WO2009068377A1 - Polyurethane compounds containing uretdione groups and hardenable at low temperature and also containing adhesion-improving resins - Google Patents
Polyurethane compounds containing uretdione groups and hardenable at low temperature and also containing adhesion-improving resins Download PDFInfo
- Publication number
- WO2009068377A1 WO2009068377A1 PCT/EP2008/064357 EP2008064357W WO2009068377A1 WO 2009068377 A1 WO2009068377 A1 WO 2009068377A1 EP 2008064357 W EP2008064357 W EP 2008064357W WO 2009068377 A1 WO2009068377 A1 WO 2009068377A1
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- WIPO (PCT)
- Prior art keywords
- acid
- compositions according
- alcoholate
- hydroxide
- polyurethane compositions
- Prior art date
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 69
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 68
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 239000011347 resin Substances 0.000 title abstract description 7
- 229920005989 resin Polymers 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 120
- 239000000203 mixture Substances 0.000 claims description 103
- 239000002253 acid Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 229920000728 polyester Polymers 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 35
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 22
- 238000009472 formulation Methods 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 14
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- -1 hydroxyalkylamides Chemical class 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000008199 coating composition Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 11
- 235000011037 adipic acid Nutrition 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 239000004848 polyfunctional curative Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- 229930194542 Keto Natural products 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 125000000468 ketone group Chemical group 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims description 7
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010985 leather Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 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 claims description 6
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 5
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 229920006125 amorphous polymer Polymers 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 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 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 claims description 3
- BUYHVRZQBLVJOO-UHFFFAOYSA-N 2-ethyl-2,4-dimethylhexane-1,3-diol Chemical compound CCC(C)C(O)C(C)(CC)CO BUYHVRZQBLVJOO-UHFFFAOYSA-N 0.000 claims description 3
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- MMENAPDIXQUKQD-UHFFFAOYSA-N O-ethyl N-oxocarbamothioate Chemical compound CCOC(=S)N=O MMENAPDIXQUKQD-UHFFFAOYSA-N 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- 150000000376 2-oxazolines Chemical class 0.000 claims description 2
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 229920001634 Copolyester Polymers 0.000 claims description 2
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- HMOHOVASWYMMHA-UHFFFAOYSA-L barium(2+);diphenoxide Chemical compound [Ba+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 HMOHOVASWYMMHA-UHFFFAOYSA-L 0.000 claims description 2
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 claims description 2
- BQDSDRAVKYTTTH-UHFFFAOYSA-N barium(2+);methanolate Chemical compound [Ba+2].[O-]C.[O-]C BQDSDRAVKYTTTH-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 claims description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 2
- SMKNBYSXDYPBME-UHFFFAOYSA-M butanoate;tetrabutylazanium Chemical compound CCCC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC SMKNBYSXDYPBME-UHFFFAOYSA-M 0.000 claims description 2
- BLWUXYZPUFJVSE-UHFFFAOYSA-M butanoate;tetraethylazanium Chemical compound CCCC([O-])=O.CC[N+](CC)(CC)CC BLWUXYZPUFJVSE-UHFFFAOYSA-M 0.000 claims description 2
- OYGSFKZFXQKZDS-UHFFFAOYSA-M butanoate;tetramethylazanium Chemical compound C[N+](C)(C)C.CCCC([O-])=O OYGSFKZFXQKZDS-UHFFFAOYSA-M 0.000 claims description 2
- KWAJGRXLJIZCBX-UHFFFAOYSA-M butanoate;tetrapropylazanium Chemical compound CCCC([O-])=O.CCC[N+](CCC)(CCC)CCC KWAJGRXLJIZCBX-UHFFFAOYSA-M 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims description 2
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 claims description 2
- AMJQWGIYCROUQF-UHFFFAOYSA-N calcium;methanolate Chemical compound [Ca+2].[O-]C.[O-]C AMJQWGIYCROUQF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- HZZUMXSLPJFMCB-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;acetate Chemical compound CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 HZZUMXSLPJFMCB-UHFFFAOYSA-M 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- XAVQZBGEXVFCJI-UHFFFAOYSA-M lithium;phenoxide Chemical compound [Li+].[O-]C1=CC=CC=C1 XAVQZBGEXVFCJI-UHFFFAOYSA-M 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- KRPXAHXWPZLBKL-UHFFFAOYSA-L magnesium;diphenoxide Chemical compound [Mg+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 KRPXAHXWPZLBKL-UHFFFAOYSA-L 0.000 claims description 2
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 claims description 2
- AOLHFTSRLXHBNU-UHFFFAOYSA-M propanoate;tetrabutylazanium Chemical compound CCC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC AOLHFTSRLXHBNU-UHFFFAOYSA-M 0.000 claims description 2
- ZEKIXPPWVVMOMQ-UHFFFAOYSA-M propanoate;tetraethylazanium Chemical compound CCC([O-])=O.CC[N+](CC)(CC)CC ZEKIXPPWVVMOMQ-UHFFFAOYSA-M 0.000 claims description 2
- XNWSMNKRGNKRKP-UHFFFAOYSA-M propanoate;tetramethylazanium Chemical compound CCC([O-])=O.C[N+](C)(C)C XNWSMNKRGNKRKP-UHFFFAOYSA-M 0.000 claims description 2
- VTIZRIDYIWLCRE-UHFFFAOYSA-M propanoate;tetrapropylazanium Chemical compound CCC([O-])=O.CCC[N+](CCC)(CCC)CCC VTIZRIDYIWLCRE-UHFFFAOYSA-M 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
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- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 2
- WGYONVRJGWHMKV-UHFFFAOYSA-M tetrabutylazanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.CCCC[N+](CCCC)(CCCC)CCCC WGYONVRJGWHMKV-UHFFFAOYSA-M 0.000 claims description 2
- SNMZANHSFVMKKA-UHFFFAOYSA-M tetrabutylazanium;formate Chemical compound [O-]C=O.CCCC[N+](CCCC)(CCCC)CCCC SNMZANHSFVMKKA-UHFFFAOYSA-M 0.000 claims description 2
- HJBZFPLBRXFZNE-UHFFFAOYSA-M tetrabutylphosphanium fluoride hydrofluoride Chemical compound F.[F-].CCCC[P+](CCCC)(CCCC)CCCC HJBZFPLBRXFZNE-UHFFFAOYSA-M 0.000 claims description 2
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 claims description 2
- WHDWTYUVZOXXKX-UHFFFAOYSA-M tetrabutylphosphanium;formate Chemical compound [O-]C=O.CCCC[P+](CCCC)(CCCC)CCCC WHDWTYUVZOXXKX-UHFFFAOYSA-M 0.000 claims description 2
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 2
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 claims description 2
- DDDVBYGLVAHHCD-UHFFFAOYSA-M tetraethylazanium;formate Chemical compound [O-]C=O.CC[N+](CC)(CC)CC DDDVBYGLVAHHCD-UHFFFAOYSA-M 0.000 claims description 2
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 claims description 2
- IEVVGBFMAHJELO-UHFFFAOYSA-M tetramethylazanium;benzoate Chemical compound C[N+](C)(C)C.[O-]C(=O)C1=CC=CC=C1 IEVVGBFMAHJELO-UHFFFAOYSA-M 0.000 claims description 2
- WWIYWFVQZQOECA-UHFFFAOYSA-M tetramethylazanium;formate Chemical compound [O-]C=O.C[N+](C)(C)C WWIYWFVQZQOECA-UHFFFAOYSA-M 0.000 claims description 2
- HNRXDBMBQAOWFV-UHFFFAOYSA-M tetraoctadecylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCCCC[N+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC HNRXDBMBQAOWFV-UHFFFAOYSA-M 0.000 claims description 2
- PXJUBOLFJDSAQQ-UHFFFAOYSA-M tetrapropylazanium;acetate Chemical compound CC([O-])=O.CCC[N+](CCC)(CCC)CCC PXJUBOLFJDSAQQ-UHFFFAOYSA-M 0.000 claims description 2
- QOHLYFXRPYZSJX-UHFFFAOYSA-M tetrapropylazanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.CCC[N+](CCC)(CCC)CCC QOHLYFXRPYZSJX-UHFFFAOYSA-M 0.000 claims description 2
- LENBOWGJEQXFCI-UHFFFAOYSA-M tetrapropylazanium;formate Chemical compound [O-]C=O.CCC[N+](CCC)(CCC)CCC LENBOWGJEQXFCI-UHFFFAOYSA-M 0.000 claims description 2
- MNWUNZHJAPWUOT-UHFFFAOYSA-M trihexyl(tetradecyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC MNWUNZHJAPWUOT-UHFFFAOYSA-M 0.000 claims description 2
- 150000004072 triols Chemical class 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
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- 235000011187 glycerol Nutrition 0.000 claims 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims 2
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- HQIPXXNWLGIFAY-UHFFFAOYSA-M decanoate;trihexyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC HQIPXXNWLGIFAY-UHFFFAOYSA-M 0.000 claims 1
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- QGAKFUJUPKPDCN-UHFFFAOYSA-M tetraoctylazanium;fluoride Chemical compound [F-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QGAKFUJUPKPDCN-UHFFFAOYSA-M 0.000 claims 1
- DCFYRBLFVWYBIJ-UHFFFAOYSA-M tetraoctylazanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC DCFYRBLFVWYBIJ-UHFFFAOYSA-M 0.000 claims 1
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- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- WXOVEFQVRRZZJF-UHFFFAOYSA-N 3-methylbut-2-en-2-ylazanium;hydroxide Chemical compound [OH-].CC(C)=C(C)[NH3+] WXOVEFQVRRZZJF-UHFFFAOYSA-N 0.000 description 1
- HSROVARPCNJMKS-UHFFFAOYSA-N 5-(4,5-dihydro-1,3-oxazol-2-yl)pentan-1-ol Chemical compound OCCCCCC1=NCCO1 HSROVARPCNJMKS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- XCVMAWBVFCELLB-UHFFFAOYSA-N C(CCCCCCC)[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C(CCC)[N+](CCCC)(CCCC)CCCC Chemical compound C(CCCCCCC)[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C(CCC)[N+](CCCC)(CCCC)CCCC XCVMAWBVFCELLB-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NAUBYZNGDGDCHH-UHFFFAOYSA-N N=C=O.N=C=O.CCCC(C)C Chemical compound N=C=O.N=C=O.CCCC(C)C NAUBYZNGDGDCHH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RLMOMHNXIWBGTF-UHFFFAOYSA-N diaminophosphinoamine Chemical class NP(N)N RLMOMHNXIWBGTF-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- ZVONPTCZRBWHKG-UHFFFAOYSA-N tetradecylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCC[NH3+] ZVONPTCZRBWHKG-UHFFFAOYSA-N 0.000 description 1
- DTIFFPXSSXFQCJ-UHFFFAOYSA-N tetrahexylazanium Chemical compound CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC DTIFFPXSSXFQCJ-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- CHYBTAZWINMGHA-UHFFFAOYSA-N tetraoctylazanium Chemical compound CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CHYBTAZWINMGHA-UHFFFAOYSA-N 0.000 description 1
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical compound C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 description 1
- RRBYUSWBLVXTQN-VZCHMASFSA-N tricyclene Natural products C([C@@H]12)C3C[C@H]1C2(C)C3(C)C RRBYUSWBLVXTQN-VZCHMASFSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
- C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the invention relates to uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins, in particular for polyurethane powder coating and adhesive compositions which are curable at low temperature, a process for their preparation and their use.
- Solid at room temperature, externally or internally blocked polyisocyanates are valuable crosslinkers for thermally crosslinkable polyurethane (PUR) -Pulverlack- and adhesive compositions.
- PUR thermally crosslinkable polyurethane
- DE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione-containing polyaddition compounds whose terminal
- Isocyanate groups with monoalcohols or monoamines are irreversibly blocked. Disadvantages are, in particular, the chain-breaking constituents of the crosslinkers which lead to low network densities of the PU powder coating and thus to moderate solvent resistances.
- Hydroxyl-terminated, polyaddition compounds containing uretdione groups are the subject of EP 669 353. Due to their functionality of two, they have improved resistance to solvents.
- the powder coating compositions based on these polyisocyanates containing uretdione groups have in common that they do not emit volatile compounds during the curing reaction. However, the baking temperatures are at least 180 0 C at a high level.
- Certain catalysts greatly reduce the activation energy for the cleavage of uretdione groups, so that when uretdione group-containing curing agents are used, the curing temperature of powder coating or adhesive compositions can be considerably lowered. This is beneficial since This way energy can be saved and it is possible to coat thermosensitive substrates by means of powder coatings. Due to the low curing temperature, there is a high melt viscosity of the applied paint formulation. This leads to development problems and surface defects of the powder coating films. In addition, owing to the high melt viscosity, a significantly lower wetting of the substrate surface is frequently observed, which manifests itself in the reduction of the values for mechanical characteristics and in particular in the deterioration of the substrate adhesion. Course problems and surface defects can, as described in DE 10 2004 020 451, be remedied by addition of hydroxyl-containing (partially) khallins polymers, improved substrate wetting is not achieved, so that the substrate adhesion is still problematic.
- the object of the present invention was therefore to find highly reactive uretdione-containing polyurethane compositions which can be cured even at very low temperatures and are particularly suitable for the production of light- and weather-stable powder coatings and which have comparable good substrate adhesion values, as correspondingly at higher temperatures hardened Puvehackformulmaschineen.
- uretdione-containing paint or adhesive compositions can be cured under normal conditions (DBTL catalysis) only from 180 0 C, thereby resulting in coatings, which are usually to the substrate, eg. B. not pretreated steel, have excellent adhesion.
- inventive low-temperature curing compositions can at 100 to 160 0 C curing not only energy and curing time can be saved, but it can also coat many temperature-sensitive substrates or stick, which would show at 180 0 C undesirable yellowing, decomposition and / or embrittlement phenomena.
- certain aluminum substrates are also predestined. In the latter case, an excessively high temperature load sometimes leads to an undesired change in the crystal structure and thus to the loss of the desired mechanical properties.
- the present invention relates to solid, highly reactive uretdione-containing polyurethane compositions having a melting point above 40 0 C, a very good substrate wetting and a very good adhesion, essentially containing
- Tricyclene and the bridging atoms in addition to carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R 1 to R 4 additionally one or more alcohol, amino, ester, keto, thio, urethane, urea , Allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is an alkyl,
- Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol, May have amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms,
- R 1 to R 4 bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1 to 18 carbon atoms and each radical R 1 to R 4 additionally one or more alcohol, amino , Ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds,
- R 5 is either OH or F
- radicals R 1 to R 6 mean independently or independently of one another hydrogen or alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals having 1 to 8 carbon atoms and the radicals are in each case linear or branched, unbridged or bridged with other radicals, with the formation of cycles, bicyclic or tricyclic compounds and
- Bridging atoms in addition to carbon may also be heteroatoms and may additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, said catalysts from groups 1 to 3 are contained individually or in mixtures and C) at least one hydroxyl- and carboxyl-containing unsaturated, amorphous polyester, substantially containing at least one ⁇ , ßunsaturated dicarboxylic acid component and an alcohol component, wherein the alcohol component of a Dicidolgemisch the isomeric Compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4.8- Bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, each isomer in an amount of 20 to 40% by weight in the mixture may be contained and the sum of the three isomers
- Polyester is present, with an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and acid number is always> 1, with a weight fraction based on the total formulation, from 1 to 12%; D) optionally at least one acid group-reactive compound;
- Total formulation is and the sum of the starting materials A) to H) 100 wt .-% results.
- Another object of the invention is also a process for the preparation of the polyurethane composition.
- the invention also provides powder coating compositions and pulverulent adhesive compositions and the use of the polyurethane compositions according to the invention for the production of powder coating coatings on metal, plastic, glass, wood or leather substrates or other heat-sensitive substrates or for the production of powdered adhesive coatings on metallic coatings.
- Plastic, glass, wood or leather substrates or other heat-sensitive substrates are preferred.
- the invention likewise relates to powder coating compositions for metal, in particular for automobile bodies, motorcycles and bicycles, building parts and household appliances, powder coating compositions for wood, glass, leather and plastics.
- Polyisocyanates containing uretdione groups are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 0 417 603.
- J. Prakt. Chem. 336 (1994) 185-200 J. Prakt. Chem. 336 (1994) 185-200.
- the reaction of isocyanates to uretdiones in the presence of soluble Dimehs mecanicskatalysatoren such as.
- dialkylaminopyridines Thalkylphosphinen, phosphorous acid triamides or imidazoles.
- the reaction - optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons. Excess monomeric isocyanate is subsequently separated by short path evaporation. If the catalyst is volatile enough, the reaction mixture can be freed from the catalyst in the course of the monomer separation. The addition of catalyst poisons can be dispensed with in this case.
- isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups. According to the invention, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),
- Uretdione group-containing hardeners A includes the reaction of the free NCO groups with hydroxyl-containing monomers or polymers, such as.
- polyesters polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been described frequently (EP 669 353, EP 669 354, DE 30 30 572, EP 639 598 or EP 803 524).
- polyesters having an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol and low molecular weight dialcohols.
- Preferred uretdione hardeners A) have a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight (calculated as C 2 N 2 O 2 , molecular weight 84).
- the hardeners A) may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.
