SI9200176A - Process for the production of cationic adhesives for lacquer - Google Patents

Abstract

The invention relates to a process for preparation cationic binders for self-crosslinking varnishes and are water-soluble, based on protonation modified aminoalkylated products of phenol, as also prepared binders after this process and use them to formulate water-soluble varnishes, especially the electrocotting varnishes that are secreted cathodic. The process is characterized in that at an aminoalkylated product of phenol containing at least one secondary amine group, acts with epoxy compounds, and the reaction product is by temperature reacts with partially blocked isocyanate compounds. The process allows the use of funds for blocking permitting oven drying temperatures from 130 to 150 degrees Celsius.

Description

PROCEDURE FOR OBTAINING KATIONSKI LINKS

The invention relates to a process for the production of cationic binders for self-crosslinking lacquers which are water-soluble after protonation, based on modified aminoalkylated phenol products used for the production of water-soluble lacquers, especially for cathode-solubilized varnishes.

EP-Bl-209 857 discloses a process for producing cationic binders for self-crosslinking lacquers that are water-soluble after protonation.

EP-Bl-0 209 8557 discloses a process for obtaining, after protonation, of water-soluble cationic binders for self-crosslinking lacquers, which are obtained by acting on a semi-blocked diisocyanate on an aminoalkylated product of phenol containing secondary amino groups and then by reaction of phenolic hydroxyl groups with epoxy compounds. The products described are used to produce varnishes whose films have exceptional anticorrosive properties after oven drying, as required e.g. in the automotive industry.

However, the process reported in this literature does not allow any use of blocking agents for isocyanate groups with a cleavage temperature below 140 ° C on the basis of the reaction. Temperatures required for treating epoxy compounds with phenolic hydroxyl groups of at least 95 ° C, when using such blocking agent, lead to unmanageable reactions that can cause gelling of the mixture. Binder-based varnishes according to EP-Bl-0 209 857 therefore require oven-drying temperatures above 150 ° C, and especially above 160 ° C, to achieve the desired film properties.

In addition, this process produces relatively high viscous products, which, on the one hand, necessitates the use of larger quantities of organic auxiliary solvents on the one hand, and on the other hand makes it difficult to extract thicker coatings in the electrocoating process.

It is now apparent that the disadvantages of the products obtained by EP-B1-0 209 857 can be remedied by a change in the process without compromising the favorable overall picture of the properties. The invention therefore relates to a process for the production of cationic binders for self-crosslinking lacquers which, after protonation, are water-soluble, based on modified aminoalkylated products of phenol, characterized in that (1) an aminoalkylated product containing at least one NH group according to molecules, from 1 mole of monoalkylphenol and / or monoarylphenol and / or monoarylalkylphenol with one phenolic hydroxyl group or optionally with two phenolic hydroxyl groups, from 1 to 2 moles of primary alkylamine and / or primary alkanolamine and / or primary-tertiary alkyldiamine buy equimolar amounts of formaldehyde, treat (2) with an amount of aliphatic and / or aromatic diepoxide compound equivalent to the secondary amine groups present, and optionally a mono-epoxy compound, (3) react then or simultaneously 50 to 100% % by weight, primarily 95 to 100% by weight of phenolic hydroxyl groups with mainly aliphatic mono (4) after complete conversion of the epoxy groups, leave the mixture at a temperature of 100 to 130 ° C, first of all 115 to 125 ° C, until a minimum viscosity is reached and secondary hydroxyl groups of the product react at the end (5) reactions in whole or in part with semi-blocked diisocyanates and / or polyisocyanate compounds with one free NCO group.

The invention further relates to the products obtained by this process and their use, optionally in combination with additional cross-linking components and / or binder components containing hydroxyl groups, for the formulation of water-soluble varnishes, especially cathode-soluble varnishes .

The production of suitable aminoalkylated phenol products for the process according to the invention is carried out according to methods known in the literature, e.g. according to HOUBEN WEYL, Methoden der Organischen Chemie, Volume ΧΙ / 1 (1957).

Phenols are those substituted phenols, such as monoalkylphenols, whose alkyl radicals have at least 4 carbon atoms. The representatives of this group are or. p-butylphenols and their higher homologs. Arylphenols, such as e.g. phenylphenol or arylalkyl-phenols, such as e.g. Bisphenol A.

