EP0000737A1 - Monoazo pigments of the acetoacetylamino benzimidazolone series, their preparation and their use for colouring organic material of high molecular weight - Google Patents

Monoazo pigments of the acetoacetylamino benzimidazolone series, their preparation and their use for colouring organic material of high molecular weight Download PDF

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EP0000737A1
EP0000737A1 EP7878100516A EP78100516A EP0000737A1 EP 0000737 A1 EP0000737 A1 EP 0000737A1 EP 7878100516 A EP7878100516 A EP 7878100516A EP 78100516 A EP78100516 A EP 78100516A EP 0000737 A1 EP0000737 A1 EP 0000737A1
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formula
hydrogen
alkyl
atoms
group
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EP0000737B1 (en
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Rolf Müller
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Novartis AG
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Ciba Geigy AG
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    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/32—Monoazo dyes prepared by diazotising and coupling from coupling components containing a reactive methylene group
    • C09B29/33—Aceto- or benzoylacetylarylides
    • C09B29/335—Aceto- or benzoylacetylarylides free of acid groups
    • C09B29/338—Heterocyclic arylides, e.g. acetoacetylaminobenzimidazolone
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C09B29/0011—Monoazo dyes prepared by diazotising and coupling from diazotized anilines from diazotized anilines directly substituted by a heterocyclic ring (not condensed)
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds

Definitions

  • X and Y are hydrogen, halogen, alkyl or alkoxy having 1 to 4 carbon atoms
  • Q is a group of the formulas -CONH- or -NHCO-
  • Preferred compounds of the formula (1) are those in which Q is a group of the formula -CONH- and Z is an O atom or a group of the formulas -NH- or -NHCO-.
  • X is preferably hydrogen, chlorine, methyl or methoxy and Y is hydrogen, chlorine, methyl, methoxy or ethoxy.
  • Acetessigarylides of the formula are preferably used as coupling components. where X has the meaning given above.
  • the acetoacetic arylides to be used as the coupling component are obtained, for example, by adding diketene to the corresponding aminobenzimidazolones.
  • the coupling is expediently carried out by gradually combining the aqueous alkaline solution of the coupling component with the acidic solution of the diazonium salt, preferably at a pH of 4 to 6.
  • the pH is advantageously adjusted by adding a buffer.
  • suitable buffers are the salts, in particular alkali metal salts, of formic acid, phosphoric acid or, in particular, of acetic acid.
  • the alkaline solution of the coupling component expediently contains a wetting, dispersing or emulsifying agent, for example an aralkyl sulfonate, such as dodecylbenzenesulfonate or the sodium salt of 1,1'-dinaphthylmethanesulfonic acid, polycondensation products of alkylene oxides, such as the action product of ethylene oxide on p-tert-octylphenol, and also alkyl esters of sulforicinoleates, for example n-butylsulforicinoleate.
  • aralkyl sulfonate such as dodecylbenzenesulfonate or the sodium salt of 1,1'-dinaphthylmethane
  • the dispersion of the coupling component can also advantageously contain protective colloids, for example methyl cellulose or smaller amounts of inert organic solvents which are sparingly soluble or insoluble in water, for example halogenated or nitrated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzenes or nitrobenzene, and aliphatic halogenated hydrocarbons such as for example carbon tetrachloride or trichlorethylene, and also water-miscible organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol or isopropanol, especially dimethylformamide.
  • protective colloids for example methyl cellulose or smaller amounts of inert organic solvents which are sparingly soluble or insoluble in water, for example halogenated or nitrated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlor
  • the coupling can also advantageously be carried out by continuously combining an acidic solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle, the components being coupled immediately.
  • the resulting dye dispersion is continuously removed from the mixing nozzle and the dye is separated off by filtration.
  • the coupling can also be carried out by suspending the amine with the coupling component in a molar ratio of 1: 1 in an organic solvent and with a diazotizing agent, in particular an ester of nitrous acid, such as methyl, ethyl, butyl or amyl or octyl nitrite.
  • a diazotizing agent in particular an ester of nitrous acid, such as methyl, ethyl, butyl or amyl or octyl nitrite.
  • the pigments obtained can be isolated from the reaction mixtures by filtration.
  • the pigments obtained are obtained in excellent purity.
  • the pigments obtained generally have a good texture and can be widely used as raw products. If necessary or desired, the raw products can be converted into a finely dispersed form by grinding or kneading. It is useful to use grinding aids such as inorganic and / or organic salts in the presence or absence of organic solvents. After grinding, auxiliary agents are removed as usual, soluble inorganic salts e.g. with water and water-insoluble organic auxiliaries, for example by steam distillation. An improvement in the properties can often also be achieved by treating the raw pigments with organic solvents, preferably those which boil above 100 ° C.
  • benzenes substituted by halogen atoms, alkyl or nitro groups such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, and pyridine bases, such as pyridine, picoline or quinoline, and also ketones, such as cyclohexanone, ethers, such as ethylene glycol monomethyl or monoethyl ether, amides , such as dimethylformamide or N-methyl-pyrrolidone, and also dimethyl sulfoxide, sulfolane or water alone, optionally under pressure.
  • the aftertreatment can also be carried out in water in the presence of organic solvents and / or with the addition of surface-active substances.
  • the aftertreatment is preferably carried out by heating the pigment in the solvent to 100 to 150 ° C, in many cases coarsening of the grain occurs, which has a favorable effect on the light and migration fastness of the pigments obtained.
  • the new dyes are valuable, mostly strong-colored pigments with good migration, light, weather and heat fastness. They can be used individually or in mixtures of finely divided form for pigmenting high-molecular organic material, e.g. cellulose ethers and esters, polyamides, polyurethanes, polyesters, acetyl cellulose, nitrocellulose, natural resins or synthetic resins such as polymerization or condensation resins, e.g.
  • Aminoplasts in particular urea and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicone and silicone resins.
  • 6-Amino-5-methylbenzoxazolone is prepared by known processes, but preferably analogously to the preparation of benzimidazolones, as described in DE-OS 2 725 957.
  • the fastness and the texture of the pigment are further improved by heating the crude pigment in water in the presence of 1% of a condensation product of 1 mol of oleyl alcohol and 20 mol of ethylene oxide at 150 ° C. under pressure for 6 hours.
  • a pigment is obtained which colors PVC in a reddish yellow shade with very good fastness to migration, light and weather.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coloring (AREA)