- the catalysts B) essential to the invention satisfy 1. the formula [XR 1 R 2 R 3 R 4 I + [R 5 COO] " , where X is N or P, where R 1 to R 4 are simultaneously or independently alkyl-, aryl- , Aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R 1 to R 4 , forming cyclics, bicyclic or tricyclic radicals and the bridging atoms besides carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R 1 to R 4 may additionally have one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is an alkyl, , Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol
- Examples of such catalysts under 1. are tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate,
- Tetraethylammonium benzoate tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate,
- Tetrabutylammonium benzoate tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate,
- Trihexyltetradecylphosphoniumdecanoat examples of such catalysts under 2. are methyltributylammonium, methyltriethylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, Tetradecylammoniumhydroxid, Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid, benzyltrimethylammonium, benzyltriethylammonium, trimethylphenylammonium, Thethylmethylamnnoniunnhydroxid, Trimethylvinylammoniumhydroxid, tetramethylammonium fluoride, tetraethylammonium, te
- Examples of such catalysts under 3. are lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, zinc hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, magnesium methoxide, calcium methoxide, barium methoxide, lithium ethoxide, sodium ethanolate, potassium ethanolate, Magnesium ethanolate, calcium ethanolate, barium ethanolate, lithium propyl alcoholate, sodium propyl alcoholate, potassium propyl alcoholate, magnesium propyl alcoholate, calcium propyl alcoholate, barium propyl alcoholate, lithium isopropyl alcoholate, sodium isopropyl alcoholate, potassium isopropyl alcoholate, magnesium isopropyl alcoholate, calcium isopropyl alcoholate, barium isopropyl alcoholate, lithium 1-butyl alcohol
- the catalysts are contained in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 3 wt .-%, based on the total formulation, in the polyurethane composition.
- the catalysts may contain water of crystallization, which is not taken into account in the calculation of the amount of catalyst used, d. H. the amount of water is deducted. Particular preference is given to using tetraethylammonium benzoate and tetrabutylammonium hydroxide.
- a variant according to the invention includes the polymeric attachment of such catalysts B) to the curing agents A) or hydroxyl-containing polymers C) or F).
- So z. B. free alcohol, thio or amino groups of the ammonium salts with acid, isocyanate, or glycidyl groups of the powder coating hardener A) or hydroxyl-containing polymers C) or F) are reacted to integrate the catalysts B) in the polymeric composite.
- These catalysts may also be encased in a shell and encapsulated therewith.
- As component C) is at least one hydroxyl and carboxyl-containing unsaturated, amorphous polyester having an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and Acid number is always> 1, with a
- Weight fraction based on the total formulation, from 1 to 12% used.
- Component C) comprises unsaturated polyesters containing amorphous hydroxyl and carboxyl groups, essentially containing at least one ⁇ , ⁇ -unsaturated dicarboxylic acid component and an alcohol component, the alcohol component of a mixture of dicidol of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-% results, and the mixture at least 5 wt .-% in the alcohol component of the polyester is present.
- the unsaturated amorphous polyester resins C) are obtained by reacting the alcohol component and the acid component.
- the alcohol component according to the invention is a Dicidolgemisch the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5.8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane used, wherein each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-%, preferably 95 to 100% by weight, and the mixture is at least 5% by weight in the alcohol component of the polyester.
- the isomer content of the Dicidolgemisches can qualitatively and quantitatively z. B.
- the Dicidolgemisch may contain up to 10 wt .-% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene.
- the alcohol component consists of 20 wt .-%, from 50 wt .-%, preferably from 90 wt .-%, particularly preferably from 100 wt .-% Dicidolgemisch, this more preferably 95 to 100 wt .-% of the above contains three isomeric compounds.
- the alcohol component may contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols.
- Preferred additional alcohols are ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-butylethylpropanediol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-di
- the unsaturated, amorphous polyester resins C) contain as starting acid component at least one ⁇ , ß-unsaturated dicarboxylic acid.
- the unsaturated polyester resins preferably contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid.
- Phthalic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid,
- Tetrahydrophthalic acid Tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid.
- Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.
- the acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.
- the alcohol component is contained in the molar ratio of 0.5 to 2.0 to 1 to the acid component, preferably 0.8 to 1, 5 to 1. Particularly preferred is the implementation of the alcohol component in the molar ratio of 1, 0 to 1, 1 to 1 to the acid component instead.
- the unsaturated, amorphous polyesters C) may have an acid number between 1 and 75 mg KOH / g, preferably between 1 and 50, more preferably between 1 and 35 mg KOH / g and an OH number between 1 and 100 mg KOH / g between 1 and 75, more preferably between 1 and 50 mg KOH / g, wherein the ratio of OH and acid number is always> 1.
- the Tg of the unsaturated amorphous polyester C) varies from -30 to +80 0 C, preferably from -20 to +50 0 C, more preferably - 10 to + 40 0 C.
- the unsaturated polyester resins C) consist of an alcohol component having at least 90% by weight, preferably 95% by weight, particularly preferably 100% by weight, of the dicidol mixture of the isomeric compounds 3,8 Bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and from fumaric acid and / or maleic acid (anhydride).
- the polyesters C) contain the abovementioned starting components as under I, but additionally an additional acid selected from adipic acid or phthalic acid (anhydride), the ratio of the ⁇ , ⁇ -unsaturated to the additional acid being from 2: 1 to 1: 1 can vary to 4. Ratios of about 1 to 1 to 1 to 2 are preferred.
- polyesters generally have acid numbers of 1 to 75 mg KOH / g, preferably 1 to 50 mg KOH / g, particularly preferably 1 to 35 mg KOH / g, OH numbers from 1 to 100 mg KOH / g, preferably 1 to 75 mg KOH / g, particularly preferably 1 to 50 mg KOH / g, the ratio of OH and acid number always being> 1, and a Tg of -30 to +80 0 C, preferably -20 to +50 0 C, more preferably -10 to +40 0 C on.
- the polyesters C) may also contain auxiliaries and additives selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, anti-skinning agents, defoamers, antistatic agents, thickeners .
- auxiliaries and additives selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, anti-skinning agents, defoamers, antistatic agents, thickeners .
- thermoplastic additives dyes, pigments, fire retardants, internal release agents, fillers and / or blowing agents.
- the polyesters C) are prepared by (semi) continuous or discontinuous esterification and condensation of the starting acids and alcohols in a one-stage or two-stage procedure.
- Polyester resins based on dicidol as diol component are also known from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988, EP 1 492 834.
- EP 1 398 337 describes adhesion-improving additives of an unsaturated, amorphous polyester.
- the adhesion-improving additives are polymer-containing in aqueous, solvent-containing (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid), thermosetting, radiation-curable, air-drying (oxidative and physical) coating materials, fillers and / or sealants and adhesives and are suitable as a modification resin for primers, fillers, basecoats, single-coat finishes, clearcoats, adhesives, sealants, road marking paints, anti-corrosive paints.
- Polymers according to EP 1 398 337 can carry OH and carboxylic acid groups, wherein both the OH number and the acid number can assume values between 1 and 200 mg KOH / g.
- the polymers described in EP 1 398 337 can have a high carboxylic acid and low OH functionality.
- their use would be in highly reactive uretdione-containing polyurethane compositions
- polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 10 to 500 (in mg KOH / gram) are preferably used in the hydroxyl-containing (partially) khallene polymers G).
- Particularly preferred are hydroxyl-containing polyesters having an OH number of 15 to 150 and an average molecular weight of 500 to 6,000 g / mol.
- mixtures of such polymers can be used.
- the proportion by weight of this (partially) crystalline component G) in the overall formulation A-H can be between 1 and 95% by weight, preferably from 2 to 50% by weight.
- Preferred (partial) crystalline hydroxyl-containing polyesters G) are prepared by polycondensation.
- an acid component consisting of 80 to 100 mole percent of a saturated, linear aliphatic or cycloaliphatic dicarboxylic acid having 4 to 14 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic or aromatic di- or polycarboxylic acid, having an alcohol component consisting of 80 to 100 Mole percent of a linear aliphatic diol of 2 to 15 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic di or polyol of 2 to 15 carbon atoms.
- the (partially) crystalline hydroxyl-containing polyesters thus produced have an OH number of 15 to 150 mg KOH / g, an acid number ⁇ 5 mg KOH / g and a melting point of 40 to 130 ° C.
- Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, are preferred carboxylic acids for the preparation of (partly) khallins polyesters G),
- Hexahydroterephthal Acid endomethylene tetrahydrophthalic acid, glutaric acid or - as far as accessible - their anhydrides.
- Particularly suitable and preferred is dodecanedioic acid.
- the following diols are ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropanediol (1, 3), butanediol (1, 4), pentanediol (1, 5) , Hexanediol (1, 6), 2-methylpentanediol (1, 5), 2,2,4-trimethylhexanediol (1,6), 2,4,4-thymethylhexanediol (1,6), Heptanediol (1, 7), decanediol (1, 10), dodecanediol (1, 12), octadecene-9, 10-diol (1, 12), octadecanediol (1, 18), 2,4- Dimethyl-2-propylheptandiol- (1, 3), butenediol (1, 4), butynediol (1, 4), diethylene glycol,
- the activity of the catalysts under B) in the presence of acids decreases significantly.
- the conventional reactants of the uretdione-containing paint or adhesive hardener include hydroxyl-containing polyester. Due to the method of preparation of polyesters, they sometimes carry acid groups to a small extent. In the presence of such acid groups-bearing polyesters, it is advisable to use the catalysts mentioned either in excess, based on the acid groups, or to add reactive compounds which are capable of intercepting acid groups. Both monofunctional and polyfunctional compounds can be used for this purpose.
- Reactive acid scavenging compounds D are well known in paint chemistry.
- inorganic salts such as hydroxides, bicarbonates or carbonates
- triglycidyl ether isocyanurate TGIC
- EPIKOTE ® 828 diglycidyl ether based on bisphenol A, Schell
- versatic ethylhexyl glycidyl ether
- butyl glycidyl ether Polypox R 16 (pentaerythritol tetraglycidyl ether, UPPC AG) as well as other Polypoxtypen having free epoxy groups, .beta.-hydroxyalkylamides (z. B.
- Acids which are mentioned under E) are all substances, solid or liquid, organic or inorganic, monomeric or polymeric, which have the properties of a Bronsted or a Lewis acid. Examples include: sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, but also copolyester or
- Copolyamides having an acid number of at least 20 mg KOH / g. They are contained, if present, in a proportion by weight, based on the total formulation, of 0.1 to 10%.
- hydroxyl-containing amorphous polymers F preference is given to using polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 20 to 500 mg KOH / gram. Particularly preferred are hydroxyl-containing polyesters having an OH number of 20 to 150 mg / KOH / g, an average molecular weight of 500 to 6000 g / mol. Of course, mixtures of such polymers can be used. Such amorphous polymers can, if present, be used in a proportion by weight of 1 to 95%, preferably 1 to 90%, based on the total formulation.
- aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols can be contained.
- dicidol ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-Butylethylpropandiol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-dimethyl-2
- the acid component for the preparation of the polyester can linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic monocarboxylic acids and / or dicarboxylic acids and / or polycarboxylic acids may be contained, such as.
- Phthalic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.
- the acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.
- auxiliaries and additives H as leveling agents, for.
- additional catalysts such as are already known in polyurethane chemistry may be included.
- organometallic catalysts such as. As dibutyltin dilaurate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2,] octane, in amounts of 0.001 to 1 wt .-%.
- the total amount of H) may be from 0.001 to 55% by weight, based on the total formulation.
- the homogenization of all constituents for the preparation of the polyurethane composition according to the invention can be carried out in suitable aggregates, such. B. heated kneaders, but especially in extruders at temperatures of 40 to 130 0 C, carried out, with upper temperature limits of 120 to 130 0 C not exceeded should be.
- the well-mixed mass is removed by suitable application, eg. As rollers, spraying, applied to the substrate.
- suitable application of ready-to-spray powders on suitable substrates can according to the known methods, such. B. by electrostatic powder spraying, vortex sintering, or electrostatic vortex sintering done.
- the coated workpieces are cured for 4 to 60 minutes at a temperature of 60 to 220 0 C, preferably 6 to 30 minutes at 80 to 150 0 C heated.
- the comminuted feedstocks according to Table 2 are intimately mixed in a pug mill and then homogenized in the extruder at temperatures up to 130 0 C maximum. After cooling, the extrudate is crushed and ground with a pin mill to a particle size ⁇ 100 microns and sieved by means of a screening machine to ⁇ 63 microns.
- the powder thus produced is applied with an electrostatic powder spray system at 60 KV on degreased iron sheets and baked in a convection oven for 30 minutes at 150 0 C and 30 minutes at 130 0 C. (Layer thickness 70 to 80 microns). The results of the test data are shown in Tables 3 to 4.
Abstract
The invention relates to polyurethane compounds, which contain uretdione groups and are hardenable at low temperature and also contain adhesion-improving resins, in particular for polyurethane powder coating and adhesive compounds, which can be hardened at low temperature, to a method for the production thereof, and to the use thereof.
Description
Uretdiongruppen haltige Polyurethanzusammensetzungen, welche bei niedriger Temperatur härtbar sind und haftungsverbessernde Harze enthalten Uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins
Die Erfindung betrifft Uretdiongruppen haltige Polyurethanzusammensetzungen, welche bei niedriger Temperatur härtbar sind und haftungsverbessernde Harze enthalten, insbesondere für Polyurethan-Pulverlack- und Klebstoffzusammensetzungen, welche bei niedriger Temperatur härtbar sind, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung.The invention relates to uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins, in particular for polyurethane powder coating and adhesive compositions which are curable at low temperature, a process for their preparation and their use.
Bei Raumtemperatur feste, extern oder intern blockierte Polyisocyanate stellen wertvolle Vernetzer für thermisch vernetzbare Polyurethan (PUR)-Pulverlack- und Klebstoffzusammensetzungen dar.Solid at room temperature, externally or internally blocked polyisocyanates are valuable crosslinkers for thermally crosslinkable polyurethane (PUR) -Pulverlack- and adhesive compositions.
Die DE-OS 30 30 539 und DE-OS 30 30 572 beschreiben Verfahren zur Herstellung von Uretdiongruppen haltigen Polyadditionsverbindungen, deren terminaleDE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione-containing polyaddition compounds whose terminal
Isocyanatgruppen mit Monoalkoholen oder Monoaminen irreversibel blockiert sind. Nachteilig sind insbesondere die Ketten abbrechenden Bestandteile der Vernetzer, die zu geringen Netzwerkdichten der PUR-Pulverlackbeschichtungen und damit zu mäßigen Lösemittelbeständigkeiten führen.Isocyanate groups with monoalcohols or monoamines are irreversibly blocked. Disadvantages are, in particular, the chain-breaking constituents of the crosslinkers which lead to low network densities of the PU powder coating and thus to moderate solvent resistances.
Hydroxylgruppen terminierte, Uretdiongruppen haltige Polyadditionsverbindungen sind Gegenstand der EP 669 353. Sie weisen aufgrund ihrer Funktionalität von zwei eine verbesserte Resistenz gegenüber Lösemitteln auf. Den Pulverlackzusammensetzungen auf Basis dieser Uretdiongruppen haltigen Polyisocyanate ist gemeinsam, dass sie bei der Härtungsreaktion keine flüchtigen Verbindungen emittieren. Allerdings liegen die Einbrenntemperaturen mit mindestens 180 0C auf hohem Niveau.Hydroxyl-terminated, polyaddition compounds containing uretdione groups are the subject of EP 669 353. Due to their functionality of two, they have improved resistance to solvents. The powder coating compositions based on these polyisocyanates containing uretdione groups have in common that they do not emit volatile compounds during the curing reaction. However, the baking temperatures are at least 180 0 C at a high level.
Bestimmte Katalysatoren setzen die Aktivierungsenergie für die Spaltung von Uretdiongruppen stark herunter, so dass sich bei Verwendung Uretdiongruppen haltiger Härter die Aushärtetemperatur von Pulverlack- bzw. Klebstoffzusammensetzungen beträchtlich erniedrigen lässt. Dies ist vorteilhaft, da auf
diese Weise Energie eingespart werden kann und es ermöglicht wird, thermosensitive Substrate mittels Pulverlacken zu beschichten. Aufgrund der niedrigen Aushärtungstemperatur liegt eine hohe Schmelzviskosität der applizierten Lackformulierung vor. Dies führt zu Verlaufsproblemen und Oberflächenstörungen der Pulverlackfilme. Zusätzlich wird häufig wegen der hohen Schmelzviskosität eine deutlich geringere Benetzung der Substratoberfläche beobachtet, was sich in der Reduzierung der Werte für mechanische Kenndaten und insbesondere in der Verschlechterung der Substrathaftung äußert. Verlaufsprobleme und Oberflächenstörungen können, wie in der DE 10 2004 020 451 beschrieben, durch Zugabe von Hydroxylgruppen haltigen (teil-)khstallinen Polymeren behoben werden, eine verbesserte Substratbenetzung wird dadurch nicht erreicht, so dass die Substrathaftung weiterhin problematisch ist.Certain catalysts greatly reduce the activation energy for the cleavage of uretdione groups, so that when uretdione group-containing curing agents are used, the curing temperature of powder coating or adhesive compositions can be considerably lowered. This is beneficial since This way energy can be saved and it is possible to coat thermosensitive substrates by means of powder coatings. Due to the low curing temperature, there is a high melt viscosity of the applied paint formulation. This leads to development problems and surface defects of the powder coating films. In addition, owing to the high melt viscosity, a significantly lower wetting of the substrate surface is frequently observed, which manifests itself in the reduction of the values for mechanical characteristics and in particular in the deterioration of the substrate adhesion. Course problems and surface defects can, as described in DE 10 2004 020 451, be remedied by addition of hydroxyl-containing (partially) khallins polymers, improved substrate wetting is not achieved, so that the substrate adhesion is still problematic.
