WO2003099936A1 - Novel derivatives of c.i. pigment red 170 - Google Patents

Novel derivatives of c.i. pigment red 170 Download PDF

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Publication number
WO2003099936A1
WO2003099936A1 PCT/EP2003/004966 EP0304966W WO03099936A1 WO 2003099936 A1 WO2003099936 A1 WO 2003099936A1 EP 0304966 W EP0304966 W EP 0304966W WO 03099936 A1 WO03099936 A1 WO 03099936A1
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Prior art keywords
compound
formula
acid
meaning
pigment
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PCT/EP2003/004966
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German (de)
French (fr)
Inventor
Martin U. Schmidt
Andreas Wacker
Hans Joachim Metz
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Clariant Gmbh
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Publication of WO2003099936A1 publication Critical patent/WO2003099936A1/en

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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
    • C09B29/0003—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
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/18—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides
    • C09B29/20—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides of the naphthalene series
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0025—Crystal modifications; Special X-ray patterns
    • C09B67/0028—Crystal modifications; Special X-ray patterns of azo compounds
    • C09B67/0029—Crystal modifications; Special X-ray patterns of azo compounds of monoazo compounds

Definitions

  • the present invention relates to new azo pigments based on C.I. Pigment Red 170 and process for its manufacture.
  • the ⁇ phase is mainly used in automotive paints.
  • the ß phase is much more transparent and bluish than the ⁇ phase.
  • the ⁇ phase has significantly poorer fastness properties and is therefore not suitable as an organic pigment.
  • C.I. Pigment Red 170 is described in DE 1 228 731.
  • the ⁇ , ⁇ and ⁇ phases are described in DE 2 043 482.
  • the aim of the present invention was to provide azo red pigments with good general fastness properties, which are more transparent and at the same time more yellowish than the C.I. Pigment Red 170 in the ⁇ phase.
  • the present invention relates to compounds of the formula (1) wherein
  • X has the meaning F, Cl, Br, methyl or nitro.
  • Formula (1) is to be understood as an idealized representation and also includes the corresponding tautomeric forms and the possible configuration isomers of each tautomeric form.
  • the compound of formula (1) where X is methyl can occur in two different crystal modifications.
  • the compound of formula (1) where X is nitro can occur in three different crystal modifications.
  • the line positions of all phases are usually affected by an inaccuracy of 0.2 ° in 2 ⁇ .
  • the crystal phases of the compound of formula (1) with X equal to nitro are characterized by the following characteristic lines (Cu-K ⁇ radiation, 2 ⁇ values in degrees, d values in A " ⁇ relative intensity in%).
  • the ⁇ -phase of the nitro compound arises, for example, when the pigment is heated at 100 to 110 ° C. in dimethylformamide after the synthesis.
  • the ß phase of the nitro compound arises, for example, if the pigment is heated to 90 to 100 ° C. in water after the synthesis.
  • the ⁇ phase of the nitro compound arises, for example, if the pigment is heated to 130 to 150 ° C. in water after the synthesis.
  • the crystal phases of the compound of formula (1) with X equal to methyl are characterized by the following characteristic lines (Cu-K ⁇ radiation, 2 ⁇ values in degrees, d values in ⁇ "1 , relative intensity in%):
  • the ⁇ -phase of the methyl compound is formed, for example, if the pigment is heated to 90 to 110 ° C after the synthesis in acetic acid or heated to 130 to 140 ° C in water.
  • the ⁇ -phase of the methyl compound arises, for example, if the pigment is heated to 100 to 130 ° C. in chlorobenzene after the synthesis.
  • the pigments according to the invention can be obtained by diazotizing an amine of the formula (2)
  • Alkali metal nitrites or the alkyl nitrites of short-chain alkanes, together with strong mineral acids, are suitable for the diazotization reaction.
  • Sodium nitrite and hydrochloric acid are particularly suitable.
  • the reaction can be carried out in a temperature range from -5 ° C to + 30 ° C, preferably between 0 ° C and 10 ° C.
  • non-ionic, anionic or cationic surface-active substances can be present in the diazotization.
  • other auxiliaries such as natural or synthetic resins or resin derivatives, can also be used. Coupling is possible by the direct or inverse method, but is preferably carried out indirectly, ie the coupling component is added to the diazonium salt provided.
  • the coupling reaction can be carried out in a temperature range between -5 ° C and 80 ° C, preferably between 5 ° C and 25 ° C, and at a pH between pH 4 and pH 14, in particular between pH 9 and pH 12.
  • Die Azo coupling reaction is preferably carried out in aqueous solution or suspension, but it is also possible to use organic solvents, if appropriate in a mixture with water, for example alcohols having 1 to 10 carbon atoms, such as, for example, methanol, ethanol, n-propanol, isopropanol, butanols, such as n -Butanol, sec-butanol, tert-butanol, pentanols, such as n-pentanol, 2-methyl-2-butanol, hexanols, such as 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2-methyl -2-hexanol, 3-ethyl-3-pentanol
  • Monoethyl ether of ethylene or propylene glycol diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl glycols or methoxybutanol; Ketones such as acetone, diethyl ketone, methyl isobutyl ketone, methyl ethyl ketone or cyclohexanone; aliphatic acid amides such as formamide, dimethylformamide, N-methylacetamide or N, N-dimethylacetamide; Urea derivatives, such as
  • Tetramethylurea Tetramethylurea; or cyclic carboxamides, such as N-methylpyrrolidone, valero- or caprolactam; Esters, such as carboxylic acid C 1 -C 6 -alkyl esters, such as butyl formate, ethyl acetate or propyl propionate; or carboxylic acid -C 6 glycol ester; or glycol ether acetates, such as 1-methoxy-2-propyl acetate; or phthalic or benzoic acid CrC 6 alkyl esters, such as
  • benzoate cyclic esters such as caprolactone; Nitriles such as acetonitrile or benzonitrile; aliphatic or aromatic hydrocarbons, such as cyclohexane or benzene; or by alkyl, alkoxy, nitro or halogen substituted benzene, such as toluene, xylenes, ethylbenzene, anisole, nitrobenzene, chlorobenzene, o-dichlorobenzene, 1, 2,4-trichlorobenzene or bromobenzene; or other substituted aromatics such as benzoic acid or phenol; aromatic heterocycles such as pyridine, morpholine, picoline or quinoline; as well as hexamethylphosphoric triamide, 1, 3-dimetyl-2-imidazolidinone, dimethyl sulfoxide and sulfolane.
  • the solvents mentioned can also be used as mixtures. Water-miscible solvents
  • auxiliaries such as, for example, coupling auxiliaries, surfactants, pigmentary and non-pigmentary dispersants, fillers, adjusting agents, resins, waxes, defoamers, anti-dust agents, extenders, colorants for shading, preservatives, drying retardants, additives for controlling the rheology, wetting agents, antioxidants, UV absorbers, light stabilizers, or a combination thereof can be used.
  • the total amount of auxiliaries added can be 0 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 2.5 to 25% by weight, based on the azo pigment.
  • Suitable surfactants are anionic or anionic, cationic or cationic and nonionic substances or mixtures of these agents.
  • anionic substances are fatty acid taurides, fatty acid N-methyl taurides, fatty acid isethionates, alkylphenyl sulfonates, alkyl naphthalene sulfonates, alkylphenol polyglycol ether sulfates, fatty alcohol polyglycol ether sulfates, fatty acid amide polyglycol ether sulfates, alkyl sulfosuccinamate succinate acid, alkenyl sulfonate urate sulfate, alkenyl sulfonate urate Fatty acids, for example palmitic, stearic and oleic acid; Soaps, for example alkali salts of fatty acids, naphthenic acids and resin acids, for example abietic acid, alkali-soluble resins, for example
  • alkali-soluble resinous auxiliaries or mixtures thereof during or after the coupling, and before or during the lacquering improves the dispersibility of the pigments.
  • the resinous auxiliaries or mixtures thereof are expediently used in the form of their aqueous-alkaline solutions.
  • Natural and synthetic resins are suitable as resinous auxiliaries. Rosin, disproportionated or hydrogenated rosin and rosin derivatives are to be mentioned as advantageous.
  • Natural resin acids such as abietic acid, dihydroabietic acid, tetrahydroabietic acid, laevopimaric acid, dextropimaric acid and isodextropimaric acid, as are present in commercially available types of rosin, are preferred.
  • the commercially available resin Rosin N which contains the resin acids abietic acid, dehydroabetic acid, neoabietic acid, palustric acid, isopimaric acid, pimaric acid and sandaracopimaric acid, or a commercial product equivalent to Rosin N, is particularly preferred.
  • alkyd resins or synthetic hydrocarbon resins with a high acid number can also be used.
  • the resins mentioned are preferably added to the reaction mixture following the coupling reaction.
  • Suitable cationic substances are quaternary ammonium salts, fatty amine oxyalkylates, oxyalkylated polyamines, fatty amine polyglycol ethers, fatty amines, di- and polyamines derived from fatty amines or fatty alcohols and their oxyalkylates, imidazolines derived from fatty acids, and salts of these cationic substances, such as acetates.
  • nonionic substances include amine oxides, fatty alcohol polyglycol ethers, fatty acid polyglycol esters, betaines such as fatty acid amide-N-propyl-betaine, phosphoric acid esters of aliphatic and aromatic alcohols, fatty alcohols or fatty alcohol polyglycol ethers, fatty acid amide ethoxylates, fatty alcohol-alkylene oxide adducts and alkylphenol adducts and alkylphenol in consideration.
  • Nonpigmentary dispersants mean substances that are not derived from organic pigments by chemical modification. They are used as dispersants either in the manufacture of pigments, but often also in the incorporation of the pigments into the application media to be colored, for example in the manufacture of paints or printing inks
  • Dispersion of the pigments in the corresponding binders can be polymeric substances, for example polyolefins, polyesters, polyethers, polyamides, polyimines, polyacrylates, polyisocyanates, block copolymers thereof, copolymers from the corresponding monomers or polymers from one class which have been modified with a few monomers from another class.
  • These polymeric substances carry polar anchor groups such as, for example, hydroxyl, amino, imino and ammonium groups, carboxylic acid and carboxylate groups, sulfonic acid and sulfonate groups or phosphonic acid and phosphonate groups, and can also be modified with aromatic, non-pigmentary substances.
  • Non-pigmentary dispersants can furthermore also be aromatic substances which are chemically modified with functional groups and are not derived from organic pigments.
  • Nonpigmentary dispersants are known in the art and some are available commercially (for example, Solsperse ®, Avecia; Disperbyk ®, Byk, Efka ®, Efka).
  • Pigmentary dispersants mean pigment dispersants which are derived from an organic pigment as the base body and are produced by chemical modification of this base body, for example saccharin-containing pigment dispersants, piperidyl-containing pigment dispersants, naphthalene or perylene-derived pigment dispersants, pigment dispersants with functional groups which have a methylene group with the Basic pigment bodies are linked, chemically modified basic pigment bodies, pigment dispersants containing sulfonic acid groups, pigment dispersants containing sulfonamide groups, pigment dispersants containing ether groups, or pigment dispersants containing carboxylic acid, carboxylic acid ester or carbonamide groups.
