DE3623297A1 - Addition compounds, process for their preparation, and their use - Google Patents

Abstract

Addition compounds which are suitable as dispersants for solids in organic media are obtained from polyepoxides based on novolaks having 3 to 11 rings and a mixture of aliphatic, aromatic and/or heterocyclic amines.

Description

The invention relates to addition compounds by Reaction of polyepoxides with amines can be obtained can, as well as the salts of the addition compounds. The The invention also relates to the manufacture of the Addition compounds and their salts and their Use as a dispersant for solids, especially pigments, in natural and synthetic, preferably organic media.

In the manufacture of solid dispersions often used surfactants that the mechanical effort in dispersing the solids should decrease in liquid media. These As a rule, they also have surface-active substances Influence on the application properties the solid dispersions. For pigment binder systems usually the highest possible flocculation stability, Color strength and gloss as well as good rheological properties sought.

The object of the invention is to provide tools for Provide solid dispersions that the application technology, especially the above Improve the properties of the solid dispersions.

Addition compounds are known from US Pat. No. 3,853,770 Polyepoxides and secondary amines known as Fabric softeners are suitable. The Polyepoxides are phenol-formaldehyde novolaks with 2 to 7 Cores whose hydroxyl groups contain 2,3-epoxypropyl groups are etherified. The secondary amines used have two long chain alkyl or alkenyl residues.

Furthermore, from EP-A-00 44 816 as hardening agents addition compounds known for epoxy haze are known, by reacting a polyepoxide with a multiple  Excess diamines or polyamines are obtained, the polyepoxide being one with 2,3-epoxypropyl groups etherified cresol-formaldehyde novolak with a medium Number of cores is between 2.2 and 5.4.

The aforementioned addition compounds from the prior art however, result in little or none Improvement of the application properties of pigment binder systems, such as Flocculation stability, gloss behavior, color strength or Flowability.

The invention relates to addition compounds and their salts, obtainable by reacting polyepoxides with Amines and optionally subsequent salt formation with Acids, characterized in that the addition compounds are available in a process in which a polyepoxide or more polyepoxides of the idealized general Formula (I)

in the

n is a number from 2 to 10, preferably 4 to 6, pure hydrogen atom or an alkyl group, preferably C₁-C₄-alkyl, in particular methyl, and X is the 2,3-epoxypropyl radical

with an amine or more amines of the general Formula (II)

(H ₂ N-R²-) _p N (H) _{2- p} -R¹ (II)

in the

p is an integer from 0 to 2, preferably 1 or 2, R¹ is a saturated or unsaturated aliphatic alkyl radical having 8 to 24 carbon atoms, preferably having 12 to 20 carbon atoms, and R² is an alkylene group, preferably C₂-C₆-alkylene, in particular propylene mean

and with one or more amines of the general Formula (III) and / or the general formula (IV)

H₂N-R³-R⁶ (III)

H₂N-R⁴-NR⁵- (R³) _p -R⁶ (IV)

in which

p is 0 or 1, preferably 1, R³ for an alkylene group, preferably C ₁ -C ₁₀ alkylene, in particular C₁ to C₆ alkylene, R⁴ for an alkylene group, preferably C₂-C₆ alkylene, in particular ethylene or propylene, R⁵ for -H or an alkyl group, in particular -H or C₁-C₄-alkyl group, and R⁶ for a saturated or unsaturated, mono- or polynuclear heterocyclic or carbocyclic ring system, which by one or more of the radicals R⁷, halogen such as -F, -Cl and -Br, - OR⁷, -NR⁷R⁸, -COOR⁷, -CONR⁷R⁸, -NR⁷-CO-R⁸, -CN, -CF₃ or -NO₂, in which R⁷ and R⁸ independently of one another the radical -H or alkyl, in particular -H or C₁-C₄-alkyl mean stand

are implemented in such a ratio that 1 to 99%, preferably 10 to 90%, in particular 20 to 70% of the  Epoxy groups of the polyepoxide of formula (I) with the amine or the amines of the formula (II) and 99% to 1%, preferably 90 to 10%, in particular 80 to 30% of the Epoxy groups with the amine or the amines of the formula (III) and / or the formula (IV) are implemented, and optionally the product obtained with an acid is implemented.

Of particular interest are inventive Addition compounds and their salts, in which in the amine of the formula (III) or (IV) R⁶ for a single-core or multi-core, preferably mononuclear, carbocyclic aromatic ring system, which is optionally further substituted.

Of particular interest are also inventive Addition compounds and their salts, in which in the amine of the formula (III) or (IV) R⁶ represents a heterocyclic ring system that is optionally further substituted, and that preferably a heterocyclic ring with 5 or 6 Contains ring atoms on which another benzene nucleus or several benzene cores can be condensed.

Addition compounds and are preferred their salts in which the amines are derived from amines of the formula (II) and formula (III) are selected.

The invention also relates to the method for Preparation of the above addition compounds and of their salts.

The addition products according to the invention are by Reaction of polyepoxides with primary and secondary Compounds containing amino groups, here briefly as amines designated, manufactured.

Commercial polyfunctional ones are suitable as epoxides Epoxies based on novolaks, accordingly  above general formula (I) as by Condensation of phenol or alkylphenols with formaldehyde and then reacting the phenolic hydroxy groups accessible with epichlorohydrin according to the prior art are, see e.g. B. Y. Chin in Epoxy Resins, Supplm. A, SRI International (1983). They have medium functionality from 3 to 11, preferably from 5 to 7, and a Epoxy equivalent weight of 150 to 300 g, preferably 170 to 240 g / mol epoxy groups. The middle functionality is the quotient of the average molecular weight and the epoxy equivalent weight.

The polyepoxides are of particular interest general formula (I) in which R represents a hydrogen atom or a C₁-C₄ alkyl radical, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-prop-1-yl, preferably methyl.

The general formula (I) is an idealized formula specified and stands above all for the commercially available polyepoxides, where due to No side reactions when introducing the epoxy group 100% of all radicals X mean the 2,3-epoxypropyl radical. The Idealized formula (I) includes polyepoxides in which up to 25% of all X mean other residues, like the rest 2,3-dihydroxy-prop-1-yl and 3-chloro-2-hydroxy-prop-1-yl as well as residues of polymeric ethers used in the manufacture of polyepoxides usually arise.

