EP0000505A1 - Complexes de métaux, leur procédé de préparation et leur application comme pigments - Google Patents

Complexes de métaux, leur procédé de préparation et leur application comme pigments Download PDF

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Publication number
EP0000505A1
EP0000505A1 EP78100373A EP78100373A EP0000505A1 EP 0000505 A1 EP0000505 A1 EP 0000505A1 EP 78100373 A EP78100373 A EP 78100373A EP 78100373 A EP78100373 A EP 78100373A EP 0000505 A1 EP0000505 A1 EP 0000505A1
Authority
EP
European Patent Office
Prior art keywords
metal complexes
substituted
benzene
parts
formula
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.)
Granted
Application number
EP78100373A
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German (de)
English (en)
Other versions
EP0000505B1 (fr
Inventor
Horst Dr. Tappe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
Original Assignee
Cassella AG
Cassella Farbwerke Mainkur AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US05/819,756 external-priority patent/US4157446A/en
Application filed by Cassella AG, Cassella Farbwerke Mainkur AG filed Critical Cassella AG
Publication of EP0000505A1 publication Critical patent/EP0000505A1/fr
Application granted granted Critical
Publication of EP0000505B1 publication Critical patent/EP0000505B1/fr
Expired legal-status Critical Current

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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

  • the invention relates to valuable metal complexes of the formula where X for and the benzene or naphthalene nucleus formed by X with the rest of the molecule also by one or two substituents from the series methyl, methoxy, chlorine, bromine, trifluoromethyl, nitro, cyano, CONR 1 R 2 or COOR 3 , where R 1 and R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms and R 3 represents alkyl having 1 to 4 carbon atoms, which may be substituted, and Me represents a nickel, copper, zinc or cobalt atom.
  • the invention further relates to the use of the metal complexes as pigments and for pigmenting lacquers, high-molecular plastic compositions and printing pastes.
  • 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.
  • the new metal complexes can be prepared by mam 3-formyl-4-methyl-2,6-dihydroxy-pyridine or an alkali or alkaline earth salt thereof with an ortho-aminohydroxy compound of the formula III wherein X has the meaning given above and a benzene or naphthalene nucleus, as indicated above, can be substituted, reacted according to methods known per se and the resulting condensation product metallized according to a method known per se.
  • ortho-aminohydroxy compounds are suitable as starting products: 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-) methoxycarbonyl phenol, 2-amino-4- (or 3- or 5- or 6-) ethoxycarbonyl phenol, 2-amino-4- (or 3-) butoxycarbonyl -phenol, 2-amino-4- (or 5-) trifluoromethyl-phenol, 2-amino-4- (or 5 -) - carbonamido-phenol, 2-amino-4- (or 5-) dimethylcarbonamidophenol, 2 -Amino-4- (or 5-) ethylcarbonamido-phenol, 2-amino-1-nap
  • the compounds of the formula III are mostly known or can easily be synthesized by the methods known for the preparation of ertho-aminohydroxy 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.
  • the sodium and potassium salts are particularly suitable.
  • Other tautomeric forms of the metal complexes of the general formula I are also conceivable.
  • 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 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 C- Atoms, glycol ethers. such as. Ethylene glycol dimethyl ether, glacial acetic acid, aprotic solvents. like z, ld. Toluene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran and the like, especially dipolar aprotic. Solvents, e.g.
  • 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 in the solvent or solvent mixture used for the azomethine condensation is mixed with a metal salt, preferably an acetate, e.g. Copper II acetate, among the same
  • Conditions implemented in the production of azomethine It may be useful to keep the pH of the solution between 5 and 6, which e.g. can be done by successively adding sodium acetate solution.
  • the metal-free azomethines are yellow-orange to brown products, while the metal-containing new metal complexes are usually yellowish green to olive green and are only slightly or very slightly soluble 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.
  • 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.
  • the product is filtered off hot and washed with 1200 parts of 80 ° C hot water and dried at 40 ° C in a vacuum. 44 parts of the azomethine-copper complex of the formula are obtained.
  • 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.
  • An automotive baking varnish produced in the usual manner using the pigment obtained showed very good light fastness, weather fastness and over-spray fastness after baking.
  • 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 in 200 parts of a mixture of 160 parts len acetic acid and 40 parts of water are suspended and the reaction mixture is concentrated in vacuo to 50 parts. 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-di-hydroxypyridine with a melting point of 180 to 182 ° C. is obtained.
  • 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 alkyd resin lacquer in xylene on the vibratory ball mill for 45 minutes, with 60 g clear lacquer consisting of 52.5 g a 70% alkyd resin solution in xylod, 35 g of a 55% melamine resin solution in butanol, 2.5 g of bunyl glycol, 5 g of butanol and 5 g of mineral spirits. You get a clear yellowish-green full tone detail. the ned emn aluminum sheet is injected and 30 minutes at burns a yellowish-green color of Einwsodiseiom fastness to overcoating and excellent light and weather fastness results.
  • a rub-on lacquer consisting of a 20% solution of alkyd resin lacquer in xylene on the vibratory ball mill for 45 minutes
  • 60 g clear lacquer consisting of 5
  • a mixture of 62.5 ml of glass beads, 3 mm in diameter, 4.5 g of the metal complex obtained according to Example 2 and 25.2 g of acrylic grinding 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.
  • the 5% full-tone paint produced in this way with respect to the organic pigment is coated with an acrylic melamine resin paint containing 3% aluminum pigment in a weight ratio of 3: 5 mixed.
  • 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 then the glass balls are removed by sieving.
  • the full-tone color lacquer produced in this way, containing 5 percent by weight of pigment, is applied to a white card with a black horizontal stripe in a wet film thickness of 75 ⁇ m by means of 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.
  • This whitening is applied with the help of a hand coater in a wet film thickness of 75 .mu.m to a white hardness and the spread is baked in the drying cabinet at 140 ° C. for 30 minutes.

