-component lacquers still contain appreciable amounts of solvent and therefore possess disadvantages from the point of view of current environmental policies.
The object of the present invention is the preparation of a vehicle composition which is suitable for the production of aqueous coating media with a low solvent content and which can be hardened rapidly at low temperatures, e.g. at room temperature, to form films of good hardness and good ` resistance to water and solvents.
It has been shown that this object can be achieved by means of an aqueous vehicle composition, which forms one subject to which the present invention relates, and which contains~
~ , . . .
:
A) 10 - 90 weight % of one or more compounds acting as crosslinking agents with an average of at least two acidic CH hydrogen atoms and B) 10 - 90 weight % of one or more (meth)acrylic copolymers, polyester- and/or polyurethane resins suitable for the Michael addition, with at least two ~,B-unsaturated groups bonded via the carbonyl carbon atom of 1 0 0 0 o : . ~
Il 11 ~I I .
-C-, -C-O- and/or -C-N-, with a C=C equivalent weight of 85 - 1800 and a number average molecular weight (Mn) of 170 - 10,000 g/mole, wherein the equivalent ratio of A:B is 2:1 to 1:2;
C) 0.01 - 5 weight %, based on the sum of the weights of ;
components A) and B), of a catalyst in the form of a `
; 20 Lewis or Bronsted base, wherein the conjugate acids of ~ ~- the latter have a pKa value of at least 10, `
and also water, and optionally solvents, pigments, extenders, and the usual lacquer auxiliary process materials and/or additives.
The aqueous vehicle compositions according to the invention ~ -can be processed to form aqueous coating media which in addition to the vehicle composition contain one or more organic solvents, and optionally pigments and/or extenders and/or the usual lacquer additives. They may optionally also -~
contain other vehicle components.
~;, : .,:: :.
The acidic CH crosslinking agents used as component A) in the coating media according to the invention preferably comprise ~ . .
those which contain at least two acidic CH hydrogen atoms ;~ which originate from one or more of the following groupings, which may be the same or different:
.
I
-'` 21~170 I
Wl o O O
Il 11 11 1 \
wherein W1 = -C-, -C-O-, C-N-, -P=O, -CN or NO2 O o o Il ll I~ I \ .. .:
W2 = -C-, -C-O-, -C-N-, -P=0 or -CN, O O o Il 11 11 1 :-, W3 = -C-, -C-0-, -C-N-, -H, alkyl or alkyls, ;
, wherein the alkyl and alkyls preferably have 1 to 6 C atoms and wherein the carboxyl or carbonamide groupæ defined above :
for the W1, W2 and/or W3 radicals are each bonded via the carbon atom to the CH group and the CH group is bonded via at least one of the W1, W2 and/or W3 radicals to a polymeric or ~ oligomeric unit. The acidic CH functionality of component A) r`~ ; amounts on average to > 2 per molecule. Therefore, when W3 ^~ 30 in the above general formula denotes a hydrogen atom, one group of this type is sufficient, since it has two acidïc hydrogen atoms.
As`mentioned above, the acidic CH functionality of component A? is on average > 2. This means that monofunctional molecules mày also be used in admixture with molecules of higher functionality.
.~. .,: , ,~ The acidic C~ crosslinking compounds are preferably ,~ 40 substantially free from primary, secondary or tertiary amino groups, since these can have a negative effect on storage stability and light-fastness.
, ~ ~
~ ~.
~` 2102~ 70 Examples of acidic CH crosslinking components A) which correspond to the above general formula are given below.
These examples are subdivided below into three groups: A1, A2, and A3.
Group A1 contains components with an average of at least two groups with active hydrogen atoms, of the type - C - H, I
in the molecule, which are derived from methanecarboxylic acid monoamide units or acetoacetic acid ester-2-carboxylic acid amides.
Examples of suitable A1 compounds comprise reaction products of malonic acid, such as malonic acid dimethyl, diethyl, dibutyl or dipentyl esters, or acetoacetic acid esters, such as acetoacetic acid methyl, ethyl, butyl or pentyl esters, with polyisocyanates.
Examples of isocyanates of this type which may be used according to the invention comprise (cyclo)aliphatic or aromatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane 1,3- and 1,4-diisocyanates, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (= isophorone diisocyanate;IPDI), perhydro-2,4'- and/or4,4'-diphenylmethane diisocyanate, phenylene 1,3-, and 1,4-diisocyanates, toluene 2,4- and 2,6-diisocyanates, diphenylmethane 2,4'- and/or 4,4'-diisocyanate, 3,2'- and/or 3,4-diisocyanato-4-methyl-diphenylmethane, naphthalene 1,5-diisocyanate, triphenylmethane 4,4'-triisocyanate, tetramethylxylylene diisocyanate or mixtures of these compounds.
;~
~ "
-- 21~2170 In addition to these simple isocyanates, other isocyanates which contain heteroatoms in the radical linking the isocyanate groups are also suitable. Examples of these include carbodimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups and polyisocyanates containing biuret groups.
The known polyisocyanates which are mainly used in the production of lacquers are particularly suitable for the process according to the invention, e.g. modification products of the above-mentioned simple polyisocyanates which contain biuret, isocyanurate or urethane groups, particularly tris-(6-isocyanatohexyl)-biuret or polyisocyanates containing low molecular weight urethane groups, such as those which can be obtained by the reaction of IPDI present in excess with simple polyhydric alcohols with molecular weights in the range 62-300, particularly trimethylolpropane. Any mixtures of the above-mentioned polyisocyanates may also of course be used for the production of the products according to the invention. -Other suitable polyisocyanates comprise the known prepolymers containing terminal isocyanate groups, such as those which are obtainable by the reaction of the above-mentioned simple polyisocyanates, primarily diisocyanates, with substoichiometric amounts of organic compounds with at least two groups which are capable of reacting with isocyanate groups. Isocyanates such as these which are preferably used comprise compounds with a total of at least two amino groups and/or hydroxyl groups, and with a number average molecular weight of 300 to 10,000, preferably 400 to 6000. The corresponding polyhydroxyl compounds are preferably used, e.g. ~-the hydroxypolyesters, hydroxpolyethers and/or the acrylic resins containing hydroxyl groups which are known in the art in polyurethane chemistry.
In these known prepolymers the ratio of isocyanate groups to hydrogen atoms which are reactive towards NCO corresponds to .
~ ` 2~2170 1.05 to 10:1, preferably 1.1 to 3:1, the hydrogen atoms preferably originating from hydroxyl groups.
In addition, the type and quantitative proportions of the starting materials used in the preparation of the NCO
prepolymers are preferably selected so that the NCO
prepolymers a) have an average NCO functionality of 2 to 4, preferably of 2 to 3, and b) have a number average molecular weight of 500 - 10,000, preferably of 800 - 4000.
Reaction products of monoisocyanates with esters and partial esters formed between polyhydric alcohols and malonic acid are also suitable as Al compounds, however. Examples of polyhydric alcohols include dihydric to pentahydric alcohols such as ethanediol, the various propane-, butane-, pentane-and hexanediols, polyethylene- and polypropylene diols, glycerine, trimethylolethane and -propane, pentaerythritol, hexanetriol and sorbitol. Examples of suitable monoisocyanates include aliphatic isocyanates such as n-butyl isocyanate, octadecyl isocyanate, cycloaliphatic isocyanates such as cyclohexyl isocyanate, aryl-aliphatic isocyanates such as benzyl isocyanate or aromatic isocyanates such as phenyl isocyanate.
Also suitable are the corresponding malonic esters of acrylic resins containing OH groups, polyesters, polyurethanes, polyethers, polyester amides and imides and/or the reaction products of malonic acid half esters such as malonic acid monoethyl ester with aliphatic and aromatic epoxy resins, e.g.
acrylate resins containing epoxide groups, glycidyl ethers of polyols such as hexanediol, neopentyl glycol, diphenylolpropane and -methane and hydantoins containing glycidyl groups. Mixtures of these compounds are also suitable.
. .
` 21~2170 The examples of Group A2 given below comprise a suitable hardener component with active CH groups, which contains at least two groups corresponding to formula (I) X
\
CH - K -~:
or structural units corresponding to formula (I') or (I'') : :~
[ - X ' - CH -- K ' ] (I ' ~ [ X ' - f~H - K ' ] (I ' ' ) ~ ;
y, :~
where K represents O O
C or C - O, and where the latter group is bonded via the C atom to the CH
. group;
,:~
X and Y are the same or different Rl ll ~: CO2R1, CN, NO2, CONH2, CONHRlH, CONR1R1, wherein the R1 radicals may be the same or different and represent a hydrocarbon radical, preferably an alkyl radical with 1 to 12, most preferably 1 to 6 C atoms, which may also be interrupted by oxygen or an N-alkyl radical, subject to the proviso that only one of the two radicals X, Y may represent an N02 group;
` ::
. O o ~ 35 K' = C or C - O, :
`~ wherein the latter group is bonded to the CH group via the C
~ atom;
'. ' ~;:
~; ' ~: , 21021 7~
X', Y' are the same or different O ~:
C - O or C - N, subject to the proviso that when K' and X' represent ~ :~
::
C - o ., ~ ~
the Y' radical is not the same as ~ -C - N .
The number of groups (I) in the hardener according to the invention is preferably 2 to 200, most preferably 2 to 10, the larger numbers relating to oligomeric or polymeric products and representing average values here.
The hardener components A2 which can be used according to the invention preferably correspond to formula (II) ~:. /X
l CH - K -J R2 :~ ~Y / n `~
`~ where X, Y and K have the meanings given above, R2 represents ~-` a polyol radical :~ O
~:1 R2 (OH)n (K a ~ _ O) ~'~ or a polycarboxylic acid radical R2 :~
:~ 35 ~` R2 (CO2H)n (K = C) , :
` ' ~ ', ' ~' :' . ~
~ .
2102~7~
g , and n is at least 2, preferably 2 to 200, most preferably 2 to lO. In the case of oligomeric or polymeric hardener components these numbers are again average values.
Also preferred are hardener components which fall within Group A2 and which are obtained by the alcoholysis of compounds of formula (III) or formula (IV) R102 C ~ R102 C ~
CH - K _ Rl (III) / CH - K _ xl (IV) with polyols R2(OH) n~ where X, K and Rl have the meanings given above.
The above-mentioned polyols R2(OH)n may be polyhydric alcohols which preferably contain 2 to 12, most preferably 2 to 6, carbon atoms. Examples of these include: ethylene glycol, 1,2-, and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 20 di-B-hydroxyethyl butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,6-cyclohexanediol, 1,4-bis-(hydroxymethyl)-cyclohexane, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,2-bis-(4-~-hydroxyethoxy)phenylpropane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, 1,2,6-` 25 hexanetriol, 1,2,4-butanetriol, tris-(B-hydroxyethyl)-isocyanurate, trimethylolethane, pentaerythritol and their ~;~ hydroxyalkylation products, and also diethylene glycol, -~
triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, ~
30 polypropylene glycols, dibutylene glycol, polybutylenegly¢ols- ~ ;
; and xylynene glycol. Moreover, polyesters can be used which are obtained from or using lactones, e.g. ~-caprolactones, or hydroxycarboxylic acids, such as hydroxypivalic acid, ~-hydroxydecanoic acid, ~-hydroxycaproic acid or thioglycollic 35 acid, for example. In the case of polyhydric alcohols of this ~ type, the subscript n in the above formula (II) preferably -~ represents 2 to 4.