Examples of suitable commercially available polyepoxides of the formula (I) are ®Araldit ECN 1273 (average n = 5, R = 2-methyl, epoxy equivalent weight 225), Araldit ECN 1299 (average n = 6, R = 2-methyl, epoxy equivalent weight 235), Araldit ECN 1280 (mean n = 4.1 R = 2-methyl, epoxy equivalent weight 230) from Ciba Geigy AG and ®Grilonit ESN 138 (R = H, epoxy equivalent weight approx. 180) from EMS-Chemie and Epo Tohto YCDN -701, 702, 703, 704 (R = 2-methyl, epoxy equivalent weight 200 to 230) and Epo Tohto YDPN-638 (R = H, epoxy equivalent weight approx. 180) from Totho-Kasei and Epiclon N-665, 673, 680, 695 (R = 2-methyl, epoxy equivalent weight 200 to 250) from Dainippon and Rütapox 0300 (R = H, epoxy equivalent weight approx. 185) from Bakelite.

The amines are in the general formulas mentioned above (II), (III) and (IV) summarized.

Representatives of formula (II) are, for example, the following long-chain aliphatic amines, especially fatty amines:
Octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, octadecenylamine, coconut fatty amine, oleylamine, stearylamine, tallow fatty amine and, in particular, corresponding derivatives with aminopropyl groups, such as, for example, tallow fat propylene diamine, lauryl propylene diamine (amine) -amine-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N.

Suitable amines of the formulas (III) and (IV) are with Aminoalkyl, aminoalkylamino or Aminoalkylaminoalkyl groups substituted carbocyclic aromatic compounds or heterocyclic compounds, the other substituents on the respective ring system can wear.

Ring systems are, for example, benzene, naphthalene, triazole, pyridine, pyrimidine, piperidine, pyrrole, pyrrolidine, piperazine, imidazole, imidazoline, morpholine, triazine, benzimidazole, benzothiazole and carbazole. The following groups are preferred as further substituents:
C₁-C₄-alkyl, halogen such as -F, -Cl and -Br, hydroxy, C₁-C₄-alkoxy, amino, alkylamino, dialkylamino, carboxy, carboalkoxy, carbamide, carboalkylamide, carbodialkylamide, alkanoylamino, N, N-alkanoyl-alkyl -amino, N, N, N-alkanoyldialkylamino, cyano, trifluoromethyl and nitro, where the alkyl or alkanoyl radicals mentioned in each case preferably contain 1 to 4 or 2 to 5 carbon atoms.

Preferred representatives of the amines of the formula (III) and (IV) are, for example:
2- (1-pyrrolidyl) ethylamine, 2- (1-piperidyl) ethylamine, 1- (2-aminopropyl) piperidine, 1- (2-aminoethyl) piperazine, 4- (3-aminopropyl) morpholine, 2- (4-morpholinyl) ethylamine, 1- (3-aminopropyl) imidazole, 1- (2-aminoethyl) imidazoline, (2-aminoethyl) pyridines, picolyamines, tryptamine, furfurylamine, tetrahydrofurfurylamine, 2,5- Dihydro-2,5-dimethoxy-furfurylamine, 2-aminomethylthiophene, benzylamine, phenylethylamine, methoxyphenylethylamine, 1-methyl-3-phenylpropylamine, N-ethyl-N-aminomethyl-3-methylaniline, 6-phenyl-2-methylhexylamine-4 and N-aminopropylbenzylamine.

In the production of more preferred according to the invention Addition compounds are combinations of amines of formula (II) and of formula (III) and / or (IV), which are not significantly different in their reactivity differentiate. The use of more than 2 amines can be beneficial. When implementing the amines with the Polyepoxide of formula (I) are preferably 10 to 90%, in particular 20 to 70% of all epoxy groups of the polyfunctional epoxy with primary amino groups of Amine or the amines of formula (II) and preferably 90 up to 10%, in particular 80 to 30% of all epoxy groups primary amino groups of the amine or amines of the formula (III) and / or (IV) reacted. The relationship the number of epoxy groups to the total number of amine molecules of the formula (II) to (IV) can be 1: 0.8 to 1: 1, preferably 1: 0.9 to 1: 1. Is the relationship the number of epoxy groups to the total number of amine molecules  of formulas (II) to (IV) greater than 1: 0.8 arise in increasingly through crosslinking of higher molecular weight products, which no longer dissolve in the solvents used.

There are preferred addition compounds The following options: The polyfunctional epoxy Formula (I) is preferably used in one reaction step a mixture of the amines of the formula (II) and (III) and / or (IV) reacted. It can

• a) submitted the polyfunctional epoxy and the mixture the amines are added rapidly or preferably
• b) submitted the mixture of the amines and that polyfunctional epoxy can be added.

The preparation of the addition products according to the invention takes place in organic solvents which are compared to the Reactants are inert or their reactivity is negligible towards the reaction partners and in which the reactants as well as the reaction products at least partially soluble, but preferably completely are soluble. Examples include: Hydrocarbons, especially aromatic Hydrocarbons such as toluene, xylenes, ethylbenzenes, chlorinated hydrocarbons such as 1,2-dichloroethane, Trichloroethane and especially chlorobenzenes, alcohols, preferably butanol, isobutanol, pentanol and hexanol, Ethylene glycol ether and propylene glycol ether, for example Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol dimethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, Esters such as N-butyl acetate, methyl glycol acetate and ethyl glycol acetate and amides such as dimethylformamide and N-methyl-pyrrolidone- (2).  

The reaction for the preparation of the invention Addition compounds is at a temperature of 0 ° C to 180 ° C, preferably 40 ° C to 120 ° C. Preferably the reactants are initially at an elevated temperature of Bring 40 ° C to 120 ° C in contact. The solvents can depending on the application, either in the reaction mixture remain, the solids content of the solution is preferably up to 40%, in particular 15 to 30%, or they are removed by distillation.

Should the addition compounds of the invention in the form their salts are used in aqueous solution usually becomes organic beforehand Solvent distilled off in vacuo and the remaining Residue preferably with one of the number of available basic groups corresponding stoichiometric amount neutralized with an inorganic or organic acid. Salts of an organic monocarboxylic acid are preferred such as formic acid, acetic acid or Propionic acid. However, it can also be polyfunctional Carboxylic acids, such as maleic acid, fumaric acid, Oxalic acid, tartaric acid or citric acid can be used.

Reaction speed and course of the reaction of the polyfunctional epoxy with the components of the formula (II) and (III) and / or (IV) does not depend solely on the type of the reactants themselves and the reaction temperature, but also on the nature of the solvent used from. If necessary, the presence of a catalyst required. Acidic and basic catalysts are suitable; unsubstituted and substituted are particularly preferred Phenols, aromatic and aliphatic carboxylic acids such as Salicylic acid, bezoic acid and lactic acid as well as Lewis acids, for example boron trifluoride and aluminum trichloride.

