EP0000505B1 - Metal complexes, process for their preparation and their application as pigments - Google Patents
Metal complexes, process for their preparation and their application as pigments Download PDFInfo
- Publication number
- EP0000505B1 EP0000505B1 EP78100373A EP78100373A EP0000505B1 EP 0000505 B1 EP0000505 B1 EP 0000505B1 EP 78100373 A EP78100373 A EP 78100373A EP 78100373 A EP78100373 A EP 78100373A EP 0000505 B1 EP0000505 B1 EP 0000505B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal complex
- complex compounds
- substituted
- parts
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000049 pigment Substances 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 title description 17
- 239000002184 metal Substances 0.000 title description 17
- 238000002360 preparation method Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000004922 lacquer Substances 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- -1 Metal complex compounds Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- AMAQHIAMQNRYPP-UHFFFAOYSA-N 2-hydroxy-4-methyl-6-oxo-1H-pyridine-3-carbaldehyde Chemical compound CC1=CC(O)=NC(O)=C1C=O AMAQHIAMQNRYPP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000000485 pigmenting effect Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 125000001624 naphthyl group Chemical group 0.000 claims 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000003973 paint Substances 0.000 description 14
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000004696 coordination complex Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- JJHVYGVVMBYCMQ-UHFFFAOYSA-N 6-hydroxy-4-methyl-1h-pyridin-2-one Chemical compound CC=1C=C(O)NC(=O)C=1 JJHVYGVVMBYCMQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 0 CC(C(CNc1c(*)ccc(Cl)c1)=C(N1)O*)=C[C@@]1O Chemical compound CC(C(CNc1c(*)ccc(Cl)c1)=C(N1)O*)=C[C@@]1O 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FHMMQQXRSYSWCM-UHFFFAOYSA-N 1-aminonaphthalen-2-ol Chemical compound C1=CC=C2C(N)=C(O)C=CC2=C1 FHMMQQXRSYSWCM-UHFFFAOYSA-N 0.000 description 1
- RMSOEGBYNWXXBG-UHFFFAOYSA-N 1-chloronaphthalen-2-ol Chemical compound C1=CC=CC2=C(Cl)C(O)=CC=C21 RMSOEGBYNWXXBG-UHFFFAOYSA-N 0.000 description 1
- SSHIVHKMGVBXTJ-UHFFFAOYSA-N 1-nitronaphthalen-2-ol Chemical compound C1=CC=CC2=C([N+]([O-])=O)C(O)=CC=C21 SSHIVHKMGVBXTJ-UHFFFAOYSA-N 0.000 description 1
- ZOQOPXVJANRGJZ-UHFFFAOYSA-N 2-(trifluoromethyl)phenol Chemical compound OC1=CC=CC=C1C(F)(F)F ZOQOPXVJANRGJZ-UHFFFAOYSA-N 0.000 description 1
- SWFNPENEBHAHEB-UHFFFAOYSA-N 2-amino-4-chlorophenol Chemical compound NC1=CC(Cl)=CC=C1O SWFNPENEBHAHEB-UHFFFAOYSA-N 0.000 description 1
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WONRDHPFOHAWOG-UHFFFAOYSA-N 2-chloronaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C(Cl)C=CC2=C1 WONRDHPFOHAWOG-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- ZHVPTERSBUMMHK-UHFFFAOYSA-N 3-aminonaphthalen-2-ol Chemical compound C1=CC=C2C=C(O)C(N)=CC2=C1 ZHVPTERSBUMMHK-UHFFFAOYSA-N 0.000 description 1
- GJQLGNVVWXJVMA-UHFFFAOYSA-N 5-ethyl-6-hydroxy-4-methyl-1h-pyridin-2-one Chemical compound CCC=1C(C)=CC(=O)NC=1O GJQLGNVVWXJVMA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- YFDUWSBGVPBWKF-UHFFFAOYSA-N Butyl salicylate Chemical compound CCCCOC(=O)C1=CC=CC=C1O YFDUWSBGVPBWKF-UHFFFAOYSA-N 0.000 description 1
- RVTMFKLYYJMPGT-UHFFFAOYSA-N C(=O)C=1C(=NC(=CC1C)O)O.[K] Chemical compound C(=O)C=1C(=NC(=CC1C)O)O.[K] RVTMFKLYYJMPGT-UHFFFAOYSA-N 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 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
- 239000012043 crude product Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- UCFFGYASXIPWPD-UHFFFAOYSA-N methyl hypochlorite Chemical compound COCl UCFFGYASXIPWPD-UHFFFAOYSA-N 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229940035339 tri-chlor Drugs 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/69—Two or more oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
- C09B55/002—Monoazomethine dyes
- C09B55/003—Monoazomethine dyes with the -C=N- group attached to an heteroring
Definitions
- Metal complexes of the formula II the benzene nucleus I can also be substituted as stated above, in particular simply in the para position to the oxygen, that is to say the 4-position, are of particular interest.
