EP1444300A1 - Method for solidification of a liquid paint component - Google Patents
Method for solidification of a liquid paint componentInfo
- Publication number
- EP1444300A1 EP1444300A1 EP02763086A EP02763086A EP1444300A1 EP 1444300 A1 EP1444300 A1 EP 1444300A1 EP 02763086 A EP02763086 A EP 02763086A EP 02763086 A EP02763086 A EP 02763086A EP 1444300 A1 EP1444300 A1 EP 1444300A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid
- component
- liquid paint
- paint component
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003973 paint Substances 0.000 title claims abstract description 178
- 239000007788 liquid Substances 0.000 title claims abstract description 167
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000007711 solidification Methods 0.000 title claims abstract description 13
- 230000008023 solidification Effects 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 93
- 239000007787 solid Substances 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000004971 Cross linker Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920000180 alkyd Polymers 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 235000019383 crystalline wax Nutrition 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004169 Hydrogenated Poly-1-Decene Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 239000000306 component Substances 0.000 description 128
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 12
- -1 2-hydroxyethyl- Chemical group 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000013638 trimer Substances 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 6
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- YNOWBNNLZSSIHM-UHFFFAOYSA-N tris(oxiran-2-ylmethyl) benzene-1,2,4-tricarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 YNOWBNNLZSSIHM-UHFFFAOYSA-N 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- OYWUEIOUTXQFRH-UHFFFAOYSA-N 1,1,1-triisocyanatononane Chemical compound CCCCCCCCC(N=C=O)(N=C=O)N=C=O OYWUEIOUTXQFRH-UHFFFAOYSA-N 0.000 description 1
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- IMJOXZCOZRQGSX-UHFFFAOYSA-N 1,7-diisocyanato-3-(2-isocyanatoethyl)heptane Chemical compound O=C=NCCCCC(CCN=C=O)CCN=C=O IMJOXZCOZRQGSX-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- JFZBUNLOTDDXNY-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OCC(C)OC(=O)C(C)=C JFZBUNLOTDDXNY-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- OWDBMKZHFCSOOL-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)propoxy]propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(C)COC(C)COC(=O)C(C)=C OWDBMKZHFCSOOL-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-UHFFFAOYSA-N 2-dodec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCC=CC(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- UYCICMIUKYEYEU-ZHACJKMWSA-N 3-[(e)-dodec-2-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCC\C=C\CC1CC(=O)OC1=O UYCICMIUKYEYEU-ZHACJKMWSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- TVLYPTZVJFAYSU-UHFFFAOYSA-N 4-hydroperoxy-4-methylpentan-2-one Chemical compound CC(=O)CC(C)(C)OO TVLYPTZVJFAYSU-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- WSGFXVFLWVXTCJ-VOTSOKGWSA-N Dihydro-3-(2-octenyl)-2,5-furandione Chemical compound CCCCC\C=C\CC1CC(=O)OC1=O WSGFXVFLWVXTCJ-VOTSOKGWSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- YHEWVUZCWXKWFW-UHFFFAOYSA-N [O-2].[Fe+2].[S-2].[Zn+2] Chemical compound [O-2].[Fe+2].[S-2].[Zn+2] YHEWVUZCWXKWFW-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- HKQOBOMRSSHSTC-UHFFFAOYSA-N cellulose acetate Chemical compound OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(O)C(O)C1O.CC(=O)OCC1OC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(COC(C)=O)O1.CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 HKQOBOMRSSHSTC-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005428 food component Substances 0.000 description 1
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- KCYQMQGPYWZZNJ-UHFFFAOYSA-N hydron;2-oct-1-enylbutanedioate Chemical compound CCCCCCC=CC(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229940091853 isobornyl acrylate Drugs 0.000 description 1
- HLJDOURGTRAFHE-UHFFFAOYSA-N isocyanic acid;3,5,5-trimethylcyclohex-2-en-1-one Chemical compound N=C=O.N=C=O.CC1=CC(=O)CC(C)(C)C1 HLJDOURGTRAFHE-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 235000021056 liquid food Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KXYJPVZMZBJJBZ-UHFFFAOYSA-N tert-butyl 2-ethylbutaneperoxoate Chemical compound CCC(CC)C(=O)OOC(C)(C)C KXYJPVZMZBJJBZ-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- VSJBBIJIXZVVLQ-UHFFFAOYSA-N tert-butyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(C)(C)C VSJBBIJIXZVVLQ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 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
Definitions
- the invention relates to a method for solidification of a liquid paint component. Furthermore it relates to a solidified liquid paint component, to the use of a solidified liquid paint component in a powder paint, to a method for producing a powder paint, to a coating produced by curing a powder paint binder composition, and to a fully or partly coated substrate.
- Components that are used for powder paint binder compositions are usually not liquid at room temperature for several reasons. One of these reasons is that liquid components would normally not result in a solid end product from which a powder can be made that is stable at room temperature.
- Liquid components are here and hereafter defined as components with a melt or glass transition temperature below room temperature. One might be able to form a powder from the liquid component by cooling down the liquid sufficiently.
- the powder should be kept cooled down, also during storage time and processing, which would cost a lot of energy, if even possible.
- Another reason lies in the efficiency of the mixing process.
- the stoichiometry of the added components is of crucial relevance for the properties of the final coating. Therefore these components are to be adequately mixed, resulting in a relative homogeneous mixture.
- the flow pattern of liquid components differs from the flow pattern of solid components, resulting in an inhomogeneous mixture. This could lead to problems, for example blocked or fouled equipment.
- the object of the present invention is to provide a method for making a liquid component suitable for a powder paint binder composition whilst overcoming the above-mentioned disadvantages.
- a solidified liquid paint component is here and hereafter defined as a liquid paint component that is packed with a solid auxiliary component resulting in a stable liquid- solid agglomerate that behaves like a solid particle at temperatures below room temperature.
- the liquid paint component is still present, but encapsulated by the solid auxiliary component.
- All liquid paint components are suitable for the present invention.
- the liquid paint components suitable for the present invention are liquid binder components.
- Liquid binder components are here and hereafter defined as liquid components that are part of the powder paint binder composition.
- a powder paint binder composition is here and hereafter defined as the paint components that are needed to form a network.
- Liquid binder components suitable for the present invention are for example liquid crosslinkers, liquid initiators, liquid catalysts and/or liquid resins, for example liquid alkyd resins, and/or liquid UV-curable compounds. Also mixtures of liquid components may be used.
- the combination of a resin and a crosslinker with optionally an initiator and/or a catalyst is generally used in known for the powder paint binder compositions, and is usually referred to in the art as a so-called 2K system (2 component system).
- the crosslinker is then defined as the compound of which less than 50 wt% in the binder composition, with the resin being the compound of which is equal to or more than 50 wt% is present in the binder composition, the total of both components being 100 wt%.
- the present invention makes it possible to use other compositions as usually used in the powder paint industry, for example alkyd resins, or liquid UV-curable compounds, which do not require an additional component to react with to form a network.
- This is usually referred to in the art as a so-called 1K system (1 component system).
- 1K system (1 component system)
- the 1 K components can for purposes of describing the present invention be part of or constitute a powder paint binder composition. It is preferred that in case of 2K systems a combination of a liquid crosslinker with a liquid resin is avoided, to prevent problems with early network formation.