  • buffer solutions can be added, preferably of organic acids and their salts, such as, for example, formic acid / formate buffer, acetic acid / acetate buffer, citric acid / citrate buffer; or of inorganic acids and their salts, such as, for example, phosphoric acid / phosphate buffer or carbonic acid / bicarbonate or carbonate buffer.
  • organic acids and their salts such as, for example, formic acid / formate buffer, acetic acid / acetate buffer, citric acid / citrate buffer
  • inorganic acids and their salts such as, for example, phosphoric acid / phosphate buffer or carbonic acid / bicarbonate or carbonate buffer.
  • the coupling component based on the diazonium compound, is used in a slight excess, preferably 1 equivalent of diazo component is reacted with 1,001 to 1,10 equivalents of the coupling component.
  • the compounds according to the invention are preferably subjected to heat treatment in an aqueous, aqueous-organic or organic medium using the solvents described above
  • the compounds of formula (1) can be used for pigmenting high molecular weight organic materials of natural or synthetic origin, for example plastics, resins, lacquers, paints or electrophotographic toners and developers, as well as inks and printing inks.
  • High molecular weight organic materials which can be pigmented with the compounds according to the invention are, for example, cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerization resins or condensation resins, for example aminoplasts, in particular urea and melamine formaldehyde resins, alkyd resins, Acrylic resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, individually or in mixtures.
  • cellulose ethers and esters such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose butyrate
  • natural resins or synthetic resins such as polymerization resins or condensation resins, for
  • the compounds according to the invention are used in an amount of 0.05 to 30% by weight, preferably 0.1 to 15% by weight.
  • the pigments according to the invention are suitable as colorants in electrophotographic toners and developers, such as, for example, one- or two-component powder toners (also one- or two-component developers called), magnetic toner, liquid toner, latex toner, polymerization toner and special toner.
  • electrophotographic toners and developers such as, for example, one- or two-component powder toners (also one- or two-component developers called), magnetic toner, liquid toner, latex toner, polymerization toner and special toner.
  • Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and polyethylene and polypropylene, which also contain other ingredients, such as charge control agents, waxes or flow aids, or can be modified with these additives afterwards.
  • resins such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and polyethylene and polypropylene, which also contain other ingredients, such as charge control agents, waxes or flow aids, or can be modified with these additives afterwards.
  • the pigments according to the invention are suitable as colorants in powders and powder coatings, in particular in triboelectrically or electrokinetically sprayable powder coatings which are used for the surface coating of objects made of, for example, metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber.
  • Epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethane and acrylic resins are typically used as powder coating resins together with conventional hardeners. Combinations of resins are also used. For example, epoxy resins are often used in combination with carboxyl- and hydroxyl-containing polyester resins.
  • Typical hardener components are, for example, acid anhydrides, imidazoles and dicyandiamide and their derivatives, blocked isocyanates, bisacyl urethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids.
  • the pigments according to the invention are suitable as colorants in inks, preferably ink-jet inks, such as, for example, on an aqueous or non-aqueous basis, microemulsion inks and in such inks which work according to the hot-melt process.
  • Ink-jet inks generally contain a total of 0.5 to 15% by weight, preferably 1.5 to 8% by weight (calculated on a dry basis) of one or more of the compounds according to the invention.
  • Microemulsion inks are based on organic solvents, water and possibly an additional hydrotropic substance (interface mediator).
  • Microemulsion inks contain 0.5 to 15% by weight, preferably 1.5 to 8% by weight, of one or more of the compounds according to the invention, 5 to 99% by weight of water and 0.5 to 94.5% by weight organic solvent and / or hydrotropic compound.
  • solvent based ink-jet inks preferably contain 0.5 to 15% by weight of one or more compounds according to the invention, 85 to 99.5% by weight of organic solvent and / or hydrotropic compounds.
  • Hot-melt inks are mostly based on waxes, fatty acids, fatty alcohols or sulfonamides, which are solid at room temperature and become liquid when heated, the preferred melting range being between approx. 60 ° C and approx. 140 ° C.
  • Hot melt ink jet inks are e.g. essentially from 20 to 90% by weight of wax and 1 to 10% by weight of one or more of the compounds according to the invention.
  • an additional polymer as a "dye dissolver”
  • dispersing aid 0 to 20% by weight of viscosity modifier
  • plasticizer 0 to 10% by weight % Tack additive
  • the compounds according to the invention are also suitable as colorants for color filters, both for additive and for subtractive color production.
  • the compounds according to the invention are also suitable for coloring seed.
  • the pigments according to the invention are notable for good fastness properties and high transparency. They are essential more yellowish than CI Pigment Red 170. They do not contain any heavy metals that are harmful to the environment.
  • the properties listed qualify the pigments of the invention in particular for use as colorants in paints, preferably automotive paints, and in plastics, and in printing inks.
  • the synthesis takes place as in comparative example 1a, but instead of 4-aminobenzamide 15.4 parts of 4-amino-3-fluoro-benzamide.
  • the press cake is heated in acetic acid at 114 ° C. for 50 minutes, filtered off, washed with water and dried.
  • Example 2a The synthesis is carried out as in Example 2a.
  • the press cake is heated in acetic acid at 100 ° C. for 20 minutes, filtered off, washed with water and dried.
  • Example 4 The synthesis is carried out as in Example 4.
  • the press cake is heated in water at 98 ° C. for 2 hours, filtered off, washed with water and dried.
  • the ⁇ -phase of the nitroderivative is obtained with smaller additions of the ⁇ -phase of the nitroderivative.
  • Example 4 The press cake is used for aftertreatment Heated in water at 140 ° C. for 1 hour, filtered off, washed with water and dried.
  • the ⁇ -phase of the nitroderivative is obtained with smaller additions of the ⁇ - and ß-phase of the nitroderivative.
  • Example 7 The synthesis takes place as in Example 7.
  • the press cake is heated in chlorobenzene for 1 hour at 120 ° C., filtered off, washed with chlorobenzene and dried.
  • an aromatic-containing alkyd melamine resin paint (AM) based on a medium-oil alkyd resin and a butanol-etherified melamine resin was selected from the large number of known paints.
  • AM aromatic-containing alkyd melamine resin paint
  • white lightenings were created with a pigment: TiO 2 ratio of 1:10.
  • ⁇ H is the color difference between the coating of the pigment and the coating of the product of Comparative Example 1.
  • a positive ⁇ H value means that the pigment is more yellow than the comparative example.
  • PVC coloring is made and coloristically compared to a PVC coloring of Comparative Example 1.
  • the PVC colorations of the pigments according to the invention from Examples 7 and 8 are significantly more yellow and more transparent than the PVC coloration of Comparative Example 1.
  • Application example 9a-d light and weather fastness
  • the pigments are dispersed in an aromatic alkyd melamine resin paint (AM) based on a medium oil alkyd resin and a butanol etherified melamine resin and subjected to a light and weather fastness test in a rapid exposure or rapid weathering apparatus.
  • the tests were carried out both in full tone and in brightening.
  • the overall coloristic distance ⁇ E in the CIELAB system
  • the exposures were carried out in synchronism in the Xenotest Beta device.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention relates to compounds of formula (1), in which X represents F, Cl, Br, methyl or nitro, or to the tautomers thereof. Said compounds are characterised by a strong yellow tone, transparency and fastness to weathering in relation to the unsubstituted pigment red 170.

Description

Neue Derivate von C.I. Pigment Red 170 New derivatives from C.I. Pigment Red 170
Die vorliegende Erfindung betrifft neue Azopigmente auf der Basis von C.I. Pigment Red 170 und Verfahren zu deren Herstellung.The present invention relates to new azo pigments based on C.I. Pigment Red 170 and process for its manufacture.
C.I. Pigment Red 170 (Formel (1 ), X=H) ist aufgrund seiner guten allgemeinen Echtheiten ein wichtiges Rotpigment zur Einfärbung von Lacken, insbesondere von Automobillacken. Das Pigment kommt in drei unterschiedlichenC.I. Because of its good general fastness properties, Pigment Red 170 (formula (1), X = H) is an important red pigment for coloring paints, especially automotive paints. The pigment comes in three different
Kristallmodifikationen vor: In Automobillacken wird vor allem die γ-Phase eingesetzt. Die ß-Phase ist wesentlich transparenter und blaustichiger als die γ-Phase. Die α-Phase hat wesentlich schlechtere Echtheitseigenschaften und eignet sich daher nicht als organisches Pigment.Crystal modifications before: The γ phase is mainly used in automotive paints. The ß phase is much more transparent and bluish than the γ phase. The α phase has significantly poorer fastness properties and is therefore not suitable as an organic pigment.
C.I. Pigment Red 170 ist in DE 1 228 731 beschrieben. Die α-, ß- und γ-Phase werden in DE 2 043 482 beschrieben.C.I. Pigment Red 170 is described in DE 1 228 731. The α, β and γ phases are described in DE 2 043 482.
Ziel der vorliegenden Erfindung war es, Azorotpigmente mit guten allgemeinen Echtheiten bereitzustellen, die transparenter und gleichzeitig gelbstichiger sind als das genannte C.I. Pigment Red 170 in der γ-Phase.The aim of the present invention was to provide azo red pigments with good general fastness properties, which are more transparent and at the same time more yellowish than the C.I. Pigment Red 170 in the γ phase.
Es wurde gefunden, dass die nachstehend definierten Derivate der Formel (1) überraschenderweise diese Aufgabe lösen.It has been found that the derivatives of the formula (1) defined below surprisingly achieve this object.
Gegenstand der vorliegenden Erfindung sind Verbindungen der Formel (1)
Figure imgf000003_0001
worinThe present invention relates to compounds of the formula (1)
Figure imgf000003_0001
wherein
X die Bedeutung F, Cl, Br, Methyl oder Nitro hat.X has the meaning F, Cl, Br, methyl or nitro.
Die Formel (1) ist als idealisierte Darstellung zu verstehen und umfasst auch die entsprechenden tautomeren Formen sowie die möglichen Konfigurationsisomere jeder tautomeren Form.Formula (1) is to be understood as an idealized representation and also includes the corresponding tautomeric forms and the possible configuration isomers of each tautomeric form.
Die Verbindung der Formel (1) mit X gleich Methyl kann in zwei verschiedenen Kristallmodifikationen auftreten. Die Verbindung der Formel (1) mit X gleich Nitro kann in drei verschiedenen Kristallmodifikationen auftreten.The compound of formula (1) where X is methyl can occur in two different crystal modifications. The compound of formula (1) where X is nitro can occur in three different crystal modifications.
Alle Phasen werden durch Röntgenpulverdiffraktometrie nachgewiesen.All phases are detected by X-ray powder diffractometry.
Die Linienlagen aller Phasen sind üblicherweise mit einer Ungenauigkeit von 0.2° in 2Θ behaftet.The line positions of all phases are usually affected by an inaccuracy of 0.2 ° in 2Θ.
Die Kristallphasen der Verbindung der Formel (1 ) mit X gleich Nitro zeichnen sich durch folgende charakteristische Linien aus (Cu-Kα-Strahlung, 2Θ-Werte in Grad, d-Werte in A"\ relative Intensität in %).The crystal phases of the compound of formula (1) with X equal to nitro are characterized by the following characteristic lines (Cu-K α radiation, 2Θ values in degrees, d values in A " \ relative intensity in%).