; .:
21021~0 ;~
Alternatively, the polyol may comprise an oligomeric or polymeric polyol compound (polyol resin), the number average molecular weight of which (determined by gel chromatography using polystyrene as the calibration standard) is usually in the range from about 170 to 10,000, preferably about 500 to about 5000. However, in special cases the molecular weight may be 10,000 and above. The oligomers/polymers comprise polymerides, condensation polymers or addition polymer compounds. Their hydroxyl number is generally 30 to 250, preferably 45 to 200, most preferably 50 to 180 mg KOH/g.
These compounds, which contain OH groups, may also optionally contain other functional groups such as carboxyl groups.
Examples of polyols of this type include polyether polyols, polyacetal polyols, polyester amide polyols, polyamide polyols, epoxy resin polyols or their reaction products with C02, phenol resin polyols, polyurea polyols, polyurethane polyols, polyols of cellulose esters and ethers, partially saponified homo- or copolymers of vinyl esters, partially acetalated polyvinyl alcohols, polycarbonate polyols, polyester polyols or acrylic resin polyols. Polyether polyols, polyester polyols, acrylic resin polyols and polyurethane polyols are preferred. Polyols of this type, ~- which may also be used in admixture, are described in DE-A-31 24 784, for example.
. .
Examples of polyurethane polyols include those which are formed by the reaction of di- and polyisocyanates with an excess of di- and/or polyols. Examples of suitable isocyanates include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and also isocyanates formed ` from three moles of a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate, and biurets produced from the reaction of one mole of a diisocyanate with one mole ~ 35 of water. Suitable polyurea polyols may be obtained in a : similar manner by the reaction of di- and polyisocyanates with .
;
.~ 21~21 rl f~
ll equimolar amounts of aminoalcohols, e.g. ethanolamine or diethanolamine.
Examples of polyester polyols include the known polycondensation products of di- or polycarboxylic acids or their anhydrides, such as phthalic anhydride, adipic acid, etc., and polyols such as ethylene glycol, trimethylolpropane, glycerine, etc.
lo Suitable polyamide polyols may be obtained in a similar manner to the polyesters, by replacing the polyols at least in part by polyamines such as isophorone diamine, hexamethylene diamine, diethylene triamine, etc.
Examples of polyacrylate polyols or polyvinyl compounds containing OH groups include the known copolymers obtained from (meth)acrylic acid esters containing hydroxyl groups or vinyl alcohol and other vinyl compounds, such as styrene or (meth)acrylic acid esters, for example.
The above polycarboxylic acids R2(CO2H)n, where n is preferably 2 to 4 here, may be of an aliphatic, cycloaliphatic, aromatic and/or heterocyclic nature, and may optionally be substituted and/or saturated, by halogen atoms for example. Examples of carboxylic acids such as these and their derivatives include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane 1,3- and 1,4-dicarboxylic acids, di- and tetrachlorophthalic acids, endomethylene tetrahydrophthalic acid and its hexachloro derivative, glutaric acid, maleic acid, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally in admixture with monomeric fatty acids or cyclic monocarboxylic acids such as benzoic acid, p-tert.-butyl bènzoic acid or hexahydrobenzoic acid, and also the reaction -: .
210217~
products of the above-mentioned polyols R2(OH) n with cyclic carboxylic acid anhydrides.
Depending on the type of the polyol or polycarboxylic acid component, the hardener components A2 which can be used according to the invention comprise more or less viscous liquids, or solids which are substantially soluble at least in the usual lacquer solvents and which preferably contain less than 5 weight %, most preferably less than 1 weight %, of crosslinked constituents. The CH equivalent weight, which is a measure of the amount of groups (I) or structural units (I')l(II ") in (A2), is generally between 100 and 5000, preferably between 200 and 2000, and the number average molecular weight (Mn) is generally 200 to 10,000, preferably 500 to 5000 (determined by gel chromatography using polystyrene as the calibration standard). Methods of preparing compounds such as these are described in more detail in EP-A-O 310 011.
Additional examples of hardener components which can be used according to the invention are those of Type A3, in which the CH grouping is derived from a compound containing a -Co-CHR3-~; CO-, NC-CHR3-Co, NC-CH2-CN, =Po-CHR3-Co-, =Po-CHR3-CN, =PO-CHR3-Po= or -Co-CHR3-No2 grouping, wherein R3 is preferably a Cl - C8 alkyl or H, most preferably hydrogen. B-dioxo compounds are preferred.
The above A3 groupings may be bonded to at least one polyvalent monomeric or polymeric compound. For example, they ~may be bonded to at least one compound of the group comprising monohydric or polyhydric alcohols, polymers containing OH
groups, polyamines and polymercaptans. They are polyvalent with respect to their CH function. They may be prepared, for example, by the esterification of a polyepoxide with a -CH
carboxylic acid forming the grouping, e.g. acetoacetic acid.
An A3 component with two active H atoms for each epoxide ` 210217~3 group is obtained in this manner. Aromatic or aliphatic polyepoxides may be used for this purpose.
Examples of suitable compounds of the A3 type include ketones such as acetylacetone, benzoyl acetone or acetyl dibenzoylmethane; esters of optionally alkyl-substituted acetoacetic acid such as ~- and/or ~-methyl acetoacetic acid or of acetone dicarboxylic acid; malonic acid units of malonic acid with ester-like bonds, and their monoalkyl derivatives, either straight-chain or branched, with 1 to 6 C atoms in the alkyl radical, e.g. methyl, ethyl and n-butyl and also phenyl;
or esters of cyanoacetic acid with monohydric to hexahydric alcohols with 1 to 10 C atoms. The alkyl-substituted esters, e.g. ~-methyl or ~,~-dimethyl acetoacetic ester, have only one active H atom and are therefore preferably used in the form of di- or polyesters of polyhydric alcohols, in order to make a sufficient number of reactive groups available. Examples of suitable alcohols for the esterification of the above acids include methanol, ethanol, butanol, octanol and/or polyhydric alcohols or polyhydroxy compounds, the latter two types being preferred. Further examples of A3 compounds include acetoacetic ester, ethanediol-bis-acetoacetic ester, glycerine-tris-malonic acid ester, trimethylolpropane-tris-acetoacetic ester, partial esters of these acids with polyhydric alcohols, and also the corresponding esters of OH
group-containing acrylic resins, polyesters, polyethers, polyester amides and imides, polyhydroxylamines, and also nitriles of these acids inasmuch as these exist, e.g. malonic acid mono- or dinitrile, alkoxycarbonyl methanephosphonic acid and the corresponding bis-methanephosphonic acid esters. ! The above-mentioned acids may also be bonded in the form of amides to amines, preferably polyamines, which may also comprise oligomers and/or polymers, including amine resins, aliphatic amines being preferred.
If polyamines are used as the starting materials, the A3 compounds can be prepared in the form of amides. For example - :
21021 7i~
the starting material may comprise 1 mole o~` an alkylene diamine, which is reacted with 2 moles of acetoacetic ester with the formation of a compound which also has four H atoms activated by amide groups.
Reactive nitro compounds are also suitable as A3 compounds, e.g. nitroacetic acid derivatives such as tri-(nitroacetic acid)-glycerine ester or trimethylolpropane nitroacetic acid ester.
Examples of A3 compounds which form -CH- type groups include diketene and its monoalkyl substitution products, and also tetrahydrodioxin, which can react with suitable components with the formation of acetoacetic ester or amide groups.
The hardener components A) may be prepared in the usual solvents. It is advantageous if solvents are used which do not impair the subsequent production of the coating medium.
It is also advantageous if the content of organic solvents is kept as low as possible. If the hardener component A) contains polar groups, e.g. amide or urethane groupings, it is possible to disperse it easily in water. This may optionally be assisted if the crosslinking components contain ionic groups which can be neutralised, e.g. carboxyl groups, in the oligomer or polymer skeleton. Crosslinking agents with ionic groups such as these may be dispersed in water well.
At the same time, the content of organic solvents can be reduced to a low value without significantly increasing the viscosity of the crosslinking agent solution.
(Meth)acrylic copolymers or polyester- and/or polyurethane resins, which are suitable for the Michael addition and which are as defined above, are used according to the invention as component B). They contain at least two groups capable of participating in the Michael addition, i.e. groups which contain double bonds activated by at least one negatively polarising group (Michael acceptor). These comprise ~,B-2102~'~0 unsaturated groups which can be incorporated in the chains of the copolymers or resins. They may also preferably be side groups and/or terminal groups. Suitable B) compounds are described in DE-PS-835 809, in US-PS-4,408,018 and in EP-A- -16 16 79 and EP-A- 22 41 58, for example, to which reference is made here. These are compounds (B) with at least two groups corresponding to the formula R5R4C = CR4- Z (V) ' `' in which:
R5 represents hydrogen or a hydrocarbon radical, preferably ;~
an alkyl radical with 1 to 12, most preferably 1 to 4, -C atoms such as a methyl, ethyl, n-propyl, iso-propyl, n-butyl or tert.-butyl group;
R4 denotes entities which are the same or different, representing hydrogen, a hydrocarbon radical, preferably an alkyl radical with 1 to 10, most preferably 1 to 4, C atoms, an ester group -C02Rl, a -CN, -NO2, -S02-, -CONHRl, -CONRlRl or -CORl group, wherein the Rls are the same or different and are as defined above for formula ~ - -I; and ` 25 : o o o : :, Z represents -C-, -~ - O, or -C - N- , :~
wherein the two latter groups are bonded to the CR4 group via the C atom.
RS and R4 in the above R5R4-C group preferably each represent ~ ~
hydrogen. -The above groups V are indirectly bonded to each other. The indirect linkage concerned may be a hydrocarbon radical, for example, but is preferably the radical of a polyhydric alcohol 2~02~ ~ ~
or of a polyvalent amine or aminoalcohol. At the same time, this indirect linkage may also be part of the chain of an oligomer and/or polymer, i.e. the group V may exist in the side chains of the oligomers or polymers or may form these side chains.
According to a particular embodiment, the compound B) corresponds to the formula (R5R4C = CR4 -z) R2 (VI) in which R5, R4 and Z have the same meaning as in formula (V), R2 has the same meaning as in formula (II) and m is at least 2, preferably 2 to 200.
The R5R4C = CR4- Z group - (V) may be derived from a singly or poly-unsaturated mono- or dicarboxylic acid with 2 to 20, preferably 3 to 10, C atoms, for example.
Examples of carboxylic acids such as these include crotonic acid and citraconic acid or their anhydrides, sorbic acid, fumaric acid, mesaconic acid, substituted and unsubstituted cinnamic acids, dihydrolevulinic acid, malonic acid mononitrile, a-cyanacrylic acid, alkylidene malonic acid, alkylidene acetoacetic acid, and preferably acrylic acid, methacrylic acid and/or maleic acid or their anhydrides. The linkage of the Michael acceptor to the bonding component which is possible via the group Z or also via the R4 radical may be effected via ester, amide, urethane or urea groups, as in a polymeric carrier.