- the composition is called a powder paint composition.
- the composition is called a powder paint.
- the powder paint can then be applied to a substrate and cured, to form a coating. This results in a fully or partly coated substrate.
- liquid crosslinkers are liquid epoxides, liquid acrylates, liquid methacrylates, liquid vinylethers, liquid isocyanates, liquid amines, liquid glycidyl ethers, liquid glycidyl esters, liquid hydroxyalkylamides, liquid anhydrides, liquid acids and/or liquid amino resins. Also mixtures of crosslinkers can be used.
- suitable liquid epoxides are epoxidised fatty acids, esters and oils, for example epoxidized linseed oil, epoxidized soybean oil.
- suitable liquid acrylates are ethyleneglycoldiacrylate, diethyleneglycoldiacrylate, triethyleneglycoldiacrylate, propyleneglycoldiacrylate, dipropyleneglycoldiacrylate, tripropyleneglycoldiacrylate, ethoxylated trismethylolpropanetriacrylate, ethoxylated bisphenol-A-diacrylate, trismethylolpropanetriacrylate, bisphenol-A-diacrylate, laurylacrylate, isobornylacrylate, adducts of 2-hydroxyethyl-, 3-hydroxypropyl, 4-hydroxybutylacrylate with diisocyanates and/or the isocyanurate trimers thereof.
- liquid methacrylates examples include ethyleneglycoldimethacrylate, diethyleneglycoldimethacrylate, triethyleneglycoldimethacrylate, propyleneglycoldimethacrylate, ethoxylated trismethylolpropanetrimethacrylate, ethoxylated bisphenol-A-dimethacrylate, dipropyleneglycoldimethacrylate, tripropyleneglycoldimethacrylate, trismethylolpropanetrimethacrylate, bisphenol-A-dimethacrylate, laurylmethacrylate, isobomylmethacrylate, adducts of 2-hydroxyethyl-, 3-hydroxypropyl, 4-hydroxybutylmethacrylate with diisocyanates and/or the isocyanurate trimers thereof.
- liquid vinylethers examples include ethyleneglycoldivinylether, diethyleneglycoldivinylether, triethyleneglycoldivinylether, cyclohexanedimethanoldivinylether, butanedioldivinylether, adducts of hydroxyethylvinylether, hydroxybutylvinylether, cyclohexanedimethanolvinylether with diisocyanates and/or the isocyanurate trimers thereof.
- suitable liquid isocyanates are 1 ,6-hexanediisocyanate and/or the isocyanurate trimer thereof, 1 ,12-docdecanediisocyanate and/or the isocyanurate trimer thereof, tris-isocyanatononane (3-isocyanatoethyl- 1 ,7diisocyanatoheptane, isophorondiisocyanate, 3,4-isocyanatomethyl-1-methyl- cyclohexyldiisocyanate, and/or 4,4-methylenebis(cyclohexylisocyanate) and/or the isocyanurate trimer thereof.
- the liquid isocyanates are preferably blocked with for example, caprolactam, methylethylketonoxim, butanol or triazole. Also the so-called internally blocked derivatives of the liquid isocyanates are suitable for this invention. These derivatives are usually referred to as uretdiones.
- suitable liquid amines are hexanediamine, bis(ethylene)triamine, bis(hexamethylene)triamine, 3-aminoethyl-1,7-aminoheptane, and/or tris(aminoethyl)amine.
- suitable liquid glycidyl ethers are ethyleenglycoldiglycidylether, butaandioldiglycidylether, hexaandioldiglyicdylether and/or trimethylolpropanetriglycidylether, bisphenol-A-diglycidylether and oligomers thereof.
- liquid glycidyl esters examples include triglycidyltrimellitate, trigylicdylcitrate, diglycidyladipate, and/or diglycidyl-o-phthalate.
- triglycidyltrimellitate examples include triglycidyltrimellitate, trigylicdylcitrate, diglycidyladipate, and/or diglycidyl-o-phthalate.
- mixtures of triglycidyltrimellitate and diglycidylterephthalate and/or diglycidylisophthalate examples of suitable liquid glycidyl esters.
- liquid hydroxyalkylamides are N,N-di-2- hydroxyethyl-acetamide, N,N-di-2-hydroxyethyl-formamide, N,N-di-2-hydroxyethyl- propionamide, N,N-di-2-hydroxyethyl-lauramide, N,N-di-2-hydroxypropyl-acetamide, N,N-di-2-hydroxypropyl- formamide, N,N-di-2-hydroxypropyl- propionamide, N,N-di-2- hydroxypropyl-lauramide, bis(N,N-di-2-hydroxyethyl)-succinamide, bis(N,N-di-2- hydroxyethyl)-glutaramide, bis(N,N-di-2-hydroxypropyl)- succinamide, and/or bis(N,N- di-2-hydroxypropyl)-glutaramide, and mixtures of the above with bis(N,N-di-2-di
- liquid aminoresins examples include methylolated melamines, urea, benzoguanamines and glycourils, and methyl- and/or butylethers thereof, UramexTM U238, NF821 , NF822(DSM Resins), CymelTM 303, 325, 328 (DSM Resins), SetamineTM US138 (AKZO-Nobel), ResamineTM HF155 (Solutia), and/or MaprenalTM MF820 (BASF).
- suitable liquid acids and their anhydrides are fatty acid dimers, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, 2- octenylsuccinic acid, 2-octenyl-succinic anhydride, 2-dodecenyl-succinic acid and/or 2-dodecenyl-succinic anhydride.
- liquid resins suitable for the present invention are all resins that are liquid at room temperature.
- Suitable resins can be for example liquid polyesters, liquid polyacrylates, liquid polyurethanes and/or liquid epoxide resins, for example bisphenol-A-diglycidylether and oligomers thereof with bisphenol-A.
- the liquid resins are alkyd resins and/or UV-curable compounds.
- Suitable alkyd resins are for example chain stopped alkyd resins, high solid alkyd resins, waterborne alkyd resins, and/or longoil alkyds, for example based on soybean oil.
- the alkyd resin can be in pure form, emulsified or dissolved in a solvent.
- Suitable UV-curable compounds are for example liquid unsaturated compounds for example (low molecular) epoxy acrylates, polyurethane acrylates, polyester acrylates, acrylic acrylates, vinyl ethers, allyl ethers, epoxy methacrylates, polyester methacrylates, polyurethane methacrylates, acrylic methacrylates, unsaturated polyesters (based on maleic acid, fumaric acid, itaconic acid).
- These UV-curable compounds can be monomers, oligomers and/or polymers.
- the unsaturation of the UV-curable compounds can for example range from 1-8 unsaturations per molecule.
- the UV-curable compound preferably is a mono-, di-, or polyfunctional acrylate, mono-, di-or polyfunctional methacrylate, or a mixture of any of them.
- Suitable liquid initiators can be for example liquid photo-initiators, liquid peroxides and/or liquid azodinitriles.
