EP2137265A2

EP2137265A2 - Method for the formation of organic pigments

Info

Publication number: EP2137265A2
Application number: EP08736136A
Authority: EP
Inventors: Joachim Jesse; Benno Sens; Andres Carlos Garcia Espino; Richard Van Gelder; Matthias KLÜGLEIN; Ines Pietsch; Wolfgang Best; Rainer Henning
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-04-13
Filing date: 2008-04-11
Publication date: 2009-12-30
Also published as: WO2008125628A2; US20100043672A1; JP2010523783A; WO2008125628A3; CN101657508A; KR20100016078A

Abstract

The invention relates to a method for the formation of an organic pigment, wherein the pigment is dissolved or dispersed in an aqueous solvent or a mineral acid and is allowed to crystallize from the solution or dispersion in the presence of a crystallization modifier and is subsequently isolated as a solid, wherein the crystallization modifier is a condensation product of at least one hydroxyaryl sulfonic acid having sulfonate groups and/or at least one hydroxydiaryl sulfone compound and at least one aliphatic aldehyde with 1-6 carbon atoms, optionally containing urea and possibly an alkali sulfite, or a mixture of such condensation products.

Description

Process for the formation of organic pigments

The invention relates to a process for the formation of organic pigments using condensation products based on hydroxyarylsulfonic acids or hydroxydiarylsulfone compounds as crystallization modifiers, the resulting organic pigments themselves and the use of the condensation products as crystallization modifiers for the formation of organic pigments. The term "sulfonate groups" below means both the (acidic) sulfonic acid group -SO ₃ H and its salt -SO ₃ M (M = metal, ammonium).

Organic pigments often accumulate in the synthesis in coarsely crystalline form with very heterogeneous particle size distribution. For conversion into a coloristically useful pigment form suitable for the application, the crude pigments are therefore usually subjected to a formation.

For this purpose, a grinding of the crude pigment and subsequent recrystallization of the millbase in an organic solvent is known, or the grinding is carried out as a wet grinding in aqueous suspension in high-speed stirred ball mills. Although the methods described achieve particle size reduction and thus an improvement in the coloristic properties of the pigments, sometimes with a high expenditure of time, it is difficult to control the particle size of the pigments obtained, and the pigments are frequently used in a number of applications. For example, as a colorant for paints and in ink-jet inks, insufficient, because too broad particle size distribution on.

WO 02/00643 discloses a process for the formation of quinophthalone crude pigments, in which the crude pigment obtained in the synthesis is subjected to milling in the absence of grinding aids and the resulting millbase is subsequently treated in the presence of a quinophthalone derivative in an organic solvent or a mixed organic solvent and water crystallize. Examples of derivatives which are mentioned are sulfonic acid derivatives of quinophthalone pigments.

WO 2004/048482 discloses a process for the formation of organic pigments, in which the pigment is dissolved in concentrated sulfuric acid and the sulfuric acid solution is mixed with water in the presence of a condensation product of naphthalenesulfonic acid and formaldehyde as crystallization modifier. The crystallization modifier Tor is added to the sulfuric acid pigment solution or it is generated in this by reacting 1- and 2-naphthalenesulfonic acid with formaldehyde in situ.

The object of the invention is to provide further advantageous processes for the formation of organic pigments, which give pigments with very good coloristic properties.

The object is achieved by a process for forming ("finishing") an organic pigment, in which the pigment is dissolved or dispersed in an aqueous solvent or a mineral acid and crystallized from the solution or dispersion, the pigment in the presence of a crystallization modifier and then the Isolated pigment as a solid, which is characterized in that the crystallization modifier a sulfonate containing condensation product of at least one Hydroxyarylsulfonsäure and / or at least one Hydroxydiarylsulfonverbindung and at least one aliphatic aldehyde having 1 to 6 carbon atoms, optionally urea and optionally an alkali metal sulfite, or a mixture of such condensation products.

Crystallization or crystallization in the sense of the present invention is not only the precipitation of the pigment as a solid from its solution, but also the "finishing" of the pigment, which is accompanied by a partial recrystallization of the pigment.

