MXPA96001620A - Additives of aliphatic-amine epoxide with substantial branch of side chain, procedure for its preparation and its - Google Patents

Abstract

Epoxide-amine adducts having a mass ratio of at least 20% of aliphatic or amine epoxide units, comprising at least one tertiary or quaternary carbon atom are prepared by reacting monoepoxides with mono- or diamines or diepoxides with monoamines. They are used as binders for coating of relatively high environmental friendliness, if desired, in a mixture with other binders with hydroxy functionality, as a reactive component in corresponding adhesive compositions and in corresponding sealant compounds.

Description

ALUCIATIC-AMINO EPQXIDO ADUCTQS WITH SUBSTANTIAL BRANCH OF SIDE CHAIN; PROCEDURE FOR ITS PREPARATION AND ITS USE DESCRIPTION OF THE INVENTION To protect the environment, the objective of reducing the emission of organic compounds, especially the amount of solvent, has been set. The solvent content of adhesives, sealing compounds and coating materials in the future should be reduced from the values that are still common today, based on statutory regulations (for example, VOC regulations (volatile organic compounds ) in the United States of America and in Great Britain and "TA Luft" Clos German regulations for the control of air pollution in Germany). This specific statutory pressure of the countries is exercised with varying degrees of severity in different countries. The statutory authority allows different valuations (individual considerations, combined considerations) that force the producer of said coating products, adhesives and / or sealants, to new and different levels of technical operation. This has reached the degree to which the normally high level of funtion of these products must be cut with environmental bases, so that it is at a minimum level. Transparent coatings, such as non-pigmented systems, are used in automotive refinishing, for example, as the top coating. Its function is to protect the lower coating (base coat) pigmented, against mechanical stress, against the climatic effect and against dirt and give the total coating system the necessary brightness. This clear coat has been formulated predominantly with polymeric binders which have usually been used simultaneously in pigmented upper coatings as well. The severe VOC regulations, however, force the raw material producer to formulate the transparent coating separately, in some cases with the addition of low molecular weight polyols, as a "mixing system" (EP-A-0 5flß 314, EP-A-0 129 124, US-A-5,096,956). Various methods can be used to reduce the solvent content. For example, extremely low molecular weight polymeric binders are used, alone or in admixture with higher molecular weight binder components. Strongly complex binding systems are known, for example, those comprising mixtures of oligomeric caprolactone polyols, ie, polyester polyols with acrylate polyols and / or acrylate initiator polymers (WO 92 / 2261fi). The defined organic compounds, for example, the aspartic acid derivatives, the aldimines, the ketimines or the oxazolidines (EP-A-0 470 461, EP-A-0 403 921, US-A-5,214,066"Polyurethane coating systems high performance, using oxazolidine-based reactive thinners ", by GN Robinson, TL Johnson, MD Hoffman, 21st Symposium on High Water-based Solids Content Coatings (February 1994), New Orleans, Louisiana, USA ), are also described as reactive diluent systems, or as binders alone. For the clearcoat in automotive refinishing in California, for example, a maximum of 0.42 kg / dm3 of volatile organic constituents is permitted, ie approximately 59% in the context of bulk solids in the reverse material ( DIN cup 4, 21 sec flow time at 23 ° C). The restrictions become more severe when a conventional base reversal is applied; the clear covering coating must not exceed a VOC limit of 0.25 kg / d * 9, that is to say, approximately 75% mass solids content). Important processing properties are then lost when extremely low molecular weight polyols are used, for example, rapid drying. When defined organic compounds are used, like those mentioned above, there is no guarantee of a long container life (processing time). In addition, partial dissolution of the base coating or creaming is observed, in some cases, turbidity and gas leakage flaws, with the rapid reactive diluent systems. The original goal of allowing the use of binders in pigmented systems, as well as non-pigmented ones, is also abandoned in this case. Accordingly, the object of the present invention was to develop environmentally friendly binding systems having a low solvent content, which give rise to rapid drying, a prolonged container life, little or no partial dissolution of the base coating, and no formation of cream, turbidity or defects of gas escapes, and allowing universal use in non-pigmented and pigmented systems. In addition, it should be possible to use these systems in environmentally friendly adhesives and sealing compounds. It has been found, surprisingly, that the addition of aliphatic-amine epoxide adducts having special structures in the units, allows the development of binder systems of this type, which have the properties mentioned above. Therefore, the invention relates to epoxide-amine adducts having a mass ratio of at least 20 aliphatic epoxide and / or amine units, comprising at least one tertiary or quaternary carbon atom. The mass proportion of said units is preferably at least 25%, particularly preferably at least 30%. The term "branched chain units" is used hereinafter to refer to those units having at least one tertiary or quaternary aliphatic carbon atom. The invention furthermore relates to the preparation of the epoxide-amine adducts with substantial side chain branching, to binding systems comprising these adducts and to environmentally friendly coating systems formulated therefrom, as well as to the possibility of its use in coatings, adhesives and sealing compounds to be friendly. With polymer based, high solids binder systems, it is possible to obtain solids contents in clear coatings of up to about 67% by mass. The solids contents of dough above this, are obtained only with the help of organic compounds of low molecular weight ("monomeric") of defined functionality. Compounds comprising structural units similar to those of low molecular weight polyacrylate resins, which are used in customary systems with a high solids content, should be able to mix homogeneously with these resins (reactive diluent system) and, when applied , they must improve the drying properties. In this way, it should be possible to obtain the goal of a solids content of up to 75% by mass. The branched-amine epoxide adducts which are suitable for the invention can be prepared by reacting: a) aliphatic and / or cycloaliphatic onoepoxides having from 7 to 33 carbon atoms; and b) amines having at least two primary or secondary amino groups and from 2 to 30 carbon atoms, whose primary or secondary amino groups are not directly bound to an aromatic structure; wherein a mass proportion of at least 20% of the monoepoxides is selected from aliphatic and cycloaliphatic monoepoxides having at least one tertiary or quaternary carbon atom. Preference is given to those epoxide-amine adducts for the preparation of which the monoepoxides of glycidyl esters of alkyl-alkylammonocarboxylic acids and glycidyl esters of dialkylcarboxylic acids having, in each case, 6-alkylcarboxylic acids are selected. to 21 carbon atoms in the esters. Other suitable epoxide-amine adducts can be prepared by reacting: a) aliphatic and / or cycloaliphatic diepoxides having from 6 to 50 carbon atoms; and b) primary and secondary monoates having from 4 to 30 carbon atoms, whose amino groups are not directly bound to an aromatic structure; wherein a mass proportion of at least 20% of the β-monoamines is selected from monoamines having at least one tertiary or quaternary carbon atom. Preference is given to those epoxide amine adducts for the preparation of which the diepoxides of diglycidyl ethers of dihydric aliphatic alcohols and the diglycidyl esters of dibasic aliphatic carboxylic acids having from 6 to 16 carbon atoms in the ethers and, respectively, are selected. from 12 to 42 carbon atoms in the esters. Other suitable epoxide-amine adducts can be prepared by reacting: a) aliphatic and / or cycloaliphatic mono-epoxies having from 7 to 33 carbon atoms; and b) monoamines selected from primary and secondary monoamines having 4 to 30 carbon atoms, whose amino groups are not directly bound to an aromatic structure; wherein a mass proportion of at least% of the monoamines is selected from monoamines having at least one tertiary or quaternary carbon atom and a mass proportion of at least 2% of monoepoxides of the monoepoxides is selected aliphatic and cycloal ific having at least one tertiary or quaternary carbon atom; each being a and b greater than O and the sum of a and b being at least 20, preferably at least 25 and, with particular preference, at least 30. Preference is given to those epoxide-amine adducts for which preparation is they select the monoepoxides of the glycidyl esters of alkylalkanocarboxylic acids and the glycidyl esters of dialkylalkanecarboxylic acids, each having from 6 to 21 carbon atoms in the esters. The epoxide-amine adducts according to the invention have at least one secondary OH group and at least one secondary amino group (in the case of primary amines as precursors) or tertiary (in the case of secondary amines as precursors), per molecule. It is also known that epoxide-amine adducts, which are based on the glycidyl esters of dialkyl, lalcanomonocarboxylic acids, with isophorone diamine, can be employed by extending the chain length of the isocyanate-terminated urethane prepolymers (JP. 02251516 A2), with reaction only of the amino groups, with the secondary OH groups being retained. However, it is not known that these compounds can be used as reactive diluents both with amino groups and with hydroxyl groups that react. These defined functional compounds, as a mixing component with polyisocyanates, simultaneously lead to polyurethane and polyurea structures; and this last guarantees fast curing and a high hardness to the pendulum. Due to the high weathering stability and the high reactivity, the adducts are prepared preferably using sterically hindered aliphatic amines or cyclic amines. Sterically hindered, in this context, means the presence of aliphatic structures or cycloaliphatic structures or branched, aromatic structures. Examples of suitable diamines are: neopentanediane (2,2-dydroethyl-1,3-propanediane), 1,2-diao-2-methanedipropane, diaocyclohexanes, such as 1,2-diaminecyclohexane and 1,4- diacyclohexane, γ-ylenediamines, such as m-xylylenediamine, 1,3-bis- (aminomethyl) cyclohexane, l-amino-2-a-inomethyl-3,3,5 (3, 5, 5) -tri et i le iclopentano, triacetonodiamina (4-amino-2,2,6,6-tetramet ilpiperidina), 1, 6-diamino-p-ment no, isoforonodi ina (3-aminome il-3, 5, 5-trimet iliciclohe i lamina ), 4,4'-dia inodicyclohexyl ethane, 3,3 '-dimet i 1-4, 4'-diaminodicyclohexylmethane, 3 (4), 6C9) -bisaminomethyl) tricycloC5.2.1.058 »*] decane. Examples of suitable monoamines are: ethylamine, butylamine, isobutylamine, tert-butylamine, hexylamine, cyclohexyl ina, 2-ethyl-hexylamine, Primente 61R <; R > (from Rohm &Haas, mixture of primary amines substituted with tertiary alkyl). It is also possible to use mixtures of these amines. Suitable epoxide-amine adducts can also be prepared from aliphatic diepoxides and branched aliphatic monoamines, as is known for the deposition of aqueous epoxide-amine reversal materials and is frequently used as a The principle of interlacing reactions. The aliphatic diepoxides of the glycidyl alcohol esters and ethers are selected with aliphatic dicarboxylic acids or, respectively, aliphatic diols. Examples are: the diglycidyl ether of ethylene glycol and the diglycidyl ether of butanediol; suitable esters are: digly idyl esters of dicarboxylic acids (cyclo) aliphatic, branched or unbranched, having from 2 to 40 carbon atoms, for example, the diglycidyl esters of succinic acid, adipic acid, hexahydroterephthalic acid or Dimeric fatty acids. For clearcoat applications, diglycidyl ethers are less preferred since, when used for outdoor applications, they usually have poor weather resistance. Suitable monoamines contain at least one tertiary or quaternary carbon atom and a total of 4 to 30 carbon atoms. Examples that may be mentioned are: isobutylnane, tertiarybutyl, 2-ylhethylamine and Primente 61R < R > (from Rohm &Haas, mixture of primary amines substituted with tertiary alkyl). The epoxide-amine adducts according to the invention are prepared here in a conventional manner, ie not in an aqueous medium, and initially as epoxide-amine-terminated adducts having up to four functional groups (secondary hydroxyl groups, amino groups secondary or tertiary), and then diluted, if desired, in organic solvents or solvent mixtures, and then subjected to entanglement. The reaction products of mono-epoxide and diamine or monoamine or diepoxide and monoamine can be obtained easily with or without catalysts. Said products have a weight average molecular mass of less than 3,000 g / mol, especially less than 2,000 g / mol and, in particular, less than 1,500 g / mol. The addition of these compounds to coating systems, for example, mixtures of two or more polyols, ie, polyacrylate polyols or polyester polyols, with or without the addition of known reactive diluents, pure polyols ("binders alone") and combinations of these possibilities, leads to solid contents up to about 75% by mass. This goal is achieved in any case by the use of the epoxide-amine adducts alone with appropriate curing components. The ido-amine epoxide adducts according to the invention can be prepared by adding the amine to the epoxide at an elevated temperature. Preferably the amine is taken as the initial charge and reacted with the epoxide, usually without a catalyst, under an atmosphere of inert gas, at temperatures of 50 to 150 ° C, until it is no longer present epoxide. The prepared adducts can be diluted to a selectable degree, with solvents or solvent mixtures, whose selection has no restrictions. The binders or blends of binders, of low molecular weight, which are mentioned at the beginning, can increase, by the addition of these epoxide-amine adducts, their proportion of solids in the coating material from about 67 up to about 71% by mass (DIN cup 4, 21 sec, 23 ° C) and its reactivity. As unique binders, these epoxide-amine adducts are extremely reactive and can be used in combination with proprietary curing agents in two component adhesives or sealant compounds. The use of said adducts as the sole binders in the coating technology presupposes slowing the curing reaction. The retarding additives (retarders) are, for example, organometallic compounds, electron-deficient compounds, certain acids or salts. Examples of suitable organometallic compounds are tin compounds, such as dibuyltin dilaurate, dibutyltin diacetate and iloxo tin dibutyl, and also zinc octoate or zirconium compounds. Examples of electron-deficient compounds are boron trifluoride, aluminum compounds and carbocat ions. The acids are, for example: formic acid, acetic acid, perchloric acid or trichloroacetic acid. It is also possible to use salts, such as triphenylmetyl perchlorate, trophobium hemonitrile and acetyl perchlorate. These compounds are premixed with the epoxide-to-ad-adducts, for example, and then form, with the nitrogen atoms of the amino groups and with the oxygen atoms of the alcohol groups, "chelate-like" complexes. which, depending on the strength of the complex, compete with the curing reaction.- The solids contents of said coating systems comprising the binder adduct and the curing agent are up to 75% by weight (DIN cup 4, 21 sec, 23 ° C). In order to slow down or retard the curing reaction it is also possible to reduce the functionality of said epoxide-amine adducts, subsequently modifying them in whole or in part. Such modifications may include protection (temporary) of groups or may be permanent. For example, secondary amino functions can be inactivated by reaction with isocyanate compounds, each of whose molecules contains on average from 0.6 to 1.5 free NCO groups and at least one tertiary amino group. As examples of temporary protecting groups, the secondary alcohol and the amine function can be reacted with aldehydes or ketones. The oxazolidines formed can be easily decomposed again, using atmospheric moisture / water to form the original functionalities, which are then available, in turn, for the curing reactions. Said protected epoxide-amine adducts are also part of the invention and, therefore, are included under the term "epoxide-amine adducts" according to the invention. The epoxide-amine adducts according to the invention, in combination with polyacylate polyols, are particularly suitable for coating applications in single-component or two-component systems, especially for systems with a high solids content. say, for mixtures containing solvent, which have a high solids content. In these combinations preference is given to the use of mixtures comprising mass proportions of: a) from 0.1 to 99.9 percent hydrophilic containing copolymers; and b) from 99.9 to 0.1 & of the epoxide-amine adducts according to the invention. Examples of hydroxyl-containing copolymers are polyacrylates or polyesters. Also included are acrylate resins modified with polyester. Particularly suitable hydrophilic-containing copolymers can be selected from: aa) copolymers obtainable by co-polymerization of at least two vinyl monomers, at least one of which comprises at least one hydro group; ilo; and ab) copolymers obtainable by copolymerization of at least two vinyl monomers, at least one of which has at least one acid group, and which are reacted before, during or after polymerization , with at least one compound that reacts with the acid groups to form an ester with the formation of at least one hydrophilic group; ac) copolymers obtainable by copolymerization of at least two vinyl monomers, at least one of which has at least one hydrophilic group and which are reacted before, during or after polymerization , with at least one compound that reacts partially or completely with the hydroxyl groups to form an ester, with the formation of at least one hydroxyl group. The copolymers of aa) are usually prepared in a solution polymerization with free radical. Only products based on maleic esters can also be prepared in a bulk polymerization, that is, without solvents. In the copolymers of type ab) or ac), this additional freedom to select the polymerization method (solution or bulk polymerization) is brought about by the addition of specific compounds of relatively high boiling point. Examples of these compounds are, in the case of type ab), the glycidyl esters or the glycidyl ethers and, in the case of type a, the lactones. Particular preference is given to those mixtures in which epoxide-amine adducts according to the invention are added to a mixture of hydrophilic-containing copolymers, each of which has a hydrophilic number of 10 to 250. 9 / g »and of which at least one has a weight average molecular mass of more than 3,500 g / mol and at least one has a weight average molecular weight of menoß of 3,500 g / mol. Examples of suitable solvents for the products obtained according to the invention are aliphatic, cycloaliphatic and aromatic hydrocarbons, such as alkylbenzenes, for example xylene, toluene; esters, such as ethyl acetate, butyl acetate, acetates with longer alcohol residues, butyl propionate, pentyl propionate, ethylene glycol onoethyl ether acetate, the corresponding methyl ether acetate or propylene glycol methyl ether acetate; the ethers, such as the monoethyl, monomethyl or monobutyl ether of ethylene glycol acetate; glycols, alcohols, ketones, such as methyl isoamyl ketone, methyl isobutyl ketuate; the lactones and the mixtures of said solvents. Other solvents that can be used are the reaction products of lactones with glycols or alcohols. The present invention further relates to coating compositions comprising epoxide-amine adducts according to the invention, as the agglutinating component. In this context, preference is given to coating compositions comprising at least one epoxide-amine adduct according to the invention, as a reactive diluent and at least one other hydroxy-functional binder and at least one agent curator. These reactive diluent systems can be cured in the presence of suitable interlacing agents, without heating or carrying them to elevated temperatures.

The compounds which are suitable as the curing component in these coating compositions are amino resins, polyisocyanates, or compounds comprising acid and / or acid anhydride groups, individually or in combination. In each case, the entanglement agent is added in an amount such that the proportion of the number of OH or NH groups present in the binder or binder system with respect to the number of reactive groups present in the entanglement agent is between 0.3: 1 and 3: 1 Suitable amino resins as curative components are preferably urea resins, melamine resins and benzoguanamine resins, individually or in a mixture. These are etherified products of the condensation of urea, melamine or benzoguanamine with formaldehyde. Suitable mixing ratios are in the range of 50:50 to 90:10 of agglutinating system containing hydro? Il or amino to amino resin crosslinking agent, based on the mass of the solid resin. The appropriate phenolic resins and their derivatives can also be used as curing agents. In the presence of acids, for example, p-toluenesulfonic acid, these crosslinking agents lead to cure of the reverse. The hot curing can be carried out, in the usual manner, at temperatures of 90 to 200 ° C, for example, for 10 to 30 minutes. The polyisocyanates are suitable for curing the Preferred include N, N ', N "-tris (6-isocyanatohexyl) biuret and their mixtures with their higher homologs and N, N', N" -tris (6-isocyanatohexyl) isocyanurate and their mixtures with their higher homologs containing more than one isocyanurate ring. Compounds that are also suitable for curing at elevated temperature are the capped polyisocyanates, the polycarboxylic acids and their anhydrides. The epoxide-amine adducts according to the invention are particularly suitable for the preparation of transparent coatings and surface coatings containing solvent, of high solids content, as well as for fillers. In the reversing compositions prepared with the epoxide-amine adducts according to the invention it is also possible that other au? Iliares and additives that are accustomed to the technology of coatings, although they have not been mentioned yet. These include, in particular, catalysts, leveling agents, silicone oils, plasticizers, such as phosphates and phthalates, pigments, such as iron oxides, lead oxides, lead silicates, titanium dioxide, barium sulfate, zinc sulphide, f-alocianine complexes, etc .; and fillers, such as talc, mica, kaolin, gypsum, ground quartz, ground asbestos, ground slate, various silicas, silicates, etc .; control additives 16 products according to the invention with entanglement, especially at moderate temperatures or at room temperature. Suitable polyisocyanate components, in principle, are all those aliphatic, cycloaliphatic or aromatic polyisocyanates derived from the chemistry of the polyurethanes, individually or as a mixture. Highly suitable examples are low molecular weight polyisocyanates, for example: hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethyl-1-1,6-heme-methylene diisocyanate, diisocyanate dodeca et ileno, tetramethyl-p-β-1-ylene isocyanate, 1,4-di-isocyanatocyclohexane, l-isocyanato-3,3,5-tri and yl-5-isocyanatomethyl-cyclohexane (IPDI), 2,4 ' - and / or 4,4'-di isocyanatodicyclohexymethane, 2,4"- and / or 4,4'-diisocyanatodiphenyl ethane or mixtures of these isomers with their higher homologs, such as those obtainable in a known manner per se by phosgenation of the condensation products of aniline / formaldehyde, 2,4- and / or 2,6-diisocyanatotoluene or any desired mixtures of said compounds, however, it is preferred to use derivatives of these simple polyisocyanates, such as It is customary in coatings technology, which include polyisocyanates having, for example, biurethane, uretadione, isocyanurate, urethane, carbodiimide or allophanate, such as those described, for example, in EP-A 0 470 461. The modified polyisocyanates, particularly viscosity, matte finishing agents, UV absorbers and photostabilizers, antioxidants and / or peroxide scavengers, antifoams before and / or wetting agents, active diluents (in addition reactive diluents) and the like. The coating compositions can be applied to the respective substrate by known methods, for example, by brush application, by dipping, by flow coating or with the aid of rollers or spatulas, but in particular, by spray. They can be applied under hot conditions and, if desired, can be brought to a ready-for-application form by injecting supercritical solvents (eg, C0a). Binders prepared using epoxide-amine adducts according to the invention can be used to render automotive refinishes, industrial coatings, wood coatings, plastic coatings, building coatings and textile finishes having outstanding properties. These binders can be used to prepare both intermediate coatings and pigmented or non-pigmented final or surface coatings. For this purpose, the coating materials are generally cured within a temperature range of -20 to + 100 ° C, preferably -10 to + 60 ° C. The invention is illustrated in greater detail in the following examples. In the working examples all percentages are in mass.

EXAMPLES PREPARATION OF THE EPOXIDE-AMINE ADUCTQS WITHOUT A PROTECTIVE GROUP.

The diamine is charged in a reactor equipped with a stirring mechanism, an inlet for inert gas, a heating and cooling system and a metering device; and it is heated under an inert gas up to the reaction temperature. The glycidyl ester of a C 1-dialkylalkanomonocarboxylic acid is then metered, for example, the glycidyl ester of versatic acid 10 (trade name: Cardura "" E 10, Shell Chemicals)] over the course of three hours (example a ) or 4 hours (example b). The subsequent reaction time is selected so as to give an epoxide content of 0 (Table 1). The epoxide-amine adducts are diluted in appropriate solvents or in solvent mixtures.

TABLE 1 PREPARATION AND PROPERTIES OF EPQXIDO-AMINE ADDUCTS Load the Ib 3,3'-d imet i 1-4, 4 '-diamino dicyclohexylmethane (1) 236.4 ------ Isophorone diamine (2) 170.3 Glycidyl ester (3) 500.0 500.0 Reaction temperature 10 ° C 12O0C Dosing time in hours 3 4 Post-reaction in hours 3 4 Epoxide content in% (a) 0. 0 0.0 Characteristics: 90% form in supply acetate (f.s.) bu i lo (BuOAc) Viscosity (50% in BuOAc), mPa.s 12.2 6.6 Gas phase chromatography (PS calibration) (b) Mw in g / mol 1026 910 U = Mw / M "1 .09 1.03 Hazen color number (f.s.) (DIN 53 995) 15 33 (1) Trade name: Laromin < R > C269 (BASF, Ludwighafen) (2) Isophorone diamine (Hüls, larl) (3) Glycidyl ester of versatic acid 10 (trade name: Cardura < '»> E10, Shell Chemicals, Rotterdam). Determination of the epoxide number (including the amine) characteristics: amine number and viscosity - for the standards, see Analytical Determ ination Methods, brochure Hoechst AG Kunstharze, 1962 edition. A) The epoxide content can be determined by the difference between the epoxide number, including the amine (with tetrabutyl bromide) and the number of amine (primary or secondary - without tetrabuyl bromide) onio). b) Gas phase chromatography: Mw, M, -,: lv1illipo ^ e < •, »Waters Chromatography System 660. Pump: Waters, model 590, IR detector: Waters model 410. Column packing: Ultrastyragel from Waters, 1? 1000 angstrb s + 1? 500 angstroms + 1 x 100 apgstroms. Solvent: tetrahydrofuran at 40 ° C. Flow rate: 1 ml / min, concentration: 1% based on solids. Calibration: polystyrene (from PSS, Mainz) The prepared epoxy-amine adducts are reacted completely (determined by the epoxide content). Gas-phase chromatography shows only the relative molecular mass in relation to the polystyrene calibration. The products are uniform (U 1.1). The prepared epoxide-amine adducts have very low solution viscosities (50% in butyl acetate).

Ib. PREPARATION OF OXAZQLIDINE - ADOXIDE-AMINE ADUCTQS WITH TEMPORARY PROTECTIVE GROUP. 300 g of the epoxide-amine adduct Ib, 90% concentration (0.403 mol) are initially introduced into a 500 ml, three-necked flask, with agitator mechanism, inlet for inert gas, heating system and metering funnel, and they give 61.0 g (0.645 mol) of isobutyl aldehyde, with stirring, at 55 ° C, during the course of 4 hours. Then 50 ml of toluene are added and the water / solvent mixture (including the azeotrope) is distilled off over the course of two hours. The colorless to pale yellowish oxazolidine formed, le, can be identified by FT-IR: OH band 3450 cm-1 (weak); system 0-C-N: triplet 1060-1200 in .- *.

II. PREPARATION OF COATING MATERIALS In order to prepare the curable coating compositions, according to the invention, the components, which consist of at least one epoxide-amine adduct according to the invention, or a mixture of one or more copolymers with the epoxide-amine adducts according to the invention are mixed with auxiliaries and additives, the solvents and the crosslinking agents in the mixing ratio described (table 2) and the mixtures are adjusted using more diluent, at the spray viscosity of 21 to 22 seconds, with the flow cup (DIN 52 211, 4 mm, 23 ° C). This can be done with the low viscosity copolymer components, without solvent, by heating to higher temperatures, if necessary. In a preliminary step, it is necessary to add retarding additives to the epoxide-amine adducts and bring the mixtures to an appropriately prediluted state. It is advisable to use the isocyanates in prediluted form as well. The products of relatively high viscosity are dissolved - if the curable mixtures are not used as a powder coating -, or they are dispersed in the aforementioned diluents, before mixing. In the case of the pigmented systems, a dispersion step is carried out first where the appropriate pigments are dispersed together with the epoxide-amine adducts according to the invention or with a mixture thereof, with copolymers containing hydro? Il, with or without the addition of a suitable, special grinding resin, in a dispersion apparatus of suitable construction to form a pigment paste. This paste is mixed, as it is or with the addition of more binder, which is compatible with the other components of the related coating system, and is constituted with the addition of other diluents or typical coating additives. In this context, the life of the container and the properties of the resulting films depend on the process conditions, ie the nature and quantity of the starting materials, the amount of catalyst added, the temperature regime, etc. . The curing may be carried out discontinuously or continuously, for example, by means of an automatic coating apparatus.

TABLE 2 PREPARATION OF CLEAR COATINGS OF HIGH CONTENTS OF SOLIDS WITH EPOXIDQ-AMINE ADDITION Agluante System DR DR mixed system High molecular weight copolymer A2 (DE-A 43 24 601), (70%) 20 - Copolymer of the application DE-P 195 15 919.5, Example la (66.5%) 20 63 Epoxide-amine Ib * (90%) 20 7 Tinuvin < '",> 292 0.49 0.43 Tinuvin < R > 1130 1.46 1.26 Si Oil LO 50% (10% concentration) 0.96 0.65 Mixture of solvents (2: 3: 10) 14.63 12.60 Solvesso < R > 100 / xylene / BuOAc Desmodur < R > N 3390 36.2 36.5 ** Flow cup (DIN 53 211) in seconds 21 21 Coating Designation Coating Coating 1. to 2 DR Reactive diluent (epoxide-amine Ib). * The ido-amine epoxide adduct was premixed with 0.6 part by weight of a solution of dibutyltin dilaurate (concentration, 10%). ** 60% concentration. Tinuvin < R > 292"HALS" (Ciba-Geigy, Basel) Tinuvin < R > 1130 UV absorber (Ciba Geigy, Baßilea) Si Oil LO 50% Leveling agent (silicone oil from Wacker GmbH, Burghaußen) Desmodur < R > N 3390 Polyisocyanate containing isocyanurate groups (Bayer AG, Leverkusen) BuOAc Butyl acetate After predilution as before, the clear coatings were adjusted precisely at 21 sec, using the same solvent mixture (Solvesso <R / 100 /? ileno / BuOAc).

III.- FUNCTIONING TEST a) Clear Coatings The coating systems prepared as in II were applied to clean glass panels, using a 100 um applicator spatula, and applied coatings were tested under air drying conditions.

TABLE E PROOF OF OPERATION OF CLEAR COATINGS. OF ELEVATED CONTENTS OF SOLIDS WITH EPOXIDE-AMINE ADDITIVE Coating designation Revest L- Coating 1 for 2 Transparent transparent cover Initial / container life > 3 hours > 6 hours Drying time of dust 20 '41' Drying without tackiness 90 '166' CS - 1 hour, 125 ° C 66.1 70.1 Pendulum hardness after 24 hours 155 66 2 days 179 102 4 days 191 126 10 days 201 161 Gasoline of special quality, after 10 days, in minutes > 30 > twenty Pendulum hardness according to onig (seconds). CS = solids content, when determined by DIN 53 216. '= minutes.

RECAPITULATION The high solids polyacrylate polyol / polyacrylate polyol of extremely low molecular weight / epoxide-amine adduct system has a mass solids content whose level (about 66%) is similar to that of the weight polyacrylate polyol and extremely low molecular weight as sole binder (coating 3 in the German application DE-P 195 15 919.5 filed simultaneously with the present), but with good drying and good resistance to special grade gasoline. The extremely low molecular weight polyacrylate polyol system / epoxide-amine adduct has an even higher solids content, in bulk, with improved drying, improved pendulum toughness and improved resistance to the reversal designated 3 in the DE-P 195 15 919.5, filed concurrently with the present. b) CAPACITY FOR PIGMENTATION OF REVERSING MATERIALS.

The measure used for the pigmentation capacity of the coating materials was the "oil absorption" at the wetting point (Glasurit manual "Lacke und Farben", 10th edition (1969), pages 144 et seq.). A defined amount (5 to 10 g) of Kronos 2310 white pigment (Kronos Titan GmbH, Leverkusen) was taken and treated dropwise with a solution of the binder, of approximately 70% concentration (copolymer A2 of DE-A 43 24 601, copolymer of the application DE-P 195 15 919.5 presented concurrently) or the mixtures (mixed RD system), the mixing being carried out perfectly with a spatula after each drop. The wetting point was reached when the mass begins to form clods and takes on a dark appearance (Table 4).

TABLE 4 CAPACITY FOR PIGMENTATION - POINT OF HUMECTATION OF AGGLUTINANT SYSTEMS (PROPORTION IN PERCENTAGE IN MASS, BASED ON SOLIDS) Copolymer A2 Copolymer System (comparison) (comparison) DR System DE-A 4324601 DE-P19515919.5 mixed.

Binder to the wetting point 19.1 17.6 15.6 (mass solids content) RECAPITULATION: The comparison polymer A2 consumes most of the binder in order to reach the wetting point. This is followed by the copolymer of very low molecular weight (comparison), although this exhibits the problem of poor drying in the clear coating. The lowest binder absorption is shown by the mixing system with the epoxide-amine adduct, which also showed rapid drying in the clear coating test.

IV.- PROOF OF SOLUBILITY IN THE APPLICATION OF TWO COMPONENTS a) Coating compositions. b) Adhesives or sealing compounds.

The Ib-epoxide-amine adduct and its oxazolidine (epoxide-protected amine adduct of Ib) were taken individually as the initial charge and tested to see if they are suitable by the slow addition of polyisocyanate (Desmodur <R> N 3390, Bayer AG, Leverkusen), under normal climatic conditions (table 5).

TABLE 5 TEST TO SEE IF THE EPOXIDE-AMINE / OXAZOLIDINE ADDITIVE IS ADEQUATE Reaction Climatic conditions ñor- 10% 65% humidity, 23 ° C. relative in atmosphere.

Adducto Ib of epoxide-amine Extremely fast very fast O? Azolidine very slow moderate RECAPITULATION: The adduct of epoxide-amine Ib can only be used preferably in the industry of adhesives or sealing compounds, while the adduct of epoxide-protected amine (or? Azolidine) has its main application only in the coatings industry.

Claims (7)

NOVELTY OF THE INVENTION CLAIMS

1. - An epoxide-amine adduct, characterized in that it has a mass proportion of at least 20% aliphatic and / or amine epoxide units, comprising at least one tertiary or quaternary carbon atom.

2. An epoxide amine adduct according to claim 1, further characterized in that it can be prepared by reacting: a) aliphatic and / or cycloaliphatic monoepoxides having from 7 to 33 carbon atoms; and b) amines having at least two primary or secondary amino groups and from 2 to 30 carbon atoms, whose primary or secondary amino groups are not directly bonded to an aromatic structure; where you select a proportion in raisins of at least 20% of the onoeploidos of aliphatic and cycloaliphatic monoepoxides having at least one tertiary or quaternary carbon atom.

3. An epoxide-amine adduct according to claim 1, further characterized in that it can be prepared by reacting: a) aliphatic and / or cycloaliphatic diepoxides having from 6 to 50 carbon atoms; and b) primary or secondary monoamines having from 4 to 30 carbon atoms, whose amino groups are not directly bound to an aromatic structure; wherein a mass proportion of at least 20% of the monoamines of monoamines having at least one tertiary or quaternary carbon atom is selected.

4. An epoxide-amine adduct according to claim 1, further characterized in that it can be prepared by reacting: a) aliphatic and / or cycloaliphatic ono-epoetics having from 7 to 33 carbon atoms; and b) monoamines selected from primary and secondary monoamines having 4 to 30 carbon atoms; whose amino groups are not directly linked to an aromatic structure; wherein selects a mass proportion of at least a% of the monoamines of monoamines having at least one tertiary or quaternary carbon atom, and a mass proportion of at least b% of the mono-epoxides is selected, aliphatic and cycloaliphatic monoepoxides having at least one tertiary or quaternary carbon atom; the sum of 1 and b being at least 20 and each being a and b greater than zero.

5. An epoxide-amine adduct according to claim 2, further characterized in that the monoepoxides of the glycidyl esters of alpha-alkylalkanecarboxylic acids and the glycidyl esters of alpha, dialkyl dialkylcarboxylic acids are selected, having, in each case, from 6 to 21 carbon atoms in the esters.

6. An epoxide-amine adduct according to claim 3, further characterized in that the diepido? Are selected from the diglycidyl ethers of dihydric aliphatic alcohols and diglycidic esters of carbohydric acid aliphatic dibasic? 6 to 16 carbon atoms in the ethers and, respectively, from 12 to 42 carbon atoms in the esters.

7. An epoxide-amine adduct according to claim 4, further characterized in that the mono-epoxides of the glycidyl esters of alpha-alkylalkanocarboxylic acids and the glycidyl esters of the alpha, alkoxy acids are selected. -dialkylalcanomono-carbo? licoß, which have in each case, from 6 to 21 carbon atoms in the esters. 6. An epoxide-amine adduct according to any of claims 2, 3 and 4, further characterized in that its functionality is reduced by partial or complete reaction of the hydroxyl and amino functional groups. 9. An epoxide-amine adduct according to claim 6, characterized in that the functional groups are blocked by reaction to form temporary protective groups. 10. An epoxide-amine adduct according to claim 9, further characterized in that the temporary protecting groups are o? Azolidine compounds. 11. A binder for coatings, characterized in that they comprise at least one epoxide-amine adduct as claimed in claim 1. 12. A mixture, characterized in that it comprises proportions in mass of: a) from 0.1 to 99.9 percent of copolymers containing hydro? yl; b) from 99.9 to 0.1% of epoxide-amine adduct as claimed in claim 1. 13. A mixture according to claim 12, further raised because the β-hydrophilic-containing copolymers are selected. of acrylate copolymers, polyesters and acrylate copolymers modified with polyether 14. A mixture according to claim 12, further characterized in that the hydrophilic-containing copolymers of: aa) copolymers which can be obtained by copolymerization are selected When at least two vinyl monomers are present, at least one of them comprises at least one hydroxyl group; and ab) copolymers obtainable by copolymerization of at least two vinyl monomersß, at least one of which has at least one acidic group and which are reacted, before, during or after polymerization, with at least one compound that reacts with the acid groups to form an ester with the formation of at least one hydroyl group; and ac) copolymers which can be obtained by copolymerization of at least two vinyl monomers, at least one of which has at least one hydrophilic group, and which they react before, during or after the polymerization, with at least one compound that reacts partially or completely with the hydroyl groups to form an ester with the formation of at least one hydroxyl group. 15. A mixture according to the claim 12, further characterized in that it employs a mixture of hydroxyl-containing copolymers, each of which has a hydroxyl number of 10 to 250 mg / g and at least one of which has a weight average molecular mass of more than 3,500 g. / mol and at least one has an average molecular weight of menoß fat of 3,500 g / mol. 16. A binder for coatings, characterized in that it comprises a mixture as claimed in claim 12. 17. A binder for coatings, characterized in that it comprises a mixture as claimed in claim 15. 16.- A composition of coating comprising at least one binder as claimed in any of claims 11, 16 or 17, and at least one curing agent selected from the group consisting of amino, polyfunctional and non-crowned polyfunctional isocyanate resins, and organic compounds containing acid groups and / or acid anhydride groups. 19. The use of an epoxide-amine adduct, as claimed in claim 1, in sißtemaß adheßivoe of doß componenteß or in systems of sealing compound. ADHESIVES OF ALIPHATIC-AMINE EPOXIDE WITH SUBSTANTIAL BRANCH OF SIDE CHAIN: PROCEDURE FOR ITS PREPARATION AND ITS USE. SUMMARY OF THE INVENTION The epoxide-amine adducts having a mass ratio of at least 20% of aliphatic or amine epoxide units, which at least comprise a tertiary or quaternary carbon atom, are prepared by reacting monoepoid with mono- or diamines or diepides with monoamines. They are used as binders for coatings of relatively high environmental friendliness, if desired, in a mixture with other binders with hydroxy functionality, and as a reactive component in corresponding adhesive compositions and in corresponding sealants. CR / crm *