JPS6036210B2 - Method for producing water-dilutable epoxy resin ester containing oxazolidine group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for making water-soluble epoxy resin esters containing oxazolidine groups, and more particularly to water-soluble epoxy resin esters suitable for forming cathodically depositable coating compositions. It concerns resin esters.

Austrian Patent Specification No. 342169, No. 348
No. 635, No. 34377, No. 343771, No. 3
It is known from No. 4698y to introduce the basic groups necessary for cathodic attachment into hydroxyl-containing polymer molecules via intermediates having one free isocyanate and at least one basic nitrogen group.

Such monoisocyanate compounds are prepared by reacting diisocyanates or polyisocyanates, depending on the technology, with the corresponding amount of dialkylkanolamine. During baking of the electrophoretically deposited thin film, the above-mentioned amine partially separates and
incur significant losses. This must be removed from the burner exhaust. The same problem can be found in, for example, German Publication No. 2057799 or Tanukikoku Publication No. 22523.
No. 6 as well as in the products described in No. 2265195.

There, the cathodically deposited binding crosslinks to form a urethane after blocking agent splitting of the blocked isocyanate. From GB 1,391,922 the reaction products of tertiary oxyamines, dicarboxylic anhydrides and epoxy resins are known.

It is essential in the case of these products that some of the epoxy groups remain intact during the reaction so that the system can handle groups capable of crosslinking. As is known, these groups have only a very short time stability in aqueous solutions, e.g. in catalytic baths, which means that such baths cannot be used, especially in the presence of the required catalyst. This means that it will become unusable after a short period of time. The object of the invention is to meet the requirements of customers, especially those in the automotive industry, in terms of durability.

It is an object of the present invention to provide a binder for cathodic electrodeposition, and further to provide a binder that not only requires lower baking temperatures due to the necessary crosslinking, but also exhibits reduced losses during baking. If dicarboxyl anhydride N-2-hydroxyalkyl oxazolidine sester (hereinafter sometimes referred to as oxazolidine semiester) is used to introduce a basic group into an epoxy group-containing polymer molecule. , it has been discovered that these requirements can be met.

The invention thus provides at least two 1,2
- The epoxy group of a resin-like compound having an epoxy group and an epoxy equivalent weight of at least 160 is combined with an aliphatic dicarboxylic acid, a cycloaliphatic dicarboxylic acid or an aromatic dicarboxylic acid at 60 to 7500 N -2-Hydroxyalkyl oxazolidine (wherein R: saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group, R2: one or more hydrogen atoms are alkyl an ethylene group which may be substituted by a group, R3: a hydrogen atom or an alkyl group, R4: a hydrogen atom or an alkyl group of up to 6 carbon atoms)
Semester of N-2-hydroxyalkyloxazolidine having and the amount of oxazolidine semiester is adjusted to such an extent that the epoxy-free final product is at least 35 tKO
Partially or wholly with inorganic and/or organic acids, based on epoxy resins, characterized in that they are selected to have a theoretical amine value of 50 to 140 KOH/unit, preferably from 50 to 140 KOH/unit. The present invention relates to a method for producing a water-dilutable binder by neutralizing the water-dilutable binder.

These oxazolidine semiesters introduce basic groups as well as the groups necessary for thin film crosslinking into the polymer in one step.

In this way, it is not necessary to maintain a portion of the epoxy groups in an unreacted state, but through these epoxy groups, other stable crosslinking functions and/or functions dominating the thin film composition or the thin film surface can be achieved. can be introduced. Surprisingly, resins that are wholly or partially dissolved by N-2-hydroxyalkyloxazolidines
It has further been found that even at low degrees of neutralization, good water solubility is exhibited. Another advantage over the state of the art is the possibility of reducing baking temperatures and/or baking times.
This is because the inventive binder crosslinks already at temperatures as low as 130°C. Optimal durability is obtained with a baking schedule of 140-18,000 for 10-30 minutes. The low burning loss of this Visoda is a special feature worth mentioning, namely 30
After minutes, it is less than 7%. (Calculated based on a thin film cured at 100oo). Baked thin films exhibit excellent solvent resistance and outstanding corrosion resistance. These surprising effects are
It can be assumed that the following reaction occurs and is caused by the opening of the oxazolidine trench under the action of water in an acid medium.

Based on the results obtained with the products of the invention, it seems justified to assume that the advantageous properties are essentially due to the reactivity of the optionally substituted N-methylol groups.