The crystallization modifier may be a condensation product of one or more different hydroxyarylsulfonic acids and one or more different aliphatic aldehydes of 1 to 6 carbon atoms. Generally, with 0.25 to 4 moles of aliphatic aldehyde is condensed per mole of hydroxyaryl units present. If urea is used, it is generally used in amounts of from 0.25 to 4 mol of urea per mole of hydroxyaryl units present. In addition to hydroxyarylsulfonic acid, one or more different hydroxydiarylsulfone compounds can be condensed in the condensation product. The preparation of the condensation product can furthermore be carried out in the presence of an alkali metal sulfite, preferably sodium sulfite, with further sulfonate groups being introduced into the condensation product in addition to the sulfonate groups introduced by the hydroxyarylsulfonic acid.

The crystallization modifier may be a condensation product of one or more different hydroxydiarylsulfone compounds, one or more different aliphatic aldehydes having 1 to 6 carbon atoms and an alkali metal sulfite, preferably sodium sulfite. The sulfonate groups are here introduced as Alkylsulfonatgruppen in the condensation product. In general, the hydroxydiarylsulfone compound is reacted with 0.5 to 5 mol of the aliphatic aldehyde and 0.4 to 2 mol of the alkali metal sulfite per mole of hydroxydiarylsulfone compound.

Suitable hydroxyarylsulfonic acids which can be used to prepare the crystallization modifiers used according to the invention are, for example, hydroxyphenylsulfonic acids or hydroxynaphthylsulfonic acids. These may also have several hydroxyl groups. Preferred hydroxyarylsulfonic acid is phenolsulfonic acid.

Suitable hydroxydiarylsulfone compounds which can be used for the preparation of the condensation products used according to the invention are, for example, dihydroxydiphenylsulfones or, more generally, polyhydroxydiphenylsulfones and dihydroxydinaphthylsulfones or, more generally, polyhydroxydinaphthylsulfones. Preferred hydroxydiarylsulfone compound is dihydroxydiphenylsulfone (DHDPS).

In general, hydroxyarylsulfonic acids and hydroxydiarylsulfones are prepared by sulfonation of the corresponding hydroxyaryl compounds, for example of naphthols, phenol or polyphenols, with concentrated sulfuric acid or oleum. In general, mixtures of hydroxyarylsulfonic acids and hydroxydiarylsulfones are formed.

In a preferred embodiment of the process according to the invention, a crystallization modifier is used which is obtainable by treating phenol with concentrated sulfuric acid, with an oleic acid having a content of from 20 to 65% by weight or with a mixture of sulfuric acid and oleum Molar ratio of total sulfuric acid, calculated as SO ₃ , to phenol from 0.7: 1 to 1, 5: 1, at a temperature of 100 to 180 ⁰ C to a mixture containing phenolsulfonic acid, dihydroxydiphenylsulfone and sulfuric acid react, or by mixing the individual Components produces a corresponding mixture, and then at 40 to 90 ⁰ C per mole of phenol units present with 0.5 to 4 mol of an aliphatic aldehyde having 1 to 6 carbon atoms, preferably formaldehyde, and - optionally - with 0.25 to 4 mol Urea condenses.

In a further preferred embodiment, a crystallization modifier is used which is obtainable by reacting dihydroxydiphenylsulfone with 0.5 to 5 mol of an aliquot of - A -

tables of aldehyde having 1 to 6 carbon atoms, preferably formaldehyde, and 0.4 to 2 moles of sodium sulfite per mole of dihydroxydiphenyl sulfone at a temperature of 90 to 180 ⁰ C react.

It is also possible to use mixtures of the condensation products described above.

The condensation products generally act as crystallization inhibitors.

From the solutions obtained, the condensation product containing sulfonate groups can be isolated, for example by precipitation of the condensation product by addition of a water-miscible liquid in which the condensation product is insoluble, or by evaporation of the liquid reaction medium, for example by spray drying.

In the method of formation of the present invention, the organic pigment is dissolved or dispersed in an aqueous solvent or in a mineral acid and allowed to crystallize from the solution or dispersion in the presence of the crystallization modifier. In one embodiment of the process of the invention, the pigment is dissolved in concentrated sulfuric acid and allowed to crystallize by mixing the solution with an aqueous diluent. In this case, the crystallization modifier may be contained both in the sulfuric acid solution of the pigment and in the aqueous diluent. In a variant of this process, the mixing takes place by combining the sulfuric acid pigment solution and the aqueous diluent by means of a mixing nozzle. Aqueous diluent here is generally water which may contain the crystallization modifier. The crystallization can also be effected by pouring the sulfuric acid pigment solution into water, preferably ice-water.

