EP0000737B1 - 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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EP0000737B1
EP0000737B1 EP19780100516 EP78100516A EP0000737B1 EP 0000737 B1 EP0000737 B1 EP 0000737B1 EP 19780100516 EP19780100516 EP 19780100516 EP 78100516 A EP78100516 A EP 78100516A EP 0000737 B1 EP0000737 B1 EP 0000737B1
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formula
amino
methyl
azo pigments
hydrogen
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French (fr)
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EP0000737A1 (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

  • the invention relates to new monoazo pigments based on heterocyclic diazo components coupled with acetomethylaminobenzimidazolone.
  • French patent publication 2,128,514 already describes monoazo pigments which are prepared by coupling the diazotized amines, in particular benzoxazolones and benzimidazolones, with acetoacetylamino-benzimidazolones which are substituted on an nitrogen atom by an alkyl, cycloalkyl or aryl group.
  • the azo pigments obtained have low light fastness, so that they are not very suitable for pigmenting high molecular weight organic material.
  • Acetoacetylamino-benzimidazolones with unsubstituted nitrogen atoms as coupling components are already known from French patent publications 2,167,629 and 2,233,373, but in combination with other heterocyclic diazo components which differ structurally from the diazo components of the new monoazo pigments.
  • 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 formula -CONH and Z is a 0 atom or a group of the formulas -NH- or -NHCO - mean.
  • X is preferably hydrogen, chlorine, methyl or methoxy and Y is hydrogen, chlorine, methyl, methoxy or ethoxy.
  • the acetoacetic arylides to be used as coupling component are obtained, for example, by addition of 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.
  • a buffer come e.g. the salts, in particular alkali salts, of formic acid, phosphoric acid or in particular acetic acid.
  • the alkaline solution of the coupling component suitably 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 also alkyl esters of sulforicinoleates, for example n-butylsulforicinoleate.
  • aralkyl sulfonate such as dodecylbenzenesulfonate or the sodium salt of 1,1'-dinaphthylmethanesul
  • 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 e.g. 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, chlorobenzen
  • the coupling can also be carried out advantageously in such a way that an acidic solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle continuously combined, with an immediate coupling of the components.
  • 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 often be 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., which in many cases leads to coarsening of the grain, which has a favorable effect on the fastness to light and migration 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 in finely divided form to pigment high-molecular organic material, e.g. of cellulose ethers and esters, polyamides, polyurethanes, polyesters, acetyl cellulose, nitrocellulose, natural resins or synthetic resins, such as polymerization or condensation resins, e.g.
  • Aminoplasts especially 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Coloring (AREA)

Description

Gegenstand der Erfindung sind neue Monoazopigmente auf Basis von mit Acetomethylaminobenzimidazolon gekuppelten heterocyclischen Diazokomponenten.The invention relates to new monoazo pigments based on heterocyclic diazo components coupled with acetomethylaminobenzimidazolone.

In der französischen Patentpublikation 2.128.514 sind bereits Monoazopigmente beschrieben, die durch Kupplung der diazotierten Amine von insbesondere Benzoxazolonen und Benzimidazolonen mit Acetoacetylamino-benzimidazolonen, die an einem Stickstoffatom durch eine Alkyl-, Cycloalkyl-oder Arylgruppe substituiert sind, hergestellt werden. Die erhaltenen Azopigmente weisen jedoch eine geringe Lichtechtheit auf, so dass sie für die Pigmentierung von hochmolekularem organischem Material wenig geeignet sind.French patent publication 2,128,514 already describes monoazo pigments which are prepared by coupling the diazotized amines, in particular benzoxazolones and benzimidazolones, with acetoacetylamino-benzimidazolones which are substituted on an nitrogen atom by an alkyl, cycloalkyl or aryl group. However, the azo pigments obtained have low light fastness, so that they are not very suitable for pigmenting high molecular weight organic material.