- suitable liquid photo-initiators are DarocureTM 1173, 4265 (CIBA), IrgacureTM 149, 500, 1000, 1700 (CIBA),
- liquid peroxides examples include dilaurylperoxide, methylethylketonperoxide, tert-amylperoxypivalate (TrigonoxTM 125 (AKZO-Nobel)), tert-butylperoxypivalate (TrigonoxTM 25), 1 ,1-bis(tert-butylbis(3,5,5-trimethylhexanoyl)peroxide (TrigonoxTM 36), 2-5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TrigonoxTM 141), tert-amylperoxy- 2-ethylhexanoate (TrigonoxTM 121 , TBPEH), tert-butylperoxy-2-ethylhexanoate (TrigonoxTM 21 S), tert-butylperoxydiethylacetate (TrigonoxTM 27), tert- butylperoxyisobutanoate (Trigonox
- Suitable solid auxiliary compounds for the invention are all components that are solid at room temperature. It is preferred that the used solid auxiliary component to pack the liquid paint component, will not fully dissolve in the liquid paint component at atmospheric pressure and at room temperature. It is even more preferred that the used solid auxiliary component does not dissolve at all in the liquid paint component at atmospheric pressure and at room temperature.
- suitable solid auxiliary components are all solid components that are suitable for use in a powder paint binder composition or a powder paint, such as solid resins, solid crosslinkers, solid initiators, solid fillers, solid pigments and/or solid usual additives.
- suitable solid resins are solid polyesters, solid polyacrylates, solid, polyurethanes and/or solid epoxy resins.
- suitable solid crosslinkers are solid aminoresins, solid epoxides, solid acrylates, solid methacrylates, solid vinylethers, solid isocyanates, solid amines, solid glycidyl ethers, solid glycidyl esters, solid hydroxyalkylamides, solid anhydrides and/or solid acids. Also mixtures of crosslinkers can be used.
- suitable solid fillers are silicium oxide, aluminium hydroxide, aluminium oxide, calcium carbonate, talcum, mica, magnesium carbonate, barium sulfate, calcium sulfate (gypsum).
- Pigments suitable for the invention can be both inorganic and organic.
- suitable inorganic pigments are titanium dioxide, zinc sulphide iron oxide and/or chromium oxide.
- suitable organic pigments are azo compounds.
- suitable solid additives are mould release agents (calcium stearate, magnesium stearate), anti-oxidants (phosphites, hydroquinones, aromatic amines), tribocharging agents (tertiary amines), wetting agents (polybutylacrylate, BYK361 , Acronal), degassing agents, flow agents, stabilisers, adhesion promoters and/or anti-foaming agents.
- suitable solid components are (semi)crystalline waxes, for example CeridustTM (Clariant GmbH), LuwaxTM (BASF), COPO-WaxTM (Coting Products), CeraflourTM (Byk Cera Chemie), OrgasolTM (Elf Atochem) and/or Lanco WaxTM (Lubrizol Coating Additives).
- suitable solid auxiliary components are silicic acid, zirconium dioxide, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, glass, clays (e.g.
- the present invention allows all kinds of combinations between the liquid paint component and the solid auxiliary component.
- the liquid paint component is packed with a solid auxiliary component which is usually present in a powder paint.
- a solid auxiliary component which is usually present in a powder paint.
- the liquid crosslinker and/or radical initiator is solidified with help of a solid resin and/or the usual additives, fillers and/or pigments.
- the liquid paint component is a trimer of HDI, preferably blocked with caprolactam.
- the resulting solidified liquid paint component is used as a crosslinker in polyester-based powder paint binder compositions.
- a powder paint comprising this powder paint binder composition is especially suitable for outdoor durable, and flexible coatings.
- the amount of used liquid paint component, with respect to the used solid auxiliary component is preferably larger than 50 wt%, more preferably larger than 60 wt%, even more preferably larger than 80 wt% and most preferably larger than 90 wt%, the total weight of liquid paint component and solid auxiliary component being 100 wt%.
- a suitable method for solidification of a liquid paint component is mixing the liquid paint component with a molten solid auxiliary component, upon which a solidified paint component is obtained by cooling the resulting mixture.
- the resulting solidified liquid paint component can then be formed into a powder.
- the molten solid auxiliary component preferably is a (semi)crystalline wax and/or resins.
- a compressible fluid is added to the liquid paint component and the molten solid auxiliary component under pressure and the free flowing powder is obtained by expanding the pressurized mixture through a nozzle.
- the molten solid auxiliary component is not dissolvable in the liquid paint component at a pressure of 10 5 Pa and temperatures below room temperature.
- Another method to solidify liquid components is to provide the liquid paint component in a pressurised container, where after a gas or a compressible fluid is dissolved in the liquid paint component at high pressure, resulting in a solution, which is subsequently expanded in the presence of a solid auxiliary component, yielding a solidified liquid paint component.
- An analogous method is described in WO 99/17868, wherein a powder product suitable for the food industry is formed from a liquid food substance or mixture of food substances. It is surprising however that this method is also suitable for liquid paint components, since in the paint industry chemically reactive components are used instead of the relative inert food components.
- hydrophobic liquid paint components also the following method is suitable for solidification.
- the hydrophobic liquid paint component is dispersed in an aqueous solution, subsequently adding silicic acid to the dispersion, followed by spray drying.
- Another suitable method for solidification of hydrophobic liquid paint components comprises dispersing the hydrophobic liquid paint component in an aqueous solution containing a dispersion stabilisation agent and a solid auxiliary component, followed by adding acid to the dispersion and heating, upon which a solidified paint component can be obtained by drying.
- the solid auxiliary component is dissolved in the aqueous solution.
- the solid auxiliary compound suitable for the above method has to be a compound which will form a network upon reaction in the presence of an acid.
- Suitable solid auxiliary compounds for the above method are for example urea/formaldehyde resin, melamine/formaldehyde resin, sodium silicate, and/or urea/melamine/formaldehyde resin.
- the solidified liquid paint component according to the invention can be used in a powder paint binder composition.
- This powder paint binder composition can be used in a powder paint composition, after adding fillers, pigments and/or usual additives. After obtaining the desired powder particle size, for example by grinding and sieving the powder paint composition, a powder paint is yielded.
- the solidified liquid paint component according to the invention can thus also be used in a powder paint.
- the present invention also relates to a method to produce a powder paint binder composition, a powder paint composition and a powder paint. Where in the following part a powder paint binder composition is mentioned, also a powder paint composition and/or a powder paint are to be included unless otherwise stated.
- a suitable method according to the invention for producing a powder paint binder composition involves feeding the solidified liquid paint component according to the invention, or a mixture thereof, to a mixing device with the other components of a powder paint binder composition.
- a powder paint is produced by feeding the solidified liquid paint component according to the invention, or a mixture thereof, to a mixing device with the other components of a powder paint, as pigments, fillers and/or usual additives.
- the particle size of the solidified liquid paint component is not critical, as long as the solidified liquid paint component behaves as a free flowing powder.
- the liquid paint component is preferably released from the solidified liquid paint component, so that the liquid paint component is evenly distributed throughout the resultant coating.
- the release of liquid component can take place during curing of the powder paint and/or during preparation of the powder paint.
- the release of liquid paint component can for example be controlled by the choice of the solid auxiliary component.
