FR2655051A1 - - Google Patents

Abstract

Compositions based on dioxo-pyrrolopyrroles They contain a) at least one dioxo-pyrrolopyrrole corresponding to the formula I: (CF DRAWING IN BOPI) in which R1, R2, R3 and R4 each represent, -H, -Cl, Br, - CH3, -OCH3, -C6 H5 or -CN, and b) from 0.5 to 10% by weight, relative to a), of a mixture of at least 3 symmetrical and unsymmetrical dioxopyrrolopyrroles corresponding to formula I in in which R1, R2, R3 and R4 each represent -H, -Cl, -Br, -CH3, -OCH3, -C6 H5 or a radical -SO3 - X + whose symbol X + represents H +, an equivalent of a metal cation or an ammonium cation, with the proviso that, in this mixture, at least one of the symbols R1, R2, R3 and R4 represents an -SO3 - X + radical. They are remarkably suitable for dyeing macromolecular organic materials.

Description

The present invention relates to novel compositions containing a

  dioxo-pyrrolopyrrole and a small amount of one

  partially sulphonated mixture of at least 3 dioxo

  pyrrolopyrroles. Dioxopyrrolopyrroles are known compounds which are described for example in US Pat. Nos. 4,415,685 and 4,585,878 as pigments for dyeing organic polymers. US Pat. No. 4,791,204 discloses that by adding a small amount of a sulfonated dioxopyrrolopyrrole,

  carboxylated, phosphonated or N-imidomethylated with a

  Pyrrolopyrrole can improve its pigment properties and also improve its rheological behavior It has, however, been shown that the properties, already remarkable, these mixtures are not always satisfactory in view of the current severe requirements of the industry Moreover, their preparation is complicated and, therefore, great

energy consumer.

  That being so, the present inventors have found that the pigment properties of dioxopyrrolopyrroles can be further improved, particularly their rheological behavior and some of their coloring properties, especially saturation, if added to a dioxopyrrolopyrrole. a small amount of a mixture, at

  less partially sulphonated, of at least 3 dioxins

  different, symmetrical and dissymmetrical pyrrolopyrroles The mixtures of sulphonated dioxopyrrolopyrroles to be used may -

  be prepared, which is not the case with dioxins

  the most closely related sulfonated pyrrolopyrroles which are known from US Pat. No. 4,791,204, for the preparation of which 4 stages are required in only two steps, therefore with a lower consumption of energy and, consequently, in more ecological conditions. The present invention more specifically relates to a composition which contains: a) at least one dioxopyrrolopyrrole corresponding to formula I:

RI R 2

l 11 1

HN NH (I)

R 3 R 4

  wherein R 1, R 2, R 3 and R 4 each represent independently

  respectively, -H, -Cl, -Br, -CH 3, -OCH 3, -C 6 H 5 or -CN, and b) from 0.5 to 10% by weight, relative to the dioxygen pyrrolopyrrole a), a mixture of at least 3 different symmetrical and asymmetrical dioxopyrrolopyrroles corresponding to formula I in which R 1, R 2, R 3 and R 4 each independently represent - H, -Cl, -Br, -CH 3, -OCH 3, -C 6 H 5 or a radical -SO 3 e X 9 whose Xe symbol represents He or a radical Mn or Born (R 5) (R 6) (R 7) (Rs), the n symbol Mn O representing a metal cation of valency equal to n, N representing a number equal to 1, to 2 or to 3, R 5, R 6, R 7 and R 8 representing each , independently of one another, hydrogen, C 1 -C 18 alkyl, C 5 or C 6 cycloalkyl, unsubstituted phenyl or phenyl bearing a C 1 -C 18 alkyl, or R 7 and R 8 forming together, and with the nitrogen atom, a radical of pyrrolidine, imidazolidine, piperidine, piperazine or mor pholine, or R 6, R 7 and R 8 forming together, and with the nitrogen atom, a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical, with the proviso that, in this mixture, at least one of the symbols R 1, R 2, R 3 and R 4 represents a radical of formula

-SO 38 Xe.