Aufgabe der vorliegenden Erfindung war es daher, hochreaktive Uretdiongruppen haltige Polyurethanzusammensetzungen zu finden, die sich bereits bei sehr niedrigen Temperaturen aushärten lassen und sich insbesondere zur Herstellung von licht- und wetterstabilen Pulverlackbeschichtungen eignen und die bezüglich Substrathaftung vergleichbar gute Werte aufweisen, wie entsprechend bei höheren Temperaturen gehärtete Puvehackformulierungen.The object of the present invention was therefore to find highly reactive uretdione-containing polyurethane compositions which can be cured even at very low temperatures and are particularly suitable for the production of light- and weather-stable powder coatings and which have comparable good substrate adhesion values, as correspondingly at higher temperatures hardened Puvehackformulierungen.
Überraschend wurde gefunden, dass in Niedrigtemperatur härtenden Uretdiongruppen haltigen Systemen der Einsatz von speziellen Haftharzen auf Basis ungesättigter Polyester die Substratbenetzung und damit die Haftung solcher Pulverlackformulierungen, mit und ohne Zusatz Hydroxylgruppen haltiger (teil-) kristalliner Polymeren, deutlich verbessert, ohne Beständigkeitseigenschaften negativ zu beeinflussen.Surprisingly, it has been found that in low-temperature curing uretdione-containing systems, the use of special adhesion resins based on unsaturated polyester substrate wetting and thus the adhesion of such powder coating formulations, with and without the addition of hydroxyl-containing (partially) crystalline polymers, significantly improved without negatively affecting resistance properties ,
Herkömmliche Uretdiongruppen haltige Lack- bzw. Klebstoffzusammensetzungen lassen sich unter normalen Bedingungen (DBTL-Katalyse) erst ab 180 0C aushärten, dabei entstehen Beschichtungen, die in der Regel zum Substrat, z. B. nicht vorbehandelter Stahl, eine ausgezeichnete Haftung aufweisen. Mit Hilfe der erfindungsgemäßen bei Niedrigtemperatur härtenden Zusammensetzungen kann bei
100 bis 160 0C Aushärtungstemperatur nicht nur Energie und Aushärtungszeit gespart werden, sondern es lassen sich auch viele temperatursensible Substrate beschichten bzw. verkleben, die bei 180 0C unerwünschte Vergilbungs-, Zersetzungs- und/oder Versprödungserscheinungen zeigen würden. Neben Metall, Glas, Holz, Leder, Kunststoffen und MDF-Platten sind auch bestimmte Aluminiumuntergründe prädestiniert. Bei letzteren führt eine zu hohe Temperaturbelastung mitunter zu einer unerwünschten Änderung der Kristallstruktur und damit zum Verlust der erwünschten mechanischen Eigenschaften.Conventional uretdione-containing paint or adhesive compositions can be cured under normal conditions (DBTL catalysis) only from 180 0 C, thereby resulting in coatings, which are usually to the substrate, eg. B. not pretreated steel, have excellent adhesion. With the aid of the inventive low-temperature curing compositions can at 100 to 160 0 C curing not only energy and curing time can be saved, but it can also coat many temperature-sensitive substrates or stick, which would show at 180 0 C undesirable yellowing, decomposition and / or embrittlement phenomena. In addition to metal, glass, wood, leather, plastics and MDF boards, certain aluminum substrates are also predestined. In the latter case, an excessively high temperature load sometimes leads to an undesired change in the crystal structure and thus to the loss of the desired mechanical properties.
Gegenstand der vorliegenden Erfindung sind feste, hochreaktive Uretdiongruppen haltige Polyurethanzusammensetzungen mit einem Schmelzpunkt oberhalb von 40 0C, einer sehr guten Substratbenetzung und einer sehr guten Haftung, im Wesentlichen enthaltendThe present invention relates to solid, highly reactive uretdione-containing polyurethane compositions having a melting point above 40 0 C, a very good substrate wetting and a very good adhesion, essentially containing
A) mindestens einen Uretdiongruppen haltigen Härter, basierend auf aromatischen, aliphatischen, (cyclo)aliphatischen und/oder cycloaliphatischen Polyisocyanaten und Hydroxylgruppen haltigen Verbindungen mit einem freien NCO-Gehalt von kleiner 5 Gew.-% und einem Uretdiongruppengehalt von 1 bis 18 Gew.-%, in Mengen zwischen 15 und 45 Gew.-% bezogen auf die Gesamtformulierung; undA) at least one hardener containing uretdione groups, based on aromatic, aliphatic, (cyclo) aliphatic and / or cycloaliphatic polyisocyanates and hydroxyl-containing compounds having a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight. %, in amounts between 15 and 45 wt .-% based on the total formulation; and
B) mindestens einen KatalysatorB) at least one catalyst
1. der Formel [XR1R2R3R4I+ [R5COO]", mit X gleich N oder P, wobei R1 bis R4 gleichzeitig oder unabhängig voneinander Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste, jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten R1 bis R4 verbrückt, unter Ausbildung von Cyclen, Bicyclen oder1. of the formula [XR 1 R 2 R 3 R 4 I + [R 5 COO] " , where X is N or P, where R 1 to R 4 are simultaneously or independently alkyl, aryl, aralkyl, heteroaryl Alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R 1 to R 4 , with the formation of cycles, bicycles or
Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können, mit 1 bis 18 Kohlenstoffatomen bedeuten und jeder Rest R1 bis R4 zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann, und R5 ein Alkyl-,Tricyclene and the bridging atoms in addition to carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R 1 to R 4 additionally one or more alcohol, amino, ester, keto, thio, urethane, urea , Allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is an alkyl,
Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylrest, linear oder verzweigt, mit 1 bis 18 Kohlenstoffatomen darstellt und zusätzlich noch eine oder mehrere Alkohol-,
Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann,Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol, May have amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms,
2. der Formel [XR1R2R3R4I+ [R5]", mit X gleich N oder P, wobei R1 bis R4 gleichzeitig oder unabhängig voneinander Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste, jeweils linear oder verzweigt, unverbrückt oder mit anderen2. of the formula [XR 1 R 2 R 3 R 4 I + [R 5 ] " , where X is N or P, where R 1 to R 4 are simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, in each case linear or branched, unbridged or with others
Resten R1 bis R4 verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können, mit 1 bis 18 Kohlenstoffatomen darstellen und jeder Rest R1 bis R4 zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen,R 1 to R 4 bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1 to 18 carbon atoms and each radical R 1 to R 4 additionally one or more alcohol, amino , Ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds,
Dreifachbindungen oder Halogenatome aufweisen kann, und R5 entweder OH oder F bedeutet,May have triple bonds or halogen atoms, and R 5 is either OH or F,
3. der Formel M (OR1 )n (OR2)m (OR3)O (OR4)P (OR5)q (OR6)r, wobei M ein Metall in beliebiger positiver Oxidationsstufe und identisch mit der Summe n+m+o+p+q+r ist, m, o, p, q, r ganze Zahlen von 0 bis 6 darstellen und für die3. of the formula M (OR 1 ) n (OR 2 ) m (OR 3 ) O (OR 4 ) P (OR 5 ) q (OR 6 ) r , where M is a metal in any positive oxidation state and identical to the sum n + m + o + p + q + r, m, o, p, q, r represent integers from 0 to 6 and for the
Summe n+m+o+p+q+r = 1 bis 6 gilt, die Reste R1 bis R6 gleichzeitig oder unabhängig voneinander Wasserstoff oder Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste mit 1 bis 8 Kohlenstoffatomen bedeuten und die Reste jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und dieTotal n + m + o + p + q + r = 1 to 6 applies, the radicals R 1 to R 6 mean independently or independently of one another hydrogen or alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals having 1 to 8 carbon atoms and the radicals are in each case linear or branched, unbridged or bridged with other radicals, with the formation of cycles, bicyclic or tricyclic compounds and
Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können und zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen können, wobei diese Katalysatoren aus den Gruppen 1 bis 3 einzeln oder in Mischungen enthalten sind und C) mindestens einen Hydroxyl- und Carboxylgruppen haltigen ungesättigten, amorphen Polyester, im Wesentlichen enthaltend mindestens eine α, ß- ungesättigte Dicarbonsäurekomponente und eine Alkoholkomponente, wobei die Alkoholkomponente aus einem Dicidolgemisch der isomeren Verbindungen 3,8-Bis(hydroxymethyl)tricyclo [5.2.1.02'6]decan, 4,8-
Bis(hydroxymethyl)tricyclo [5.2.1.02'6]decan und 5,8-Bis(hydroxymethyl)tricyclo [5.2.1.026]decan besteht, wobei jedes Isomere zu einem Anteil von 20 bis 40 Gew.-% in dem Gemisch enthalten sein kann und die Summe der drei Isomeren 90 bis 100 Gew.-% ergibt, und das Gemisch mindestens zu 5 Gew.-% in der Alkoholkomponente desBridging atoms in addition to carbon may also be heteroatoms and may additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, said catalysts from groups 1 to 3 are contained individually or in mixtures and C) at least one hydroxyl- and carboxyl-containing unsaturated, amorphous polyester, substantially containing at least one α, ßunsaturated dicarboxylic acid component and an alcohol component, wherein the alcohol component of a Dicidolgemisch the isomeric Compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4.8- Bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, each isomer in an amount of 20 to 40% by weight in the mixture may be contained and the sum of the three isomers 90 to 100 wt .-%, and the mixture at least 5 wt .-% in the alcohol component of
Polyesters vorhanden ist, mit einer OH-Zahl zwischen 1 und 100 mg KOH/Gramm und einer COOH-Zahl zwischen 1 und 75 mg KOH/Gramm, wobei das Verhältnis aus OH- und Säurezahl stets >1 beträgt, mit einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 1 bis 12 %; D) gegebenenfalls mindestens eine gegenüber Säuregruppen reaktive Verbindung;Polyester is present, with an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and acid number is always> 1, with a weight fraction based on the total formulation, from 1 to 12%; D) optionally at least one acid group-reactive compound;
E) gegebenenfalls mindestens eine Säure in monomerer oder polymerer Form;E) optionally at least one acid in monomeric or polymeric form;
F) gegebenenfalls mindestens ein amorphes Hydroxylgruppen haltiges oder Amingruppen haltiges Polymer mit einer OH-Zahl zwischen 20 undF) optionally at least one amorphous hydroxyl-containing or amine-containing polymer having an OH number between 20 and
500 mg KOH/Gramm beziehungsweise einem vergleichbaren Amingehalt; G) mindestens ein (teil-)khstallines Hydroxylgruppen haltiges Polymer mit einer OH- Zahl zwischen 10 und 500 mg KOH/Gramm mit einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 1 bis 35 %; H) gegebenenfalls Hilfs- und Zusatzstoffe und/oder weitere Katalysatoren;500 mg KOH / gram or a comparable amine content; G) at least one (partially) khstallines hydroxyl-containing polymer having an OH number between 10 and 500 mg KOH / gram with a weight fraction, based on the total formulation, of 1 to 35%; H) optionally auxiliaries and additives and / or further catalysts;
wobei der Anteil des Katalysators unter B) 0,001 bis 5 Gew.-% an derwherein the proportion of the catalyst under B) 0.001 to 5 wt .-% of the
Gesamtformulierung beträgt und die Summe der Einsatzstoffe A) bis H) 100 Gew.-% ergibt.Total formulation is and the sum of the starting materials A) to H) 100 wt .-% results.
Weiterer Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung der Polyurethanzusammensetzung.Another object of the invention is also a process for the preparation of the polyurethane composition.
Gegenstand der Erfindung sind auch Pulverlackzusammensetzungen und pulverförmige Klebstoffzusammensetzungen und die Verwendung der erfindungsgemäßen Polyurethanzusammensetzungen zur Herstellung von Pulver- Lackbeschichtungen auf Metall-, Kunststoff-, Glas-, Holz-, oder Ledersubstraten oder sonstigen hitzeempfindlichen Untergründen bzw. zur Herstellung von pulverförmigen Klebstoffbeschichtungen auf Metall-, Kunststoff-, Glas-, Holz-, oder Ledersubstraten
oder sonstigen hitzeempfindlichen Untergründen.The invention also provides powder coating compositions and pulverulent adhesive compositions and the use of the polyurethane compositions according to the invention for the production of powder coating coatings on metal, plastic, glass, wood or leather substrates or other heat-sensitive substrates or for the production of powdered adhesive coatings on metallic coatings. , Plastic, glass, wood or leather substrates or other heat-sensitive substrates.
Ebenfalls Gegenstand der Erfindung sind Pulverbeschichtungszusammensetzungen für Metall, insbesondere für Automobil karossen, Motor- und Fahrräder, Gebäudeteile und Haushaltsgeräte, Pulverbeschichtungszusammensetzungen für Holz, Glas, Leder und Kunststoffe.The invention likewise relates to powder coating compositions for metal, in particular for automobile bodies, motorcycles and bicycles, building parts and household appliances, powder coating compositions for wood, glass, leather and plastics.
Darüber hinaus sind die so beschichteten Gegenstände Bestandteil der Erfindung.In addition, the articles coated in this way are part of the invention.
Uretdiongruppen enthaltende Polyisocyanate sind wohlbekannt und werden beispielsweise in US 4,476,054, US 4,912,210, US 4,929,724 sowie EP 0 417 603 beschrieben. Einen umfassenden Überblick über industriell relevante Verfahren zur Dimerisierung von Isocyanaten zu Uretdionen liefert das J. Prakt. Chem. 336 (1994) 185-200. Im Allgemeinen erfolgt die Umsetzung von Isocyanaten zu Uretdionen in Gegenwart löslicher Dimehsierungskatalysatoren, wie z. B. Dialkylaminopyridinen, Thalkylphosphinen, Phosphorigsäure-triamiden oder Imdidazolen. Die Reaktion - optional in Lösemitteln, bevorzugt aber in Abwesenheit von Lösemitteln durchgeführt - wird bei Erreichen eines gewünschten Umsatzes durch Zusatz von Katalysatorgiften abgestoppt. Überschüssiges monomeres Isocyanat wird im Anschluss durch Kurzwegverdampfung abgetrennt. Ist der Katalysator flüchtig genug, kann das Reaktionsgemisch im Zuge der Monomerabtrennung vom Katalysator befreit werden. Auf den Zusatz von Katalysatorgiften kann in diesem Fall verzichtet werden. Grundsätzlich ist zur Herstellung von Uretdiongruppen enthaltenden Polyisocyanaten eine breite Palette von Isocyanaten geeignet. Erfindungsgemäß werden Isophorondiisocyanat (IPDI), Hexamethylendiisocyanat (HDI),Polyisocyanates containing uretdione groups are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 0 417 603. For a comprehensive overview of industrially relevant processes for the dimerization of isocyanates to uretdiones J. Prakt. Chem. 336 (1994) 185-200. In general, the reaction of isocyanates to uretdiones in the presence of soluble Dimehsierungskatalysatoren, such as. As dialkylaminopyridines, Thalkylphosphinen, phosphorous acid triamides or imidazoles. The reaction - optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons. Excess monomeric isocyanate is subsequently separated by short path evaporation. If the catalyst is volatile enough, the reaction mixture can be freed from the catalyst in the course of the monomer separation. The addition of catalyst poisons can be dispensed with in this case. In principle, a wide range of isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups. According to the invention, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),
Diisocyanatodicyclohexylmethan (Hi2MDI), 2-Methylpentandiisocyanat (MPDI), 2,2,4- Thmethylhexamethylendiisocyanat^^^-Thmethylhexamethylendiisocyanat (TMDI), Norbornandiisocyanat (NBDI), Methylendiphenyldiisocyanat (MDI), Toluidindiisocyanat (TDI) und Tetramethylxylylendiisocyanat (TMXDI) bevorzugt verwendet. Ganz besonders bevorzugt werden IPDI und HDI.Diisocyanatodicyclohexylmethane (Hi 2 MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-thmethylhexamethylene diisocyanate ^^^ thymethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate (TMXDI) used. Very particular preference is given to IPDI and HDI.
Die Umsetzung dieser Uretdiongruppen tragenden Polyisocyanate zu
Uretdiongruppen aufweisenden Härtern A) beinhaltet die Reaktion der freien NCO- Gruppen mit Hydroxylgruppen haltigen Monomeren oder Polymeren, wie z. B. Polyestern, Polythioethern, Polyethern, Polycaprolactamen, Polyepoxiden, Polyesteramiden, Polyurethanen oder nieder-molekularen Di-, Tri- und/oder Tetraalkoholen als Kettenverlängerer und gegebenenfalls Monoaminen und/oder Monoalkoholen als Kettenabbrecher und wurde schon häufig beschrieben (EP 669 353, EP 669 354, DE 30 30 572, EP 639 598 oder EP 803 524). Bevorzugt werden Polyester mit einer OH-Zahl von 30 bis 150 mg KOH/g und einem mittleren Molekulargewicht von 500 bis 6000 g/mol und niedermolekulare Dialkohole. Bevorzugte Uretdiongruppen aufweisende Härter A) haben einen freien NCO-Gehalt von weniger als 5 Gew.-% und einen Gehalt an Uretdiongruppen von 1 bis 18 Gew.-% (berechnet als C2N2O2, Molekulargewicht 84). Außer den Uretdiongruppen können die Härter A) auch Isocyanurat-, Biuret-, Allophanat-, Urethan- und/oder Harnstoff- Strukturen aufweisen.The implementation of these uretdione group-bearing polyisocyanates Uretdione group-containing hardeners A) includes the reaction of the free NCO groups with hydroxyl-containing monomers or polymers, such as. As polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been described frequently (EP 669 353, EP 669 354, DE 30 30 572, EP 639 598 or EP 803 524). Preference is given to polyesters having an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol and low molecular weight dialcohols. Preferred uretdione hardeners A) have a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight (calculated as C 2 N 2 O 2 , molecular weight 84). In addition to the uretdione groups, the hardeners A) may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.