In accordance with the above, the groups corresponding to formula (V) may be bonded to the radical of a polyol, a polyamine, a polyamide or a polyiminoamide, wherein this radical may also be an oligomer or polymer.
The polyols concerned here are basically the same as those listed in detail above in connection with the Michael donor, i.e. polyhydric alcohols or oligomeric or polymeric polyol ~~' 2ln2l7n compounds, e.g. polyether polyols, polyester polyols, acrylic resin polyols and polyurethane polyols.
The amino group-containing carriers (polyamines) comprise, for example, the above-mentioned alkylene diamines and their oligomers, such as ethylene diamine, propylene diamine, butylene diamine, diethylene triamine, tetramine and higher homologues of these amines, and also amino alcohols such as diethanolamine or the like.
Examples of compounds suitable as component B) include: alkyl glycol di(meth)acrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, trimethylene glycol diacrylate, neopentyl glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1.6-hexamethylene glycol diacrylate, 1,10-decamethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate and the corresponding methacrylates, and alkoxylated and propoxylated derivatives.
Moreover, the ~,~-unsaturated group which is bonded via a carbonyl carbon atom may be bonded to polymers, e.g.
condensation polymers such as polyesters or addition polymers such as polyurethanes, polyethers or (meth)acrylic copolymers or vinyl polymers, such as glycidyl (meth)acrylate copolymers.
Polymers which should be mentioned here by way of example include urethane acrylates, obtained by the reaction of polyisocyanate such as hexamethylene diisocyanate with hydroxyalkyl acrylates suc~ as hydroxyethyl acrylate, or by the reaction of hydroxyl group-containing polyesters, polyethers or polyacrylates with polyisocyanates and hydroxyalkyl acrylates, urethane acrylates obtained by the reaction of caprolactonediol or -triol with polyisocyanates and hydroxyalkylacrylates, polyether acrylates obtained by the esterification of hydroxypolyethers with acrylic acid, polyester acrylates obtained by the esterification of .,. :. ~ , -. . , f.~.~ ,. . , . ~ . : :
2102~70 hydroxypolyesters with acrylic acid, polyacrylates obtained by the reaction of acrylic acid with vinyl polymers containing epoxide groups, e.g. copolymers of glycidyl (meth)acrylate or vinyl glycidyl ether. The term "(meth)acrylic" is to be understood, both here and below, as representing acrylic and/or methacrylic.
Mixtures of the above compounds may also be used as component B).
The C=C equivalent weight of component B) is 85 to 1800, for example, preferably 180 to 1200, and the number average molecular weight (Mn) is 170 to 10,000, for example;
preferably 500 to 5000.
The vehicle compositions according to the invention may also contain 2-acetoacetoxy-ethyl(meth)acrylate as a reactive diluent for adjusting the viscosity.
The coating medium according to the invention comprises a mixture of the acidic CH crosslinking component A) and the vehicle B). Mixtures of different components A) or B) may also be used. The vehicles are compatible with each other and may optionally contain solvents to improve their miscibility.
The preferred solvents for this purpose are those which do not subsequently have a negative effect in the lacquer.
The ratio of the two components A) and B) depends upon the number of available acidic C-H hydrogen atoms in the crosslinking component and on the number of unsaturated groups of the ~ unsaturated bond. Since the reactive groups can be determined titrimetrically, accurately adjusted stoichiometric mixture ratios can be achieved. The equivalent ratio of the acidic CH groups to the ~,~-unsaturated groups is preferably 0.75:1 to 1.25:1. By this means a sufficient density of crosslinking is generally obtained. --2 ~ ~ 2 ~
The elasticity of the crosslinked product can be controlled within a range of tolerance, e.g. by means of the chain length of the oligomers and/or polymers used for A) and B). The oligomers and/or polymers used may thus be selected according to the desired elasticity of the crosslinked product. The degree of crosslinking can be controlled via the functionality of the compounds A) and B) which are used. Thus the degree of crosslinking can be increased when three or more reactive groups are present in at least one of the compounds A) and B).
Component C) consists of catalysts in the form of Lewis bases or Bronsted bases, the conjugate acids of the latter having a pKa value of at least 10. Component C) may consist of one or more catalysts. Examples of Lewis bases which have proved to be particularly suitable include those of the cycloaliphatic amine group such as diazabicyclooctane (DABCO), tert.-aliphatic amines such as triethylamine, tripropylamine, N-methyl diethanolamine, N-methyl diisopropylamine or N-butyl diethanolamine, and amidines such as diazabicycloundecene (DBU) and guanidines such as N,N,N'N'-tetramethyl guanidine.
Other examples include alkyl- or aryl-substituted phosphanes such as tributyl phosphane, triphenyl phosphane, tris-p-tolyl phosphane, methyl diphenyl phosphane, and hydroxy- and aminofunctionalphosphanessuchastris-hydroxymethylphosphane and tris-dimethylamino ethyl phosphane.
Examples of Bronsted bases which may be used include alcoholates such as sodium or potassium ethanolate, quaternary ammonium compounds such as alkyl-, aryl- or benzyl ammonium hydroxides or halides, such as tetraethyl or tetrabutylammonium hydroxide or fluoride for example, and trialkyl or triaryl phosphonium salts or hydroxides.
The amount of catalysts is generally 0.01 to 5 weight %, preferably 0.02 to 2 weight %, based on the total solids content of components A) and B).
210217~
The crosslinking component A) and the vehicle component B) or the mixtures thereof are used in agueous form according to the invention.
For this purpose the crosslinking component A) and the vehicle component B) are converted into an aqueous phase, optionally with a low proportion of solvents and optionally together with emulsifying agents. The preferred solvents are those which are miscible with water. The amount of solvent may be up to 20 weight % for example, preferably up to 10 weight %, based on the final aqueous composition. Ionic or non-ionic emulsifying agents, preferably non-ionic emulsifying agents, may be used as the emulsifying agents. The content of emulsifying agent may be 0.5 to 30 weight % for example, preferably between 1.5 and 15 weight %, based on the solids content of component A) and component B) in the final aqueous coating medium.
The usual methods familiar to one skilled in the art may be employed for the preparation of the aqueous dispersions.
Thus, for example, the solvent-containing forms of components A) and B) or mixtures thereof may be substantially freed from solvents, preferably by distillation under reduced pressure, whereupon the emulsifying agent can be dispersed therein, preferably in the resins or resin mixtures whilst the latter are still warm and of low viscosity. This mixture can then be added to the aqueous phase, with intensive mixing for example. The preparation of the dispersion may also be assisted by heating the aqueous phase. Examples of suitable mixer units include high speed stirrers or rotor/stator mixers. It is also possible to improve the quality of the dispersion by means of high-pressure or ultrasonic homogenisers. -.
Components A) and B) may be mixed first and then emulsified together. However the crosslinking component A) and the ;~
-` 2~02~
vehicle component B) may of course be emulsified separately and then mixed.
::
The process may be carried out continuously or batch-wise.
The dispersions produced may also be mixed with each other at this time. An aqueous oil-in-water dispersion is obtained which is stable on storage and which can be adjusted with water to give solids contents which are suitable for application. The aqueous dispersions obtained according to the invention may have a solids content in the range of 25 -55 weight %, for example, based on the final dispersion. They may optionally be diluted with water before their application, e.g. to a viscosity suitable for spraying.
:
Commercially available ionic or non-ionic emulsifying agents are suitable as emulsifying agents. For example, the reaction products of alkyl phenols with alkylene oxides may be used, as may the reaction products of sorbitane fatty acid esters with alkylene oxides, e.g. C1 -C12 alkylphenol ethoxylates.
As a rule, component C) is water-soluble, but can be ;~ emulsified as described if required.
The vehicle compositions according to the invention comprise so-called two-component systems.
Components A) and B) are stored jointly as the vehicle component 1 and component C) is stored as the hardener component 2. If necessary, it is also possible to store component B) as the vehicle component 1 and components A) and C) as the hardener component 2, as long as A) and C) do not react with each other.
This means that components 1 and 2 are stored separately and are only mixed before or on their use, for the production of coating media, for example.
~ .
:. . ~':
~ '~: ' '- ':
. ,: , ... . . . .
210217 ~3 The coating media according to the invention may be produced by the usual methods familiar to one skilled in the art. For the production of coating media, the usual industrial lacquer additives may optionally be added to the crosslinking and vehicle components which are used according to the invention.
Examples of such additives include anti-crater agents, anti-foaming agents, flow media, anti-settling agents, viscosity regulators, W stabilisers and bonding agents. The properties affecting application and film formation can be influenced by the amount of additives.
Known pigments and/or extenders may optionally also be incorporated in the coating media. The relevant methods, e.g.
dispersion or milling, have frequently been described in the lS literature. The usual pigments for clear or covering lacquers are suitable as pigments, for example carbon black, titanium dioxide, finely dispersed silica, aluminium silicate, French chalk, organic and inorganic colorant pigments, transparent colcrants, metallic pigments or crosslinked polymer microparticles. Primers, extenders, metallic lacquers, coloured covering lacquers or clear lacquers may be produced ~-depending on the pigment selected.
In addition to water, the coating media according to the invention may contain non-reactive co-solvents. These serve to adjust the viscosity on application and to influence the flow behaviour, and also to achieve a given lacquer effect.
Examples of such solvents include aromatic hydrocarbons, e.g.
xylenes; aliphatic hydrocarbons, e.g. n-hexane or cyclohexane;
ketones, such as acetone or methyl isopropyl ketone for example; esters, such as butyl acetate or ethyl acetate, for example; and ethers, such as methoxypropanol or butoxypropanol, for example. However, alcohols may also be used, such as isopropanol, hexanol or ethyl glycol, for example. The properties relating to application and flow behaviour can be influenced by the boiling point or the different dissolving powers of the solvents. The amount of -' :' 23 2102~7 ~ :
solvent added thus depends on the desired properties, particularly on the viscosity properties, of the coating medium. True solutions, emulsions or dispersions are formed when water is used as the solvent. Coating media which contain water have a particularly low content of volatile organic solvents.
The coating media produced from the vehicles according to the invention may be adjusted to the desired viscosity for application by correspondingly re~ulating the addition of water and/or additives.
Depending on the quantitative proportion of component 1 to component 2, on the equivalent weight and on the amount of catalyst, the coating media can be adjusted to give a pot life between a few minutes and several hours.
The coating media produced in this manner may be applied in the usual way, for example by immersion, spraying, brushing or by an electrostatic route.
The coatings produced from the coating media may be hardened over a broad temperature range, from +5C to 180C, for example. The temperature range is preferably 20C to 180C, for example room temperature.
The coating media produced from the vehicles according to the invention are suitable for coatings which adhere to a multiplicity of substrates, such as wood, textiles, plastics, glass, ceramics, and metals in particular. The coating media may also be used in a multilayer process. For example, they may be applied to the usual primers, base lacquers or extenders, or to covering lacquers which already exist. The vehicles according to the invention are particularly suitable for base lacquer, covering lacquer and clear lacquer ~` compositions.
24 2~0217~3 One preferred embodiment comprises the application of the coating medium according to the invention as a clear lacquer overcoat on to an aqueous base lacquer according to the invention. In this connection, a wet-in-wet procedure may be employed, or the base lacquer may be previously dried by heating. This results in the bonding of both layers being particularly good.