Furthermore, hydroxyl group formation aids in the water solubility of the resin, which in turn reduces the amount of acid required to achieve water dilutability. During curing, a portion of these hydroxyl groups are consumed. In this way, the water resistance of the cured film is not adversely affected by the hydrophilicity of the resin. The preparation of N-2-hydroxyalkyloxazolidines is carried out in known manner by reacting dialkanolamines with aldehydes or ketones at temperatures up to 130 qo and separating off the water. Suitable dialkanolamines are, first and foremost,
They are diethanolamine and diisopropanolamine. In some cases, dialkanolamines with longer alkyl groups can also be used. A suitable carbonyl compound is preferably formaldehyde, but higher aldehydes or ketones having up to 6 carbon atoms in the alkyl group may also be used. The N-2-hydroxyalkyloxazolidine thus obtained is (in the above formula -
One or more hydrogen atoms in CH2-CH2- may be replaced by an alkyl group).

The oxazolidine semiester used in the reaction of the epoxy group of the basic polymer has the following general formula.

Here, R: saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group, R2: ethylene group in which one or more hydrogen atoms may be substituted with an alkyl group, R3: hydrogen atom or an alkyl group, R4: a hydrogen atom or an alkyl group of up to 6 carbon atoms.

The preparation of these oxazolidine semisters is based on N-2-
This can be carried out in a simple manner by reacting a hydroxyalkyloxazolidine with a cyclic dicarboxylic anhydride.

Suitable cyclic dicarboxylic acid anhydrides include, for example, anhydrides of aromatic dicarboxylic acids such as 0-1 dicarboxylic acid,
Naphthalene dicarboxylic anhydride. Suitable anhydride-forming alicyclic dicarboxylic acids are, for example, tetrahydrophthalic acid or hexahydrophthalic acid, endoalkylenetetrahydrophthalic acids, halogen-substituted phthalic acids and other similar derivatives of aromatic dicarboxylic acids. It is a kind. Suitable aliphatic dicarboxylic acid anhydrides are, for example, Keio white acid and its homologs forming cyclic anhydrides;
Suitable unsaturated aliphatic dicarboxylic acids are maleic acid and its halogenated products. The reaction of the N-2-hydroxyalkyloxazolidine with the dicarboxylic anhydride is carried out in stoichiometric weight ratios, preferably in the presence of esters, ethers, ketones or aromatic solvents.

The basic group accelerates the reaction and allows it to proceed quickly even at low temperatures. Temperatures between 40 and 8000, usually between 30 and 120
After minutes, the theoretical acid value of Semester is reached.

Temperatures above 80 o C should not be applied in the preparation of semiesters, since in this case crosslinking reactions can already occur, leading to useless intermediates.

The thus obtained N-2-hydroxyalkyloxazolidine dicarboxylic acid semister was mixed with 60 to 7
React with a compound containing 1,2 epoxy groups at 0 qo.

Suitable compounds to be used as base resins include the various known epoxy resins based on phenols, in particular bisphenol A and phenol nopolacs, as well as fatty alcohols and glycidyl groups with an epoxy content of at least 160. It is an epoxy resin based on a copolymer with To ensure sufficient sensuality,
The epoxy compounds used have at least two 1,2 epoxy groups per molecule. This type of compound is
Published in 1967 by McCraw-Hill, New York, published by H. Dee and K. Nebile.
The weight ratio between the components is at least 35 9K.
The theoretical amine value of OH/unit is preferably chosen to yield a value between QKOH/unit of final product c paper 0 and 140 female KOH/unit. In many cases, not all the epoxy groups are consumed in this reaction, thus offering the possibility of modification.

Thereby, the properties of the binder can be adjusted within a wide range depending on the implementation requirements. The possibilities listed below can be implemented either alone or in combination for modifying the epoxy resin esters containing oxazolidine groups. 1 Epoxy groups not consumed in the reaction for introducing oxazolidine semiesters can be reacted with saturated and/or unsaturated carboxylic acids.

As is known to those skilled in the art, longer chain monocarboxylic acids particularly affect surface properties, but the crosslinking density is increased by the addition of Q-3 ethylenically unsaturated carboxylic acids. Strengthened by polymerization ratio.

The use of unsaturated acids is particularly recommended for resins to be processed to obtain coating compositions for curing at 16,000 and above. Suitable Q,8 ethylenically unsaturated monocarboxylic acids are the corresponding semiesters of acrylic acid, methacrylic acid or dicarboxylic acids and hydroxy(meth)acryleil. Suitable longer chain monocarboxylic acids are, for example, saturated or unsaturated fatty acids. If a semiester of a dicarboxylic acid and an oxyalkyl (meth)acrylate is used as the monocarboxylic acid, this sesester can be prepared simultaneously with the oxazolidine semiester in the same reactor.