  The dioxopyrrolopyrroles which are present in the compositions according to the invention are preferably, for both component a) and component b), compounds of this kind in which R 2 and R 4 each represent hydrogen. and R 1 and R 3 are each, independently of one another, -Cl at 4, -Br at 4, -CH 3 at 4, -OCH 3 at 4, -C 6 H 5 at 4 or -CN in 3 or, more particularly, hydrogen

or -Cl in 4.

  The sulphonated mixture of dioxopyrrolopyrroles b) is added to the dioxopyrrolopyrrole a) in amounts which are preferably between 1.5 and 7% by weight relative to

dioxo-pyrrolopyrrole a).

  The symbol X 9 preferably represents H 6 or, better still, Mn OE Mn E, a radical of formula In the latter, it may be n Dascnene, -pur

  especially an alkali metal, alkali metal

  earth, aluminum or a transition metal, for example Na E, KE, Mg 28, Ca 2 E, Sr 2 E, Ba 28, Mn 2 &, Cu 2 e, Ni 2 E, Cd 2 G, Co 3 E, A 13 or Cr 38, but more particularly an alkali or alkaline earth metal cation (n = 1 or 2) and, preferably, Ca 2 G. C 1 -C 18 alkyls, optionally substituents , are chosen for example from the following radicals: methyl,

  ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-

  4-butyl, n-pentyl, tert-pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl and octadecyl. As C 5 or C 6 cycloalkyl, R 5, R 6, R 7 or R 8 is for example a cyclopentyl radical or, more specifically, cyclohexyl. As phenyl bearing a C 1 -C 18 alkyl, R 5, R 6, R 7 or R 8 is preferably a phenyl bearing an alkyl having

C 12-C 18 -

  Examples of radicals Ne (R 5) (R 6) (R 7) (R 8) are the following: ## STR1 ## 5, N @ H 2 (C 2 H 5) 2,

  N H 3 C 3 H 7 -iso, N H 3-n-octadecyl, N H 3 -cyclohexyl, NEH 2

  (cyclohexyl) 2, N H 2 (CH 3) (C 6 H 5), N 9 H 3 C 6 H 5, No H 3 -poctadecyl-

  phenyl, N @ (CH 3) 4 and N @ (CH 3) 3-n-hexadecyl.

  The dioxopyrrolopyrroles of formula I are, as

  has already said, known compounds.

  The sulfonated mixtures of dioxopyrrolopyrroles b) are novel and, with the same preferred meanings as those indicated above for R 1, are

  R 2, R 3, R 4 and XO, another subject of the invention.

  Their preparation is also an object of the present invention. It consists, for example, in reacting, in the presence of a strong base, 1 mol of a diester of succinic acid corresponding to formula II:

ROOC-CH 2 -CH 2-COOR (II)

  in which R represents a lower alkyl radical, with 2 mol of a mixture of two different nitriles corresponding to the formulas:

R 1 R 2 R 3 R 4

t and s

CN CN

  in which R 1, R 2, R 3 and R 4 each independently represent -H, -C 1, -Br, -CH 3, -OCH 3 or -C 6 H 5, at least one of the symbols R 1, R 2, R 3 and R 4 to represent hydrogen, in a molar ratio of III to IV of between 9: 1 and 1: 9, preferably between 3: 1 and 1 : 3 and more particularly equal to 1: 1, then the resulting mixture is sulfonated, by known methods, using an oleum, concentrated sulfuric acid, liquid sulfur trioxide or chlorosulfonic acid The products which have The two-stage products obtained are then optionally converted by reaction with one of the metal salts which can be envisaged according to the invention, for example with an acetate, a carbonate, a chloride, a nitrate or a sulphate, or with an amine or an amine salt, in metal salts or amine salts

correspondents.

  As lower alkyl, R represents, for example, a methyl, ethyl or, more particularly, isopropyl radical,

tert-butyl or tert-pentyl.

  The succinic diesters of formula II and the nitriles of formulas III and IV are known compounds which can

  be prepared by known methods.