- reaction temperatures Temperatures from 60 ° C. to the reflux temperature of the solvent can be considered as reaction temperatures.
- the preferred reaction temperatures are from 80 to 120 ° C.
- the reaction is usually complete within 2 to 8 hours.
- the azomethine formed in this reaction can be metallized without isolation, but isolation of the azomethine before the metallization is also possible. However, it is generally sufficient to metallize the azomethine in a suitable solvent without isolation.
- the metal-free azomethine is reacted in the solvent or solvent mixture used for the azomethine condensation with a metal salt, preferably an acetate, for example copper (II) acetate, under the same conditions as in the production of azomethine. It may be advisable to keep the pH of the solution between 5 and 6, which can be done, for example, by the successive addition of sodium acetate solution.
- the conversion of the potassium or sodium salt into the metal-free compound takes place in such a way that 19.1 parts of the product obtained are suspended in 200 parts of a mixture of 160 parts of acetic acid and 40 parts of water and the reaction mixture is concentrated to 50 parts in vacuo. After the concentrated solution has been left to stand, the metal-free compound crystallizes out. By redissolving and recrystallizing from a mixture of 160 parts of ethanol and 40 parts of water, the pure 3-formyl-4-methyl-2,6-dihydroxypyridine with a melting point of 180 to 182 ° C. is obtained.
- alkyd-melamine resin stoving enamel Containing 2 parts by weight of a 5 weight percent of pigment, by for 60 minutes rubbing on the Paint Shaker according to Example 5 prepared alkyd-melamine resin stoving enamel be 2.5 parts by weight of mixed a Einbrenn volunteerlacks which also contains alkyd-melamine resin-based 20 weight percent TiO 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pyridine Compounds (AREA)
- Paints Or Removers (AREA)
Description
Die Erfindung betrifft wertvolle Metallkomplexe der Formel I
Metallkomplexe der Formel II
Die neuen Metallkomplexe können dadurch hersetellt werden, daß man 3 - Formyl - 4 - methyl - 2,6 - dihydroxy - pyridin bzw. ein Alkali- oder Erdalkalisalz davon mit einer ortho-Aminohydroxyverbindung der Formel III
Als Ausgangsprodukte sind z.B. folgende ortho - Aminohydroxy - verbindungen geeignet: ortho-Aminophenol, 2 - Amino - 4 - (oder 3- oder 5-oder 6-)nitrophenol, 2 - Amino - 4 - (oder 3-oder 5-oder 6-)chloro - phenol, 2 - Amino - 4 - (oder 3- oder 5-oder 6-)bromo - phenol, 2 - Amino - 4 - (oder 3- oder 5- oder 6-)cyano - phenol, 2 - Amino - 4 - (oder 3- oder 5- oder 6-) methoxycarbonylphenol, 2 - Amino - 4 - (oder 3- oder 5- oder 6-)äthoxycarbonylphenol, 2-Amino - 4 - (oder 3-)butoxycarbonyl-phenol, 2 - Amino- 4 - (oder 5-) trifluormethyl - phenol, 2 - Amino - 4 - (oder 5-) - carbonamido - phenol, 2 - Amino - 4- (oder 5-)dimethylcarbonamido - phenol, 2 - Amino - 4 - (oder 5-) äthylcarbonamido - phenol, 2 - Amino - 1 - naphthol, 1 - Amino - 2 - naphthol, 2 - Amino - 3 - naphthol, 2 - Amino - 4 - (oder 5 - oder 7 -)chloro - 1 - naphthol, 1 - Amino - 4 - (oder 5-, 6- oder 7-)chloro - 2 - naphthol, 1 - Amino - 3 - (oder 4-oder 8-)nitro - 2 - naphthol.The starting products are e.g. the following ortho-aminohydroxy compounds are suitable: ortho-aminophenol, 2 - amino - 4 - (or 3 or 5 or 6) nitrophenol, 2 - amino - 4 - (or 3 or 5 or 6) chloro - phenol, 2 - amino - 4 - (or 3 or 5 or 6) bromo - phenol, 2 - amino - 4 - (or 3 or 5 or 6) cyano - phenol, 2 - amino - 4 - (or 3- or 5- or 6-) methoxycarbonylphenol, 2 - amino - 4 - (or 3- or 5- or 6-) ethoxycarbonylphenol, 2-amino - 4 - (or 3-) butoxycarbonylphenol, 2 - amino - 4 - (or 5-) trifluoromethylphenol, 2 - amino - 4 - (or 5-) - carbonamido - phenol, 2 - amino - 4- (or 5-) dimethylcarbonamido - phenol, 2 - amino - 4 - ( or 5-) ethylcarbonamido - phenol, 2 - amino - 1 - naphthol, 1 - amino - 2 - naphthol, 2 - amino - 3 - naphthol, 2 - amino - 4 - (or 5 - or 7 -) chloro - 1 - naphthol, 1 - amino - 4 - (or 5, 6 or 7) chloro - 2 - naphthol, 1 - amino - 3 - (or 4 or 8 -) nitro - 2 - naphthol.