This method is particularly advantageous. Because, based on the basic nature of oxazolidine, the reaction between the acid anhydride and the oxyalkyl (meth)acrylate is catalyzed, so that the entire reaction can proceed quickly even at low temperatures (40-8000 °C). It is from. When using dicarboxylic acids such as silicic acid and its congeners, rhein, phthalic acid, etc., they form higher molecular weight units with additional crosslinking of the epoxy resin.

This in turn has a beneficial effect on the properties of the resin and therefore of the coating compositions prepared therefrom. Furthermore, in the case of mixtures of epoxy resins, the various epoxy resins used are homogenized, thus resulting in improved resin properties. If appropriate, monocarboxylic acids can also be used additionally in this example as well. When using dicarboxylic acids, small amounts of monoepoxy compounds can be used to adjust the viscosity. 2 A further modification possibility is the reaction of epoxy groups with primary and/or secondary amines, which remain reactive after reaction with oxazolidine semiesters.

If oxazolidine semiesters are used as the only basic/cinder component in cathodically deposited coatings, the low basicity of the oxazolidine groups has a detrimental effect.

Although the resin is actually water-soluble with a low degree of neutralization, the solution exhibits a low pH value (below 6, sometimes even below 5). Consumers may consider this to be a disadvantage. This is because low pH values are thought to cause corrosion of the metal parts of the application equipment that come into contact with the resin solution. This disadvantage can be overcome by partial introduction of semiesters of dicarboxylic acids and tertiary amine alcohols without sacrificing the advantages obtained by the oxazolidine groups.

The modification consists essentially of reacting 30 to 99.5 mol%, preferably 40 to 60 mol%, of epoxy groups with the oxazolidine semiester, and 0.5 to 70 mol%, preferably 5 to 35 mol%. % with primary and/or secondary amines and optionally the remainder of the epoxy groups with saturated and/or unsaturated carboxylic acids.

A preferred embodiment consists in the use of primary amines, more particularly in combination with secondary amines or in the form of primary-tertiary amines.

The primary amine can react with two 1,2-epoxy groups, resulting in crosslinking of two molecules of epoxy resin. Since the nitrogen introduced during this reaction has only a low basicity, secondary amines must be added or primary-tertiary amines must be added to increase the pH value of the aqueous resin solution. Either it is used in place of a monoamine. Thereby, the primary amine groups serve to crosslink the epoxy resin molecules, while the tertiary amine groups do not react with the epoxy groups and form a strong base component. The use of primary amines has proven advantageous, especially when mixtures of various epoxy compounds are utilized. This is because difunctional amines cause a certain homogenization of heterogeneous mixtures. When using primary amines, small amounts of monoepoxy compounds can be used to adjust the viscosity. When using secondary amines, which are monofunctional with respect to epoxy groups, no substantial increase in viscosity can be observed. One amine molecule reacts with one epoxy group. Generally, to raise the pH value by 1 to 1.5,
It is sufficient to react a relatively small portion of the epoxy groups with the amine.

Assuming no more than 30 mole % of the epoxy groups react with the oxazolidine semiester, 0.5 to 7 mole % of the moiety can react with the amine.
Preferably, the portion of oxazolidine semiester is from 40 to 60 mol % and the portion of amine is from 5 to 35 mol %, calculated in terms of reactable epoxy groups. Suitable primary amines are monoalkylamines of the R-NH2 type.

Here, R is an aliphatic group, an alicyclic group, or an aromatic group,
It can have certain functional groups that are inert to epoxy groups, such as tertiary amine groups. Examples for such primary amines are monoalkylamines such as monoethylamine, monopropylamine, monobutylamine and their homologs and isotopes.

Also, monocycloalkylamines such as cyclohexylamine. Also, aromatic monoamines such as aniline and its congeners. Preferred primary amines, with additional tertiary amine groups, are N,N dialkylaminoalkylamines, such as dimethylaminopropylamine, diethylaminopropylamine, diethylaminobutylamine, and the like. A suitable secondary amine is R
, -NH-R2 type, or R and R2 together form a 5- or 6-membered ring. Examples are the corresponding dialkylamines, such as diethylamine, dibutylamine, etc., or morpholine. The amine can be reacted with the epoxy compound either subsequent to or simultaneously with the reaction with the oxazolidine semiester and the carboxylic acid.