A particularly preferred area of application for the vehicles according to the invention is the preparation of coating media for coatings in the motor vehicle industry. The favourable hardening conditions of the coating media produced from the vehicles according to the invention make them particularly suitable for motor vehicle repair coatings also.
Accordingly, the present invention also relates to a process `
for the production of coatings on various substrates, in which a coating medium produced from the vehicle according to the ~;
invention is applied, and then dried and hardened. The present invention also relates to the use of the vehicle compositions according to the invention in primers, base lacquers, covering lacquers and clear lacquers.
.
The following examples serve to explain the invention. All ~ -parts (pts.) and percentages (%) are given by weight. `~
Example 1 Preparation of acetoacetic ester-functionalised component 1 670 pts. trimethylolpropane and 1950 pts. acetoacetic ester were placed in a 4 litre three-necked flask fitted with a stirrer, reflux condenser, thermometer and dropping funnel.
The mixture was heated with stirring until ethanol was split off. After 4 hours, 488 g distillate was obtained; the temperature was 175C. A vacuum was applied and the ` distillation was continued until a total of 806 g distillate :~ .
was obtained. The acetoacetic ester-functional component 1 produced then had a theoretical solids content of 96.5 ~, a viscosity of 172 mPas and an acid number of 131.6 mg KOH/g solid resin.
In the following, trimethylolpropane triacrylate tTMPTA) was used as the polyacryloyl compound.
Example 2 Preparation of an aqueous emulsion from components 1 and 2 (emulsion 3).
155.2 g of a 10 % aqueous solution of an emulsifying agent based on a polyoxypropylene polyoxyethylene sorbitanic acid diester were placed in a 1 litre flask at 60C. The mixture was stirred using a stirrer rotating at a speed of about 7500 revolutions per minute. A mixture of 198.3 pts. of the acetoacetic ester-functionalised component 1 and 151.7 pts.
TMPTA was added at 60C over three minutes. 50 g demineralised water were added. The milky-white emulsion ~ -~
obtained had a solids content of 66.1 %.
Exam~le 3 -~
Preparation of an aqueous base lacquer: ~
: -: .::
a) 100 pts. of the aqueous emulsion 3) were homogenised with 23.61 pts. demineralised water and 24.9 pts. of a commercially available 3 % thickener paste (rheologi¢al additive) with intensive stirring.
;~ b) 4.77 pts. of a 65 % solution of a commercially available aluminium paste in white spirit/demineralised water (17.5 %/17.5 %), 3.74 pts. butyl glycol, 0.35 pts. of a ` commercially available corrosion inhibitor to prevent gassing of the aluminium, 0.7 pts. N-methyl pyrrolidone and 2.34 pts. butanol were mixed separately. The mixture was adjusted to a spraying viscosity of 20"
using demineralised water.
Example 4 Preparation of an aqueous clear lacquer~
a) 49.1 pts. of the aqueous emulsion 3) were mixed with 10 10pts. of a commercially available thickener and 40.9 pts.
demineralised water, and then homogenised with 100 pts.
of a 10 % solution of DBU in demineralised water, followed by adjusting to a spraying viscosity of 20".
Example 5 ~ ' , The base lacquer from Example 3 was applied by spraying to a metal sheet provided with a commercially available two- -component polyurethane extender, aerated for 35 minutes at room temperature, and the clear lacquer from Example 4 was then applied. The sample was aerated again for 40 minutes and then stoved at 60C for 45 minutes.
The film obtained had a good hardness, exhibited good flop and good body and gloss.
, ;~
~ , ``~` ;
Coating media are known which are based on acidic CH compounds and olefinically unsaturated compounds. For example, EP-A-0 224 158 describes two-component lacquers which contain components of this type. These two-component lacquers can be thermally hardened; the hardening reaction is catalysed by Lewis and/or Bronsted bases. Acetoacetate polymers as crosslinking agents for acryloyl-unsaturated acrylates are described in EP-A-0 027 454. Systems of this type are suitable for the production of various coatings. These two-component lacquers still contain appreciable amounts of solvent and therefore possess disadvantages from the point of view of current environmental policies.
The object of the present invention is the preparation of a vehicle composition which is suitable for the production of aqueous coating media with a low solvent content and which can be hardened rapidly at low temperatures, e.g. at room temperature, to form films of good hardness and good ` resistance to water and solvents.
It has been shown that this object can be achieved by means of an aqueous vehicle composition, which forms one subject to which the present invention relates, and which contains~
~ , . . .
:
A) 10 - 90 weight % of one or more compounds acting as crosslinking agents with an average of at least two acidic CH hydrogen atoms and B) 10 - 90 weight % of one or more (meth)acrylic copolymers, polyester- and/or polyurethane resins suitable for the Michael addition, with at least two ~,B-unsaturated groups bonded via the carbonyl carbon atom of 1 0 0 0 o : . ~
Il 11 ~I I .
-C-, -C-O- and/or -C-N-, with a C=C equivalent weight of 85 - 1800 and a number average molecular weight (Mn) of 170 - 10,000 g/mole, wherein the equivalent ratio of A:B is 2:1 to 1:2;
C) 0.01 - 5 weight %, based on the sum of the weights of ;
components A) and B), of a catalyst in the form of a `
; 20 Lewis or Bronsted base, wherein the conjugate acids of ~ ~- the latter have a pKa value of at least 10, `
and also water, and optionally solvents, pigments, extenders, and the usual lacquer auxiliary process materials and/or additives.
The aqueous vehicle compositions according to the invention ~ -can be processed to form aqueous coating media which in addition to the vehicle composition contain one or more organic solvents, and optionally pigments and/or extenders and/or the usual lacquer additives. They may optionally also -~
contain other vehicle components.
~;, : .,:: :.
The acidic CH crosslinking agents used as component A) in the coating media according to the invention preferably comprise ~ . .
those which contain at least two acidic CH hydrogen atoms ;~ which originate from one or more of the following groupings, which may be the same or different:
.
I
-'` 21~170 I
Wl o O O
Il 11 11 1 \
wherein W1 = -C-, -C-O-, C-N-, -P=O, -CN or NO2 O o o Il ll I~ I \ .. .:
W2 = -C-, -C-O-, -C-N-, -P=0 or -CN, O O o Il 11 11 1 :-, W3 = -C-, -C-0-, -C-N-, -H, alkyl or alkyls, ;
, wherein the alkyl and alkyls preferably have 1 to 6 C atoms and wherein the carboxyl or carbonamide groupæ defined above :
for the W1, W2 and/or W3 radicals are each bonded via the carbon atom to the CH group and the CH group is bonded via at least one of the W1, W2 and/or W3 radicals to a polymeric or ~ oligomeric unit. The acidic CH functionality of component A) r`~ ; amounts on average to > 2 per molecule. Therefore, when W3 ^~ 30 in the above general formula denotes a hydrogen atom, one group of this type is sufficient, since it has two acidïc hydrogen atoms.
As`mentioned above, the acidic CH functionality of component A? is on average > 2. This means that monofunctional molecules mày also be used in admixture with molecules of higher functionality.
.~. .,: , ,~ The acidic C~ crosslinking compounds are preferably ,~ 40 substantially free from primary, secondary or tertiary amino groups, since these can have a negative effect on storage stability and light-fastness.
, ~ ~
~ ~.
~` 2102~ 70 Examples of acidic CH crosslinking components A) which correspond to the above general formula are given below.
These examples are subdivided below into three groups: A1, A2, and A3.
Group A1 contains components with an average of at least two groups with active hydrogen atoms, of the type - C - H, I
in the molecule, which are derived from methanecarboxylic acid monoamide units or acetoacetic acid ester-2-carboxylic acid amides.
Examples of suitable A1 compounds comprise reaction products of malonic acid, such as malonic acid dimethyl, diethyl, dibutyl or dipentyl esters, or acetoacetic acid esters, such as acetoacetic acid methyl, ethyl, butyl or pentyl esters, with polyisocyanates.
Examples of isocyanates of this type which may be used according to the invention comprise (cyclo)aliphatic or aromatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane 1,3- and 1,4-diisocyanates, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (= isophorone diisocyanate;IPDI), perhydro-2,4'- and/or4,4'-diphenylmethane diisocyanate, phenylene 1,3-, and 1,4-diisocyanates, toluene 2,4- and 2,6-diisocyanates, diphenylmethane 2,4'- and/or 4,4'-diisocyanate, 3,2'- and/or 3,4-diisocyanato-4-methyl-diphenylmethane, naphthalene 1,5-diisocyanate, triphenylmethane 4,4'-triisocyanate, tetramethylxylylene diisocyanate or mixtures of these compounds.
;~
~ "
-- 21~2170 In addition to these simple isocyanates, other isocyanates which contain heteroatoms in the radical linking the isocyanate groups are also suitable. Examples of these include carbodimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups and polyisocyanates containing biuret groups.
The known polyisocyanates which are mainly used in the production of lacquers are particularly suitable for the process according to the invention, e.g. modification products of the above-mentioned simple polyisocyanates which contain biuret, isocyanurate or urethane groups, particularly tris-(6-isocyanatohexyl)-biuret or polyisocyanates containing low molecular weight urethane groups, such as those which can be obtained by the reaction of IPDI present in excess with simple polyhydric alcohols with molecular weights in the range 62-300, particularly trimethylolpropane. Any mixtures of the above-mentioned polyisocyanates may also of course be used for the production of the products according to the invention. -Other suitable polyisocyanates comprise the known prepolymers containing terminal isocyanate groups, such as those which are obtainable by the reaction of the above-mentioned simple polyisocyanates, primarily diisocyanates, with substoichiometric amounts of organic compounds with at least two groups which are capable of reacting with isocyanate groups. Isocyanates such as these which are preferably used comprise compounds with a total of at least two amino groups and/or hydroxyl groups, and with a number average molecular weight of 300 to 10,000, preferably 400 to 6000. The corresponding polyhydroxyl compounds are preferably used, e.g. ~-the hydroxypolyesters, hydroxpolyethers and/or the acrylic resins containing hydroxyl groups which are known in the art in polyurethane chemistry.
In these known prepolymers the ratio of isocyanate groups to hydrogen atoms which are reactive towards NCO corresponds to .
~ ` 2~2170 1.05 to 10:1, preferably 1.1 to 3:1, the hydrogen atoms preferably originating from hydroxyl groups.
In addition, the type and quantitative proportions of the starting materials used in the preparation of the NCO
prepolymers are preferably selected so that the NCO
prepolymers a) have an average NCO functionality of 2 to 4, preferably of 2 to 3, and b) have a number average molecular weight of 500 - 10,000, preferably of 800 - 4000.
Reaction products of monoisocyanates with esters and partial esters formed between polyhydric alcohols and malonic acid are also suitable as Al compounds, however. Examples of polyhydric alcohols include dihydric to pentahydric alcohols such as ethanediol, the various propane-, butane-, pentane-and hexanediols, polyethylene- and polypropylene diols, glycerine, trimethylolethane and -propane, pentaerythritol, hexanetriol and sorbitol. Examples of suitable monoisocyanates include aliphatic isocyanates such as n-butyl isocyanate, octadecyl isocyanate, cycloaliphatic isocyanates such as cyclohexyl isocyanate, aryl-aliphatic isocyanates such as benzyl isocyanate or aromatic isocyanates such as phenyl isocyanate.