One to 2 moles of primary monoalkyl amine, such as butylamine or its isomers and homologs and / or primary alkanolamine, such as monoethanolamine or its homologues and / or primary tertiary alkyldiamine, such as diethylaminoethylamine or diethylaminopropylamine, and amounts of primers are used per one mole of phenol. amine groups equimolar amount of formaldehyde.

Aminoalkylation is carried out in such a way that the mixture with the constituents in the presence of a solvent that builds an azeotrope with water, such as toluene - taking into account any exotherm - is heated to the temperature required for the azeotropic removal of the reaction water.

After removal of the calculated amount of water, the reaction product thus obtained, containing on average at least one secondary amine group per molecule, is optionally diluted with an aprotic solvent and treated in the next reaction step with an amount of aliphatic and / or aromatic diepoxide compound equivalent to secondary amine groups. Part of the secondary amino groups above 1 equivalent may optionally also be reacted with mono-epoxide compounds.

Commercial epoxy resins are used as diepoxy compounds, e.g. based on Bisphenol A or polyol. Their epoxy equivalent weight is in particular from 180 to 1000.

Glycidyl esters of monocarboxylic acids are used as monoepoxide compounds, especially those so-called. KOCH-acids and glycidyl ether, such as 2-ethylhexylglycidyl ether.

The conversion is carried out at a temperature of 95 to 110 ° C to an epoxy value which is practically zero.

Then or simultaneously with this reaction, 50 to 100% by weight of the material, primarily 95 to 100% by weight of the phenolic hydroxyl groups with the predominantly aliphatic mono-epoxy compound are converted.

After complete conversion of the epoxy compounds, the mixture is heated to a temperature of 100 to 130 ° C and allowed to stand at this temperature until a minimum viscosity is reached. This phase of the process, which is essential to achieve a low and therefore particularly suitable viscosity of the final product, takes place mainly at a temperature of 115 to 125 ° C. This demonstrates that such a temperature leads to the decomposition of hydrogen bridges. Finally, the secondary hydroxyl groups of the reaction product react in part or in full with the semi-blocked diisocyanates and / or polyisocyanate compounds having one free NCO group.

Semi-blocked diisocyanates are obtained in a known manner using mainly diisocyanates with NCO groups with different reactivity, such as e.g. toluylenediisocyanate or isophorondiisocyanate. When using symmetric diisocyanates such as diphenylmethane diisocyanate, the free diisocyanate content should be kept as low as possible in order to minimize the undesirable increase in the molecule.

In particular, aliphatic or aromatic mono-alcohols are used as blocking agents which, under the conditions of oven drying, in the presence of conventional catalysts, are cleaved. Other blocking agents are e.g. phenols, oximes, amines, unsaturated alcohols, caprolactam, etc.

Based on the method of production by the process, lower blocking temperature agents such as butanonoxime or activated primary monoalcohols, e.g. diethylene glycol monobutyl ether or benzyl alcohol.

Suitable polyisocyanate compounds with one free NCO group are e.g. suitable polymers of diisocyanate and polyol or allophanates obtained by the intermolecular addition reactions of semi-blocked diisocyanates under basic catalysis conditions.

In the formulation of the mixture, care must be taken to ensure that the final products have the necessary basicity to achieve sufficient stability of the aqueous solution of the binder. This basicity, based mainly on tertiary amino groups and corresponding to an amine number of at least 30 mg KOH / g, can be achieved on the one hand by the use of primary-tertiary diamines in aminoalkylation and, on the other, by the addition of the corresponding amines as semi-blocking agents for diisocyanates .

In order to achieve water solubility, the alkaline groups of the reaction product are partially or completely neutralized by formic, acetic or lactic acid. In practice, a useful dilution is usually sufficient to neutralize 20 to 60% of the alkaline groups, corresponding to an amount of ca. 20 to 60 millimoles of acid per 100 g of solid resin. The binders are then diluted with deionized water to the desired concentration. In this case, prior to neutralization or dilution, respectively. in partially diluted state, they are transformed into pigmented lacquers with crosslinking catalysts, pigments, fillers and other additives. The formulation of such lacquers and their use in the process of electrotopic lacquering are known to those skilled in the art and described in the literature. The cured coatings are cured for 10 to 30 minutes at temperatures between 130 and 150 ° C.