α-Phase: (Nitro)α phase: (nitro)
2Θ d rel. Intensität 5.2 17.11 44 7.4 11.89 1002Θ d rel. Intensity 5.2 17.11 44 7.4 11.89 100
8.2 10.80 858.2 10.80 85
11.5 7.67 8611.5 7.67 86
11.7 7.53 3711.7 7.53 37
13.3 6.63 5013.3 6.63 50
14.6 6.07 3614.6 6.07 36
15.0 5.90 3715.0 5.90 37
15.4 5.75 4315.4 5.75 43
15.6 5.65 5015.6 5.65 50
18.5 4.78 3818.5 4.78 38
23.0 3.86 3823.0 3.86 38
23.7 3.75 3023.7 3.75 30
24.2 3.67 3224.2 3.67 32
25.1 3.55 6025.1 3.55 60
25.5 3.49 5925.5 3.49 59
26.4 3.37 7626.4 3.37 76
27.5 3.23 3827.5 3.23 38
29.4 3.03 2529.4 3.03 25
ß-Phase: (Nitro)ß phase: (nitro)
2Θ d rel. Intensität2Θ d rel. intensity
9.5 9.30 1009.5 9.30 100
11.7 7.54 1011.7 7.54 10
12.7 6.99 1712.7 6.99 17
14.4 6.16 2014.4 6.16 20
16.7 5.30 1116.7 5.30 11
18.2 4.86 1718.2 4.86 17
19.9 4.45 1119.9 4.45 11
20.5 4.31 2520.5 4.31 25
21.5 4.12 1021.5 4.12 10
22.1 4.01 2122.1 4.01 21
23.3 3.81 7123.3 3.81 71
23.6 3.76 16 27.4 3.25 2023.6 3.76 16 27.4 3.25 20
29.1 3.06 1329.1 3.06 13
γ-Phase: (Nitro)γ phase: (nitro)
2Θ d rel. Intensität2Θ d rel. intensity
8.9 9.98 1008.9 9.98 100
11.5 7.71 3611.5 7.71 36
13.5 6.57 1913.5 6.57 19
16.2 5.48 2416.2 5.48 24
16.6 5.33 2316.6 5.33 23
17.0 5.20 2517.0 5.20 25
17.8 4.99 1417.8 4.99 14
19.2 4.62 3319.2 4.62 33
19.9 4.47 2519.9 4.47 25
20.3 4.36 8620.3 4.36 86
20.9 4.26 2820.9 4.26 28
21.8 4.08 1921.8 4.08 19
22.4 3.97 3122.4 3.97 31
23.5 3.78 9123.5 3.78 91
24.0 3.71 3124.0 3.71 31
25.0 3.55 2825.0 3.55 28
25.4 3.50 3225.4 3.50 32
26.2 3.40 2526.2 3.40 25
27.1 3.28 5327.1 3.28 53
31.0 2.88 1331.0 2.88 13
Die α-Phase der Nitro- Verbindung entsteht beispielsweise, wenn man das Pigment nach der Synthese bei 100 bis 110°C in Dimethylformamid erhitzt. Die ß-Phase der Nitro-Verbindung entsteht beispielsweise, wenn man das Pigment nach der Synthese auf 90 bis 100°C in Wasser erhitzt.The α-phase of the nitro compound arises, for example, when the pigment is heated at 100 to 110 ° C. in dimethylformamide after the synthesis. The ß phase of the nitro compound arises, for example, if the pigment is heated to 90 to 100 ° C. in water after the synthesis.
Die γ-Phase der Nitro-Verbindung, mit kleineren Beimengungen an α- und ß-Phase, entsteht beispielsweise, wenn man das Pigment nach der Synthese auf 130 bis 150°C in Wasser erhitzt. Die Kristallphasen der Verbindung der Formel (1) mit X gleich Methyl zeichnen sich durch folgende charakteristische Linien aus (Cu-Kα-Strahlung, 2Θ-Werte in Grad, d-Werte in Ä"1, relative Intensität in %):The γ phase of the nitro compound, with minor additions to the α and ß phases, arises, for example, if the pigment is heated to 130 to 150 ° C. in water after the synthesis. The crystal phases of the compound of formula (1) with X equal to methyl are characterized by the following characteristic lines (Cu-K α radiation, 2Θ values in degrees, d values in Ä "1 , relative intensity in%):
α-Phase: (Methyl)α phase: (methyl)
2Θ d relative Intensität2Θ d relative intensity
5.2 16.9 345.2 16.9 34
7.1 12.4 347.1 12.4 34
7.7 11.5 1007.7 11.5 100
8.1 10.9 518.1 10.9 51
11.4 7.7 8611.4 7.7 86
12.1 7.3 2812.1 7.3 28
13.6 6.5 4313.6 6.5 43
15.8 5.6 4715.8 5.6 47
18.9 4.7 4118.9 4.7 41
20.7 4.3 2820.7 4.3 28
22.9 3.9 4222.9 3.9 42
23.8 3.73 4423.8 3.73 44
24.1 3.69 4724.1 3.69 47
25.0 3.56 7025.0 3.56 70
25.4 3.50 6325.4 3.50 63
25.7 3.46 7125.7 3.46 71
26.5 3.37 4426.5 3.37 44
27.7 3.22 4427.7 3.22 44
-Phase: (Methyl)-Phase: (methyl)
2Θ d rel. Intensität2Θ d rel. intensity
7.1 12.6 287.1 12.6 28
8.4 10.5 178.4 10.5 17
11.3 7.9 2011.3 7.9 20
13.0 6.8 813.0 6.8 8
15.1 5.9 815.1 5.9 8
15.4 5.8 11 17.7 5.0 1015.4 5.8 11 17.7 5.0 10
25.4 3.5 10025.4 3.5 100
26.1 3.4 1326.1 3.4 13
29.6 3.0 1129.6 3.0 11
Die α-Phase der Methyl-Verbindung entsteht beispielsweise, wenn man das Pigment nach der Synthese in Essigsäure auf 90 bis 110°C erhitzt oder in Wasser auf 130 bis 140°C erhitzt.The α-phase of the methyl compound is formed, for example, if the pigment is heated to 90 to 110 ° C after the synthesis in acetic acid or heated to 130 to 140 ° C in water.
Die ß-Phase der Methyl-Verbindung entsteht beispielsweise, wenn man das Pigment nach der Synthese auf 100 bis 130°C in Chlorbenzol erhitzt.The β-phase of the methyl compound arises, for example, if the pigment is heated to 100 to 130 ° C. in chlorobenzene after the synthesis.
Die erfindungsgemäßen Pigmente können durch Diazotierung eines Amins der Formel (2)The pigments according to the invention can be obtained by diazotizing an amine of the formula (2)
Figure imgf000007_0001
Figure imgf000007_0001
wobei X die in Formel (1) genannte Bedeutung hat, und anschließende Kupplung mit der Verbindung der Formel (3)where X has the meaning given in formula (1), and subsequent coupling with the compound of formula (3)
Figure imgf000007_0002
hergestellt werden.
Figure imgf000007_0002
getting produced.
Für die Diazotierungsreaktion eignen sich Alkalimetallnitrite oder die Alkylnitrite kurzkettiger Alkane, zusammen mit starken Mineralsäuren. Besonders geeignet sind Natriumnitrit und Salzsäure. Die Reaktion kann in einem Temperaturbereich von -5°C bis + 30°C durchgeführt werden, vorzugsweise zwischen 0°C und 10°C. Obwohl nicht erforderlich, können bei der Diazotierung nichtionogene, anionische oder kationische oberflächenaktive Substanzen zugegen sein. Gegebenenfalls können auch weitere Hilfsmittel, wie natürliche oder synthetische Harze oder Harzderivate, verwendet werden. Die Kupplung ist nach der direkten oder inversen Methode möglich, erfolgt vorzugsweise jedoch indirekt, d.h. die Kuppelkomponente wird zum vorgelegten Diazoniumsalz gegeben. Die Kuppelreaktion kann in einem Temperaturbereich zwischen -5°C und 80°C durchgeführt werden, vorzugsweise zwischen 5°C und 25°C, und bei einem pH-Wert zwischen pH 4 und pH 14, insbesondere zwischen pH 9 und pH 12. Die Azokupplungsreaktion erfolgt vorzugsweise in wässriger Lösung oder Suspension, es können aber auch organische Lösemittel, gegebenenfalls im Gemisch mit Wasser eingesetzt werden, beispielsweise Alkohole mit 1 bis 10 C-Atomen, wie beispielsweise Methanol, Ethanol, n-Propanol, Isopropanol, Butanole, wie n-Butanol, sek.-Butanol, tert.-Butanol, Pentanole, wie n-Pentanol, 2-Methyl-2-butanol, Hexanole, wie 2-Methyl-2- pentanol, 3-Methyl-3-pentanol, 2-Methyl-2-hexanol, 3-Ethyl-3-pentanol, Octanole, wie 2,4,4-Trimethyl-2-pentanol, Cyclohexanol; oder Glykole, wie Ethylenglykol, Diethylenglykol, Propylenglykoi, Dipropylenglykol, oder Glycerin; Polyglykole, wie Polyethylenglykole oder Polypropylenglykole; Ether, wie Methylisobutylether, Tetrahydrofuran oder Dimethoxyethan; Glykolether, wie Monomethyl- oderAlkali metal nitrites or the alkyl nitrites of short-chain alkanes, together with strong mineral acids, are suitable for the diazotization reaction. Sodium nitrite and hydrochloric acid are particularly suitable. The reaction can be carried out in a temperature range from -5 ° C to + 30 ° C, preferably between 0 ° C and 10 ° C. Although not required, non-ionic, anionic or cationic surface-active substances can be present in the diazotization. If necessary, other auxiliaries, such as natural or synthetic resins or resin derivatives, can also be used. Coupling is possible by the direct or inverse method, but is preferably carried out indirectly, ie the coupling component is added to the diazonium salt provided. The coupling reaction can be carried out in a temperature range between -5 ° C and 80 ° C, preferably between 5 ° C and 25 ° C, and at a pH between pH 4 and pH 14, in particular between pH 9 and pH 12. Die Azo coupling reaction is preferably carried out in aqueous solution or suspension, but it is also possible to use organic solvents, if appropriate in a mixture with water, for example alcohols having 1 to 10 carbon atoms, such as, for example, methanol, ethanol, n-propanol, isopropanol, butanols, such as n -Butanol, sec-butanol, tert-butanol, pentanols, such as n-pentanol, 2-methyl-2-butanol, hexanols, such as 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2-methyl -2-hexanol, 3-ethyl-3-pentanol, octanols such as 2,4,4-trimethyl-2-pentanol, cyclohexanol; or glycols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, or glycerin; Polyglycols, such as polyethylene glycols or polypropylene glycols; Ethers such as methyl isobutyl ether, tetrahydrofuran or dimethoxyethane; Glycol ethers, such as monomethyl or
Monoethylether des Ethylen- oder Propylenglykols, Diethylenglykolmonomethyl- ether, Diethylenglykol-monoethylether, Butylglykole oder Methoxybutanol; Ketone, wie Aceton, Diethylketon, Methylisobutylketon, Methylethylketon oder Cyclohexanon; aliphatische Säureamide, wie Formamid, Dimethylformamid, N-Methylacetamid oder N,N-Dimethylacetamid; Harnstoffderivate, wieMonoethyl ether of ethylene or propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl glycols or methoxybutanol; Ketones such as acetone, diethyl ketone, methyl isobutyl ketone, methyl ethyl ketone or cyclohexanone; aliphatic acid amides such as formamide, dimethylformamide, N-methylacetamide or N, N-dimethylacetamide; Urea derivatives, such as
Tetramethylharnstoff; oder cyclische Carbonsäureamide, wie N-Methylpyrrolidon, Valero- oder Caprolactam; Ester, wie Carbonsäure-C-ι-C6-alkylester, wie Ameisensäurebutylester, Essigsäureethylester oder Propionsäurepropylester; oder Carbonsäure-Cι-C6-glykolester; oder Glykoletheracetate, wie 1-Methoxy-2- propylacetat; oder Phthalsäure- oder Benzoesäure-CrC6-alkylester, wieTetramethylurea; or cyclic carboxamides, such as N-methylpyrrolidone, valero- or caprolactam; Esters, such as carboxylic acid C 1 -C 6 -alkyl esters, such as butyl formate, ethyl acetate or propyl propionate; or carboxylic acid -C 6 glycol ester; or glycol ether acetates, such as 1-methoxy-2-propyl acetate; or phthalic or benzoic acid CrC 6 alkyl esters, such as
Benzoesäureethylester; cyclische Ester, wie Caprolacton; Nitrile, wie Acetonitril oder Benzonitril; aliphatische oder aromatische Kohlenwasserstoffe, wie Cyclohexan oder Benzol; oder durch Alkyl, Alkoxy, Nitro oder Halogen substituiertes Benzol, wie Toluol, Xylole, Ethylbenzol, Anisol, Nitrobenzol, Chlorbenzol, o-Dichlorbenzol, 1 ,2,4-Trichlorbenzol oder Brombenzol; oder andere substituierte Aromaten, wie Benzoesäure oder Phenol; aromatische Heterocyclen, wie Pyridin, Morpholin, Picolin oder Chinolin; sowie Hexamethylphosphorsäuretriamid, 1 ,3-Dimetyl-2-imidazolidinon, Dimethylsulfoxid und Sulfolan. Die genannten Lösemittel können auch als Mischungen eingesetzt werden. Vorzugsweise werden mit Wasser mischbare Lösemittel eingesetzt.benzoate; cyclic esters such as caprolactone; Nitriles such as acetonitrile or benzonitrile; aliphatic or aromatic hydrocarbons, such as cyclohexane or benzene; or by alkyl, alkoxy, nitro or halogen substituted benzene, such as toluene, xylenes, ethylbenzene, anisole, nitrobenzene, chlorobenzene, o-dichlorobenzene, 1, 2,4-trichlorobenzene or bromobenzene; or other substituted aromatics such as benzoic acid or phenol; aromatic heterocycles such as pyridine, morpholine, picoline or quinoline; as well as hexamethylphosphoric triamide, 1, 3-dimetyl-2-imidazolidinone, dimethyl sulfoxide and sulfolane. The solvents mentioned can also be used as mixtures. Water-miscible solvents are preferably used.