Also suitable are the corresponding malonic esters of acrylic resins containing OH groups, polyesters, polyurethanes, polyethers, polyester amides and imides and/or the reaction products of malonic acid half esters such as malonic acid monoethyl ester with aliphatic and aromatic epoxy resins, e.g.
acrylate resins containing epoxide groups, glycidyl ethers of polyols such as hexanediol, neopentyl glycol, diphenylolpropane and -methane and hydantoins containing glycidyl groups. Mixtures of these compounds are also suitable.
. .
` 21~2170 The examples of Group A2 given below comprise a suitable hardener component with active CH groups, which contains at least two groups corresponding to formula (I) X
\
CH - K -~:
or structural units corresponding to formula (I') or (I'') : :~
[ - X ' - CH -- K ' ] (I ' ~ [ X ' - f~H - K ' ] (I ' ' ) ~ ;
y, :~
where K represents O O
C or C - O, and where the latter group is bonded via the C atom to the CH
. group;
,:~
X and Y are the same or different Rl ll ~: CO2R1, CN, NO2, CONH2, CONHRlH, CONR1R1, wherein the R1 radicals may be the same or different and represent a hydrocarbon radical, preferably an alkyl radical with 1 to 12, most preferably 1 to 6 C atoms, which may also be interrupted by oxygen or an N-alkyl radical, subject to the proviso that only one of the two radicals X, Y may represent an N02 group;
` ::
. O o ~ 35 K' = C or C - O, :
`~ wherein the latter group is bonded to the CH group via the C
~ atom;
'. ' ~;:
~; ' ~: , 21021 7~
X', Y' are the same or different O ~:
C - O or C - N, subject to the proviso that when K' and X' represent ~ :~
::
C - o ., ~ ~
the Y' radical is not the same as ~ -C - N .
The number of groups (I) in the hardener according to the invention is preferably 2 to 200, most preferably 2 to 10, the larger numbers relating to oligomeric or polymeric products and representing average values here.
The hardener components A2 which can be used according to the invention preferably correspond to formula (II) ~:. /X
l CH - K -J R2 :~ ~Y / n `~
`~ where X, Y and K have the meanings given above, R2 represents ~-` a polyol radical :~ O
~:1 R2 (OH)n (K a ~ _ O) ~'~ or a polycarboxylic acid radical R2 :~
:~ 35 ~` R2 (CO2H)n (K = C) , :
` ' ~ ', ' ~' :' . ~
~ .
2102~7~
g , and n is at least 2, preferably 2 to 200, most preferably 2 to lO. In the case of oligomeric or polymeric hardener components these numbers are again average values.
Also preferred are hardener components which fall within Group A2 and which are obtained by the alcoholysis of compounds of formula (III) or formula (IV) R102 C ~ R102 C ~
CH - K _ Rl (III) / CH - K _ xl (IV) with polyols R2(OH) n~ where X, K and Rl have the meanings given above.
The above-mentioned polyols R2(OH)n may be polyhydric alcohols which preferably contain 2 to 12, most preferably 2 to 6, carbon atoms. Examples of these include: ethylene glycol, 1,2-, and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 20 di-B-hydroxyethyl butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,6-cyclohexanediol, 1,4-bis-(hydroxymethyl)-cyclohexane, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,2-bis-(4-~-hydroxyethoxy)phenylpropane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, 1,2,6-` 25 hexanetriol, 1,2,4-butanetriol, tris-(B-hydroxyethyl)-isocyanurate, trimethylolethane, pentaerythritol and their ~;~ hydroxyalkylation products, and also diethylene glycol, -~
triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, ~
30 polypropylene glycols, dibutylene glycol, polybutylenegly¢ols- ~ ;
; and xylynene glycol. Moreover, polyesters can be used which are obtained from or using lactones, e.g. ~-caprolactones, or hydroxycarboxylic acids, such as hydroxypivalic acid, ~-hydroxydecanoic acid, ~-hydroxycaproic acid or thioglycollic 35 acid, for example. In the case of polyhydric alcohols of this ~ type, the subscript n in the above formula (II) preferably -~ represents 2 to 4.
; .:
21021~0 ;~
Alternatively, the polyol may comprise an oligomeric or polymeric polyol compound (polyol resin), the number average molecular weight of which (determined by gel chromatography using polystyrene as the calibration standard) is usually in the range from about 170 to 10,000, preferably about 500 to about 5000. However, in special cases the molecular weight may be 10,000 and above. The oligomers/polymers comprise polymerides, condensation polymers or addition polymer compounds. Their hydroxyl number is generally 30 to 250, preferably 45 to 200, most preferably 50 to 180 mg KOH/g.
These compounds, which contain OH groups, may also optionally contain other functional groups such as carboxyl groups.
Examples of polyols of this type include polyether polyols, polyacetal polyols, polyester amide polyols, polyamide polyols, epoxy resin polyols or their reaction products with C02, phenol resin polyols, polyurea polyols, polyurethane polyols, polyols of cellulose esters and ethers, partially saponified homo- or copolymers of vinyl esters, partially acetalated polyvinyl alcohols, polycarbonate polyols, polyester polyols or acrylic resin polyols. Polyether polyols, polyester polyols, acrylic resin polyols and polyurethane polyols are preferred. Polyols of this type, ~- which may also be used in admixture, are described in DE-A-31 24 784, for example.
. .
Examples of polyurethane polyols include those which are formed by the reaction of di- and polyisocyanates with an excess of di- and/or polyols. Examples of suitable isocyanates include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and also isocyanates formed ` from three moles of a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate, and biurets produced from the reaction of one mole of a diisocyanate with one mole ~ 35 of water. Suitable polyurea polyols may be obtained in a : similar manner by the reaction of di- and polyisocyanates with .
;
.~ 21~21 rl f~
ll equimolar amounts of aminoalcohols, e.g. ethanolamine or diethanolamine.
Examples of polyester polyols include the known polycondensation products of di- or polycarboxylic acids or their anhydrides, such as phthalic anhydride, adipic acid, etc., and polyols such as ethylene glycol, trimethylolpropane, glycerine, etc.
lo Suitable polyamide polyols may be obtained in a similar manner to the polyesters, by replacing the polyols at least in part by polyamines such as isophorone diamine, hexamethylene diamine, diethylene triamine, etc.
Examples of polyacrylate polyols or polyvinyl compounds containing OH groups include the known copolymers obtained from (meth)acrylic acid esters containing hydroxyl groups or vinyl alcohol and other vinyl compounds, such as styrene or (meth)acrylic acid esters, for example.
The above polycarboxylic acids R2(CO2H)n, where n is preferably 2 to 4 here, may be of an aliphatic, cycloaliphatic, aromatic and/or heterocyclic nature, and may optionally be substituted and/or saturated, by halogen atoms for example. Examples of carboxylic acids such as these and their derivatives include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane 1,3- and 1,4-dicarboxylic acids, di- and tetrachlorophthalic acids, endomethylene tetrahydrophthalic acid and its hexachloro derivative, glutaric acid, maleic acid, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally in admixture with monomeric fatty acids or cyclic monocarboxylic acids such as benzoic acid, p-tert.-butyl bènzoic acid or hexahydrobenzoic acid, and also the reaction -: .
210217~
products of the above-mentioned polyols R2(OH) n with cyclic carboxylic acid anhydrides.
Depending on the type of the polyol or polycarboxylic acid component, the hardener components A2 which can be used according to the invention comprise more or less viscous liquids, or solids which are substantially soluble at least in the usual lacquer solvents and which preferably contain less than 5 weight %, most preferably less than 1 weight %, of crosslinked constituents. The CH equivalent weight, which is a measure of the amount of groups (I) or structural units (I')l(II ") in (A2), is generally between 100 and 5000, preferably between 200 and 2000, and the number average molecular weight (Mn) is generally 200 to 10,000, preferably 500 to 5000 (determined by gel chromatography using polystyrene as the calibration standard). Methods of preparing compounds such as these are described in more detail in EP-A-O 310 011.
Additional examples of hardener components which can be used according to the invention are those of Type A3, in which the CH grouping is derived from a compound containing a -Co-CHR3-~; CO-, NC-CHR3-Co, NC-CH2-CN, =Po-CHR3-Co-, =Po-CHR3-CN, =PO-CHR3-Po= or -Co-CHR3-No2 grouping, wherein R3 is preferably a Cl - C8 alkyl or H, most preferably hydrogen. B-dioxo compounds are preferred.
The above A3 groupings may be bonded to at least one polyvalent monomeric or polymeric compound. For example, they ~may be bonded to at least one compound of the group comprising monohydric or polyhydric alcohols, polymers containing OH
groups, polyamines and polymercaptans. They are polyvalent with respect to their CH function. They may be prepared, for example, by the esterification of a polyepoxide with a -CH
carboxylic acid forming the grouping, e.g. acetoacetic acid.
An A3 component with two active H atoms for each epoxide ` 210217~3 group is obtained in this manner. Aromatic or aliphatic polyepoxides may be used for this purpose.
Examples of suitable compounds of the A3 type include ketones such as acetylacetone, benzoyl acetone or acetyl dibenzoylmethane; esters of optionally alkyl-substituted acetoacetic acid such as ~- and/or ~-methyl acetoacetic acid or of acetone dicarboxylic acid; malonic acid units of malonic acid with ester-like bonds, and their monoalkyl derivatives, either straight-chain or branched, with 1 to 6 C atoms in the alkyl radical, e.g. methyl, ethyl and n-butyl and also phenyl;
or esters of cyanoacetic acid with monohydric to hexahydric alcohols with 1 to 10 C atoms. The alkyl-substituted esters, e.g. ~-methyl or ~,~-dimethyl acetoacetic ester, have only one active H atom and are therefore preferably used in the form of di- or polyesters of polyhydric alcohols, in order to make a sufficient number of reactive groups available. Examples of suitable alcohols for the esterification of the above acids include methanol, ethanol, butanol, octanol and/or polyhydric alcohols or polyhydroxy compounds, the latter two types being preferred. Further examples of A3 compounds include acetoacetic ester, ethanediol-bis-acetoacetic ester, glycerine-tris-malonic acid ester, trimethylolpropane-tris-acetoacetic ester, partial esters of these acids with polyhydric alcohols, and also the corresponding esters of OH
group-containing acrylic resins, polyesters, polyethers, polyester amides and imides, polyhydroxylamines, and also nitriles of these acids inasmuch as these exist, e.g. malonic acid mono- or dinitrile, alkoxycarbonyl methanephosphonic acid and the corresponding bis-methanephosphonic acid esters. ! The above-mentioned acids may also be bonded in the form of amides to amines, preferably polyamines, which may also comprise oligomers and/or polymers, including amine resins, aliphatic amines being preferred.
If polyamines are used as the starting materials, the A3 compounds can be prepared in the form of amides. For example - :
21021 7i~
the starting material may comprise 1 mole o~` an alkylene diamine, which is reacted with 2 moles of acetoacetic ester with the formation of a compound which also has four H atoms activated by amide groups.