Abstract

1. Azo pigments of the formula see diagramm : EP0000737,P11,F1 wherein X and Y are each hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, Q is a group of the formula -CONH- or -NHCO-, and Z is an O atom or is a group of the formula -NR-, -NHCO-, -CONH-, -CH=N- or see diagramm : EP0000737,P11,F2 in which R is hydrogen, alkyl having 1-4 C atoms, or phenyl unsubstituted or substituted by halogen, alkyl or alkoxy having 1-4 C atoms, and V is hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, and the azo group is bound to the phenyl group A or B.

Description

Es wurde gefunden, dass man zu neuen Azopigmenten der Formel

Figure imgb0001
gelangt, worin X und Y Wasserstoff, Halogen, Alkyl oder Alkoxy mit l bis 4 C-Atomen, Q eine Gruppe der Formeln -CONH- oder -NHCO- und Z ein 0-Atom oder eine Gruppe der Formeln -NR-, -NHCO-, -CONH-, -CH=N- oder
Figure imgb0002
darstellen, wobei R Wasserstoff, Alkyl mit 1-4 C-Atomen oder gegebenenfalls durch Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen substituiertes Phenyl und V Wasserstoff, Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen bedeuten und die Azogruppe an die Phenylreste A oder B gebunden sein kann, wenn man die Diazoverbindung eines Amins der Formel
Figure imgb0003
worin Y; Q und Z die oben angegebene Bedeutung haben und die Aminogruppe an die Phenylreste A oder B gebunden sein kann, mit einem Acetessigarylid der Formel
Figure imgb0004
worin X die oben angegebene Bedeutung hat, kuppelt.It has been found that new azo pigments of the formula
Figure imgb0001
 arrives, where X and Y are hydrogen, halogen, alkyl or alkoxy having 1 to 4 carbon atoms, Q is a group of the formulas -CONH- or -NHCO- and Z is a 0-atom or a group of formulas -NR-, -NHCO -, -CONH-, -CH = N- or
Figure imgb0002
 represent, where R is hydrogen, alkyl having 1-4 C atoms or phenyl optionally substituted by halogen, alkyl or alkoxy having 1-4 C atoms and V is hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms ten and the azo group can be bonded to the phenyl radicals A or B if the diazo compound of an amine of the formula
Figure imgb0003
 where Y; Q and Z have the meaning given above and the amino group can be bonded to the phenyl radicals A or B, with an acetoacetic arylide of the formula
Figure imgb0004
 where X has the meaning given above, couples.

Bevorzugt sind jene Verbindungen der Formel (1), worin Q eine Gruppe der Formel -CONH- und Z ein O-Atom oder eine Gruppe der Formeln -NH- oder -NHCO- bedeuten. X ist dabei vorzugsweise Wasserstoff, Chlor, Methyl oder Methoxy und Y Wasserstoff, Chlor, Methyl, Methoxy oder Aethoxy.Preferred compounds of the formula (1) are those in which Q is a group of the formula -CONH- and Z is an O atom or a group of the formulas -NH- or -NHCO-. X is preferably hydrogen, chlorine, methyl or methoxy and Y is hydrogen, chlorine, methyl, methoxy or ethoxy.

Von besonderem Interesse sind Verbindungen der Formeln

Figure imgb0005
und insbesondere solche der Formel
Figure imgb0006
Als Beispiele für Diazokomponenten, in denen Q, Y und Z die oben angegebene Bedeutung haben, seien die folgenden genannt:

  • 1. Aminobenzoxazolone der Formel
    Figure imgb0007
  • 2. Aminobenzimidazolone der Formel
    Figure imgb0008
  • 3. Aminochinazolin-2,4-dione der Formel
    Figure imgb0009
  • 4. Aminochinoxalin-2,3-dione der Formel
    Figure imgb0010
  • 5. Aminochinazolin-4-one der Formel
    Figure imgb0011
  • 6. 2-(Aminophenyl)chinazolin-4-one der Formel
    Figure imgb0012
Compounds of the formulas are of particular interest
Figure imgb0005
 and especially those of the formula
Figure imgb0006
 Examples of diazo components in which Q, Y and Z have the meaning given above are the following:
  • 1. Aminobenzoxazolones of the formula
    Figure imgb0007
  • 2. Aminobenzimidazolones of the formula
    Figure imgb0008
  • 3. aminoquinazoline-2,4-diones of the formula
    Figure imgb0009
  • 4. aminoquinoxaline-2,3-diones of the formula
    Figure imgb0010
  • 5. aminoquinazolin-4-ones of the formula
    Figure imgb0011
  • 6. 2- (aminophenyl) quinazolin-4-ones of the formula
    Figure imgb0012

Als Beispiele fUr Diazokomponenten seien, nach den oben erwähnten Gruppen geordnet, die folgenden genannt:

  • 1) 5-Aminobenzoxazolon
    • 6-Aminobenzoxazolon
    • 5-Amino-6-chlor-benzoxazolon
    • 5-Amino-7-chlor-benzoxazolon
    • S-Amino-6-methyl-benzoxazolon
    • 5-Amino-7-methyl-benzoxazolon
    • 5-Amino-6-methoxy-benzoxazolon
    • 6-Arnino-benzoxazolon
    • 6-Amino-5-chlorbenzoxazolon
    • 6-Amino-5-methyl-benzoxazolon
  • 2) 5-Amino-benzimidazolon
    • 5-AtDino-6-chlor-benzimidazolon
    • 5-Amino-7-chlor-benzimidazolon
    • 5-Amino-6-methyl-benzimidazolon
    • 5-Amino-7-methyl-benzimidazolon
    • 5-Amine-6-äthoxy-benzimidazolon
  • 3) 6-Aminochinazolin-2,4-dion
    • 7-Aminochinazolin-2,4-dion
  • 4) 6-Aminochinoxalin-2,3-dion
    • 7-Aminochinoxalin-2,3-dion
  • 5) 6-Aminochinazolin-4-on
    • 7-Aminochinäzolin-4-on
    • 5-Amino-6-chlorchinazolin-4-on
  • 6) 2-(3'-Amino-4'-methoxyprienyl)-chinazolin-4-on
    • 2-(3'-Amino-4'-chlorphenyl)-6-chlorchinazolin-4-on
    • 2-(4'-Amino-3'-methylphenyl)-chinazolin-4-on
    • 2-(3'-Amino-4'-methylphenyl)-chinazolin-4-on
    • 2-(3'-Amino-4'-chlorphenyl)-chinazolin-4-on
The following are cited as examples of diazo components, arranged according to the groups mentioned above:
  • 1) 5-aminobenzoxazolone
    • 6-aminobenzoxazolone
    • 5-amino-6-chloro-benzoxazolone
    • 5-amino-7-chloro-benzoxazolone
    • S-amino-6-methyl-benzoxazolone
    • 5-amino-7-methyl-benzoxazolone
    • 5-amino-6-methoxy-benzoxazolone
    • 6-aminino-benzoxazolone
    • 6-amino-5-chlorobenzoxazolone
    • 6-amino-5-methyl-benzoxazolone
  • 2) 5-amino-benzimidazolone
    • 5-AtDino-6-chloro-benzimidazolone
    • 5-amino-7-chloro-benzimidazolone
    • 5-amino-6-methyl-benzimidazolone
    • 5-amino-7-methyl-benzimidazolone
    • 5-amine-6-ethoxy-benzimidazolone
  • 3) 6-aminoquinazoline-2,4-dione
    • 7-aminoquinazoline-2,4-dione
  • 4) 6-aminoquinoxaline-2,3-dione
    • 7-aminoquinoxaline-2,3-dione
  • 5) 6-aminoquinazolin-4-one
    • 7-aminoquinazolin-4-one
    • 5-amino-6-chloroquinazolin-4-one
  • 6) 2- (3'-Amino-4'-methoxyprienyl) -quinazolin-4-one
    • 2- (3'-amino-4'-chlorophenyl) -6-chloroquinazolin-4-one
    • 2- (4'-amino-3'-methylphenyl) -quinazolin-4-one
    • 2- (3'-amino-4'-methylphenyl) -quinazolin-4-one
    • 2- (3'-amino-4'-chlorophenyl) -quinazolin-4-one

Als Kupplungskomponenten verwendet man vorzugsweise Acetessigarylide der Formel.

Figure imgb0013
worin X die oben angegebene Bedeutung hat.Acetessigarylides of the formula are preferably used as coupling components.
Figure imgb0013
 where X has the meaning given above.

Die als Kupplungskomponente zu verwendenden Acetessigarylide erhält man beispielsweise durch Anlagerung von Diketen an die entsprechenden Aminobenzimidazolone.The acetoacetic arylides to be used as the coupling component are obtained, for example, by adding diketene to the corresponding aminobenzimidazolones.

Die Kupplung wird zweckmässig durch allmähliche Vereinigung der wässrig-alkalischen Lösung der Kupplungskomponente mit der sauren Lösung des Diazoniumsalzes, vorzugsweise bei einem pH-Wert von 4 bis 6, durchgeführt.The coupling is expediently carried out by gradually combining the aqueous alkaline solution of the coupling component with the acidic solution of the diazonium salt, preferably at a pH of 4 to 6.

