MXPA98003357A - Emulsifiantes no ioni - Google Patents

Abstract

This invention relates to non-ionic emulsifiers based on fatty acid esters of polyakoxylated polyhydric alcohols as fundamental constituents, at least two fundamental constituents are linked to one another by the reaction of hydroxyl groups with a polyisocyanate, with the formulation of urethane linkages.

Description

NON-IONIC EMULSIFIERS DESCRIPTIVE MEMORY This invention relates to nonionic emulsifiers based on fatty acid esters of polyalkoxylated polyhydric alcohols as fundamental constituents, and to the production and use thereof. Nonionic emulsifiers for the stabilization of dispersed systems have been known for a long time in the literature. Apart from the alkoxylates of fatty alcohol and alkylphenol of linear structure, emulsifiers based on polyhydric alcohols esterified with fatty acids, such as glycerol, pentaerythritol, sorbitol and by-products thereof (eg, sorbitan and its isomers) are known. see HOUBEN-WEYL), and which are further characterized because stable emulsions can be produced using smaller amounts of the ulsifier than when using the linear types. The fatty acids in these emulsifiers can be saturated or unsaturated. Examples include palmitic acid, stearic acid, lauric acid, linoleic or linolenic acid and dehydrated castoric acid. The alkoxylation is carried out by means of ethylene oxide and / or propylene oxide. The degree of alkoxylation is between 10 and 100. Examples of alkoxylated fatty acid esters of polyhydric alcohols include the polyethoxylated sorbitan fatty acid esters which are commercially available under the tradename TWEEN (a trademark of ICI). Its synthesis and production are described in: Paul Becher: Encyclopedia of Emulsion Technology Vol.l p. 337 et seq. . Dekker Inc. New York, Basle, 1983 Kozo Shinoda & Stig Friberg: Emulsion & Solubilization p. 74 et seq. John Wiley & Son, 1986 Drew Myers: Surfactant Science and Technology p. 67 et seq. VCH Publishers, Inc. 1988 Dr. R. Reusch in: Ullmann Enzyklopádie der technischen Chemie Volume 10, pgs. 449-473 Verlag Chemie, Weinheim, 1975 Dr. M. Ouadvlieg: "Emulgieren, Emulgatoren" in HOUBEN-WEYL: "Methoden der organischen Chemie" p. 97 et seq. Vol. 1/2, Thieme-Verlag, Stuttgart 4th Edition, 1959, and in EU-A-3647 477 EU-A-2 374 931 EU-A-2 380 166.

The ethoxylation can be carried out by the reaction of basic OH-functional substances (fatty acids, fatty alcohols, polyhydric alcohols and by-products thereof, such as sorbitan, for example) with polyalkylene oxides such as polyethylene oxide for example. , or by polyalkoxylation of the aforesaid basic substances with ethylene oxide and / or propylene oxide with basic catalysis and under pressure. Examples of ethoxylated sorbitan fatty acid esters include the commercial products TWEEN 20 (sorbitan monolaurate comprising 20 moles of ethylene oxide) and Atlas G-4252 comprising 80 moles of ethylene oxide. Emulsifiers such as these will be hereinafter referred to as fundamental constituents, from which the emulsifiers according to the invention are synthesized. A disadvantage of these emulsifiers during the production of synthetic resin emulsions for the formulation of lacquers, particularly coating lacquers, is the large amount thereof that has to be used; which results in a serious deterioration of the weather resistance and other parameters of the lacquer technology. It has now been shown that these disadvantages can be substantially eliminated by increasing the molecular weight by binding the fundamental constituents. In this way, an emulsifier is obtained under the trade name "G1350" (ICI) based on ethoxylated sorbitan fatty acid esters and in which the fundamental constituents are accumulated to form structures of higher molecular weight by reaction with anhydride phthalic, and which has an average molecular weight Pm of 17,000. Stable emulsions are obtained here even when 3% amounts are used with respect to the phase that will be ulsified, whereas when the corresponding fundamental constituents are used, at least 10-20% is required with respect to the phase to be emulsified. A disadvantage of this emulsifier is the tendency of the lacquer film to yellow, due to its chemical structure, and its tendency to form a strongly structured surface. This last disadvantage is particularly problematic for coating lacquers and severely restricts the use of these emulsifiers for this application. Moreover, the coating lacquers containing this emulsifier are very sensitive to hydrolysis. The object of the present invention is therefore to provide emulsifiers which do not exhibit these disadvantages and which also make possible the production of very smooth surfaces, with a good state of the coating lacquer. This object is achieved by means of nonionic emulsifiers of the type mentioned at the start, which are further characterized because at least two fundamental constituents are linked to one another by the reaction of hydroxyl groups with a polyisocyanate, with the formation of bonds of urethane. Advantageous forms of these emulsifiers are given in the appended claims. Preferred polyalkylene oxides are polyoxyethylene (POE) and polyoxypropylene (POP) or block copolymers of POE and POP. The degree of alkoxylation is between 25 and 300, preferably between 30 and 200. The fatty acids can be saturated or unsaturated in nature. Its chain length is between Ce and C24. Examples thereof include palmitic acid, stearic acid, lauric acid, linoleic and linolenic acids and dehydrated castoric acid. Preferably saturated fatty acids are used. Lauric acid is much preferred. The core unit of the emulsifiers according to the invention consists of polyols, which may be either linear or branched. Preferred polyols have the general composition C n H 2n + 2 n n, such as glycerol, (n = 3), trimethylolpropane, pentaerythritol or sorbitol (n = 6). The cyclic condensation products of these polyols, e.g., sorbitan and isomers thereof, are most preferably used. Apart from the simple polyols, polymeric polyols such as polyglycerols and the hydroxyl-functional cores of the emulsifiers according to the invention are also suitable. The molecular weights of polyols of this type are usually between 92 and 1000. The preferred constituents are the fatty acid esters of sorbitan, which are coupled with saturated fatty acids. Therefore, the fundamental constituents that are particularly preferred are the sorbitan monolaurates which have alkoxylation degrees of 25 to 300 moles of ethylene oxide per mole of emulsifier, and which correspond to a PM (GPC; polystyrene) from 500 to 14,000. Its composition corresponds to a molar ratio of sorbitol: lauric acid: alkylene oxide = 1: 1: 25-300. The fundamental constituents are reacted with polyisocyanates to increase the molecular weight. Examples of polyisocyanates that can be used according to the invention include cycloaliphatic, aliphatic or aromatic polyisocyanates, such as 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (= isophorone diisocyanate IPDI), perhydro-2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-diphenylene diisocyanate, 2,4- and 2,6-diisocyanate toluene, 2,4'- and / or -4-4'- diphenylmethane diisocyanate, 3,2'- and / or 3,4-diisocionate-4-methyl-diphenyl ethane, 1,5-naphthylene diisocyanate, diisocyanate of m-xylene, p-xylylene diisocyanate, 4,4'-triphenylmethane triisocyanate, tetramethylxylylene diisocyanate, lysine diisocyanate or mixtures of these compounds. The aliphatic and cycloaliphatic polyisocyanates are preferred. Apart from these simple isocyanates, isocyanates containing heterogeneous atoms in the radical which binds to the isocyanate groups are also suitable. Examples thereof include polyisocyanates comprising carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups and biuret groups. The known polyisocyanates which are used mainly for the production of lacquers are also suitable, eg, modification products of the aforementioned simple polyisocyanates containing biuret, isocyanurate or urethane groups, particularly tris- (6-isocyanatohexyl) -biuret, as well as isocyanurates of 1,6-hexamethylene diisocyanate or isophorone, or low molecular weight polyisocyanates comprising urethane groups, such as those obtainable by the reaction of excess IPDI with simple polyhydric alcohols of a molecular weight scale from 62 to 300, particularly with trimethylolpropane. Any mixtures of these polyisocyanates can, of course, also be used for the production of the emulsifiers according to the invention. Other suitable polyisocyanates are the known prepolymers comprising terminal isocyanate groups, which can be obtained in particular by the reaction of the above-mentioned simple polyisocyanates, particularly diisocyanates, with substoichiometric amounts of organic compounds comprising at least two groups which are capable of reacting with isocyanate groups. Also used as such are compounds containing a total of at least two amino groups and / or hydroxyl groups and having an average molecular weight number of from 300 to 10,000, preferably 400 to 6,000. Preferably used are the corresponding polyhydroxyl compounds, e.g., the hydroxyl polyesters, hydroxypolyethers and / or acrylate resins containing hydroxyl groups which are known in the art of polyurethane chemistry. In these known prepolymers, the ratio of isocyanate groups to hydrogen atoms that are reactive toward NCO corresponds to 1.05 to 10: 1, preferably 1.1 to 3: 1, wherein the hydrogen atoms are preferably originated from hydroxyl groups. Moreover, the type and quantitative ratios of the starting materials used for the production of the NCO prepolymers are preferably selected so that the NCO prepolymers have an average NCO functionality of 0.5 to 4, preferably from 1.2 to 3, and a number of average molecular weight from 500 to 10,000, preferably 800 to 4,000. It is also possible to use copolymers of the vinyl-unsaturated monoisocyanate dimethyl-m-isopropylbenzylisocyanate, such as those described, among other features, in DE-A-41 37 615. The isocyanate groups of the polyisocyanates that are used are partially blocked in optional form. Normal blocking agents, e.g., 1,2-propanediol, dimethyl malonate, diethyl malonate, ethyl acetoacetate and / or butanone oxime, as well as other blocking agents that are familiar to an expert in the art may be used. The technique. Other suitable blocking agents include compounds that contain only a single amine, amide, imide, lactam, thio or hydroxyl group. Examples include aliphatic or cycloaliphatic alcohols such as n-butanol, isopropanol, tert-butanol, furfurol, 2-ethylhexanol and cyclohexanol, phenols; cresol, tert-butylphenols, dialkylamine alcohols such as dimethylammoethanol, oxyas such as methyl ethyl ketoxime, acetone oxime, cyclohexanone oxime or acetophenone oxime, lactams such as epsilon-caprolactam or pyrrolidone-2, imides such as phthalimide or N- hydroxyaline, hydroxyalkyl esters, hydroxyamic acids and esters thereof, N-alkylamides such as methylacetamide, imidazoles such as 2-methylimidazole and pyrazoles such as 2,3-dimethylpyrazole. However, mixtures of these blocking agents can also be used. The molar ratio of the acid-containing blocking agents to the NCO groups of the isocyanates can be varied, for example from 0.1 to 0.5: 1.