To the extent that binders do not sufficiently exhibit self-cross-linking structures, additional cross-linking components, such as blocked isocyanates, amino and phenolic resins, or additional components containing hydroxyl groups such as epoxy resins may also be used. amine adducts.

Lacquers are also applied to other processes, such as e.g. by immersion, roller application or injection molding.

If necessary, binders are also processed in organic solvents.

A special form of the process described by the invention provides cathode-based lacquer binders, which can be used to formulate electro-solubility varnishes that, under normal process conditions, provide varnish films with higher layer strengths so that no substances with high boiling point.

This variant of the process is characterized in that (IA) is a product of aminoalkylation containing, on average, in the molecule 2 NH groups, of 1 mol of monoalkyl monophenol, 2 moles of primary alkyl amine and / or primary tertiary alkyl diamine and 2 moles of formaldehyde (2A) simultaneously or sequentially converted from 50% by weight of the monoepoxide compound (given given secondary amine groups) and aliphatic and / or aromatic diepoxide compounds, (3A) then reacts 95 to 100% by weight of the phenolic hydroxyl groups with, in particular, the aliphatic monoepoxide compound, (4A) after complete conversion of the epoxy groups, the mixture is allowed to stand at 100 to 130 ° C, especially at 115 to 125 ° C, until a minimum viscosity is reached, and (5A) the last secondary hydroxyl groups of the reaction product partially or fully react with semi-blocked diisocyanates and / or polyisocyanate compounds with one free NCO group.

Monoalkylphenols with an alkyl residue of at least 4 carbon atoms are used to obtain the aminoalkylation products (component IA).

In the first place, aliphatic monoepoxide compounds with a molar mass of at least 180 are used as mono-epoxy compounds, as the aforementioned glycidyl esters of monocarboxylic acids and glycidyl ether, and epoxy compounds as dodecenoxide, the epoxide group of which is directly on the aliphatic chain or ring.

For technical use, particularly favorable results are obtained if the products obtained by a specific process, even after protonation, are water-soluble to a limited extent. To improve the stability of the bath, such lacquer binders are combined with cationic adducts based on epoxy resins and amines, which can be diluted well with water after protonation. The proportion of these components ranges from 20 to 7 0 wt. %, respectively. even better between 3 0 and 6 0 wt. %, based on the binder solid in combinations i.

The following examples illustrate the invention without limiting its scope. All data in parts or. percentages refer to units of weight, unless otherwise stated. (EEW stands for epoxy equivalent mass)

Example 1: In a suitable reaction vessel, 94 parts of phenol (1 mol) and 64 parts of 2-ethyl hexylamine (0.5 mol), 65 parts of diethylaminopropylamine (0.5 mol) and 91 parts of toluene are heated to 75 ° C. Then, with gentle cooling of the mixture, 33 parts of 91% paraformaldehyde (1 mol) were added. Increase the temperature slowly until rapid azeotropic distillation occurs. After 21 parts of the reaction water were removed, the mixture was cooled to 75 ° C by the addition of 450 parts of toluene, and 475 parts of Bisphenol A-based diepoxide resin (EEW 475) were added portionwise over 30 to 60 minutes. The mixture was allowed to stand at 95 ° C until the epoxy value was reduced to zero. After the addition of 250 parts (1 mol) of the glycidyl ester of the saturated, tertiary monocarboxylic acid C9-C11 (CARDURA ^R E 10, SHELL) at a temperature of 95 to 110 ° C, the reaction is reactivated to an epoxy value of 0.