The sum of amine equivalents and acid equivalents should substantially correspond to the number of epoxy equivalents of the epoxy compound used. The result is a final product virtually free of epoxy groups. In order to obtain satisfactory water solubility, the product has an amine equivalent weight of at least 35 9KOH/unit, preferably between 50 female KOH/unit and 140 female KOH/unit, as already mentioned. have. 3. Synthesis of binders containing oxazolidine groups A further possibility for increasing the basicity is the proportional introduction of dicarboxylic acids and tertiary amine alcohols in amounts without losing the advantages obtained by the oxazolidine groups.

This modification involves reacting 30 to 99 preferably 40 to 70 mol% of the epoxy groups with the oxazolidine semiester and 1 to 30, preferably 5 to 15 mol% of the epoxy groups reacting with the semiester of the dicarboxylic acid and the tertiary amine alcohol. and optionally, the remainder of the epoxy group is
It is essentially characterized by reaction with a saturated carboxylic acid and/or an unsaturated carboxylic acid.

According to the present invention, the pH of the aqueous resin solution is raised to a preferred range by the simultaneous use of a strongly basic semiester of a dicarboxylic acid and a tertiary amine alcohol.

However, the excellent solubility afforded by oxazolidine semiesters is adversely affected by the simultaneous use of basic semiesters, so that only 1 to 30 mol%, especially 5 to 15 mol%, of epoxy groups react with this component. . In the case of higher amounts, the degree of neutralization required to obtain solubility in water must increase. This in turn adversely affects the properties of the material. The proportion of oxazolidine semiester is therefore between 30 and 99 mol %, calculated with respect to the epoxy groups. The production of these basic semiesters requires aliphatic dicarboxylic acids,
It is carried out in a known manner by reacting anhydrides of aliphatic dicarboxylic acids or aromatic dicarboxylic acids with tertiary amine alcohols at 60 DEG to 90 DEG C. in the presence of a suitable inert solvent.

Preferred dicarboxylic acid components are anhydrides and partially or fully hydrogenated or substituted derivatives of cyclic dicarboxylic acids, such as o-phthalic anhydride. Suitable tertiary amine alcohols are, for example, dimethyl, diethyl, dipropyl, dibutylamine/ethanol and the corresponding propanols and butanols. A preferred example of this type of modification is a combination of an oxazolidine semiester, a basic semiester and a dicarboxylic acid as esterification compound for the epoxy group of the resinous compound.

If a semiester of a dicarboxylic acid and a hydroxyalkyl (meth)acrylate is used as a modification of the monocarboxylic acid, this semiester is
” may be prepared simultaneously with the ginsemester and the basic semiester in one step. This method is particularly advantageous.
This is because the basic nature of oxazolidines catalyzes the reaction between the anhydride and the hydroxyalkyl (meth)acrylate, where virtually complete reaction is quickly reached even at low temperatures (40 to 80 oC). The binder can be milled together with the pigment in known manner. and to produce the final processable material.
Partially or totally neutralized with inorganic and/or organic acids to a pH value of 4 to 7 and diluted preferably with deionized water for dew to a solids content of 5%. 2
It is between 0%. The binder prepared according to the present invention is
It exhibits excellent water dilutability even at low degrees of neutralization. The use of additives and auxiliary materials as well as the conditions for coating the base as a cathode are well known to those skilled in the art and require no further explanation. The following examples are intended to illustrate the invention without limiting its scope.

All parts and percentages are by weight unless otherwise stated. The following abbreviations are used in the examples.

THPA Tetrahydroxyphthalic anhydride PA ○-phthalic anhydride MA Maleic anhydride HETOX N-2-hydroxyethylluoxazolidine HIPOX N-2-hydroxypropyl-5-methyl-oxazolidine MIBK Methyl isobutyl ketone AEGLAC ethylene glycol monoethyl ether 7 Ruacetate AEGL Ethylene glycol monoethyl ether EPH Epoxy compound 1: Epoxy resin based on bisphenol A, epoxy equivalent: approx. 200 0: Epoxy resin based on bisphenol A, epoxy equivalent: approx. 550 m Based on epoxidized phenol novolak Epoxy resin, epixy equivalent: approx. 200 S5: Semiester of PA and hydroxyethyl methacrylate S6: Tall oil fatty acid DCA Dicarboxylic acid S9: Adipic acid SIO: Terephthalic acid SII: Keio white acid BA Butylamine DMAPA Dimethylaminof.