The end of the reaction can be judged by the epoxy content of the Recognize the reaction mixture. The epoxy content can  IR spectroscopic or as epoxy equivalent weight can be determined analytically by titration. The titrametric determination is carried out so that a exactly weighed sample with a dichloromethane / glacial acetic acid mixture diluted and with a certain amount of one quaternary ammonium halide salt, such as. B. Tetrabutylammonium iodide is added. Subsequently the solution is counteracted with perchloric acid in glacial acetic acid Crystal violet titrated as an indicator, indicating the acidity Releases hydrogen halide, which quickly adapts to the Epoxy groups added. The indicator turns over when no more hydrogen halide is added and this therefore exists in excess. To determine the exact Epoxy equivalent weight of the reaction mixture is required Start of the reaction of the blank value for the pure Amine components determined and at the end of the titration Reaction are taken into account.

Addition products according to the invention are particularly preferred, those in water-dilutable organic solvent systems on the surface of solids, especially pigments, can be applied, as well as their salts, which in aqueous systems to which solids are applied can. The solids prepared in this way, especially pigments, are then in organic media particularly well dispersible. Improved dispersibility is also evident when the addition products according to the invention to solids their dispersion in the organic medium.

The invention therefore also relates to the use the addition compounds according to the invention and their Salts as dispersants for solids. Is preferred the use of the addition compounds according to the invention as dispersants for solids, especially pigments, in organic media.  

For example, white pigments are suitable as inorganic pigments. and colored pigments, such as. B. titanium dioxide, titanium oxides, Zinc oxides, zinc sulfides, cadmium sulfides, cadmium selenides, Iron oxides, chromium oxides, chromate pigments, as pigments suitable mixed oxides from the elements aluminum, antimony, Chromium, iron, cobalt, copper, nickel, titanium and zinc as well Waste pigments and especially carbon blacks.

Suitable organic pigments include, for example name: azo pigments, azamethines, azaporphines, quinacridones, Flavanthrone, anthanthrone and pyranthrone bodies, derivatives the naphthalene tetracarboxylic acid, the Perylenetetracarboxylic acid, thioindigo, dioxazine and of tetrachlorisoindolinone, lacquered pigments, such as salts of acid group-containing dyes with the elements Magnesium, calcium, strontium, barium, aluminum, manganese, Cobalt and nickel, as well as pigment mixtures of pigments mentioned above.

There are several possibilities for the invention Addition compounds on the solid surface to apply. This process can take place during or after the Synthesis of pigments, in a finishing process or in the further processing of the pigment in the application medium respectively. The application of the is particularly preferred Aids during pigment synthesis or in conjunction with a finishing process.

Depending on the design, the application of the invention Addition compounds, in the following text briefly dispersants called, on the pigments in aqueous suspension, in Water-solvent mixtures and in solvents or the dispersant can be in powder form with the Pigment powder to be mixed.

To produce the powder mixtures, for example first the solvent of the dispersant is distilled off,  the remaining active substance is ground with deep freezing and then the pigment and dispersant are mixed well. Isolation of the active substance of the dispersant can also done by other drying methods.

To achieve optimal rheological and coloristic Properties, the pigments are preferred with 0.3 to 10 mg / m² pigment surface, in particular 0.6 to 5 mg / m² Pigment surface, the dispersants of the invention coated or mixed. The coating of the pigments in suspension at temperatures from 20 ° C to Finish temperature of the corresponding pigments, preferably at 50 to 150 ° C, within 1 to 6 hours in the 5 times to 15 times the amount of liquid carried out. When applying the active substance of the dispersant to the Surface of the pigment in aqueous suspension can be advantageous if the dispersant solvent at least is partially water-soluble. After winding up the The pigment can be dispersed on the pigment surface be isolated directly.

In a further preferred embodiment, the Dispersant solvents, e.g. B. isobutanol, toluene, xylene or Chlorobenzene is distilled off with steam at the end and that Pigment isolated from the aqueous suspension.

Furthermore, the dipergator can be applied in an aqueous saline solution can be transferred. This overpass can be done in a very simple way if the dispersant in a readily volatile with water vapor Solvent is present. The dispersant solution is included at least the equivalent amount of an acid, e.g. B. lower carboxylic acids such as formic acid, acetic acid or Propionic acid. Then the solvent with Steam distilled off, possibly with simultaneous Adding water. The aqueous solution of Dispersant salt is added to the pigment suspension and  mixed up for some time. Then add basic compounds, e.g. B. caustic soda, the basic Dispersant released and after a subsequent stirring time Pigment isolated.

In a further process variant, the Dispersant solution with at least the equivalent amount an acid such as B. added lower carboxylic acids and Coating of the pigments is carried out with this solution. The pigment can then be released directly or after the basic dispersant as described above, preferably after removing the dispersant solvent the aqueous pigment suspension z. B. by Steam distillation can be isolated. The coating of the pigments is also advantageous in Water / solvent mixtures or solvents such as z. B. with the pigment finish. It is advantageous if the dispersant solvent and the solvent of the pigment suspension are the same, so not another after removing the solvents additional fractionation of the solvents carried out must become.

If the dispersant is not in the appropriate solvent available, it makes sense to determine the active substance of the Dispersers in an applicable one, for each Pigment-solvent system to convert suitable form, d. H. isolate the active substance and in one for the Dissolve the appropriate solvent. The use of lower organic carboxylic acids than Solvents are particularly recommended because they are used Addition compounds have a weakly basic character. In In these cases, it can be useful after preparation neutralize the organic acid or the Make the pigment suspension weakly alkaline.  

It can also be advantageous to use the inventive Use dispersants in combination with surfactants. As Surfactants are anionic, cationic and non-ionic products such as B. alkyl sulfates, Alkyl sulfonates, alkyl phosphates, alkyl benzene sulfonates, in particular lauryl sulfate, stearyl sulfate, dodecyl sulfonates, Octadecylphosphates, dodecylbenzenesulfonates and Sulfosuccinic acid esters, condensation products Fatty acid and taurine or hydroxyethanesulfonic acid, Resin soaps, alkoxylation products of alkylphenols, Fatty alcohols, fatty amines, fatty acids and fatty acid amides, in particular reaction products from nonylphenol, Dodecylphenol, lauryl alcohol, coconut fatty alcohol, Stearyl alcohol, oleyl alcohol, coconut fatty amine, tallow fatty amine, Stearylamine, oleylamine, coconut fatty acid, stearic acid or oleic acid with 2-100 mol, preferably 5-30 mol Ethylene oxide, reaction products from ethoxylated Alkylphenols and fatty alcohols with chlorosulfonic acid and Phosphorus oxychlorides. Come on cationic surfactants quaternary ammonium salts such as B. Hexadecyl trimethyl ammonium chloride.

The surfactants mentioned can be used alone or as a mixture be used. These surfactants can be added before, during or done after the finish, but it is not necessary Surfactant and dispersant in the same stage of Add pigment formation.

