DE2526872A1 - PROCESS FOR THE PRODUCTION OF YELLOW ACRYLAMIDE PIGMENTS - Google Patents

Description

BA-GEIGY

CLBA-GEIGY AG, CH-4002 Ba »al

Case 3-9468 / MA 1584+

Germany

Dr. F. Zumstain Sr. - Dr. E Acsmann

Dr. R.Koenigeto -.; -. ' - Ό>, Λ. Fii. ·.,. "(. I-lzbauer

Dip !. - lny. i ^:. Ki,; s.; E. - Or.! ^: . '-j.Jtein jutl.

r 'a' c Ii ta η wa I t 2 8 Munich 2, BtäuhausstraHe 4

Process for the production of yellow acrylic amide pigments

The invention relates to yellow acrylamide pigments and a process for their production.

Pigments made by coupling the diazoniuin compound of 2-methoxy-4-nitroaniline with acetoacet-2-anisidide are described in US Pat. No. 3,032,546 and are stated to have a very strong, bright, yellow color own green clay.

It has been found that treatment of this pigment with a combination of a suitable amine salt and a natural rosin or rosin derivative results in a pigment which is less opaque, has superior heat stability, flowability and dispersibility in printing inks.

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The invention relates to a method for production an improved azo pigment that is characterized is that you have a diazoniura compound of 2-methoxy-4-nitroaniline with acetoacet-2-anisidide and from 1 to 20 wt. ^, based on the weight of the pigment, a salt of a primary, secondary or tertiary alkylamine or one Arylalkylamine or a rosin amine and 2.5 Ms 75% by weight, based on the weight of the pigment, of a natural one Add rosin or rosin derivative and then isolate the pigment at a pH below 7.

The amines used in the present invention preferably contain at least 12 carbon atoms. Examples of amines, which can be used are long chain primary amines such as stearylamine, palmitylamine, laurylamine and unsaturated primary amines such as oleylamine and linoleylamine. Commercially available amines such as tallow amine, coconut amine and soybean amine are commonly used Mixtures of these long chain amines are particularly suitable. Suitable secondary amines to be used are long-chain symmetrical dialkylamines such as distearylamine, dipalmitylamine or dioleylamine or long-chain unsymmetrical dialkylamines such as N-palmityl-N-oleylamine or commercially available mixtures of these amines. Suitable tertiary amines are long-chain trialkylamines in which at least one of the alkyl groups contains a long chain group having 12 to 18 carbon atoms and the other Alkyl groups can contain 1 to 18 and including 18 carbon atoms. Commercially available mixtures of these amines can also be used.

Rosin amines can also be used, and these can be derived from abietic acid and examples are dehydroabietylamine, Dihydroabietylamine, tetrahydroabietylamine and dextropimarylamine and mixtures of two or more of these connections. A preferred rosin amine is "Amine D" (Hercules Pov / the Company) which is essentially consists of dehydroabietylamine and small proportions of the others

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Contains rosin amines mentioned above. Ethoxylated derivatives of rosin arains can also be used. Alkylenediamines with a long chain on the nitrogen atom such as N-stearylpropylenediamine or commercially available mixtures of such diamines in which the long chain can contain from 8 to 18 carbon atoms are also suitable. Other suitable products are polyamines such as N-cocostrimethylenediamine-N-propylamine, where the term "coconut" means a long-chain alkyl group which is derived from coconut fatty acids and is a mixture of Cg-C ₁₈ saturated and unsaturated alkyl groups or similar amines, where the derive long-chain alkyl groups from other fatty materials such as tallow or soybean oil, and polyamide / polyamine derivatives, which are prepared by reacting polyamines with alkyl-aryl polycarboxylic acids in such a way that the product contains a number of free amino groups that are necessary for further reaction be available.