The reaction of the basic constituents with polyisocyanates is preferably conducted, for example, by placing a molten material or an organic solution of the fundamental constituents in aprotic solvents in the reaction vessel and treating it by dripping at elevated temperatures, for example at 80 ° C, with the polyisocyanate, which is optionally dissolved in organic solvents. The course of the reaction is monitored by means of the NCO content. The reaction is allowed to proceed to an NCO content of < 0.1%, for example. After completion of the reaction, the resulting emulsifier can be freed from the organic solvent, if necessary, by distillation, and can be diluted with water. Examples of solvents that can be used include organic solvents such as aliphatic and aromatic hydrocarbons, for example xylene, and mixtures of aliphatic and / or aromatic hydrocarbons, esters or ethers. The reaction is preferably conducted in the absence of solvent. If the fundamental constituents contain water from their production process, it must be removed substantially, up to a maximum content of 2% for example, before the reaction with polyisocyanates. Suitable dehydration methods are familiar to a person skilled in the art, e.g., azeotropic dehydration using a trapping agent such as xylene for example, distillative drying, freeze drying, the use of drying agents, etc. In order to suppress the effect of basic catalysts which may be contained and which may originate from the production process for the fundamental constituents, it may be useful to neutralize them by the addition of organic or inorganic acids such as acetic acid and / or phosphoric acid, example. The molecular weights are increased by the reaction, in accordance with the invention, of the basic constituents with di-, tri-or polyisocyanates. The molecular weights of the emulsifiers produced are within a range of Pm (average molecular weight) of 20,000 to 150,000. The emulsifiers according to the invention are suitable for the emulsification of very different binders. Binders can be free of functional groups and can be binders that dry purely by physical action, or can comprise functional groups. The functionalized binder vehicles can be self-latching or externally interlacing. In the case of externally interlacing binders, the binder vehicle and the interlacing agent can exist either together for an extended period of time (single-component formulation) or are not mixed until just before application (two-component formulation) ). The binder vehicle and the entanglement agent can both be emulsified using the emulsifier according to the invention, but it is also possible to stabilize one of the two components in another way, e.g., ionically, or that a component is used in a anhydrous, so that this component does not require an ulsifier. Examples of binder vehicles which can be emulsified with the emulsifier according to the invention include polyurethanes, polyesters, polyethers, polyester polymethacrylates or polyethacrylates, as well as mixtures of these binder vehicles. Binders may, for example, be hydroxyl-, carboxyl-, epoxy-, amino- or acryloyl-functional, and / or may comprise acidic CH groups. A combination of different functional groups is also possible. Examples of hydroxyl-functional binding vehicles include polyether polyols, polyacetal polyols, polyesteramide polyols, polyamide polyols, epoxy resin polyols or reaction products thereof with CO, phenolic resin polyols, polyurea polyols, polyurethane polyols. , ester polyols and cellulose ether, partially saponified homo- and copolymers of vinyl esters, partially acetallated polyvinyl alcohols, polycarbonate polyols, polyester polyols, polyester polymethacrylic polyols or polymethacrylic polyols. Preferred are polyether polyols, polyester polyols, polyester polymethacrylic polyols, polymethacrylic polyols and polyurethane polyols. Polyols of this type, which can also be used mixed, are described in DE-OS 31 24 784.

Examples of polyurethane polyols are those that are produced by the reaction of di- and polyisocyanates with an excess of di- and / or polyols. Examples of suitable isocyanates include hexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate, as well as isocyanates which are formed from three moles of a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate and biurets resulting from the reaction of three moles of a diisocyanate with one mole of water. Other isocyanates that can be used have already been described in the text. Suitable polyurea polyols can be obtained in a similar manner by the reaction of di- and polyisocyanates with equimolar amounts of amino alcohols, e.g. ethanolamine or diethanolamine. Examples of polyester polyols are the known condensation polymers of di- or polycarboxylic acids or the anhydrides thereof, namely phthalic anhydride, adipic acid etc., with polyols such as ethylene glycol, trimethylolpropane, glycerol etc. Suitable polyamide polyols can be obtained in a manner similar to polyesters by replacing the polyols, at least in part, with polyamine such as isophorone diamine, hexamethylenediamine, diethylenetriamine, etc. Examples of polymethylacrylate polyols or polyvinyl compounds containing OH groups include the known copolymers of methacrylic esters containing hydroxyl groups, or vinyl alcohol, and other vinyl compounds, such as styrene or methacrylic esters. Examples of polyester polymethacrylic polyols include polymethacrylates which are synthesized in the presence of one or more polyester resins. Suitable methacrylic monomers are described in the following description of COOH-functional methacrylate polyols. Hydroxyl-functional binding vehicles are capable of reacting all the crosslinking agents which are capable of reacting with OH groups. Examples of entangling agents such as these include polyisocyanates, such as those already described with reference to the reaction of the fundamental constituents with polyisocyanates, blocked polyisocyanates, transesterification crosslinking agents such as the reaction products of polyisocyanates with ethyl acetoacetate. or diethyl malonate, the reaction products of ethyl acetoacetate with polyols, tris (alkoxycarbonylamino) triazine and amine resins. Examples of melamine resins include methyl-etherified melamine resins, such as the commercial products Cy 325, Cymel 327, Cymel 350 and Maprenal MF 927. Other examples of melamine resins that may be used include butanol- or isobutanol-etherified melamines. , such as commercial products Setamin US 138 or Maprenal MF 610 for example; mixed-etherified melamine resins that are etherified with both butanol and methanol, such as Cymel 254 for example, as well as hexamethyl-oxymethylmelamine (HMM melamine) eg, Cymel 301 or Cymel 303, where the latter may require a external acid catalyst for the interlacing, such as p-toluenesulfonic acid, which optionally can be ionically or non-ionically blocked with amines or polyepoxides. Examples of carboxy-functionalized binder vehicles include carboxy-functionalized polymethacrylic copolymers and / or carboxyl-functionalized polyurethanes or polyesters. During the production of the polymethacrylic copolymers or polyesters containing carboxyl groups, the carboxyl groups can be incorporated directly using constituents containing carboxyl groups, for example, during the synthesis of polymers such as methacrylic copolymers. Examples of suitable monomers containing carboxyl groups and which can be used for this purpose include unsaturated carboxylic acids such as acrylic, methacrylic, itaconic, crotonic, isocrotonic, aconitic, maleic and fumaric acids, for example, medium esters of maleic and fumaric acids, and also acrylate (J-carboxyethyl) and hydroxyalkyl ester addition products of acrylic acid and / or methacrylic acid with carboxylic acid anhydrides, such as phthalic acid mono-2-methacryloxy-oxyethyl ester, for example.