In general, the concentration of the pigment in the concentrated sulfuric acid is 1 to 30% by weight. The crystallization modifier is generally present in amounts of from 0.1 to 30% by weight, based on the pigment. The volume of the aqueous diluent is generally 1 to 12 times the volume of the sulfuric acid pigment solution.

In a variant of this embodiment, the crystallization modifier is generated in situ in the sulfuric acid solution of the pigment. These are the individual components of the condensing agent is introduced into the sulfuric acid pigment solution and allowed to condense.

In a further variant of this embodiment, after crystallization, the crystallized organic pigment is allowed to mature in the presence of a surfactant. The surfactant may already be added to the aqueous diluent or added after the crystallization step to the pigment suspension, generally as an aqueous solution. The ripening of the crystallized organic pigment is generally carried out by stirring the pigment suspension at temperatures generally from 40 to 100 ^° C. over a period of from 0.5 to 5 hours. This leads to the growth of larger pigment particles at the expense of smaller pigment particles and / or to a smoothing / healing of the crystal surface of the pigment particles. Since work is carried out in the presence of a surfactant, this process already takes place in the aqueous sulfuric acid pigment suspension having a comparatively low sulfuric acid content and a comparatively low temperature, as is present after the mixing of sulfuric acid pigment solution with the aqueous diluent.

Suitable surfactants are the anionic, cationic, nonionic and amphoteric surfactants mentioned below.

In a further embodiment of the process according to the invention, the pigment is dispersed in dilute aqueous sulfuric acid and swollen in the presence of the crystallization modifier. It is advantageous to grind the pigment together with the crystallization modifier before swelling, for example in a stirred ball mill. It is particularly advantageous to mill the pigment together with the crystallization modifier and a surface-active agent, in particular a synthetic and / or natural resin such as rosin, hydrogenated, partially hydrogenated, disproportionated, dimensiertem or polymerized Kolophorium before swelling. The swelling results in the growth of larger pigment particles at the expense of smaller pigment particles and / or in a smoothing / healing of the crystal surfaces of the pigment particles. Suitable dilute sulfuric acid generally has a concentration of 50 to 85, preferably 60 to 85 wt .-% on. The swelling of the pigment in the dilute aqueous sulfuric acid in the presence of the crystallization modifier is generally carried out at temperatures of 15 to 90 ⁰ C over a period of generally 0.5 to 24 hours. The optimum swelling conditions can be determined for each type of pigment in preliminary tests. Then it is diluted with water. This is generally to the Sulfuric acid pigment dispersion 2 to 6 times added to water. Subsequently, stirring is generally continued for 0.5 to 2 hours.

The swelling of the pigment may also be carried out as an aftertreatment step, preferably with the pigment obtained by the above-described method of precipitation with an aqueous diluent and isolated as a solid.

In a further embodiment of the process according to the invention, the pigment obtained, for example, by precipitation is dispersed in water and crystallized in the presence of the crystallization modifier and an additive which increases the solubility of the pigment. Generally, as the solubility enhancing additive, an organic solvent is added. Suitable organic solvents are, for example, xylenes, glycols, alcohols, THF, acetone, NMP, DMF and nitrobenzene. These are, based on the aqueous pigment suspension, generally in an amount of 0.1 to 50 wt .-% added. The amount of crystallization modifier is generally 0.1 to 30 wt .-%, based on the aqueous pigment suspension (without organic solvent). In general, the suspension is stirred in the presence of the organic solvent at temperatures in the range of 15 ^° C. to the boiling point and then the organic solvent is distilled off. Alternatively, the process can also be carried out without solvent under elevated pressure. In this case, a controlled by the crystallization modifier crystal growth of the pigment by Ostwald ripening takes place. The step can also be carried out as an aftertreatment step, for example with the pigment obtained by the above-described method of precipitation with an aqueous diluent and isolated as a solid.

In all cases, the pigment crystallized in the presence of the crystallization modifier is subsequently isolated as a solid by filtration of the aqueous suspension.