Further examples of amines that can be used are derivatives of fatty arains, as described, such as ethoxylated Derivatives that are produced by reacting the primary or secondary amino groups with 1 to 20 moles of ethylene oxide, so that the amino group is substituted by a polyether chain or chains, for example ethoxylated stearylamine or ethoxylated N-stearylpropylenediamine.

Aryl-substituted amines can be used similarly to phenylstearylamine (CgHcC ₁₈ H, gNH ₂ ) or secondary amines such as di- (phenylstearyl) amine (CgHcC ₁₈ H, g) ₂ NH or N-aralkylalkylenediamines such as N-phenylstearylpropylenediamine (CgH ₅ C ₁₈ H ₃₆ .NH.CH ₂ CH ₂ CH ₂ NH ₂ ) or commercially available amines of this type, which are usually in the form of mixtures.

In all of the amines mentioned above, the long chain alkyl groups need not be straight chain and branched chain amines such as commercially available ß-primary monoamines or N-ß-alkylpropylenediamines (C ₁ 7H ₃₂ CH (CH ₃ ) NH.CH ₂ CH ₂ CH ₂ NH ₂ ) can also-

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if used. Suitable commercially available products are those sold under the trademarks "Armeen T", a long chain aliphatic primary amine composed primarily of the C 1-6 unsaturated amine, namely oleylamine, and the C 1-6 and C 1-4 saturated g-amines, namely palmityl amine and stearyl amine, consists of "Armeen 2HT", a long chain secondary amine whose alkyl groups are primarily the stearyl (C, o) and palmityl ( C ^ c) chains, and "Armeen DMHTD" tertiary amine, the alkyl groups of which are very similar to those of Armeen 2HT ". Among the rosin amines that can be used, mention may be made, for example, of the product sold under the symbol" Amine D ". Examples of alkyl-alkylenediamines with a long chain on the nitrogen atom are those sold under the trademarks "Duomeen T" and "Duo-. meen C ". Polyamide / polyamine derivatives are commercially available under the trademark" Merginamide ". Examples of β-amines are products such as those sold under the trademarks" Armeen L.11 "and" Duomeen L.15 " Suitable ethoxylated fatty amines and ethoxylated fatty diamines are available under the trademarks "Ethomeen" and "Ethoduomeen", primary and secondary aralkyl monoamines are available under the trademarks "Armeen L-PS" and "Armeen L-2PS" and N-aralkyl- alkylenediamines are available under the trademark "Duomeen L-PS".

The amine selected is best used as a solution of a soluble salt such as the acetate or chloride.

The alkyl chain of the amine preferably contains a maximum of 22 carbon atoms atoms.

Examples of natural resins are the various grades of gum rosin, wood rosin, and tall oil rosin derived from pine oleoresin. You insist mainly composed of abietin-type acids such as abietic acid, neoabietic acid, dehydroabietic acid and palustric acid and acids of the pimaric acid type such as pimaric acid and iso-

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pimaric acid. The proportions of the various acids present depend on the source and type of rosin. The following rosins were used: American WW Gum Rosin, American WW Wood Rosin and a tall oil rosin, which is available under the Trademark "PRIIiAREX 80" is sold.

The rosin derivatives that are used are made from natural ones Types of rosin (when "rosin" is used in the present application, this word should be used in be used in its broadest sense) by various processes such as isomerization, addition reactions, hydrogenation, Dehydration, polymerization and esterification produced. Examples of such products are the hydrogenated resin known under the Trademark "Staybelite Resin" is sold polymerized rosins such as those under the trademarks "Polypale Resin" and "Dymered Resin" are sold dehydrated Rosin as sold under the trademark "Hercules Resin 731D" and modified rosin "Hercules Resin 861". Other rosin derivatives that are also suitable are those modified with maleic acid and fumaric acid Rosins, phenolic resins modified with rosin with a high acid number and partial esters of rosin or rosin derivatives with saturated aliphatic alcohols containing 1 to 6 carbon atoms and 1 to 6 hydroxyl groups contained per molecule; these partial esters have an acid number of at least 80.