The powder pigments prepared according to the invention show in all paint systems, but especially in the usual ones systems that are difficult to pigment, such as TSA-NAD (abbreviation for "thermosetting acrylic - non aqueous dispersion") and "high solids "impeccable rheological properties, for example excellent values in gloss, flowability and flocculation stability while being positive Influencing the coloristic properties, such as B.  Transparency in full tone paintwork and purity of the Hues.

For the suitability test the following are Examples of addition products described either Pigments applied or they are used to disperse Solids, especially pigments, in organic Liquids or used in paint systems. As Varnish systems have emerged from the multitude of known systems an alkyd melamine resin paint (AM) based on a medium-oil, non-drying alkyd resin synthetic fatty acids and phthalic anhydride and one butanol etherified melamine resin and a Acrylic stoving enamel based on a non-aqueous Dispersion (TSA-NAD) selected. On those with these paints stoving paints were created application properties, especially the gloss, checked. The gloss measurement was carried out on foil infusions under an angle of 20 ° according to DIN 67 530 (ASTM D 523) with the "multigloss" gloss meter from Byk. Besides, could after dispersion in the dispersing lacquer, the viscosity of the Systems can be assessed with a viscous spatula. In almost all cases resulted in the use of the invention Addition compounds to a significant reduction in the Viscosity of the pigmented paints. The Viscosity measurements of the additive solutions were carried out with the Rotational viscometer RV 3 made by Haake, Viscosity data refer to a Shear rate of 292.5 per second at 20 ° C. The following examples illustrate the production and the application of the invention Addition connections. Parts mean parts by weight, provided nothing else is specified.

Production Example 1

13.5 parts of octadecylamine, 4.9 parts of furfurylamine and 95 parts of diethylene glycol dimethyl ether were combined in a stirred vessel and heated to 60.degree. At this temperature, 22.5 parts of a polyepoxide corresponding to the idealized structure in formula (I) [R = 2-methyl, n = 5, epoxy equivalent 225, Araldit®ECN 1273 from Ciba-Geigy AG] were dissolved in the solution at this temperature 50 parts of diethylene glycol dimethyl ether, added rapidly and the reaction mixture was stirred at 90 ° C. for 5 hours. The solution obtained was light yellow in color, clear, with a viscosity η = 25 mPa · s and a solids content of 22%.

Preparation example 1a

In Production Example 1, 8.1 parts are used. Octadecylamine and 6.9 parts furfurylamine, so you get one Product with slightly improved application technology Properties.

Production Example 2

10.2 parts of dodecylamine, 4.2 parts of 1-phenylethylamine and 50.7 parts of a mixture consisting of 43.5 parts of n-butyl acetate and 7.2 parts of methylglycol acetate were combined in a stirred vessel and brought to 100.degree warmed. 22.5 parts of the polyepoxide from Preparation Example 1, dissolved in 60 parts of xylene, were added to the solution at this temperature and the reaction mixture was stirred at 120 ° C. for 6 hours. The solution obtained was slightly yellowish in color, clear, with a viscosity η = 0.12 mPa · s and a solids content of 25%.

Production Example 3

14.1 parts of oleylamine (composition: 83% C ₁₈ , 12% C ₁₆ , 4% C ₁₄ , 1% C ₁₂ , iodine value 78 ± 5), 6.3 parts of 1- (3-aminopropyl ) -imidazole, 0.7 parts of salicylic acid and 125.6 parts of ethylene glycol monoethyl ether combined and heated to 70 ° C. At this temperature, 23.5 parts of a polyepoxide corresponding to the idealized structure in formula (I) [R = 2-methyl, n = 6, epoxy equivalent 235, Araldit®ECN 1299 from Ciba-Geigy AG] were dissolved in the solution at this temperature 50 parts ethylene glycol monoethyl ether, added rapidly and the reaction mixture stirred at 85 ° C. for 4 hours. The solution obtained was light yellow in color, clear, with a viscosity η = 17 mPa · s and a solids content of 20%.

Production example 3a

If 22.5 parts of the polyepoxide from preparation example 1 are used in preparation example 3, a product is obtained with equally good application properties (viscosity of the solution η = 14 mPa · s).

Production Example 4

12.6 parts of laurylpropylenediamine (composition of the lauryl radical: 3% C ₁₆ , 23% C ₁₄ , 73% C ₁₂ , 1% C ₁₀ , iodine number <3), 6.5 parts 2- (4- Morpholinyl) ethylamine, 0.7 parts phenol and 100 parts methoxypropanol combined and heated to 80 ° C. 22.5 parts of the polyepoxide from Preparation Example 1, dissolved in 56.5 parts of methoxypropanol, were added to the solution at this temperature and the reaction mixture was stirred at 90 ° C. for 5 hours. The solution obtained was light yellow in color, clear, with a viscosity η = 21 mPa · s and a solids content of 21%.

Preparation example 4a

In preparation example 4, 20.1 parts are used. Laurylpropylenediamine and 2.6 parts 2- (4-morpholinyl) ethylamine, so you get a product with similar ones application properties.  

Production Example 5

19.1 parts of tallow fat propylene diamine (composition of the tallow fat residue: 65% C ₁₈ , 30% C ₁₆ , 5% C ₁₄ , iodine number 36 ± 5), 4.0 parts 2- (1-pyrrolidyl) ethylamine were placed in a stirred vessel and 122.4 parts ethylene glycol monoethyl ether combined and heated to 50 ° C. 22.5 parts of the polyepoxide from Preparation Example 1, dissolved in 60 parts of ethylene glycol monoethyl ether, were added to the solution at this temperature and the reaction mixture was stirred at 80 ° C. for 4 hours. The solution obtained was light yellow in color, clear, with a viscosity η = 15 mPa · s and a solids content of 20%.

Preparation example 5a

Replacing 2- (1-pyrrolidyl) ethylamine with 4.3 parts of 4- (2-aminoethyl) pyridine in Preparation Example 5 gives a product with comparable dispersing properties (viscosity of the solution η = 28 mPa · s).

Production example 5b

Replacing 2- (1-pyrrolidyl) ethylamine in Preparation Example 5 with 4.3 parts of 1- (2-aminoethyl) piperazine gives a product with similar application properties (viscosity of the solution η = 23 mPa · s) .

Preparation example 5c

Replacing 2- (1-pyrrolidyl) ethylamine in Preparation Example 5 with 5.0 parts of 4- (3-aminopropyl) morpholine gives a product with an equally good dispersing action (viscosity of the solution η = 14 mPa · s).