Es wurde nun gefunden, dass Azopigmente, welche die gleiche Diazokomponente aufweisen, aber mit Acetoacetylaminobenzimidazolonen gekuppelt sind, deren Stickstoffatome unsubstituiert sind, ausgezeichnet lichtecht sind.It has now been found that azo pigments which have the same diazo component but are coupled to acetoacetylaminobenzimidazolones, the nitrogen atoms of which are unsubstituted, have excellent lightfastness.

Acetoacetylamino-benzimidazolone mit unsubstituierten Stickstoffatomen als Kupplungskomponente sind bereits aus den französischen Patentpublikationen 2.167.629 und 2.233.373 bekannt, jedoch in Kombination mit anderen heterocyclischen Diazokomponenten, die sich von den Diazokomponenten der neuen Monoazopigmente strukturell unterscheiden.Acetoacetylamino-benzimidazolones with unsubstituted nitrogen atoms as coupling components are already known from French patent publications 2,167,629 and 2,233,373, but in combination with other heterocyclic diazo components which differ structurally from the diazo components of the new monoazo pigments.

Die neuen Azopigmente entsprechen der Formel

Figure imgb0001
worin X und Y Wasserstoff, Halogen, Alkyl oder Alkoxy mit 1 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=H- 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 ist. Sie werden dadurch hergestellt, dass man die Diazoverbindung eines Amins der Formel
Figure imgb0003
mit einem Acetessigarylid der Formel
Figure imgb0004
kuppelt.The new azo pigments correspond to the formula
Figure imgb0001
 in which 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 the formulas -NR-, -NHCO-, -CONH-, -CH = H- or
Figure imgb0002
 represent, wherein R is hydrogen, alkyl with 1-4 C atoms or optionally by halogen, alkyl or alkoxy with 1-4. C atoms are substituted phenyl and V is hydrogen, halogen, alkyl or alkoxy with 1-4 C atoms and the azo group is bonded to the phenyl radicals A or B. They are prepared by using the diazo compound of an amine of the formula
Figure imgb0003
 with an acetoessigarylide of the formula
Figure imgb0004
 couples.

Bevorzugt sind jene Verbindungen der Formel (1), worin Q eine Gruppe der Formel -CONH-und Z ein O-Atom oder eine Gruppe der Formel -CONH- und Z ein 0-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 formula -CONH and Z is a 0 atom or a group of the formulas -NH- or -NHCO - mean. 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
 Compounds of the formulas are of particular interest
Figure imgb0005
 and especially those of the formula
Figure imgb0006

Als Beispiele für (Amine, deren Diazoverbindungen verwendet werden und) 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
Examples of (amines whose diazo compounds are used and) 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 für die vorstehenden Amine 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
    • 5-Amino-6-methyl-benzoxazolon
    • 5-Amino-7-methyl-benzoxazolon
    • 5-Amino-6-methoxy-benzoxazolon
    • 6-Amino-benzoxazolon
    • 6-Amino-5-chlorbenzoxazolon
    • 6-Amino-5-methyl-benzoxazolon
  • 2) 5-Amino-benzimidazolon
    • 5-Amino-6-chlor-benzimidazolon
    • 5-Amino-7-chlor-benzimidazolon
    • 5-Amino-6-methyl-benzimidazolon
    • 5-Amino-7-methyl-benzimidazolon
    • 5-Amino-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-Aminochinazolin-4-on
    • 5-Amino-6-chlorchinazolin-4-on
  • 6) 2-(3'-Amino-4'-methoxyphenyl)-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

Als Kupplungskomponenten verwendet man vorzugsweise Acetessigarylide der Formel
Figure imgb0013
worin X die oben angegebene Bedeutung hat.Examples of the above amines, categorized according to the groups mentioned above, are the following:
  • 1) 5-aminobenzoxazolone
    • 6-aminobenzoxazolone
    • 5-amino-6-chloro-benzoxazolone
    • 5-amino-7-chloro-benzoxazolone
    • 5-amino-6-methyl-benzoxazolone
    • 5-amino-7-methyl-benzoxazolone
    • 5-amino-6-methoxy-benzoxazolone
    • 6-amino-benzoxazolone
    • 6-amino-5-chlorobenzoxazolone
    • 6-amino-5-methyl-benzoxazolone
  • 2) 5-amino-benzimidazolone
    • 5-amino-6-chloro-benzimidazolone
    • 5-amino-7-chloro-benzimidazolone
    • 5-amino-6-methyl-benzimidazolone
    • 5-amino-7-methyl-benzimidazolone
    • 5-amino-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'-methoxyphenyl) -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