Increase the temperature to 120 ° C for 30 minutes and keep it at this temperature until after approx. Minimum viscosity is not reached for 1 to 2 hours (eg measured with a BROOKFIELD rotary viscometer). After cooling to 60 ° C, 1008 parts (3 moles) of toluylenediisocyanate semi-blocked with diethylene glycol monobutyl ether are continuously added, without exceeding 90 ° C. After the addition is complete, the mixture is stirred at 80 ° C for 30 minutes. The solids content is 83%.

of the parts (solids) of the final product of Example 1 were mixed with 30 parts (solids) of the epoxy amine adduct as an additional component of ZK I (yield described below) and stirred for 15 minutes at 80 ° C. The solvent is then vacuum removed until a solids content of 93 to 95% is reached. After neutralization with ca. 30 millimoles of formic acid per 100 g of solid resin was added with stirring, deionized water and diluted to ca. 45%. This gives a dispersion with a viscosity of 300 - 500 mPa.s.

Examples 2 to 8: In the same manner as in Example 1, other binders are obtained according to the data in Table 1. The following abbreviations are used in the table:

ΡΗΡΗ I Bisphenol A diepoxide resin (EEW ca. 475) ΕΡΗ II Bisphenol A diepoxide resin (EEW ca. 190) ΕΡΗ III polypropylene glycol-based diepoxide resin (EEW ca. 320) ME I tertiary C9-C11 monocarboxylic acid glycidyl ester (RARDURA ^R E 10; EEW ca. 250) ME II 2-ethylhexylmonoglycidyl ether (EEW 186) PH phenol NPH p-nonylphenol BPH p-tert. butylphenol BPHA Bisphenol A DEAPA diethylaminopropylamine EHA 2-ethylhexylamine MOLA monoethanolamine BDGL diethylene glycol monobutyl ether BA benzyl alcohol ΒΟΧ butanonexime TDI toluylenediisocyanate (normal commercial mixture of isomers, 80/20) DPMDI diphenylmethanediisocyanate HCOOH myavic acid

In the case of the compounds used, the isocyanate with one free NCO group:

IC I TDI / BDGL

IC II DPMDI / BDGL

IC III DPMDI / BA

IC IV TDI / ΒΟΧ

IC V DPMDI / BOX

IC VI allophanate obtained by the DPMDI reaction, semi-blocked 10 g with BDGL in basic catalysis (molar mass ca. 1236)

IC VII allophanate based on DPMDl / BA (molar mass ca. 1974)

Example 9; In a suitable reaction vessel, 220 parts of nonylphenol (1 mol) are heated with 258 parts of 2-ethylhexylamine (2 moles) and 200 parts of toluene to a temperature of 7 5 ° C. After this mixture, 66 parts of 91% paraformaldehyde (2 mol) were added under gentle cooling. The temperature is gradually increased until turbulent azeotropic distillation occurs. After the removal of 42 parts of the reaction water, the mixture was cooled to 75 ° C with addition of 500 parts of toluene and 250 parts of glycidyl ester of saturated, tertiary C9-C11 monocarboxylic acids (Cardura ^R E 10, SHELL; EEW ca. 250) were added in portions for 30-60 minutes. ). The mixture was allowed to stand at 80 to 90 ° C until an epoxy value of 0. was reached. After the addition of 475 parts of Bisphenol A based Epoxy Resin (EEW 475) at a temperature of 95 to 110 ° C, the reaction was reactivated to an epoxy value of 0. Then the following were added 186 parts of 2-ethylhexylmonoglycidyl ether (EEW 186) and at 95-110 ° C was reactivated to an epoxy value of 0.

Increase the temperature to 120 ° C for 30 minutes and allow to stand at this altitude until after approx. 1 oz. The mixture does not reach the minimum viscosity for 2 hours (eg measured with a BROOKFIELD rotary viscometer). After cooling to 60 ° C, 1008 parts (3 moles) of tolylenediisocyanate semi-blocked with diethylene glycol monobutyl ether are continuously added, without exceeding 90 ° C. After the addition is complete, the mixture is stirred at 80 ° C for 30 minutes. The solids content is now 78%. The 60 parts (solids) of the final product of Example 10 were mixed with 40 parts (solids) of the epoxy amine adduct as an additional component of ZK III (recovery is described below) and stirred at 80 ° C for 15 minutes. The solvent is then vacuum removed until a solids content of 93-95% is reached. After neutralization with ca. 32 milliliters of formic acid per 100 g of solid resin was added with deionized water during stirring until 45% concentration and dispersion were obtained with a viscosity of 300-500 mPa.s.

Examples 10-16; In the same way as in Example 9, according to the data in Table 2, other bonding agents will be obtained.