Der pH-Wert wird vorteilhaft durch Zugabe eines Puffers eingestellt. Als Puffer kommen z.B. die Salze, insbesondere Alkalisalze, der Ameisensäure, Phosphorsäure oder insbesondere der Essigsäure in Betracht. Die alkalische Lösung der Kupplungskomponente enthält zweckmässig ein Netz-, Dispergier- oder Emulgiermittel,beispielsweise ein Aralkylsulfonat, wie Dodecylbenzolsulfonat oder das Natriumsalz der 1,1'-Dinaphthylmethansulfonsäure, Polykondensationsprodukte von Alkylenoxyden, wie das Einwirkungsprodukt von Aethylenoxyd auf p-tert.-Octylphenol, ferner Alkylester von Sulforicinoleaten, beispielsweise n-Butylsulforicinoleat. Die Dispersion der Kupplungskomponente kann auch vorteilhaft Schutzkolloide, beispielsweise Methylcellulose oder kleinere Mengen inerter, in Wasser schwerlöslicher oder unlöslicher organischer Lösungsmittel enthalten, beispielsweise gegebenenfalls halogenierte oder nitrierte aromatische Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Chlorbenzol, Dichlorbenzole oder Nitrobenzol, sowie aliphatische Halogenkohlenwasserstoffe wie z.B. Tetrachlorkohlenstoff oder Trichloräthylen, ferner mit Wasser mischbare organische Lösungsmittel, wie Aceton, Methyläthylketon, Methanol, Aethanol oder Isopropanol, insbesondere Dimethylformamid.The pH is advantageously adjusted by adding a buffer. Examples of suitable buffers are the salts, in particular alkali metal salts, of formic acid, phosphoric acid or, in particular, of acetic acid. The alkaline solution of the coupling component expediently contains a wetting, dispersing or emulsifying agent, for example an aralkyl sulfonate, such as dodecylbenzenesulfonate or the sodium salt of 1,1'-dinaphthylmethanesulfonic acid, polycondensation products of alkylene oxides, such as the action product of ethylene oxide on p-tert-octylphenol, and also alkyl esters of sulforicinoleates, for example n-butylsulforicinoleate. The dispersion of the coupling component can also advantageously contain protective colloids, for example methyl cellulose or smaller amounts of inert organic solvents which are sparingly soluble or insoluble in water, for example halogenated or nitrated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzenes or nitrobenzene, and aliphatic halogenated hydrocarbons such as for example carbon tetrachloride or trichlorethylene, and also water-miscible organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol or isopropanol, especially dimethylformamide.

Man kann die Kupplung auch vorteilhaft in der Weise durchführen, dass man eine saure Lösung des Diazoniumsalzes mit einer alkalischen Lösung der Kupplungskomponente in einer Mischdüse kontinuierlich vereinigt, wobei eine sofortige Kupplung der Komponenten erfolgt. Die entstandene Farbstoffdispersion wird der Mischdüse laufend entzogen und der Farbstoff durch Filtrieren abgetrennt.The coupling can also advantageously be carried out by continuously combining an acidic solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle, the components being coupled immediately. The resulting dye dispersion is continuously removed from the mixing nozzle and the dye is separated off by filtration.

Schliesslich kann die Kupplung auch so vollzogen werden, dass man das Amin mit der Kupplungskomponente im Molverhältnis 1:1 in einem organischen Lösungsmittel suspendiert und mit einem diazotierenden Mittel, insbesondere einem Ester der salpetrigen Säure, wie Methyl-, Aethyl-, Butyl-, Amyl oder Octylnitrit, behandelt.Finally, the coupling can also be carried out by suspending the amine with the coupling component in a molar ratio of 1: 1 in an organic solvent and with a diazotizing agent, in particular an ester of nitrous acid, such as methyl, ethyl, butyl or amyl or octyl nitrite.

Dank ihrer Unlöslichkeit können die erhaltenen Pigmente aus den Reaktionsgemischen durch Abfiltrieren isoliert werden.Thanks to their insolubility, the pigments obtained can be isolated from the reaction mixtures by filtration.

Da die Nebenprodukte in Lösung bleiben, fallen die erhaltenen Pigmente-in hervorragender Reinheit an.Since the by-products remain in solution, the pigments obtained are obtained in excellent purity.