Production Example 6

19.1 parts of tallow fat propylene diamine, 4.4 parts of 1- (3-aminopropyl) imidazole, 0.7 parts of phenol and 47.3 parts of xylene were combined in a stirred vessel and heated to 80.degree. 22.5 parts of the polyepoxide from Preparation Example 1, dissolved in 60 parts of xylene, were rapidly added to the solution at this temperature and the reaction mixture was stirred at 100 ° C. for 4 hours. The solution obtained was amber-colored, clear, with a viscosity η = 0.41 mPa · s and a solids content of 30%.

Preparation example 6a

Replacing xylene in production example 6 with ethylene glycol monoethyl ether and allowing it to react at 80 ° C. gives a product with comparable dispersing properties (viscosity of the solution η = 0.37 mPa · s).

Preparation example 6b

Replacing 6 xylene with isobutanol in preparation examples and carrying out all the reaction steps at 105 ° C. gives a product with an equally good dispersing action (viscosity of the solution η = 0.26 mPa · s).

Preparation example 6c

If one uses 18 parts in production example 6 Polyepoxide according to the idealized structure in Formula (I) with R = H and an epoxy equivalent of 180 (Grilonit ESN 138 from EMS-Chemie), you get one Product with slightly poorer application technology Properties.  

Production Example 7

7.6 parts of N, N-bis (aminopropyl) tallow fatty amine, 8.5 parts of oleylamine, 5.5 parts of 4-methoxybenzylamine and 80 parts of pentanol were combined in a stirred vessel and heated to 100.degree. At this temperature, 18 parts of the polyepoxide from preparation example 6c, dissolved in 57.2 parts of pentanol, were added to the solution and the reaction mixture was stirred at 110 ° C. for 5 hours. The solution obtained was light yellow in color, clear, with a viscosity η = 79 mPa · s and a solids content of 22.4%.

Production Example 8

13.1 parts of stearylamine (composition: 65% C ₁₈ , 30% C ₁₆ , 5% C ₁₄ , iodine number <4), 3.2 parts of 2- (1-piperidyl) ethylamine, 2.8 Parts 2-aminomethylthiophene and 50.4 parts diethylene glycol dimethyl ether combined and heated to 70 ° C. At this temperature, 23 parts of a polyepoxide corresponding to the idealized structure in formula (I) [R = 2-methyl, n = 4.1, epoxy equivalent 230, Araldit®ECN 1280 from Ciba-Geigy AG] were dissolved in the solution at 60 parts methoxypropanol, added and the reaction mixture stirred at 95 ° C for 4 hours. The solution obtained was amber-colored, clear, with a viscosity η = 0.12 mPa · s and a solids content of 27.6%.

Production Example 9

500 parts of the 30% pure obtained according to Preparation Example 6b Dispersant solution in isobutanol are stirred with 1000 parts of isobutanol and 200 parts of formic acid added and stirred at 50 ° C for 30 minutes. Then 1000  Parts of water are added and the isobutanol is azeotropic distilled off. The aqueous phase of the condensed Azeotropes is returned to the distillation sump. After the distillation has ended, 190-200 parts of a weakly acidic acid approx. 8% solution of the acidic acid Salt of the dispersant obtained.

Production Example 10

The procedure is as in Production Example 9, but is replaced formic acid by acetic acid, you get about 200 Share approx. 8% solution of the corresponding acetic acid Salt of the dispersant.

Production Example 11

200 parts of the 20% pure obtained according to preparation example 5b Dispersant solution in ethylene glycol monoethyl ether are evaporated in vacuo. The remaining one resinous residue is frozen with z. B. by Grind the addition of solid CO₂. You get a white one fine powder.

Production Example 12

200 parts of a 21% dispersant solution in Methoxypropanol obtained according to Preparation Example 4, are stirred with 50 parts of water and 275 parts Propionic acid added. Then it is stirred under vacuum 20-30 torr a mixture of methoxypropanol, water and Distilled off propionic acid. The result is an approx. 20% Solution of the dispersant in propionic acid.

Production Example 13

200 parts of a 20% dispersant solution in Ethylene glycol monoethyl ether, obtained according to  Production example 5c, are dried in vacuo evaporated. The resulting resinous residue is in So much propionic acid dissolved that a 20% solution of Dispersant is obtained.

Production Example 14

200 parts of a 30% dispersant solution in isobutanol, obtained according to preparation example 6c, are in vacuo evaporated to dryness. The resulting resinous Residue is added to a laboratory mill with the addition of Grind dry ice into a fine powder.

Production Example 15

100 parts of the 21% obtained according to Preparation Example 4 Dispersant solution with 4.1 parts of glacial acetic acid added, stirred for 10 minutes at 60 ° C and then under Vacuum distilled off the solvent. Then at 60 ° C a 15.7% aqueous solution of the dispersant produced.

Production Example 16

100 parts of the 20% obtained according to Preparation Example 5 Dispersing solution are mixed with 30 parts C. I. Pigment Yellow 154 mixed and the solvent under Vacuum distilled off. The residue obtained is on a laboratory mill to a fine powder with 40% Active ingredient ground.

Application example 1

In 100 parts of AM or TSA-NAD lacquer, 10 parts of C.I. Pigment Yellow 154 (specific surface according to BET 24 m² / g)  with the addition of the solution of the addition product Preparation example 1-8 (1.5 parts. 100% Addition product) dispersed, created with it Branded paintwork and measured the gloss.

Example of use 2

In 100 parts of AM or TSA-NAD lacquer, 4 parts of C.I. Pigment Red 122 (specific surface according to BET 62 m² / g) below Add the solution of the addition product Production example 1-8 (0.4 parts 100% Addition example) dispersed, created with it Branded paintwork and measured the gloss.

Example of use 3

In 100 parts of AM or TSA-NAD lacquer, 7 parts of C.I. Pigment Violet 19 (specific surface according to BET 34 m² / g) with the addition of the solution of the addition product Preparation example 1-8 (0.7 parts 100% Addition product) dispersed, created with it Branded paintwork and measured the gloss.

Example of use 4

1000 parts of an aqueous pigment suspension (pigment content 6%) of the opaque γ crystal modification of CI Pigment Violet 19, CI no. 73 900 are mixed at 50 ° C. with 16.4 parts of the 22% strength dispersant solution obtained according to Preparation Example 1, diluted with 24 parts of isobutanol, at boiling temperature over the course of one hour. After stirring for 3 hours, the isobutanol is distilled off with steam, the pigment is filtered off, washed with water and dried. 62.5 parts of a bluish-red pigment powder are obtained. For comparison, a pigment was produced under otherwise identical conditions but without the addition of a dispersant. The comparative color is clearly matt with a milky haze in full-tone lacquers.