The natural rosins or rosin derivatives are best added to the pigment slurry as aqueous Solutions or suspensions of their sodium, potassium or ammonium salts are added and then precipitated on the pigment, by adjusting the pH to 6.0 with, for example, hydrochloric acid.

The amount of amine is preferably 3 to 10% by weight, based on based on the weight of the pigment, and the amount of natural rosin or rosin derivatives is preferably 5 to

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50 wt.% And particularly preferably 15 to 45 wt.%, Based on the weight of the pigment.

The amine and the natural rosin or rosin derivative can either be separated in any order or added together or after coupling.

The pigment produced according to the invention is a strongly greenish one Yellow and, if desired, the tint of the pigment can be modified by adding small amounts of a yellow pigment with a stronger red hue adds, for example, compounds produced by coupling of 2-methoxy-4-nitroaniline with 1-phenyl-3-methyl-5-pyrazolone or 2,5-dimethoxy-4-chloroanilide to obtain a pigment with a more red tint, which is suitable for three-color printing applications is more suitable.

Coupling can be carried out by any suitable method and it is preferably carried out in aqueous, preferably weakly acidic, solution or suspension.

The pigments of the invention can be used in a variety of applications, but they are particularly useful for -suitable for printing. The invention also relates to compositions, in particular printing inks, the pigments which are produced by the process according to the invention.

The following examples illustrate the invention.

example 1

63 »0 parts of 2-methoxy-4-nitroaniline are stirred with 86.4 parts of concentrated hydrochloric acid and 300 parts of water for 1 hour. ^{The temperature is lowered to 0} ° C. by adding crushed ice and 25.9 parts of sodium nitrite, dissolved in 70 parts of water, are added over the course of 45 minutes at such a rate that always

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a weak positive test for nitrous acid is obtained with starch / potassium iodide paper. The temperature will kept below 2 ° C by external cooling. After all of the nitrite has been added, it becomes 6.0 parts of "Supercel" filter aid and 2.0 parts of activated charcoal are added and the mixture is then stirred at 0 to 2 ° C. for a further 30 minutes. The solution is then filtered and 800 parts of a clear, pale yellow solution are obtained at 0.2 ° C.

80.0 parts of acetoacet-2-anisidide are dissolved in 700 parts of water which contains 16.2 parts of sodium hydroxide. The solution is stirred and the acetoacet-o-anisidide is precipitated again by adding 240 parts of 10% acetic acid solution. Then 40 parts of sodium acetate were added and then ^ is a solution of 7.2 parts of Amine D, dissolved in 35 parts 20% acetic acid, added. The pH of the slurry is then adjusted to approximately 6.0 and the volume is increased to 1500 parts at 15 ° by adding some ice-water set.

The diazo solution prepared from 2-methoxy-4-nitroaniline is then added at such a rate that a little alkaline H-acid solution no unreacted diazonium compound can be determined. When the pH has dropped to about 4.5, dilute sodium hydroxide solution is used added at the same time as the diazo solution to keep the pH between 4.5 and 5.0. The entire diazo compound was added within 1 hour. After coupling is complete, the pH is adjusted with dilute sodium hydroxide solution increased to 9.0. A solution of Staybelite Resin is made by adding 72.0 parts of Staybelite Resin dissolve in 500 parts of 2% sodium hydroxide by heating and stirring, and after all of the resin has dissolved 1500 parts diluted with cold water at 10 °. This solution is added to the pigment slurry. The pH will be carefully reduced to 6.0 with dilute hydrochloric acid good stirring set. The temperature is increased to 90 ° C

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increased, held for 10 minutes, and then the slurry is filtered and the light yellow pigment is washed free of chloride with water and ^{dried at 50 0} C in an oven with hot air. This product disperses very easily in a typical long oil alkyd based lithographic printing ink. It has a similar coloring power to a product made by the above process but without treatment with "Amine D" and Staybelite Resin, but it is considerably more transparent, it has a brighter, greener tone and a significantly improved texture. The ink is much less opaque after high speed dispersion, with a significant increase in temperature being observed, than ink made using untreated pigment. She also has excellent theological qualities.