Reactive nitro compounds are also suitable as A3 compounds, e.g. nitroacetic acid derivatives such as tri-(nitroacetic acid)-glycerine ester or trimethylolpropane nitroacetic acid ester.
Examples of A3 compounds which form -CH- type groups include diketene and its monoalkyl substitution products, and also tetrahydrodioxin, which can react with suitable components with the formation of acetoacetic ester or amide groups.
The hardener components A) may be prepared in the usual solvents. It is advantageous if solvents are used which do not impair the subsequent production of the coating medium.
It is also advantageous if the content of organic solvents is kept as low as possible. If the hardener component A) contains polar groups, e.g. amide or urethane groupings, it is possible to disperse it easily in water. This may optionally be assisted if the crosslinking components contain ionic groups which can be neutralised, e.g. carboxyl groups, in the oligomer or polymer skeleton. Crosslinking agents with ionic groups such as these may be dispersed in water well.
At the same time, the content of organic solvents can be reduced to a low value without significantly increasing the viscosity of the crosslinking agent solution.
(Meth)acrylic copolymers or polyester- and/or polyurethane resins, which are suitable for the Michael addition and which are as defined above, are used according to the invention as component B). They contain at least two groups capable of participating in the Michael addition, i.e. groups which contain double bonds activated by at least one negatively polarising group (Michael acceptor). These comprise ~,B-2102~'~0 unsaturated groups which can be incorporated in the chains of the copolymers or resins. They may also preferably be side groups and/or terminal groups. Suitable B) compounds are described in DE-PS-835 809, in US-PS-4,408,018 and in EP-A- -16 16 79 and EP-A- 22 41 58, for example, to which reference is made here. These are compounds (B) with at least two groups corresponding to the formula R5R4C = CR4- Z (V) ' `' in which:
R5 represents hydrogen or a hydrocarbon radical, preferably ;~
an alkyl radical with 1 to 12, most preferably 1 to 4, -C atoms such as a methyl, ethyl, n-propyl, iso-propyl, n-butyl or tert.-butyl group;
R4 denotes entities which are the same or different, representing hydrogen, a hydrocarbon radical, preferably an alkyl radical with 1 to 10, most preferably 1 to 4, C atoms, an ester group -C02Rl, a -CN, -NO2, -S02-, -CONHRl, -CONRlRl or -CORl group, wherein the Rls are the same or different and are as defined above for formula ~ - -I; and ` 25 : o o o : :, Z represents -C-, -~ - O, or -C - N- , :~
wherein the two latter groups are bonded to the CR4 group via the C atom.
RS and R4 in the above R5R4-C group preferably each represent ~ ~
hydrogen. -The above groups V are indirectly bonded to each other. The indirect linkage concerned may be a hydrocarbon radical, for example, but is preferably the radical of a polyhydric alcohol 2~02~ ~ ~
or of a polyvalent amine or aminoalcohol. At the same time, this indirect linkage may also be part of the chain of an oligomer and/or polymer, i.e. the group V may exist in the side chains of the oligomers or polymers or may form these side chains.
According to a particular embodiment, the compound B) corresponds to the formula (R5R4C = CR4 -z) R2 (VI) in which R5, R4 and Z have the same meaning as in formula (V), R2 has the same meaning as in formula (II) and m is at least 2, preferably 2 to 200.
The R5R4C = CR4- Z group - (V) may be derived from a singly or poly-unsaturated mono- or dicarboxylic acid with 2 to 20, preferably 3 to 10, C atoms, for example.
Examples of carboxylic acids such as these include crotonic acid and citraconic acid or their anhydrides, sorbic acid, fumaric acid, mesaconic acid, substituted and unsubstituted cinnamic acids, dihydrolevulinic acid, malonic acid mononitrile, a-cyanacrylic acid, alkylidene malonic acid, alkylidene acetoacetic acid, and preferably acrylic acid, methacrylic acid and/or maleic acid or their anhydrides. The linkage of the Michael acceptor to the bonding component which is possible via the group Z or also via the R4 radical may be effected via ester, amide, urethane or urea groups, as in a polymeric carrier.
In accordance with the above, the groups corresponding to formula (V) may be bonded to the radical of a polyol, a polyamine, a polyamide or a polyiminoamide, wherein this radical may also be an oligomer or polymer.
The polyols concerned here are basically the same as those listed in detail above in connection with the Michael donor, i.e. polyhydric alcohols or oligomeric or polymeric polyol ~~' 2ln2l7n compounds, e.g. polyether polyols, polyester polyols, acrylic resin polyols and polyurethane polyols.
The amino group-containing carriers (polyamines) comprise, for example, the above-mentioned alkylene diamines and their oligomers, such as ethylene diamine, propylene diamine, butylene diamine, diethylene triamine, tetramine and higher homologues of these amines, and also amino alcohols such as diethanolamine or the like.
Examples of compounds suitable as component B) include: alkyl glycol di(meth)acrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, trimethylene glycol diacrylate, neopentyl glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1.6-hexamethylene glycol diacrylate, 1,10-decamethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate and the corresponding methacrylates, and alkoxylated and propoxylated derivatives.
Moreover, the ~,~-unsaturated group which is bonded via a carbonyl carbon atom may be bonded to polymers, e.g.
condensation polymers such as polyesters or addition polymers such as polyurethanes, polyethers or (meth)acrylic copolymers or vinyl polymers, such as glycidyl (meth)acrylate copolymers.
Polymers which should be mentioned here by way of example include urethane acrylates, obtained by the reaction of polyisocyanate such as hexamethylene diisocyanate with hydroxyalkyl acrylates suc~ as hydroxyethyl acrylate, or by the reaction of hydroxyl group-containing polyesters, polyethers or polyacrylates with polyisocyanates and hydroxyalkyl acrylates, urethane acrylates obtained by the reaction of caprolactonediol or -triol with polyisocyanates and hydroxyalkylacrylates, polyether acrylates obtained by the esterification of hydroxypolyethers with acrylic acid, polyester acrylates obtained by the esterification of .,. :. ~ , -. . , f.~.~ ,. . , . ~ . : :
2102~70 hydroxypolyesters with acrylic acid, polyacrylates obtained by the reaction of acrylic acid with vinyl polymers containing epoxide groups, e.g. copolymers of glycidyl (meth)acrylate or vinyl glycidyl ether. The term "(meth)acrylic" is to be understood, both here and below, as representing acrylic and/or methacrylic.
Mixtures of the above compounds may also be used as component B).
The C=C equivalent weight of component B) is 85 to 1800, for example, preferably 180 to 1200, and the number average molecular weight (Mn) is 170 to 10,000, for example;
preferably 500 to 5000.
The vehicle compositions according to the invention may also contain 2-acetoacetoxy-ethyl(meth)acrylate as a reactive diluent for adjusting the viscosity.
The coating medium according to the invention comprises a mixture of the acidic CH crosslinking component A) and the vehicle B). Mixtures of different components A) or B) may also be used. The vehicles are compatible with each other and may optionally contain solvents to improve their miscibility.
The preferred solvents for this purpose are those which do not subsequently have a negative effect in the lacquer.
The ratio of the two components A) and B) depends upon the number of available acidic C-H hydrogen atoms in the crosslinking component and on the number of unsaturated groups of the ~ unsaturated bond. Since the reactive groups can be determined titrimetrically, accurately adjusted stoichiometric mixture ratios can be achieved. The equivalent ratio of the acidic CH groups to the ~,~-unsaturated groups is preferably 0.75:1 to 1.25:1. By this means a sufficient density of crosslinking is generally obtained. --2 ~ ~ 2 ~
The elasticity of the crosslinked product can be controlled within a range of tolerance, e.g. by means of the chain length of the oligomers and/or polymers used for A) and B). The oligomers and/or polymers used may thus be selected according to the desired elasticity of the crosslinked product. The degree of crosslinking can be controlled via the functionality of the compounds A) and B) which are used. Thus the degree of crosslinking can be increased when three or more reactive groups are present in at least one of the compounds A) and B).
Component C) consists of catalysts in the form of Lewis bases or Bronsted bases, the conjugate acids of the latter having a pKa value of at least 10. Component C) may consist of one or more catalysts. Examples of Lewis bases which have proved to be particularly suitable include those of the cycloaliphatic amine group such as diazabicyclooctane (DABCO), tert.-aliphatic amines such as triethylamine, tripropylamine, N-methyl diethanolamine, N-methyl diisopropylamine or N-butyl diethanolamine, and amidines such as diazabicycloundecene (DBU) and guanidines such as N,N,N'N'-tetramethyl guanidine.
Other examples include alkyl- or aryl-substituted phosphanes such as tributyl phosphane, triphenyl phosphane, tris-p-tolyl phosphane, methyl diphenyl phosphane, and hydroxy- and aminofunctionalphosphanessuchastris-hydroxymethylphosphane and tris-dimethylamino ethyl phosphane.
Examples of Bronsted bases which may be used include alcoholates such as sodium or potassium ethanolate, quaternary ammonium compounds such as alkyl-, aryl- or benzyl ammonium hydroxides or halides, such as tetraethyl or tetrabutylammonium hydroxide or fluoride for example, and trialkyl or triaryl phosphonium salts or hydroxides.
The amount of catalysts is generally 0.01 to 5 weight %, preferably 0.02 to 2 weight %, based on the total solids content of components A) and B).
210217~
The crosslinking component A) and the vehicle component B) or the mixtures thereof are used in agueous form according to the invention.
For this purpose the crosslinking component A) and the vehicle component B) are converted into an aqueous phase, optionally with a low proportion of solvents and optionally together with emulsifying agents. The preferred solvents are those which are miscible with water. The amount of solvent may be up to 20 weight % for example, preferably up to 10 weight %, based on the final aqueous composition. Ionic or non-ionic emulsifying agents, preferably non-ionic emulsifying agents, may be used as the emulsifying agents. The content of emulsifying agent may be 0.5 to 30 weight % for example, preferably between 1.5 and 15 weight %, based on the solids content of component A) and component B) in the final aqueous coating medium.
The usual methods familiar to one skilled in the art may be employed for the preparation of the aqueous dispersions.
Thus, for example, the solvent-containing forms of components A) and B) or mixtures thereof may be substantially freed from solvents, preferably by distillation under reduced pressure, whereupon the emulsifying agent can be dispersed therein, preferably in the resins or resin mixtures whilst the latter are still warm and of low viscosity. This mixture can then be added to the aqueous phase, with intensive mixing for example. The preparation of the dispersion may also be assisted by heating the aqueous phase. Examples of suitable mixer units include high speed stirrers or rotor/stator mixers. It is also possible to improve the quality of the dispersion by means of high-pressure or ultrasonic homogenisers. -.
Components A) and B) may be mixed first and then emulsified together. However the crosslinking component A) and the ;~
-` 2~02~
vehicle component B) may of course be emulsified separately and then mixed.
::
The process may be carried out continuously or batch-wise.
The dispersions produced may also be mixed with each other at this time. An aqueous oil-in-water dispersion is obtained which is stable on storage and which can be adjusted with water to give solids contents which are suitable for application. The aqueous dispersions obtained according to the invention may have a solids content in the range of 25 -55 weight %, for example, based on the final dispersion. They may optionally be diluted with water before their application, e.g. to a viscosity suitable for spraying.