Die Verbindungen der Formel lll sind zumeist bekannt bzw. können leicht nach den für die Herstellung von ortho - Amino - hydroxyverbindungen bekannten Methoden synthetisiert werden. Das 3 - Formyl - 4 - methyl - 2,6 - dihydroxy - pyridin und seine Alkali - oder Erdalkalisalze sind neu. Es kann leicht, wie in den nachfolgenden Beispielen beschrieben, hergestellt werden. Von dem 3 - Formyl - 4 - methyl - 2,6 - dihydroxy - pyridin sind auch andere tautomere Formen, z.B. das 2 - Hydroxy - 3 - formyl - 4 - methylpyridon - (6) denkbar. Von seinen Salzen sind besonders das Natrium- und Kaliumsalz geeignet. Auch von den Metallkomplexen der allgemeinen Formel sind noch andere tautomere Formen denkbar. Selbstverständlich wird von der vorliegenden Erfindung jede der möglichen tautomeren Formen umfaßt. Die Umsetzung des 3-Formyl-4-methyl-2,6-dihydroxy-pyridins oder des entsprechenden Alkali- oder Erdalkalisalzes mit der ortho-Amino-hydroxy-Verbindung wird in geeigneten organischen Lösungsmitteln, beispielsweise Alkoholen mit 1 bis 5 C-Atomen, Glykoläthern, wie z.B. Äthylenglykoldimethyläther, Eisessig, aprotischen Lösungsmitteln, wie z.B. Toluol, Tetrachlorkohlenstoff, 1,4-Dioxan, Tetrahydrofuran und dergleichen, insbesondere dipolar aprotischen Lösemitteln, wie z.B. Dimethylformamid, Dimethylsulfoxid, N-Methylpyrolidon, Tetramethylensulfon und dergleichen oder Wasser oder Gemischen davon, zweckmäßigerweise unter einer Atmosphäre eines Inertgases, wie Stickstoff, bei erhöhten Temperaturen durchgeführt. Als Reaktionstemperaturen können Temperaturen von 60°C bis zur Rückflußtemperatur des Lösungsmittels in Betracht kommen. Die bevorzugten Reaktionstemperaturen betragen von 80 bis 120°C. Die Umsetzung ist normalerweise innerhalb von 2 bis 8 Stunden beendet. Das bei dieser Umsetzung entstandene Azomethin kann ohne Isolierung metallisiert werden, aber auch eine Isolierung des Azomethins vor der Metallisierung ist möglich. Es genügt jedoch im allgemeinen, das Azomethin ohne Isolierung in einem geeigneten Lösungsmittel zu metallisieren. Zu diesem Zweck wird das metallfreie Azomethin in dem zur Azomethinkondensation benutzten Lösungsmittel oder Lösungsmittelgemisch mit einem Metallsalz, vorzugsweise einem Acetat, z.B. Kupfer - II - acetat, unter den gleichen Bedingungen wie bei der Azomethinherstellung umgesetzt. Dabei kann es zweckmäßig sein, den pH-Wert der Lösung zwischen 5 und 6 zu halten, was z.B. durch sukzessive Zugabe von Natriumacetatlösung erfolgen kann.The compounds of the formula III are mostly known or can easily be synthesized by the methods known for the preparation of ortho-amino-hydroxy compounds. The 3-formyl-4-methyl-2,6-dihydroxy-pyridine and its alkali or alkaline earth salts are new. It can be easily prepared as described in the examples below. Other tautomeric forms of 3-formyl-4-methyl-2,6-dihydroxy-pyridine, for example 2-hydroxy-3-formyl-4-methylpyridone - (6), are also conceivable. Of its salts, the sodium and potassium salts are particularly suitable. Other tautomeric forms of the metal complexes of the general formula are also conceivable. Of course, the present invention encompasses any of the possible tautomeric forms. The reaction of the 3-formyl-4-methyl-2,6-dihydroxy-pyridine or the corresponding alkali metal or alkaline earth metal salt with the ortho-amino-hydroxy compound is carried out in suitable organic solvents, for example alcohols with 1 to 5 carbon atoms, Glycol ethers such as ethylene glycol dimethyl ether, glacial acetic