Basf Aktiengesellschaft

Joachim Kranz

Rudolf Polster

Wolfgang Habermann

Reinhard Sappok

Wolf D Fechner

Rolf Schneider

Helmut Knittel

Peter Thoma

Alois Wiesenberger

Karl-Ludwig Hock

Udo Mayer

Walter Kurtz

Peter Hammes

Harry Distler

Wolfgang Fabian

Fritz Brunnmueller

Horst Belde

Karl Schmeidl

Eduard Hartmann

Werner Jettmar

Friedrich Brunnmueller

Guenter Stoeckelmann

Bernd Landmann

Karl Muench

Joachim Felger

A process is described for preparing metal phthalocyanines by reacting orthodinitriles dissolved or suspended in organic solvents or pulverulent mixtures of ortho-dinitriles with anhydrous ammine-metal carboxylate salts or metal-aminocarboxylic acid complexes without alkaline or chloride-containing additaments using an ortho-dinitrile excess of from 0.1 to 5% by weight.

Preparation of metal phthalocyanines by reacting ortho-dinitriles with

Solid pigment formulations containing from 70 to 97% by weight, based on the total weight of the formulation, of one or more pigments and also from 3 to 30% by weight, based on the total weight of the formulation, of at least one surfactant which is an adduct of ethylene oxide and optionally propylene oxide with ethylenediamine, the proportion of ethylene oxide being from 46 to 100% by weight, based on the total weight of ethylene oxide and propylene oxide in the adduct, and the adduct having an average molecular weight of from 5000 to 40,000, are useful for pigmenting printing ink and gloss paint compositions.

Highly concentrated solid pigment formulations

Grinding crude pigments together with inorganic grinding aids, for example rock salt and dialkyl phthalates, phenoxyethanol, 2-phenylethanol and/or dialkyl benzoates gives soft-textured pigments which produce strong colorings of higher transparency and/or higher cleanliness of hue than prior art pigments.

Preparation of strong and soft-textured surface coating pigments

Isoindolenines of the general formula (I) ##STR1## where R.sup.1 is hydrogen, unsubstituted or chlorine-, hydroxylphenyl- or cyano-substituted C.sub.1 -C.sub.12 -alkyl or C.sub.5 -C.sub.8 -cycloalkyl or unsubstituted or chlorine- or methyl-substituted phenyl,

(4-amino-2-hydroxyphenyl-1-oxoisoindolenines, preparation thereof and

Polyhalocopper phthalocyanine pigments of high color strength are prepared by recrystallizing the finely divided agglomerated crude pigment in a heterogeneous aqueous organic phase at elevated temperatures by a process in which the aqueous organic phase used is a heterogeneous mixture of an aliphatic ketone having a total of 3 to 9 carbon atoms and water. The process gives the pigments in the form of spherical granules which are dust-free or have a low dust content. The pigments give deep, brilliant colorations of pure hues.

Preparation of polyhalocopper phthalocyanine pigments of high color

Finely divided, agglomerated crude polyhalo-copper phthalocyanine is recrystallized (conditioned) by heating the crude pigment with benzoic acid, toluic acid, ethylbenzoic acid or a mixture of these, in the presence of water, at from 80.degree. to 130.degree. C. The resulting polyhalo-copper phthalocyanine pigments are readily dispersible and of high color strength, and pigmentary forms ranging from transparent to high-hiding can be obtained in a selective manner. The carboxylic acids used as conditioning media can readily be recovered by acidifying the mother liquor.