Acquisition of additional components

DK I: 1 mol of Bisphenol A-based diepoxy resin (EEW ca.

475) is treated in a known manner with 2 moles of diethanolamine. Solution: 70% solution in methoxypropanol or toluene (optional).

DK II: From 640 parts of ΕΡΗ III and 129 parts (1 mole) of 2-ethylhexylamine and 61 parts (1 mol) of MOLA at 80 ° C with complete conversion of epoxy groups, 1 mole of disseminated amine is produced. Add 1900 parts by weight dissolved in 814 parts of methoxypropanol and react with the amine at 80 ° C until the epoxy groups corresponding to the secondary amino groups are consumed.

204 parts (2.0 mol) of dimethylaminopropylamine and 66 parts (2.0 mol) of paraformaldehyde and xylene are now added as a circulating agent for azeotropic distillation at 90-140 ° C. After the formation of oxazolidine from the reaction medium, xylol is separated from the reaction medium by distillation and the mixture is diluted with 250 parts of ethylene glycol monobutyl ether. The hydroxyl number on the primary hydroxyl groups is ca. 19 mg KOH / g, calculated molar mass ca. 2960 and a solids content of 74%,

For testing binders manufactured according to Examples 1 to 15 using a pigment paste and water described below, lacquers with a solids content of 18% and a pigment-binder ratio of 0.5: 1 are obtained. After a 24-hour homogenisation phase, the electrocoating is applied to the cleaned, non-phosphated steel sheet. The electrical deposition conditions shall be chosen such that the thickness of the dry coatings is 22 ± 2 pm.

Ingredients of pigment paste used:

1000 parts of resin paste (solid)

252 parts of dibutylstann oxide (as catalyst)

421 parts of lead lead silicate parts of colored carbon black 5519 parts of titanium dioxide

The binder, described in EP-B1-0209 857 (PHV 1, after water-soluble protonation, OH equivalent of ca. 300), is obtained as a paste in the form of a paste, obtained as follows:

500 parts of Bisphenol A-based epoxy resin (equivalent weight of epoxide ca 500) were dissolved in 214 parts of propylene glycol monomethyl ether and allowed to react at 110 ° 7 C with 83 parts of phthalic anhydride and 2-ethylhexanol polyester with 0.5 g of triethylamine as catalyst , up to an acid number of 3 mg KOH / g. To the mixture was added 120 parts NH-functional oxazolidine from aminoethylethanolamine, 2-ethylhexylacrylate and formaldehyde and 26 parts diethylaminopiopylamine and allowed to react to 80% C to epoxy 0. The mixture was diluted with 200 parts propylene glycol monomethyl ether to a solids content of 64%.

Depending on the blocking agents used in the production of the individual binders, we select the appropriate oven drying temperature:

for cases l to 3, 7, 9 to 12, 14 and 15 (BDGL); 150 ° c for cases 4, 8, 13 (BA): 145 ° C or. for cases 5 and 6 (ΒΟΧ): 130 ° C

The drying time in the oven is in all cases 20 minutes.

All varnish coatings have excellent mechanical properties (impact test according to ASTM-D-2794: at least 80 ip; the coating on the punch according to ASTMD-522-60 did not settle on the coated surface. They also have excellent corrosion resistance on sheet metal, not previously pretreated (salt mist test according to ASTM-B-117-64: rust operation on a cross-section after 360 hours of test duration: max. 2 mm).

For products made to specification EP-B1-0 209 857, the same results were achieved only at drying temperatures of at least 160 ° C.

In order to increase the film thickness under normal application conditions to 20 to 30 [mu] m (at a flawless surface), only minor additions of texanol (5% by weight relative to the weight of texanol (5% by weight relative to solids content in the binder), while lacquers containing the products of Examples 9 to 15 can be formulated without the addition of Texanol or other high boiling additives.