acid, aprotic solvents such as toluene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran and the like, especially dipolar aprotic solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrolidone, tetra methylene sulfone and the like or water or mixtures thereof, conveniently carried out under an atmosphere of an inert gas such as nitrogen at elevated temperatures. Temperatures from 60 ° C. to the reflux temperature of the solvent can be considered as reaction temperatures. The preferred reaction temperatures are from 80 to 120 ° C. The reaction is usually complete within 2 to 8 hours. The azomethine formed in this reaction can be metallized without isolation, but isolation of the azomethine before the metallization is also possible. However, it is generally sufficient to metallize the azomethine in a suitable solvent without isolation. For this purpose, the metal-free azomethine is reacted in the solvent or solvent mixture used for the azomethine condensation with a metal salt, preferably an acetate, for example copper (II) acetate, under the same conditions as in the production of azomethine. It may be advisable to keep the pH of the solution between 5 and 6, which can be done, for example, by the successive addition of sodium acetate solution.
Die metallfreien Azomethine sind gelborgangefarbene bis braune Produkte, während die metallhaltigen neuen Metallkomplexe normalerweise gelbstichig-grün bis olivgrün und in den üblichen Lö-, sungsmitteln nur schwer bis sehr schwer löslich sind. Die neuen Metallkomplexe eignen sich daher als farbstarke lösungs- und temperaturbeständige, besonders aber hervorragend licht- und wetterechte Pigmente zur Herstellung von Druckfarben, zum Färben von Kunststoffen in der Masse und als Spinnfarbstoffe und insbesondere zur Herstellung von Lacken und Anstrichstoffen. Aufgrund der guten Echtheiten sind die Pigmente besonders auch in Form ihrer Metallic-Lacke (Aluminium-Lacke) für hochwertige Außen-(Auto-)lacke interessant.The metal-free azomethines are yellow-orange to brown-colored products, while the metal-containing new metal complexes are usually yellowish-green to olive-green and are difficult to very difficult to dissolve in the usual solvents. The new metal complexes are therefore suitable as strong-color, solution-resistant and temperature-resistant, but especially excellent light and weather-resistant pigments for the production of printing inks, for coloring plastics in bulk and as spinning dyes and in particular for the production of lacquers and paints. Due to the good fastness properties, the pigments are particularly interesting in the form of their metallic paints (aluminum paints) for high-quality exterior (car) paints.
Die metallfreien und metallhaltigen Azomethine weisen im Pyridinkern eine freie Stellung auf, an die noch Diazokomponenten angekuppelt werden können. So ist es möglich, wertvolle metallfreie und metallhaltige Azomethine herzustellen, die noch eine Azogruppe enthalten.The metal-free and metal-containing azomethines have a free position in the pyridine nucleus to which diazo components can still be coupled. This makes it possible to produce valuable metal-free and metal-containing azomethines which still contain an azo group.
Wenn nichts anderes angegeben ist, sind in den nachfolgenden Beispielen Teile in Gewichtsteilen und Temperaturen in Grad Celcius angegeben.Unless otherwise indicated, parts in parts by weight and temperatures in degrees Celsius are given in the examples below.