Die erfindungswesentlichen Katalysatoren B) genügen 1. der Formel [XR1R2R3R4I+ [R5COO]", mit X gleich N oder P, wobei R1 bis R4 gleichzeitig oder unabhängig voneinander Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste, jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten R1 bis R4 verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können, mit 1 bis 18 Kohlenstoffatomen bedeuten und jeder Rest R1 bis R4 zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann, und R5 ein Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylrest, linear oder verzweigt, mit 1 bis 18 Kohlenstoffatomen darstellt und zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann, oder 2. der Formel [XR1R2R3R4J+ [R5]", mit X gleich N oder P, wobei R1 bis R4 gleichzeitig oder unabhängig voneinander Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste, jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten R1 bis R4
verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können, mit 1 bis 18 Kohlenstoffatomen darstellen und jeder Rest R1 bis R4 zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann, und R5 entweder OH oder F bedeutet, oder 3. der Formel M (OR1 )n (OR2)m (OR3)O (OR4)P (OR5)q (OR6)r, wobei M ein Metall in beliebiger positiver Oxidationsstufe und identisch mit der Summe n+m+o+p+q+r ist, m, o, p, q, r ganze Zahlen von 0 bis 6 darstellen und für die Summe n+m+o+p+q+r = 1 bis 6 gilt, die Reste R1 bis R6 gleichzeitig oder unabhängig voneinander Wasserstoff oder Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste, mit 1 bis 8 Kohlenstoffatomen bedeuten und die Reste jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können und zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen können.The catalysts B) essential to the invention satisfy 1. the formula [XR 1 R 2 R 3 R 4 I + [R 5 COO] " , where X is N or P, where R 1 to R 4 are simultaneously or independently alkyl-, aryl- , Aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R 1 to R 4 , forming cyclics, bicyclic or tricyclic radicals and the bridging atoms besides carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R 1 to R 4 may additionally have one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is an alkyl, , Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea -, allophanate groups, double bonds, triple or of the formula [XR 1 R 2 R 3 R 4 J + [R 5 ] " , where X is N or P, where R 1 to R 4 are simultaneously or independently alkyl-, aryl- , Aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or with other radicals R 1 to R 4 bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1 to 18 carbon atoms and each radical R 1 to R 4 additionally one or more alcohol, amino, ester, keto , Thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is either OH or F, or 3. of the formula M (OR 1 ) n (OR 2 ) m (OR 3 ) O (OR 4 ) P (OR 5 ) q (OR 6 ) r , where M is a metal in any positive oxidation state and is identical to the sum n + m + o + p + q + r, m, o, p , q, r represent integers from 0 to 6, and for the sum n + m + o + p + q + r = 1 to 6, the radicals R 1 to R 6 simultaneously or independently of one another denote hydrogen or alkyl, aryl , Aralkyl, heteroaryl, alkoxyalkyl, having 1 to 8 carbon atoms and the radicals in each case linear or branched, unbridged or bridged with other radicals, inter alia Formation of cyclen, bicyclic or tricyclic compounds and the bridging atoms besides carbon may also be heteroatoms and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, May have triple bonds or halogen atoms.
Beispiele für solche Katalysatoren unter 1. sind Tetramethylammoniumformiat, Tetramethylammoniumacetat, Tetramethylammonium-propionat,Examples of such catalysts under 1. are tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate,
Tetramethylammoniumbutyrat, Tetramethylammoniumbenzoat,Tetramethylammonium butyrate, tetramethylammonium benzoate,
Tetraethylammoniumformiat, Tetraethylammoniumacetat,Tetraethylammonium formate, tetraethylammonium acetate,
Tetraethylammoniumpropionat, Tetraethylammoniumbutyrat,Tetraethylammonium propionate, tetraethylammonium butyrate,
Tetraethylammoniumbenzoat, Tetrapropylammoniumformiat, Tetrapropylammoniumacetat, Tetrapropylammoniumpropionat,Tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate,
Tetrapropylammoniumbutyrat, TetrapropylammoniumbenzoatTetrapropylammonium butyrate, tetrapropylammonium benzoate
Tetrabutylammoniumformiat, Tetrabutylammoniumacetat,Tetrabutylammonium formate, tetrabutylammonium acetate,
Tetrabutylammoniumpropionat, Tetrabutylammoniumbutyrat,Tetrabutylammonium propionate, tetrabutylammonium butyrate,
Tetrabutylammoniumbenzoat, Tetrabutylphosphoniumacetat, Tetrabutylphosphoniumformiat, Ethyltriphenylphosphoniumacetat,Tetrabutylammonium benzoate, tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate,
Tetrabutylphosphoniumbenzothazolat, Tetraphenylphosphoniumphenolat undTetrabutylphosphoniumbenzothazolate, Tetraphenylphosphoniumphenolat and
Trihexyltetradecylphosphoniumdecanoat.
Beispiele für solche Katalysatoren unter 2. sind Methyltributylammoniumhydroxid, Methyltriethylammoniumhydroxid, Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetrapropylammoniumhydroxid, Tetrabutylammoniumhydroxid, Tetrapentylammoniumhydroxid, Tetrahexylammoniumhydroxid, Tetraoctylammoniumhydroxid, Tetradecylammoniumhydroxid, Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid, Benzyltrimethylammoniumhydroxid, Benzyltriethylammoniumhydroxid, Trimethylphenylammoniumhydroxid, Thethylmethylamnnoniunnhydroxid, Trimethylvinylammoniumhydroxid, Tetramethylammoniumfluorid, Tetraethylammoniumfluorid, Tetrabutylammoniumfluorid, Tetraoctylammoniumfluorid, Benzyltrimethylammoniumfluorid, Tetrabutylphosphoniumhydroxid und Tetrabutylphosphoniumfluorid.Trihexyltetradecylphosphoniumdecanoat. Examples of such catalysts under 2. are methyltributylammonium, methyltriethylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, Tetradecylammoniumhydroxid, Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid, benzyltrimethylammonium, benzyltriethylammonium, trimethylphenylammonium, Thethylmethylamnnoniunnhydroxid, Trimethylvinylammoniumhydroxid, tetramethylammonium fluoride, tetraethylammonium, tetrabutylammonium tetraoctylammonium, Benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide and tetrabutylphosphonium fluoride.
Beispiele für solche Katalysatoren unter 3. sind Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid, Rubidiumhydroxid, Cäsiumhydroxid, Berilliumhydroxid, Magnesiumhydroxid, Calziumhydroxid, Strontiumhydroxid, Bariumhydroxid, Aluminiumhydroxid, Zinkhydroxid, Lithiummethanolat, Natriummethanolat, Kaliummethanolat, Magnesiummethanolat, Calziummethanolat, Bariummethanolat, Lithiumethanolat, Natriumethanolat, Kaliumethanolat, Magnesiumethanolat, Calziumethanolat, Bariumethanolat, Lithiumpropylalkoholat, Natriumpropylalkoholat, Kaliumpropylalkoholat, Magnesiumpropylalkoholat, Calziumpropylalkoholat, Bariumpropylalkoholat, Lithiumisopropylalkoholat, Natriumisopropylalkoholat, Kaliumisopropylalkoholat, Magnesiumisopropylalkoholat, Calziumisopropylalkoholat, Bariumisopropylalkoholat, Lithium-1 -butylalkoholat, Natrium-1 -butylalkoholat, Kalium- 1 -butylalkoholat, Magnesium-1 -butylalkoholat, Calzium-1 -butylalkoholat, Barium-1 - butylalkoholat, Lithium-2-butylalkoholat, Natrium-2-butylalkoholat, Kalium-2- butylalkoholat, Magnesium-2-butylalkoholat, Calzium-2-butylalkoholat, Barium-2- butylalkoholat, Lithiumisobutylalkoholat, Natriumisobutylalkoholat,Examples of such catalysts under 3. are lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, zinc hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, magnesium methoxide, calcium methoxide, barium methoxide, lithium ethoxide, sodium ethanolate, potassium ethanolate, Magnesium ethanolate, calcium ethanolate, barium ethanolate, lithium propyl alcoholate, sodium propyl alcoholate, potassium propyl alcoholate, magnesium propyl alcoholate, calcium propyl alcoholate, barium propyl alcoholate, lithium isopropyl alcoholate, sodium isopropyl alcoholate, potassium isopropyl alcoholate, magnesium isopropyl alcoholate, calcium isopropyl alcoholate, barium isopropyl alcoholate, lithium 1-butyl alcoholate, sodium 1-butyl alcoholate, potassium 1-butyl alcoholate, magnesium 1-butyl alcoholate, calcium 1-butyl alcoholate, barium 1-butyl alcoholate, lithium 2-butyl alcoholate, sodium 2-butyl alcoholate , Potassium 2-butyl alcoholate, magnesium 2-butyl alcoholate, calcium 2-butyl alcoholate, barium 2-butyl alcoholate, lithium isobutyl alcoholate, sodium isobutyl alcoholate,
Kaliumisobutylalkoholat, Magnesiumisobutylalkoholat, Calziumisobutylalkoholat, Bariumisobutylalkoholat, Lithium-tert. -butylalkoholat, Natrium-tert. -butylalkoholat,
Kalium-tert.-butylalkoholat, Magnesium-tert.-butylalkoholat, Calzium-tert.- butylalkoholat, Barium-tert.-butylalkoholat, Lithiumphenolat, Natriumphenolat, Kaliumphenolat, Magnesiumphenolat, Calziumphenolat und Bariumphenolat.Potassium isobutyl alcoholate, magnesium isobutyl alcoholate, calcium isobutyl alcoholate, barium isobutyl alcoholate, lithium tert. butyl alcoholate, sodium tert. -butylalkoholat, Potassium tert-butyl alcoholate, magnesium tert-butyl alcoholate, calcium tert-butyl alcoholate, barium tert-butyl alcoholate, lithium phenolate, sodium phenolate, potassium phenolate, magnesium phenolate, calcium phenolate and barium phenolate.
Selbstverständlich können auch Mischungen solcher Katalysatoren verwendet werden. Die Katalysatoren sind in einer Menge von 0,001 bis 5 Gew.-%, bevorzugt 0,01 bis 3 Gew.-%, bezogen auf die Gesamtformulierung, in der Polyurethanzusammensetzung enthalten. Die Katalysatoren können Kristallwasser enthalten, wobei dieses bei der Berechnung der eingesetzten Katalysatorenmenge nicht berücksichtigt wird, d. h. die Wassermenge wird herausgerechnet. Besonders bevorzugt werden Tetraethylammoniumbenzoat und Tetrabutylammoniumhydroxyd eingesetzt.Of course, mixtures of such catalysts can be used. The catalysts are contained in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 3 wt .-%, based on the total formulation, in the polyurethane composition. The catalysts may contain water of crystallization, which is not taken into account in the calculation of the amount of catalyst used, d. H. the amount of water is deducted. Particular preference is given to using tetraethylammonium benzoate and tetrabutylammonium hydroxide.
Eine erfindungsgemäße Variante schließt die polymere Anbindung solcher Katalysatoren B) an die Härter A) oder hydroxylgruppenhaltige Polymere C) oder F) mit ein. So können z. B. freie Alkohol-, Thio- oder Aminogruppen der Ammoniumsalze mit Säure-, Isocyanat-, oder Glycidylgruppen der Pulverlackhärter A) oder hydroxylgruppenhaltige Polymere C) oder F) umgesetzt werden, um die Katalysatoren B) in den polymeren Verbund zu integrieren. Diese Katalysatoren können außerdem mit einer Hülle umgeben sein und damit verkapselt.A variant according to the invention includes the polymeric attachment of such catalysts B) to the curing agents A) or hydroxyl-containing polymers C) or F). So z. B. free alcohol, thio or amino groups of the ammonium salts with acid, isocyanate, or glycidyl groups of the powder coating hardener A) or hydroxyl-containing polymers C) or F) are reacted to integrate the catalysts B) in the polymeric composite. These catalysts may also be encased in a shell and encapsulated therewith.
Als Komponente C) wird mindestens ein Hydroxyl- und Carboxylgruppen haltiger ungesättigter, amorpher Polyester mit einer OH-Zahl zwischen 1 und 100 mg KOH/Gramm und einer COOH-Zahl zwischen 1 und 75 mg KOH/Gramm, wobei das Verhältnis aus OH- und Säurezahl stets > 1 beträgt, mit einemAs component C) is at least one hydroxyl and carboxyl-containing unsaturated, amorphous polyester having an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and Acid number is always> 1, with a
Gewichtsanteil, bezogen auf die Gesamtformulierung, von 1 bis 12 %, verwendet.Weight fraction, based on the total formulation, from 1 to 12% used.
Bei der Komponente C) handelt es sich um ungesättigte, amorphe Hydroxy- und Carboxylgruppen haltige Polyester, im Wesentlichen enthaltend mindestens eine α, ß- ungesättigte Dicarbonsäurekomponente und eine Alkoholkomponente, die Alkoholkomponente aus einem Dicidolgemisch der isomeren Verbindungen
3,8-Bis(hydroxymethyl)tricyclo [5.2.1.02'6]decan, 4,8-Bis(hydroxymethyl)tricyclo [5.2.1.026]decan und 5,8-Bis(hydroxymethyl)tricyclo [5.2.1.026]decan besteht, wobei jedes Isomere zu einem Anteil von 20 bis 40 Gew.-% in dem Gemisch enthalten sein kann und die Summe der drei Isomeren 90 bis 100 Gew.-% ergibt, und das Gemisch mindestens zu 5 Gew.-% in der Alkoholkomponente des Polyesters vorhanden ist.Component C) comprises unsaturated polyesters containing amorphous hydroxyl and carboxyl groups, essentially containing at least one α, β-unsaturated dicarboxylic acid component and an alcohol component, the alcohol component of a mixture of dicidol of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-% results, and the mixture at least 5 wt .-% in the alcohol component of the polyester is present.
Die ungesättigten, amorphen Polyesterharze C) werden durch Umsetzung der Alkoholkomponente und der Säurekomponente erhalten.The unsaturated amorphous polyester resins C) are obtained by reacting the alcohol component and the acid component.
Als Alkoholkomponente wird erfindungsgemäß ein Dicidolgemisch der isomeren Verbindungen 3,8-Bis(hydroxymethyl)tricyclo [5.2.1.02'6]decan, 4,8- Bis(hydroxymethyl)tricyclo [5.2.1.026]decan und 5,8-Bis(hydroxymethyl)tricyclo [5.2.1.026]decan eingesetzt, wobei jedes Isomere zu einem Anteil von 20 bis 40 Gew.-% in dem Gemisch enthalten sein kann und die Summe der drei Isomeren 90 bis 100 Gew.-%, bevorzugt 95 bis 100 Gew.-%, ergibt, und das Gemisch mindestens zu 5 Gew.-% in der Alkoholkomponente des Polyesters vorhanden ist, eingesetzt. Der Isomergehalt des Dicidolgemisches kann qualitativ und quantitativ z. B. durch GC- Analyse oder quantitativ durch Trennung mittels präparativer GC oder HPLC und anschließender NMR-Spektroskopie bestimmt werden. Alle entsprechenden Isomeren des Dicidols in 9-Stellung sind genau so geeignet, aber auf Grund der Spiegelsymmetrie von den o. g. Isomeren, wie auch die eis- und trans-lsomeren, unter normalen, praxisbezogenen Umständen nicht unterscheidbar.The alcohol component according to the invention is a Dicidolgemisch the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5.8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane used, wherein each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-%, preferably 95 to 100% by weight, and the mixture is at least 5% by weight in the alcohol component of the polyester. The isomer content of the Dicidolgemisches can qualitatively and quantitatively z. B. by GC analysis or quantitatively determined by separation by preparative GC or HPLC and subsequent NMR spectroscopy. All corresponding isomers of dicidol in the 9-position are just as suitable, but due to the mirror symmetry of the above isomers, as well as the cis and trans isomers, indistinguishable under normal, practical circumstances.
Außerdem kann das Dicidolgemisch bis zu 10 Gew.-% weitere Isomere des Dicidol und/oder trimere und/oder höhere isomere Diole des Diels-Alder- Umsetzungsproduktes aus Cyclopentadien enthalten. Bevorzugt besteht die Alkoholkomponente aus 20 Gew.-%, aus 50 Gew.-%, bevorzugt aus 90 Gew.-%, besonders bevorzugt aus 100 Gew.-% Dicidolgemisch, wobei dieses besonders bevorzugt 95 bis 100 Gew.-% der oben genannten drei isomeren Verbindungen enthält.