In a variant of this embodiment, a solution of the pigment in concentrated sulfuric acid is prepared and mixed with water, preferably using a mixing nozzle. The suspension is stirred, generally at a temperature in the range of 15 to 90 ⁰ C over a period of 0.5 to 8 hours, the pigment is filtered off and preferably washed with water. The resulting pigment is suspended in water and allowed to crystallize in the presence of crystallization modifier and solubility enhancing additive. Suitable dispersants are, for example, sulfonic acid-containing pigment derivatives such as copper phthalocyaninesulfonic acid. Suitable pigments which can be formed by the process according to the invention are, for example, azo, azomethine, methine, anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioindigo, thiazine indigo, dioxazine, iminoisoindoline , Iminoisoindolinone, quinacridone, flavanthrone, indanthrone, anthrapyrimidine and quinophthalone pigments. Preferred pigments are phthalocyanines, perylenes, quinacridones, indanthrones, quinaphthalones, dioxazines and diketopyrroles, particular preference is given to phthalocyanines, perylenes and indanthrones.

Of the perylenes, preferred are the pigments of the type Cl. Pigment Red 179. These can be prepared by various methods. Thus, perylene-3,4,9,10-tetracarboxylic diimide with a methylating agent to Cl. Pigment Red 179 be methylated or perylenetetracarboxylic anhydride with methylamine to Cl. Pigment Red 179 to be condensed. The latter is preferably used. However, it is also possible to use mixtures of the pigments prepared by these two methods. It is also possible to use pigment derivatives prepared by these methods or mixtures thereof.

The crystallization modifier used according to the invention is generally present during crystallization in amounts of from 0.1 to 30% by weight, preferably from 0.3 to 25% by weight, more preferably from 1 to 22% by weight, based on the pigment suspension , in front. In some cases it may be advantageous to use besides other crystallization modifiers, dispersants, surfactants or special polymers. Examples of further crystallization modifiers are imidazolemethyl or pyrazolemethylquinacridone pigment sulfonic acids. Examples of suitable surfactants are anionic surfactants such as alkylbenzenesulfonates or alkylnaphthalenesulfonates or alkylsulfosuccinates, cationic surfactants such as quaternary ammonium salts, for example benzyltributylammonium chloride, or nonionic or amphoteric surfactants such as polyoxyethylene surfactants and alkyl or amidopropyl betaines.

Suitable special polymers are, for example, homo- and copolymers of maleic acid, polyacrylic acid, polymethacrylic acid, polyurethanes, polyvinyl alcohol, polyvinylpyrrolidone or cellulose derivatives.

It may be followed by further formation steps. Thus, preferably, the pigment isolated as a solid is mixed with a pigment synergist. It is generally a sulfonate or carbonate group-containing derivative of an organic pigment or its salt, or a basic derivative of the aforementioned pigments. Preferably, the pigment synergist is a derivative of the pigment with which the Synergist is mixed. In general, the pigment synergist is used in amounts of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on the finished pigment formulation.

The average particle size of the formed pigments is generally in the range of 10 to 400 nm, preferably 20 to 200 nm.

The pigments formed by the process according to the invention may contain the crystallization modifier on the surface of the pigment particles. The subject matter therefore also includes pigment preparations comprising particles of an organic pigment with a superficial coverage of the pigment particles with the crystallization modifier used according to the invention. The pigment preparations may contain, in addition to the already mentioned pigment synergists, further additives, generally in amounts of up to 15% by weight. Further additives are, for example, wetting agents, surfactants, antifoams, antioxidants, UV absorbers, stabilizers, plasticizers and texturizing aids. These additives can be added already during the forming step.

The pigment preparations are used for dyeing and coating natural and synthetic materials.

The invention is further illustrated by the following examples.

Examples

The testing of the pigment preparations according to the invention takes place in an aqueous lacquer system.

For this purpose, a water tinting paste is first prepared based on a water-dilutable polyurethane resin. 100 g of the polyurethane resin dispersion described in Example 1.3 of WO-A-92/15405, 30 g of the pigment preparation and 50 g of water are suspended, adjusted to a pH of 8 with dimethylethanolamine and placed in a ball mill (loading with 1.0%). 1.6 mm SAZ beads [SAZ = silicon / aluminum / zirconium oxide]) are ground for 4 hours.