Im erfindungsgemäßen Verfahren können auch übliche Hilfsmittel wie beispielsweise Kupplungshilfsmittel, Tenside, pigmentäre und nichtpigmentäre Dispergiermittel, Füllstoffe, Stellmittel, Harze, Wachse, Entschäumer, Antistaubmittel, Extender, Farbmittel zum Nuancieren, Konservierungsmittel, Trocknungsverzögerungsmittel, Additive zur Steuerung der Rheologie, Netzmittel, Antioxidantien, UV-Absorber, Lichtstabilisatoren, oder eine Kombination davon eingesetzt werden.In the process according to the invention it is also possible to use conventional auxiliaries such as, for example, coupling auxiliaries, surfactants, pigmentary and non-pigmentary dispersants, fillers, adjusting agents, resins, waxes, defoamers, anti-dust agents, extenders, colorants for shading, preservatives, drying retardants, additives for controlling the rheology, wetting agents, antioxidants, UV absorbers, light stabilizers, or a combination thereof can be used.
Die Gesamtmenge der zugegebenen Hilfsmittel kann 0 bis 40 Gew.-%, bevorzugt 1 bis 30 Gew.-%, besonders bevorzugt 2,5 bis 25 Gew.-%, bezogen auf das Azopigment, betragen.The total amount of auxiliaries added can be 0 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 2.5 to 25% by weight, based on the azo pigment.
Als Tenside kommen anionische oder anionaktive, kationische oder kationaktive und nichtionische Substanzen oder Mischungen dieser Mittel in Betracht. Als anionaktive Substanzen kommen beispielsweise Fettsäuretauride, Fettsäure- N-methyltauride, Fettsäureisethionate, Alkylphenylsulfonate, Alkylnaphthalinsulfonate, Alkylphenolpolyglykolethersulfate, Fettalkoholpolyglykolethersulfate, Fettsäureamid-polyglykolethersulfate, Alkylsulfosuccinamate, Alkenylbernsteinsäurehalbester, Fettalkoholpolyglykolethersulfosuccinate, Alkansulfonate, Fettsäureglutamate, Alkylsulfosuccinate, Fettsäuresarkoside; Fettsäuren, beispielsweise Palmitin-, Stearin- und Ölsäure; Seifen, beispielsweise Alkalisalze von Fettsäuren, Naphthensäuren und Harzsäuren, beispielsweise Abietinsäure, alkalilösliche Harze, beispielsweise kolophoniummodifizierte Maleinatharze und Kondensationsprodukte auf Basis von Cyanurchlorid, Taurin, N,N'-Diethylaminopropylamin und p-Phenylendiamin in Betracht. Besonders bevorzugt sind Harzseifen, d.h. Alkalisalze von Harzsäuren.Suitable surfactants are anionic or anionic, cationic or cationic and nonionic substances or mixtures of these agents. Examples of anionic substances are fatty acid taurides, fatty acid N-methyl taurides, fatty acid isethionates, alkylphenyl sulfonates, alkyl naphthalene sulfonates, alkylphenol polyglycol ether sulfates, fatty alcohol polyglycol ether sulfates, fatty acid amide polyglycol ether sulfates, alkyl sulfosuccinamate succinate acid, alkenyl sulfonate urate sulfate, alkenyl sulfonate urate Fatty acids, for example palmitic, stearic and oleic acid; Soaps, for example alkali salts of fatty acids, naphthenic acids and resin acids, for example abietic acid, alkali-soluble resins, for example rosin-modified maleate resins and condensation products based on cyanuric chloride, taurine, N, N'-diethylaminopropylamine and p-phenylenediamine are considered. Resin soaps, ie alkali salts of resin acids, are particularly preferred.
Der Zusatz von alkalilöslichen harzartigen Hilfsmitteln oder Mischungen davon während oder nach der Kupplung, sowie vor oder während der Verlackung verbessert die Dispergierbarkeit der Pigmente. Zweckmäßigerweise werden die harzartigen Hilfsmittel oder Mischungen davon in Form ihrer wässrig-alkalischen Lösungen eingesetzt. Als harzartige Hilfsmittel eignen sich natürliche und synthetische Harze. Als vorteilhaft sind Kolophonium, disproportioniertes bzw. hydriertes Kolophonium, sowie Kolophoniumderivate zu nennen. Bevorzugt sind natürliche Harzsäuren, wie Abietinsäure, Dihydroabietinsäure, Tetrahydroabietinsäure, Laevopimarsäure, Dextropimarsäure und Isodextropimarsäure, wie sie in handelsüblichen Kolophoniumarten vorliegen. Besonders bevorzugt ist das kommerziell erhältliche Harz Rosin N, das die Harzsäuren Abietinsäure, Dehydroabetinsäure, Neoabietinsäure, Palustrinsäure, Isopimarsäure, Pimarsäure und Sandaracopimarsäure enthält, oder ein dem Rosin N äquivalentes Handelsprodukt. Neben den aufgezählten Harzen und deren Derivaten, können auch Alkydharze oder synthetische Kohlenwasserstoffharze mit hoher Säurezahl eingesetzt werden. Die genannten Harze werden vorzugsweise im Anschluß an die Kupplungsreaktion der Reaktionsmischung zugefügt.The addition of alkali-soluble resinous auxiliaries or mixtures thereof during or after the coupling, and before or during the lacquering improves the dispersibility of the pigments. The resinous auxiliaries or mixtures thereof are expediently used in the form of their aqueous-alkaline solutions. Natural and synthetic resins are suitable as resinous auxiliaries. Rosin, disproportionated or hydrogenated rosin and rosin derivatives are to be mentioned as advantageous. Natural resin acids, such as abietic acid, dihydroabietic acid, tetrahydroabietic acid, laevopimaric acid, dextropimaric acid and isodextropimaric acid, as are present in commercially available types of rosin, are preferred. The commercially available resin Rosin N, which contains the resin acids abietic acid, dehydroabetic acid, neoabietic acid, palustric acid, isopimaric acid, pimaric acid and sandaracopimaric acid, or a commercial product equivalent to Rosin N, is particularly preferred. In addition to the resins listed and their derivatives, alkyd resins or synthetic hydrocarbon resins with a high acid number can also be used. The resins mentioned are preferably added to the reaction mixture following the coupling reaction.
Als kationaktive Substanzen kommen beispielsweise quatemäre Ammoniumsalze, Fettaminoxalkylate, oxalkylierte Polyamine, Fettaminpolyglykolether, Fettamine, von Fettaminen oder Fettalkoholen abgeleitete Di- und Polyamine und deren Oxalkylate, von Fettsäuren abgeleitete Imidazoline, und Salze dieser kationenaktiven Substanzen, wie beispielsweise Acetate, in Betracht.Examples of suitable cationic substances are quaternary ammonium salts, fatty amine oxyalkylates, oxyalkylated polyamines, fatty amine polyglycol ethers, fatty amines, di- and polyamines derived from fatty amines or fatty alcohols and their oxyalkylates, imidazolines derived from fatty acids, and salts of these cationic substances, such as acetates.