Die erhaltenen Pigmente besitzen im allgemeinen eine gute Textur und können vielfach als Rohprodukte verwendet werden. Falls nötig oder erwünscht, kann man die Rohprodukte durch Mahlen oder Kneten in eine feindisperse Form überführen. Dabei werden zweckmässig Mahlhilfsmittel, wie anorganische und/oder organische Salze in Gegenwart oder Abwesenheit organischer Lösungsmittel verwendet. Nach dem Mahlen werden Hilfsmittel wie üblich entfernt, lösliche anorganische Salze z.B. mit Wasser und wasserunlösliche organische Hilfsmittel beispielsweise durch Wasserdampfdestillation. Auch durch Behandeln der Rohpigmente mit organischen Lösungsmitteln, vorzugsweise solchen, die über 100° C sieden, kann oft eine Verbesserung der Eigenschaften erreicht werden. Als besonders geeignet erweisen sich durch Halogenatome, Alkyl- oder Nitrogruppen substituierte Benzole, wie Xylole, Chlorbenzol, o-Dichlorbenzol oder Nitrobenzol sowie Pyridinbasen, wie Pyridin, Picolin oder Chinolin, ferner Ketone, wie Cyclohexanon, Aether, wie Aethylenglykolmonomethyl- oder monoäthyläther, Amide, wie Dimethylformamid oder N-Methyl-pyrrolidon, sowie Dimethylsulfoxyd, Sulfolan Oder Wasser allein, gegebenenfalls unter Druck. Man kann die Nachbehandlung auch in Wasser in Gegenwart von organischen Lösungsmitteln und/oder mit Zusatz von oberflächenaktiven Substanzen durchführen.The pigments obtained generally have a good texture and can be widely used as raw products. If necessary or desired, the raw products can be converted into a finely dispersed form by grinding or kneading. It is useful to use grinding aids such as inorganic and / or organic salts in the presence or absence of organic solvents. After grinding, auxiliary agents are removed as usual, soluble inorganic salts e.g. with water and water-insoluble organic auxiliaries, for example by steam distillation. An improvement in the properties can often also be achieved by treating the raw pigments with organic solvents, preferably those which boil above 100 ° C. Particularly suitable have been found to be benzenes substituted by halogen atoms, alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, and pyridine bases, such as pyridine, picoline or quinoline, and also ketones, such as cyclohexanone, ethers, such as ethylene glycol monomethyl or monoethyl ether, amides , such as dimethylformamide or N-methyl-pyrrolidone, and also dimethyl sulfoxide, sulfolane or water alone, optionally under pressure. The aftertreatment can also be carried out in water in the presence of organic solvents and / or with the addition of surface-active substances.

Die Nachbehandlung erfolgt vorzugsweise durch Erhitzen des Pigmentes im Lösungsmittel auf 100 bis 150° C, wobei in vielen Fällen eine Kornvergröberung eintritt, was sich günstig auf die Licht- und Migrationsechtheit der erhaltenen Pigmente auswirkt.The aftertreatment is preferably carried out by heating the pigment in the solvent to 100 to 150 ° C, in many cases coarsening of the grain occurs, which has a favorable effect on the light and migration fastness of the pigments obtained.

Die neuen Farbstoffe stellen wertvolle, meist farbstarke Pigmente von guter Migrations-, Licht, Wetter- und Hitzeechtheit dar. Sie können einzeln oder in Mischungen infeinverteilter Form zum Pigmentieren von hochmolekularem organischen Material verwendet werden, z.B. von Cellulose- äthern und -estern, Polyamiden, Polyurethanen, Polyestern, Acetylcellulose, Nitrocellulose, natürlichen Harzen oder Kunstharzen, wie Polymerisations- oder Kondensationsharzen, z.B. Aminoplasten, insbesondere Harnstoff- und Melamin-Formaldehydharzen, Alkydharzen, Phenoplasten, Polycarbonaten, Polyolefinen, wie Polystyrol, Polyvinylchlorid, Polyäthylen, Polypropylen, Polyacrylnitril, Polyacrylsäureester, Gummi, Casein, Silikon und Silikonharzen.The new dyes are valuable, mostly strong-colored pigments with good migration, light, weather and heat fastness. They can be used individually or in mixtures of finely divided form for pigmenting high-molecular organic material, e.g. cellulose ethers and esters, polyamides, polyurethanes, polyesters, acetyl cellulose, nitrocellulose, natural resins or synthetic resins such as polymerization or condensation resins, e.g. Aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicone and silicone resins.

Dabei spielt es keine Rolle, ob die erwähnten hochmolekularen Verbindungen als plastische Massen, Schmelzen oder in Form von Spinnlösungen, Lacken oder Druckfarben vorliegen. Je nach Verwendungszweck erweist es sich als vor- teilhaft, die neuen Pigmente als Toner oder in Form von Präparaten zu verwenden.It does not matter whether the high molecular weight compounds mentioned are in the form of plastic masses, melts or in the form of spinning solutions, lacquers or printing inks. Depending on the intended use, it may prove advantageous to use the new pigments as toners or in the form of preparations.

In den nachfolgenden Beispielen bedeuten die Teile, sofern nichts anderes angegeben wird, Gewichtsteile, die Prozente Gewichtsprozente, und die Temperaturen sind in Celsiusgraden angegeben.In the following examples, the parts mean parts by weight, the percentages by weight, unless stated otherwise, and the temperatures are given in degrees Celsius.