21,1 g 2 - Hydroxy - 3 - formyl - 4 - methylpyridon - (6) als Kaliumsalz werden zusammen mit 14,9 g 4 - Chlor - 2 - aminophenol in 300 ml Eisessig suspendiert und unter Stickstoffatmosphäre 3 Stunden zum Sieden erhitzt (ca. 118°C). Dann werden 10 g Kupfer - II - acetat, gelöst in 300 ml Dimethylformamid, zugegeben, und es wird eine Stunde bei 140°C gehalten. Nach Abkühlen wird abgesaugt, mit Methanol und Wasser gewaschen und getrocknet. Man erhält 33,5 g eines gelbstichig-grünen Metallkomplexes der Formel
1200 Teile Wasser werden unter Einleiten von Stickstoff zum Sieden erhitzt und unter Stickstoffeinleitung auf 20°C abgekühlt. Dann gibt man 57,3 Teile 2 - Hydroxy - 3 - formyl - 4 - methylpyridon-(6) und 3,4,5 Teile o-Aniinophenol zu, erhitzt 4 Stunden am Rückfluß, saugt heiß ab und wäscht mit 1000 Teilen 80°C heißem Wasser. Die erhaltene gelbe Paste des Azomethins gibt man in 6000 Teile Wasser, fügt 60 Teile Kupfer - 11 - acetat zu und erhitzt 3 1/2 Stunden am Rückfluß, wobei man durch sukzessive Zugabe von 1100 Teilen 10%iger Natrium-acetat-Lösung den pH-Wert zwischen 5 und 6 hält. Am Ende der Reaktion beträgt der pH-Wert 5,4. Das Produkt wird heiß abgesaugt und mit 1200 Teilen 80°C heißem Wasser gewaschen und bei 40°C im Vakuum getrocknet, Man erhält 44 Teile des Azomethin-Kupfer-Komplexes der Formel
Das erhaltene olivgrüne Pigment kann in üblicher Weise zu einer Druckfarbe verarbeitet werden, die farbstarke Drucke von hervorragender Lichtechtheit liefert.The olive-green pigment obtained can be processed in the customary manner to give a printing ink which gives strong-color prints with excellent lightfastness.
Ein unter Verwendung des erhaltenen Pigments in üblicher Weise hergestellter Autoeinbrennlack zeigte nach dem Einbrennen sehr gute Lichtechtheit, Wetterrechtheit und Überspritzechtheit.An automotive stoving varnish produced in the usual way using the pigment obtained showed very good lightfastness, weatherfastness and overspray fastness after the stoving.
Ähnlich wie im vorstehenden Beispiel 2 wurden die in den nachfolgenden Tabellen angegebenen Metallkomplexe hergestellt:
Das in den vorstehenden Beispielen als Ausgangsprodukt benutzte 6 - Hydroxy - 3 - formyl 4 - methylpyridon - (6) bzw. sein Natriumsalz kann, ausgehend vom 4 - Methyl - 2,6 - dihydroxypyridin, folgendermaßen hergestellt werden:
- 125 Teile 4 - Methyl - 2,6 - dihydroxypyridin in 400 Teilen Äthanol werden mit 80 Teilen Natriumacetat, gelöst in 100 Teilen Wasser, und 148 Teilen Chloral in 400 Teilen Wasser zusammengegeben und das Gemisch 8 Stunden bei 20°C gerührt, anschließend läßt man weitere 48 Stunden bei Zimmertemperatur stehen, saugt dann das ausgefallene Produkt ab, wäscht den Rückstand mit Wasser und trocknet bei 30°C im Vakuum. Man erhält so 218 Teile (=80% d.Th.) 3 - (ß,ß, ß - TrichIor - α - hydroxy) - äthyl - 4 - methyl - 2,6 - dihydroxypyridin, das nach Umkristallisation aus Essigsäureäthylester einen Schmelzpunkt von 195°C besitzt.
- 272,5 Teile 3-(ß,ß,ß - Trichlor - a - hydroxy)äthyl - 4 - methyl - 2,6 - dihydroxypyridin werden in 3000 Teile Äthanol eingetragen und mit einer Lösung von 500 Teilen Kaliumhydroxid in 400 Teilen Wasser und 1700 Teilen Äthanol versetzt. Das Reaktionsgemisch wird 30 Minuten am Rückfluß unter Rühren am Sieden gehalten, dann auf 20°C abgekühlt. Das hierbei ausgeschiedene Produkt wird abgesaugt, mit 200 Teilen Äthanol gewaschen und getrocknet. Das so erhaltene Rohprodukt kann durch Waschen bis zur neutralen Reaktion mit verdünnter Essigsäure von anhaftender überschüssiger Kalilauge befreit werden. Man erhält so 94 Teile des Kalium - 3 - formyl - 4 - methyl - 2,6 - dihydroxypyridins (= 49% d.Th.), das nach Umkristallisation aus Wasser einen Schmelzpunkt von über 350°C besitzt.