Example 2

A pigment composition is described exactly as in Example 1 except that 1.0 part of acetoacet-o-anisidide was replaced by 1.0 part of 1-phenyl-3-methyl-5-pyrazolone be replaced. The resulting product is a pigment with a stronger red hue, closer to the tone of the C.I. pigment yellow 17 »than that of Example 1, but otherwise it has the same advantageous properties as the pigment of Example 1.

Example 5

63.0 parts of 2-methoxy-4-nitroaniline are diazotized as described in Example 1. 11 ·, 25 parts of acetoacet-2,5-dimethoxy-4-chloroanilide are dissolved in 250 parts of water which contains 1.6 parts of sodium hydroxide. 16.0 parts of sodium acetate are dissolved in 250 parts of water and 25 parts of the acetoacet-2,5-dimethoxy-4-chloroanilide solution are added. The pH is carefully adjusted to 5.0 by adding dilute acetic acid. The remaining acetoacet-2,5-dimethoxy-4-chloroanilide solution is then gradually added to the stirred suspension at the same rate with 10% (80 parts) of the diazo solution. An excess of diazo solution becomes

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avoided. The pH is maintained between 4.5 and 5.0 by adding dilute sodium hydroxide or hydrochloric acid as required. After coupling is complete, another 144 parts of sodium acetate are added to the suspension and then 75 parts of a solution prepared by dissolving 73.4 parts of acetoacet-2-anisidide in 750 parts of 2% sodium hydroxide solution are added. The pH is adjusted to 5.0 by adding hydrochloric acid. The remainder of the diazo solution and the acetoacet-o-anisidide solutions are introduced simultaneously over the course of 1 hour at the same rates, an excess of diazo solution being avoided and the pH - The value is kept between 4.5 and 5.0 by adding dilute sodium hydroxide or hydrochloric acid solution, as required.

After the reaction has ended, 7.2 parts of "Amine D", dissolved in 150 parts of 5% acetic acid, are added with stirring. The pH is raised to 9.0 by adding dilute sodium hydroxide and 44.4 parts of Staybelite Resin dissolved in 500 parts of water containing 5.2 parts of sodium hydroxide are added. The pH is then adjusted to 6.0 by adding hydrochloric acid and the slurry is ^{heated to 90 °} C. and filtered. The resulting pigment composition can be easily dispersed in a lithographic printing ink based on long oil alkyd. It is much stronger and redder in its tint compared to a pigment made in the manner described above, but with the omission of acetoacet-2,5-dimethoxy-4-chloroanilide, Amine D and Staybelite Resin. After printing, a luminous, glossy, pleasant print is obtained, similar in tone to that obtained with CIPigment Yellow 13.

Example 4

47.3 parts of 2-methoxy-4-nitroaniline are as in Example 1 described diazotized, giving 800 parts of diazo solution.

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10.0 parts of acetoacet-2,5-dimethoxy-4-chloroanilide are in 350 parts of water containing 1.5 parts of sodium hydroxide dissolved. A solution of 1.0 part of Lubrol W, dissolved in 50 parts of water is added and then 300 parts of sodium acetate are added. The solution is made with water diluted to 850 parts and the pH is fourth by adding diluted hydrochloric acid adjusted to 5.0. 100 parts the diazo solution are then gradually added, an excess of diazo solution being avoided.