In the second step, 34 g of this water tinting paste (15% strength by weight based on pigment) are added to 225 g of a polyurethane-based compounding varnish (described in Example 3 of WO-A 92/15405). After adding 7.5 g of water with aminoethanol becomes a pH set by 8. The resulting suspension is stirred for 15 minutes with a propeller stirrer at 1000 rpm.

On the basis of the aqueous basecoat materials produced metallic paints are prepared and applied by spraying.

example 1

Preparation of the Crystallization Modifier K1 The crystallization modifier K1 is prepared according to Example 2 of DE-A 101 40 551.

In a pressure reactor 1300 kg of deionized water at room temperature together with 4100 kg (9.5 kmol) technical Dihydroxydiphenylsulfon (containing about 85 wt .-% 4,4'-Dihydroxydiphenylsulfon, about 15 wt .-% 2,4'- Dihydroxydiphenylsulfon and small amounts of p-phenolsulfonic acid) as a 60 wt .-% aqueous solution and 1155 kg 30 wt .-% aqueous solution of formaldehyde (1 1, 5 kmol) and 800 kg (3 kmol) of solid sodium sulfite (anhydrous ) added. By adding a little 20 wt .-% aqueous solution of sodium hydroxide is adjusted in the reaction mixture, a pH of 8 to 8.5 a. Subsequently, the pressure reactor is closed and the reaction mixture is heated to 115 ⁰ C with stirring. After a short time at this temperature the reaction starts. The temperature of the reaction mixture rise to 150 to 160 ⁰ C and the pressure in the pressure reactor to 4 to 5 bar (pressure) at. By external heating, the temperature of the reaction mixture is maintained at 160 ⁰ C. After stirring the reaction mixture for 3 hours at 160 ^° C., the reaction mixture is cooled to room temperature and mixed with 400 kg of sodium bisulfate. The resulting solution has a solids content of about 46 wt .-%.

Example 2

140 parts of perylene-3,4,9,10-tetracarboxylic acid N, N'-dimethyldiimide (CI Pigment Red 179) are dissolved in 2576 parts of sulfuric acid (96% strength by weight) and heated to 25 ^° C. The pigment preparation is then from the acid with a 25 ⁰ C warm solution of 56.4 parts of a 45.4 wt .-% solution of K1 in 10,000 parts of water by jet precipitation by means of a Y-nozzle (0.5 mm holes for the Educt streams) with the following precipitation parameters: delivery rate of water 400 g / min, delivery rate of pigment solution 100 g / min. The pigment is filtered, washed and dried. A pigment preparation is obtained which, in an aqueous coating system based on a water-dilutable polyurethane resin, gives a strongly colored and transparent coating having a yellowish red hue. The metallic finish is strong and brilliant.

Example 3

50 parts of the pigment preparation from Example 2 are ground together with 2.5 parts of a perfluoro-containing perylene compound prepared according to EP 0 636 666 A2 (derivative (b2) from page 7, line 27 of EP 0 636 666 A2). The metallic coating containing the pigment preparation is even more transparent and yellower than that according to Example 2.

Example 4

50 parts of the pigment preparation from Example 2 are ground together with 3.75 parts of a sulfonic acid-containing perylene compound (prepared according to Example 3 of EP 0 486 531 B1). The metallic finish of this pigment preparation is even more transparent and yellower than that according to Example 2.

Example 5

140 parts of perylene-3,4,9,10-tetracarboxylic acid-N, N'-dimethyldiimide (CI Pigment Red 179) and 61, 7 parts of a 45.4 wt .-% solution of K1 be in 2576 parts of 96 wt .-% sulfuric acid dissolved and tempered to 25 ⁰ C. The pigment preparation is then precipitated from the sulfuric acid solution with 25 ⁰ C warm water by jet precipitation by means of a Y-mixing nozzle (0.5 mm bores for the educt streams) with the following flow rates: water 400 g / min, pigment solution in acid 100 g / min. There is obtained a precipitation suspension with a temperature of 60 ⁰ C. The pigment preparation is filtered through a suction filter, washed to <100 μS (conductivity of the wash water), dried in a drying oven at 80 ^° C. in vacuo and ground.