- the solid auxiliary component Generally there are two relevant factors that can be influenced by the solid auxiliary component, namely the stability of the solidified liquid paint component under certain mechanical stresses and the stability of the solidified liquid paint component under certain temperatures.
- a solid auxiliary component with a glass transition temperature or melting point such that it is solid at the mixing temperature whilst it is liquid at the curing temperature it is possible to keep the solidified liquid paint component stable, and thus unreactive, during production of the powder paint binder composition or powder paint composition, but reactive during curing of the powder paint.
- the solidified liquid paint component preferably has a particle size of less than 120 ⁇ m.
- This particle size can for example be obtained by using the right temperature and/or pressure during the solidification process involving an expansion step.
- This preference has the additional advantage that a 1-step method for preparing a powder paint, without the usual grinding and sieving can be used, in case the solidified liquid paint component is mixed with other powder paint components with a similar or smaller particle size.
- the invention also relates to a new coating, based on a powder paint.
- powder paints have been developed later than wet paints.
- wet paints a whole scala of wet components, for example liquid crosslinkers are available.
- wet paints a whole scala of wet components, for example liquid crosslinkers are available.
- no solid equivalent has yet been found with respect to material properties of the resultant coating, for example flexibility and outdoor durability.
- Another object of the invention is to provide a coating in which these materials are used, whilst having good coating properties. This object is reached by curing the powder paint composition according to the invention, yielding a coating.
- the powder paint according to the invention can be applied to a substrate by the general method of application of a powder paint.
- Methods of applying powder paints to a substrate is for example described in 'Powder Coatings, Chemistry and Technology' van A. Misev (1991, John Wiley) chapter 6.
- the substrate is not critical. Examples of suitable substrates are both anorganic and organic substrates.
- suitable anorganic substrates are metal, glas, ceramics, stone, concrete.
- suitable organic materials are paper, cardboard, wood, leather and cork.
- the solidified liquid paint component can be used in powder paints for all kinds of applications in all kinds of sectors, for example decorative, outdoor, industrial, automotive, planes, maritime, and/or laundry and household appliances.
- a liquid aliphatic oxirane crosslinker was solidified using a method analogous to the method described in WO 99/17868 with SiO 2 (SipernatTM LS 500 of Degussa) as solid auxiliary component, resulting in a free flowing powder consisting of encapsulated aliphatic oxirane crosslinker.
- Example I yielded an encapsulated aliphatic oxirane crosslinker containing 55% of the liquid aliphatic oxirane crosslinker.
- Example II yielded an encapsulated aliphatic oxirane crosslinker, containing 68% of the liquid aliphatic oxirane crosslinker.
- These encapsulated crosslinkers are examples of solidified liquid paint components. In the following examples is shown that a coating ban be obtained when using these solidified liquid paint components in a powder paint composition that is cured.
- the encapsulated aliphatic oxirane crosslinkers obtained in Example I and II were used in a powder coating composition.
- Encapsulated aliphatic oxirane crosslinker of Example I The percentage refers to the amount of active aliphatic oxirane. Epoxy equivalent weight of the aliphatic oxirane is 168. c) Encapsulated aliphatic oxirane crosslinker of Example II. d) The pigment is of the type KronosTM 2160 e) UranoxTM P7120 is a catalyst masterbatch with 0.72 weight % of catalyst in a polyester resin. (DSM Resins B.V. the Netherlands) f) The flow agent is ResiflowTM-PV5 (Worlee) g) Degassing agent. All compounds were first blended in a BRAUN mixer (MX-40).
- the mixtures were then extruded through a PRISM TCE 16 PC (extrusion temperature 120 °C, 200 rpm) The extruded material was then grounded and classified to a particle size lower than 90 ⁇ m.
- the finished powders were electrostatically sprayed onto test panels (Q-Panel S-46). The coated panels were cured for 10 minutes at 200°C in a hot air oven (Hereaus UT 6120).
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a method for solidification of a liquid paint component wherein the liquid paint component is packed with a solid auxiliary component to form a solidified liquid paint component. The invention further relates to a solidified liquid paint component, to the use of a solidified liquid paint component in a powder paint, to a method for producing a powder paint, to a coating produced by curing a powder paint binder composition, and to a fully or partly coated substrate.
Description
METHOD FOR SOLIDIFICATION OF A LIQUID PAINT COMPONENT
The invention relates to a method for solidification of a liquid paint component. Furthermore it relates to a solidified liquid paint component, to the use of a solidified liquid paint component in a powder paint, to a method for producing a powder paint, to a coating produced by curing a powder paint binder composition, and to a fully or partly coated substrate. Components that are used for powder paint binder compositions are usually not liquid at room temperature for several reasons. One of these reasons is that liquid components would normally not result in a solid end product from which a powder can be made that is stable at room temperature. Liquid components are here and hereafter defined as components with a melt or glass transition temperature below room temperature. One might be able to form a powder from the liquid component by cooling down the liquid sufficiently. To maintain the powder structure, however, the powder should be kept cooled down, also during storage time and processing, which would cost a lot of energy, if even possible. Another reason lies in the efficiency of the mixing process. For powder paint compositions the stoichiometry of the added components is of crucial relevance for the properties of the final coating. Therefore these components are to be adequately mixed, resulting in a relative homogeneous mixture. As is known to the man skilled in the art, however, the flow pattern of liquid components differs from the flow pattern of solid components, resulting in an inhomogeneous mixture. This could lead to problems, for example blocked or fouled equipment.
The object of the present invention is to provide a method for making a liquid component suitable for a powder paint binder composition whilst overcoming the above-mentioned disadvantages.
This object is reached by the present invention in that it provides a method for solidification of a liquid paint component wherein the liquid paint component is packed with a solid auxiliary component to form a solidified liquid paint component. A solidified liquid paint component is here and hereafter defined as a liquid paint component that is packed with a solid auxiliary component resulting in a stable liquid- solid agglomerate that behaves like a solid particle at temperatures below room temperature. In the solidified liquid paint component, the liquid paint component is still present, but encapsulated by the solid auxiliary component.
All liquid paint components are suitable for the present invention. Preferably, the liquid paint components suitable for the present invention are liquid binder components. Liquid binder components are here and hereafter defined as liquid components that are part of the powder paint binder composition. A powder paint binder composition is here and hereafter defined as the paint components that are needed to form a network.
Liquid binder components suitable for the present invention are for example liquid crosslinkers, liquid initiators, liquid catalysts and/or liquid resins, for example liquid alkyd resins, and/or liquid UV-curable compounds. Also mixtures of liquid components may be used.
The combination of a resin and a crosslinker with optionally an initiator and/or a catalyst is generally used in known for the powder paint binder compositions, and is usually referred to in the art as a so-called 2K system (2 component system). The crosslinker is then defined as the compound of which less than 50 wt% in the binder composition, with the resin being the compound of which is equal to or more than 50 wt% is present in the binder composition, the total of both components being 100 wt%.
The present invention, however, makes it possible to use other compositions as usually used in the powder paint industry, for example alkyd resins, or liquid UV-curable compounds, which do not require an additional component to react with to form a network. This is usually referred to in the art as a so-called 1K system (1 component system). It is also possible to have an additional initiator or catalyst in the powder paint binder composition. The 1 K components can for purposes of describing the present invention be part of or constitute a powder paint binder composition. It is preferred that in case of 2K systems a combination of a liquid crosslinker with a liquid resin is avoided, to prevent problems with early network formation.