53ι5 parts of acetoacet-2-anisidide are dissolved in 800 parts of water / water containing 14.4 parts of sodium hydroxide. This solution is added to the slurry with stirring and the pH is adjusted to 5.0 by the addition of acetic acid. The remaining diazo solution is added over the course of 1 hour, avoiding an excess of diazo solution. After the coupling is complete, 5.4 parts of "Amine D", dissolved in 50 parts of dilute acetic acid, are added. The pH is adjusted to 9.0 with dilute sodium hydroxide and 375 parts of a 7% solution of Staybelite Resin in dilute sodium hydroxide are added. The pH is then adjusted to 6.0 by adding dilute hydrochloric acid. The slurry then rird \\ ⁰ to 90 C heated -filtriert, GeV / waste and dried.

The composition has essentially the same properties like the product of example 3.

Example 5

A pigment composition is described exactly as in Example 1 except that 20.0 parts of Staybelite Resin was replaced with 140 parts of 2% sodium hydroxide of 72.0 parts can be used. The product has practically the same properties as that of Example 1.

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example

A pigment composition is made in the same way as in Beiq? iel 4 "described, with the exception - that 157 parts of a 7? Solution of Staybelite Resin in dilute Sodium hydroxide can be added instead of 37.5 parts. The product has properties similar to that Product of example 4.

Example 7

A pigment composition is prepared in the same manner as described in Example 2 with the exception that 72.0 parts Primarex 80 Resin, a sebum oil rosin, can be used in place of Staybeiite Resin. The product owns the same properties as the product of example 2.

Example 8

A pigment composition is prepared in the same manner as described in Example 2 with the exception that 72.0 parts Hercules Resin 861 used in place of Staybelite Resin. The product has the same properties like the product of example 2.

Example 9

A pigment composition is prepared in the same manner as described in Example 2 with the exception that 72.0 parts Hercules Resin 731D can be used in place of Staybelite Resin. The product has the same properties like the product of example 2.

Example 10

150 parts of the product of Example 1 are mixed by hand with 175 parts of a long oil terephthalalkyd compound having a viscosity from about 20 to 30 parts and 175 parts of a modified one Phenolic resin with a viscosity of about 3000 P. mixed. The paste is then made on a Cox Pilot 3 roll mill grind, first of all using a low-pressure Benet-

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tion passage and then two high pressure passages are used. The resulting ink does not contain any undispersed particles as shown by a Hegman Gauge land has excellent fluidity. When printing on a typical lithographic printing press, one obtains a bright, strong, glossy, transparent print.

Examples 11-19

Pigment compositions are prepared as described in Example 2, except that 7.2 g of Amine D are replaced by the same Weight of the specified amines replaces v / ground. The amounts of acetic acid required will also vary some. All products show advantageous properties similar to those of the product of Example 2.

Example amine no.

Chemical type

Amount of acetic acid used to dissolve the amine

11

12th

13th

14th

15th

16

17th

DINORAM

(Pierrefitte-

Auby)

TRINORAM S

(Pierrefitte-

Auby)

ARMIES (Armor Hess)

ARMEEN T (Armor Hess)

PRIMENE JM-T (Rohm & Haas)

N-alkylpropylenediamine, the alkyl groups being Cp ₀ / ^ 22 g ^em ischt N-alkyldipropylenetriamine, the alkyl groups are derived from tallow

primary alkyl monoamine, 95% of the alkyl groups are lauryl (C ₁₂ ) groups primary alkyl monoamine, the alkyl group is derived from tallow

primary alkyl monoamine, the alkyl group is highly branched and is mainly in the C ₁ QB

100 parts

ARMEEN 2HT (Armor Hess)

75

100

80

80

80

secondary dialkylamine, the alkyl groups are derived from hydrogenated tallow

DUOMEEN L15 N-Alkylpropylenediamine, 75 (Armor Industrial is the C - ^ - alkyl group Chemicals) to the anine to one