The gloss measurement on foil infusions (AM varnish) delivers following values:

Pigment according to application example 4:80 Comparative example: 29

Application example 5

To 1000 parts of an aqueous pigment suspension of the opaque γ crystal modification of Pigment Violet 19, CI no. 73 900 48 parts of the dispersant solution obtained according to Preparation Example 9 are added dropwise with stirring at 60-65 ° C in one hour. After stirring for 2 hours at 60-65 ° C., the pH is adjusted to 9-9.5 in 10 minutes with 10% sodium hydroxide solution, then the mixture is stirred for a further 2 hours, the pigment is separated off by filtration and washed with water and dried at 80-100 ° C. A gloss value of 81 is obtained in the AM lacquer.

Example of use 6

If one proceeds as described in application example 4, sets but 1000 parts of an aqueous isobutanolic Pigment suspension (pigment content 6%, isobutanol content 35-40%) with otherwise the same working method, you get a bluish red with a yield of over 98% Pigment, which results in a highly opaque, fog-free Full tone painting in the TSA-NAD paint system with excellent Luster and excellent viscosity of the paint leads. At the gloss measurement of the film infusion was 85 determined.

Application example 7

200 parts of a weakly alkaline aqueous isobutanolic Pigment suspension (isobutanol content 60%; 0.5% NaOH) with a pigment content of 8% C.I. Pigment Red 122, C.I. 73 915 are heated to 75 ° C and with stirring by adding from 50% propionic acid to a pH of 6.5-7 posed. Then 9 parts of the after Production example 12 obtained about 20% Dispersant solution slowly added and 2 hours at 70-75 ° C. stirred. After that, at this temperature inside 45 minutes with 20% sodium hydroxide solution to pH 9.5 and Stirred for 2 hours at 70-75 ° C. Then the pigment filtered off, washed with water and dried. It will 19 parts of a magenta pigment with excellent maintain rheological and coloristic properties.

When measuring the gloss of the full-tone film infusion (AM lacquer) the following values were obtained:

Pigment according to application example 7:88 Comparative example unprepared: 23  

Application example 8

500 parts of a 7% aqueous suspension of the β- crystal modification of CI Pigment Violet 19, CI no. 73 900 are slowly added at 70 ° C. with 44 parts of the dispersant solution obtained according to Preparation Example 10. The mixture is then stirred at 70 ° C. for 5 hours, then adjusted to pH 9-9.5 within 45 minutes with aqueous sodium hydroxide solution, stirred at 70 ° C. for 1 hour, the pigment is isolated and dried at 80 ° C. The red-violet pigment obtained with a yield of over 98% is characterized by excellent rheological and coloristic properties. The gloss measurement as a measure of flocculation of the red-violet, haze-free full-tone coating on film (AM coating) gave a gloss value of 87 compared to the unprepared comparison, in which a value of 73 was measured.

Application example 9

To 200 parts of a 5% suspension of CI pigment Violet 19, CI no. 73 900 - pH 7-7.5 - of the β- crystal modification, which still contains 7.5% ethyl alcohol and 14% sodium chloride, 5 parts of the dispersant solution obtained according to Preparation Example 13 are added in 30 minutes and a further 10 parts of ethyl alcohol at 40 ° C added. The mixture is then stirred at 40-45 ° C. for 8 hours, then adjusted to pH 9.5 with dilute NaOH and stirred at 40 ° C. for a further 5 hours. Then the pigment is isolated, washed salt-free and dried. An application example 8 comparable result is obtained.

Example of use 10

To 400 parts of an aqueous isobutanolic Quinacridone suspension [isobutanol content 50%, pigment content  8.8% of a quinacridone mixed crystal from 3 parts 2,9-dimethylquinacridone (C.I. Pigment Red 122, C.I. No. 73 915) and 1 part of unsubstituted quinacridone (C.I. Pigment Violet 19, C.I. 73 900) in the crystal lattice of the 2,9-dimethylquinacridone) are at 50 ° C in 30 minutes 14.1 parts of the 20% dispersant solution according to Production example 5b added and 10 parts of propionic acid and 20 parts of isobutanol were added.

The mixture is then stirred at 50 ° C for 2 hours, then in Adjusted to pH 9.5 with 16.5% sodium hydroxide solution for 1 hour, stirred for a further 2 hours, the isobutanol with steam distilled off, the pigment filtered off, washed free of salt and dried.

The pigment, a bright magenta, has good rheological properties and leads in both paint systems (AM and TSA-NAD) for brilliant paintwork.

Gloss value (AM lacquer): 90 Unprepared comparison: 50

Example of use 11

Are added to 400 parts of a pigment suspension (Isobutanol content 30%, pigment content 8% one Mixed crystal of 3 parts C.I. Pigment Red 122, C.I. 73 915 and 1 part of C.I. Pigment Violet 19, C.I. 73,900 in Crystal lattice of C.I. Pigment Red 122) at 70 ° C in 30-45 Minutes with stirring 15.9 parts of a dispersant, obtained according to preparation example 5a, stirring another 3 Hours at 70 ° C and distilled the solvent Steam from, so you get after isolation and drying a pigment obtained in Application Example 10 comparable product.

Gloss value: 86  

Example of use 12

If one proceeds as described in application example 11, replaces the dispersant used there 15.9 Parts of dispersant obtained according to Preparation Example 5c, a pigment is obtained with the same good yield with similarly good properties.

Gloss value (AM varnish): 100 Unprepared comparison: 45

Area of application 13

To 1000 parts of an isobutanolic pigment suspension of the opaque γ modification of CI Pigment Violet 19 (pigment content 8%, isobutanol content 30%), a solution of 24 parts of dispersant obtained in Preparation Example 3a and 48 parts of isobutanol is added dropwise at 50 ° C. in 45 minutes . After stirring for 3 hours at 50-60 ° C., the isobutanol is distilled off and the pigment is isolated by filtration. A bluish-red pigment with excellent rheological and coloristic properties is obtained.

Gloss value (AM lacquer): 88 Gloss value (AM lacquer)
unprepared comparison: 28

Example of use 14

500 parts of an aqueous suspension containing 7.5% C.I. Pigment Red 122, C.I. 73 915, 0.5% sodium hydroxide solution and 30% Contains isobutanol, are heated to 50 ° C and at this Temperature with a solution of 18.75 parts of one Dispersants obtained according to Preparation 3a, and 35 parts of isobutanol added and 3 hours at 50-70 ° C. touched. Then the isobutanol is distilled off Pigment isolated and dried. You get one Quinacridone magenta with excellent rheological Properties.

Gloss value (AM paint): 81  

Example of use 15

If one replaces the one in application example 14 used dispersant solution 17.86 parts after Preparation Example 4 obtained dispersant solution otherwise the same procedure, you get a pigment improved application properties.