However, during the production of these copolymers, polyurethanes or methacrylic polyesters containing carboxyl groups, it is also possible to first synthesize a polymer containing hydroxyl and optionally carboxyl groups, and to introduce completely or partially the carboxyl groups in a second step by the reaction of the hydroxyl-containing polymers and optionally carboxyl groups with carboxylic acid anhydrides. The carboxylic acid anhydrides which are suitable for addition to the polymers containing hydroxyl groups are the anhydrides of saturated and / or unsaturated, aliphatic, cycloaliphatic and aromatic di- and polycarboxylic acids, such as the anhydrides of phthalic acid, tetrahydroftalic acid, hexahydrophthalic acid, succinic acid, maleic acid, itaconic acid, glutaric acid, trimellitic acid and pyromellitic acid, as well as the halogenated or alkylated derivatives thereof. The anhydrides of phthalic acid, tetrahydro- and hexahydrophthalic acid and 5-methylhexahydrophthalic anhydride are preferably used. Examples of hydroxyalkyl esters of α, 0-unsaturated carboxylic acids comprising primary hydroxyl groups and which are suitable for the production of hydroxyl-functional polymethacrylates include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates. The 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates can be cited as examples of hydroxyalkyl esters comprising a secondary hydroxyl group which can be used. The hydroxyl-functionalized component can advantageously consist, at least in part, of a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and on average two moles of epsilon-carpolactone. A reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a carboxylic acid comprising a tertiary α-carbon atom can also be used, at least in part, as the hydroxyl-functionalized component. The glycidyl esters of strongly branched monocarboxylic acids are obtainable under the tradename "Cardura E". The reaction of acrylic acid or methacrylic acid with the glycidyl ester of a carboxylic acid comprising a tertiary α-carbon atom can be carried out before, during or after the polymerization reaction. Ethylenically unsaturated monomers in addition to the aforementioned monomers can also be used in the production of the methacrylic copolymers. The selection of these ethylenically unsaturated monomers is not critical. It simply has to be ensured that the incorporation of these monomers does not result in unwanted properties of the copolymer. Substances that are particularly suitable as an ethylenically unsaturated component include alkyl esters of acrylic and methacrylic acid, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, 3,5,5-tri ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate and octadecenyl methacrylate. Other ethylenically unsaturated monomers can be used in place of the aforementioned alkyl esters of acrylic or methacrylic acid, or together with these alkyl esters for the production of methacrylic copolymers, in which the selection of these monomers depends substantially on the desired properties of the medium of coating in terms of hardness, elasticity, compatibility and polarity. Examples of other suitable ethylenically unsaturated monomers include the alkyl esters of maleic acid, fumaric, tetrahydrophthalic, crotonic, isocrotonic, vinylacetic and itaconic, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, pentyl, amyl, isoamyl, hexyl, cyclohexyl, 2-hexylyl, octyl, 3,5,5 esters - corresponding trimethylhexyl, decyl, dodecyl, hexadecyl, octadecyl and octadecenyl, for example. An aromatic monovinyl compound is another suitable compound. It preferably contains 8 to 10 carbon atoms per molecule. Examples of suitable compounds include styrene, vinyltoluenes, α-methylstyrene, cι roesti renes, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxystyrene, p-tert-butylstyrene, p, m-dimethylaminostyrene, p-acetamidostyrene and m-vinylphenol. Vinyltoluenes, and styrene in particular, are preferably used. Polyesters containing carboxyl groups can be synthesized by standard methods (see, for example, B. Vollmert, Grundriß der makro olekularen Chemie, E. Vollmert-Verlag Karleruhe 1982, Volume II, page 5 et seq.) From di-, tri- or polyhydric aliphatic and / or cycloaliphatic alcohols, optionally together with monohydric alcohols and aliphatic, aromatic and / or cycloaliphatic carboxylic acids, as well as polybasic polycarboxylic acids. Examples of suitable alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butapodiol, 1,3-butanediol, 1,4-butanediol, , 5-pentanediol, 3-methyl-l, 5-pentanediol, 1,6-hexanediol, 2-ethyl-l, 6-hexanediol, 2,2, 4-1 rimeti 1 -1, 6-hexanediol, 1, 4 dimethylcyclohexane, glycerol, trimethylethane, trimethylolpropane, pentaerythritol, etherification products of diols and polyols, e.g., di- and triethylene glycol, polyethylene glycol and neopentyl glycol esters of hydroxypivalic acid. Examples of suitable carboxylic acids include adipic, azelaic, 1,3- and 1,4-cyclohexane-dicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethyltetrahydrophthalic acid, isophthalic acid, o-phthalic acid, terephthalic acid or anhydrides thereof, as well as as the derivatives thereof which are capable of esterification. Examples of carboxyl-functional polyurethanes are those resulting from the reaction of di- and polyisocyanates with an excess of di- and / or polyols and hydroxycarboxylic acids; Dimethylolpropionic acid is a particularly suitable hydroxycarboxylic acid. Examples of suitable isocyanates include hexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate, and also isocyanates that are formed from three moles of a diisocyanate, such as hexamethylene diisocyanate or isophorone diisocyanate, and biurets that are formed from of the reaction of three moles of a diisocyanate with one mole of water. The carboxyl-functional binders can be entangled with the crosslinking agents by compounds containing carboxyl groups that are familiar to one skilled in the art. Examples of entanglement agents such as these include epoxy-functional binding vehicles, which are also described in greater detail below, and amine resins, such as those which have already been described as entanglement agents for hydroxyl-functional binding vehicles. Examples of an epoxy functional binder include di- or polyfunctional epoxy compounds which are prepared by the use of di- or polyfunctional epoxy compounds, such as diglycidyl or polyglycidyl ethers of hydroxyl (cyclo) aliphatic or aromatic compounds such as ethylene glycol, glycerol, 1,2- and 1,4-cyclohexanediol, bisphenols such as bisphenol A, polyglycidyl ethers of phenol-formaldehyde novolaks, polymeric ethylenically unsaturated compounds containing epoxy groups such as glycidyl methacrylate, N-glycidyl methacrylate and / or allyl glycidyl ether, optionally copolymerized with various other ethylenically unsaturated monomers, glycidyl ethers or fatty acids comprising 6 to 24 carbon atoms, epoxidized polyalkanedienes such as epoxidized polybutadiene, hydantoin-epoxy resins, resins containing resins of glycidyl groups such as polyesters and polyurethanes containing one or more g glycidyl moieties per molecule, and mixtures of said resins and compounds. The entanglement of the resins containing carboxyl groups by epoxy-functional components can also optionally be catalyzed with catalysts that are used in an amount of between 0.1 and 10% with respect to the total solid resin content. Examples of catalysts such as these include phosphonium salts such as benzyltriphenylphosphonium acetate, chloride, bromide or iodide, or ammonium compounds such as tetraethylammonium chloride or fluoride. The epoxy-functional binders can also be entangled with other entangling agents familiar to one skilled in the art, e.g., with amino-functional components, in addition to the carboxyl-functional components described above. Examples of amino-functional components include polyamines comprising at least two functional groups of the formula RHN, wherein R can be a hydrogen atom or a straight or branched alkyl radical comprising 1 to 10 carbon atoms or a cycloalkyl radical comprising 3 to 8, preferably 5 or 6 carbon atoms. Suitable polyamines include diamines and polyamines comprising at least two amino groups, wherein the amino groups may be primary and / or secondary. In addition, suitable polyamines include polyamine-containing addition products comprising at least two primary amino groups and at least one, preferably one, secondary amino group with epoxy compounds, polyisocyanates and acryloyl compounds. Furthermore, aminoamides and addition products of acrylates and carboxyl-functionalized amines comprising at least two amino groups are also suitable.