ß-carbon atom bonded

Share at 7.13%

Parts at 2.5%

Share at 3.95%

Parts at 2.52%

Share at 1.26%

Share at 3.36%

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Example amine Chemical type Amount of vinegar no. acid, the zua lo

sen of the amine is used

18 MERGINAIiIDE L275 polyaraid / polyamine- 80 parts included (BIBBY) derivative 0.92%

19 ETHOMEEN 18/12 Stearylamine (Gis) »80 parts at (Armor Hess) with 2 moles of ethylene - 1.58%

oxide ethoxylated

Example 20

50.0 parts of 2-methoxy-4-nitroaniline are made into a smooth paste with 100.0 parts of water and 68.5 parts of hydrochloric acid, specific gravity 1.18, are added. The mixture is stirred for 30 minutes and then ^{cooled to −2 °} C. and diazotized by adding a solution of 20.5 parts of sodium nitrite in 50 parts of water. The temperature is ^{kept at 0} ° C. during the diazotization. After the reaction has ended, 1.0 part of CELITE J2 filter aid and 0.5 part of activated carbon are added and the mixture is then stirred for 5 minutes. The mixture is then filtered, a pale yellow solution is obtained. 5.7 parts of amine D, dissolved in 100.0 parts of water / water containing 2.8 parts of acetic acid, are then added to the clarified diazo solution and finally 700.0 parts of solution with a temperature of ⁰ ° C. are obtained.

-64.1 parts acetoacet-2-anisidide and 0.5 part 1-phenyl-3-methyl-5-pyrazolone are dissolved in 650 parts by volume of water containing 12.5 parts of sodium hydroxide. To this solution 57.0 parts of Staybelite Resin, dissolved in 500.0 parts of water, which contains 7.0 parts of sodium hydroxide, are then added. the Mixture is made up to 1500 parts with water.

The diazo and coupling components that were prepared as described above are simultaneously added over 1 hour to 400.0 parts of water, which can be found ktionsgefäß be in a Re ^ and stirred. The rate of addition is controlled so that the correct ratio of diazo compound to coupling component for complete conversion

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Settlement is obtained. During the dome, the pH is maintained at 5.8 to 6.0 by adding acetic acid or sodium hydroxide solution as required. The temperature is 19 to 21 ⁰ C. After completion of the coupling, the Pigmentauf slurry at a pH Y / ert of 6.0 to 90 ° C heated
Maintained at 90 ° C. for 10 minutes and then filtered. The yellow one
Filter cake is washed until it is free of water-soluble material, and then at 5O ⁰ C in an oven with hot air. dried. The product has the same good properties as the product of Example 2.

Example 21

The same pigment composition was prepared as in Example 1, except that 1 part of acetoacet-2-anisidide was replaced by 1 part of l-4'-tolyl-3-methyl-5-pyrazolone. The product obtained had the same advantageous properties
redder shade than the product obtained according to Example 1.

Example 22

The same pigment composition was used as in Example 1 produced, but 1 part of acetoacet-2-anisidide was replaced by 1 part of 1-phenyl-S-carbethoxy-S-pyrazolone. The received The product had a redder shade than that obtained according to Example 1 with the same advantageous properties Product.

Example 23

(1) 47.3 parts of 2-methoxy-4-nitroaniline were diazotized using 65.5 parts of hydrochloric acid having a specific gravity of 1.18 and 19.7 parts of sodium nitrite. The diazonium solution was diluted to 800 parts ^{at 0 ° C. with ice and water.}

(2) 3.8 parts of 1-phenyl-3-methyl-5-pyrazolone were dissolved in 0.9 parts of sodium hydroxide in 200 parts of water.
30.0 parts of sodium acetate trihydrate were added

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and the solution is diluted to 800 parts at 10 to 15 ^{° C.} The pH was adjusted to 6.0 by adding dilute acetic acid.

(3) 57.0 parts of acetoacet-2-anisidide was dissolved in 19.4 parts of aqueous sodium hydroxide solution and diluted to 800 parts of at 10 to 15 ⁰ C.