- 125 parts of 4-methyl-2,6-dihydroxypyridine in 400 parts of ethanol are combined with 80 parts of sodium acetate, dissolved in 100 parts of water, and 148 parts of chloral in 400 parts of water, and the mixture is stirred at 20 ° C. for 8 hours, after which the mixture is left stand for a further 48 hours at room temperature, then the precipitated product is suctioned off, the residue is washed with water and dried at 30 ° C. in vacuo. This gives 218 parts (= 80% of theory) of 3 - (ß, ß, ß - TrichIor - α - hydroxy) - ethyl - 4 - methyl - 2,6 - dihydroxypyridine which, after recrystallization from ethyl acetate, has a melting point of 195 ° C.
- 272.5 parts of 3- (ß, ß, ß-trichloro-a-hydroxy) ethyl-4-methyl-2,6-dihydroxypyridine are introduced into 3000 parts of ethanol and with a solution of 500 parts of potassium hydroxide in 400 parts of water and 1700 Parts of ethanol are added. The reaction mixture is refluxed with stirring for 30 minutes, then cooled to 20 ° C. The product which separates out is filtered off with suction, washed with 200 parts of ethanol and dried. The crude product thus obtained can be freed from adhering excess potassium hydroxide solution until the reaction with neutral acetic acid is neutral. This gives 94 parts of potassium-3-formyl-4-methyl-2,6-dihydroxypyridine (= 49% of theory) which, after recrystallization from water, has a melting point of above 350 ° C.
Verwendet man anstelle von Kaliumhydroxid Natriumhydroxid, so erhält man das entsprechende Natriumsalz.If sodium hydroxide is used instead of potassium hydroxide, the corresponding sodium salt is obtained.
Die Überführung des Kalium- oder Natriumsalzes in die Metallfreie Verbindung geschieht in der Weise, daß 19,1 Teile des erhaltenen Produkts in 200 Teilen eines Gemischs aus 160 Teilen Essigsäure und 40 Teilen Wasser suspendiert werden und das Reaktionsgemisch im Vakuum auf 50 Teile eingeengt wird. Nach Stehenlassen der eingeengten Lösung kristallisiert die metallfreie Verbindung aus. Durch Umlösen und Umkristallisieren aus einem Gemisch aus 160 Teilen Äthanol und 40 Teilen Wasser erhält man das reine 3 - Formyl - 4 - methyl - 2,6 - dihydroxypyridin vom Schmelzpunkt 180 bis 182°C.
4,5 g des nach Beispiel 1 erhaltenen Metallkomplexes werden mit 25,5 g eines Anreibelacks, bestehend aus einer 20%igen Lösung von Alkyldharzlack in Xylol auf der Vibrationskugelmühle 45 Minuten geschüttelt, mit 60 g Klarlack, bestehend aus 52,5 g einer 70%igen Alkydharzlösung in Xylol, 35 g einer 55%igen Melaminharzlösung in Butanol, 2,5 g Butylglykol, 5 g Butanol und 5 g Lackbenzin versetzt. Man erhält so einen klaren gelbstichig-grünen Volltonlack, der auf ein Aluminiumblech gespritzt und 30 Minuten bei 140°C eingebrannt eine gelbstichig-grüne Färbung von einwandfreier Uberlackierechtheit und ausgezeichneter Licht- und Wetterechtheit ergibt.4.5 g of the metal complex obtained according to Example 1 are shaken with 25.5 g of a rub-on lacquer consisting of a 20% solution of alkyl resin lacquer in xylene on the vibrating ball mill for 45 minutes, with 60 g clear lacquer consisting of 52.5 g of a 70 % alkyd resin solution in xylene, 35 g of a 55% melamine resin solution in butanol, 2.5 g butyl glycol, 5 g butanol and 5 g white spirit. This gives a clear yellowish-green full-tone lacquer, which is sprayed onto an aluminum sheet and baked for 30 minutes at 140 ° C. gives a yellowish-green coloration of perfect fastness to overcoating and excellent light and weather fastness.