Once fillers, pigments and usual additives are added to the powder paint binder composition, the composition is called a powder paint composition. After obtaining the desired powder particle size, for example by grinding and sieving the powder paint composition, the composition is called a powder paint. The powder paint can then be applied to a substrate and cured, to form a coating. This results in a fully or partly coated substrate.
Examples of suitable liquid crosslinkers are liquid epoxides, liquid acrylates, liquid methacrylates, liquid vinylethers, liquid isocyanates, liquid amines,
liquid glycidyl ethers, liquid glycidyl esters, liquid hydroxyalkylamides, liquid anhydrides, liquid acids and/or liquid amino resins. Also mixtures of crosslinkers can be used. Examples of suitable liquid epoxides are epoxidised fatty acids, esters and oils, for example epoxidized linseed oil, epoxidized soybean oil. Examples of suitable liquid acrylates are ethyleneglycoldiacrylate, diethyleneglycoldiacrylate, triethyleneglycoldiacrylate, propyleneglycoldiacrylate, dipropyleneglycoldiacrylate, tripropyleneglycoldiacrylate, ethoxylated trismethylolpropanetriacrylate, ethoxylated bisphenol-A-diacrylate, trismethylolpropanetriacrylate, bisphenol-A-diacrylate, laurylacrylate, isobornylacrylate, adducts of 2-hydroxyethyl-, 3-hydroxypropyl, 4-hydroxybutylacrylate with diisocyanates and/or the isocyanurate trimers thereof.
Examples of suitable liquid methacrylates are ethyleneglycoldimethacrylate, diethyleneglycoldimethacrylate, triethyleneglycoldimethacrylate, propyleneglycoldimethacrylate, ethoxylated trismethylolpropanetrimethacrylate, ethoxylated bisphenol-A-dimethacrylate, dipropyleneglycoldimethacrylate, tripropyleneglycoldimethacrylate, trismethylolpropanetrimethacrylate, bisphenol-A-dimethacrylate, laurylmethacrylate, isobomylmethacrylate, adducts of 2-hydroxyethyl-, 3-hydroxypropyl, 4-hydroxybutylmethacrylate with diisocyanates and/or the isocyanurate trimers thereof. Examples of suitable liquid vinylethers are ethyleneglycoldivinylether, diethyleneglycoldivinylether, triethyleneglycoldivinylether, cyclohexanedimethanoldivinylether, butanedioldivinylether, adducts of hydroxyethylvinylether, hydroxybutylvinylether, cyclohexanedimethanolvinylether with diisocyanates and/or the isocyanurate trimers thereof. Examples of suitable liquid isocyanates are 1 ,6-hexanediisocyanate and/or the isocyanurate trimer thereof, 1 ,12-docdecanediisocyanate and/or the isocyanurate trimer thereof, tris-isocyanatononane (3-isocyanatoethyl- 1 ,7diisocyanatoheptane, isophorondiisocyanate, 3,4-isocyanatomethyl-1-methyl- cyclohexyldiisocyanate, and/or 4,4-methylenebis(cyclohexylisocyanate) and/or the isocyanurate trimer thereof. The liquid isocyanates are preferably blocked with for example, caprolactam, methylethylketonoxim, butanol or triazole. Also the so-called internally blocked derivatives of the liquid isocyanates are suitable for this invention. These derivatives are usually referred to as uretdiones.
Examples of suitable liquid amines are hexanediamine, bis(ethylene)triamine, bis(hexamethylene)triamine, 3-aminoethyl-1,7-aminoheptane, and/or tris(aminoethyl)amine.
Examples of suitable liquid glycidyl ethers are ethyleenglycoldiglycidylether, butaandioldiglycidylether, hexaandioldiglyicdylether and/or trimethylolpropanetriglycidylether, bisphenol-A-diglycidylether and oligomers thereof. Examples of suitable liquid glycidyl esters are triglycidyltrimellitate, trigylicdylcitrate, diglycidyladipate, and/or diglycidyl-o-phthalate. Especially suitable are mixtures of triglycidyltrimellitate and diglycidylterephthalate and/or diglycidylisophthalate.
Examples of suitable liquid hydroxyalkylamides are N,N-di-2- hydroxyethyl-acetamide, N,N-di-2-hydroxyethyl-formamide, N,N-di-2-hydroxyethyl- propionamide, N,N-di-2-hydroxyethyl-lauramide, N,N-di-2-hydroxypropyl-acetamide, N,N-di-2-hydroxypropyl- formamide, N,N-di-2-hydroxypropyl- propionamide, N,N-di-2- hydroxypropyl-lauramide, bis(N,N-di-2-hydroxyethyl)-succinamide, bis(N,N-di-2- hydroxyethyl)-glutaramide, bis(N,N-di-2-hydroxypropyl)- succinamide, and/or bis(N,N- di-2-hydroxypropyl)-glutaramide, and mixtures of the above with bis(N,N-di-2- hydroxyethyl)-adipamide and/or bis(N, N-di-2-hydroxypropyl)-adipamide.
Examples of suitable liquid aminoresins are methylolated melamines, urea, benzoguanamines and glycourils, and methyl- and/or butylethers thereof, Uramex™ U238, NF821 , NF822(DSM Resins), Cymel™ 303, 325, 328 (DSM Resins), Setamine™ US138 (AKZO-Nobel), Resamine™ HF155 (Solutia), and/or Maprenal™ MF820 (BASF).
Examples of suitable liquid acids and their anhydrides are fatty acid dimers, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, 2- octenylsuccinic acid, 2-octenyl-succinic anhydride, 2-dodecenyl-succinic acid and/or 2-dodecenyl-succinic anhydride.
Examples of liquid resins suitable for the present invention are all resins that are liquid at room temperature. Suitable resins can be for example liquid polyesters, liquid polyacrylates, liquid polyurethanes and/or liquid epoxide resins, for example bisphenol-A-diglycidylether and oligomers thereof with bisphenol-A. Preferably the liquid resins are alkyd resins and/or UV-curable compounds.
Suitable alkyd resins are for example chain stopped alkyd resins, high solid alkyd resins, waterborne alkyd resins, and/or longoil alkyds, for example based on soybean oil. The alkyd resin can be in pure form, emulsified or dissolved in a solvent.
Suitable UV-curable compounds are for example liquid unsaturated compounds for example (low molecular) epoxy acrylates, polyurethane acrylates, polyester acrylates, acrylic acrylates, vinyl ethers, allyl ethers, epoxy methacrylates,
polyester methacrylates, polyurethane methacrylates, acrylic methacrylates, unsaturated polyesters (based on maleic acid, fumaric acid, itaconic acid). These UV-curable compounds can be monomers, oligomers and/or polymers. The unsaturation of the UV-curable compounds can for example range from 1-8 unsaturations per molecule. The UV-curable compound preferably is a mono-, di-, or polyfunctional acrylate, mono-, di-or polyfunctional methacrylate, or a mixture of any of them.