A pigment preparation is obtained which, in an aqueous coating system based on a water-dilutable polyurethane resin, gives a strongly colored and transparent coating having a yellowish red hue. The metallic finish is strong and brilliant. Example 6

50 parts of the pigment preparation from Example 5 are ground together with 3.75 parts of a sulfonic acid-containing perylene compound (prepared according to Example 3 of EP 0 486 531 B1). The metallic finish of this pigment preparation is even more transparent and yellower than that according to Example 5.

Example 7

1000 parts of the suspension of the pigment preparation 4 are mixed with 2.56 parts of a betaphtholethoxylats (Lugalvan ^® BNO 12, BASF AG) and stirred at 60 ⁰ C for 5 hours. Thereafter, the pigment preparation is filtered through a suction filter, washed to <100 μS, dried in a drying oven at 80 ⁰ C in vacuo and ground.

50 parts of this pigment preparation are ground together with 3.75 parts of a sulfonic acid-containing perylene compound (prepared according to Example 3 of EP 0 486 531 B1). With high transparency and yellowish red hue of the metallic coating, the aqueous coating system based on a water-dilutable polyurethane resin has a lower viscosity than that of Example 6.

Example 8

28.5 parts of perylene-3,4,9,10-tetracarboxylic acid N, N'-dimethyldiimide (CI Pigment Red 179) are used together with 6.2 parts of a 45.4% by weight solution of K1 in 600 Parts of 96 wt .-% sulfuric acid at 5 - 8 ⁰ C dissolved. The solution is stirred for 3 hours at this temperature and then added slowly in 5 liters of ice water. After stirring for a further 30 minutes, the pigment is filtered off with suction filter, washed neutral with water, dried in a circulating air oven and ground.

A pigment preparation is obtained which, in an aqueous coating system based on a water-dilutable polyurethane resin, gives a strongly colored and transparent coating having a yellowish red hue. The metallic finish is strong and brilliant.

Example 9

100 parts of the pigment preparation from Example 8 are used together with 5 parts of a sulfonic acid-containing perylene compound (prepared according to Example 3 of EP 0 486 531 B1) ground. There is obtained a preparation with high transparency, which has a much more yellowish hue in aqueous metallic paints than the pigment preparation according to Example 8.

Example 10

50 parts of a prior art ground in a ball mill for 30 h at 80 ⁰ C perylene-3,4,9,10-tetracarboxylic acid N, N'-dimethyldiimids (CI Pigment Red 179) are used together with 1 1, 4 Parts of a 44 wt .-% solution of K1 in 500 g of 77 wt .-% sulfuric acid for 16 hours at 50 ⁰ C swollen. The mixture is diluted with 2 l of ice water, stirred for 30 min, filtered, washed neutral and ground together with 3.75 parts of a sulfonic acid-containing perylene compound (prepared according to Example 3 of EP 0 486 531 B1).

The preparation has a much higher transparency and a yellower hue than a corresponding preparation prepared without the crystallization inhibitor.

Example 11

95 9 perylene-3,4,9,10-tetracarboxylic acid-N, N'-dimethyldiimide (CI Pigment Red 179) are combined with 5 9 dry K1 according to the prior art in a with 1, 5 kg steel balls (diameter 25 mm) equipped 0.75 I double-walled container for 50 h at 50 ⁰ C ground. 30 g of the dry-ground product are then swollen in 300 g of 76 wt .-% sulfuric acid for 16 hours at room temperature. The mixture is diluted with 2 l of ice water, stirred for 30 min, filtered, washed neutral and ground together with 3.75 parts of a sulfonic acid-containing perylene compound (prepared according to Example 3 of EP 0 486 531 B1).

Example 12

80 g of perylene-3,4,9,10-tetracarboxylic acid N, N ^{'-dimethyl-diimide} (CI. Pigment Red 179, formula no. 71130), 10 g of Resin (Dertopol®, DRT) and 4.2 g Dry K1 will be in one with 1, 5 kg of steel balls (diameter 25 mm) equipped 0.75 I Doppelmantmahlbehälter 50 h at 50 ⁰ C ground on a vibrating mill. 30 g of the dry-milled product are then swollen in 300 g of 76% sulfuric acid for 16 hours at room temperature. The mixture is diluted with 2 l of ice water, stirred for 30 min, filtered, washed neutral and ground together with 3.75 parts of a sulfonic acid-containing perylene compound (prepared according to Example 3 of EP 0 486 531 B1).