Preparation of polyhalo-copper phthalocyanines having a high color

Readily dispersible formulations comprising (a) finely divided copper phthalocyanine and (b) an iron hexacyanoferrate-III pigment are obtained by thoroughly milling a mixture of (a) and (b). The performance characteristics and tinctorial properties of the formulations comprising (a) and (b) can be improved by incorporating (c) a Mannich condensate obtained from 2-hydroxynaphthalene which may or may not possess 1 or 2 further .beta.-OH groups, formaldehyde and a primary or secondary amine, (d) a compound of the formula K(-NH-CONH-R).sub.2, where K is 1,5-naphthylene or 4,4'-diphenylenemethane and R is C.sub.12 -C.sub.18 -alkyl, C.sub.12 -C.sub.18 -alkenyl, C.sub.8 -C.sub.18 -alkoxypropyl or C.sub.2 -C.sub.8 -alkoxyethyleneoxypropyl, (e) a C.sub.6 -C.sub.18 -alkylbenzenesulfonic acid and (f) a mixture of (e) with a basic copper phthalocyanine and/or a salt obtained by reacting (e) with the basic copper phthalocyanine. The finishes and printing inks produced using the formulations have tinctorial properties and performance characteristics which are superior to those of finishes and inks obtained by mixing individually milled or dispersed components.

Pigment formulations and their use of pigmenting gravure printing inks

Stable, fluid formulations contain (a) finely divided iron cyano complexes, iron-III oxides or iron-III oxide hydrates, (b) one or more C.sub.6 -C.sub.18 -alkylbenzenesulfonic acid, (c) one or more compounds which are obtained by Mannich condensation from 2-hydroxynaphthalene, which may or may not contain 1 or 2 additional .beta.-hydroxyl groups, formaldehyde and primary or secondary aliphatic, cycloaliphatic or aromatic monoamines, diamines, triamines or polyamines or 5- or 6-membered heterocyclic compounds, and which contain from 1 to 6 .beta.-hydroxynaphthyl groups, and (d) one or more organic liquids, the ratio of (b):(c) being from 1:8 to 2:1 and the amount of (c) being from 10 to 20% by weight, based on (a). The formulations are fluid or pourable at pigment concentrations of from 20 to 55% by weight and give very deeply colored, very glossy finishes.

Fluid, stable formulations

Blue iron hexacyanoferrate-III pigments are produced by a process wherein complex iron-II hexacyanoferrate-II (Berlin white) is prepared by electrolysis of an aqueous catholyte solution containing (a) an iron-II salt, (b) an alkali metal salt, an ammonium salt or a mixture of these, and (c) hydrogen cyanide, in an electrolysis cell in which the anode chamber and cathode chamber are separated by an ion exchange membrane, using an electrically conductive aqueous liquid in the anode chamber, and the iron-II hexacyanoferrate-II obtained is then converted to the blue pigment. The process gives Berlin white, which is substantially free from salt, in high yield and high purity. Pollution caused by the process is very low, since only a small amount of salt is produced. Compared with the corresponding blue pigments produced by prior art processes, the pigments obtained give purer colorations with better gloss, and are of higher color strength.

Production of blue iron hexacyanoferrate-III pigments

Blue iron hexacyanoferrate-III pigments (I) are prepared by anodic oxidation of metallic iron in hydrogen cyanide, or a reaction medium containing hydrogen cyanide, at pH&lt;7 and at an anode potential of .ltoreq.0.76 V (measured against a standard hydrogen electrode) to complex iron-II hexacyanoferrate-II compounds (II), which are then oxidized to (I) in a conventional manner. The oxidation of (II) is advantageously carried out with air or oxygen at pH 0-4 and at from 70 to 95.degree. C., but can also be carried out at pH&gt;8. The process gives readily dispersible pigments (I) which are of high color strength and give brilliant, glossy colorations.

Preparation of blue iron hexacyanoferrate-III pigments, and the pigments

A stable fluid formulation which comprises (a) finely divided .alpha.- or .beta.-copper phthalocyanines or finely divided indanthrone, one or more C.sub.6 -C.sub.18 -alkylbenzenesulfonic acids (b), a basic copper phthalocyanine (c) of the formula ##STR1## where CuPc is an n-valent copper phthalocyanine radical, R.sup.1 and R.sup.2 independently of one another are H or C.sub.1 -C.sub.8 -alkyl and n is 1, 2, 3 or 4, one or more compounds (d) which are obtained by Mannich condensation of 2-hydroxy-naphthalene, which may or may not contain 1 or 2 additional .beta.-hydroxyl groups, formaldehyde and primary or secondary aliphatic, cycloaliphatic or aromatic monoamines, diamines, triamines or polyamines or 5-membered or 6-membered heterocyclic compounds which contain an &gt;NH-- group as a ring member and which contain from 1 to 6 .beta.-hydroxynaphthyl groups, and one or more organic liquids (e). The weight ratio (b):(c):(d) is from 1:1:1 to 2.5:1.25:1. The formulations give very deeply colored finishes with which very glossy and highly transparent coatings are obtained.