Lopylamin DEAPA Diethylaminof. Lopylamine DEA Diethylamine DBA Dibutylamine ES Acetic acid AS Formic acid DBN Number of double bonds = 1000 ta The number of moles of double bonds at the end of the chain in the resin group AN Number of amines: 9 KOH/ta NEUTR Neutralization: 100 ta kite molar acid Vmax per resin solid Breakdown Voltage, Volts All quantities in the table refer to the solid resin even if solutions were obtained in the preparation of the intermediate product according to the instructions.

Preparation of intermediates N- Preparation of 2-hydroxyalkyloxazolidine N-
2-Hydroxyalkyloxazolidine (HETOX)
: Mix 105 days of diethanolamine and 33 days of paraformaldehyde, use toluene as a solvent,
Heat slowly to 2000 ℃.

At the end of water production, the solvent is removed in vacuo. N-2-hydroxyph.

Lopyl-5-methyl-oxazolidine (HIPOX):
133 minutes of diisopropanolamine and 33 minutes of paraformaldehyde are reacted as described above.

Preparation of oxazolidine-semester (OSE): N-2-hydroxyalkyl oxazo 1'zine dicarboxylic acid semiester is prepared according to Table 1.

The reaction is carried out until the theoretical value of semiester is reached, that is, until the acid value becomes constant. Table 1 Preparation of basic semiester (E): S7:152 Tetrahydrophthal anhydride and 117
Jethylaminoethanol in the evening and AEGL in the evening of 115
Dissolve in AC and keep at 7000 until the acid value becomes constant.

S8: 152 evening tetrahydrophthal anhydride and 173
The dibutylaminoethal and dibutylaminoethal were dissolved in the MIBK and kept at 70° C. until the acid value became constant.

Examples 1 to 9 (Reaction between oxazolidine semiester and epoxy compound.

(combination with monocarboxylic acid) The oxazolidine semiester, eboxy compound, and monocarboxylic acid are dissolved in AEGIA solution to obtain a solution containing 70% solids.

Heat the batch to 75°C and hold at this temperature until the acid value falls below 3 female KOH/ta. Then this batch
Dilute to 60% solids with ethylene glycomonoethyl ether. (See Table 2) The evaluation of the binders in Table 2 is carried out by measuring the hardness and water resistance of transparent varnish coatings on degreased, unpretreated steel panels.

For salt spray testing, degreased, unpretreated steel panels were coated with a colored paint (10 parts solid resin, 16 parts aluminum silicate pigment, 2 parts carbon black, 2 parts lead silicate). The optimum voltage conditions gave a dry film of 16-20 m thick, and the phosphorization schedule was 16000 m for 30 minutes. When tested for water resistance by immersion in water at a temperature of 4000, the coating showed no corrosion, no irregularities, and no visible changes after 38 hours.

The thin films of Examples 3, 6, 8 and 9 were slightly blistered. That is, the membrane can be scratched in humid conditions. In the case of salt spray testing according to ASTM B I17-64, after 34 feeding hours all coatings show corrosion with no more than 2 cross cuts.

(Scotch Tape Stripping Test) To measure the burn loss, the transparent varnish is cured at 100 oo until the weight is constant.

The weight difference (taking the resulting weight as 100%) is measured in comparison to the normal cured film.

Neutralization, adhesion and curing conditions as well as hardness and baking loss are listed in Table 3.

Table 3 Table 3 Explanation [1] mmol per I0O solid resin [2] Type of acid Glue breakdown voltage '4' Adhesion voltage ■ Baking time 3 minutes '6} seconds ○ IN53157 (German industrial rating) )Example
10-21 - Dilute the ingredients listed in the fourth review with EGL to a solids content of 65%.

and 75 to 8 until reaching an acid value of 5 female KOH/ta or less.
Heat at 0C○. The results obtained when using mixed semiesters are identical to those prepared individually. The preparation of mixed semiesters involves the preparation of N-2-hydroxyalkyl oxazolidine, hydroxyalkyl (meth)acrylate and dicarboxylic anhydride, optionally in the presence of an inert solvent such as an ester, ketone or aromatic hydrocarbon, at a constant acid value. Heat from 70 to 8,000 ℃ until .

Table 4 Evaluation of the products obtained according to Table 4 is as follows: Example 1
It was carried out in the same manner as for 9.

When testing water resistance using a water immersion register under 40do,
After 380 hours, the coating is free of corrosion, unevenness, and shows no visible changes.

For salt spray testing according to ASTMBI 17-64, all coatings were rated at 34 cm with a cross cut of no more than 2 skins.
Shows corrosion after aging (Scotch tape stripping test).