The pigment preparation of Example 12 has a higher transparency and a yellower and more chromatic hue than that of Example 1. With excellent rheological properties it is moreover readily dispersible in water-dilutable coating systems. Due to the high transparency, the pigment of Example 12 is particularly suitable for the pigmentation of metallic paints.

Example 13

A solution of 80 g of indanthrone PB 60 in 987 g of 96 wt .-% sulfuric acid is stirred for two hours and while heated to 25 ⁰ C. This solution is combined with a 0.3 wt.% Aqueous solution of K1 in a ratio of 2.5 parts of K1 solution to one part of pigment solution via a mixing nozzle. The temperature rises to DA at 60 ⁰ C. The mixture is then stirred at 60 ⁰ C for 30 minutes. The suspension is filtered, washed with deionized water until <100 μS, then dried in a drying oven at 80 ⁰ C under vacuum. Then the coffee grinder is ground for 20 seconds at maximum speed. The resulting pigment has a high transparency and a good flop behavior, ie a low viewing angle-dependent hue shift.

Example 14

A pigment solution prepared as in Example 12 is mixed with 2.5 parts of water over a mixing nozzle together. The temperature rises to 60 ⁰ C. The mixture is then stirred at 60 ⁰ C for 30 minutes. The suspension is filtered and the filter cake is washed with demineralized water to <100 μS. Subsequently, the filter cake is stirred up again in demineralized water and 10 wt .-% K1, based on the pigment was added. The suspension is charged in a jacketed reactor, heated to 60 ⁰ C within one hour. At the temperature, 20 g of p-xylene is added and stirred for two hours. The mixture is then distilled off at 100 ⁰ C xylene. Then the suspension is filtered off, the filter cake washed with a little water and dried at 80 ⁰ C in a vacuum oven. The pigment has a high transparency and a high chroma.

Example 15

In the pigment solution prepared as in Example 12, 4 g of Cu phthalocyanine is added. This solution is then run with 2.5 parts of water through a mixing nozzle together. The temperature rises to 60 ⁰ C. The mixture is then stirred at 60 ⁰ C for 30 minutes. The suspension is filtered and the filter cake is washed with demineralized water to <100 μS. Subsequently, the filter cake is stirred up again in demineralized water and 10 wt .-% K1, based on the pigment added. The suspension is introduced into a jacketed reactor and heated to 60 ⁰ C within one hour. At the temperature, 20 g of p-xylene is added and stirred for two hours. The mixture is then distilled off at 100 ⁰ C xylene.

Then the suspension is filtered off, the filter cake washed with a little water and dried at 80 ⁰ C in a vacuum oven. The pigment has a high transparency and a high chroma.

Example 16

Preparation of the crystallization modifier K2

The preparation of the crystallization modifier K2 is carried out according to Example 1 of DE-A 101 40 551. 40 kmol heated to 60 ⁰ C phenol are added within 1 hour with 40 kmol oleum with an SO _ß content of 24 wt .-%. The resulting mixture is heated to 160 ⁰ C and stirred for 4 hours at this temperature. The mixture is then allowed to cool to 80 ⁰ C and 25 kmol urea are stirred as a 68 wt .-% solution and then metered within 1, 5 hours 40 kmol formaldehyde as a 30 wt .-% aqueous solution. The resulting mixture is then mixed with about 34 kmol NaOH in the form of a 50 wt .-% aqueous solution, wherein a pH of 4.5 sets.

The content of dihydroxydiphenylsulfone is 10 wt .-%, based on the dry weight. Example 17

140 parts of perylene-3,4,9,10-tetracarboxylic acid N, N'-dimethyldiimide (CI Pigment Red 179) and 40 parts of K 2 (as a 35% strength by weight solution) are added in 2576 parts to 96% by weight. dissolved figer acid and tempered to 25 ⁰ C. The pigment preparation is then precipitated from the sulfuric acid solution with 25 ⁰ C warm water by jet precipitation using a Y-mixing nozzle (0.5 mm holes for the educt streams) with the following flow rates: 400 g / min water, 100 g / min pigment solution in Acid. There is obtained a precipitation suspension with a temperature of 60 ⁰ C. The pigment preparation is filtered through a suction filter, washed with water, dried in a drying oven at 80 ^° C. under reduced pressure and then ground.