Fluid, stable formulations of copper phthalocyanine or indanthrone

Phthalocyanine formulations which comprise a mixture of (a) phthalocyanine and (b) from 2 to 20% by weight, based on (a) of one or more urea derivatives of the formula K-(-NHCO-NH-R).sub.2 (I), where K is 1,5-naphthylene or 4,4'-diphenylenemethane, R is alkyl of 12 to 18 carbon atoms, alkenyl of 12 to 18 carbon atoms, 3-(alkoxy of 8 to 18 carbon atoms)-propyl, 2-(alkylamino of 8 to 18 carbon atoms)-ethyl or (CH.sub.2).sub.3 --O--(CH.sub.2 --CH.sub.2 O).sub.n --R.sup.1, R.sup.1 is alkyl of 2 to 8 carbon atoms or phenyl and n is 1, 2, 3 or 4, and which are obtained by milling (a) with (b) in the absence of a grinding medium. When used in printing inks, such as offset printing inks, the formulations give deeply colored prints in very pure hues, with very low graininess of the ink.

Phthalocyanine formulations

Formulations of flavanthrone, pyranthrone, indanthrone, indigo, quinacridone, perylene-3,4,9,10-tetracarboxylic acid dianhydride and perylene-3,4,9,10-tetracarboxylic acid diimide pigments which contain, as additives, one or more compounds of the formula ##STR1## where X is an n-valent radical of a flavanthrone, pyranthrone, indigo, quinacridone, perylene-3,4,9,10-tetracarboxylic acid dianhydride or perylene-3,4,9,10-tetracarboxylic acid diimide pigment, R.sup.1, R.sup.3 and R.sup.4 are hydrogen or chlorine, R.sup.2 is hydrogen, chlorine, carboxyl, bromine, nitro, N-C.sub.1 -C.sub.5 -alkylcarbamyl, N-phenylcarbamyl or benzoylamino and n is 1, 2, 3 or 4. In solutions of surface-coating binders or of surface coatings, the above formulations give very deep colorations, coupled with high gloss and high transparency of the resulting films.

Pigment formulations

A pigment formulation which comprises (a) a finely divided organic pigment and (b) one or more urea derivatives of the formula K--(NH--CO--NH--R).sub.2, where R is C.sub.12 -C.sub.18 -alkyl, C.sub.12 -C.sub.18 -alkenyl, C.sub.8 -C.sub.18 -alkoxypropyl or --(CH.sub.2).sub.3 --O--(C.sub.2 H.sub.4 O).sub.n --R.sup.1, R.sup.1 is C.sub.2 -C.sub.8 -alkyl or phenyl, n is 1, 2, 3 or 4 and K is 1,5-naphthylene or 4,4'-diphenylenemethane, with or without (c) up to 5% by weight, based on (a and b), of agents conventionally present in pigment formulations. In binder solutions, the pigment formulations give printing inks and paints possessing excellent tinctorial properties. Some of the compounds (b) prevent the conversion of .alpha.-copper phthalocyanine to the .beta.-modification.

Easily water-dispersed formulations of a phthalocyanine pigment which contain--based on the formulation--(a) from 70 to 95% by weight of finely divided phthalocyanine pigment of which the mean primary particle size is less than 0.5 .mu.m, and (b) from 30 to 5% by weight of one or more alkylarylsulfonic acids, where alkyl is of 4 to 20 carbon atoms, but the sum of the alkyl carbon atoms is not less than 8, which alkylarylsulfonic acids may be in the form of water-soluble salts. A fine dispersion of the formulations is obtainable by sprinkling the formulations into water and shaking. The dispersions obtained are stable and can be filtered through a paper filter without leaving a residue. The finely dispersed pigment is absorbed quantitatively on wool, cotton or paper pulp.

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Ludwigshafen, Germany

Joachim Kranz