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)
EP78100373A 1977-07-29 1978-07-12 Complexes de métaux, leur procédé de préparation et leur application comme pigments Expired EP0000505B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/819,756 US4157446A (en) 1976-08-05 1977-07-29 3-Formyl-pyridines and process for making them
US819756 1977-07-29

Publications (2)

Publication Number Publication Date
EP0000505A1 true EP0000505A1 (fr) 1979-02-07
EP0000505B1 EP0000505B1 (fr) 1980-09-03

Family

ID=25228969

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100373A Expired EP0000505B1 (fr) 1977-07-29 1978-07-12 Complexes de métaux, leur procédé de préparation et leur application comme pigments

Country Status (6)

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EP (1) EP0000505B1 (fr)
JP (1) JPS5440825A (fr)
BR (1) BR7804874A (fr)
CA (1) CA1107738A (fr)
DE (1) DE2860135D1 (fr)
IT (1) IT1097775B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3315596A1 (de) * 1983-04-29 1984-10-31 Basf Ag, 6700 Ludwigshafen Verwendung von polyurethanpraepolymeren als flockungsmittel

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4494745A (en) * 1981-12-16 1985-01-22 The Ward Machinery Company Feeding apparatus for paperboard sheets
JPS6293142A (ja) * 1985-10-18 1987-04-28 Fuji Xerox Co Ltd 用紙送行装置
JPH02225218A (ja) * 1989-02-27 1990-09-07 Tomomura Seisakusho:Kk 板状物の送り出し装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2008938A1 (en) * 1970-02-26 1971-09-09 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Azomethine-metal complex pigment dyes
FR2163519A1 (fr) * 1971-12-13 1973-07-27 Ciba Geigy Ag

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2008938A1 (en) * 1970-02-26 1971-09-09 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Azomethine-metal complex pigment dyes
FR2163519A1 (fr) * 1971-12-13 1973-07-27 Ciba Geigy Ag

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HOUBEN-WEYL, Band I/2, Seite 325-326 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3315596A1 (de) * 1983-04-29 1984-10-31 Basf Ag, 6700 Ludwigshafen Verwendung von polyurethanpraepolymeren als flockungsmittel

Also Published As

Publication number Publication date
IT1097775B (it) 1985-08-31
CA1107738A (fr) 1981-08-25
BR7804874A (pt) 1979-04-24
JPS5440825A (en) 1979-03-31
EP0000505B1 (fr) 1980-09-03
DE2860135D1 (en) 1980-12-11
IT7826284A0 (it) 1978-07-28

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