Als nichtionogene Substanzen kommen beispielsweise Aminoxide, Fettalkoholpolyglykolether, Fettsäurepolyglykolester, Betaine, wie Fettsäureamid- N-propyl-betaine, Phosphorsäureester von aliphatischen und aromatischen Alkoholen, Fettalkoholen oder Fettalkoholpolyglykolethem, Fettsäureamidethoxylate, Fettalkohol-alkylenoxid-Addukte und Alkylphenolpolyglykolether in Betracht. Mit nichtpigmentären Dispergiermittel sind Substanzen gemeint, die nicht durch chemische Modifikation von organischen Pigmente abgeleitet sind. Sie werden als Dispergiermittel entweder bereits bei der Herstellung von Pigmenten, oft aber auch bei der Einarbeitung der Pigmente in die zu färbenden Anwendungsmedien, beispielsweise bei der Herstellung von Lacken oder Druckfarben durchExamples of nonionic substances include amine oxides, fatty alcohol polyglycol ethers, fatty acid polyglycol esters, betaines such as fatty acid amide-N-propyl-betaine, phosphoric acid esters of aliphatic and aromatic alcohols, fatty alcohols or fatty alcohol polyglycol ethers, fatty acid amide ethoxylates, fatty alcohol-alkylene oxide adducts and alkylphenol adducts and alkylphenol in consideration. Nonpigmentary dispersants mean substances that are not derived from organic pigments by chemical modification. They are used as dispersants either in the manufacture of pigments, but often also in the incorporation of the pigments into the application media to be colored, for example in the manufacture of paints or printing inks
Dispergierung der Pigmente in den entsprechenden Bindemitteln, zugegeben. Es können polymere Substanzen, beispielsweise Polyolefine, Polyester, Polyether, Polyamide, Polyimine, Polyacrylate, Polyisocyanate, Block-Copolymere daraus, Copolymere aus den entsprechenden Monomeren oder Polymere einer Klasse, die mit wenigen Monomeren einer anderen Klasse modifiziert sind, sein. Diese polymeren Substanzen tragen polare Ankergruppen wie beispielsweise Hydroxy-, Amino-, Imino- und Ammoniumgruppen, Carbonsäure- und Carboxylatgruppen, Sulfonsäure- und Sulfonatgruppen oder Phosphonsäure- und Phosphonatgruppen, und können auch mit aromatischen, nicht pigmentären Substanzen modifiziert sein. Nichtpigmentäre Dispergiermittel können des weiteren auch chemisch mit funktioneilen Gruppen modifizierte aromatische, nicht von organischen Pigmenten abgeleitete Substanzen sein. Derartige nichtpigmentäre Dispergiermittel sind dem Fachmann bekannt und zum Teil im Handel erhältlich (z.B. Solsperse®, Avecia; Disperbyk®, Byk, Efka®, Efka). Es sollen im Folgenden stellvertretend einige Typen genannt werden, zum Einsatz können jedoch prinzipiell beliebige andere, beschriebene Substanzen kommen, beispielsweise Kondensationsprodukte aus Isocyanaten und Alkoholen, Di- oder Polyolen, Aminoalkoholen oder Di- oder Polyaminen, Polymere aus Hydroxycarbonsäuren, Copolymere aus Olefinenmonomeren oder Vinylmonomeren und ethylenisch ungesättigten Carbonsäureestern, urethanhaltige Polymere von ethylenisch ungesättigten Monomeren, urethanmodifizierte Polyester, Kondensationsprodukte auf Basis von Cyanurhalogeniden, Nitroxylverbindungen enthaltende Polymere, Polyesteramide, modifizierte Polyamide, modifizierte Acryl polymere, Kammdispergiermittel aus Polyestern und Acrylpolymeren, Phosphorsäureester, von Triazin abgeleitete Polymere, modifizierte Polyether, oder von aromatischen, nichtpigmentären Substanzen abgeleitete Dispergiermittel. Dabei werden diese Grundstrukturen vielfach weiter modifiziert, beispielsweise durch chemische Umsetzung mit weiteren, funktionelle Gruppen tragenden Substanzen oder durch Salzbildung.Dispersion of the pigments in the corresponding binders, added. They can be polymeric substances, for example polyolefins, polyesters, polyethers, polyamides, polyimines, polyacrylates, polyisocyanates, block copolymers thereof, copolymers from the corresponding monomers or polymers from one class which have been modified with a few monomers from another class. These polymeric substances carry polar anchor groups such as, for example, hydroxyl, amino, imino and ammonium groups, carboxylic acid and carboxylate groups, sulfonic acid and sulfonate groups or phosphonic acid and phosphonate groups, and can also be modified with aromatic, non-pigmentary substances. Non-pigmentary dispersants can furthermore also be aromatic substances which are chemically modified with functional groups and are not derived from organic pigments. Nonpigmentary dispersants are known in the art and some are available commercially (for example, Solsperse ®, Avecia; Disperbyk ®, Byk, Efka ®, Efka). A few types are to be mentioned in the following as examples, but in principle any other substances described can be used, for example condensation products from isocyanates and alcohols, di- or polyols, amino alcohols or di- or polyamines, polymers from hydroxycarboxylic acids, copolymers from olefin monomers or vinyl monomers and ethylenically unsaturated carboxylic acid esters, urethane-containing polymers of ethylenically unsaturated monomers, urethane-modified polyesters, condensation products based on cyanuric halides, polymers containing nitroxyl compounds, polyester amides, modified polyamides, modified acrylic polymers, comb dispersants from polyesters and acrylic polymers, phosphoric acid esters, polymers derived from triazine, modified polymers or dispersants derived from aromatic, non-pigmentary substances. In doing so, these basic structures modified many times further, for example by chemical reaction with further substances carrying functional groups or by salt formation.
Mit pigmentären Dispergiermitteln sind Pigmentdispergatoren gemeint, die sich von einem organischen Pigment als Grundkörper ableiten und durch chemische Modifizierung dieses Grundkörpers hergestellt werden, beispielsweise saccharinhaltige Pigmentdispergatoren, piperidylhaltige Pigmentdispergatoren, von Naphthalin oder Perylen abgeleitete Pigmentdispergatoren, Pigmentdispergatoren mit funktionellen Gruppen, die über eine Methylengruppe mit dem Pigmentgrundkörper verknüpft sind, mit Polymeren chemisch modifizierte Pigmentgrundkörper, Sulfosäuregruppen haltige Pigmentdispergatoren, Sulfonamidgruppen haltige Pigmentdispergatoren, Ethergruppen haltige Pigmentdispergatoren, oder Carbonsäure-, Carbonsäureester- oder Carbonamidgruppen haltige Pigmentdispergatoren.Pigmentary dispersants mean pigment dispersants which are derived from an organic pigment as the base body and are produced by chemical modification of this base body, for example saccharin-containing pigment dispersants, piperidyl-containing pigment dispersants, naphthalene or perylene-derived pigment dispersants, pigment dispersants with functional groups which have a methylene group with the Basic pigment bodies are linked, chemically modified basic pigment bodies, pigment dispersants containing sulfonic acid groups, pigment dispersants containing sulfonamide groups, pigment dispersants containing ether groups, or pigment dispersants containing carboxylic acid, carboxylic acid ester or carbonamide groups.
Zum Einstellen eines gewünschten pH-Wertes können Pufferlösungen zugeführt werden, vorzugsweise von organischen Säuren und deren Salzen, wie beispielsweise Ameisensäure/Formiat-Puffer, Essigsäure/Acetat-Puffer, Zitronensäure/Citrat-Puffer; oder von anorganischen Säuren und deren Salzen, wie beispielsweise Phosphorsäure/Phosphat-Puffer oder Kohlensäure/ Hydrogencarbonat- bzw. Carbonat-Puffer.To set a desired pH, buffer solutions can be added, preferably of organic acids and their salts, such as, for example, formic acid / formate buffer, acetic acid / acetate buffer, citric acid / citrate buffer; or of inorganic acids and their salts, such as, for example, phosphoric acid / phosphate buffer or carbonic acid / bicarbonate or carbonate buffer.
Im allgemeinen wird die Kuppelkomponente, bezogen auf die Diazoniumverbindung, in einem leichten Überschuß eingesetzt, vorzugsweise wird 1 Äquivalent Diazokomponente mit 1 ,001 bis 1 ,10 Äquivalenten der Kuppelkomponente umgesetzt.In general, the coupling component, based on the diazonium compound, is used in a slight excess, preferably 1 equivalent of diazo component is reacted with 1,001 to 1,10 equivalents of the coupling component.
Nach der Kupplung werden die erfindungsgemäßen Verbindungen bevorzugt einer Wärmebehandlung in wässrigem, wässrig-organischem oder organischem Medium unter Verwendung der vorstehend beschriebenen Lösemitteln beiAfter the coupling, the compounds according to the invention are preferably subjected to heat treatment in an aqueous, aqueous-organic or organic medium using the solvents described above
Temperaturen zwischen 80 und 200°C, ggf. unter Druck, und zweckmäßigerweise für 1 bis 6 Stunden unterworfen, insbesondere in Gegenwart von C1-C3- Carbonsäuren. Wie vorstehend beschrieben, können dabei bestimmte Kristallphasen entstehen oder Phasenumwandlungen eintreten. Anschließend können die erhaltenen Pigmentsuspensionen auf die übliche Weise filtriert, der Presskuchen mit Wasser salzfrei gewaschen, getrocknet und gemahlen werden.Temperatures between 80 and 200 ° C, optionally under pressure, and expediently for 1 to 6 hours, especially in the presence of C 1 -C 3 carboxylic acids. As described above, certain can Crystal phases arise or phase changes occur. The pigment suspensions obtained can then be filtered in the customary manner, the presscake washed with salt-free water, dried and ground.
Die Verbindungen der Formel (1) lassen sich zum Pigmentieren von hochmolekularen organischen Materialien natürlicher oder synthetischer Herkunft einsetzen, beispielsweise von Kunststoffen, Harzen, Lacken, Anstrichfarben oder elektrophotographischen Tonern und Entwicklern, sowie von Tinten und Druckfarben.The compounds of formula (1) can be used for pigmenting high molecular weight organic materials of natural or synthetic origin, for example plastics, resins, lacquers, paints or electrophotographic toners and developers, as well as inks and printing inks.
Hochmolekulare organische Materialien, die mit den erfindungsgemäßen Verbindungen pigmentiert werden können, sind beispielsweise Celluloseether und -ester, wie Ethylcellulose, Nitrocellulose, Celluloseacetat oder Cellulosebutyrat, natürliche Harze oder Kunstharze, wie Polymerisationsharze oder Kondensationsharze, beispielsweise Aminoplaste, insbesondere Harnstoff- und Melaminformaldehydharze, Alkydharze, Acrylharze, Phenoplaste, Polycarbonate, Polyolefine, wie Polystyrol, Polyvinylchlorid, Polyethylen, Polypropylen, Polyacrylnitril, Polyacrylsäureester, Polyamide, Polyurethane oder Polyester, Gummi, Casein, Silikon und Silikonharze, einzeln oder in Mischungen. Dabei spielt es keine Rolle, ob die erwähnten hochmolekularen organischen Verbindungen als plastische Massen, Schmelzen oder in Form von Spinnlösungen, Lacken, Anstrichstoffen oder Druckfarben vorliegen. Je nach Verwendungszweck erweist es sich als vorteilhaft, die erfindungsgemäßen Verbindungen in Form von Pulvern, Granulaten, Präparationen, Flushpasten, Masterbatches oder Dispersionen zu einzusetzen. Bezogen auf das zu pigmentierende, hochmolekulare organische Material setzt man die erfindungsgemäßen Verbindungen in einer Menge von 0,05 bis 30 Gew.-%, vorzugsweise 0,1 bis 15 Gew.-% ein.High molecular weight organic materials which can be pigmented with the compounds according to the invention are, for example, cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerization resins or condensation resins, for example aminoplasts, in particular urea and melamine formaldehyde resins, alkyd resins, Acrylic resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, individually or in mixtures. It does not matter whether the high-molecular organic compounds mentioned are present as plastic masses, melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the intended use, it has proven advantageous to use the compounds according to the invention in the form of powders, granules, preparations, flush pastes, masterbatches or dispersions. Based on the high molecular weight organic material to be pigmented, the compounds according to the invention are used in an amount of 0.05 to 30% by weight, preferably 0.1 to 15% by weight.