Neben dem Dicidolgemisch kann die Alkoholkomponente weitere lineare und/oder verzweigte, aliphatische und/oder cycloaliphatische und/oder aromatische Diole und/oder Polyole enthalten. Bevorzugt werden als zusätzliche Alkohole Ethylenglykol, 1 ,2- und/oder 1 ,3-Propandiol, Diethylen-, Dipropylen-, Thethylen-, Tetraethylenglykol, 1 ,2- und/oder 1 ,4-Butandiol, 1 ,3-Butylethylpropandiol, 1 ,3-Methylpropandiol, 1 ,5- Pentandiol, Cyclohexandimethanol, Glycerin, Hexandiol, Neopentylglycol, Trimethylolethan, Trimethylolpropan und/oder Pentaerythrit sowie Bisphenol A, B, C, F, Norbornylenglykol, 1 ,4-Benzyldimethanol und -ethanol, 2,4-Dimethyl-2-ethylhexan- 1 ,3-diol eingesetzt.In addition, the Dicidolgemisch may contain up to 10 wt .-% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene. Preferably, the alcohol component consists of 20 wt .-%, from 50 wt .-%, preferably from 90 wt .-%, particularly preferably from 100 wt .-% Dicidolgemisch, this more preferably 95 to 100 wt .-% of the above contains three isomeric compounds. In addition to the dicidol mixture, the alcohol component may contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols. Preferred additional alcohols are ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-butylethylpropanediol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol used.
Die ungesättigten, amorphen Polyesterharze C) enthalten als Ausgangssäurekomponente mindestens eine α, ß-ungesättigte Dicarbonsäure. Bevorzugt enthalten die ungesättigten Polyesterharze Citracon-, Fumar-, Itacon-, Malein- und/oder Mesaconsäure.The unsaturated, amorphous polyester resins C) contain as starting acid component at least one α, ß-unsaturated dicarboxylic acid. The unsaturated polyester resins preferably contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid.
Es können auch zusätzlich aromatische und/oder aliphatische und/oder cycloaliphatische Monocarbonsäuren und/oder Dicarbonsäuren und/oder Polycarbonsäuren enthalten sein, wie z. B. Phthalsäure, Isophthalsäure, Terephthalsäure, 1 ,4-Cyclohexandicarbonsäure, Bernsteinsäure, Sebazinsäure, Methyltetra-, Methylhexahydrophthalsäure, Hexahydro-phthalsäure,It may also contain additional aromatic and / or aliphatic and / or cycloaliphatic monocarboxylic acids and / or dicarboxylic acids and / or polycarboxylic acids, such as. Phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid,
Tetrahydrophthalsäure, Dodecandisäure, Adipinsäure, Azelainsäure, Isononansäure, 2-Ethylhexansäure, Pyromellitsäure und/oder Trimellitsäure. Bevorzugt sind Phthalsäure, Hexahydrophthalsäure, Tetrahydrophthalsäure, Adipin- und/oder Azelainsäure.Tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.
Die Säurekomponente kann teilweise oder vollständig aus Anhydriden und/oder Alkylestern, bevorzugt Methylestern, bestehen.The acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.
Im Allgemeinen ist die Alkoholkomponente im Mol-Verhältnis von 0,5 bis 2,0 zu 1 zur Säurekomponente enthalten, bevorzugt 0,8 bis 1 ,5 zu 1. Besonders bevorzugt findet die Umsetzung der Alkoholkomponente im Mol-Verhältnis von 1 ,0 bis 1 ,1 zu 1 zur Säurekomponente statt.
Die ungesättigten, amorphen Polyester C) können eine Säurezahl zwischen 1 und 75 mg KOH/g, bevorzugt zwischen 1 und 50, besonders bevorzugt zwischen 1 und 35 mg KOH/g sowie eine OH-Zahl zwischen 1 und 100 mg KOH/g, bevorzugt zwischen 1 und 75, besonders bevorzugt zwischen 1 und 50 mg KOH/g aufweisen, wobei das Verhältnis aus OH- und Säurezahl stets >1 beträgt.In general, the alcohol component is contained in the molar ratio of 0.5 to 2.0 to 1 to the acid component, preferably 0.8 to 1, 5 to 1. Particularly preferred is the implementation of the alcohol component in the molar ratio of 1, 0 to 1, 1 to 1 to the acid component instead. The unsaturated, amorphous polyesters C) may have an acid number between 1 and 75 mg KOH / g, preferably between 1 and 50, more preferably between 1 and 35 mg KOH / g and an OH number between 1 and 100 mg KOH / g between 1 and 75, more preferably between 1 and 50 mg KOH / g, wherein the ratio of OH and acid number is always> 1.
Der Tg der ungesättigten, amorphen Polyester C) variiert von -30 bis +80 0C, bevorzugt -20 bis +50 0C, besonders bevorzugt - 10 bis + 40 0C.The Tg of the unsaturated amorphous polyester C) varies from -30 to +80 0 C, preferably from -20 to +50 0 C, more preferably - 10 to + 40 0 C.
In einer bevorzugten Ausführungsform I bestehen die ungesättigten Polyesterharze C) (UP-Harze) aus einer Alkoholkomponente mit mindestens 90 Gew.-%, bevorzugt 95 Gew.-%, besonders bevorzugt zu 100 Gew.-% des Dicidolgemisches der isomeren Verbindungen 3,8-Bis(hydroxymethyl)tricyclo [5.2.1.02'6]decan, 4,8- Bis(hydroxymethyl)tricyclo [5.2.1.026]decan und 5,8-Bis(hydroxymethyl)tricyclo [5.2.1.026]decan und aus Fumarsäure und/oder Maleinsäure (anhydrid). In einer weiteren bevorzugten Ausführungsform Il enthalten die Polyester C) die o. g. Ausgangskomponenten wie unter I, aber zusätzlich eine weitere Säure ausgewählt aus Adipinsäure oder Phthalsäure(anhydrid), wobei das Verhältnis der α, ß- ungesättigten zur zusätzlichen Säure von 2 zu 1 bis 1 zu 4 variieren kann. Bevorzugt werden Verhältnisse von ca. 1 zu 1 bis 1 zu 2. Diese Polyester weisen allgemein Säurezahlen von 1 bis 75 mg KOH/g, bevorzugt 1 bis 50 mg KOH/g, besonders bevorzugt 1 bis 35 mg KOH/g, OH-Zahlen von 1 bis 100 mg KOH/g, bevorzugt 1 bis 75 mg KOH/g, besonders bevorzugt 1 bis 50 mg KOH/g, wobei das Verhältnis aus OH- und Säurezahl stets >1 beträgt, und einen Tg von -30 bis +80 0C, bevorzugt -20 bis +50 0C, besonders bevorzugt -10 bis +40 0C auf.In a preferred embodiment I, the unsaturated polyester resins C) (UP resins) consist of an alcohol component having at least 90% by weight, preferably 95% by weight, particularly preferably 100% by weight, of the dicidol mixture of the isomeric compounds 3,8 Bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and from fumaric acid and / or maleic acid (anhydride). In a further preferred embodiment II, the polyesters C) contain the abovementioned starting components as under I, but additionally an additional acid selected from adipic acid or phthalic acid (anhydride), the ratio of the α, β-unsaturated to the additional acid being from 2: 1 to 1: 1 can vary to 4. Ratios of about 1 to 1 to 1 to 2 are preferred. These polyesters generally have acid numbers of 1 to 75 mg KOH / g, preferably 1 to 50 mg KOH / g, particularly preferably 1 to 35 mg KOH / g, OH numbers from 1 to 100 mg KOH / g, preferably 1 to 75 mg KOH / g, particularly preferably 1 to 50 mg KOH / g, the ratio of OH and acid number always being> 1, and a Tg of -30 to +80 0 C, preferably -20 to +50 0 C, more preferably -10 to +40 0 C on.
Die Polyester C) können auch Hilfs- und Zusatzstoffe ausgewählt aus Inhibitoren, Wasser und/oder organischen Lösemitteln, Neutralisationsmitteln, grenzflächenaktiven Substanzen, Sauerstoff- und/oder Radikalfängern, Katalysatoren, Lichtschutzmitteln, Farbaufhellern, Photosensibilisatoren, Thixotropiermitteln, Hautverhinderungsmitteln, Entschäumern, Antistatika, Eindickungsmitteln,
thermoplastischen Additiven, Farbstoffen, Pigmenten, Brandschutzausrüstungen, internen Trennmitteln, Füllstoffen und/oder Treibmitteln, enthalten.The polyesters C) may also contain auxiliaries and additives selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, anti-skinning agents, defoamers, antistatic agents, thickeners . thermoplastic additives, dyes, pigments, fire retardants, internal release agents, fillers and / or blowing agents.
Hergestellt werden die Polyester C) durch (halb)kontinuierliche oder diskontinuierliche Veresterung und Kondensation der Ausgangssäuren und -alkohole in einstufiger oder zweistufiger Fahrweise.The polyesters C) are prepared by (semi) continuous or discontinuous esterification and condensation of the starting acids and alcohols in a one-stage or two-stage procedure.
Polyesterharze auf Basis von Dicidol als Diolkomponente sind außerdem bekannt aus DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988, EP 1 492 834.Polyester resins based on dicidol as diol component are also known from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988, EP 1 492 834.
EP 1 398 337 beschreibt haftungsverbessernde Zusätze aus einem ungesättigten, amorphen Polyester. Die haftungsverbessernden Zusätze werden mit Polymeren in wässrigen, lösemittelhaltigen (normal, medium, high, very high solids) und/oder lösemittelfreien (Pulver und/oder flüssig) wärmehärtbaren, strahlenhärtbaren, lufttrocknenden (oxidativ und physikalisch) Beschichtungsstoffen, Spachtel- und/oder Dichtmassen und Klebstoffen eingesetzt und sind als Modifizierungsharz geeignet für Primer, Füller, Basislacke, Einschichtdecklacke, Klarlacke, Klebstoffe, Dichtmassen, Straßenmarkierungsfarben, Korrosionsschutzanstrichen.EP 1 398 337 describes adhesion-improving additives of an unsaturated, amorphous polyester. The adhesion-improving additives are polymer-containing in aqueous, solvent-containing (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid), thermosetting, radiation-curable, air-drying (oxidative and physical) coating materials, fillers and / or sealants and adhesives and are suitable as a modification resin for primers, fillers, basecoats, single-coat finishes, clearcoats, adhesives, sealants, road marking paints, anti-corrosive paints.
Der Einsatz in Uretdiongruppen haltigen Pulverlacken, die bei geringer Temperatur vernetzen können, wird nicht beschrieben. Polymere nach EP 1 398 337 können OH- und Carbonsäuregruppen tragen, wobei sowohl die OH-Zahl als auch die Säurezahl Werte zwischen 1 und 200 mg KOH/g einnehmen kann. Damit können die in EP 1 398 337 beschriebenen Polymere eine hohe Carbonsäure- und niedrige OH-Funktionalität besitzen. Im Falle der vorliegenden Erfindung würde deren Einsatz in hochreaktiven Uretdiongruppen haltigen PolyurethanzusammensetzungenThe use in uretdione-containing powder coatings that can crosslink at low temperature is not described. Polymers according to EP 1 398 337 can carry OH and carboxylic acid groups, wherein both the OH number and the acid number can assume values between 1 and 200 mg KOH / g. Thus, the polymers described in EP 1 398 337 can have a high carboxylic acid and low OH functionality. In the case of the present invention, their use would be in highly reactive uretdione-containing polyurethane compositions
1. die Reaktivität der Formulierung, aufgrund der Anwesenheit hoher Konzentrationen an Säuregruppen reduzieren und1. reduce the reactivity of the formulation due to the presence of high concentrations of acid groups and
2. zu unvernetzten Anteilen aufgrund der geringen OH-Funktionalität führen, wodurch Beständigkeitseigenschaften negativ beeinflusst würden.2. lead to uncrosslinked portions due to the low OH functionality, which would negatively impact resistance properties.
Aus diesem Grund ist in der vorliegenden Erfindung wesentlich, dass das Verhältnis aus OH- und Säurezahl stets >1 beträgt.
Bei den Hydroxylgruppen haltigen (teil-)khstallinen Polymeren G) werden bevorzugt Polyester, Polyether, Polyacrylate, Polyurethane und/oder Polycarbonate mit einer OH-Zahl von 10 bis 500 (in mg KOH/Gramm) eingesetzt. Besonders bevorzugt werden Hydroxylgruppen haltige Polyester mit einer OH-Zahl von 15 bis 150 und einem mittleren Molekulargewicht von 500 bis 6 000 g/mol. Selbstverständlich können auch Mischungen solcher Polymere eingesetzt werden. Der Gew.-Anteil dieser (teil-) kristallinen Komponente G) an der Gesamtformulierung A - H kann zwischen 1 und 95 Gew.-% betragen, bevorzugt werden 2 bis 50 Gew.-%.For this reason, it is essential in the present invention that the ratio of OH and acid number is always> 1. Polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 10 to 500 (in mg KOH / gram) are preferably used in the hydroxyl-containing (partially) khallene polymers G). Particularly preferred are hydroxyl-containing polyesters having an OH number of 15 to 150 and an average molecular weight of 500 to 6,000 g / mol. Of course, mixtures of such polymers can be used. The proportion by weight of this (partially) crystalline component G) in the overall formulation A-H can be between 1 and 95% by weight, preferably from 2 to 50% by weight.
Bevorzugte (Teil-)Kristalline Hydroxylgruppen haltige Polyester G) werden hergestellt durch Polykondensation. Dazu wird eine Säurekomponente, bestehend aus 80 bis 100 Molprozent einer gesättigten, linearen aliphatischen oder cycloaliphatischen Dicarbonsäure mit 4 bis 14 Kohlenstoffatomen und 0 bis 20 Molprozent einer anderen aliphatischen oder cycloaliphatischen oder aromatischen Di- oder Polycarbonsäure, mit einer Alkoholkomponente, bestehend aus 80 bis 100 Molprozent eines linearen aliphatischen Diols mit 2 bis 15 Kohlenstoffatomen und 0 bis 20 Molprozent eines anderen aliphatischen oder cycloaliphatischen Di- oder Polyols mit 2 bis 15 Kohlenstoffatomen, umgesetzt. Die so hergestellten (teil-) kristallinen Hydroxylgruppen haltigen Polyester haben eine OH-Zahl von 15 bis 150 mg KOH/g, eine Säurezahl <5 mg KOH/g und einen Schmelzpunkt von 40 bis 130 0C.Preferred (partial) crystalline hydroxyl-containing polyesters G) are prepared by polycondensation. For this purpose, an acid component consisting of 80 to 100 mole percent of a saturated, linear aliphatic or cycloaliphatic dicarboxylic acid having 4 to 14 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic or aromatic di- or polycarboxylic acid, having an alcohol component consisting of 80 to 100 Mole percent of a linear aliphatic diol of 2 to 15 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic di or polyol of 2 to 15 carbon atoms. The (partially) crystalline hydroxyl-containing polyesters thus produced have an OH number of 15 to 150 mg KOH / g, an acid number <5 mg KOH / g and a melting point of 40 to 130 ° C.
Für die Herstellung von (teil-)khstallinen Polyestern G) bevorzugte Carbonsäuren sind Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Dodecandisäure, Tetrahydrophthalsäure, Hexahydrophthalsäure,Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, are preferred carboxylic acids for the preparation of (partly) khallins polyesters G),
Hexahydroterephthalsäure, Endomethylen-tetrahydrophthalsäure, Glutarsäure bzw. - soweit zugänglich - deren Anhydride. Besonders gut geeignet und bevorzugt ist Dodecandisäure.Hexahydroterephthalsäure, endomethylene tetrahydrophthalic acid, glutaric acid or - as far as accessible - their anhydrides. Particularly suitable and preferred is dodecanedioic acid.
Als Polyole sind die folgenden Diole Ethylenglykol, Propandiol-(1 ,2) und -(1 ,3), 2,2- Dimethylpropandiol-(1 ,3), Butandiol-(1 ,4), Pentandiol-(1 ,5), Hexandiol-(1 ,6), 2- Methylpentandiol-(1 ,5), 2,2,4-Trimethylhexandiol-(1 ,6), 2,4,4-Thmethylhexandiol-(1 ,6),
Heptandiol-(1 ,7), Decandiol-(1 ,10), Dodecandiol-(1 ,12), Octadecen-9,10-diol-(1 ,12), Octadecandiol-(1 ,18), 2,4-Dimethyl-2-propylheptandiol-(1 ,3), Butendiol-(1 ,4), Butindiol-(1 ,4), Diethylenglykol, Triethylenglykol, Tetraethylenglykol, trans- und cis- 1 ,4-Cyclohexandimethanol, die Triole Glycerin, Hexantriol-(1 ,2,6), 1 ,1 ,1 - Trimethylolpropan und 1 ,1 ,1 -Thmethylolethan und das Tetraol Pentaerythrit, geeignet. Bevorzugt sind Ethylenglykol, Propandiol-(1 ,2) und -(1 ,3), 2,2-Dimethylpropandiol- (1 ,3), Butandiol-(1 ,4), Pentandiol-(1 ,5), Hexandiol-(1 ,6), 2-Methylpentandiol-(1 ,5), Heptandiol-(1 ,7), Decandiol-(1 ,10), Dodecandiol-(1 ,12), Octadecen-9,10-diol-(1 ,12), Octadecandiol-(1 ,18), Butendiol-(1 ,4), Butindiol-(1 ,4), Diethylenglykol, Triethylenglykol, Tetraethylenglykol, trans- und cis-1 ,4-Cyclohexandimethanol.As polyols, the following diols are ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropanediol (1, 3), butanediol (1, 4), pentanediol (1, 5) , Hexanediol (1, 6), 2-methylpentanediol (1, 5), 2,2,4-trimethylhexanediol (1,6), 2,4,4-thymethylhexanediol (1,6), Heptanediol (1, 7), decanediol (1, 10), dodecanediol (1, 12), octadecene-9, 10-diol (1, 12), octadecanediol (1, 18), 2,4- Dimethyl-2-propylheptandiol- (1, 3), butenediol (1, 4), butynediol (1, 4), diethylene glycol, triethylene glycol, tetraethylene glycol, trans and cis 1, 4-cyclohexanedimethanol, the triols glycerol, hexanetriol - (1, 2.6), 1, 1, 1 - trimethylolpropane and 1, 1, 1 -Thmethylolethan and the tetraol pentaerythritol, suitable. Preference is given to ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropanediol (1,3), butanediol (1,4), pentanediol (1,5), hexanediol ( 1, 6), 2-methylpentanediol (1, 5), heptanediol (1, 7), decanediol (1, 10), dodecanediol (1, 12), octadecene-9, 10-diol (1, 12), octadecanediol (1,18), butenediol (1,4), butynediol (1,4), diethylene glycol, triethylene glycol, tetraethylene glycol, trans and cis 1,4-cyclohexanedimethanol.