Gloss value (AM paint): 102 Unprepared comparison: 28

Example of use 16

Becomes the dispersant used in Application Example 14 by 18.75 parts of that according to Preparation Example 3 The dispersant obtained is replaced, and the Preparation with otherwise the same method of working to have a rheologically perfect quinacridone magenta outstanding coloristic properties.

Gloss value: 82 Unprepared comparison: 28

Example of use 17

210 parts of moist raw quinacridone (20.95%) of the α modification of CI pigment Violet 19, CI no. 73,900 are suspended in 22.7 parts of 33% sodium hydroxide solution and 517 parts of water and stirred for 20 minutes. Then 13.2 parts of the dispersant obtained in Preparation Example 5 are slowly added dropwise. The mixture is heated to boiling and refluxed for 5 hours. It is then filtered and washed neutral. The neutral, aqueous, moist quinacridone is suspended in 240 parts of isobutanol, water is then added to a total of 500 parts and the mixture is stirred at 145-150 ° C. for 5 hours in a closed vessel. The solvent is then distilled off and the pigment is isolated. A highly opaque, rheologically perfect bluish-red pigment is obtained in the γ modification of the quinacridone.

Gloss value (AM varnish): 85 Unprepared comparison: 18

Example of use 18

10 parts 100% pigment Red 168, C.I. 59 300 and 1 Part of dispersant obtained according to Preparation Example 14 are mixed on a laboratory mill within 20 seconds. After incorporating the sample into an alkyd melamine resin varnish the film infusion provides a gloss value of 86. Die unprepared sample, on the other hand, only gives a gloss value of 41.

Example of use 19

650 parts of an aqueous isobutanolic pigment suspension (6.8% pigment content of C.I. Pigment Red 122, C.I. No. 73915; Isobutanol content 40%) are at 40 ° C in 20 minutes with a solution of 2.2 parts of nonylphenol polyglycol ether (HLB value 14) and 40 parts of isobutanol are added and 1 Hour stirred. Then 14.7 in 0.5 hours at 70 ° C. Parts of pigment dispersant from preparation example 6b, diluted with 30 parts of isobutanol, added and a further 2 Stirred at 70 ° C for hours. The isobutanol is through Steam distillation removed, the pigment isolated and dried.

Gloss value (AM lacquer): 91 Unprepared comparison: 28

Example of use 20

1000 parts of a pigment suspension - pigment content 7.5% a mixed crystal of 3 parts C.I. Pigment Red 122, C.I. 73915 and 2 parts C.I. Pigment Violet 19, C.I. 73 900 - with an isobutanol content of 50% with stirring  at 50 ° C with 3 parts of a lauryl ether sulfate of the formula

CH ₃ - (CH ₂ ) ₁₁ -O- (CH ₂ -CH ₂ -O-) _2-3 SO ₃ Na

in aqueous solution added and stirred for 45 minutes. Then 2.7 parts are 1% Hydrochloric acid slowly added and after 15 minutes in 30 Minutes 37.5 parts of pigment dispersant Preparation example 5c, diluted with 37.5 parts. Ethylene glycol monoethyl ether, added dropwise. Then will Stirred for 4 hours at 50 ° C, the solvent with steam distilled off, the pigment isolated and dried.

Gloss value (AM paint): 93 Unprepared comparison: 57

Example of use 21

100 parts Indanthrene Bordo RR (C.I. Vat Red 15, C.I. No. 71 100) of 98-99% purity - obtained by precipitation from Indanthren-Bordo RR from alkaline aqueous solution by adding hydrochloric acid and subsequent isolation, Washing, drying and grinding the product - are in 1560 parts. Chlorobenzene stirred in. Then you give 4 parts. 33% NaOH and stir for 1 hour at 20-30 ° C. Subsequently slowly warmed to boiling and heated for 2 hours Reflux. After cooling to 75 ° C, 33.3 parts are set. Pigment dispersant from preparation example 6b to and stir for 1 hour at 70-80 ° C. After adding water, it will Chlorobenzene is distilled off with steam, the pigment filtered off, washed neutral and dried at 60 ° C. Man receives a yellowish red pigment with flawless application properties.

Gloss value (AM varnish): 80 Unprepared comparison: 30

Example of use 22

In 100 parts of AM lacquer, 10 parts of CI Pigment Red 170 in its opaque γ modification (specific surface area according to BET: 22 m 2 / g) with the addition of the solution of the addition product from preparation example 6 (0.5 part of 100% addition product) ) dispersed and measured a gloss value of 88 on the paint thus created. If the solution of the addition product from preparation example 6 is replaced by solvent, a coating with a gloss value of 59 is obtained.

Example of use 23

200 parts of a 26.7% aqueous press cake of C. I pigment Orange 36, C.I. 11 780 are in a mixture from 270 parts of water, 180 parts of isobutanol and 20 parts the 30% obtained according to preparation example 6b Dispersant solution stirred. The suspension will then in an autoclave with stirring to 140 ° C. heated and held at this temperature for 2 hours. To cooling to room temperature is added to the mixture Steam introduced and the isobutanol azeotropic distilled off. Then the pigment is removed from the remaining aqueous suspension isolated, dried and ground.

Gloss value (AM paint): 81 Unprepared comparison: 52

Example of use 24

10 parts of C.I. Pigment Brown 25 (specific BET surface area: 80 m² / g) with the addition of the solution of the addition product from preparation example 6a (1 part 100% addition product) dispersed and with it created paint measured a gloss value of 80. Becomes the solution of the addition product from manufacturing example 6a is replaced by solvent, painting with the Get gloss value 47.  

Example of use 25

200 parts of a 29.3% aqueous press cake from C.I. Pigment Red 188, C.I. 12 467 are in 500 parts of water stirred and the pigment suspension obtained 270 parts Chlorobenzene added, after which 10 parts of the Production example 6b obtained 30% Dispersant solution are added. With stirring, the Suspension heated to 90 ° C and 2 hours at this Temperature maintained. Then the solvent is passed through Introducing steam distilled off and the pigment the aqueous suspension isolated, dried at 60-70 ° C. and ground.

Gloss value (AM paint): 83 Unprepared comparison: 44

Example of use 26

100 parts of a 5% aqueous pigment suspension of C.I. Pigment Yellow 154 are made at room temperature within 3 minutes with 4.8 parts of that according to Preparation Example 15 dispersant solution obtained with stirring, then is adjusted to pH 4 with glacial acetic acid and 30 minutes stirred. It is then heated to 60 ° C, with 6% Sodium hydroxide solution adjusted to pH 9.5 and at 90 minutes stirred this temperature. Then that will The pigment is filtered off hot, washed and dried.