Table 1

Epoxy compound Part II o ME I ME I LU II 3PJ ME I ME I ME I ME II o T— c? o Oh C \ f (1.0) cT o c? Delov 250 250 186 372 250 250 250 186 Part I Equivalent. ΡΗΡΗ I ΡΗΡΗ I ΕΡΗ II ΡΗΡΗ I ME I ΡΗΡΗ I ΡΗΡΗ I Šil ΡΗΡΗ I ΡΗΡΗ I ME I ΡΗΡΗ I ME II (1,0) tn and r- cm ci S cT c? (1.0) and and r- cm o S o_ (1,0) (LP) _ O_ O Delov 475 356 47 475 250 475 475 80 475 475 250 475 186 Aminoalkylated product Oh CM X o o o_ (1.0) θ ' eT cT (1.0) c? θ ' CM o Delov 30 30 09 30 30 ³⁰ 60 09 Amin (Mol) (0.5) EHA (0.5) DEAPA (1.0) DEAPA (2,0) MOLA (1.0) DEAPA (1.0) DEAPA (1.0) DEAPA (1,0) DEAPA (1,0) PRAY (1,0) DEAPA (1,0) PRAY Delov »T m CD CD 130 122 130 130 130 130 61 130 61 Phenol (Mol) (1.0) PH (1,0) NPH (1.0) 8PH (1,0) BPHA (1,0) NPH (1,0) NPH (1,0) NPH (1,0) NPH Delov 94 220 150 228 220 220 220 220 Pri- mer CM CD and CD Γ-- CD

Table 1 (continued)

Neutralization m Mol HCOOH / 100 g of solid resin o co CO., LTD CM Oh m o co co CM o co S o co « C V c o o. E o <0 c <0 o o Q P 30 LC I 30 LC I 1 1 1 1 15 of the Criminal Code I 25 of the Criminal Code II 10 of the Criminal Code I 25 of the Criminal Code II 15 of the Criminal Code I 15 of the Criminal Code II t 1 1 1 20 of the Criminal Code 1 30 LC II ra c o * o. (Λ ra c ra c .2 'o o N I (Mol) | (3,0) IC I (3,5) IC I (2,0) IC 1 (2,0) IC IV (3,5) IC III (3,5) IC IV (3,0) IC V (3,0) IC VI (4,0) IC VII | Delov 1008 1176 C \ J CM r- cm ω in 1253 783 1011 3708 4296 Φ E o. cu CO., LTD U7J (£ i »S- OO

1) numbers mean parts (solids) per 100 parts (solids) of the binder combination

Table 2

Epoxy compound Part II ME II ME II ME I ME II OR 2 ME II ME lil -1 (Mol) (1.0) o (1,0) Oh (0'l) (1,0) c? Delov 186 186 250 186 250 186 184 Part 1/11 ΡΗΡΗ I ΡΗΡΗ I ΕΡΗ II ΡΗΡΗ I ΕΡΗ II 1 ΕΡΗ III ΡΗΡΗ I ΕΡΗ III ΡΗΡΗ I Ekvlval. c? (1,0) o and and o o o and and f * · CM O o o Delov 475 475 190 237 95 320 475 80 475 Del 1/1 ME I Ul S ME II ME II ME 1 ME I ME III ί I (Mol) c? (1.0) (1,0) θ ' ЧТ r- Oh T · o_ Delov 250 250 186 186 250 250 184 Amine alkylation product Oh CM Z □ (Mol) θ ' CM θ ' CM (2,0) Oh CM θ ' CM o CM σ ' CM Work 09 09 09 60 09 60 09 Amin (Mol) (2,0) EHA (2,0) DEAPA (2,0) EHA (2,0) DEAPA (2,0) EHA (2,0) DEAPA (2,0) DEAPA Work 258 260 258 260 258 260 260 Phenol o S X 0. z S (1,0) NPH (1,0) BPH (1,0) NPH (1,0) BPH (1,0) NPH (1,0) NPH Del. 220 220 150 220 150 220 220 Pri- mer CD o (N CO., LTD 'i L-O

Table 2 (continued)

Neutralization rnMol HCOOH / 100 g FH 32 32 30 28 37 34 35 Additional component 1) bd S! o -3 · rt bd N o v l— bd N o u ~> 45 of the Criminal Code II id N vc τΤ > - < bd N o v bd N Isocyanate compound (Mol) Oh co p (0.3) IC I (3,5) IC II (4,0) IC II (3,0) IC III (3,0) IC VI (3,5) IC I > Z) cc S o 1442 1648 1074 oo r- ^ CC 1176 Example Ol C4 rC r * - K,