Beachtet werden muss in diesem Zusammenhang, dass die Aktivität der Katalysatoren unter B) in Anwesenheit von Säuren deutlich abnimmt. Zu den herkömmlichen Reaktionspartnern der uretdionhaltiger Lack- bzw. Klebstoffhärter gehören hydroxylgruppenhaltige Polyester. Aufgrund der Herstellungsweise von Polyestern tragen diese mitunter in geringem Umfang noch Säuregruppen. In Gegenwart von solchen Säuregruppen tragenden Polyestern bietet es sich an, die erwähnten Katalysatoren entweder im Überschuss, bezogen auf die Säuregruppen, zu verwenden, oder aber reaktive Verbindungen zuzusetzen, die in der Lage sind, Säuregruppen abzufangen. Sowohl monofunktionelle als auch mehrfachfunktionelle Verbindungen können hierzu eingesetzt werden.It should be noted in this context that the activity of the catalysts under B) in the presence of acids decreases significantly. The conventional reactants of the uretdione-containing paint or adhesive hardener include hydroxyl-containing polyester. Due to the method of preparation of polyesters, they sometimes carry acid groups to a small extent. In the presence of such acid groups-bearing polyesters, it is advisable to use the catalysts mentioned either in excess, based on the acid groups, or to add reactive compounds which are capable of intercepting acid groups. Both monofunctional and polyfunctional compounds can be used for this purpose.
Reaktive Säure abfangende Verbindungen D) sind in der Lackchemie allgemein bekannt. So setzen sich beispielsweise Epoxyverbindungen, Carbodiimide, Hydroxyalkylamide oder 2-Oxazoline, aber auch anorganische Salze, wie Hydroxide, Hydrogencarbonate oder Carbonate, mit Säuregruppen bei erhöhten Temperaturen um. In Frage kommen dabei z. B. Triglycidyletherisocyanurat (TGIC), EPIKOTE® 828 (Diglycidylether auf Basis Bisphenol A, Schell), Versaticsäureglycidylester, Ethylhexylglycidylether, Butylglycidylether, Polypox R 16 (Pentaerythrittetraglycidylether, UPPC AG) sowie andere Polypoxtypen mit freien Epoxygruppen, ß-Hydroxylalkylamide (z. B. Vestagon EP HA 320, Evonik Degussa GmbH), aber auch Phenylenbisoxazolin, 2-Methyl-2-oxazolin, 2-Hydroxyethyl-2-
oxazolin, 2-Hydroxypropyl-2-oxazolin, 5-Hydroxypentyl-2-oxazolin, Bariumhydroxid, Natriumcarbonat und Calziumcarbonat. Selbstverständlich kommen auch Mischungen solcher Substanzen in Frage. Diese reaktive Verbindungen können - falls vorhanden - in Gewichtsanteilen von 0,1 bis 10 Gew.-%, bevorzugt von 0,5 bis 3 Gew.-%, bezogen auf die Gesamtformulierung A) bis H) eingesetzt werden.Reactive acid scavenging compounds D) are well known in paint chemistry. Thus, for example, epoxy compounds, carbodiimides, hydroxyalkylamides or 2-oxazolines, but also inorganic salts, such as hydroxides, bicarbonates or carbonates, react with acid groups at elevated temperatures. In question come here z. B. triglycidyl ether isocyanurate (TGIC), EPIKOTE ® 828 (diglycidyl ether based on bisphenol A, Schell), versatic, ethylhexyl glycidyl ether, butyl glycidyl ether, Polypox R 16 (pentaerythritol tetraglycidyl ether, UPPC AG) as well as other Polypoxtypen having free epoxy groups, .beta.-hydroxyalkylamides (z. B. Vestagon EP HA 320, Evonik Degussa GmbH), but also phenylenebisoxazoline, 2-methyl-2-oxazoline, 2-hydroxyethyl-2- oxazoline, 2-hydroxypropyl-2-oxazoline, 5-hydroxypentyl-2-oxazoline, barium hydroxide, sodium carbonate and calcium carbonate. Of course, mixtures of such substances come into question. If present, these reactive compounds can be used in proportions by weight of from 0.1 to 10% by weight, preferably from 0.5 to 3% by weight, based on the total formulation A) to H).
Säuren, die unter E) genannt werden, sind alle Stoffe, fest oder flüssig, organisch oder anorganisch, monomer oder polymer, die die Eigenschaften einer Brönstedt- oder einer Lewissäure besitzen. Als Beispiele seien genannt: Schwefelsäure, Essigsäure, Benzoesäure, Malonsäure, Terephthalsäure, aber auch Copolyester oderAcids which are mentioned under E) are all substances, solid or liquid, organic or inorganic, monomeric or polymeric, which have the properties of a Bronsted or a Lewis acid. Examples include: sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, but also copolyester or
Copolyamide mit einer Säurezahl von mindestens 20 mg KOH/g. Sie sind - falls vorhanden - in einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 0,1 bis 10 %, enthalten.Copolyamides having an acid number of at least 20 mg KOH / g. They are contained, if present, in a proportion by weight, based on the total formulation, of 0.1 to 10%.
Bei den Hydroxylgruppen haltigen amorphen Polymeren F) werden bevorzugt Polyester, Polyether, Polyacrylate, Polyurethane und/oder Polycarbonate mit einer OH-Zahl von 20 bis 500 mg KOH/Gramm eingesetzt. Besonders bevorzugt werden Hydroxylgruppen haltige Polyester mit einer OH-Zahl von 20 bis 150 mg/KOH/g, einem mittleren Molekulargewicht von 500 bis 6000 g/mol. Selbstverständlich können auch Mischungen solcher Polymere eingesetzt werden. Solche amorphen Polymere können - falls vorhanden - in einem Gewichtsanteil von 1 bis 95 %, bevorzugt 1 - 90 %, bezogen auf die Gesamtformulierung eingesetzt werden. Als Alkoholkomponente zur Herstellung der Polyester können lineare und/oder verzweigte, aliphatische und/oder cycloaliphatische und/oder aromatische Diole und/oder Polyole enthalten sein. Bevorzugt werden als Dicidol, Ethylenglykol, 1 ,2- und/oder 1 ,3-Propandiol, Diethylen-, Dipropylen-, Thethylen-, Tetraethylenglykol, 1 ,2- und/oder 1 ,4-Butandiol, 1 ,3-Butylethylpropandiol, 1 ,3-Methylpropandiol, 1 ,5- Pentandiol, Cyclohexandimethanol, Glycerin, Hexandiol, Neopentylglycol, Trimethylolethan, Trimethylolpropan und/oder Pentaerythrit sowie Bisphenol A, B, C, F, Norbornylenglykol, 1 ,4-Benzyldimethanol und -ethanol, 2,4-Dimethyl-2-ethylhexan- 1 ,3-diol eingesetzt.In the case of the hydroxyl-containing amorphous polymers F), preference is given to using polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 20 to 500 mg KOH / gram. Particularly preferred are hydroxyl-containing polyesters having an OH number of 20 to 150 mg / KOH / g, an average molecular weight of 500 to 6000 g / mol. Of course, mixtures of such polymers can be used. Such amorphous polymers can, if present, be used in a proportion by weight of 1 to 95%, preferably 1 to 90%, based on the total formulation. As the alcohol component for the production of the polyesters linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols can be contained. Are preferred as dicidol, ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-Butylethylpropandiol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol used.
Als Säurekomponente zur Herstellung der Polyester können lineare und/oder
verzweigte, aliphatische und/oder cycloaliphatische und/oder aromatische Monocarbonsäuren und/oder Dicarbonsäuren und/oder Polycarbonsäuren enthalten sein, wie z. B. Phthalsäure, Isophthalsäure, Terephthalsäure, 1 ,4- Cyclohexandicarbonsäure, Bernsteinsäure, Sebazinsäure, Methyltetra-, Methylhexahydrophthalsäure, Hexahydrophthalsäure, Tetrahydrophthalsäure, Dodecandisäure, Adipinsäure, Azelainsäure, Isononansäure, 2-Ethylhexansäure, Pyromellitsäure und/oder Trimellitsäure. Bevorzugt sind Phthalsäure, Hexahydrophthalsäure, Tetrahydrophthalsäure, Adipin- und/oder Azelainsäure.As the acid component for the preparation of the polyester can linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic monocarboxylic acids and / or dicarboxylic acids and / or polycarboxylic acids may be contained, such as. Phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.
Die Säurekomponente kann teilweise oder vollständig aus Anhydriden und/oder Alkylestern, bevorzugt Methylestern, bestehen.The acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.
Für die Polyurethanzusammensetzung können die in der Lack- bzw. Klebstofftechnologie üblichen Hilfs- und Zusatzstoffe H) wie Verlaufsmittel, z. B. Polysilicone oder Polycrylate, Lichtschutzmittel z. B. sterisch gehinderte Amine, oder andere Hilfsmittel, wie sie z. B. in EP 669 353 beschrieben wurden, in einer Gesamtmenge von 0,05 bis 5 Gew.-% zugesetzt werden. Füllstoffe und Pigmente, wie z. B. Titandioxid, können - falls vorhanden - in einer Menge bis zu 50 Gew.-% der Gesamtzusammensetzung zugesetzt werden.For the polyurethane composition customary in the paint or adhesive technology auxiliaries and additives H) as leveling agents, for. As polysilicones or polyacrylates, light stabilizers z. As sterically hindered amines, or other auxiliaries, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%. Fillers and pigments, such as. Titanium dioxide, if present, can be added in an amount up to 50% by weight of the total composition.
Optional können zusätzliche Katalysatoren, wie sie in der Polyurethanchemie bereits bekannt sind, enthalten sein. Es handelt sich hierbei hauptsächlich um metallorganischen Katalysatoren, wie z. B. Dibutylzinndilaurat, oder aber tertiäre Amine, wie z. B. 1 ,4-Diazabicylco[2,2,2,]octan, in Mengen von 0,001 bis 1 Gew.-%.Optionally, additional catalysts, such as are already known in polyurethane chemistry may be included. These are mainly organometallic catalysts, such as. As dibutyltin dilaurate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2,] octane, in amounts of 0.001 to 1 wt .-%.
Die Gesamtmenge an H) kann 0,001 bis 55 Gew.-% bezogen auf die Gesamtformulierung betragen.The total amount of H) may be from 0.001 to 55% by weight, based on the total formulation.
Die Homogenisierung aller Bestandteile zur Herstellung der erfindungsgemäßen Polyurethanzusammensetzung kann in geeigneten Aggregaten, wie z. B. beheizbaren Knetern, aber insbesondere in Extrudern bei Temperaturen von 40 bis 130 0C, erfolgen, wobei Temperaturobergrenzen von 120 bis 130 0C nicht überschritten
werden sollten. Die gut vermischte Masse wird durch geeignete Auftragung, z. B. Walzen, Sprühen, auf das Substrat aufgebracht. Das Auftragen von sprühfertigen Pulvern auf geeignete Substrate kann nach den bekannten Verfahren, wie z. B. durch elektrostatisches Pulversprühen, Wirbelsintern, oder elektrostatisches Wirbelsintern, erfolgen. Nach dem Auftrag werden die beschichteten Werkstücke zur Aushärtung 4 bis 60 Minuten auf eine Temperatur von 60 bis 220 0C, vorzugsweise 6 bis 30 Minuten bei 80 bis 150 0C erhitzt.The homogenization of all constituents for the preparation of the polyurethane composition according to the invention can be carried out in suitable aggregates, such. B. heated kneaders, but especially in extruders at temperatures of 40 to 130 0 C, carried out, with upper temperature limits of 120 to 130 0 C not exceeded should be. The well-mixed mass is removed by suitable application, eg. As rollers, spraying, applied to the substrate. The application of ready-to-spray powders on suitable substrates can according to the known methods, such. B. by electrostatic powder spraying, vortex sintering, or electrostatic vortex sintering done. After application, the coated workpieces are cured for 4 to 60 minutes at a temperature of 60 to 220 0 C, preferably 6 to 30 minutes at 80 to 150 0 C heated.
Nachfolgend wird der Gegenstand der Erfindung anhand von Beispielen näher erläutert.The subject matter of the invention will be explained in more detail below with reference to examples.
Beispiel 1 zur Herstellung der Komponente C)Example 1 for the preparation of component C)
Ausgangskomponente Dicidolgemisch im Isomerverhältnis von annähernd 1 : 1 : 1 . Adipinsäure und Maleinsäure (Mol-Verhältnis 1 : 1 ) werden mit Dicidol im MoI- Verhältnis 1 : 1 ,05 bei 180 0C in Stickstoffatmosphäre zur Reaktion gebracht bis eine Säurezahl von 27 mg KOH/g und eine OH-Zahl von 36 mg KOH/g erreicht ist. Hierzu wird zunächst die Maleinsäure mit Dicidol über eine Stunde verestert und dann die Adipinsäure zugesetzt. Mn = 1800 g/mol, Mw = 4400 g/mol, Glasübergangstemperatur 14 0C.
Starting component Dicidol mixture in the isomer ratio of approximately 1: 1: 1. Adipic acid and maleic acid (molar ratio 1: 1) are reacted with dicidol in MoI ratio 1: 1, 05 at 180 0 C in a nitrogen atmosphere until an acid number of 27 mg KOH / g and an OH number of 36 mg KOH / g is reached. For this purpose, the maleic acid is first esterified with diclidol for one hour and then added to the adipic acid. M n = 1800 g / mol, M w = 4400 g / mol, glass transition temperature 14 0 C.
Beispiele zur Herstellung der Polyurethan-PulverlackeExamples for the preparation of polyurethane powder coatings
TG: Glasübergangspunkt;
Tabelle 2-1 : Polyurethan-Pulverlackformulierungen :T G : glass transition point; Table 2-1: Polyurethane Powder Coating Formulations:
Angaben in Masseanteilen ; *V nicht erfindungsgemäße VergleichsbeispieleInformation in mass fractions; * V not comparative examples according to the invention
Tabelle 2-2: Polyurethan-Pulverlackformulierungen :Table 2-2: Polyurethane Powder Coating Formulations:
Allgemeine Herstellungsvorschrift für die Pulverlacke 1 bis 3 sowie V1 bis V3: General manufacturing instructions for the powder coatings 1 to 3 and V1 to V3:
Die zerkleinerten Einsatzstoffe gemäß Tabelle 2 werden in einem Kollergang innig vermischt und anschließend im Extruder bei Temperaturen bis maximal 130 0C homogenisiert. Nach dem Erkalten wird das Extrudat gebrochen und mit einer Stiftmühle auf eine Korngröße < 100 μm gemahlen und mittels einer Siebmaschine auf < 63 μm abgesiebt. Das so hergestellte Pulver wird mit einer elektrostatischen Pulverspritzanlage bei 60 KV auf entfettete Eisenbleche appliziert und in einem Umlufttrockenschrank 30 Minuten bei 150 0C bzw. 30 Minuten bei 130 0C eingebrannt. (Schichtdicke 70 bis 80 μm). Die Ergebnisse der Testdaten sind in Tabellen 3 bis 4 dargestellt.The comminuted feedstocks according to Table 2 are intimately mixed in a pug mill and then homogenized in the extruder at temperatures up to 130 0 C maximum. After cooling, the extrudate is crushed and ground with a pin mill to a particle size <100 microns and sieved by means of a screening machine to <63 microns. The powder thus produced is applied with an electrostatic powder spray system at 60 KV on degreased iron sheets and baked in a convection oven for 30 minutes at 150 0 C and 30 minutes at 130 0 C. (Layer thickness 70 to 80 microns). The results of the test data are shown in Tables 3 to 4.