Eine Mischung von 62,5 ml Glasperlen, 3 mm Durchmesser, 4,5 g des nach Beispiel 2 erhaltenen Metallkomplexes und 25,2 g Acryl Anreibelack 25%ig wird in einem verschlossenen Plastikbecher von 125 ml Inhalt 30 Minuten auf dem Paintshaker geschüttelt. Anschließend werden 60,3 g eines 48%igen Acryl-Melaminharz-Klarlacks zugemischt und sodann die Glaskugeln durch Sieben entfernt.A mixture of 62.5 ml glass beads, 3 mm in diameter, 4.5 g of the metal complex obtained according to Example 2 and 25.2 g of acrylic rubbing varnish 25% is shaken in a sealed plastic cup of 125 ml for 30 minutes on the paint shaker. 60.3 g of a 48% acrylic melamine resin clear lacquer are then mixed in and the glass balls are then removed by sieving.
Der so hergestellte in bezug auf das organische Pigment 5%ige Volltonlack wird mit einem 3% Aluminium-Pigment enthaltenden Acryl-Melaminharzlack im Gewichtsverhältnis 3 : 5 vermischt.The 5% full-tone paint produced in this way with respect to the organic pigment is mixed with an acrylic melamine resin paint containing 3% aluminum pigment in a weight ratio of 3: 5.
Anschließend wird mit Xylol, Butanol and Solvesso 100, ein aus mehreren Aromaten bestehendes Lösemittelgemisch, (1 : 2,3 : 3,3) auf Spritzviskosität 4" (Viskospatel) eingestellt und dieser Metalleffektlack auf ein mit einem Washprimer und einem Einbrennweißlack wie üblich grundiertes Blech mit der Spritzpistole (Düse 1,5 mm Durchmesser, Spritzdruck 4 bar) in 6 waagerechten Gängen aufgebracht.Subsequently, with xylene, butanol and Solvesso 100, a solvent mixture consisting of several aromatics, (1: 2.3: 3.3) the spray viscosity is set to 4 "(visco spatula) and this metallic effect paint is primed with a wash primer and a baking white paint as usual Sheet with the spray gun (nozzle 1.5 mm diameter, spray pressure 4 bar) applied in 6 horizontal passages.
Nach dem Ablüften wird 30 Minuten bei 140°C im Trockenschrank eingebrannt. Die Echtheiten der Lackierung, insbesondere die Licht- und Wetterechtheiten, sind hervorragend.After flashing off, bake in the drying cabinet at 140 ° C for 30 minutes. The fastness of the paint, especially the light and weather fastness, are excellent.
Eine Mischung von 62,5 ml Glasperlen, 3 mm Durchmesser, 3,8 g Metallkomplexe nach Beispiel 1 und 27,4 g Alkyd-Anreibelack 25 %ig wird in einem verschlossenen Plastikbecher von 125 ml Inhalt 60 Minuten auf dem Paintshaker geschüttelt. Anschließend werden 44,8 g eines 56%igen Alkyd-Melamin-harz-Klarlacks zugemischt und sodann die Glaskugeln durch Sieben entfernt. Der so hergestellte 5 Gewichtsprozente Pigment enthaltende Vollton-Farblack wird mittels eines Handcoaters in einer Naßfilmstärke von 75 µm auf ein weißes Kärtchen mit schwarzem Querstreifen aufgezogen. Nach dem Ablüften wird 30 Minuten bei 140°C im Trockenschrank eingebrannt. Es resultiert ein farbstarker gelbstichig-grüner Überzug mit hervorragenden Echtheiten.A mixture of 62.5 ml glass beads, 3 mm in diameter, 3.8 g of metal complexes according to Example 1 and 27.4 g of 25% alkyd rubbing lacquer is shaken in a sealed plastic cup of 125 ml for 60 minutes on the paint shaker. Then 44.8 g of a 56% alkyd-melamine resin clear lacquer are mixed in and the glass balls are then removed by sieving. The solid color lacquer containing 5 percent by weight of pigment produced in this way is applied to a white card with a black horizontal stripe in a wet film thickness of 75 μm using a hand coater. After flashing off, bake in the drying cabinet at 140 ° C for 30 minutes. The result is a strong yellow-green coating with excellent fastness properties.