Die erfindungsgemäßen Pigmente sind geeignet als Farbmittel in elektrophotographischen Tonern und Entwicklern, wie z.B. Ein- oder Zweikomponentenpulvertonern (auch Ein- oder Zweikomponenten-Entwickler genannt), Magnettoner, Flüssigtoner, Latextoner, Polymerisationstoner sowie Spezialtoner.The pigments according to the invention are suitable as colorants in electrophotographic toners and developers, such as, for example, one- or two-component powder toners (also one- or two-component developers called), magnetic toner, liquid toner, latex toner, polymerization toner and special toner.
Typische Tonerbindemittel sind Polymerisations-, Polyadditions- und Polykondensationsharze, wie Styrol-, Styrolacrylat-, Styrolbutadien-, Acrylat-, Polyester-, Phenol-Epoxidharze, Polysulfone, Polyurethane, einzeln oder in Kombination, sowie Polyethylen und Polypropylen, die noch weitere Inhaltsstoffe, wie Ladungssteuermittel, Wachse oder Fließhilfsmittel, enthalten können oder im Nachhinein mit diesen Zusätzen modifiziert werden.Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and polyethylene and polypropylene, which also contain other ingredients, such as charge control agents, waxes or flow aids, or can be modified with these additives afterwards.
Des weiteren sind die erfindungsgemäßen Pigmente geeignet als Farbmittel in Pulver und Pulverlacken, insbesondere in triboelektrisch oder elektrokinetisch versprühbaren Pulverlacken, die zur Oberflächenbeschichtung von Gegenständen aus beispielsweise Metall, Holz, Kunststoff, Glas, Keramik, Beton, Textilmaterial, Papier oder Kautschuk zur Anwendung kommen.Furthermore, the pigments according to the invention are suitable as colorants in powders and powder coatings, in particular in triboelectrically or electrokinetically sprayable powder coatings which are used for the surface coating of objects made of, for example, metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber.
Als Pulverlackharze werden typischerweise Epoxidharze, carboxyl- und hydroxylgruppenhaltige Polyesterharze, Polyurethan- und Acrylharze zusammen mit üblichen Härtern eingesetzt. Auch Kombinationen von Harzen finden Verwendung. So werden beispielsweise häufig Epoxidharze in Kombination mit carboxyl- und hydroxylgruppenhaltigen Polyesterharzen eingesetzt. Typische Härterkomponenten (in Abhängigkeit vom Harzsystem) sind beispielsweise Säureanhydride, Imidazole sowie Dicyandiamid und deren Abkömmlinge, verkappte Isocyanate, Bisacylurethane, Phenol- und Melaminharze, Triglycidylisocyanurate, Oxazoline und Dicarbonsäuren.Epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethane and acrylic resins are typically used as powder coating resins together with conventional hardeners. Combinations of resins are also used. For example, epoxy resins are often used in combination with carboxyl- and hydroxyl-containing polyester resins. Typical hardener components (depending on the resin system) are, for example, acid anhydrides, imidazoles and dicyandiamide and their derivatives, blocked isocyanates, bisacyl urethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids.
Außerdem sind die erfindungsgemäßen Pigmente als Farbmittel in Tinten, vorzugsweise Ink-Jet Tinten, wie z.B. auf wäßriger oder nichtwässriger Basis, Mikroemulsionstinten sowie in solchen Tinten, die nach dem hot-melt-Verfahren arbeiten, geeignet. Ink- Jet-Tinten enthalten im allgemeinen insgesamt 0,5 bis 15 Gew.-%, vorzugsweise 1 ,5 bis 8 Gew.-%, (trocken gerechnet) einer oder mehrerer der erfindungsgemäßen Verbindungen. Mikroemulsionstinten basieren auf organischen Lösemitteln, Wasser und ggf. einer zusätzlichen hydrotropen Substanz (Grenzflächenvermittler). Mikroemulsionstinten enthalten 0,5 bis 15 Gew.-%, vorzugsweise 1,5 bis 8 Gew.-%, einer oder mehrerer der erfindungsgemäßen Verbindungen, 5 bis 99 Gew.-% Wasser und 0,5 bis 94,5 Gew.-% organisches Lösungsmittel und/oder hydrotrope Verbindung.In addition, the pigments according to the invention are suitable as colorants in inks, preferably ink-jet inks, such as, for example, on an aqueous or non-aqueous basis, microemulsion inks and in such inks which work according to the hot-melt process. Ink-jet inks generally contain a total of 0.5 to 15% by weight, preferably 1.5 to 8% by weight (calculated on a dry basis) of one or more of the compounds according to the invention. Microemulsion inks are based on organic solvents, water and possibly an additional hydrotropic substance (interface mediator). Microemulsion inks contain 0.5 to 15% by weight, preferably 1.5 to 8% by weight, of one or more of the compounds according to the invention, 5 to 99% by weight of water and 0.5 to 94.5% by weight organic solvent and / or hydrotropic compound.
"Solvent based" Ink-Jet-Tinten enthalten vorzugsweise 0,5 bis 15 Gew.-% einer oder mehrerer erfindungsgemäßer Verbindungen, 85 bis 99,5 Gew.-% organisches Lösungsmittel und/oder hydrotrope Verbindungen."Solvent based" ink-jet inks preferably contain 0.5 to 15% by weight of one or more compounds according to the invention, 85 to 99.5% by weight of organic solvent and / or hydrotropic compounds.
Hot-Melt-Tinten basieren meist auf wachsen, Fettsäuren, Fettalkoholen oder Sulfonamiden, die bei Raumtemperatur fest sind und bei Erwärmen flüssig werden, wobei der bevorzugte Schmelzbereich zwischen ca. 60°C und ca. 140°C liegt. Hot-Melt Ink-Jet-Tinten bestehen z.B. im wesentlichen aus 20 bis 90 Gew.-% Wachs und 1 bis 10 Gew.-% einer oder mehrerer der erfindungsgemäßen Verbindungen. Weiterhin können 0 bis 20 Gew.-% eines zusätzlichen Polymers (als "Farbstofflöser"), 0 bis 5 Gew.-% Dispergierhilfsmittel, 0 bis 20 Gew.-% Viskositätsveränderer, 0 bis 20 Gew.-% Plastifizierer, 0 bis 10 Gew.-% Klebrig keitszusatz, 0 bis 10 Gew.-% TransparenzstabilisatorHot-melt inks are mostly based on waxes, fatty acids, fatty alcohols or sulfonamides, which are solid at room temperature and become liquid when heated, the preferred melting range being between approx. 60 ° C and approx. 140 ° C. Hot melt ink jet inks are e.g. essentially from 20 to 90% by weight of wax and 1 to 10% by weight of one or more of the compounds according to the invention. Furthermore, 0 to 20% by weight of an additional polymer (as a "dye dissolver"), 0 to 5% by weight of dispersing aid, 0 to 20% by weight of viscosity modifier, 0 to 20% by weight of plasticizer, 0 to 10% by weight % Tack additive, 0 to 10% by weight transparency stabilizer
(verhindert z.B. Kristallisation der Wachse) sowie 0 bis 2 Gew.-% Antioxidans enthalten sein. Typische Zusatzstoffe und Hilfsmittel sind z.B. in US-PS 5,560,760 beschrieben.(e.g. prevents crystallization of the waxes) and 0 to 2% by weight of antioxidant. Typical additives and auxiliaries are e.g. in U.S. Patent 5,560,760.
Außerdem sind die erfindungsgemäßen Verbindungen auch geeignet als Farbmittel für Farbfilter, sowohl für die additive wie für die subtraktive Farberzeugung.In addition, the compounds according to the invention are also suitable as colorants for color filters, both for additive and for subtractive color production.
Weiterhin sind die erfindungsgemäßen Verbindungen auch zur Einfärbung von Saatgut geeignet.Furthermore, the compounds according to the invention are also suitable for coloring seed.
Die erfindungsgemäßen Pigmente zeichnen sich durch gute Echtheitseigenschaften sowie eine hohe Transparenz aus. Sie sind wesentlich gelbstichiger als C.I. Pigment Red 170. Sie enthalten keine für die Umwelt bedenklichen Schwermetalle. Die aufgezählten Eigenschaften qualifizieren die erfindungsgemäßen Pigmente insbesondere zum Einsatz als Farbmittel in Lacken, vorzugsweise Automobillacken, und in Kunststoffen, sowie in Druckfarben.The pigments according to the invention are notable for good fastness properties and high transparency. They are essential more yellowish than CI Pigment Red 170. They do not contain any heavy metals that are harmful to the environment. The properties listed qualify the pigments of the invention in particular for use as colorants in paints, preferably automotive paints, and in plastics, and in printing inks.
Mit dem Begriff "Teile" sind in den folgenden Beispielen und Vergleichsbeispielen Gewichtsteile gemeint.In the following examples and comparative examples, the term “parts” means parts by weight.
Vergleichsbeispiel: X = HComparative example: X = H
a) Synthese gemäß Patent DE 1 228731 Beispiel 4:a) Synthesis according to patent DE 1 228731 Example 4:
13,6 Gew.-Teile 1-Aminobenzol-4-carbonsäureamid werden mit 60 Volumenteilen 5 n-Salzsäure einige Zeit verrührt. Dann wird das Gemisch mit Wasser verdünnt und bei 10°C mit 20 Volumenteilen 5 n-Natriumnitritlösung diazotiert. Währenddessen werden 33 Gew.-Teile I-^'.S'-Oxynaphthoylamino)^- ethoxybenzol mit 450 Volumenteilen Wasser und 42 Volumenteilen 5 n-Natronlauge heiß gelöst und die Lösung geklärt. Diese Lösung lässt man innerhalb 30 bis 45 Minuten bei 10 bis 15°C unter Rühren in die Diazolösung einlaufen, der man zuvor 7 Volumenteile Eisessig und 50 Volumenteile 2 n-Natriumacetatlösung zugesetzt hat. Der erhaltene Niederschlag wird abgesaugt und gewaschen. Es entsteht die α-Phase von C.I. Pigment Red 170.13.6 parts by weight of 1-aminobenzene-4-carboxamide are stirred with 60 parts by volume of 5N hydrochloric acid for some time. The mixture is then diluted with water and diazotized at 10 ° C. with 20 parts by volume of 5N sodium nitrite solution. In the meantime, 33 parts by weight of I - ^ '. S'-oxynaphthoylamino) ^ - ethoxybenzene are dissolved hot with 450 parts by volume of water and 42 parts by volume of 5N sodium hydroxide solution and the solution is clarified. This solution is allowed to run into the diazo solution with stirring at 10 to 15 ° C. within 30 to 45 minutes, to which 7 parts by volume of glacial acetic acid and 50 parts by volume of 2N sodium acetate solution have been added beforehand. The precipitate obtained is suction filtered and washed. The α phase of C.I. Pigment Red 170.
b) Finish gemäß Patent DE 2043482 Beispiel 1 :b) Finish according to patent DE 2043482 example 1:
45 Gewichtsteile des im Vergleichsbeispiel (a) hergestellten Pigmentes in Form des wässrigen Filterkuchens werden mit 1000 Gew.-Teilen Wasser angerührt, auf eine Temperatur von 130°C erhitzt und 3 Stunden bei dieser Temperatur gehalten. Anschließend wird filtriert, mit Wasser gewaschen, getrocknet und gepulvert. Man erhält C.I. Pigment Red 170 in der γ-Phase.45 parts by weight of the pigment produced in comparative example (a) in the form of the aqueous filter cake are mixed with 1000 parts by weight of water, heated to a temperature of 130 ° C. and kept at this temperature for 3 hours. It is then filtered, washed with water, dried and powdered. C.I. Pigment Red 170 in the γ phase.