Kugelschlag nach ASTM D 2794-93Ball impact according to ASTM D 2794-93
Gitterschnitt nach DIN EN ISO 2409, Schnittabstand 2 mm
Cross cut according to DIN EN ISO 2409, cutting distance 2 mm
Claims
1. Feste, hochreaktive Uretdiongruppen haltige Polyurethanzusammensetzungen mit einem Schmelzpunkt oberhalb von 40 0C, im Wesentlichen enthaltend1. Solid, highly reactive polyurethane compositions containing uretdione groups with a melting point above 40 0 C, essentially containing
A) mindestens einen Uretdiongruppen haltigen Härter, basierend auf aromatischen, aliphatischen, (cyclo)aliphatischen und/oder cycloaliphatischen Polyisocyanaten und Hydroxylgruppen haltigen Verbindungen mit einem freien NCO-Gehalt von kleiner 5 Gew.-% und einem Uretdiongruppengehalt von 1 bis 18 Gew.-%, in Mengen zwischen 15 und 45 Gew.-% bezogen auf die Gesamtformulierung; undA) at least one hardener containing uretdione groups, based on aromatic, aliphatic, (cyclo)aliphatic and/or cycloaliphatic polyisocyanates and compounds containing hydroxyl groups with a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight. %, in amounts between 15 and 45% by weight based on the total formulation; and
B) mindestens einen KatalysatorB) at least one catalyst
1. der Formel [XR1R2R3R4I+ [R5COO]", mit X gleich N oder P, wobei R1 bis R4 gleichzeitig oder unabhängig voneinander Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste, jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten R1 bis R4 verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können, mit 1 bis 18 Kohlenstoffatomen bedeuten und jeder Rest R1 bis R4 zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann, und R5 ein Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylrest, linear oder verzweigt, mit 1 bis 18 Kohlenstoffatomen darstellt und zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann,1. of the formula [XR 1 R 2 R 3 R 4 I + [R 5 COO] " , with X equal to N or P, where R 1 to R 4 are simultaneously or independently alkyl, aryl, aralkyl, heteroaryl , alkoxyalkyl radicals, each linear or branched, unbridged or bridged with other radicals R 1 to R 4 , forming cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon, with 1 to 18 carbon atoms and each radical R 1 to R 4 may additionally have one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is an alkyl, aryl, aralkyl , heteroaryl, alkoxyalkyl radical, linear or branched, with 1 to 18 carbon atoms and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, may have triple bonds or halogen atoms,
2. der Formel [XR1R2R3R4J+ [R5]", mit X gleich N oder P, wobei R1 bis R4 gleichzeitig oder unabhängig voneinander Alkyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste, jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten R1 bis R4 verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können, mit 1 bis 18 Kohlenstoffatomen darstellen und jeder Rest R1 bis
R4 zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen kann, und R5 entweder OH oder F bedeutet,2. the formula [XR 1 R 2 R 3 R 4 J + [R 5 ] " , where X is N or P, where R 1 to R 4 simultaneously or independently of one another are alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, each linear or branched, unbridged or bridged with other radicals R 1 to R 4 , forming cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon, with 1 to 18 carbon atoms and each radical R 1 to R 4 may additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 means either OH or F,
3. der Formel M (OR1)n (OR2)m (OR3)o (OR4)p (OR5)q (OR6)r, wobei M ein Metall in beliebiger positiver Oxidationsstufe und identisch mit der Summe n+m+o+p+q+r ist, m, o, p, q, r ganze Zahlen von 0 bis 6 darstellen und für die Summe n+m+o+p+q+r = 1 bis 6 gilt, die Reste R1 bis R6 gleichzeitig oder unabhängig voneinander Wasserstoff oder AI kyl-, Aryl-, Aralkyl-, Heteroaryl-, Alkoxyalkylreste mit 1 bis 8 Kohlenstoffatomen bedeuten und die Reste jeweils linear oder verzweigt, unverbrückt oder mit anderen Resten verbrückt, unter Ausbildung von Cyclen, Bicyclen oder Tricyclen und die Verbrückungsatome neben Kohlenstoff auch Heteroatome sein können und zusätzlich noch eine oder mehrere Alkohol-, Amino-, Ester-, Keto-, Thio-, Säure-, Urethan-, Harnstoff-, Allophanatgruppen, Doppelbindungen, Dreifachbindungen oder Halogenatome aufweisen können, wobei diese Katalysatoren aus den Gruppen 1 bis 3 einzeln oder in Mischungen enthalten sind und3. the formula M (OR 1 ) n (OR 2 ) m (OR 3 ) o (OR 4 )p (OR 5 ) q (OR 6 ) r , where M is a metal in any positive oxidation state and identical to the sum n +m+o+p+q+r is, m, o, p, q, r represent integers from 0 to 6 and for the sum n+m+o+p+q+r = 1 to 6, the Radicals R 1 to R 6 simultaneously or independently of one another represent hydrogen or Al kyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals with 1 to 8 carbon atoms and the radicals are each linear or branched, unbridged or bridged with other radicals, forming Cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or May have halogen atoms, these catalysts from groups 1 to 3 being contained individually or in mixtures and
C) mindestens einen Hydroxyl- und Carboxylgruppen haltigen ungesättigten, amorphen Polyester, im Wesentlichen enthaltend mindestens eine α, ß- ungesättigte Dicarbonsäurekomponente und eine Alkoholkomponente, wobei die Alkoholkomponente aus einem Dicidolgemisch der isomerenC) at least one unsaturated, amorphous polyester containing hydroxyl and carboxyl groups, essentially containing at least one α, ß-unsaturated dicarboxylic acid component and an alcohol component, the alcohol component consisting of a dicidol mixture of the isomers
Verbindungen 3,8-Bis(hydroxymethyl)tricyclo [5.2.1.02'6]decan, 4,8-Compounds 3,8-Bis(hydroxymethyl)tricyclo [5.2.1.0 2 ' 6 ]decane, 4,8-
Bis(hydroxymethyl)tricyclo [5.2.1.026]decan und 5,8-Bis(hydroxymethyl)tricycloBis(hydroxymethyl)tricyclo [5.2.1.0 26 ]decane and 5,8-bis(hydroxymethyl)tricyclo
[5.2.1.026]decan besteht, wobei jedes Isomere zu einem Anteil von 20 bis 40 Gew.-% in dem Gemisch enthalten sein kann und die Summe der drei Isomeren 90 bis 100 Gew.-% ergibt, und das Gemisch mindestens zu 5 Gew.-% in der Alkoholkomponente des[5.2.1.0 26 ]decane, whereby each isomer can be contained in the mixture in a proportion of 20 to 40% by weight and the sum of the three isomers results in 90 to 100% by weight, and the mixture is at least 5 % by weight in the alcohol component of the
Polyesters vorhanden ist, mit einer OH-Zahl zwischen 1 undPolyester is present, with an OH number between 1 and
100 mg KOH/Gramm und einer COOH-Zahl zwischen 1 und 75 mg KOH/Gramm,
wobei das Verhältnis aus OH- und Säurezahl stets >1 beträgt, mit einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 1 bis 12 %;100 mg KOH/gram and a COOH number between 1 and 75 mg KOH/gram, where the ratio of OH number and acid number is always >1, with a proportion by weight, based on the total formulation, of 1 to 12%;
D) gegebenenfalls mindestens eine gegenüber Säuregruppen reaktive Verbindung;D) optionally at least one compound reactive towards acid groups;
E) gegebenenfalls mindestens eine Säure in monomerer oder polymerer Form;E) optionally at least one acid in monomeric or polymeric form;
F) gegebenenfalls mindestens ein amorphes Hydroxylgruppen haltiges oder Amingruppen haltiges Polymer mit einer OH-Zahl zwischen 20 undF) optionally at least one amorphous polymer containing hydroxyl groups or containing amine groups with an OH number between 20 and
500 mg KOH/Gramm beziehungsweise einem vergleichbaren Amingehalt;500 mg KOH/gram or a comparable amine content;
G) mindestens ein (teil-)khstallines Hydroxylgruppen haltiges Polymer mit einer OH-Zahl zwischen 10 und 500 mg KOH/Gramm mit einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 1 bis 35 %;G) at least one polymer containing (partially) stableline hydroxyl groups with an OH number between 10 and 500 mg KOH/gram with a weight proportion, based on the total formulation, of 1 to 35%;
H) gegebenenfalls Hilfs- und Zusatzstoffe und/oder weitere Katalysatoren;H) optionally auxiliaries and additives and/or further catalysts;
wobei der Anteil des Katalysators unter B) 0,001 bis 5 Gew.-% an der Gesamtformulierung beträgt und die Summe der Einsatzstoffe A) bis H) 100 Gew.-% ergibt.where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation and the sum of the starting materials A) to H) is 100% by weight.
2. Polyurethanzusammensetzung gemäß Anspruch 1 , dadurch gekennzeichnet,2. Polyurethane composition according to claim 1, characterized in
D) dass mindestens eine gegenüber Säuregruppen reaktive Verbindung mit einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 0,1 bis 10 %; und/oderD) that at least one compound reactive towards acid groups with a weight proportion, based on the total formulation, of 0.1 to 10%; and or
E) dass mindestens eine Säure in monomerer oder polymerer Form in einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 0,1 bis 10 %; und/oderE) that at least one acid in monomeric or polymeric form in a proportion by weight, based on the total formulation, of 0.1 to 10%; and or
F) dass mindestens ein amorphes Hydroxylgruppen haltiges oder Amingruppen haltiges Polymer mit einer OH-Zahl zwischen 20 und 500 mg KOH/Gramm beziehungsweise einem vergleichbaren Amingehalt mit einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 1 bis 95 %; enthalten ist.F) that at least one amorphous polymer containing hydroxyl groups or containing amine groups with an OH number between 20 and 500 mg KOH/gram or a comparable amine content with a weight proportion, based on the total formulation, of 1 to 95%; is included.
3. Polyurethanzusammensetzung nach Anspruch 1 oder 2,
dadurch gekennzeichnet, dass Hilfs- und Zusatzstoffe und/oder weitere Katalysatoren H) mit einem Gewichtsanteil, bezogen auf die Gesamtformulierung, von 0,001 bis 55 % enthalten sind.3. Polyurethane composition according to claim 1 or 2, characterized in that auxiliaries and additives and/or further catalysts H) are contained in a proportion by weight, based on the total formulation, of 0.001 to 55%.
4. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass Uretdiongruppen haltige Härter A) auf Basis von Isophorondiisocyanat (IPDI), Hexamethylendiisocyanat (HDI), Diisocyanatodicyclohexylmethan (Hi2MDI), 2-Methylpentadiisocyanat (MPDI), 2,2,4-4. Polyurethane compositions according to at least one of claims 1 to 3, characterized in that hardeners A) containing uretdione groups are based on isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (Hi 2 MDI), 2-methylpentadiisocyanate (MPDI), 2, 2.4-
Thmethylhexamethylendiisocyanat^^^-Thmethylhexamethylendiisocyanat (TMDI), Norbornandiisocyanat (NBDI), Methylendiphenyldiisocyanat (MDI), Toluidindiisocyanat (TDI) und Tetramethylxylylendiisocyanat (TMXDI), allein oder in Mischungen, enthalten sind.Thmethylhexamethylene diisocyanate^^^-Thmethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate (TMXDI), alone or in mixtures, are included.
5. Polyurethanzusammensetzungen nach Anspruch 4, dadurch gekennzeichnet, dass Uretdiongruppen haltige Härter auf Basis von IPDI, Hi2MDI und/oder HDI enthalten sind.5. Polyurethane compositions according to claim 4, characterized in that hardeners containing uretdione groups based on IPDI, Hi 2 MDI and / or HDI are included.
6. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass Uretdiongruppen haltige Härter A) auf Basis Hydroxylgruppen haltiger Polyester, Polythioether, Polyether, Polycaprolactame, Polyepoxide, Polyesteramide, Polyurethane, niedermolekulare Di-, Tri- und/oder Tetraalkohole, Monoamine und/oder Monoalkohole, allein oder in Mischungen, enthalten sind.6. Polyurethane compositions according to at least one of claims 1 to 5, characterized in that hardeners A) containing uretdione groups are based on polyesters containing hydroxyl groups, polythioethers, polyethers, polycaprolactams, polyepoxides, polyesteramides, polyurethanes, low molecular weight di-, tri- and / or tetra-alcohols, Monoamines and/or monoalcohols, alone or in mixtures, are contained.
7. Polyurethanzusammensetzungen nach Anspruch 6, dadurch gekennzeichnet, dass Polyester und/oder monomere Dialkohole enthalten sind.7. Polyurethane compositions according to claim 6, characterized in that polyester and/or monomeric dialcohols are contained.
8. Polyurethanzusammensetzungen nach Anspruch 7,
dadurch gekennzeichnet, dass Polyester mit einer OH-Zahl von 30 bis 150 mg KOH/g und einem mittleren8. Polyurethane compositions according to claim 7, characterized in that polyester with an OH number of 30 to 150 mg KOH/g and a medium
Molekulargewicht von 500 bis 6000 g/mol enthalten sind.Molecular weight of 500 to 6000 g / mol are included.
9. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass Härter A) auch Isocyanurat-, Biuret-, Allophanat-, Urethan- und/oder Harnstoff-Strukturen aufweisen.9. Polyurethane compositions according to at least one of claims 1 to 8, characterized in that hardener A) also has isocyanurate, biuret, allophanate, urethane and / or urea structures.
10. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass Katalysatoren 1. ausgewählt aus Tetramethylammoniumformiat, Tetramethylammoniumacetat, Tetramethylammoniumpropionat, Tetramethylammoniumbutyrat, Tetramethylammoniumbenzoat, Tetraethylammoniumformiat, Tetraethylammoniumacetat, Tetraethylammoniumpropionat, Tetraethylammoniumbutyrat, Tetraethylammoniumbenzoat, Tetrapropylammoniumformiat, Tetrapropylammoniumacetat, Tetrapropylammoniumpropionat, Tetrapropylammoniumbutyrat, Tetrapropylammoniumbenzoat, Tetrabutylammoniumformiat, Tetrabutylammoniumacetat, Tetrabutylammoniumpropionat, Tetrabutylammoniumbutyrat, Tetrabutylammoniumbenzoat, Tetrabutylphosphoniumacetat, Tetrabutylphosphoniumformiat, Ethyltriphenylphosphoniumacetat, Tetrabutylphosphoniumbenzothazolat, Tetraphenylphosphoniumphenolat und Trihexyltetradecylphosphoniumdecanoat enthalten sind.10. Polyurethane compositions according to at least one of claims 1 to 9, characterized in that catalysts 1. selected from tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium ben zoat, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate , tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium benzoate, tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate, tetrabutylphosphonium benzothazolate, tetraphenylphosphonium phenolate and trihexyltetradecylphosphonium decanoate .
11. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass Katalysatoren 2. ausgewählt aus Methyltributylammoniumhydroxid, Methyltriethylammoniumhydroxid, Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetrapropylammoniumhydroxid, Tetrabutylammoniumhydroxid, Tetrapentylammoniumhydroxid,
Tetrahexylammoniumhydroxid, Tetraoctylammoniumhydroxid, Tetradecylammoniumhydroxid, Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid, Benzyltrimethylammoniumhydroxid, Benzyltriethylammoniumhydroxid, Trimethylphenylammoniumhydroxid, Triethylmethylannnnoniunnhydroxid, Trimethylvinylannnnoniunnhydroxid, Tetramethylammoniunnfluorid, Tetraethylammoniumfluorid, Tetrabutyl- ammoniumfluorid, Tetraoctylammoniumfluorid, Benzyltrimethylammoniunnfluorid, Tetrabutylphosphoniumhydroxid und Tetrabutylphosphoniumfluorid enthalten sind.11. Polyurethane compositions according to at least one of claims 1 to 9, characterized in that catalysts 2. selected from methyltributylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, Tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecyl ammonium hydroxide, tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylannnnoniunnhydroxide, trimethylvinylannnnnoniunnhydroxide, tetramethylammonium fluoride , tetraethylammonium fluoride, tetrabutyl ammonium fluoride, tetraoctylammonium fluoride, benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide and tetrabutylphosphonium fluoride are included.
12. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass Katalysatoren 3. ausgewählt aus Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid, Rubidiumhydroxid, Cäsiumhydroxid, Berilliumhydroxid, Magnesiumhydroxid, Calziumhydroxid, Strontiumhydroxid, Bariumhydroxid, Aluminiumhydroxid, Zinkhydroxid, Lithiummethanolat, Natriummethanolat, Kaliummethanolat, Magnesiummethanolat, Calziummethanolat, Bariummethanolat, Lithiumethanolat, Nathumethanolat, Kaliumethanolat, Magnesiumethanolat, Calziumethanolat, Bariumethanolat, Lithiumpropylalkoholat, Nathumpropylalkoholat, Kaliumpropylalkoholat, Magnesiumpropylalkoholat, Calziumpropylalkoholat, Bariumpropylalkoholat, Lithiumisopropylalkoholat, Nathumisopropylalkoholat, Kaliumisopropylalkoholat, Magnesiumisopropylalkoholat, Calziumisopropylalkoholat, Bariumisopropylalkoholat, Lithium-1 -butylalkoholat, Natrium-1 -butylalkoholat, Kalium-1 -butylalkoholat, Magnesium-1 -butylalkoholat, Calzium-1 -butylalkoholat, Barium-1 -butylalkoholat, Lithium-2-butylalkoholat, Natrium-2-butylalkoholat, Kalium-2-butylalkoholat, Magnesium-2-butylalkoholat, Calzium-2-butylalkoholat, Barium-2-butylalkoholat, Lithiumisobutylalkoholat, Natriumisobutylalkoholat, Kaliumisobutylalkoholat, Magnesiumisobutylalkoholat, Calziumisobutylalkoholat, Bariumisobutylalkoholat, Lithium-tert. -butylalkoholat, Natrium-tert. -butylalkoholat, Kalium-tert. -butylalkoholat, Magnesium-tert. -butylalkoholat, Calzium-tert.- butylalkoholat, Barium-tert. -butylalkoholat, Lithiumphenolat, Nathumphenolat,
Kaliumphenolat, Magnesiumphenolat, Calziumphenolat und Bariumphenolat enthalten sind.12. Polyurethane compositions according to at least one of claims 1 to 10, characterized in that catalysts 3. selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, berillium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, zinc hydroxide, lithium methoxide, sodium methoxide, potassium methoxide , magnesium methoxide, calcium methoxide, barium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, magnesium ethoxide, calcium ethoxide, barium ethoxide, lithium propyl alcoholate, sodium propyl alcoholate, potassium propyl alcoholate, magnesium propyl alcoholate, calcium propyl alcoholate, barium propyl alcoholate, lithium isopropyl alcoholate, sodium isopropyl alcoholate, potassium isopropyl alcoholate, magnesium isopropyl alcoholate, calcium isopropyl alcoholate, barium isopropyl alcoholate , lithium-1-butyl alcoholate, sodium -1 -butyl alcoholate, potassium 1 -butyl alcoholate, magnesium 1 -butyl alcoholate, calcium 1 -butyl alcoholate, barium 1 -butyl alcoholate, lithium 2-butyl alcoholate, sodium 2-butyl alcoholate, potassium 2-butyl alcoholate, magnesium-2 -butyl alcoholate, calcium 2-butyl alcoholate, barium 2-butyl alcoholate, lithium isobutyl alcoholate, sodium isobutyl alcoholate, potassium isobutyl alcoholate, magnesium isobutyl alcoholate, calcium isobutyl alcoholate, barium isobutyl alcoholate, lithium tert. -butyl alcoholate, sodium tert. -butyl alcoholate, potassium tert. -butyl alcoholate, magnesium tert. -butyl alcoholate, calcium tert-butyl alcoholate, barium tert. -butyl alcoholate, lithium phenolate, sodium phenolate, Potassium phenolate, magnesium phenolate, calcium phenolate and barium phenolate are included.