  The reaction of the succinic diester with the nitriles is advantageously carried out in an organic solvent, which may be chosen for example from primary, secondary or tertiary alcohols containing from 1 to 10 carbon atoms, such as methanol, ethanol, naphthalene and the like. propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, n-pentanol, methyl-2-butanol-2, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol or 2,4-trimethyl-2-pentanol, glycols, such as ethylene glycol or diethylene glycol, ethers, such as tetrahydrofuran; or dioxane,

  ethers of glycols, such as methyl ether of ethylene

  glycol, the ethyl ether of ethylene glycol, the mono ether

  diethylene glycol methyl or 6-diethylene glycol monoethyl ether, and also dipolar aprotic solvents, such as acetonitrile, benzonitrile, dimethylformamide, N, N-dimethylacetamide, nitrobenzene or N-methyl- pyrrolidone, aliphatic or aromatic hydrocarbons, especially benzene or benzenes bearing an alkyl, an alkoxy or a halogen, such as toluene, xylenes, anisole or chlorobenzene, or nitrogenous heterocyclic compounds Aromatic, such as pyridine, picolines or quinoline The mixture of nitriles to be reacted can also simultaneously serve as a solvent, provided that it is liquid in the temperature range where the reaction is carried out.

  may also be involved in the form of mixtures.

  It is good to use from 5 to 20 parts by weight of the solvent to 1 part by weight of the reaction partners. It is recommended to use an alcohol as a solvent, more particularly a secondary or tertiary alcohol. The tertiary alcohols which are preferred are tertiary butanol

and tertiary pentanol.

  The reaction is carried out in the presence of a strong base.

  Suitable strong bases include alkali metal hydroxides, such as sodium hydroxide,

  potassium or lithium, alkali metal hydroxides

  earth metals, such as calcium or magnesium hydroxide, alkali metal amides, such as lithium or sodium amide, alkali metal hydrides, such as hydride

  lithium or sodium, or alkali metal alcoholates

  earth or alkali metals derived more particularly from primary, secondary or tertiary aliphatic alcohols containing from 1 to 10 carbon atoms, such as methylate, ethylate, n-propylate, iso-propylate, n-butylate , sec-butylate, tert-butylate, 2-methyl-2-butylate, 2-methyl-2-pentylate, 3-methyl-3-pentylate or 3-ethyl-3-pentylate of sodium, potassium or lithium, or phenolates or o-alkyl-phenolates of alkali metals or of alkaline earth metals, such as sodium or potassium o-cresolate. However, it is also possible to use a mixture of

cited bases.

  Alkali metal alkoxides whose alkali metal is more particularly sodium or potassium and whose alcohol is preferably a secondary or tertiary alcohol are preferably used as strong bases. The strong bases which are the most preferred are therefore, for example,

  isopropylate, sec-butylate, tert-butylate and tert-butylate

  sodium or potassium pentylate.

  The strong base may be used in an amount of more particularly between 0.1 and 4 mol, preferably between 1.9 and 2.2 mol, relative to the succinic diester to be reacted depending on the reaction partner and according to the method. procedure (for example when performing a recycling) it may happen that smaller quantities

  bases have a very advantageous effect on the yield.

  On the other hand, in some cases, an excess of the base may also have a favorable effect on the yield. However, in general, it is sufficient to use a stoichiometric quantity.

from the base.

  The strong bases mentioned can be used in combination with a phase transfer catalyst. This is particularly advantageous when the solubility of a given base in a given solvent is low. The phase transfer catalysts can be used in an amount of 0.001. at 50 mol%, preferably from 0.01 to 0.3 mol%, relative to the reactant diester of succinic acid. Suitable for this are the conventional phase transfer catalysts described in the literature. such as those mentioned for example in CHEMTECH, February 1980, page 111, Table 1, especially quaternary salts, cyclic polyethers, open-chain polyethers, N-alkyl phosphoramides or related phosphorus or sulfur oxides. by bridges

methylene.

  -8- It is good to operate at a temperature of 60 to 140 CC,

preferably from 80 to 120 ° C.

  For the reaction of the succinic diester with the nitriles it is in principle possible to place all the components in the container from the start at a low temperature, then to heat the mixture so as to bring it into the range of the reaction temperatures; we can also introduce the different components in isolation, in the order we want,

  in the range of reaction temperatures.

  A very preferred embodiment, which generally has a particularly favorable effect on the yield, consists in placing the mixture of the nitriles with the base from the start and in gradually adding the diester of the succinic acid in the interval. temperatures

reaction.

  Especially in the case of drifting alcoholates

  lower alcohols, such as methanol, ethanol, n-

  propanol, isopropanol or tertiary butanol, it may be necessary to continuously remove from the reaction medium the lower alcohol formed during the reaction, for

  obtain higher yields.