:
Commercially available ionic or non-ionic emulsifying agents are suitable as emulsifying agents. For example, the reaction products of alkyl phenols with alkylene oxides may be used, as may the reaction products of sorbitane fatty acid esters with alkylene oxides, e.g. C1 -C12 alkylphenol ethoxylates.
As a rule, component C) is water-soluble, but can be ;~ emulsified as described if required.
The vehicle compositions according to the invention comprise so-called two-component systems.
Components A) and B) are stored jointly as the vehicle component 1 and component C) is stored as the hardener component 2. If necessary, it is also possible to store component B) as the vehicle component 1 and components A) and C) as the hardener component 2, as long as A) and C) do not react with each other.
This means that components 1 and 2 are stored separately and are only mixed before or on their use, for the production of coating media, for example.
~ .
:. . ~':
~ '~: ' '- ':
. ,: , ... . . . .
210217 ~3 The coating media according to the invention may be produced by the usual methods familiar to one skilled in the art. For the production of coating media, the usual industrial lacquer additives may optionally be added to the crosslinking and vehicle components which are used according to the invention.
Examples of such additives include anti-crater agents, anti-foaming agents, flow media, anti-settling agents, viscosity regulators, W stabilisers and bonding agents. The properties affecting application and film formation can be influenced by the amount of additives.
Known pigments and/or extenders may optionally also be incorporated in the coating media. The relevant methods, e.g.
dispersion or milling, have frequently been described in the lS literature. The usual pigments for clear or covering lacquers are suitable as pigments, for example carbon black, titanium dioxide, finely dispersed silica, aluminium silicate, French chalk, organic and inorganic colorant pigments, transparent colcrants, metallic pigments or crosslinked polymer microparticles. Primers, extenders, metallic lacquers, coloured covering lacquers or clear lacquers may be produced ~-depending on the pigment selected.
In addition to water, the coating media according to the invention may contain non-reactive co-solvents. These serve to adjust the viscosity on application and to influence the flow behaviour, and also to achieve a given lacquer effect.
Examples of such solvents include aromatic hydrocarbons, e.g.
xylenes; aliphatic hydrocarbons, e.g. n-hexane or cyclohexane;
ketones, such as acetone or methyl isopropyl ketone for example; esters, such as butyl acetate or ethyl acetate, for example; and ethers, such as methoxypropanol or butoxypropanol, for example. However, alcohols may also be used, such as isopropanol, hexanol or ethyl glycol, for example. The properties relating to application and flow behaviour can be influenced by the boiling point or the different dissolving powers of the solvents. The amount of -' :' 23 2102~7 ~ :
solvent added thus depends on the desired properties, particularly on the viscosity properties, of the coating medium. True solutions, emulsions or dispersions are formed when water is used as the solvent. Coating media which contain water have a particularly low content of volatile organic solvents.
The coating media produced from the vehicles according to the invention may be adjusted to the desired viscosity for application by correspondingly re~ulating the addition of water and/or additives.
Depending on the quantitative proportion of component 1 to component 2, on the equivalent weight and on the amount of catalyst, the coating media can be adjusted to give a pot life between a few minutes and several hours.
The coating media produced in this manner may be applied in the usual way, for example by immersion, spraying, brushing or by an electrostatic route.
The coatings produced from the coating media may be hardened over a broad temperature range, from +5C to 180C, for example. The temperature range is preferably 20C to 180C, for example room temperature.
The coating media produced from the vehicles according to the invention are suitable for coatings which adhere to a multiplicity of substrates, such as wood, textiles, plastics, glass, ceramics, and metals in particular. The coating media may also be used in a multilayer process. For example, they may be applied to the usual primers, base lacquers or extenders, or to covering lacquers which already exist. The vehicles according to the invention are particularly suitable for base lacquer, covering lacquer and clear lacquer ~` compositions.
24 2~0217~3 One preferred embodiment comprises the application of the coating medium according to the invention as a clear lacquer overcoat on to an aqueous base lacquer according to the invention. In this connection, a wet-in-wet procedure may be employed, or the base lacquer may be previously dried by heating. This results in the bonding of both layers being particularly good.
A particularly preferred area of application for the vehicles according to the invention is the preparation of coating media for coatings in the motor vehicle industry. The favourable hardening conditions of the coating media produced from the vehicles according to the invention make them particularly suitable for motor vehicle repair coatings also.
Accordingly, the present invention also relates to a process `
for the production of coatings on various substrates, in which a coating medium produced from the vehicle according to the ~;
invention is applied, and then dried and hardened. The present invention also relates to the use of the vehicle compositions according to the invention in primers, base lacquers, covering lacquers and clear lacquers.
.
The following examples serve to explain the invention. All ~ -parts (pts.) and percentages (%) are given by weight. `~
Example 1 Preparation of acetoacetic ester-functionalised component 1 670 pts. trimethylolpropane and 1950 pts. acetoacetic ester were placed in a 4 litre three-necked flask fitted with a stirrer, reflux condenser, thermometer and dropping funnel.
The mixture was heated with stirring until ethanol was split off. After 4 hours, 488 g distillate was obtained; the temperature was 175C. A vacuum was applied and the ` distillation was continued until a total of 806 g distillate :~ .
was obtained. The acetoacetic ester-functional component 1 produced then had a theoretical solids content of 96.5 ~, a viscosity of 172 mPas and an acid number of 131.6 mg KOH/g solid resin.
In the following, trimethylolpropane triacrylate tTMPTA) was used as the polyacryloyl compound.
Example 2 Preparation of an aqueous emulsion from components 1 and 2 (emulsion 3).
155.2 g of a 10 % aqueous solution of an emulsifying agent based on a polyoxypropylene polyoxyethylene sorbitanic acid diester were placed in a 1 litre flask at 60C. The mixture was stirred using a stirrer rotating at a speed of about 7500 revolutions per minute. A mixture of 198.3 pts. of the acetoacetic ester-functionalised component 1 and 151.7 pts.
TMPTA was added at 60C over three minutes. 50 g demineralised water were added. The milky-white emulsion ~ -~
obtained had a solids content of 66.1 %.
Exam~le 3 -~
Preparation of an aqueous base lacquer: ~
: -: .::
a) 100 pts. of the aqueous emulsion 3) were homogenised with 23.61 pts. demineralised water and 24.9 pts. of a commercially available 3 % thickener paste (rheologi¢al additive) with intensive stirring.
;~ b) 4.77 pts. of a 65 % solution of a commercially available aluminium paste in white spirit/demineralised water (17.5 %/17.5 %), 3.74 pts. butyl glycol, 0.35 pts. of a ` commercially available corrosion inhibitor to prevent gassing of the aluminium, 0.7 pts. N-methyl pyrrolidone and 2.34 pts. butanol were mixed separately. The mixture was adjusted to a spraying viscosity of 20"
using demineralised water.
Example 4 Preparation of an aqueous clear lacquer~
a) 49.1 pts. of the aqueous emulsion 3) were mixed with 10 10pts. of a commercially available thickener and 40.9 pts.
demineralised water, and then homogenised with 100 pts.
of a 10 % solution of DBU in demineralised water, followed by adjusting to a spraying viscosity of 20".
Example 5 ~ ' , The base lacquer from Example 3 was applied by spraying to a metal sheet provided with a commercially available two- -component polyurethane extender, aerated for 35 minutes at room temperature, and the clear lacquer from Example 4 was then applied. The sample was aerated again for 40 minutes and then stoved at 60C for 45 minutes.
The film obtained had a good hardness, exhibited good flop and good body and gloss.
, ;~
~ , ``~` ;
Claims (11)
1. An aqueous vehicle composition, containing A) 10 - 90 weight % of one or more compounds acting as crosslinking agents with an average of at least two acidic CH hydrogen atoms and B) 10 - 90 weight % of one or more (meth)acrylic copolymers, polyester- and/or polyurethane resins suitable for the Michael addition, with at least two .alpha.,.beta.-unsaturated groups bonded via the carbonyl carbon atom of -?-, -?-O- and/or -?-?-, with a C=C equivalent weight of 85 - 1800 and a number average molecular weight (Mn) of 170 - 10,000 g/mole, wherein the equivalent ratio of A:B is 2:1 to 1:2;
C) 0.01 - 5 weight %, based on the sum of the weights of components A) and B), of a catalyst in the form of a Lewis or Br?nsted base, wherein the conjugate acids of the latter have a pKa value of at least 10, and also water and optionally solvents, pigments, extenders, and the usual lacquer auxiliary process materials and/or additives.
C) 0.01 - 5 weight %, based on the sum of the weights of components A) and B), of a catalyst in the form of a Lewis or Br?nsted base, wherein the conjugate acids of the latter have a pKa value of at least 10, and also water and optionally solvents, pigments, extenders, and the usual lacquer auxiliary process materials and/or additives.
2. A vehicle composition according to claim 1, containing a crosslinking component A) with an average of at least two acidic CH hydrogen atoms which originate from one or more of the following groupings, which may be the same or different:
wherein W1 = -?-, -?-O-, ?-?-, , -CN or NO2 W2 = -?-, -?-O-, -?-?-, or -CN, W3 = -?-, -?-O-, -?-?-, -H, alkyl or alkyls, wherein the -?-O- and -?-?- radicals are each bonded via the carbon atom on the CH group and the CH group is bonded via at least one of the radicals W1, W2 and/or W3 to a polymeric or oligomeric unit.
wherein W1 = -?-, -?-O-, ?-?-, , -CN or NO2 W2 = -?-, -?-O-, -?-?-, or -CN, W3 = -?-, -?-O-, -?-?-, -H, alkyl or alkyls, wherein the -?-O- and -?-?- radicals are each bonded via the carbon atom on the CH group and the CH group is bonded via at least one of the radicals W1, W2 and/or W3 to a polymeric or oligomeric unit.
3. A vehicle composition according to one of claims 1 or 2, characterised in that it exists in aqueous form with a content of organic solvents of 0-20 weight % based on the total coating medium.
4. An aqueous coating medium containing the vehicle composition according to any one of claims 1 to 3 and in addition one or more organic solvents, and optionally pigments and/or extenders and/or the usual lacquer additives.
5. A coating medium according to claim 4 as a clear lacquer, covering lacquer, base lacquer or extender.
6. A process for producing coatings by the application of a coating medium to a substrate to be coated and the subsequent thermal hardening of the coating obtained, characterised in that a coating medium according to one of claims 4 or 5 is applied.
7. A process for producing multilayer coatings by the application of an aqueous base lacquer to a substrate to be coated, optionally a brief aeration and the wet-in-wet application of a clear lacquer and subsequent joint hardening, characterised in that aqueous coating media according to one of claims 4 or 5 are used as the base lacquer and/or clear lacquer.
8. The use of the aqueous vehicle composition according to any one of claims 1 to 3 in the production of coatings.
9. A use according to claim 8 for the production of multilayer coatings.
10. The use of the aqueous vehicle composition according to any one of claims 1 to 3 for the production of coating media hardenable at temperatures from 5 to 180°C.