13. Polyurethanzusammensetzungen mach mindestens einem der vorherigen Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Katalysatoren mit einer inerten Hülle umgeben und damit verkapselt sind.13. Polyurethane compositions according to at least one of the preceding claims 1 to 12, characterized in that the catalysts are surrounded and encapsulated with an inert shell.
14. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die Katalysatoren polymer angebunden sind.14. Polyurethane compositions according to at least one of the preceding claims 1 to 13, characterized in that the catalysts are polymer-bound.
15. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche 1 bis 14, dadurch gekennzeichnet, dass als Hydroxylgruppen haltige (teil-)khstalline Polymere G) Polyester, Polyether, Polyacrylate, Polyurethane und/oder Polycarbonate mit einer OH-Zahl von 10 bis 500 mg KOH/Gramm enthalten sind.15. Polyurethane compositions according to at least one of the preceding claims 1 to 14, characterized in that (partially) khstalline polymers G) containing hydroxyl groups are polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates with an OH number of 10 to 500 mg KOH /gram are included.
16. Polyurethanzusammensetzungen nach Anspruch 15, dadurch gekennzeichnet, dass Hydroxylgruppen haltige Polyester G) mit einer OH-Zahl von 15 bis 150 und einem mittleren Molekulargewicht von 500 bis 6000 g/mol, enthalten sind.16. Polyurethane compositions according to claim 15, characterized in that hydroxyl-containing polyesters G) with an OH number of 15 to 150 and an average molecular weight of 500 to 6000 g / mol are included.
17. Polyurethanzusammensetzungen nach Anspruch 16, dadurch gekennzeichnet, dass Polyester G) auf Basis von Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Dodecandisäure, Tetrahydrophthalsäure, Hexahydrophthalsäure, Hexahydroterephthalsäure,17. Polyurethane compositions according to claim 16, characterized in that polyester G) based on succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid,
Endemethylentetrahydrophthalsäure, Glutarsäure bzw. - soweit zugänglich - deren Anhydride enthalten sind.
Endemethylenetetrahydrophthalic acid, glutaric acid or - if accessible - their anhydrides are included.
18. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 16 bis 17, dadurch gekennzeichnet, dass Polyester G) auf Basis von Ethylenglykol, Propandiol-(1 ,2) und -(1 ,3), 2,2- Dimethylpropandiol-(1 ,3), Butandiol-(1 ,4), Pentandiol-(1 ,5), Hexandiol-(1 ,6), 2- Methylpentandiol-(1 ,5), 2,2,4-Thmethylhexandiol-(1 ,6), 2,4,4-Trimethylhexandiol- (1 ,6), Heptandiol-(1 ,7), Decandiol-(1 ,10), Dodecandiol-(1 ,12), Octadecen-9,10- diol-(1 ,12), Octadecandiol-(1 ,18), 2,4-Dimethyl-2-propylheptandiol-(1 ,3), Butendiol-(1 ,4), Butindiol-(1 ,4), Diethylenglykol, Thethylenglykol, Tetraethylenglykol, trans- und cis-i ^-Cyclohexandimethanol, die Triole Glycerin, Hexantriol-(1 ,2,6), 1 ,1 ,1 -Thmethylolpropan und 1 ,1 ,1 -Thmethylolethan und das Tetraol Pentaerythrit.18. Polyurethane compositions according to at least one of claims 16 to 17, characterized in that polyester G) based on ethylene glycol, propanediol-(1,2) and -(1,3), 2,2-dimethylpropanediol-(1,3) , butanediol-(1,4), pentanediol-(1,5), hexanediol-(1,6), 2-methylpentanediol-(1,5), 2,2,4-thmethylhexanediol-(1,6), 2 ,4,4-trimethylhexanediol-(1,6), heptanediol-(1,7), decanediol-(1,10), dodecanediol-(1,12), octadecene-9,10-diol-(1,12) , octadecanediol-(1,18), 2,4-dimethyl-2-propylheptanediol-(1,3), butenediol-(1,4), butenediol-(1,4), diethylene glycol, thylene glycol, tetraethylene glycol, trans- and cis-i ^-cyclohexanedimethanol, the triols glycerol, hexanetriol-(1,2,6), 1,1,1-thmethylolpropane and 1,1,1-thmethylolethane and the tetraol pentaerythritol.
19. Polyurethansammensetzungen nach mindestens einem der Ansprüche 1 bis 18, dadurch gekennzeichnet, dass als Komponente D) Epoxyverbindungen, Carbodiimide, Hydroxyalkylamide, basische Salze und/oder 2-Oxazoline enthalten sind.19. Polyurethane compositions according to at least one of claims 1 to 18, characterized in that component D) contains epoxy compounds, carbodiimides, hydroxyalkylamides, basic salts and / or 2-oxazolines.
20. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 19, dadurch gekennzeichnet, dass als Säure E) Schwefelsäure, Essigsäure, Benzoesäure, Malonsäure, Terephthalsäure, aber auch Copolyester oder Copolyamide mit einer Säurezahl von mindestens 20 mg KOH/g enthalten sind.20. Polyurethane compositions according to at least one of claims 1 to 19, characterized in that the acid E) contains sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, but also copolyesters or copolyamides with an acid number of at least 20 mg KOH / g.
21. Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 20, dadurch gekennzeichnet, dass als Hydroxylgruppen haltige amorphe Polymere F) Polyester, Polyether, Polyacrylate, Polyurethane, Polyether und/oder Polycarbonate mit einer OH-Zahl von 20 bis 500 mg KOH/Gramm enthalten sind.
21. Polyurethane compositions according to at least one of claims 1 to 20, characterized in that amorphous polymers F) containing hydroxyl groups contain polyester, polyethers, polyacrylates, polyurethanes, polyethers and / or polycarbonates with an OH number of 20 to 500 mg KOH / gram are.
22. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) bis zu 10 % weitere Isomere des Dicidols und/oder trimere und/oder höhere isomere Diole des Diels-Alder-Umsetzungsproduktes aus Cyclopentadien enthalten sind.22. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains up to 10% further isomers of dicidol and/or trimeric and/or higher isomeric diols of the Diels-Alder reaction product from cyclopentadiene.
23. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) die Säurekomponente zusätzlich aromatische und/oder aliphatische und/oder cycloaliphatische Monocarbonsäuren und/oder Dicarbonsäuren und/oder Polycarbonsäuren enthält.23. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the acid component additionally contains aromatic and/or aliphatic and/or cycloaliphatic monocarboxylic acids and/or dicarboxylic acids and/or polycarboxylic acids.
24. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) die Säurekomponente teilweise oder ganz aus24. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the acid component is partially or completely made up
Anhydriden und/oder Alkylestern besteht.Anhydrides and/or alkyl esters exist.
25. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) die Alkoholkomponente weitere lineare und/oder verzweigte, aliphatische und/oder cycloaliphatische und/oder aromatische Diole und/oder Polyole enthält.25. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component contains further linear and/or branched, aliphatic and/or cycloaliphatic and/or aromatic diols and/or polyols.
26. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet,
dass in der Komponente C) als α,ß-ungesättigte Dicarbonsäure Citracon-, Fumar-, Itacon-, Malein- und/oder Mesaconsäure enthalten ist.26. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains citraconic, fumaric, itaconic, maleic and/or mesaconic acid as α,ß-unsaturated dicarboxylic acid.
27. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) als zusätzliche Säuren Phthalsäure, Isophthalsäure, Terephthalsäure, 1 ,4-Cyclohexandicarbonsäure, Bernsteinsäure, Sebazinsäure, Methyltetra-, Methylhexahydrophthalsäure, Hexahydrophthalsäure, Tetrahydrophthalsäure, Dodecandisäure, Adipinsäure, Azelainsäure, Pyromellitsäure und/oder Trimellitsäure, deren Säureanhydride und/oder Methylester, und/oder Isononansäure und/oder 2-Ethylhexansäure enthalten sind.27. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) as additional acids are phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid , azelaic acid, pyromellitic acid and/or trimellitic acid, whose acid anhydrides and/or methyl esters, and/or isononanoic acid and/or 2-ethylhexanoic acid are contained.
28. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) als zusätzliche Alkohole Ethylenglykol, 1 ,2- und/oder 1 ,3-Propandiol, Diethylen-, Dipropylen-, Thethylen-, Tetraethylenglykol, 1 ,2- und/oder 1 ,4-Butandiol, 1 ,3-Butylethylpropandiol, 1 ,3-Methylpropandiol, 1 ,5- Pentandiol, Cyclohexandimethanol, Glycerin, Hexandiol, Neopentylglycol, Trimethylolethan, Trimethylolpropan und/oder Pentaerythrit, Bisphenol A, B, C, F, Norbornylenglykol, 1 ,4-Benzyldimethanol und -ethanol, 2,4-Dimethyl-2- ethylhexan-1 ,3-diol enthalten sind.28. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) as additional alcohols are ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene, dipropylene, thethylene, tetraethylene glycol, 1, 2- and/or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerin, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and/or pentaerythritol, bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol and -ethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol are included.
29. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) als α,ß-ungesättigte Säurekomponente Fumarsäure und/oder Maleinsäure(anhydrid) enthalten sind.29. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains fumaric acid and/or maleic acid (anhydride) as the α,β-unsaturated acid component.
30. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche,
dadurch gekennzeichnet, dass in der Komponente C) als weitere Dicarbonsäurekomponente Adipinsäure und/oder Phthalsäure(anhydrid) enthalten sind.30. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains adipic acid and/or phthalic acid (anhydride) as a further dicarboxylic acid component.
31. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) die Alkoholkomponente im Mol-Verhältnis von 0,5 bis31. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component in a molar ratio of 0.5 to
2.0 zu 1 zur Säure-komponente enthalten ist.2.0 to 1 to the acid component is included.
32. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) die Alkoholkomponente im Mol-Verhältnis von 0,8 bis32. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component in a molar ratio of 0.8 to
1 ,5 zu 1 zur Säure-komponente enthalten ist.It contains 1.5 to 1 to the acid component.
33. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass in der Komponente C) die Alkoholkomponente im Mol-Verhältnis von 1 ,0 bis33. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component in a molar ratio of 1.0 to
1.1 zu 1 zur Säurekomponente enthalten ist.1.1 to 1 to the acid component is included.
34. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Polyester C) eine Säurezahl zwischen 1 und 50 mg KOH/g, bevorzugt zwischen 1 und 35 mg KOH/g, aufweist.34. Polyurethane compositions according to at least one of the preceding claims, characterized in that the polyester C) has an acid number between 1 and 50 mg KOH/g, preferably between 1 and 35 mg KOH/g.
35. Polyurethanzusammensetzungen nach mindestens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Polyester C) eine OH-Zahl zwischen 1 und 75, bevorzugt zwischen 1
und 50 mg KOH/g, aufweist.35. Polyurethane compositions according to at least one of the preceding claims, characterized in that the polyester C) has an OH number between 1 and 75, preferably between 1 and 50 mg KOH/g.
36. Verfahren zur Herstellung von Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 35 durch Homogenisierung bei Temperaturen von 40 bis 130 0C.36. A process for producing polyurethane compositions according to at least one of claims 1 to 35 by homogenization at temperatures of 40 to 130 0 C.
37. Pulverlackzusammensetzung, enthaltend Verbindungen nach mindestens einem der vorherigen Ansprüche 1 bis 35.37. Powder coating composition containing compounds according to at least one of the preceding claims 1 to 35.
38. Pulverförmige Klebstoffzusammensetzung, enthaltend Verbindungen nach mindestens einem der vorherigen Ansprüche 1 bis 35.38. Powdered adhesive composition containing compounds according to at least one of the preceding claims 1 to 35.
39. Verwendung der Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 36 zur Herstellung von pulverförmigen Lack- und Klebstoffbeschichtungen für Metall, Kunststoff, Holz, Glas, Leder oder sonstige Hitze empfindliche Untergründe.39. Use of the polyurethane compositions according to at least one of claims 1 to 36 for the production of powdery paint and adhesive coatings for metal, plastic, wood, glass, leather or other heat-sensitive substrates.
40. Pulverförmige Metallbeschichtungszusammensetzungen, im Wesentlichen enthaltend eine Polyurethanzusammensetzung nach mindestens einem der Ansprüche 1 bis 35.40. Powdered metal coating compositions, essentially containing a polyurethane composition according to at least one of claims 1 to 35.
41. Pulverförmige Holzbeschichtungszusammensetzung, im Wesentlichen enthaltend eine Polyurethanzusammensetzung nach mindestens einem der Ansprüche 1 bis 35.41. Powdered wood coating composition, essentially containing a polyurethane composition according to at least one of claims 1 to 35.
42. Pulverförmige Lederbeschichtungszusammensetzungen, im Wesentlichen enthaltend eine Polyurethanzusammensetzung nach mindestens einem der Ansprüche 1 bis 35.42. Powdered leather coating compositions, essentially containing a polyurethane composition according to at least one of claims 1 to 35.
43. Pulverförmige Kunststoffbeschichtungszusammensetzungen, im Wesentlichen enthaltend eine Polyurethanzusammensetzung nach mindestens einem der Ansprüche 1 bis 35.
43. Powdered plastic coating compositions, essentially containing a polyurethane composition according to at least one of claims 1 to 35.
44. Metallbeschichtungszusamnnensetzungen nach Anspruch 40 für44. Metal coating compositions according to claim 40 for
Automobil karossen, Motor- und Fahrräder, Gebäudeteile und Haushaltsgeräte.Automobile bodies, motorbikes and bicycles, building parts and household appliances.
45. Beschichtete Gegenstände mit den Polyurethanzusammensetzungen nach mindestens einem der Ansprüche 1 bis 35.
45. Coated objects with the polyurethane compositions according to at least one of claims 1 to 35.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007057057A DE102007057057A1 (en) | 2007-11-27 | 2007-11-27 | Uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins |
DE102007057057.2 | 2007-11-27 |
Publications (1)
Publication Number | Publication Date |
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WO2009068377A1 true WO2009068377A1 (en) | 2009-06-04 |
Family
ID=40292424
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2008/064357 WO2009068377A1 (en) | 2007-11-27 | 2008-10-23 | Polyurethane compounds containing uretdione groups and hardenable at low temperature and also containing adhesion-improving resins |
Country Status (3)
Country | Link |
---|---|
CN (1) | CN101445586A (en) |
DE (1) | DE102007057057A1 (en) |
WO (1) | WO2009068377A1 (en) |
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US8758862B2 (en) | 2012-06-26 | 2014-06-24 | Prc Desoto International, Inc. | Coating compositions with an isocyanate-functional prepolymer derived from a tricyclodecane polyol, methods for their use, and related coated substrates |
EP2977395A1 (en) * | 2014-07-21 | 2016-01-27 | Evonik Degussa GmbH | Highly reactive, polyurethane compositions containing uretdione groups which contain the carbonate salts |
CN111527118A (en) * | 2017-12-28 | 2020-08-11 | 科思创德国股份有限公司 | Aqueous dispersion |
WO2023176641A1 (en) * | 2022-03-17 | 2023-09-21 | 三菱ケミカル株式会社 | Tricyclodecanedimethanol composition, uv-curable composition, polymer composition, and tricyclodecanedimethanol composition production method |
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DE102010041247A1 (en) * | 2010-09-23 | 2012-03-29 | Evonik Degussa Gmbh | Process for the preparation of storage-stable polyurethane prepregs and molded articles made therefrom of polyurethane composition in solution |
WO2016158885A1 (en) * | 2015-03-27 | 2016-10-06 | 東洋製罐グループホールディングス株式会社 | Organic resin-coated and surface treated metal plate |
CA2989239C (en) * | 2015-06-15 | 2023-07-11 | Lanxess Deutschland Gmbh | Method for the synthesis of polymer carbodiimides with added cesium salts, polymer carbodiimides, use thereof |
CN107474778A (en) * | 2017-06-30 | 2017-12-15 | 努比亚技术有限公司 | A kind of production method of PUR glue |
CN107936854A (en) * | 2017-11-29 | 2018-04-20 | 温州市环球汽车衬垫有限公司 | A kind of automobile-used glue of novel plant base |
US10711155B2 (en) * | 2017-12-20 | 2020-07-14 | Ppg Industries Ohio, Inc. | Ultradurable coating composition |
WO2021262953A1 (en) * | 2020-06-25 | 2021-12-30 | Dow Global Technologies Llc | Polyol and foam made therefrom |
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DE102007057057A1 (en) | 2009-05-28 |
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