Example 18

50 parts of the pigment preparation from Example 16 are milled with 3.75 parts of the perylene compound containing sulfonic acid groups prepared according to Example 3 of EP 0 486 531 B1. A pigment preparation is obtained which, in an aqueous coating system based on a water-dilutable polyurethane resin, gives a strongly colored and transparent coating having a yellowish red hue. The metallic finish is strong and brilliant.

Claims

claims

A process for forming an organic pigment which comprises dissolving or dispersing the pigment in an aqueous solvent or a mineral acid and allowing it to crystallize from the solution or dispersion in the presence of a crystallization modifier and then isolated as a solid, characterized in that the crystallization modifier is a sulfonate group comprising condensation product of at least one hydroxyarylsulfonic acid and / or at least one hydroxydiarylsulfone compound and at least one aliphatic aldehyde having 1-6 C-atoms, optionally urea and optionally an alkali metal sulfite, or a mixture of such condensation products.

2. The method according to claim 1, characterized in that the crystallization modifier is a condensation product of at least one hydroxyarylsulfonic acid, at least one aliphatic aldehyde having 1-6 C-atoms and optionally urea.

3. The method according to any one of claims 1 or 2, characterized in that the crystallization modifier is a condensation product of at least one hydroxy diarylsulfone compound, at least one aliphatic aldehyde having 1 - 6 carbon atoms and an alkali metal sulfite.

4. The method according to any one of claims 1 to 3, characterized in that the hydroxyarylsulfonic acid phenolsulfonic acid and the Hydroxydiarylsulfonverbindung dihydroxydiphenylsulfone.

5. The method according to any one of claims 1 to 4, characterized in that the aliphatic aldehyde is formaldehyde.

6. The method according to any one of claims 1 to 5, characterized in that the pigment is dissolved in concentrated sulfuric acid and crystallized by mixing the solution with an aqueous diluent, wherein the crystallization modifier may be contained in the sulfuric acid solution or in the aqueous diluent.

7. The method according to claim 6, characterized in that the crystallized organic pigment is allowed to mature before isolation as a solid in the presence of a surfactant.

8. The method according to claim 7, characterized in that the surfactant is contained in the aqueous diluent or added after the crystallization step.

9. The method according to any one of claims 1 to 5, characterized in that dispersing the pigment in dilute aqueous sulfuric acid and allowed to swell in the presence of the crystallization modifier.

10. The method according to any one of claims 1 to 5, characterized in that one disperses the pigment in water and crystallize in the presence of the crystallization modifier and a solubility of the pigment increasing additive.

1 1. A method according to claim 10, characterized in that the solubility of the pigment increasing additive is selected from xylenes, glycols, alcohols, THF, acetone, NMP, DMF and nitrobenzene.

12. The method according to any one of claims 1 to 1 1, characterized in that one mixes the pigment isolated as a solid with a pigment synergist which is a sulfonate- or carbonate-containing derivative or a basic derivative of an organic pigment.

13. The method according to claim 12, characterized in that the pigment synergist is a derivative of the pigment.

14. The method according to any one of claims 1 to 13, characterized in that the pigment is selected from the group consisting of azo, azomethine, methine,

Anthraquinone, phthalocyanine, perinone, perylene, diketopyrrololpyrrole, thioindigo, thiazine indigo, dioxazine, iminoisoindoline, iminoisoindolinone, quinacridone, flavanthrone, indanthrone, anthrapyrimidine and quinophthalone pigments.

15. Pigment preparations containing particles of organic pigment with a superficial coverage of the pigment particles with the crystallization modifier as defined in any one of claims 1 to 14.

16. Use of sulfonate-containing condensation products of at least one hydroxyarylsulfonic acid and / or at least one hydroxydiarylsulfone compound and at least one aliphatic aldehyde having 1-6 C atoms, optionally urea and optionally an alkali metal sulfite, or mixtures of such condensation products, as crystallization modifiers for the formation of organic pigments.

17. Use of the pigment preparations according to claim 15 for dyeing and coating natural and synthetic materials.