(4) 0.84 part of 2-nitroaniline-4-sulfonic acid and 2.4 parts of hydrochloric acid were dissolved in 15 parts of water. The solution was ^{cooled to 0 °} C. with ice and the diazotization was carried out using 0.27 part of sodium nitrite.

(5) 5.4 parts of amine D and 1.1 parts of glacial acetic acid were dissolved in glacial acetic acid and diluted ^{to 125 parts at 10 to 15 ° C.}

(6) 27,15 parts of Staybelite resin and 3.2 parts of sodium hydroxide were dissolved in 200 parts of water at 1OO ° C and diluted to 400 parts of at 10 to 15 ⁰ C.

The mixture (2) and then 60 parts of the diazo solution (1) were added to the reaction vessel over the course of 15 minutes. 80 parts of solution (3) were added, the pH being adjusted to 5.0 to 5.5 with dilute hydrochloric acid. The remaining 740 parts of the solution (1) and the remaining 720 parts of the solution (3) were then allowed to run into the reaction vessel simultaneously over 45 minutes while maintaining the pH value of 5.0 to 5.5. After stirring the reaction mixture for a further 5 minutes, the diazo suspension (4) was added over 15 minutes while maintaining the pH value of 5.0 to 5.5. After stirring the reaction mixture for 10 minutes, the amine D solution (5) was added. The pH was adjusted to 9.0 using dilute sodium hydroxide solution and the Staybelite resin solution (6) was added. After stirring for 10 minutes, the pH of the mixture was adjusted to 5.5 using dilute hydrochloric acid. The mixture was then brought to the boil and cooked for 30 minutes. The yellow pigment was filtered and then dried after washing by water-soluble material at 50 ⁰ C.

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Claims (13)

Claims 1. Process for the preparation of an azo pigment, characterized in that the diazonium compound of 2-methoxy-4-nitroaniline is coupled with acetoacet-2-anisidide and from 1 to 20% by weight, based on the weight of the pigment, of a salt of a primary , secondary or tertiary alkylamine or a arylalkylamine or a rosin amine and 2.5 to 75 wt.% _t based on the weight of added pigment, a natural rosin or rosin derivative, and then the pigment at a pH-value below 7 isolated. 2. The method according to claim 1, characterized in that with a mixture of acetoacet-2-anisidide and one Pyrazolone couples. 3. The method according to claim 1, characterized in that the diazo and / or coupling component before or a pigment is added during the coupling or to the disazo pigment, which by coupling 2-methoxy-4-nitroaniline with a Pyrazolone is made. 4. The method according to any one of claims 2 or 3, characterized characterized in that the pyrazolone is 1-4'-ToIyl-3-methyl-5-pyrazolone, l-phenyl-3-carbethoxy-5-pyrazolone or l-phenyl-3-methyl-5-pyrazolone used. 5. The method according to claim 1, characterized in that the amine used contains at least 12 carbon atoms. 6. The method according to claim 1, characterized in that one. a rosin amine is used as the amine. 7. The method according to claim 6, characterized in that -as rosin amine essentially dehydroabietylamine is used together with small amounts of dihydroabietylamine, tetrahydroabietylamine and dextroprimarylamine. B09882 / 0962 8. The method according to claim 1, characterized in that an ethoxylated derivative of rosin amine is used as the amine will. 9. The method according to claim 1, characterized in that the natural rosin mainly acids of the abietin type and primary type acids. 10. The method according to claim 1, characterized in that the amount of amine used is 3 Ms 10% by weight , based on the weight of the pigment. 11. The method according to claim 1, characterized in that the amount of natural rosin or rosin derivative is from 5 to 50 Ge \ r.% _T based on the weight of the pigment. 12. The method according to claim 1, characterized in that the alkyl chain of the amine contains a maximum of 22 carbon atoms. 13. Composition, characterized in that it is a printing ink and a pigment prepared by a process according to at least one of claims 1 to 9, contains. 509882/0962