Suitable liquid initiators can be for example liquid photo-initiators, liquid peroxides and/or liquid azodinitriles. Examples of suitable liquid photo-initiators are Darocure™ 1173, 4265 (CIBA), Irgacure™ 149, 500, 1000, 1700 (CIBA),
Speedcure™ BEN, PDA (Lambson Chemicals), Lucirin™ TPO (BASF), Esacure™ TZT, KTO/25 (Visconti), Cyracure™ UVI-6974(Union Carbide), and/or 3M™ FX-512. Examples of suitable liquid peroxides are dilaurylperoxide, methylethylketonperoxide, tert-amylperoxypivalate (Trigonox™ 125 (AKZO-Nobel)), tert-butylperoxypivalate (Trigonox™ 25), 1 ,1-bis(tert-butylbis(3,5,5-trimethylhexanoyl)peroxide (Trigonox™ 36), 2-5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox™ 141), tert-amylperoxy- 2-ethylhexanoate (Trigonox™ 121 , TBPEH), tert-butylperoxy-2-ethylhexanoate (Trigonox™ 21 S), tert-butylperoxydiethylacetate (Trigonox™ 27), tert- butylperoxyisobutanoate (Trigonox™ 41), tert-butylperoxybenzoate (Trigonox™ C, TBPB-SA-M3), tert-butylcumylperoxide (Trigonox™ T), methylethylketone-peroxide, methylisobutylketoneperoxide (MIKP-NA-1 (Laporte Chemicals)), cyclohexanonperoxide (CHP-HA-1 (Laporte Chemicals)), and/or tert- butylperisononanoate (TBPIN (Laporte Chemicals)).
Suitable solid auxiliary compounds for the invention are all components that are solid at room temperature. It is preferred that the used solid auxiliary component to pack the liquid paint component, will not fully dissolve in the liquid paint component at atmospheric pressure and at room temperature. It is even more preferred that the used solid auxiliary component does not dissolve at all in the liquid paint component at atmospheric pressure and at room temperature. Examples of suitable solid auxiliary components are all solid components that are suitable for use in a powder paint binder composition or a powder paint, such as solid resins, solid crosslinkers, solid initiators, solid fillers, solid pigments and/or solid usual additives.
Examples of suitable solid resins are solid polyesters, solid polyacrylates, solid, polyurethanes and/or solid epoxy resins.
Examples of suitable solid crosslinkers are solid aminoresins, solid epoxides, solid acrylates, solid methacrylates, solid vinylethers, solid isocyanates, solid amines, solid glycidyl ethers, solid glycidyl esters, solid hydroxyalkylamides, solid anhydrides and/or solid acids. Also mixtures of crosslinkers can be used. Examples of suitable solid fillers are silicium oxide, aluminium hydroxide, aluminium oxide, calcium carbonate, talcum, mica, magnesium carbonate, barium sulfate, calcium sulfate (gypsum).
Pigments suitable for the invention can be both inorganic and organic. Examples of suitable inorganic pigments are titanium dioxide, zinc sulphide iron oxide and/or chromium oxide. Examples of suitable organic pigments are azo compounds.
Examples of suitable solid additives are mould release agents (calcium stearate, magnesium stearate), anti-oxidants (phosphites, hydroquinones, aromatic amines), tribocharging agents (tertiary amines), wetting agents (polybutylacrylate, BYK361 , Acronal), degassing agents, flow agents, stabilisers, adhesion promoters and/or anti-foaming agents.
Other examples of suitable solid components are (semi)crystalline waxes, for example Ceridust™ (Clariant GmbH), Luwax™ (BASF), COPO-Wax™ (Coting Products), Ceraflour™ (Byk Cera Chemie), Orgasol™ (Elf Atochem) and/or Lanco Wax™ (Lubrizol Coating Additives). Further examples of suitable solid auxiliary components are silicic acid, zirconium dioxide, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, glass, clays (e.g. montmorillonite, bentonite), melamine, (modified) starch, cellulose, cellulose nitrate, cellulose acetate, cellulose acetate- propionate, cellulose acetate-butyrate. The present invention allows all kinds of combinations between the liquid paint component and the solid auxiliary component.
In a preferred embodiment of the invention the liquid paint component is packed with a solid auxiliary component which is usually present in a powder paint. An example of this embodiment of the invention is wherein the liquid crosslinker and/or radical initiator is solidified with help of a solid resin and/or the usual additives, fillers and/or pigments.
In another preferred embodiment of the invention the liquid paint component is a trimer of HDI, preferably blocked with caprolactam. Preferably the resulting solidified liquid paint component is used as a crosslinker in polyester-based powder paint binder compositions. A powder paint comprising this powder paint binder composition is especially suitable for outdoor durable, and flexible coatings.
There are several methods to form a solidified liquid paint component from a liquid paint component. In' general, the solidified liquid paint component of the present invention is obtainable by packing the liquid paint component with a solid auxiliary component to form a solidified liquid paint component. The amount of used liquid paint component, with respect to the used solid auxiliary component, is preferably larger than 50 wt%, more preferably larger than 60 wt%, even more preferably larger than 80 wt% and most preferably larger than 90 wt%, the total weight of liquid paint component and solid auxiliary component being 100 wt%. For some of the methods it can be needed to adjust the viscosity of the components. It is known to the person skilled in the art how to adjust the viscosity of these components, for example by heating.
A suitable method for solidification of a liquid paint component is mixing the liquid paint component with a molten solid auxiliary component, upon which a solidified paint component is obtained by cooling the resulting mixture. The resulting solidified liquid paint component can then be formed into a powder. The molten solid auxiliary component preferably is a (semi)crystalline wax and/or resins. In a preferred embodiment of this method a compressible fluid is added to the liquid paint component and the molten solid auxiliary component under pressure and the free flowing powder is obtained by expanding the pressurized mixture through a nozzle. In an even more preferred embodiment of this method the molten solid auxiliary component is not dissolvable in the liquid paint component at a pressure of 105 Pa and temperatures below room temperature.
Another method to solidify liquid components is to provide the liquid paint component in a pressurised container, where after a gas or a compressible fluid is dissolved in the liquid paint component at high pressure, resulting in a solution, which is subsequently expanded in the presence of a solid auxiliary component, yielding a solidified liquid paint component. An analogous method is described in WO 99/17868, wherein a powder product suitable for the food industry is formed from a liquid food substance or mixture of food substances. It is surprising however that this method is also suitable for liquid paint components, since in the paint industry chemically reactive components are used instead of the relative inert food components. For hydrophobic liquid paint components also the following method is suitable for solidification. In this method the hydrophobic liquid paint component is dispersed in an aqueous solution, subsequently adding silicic acid to the dispersion, followed by spray drying. This results in solidified liquid paint components whereby the liquid paint component is encapsulated in a silica oxide layer.
Another suitable method for solidification of hydrophobic liquid paint components comprises dispersing the hydrophobic liquid paint component in an aqueous solution containing a dispersion stabilisation agent and a solid auxiliary component, followed by adding acid to the dispersion and heating, upon which a solidified paint component can be obtained by drying. Preferably the solid auxiliary component is dissolved in the aqueous solution. The solid auxiliary compound suitable for the above method has to be a compound which will form a network upon reaction in the presence of an acid. Suitable solid auxiliary compounds for the above method are for example urea/formaldehyde resin, melamine/formaldehyde resin, sodium silicate, and/or urea/melamine/formaldehyde resin.