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 coupling component are obtained, for example, by addition of 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. As a buffer come e.g. the salts, in particular alkali salts, of formic acid, phosphoric acid or in particular acetic acid. The alkaline solution of the coupling component suitably 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 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 e.g. 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 be carried out advantageously in such a way that an acidic solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle continuously combined, with an immediate coupling of the components. 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 often be 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, wobie 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., which in many cases leads to coarsening of the grain, which has a favorable effect on the fastness to light and migration 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 in feinverteilter Form zum Pigmentieren von hochmolekularem organischen Material verwendet werden, z.B. von Celluloseäthern 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 in finely divided form to pigment high-molecular organic material, e.g. of cellulose ethers and esters, polyamides, polyurethanes, polyesters, acetyl cellulose, nitrocellulose, natural resins or synthetic resins, such as polymerization or condensation resins, e.g. Aminoplasts, especially 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 vorteilhaft, die neuen Pigmente als Toner oder in Form von Präparaten zu verwenden.It does not matter whether the high-molecular 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 80°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 reddish yellow 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 des 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
 The table below describes other pigments which are obtained by coupling the diazo compound of the amine listed in column I with the acetoacetyl compound of the amine in column II and subsequent aftertreatment in the solvent indicated in column IV, the abbreviation NMP for N- in column IV Methyl-2-pyrrolidone and DMFA stand for dimethylformamide. Column III indicates the color of the PVC film colored with 0.2% of these pigments.
Figure imgb0015
Figure imgb0016

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 10°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 0 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 imgb0017
welches PVC in echtem rotstichigem Gelbton färbt.3.26 parts of 5-amino-6-methyl-benzimidazolone are added in 30 parts by volume of water. Room temperature stirred; after 5 minutes, 5 parts by volume of concentrated hydrochloric acid are added. The suspension is cooled to 10 ° C. with ice, 5.1 parts by volume of 4N sodium nitrite solution are added at 5 to 8 ° C. for 15 minutes and then diluted with 30 parts by volume of 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 imgb0017
 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 (11)

1. Azo pigments of the formula
Figure imgb0029
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 0 atom or is a group of the formula -NR-, -NHCO-, -CONH-, -CH=N- or
Figure imgb0030
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.
2. Azo pigments according to Claim 1 of the formula
Figure imgb0031
wherein Z is an O atom or a group of the formula -NH- or -NHCO-.
3. Azo pigments according to Claim 2, where, in the given formula, X is hydrogen, chlorine, methyl or methoxy, and Y is hydrogen, chlorine, methyl, methoxy or ethoxy.
4. Azo pigments according to Claim 3 of the formula
Figure imgb0032
5. Azo pigments according to Claim 3 of the formula
Figure imgb0033
6. Azo pigments according to Claim 3 of the formula
Figure imgb0034
7. Azo pigments according to Claim 1, characterised by the formula
Figure imgb0035
8. Azo pigments according to Claim 1, characterised by the formula
Figure imgb0036
9. A process for producing the azo pigments according to Claim 1, characterised in that the diazo compound of an amine of the formula,
Figure imgb0037
is coupled with an acetoacetic arylide of the formula
Figure imgb0038
10. A process according to Claim 9, characterised in that there is used a coupling component of the formula
Figure imgb0039
wherein X is hydrogen, chlorine, methyl or methoxy.
11. A process for pigmenting high-molecular organic material, characterised by the use of an azo pigment according to Claims 1 to 8.
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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