  When an alcohol is used as a solvent and an alcoholate as a base it may be advantageous to choose an alcohol and an alcoholate whose alkyl parts are the same. It may also be advantageous for the diester

  succinic contains such alkyl radicals.

  To hydrolyze the condensation product, it is possible to use an acid, an alcohol containing from 1 to 4 carbon atoms, such as methanol or ethanol, but preferably with water. The acids may in particular be carboxylic acids. or aliphatic or aromatic sulphonic compounds, such as formic acid, acetic acid, propionic acid,

  oxalic acid, benzoic acid or benzene

  sulfonic acid, or mineral acids, such as hydrogen chloride, aqueous solutions thereof, 9 - carbonic acid or dilute sulfuric or phosphoric acid. During hydrolysis, the mixture of dioxo-pyrrolopyrroles

  precipitates and can be isolated by filtration.

  During sulphonation the concentration of the sulphonating agent to be used and the reaction conditions to be respected depend closely on the number of sulpho radicals.

  which must be introduced into the dioxoxo-

  pyrrolopyrroles. The compositions according to the invention are obtained by mixing the various components a) and b) in the desired quantitative ratio either directly in the grinding medium or, during an additional mixing operation, in water or in water. sulfuric acid A trans-salification (conversion to another salt) leading to the desired metal salt may optionally be carried out subsequently by treatment of the composition according to the invention (which contains, for example, the sodium salt) with a salt of the metal.

For example, Ca (504) 1.

  The compositions according to the invention can be used as pigments for dyeing materials

  organic high molecular weight.

  The high molecular weight organic materials which can be colored or pigmented using the compositions according to the invention are, inter alia, ethers and esters of cellulose, for example ethyl cellulose, nitro-cellulose. cellulose acetate and cellulose butyrate, natural or synthetic resins, in particular polymerization resins and condensation resins, such as aminoplasts, more particularly urea / formaldehyde and melamine / formaldehyde resins, alkyd resins, phenolplasts, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters,

  fluorinated polymers, for example poly-fluorethylene, poly-

  - trifluorochlorethylene and tetrafluoroethylene / hexafluoropropylene copolymers, as well as rubber, casein, silicones and silicone resins, which can be

  used singly or in combination.

  The macromolecular organic materials mentioned may then be present as such or in mixtures, such as plastics, melts, spinning solutions, paints, varnishes, coating products or printing inks, depending on the intended application. it may be recommended to use the compositions according to the invention in the form of shaders (solid inks) or in the form of compositions The compositions in accordance with the invention may be used in an amount of from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, by

  relative to the macromolecular organic matter to be pigmented.

  In order to pigment the macromolecular organic materials with the compositions in accordance with the invention, it is possible, for example, to add such a composition, possibly in the form of a masterbatch, to these substrates by using roll kneaders, mixers or grinders. pigmented is then brought to the desired final shape, by known methods, for example by calendering, compression molding, extrusion, coating, casting or injection molding: 1 is often desirable, when it is desired to manufacture non-rigid molded articles or that it is desired to reduce their fragility, to incorporate in the macromolecular materials, prior to shaping, substances called "plasticizers", which may be, for example, esters of phosphoric acid, phthalic acid or sebacic acid The incorporation of the plasticizers into the polymers may take place before or after that of the composition according to the invention In addition to the compositions according to the invention it is furthermore possible to add in any quantities to the compositions according to the invention, to obtain different shades, fillers or other constituents giving color, such as

  only white, colored or black pigments.

  In order to pigment varnishes and printing inks, the macromolecular organic materials and the compositions in accordance with the invention are dispersed finely or dissolved, optionally with additives, such as fillers, other pigments, driers or plasticizers. in a common organic solvent or a common mixture of organic solvents It is then possible to disperse or dissolve the various components in isolation, or to disperse or dissolve several of them together and then to join together all

components.

  The dyes obtained with the compositions according to the invention, which are distinguished by good theological properties, for example dyes in plastics, fibers, paints, varnishes or printing inks, have good general properties. eg good dispersibility, high color intensity, good fastness to overlaid, migration, heat, light and atmospheric agents, and

beautiful shine.