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VIANOVA KUNSTHARZ AG AUSTRIA REPRESENTATIVE: _Λ

O D V E G'C φ J. ALEXANDER JATTEZCLJUBLJANA, Resljeva 24

Tek 311-236

Claims (11)

PATENT APPLICATIONS A process for the preparation of cationic binders for varnishes based on modified aminoalkylated phenol products which are self-crosslinked and, after protonation, water-soluble, characterized in that (1) an aminoalkylated product containing an average of at least one NH group per molecule from 1 moles of monoalkylphenol and / or monoarylphenol and / or monoarylalkylphenol with one phenolic hydroxyl group, or optionally with two phenolic hydroxyl groups, from 1 to 2 moles of primary alkylamine and / or primary alkanolamine and / or primary-tertiary alkyldiamine aminocarine aminosine amine ecolamine amine aminosine aminosulfonamide formaldehyde, treats (2) with an amount of aliphatic and / or aromatic diepoxide compound equivalent to the secondary amine groups present, and optionally a mono-epoxy compound, (3) then or simultaneously reacts from 50 to 100% by weight, primarily 95 to 100% by weight of phenolic hydroxyl groups with a predominantly aliphatic mono-epoxide compound, (4) a mixture of allow complete conversion of the epoxy groups to a temperature of 100 to 130 ° C, primarily 115 to 125 ° C, until a minimum viscosity is reached and at the end (5) the secondary hydroxyl groups of the reaction product partially or fully react with semi-blocked diisocia19 nats and / or polyisocyanate compounds with one free NCO group. A process according to claim 1, characterized in that in step (2), the fraction exceeding 1 equivalent of the secondary amine groups present is treated with the mono-epoxide compound. Process according to claim 1, characterized in that butanonexime or activated primary monoalcohols are used as a blocking agent for isocyanate compounds. Process according to Claim 1, characterized in that (1A) is applied to an aminoalkylation product containing, on average, in the molecule 2 NH groups, from 1 mol of monoalkyl monophenol, 2 moles of primary alkylamine and / or primary tertiary alkyldiamine and 2 moles of formaldehyde. e (2A) simultaneously or sequentially with 50% by weight (relative to the given secondary amine groups) of the mono-epoxide compound and aliphatic and / or aromatic diepoxide compounds, (3A) then initiates the reaction of 95 to 100% by weight of the phenolic hydroxyl groups with the predominantly aliphatic mono-epoxy compound, (4A) leaving the mixture after complete conversion of the epoxy groups at a temperature of 100 to 130 ° C, especially at 115 to 125 ° C, until a minimum viscosity is reached, and (5A) the last secondary hydroxyl group of the reaction product partially or in fully react with semi-blocked diisocyanates and / or polyisocyanate compounds with one free NCO group. Process according to claim 4, characterized in that monoalkylphenols with an alkyl residue of at least 4 carbon atoms are used as phenols for the preparation of aminoalkylated products (component IA). A process according to claim 4, characterized in that the aliphatic mono-epoxy compounds with a molar mass of at least 180, such as glycidyl esters of monocarboxylic acids and / or glycidyl ethers and / or epoxide compounds, whose epoxy groups are used as mono-epoxy compounds located directly on the aliphatic chain or aliphatic ring. Process according to claim 4, characterized in that activated primary alcohols are used as blocking agents for isocyanate compounds. Process according to claims 3 and 7, characterized in that diethylene glycol monoalkyl ether or benzyl alcohol are used as activated primary monoalcohols. 9. Self-crosslinking cationic binders which, after protonation, are water soluble, based on modified aminoalkylated phenol products, characterized in that they are prepared according to claims 1 to 8. Use of binders for lacquers prepared according to claims 1 to 3 and 8, optionally in combination with additional crosslinking components and / or binder components having hydroxyl groups for formulating water-soluble lacquers, in particular electro-solubility lacquers they secrete cathode. Use of lacquer binders according to claims 4 to 8 in combination with after-protonation of water-soluble, cationic adducts based on epoxy resins and amines, as well as optionally with cross-linking components, for the formulation of cathode-soluble lacquers .