EP0000605B1 - Hardeners for aqueous dispersions of epoxy resins, their preparation and use - Google Patents

Hardeners for aqueous dispersions of epoxy resins, their preparation and use Download PDF

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Publication number
EP0000605B1
EP0000605B1 EP78200101A EP78200101A EP0000605B1 EP 0000605 B1 EP0000605 B1 EP 0000605B1 EP 78200101 A EP78200101 A EP 78200101A EP 78200101 A EP78200101 A EP 78200101A EP 0000605 B1 EP0000605 B1 EP 0000605B1
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Prior art keywords
adduct
weight
polyamine
component
reaction
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EP78200101A
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German (de)
French (fr)
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EP0000605A1 (en
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Wilhelm Dr. Becker
Horst Karasmann
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31525—Next to glass or quartz
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal

Definitions

  • DE-A-1925941 describes epoxy resin hardener emulsions which contain, as hardener component, an aminoamide adduct which is an aminoamide of a fatty acid and an alkylene polyamine and which is the reaction product of the aminoamide with 10-40 percent by weight (based on the weight the highly volatile aminoamide adduct components) is monoepoxide, which consists of an aliphatic monoepoxide with 2-12 C atoms or of a monoepoxide substituted by a phenyl radical.
  • an aminoamide adduct which is an aminoamide of a fatty acid and an alkylene polyamine and which is the reaction product of the aminoamide with 10-40 percent by weight (based on the weight the highly volatile aminoamide adduct components) is monoepoxide, which consists of an aliphatic monoepoxide with 2-12 C atoms or of a monoepoxide substituted by a phenyl radical.
  • CH-A-487955 describes curable, aqueous dispersions which contain a hardener for the epoxy resin which is liquid at room temperature, the hydrogen being bound directly to the nitrogen in the hardener, which is formed by addition of non-aliphatic epoxide, which is only a terminal 1, Contains 2-epoxy group per molecule, or aliphatic epoxy, which contains on average one or more than one terminal, 1,2-epoxy group per molecule, and a stoichiometric excess of a poly (aminoamide) condensation product, which consists of an alkylene polyamine of the formula wherein the alkylene radical can be the ethylene, propylene, butylene, pentylene or hexylene radical, n is an integer greater than zero, and a copolymer of a conjugated unsaturated fatty acid or an amide-dying acid derivative with an aromatic vinyl compound is available.
  • a hardener for the epoxy resin which is liquid at room temperature
  • the hydrogen being bound directly to the nitrogen
  • aqueous dispersions preferably also contain an accelerator for curing.
  • accelerators are compounds which contain at least one tertiary amino nitrogen atom and one phenolic hydroxyl group.
  • the dispersions contain orthophosphoric acid or a liquid aliphatic monocarboxylic acid, e.g. B. acetic acid.
  • These epoxy hardener dispersions also have insufficient stability and only provide relatively soft and mechanically sensitive protective coatings. Furthermore, the presence of the dissociating acids leads to instability of the dispersion, since the acid anion (A) can react with the epoxy group according to the following scheme and consumes epoxy groups: O
  • FR-A-2068390 describes water-dilutable auxiliaries for the emulsification and curing of epoxy resins which consist of reaction products from glycidyl ethers of polyalkylene polyether polyols and polyamines.
  • FR-A-2128773 describes a curing agent for epoxy resins in the form of a reaction product of a) at least one diamine, b) a polyfunctional polymer, e.g. B. a butadiene homo- or copolymer and optionally c) a polyepoxide.
  • the proportion of amine a) is 20-80%, based on the reaction product from a), b) and c).
  • these mixtures are only used in organic solvent systems.
  • the polymeric components b) used there are not polyalkylene-polyether-polyols and the amine excess there is significantly higher than in the curing agents according to the invention.
  • the adduct is composed of 2 to 4 equivalents of component a1) and 0.2 to 1.5 equivalents of component a2) with 80-20% by weight of component B) and up to 0.5, preferably 0 , 1 to 0.3 equivalents of component C) available.
  • A1 is preferably water-insoluble and a2 is water-soluble.
  • Another object of the invention is also a method for producing the hardening agents, as described in claims 5 to 7.
  • the hydroxyl groups of the polyalkylene polyether polyol are preferably reacted with the epoxy groups at 20 to 200.degree.