  The sulphonated mixture of dioxopyrrolopyrroles used as component b) in the composition according to the invention can, however, also be used itself as a pigment for the coloration of the bulk of the macromolecular organic materials mentioned above. For this, it can be used as a raw product, or after having been subjected to a suitable complementary treatment (packaging), for example as described above for

  compositions according to the invention.

  The following examples illustrate the invention.

EXAMPLE 1

  a) 120 ml of tertiary pentanol (anhydrous) are placed in a sulfonation flask under nitrogen. While stirring slowly, 6.9 g of sodium and 0.1 g of sodium and bis (ethyl) sulphosuccinate are added. -2 hexyl), and the mixture is heated to 95-102 ° C. The molten sodium is then maintained at 95 ° C.

  nitrogen, while stirring vigorously, until the next day.

  After that, the solution formed is cooled to 85 ° C. and a mixture of 14.04 g of 4-chlorobenzonitrile and 3 g of benzonitrile is added. The reaction is allowed to proceed at 95 ° C. for 5 hours, then the mixture is cooled to room temperature. The mixture obtained is poured into 300 ml of cold water and the mixture is heated under reflux for 1 hour. hour and then subjected to steaming. The mixture obtained is filtered off at 60 ° C., washed with 1000 ml of water and dried at 80 ° C.

  in an oven under reduced pressure.

  23.6 g of a red powder are collected which essentially contains the compounds of formula ClCl

.

0 O

qa and EST Analysis (%)

  Found C = 64.93; H = 3.45; N, 8.38; Cl = 13.72.

  b) 160 g of an oleum (25%) and 160 g of 2-5 C sulfuric acid monohydrate are placed in a sulphonating flask. 20 g of the mixture obtained according to Example 13 are introduced over 30 minutes. 1a) The mixture is stirred for 20 hours at room temperature, then the resulting solution is poured into 1000 g of ice and 280 ml of water. The suspension obtained is stirred for 15 minutes, heated to 75 ° C. and then added thereto. 120 g of NaCl is stirred vigorously at 75 ° C. for 1 hour, then the suspension is filtered at room temperature, washed with a 5% solution of NaCl until the filtrate is colorless, and dried in the vacuum oven the product retained by the filter is collected 29.0 g of a violet powder

red.

Analysis (%):

  Found: C = 40.7; H = 2.3; N = 5.1; S = 4.8; Cl = 17.9.

Clion = 9, 6; H 2 O = 2.4.

  (c) 964 g of dioxygen are placed in a sulphonation flask

  1,4 bis- (chloro-4-phenyl) -3,6 pyrrolol 3,4-clpyrrole wet (solids content: 36.3%) The volume is brought to 8 liters with deionized water After stirring for 1 hour at room temperature is added a solution of 8.1 g of the product prepared according to Example 1b) in 900 ml of water (60 ° C.) and the mixture is stirred for 2 hours at room temperature. g of CaCl 2 in the form of a solution in approximately 500 ml of water, heated to C, stirred for 1 hour at 75 ° C. and filtered at room temperature. The product is washed well with water. retained by the filter and dried at 80 ° C. in the vacuum oven. 352 g of a red powder were collected which

  excellent coloristic and rheological properties.

EXAMPLES 2 TO 6

  The procedure is as described in Example 1c except that, instead of 1,4-dioxo-3- (4-chlorophenyl) pyrrolol 3,4-clpyrrole, the pigments mentioned in the following table are used. in the form of wet filter cake Pigment powders are obtained which have excellent

  rheological and coloristic properties.

  14 - N of Example 2 1,4-dioxo-bis (4-bromo-phenyl) -3,6 pyrrolol 3,4-pyrrole 3 1,4-dioxo-bis (4-methylphenyl) -3,6 pyrrolol 3, 4-Clpyrrole 4 1,4-dioxo-bis (3-methoxyphenyl) -3,6-pyrrolol 3,4-clpyrrole 5 1,4-dioxo-bis (4-phenylphenyl) -3,6 pyrrolol 3,4- clpyrrole 6 dioxo-1,4 bis- (3-cyano-phenyl) -3,6 pyrrolol 3,4-clpyrrole

EXAMPLE 7

  We operate as described in Example lc) except that

  Instead of Ca C 12, it uses trimethyl hexadecyl bromide.