2 Gewichtsteile eines 5 Gewichtsprozente Pigment enthaltenden, durch 60 Minuten langes Anreiben auf dem Paintshaker gemäß Beispiel 5 hergestellten Alkyd-Melaminharz-Einbrennlacks werden mit 2,5 Gewichtsteilen eines Einbrennweißlacks vermischt, der ebenfalls auf Alkyd-Melaminharz-Basis 20 Gewichtsprozente Tio2 enthält.Containing 2 parts by weight of a 5 weight percent of pigment, by for 60 minutes rubbing on the Paint Shaker according to Example 5 prepared alkyd-melamine resin stoving enamel be 2.5 parts by weight of mixed a Einbrennweißlacks which also contains alkyd-melamine resin-based 20 weight percent TiO 2.
Diese Weißaufhellung wird mit Hilfe eines Handcoaters in einer Naßfilmstärke von 75 µm auf ein weißes Kärtchen aufgezogen und der Aufstrich nach dem Ablüften 30 Minuten bei 140°C im Trockenschrank eingebrannt.This whitening is applied to a white card with the aid of a hand coater in a wet film thickness of 75 µm and the spread is baked in the drying cabinet at 140 ° C. for 30 minutes.
Von dem in Tabelle 1 in der Seitenzeile 14 aufgeführten Metallkomplex mit R4 = 4-COOCH3, R5 = H und Me = Cu wurde gemäß der Vorschrift des Beispiels 4 ein Metalleffektlack auf ein Blech aufgetragen und gemäß den Beispielen 5 und 6 ein 5%iger Volltonlack und ein mit Titandioxid 1 : 5 aufgehellter Lack auf weiße Kärtchen aufgetragen.A metal effect lacquer was applied to a metal sheet from the metal complex listed in Table 1 on page 14 with R 4 = 4-COOCH 3 , R 5 = H and Me = Cu, and a 5 according to Examples 5 and 6 % full-tone lacquer and a lacquer lightened with titanium dioxide 1: 5 applied to white cards.
Zum Vergleich wurden entsprechende Lackierungen mit dem Metallkomplex
Claims (11)
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Application Number | Priority Date | Filing Date | Title |
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US819756 | 1977-07-29 | ||
US05/819,756 US4157446A (en) | 1976-08-05 | 1977-07-29 | 3-Formyl-pyridines and process for making them |
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EP0000505A1 EP0000505A1 (en) | 1979-02-07 |
EP0000505B1 true EP0000505B1 (en) | 1980-09-03 |
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EP78100373A Expired EP0000505B1 (en) | 1977-07-29 | 1978-07-12 | Metal complexes, process for their preparation and their application as pigments |
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EP (1) | EP0000505B1 (en) |
JP (1) | JPS5440825A (en) |
BR (1) | BR7804874A (en) |
CA (1) | CA1107738A (en) |
DE (1) | DE2860135D1 (en) |
IT (1) | IT1097775B (en) |
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US4494745A (en) * | 1981-12-16 | 1985-01-22 | The Ward Machinery Company | Feeding apparatus for paperboard sheets |
DE3315596A1 (en) * | 1983-04-29 | 1984-10-31 | Basf Ag, 6700 Ludwigshafen | Use of polyurethane prepolymers as flocculating agents |
JPS6293142A (en) * | 1985-10-18 | 1987-04-28 | Fuji Xerox Co Ltd | Paper sheet separator |
JPH02225218A (en) * | 1989-02-27 | 1990-09-07 | Tomomura Seisakusho:Kk | Sending-out device for plate-shaped article |
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DE2008938A1 (en) * | 1970-02-26 | 1971-09-09 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Azomethine-metal complex pigment dyes |
CH562301A5 (en) * | 1971-12-13 | 1975-05-30 | Ciba Geigy Ag |
-
1978
- 1978-07-12 EP EP78100373A patent/EP0000505B1/en not_active Expired
- 1978-07-12 DE DE7878100373T patent/DE2860135D1/en not_active Expired
- 1978-07-26 CA CA308,186A patent/CA1107738A/en not_active Expired
- 1978-07-28 JP JP9167878A patent/JPS5440825A/en active Pending
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DE2860135D1 (en) | 1980-12-11 |
CA1107738A (en) | 1981-08-25 |
BR7804874A (en) | 1979-04-24 |
EP0000505A1 (en) | 1979-02-07 |
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