The solidified liquid paint component according to the invention can be used in a powder paint binder composition. This powder paint binder composition can be used in a powder paint composition, after adding fillers, pigments and/or usual additives. After obtaining the desired powder particle size, for example by grinding and sieving the powder paint composition, a powder paint is yielded. The solidified liquid paint component according to the invention can thus also be used in a powder paint. The present invention also relates to a method to produce a powder paint binder composition, a powder paint composition and a powder paint. Where in the following part a powder paint binder composition is mentioned, also a powder paint composition and/or a powder paint are to be included unless otherwise stated. In the current powder paint producing industry no powder paint binder composition is known using a solidified liquid paint component. This invention provides a method to produce a powder paint binder composition comprising a solidified liquid paint composition according to the invention. There are several known methods to produce a powder paint binder composition. Examples of these methods are described in 'Powder
Coatings, Chemistry and Technology' from A. Misev (1991 , John Wiley) pg. 225-226. The methods known in the art can be used to produce a powder paint binder composition comprising a solidified liquid paint component according to the invention. A suitable method according to the invention for producing a powder paint binder composition involves feeding the solidified liquid paint component according to the invention, or a mixture thereof, to a mixing device with the other components of a powder paint binder composition. According to another embodiment of this method a powder paint is produced by feeding the solidified liquid paint component according to the invention, or a mixture thereof, to a mixing device with the other components of a powder paint, as pigments, fillers and/or usual additives. For
these methods the particle size of the solidified liquid paint component is not critical, as long as the solidified liquid paint component behaves as a free flowing powder.
To ensure good coating properties, the liquid paint component is preferably released from the solidified liquid paint component, so that the liquid paint component is evenly distributed throughout the resultant coating. The release of liquid component can take place during curing of the powder paint and/or during preparation of the powder paint.
The release of liquid paint component can for example be controlled by the choice of the solid auxiliary component. Generally there are two relevant factors that can be influenced by the solid auxiliary component, namely the stability of the solidified liquid paint component under certain mechanical stresses and the stability of the solidified liquid paint component under certain temperatures. For example by choosing a solid auxiliary component with a glass transition temperature or melting point such that it is solid at the mixing temperature whilst it is liquid at the curing temperature it is possible to keep the solidified liquid paint component stable, and thus unreactive, during production of the powder paint binder composition or powder paint composition, but reactive during curing of the powder paint. Analogous one could choose for a solid auxiliary material with a glass transition temperature or melting temperature below the mixing temperature resulting in the release of the liquid component during production of the powder paint binder composition or powder paint composition. When one has chosen for release of the liquid paint component during the preparation of the paint, one should keep in mind that the resulting powder paint binder composition or powder paint composition should still be in solid form at room temperature. The man skilled in the art should therefore pay extra attention to the choice of components.
In yet another embodiment of the method for producing a powder paint binder composition of this invention the solidified liquid paint component preferably has a particle size of less than 120 μm. This particle size can for example be obtained by using the right temperature and/or pressure during the solidification process involving an expansion step. This preference has the additional advantage that a 1-step method for preparing a powder paint, without the usual grinding and sieving can be used, in case the solidified liquid paint component is mixed with other powder paint components with a similar or smaller particle size.
The invention also relates to a new coating, based on a powder paint. Currently only solid components are used in powder paints. Powder paints have been developed later than wet paints. For wet paints a whole scala of wet components, for
example liquid crosslinkers are available. For a lot of these wet components no solid equivalent has yet been found with respect to material properties of the resultant coating, for example flexibility and outdoor durability. Another object of the invention is to provide a coating in which these materials are used, whilst having good coating properties. This object is reached by curing the powder paint composition according to the invention, yielding a coating.
The powder paint according to the invention can be applied to a substrate by the general method of application of a powder paint. Methods of applying powder paints to a substrate is for example described in 'Powder Coatings, Chemistry and Technology' van A. Misev (1991, John Wiley) chapter 6. The substrate is not critical. Examples of suitable substrates are both anorganic and organic substrates.
Examples of suitable anorganic substrates are metal, glas, ceramics, stone, concrete.
Examples of suitable organic materials are paper, cardboard, wood, leather and cork.
Applying the powder paint composition according to the invention to a substrate and curing the composition yields a fully or partly coated substrate. In an preferred embodiment of the invention it is also possible to use the powder paint composition on heat sensitive substrates.
The solidified liquid paint component can be used in powder paints for all kinds of applications in all kinds of sectors, for example decorative, outdoor, industrial, automotive, planes, maritime, and/or laundry and household appliances.
It has been found that the method of the invention also can be applied to toner compositions, wherein the liquid paint component is a liquid toner component. The invention is further elucidated by to the following non-limiting experiments and examples.
Example I and II
Preparation of solidified liquid paint component
A liquid aliphatic oxirane crosslinker was solidified using a method analogous to the method described in WO 99/17868 with SiO2 (Sipernat™ LS 500 of Degussa) as solid auxiliary component, resulting in a free flowing powder consisting of encapsulated aliphatic oxirane crosslinker. Example I yielded an encapsulated aliphatic oxirane crosslinker containing 55% of the liquid aliphatic oxirane crosslinker. Example II yielded an encapsulated aliphatic oxirane crosslinker, containing 68% of the liquid aliphatic oxirane crosslinker. These encapsulated crosslinkers are examples of solidified liquid paint components.
In the following examples is shown that a coating ban be obtained when using these solidified liquid paint components in a powder paint composition that is cured.
Examples 111 and IV
Preparation of a powder coating composition and subsequently curing the composition
The encapsulated aliphatic oxirane crosslinkers obtained in Example I and II were used in a powder coating composition.
The compounds used in the powder paint compositions of Example III and IV are shown in Table 1.
Table I
This is an acid functionalised Uralac™ polyester resin with acidity number of 27
(DSM Resins B.V. the Netherlands)
Encapsulated aliphatic oxirane crosslinker of Example I. The percentage refers to the amount of active aliphatic oxirane. Epoxy equivalent weight of the aliphatic oxirane is 168. c) Encapsulated aliphatic oxirane crosslinker of Example II. d) The pigment is of the type Kronos™ 2160 e) Uranox™ P7120 is a catalyst masterbatch with 0.72 weight % of catalyst in a polyester resin. (DSM Resins B.V. the Netherlands) f) The flow agent is Resiflow™-PV5 (Worlee) g) Degassing agent.
All compounds were first blended in a BRAUN mixer (MX-40). The mixtures were then extruded through a PRISM TCE 16 PC (extrusion temperature 120 °C, 200 rpm) The extruded material was then grounded and classified to a particle size lower than 90 μm. The finished powders were electrostatically sprayed onto test panels (Q-Panel S-46). The coated panels were cured for 10 minutes at 200°C in a hot air oven (Hereaus UT 6120).
The coated panels were subsequently tested for several properties, the results of which are shown in table 2.
Table 2
Gloss was measured according to ISO 2813 under angles of respectively 20 and 60 °. The acetone double rub test was measured according to ISO 2812. It can be seen from the above results that the use of an encapsulated aliphatic oxirane crosslinker in a powder paint composition results in a well-formed network.