  Ammonium A red pigment is obtained which has excellent

  rheological and coloristic properties.

EXAMPLE 8

  The procedure is as described in Example 5 to this difference

  whereas instead of Ca C 12 trimethyl bromide is used

  hexadecylammonium A red pigment is obtained which

  excellent rheological and coloristic properties.

EXAMPLE 9

  The procedure is as described in Example 6, except that, instead of Ca C 12, trimethyl hexadecylammonium bromide is used. An orange pigment is obtained.

  has excellent rheological and coloristic properties.

EXAMPLE 10

  The procedure is as described in Example 1a) but this time, instead of chlorobenzonitrile, a corresponding amount of 4-phenylbenzonitrile is used. The resulting red pigment powder is then treated as in Examples 1b) and 1c). red pigment that has excellent

  rheological and coloristic properties.

EXAMPLE 11

  The operation is carried out as described in Example 1a) except that instead of 4-chlorobenzonitrile, a corresponding amount of methyl-4-benzonitrile is used. The resulting red pigment powder is subjected to a complementary treatment similar to that of the Example 1 under b) and c) A red pigment is obtained which has excellent rheological and coloristic properties. EXAMPLE 12 Application in an alkyd-melamine cooking paint For 72 hours, a glass flask equipped with a "twist-off" type closure is dispersed on a roller stand with a mixture of 460 g of 8 mm diameter steatite, an alkyd varnish consisting of 58.7 g of the 60% alkydal F 310 (BAYER AG) alkyd resin in xylene, 58.7 g of the Alkydal F 32 alkyd resin (BAYER AG) at 60% in xylene, 2.0 g of Silikonol A silicone oil at 1% in xylene (BAYER AG), 4.0 g of n-butanol, 4.0 g of Dowanol , 15 g of xylene, 5.6 g of Disperbyk D-160 dispersant (BYK-Chemie) and 28.0 g of the pigment mixture prepared according to Example 1. After adding 24.0 g of the melamine component Cymel 327 (Cyanamid) 90% in xylene is continued to disperse for 1 hour on the trestle The steatite balls are then separated The paint thus ground is applied to transparent sheets Milar is then cooked at 130 ° C. for a minute (thickness of the paint layer: 50 μm). A red color is obtained which has excellent properties.

coloristic and rheological.

Claims (7)