Examples 22-32 The ingredients listed in Table 5 were prepared up to a solids content of 65%.
Dilute with AEGL and heat at 75-80 qo until an acid value of less than 9 KOH/Ta is reached.

If mixed semiesters are used, they are identical to those obtained in separate preparations. Preparation of mixed semiesters: N-2-hydroxyalkyloxazolidine, hyde. xyalkyl (meth)acrylate tertiary amine alcohol and dicarboxylic anhydride, optionally in the presence of an inert solvent such as an ester, ketone or aromatic hydrocarbon, until the acid value is constant, from 702 to 8000 This is done by heating. Table 5 The evaluation of the products according to Table 5 is carried out in an analogous manner to Examples 1-9.

In the case of water resistance test using water immersion bond at 40oo,
After 38 m hours, the coating is free of corrosion irregularities and shows no visible changes.

Claims (1)

[Claims] The epoxy groups of a resinous compound having two 1,2-epoxy groups per mole and having an epoxy equivalent of at least 160 are removed at 60-75°C in the presence of an inert solvent. , General formula obtained from aliphatic, alicyclic or aromatic dicarboxylic acid and N-2-hydroxyalkyloxazolidine ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R_1 is saturated or unsaturated aliphatic, is an alicyclic or aromatic hydrocarbon group, R_2 is an ethylene group in which one or more hydrogen atoms may be substituted with an alkyl group, R_3 is a hydrogen atom or an alkyl group, and R_4 is a hydrogen atom or an alkyl group having up to 6 carbon atoms) and saturated and/or unsaturated monocarboxylic acids, primary and/or secondary amines and dicarboxylic acids. Complete reaction with one or more compounds selected from the group consisting of semi-esters of acids and tertiary amine alcohols to reduce the amount of semi-ester of N-2-hydroxyalkyloxazolidine into a final product containing no epoxy groups. partially or totally neutralized with inorganic salts and/or organic acids, characterized in that the product has a theoretical amine value of at least 35 mg KOH/g, preferably from 50 to 140 mg KOH/g. Based on epoxy resin esters, which can be diluted with water,
Binder manufacturing method. 2. Process according to claim 1, characterized in that a reaction product of diethanolamine or diisopropanolamine and formaldehyde is used as the N-2-hydroxyalkyloxazolidine. 3, characterized in that the epoxy group is partially reacted with a saturated and/or unsaturated carboxylic acid in addition to the N-2-hydroxyalkyloxazolidine semiester,
A method according to claim 1 or 2. 4 30 to 99.5 mol%, preferably 40 to 60 mol% of epoxy groups are reacted with N-2-hydroxyalkyloxazolidine semiester, 0.5 to 70,
Preferably from 5 to 35 mol % are reacted with primary and/or secondary amines and optionally the remainder of the epoxy groups are reacted with saturated or unsaturated carboxylic acids. The method according to any one of the scope items 1 to 3. 5. The method according to claim 4, characterized in that the primary amine further has a tertiary amine group. 6. Process according to claim 4, characterized in that the primary monoamine is used in combination with a secondary amine. 7. Claim No. 7, characterized in that the reaction of the epoxy group with the N-2-hydroxyalkyloxazolidine semiester, the carboxylic acid and the amine compound is carried out simultaneously or the reaction with the amine is carried out successively. The method described in any of Items 4 to 6. 8. Claim 4, characterized in that the epoxy group is reacted with an amine and a semiester intermediate prepared simultaneously from a dicarboxylic acid, an N-2-hydroxyalkyl oxazolidine and a hydroxyalkyl (meth)acrylate. The method described in any of paragraphs 7 to 7. 9 30 to 99 preferably 40 to 70 mol % of the epoxy groups are reacted with the N-2-hydroxyalkyloxazolidine semiester and 1 to 30, preferably 5 to 15 mol % of the epoxy groups are reacted with the dicarboxylic acid and the tertiary amine alcohol. Claim 1 or 2, characterized in that it is reacted with a semi-ester and optionally the remainder of the epoxy groups with saturated and/or unsaturated mono- and/or dicarboxylic acids. The method described in. 10 As an esterification component of the epoxy group, N-2-hydroxyalkyloxazolidine semiester, semiester of dicarboxylic acid and tertiary amine alcohol,
10. Process according to claim 9, characterized in that aliphatic, cycloaliphatic or aromatic dicarboxylic acids and optionally in combination with monocarboxylic acids are used.