Beispiel 1example 1

1,64 Teile 6-Amino-5-methyl-benzoxazolon werden unter Eiskühlung mit 2,5 Volumteilen 10-normaler Salzsäure und 2,5 Volumteilen 4-normaler Natriumnitritlösung in üblicher Weise diazotiert. Die Diazolösung wird klärfiltriert. 2,33 Teile 5-Acetoacetylamino-benzimidazolon werden in 130 Volumteilen Dimethylformamid bei 20° C gelöst. Nach Zugabe von 3 Teilen wasserfreiem Natriumacetat wird obige Diazolösung in ca. 15 Minuten zugetropft. Man rührt das Kupplungsgemisch noch einige Stunden bei Raumtemperatur nach, heizt dann auf 8O° C, filtriert das gebildete Pigment ab, wäscht es mit heissem Wasser und anschliessend mit kaltem Isopropanol nach. Das Filtergut wird im Vakuum bei 70 - 80° C getrocknet. Man erhält 2,9 Teile (entsprechend 71 % der Theorie) eines ockerfarbenen Pulvers der Formel

Figure imgb0014
1.64 parts of 6-amino-5-methyl-benzoxazolone are diazotized in the usual way with ice cooling with 2.5 parts by volume of 10 normal hydrochloric acid and 2.5 parts by volume of 4 normal sodium nitrite solution. The diazo solution is clarified by filtration. 2.33 parts of 5-acetoacetylamino-benzimidazolone are dissolved in 130 parts by volume of dimethylformamide at 20 ° C. After adding 3 parts of anhydrous sodium acetate, the above diazo solution is added dropwise in about 15 minutes. The coupling mixture is stirred for a few hours at room temperature, then heated to 80 ° C., the pigment formed is filtered off, washed with hot water and then with cold isopropanol. The filter material is dried in a vacuum at 70 - 80 ° C. 2.9 parts (corresponding to 71% of theory) of an ocher powder of the formula are obtained
Figure imgb0014

Durch Nachbehandlung in N-Methyl-2-pyrrolidon (30 Minuten bei Siedetemperatur) erfolgt eine Rekristallisation und man erhält ein Pigment, welches PVC in rotstichigem Gelbton von sehr guter Migrations-, Licht- und Wetterechtheit färbt. Die Herstellung von 6-Amino-5-methylbenzoxazolon erfolgt nach bekannten Verfahren, vorzugsweise aber analog der Herstellung von Benzimidazolonen, wie sie in der DE-OS 2 725 957 beschrieben ist.After-treatment in N-methyl-2-pyrrolidone (30 minutes at boiling temperature) results in recrystallization and a pigment is obtained which colors PVC in a reddish yellow shade with very good fastness to migration, light and weather. 6-Amino-5-methylbenzoxazolone is prepared by known processes, but preferably analogously to the preparation of benzimidazolones, as described in DE-OS 2 725 957.

In nachstehender Tabelle sind weitere Pigmente beschrieben, die durch Kuppeln der Diazoverbindung des in Kolonne I aufgeführten.Amins mit der Acetoacetylverbindung desThe table below describes other pigments obtained by coupling the diazo compound of the amine listed in column I with the acetoacetyl compound of

Amins der Kolonne II und anschliessender Nachbehandlung in dem in Kolonne IV angegebenen Lösungsmittel erhalten werden, wobei in Kolonne IV die Abkürzung NMP für N-Methyl-2-pyrrolidon und DMFA für Dimethylformamid stehen. Kolonne . III gibt den Farbton der mit 0,2 % dieser Pigmente gefärbten PVC-Folie an.

Figure imgb0015
Figure imgb0016
Figure imgb0017
 Amines of column II and subsequent aftertreatment are obtained in the solvent indicated in column IV, the abbreviation NMP in column IV being N-methyl-2-pyrrolidone and DMFA being dimethylformamide. Column. III specifies the color of the PVC film colored with 0.2% of these pigments.
Figure imgb0015
Figure imgb0016
Figure imgb0017

Beispiel 32Example 32

3,26 Teile 5-Amino-6-methyl-benzimidazolon werden in 30 Vol-Teilen Wasser bei Raumtemperatur'verrührt; nach ca. 5 Minuten versetzt man mit 5 Vol-Teilen konzentrierter Salzsäure. Die Suspension wird mit Eis auf 100 C gekühlt, während 15 Minuten bei 5 bis 8° C mit 5,1 Vol.-Teilen 4-n-Natriumnitritlösung versetzt und anschliessend mit 30 Vol.-Teilen Eiswasser verdünnt. Nach ca. 1 Stunde Nachrühren bei O bis 5° C wird der Ueberschuss an Nitrit mit Sulfaminsäure beseitigt; anschliessend wird das Gemisch klärfiltriert. 4,66 Teile 5-Acetoacetylamino-benzimidazolon werden in 4 Vol.-Teilen 30%-iger Natronlauge und 70 Vol.-Teilen Wasser bei Raumtemperatur gelöst, mit 0,4 Teilen Kieselgur versetzt und das Reaktionsgemisch anschliessend klärfiltriert. In die Kupplungslösung werden 1,5 Vol.-Teile 30%-iger Salzsäure und dann noch 4 Teile Soda calz. zugegeben. Bei 15 bis 20° C wird in ca. 30 Minuten die Diazolösung zur Kupplungskomponente gegeben. Der pH-Wert fällt von 12,0 bis 4,4 nach beendeter Diazozugabe. Man lässt noch 6 bis 8 Stunden bei 20 bis 25° C nachrühren, heizt dann auf 90° C, filtriert das Pigment ab und wäscht mit heissem Wasser nach. Das Filtergut wird im Vakuum bei 70 bis 80° C getrocknet. Man erhält 8,13 Teile (entsprechend 100% der Theorie) eines orangebraunen pulverförmigen Pigmentes der Formel:

Figure imgb0018
welches PVC.in echtem rotstichigem Gelbton färbt.3.26 parts of 5-amino-6-methyl-benzimidazolone are stirred in 30 parts by volume of water at room temperature; after 5 minutes, 5 parts by volume of concentrated hydrochloric acid are added. The suspension is cooled with ice to 10 0 C, for 15 minutes at 5 to 8 ° C with 5.1 parts by volume are added 4-n-sodium nitrite solution and then-parts by volume diluted with 30 ice-water. After stirring for about 1 hour at 0 to 5 ° C, the excess nitrite is eliminated with sulfamic acid; the mixture is then clarified. 4.66 parts of 5-acetoacetylamino-benzimidazolone are dissolved in 4 parts by volume of 30% sodium hydroxide solution and 70 parts by volume of water at room temperature, mixed with 0.4 parts of diatomaceous earth and the reaction mixture is then clarified. 1.5 parts by volume of 30% hydrochloric acid and then 4 parts of soda ash are added to the coupling solution. admitted. At 15 to 20 ° C, the diazo solution is added to the coupling component in about 30 minutes. The pH drops from 12.0 to 4.4 after the addition of diazo has ended. The mixture is left to stir at 20 to 25 ° C for 6 to 8 hours, then heated to 90 ° C, the pigment is filtered off and washed with hot water. The filter material is dried in a vacuum at 70 to 80 ° C. 8.13 parts (corresponding to 100% of theory) of an orange-brown powdery pigment of the formula:
Figure imgb0018
 which colors PVC in a real reddish yellow shade.

Durch 6-stündiges Erhitzen des Rohpigments in Wasser in Gegenwart von 1 % eines Kondensationsproduktes aus 1 Mol Oleylalkohol und 20 Mol Aethylenoxyd bei 150° C unter Druck werden die Echtheiten und die Textur des Pigments noch verbessert. Man erhält ein Pigment, welches PVC in rotstichigem Gelbton von sehr guter Migrations-, Licht- und Wetterechtheit färbt.The fastness and the texture of the pigment are further improved by heating the crude pigment in water in the presence of 1% of a condensation product of 1 mol of oleyl alcohol and 20 mol of ethylene oxide at 150 ° C. under pressure for 6 hours. A pigment is obtained which colors PVC in a reddish yellow shade with very good fastness to migration, light and weather.

Claims (12)