Beispiel 1: X = FExample 1: X = F
Die Synthese erfolgt wie im Vergleichsbeispiei 1a, aber man setzt statt des 4-Aminobenzamids 15,4 Teile 4-Amino-3-fluor-benzamid ein. Zur Nachbehandlung wird der Presskuchen 50 Minuten bei 114°C in Essigsäure erhitzt, abfiltriert, mit Wasser gewaschen und getrocknet.The synthesis takes place as in comparative example 1a, but instead of 4-aminobenzamide 15.4 parts of 4-amino-3-fluoro-benzamide. For the aftertreatment, the press cake is heated in acetic acid at 114 ° C. for 50 minutes, filtered off, washed with water and dried.
Beispiel 2a: X = ClExample 2a: X = Cl
Die Synthese erfolgt wie im Vergleichsbeispiel 1a, aber man setzt statt des 4-Aminobenzamids 17,1 Teile 4-Amino-3-chlor-benzamid ein. Zur Nachbehandlung wird der Presskuchen in Wasser 1 Stunde lang auf 160°C erhitzt, abfiltriert, mit Wasser gewaschen und getrocknet.The synthesis is carried out as in Comparative Example 1a, but instead of the 4-aminobenzamide, 17.1 parts of 4-amino-3-chlorobenzamide are used. For the aftertreatment, the press cake is heated in water at 160 ° C. for 1 hour, filtered off, washed with water and dried.
Beispiel 2b: X = ClExample 2b: X = Cl
Die Synthese erfolgt wie in Beispiel 2a. Zur Nachbehandlung wird der Presskuchen 20 Minuten bei 100°C in Essigsäure erhitzt, abfiltriert, mit Wasser gewaschen und getrocknet.The synthesis is carried out as in Example 2a. For the aftertreatment, the press cake is heated in acetic acid at 100 ° C. for 20 minutes, filtered off, washed with water and dried.
Beispiel 3: X = BrExample 3: X = Br
Die Synthese und die Nachbehandlung erfolgen wie im Vergleichsbeispiel 1 , aber man setzt statt des 4-Aminobenzamids 21 ,5 Teile 4-Amino-3-brom-benzamid ein.The synthesis and the aftertreatment are carried out as in Comparative Example 1, but instead of the 4-aminobenzamide 21.5 parts of 4-amino-3-bromo-benzamide are used.
Beispiel 4: X = NO2, α-PhaseExample 4: X = NO 2 , α phase
Die Synthese erfolgt wie im Vergleichsbeispiel 1a, aber man setzt statt des 4-Aminobenzamids 18,1 Teile 4-Amino-3-nitro-benzamid ein. Zur Nachbehandlung wird der Presskuchen 35 Minuten bei 106°C in Dimethylformamid erhitzt, abfiltriert, mit Wasser gewaschen und getrocknet.The synthesis is carried out as in Comparative Example 1a, but 18.1 parts of 4-amino-3-nitro-benzamide are used instead of the 4-aminobenzamide. For the aftertreatment, the press cake is heated for 35 minutes at 106 ° C. in dimethylformamide, filtered off, washed with water and dried.
Beispiel 5: X = NO2, ß-PhaseExample 5: X = NO 2 , β phase
Die Synthese erfolgt wie in Beispiel 4. Zur Nachbehandlung wird der Presskuchen 2 Stunden bei 98°C in Wasser erhitzt, abfiltriert, mit Wasser gewaschen und getrocknet. Man erhält die ß-Phase des Nitroderivates mit kleineren Beimengungen der α-Phase des Nitroderivates.The synthesis is carried out as in Example 4. For the aftertreatment, the press cake is heated in water at 98 ° C. for 2 hours, filtered off, washed with water and dried. The β-phase of the nitroderivative is obtained with smaller additions of the α-phase of the nitroderivative.
Beispiel 6: X = NO2, γ-PhaseExample 6: X = NO 2 , γ phase
Die Synthese erfolgt wie in Beispiel 4. Zur Nachbehandlung wird der Presskuchen 1 Stunde bei 140°C in Wasser erhitzt, abfiltriert, mit Wasser gewaschen und getrocknet. Man erhält die γ-Phase des Nitroderivates mit kleineren Beimengungen der α- und ß-Phase des Nitroderivates.The synthesis takes place as in Example 4. The press cake is used for aftertreatment Heated in water at 140 ° C. for 1 hour, filtered off, washed with water and dried. The γ-phase of the nitroderivative is obtained with smaller additions of the α- and ß-phase of the nitroderivative.
Beispiel 7: X = CH3, α-PhaseExample 7: X = CH3, α phase
Die Synthese erfolgt wie im Vergleichsbeispiel 1a, aber man setzt statt des 4-Aminobenzamids 15,1 Teile 4-Amino-3-methyl-benzamid ein. Zur Nachbehandlung wird der Presskuchen in Essigsäure 1 Stunde lang auf 100°C erhitzt, abfiltriert, mit Wasser gewaschen und getrocknet.The synthesis is carried out as in Comparative Example 1a, but 15.1 parts of 4-amino-3-methylbenzamide are used instead of the 4-aminobenzamide. For the aftertreatment, the press cake is heated to 100 ° C. in acetic acid for 1 hour, filtered off, washed with water and dried.
Beispiel 8: X = CH3, ß-PhaseExample 8: X = CH 3 , β phase
Die Synthese erfolgt wie in Beispiel 7. Zur Nachbehandlung wird der Presskuchen 1 Stunde bei 120°C in Chlorbenzol erhitzt, abfiltriert, mit Chlorbenzol gewaschen und getrocknet.The synthesis takes place as in Example 7. For the aftertreatment, the press cake is heated in chlorobenzene for 1 hour at 120 ° C., filtered off, washed with chlorobenzene and dried.
Anwendungsbeispiele 1 bis 5: Coloristik in LackApplication examples 1 to 5: Coloristic in lacquer
Zur Beurteilung der Eigenschaften der nach der Erfindung hergestellten Pigment- Phasen auf dem Lacksektor wurde aus der Vielzahl der bekannten Lacke ein aromatenhaltiger Alkydmelaminharzlack (AM) auf Basis eines mittelöligen Alkydharzes und eines butanolveretherten Melaminharzes ausgewählt. Zur besseren Messung der Coloristik wurden Weißaufhellungen mit einem Pigment : TiO2- Verhältnis von 1 :10 erstellt. Die Farbtöne werden nach dem CIELAB-System angegeben, wobei ΔH der Farbtonunterschied zwischen der Lackierung des Pigmentes und der Lackierung des Produktes des Vergleichsbeispiels 1 ist. Ein positiver ΔH-Wert bedeutet, dass das Pigment gelber als das Vergleichsbeispiel ist. Man erhält folgende Ergebnisse:
Figure imgf000019_0001
To assess the properties of the pigment phases produced according to the invention in the paint sector, an aromatic-containing alkyd melamine resin paint (AM) based on a medium-oil alkyd resin and a butanol-etherified melamine resin was selected from the large number of known paints. For better measurement of the coloristics, white lightenings were created with a pigment: TiO 2 ratio of 1:10. The color shades are given according to the CIELAB system, where ΔH is the color difference between the coating of the pigment and the coating of the product of Comparative Example 1. A positive ΔH value means that the pigment is more yellow than the comparative example. The following results are obtained:
Figure imgf000019_0001
Im Vollton sind alle Lackierungen der erfindungsgemäßen Pigmente bedeutend gelber und transparenter als die Lackierung des Vergleichsbeispiels 1.In the full shade, all the coatings of the pigments according to the invention are significantly more yellow and transparent than the coating of Comparative Example 1.
Anwendungsbeispiele 6 bis 7: Coloristik in KunststoffApplication examples 6 to 7: Coloristics in plastic
Zur Beurteilung der Eigenschaften in Kunststoff werden PVC-Einfärbungen angefertigt und coloristisch gegen eine PVC-Einfärbung des Vergleichsbeispiels 1 verglichen.In order to assess the properties in plastic, PVC coloring is made and coloristically compared to a PVC coloring of Comparative Example 1.
Figure imgf000019_0002
Figure imgf000019_0002
Die PVC-Einfärbungen der erfindungsgemäßen Pigmente aus Beispiel 7 und 8 sind bedeutend gelber und transparenter als die PVC-Einfärbung des Vergleichsbeispiels 1.The PVC colorations of the pigments according to the invention from Examples 7 and 8 are significantly more yellow and more transparent than the PVC coloration of Comparative Example 1.
Anwendungsbeispiel 9a-d: Licht- und Wetterechtheit Die Pigmente werden in einem aromatenhaltiger Alkydmelaminharzlack (AM) auf Basis eines mittelöligen Alkydharzes und eines butanolveretherten Melaminharzes dispergiert und einer Licht- und Wetterechtheitsprüfung in einer Schnellbelichtungs- bzw- Schnellbewitterungsapparatur unterzogen. Die Tests erfolgten sowohl im Vollton, als auch in Aufhellung. Die Lichtechtheiten wurden gegen die 8-stufige Blauskala in Anlehnung an DIN 54003 bewertet (8 = sehr gute, 1 = sehr schlechte Lichtechtheit). Bei den Wetterechtheitsprüfungen wurde der coloristische Gesamtabstand ΔE (im CIELAB-System) zwischen der bewitterten und der unbewitterten Lackierung gemessen. Die Belichtungen erfolgten im Xenotest Beta-Gerät im Gleichlauf.Application example 9a-d: light and weather fastness The pigments are dispersed in an aromatic alkyd melamine resin paint (AM) based on a medium oil alkyd resin and a butanol etherified melamine resin and subjected to a light and weather fastness test in a rapid exposure or rapid weathering apparatus. The tests were carried out both in full tone and in brightening. The light fastness was evaluated against the 8-level blue scale based on DIN 54003 (8 = very good, 1 = very bad light fastness). During the weather fastness tests, the overall coloristic distance ΔE (in the CIELAB system) between the weathered and the unweathered paintwork was measured. The exposures were carried out in synchronism in the Xenotest Beta device.