Examples of suitable di- and polyamines are described, for example, in EP-AO 240 083 and EP-AO 346 982. Examples thereof include aliphatic and / or cycloaliphatic amines comprising 2 to 24 carbon atoms and containing 2 to 24 carbon atoms. to 10 primary amino groups, preferably 2 to 4 primary amino groups and 0 to 4 amino groups. Representative examples thereof include ethylenediamine, propylene diamine, butylene diamine, pentamethylenediamine, hexamethylenediamine, 4,7-dioxa-decane-1, 10-diamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronedia ina, diethylenetriamine, dipropylenetria ina and 2,2-bis- (4-aminocyclohexyl) propane; polyether polyamines, e.g., those with the trade name Jeffamine supplied by Jefferson Chemical Company, bis- (3-aminopropyl) ethylamine, 3-amino-1- (methylamino) -propane and 3-amino-1- (cyclohexyl) -ami no) propane. Polyamines which are also suitable are the normal polyamines based on addition products of polyfunctional amine components with di- or polyfunctional epoxy compounds, for example, those which are produced using di- or polyfunctional epoxy compounds such as diglycidyl or polyglycidyl ethers of cycloaliphatic or aromatic hydroxyl compounds such as ethylene glycol, glycerol, 1,2- and 1,4-cyclohexanediol, bisphenols such as bisphenol A, polyglycidyl ethers of phenol-formaldehyde novolaks, polymers of ethylenically unsaturated monomers containing epoxy groups, such as methacrylate of glycidyl, N-glycidyl methacrylamide and / or glycidyl allyl ether, optionally copolymerized with various other ethylenically unsaturated monomers, glycidyl ethers of fatty acids comprising 6 to 24 carbon atoms, epoxidized polyalkanedienes such as epoxidized polybutadiene, hydroxy-epoxy resins, Resins that contain glycidyl groups such as polyesters or polyurethanes containing one or more glycidyl groups per molecule, and mixtures of said resins and compounds. The addition of the polyamines to said epoxy compounds occurs with the ring opening of the oxirane group. The reaction can be conducted within a temperature range of 20 to 100 ° C, for example, but is preferably carried out between 20 and 60 ° C. The reaction can optionally be catalyzed with 0.1 to 2% by weight of a Lewis base such as triethylamine or an ammonium salt such as tetrabutylammonium iodide. The polya-isocyanate addition products are also suitable polyamines. Normal isocyanates for the polyamine-isocyanate addition products include aliphatic, cycloaliphatic and / or aromatic di-, tri- or tetraisocyanates which may be ethylenically unsaturated. Examples thereof include 1,2-propylene diisocyanate or, trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, diisocyanate 2,4,4-trimethylhexamethylene, omega diisocyanate, omega '-dipropylether, 1,3-cyclopentane diisocyanate, 1,2- and 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4-methyl-1, 3- diisocyanatocyclohexane, transvinylidene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3,3'-dimethyl-1-dicyclohexylmethane-4,4'-diisocyanate, toluene diisocyanate, 1,3-bis- (1-isocyanato-1-methyl) ethyl) benzene, 1,4-bis (l-oocyanato-1-methylethyl) benzene, 4,4'-diisocyanatodiphenyl, 3,3'-dichloro-4,4'-diisocyanatodiphenyl, addition products of 2 moles of a diisocyanate, e.g., hexamethylene diisocyanate or isophorone diisocyanate, to one mole of a diol, e.g., ethylene glycol, the addition product of 3 moles of hexamethylene diisocyanate to 1 mole of ua (obtainable under the tradename Desmodur N from Bayer AG), the addition product of 1 mol of trimethylolpropane and 3 mol of toluene diisocyanate (obtainable under the tradename Desmodur L from Bayer AG) and the addition product of 1 mol of trimethylolpropane and 3 moles of isophorone diisocyanate. The addition of the polyamines to said isocyanate compounds is carried out within a temperature range of 20 to 80 ° C, for example, preferably 20 to 60 ° C. The reaction can optionally be catalyzed by the addition of 0.1 to 1% by weight of a tertiary amine such as triethylamine and / or 0.1 to 1% by weight of a Lewis acid, dibutyltin laurate.

As mentioned above, these polyamines can also be addition products with acryloyl compounds. Examples of di- or polyfunctional acryloyl unsaturated compounds for the preparation of polyamine addition products are described in EU-PS 4 303 563, v. gr. , ethylene glycol diacrylate, diethylene glycol diacrylate, t-dimethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-hexamethylene glycol diacrylate, trimethylol propane t-acrylate, pentaerythritol tertiary acrylate and pentaerythritol triacrylate. Other examples of polyfunctional acryloyl unsaturated compounds that may be used include: 1. Urethane acrylates obtained by the reaction of an isocyanate group of a polyisocyanate with a hydroxyacrylate, v. gr. , hexamethylene diisocyanate and hydroxyethyl acrylate; this preparation is described in EU-PS 3 297 745. 2.- Polyether acrylates obtained by the transesterification of a hydroxyl-terminated polyether with acrylic acid are described in EU-PS 3 380831. 3.- Polyester acrylates obtained by esterification of a polyester, containing hydroxyl groups, with acrylic acid are described in EU-PS 3 935173. 4.- Polyfunctional acrylates obtained by the reaction of hydroxyl-functionalized acrylates, such as hydroxyethyl acrylate for example, with a) dicarboxylic acids comprising 4 to 15 carbon atoms, b) polyepoxides which comprise terminal glycidyl groups, c) polyisocyanates comprising terminal isocyanate groups are described in EU-PS 3 560 237. 5.- Acrylate-terminated polyesters obtained by the reaction of acrylic acid, a polyol comprising at least two hydroxyl functions and a dicarboxylic acid are described in EU-PS 3 567 494. 6.- A polyacrylate obtained by the reaction of acrylic acid with an epoxidized oil containing epoxide functions, such as soybean or flaxseed oil is disclosed in EU-PS 3 125 592. 7. A polyacrylate obtained by the reaction of acrylic acid with the epoxide groups of a diglycidyl ether of bisphenol A is disclosed in EU-PS 3 373 075. 8. A polyacrylate obtained by the reaction of acrylic acid with an epoxide-functionalized vinyl polymer, e.g., polymers comprising glycidyl acrylate or vinyl glycidyl ether is described in EU-PS 3530 100. 9.- A polyacrylate obtained by the reaction of acrylic anhydride with polyepoxides, is described in EU-PS 3 676 398. 10.- Acrylate-urethane esters obtained by the reaction of a hydroxyalkyl acrylate with a diisocyanate and a hydroxyl-functionalized alkyl resin are disclosed in EU-PS 3 676140. 11.- Acrylate-urethane polyesters obtained by the reaction of a diol or triol of polycaprolactone with an organic polyisocyanate and with a hydroxyalkyl acrylate are described in EU-PS 3 700634. 12. A urethane polyacrylate obtained by the reaction of hydroxyl-functionalized polyester with acrylic acid and polyisocyanate is disclosed in US Pat. No. 3,759,999. Terminal acryloyl groups of the di- or polyacrylic monomers of the polyacrylates of examples 1 to 12 can be functionalized with polyamines. The addition reaction can be conducted, for example, within a temperature range of 20 to 100 ° C, preferably 40 to 60 ° C. Another method for synthesizing an amino-functionalized hardener is described in EP-A-0 2801. Acrylic acid ester copolymers are here amidized with diamines with the removal of alcohol. The acrylic acid ester copolymer has a number average molecular weight PM n of 1000 to 10,000, preferably 1000 to 5000. Examples of possible comonomers include methacrylic acid esters such as methyl, ethyl, butyl or cyclohexyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, as well as methacrylic acid, styrene and vinyltoluene. Methyl acrylate is particularly preferred, since this monomer is readily accessible for inolysis. The ratio of methyl acrylate to copolymer is from 2 to 35% by weight. The copolymers are produced by solution polymerization in customary solvents such as toluene, xylene, acetates, for example, butyl acetate, ethyl glycol acetate, ethers such tetrahydrofuran, or mixtures of aromatic compounds such as the commercial product Solvesso 100. The synthesis of these copolymers is known to those skilled in the art and does not require further explanation . The polyamines which are used for aminolysis must contain at least two primary or secondary amino groups and are already described above. Other amino functional compounds are present as reaction products of a methacrylic acid copolymer with alkyleneimines, such as those described in EP-A-0 179 954. In addition to methacrylic acid, the copolymer may contain methacrylic esters or compounds of vinyl such as styrene. The comonomers which can be used have already been described under the definition of polymethacrylates containing hydroxyl groups. Examples of alkyleneimines include propylene- or butyleneimine. Examples of polyamines which can also be used as curing agents according to the invention also include those which are produced by the reaction of isocyanate copolymers of a-dimethyl-m-isopropenylbenzyl (TMI), which have a number-average molecular weight. PMn from 1000 to 10,000, with mono- or diketimines containing either an OH or a sec.-NH group. All customarily copolymerizable vinyl monomers without OH functionality can be selected for use as comonomers for the production of TMI copolymers, such as methacrylic acid esters, for example, methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl and / or methacrylate. or lauryl, as well as styrene, vinyltoluene and / or methylstyrene. The copolymers are produced by custom radical solution polymerization, as recognized in the art. The polymerization is conducted, for example, in aprotic organic solvents, for example, toluene and xylene, and in esters, for example, butyl acetate. In general, all customary radical initiators such as azo and peroxide compounds are used for this purpose. The reaction is carried out by heating, for example, at temperatures of 80 to 140 ° C. The monomeric TMI can be polymerized on a scale of 2 to 40% by weight, based on the weight of all monomers, but is preferably polymerized on a scale of 2 to 25% by weight. The isocyanate-terminated copolymer is subsequently reacted with one or more mono- and / or diketenins and / or mono- and / or OH- or sec-NH-functionalized dialdimines. The production of ketimines and / or aldi inas (the expression "ketimines" is used hereafter for reasons of simplification, but also include aldimines) is effected, for example, by the reaction of alkanolamines or di- or triamines comprising at least one primary amino group, and which in the case of the di- or triamines further comprises a secondary amine function, with aldehydes and / or ketones with the removal of water. Examples of alkanolamines include monoethanolamine, monopropanolamine, monohexanolamine or 2-amino-2-hydroxy-propane. Examples of di- or triamines comprising at least one primary amino group and a secondary amino group include: N-methylpropylamine, diethylenetriamine, dipropylenetriamine or bishexamethylenetriamine. The primary amino groups of the amines mentioned above must be blocked for the production of the TMI acrylate / ketimine addition products. In this regard, the primary amines are reacted with aldehydes or ketones, with the removal of water, to form Schiff bases. Examples of aldehydes and ketones such as these include: C3-C10 compounds such as hexylaldehyde, octylaldehyde, diisopropylacetone and / or methyl isobutyl ketone. The last two compounds are particularly preferred, since they have only a slight tendency to undergo secondary reactions. The OH- or sec-NH-functionalized mono- or diketimines are preferably used in excess during the addition to the isocyanate-terminated copolymer.; 90 to 95% of the isocyanate groups are preferably reacted with OH or NH groups. The remaining excess isocyanate groups are urethanized with monoalcohols such as ethanol, propanol or butanol in a final reaction step. For the synthesis of ketimines or aldimines, ie, polyamines, for example, an alkanolamine or di- or triamine, comprising at least one primary amine function and also a secondary amine function, is placed in the reaction vessel, with the desired aldehyde or ketone blocking agent, in an organic solvent that forms an azeotropic mixture with water, the reaction water that is formed is azeotically distilled by heating this mixture. The preparation is advantageously conducted under inert gas. The blocking agent can be used in excess and can be distilled after the reaction. It is advisable to select, as the blocking agent, a ketone / aldehyde that by itself forms an azeotrope with water, so that the use of an additional organic solvent can be avoided. For the addition of the ketone or aldimine OH- or sec-NH-functionalized to the isocyanate-terminated TMI copolymer, the ketimine is placed in the reaction vessel, for example at 80 ° C, under inert gas, and the copolymer is added , for example, for two hours. The reaction can optionally be channeled, for example, by means of a Lewis acid such as dibutyltin laurate. After the addition of the copolymer has been completed, and whenever a ketimine deficit is present, an alcohol, for example, butanol, is added.

The batch is optionally stirred further at elevated temperature, for example for about 10 to 30 minutes. The above method of preparation simply constitutes an example of a procedure. The reaction can also be conducted by placing the copolymer in the reaction vessel and adding the ketimine. It may be advisable to react the terminal amino groups of said polyamines with aldehydes or ketones, with the elimination of water, to form Schiff bases or aldimines or ketimines. The procedure used for this purpose is analogous to the synthesis of aldimine or ketimine described above. The amino-functional binding vehicles can be entangled with acryloyl-functional resins, epoxy-functional resins, acetoacetic-functional ester resins and with other customary cross-linking agents for amino-functional binding vehicles which are known to those skilled in the art. Examples of acryloyl-functional components have already been described during the explanation of the formation of addition products from polyamines and acryloyl compounds. Acryloyl-functional binder vehicles such as these are capable of reacting with the crosslinking agents known to those skilled in the art. Examples of crosslinking agents such as these include acidic CH interlacing agents. It is also possible to effect entanglement by a radical mechanism, for example, oxidative entanglement in the presence of unsaturated fatty acids, entanglement by an electron beam, UV entanglement, or hardening by a radical mechanism in the presence of thermally divisible radical initiators. Examples of acidic CH compounds include those that are prepared by the transesterification of an α-keto carboxylic acid ether with a polyol. Examples of suitable (J-ketocarboxylic acid esters include esters of acetoacetic acid or of a substituted alkyl acetoacetic acid, such as a- and / or t-methylacetoacetic acid Suitable esters of these acids are those having aliphatic alcohols, preferably lower alcohols which comprise from 1 to 4 carbon atoms, such as methanol, ethanol or butanol, hydroxyl-functional binding vehicles and compounds such as those already described under hydroxyl-functional compounds are suitable as polyols for reaction with the esters of β-acid The synthesis of the acidic CH component can be effected, for example, by a plurality of steps.After removing solvent that may possibly be present, the polyol is first transesterified with the ether of aliphatic lacetocarboxylic acid. for the transesterification of the polyol, for example, in which the polyol, which ue is released from solvent if necessary by applying vacuum, is placed in the reaction vessel. The < RTI ID = 0.0 > or < / RTI > carboxylic acid ester is added in excess, for example, by dropwise addition. The reaction is carried out at elevated temperature; the alcohol that has been released has been removed from the system. It is also possible to add a catalyst to accelerate the reaction. Examples of catalysts of this type include acids such as formic acid or p-toluenesulfonic acid. It is advantageous if the reaction temperature increases continuously during transesterification (for example) in steps of 10 ° C / 20 min.), Until a temperature which is just below the boiling point (approximately 100 ° C) is reached. of the β-ketoc carboxylic acid ester. After the quantitative transeeterification, the excess of & -carboxylic acid ester is removed, for example, by the application of a vacuum. The mixture can then be cooled and adjusted to the desired content of solids with an inert solvent. The binder vehicle may also contain 2-acetoacetoxy-ethyl methacrylate as a reactive thinner to adjust the viscosity. The CH acidity of acetoacetic-functionalized ester components ee can be increased by the reaction of the β-carbonyl groups with primary monoamines and / or secondaries, as described, for example, in DE-A3932517. The acidic CH binder vehicle optionally contains one or more catalysts blended therewith in the form of Lewis bases or Bronested bases, wherein the acid conjugates of the latter have a pKA value of at least 10. The Lewis bases have shown to be particularly suitable, such as those from the group comprising cycloaliphatic amines such as diazabicyclooctane (DABCO), ter-aliphatic amines such as triethylamine, tripropylamine, N-methyldiethanolamine, N-methyl-diieopropylamine or N-butyldiethanolamine, and such amidines. such as diaza-bicycloundecene (DBU), and guanidines such as, for example, N, N, N'N'-tetramethylguanidine. Other examples include alkyl or aryl subfituid phosphines such as tributylphosphine, triphenylphosphane, tris-p-tolylfoefano, ethyldiphenylphosphane, as well as araphinated and araino-functionalized phosphines such as, for example, triehydroxymethylphenefano and tris-dimethylaminoethylphosphane. Examples of Brónsted bases that may be used include alcoholates such as eodium or potassium methylate, quaternary ammonium compounds such as alkyl-, aryl- or benzyl-ammonium hydroxides or halides, for example tetraethyl or tetrabutylammonium hydroxide or fluoride, as well as trialkyl or triarylphosphonium salts or hydroxide. The amount of catalysts is from 0.01 to 5% by weight for example, preferably from 0.02 to 2% by weight, with respect to the total solids content of the binder vehicle. The transesterification crosslinking agents which are capable of crosslinking with hydroxyl functional compounds are those which contain at least two groups which are capable of undergoing transesterification. These crosslinking agents that are capable of undergoing transeeterification are preferably eubertically free of primary, secondary or tertiary amino groups, since the latter can have a negative effect on storage life and light resistance. Examples of binding vehicles which are capable of undergoing transesterification include compounds which on average contain at least two groups in their molecule which are derivatives of monoamide units of methantricarboxylic acid or acetoacetic ester units of 2-carboxylic acid. Examples of suitable compounds include the reaction products of malonic acid diesters, such as dimethyl, diethyl, dibutyl or dipentyl esters of malonic acid, or esters of acetoacetic acid such as methyl, ethyl, butyl or acetylacetic pentyl esters, with polyisocyanates . Examples of isocyanates of this type that can be used according to the invention are known to those skilled in the art. The same compounds can be used are those that have already been described for the reaction of the fundamental constituents with polyisocyanates. However, other compounds which are capable of undergoing transesterification and which are also suitable include the reaction products of ether esters and partial esters of polyhydric alcohols and malonic acid with monoethanocyanates. Examples of polyhydric alcohols include dihydric alcohols, pentahydric alcohols such as ethanediol, the various propane-, butane-, pentane- and hexanediols, polyethylene- and polypropylenediolee, glycerol, trimethylolethane and -propane, pentaerythritol, hexanetriol and eorbitol. Examples of suitable monoisocyanates include aliphatic isocyanate such as n-butyl isocyanate, octadecyl isocyanate, cycloaliphatic isocyanate as cyclohexyl isocyanate, araliphatic isocyanates such as benzyl isocyanate, or aromatic isocyanates such as phenyl isocyanate. Substances which are also suitable include the corresponding malonic acid esters of acrylic resins containing OH groups, polyesters, polyurethanes, polyethers, polyestera ides and -imides and / or the reaction product of malonic acid esters such as onoethyl ester of malonic acid with Aliphatic and aromatic epoxy resins, for example, acrylate resins containing epoxide groups, glycidyl ethers of polyols such as hexanediol, neopen ilglycol, diphenylolpropane and methane and hydantoin containing glycidyl groups, as well as mixtures of their compounds. Substances that are also preferred include hardening components that are obtained by the non-quantitative transesterification, with polyols, of compounds containing more than two groups that are capable of undergoing transeterification in their molecule. The aforementioned polyols can be a polyhydric alcohol preferably containing 2 to 12, particularly 2 to 6, carbon atoms. Examples of these include: ethylene glycol, propylene glycol- (1, 2) and (1, 3), butylene glycol- (1, 4) and - (2,3), di-β-hydroxyethylbutanediol, xanodiol- (1, 6), octanediol- (1, 8), neopentyl glycol, cyclohexanediol- (1, 6), 1,4-bis- (hixymethyl-cyclohexane, 2,2- bis- (4-hydroxycyclohexyl) -propane, 2,2-Bis- (4- (β-hid roxie oxy) -phen 1) -p clothing, 2-methyl-1,3-p-propanediol, glycerol , trimethylolpropane, hexanetriol- (l, 2,6) .butanotriol- (1,2,4), tris - (- (ß-hydroxyethyl) isocyanate, trimethylol-ethane, pentaerythiol and hydroxyalkylation products thereof, as well as Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycol and xylene glycol can also be used as polyesterers obtained from or with lactones, for example, epsilon-caprolactone, or from a hydroxy acid. carboxylic acid such as hydroxypivalic acid, gamma-hydroxydecanoic acid, gamma-hydro-icaproic acid or thioglycolic acid Alternatively, the polyol can constitute an oligomeric or polymeric polyol compound (a polyol resin), whose average molecular weight number PMn (as ee determined by means of chromatography gel with a polystyrene pattern) is usually within the range of about 170 to 10,000, preferably about 500 to about 5000. However, in special cases, PM n may be 10,000 g / mol or more. Suitable oligomers / polymers include polymers, condensation polymers or polyadditions. Their hydroxyl number is generally from 30 to 250, preferably from 45 to 200 and particularly from 50 to 180 mg KOH / g. These compounds containing OH groups may also optionally contain other functional groups, such as carboxyl group. Examples of polyols of this type include hydroxyl-functional compounds that have already been described elsewhere. Other examples of compounds which are capable of undergoing transesterification can be produced, for example, by the esterification of a polyepoxide with a monoester of dicarboxylic acid forming the group capable of undergoing transesterification, for example, a monoester of malonic acid. A component is obtained in this manner comprising a group that is capable of undergoing transesterification for each epoxide group. Here also aromatic polyepoxides or aliphatic may be used. Further examples of suitable dicarboxylic acid monoester include monoalkyl ester of malonic acid and monoalkyl acetondicarboxylic acid esters wherein the alkyl radical can be straight or branched chain with 1 to 6 atoms, for example methyl, ethyl, n-butyl or t-butyl. Binders comprising acidic CH groups can be entangled with acryloyl-functional compounds in the sense of a Michael reaction. Binders can be produced in co-solvent. It is advantageous that they use solvents which do not have a subsequent adverse effect during the production of the revealing medium. It is also advantageous if the content of organic solvents is kept low. The emulsifier can provide workgroups to improve their ability to be incorporated into entanglement lacquer systems. Example of functional groups such as ethers are the same groups as described for functionalized binding vehicles, for example, hydroxyl groups, carboxyl groups, epoxy groups, amino groups, acryloyl groups and acidic CH groups. If the fundamental constituent is modified with an isocyanate deficit, the modified emulsifier can still contain OH groups. However, if an excess isocyanate is used, the modified ulsifier becomes isocyanate-functional. The functional groups recently introduced can therefore be linked to the emulsifier either through the remaining hydroxyl groups or through the isocyanate groups. If an additional polyol is added during the reaction of the fundamental constituent with polyisocyanate, for example, this polyol can be bound to the emulsifier through a urethane linkage. Examples of suitable polyhydric alcohols include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-, 1,4- or 2,3-butanediol, 1,6-hexanediol, 2,5-hexanediol, trimethyl-hexanediol, diethylene glycol, triethylene glycol, bisphene hydrogenated , 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, t-cyclohexanediol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythiol, trimethylpentanediol, dipentaerythritol, and mixtures thereof. It is also possible to bind polyester polyols, polyether polyols, etc. , to the emulsifier through the urethane group. The hydroxyl functional emulsifiers are capable of reacting with all the crosslinking agents which can react with OH groups. Examples of crosslinking agents such as these have already been described as crosslinking agents for hydroxyl-functional binding vehicles. The carboxyl groups can be introduced into the emulsifier by the reaction of a hydroxyl-functional emulsifier such as that described above with polycarboxylic acids or polycarboxylic anhydrides thereof. Examples of suitable polycarboxylic acids (anhydrides) include phthalic acid (anhydride), isophthalic acid, terephthalic acid, tetrahydroftalic acid (anhydride), acid (anhydride), hexahydrophthalic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, anhydride) maleic, euccinic acid (anhydride), fumaric acid, adipic acid, sebasic acid, azelaic acid, dimeric fatty acids, trimeric fatty acids, trimellitic acid (anhydride), pyrolitic acid (anhydride) and mixtures of estoe or other acids. Aliphatic and cycloaliphatic dicyboxylic acids or anhydrides are preferred. The reaction of the hydroxyl-functional ulsifiers with the polycarboxylic acids or polycarboxylic anhydrides is conducted, for example, by mixing the hydroxyl-functional emulsifier in the molten bath or in an aprotic solvent, with the (anhydride) polycarboxylic acid and reacting therewith, for example, at 100 to 190 * C, until the desired acid number is reached. The same solvents can be used as those already described for the reaction of the fundamental constituents with polyisocyanates. The carboxyl-functional emulsifiers can be intertwined with the crosslinking agents for compounds containing carboxyl groups which are known to those skilled in the art. Interlacing agents such as these have been described as crosslinking agents for carboxyl-functional binding vehicles. Amino groups can also be introduced into the emulsifier through the polyisocyanate. For this purpose, the polyisocyanate is reacted before, during or after the reaction with the basic constituent, with one or more mono- and / or diketeniins and / or mono- and / or dialdi inas OH- or sec-NH- functionalized In the conversion to the aqueous phase, the ketones / aldimines are hydrolyzed and the amino groups become free. Another option is the reaction of acryloyl-functional emulsifiers with polyamines. Another possibility consists in reacting the polyisocyanates to a certain degree with the fundamental constituent and converting the isocyanate-functional emulsifier which is thus functionalized in the aqueous phase. The hydrolysis of the NCO groups is then produced to form amino groups, with removal of CO ?. The epoxy groups can be introduced into the emulsifier by reaction of hydroxyl-functional emulsifiers, for example, with epichlorohydrin. Another possibility is the reaction of epoxypolyoles with the polyisocyanates used for modification. This reaction can be carried out before, during or after the reaction of the polyisocyanates with the basic constituents. The acryloyl groups can be introduced into the emulsifier by reacting the polyisocyanate groups of the emulsifiers with hydroxyl-functional methacrylic monomers. This reaction can be carried out before, during or after the polyisocyanate reaction with the basic constituents. Examples of hydroxyl-functional methacrylates that may be used include monomers comprising primary and secondary hydroxyl functional, such as those already described. The reaction of the polyisocyanate with the hydroxyl functional monomers is conducted, for example, by treating the polyisocyanate in the absence of an eoliant or in an aprotic solvent, with the hydroxyl functional monomer added dropwise and reacting the batch at 40 to 80. * C for example until the desired NCO number is reached. The same solvents can be used as those already described for the reaction of the fundamental constituents with polyisocyanates. It is also possible to place the hydroxyl functional monomers in the reaction vessel together with the fundamental constituents and react them together with the polyisocyanates, or to add them to the hydroxyl functional monomers after the partial reaction of the polyisocyanates with the fundamental constituents has occurred. . The acidic CH groups ee can be introduced into the emulsifier by several routes. In this way, it is possible to react a hydroxyl-functional emulsifier with a β-ketocarboxylic acid such as ethyl acetoacetate, with transesterification. For example, the transesterification of the hydroxyl-functional emulsifier with an acid ester &-carboxylic acid can be carried out by placing the fundamental constituent in the reaction vessel and then adding the excess 3-ketocarboxylic acid ester, and dropwise, for example. The reaction is conducted at elevated temperature, and the alcohol released is removed from the seventh. It is also possible to add a catalyst to accelerate the reaction. Examples of catalysts of this type include acids such as formic acid or p-toluenesulfonic acid. It is advantageous if the reaction temperature increases continuously during transesterification (for example, in steps of 10 β C / 2 O min), that a temperature that is below (approximately 100 ° C) the boiling point of the acid ester is reached & -carboxylic acid. After the quantitative transesterification, the excess of ß-ketocarboxylic acid ether was removed by applying, for example, a vacuum. The mixture can then be cooled and adjusted to the desired solids content with an inert solvent. It is also possible to introduce acidic CH groups by reacting polyisocyanates with CH acid compounds such as ethyl acetate or diethyl malonate. The modification with acidic CH groups can be carried out before, during or after the reaction of the basic constituents with polyisocyanates. The reaction of the polyisocyanate groups of the emulsifiers with CH acid compounds is conducted, for example, by treating the polyisocyanate-functional emulsifier in the absence of solvent or in aprotic solvent, with the acidic CH compound being added dropwise, and react the batch at 60 to 100 * C for example, until the desired NCO number is reached. The same solvents can be used as those already described for the reaction of the fundamental constituents with polyieocyanates. It is also possible to react the acidic CH compounds with the polyisocyanates or add the acidic CH compounds after the partial reaction of the polyisocyanates with the fundamental constituents has occurred. It is also advisable to catalyze the reaction with the acidic CH compounds. The catalysts which are used for the reaction of the polyisocyanates with CH acid compounds are preferably alkali metal alcoholates such as lithium methanolate or alkali metal hydroxides, for example, alkali metal hydroxides such as lithium, sodium and / or potassium hydroxide. Preferably, anhydrous alkali metal hydroxides are used. Most preferably, lithium hydroxide is used. The catalysts are used in catalytic amounts, for example, in amounts of 0.1 to 2% by weight, preferably 0.3 to 1% by weight, based on the weight of isocyanate and acidic CH component. The catalysts are used in solid form, for example in pulverized form. In principle, all customary methods which are known to those skilled in the art are suitable for preparing the emulsions, such as, for example, stirring processes with high speed blade agitators and disperfect discs (flat or serrated), units of rotor-stator (Ultra-Turrax machine, Cavitron, Supraton, Siefer Trigonal, olinoe of colloid), dispoeitivos that operate with injection of the phase that is going to be emulsified in the external phase or in which the two phases are carried towards collision under high pressure and countercurrent injection, ultrasound homogenizers, high pressure homogenizer and static mixers. The emuleification can be carried out by the direct method or by the inverse method, and it can be carried out continuously or intermittently. The preferred method is the continuous production of an emulsion using nozzle injection devices, high pressure homogenizers, ultrasonic homogenizers and in-line rotor-stator homogenizer, in which the two phases are added to the homogenizer until they are in a ratio of partial volume flows that correspond to the final formulation. Direct emulsification using a continuous process with in-line rotor-stator machines (Cavitron) is particularly preferred. The construction and mode of operation of machines such as these are known to those skilled in the art. Rotor-stator machines can be equipped with slotted or perforated rings or with a combination of both. To intensify the emulsification effect, part of the final amount of aqueous phase can first be omitted during the preparation of the emulsion, and then it can be added to the concentrate after the solution is complete. This is effected either intermittently in a supply tank, or preferably continuously by subsequently adding the amount of water that is still missing to the homogenizing unit or to one of the external rotor-stator stages while the process is proceeding. An advantage of this process is that the emulsion concentrate is cooled, immediately after it is produced, at temperatures of 30 * C, for example, at which there is no risk of the quality of the emulsion being altered by the high temperatures that result from the cutting forces. During the emulsification, the emulsifiers according to the invention can be used complete with the vehicle binder phase, complete with the aqueous phase or distributed over both phases. For physical reasons that are known to those skilled in the art, they are preferably used with the aqueous phase or dietributed in both phases.

EXAMPLES (All parts are given as parts by weight) The free OH-functional solvent polyether Deemophen 670 (a commercial product of Bayer AG), which had an OH number of 142 mg KOH / G and an acid number of 2 mg KOH / g, was used as the binder vehicle.

Production of a fundamental constituent The process was carried out analogously to a method described in E.U.A. 2 380 166 (examples 2 and 4 therein). 800 parts of lauric acid and 782 parts of sorbitol were heated at 250 ° C for 70 minutes, with stirring and under an inert gae atmosphere, in a 4-liter 3-necked flask equipped with a reflux condenser, thermometer and stirrer in presence of 5 parts of sodium hydroxide solution, and the batch was kept under these conditions for 5 hours. 30 parts of activated carbon were added and the batch filtered eubsequently. The resulting serous product had a theoretical OH number of 486 mg KOH / g. 34-6 parts of this product were melted and introduced into an autoclave equipped with an agitator. The batch was heated to 100 ° C and 17 parts of potassium methanolate was added. The batch was heated to 110 ° C and 2200 parts of liquid ethylene oxide were added dropwise over a period of 150 minutes. The temperature was maintained within a range between 105 ° C and 110 ° C until all the ethylene oxide had reacted. The decrease in pressure in the autoclave at a normal pressure was used here as an indicator. The product obtained was subsequently purified by steam distillation under vacuum (10 mm of mercury) and with stirring. Finally, 30 parts of activated carbon were added and the batch was stirred for an additional 15 minutes and filtered. The product obtained was waxy and had a honey yellow color. Its number average molecular weight (GPC, polyethene reindeer pattern) was 2400; The average molecular weight in peeo was 3100. An OH number of 68 mg KOH / g was measured.

EXAMPLE 1 Production of an elongated isocyanate chain emulsifier based on the above-described basic constituent 938 parts of the above basic constituent were melted at 60 ° C in a 2-liter four-necked flask equipped with a stirrer, reflux condenser, thermometer and funnel drip. 62 parts of isophorone diisocyanate were then continuously added at 60 ° C to the molten bath for a period of 1 hour. The batch was heated to 80 ° C and stirred at that temperature until the NCO number had fallen to less than 0.1%. The product had a molecular weight (weight average molecular weight) of 23,000 (GGPC with a polystyrene standard).

Use of emulsifiers Intermittent emulsification General procedure 300 parts of the above binder vehicle were heated to 60 ° C and emptied, with high speed agitation (Getzmann Dispermat, 6-blade agitator, diameter: 35 mm, peripheral speed: 15.7 m / sec at a rotational speed of 8000 rp), in 150 parts of an aqueous solution of 27 parts of emulsifier heated at 40 ° C corresponding to 9% with respect to the resin phase. The addition had to be made in such a way that the resin was emptied in a "thin stream" on the periphery of the agitator. The agitator was placed so that maximum turbulence would occur. After the addition was complete, the emulsion, which was still hot, was allowed to cool to room temperature with moderate agitation.

COMPARATIVE EXAMPLE 1 Production of an emulation using the previous fundamental constituent; procedure as given above. The emulsion was not stable. The particle size could not be measured.

COMPARATIVE EXAMPLE 2 Production of an emulsion using the fundamental constituent. Same as in comparative example 1, except that the content of the emulsifier was increased from 9% to 15%. The emulsion was not stable. Particle size: approximately 50-150 μ (microscopically determined) EXAMPLE 2 Production of an emulsion using a polymeric emulsifier according to example 1.

Emulsifier of synthesis example 1; procedure as described above. The emulsion was stable. Particle size: 0.5-5 μ (microscopically determined).

EXAMPLE 3 Continuous production of an emulsion Composition of an emulsion as in example 2. The adjustment was carried out using a CAVITRON in-line rotor-stator homogenizer equipped as follows: Rotor 1: blade wheel Rotor 2: slotted ring Rotor 3: perforated ring; 1.5 mm holes Rotor 4: perforated ring; 0.5 mm holes Stator 1: slotted ring Eetator 2: perforated ring; 1.5mm hole Stator 3: perforated ring; 0.5 mm holes The rotation speed was 6000 rpm, corresponding to the peripheral speed of 25 m / sec with respect to the external rotor ring. The resin and the aqueous phase were fed to the etching through dosing pumps, at a ratio of 2: 1 and at a total assortment speed of 30 kg / hour. The emulsifier of Example 1 was distributed over the two phases in a ratio of 1: 1. The proportion thereof with respect to the resin phase was 9%. An installation pressure of approximately 1.5 bar was established by a pressure maintenance valve at the inlet of the homogenizer, in order to prevent the machine from sucking material through the operation independently of the volume flow that was predetermined by the pumps Dosing The resin containing emulsifier was heated to 70 ° C. The aquatic fae that contained emulsifier eetaba at room temperature (23 ° C). Directly after leaving the homogenizer, the emulsion was cooled to room temperature in a cooling operation. Emulsion particle size: 0.5-2.5 μ (microscopically determined).

EXAMPLE 4 Continuous production of an emulsion; variant of example 3. The procedure corresponded to that used in example 3, except that an additional stator with holes of 0.5 mm was installed, with the purpose of adding the proportion of water by which the aqueous phase had been reduced previously for the purpose of an effective mae transfer of shear force (corresponding to 15% of the total amount of emulent water) to the emulement concentrate finished at this point between rotor 4 and stator 4. By this means, the heater was removed rapidly of the concentrate and any emulsion portion of the "water-in-oil" type that was present were reinserted to the "oil in water" type. Emuleion particle size: 0.5-1.5 μ (microecpically determined).

Emulsion evaluation Comparative examples Examples 1 2 2 3 4 Size of nm 50-150 0.5.5 0.5-2.5 0.5-1.5 particle * n. a n. a a. to . to . * in μ, icroecopically determined nm: not measurable a .: acceptable n.a. : not acceptable

Claims (7)

NOVELTY OF THE INVENTION CLAIMS

1. Aqueous emulsion of einthetic resin containing nonionic emulsifiers based on the fatty acid ester of polyalkoxylated polyhydric alcohols as fundamental constituents, characterized in that at least two fundamental constituents are linked to one another by the reaction of hydroxyl groups with a polyisocyanate, with the formation of urethane bonds.

2. Aqueous emulsions of synthetic resin containing emulsifiers according to claim 1, further characterized in that the polyhydric alcohols are politoxylated and / or polypropoxylated.

3. Emuleionee acuoeae synthetic resin containing emulsifier according to claim 1 or 2, further characterized in that the polyhydric alcohols comprise at least partially glycerol and / or sorbitol.

4. Emulsionee acuoeae of synthetic resin containing emulsifiers according to any of claims 1 to 3, further characterized in that the fundamental constituents which are linked by polyisocyanate correspond to the general formula Residue of an alcohol (0H) polyhydric p where EO denotes an ethoxy unit and PO denotes a propoxyl unit, and the subindexes have the following meaning: xA »and» P: l-5, n = 0-300, m = 0-300, and n + m > 2

5. 5. A method for producing aqueous emulsions of synthetic resin containing non-ionic emulsifiers by the fatty acid ether bond of polyalkoxylated polyhydric alcohols as fundamental constituents, characterized in that the fundamental constituents are linked to one another by the reaction of groups free hydroxyl with polyisocyanate, with the formation of urethane groups and with an increase in molecular weight.

6. A method according to claim 5, further characterized by the fundamental constituents of the general formula Residue of a polyhydric alcohol • (0H) p where EO denotes an ethoxy unit and PO denotes a propoxyl unit, and the subindexes have the following meaning: x > l, and > ., p = l-5, n = 0-300, m = 0-30O, and n + m > 25. and linked to each other by reaction with polyisocyanates

7. The use of the emulsifiers according to claim 1 or 4 to emulsify lacquer binders.