1. Azopigmente der Formel
Figure imgb0019
worin X und Y Wasserstoff, Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen, Q eine Gruppe der Formeln -CONH- oder -NHCO- und Z ein 0-Atom oder eine Gruppe der Formeln -NR-, -NHCO-, -CONH-, -CH=N- oder
Figure imgb0020
darstellen, wobei R Wasserstoff, Alkyl mit 1-4 C-Atomen oder gegebenenfalls durch Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen substituiertes Phenyl und V Wasserstoff, Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen bedeuten und die Azogruppe an die Phenylreste A oder B gebunden sein kann.1. Azo pigments of the formula
Figure imgb0019
 in which X and Y are hydrogen, halogen, alkyl or alkoxy with 1-4 C atoms, Q is a group of the formulas -CONH- or -NHCO- and Z is a 0 atom or a group of the formulas -NR-, -NHCO-, -CONH-, -CH = N- or
Figure imgb0020
 represent, where R is hydrogen, alkyl with 1-4 C atoms or phenyl optionally substituted by halogen, alkyl or alkoxy with 1-4 C atoms and V is hydrogen, halogen, alkyl or alkoxy with 1-4 C atoms and the Azo group to which phenyl radicals A or B can be bonded. 2. Azopigmente gemäss Anspruch l der Formel
Figure imgb0021
worin Z ein O-Atom oder eine Gruppe der Formeln -NH-oder -NHCO- und X und Y die im Anspruch 1 angegebene Bedeutung haben.2. Azo pigments according to claim 1 of the formula
Figure imgb0021
 wherein Z is an O atom or a group of the formulas -NH- or -NHCO- and X and Y have the meaning given in claim 1. 3. Azopigmente gemäss Anspruch 2, wobei in der angegebenen Formel X Wasserstoff, Chlor, Methyl oder Methoxy und Y Wasserstoff, Chlor, Methyl, Methoxy oder Aethoxy bedeuten.3. azo pigments according to claim 2, wherein in the formula X is hydrogen, chlorine, methyl or methoxy and Y is hydrogen, chlorine, methyl, methoxy or ethoxy. 4. Azopigmente gemäss Anspruch 2 der Formel
Figure imgb0022
worin X und Y die in Anspruch 3 angegebene Bedeutung haben.4. Azo pigments according to claim 2 of the formula
Figure imgb0022
 wherein X and Y have the meaning given in claim 3. 5. Azopigmente gemäss Anspruch 2 der Formel
Figure imgb0023
worin X und Y die im Anspruch 3 angegebene Bedeutung haben.5. Azo pigments according to claim 2 of the formula
Figure imgb0023
 wherein X and Y have the meaning given in claim 3. 6. Azopigmente gemäss Anspruch 2 der Formel
Figure imgb0024
worin X und Y die in Anspruch 3 angegebene Bedeutung haben.6. Azo pigments according to claim 2 of the formula
Figure imgb0024
 wherein X and Y have the meaning given in claim 3. 7. Azopigmente gemäss Anspruch 1, gekennzeichnet durch die Formel
Figure imgb0025
worin X die im Anspruch 3 angegebene Bedeutung hat.7. Azo pigments according to claim 1, characterized by the formula
Figure imgb0025
 wherein X has the meaning given in claim 3. 8. Azopigmente gemäss Anspruch 1, gekennzeichnet durch die Formel
Figure imgb0026
worin X und Y die im Anspruch 3 angegebene Bedeutung haben.8. Azo pigments according to claim 1, characterized by the formula
Figure imgb0026
 wherein X and Y have the meaning given in claim 3. 9. Verfahren zur Herstellung von Azopigmenten der Formel
Figure imgb0027
worin X und Y Wasserstoff, Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen, Q eine Gruppe der Formeln -CONH- oder -NHCO-und Z ein O-Atom oder eine Gruppe der Formeln -NR-, -NHCO-, -CONH-, -CH=N- oder
Figure imgb0028
darstellen, wobei R Wasserstoff, Alkyl mit 1-4 C-Atomen oder gegebenenfalls durch Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen substituiertes Phenyl und V Wasserstoff, Halogen, Alkyl oder Alkoxy mit 1-4 C-Atomen bedeuten und die Azogruppe an die Phenylreste A oder B gebunden sein kann, dadurch gekennzeichnet, dass man die Diazoverbindung eines Amins der Formel
Figure imgb0029
worin Y, Q und Z die oben angegebene Bedeutung haben und die Aminogruppe an die Phenylreste A oder B gebunden sein kann, mit einem Acetessigarylid der Formel
Figure imgb0030
worin X die oben angegebene Bedeutung hat, kuppelt.9. Process for the preparation of azo pigments of the formula
Figure imgb0027
 in which X and Y are hydrogen, halogen, alkyl or alkoxy with 1-4 C atoms, Q is a group of the formulas -CONH- or -NHCO- and Z is an O atom or a group of the formulas -NR-, -NHCO-, -CONH-, -CH = N- or
Figure imgb0028
 represent where R is hydrogen, alkyl with 1-4 C atoms or phenyl optionally substituted by halogen, alkyl or alkoxy with 1-4 C atoms and V is hydrogen, halogen, alkyl or alkoxy with 1-4 C atoms and the azo group the phenyl radicals A or B can be bound, characterized in that the diazo compound of an amine of the formula
Figure imgb0029
 wherein Y, Q and Z have the meaning given above and the amino group can be bound to the phenyl radicals A or B, with an acetoacetic arylide of the formula
Figure imgb0030
 where X has the meaning given above, couples. lo. Verfahren gemäss Anspruch 9,. dadurch gekennzeichnet, dass man eine Kupplungskomponente der Formel
Figure imgb0031
verwendet, worin X Wasserstoff, Chlor, Methyl oder Methoxy bedeutet.lo. Method according to claim 9. characterized in that a coupling component of the formula
Figure imgb0031
 used, wherein X is hydrogen, chlorine, methyl or methoxy. 11. Verfahren zum Pigmentieren von hochmolekularem organischem Material, gekennzeichnet durch die Verwendung eines Azopigments gemäss den Ansprüchen 1 bis 8.11. A method for pigmenting high molecular weight organic material, characterized by the use of an azo pigment according to claims 1 to 8. 12. Das gemäss Anspruch 11 erhaltene pigmentierte hochmolekulare organische Material.12. The pigmented high molecular weight organic material obtained according to claim 11.
EP19780100516 1977-08-04 1978-07-27 Monoazo pigments of the acetoacetylamino benzimidazolone series, their preparation and their use for colouring organic material of high molecular weight Expired EP0000737B1 (en)

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EP0010722A1 (en) * 1978-10-31 1980-05-14 Hoechst Aktiengesellschaft Monoazo-compounds, process for their preparation and their use

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DE4007535A1 (en) * 1990-03-09 1991-09-12 Hoechst Ag WATER-INSOLUBLE AZO PAINTS, THEIR PRODUCTION AND USE

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Publication number Priority date Publication date Assignee Title
FR2128514A1 (en) * 1971-03-03 1972-10-20 Ciba Geigy Ag
FR2167629A1 (en) * 1972-01-03 1973-08-24 Hoechst Ag
FR2233373A1 (en) * 1973-06-12 1975-01-10 Hoechst Ag
FR2370082A1 (en) * 1976-11-09 1978-06-02 Ciba Geigy Ag MONO-AZOIC PIGMENTS AND THEIR PREPARATION

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2128514A1 (en) * 1971-03-03 1972-10-20 Ciba Geigy Ag
FR2167629A1 (en) * 1972-01-03 1973-08-24 Hoechst Ag
FR2233373A1 (en) * 1973-06-12 1975-01-10 Hoechst Ag
FR2370082A1 (en) * 1976-11-09 1978-06-02 Ciba Geigy Ag MONO-AZOIC PIGMENTS AND THEIR PREPARATION

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010722A1 (en) * 1978-10-31 1980-05-14 Hoechst Aktiengesellschaft Monoazo-compounds, process for their preparation and their use

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