Es ergaben sich folgende Ergebnisse: a) Lichtechtheit Aufhellung (Verhältnis Pigment :TiO2 = 1 : 5,5):The following results were obtained: a) lightfastness brightening (pigment: TiO 2 ratio = 1: 5.5):
- Lackierung von Beispiel 2b: Stufe 7 - Lackierung von Beispiel 4: Stufe 8- Painting of example 2b: level 7 - Painting of example 4: level 8
- Lackierung von Vergleichsbeispiel 1 : Stufe 6-7 (also schlechter) b) Lichtechtheit Vollton, gemessen in Graustufen- Painting of Comparative Example 1: Level 6-7 (ie worse) b) Light fastness, full tone, measured in grayscale
- Lackierung von Beispiel 2b: Stufe 8- Painting of example 2b: level 8
- Lackierung von Vergleichsbeispiel 1 : Stufe 7 (also schlechter) c) Lichtechtheit Vollton, gemessen in ΔE, Xenotest X1200, 2000 Stunden:- Painting of Comparative Example 1: Level 7 (i.e. worse) c) Light fastness, full tone, measured in ΔE, Xenotest X1200, 2000 hours:
- Lackierung von Beispiel 1 : ΔE = 3,5- Painting of Example 1: ΔE = 3.5
- Lackierung von Beispiel 4: ΔE = 2,7- Painting of Example 4: ΔE = 2.7
- Lackierung von Vergleichsbeispiel 1 : ΔE = 5,7 (also schlechter) d) Wetterechtheit, Aufhellung (Verhältnis Pigment :TiO2 = 1 : 5,5), Xenotest X1200,- Painting of comparative example 1: ΔE = 5.7 (ie worse) d) weather fastness, brightening (ratio pigment: TiO 2 = 1: 5.5), Xenotest X1200,
500 Stunden:500 hours:
- Lackierung von Beispiel 2b: ΔE = 2.7- Painting of Example 2b: ΔE = 2.7
- Lackierung von Vergleichsbeispiel 1 : ΔE = 2.9 (also schlechter) e) Wetterechtheit, Aufhellung (Verhältnis Pigment :Ti02 = 1 : 10), Weatherometer C-5000, 500 Stunden:- Painting of comparative example 1: ΔE = 2.9 (ie worse) e) weather fastness, brightening (pigment: Ti0 2 = 1:10 ratio), weatherometer C-5000, 500 hours:
■ Lackierung von Beispiel 4: ΔE = 3,8 ■ Painting of example 4: ΔE = 3.8
- Lackierung von Vergleichsbeispiel 1 : ΔE = 4,8 - Painting of Comparative Example 1: ΔE = 4.8

Claims

Patentansprüche:claims:
1) Verbindung der Formel (1)1) compound of formula (1)
Figure imgf000021_0001
Figure imgf000021_0001
oder Tautomere davon, worinor tautomers thereof, wherein
X die Bedeutung F, Cl, Br, Methyl oder Nitro hat.X has the meaning F, Cl, Br, methyl or nitro.
2) Verbindung der Formel (1 ) gemäß Anspruch 1 , wobei X die Bedeutung Methyl hat, gekennzeichnet durch folgende Linien im Röntgenpulverdiagramm (Cu-Kα-Strahlung, doppelte Beugungswinkel 2 Theta in Grad, relative Intensität in Prozent):2) Compound of formula (1) according to claim 1, wherein X has the meaning methyl, characterized by the following lines in the X-ray powder diagram (Cu-K α radiation, double diffraction angle 2 theta in degrees, relative intensity in percent):
2Θ d relative Intensität2Θ d relative intensity
5.2 16.9 345.2 16.9 34
7.1 12.4 347.1 12.4 34
7.7 11.5 1007.7 11.5 100
8.1 10.9 518.1 10.9 51
11.4 7.7 8611.4 7.7 86
12.1 7.3 2812.1 7.3 28
13.6 6.5 4313.6 6.5 43
15.8 5.6 47 15.8 5.6 47
18.9 4.7 4118.9 4.7 41
20.7 4.3 2820.7 4.3 28
22.9 3.9 4222.9 3.9 42
23.8 3.73 4423.8 3.73 44
24.1 3.69 4724.1 3.69 47
25.0 3.56 7025.0 3.56 70
25.4 3.50 6325.4 3.50 63
25.7 3.46 7125.7 3.46 71
26.5 3.37 4426.5 3.37 44
27.7 3.22 4427.7 3.22 44
3) Verbindung der Formel (1 ) gemäß Anspruch 1 , wobei X die Bedeutung Methyl hat, gekennzeichnet durch folgende Linien im Röntgenpulverdiagramm (Cu-Kα-Strahlung, doppelte Beugungswinkel 2 Theta in Grad):3) Compound of formula (1) according to claim 1, wherein X has the meaning methyl, characterized by the following lines in the X-ray powder diagram (Cu-K α radiation, double diffraction angle 2 theta in degrees):
2Θ d rel. Intensität2Θ d rel. intensity
7.1 12.6 287.1 12.6 28
8.4 10.5 178.4 10.5 17
11.3 7.9 2011.3 7.9 20
13.0 6.8 813.0 6.8 8
15.1 5.9 815.1 5.9 8
15.4 5.8 1115.4 5.8 11
17.7 5.0 1017.7 5.0 10
25.4 3.5 10025.4 3.5 100
26.1 3.4 1326.1 3.4 13
29.6 3.0 1129.6 3.0 11
4) Verbindung der Formel (1 ) gemäß Anspruch 1 , wobei X die Bedeutung Nitro hat, gekennzeichnet durch folgende Linien im Röntgenpulverdiagramm (Cu- Kα-Strahlung, doppelte Beugungswinkel 2 Theta in Grad):4) Compound of formula (1) according to claim 1, wherein X has the meaning nitro, characterized by the following lines in the X-ray powder diagram (Cu-K α radiation, double diffraction angle 2 theta in degrees):
2Θ d rel. Intensität2Θ d rel. intensity
5.2 17.11 44 5.2 17.11 44
7.4 11.89 1007.4 11.89 100
8.2 10.80 858.2 10.80 85
11.5 7.67 8611.5 7.67 86
11.7 7.53 3711.7 7.53 37
13.3 6.63 5013.3 6.63 50
14.6 6.07 3614.6 6.07 36
15.0 5.90 3715.0 5.90 37
15.4 5.75 4315.4 5.75 43
15.6 5.65 5015.6 5.65 50
18.5 4.78 3818.5 4.78 38
23.0 3.86 3823.0 3.86 38
23.7 3.75 3023.7 3.75 30
24.2 3.67 3224.2 3.67 32
25.1 3.55 6025.1 3.55 60
25.5 3.49 5925.5 3.49 59
26.4 3.37 7626.4 3.37 76
27.5 3.23 3827.5 3.23 38
29.4 3.03 2529.4 3.03 25
5) Verbindung der Formel (1 ) gemäß Anspruch 1 , wobei X die Bedeutung Nitro hat, gekennzeichnet durch folgende Linien im Röntgenpulverdiagramm (Cu- Kα-Strahlung, doppelte Beugungswinkel 2 Theta in Grad):5) Compound of formula (1) according to claim 1, wherein X has the meaning nitro, characterized by the following lines in the X-ray powder diagram (Cu-K α radiation, double diffraction angle 2 theta in degrees):
2Θ d rel. Intensität2Θ d rel. intensity
9.5 9.30 1009.5 9.30 100
11.7 7.54 1011.7 7.54 10
12.7 6.99 1712.7 6.99 17
14.4 6.16 2014.4 6.16 20
16.7 5.30 1116.7 5.30 11
18.2 4.86 1718.2 4.86 17
19.9 4.45 1119.9 4.45 11
20.5 4.31 2520.5 4.31 25
21.5 4.12 10 21.5 4.12 10
22.1 4.01 2122.1 4.01 21
23.3 3.81 7123.3 3.81 71
23.6 3.76 1623.6 3.76 16
27.4 3.25 2027.4 3.25 20
29.1 3.06 1329.1 3.06 13
6) Verbindung der Formel (1 ) gemäß Anspruch 1 , wobei X die Bedeutung Nitro hat, gekennzeichnet durch folgende Linien im Röntgenpulverdiagramm (Cu- Kα-Strahlung, doppelte Beugungswinkel 2 Theta in Grad):6) Compound of formula (1) according to claim 1, wherein X has the meaning nitro, characterized by the following lines in the X-ray powder diagram (Cu-K α radiation, double diffraction angle 2 theta in degrees):
2Θ d rel. Intensität2Θ d rel. intensity
8.9 9.98 1008.9 9.98 100
11.5 7.71 3611.5 7.71 36
13.5 6.57 1913.5 6.57 19
16.2 5.48 2416.2 5.48 24
16.6 5.33 2316.6 5.33 23
17.0 5.20 2517.0 5.20 25
17.8 4.99 1417.8 4.99 14
19.2 4.62 3319.2 4.62 33
19.9 4.47 2519.9 4.47 25
20.3 4.36 8620.3 4.36 86
20.9 4.26 2820.9 4.26 28
21.8 4.08 1921.8 4.08 19
22.4 3.97 3122.4 3.97 31
23.5 3.78 9123.5 3.78 91
24.0 3.71 3124.0 3.71 31
25.0 3.55 2825.0 3.55 28
25.4 3.50 3225.4 3.50 32
26.2 3.40 2526.2 3.40 25
27.1 3.28 5327.1 3.28 53
31.0 2.88 1331.0 2.88 13
7) Verfahren zur Herstellung einer Verbindung der Formel (1) nach einem oder mehreren der Ansprüche 1 bis 6, durch Diazotierung eines Amins der Formel (2)
Figure imgf000025_0001
7) Process for the preparation of a compound of formula (1) according to one or more of claims 1 to 6, by diazotization of an amine of formula (2)
Figure imgf000025_0001
wobei X die in Anspruch 1 angegebene Bedeutung hat, und anschließende Kupplung mit der Verbindung der Formel (3)where X has the meaning given in claim 1, and subsequent coupling with the compound of the formula (3)
Figure imgf000025_0002
Figure imgf000025_0002
8) Verwendung einer Verbindung nach einem oder mehreren der Ansprüche 1 bis 6 zum Pigmentieren von hochmolekularen organischen Materialien natürlicher oder synthetischer Herkunft.8) Use of a compound according to one or more of claims 1 to 6 for pigmenting high molecular weight organic materials of natural or synthetic origin.
9) Verwendung einer Verbindung nach einem oder mehreren der Ansprüche 1 bis 6 zum Pigmentieren von Kunststoffen, Harzen, Lacken, Anstrichfarben oder elektrophotographischen Tonern und Entwicklern, Tinten, Druckfarben und Saatgut.9) Use of a compound according to one or more of claims 1 to 6 for pigmenting plastics, resins, lacquers, paints or electrophotographic toners and developers, inks, printing inks and seeds.
10) Verwendung nach Anspruch 8 oder 9 zum Pigmentieren von Automobillacken. 10) Use according to claim 8 or 9 for pigmenting automotive paints.
PCT/EP2003/004966 2002-05-28 2003-05-13 Novel derivatives of c.i. pigment red 170 WO2003099936A1 (en)

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Cited By (2)

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CN102816456A (en) * 2012-08-29 2012-12-12 天津城市建设学院 Method for preparing core pigment red 170 by inorganic nano material modification
WO2016206928A1 (en) * 2015-06-25 2016-12-29 Clariant International Ltd Use of novel naphthol as-pigment-mixtures in printing-materials

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DE502004002125D1 (en) * 2003-08-19 2007-01-04 Clariant Produkte Deutschland MIXED CRYSTALS WITH DERIVATIVES OF C.I. PIGMENT RED 170

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FR1411277A (en) * 1963-08-22 1965-09-17 Bayer Ag Water-insoluble azo dyes and process for their manufacture
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Publication number Priority date Publication date Assignee Title
CN102816456A (en) * 2012-08-29 2012-12-12 天津城市建设学院 Method for preparing core pigment red 170 by inorganic nano material modification
CN102816456B (en) * 2012-08-29 2013-10-23 天津城市建设学院 Method for preparing core pigment red 170 by inorganic nano material modification
WO2016206928A1 (en) * 2015-06-25 2016-12-29 Clariant International Ltd Use of novel naphthol as-pigment-mixtures in printing-materials
US10782625B2 (en) 2015-06-25 2020-09-22 Clariant Plastics & Coatings Ltd Use of novel naphthol AS-pigment-mixtures in printing-materials

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