11. The use of the coating medium according to claim 4 or 5 for the production of coatings for motor vehicle series manufacture and repair.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DEP4237492.8 | 1992-11-06 | ||
DE4237492A DE4237492A1 (en) | 1992-11-06 | 1992-11-06 | Aqueous binder composition, coating compositions containing it and their use |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2102170A1 true CA2102170A1 (en) | 1994-05-07 |
Family
ID=6472260
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002102170A Abandoned CA2102170A1 (en) | 1992-11-06 | 1993-11-01 | Aqueous vehicle composition, coating media containing this composition, and their use |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0596461B2 (en) |
JP (1) | JPH06234954A (en) |
AT (1) | ATE164872T1 (en) |
CA (1) | CA2102170A1 (en) |
DE (2) | DE4237492A1 (en) |
DK (1) | DK0596461T3 (en) |
ES (1) | ES2115706T5 (en) |
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US6583214B1 (en) | 1999-04-01 | 2003-06-24 | Basf Coatings Ag | Aqueous coating material that is cured thermally and/or by actinic radiation, and its use |
US6630211B1 (en) | 1999-02-25 | 2003-10-07 | Basf Coatings Ag | Utilization of tricyclodecandimethanol for producing multilayer lacquers |
US6652919B1 (en) | 1999-02-25 | 2003-11-25 | Basf Coatings Ag | Highly scratch-resistant multilayer coat, method for producing and use of the same |
US6652915B1 (en) | 1999-05-25 | 2003-11-25 | Basf Coatings Ag | Coating material containing a mixture of silicic acids and urea and/or urea derivatives |
US6685985B2 (en) | 2001-02-09 | 2004-02-03 | Basf Corporation | Method of improving the appearance of coated articles having both vertical and horizontal surfaces, and coating compositions for use therein |
US6713559B1 (en) | 1999-08-27 | 2004-03-30 | Basf Coatings Ag | Sol-gel coating |
US6747091B1 (en) | 1999-02-25 | 2004-06-08 | Basf Coatings Ag | Powder-slurry that can be hardened by actinic radiation or optionally by thermal means, method for producing said slurry and use of the same |
US6750286B1 (en) | 1999-02-03 | 2004-06-15 | Basf Coatings Ag | Polyurethane and its use in aqueous painting plastic |
US6774177B1 (en) | 1999-10-09 | 2004-08-10 | Basf Coatings Ag | Electrically conducting hydroprimer for plastics |
US6828381B1 (en) | 1999-08-27 | 2004-12-07 | Basf Coatings Ag | Sol-gel coating |
US6835420B1 (en) | 1999-08-16 | 2004-12-28 | Basf Coatings Ac | Coating material and its use for producing highly scratch resistant multilayer transparent lacquers |
US6872765B1 (en) | 1999-03-06 | 2005-03-29 | Basf Coatings Ag | Sol-gel coating for single-layer or multi-layer varnishes |
US6887526B1 (en) | 1999-09-16 | 2005-05-03 | Basf Coatings Ag | Integrated coating method for auto body parts containing plastic parts or for cabins of passenger cars and utility vehicles as well as for their replacement parts and add-on parts |
US6949591B1 (en) | 1999-05-06 | 2005-09-27 | Basf Coatings Ag | Coating material which can be thermally cured and hardened by actinic radiation and use thereof |
US6997980B2 (en) * | 2001-01-04 | 2006-02-14 | Basf Coatings Ag | Aqueous, effect-producing coating material, method for the production thereof and use of the same |
US7138451B2 (en) | 2000-09-06 | 2006-11-21 | Basf Coatings Ag | Bonding material solution and the use thereof in an automotive spot repair kit |
US7175883B2 (en) | 2002-01-12 | 2007-02-13 | Basf Coatings Ag | Polysiloxane sols method for the production and use thereof |
US7504134B2 (en) | 2000-02-25 | 2009-03-17 | Basf Coatings Ag | Method for producing color and/or effect-producing multilayer paints on car bodies |
US7932317B1 (en) | 1999-05-08 | 2011-04-26 | Basf Coatings Ag | Aqueous coating material and modular system for producing same |
US8211504B2 (en) | 2000-09-04 | 2012-07-03 | Basf Coatings Gmbh | Method for producing color giving and/or effect giving lacquer coatings |
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US5643977A (en) | 1994-08-09 | 1997-07-01 | Nippon Paint Co., Ltd. | Room-temperature curable waterbased coating compositions |
JPH08283626A (en) * | 1995-04-12 | 1996-10-29 | Nippon Paint Co Ltd | Curable resin composition for coating material |
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DE10130972C1 (en) | 2001-06-27 | 2002-11-07 | Basf Coatings Ag | Production of hard, scratch-resistant coatings, e.g. on automobile bodywork, using lacquer containing (meth)acrylate copolymer and photoinitiator, hardened by heat and irradiation in oxygen-depleted atmosphere |
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Family Cites Families (9)
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NL8201224A (en) * | 1981-07-29 | 1983-02-16 | Ppg Industries Inc | Resinous materials which are curable by means of an transesterification hardening mechanism. |
US4408018A (en) † | 1982-10-29 | 1983-10-04 | Rohm And Haas Company | Acetoacetate functionalized polymers and monomers useful for crosslinking formulations |
DE3315469A1 (en) * | 1983-04-28 | 1984-10-31 | Hoechst Ag, 6230 Frankfurt | HARDENING COMPONENT FOR SYNTHETIC RESINS CONTAINING GROUPS APPROPRIATE FOR AMID OR ESTER FORMATION WITH CARBONIC ACIDS |
DE3324211A1 (en) * | 1983-07-05 | 1985-01-17 | Basf Farben + Fasern Ag, 2000 Hamburg | HEAT-CURABLE BINDING MIXTURE |
DE3541140A1 (en) * | 1985-11-21 | 1987-05-27 | Hoechst Ag | CURING PRODUCT BASED ON OLEFINICALLY UNSATURATED COMPOUNDS AND HYDROGEN-ACTIVE COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND BASED TWO-COMPONENT PAINTS |
US5017649A (en) † | 1988-01-19 | 1991-05-21 | Eastman Kodak Company | Low temperature Michael addition reactions |
DE3932517A1 (en) † | 1989-09-29 | 1991-04-11 | Herberts Gmbh | BINDING COMPOSITION AND THEIR USE IN COATING AGENTS |
DE4137613A1 (en) † | 1991-11-15 | 1993-05-19 | Herberts Gmbh | BINDING COMPOSITION, THESE COATING AGENTS AND THEIR USE |
DE4225104C1 (en) * | 1992-07-30 | 1993-12-09 | Herberts Gmbh | Coating compositions and their use in the manufacture of coatings with rapid processing surface |
-
1992
- 1992-11-06 DE DE4237492A patent/DE4237492A1/en not_active Withdrawn
-
1993
- 1993-11-01 CA CA002102170A patent/CA2102170A1/en not_active Abandoned
- 1993-11-03 DE DE59308380T patent/DE59308380D1/en not_active Expired - Lifetime
- 1993-11-03 EP EP93117776A patent/EP0596461B2/en not_active Expired - Lifetime
- 1993-11-03 DK DK93117776T patent/DK0596461T3/en active
- 1993-11-03 AT AT93117776T patent/ATE164872T1/en not_active IP Right Cessation
- 1993-11-03 ES ES93117776T patent/ES2115706T5/en not_active Expired - Lifetime
- 1993-11-05 JP JP5276392A patent/JPH06234954A/en active Pending
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6750286B1 (en) | 1999-02-03 | 2004-06-15 | Basf Coatings Ag | Polyurethane and its use in aqueous painting plastic |
US6630211B1 (en) | 1999-02-25 | 2003-10-07 | Basf Coatings Ag | Utilization of tricyclodecandimethanol for producing multilayer lacquers |
US6652919B1 (en) | 1999-02-25 | 2003-11-25 | Basf Coatings Ag | Highly scratch-resistant multilayer coat, method for producing and use of the same |
US6747091B1 (en) | 1999-02-25 | 2004-06-08 | Basf Coatings Ag | Powder-slurry that can be hardened by actinic radiation or optionally by thermal means, method for producing said slurry and use of the same |
US6872765B1 (en) | 1999-03-06 | 2005-03-29 | Basf Coatings Ag | Sol-gel coating for single-layer or multi-layer varnishes |
US6583214B1 (en) | 1999-04-01 | 2003-06-24 | Basf Coatings Ag | Aqueous coating material that is cured thermally and/or by actinic radiation, and its use |
US6949591B1 (en) | 1999-05-06 | 2005-09-27 | Basf Coatings Ag | Coating material which can be thermally cured and hardened by actinic radiation and use thereof |
US7932317B1 (en) | 1999-05-08 | 2011-04-26 | Basf Coatings Ag | Aqueous coating material and modular system for producing same |
US6652915B1 (en) | 1999-05-25 | 2003-11-25 | Basf Coatings Ag | Coating material containing a mixture of silicic acids and urea and/or urea derivatives |
US6835420B1 (en) | 1999-08-16 | 2004-12-28 | Basf Coatings Ac | Coating material and its use for producing highly scratch resistant multilayer transparent lacquers |
US6713559B1 (en) | 1999-08-27 | 2004-03-30 | Basf Coatings Ag | Sol-gel coating |
US6828381B1 (en) | 1999-08-27 | 2004-12-07 | Basf Coatings Ag | Sol-gel coating |
US6887526B1 (en) | 1999-09-16 | 2005-05-03 | Basf Coatings Ag | Integrated coating method for auto body parts containing plastic parts or for cabins of passenger cars and utility vehicles as well as for their replacement parts and add-on parts |
US6774177B1 (en) | 1999-10-09 | 2004-08-10 | Basf Coatings Ag | Electrically conducting hydroprimer for plastics |
US7504134B2 (en) | 2000-02-25 | 2009-03-17 | Basf Coatings Ag | Method for producing color and/or effect-producing multilayer paints on car bodies |
US8211504B2 (en) | 2000-09-04 | 2012-07-03 | Basf Coatings Gmbh | Method for producing color giving and/or effect giving lacquer coatings |
US7138451B2 (en) | 2000-09-06 | 2006-11-21 | Basf Coatings Ag | Bonding material solution and the use thereof in an automotive spot repair kit |
US6997980B2 (en) * | 2001-01-04 | 2006-02-14 | Basf Coatings Ag | Aqueous, effect-producing coating material, method for the production thereof and use of the same |
US6685985B2 (en) | 2001-02-09 | 2004-02-03 | Basf Corporation | Method of improving the appearance of coated articles having both vertical and horizontal surfaces, and coating compositions for use therein |
US7175883B2 (en) | 2002-01-12 | 2007-02-13 | Basf Coatings Ag | Polysiloxane sols method for the production and use thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH06234954A (en) | 1994-08-23 |
EP0596461A2 (en) | 1994-05-11 |
DK0596461T3 (en) | 1998-12-07 |
DE4237492A1 (en) | 1994-05-11 |
ES2115706T3 (en) | 1998-07-01 |
EP0596461B1 (en) | 1998-04-08 |
ES2115706T5 (en) | 2003-05-16 |
EP0596461B2 (en) | 2002-10-30 |
DE59308380D1 (en) | 1998-05-14 |
ATE164872T1 (en) | 1998-04-15 |
EP0596461A3 (en) | 1995-04-26 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |