DE3824496A1 - Epoxide/amine adducts and use thereof - Google Patents

Abstract

The invention relates to epoxide/amine adducts which are obtainable by reacting one or more di- and/or polyepoxides with 1 or more amino compounds having at least 1 active aminohydrogen atom and subsequent neutralisation or oxidation of the tertiary amino groups of the resulting epoxide/amine adducts with an acid or an oxidising agent. These epoxide/amine adducts can be used alone or together with 1 or more hardeners in the form of solvent-free, low-solvent, solvent-containing, water-soluble or water-thinnable binder systems in the clear or pigmented state for protecting mineral and metallic substrates, fabric, wood, paperboard, gypsum, cardboard, paper or plastics, for modifying hydraulic or mineral render or concrete and for producing electrical insulation laminates, fibre-reinforced plastics or thermally stable mouldings, and as hot-curing one-component systems for producing polyethers of enhanced chemical resistance.

Description

The invention relates to epoxy/amine adducts with increased storage stability and their use alone or together with a hardener as solvent-free, low-solvent, solvent-containing, water-soluble or water-dilutable binder systems for protecting mineral and metallic substrates, fabric, wood, cardboard, plaster, paper or plastics, modifying hydraulic or mineral screed or concrete and for cataphoretic dip painting and for producing electrical insulating laminates, fiber-reinforced plastics and temperature-resistant molded parts and as heat-curing one-component systems for producing polyethers with increased chemical resistance. Through this use, these substrates are made chemically, thermally and/or mechanically resistant.

The production of modified epoxy resins containing oxazolidine groups, which are used in particular as grinding media for pigments and fillers, is known from DE-OS 33 00 555. These epoxy resins are produced by reacting a hydroxyl-free secondary amine with a carboxylic acid anhydride to form a half-ester, after which this half-ester is reacted with an epoxy resin in a further process step.

DE-OS 31 09 900 describes water-dilutable epoxides which are free of glycidyl ester and ether groups, the polyepoxide containing at least one epoxy group, at least one ester group of a monocarboxylic acid and a further ester group adjacent to this, which was formed by reacting an OH group with a polycarboxylic acid monoanhydride, the second carboxyl group formed from the anhydride during esterification being present entirely or partially in the form of a salt of a base. These epoxides are used as binders in aqueous or water-compatible media, in particular for producing hardened coatings, and also as an additive to dispersions of monomers and/or polymers.

DE-OS 34 39 130 describes a process for the preparation of cationic epoxy resins bearing oxazolidine groups, which are used as paint binders, by reacting an epoxy resin with an OH-functional oxazolidine compound.

DE-OS 33 18 596 relates to hydroxyalkoxycarboxylic acids and their salts, which are produced from the epoxides of unsaturated fatty acid esters by ring opening and saponification with alcohols. These products are used as solubilizers in aqueous paint preparations.

It is also known that water-emulsifiable epoxy resins and hardeners can be used as two-component dispersion paints for cement-bound and metallic substrates. It is also known that aqueous dispersions are unsuitable as primers or impregnators because, due to their colloidal structure, they are unable to penetrate absorbent substrates. Such dispersions, which are produced by adding emulsifiers or protective colloids and are generally of medium to high viscosity, also have a number of other disadvantages, such as limited workability, poor flow, filling capacity and pigmentability, and result in an unsatisfactory gloss.

It is also known that the production of storage-stable epoxy/amine adducts with intact epoxy groups has not been possible so far, since the tertiary amine groups formed catalytically attack the epoxy groups and convert them into solid polyethers as follows:

The object of the invention is to provide adducts with broad variability, which have superior properties, such as increased storage stability and/or abrasion resistance and resistance to water, de-icing salt and mineral oils, and their use.

This object is achieved by the epoxy/amine adducts of claim 1. The use of the epoxy/amine adducts is the subject of patent claim 14.

Preferred embodiments of the epoxy/amine adducts according to the invention are the subject of patent claims 2 to 13 and those of their use are the subject of patent claims 14 to 17.

All types of polyepoxides having at least two epoxy groups, preferably 2 to 10 and in particular 2 to 4 epoxy groups, are suitable for preparing the epoxy/amine adducts according to the invention.

Preferably, R₄ and/or R₅ in formula II are hydrogen and/or methyl radical(s).

Particularly preferred radicals R₁ in the formula I are those of bisphenol A, bisphenol F and novolaks.

In particular, all di- or polyfunctional epoxy resins obtained by reacting epichlorohydrin with phenols or phenol novolaks are suitable, as well as epoxy resins based on aliphatic alcohols, copolymers containing glycid groups, epoxidized fatty acids, cycloaliphatic epoxy resins, halogenated epoxy resins and, for example, with polycarboxylic anhydrides, monocarboxylic acids, polyurethane resins, ureas, melamine resins, phenolic resins, polyisocyanates or silicones modified epoxy resins.

Of the primary and secondary amino alcohols of the general formulas III and IV, the straight-chain and branched, i.e. aliphatic, ones are preferred. Mono- and diethanolamine are used as particularly preferred primary and secondary amino alcohols. Other preferred examples are mono- and dipropanolamine, mono- and diisopropanolamine and mono- and dibutanolamine and the isomers of the latter. The aromatic primary and secondary amino alcohols can be purely aromatic and aromatic-aliphatic. Of the aromatic amino alcohols, mono- and di-(hydroxyphenyl)amine are particularly preferred. Of the aromatic-aliphatic amino alcohols, hydroxyphenylamines with 1 to 4, very particularly 1 or 2, carbon atoms in the or each alkyl side chain, especially mono- and di-(hydroxybenzyl)amine, are particularly preferred. Of the cycloaliphatic amino alcohols, those having 5 to 7 carbon atoms in the or each cycloalkyl radical, especially mono- or di-(hydroxycyclophenyl)amine, are particularly preferred.

Preferred straight-chain and branched primary and secondary amines are propyl and butylamines, as well as diethyl, dipropyl and dibutylamines. The primary and secondary aromatic amines and cycloalkylamines are more preferred. The aromatic ones can be purely aromatic and aromatic-aliphatic. Of the aromatic amines, aminobenzene and diphenylamine are particularly preferred. Of the aromatic-aliphatic amines, phenylalkylamines with 1 to 4, very particularly 1 or 2, carbon atoms in the or each alkyl side chain, especially benzylamine and dibenzylamine, are particularly preferred. Of the cycloaliphatic amines, those with 5 to 7 carbon atoms in the or each cycloalkyl radical, especially cyclohexylamine and dicyclohexylamine, are particularly preferred. Of the cyclic amines, the heterocyclic ones such as piperazine and its derivatives are preferred.

Preferred straight-chain or branched primary and secondary diamines are methylenediamine, ethylenediamine, propylenediamine and butylenediamine, as well as the N-substituted variants thereof by 2 methyl, ethyl, propyl or butyl radicals. The primary and secondary aromatic diamines are more preferred. The aromatic diamines can be purely aromatic and aromatic-aliphatic. Of the aromatic diamines, phenylenediamine is particularly preferred. Of the aromatic-aliphatic diamines, phenylenedi(alkylamines) with 1 to 4, very particularly 1 or 2, carbon atoms in each alkyl side chain, especially phenylenedi(methylamines), are particularly preferred. Of the cycloaliphatic diamines, those with 5 to 7 carbon atoms in the cycloalkylene radical, especially cyclohexylenediamine, are particularly preferred.

Further examples of amino compounds with at least 1 active hydrogen atom are polyaminoamides, polyamine adducts, polyaminoimidazolines, polyaminoamide adducts, Mannich bases, alkoxyalkylamines and aminophenols.

To produce the epoxy/amine adducts according to the invention, EP equivalent masses of the epoxy compounds used are reacted with preferably 10 to 90% of the NH equivalent masses of the amino alcohols and/or amines, the reaction preferably being carried out at room temperature. The EP equivalent mass is the amount of resin in grams that contains 1 mole of epoxy, while an NH equivalent mass is the amount of amino alcohol or amine in grams that contains 1 mole of NH. The reaction is advantageously carried out in the presence of a solvent. A glycol ether, alkoxyalkanol, preferably alkoxypropanol, and/or alkylpyrrolidone, in particular butylglycol, 1-methoxypropanol-2 and/or N-methylpyrrolidone, is preferably used as the solvent. The adduct formation is carried out until no more secondary amine groups can be detected. Relevant analytical detection methods for the secondary amine are known from the literature, for example "The Organic Analysis" Polondek/Fabini, Geest & Portig, Leipzig 1980.

The monocarboxylic acid preferably used to neutralize the tertiary amine groups of the epoxide/amine adducts obtained in the reaction is in particular formic acid and/or acetic acid.

The peroxide which is preferably used as an oxidizing agent for the oxidation of the tertiary amine groups of the epoxide/amine adducts obtained in the reaction is particularly preferably hydrogen peroxide and the peroxosulfuric acid which is also preferably used is particularly preferably Caro's acid and peroxodisulfuric acid, especially the former. Ozone is also particularly preferred.

The embodiment according to the invention, in which the tertiary amine groups of the resulting epoxy/amine adducts are oxidized with an oxidizing agent, brings with it the additional advantage of a further increase in storage stability.

The epoxy/amine adducts obtained can, if acid residues are present, for example sulphuric acid residues in the case of using Caro's acid and stabilising acid residues in the case of hydrogen peroxide, be diluted to the desired viscosity, preferably with water, preferably deionised water, after their removal, for example by neutralisation with sodium hydroxide solution or potassium hydroxide solution.

The reaction mechanisms by which the preparation of the epoxide/amine adducts according to the invention takes place can be reproduced as follows for the specific example of the use of secondary amino alcohols as amino compounds with at least 1 active hydrogen atom. A) Variant of the neutralization of the tertiary amine groups of the resulting epoxide/amine adducts
B) Variant of the oxidation of the tertiary amine groups of the resulting epoxide/amine adducts

In the above reaction mechanisms, R, R₁ to R₃ and n have the meanings given above.

The reaction schemes in the above two processes are corresponding in the case of using other polyepoxides or diepoxides and/or other amino compounds with at least 1 amino hydrogen atom.

The epoxy/amine adducts according to the invention can be prepared in any solvent-free, solvent-containing or aqueous form by carefully selecting the starting components. They can be used as sole binders or preferably with amine hardeners, in particular those specified as particularly preferred in claim 15. The polyamines, polyamides, polyaminoamides, polyaminoamide adducts and/or polyaminoimidazolines used are expediently those with NH equivalent masses of about 11.5 to about 1000.

All commercially available hardeners can be used as polyamine hardeners, such as Rütapox® (Bakelite), Grilonit® (EMS), Euredur® (Schering), such as No. 12 and 430, Epilink® (AKZO), such as No. 360 and 370.

The amount of hardener in grams used per 100 grams of EP resin preferably corresponds to the product of the EP value and the NH equivalent mass. However, a variation is also possible, which can result in under-crosslinking of as little as 80% or over-crosslinking of as much as 120%.

The epoxy/amine adducts according to the invention can be used as clear formulations or together with pigments and fillers, with which they are expediently ground in order to use them as air- and/or oven-drying systems. The epoxy/amine adducts according to the invention are also suitable for cataphoretic dip painting, for example. Other examples of their use are the modification of hydraulic or mineral screed or concrete or for the production of electrical insulation laminates, fiber-reinforced plastics or temperature-resistant molded parts or as heat-curing one-component systems for the production of polyethers with increased chemical resistance.

In the latter application, the existing tertiary amine salt or amine oxide structure breaks down into oxygen or acid and tertiary amine by heating. The tertiary amine structure of the resulting epoxy/amine adduct in turn catalytically attacks the existing epoxy groups and, as in known one-component systems based on boron trifluoride-amine complexes, is converted into polyether by cross-linking via ether groups, whereby particularly chemical-resistant films are obtained.

• A: Eine EP-Äquivalentmasse eines Polyepoxids (43 bis ca. 1000) wird mit etwa 30 bis 60% der NH-Äquivalentmasse eines sekundären Aminoalkohols, wie Diethanolamin, gegebenenfalls in Abwesenheit eines Hilfslösungsmittels, wie Butylglykol, durch Stehenlassen vorzugsweise bei Zimmertemperatur zur Adduktbildung umgesetzt.
• B: Die Umsetzung der sekundären Amine (in diesem Beispiel speziell sekundärer Aminoalkohol) zu tertiären Aminen (in diesem Beispiel speziell tertiärer Aminoalkohol) muß vollständig durchgeführt werden, wobei der Nachweis des sekundären Amins wie folgt durchgeführt werden kann: 1 Tropfen des zu prüfenden Addukts wird auf die Tüpfelplatte und 1 Tropfen der Reagenslösung (1 gew.-%ige Lösung von Nitroprussid- Natrium, der ¹/&sub1;&sub0; des Volumens Acetaldehyd zugegeben wurde) versetzt. Eine tiefblaue bis violette Färbung deutet auf ein sekundäres Amin hin (erfahrungsgemäß nach einigen Minuten).
  Die Reaktionszeit kann bei Raumtemperatur mehrere Stunden betragen, welche durch Erwärmen bzw. durch Erhitzen auf Temperaturen unterhalb der Siedetemperatur des verwendeten Aminoalkohols, in diesem Falle unter 140°C, verkürzt werden kann.
• C: Dann erfolgt eine der folgenden beiden Alternativen:
  • a) Vollständige Neutralisation mit einer organischen und/oder anorganischen Säure, wie Ameisensäure oder Essigsäure, bis zur Erzielung eines etwa 100%igen Neutralisationsgrads nach der folgenden Gleichung:
    °KG°TS°k°t = @W:°KM°kɤ´¤°KMw°k:°KM°kÊ&udf54;,&udf50;
    wobei G _S das benötigte Säuregewicht, um einen 100%igen Neutralisationsgrad zu erzielen, ist, M&sub1; die Masse des Aminoalkohols, Amins bzw. Diamins ist, M&sub2; die NH-Aktiväquivalentmasse des Aminoalkohols, Amins bzw. Diamins ist und Mwdas Molekulargewicht der eingesetzten Monocarbonsäure ist.
  • b) Vollständige Oxidation mit einem Oxidationsmittel, wie Wasserstoffperoxid, Ozon oder Caroscher Säure, bis zur Erzielung eines etwa 100%igen Oxidationsgrads nach der folgenden Gleichung:
    °KG°To°k°t = @W:°KM°To°k°t¤´¤°KG°Ta°k°t:°KM°Ta°k°t&udf54;,&udf50;
    wobei G _o das benötigte Oxidationsmittelgewicht, um eine 100%ige Oxidation zu erreichen, ist, M _o das Molekulargewicht des Oxidationsmittels darstellt, G _a die Masse des Aminoalkohols, Amins bzw. Diamins ist und M _a das Molekulargewicht des Aminoalkohols, Amins bzw. Diamins darstellt.
    Erfahrungsgemäß wird im Falle von Wasserstoffperoxid und Ozon weit mehr verbraucht, als errechnet wurde, da der Oxidationsvorgang durch Entstehen exothermer Energien gestört wird, was zum Verlust an Oxidationsmittel führt.
    Entscheidend ist, daß der Oxidationsvorgang durch Abkühlenlassen und weitere Zugabe an Oxidationsmitteln so lange durchgeführt werden muß, bis keine tertiären Amingruppen mehr nachzuweisen sind.
    Nachweise der tertiären Amingruppen:
    Etwa 100 mg des Adduktes werden in 1 bis 2 ml Pyridin gelöst, es wird 0,5 ml einer 10 gew.-%igen Natronlauge zugesetzt, gut umgeschüttelt, ein Tropfen Benzolsulfochlorid zugesetzt und erneut umgeschüttelt. Eine rosafarbene bis tiefpurpurrote Färbung deutet auf ein tertiäres Amin hin.
    Im Falle von Wasserstoffperoxid, welches zum Teil Säure als Stabilisator enthält, bzw. im Falle von Caroscher Säure wird im Nachhinein mit einer Lauge stöchiometrisch neutralisiert, zum Beispiel mit Natronlauge.
• D: Gegebenenfalls wird der Rest an Lösungsmittel bis zur Einstellung eines Gesamtlösungsmittelgehalts von 5 bis 15 Gew.-% zugesetzt.
• E: Vorzugsweise entionisiertes Wasser wird bis zu einem Feststoffgehalt von 10 bis 50% als Verdünnungsmittel zugesetzt.

An epoxy/amine adduct according to the invention is described below as an example of a water-soluble formulation (see table, among others):

• A: An EP equivalent mass of a polyepoxide (43 to about 1000) is reacted with about 30 to 60% of the NH equivalent mass of a secondary amino alcohol, such as diethanolamine, optionally in the absence of an auxiliary solvent, such as butyl glycol, by allowing to stand, preferably at room temperature, to form an adduct.
• B: The conversion of secondary amines (in this example specifically secondary amino alcohol) to tertiary amines (in this example specifically tertiary amino alcohol) must be carried out to completion, whereby the detection of the secondary amine can be carried out as follows: 1 drop of the adduct to be tested is placed on the spot plate and 1 drop of the reagent solution (1 wt.% solution of sodium nitroprusside to which ¹/₁₀ of the volume of acetaldehyde has been added). A deep blue to violet color indicates a secondary amine (experience shows that this occurs after a few minutes).
  The reaction time can be several hours at room temperature, which can be shortened by warming or by heating to temperatures below the boiling point of the amino alcohol used, in this case below 140°C.
• C: Then one of the following two alternatives occurs:
  • (a) Complete neutralisation with an organic and/or inorganic acid, such as formic acid or acetic acid, until a degree of neutralisation of approximately 100% is achieved according to the following equation:
    °KG°TS°k°t = @W:°KM°kɤ´¤°KMw°k:°KM°kÊ&udf54;,&udf50;
    where G _S is the acid weight required to achieve a 100% degree of neutralization, M 1 is the mass of the amino alcohol, amine or diamine, M 2 is the NH active equivalent mass of the amino alcohol, amine or diamine and Mw is the molecular weight of the monocarboxylic acid used.
  • b) Complete oxidation with an oxidising agent such as hydrogen peroxide, ozone or Caro’s acid until approximately 100% oxidation is achieved according to the following equation:
    °KG°To°k°t = @W:°KM°To°k°t¤´¤°KG°Ta°k°t:°KM°Ta°k°t&udf54;,&udf50;
    where G _o is the weight of oxidant required to achieve 100% oxidation, M _o is the molecular weight of the oxidant, G _a is the mass of the amino alcohol, amine or diamine, and M _{a is} the molecular weight of the amino alcohol, amine or diamine.
    Experience has shown that in the case of hydrogen peroxide and ozone, far more is consumed than calculated, since the oxidation process is disturbed by the generation of exothermic energies, which leads to the loss of oxidizing agent.
    It is crucial that the oxidation process is carried out by cooling and further addition of oxidizing agents until no more tertiary amine groups can be detected.
    Detection of tertiary amine groups:
    About 100 mg of the adduct is dissolved in 1 to 2 ml of pyridine, 0.5 ml of a 10% by weight sodium hydroxide solution is added, shaken well, a drop of benzene sulfochloride is added and shaken again. A pink to deep purple color indicates a tertiary amine.
    In the case of hydrogen peroxide, which partly contains acid as a stabilizer, or in the case of Caro's acid, it is subsequently neutralized stoichiometrically with a base, for example with sodium hydroxide solution.
• D: If necessary, the remainder of the solvent is added until a total solvent content of 5 to 15 wt.% is achieved.
• E: Preferably deionized water is added as a diluent up to a solids content of 10 to 50%.

The invention is explained in more detail with reference to the following examples.

Examples 1 to 4

In the following Table 1, in addition to Examples 1 to 4 according to the invention, comparative examples are also included as Examples A and B. Table 1

Examples 5 to 8

In the following Tables 2 and 3, in addition to Examples 5 to 8 according to the invention, comparative examples (solvent-containing and dispersion) are also included as Examples C and D.

The components specified in Table 2 below are mixed or reacted in the manner described and the resulting samples are applied to concrete slabs (B 35), whereby 400 g/m² are used in two work steps and a waiting period of one day is allowed between the work steps. After curing for 7 days at approx. 20°C, the samples were tested for their abrasion resistance in comparison to an untreated concrete slab. The results are shown in Table 3. Table 2

The EP resin or polyepoxide used is Rütapox 300® (from Bakelite), a semi-solid polyfunctional epoxy resin with an epoxy number of 24.2±0.5%, an epoxy equivalent of 178±2 g/equivalent, an epoxy value of 0.56±0.01 equivalents/100 g and a viscosity of 1500±300 mPa · s at 80°C, the polyamine adduct Euredur 30® from Schering, a polyamine adduct with an H-active equivalent mass of about 370 and an amine number of 105 to 200, the polyaminoamide epoxy adduct (polyaminoamide adduct) XE 430 (=Epilink 360), a condensation product of e.g. ethylenediamine and dimerized fatty acid, and the modified polyamine Euredur 12, a Mannich base consisting of a condensation product of phenol, formaldehyde and trimethylhexamethylenediamine, from Schering, was used. Table 3
&udf53;ta1,6:8:37,6:8:14,6:18,6:22,6:26,6:30,6:34,6:37,6&udf54;&udf53;tw,4&udf54;&udf53;tz5&udf54;&udf53;sg8&udf54;\Exam\ Version\ 0&udf50;Probe\ Example&udf50;C\ Example&udf50;D\ Example&udf50;5\ Example&udf50;6\ Example&udf50;7\ Example&udf50;8&udf53;tz5,10&udf54;&udf53;tw,4&udf54;&udf53;sg9&udf54;&udf53;ta1,6:8:14,6:18,6:22,6:26,6:30,6:34,6:37,6&udf54;\1. Abrasion according to BÐhme&udf50;in cm&peseta;/50 cm¥ (DIN 51108)\ 11,70\ 8,79\ 11,64\ 7,76\ 7,41\ 7,38\ 7,85&udf53;tz5&udf54; \2. Chem. resistance&udf50;after days&udf53;tz&udf54; \^ Water&udf50;^ started. De-icing salt&udf50;^ Diesel&udf50;^ Petrol&udf50;^ Brake oil&udf50;^ Engine oil\ The test media&udf50;penetrate the&udf50;subsoil\ 1&udf50;1&udf50;3^4&udf50;3^4&udf50;3&udf50;3\ 2&udf50;2&udf5\ 0;4&udf50;4&udf50;3&udf50;3\ 2&udf50;2&udf50;1^2&udf50;2&udf50;1^2&udf50;1^2\ 1^2&udf50;1^2&udf50;1^2&udf50;2&udf50;1^2&udf50;1^2\ 1^2&udf50;1&udf50;1&udf50;1&udf50;1&udf50;1\ 1^2&udf50;1^2&udf50;1^2&udf50;1^2&udf50;1^2&udf50;1^2&udf53;tz5&udf54;&udf53;te&udf54;&udf53;sg8&udf54;Abbreviations:&udf50;LM@2=solvent&udf50;@02-komp.@2=two-component&udf50;@0WE@2=water-emulsifiable&udf50;@0WV@2=water-dilutable&udf50;@0EP@2=epoxy&udf50;@0NH-A»@2= NH-active equivalent&udf50;@0PAA@2= polyamine adduct&udf50;@0PAAA@2= polyaminoamide adduct&udf50;@0ModPA@2= modified polyamine&udf50;@0&udf53;sg9&udf54;

From the test results in Table 3 above, it is clear that the water-dilutable or water-soluble epoxy/amine adducts of Examples 5, 6, 7 and 8 according to the invention provide better abrasion resistance than the solvent-containing system of Comparative Example C. The dispersion of Comparative Example D penetrates poorly and therefore the abrasion resistance is comparable to that of Comparative Sample 0.

As far as water resistance is concerned, the epoxy/amine adducts according to the invention used in Examples 5 and 6 initially show a slight swelling behavior, due to the acetic acid salt structure still present. However, acetic acid deblocking gradually takes place at room temperature, which can be accelerated by the application of heat, and the films then become water-resistant in a few days.

The epoxy/amine adducts of Examples 5, 6, 7 and 8 show better resistance to diesel, gasoline, brake oil and engine oil than those of Comparative Examples C and D.

Claims (17)

1.) Epoxide/amine adducts, characterized in that they are obtainable by reacting 1 or more di- and/or polyepoxide(s) with 1 or more amino compound(s) having at least 1 active amino hydrogen atom and subsequent neutralization of the tertiary amine groups of the resulting epoxide/amine adducts with an acid or oxidation thereof with an oxidizing agent. 2.) Epoxide/amine adducts according to claim 1, characterized in that for the reaction for their preparation as amino compound(s) with at least 1 active amino hydrogen atom 1 or more primary and/or secondary amino alcohol(s) and/or other amine(s) is/are used. 3.) Epoxy/amine adducts according to claim 1 or 2, characterized in that they are obtainable by reacting EP equivalent masses of the epoxy compound(s) with 10 to 90% of the NH equivalent masses of the amino alcohol(s) and/or other amine(s). 4.) Epoxide/amine adducts according to claims 1 to 3, characterized in that they are obtainable by reacting the epoxide compound(s) with the amino alcohol(s) and/or other amine(s) at temperatures of 20 to 25°C. 5.) Epoxy/amine adducts according to claims 1 to 4, characterized in that they are obtainable by reacting the epoxy compound(s) with the amino alcohol(s) and/or amine(s) in the presence of 1 or more solvent(s). 6.) Epoxide/amine adducts according to claims 1 to 5, characterized in that the polyepoxides used have the general formula

where R₁ represents residues of polyhydric phenols of the general formula

wherein R₄ and R₅ independently of one another represent hydrogen or alkyl radicals having 1 to 4 carbon atoms, p is an integer from 0 to 5 and n is an integer from 2 to 10, in particular 2 to 4. 7.) Epoxide/amine adducts according to claims 1 to 6, characterized in that the primary amino alcohols used have the general formula
H₂NR₂OH III
and the secondary amino alcohols used of the general formula

are equivalent to,
wherein R₂ and R₃ represent methylene radicals and/or straight-chain and/or branched and/or cyclic alkylene radicals having 2 to 12, in particular 2 to 6, carbon atoms and/or aromatic hydrocarbon radicals having 6 to 12, in particular 6 to 10, carbon atoms. 8.) Epoxide/amine adducts according to claims 1 to 7, characterized in that [the] primary amines used are monoamines of the general formula
H₂NR₆ V
and [the] secondary amines used are monoamines of the general formula

are,
wherein R₆ and R₇ represent straight-chain and/or branched and/or cyclic alkyl radicals having 1 to 12, in particular 1 to 6, carbon atoms and/or aromatic hydrocarbon radicals having 6 to 12, in particular 6 to 10, carbon atoms, optionally interrupted by 1 heteroatom, in particular nitrogen atom. 9.) Epoxide/amine adducts according to claims 1 to 8, characterized in that [the] primary amines or secondary amines used are diamines of the general formula

are,
wherein
R₆ and R₇ represent hydrogen or have the meanings given in claim 8 and
R�8 represents a methylene radical or a straight-chain or branched or cyclic alkylene radical having 1 to 12, in particular 1 to 6, carbon atoms or an arylene radical having 6 to 12, in particular 6 to 10, carbon atoms. 10.) Epoxy/amine adducts according to claims 1 to 9, characterized in that the acid used is a monocarboxylic acid. 11.) Epoxy/amine adducts according to claims 1 to 9, characterized in that the oxidizing agent used is a peroxide, a peroxoacid, in particular peroxosulfuric acid, or ozone. 12.) Epoxy/amine adducts according to claims 1 to 10 of the general formulas


or

wherein
R₁ and n have the meanings given in claim 6,
R₂ and R₃ have the meanings given in claim 7,
R represents hydrogen, a straight-chain, branched or cyclic alkyl radical having 1 to 12, in particular 1 to 6, carbon atoms or an aromatic hydrocarbon radical having 6 to 12, in particular 6 to 10, carbon atoms and
R₆ and R₇ have the meanings given in claim 8. 13.) Epoxy/amine oxide adducts according to claims 1 to 9, or 11 of the general formulas

or

wherein
R₁ and n have the meanings given in claim 6,
R₂ and R₃ have the meanings given in claim 7 and
R₆ and R₇ have the meanings given in claim 8. 14.) Use of the epoxy/amine adducts according to claims 1 to 13 alone or together with 1 or more hardener(s) as solvent-free, low-solvent, solvent-containing, water-soluble or water-dilutable binder systems in a clear or pigmented state for protecting mineral and metallic substrates, fabric, wood, cardboard, plaster, paper or plastics, for modifying hydraulic or mineral screed or concrete and for cataphoretic dip painting and for producing electrical insulating laminates, fiber-reinforced plastics and temperature-resistant molded parts and as heat-curing one-component systems for producing polyethers with increased chemical resistance. 15.) Use according to claim 14, characterized in that the hardener consists of or contains 1 or more amine hardener(s), in particular polyamine(s), polyamide(s), polyaminoamide(s), polyaminoamide adduct(s) and/or polyaminoimidazoline(s) and/or boron trifluoride and/or adduct(s) thereof, polycarboxylic anhydride(s), Mannich base(s), polyphenol(s), polyisocyanate(s), hydroxyl-containing synthetic resin(s), in particular urea, melamine and/or phenolic resin(s), silicone(s) and/or mercaptan(s). 16.) Use according to claim 14 or 15, characterized in that a portion, in particular 10 to 90, of the active NH groups of the amine hardener used have been reacted with a polyepoxide. 17.) Use according to claims 14 to 16, characterized in that the hardener contains the amine hardener(s) in combination with 1 or more polycarboxylic acid anhydride(s), polyphenol(s), polyisocyanate(s) and/or hydroxyl-containing synthetic resin(s), in particular urea, melamine and/or phenolic resin(s).