Claims
1. Method for solidification of a liquid paint component wherein the liquid paint component is packed with a solid auxiliary component to form a solidified liquid paint component.
2. Method for solidification of a liquid paint component according to claim 1 , characterized in that the liquid paint component is mixed with a molten (semi)crystalline wax and/or molten resin, subsequently cooled down to yield a solidified liquid paint component.
3. Method for solidification of a liquid paint component according to claim 1 , characterised in that the liquid paint component is provided in a pressurised container, where after a gas or a compressible fluid is dissolved in the liquid component at high pressure, resulting in a solution, which is subsequently expanded in the presence of a solid component, yielding a solidified liquid paint component.
4. Method for solidification of a liquid paint component according to claim 1 , characterised in that the liquid paint component is hydrophobic and is dispersed in a suitable liquid, subsequently adding silicic acid to the dispersion, followed by spray drying.
5. Solidified liquid paint component obtainable by the method according to any of claims 1-4.
6. Solidified liquid paint component according to claim 5, characterized in that the liquid paint component is a liquid binder component.
7. Solidified liquid paint component according to any one of claims 5-6, characterized in that the liquid paint component is a crosslinker, preferably with the solid auxiliary component being a solid resin and/or the usual additives, fillers and/or pigments.
8. Solidified liquid paint component according to any one of claims 5-6, characterized in that the liquid paint component is a resin, preferably an alkyd resin or an UV-curable compound, preferably a mono-, di-, or polyfunctional acrylate, mono-, di-, or polyfunctional methacrylate, or a mixture of any of them.
9. Powder paint binder composition comprising a solidified liquid paint component according to claims 5-8.
10. Powder paint comprising a binder composition according to claim 9.
11. The use of a solidified liquid paint component according to any one of claims 5-8 to produce a powder paint.
12. Method for producing a powder paint according to claim 9, characterised in that the solidified liquid paint component according to any one of claims 5-8, preferably with a particle size of less than 120 μm, is fed into a mixing device to be mixed with the other components of the powder paint.
13. Coating produced by curing the powder paint according to any of claims 10-12.
14. Fully or partly coated substrate with the coating according to claim 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02763086A EP1444300A1 (en) | 2001-09-21 | 2002-09-23 | Method for solidification of a liquid paint component |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01000493 | 2001-09-21 | ||
| EP01000493A EP1295915A1 (en) | 2001-09-21 | 2001-09-21 | Method for solidification of a liquid paint component |
| EP02763086A EP1444300A1 (en) | 2001-09-21 | 2002-09-23 | Method for solidification of a liquid paint component |
| PCT/NL2002/000609 WO2003025073A1 (en) | 2001-09-21 | 2002-09-23 | Method for solidification of a liquid paint component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1444300A1 true EP1444300A1 (en) | 2004-08-11 |
Family
ID=8176067
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01000493A Withdrawn EP1295915A1 (en) | 2001-09-21 | 2001-09-21 | Method for solidification of a liquid paint component |
| EP02763086A Withdrawn EP1444300A1 (en) | 2001-09-21 | 2002-09-23 | Method for solidification of a liquid paint component |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01000493A Withdrawn EP1295915A1 (en) | 2001-09-21 | 2001-09-21 | Method for solidification of a liquid paint component |
Country Status (2)
| Country | Link |
|---|---|
| EP (2) | EP1295915A1 (en) |
| WO (1) | WO2003025073A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997904A (en) * | 2018-07-28 | 2018-12-14 | 南京艾利克斯电子科技有限公司 | A kind of antistatic powdery paints of high adhesion force and preparation method thereof |
| EP3919573A1 (en) * | 2020-06-03 | 2021-12-08 | Akzo Nobel Coatings International B.V. | One-component powder coating composition and substrate coated with such powder coating composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102977A (en) * | 1990-01-18 | 1992-04-07 | Ruco Polymer Corporation | Internally catalyzed sulfonate bearing hydroxyl terminated powder coating polyesters |
| GB9014646D0 (en) * | 1990-07-02 | 1990-08-22 | Courtaulds Coatings Holdings | Coating compositions |
| DE4225663A1 (en) * | 1992-08-04 | 1994-02-10 | Messer Griesheim Gmbh | Powder paint with low stoving temp. and short stoving time - by heating components without hardener to give viscous melt, adding liq. hardener and cooling immediately with liq. nitrogen@ |
| US5789493A (en) * | 1993-05-11 | 1998-08-04 | Dsm N.V. | Powder print from melt-mixing and grinding binder particles and additives |
| ATE204787T1 (en) * | 1997-10-06 | 2001-09-15 | Adalbert Raps Stiftung | METHOD FOR PRODUCING A POWDERED PRODUCT FROM A LIQUID SUBSTANCE OR MIXTURE OF SUBSTANCES |
-
2001
- 2001-09-21 EP EP01000493A patent/EP1295915A1/en not_active Withdrawn
-
2002
- 2002-09-23 EP EP02763086A patent/EP1444300A1/en not_active Withdrawn
- 2002-09-23 WO PCT/NL2002/000609 patent/WO2003025073A1/en not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03025073A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003025073A1 (en) | 2003-03-27 |
| EP1295915A1 (en) | 2003-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0906360B1 (en) | Dispersion process | |
| EP1261668B1 (en) | Process for preparing an aqueous powder coating dispersion | |
| EP1593717B1 (en) | Raw mix powder compositions and methods of making the same | |
| TW314544B (en) | ||
| JP2620058B2 (en) | Aqueous coating composition for automotive painting | |
| AU772342B2 (en) | Coating material containing a mixture of silicic acids and urea and/or urea derivatives | |
| CN102007193A (en) | Powder coated proppant and method of making the same | |
| AU707368B2 (en) | Coating compositions with flow modifiers and the flow modifiers and multilayered coatings | |
| US5977258A (en) | Microgel | |
| EP0956162A1 (en) | Color-plus-clear composite coating, process for making it amd coated article | |
| CN101341219A (en) | Powder coating compostion providing low gloss | |
| CN106833364A (en) | The method for repairing defect in motor vehicle coating | |
| US9353254B1 (en) | Powder coating flow aid | |
| EP1444300A1 (en) | Method for solidification of a liquid paint component | |
| JPH10501293A (en) | Process for the preparation of powder coating compositions and their use for preparing coatings | |
| KR20000016135A (en) | Powder paint for multilayered painting | |
| EP2113537A1 (en) | Powder coating composition | |
| CZ20031076A3 (en) | Hot melt paint composition | |
| WO2001028306A2 (en) | Process for preparing an aqueous powder coating dispersion | |
| CN101248145B (en) | Process for preparing a powder coating composition | |
| US20100331456A1 (en) | Powder Coating Composition with New Pigment | |
| JPS582968B2 (en) | Aqueous desperation coating composition and application method for molded products | |
| PL235856B1 (en) | Coating composition in the form of the thermally hardened powder | |
| US9963595B2 (en) | Coating composition and method for producing powder coating | |
| WO1995028448A1 (en) | Method for preparing liquid coating compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20040302 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
| 17Q | First examination report despatched |
Effective date: 20050310 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 20120403 |