Gloss value (AM varnish): 80 Unprepared comparison: 47

Example of use 27

10 parts of C.I. Pigment Yellow 154 and 2.5 parts of dispersant, obtained according to Preparation Example 16, are within mixed from 3 hours on a rolling bench. The foil infusion the sample (AM varnish) gives a gloss value of 81, whereas the unprepared comparison sample only had a value of 19 results.

Claims (18)

1. addition compound and its salts, obtainable by reacting a polyepoxide or more polyepoxides with amines and optionally subsequent salt formation with an acid, characterized in that the addition compound is obtainable in a process in which one polyepoxide or more polyepoxides of the general formula (I) in which n is a number from 2 to 10, pure hydrogen atom or an alkyl group and Xden 2,3-epoxypropylene radical, with an amine or more amines of the general formula (II) (H₂N-R²-) _p N (H) _{2- p} -R¹ (II) in which p is an integer from 0 to 2, R¹ is a saturated or unsaturated aliphatic alkyl radical having 8 to 24 carbon atoms and R² is an alkylene group, and also with an amine or more amines of the general formula (III) and / or the general Formula (IV) H₂N-R³-R⁶ (III) H₂N-R⁴-NR⁵- (R³) _p -R⁶ (IV) in which p is 0 or 1, R³ and R⁴ independently of one another each for an alkylene group, R⁵ for -H or an alkyl group and R⁶ for a saturated or unsaturated, mono- or polynuclear heterocyclic or carbocyclic ring system, which is replaced by one or more of the radicals R⁷, halogen such as -F, -Cl and -Br, -OR⁷, -NR⁷R⁸, -COOR⁷, -CONR⁷R⁸, -NR⁷ -CO-R⁸, -CN, -CF₃ or NO₂, in which R⁷ and R⁸ independently represent the radical -H or alkyl, are in such a ratio be set that 1 to 99% of the epoxy groups of the polyepoxide of the formula (I) with the amine or the amines of the formula (II) and 99% to 1% of the epoxy groups with the amine or the amines of the formula (III) and / or of the formula (IV), and if appropriate the product obtained is reacted with an acid. 2. addition compound and its salts according to claim 1, characterized in that the polyepoxide of the formula (I) an epoxy equivalent weight of 150 to 300 g per Mol has epoxy groups. 3. addition compound and its salts according to claim 1 or 2, characterized in that R in formula (I) -H or Is C₁-C₄ alkyl.   4. addition compound and its salts according to one of the Claims 1 to 3, characterized in that the Amines of the formula (II) fatty amines with 12 to 20 carbon atoms are. 5. Addition compound and its salts according to one of the Claims 1 to 3, characterized in that the Amines of the formula (II) N- (aminopropyl) fatty amines and / or N, N-bis (aminopropyl) fatty amines. 6. addition compound and its salts according to one of claims 1 to 5, characterized in that in the amine of the formula (III) and / or the formula (IV) R³ for C ₁ -C ₁₀ alkylene, R⁴ for C₂-C₆- Alkylene and R⁵, R⁷ and R⁸ independently represent -H or C₁-C₄-alkyl. 7. Addition compound and its salts according to one of the Claims 1 to 6, characterized in that in the Amine of the formula (III) or of the formula (IV) R⁶ for mononuclear or multinuclear carbocyclic aromatic ring system that may continue is substituted. 8. Addition compound and its salts according to one of the Claims 1 to 6, characterized in that in the amine of the formula (III) or of the formula (IV) R⁶ for an optionally substituted heterocyclic ring system, which is a heterocyclic Ring with 5 to 6 ring atoms contains, on the one or several benzene cores can be fused. 9. Addition compound and its salts according to one of the Claims 1 to 8, characterized in that 10 to 90% of the epoxy groups of the polyepoxide of the formula (I)  with the amine or the amines of the general formula (II) and 90 to 10% of the epoxy groups with the amine and the Amines of the general formula (III) and / or general formula (IV) are implemented. 10. A process for the preparation of an addition compound by reacting a polyepoxide or more polyepoxides with amines and optionally subsequent salt formation with an acid, characterized in that one polyepoxide or more polyepoxides of the idealized general formula (I) in which n is a number from 2 to 10, pure hydrogen atom or an alkyl group and Xden 2,3-epoxypropyl radical, with an amine or more amines of the general formula (II) (H ₂ N-R²-) _p N (H) _{2 - p} -R 1 (II) in which p is an integer from 0 to 2, R 1 is a saturated or unsaturated aliphatic alkyl radical having 8 to 24 carbon atoms and R 2 is an alkylene group, and also an amine or more amines of the general formula (III) and / or the general formula (IV) H₂N-R³-R⁶ (III) H ₂ N-R⁴-NR⁵- (R ₃ ) _p -R⁶ (IV) in which p is 0 or 1, R³ and R⁴ independently of one another each for an alkylene group , R⁵ for -H or an alkyl group and R⁶ for a saturated or unsaturated, mono- or polynuclear heterocyclic or carbocyclic ring system, which by one or more of the radicals R⁷, halogen such as -F, -Cl and -Br, -OR⁷, -NR⁷R⁸, - COOR⁷, -CONR⁷R⁸, -NR⁷-CO-R⁸, -CN, -CF₃ or NO₂, in which R⁷ and R⁸ independently represent the radical -H or alkyl, are in such proportions is implemented that 1 to 99% of the epoxy groups of the polyepoxide of the formula (I) with the amine or the amines of the formula (II) and 99% to 1% of the epoxy groups with the amine or the amines of the formula (III) and / or of the formula (IV), and if appropriate the product obtained is reacted with an acid. 11. The method according to claim 10, characterized in that the reaction of the amines with the polyepoxide at 0 to 180 ° C is carried out. 12. The method according to claim 11, characterized in that the reaction is carried out at 40 to 120 ° C. 13. The method according to any one of claims 10 to 12, characterized characterized in that the mixture of amines of the formulas (II) and (III) and / or (IV) in one largely inert solvent is submitted and then the polyepoxide of formula (I) is added.   14. The method according to any one of claims 10 to 13, characterized characterized in that the ratio in the implementation the number of epoxy groups to the total number of Amine molecules of formulas (II) to (IV) 1: 0.8 to Is 1: 1. 15. Use of one of claims 1 to 9 defined addition compound or one of its salts as a dispersant for solids. 16. Use according to claim 15 as a dispersant for pigments in organic media. 17. Use according to claim 16, characterized in that that a pigment with that according to any one of claims 1 to 9 defined addition compound, respectively one of their salts, coated and the coated Subsequent pigment in an organic medium is dispersed. 18. Use according to claim 17, characterized in that that defined according to one of claims 1 to 9 Addition compound, or one of its salts, when dispersing a pigment the organic medium is added or contained in the organic medium is.