  1 Composition containing a) at least one dioxopyrrolopyrrole corresponding to formula I: R 1 R 2 li N NE (I) R 3 R 4   wherein R 1, R 2, R 3 and R 4 each represent independently   respectively, -H, -Cl, -Br, -CH 3, -OCH 3, -C 6 H 5 or -CN, and b) from 0.5 to 10% by weight, relative to the dioxygen pyrrolopyrrole a), a mixture of at least 3 different symmetrical and asymmetrical dioxopyrrolopyrroles corresponding to formula I in which R 1, R 2, R 3 and R 4 each independently represent - H, -Cl, -Br, -CH 3, -OCH 3, -C 6 H 5 or a radical -SO 3 e Xe whose symbol Xe represents He or a radical Mn or NO (Rs) (R 6) (R 7) (Rs), n the symbol Mne representing a metal cation of valency equal to n, N representing a number equal to 1, to 2 or to 3, R 5, R 6, R 7 and R 8 representing each independently the each other, hydrogen, C 1 -C 18 alkyl, C 5 or C 6 cycloalkyl, unsubstituted phenyl or phenyl bearing C 1 -C 18 alkyl, or R 7 and R 8 together with the nitrogen atom, a pyrrolidine, 17-imidazolidine, piperidine, piperazine or holine, or R 6, R 7 and R 8 forming together, and with the nitrogen atom, a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical, with the proviso that, in this mixture, at least one of the symbols R 1, R 2, R 3 and R 4 represents a radical of formula -5038 X @.   Composition according to Claim 1, characterized in that the dioxopyrrolopyrroles of formula I are, both in a) and in b), compounds of this type in which R 2 and R 4 each represent hydrogen, and R 1 and R 3 each independently represent hydrogen, a C 1 to 4, a Br to 4, a CH 3 to 4, an OCH 3 to 4, a C 6 H 5 to 4 or a CN in 3.   Composition according to Claim 1, characterized in that the dioxopyrrolopyrroles of formula I are, in both a) and in b), compounds of this type in which R 2 and R 4 each represent hydrogen, and R 1 and R 3 each represent, independently of one another, hydrogen or a C 1 to C 4. A composition according to claim 1 characterized in that the sulfonated mixture of dioxopyrrolopyrroles b) is added to the dioxopyrrolopyrrole. in amounts of 1.5 to 7% in   weight relative to dioxopyrrolopyrrole a).   Composition according to Claim 1, characterized in that X O represents HO or a radical of formula whose n symbol Mn 9 denotes a cation of an alkali metal, a metal   alkaline earth, aluminum or a transition metal.   6 Composition according to Claim 1, characterized in that Xe represents a radical corresponding to the formula Mne, of which n 18 -   the symbol Mn O denotes an alkali or alkaline metal cation   earthy and N denotes the number 1 or the number 2.   Composition according to Claim 1, characterized in that Xe represents a calcium cation. 8 Mixture of at least 3 symmetrical and dissymmetrical dioxopyrrolopyrroles of formula I: R 1 O R 2 NH- (I) R 3 R 4   in which R 1, R 2, R 3 and R 4 each represent, independently of each other, -H, -Cl, -Br, -CH 3, -OCH 3, -C 6 H 5 or a radical - SO 38 X Oe whose symbol Xe represents H @ or a radical M or Born (Rs) (R 6) (R 7) (R 8), the symbol Mne n representing a metal cation of valence equal to n, n representing an equal number at 1, 2 or 3, R 5, R 6, R 7 and R 8 each independently of one another being hydrogen, C 1 -C 18 alkyl, C 5 or C 6 cycloalkyl , a   unsubstituted phenyl or a C1-C6 alkyl-bearing phenyl   C 18, or R 7 and R 8 forming together, and with the nitrogen atom, a radical of pyrrolidine, imidazolidine, piperidine, piperazine or morpholine, or R 6, R 7 and R 8 forming together with the nitrogen atom a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical, with the proviso that in this mixture at least one of the symbols R 1 , R 2, R 3 and R 4 represent a radical of formula -SO 3 e XE.   Process for preparing a mixture of at least 3 different symmetrical and dissymmetrical dioxopyrrolopyrroles having formula 1: RI R 2 jki O R 3 R 4   in which R 1, R 2, R 3 and R 4 each represent, independently of each other, -H, -Cl, -Br, -CH 3, -OCH 3, -C 6 H 5 or a radical - SO 38 XO whose symbol Xe represents HO or Mne a radical ne or Ne (R 5 s) (R 6) (R 7) (R 8), the symbol Mnf n representing a metal cation of valence equal to n, n representing a number equal to 1, 2 or 3, R 5, R 6, R 7 and R 8 each independently of one another being hydrogen, C 1 -C 18 alkyl, C 5 or C 5 cycloalkyl 6, a   unsubstituted phenyl or phenyl bearing a C 1-4 alkyl   C 18, r or R 7 and R 8 forming together, and with the nitrogen atom, a radical of pyrrolidine, imidazolidine, piperidine, piperazine or morpholine, or R 6, R 7 and R 8 forming together with the nitrogen atom a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical, with the proviso that in this mixture at least one of the symbols R 1 , R 2, R 3 and R 4 represents a radical of formula -SO 3 X 2, according to which 1 mol of a diester of succinic acid corresponding to formula II is reacted: ROOC-CH 2 -CH 2-COOR (II)   in which R represents a lower alkyl radical, with 2 mol of a mixture of two different nitriles corresponding to the formulas: RI R 2 R 3 R-4   and CN (m R (v), wherein R 1, R 2, R 3 and R 4 each independently represent -H, -Cl, -Br, -CH 3, -OCH 3 or -C 6 H 5, in the presence of a strong base, at least one of the symbols R 1, R 2, R 3 and R 4 must represent hydrogen, in a molar ratio of II to IV between 9: 1 and 1: 9 and then the resulting mixture is sulfonated by known methods using oleum, concentrated sulfuric acid,   liquid sulfur or chlorosulfonic acid.   Macromolecular organic materials that contain   a composition according to claim 1.   11 Macromolecular organic substances which contain a mixture according to claim 8.