  • the invention also relates to the use of the curing agents obtained by the abovementioned processes together with polyfunctional epoxy compounds and what water and optionally emulsifiers for the production of curable, optionally film-forming dispersions as coating or coating agents.
  • the epoxies of polyunsaturated hydrocarbons (vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadienes, divinylbenzenes and the like), oligomers of epichlorohydrin and the like, epoxy ethers and polyhydric alcohols Butylene glycols, polyglycols, thiodiglycols, glycerin, pentaerythritol, sorbitol, polyvinyl alcohol, polyallyl alcohol and the like), epoxy ether of polyhydric phenols (resorcinol, hydroquinone, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane , Bis (4-hydroxy-3,5-dibromophenyl) methane, bis
  • phenylmethane and epoxides which have been prepared by conventional processes from polyunsaturated carboxylic acids or monounsaturated carboxylic acid esters of unsaturated alcohols, glycidyl esters, polyglycidyl esters which can be obtained by polymerizing or copolymerizing glycidyl esters of unsaturated acids or from other acidic compounds (cyanuric acid, diglycidyl sulfide, Trimethylene trisulfone or its derivatives and others) are available.
  • polyfunctional epoxy compounds can be reacted individually or in a mixture, if appropriate in the presence of solvents or plasticizers, by the present process or used to prepare dispersions. They can also be used in mixtures with monoepoxides.
  • monoepoxides are used in a mixture with the aforementioned epoxy compounds: epoxidized unsaturated hydrocarbons (butylene, cyclohexene, styrene oxide and others), halogen-containing epoxides, such as. B.
  • epichlorohydrin epoxy ether of monohydric alcohols (methyl, ethyl, butyl, 2-ethylhexyl, dodecyl alcohol and others), epoxy ether of monohydric phenols (phenol, cresol and other phenols substituted in the o- or p-position), glycidyl esters of unsaturated carboxylic acids , epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids and the acetals of glycidaldehyde.
  • the preferred polyhydric phenols are: resorcinol and various bisphenols, which can be obtained by condensing phenol with aldehydes and ketones such as, for. B. formaldehyde, acetaldehyde, acetone, methyl ethyl ketone and. a., receives. Resins of this type are described in US-A-2855159 and 2589245.
  • the epoxy resin has an epoxy equivalent of 160-500.
  • Suitable polyalkylene polyether polyols b) which can be used for the preparation of the curing agents according to the invention include, for example, the adducts of an alkylene oxide or an alkylene oxide with a polyhydric alcohol.
  • Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, butylene oxide, amylene oxide and hetero- or block copolymers of these oxides, but preferably ethylene oxide.
  • Suitable polyhydric alcohols are both aliphatic alcohols individually or in a mixture, e.g.
  • Ethylene glycol 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, hexane-1,2,6-triol, a-methylglucoside, pentaerythritol and sorbitol.
  • the polyalkylene polyether polyols can also be prepared from other starting materials, for. B. from tetrahydrofuran and alkylene oxide-tetrahydrofuran copolymers; Epihalohydrins, e.g. Epichlorohydrin and aralkylene oxides, e.g. Styrene oxide.
  • the polyalkylene polyether polyols can have either primary or secondary hydroxyl groups and are preferably polyethers made from alkylene oxides having 2 to 6 carbon atoms, e.g. B. polyethylene ether glycols, polypropylene ether glycols and polybutylene ether glycols.
  • the polyalkylene polyether polyols can be prepared by any known method, e.g. B. by the method specified by Wurtz 1859 and described in Encyclopedia of Chemical Technology, Vol. 7, pp. 257 to 262, Interscience Publishers, Inc (1951) or in US-A-1922459.
  • the average molar mass of component a2 is 200 to 10,000, preferably 800 to 1200.
  • aliphatic, cycloaliphatic, araliphatic and heterocyclic amines or mixtures thereof can be reacted as component B with the epoxy-polyalkylene polyether polyol adducts.
  • Examples include: aliphatic, saturated or unsaturated, bifunctional amines, e.g. B. lower aliphatic alkylene polyamines, such as ethylenediamine, 1,2-propylenediamine; 1,3-propylene diamine, 1,4-butylene diamine, hexamethylene diamine, 2,2,4- (2,4,4-) trimethyl hexamethylene diamine or polyalkylene polyamines, e.g. B.
  • lower aliphatic alkylene polyamines such as ethylenediamine, 1,2-propylenediamine; 1,3-propylene diamine, 1,4-butylene diamine, hexamethylene diamine, 2,2,4- (2,4,4-) trimethyl hexamethylene diamine or polyalkylene polyamines, e.g. B.
  • homologous polyethylene-polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or analogous polypropylene polyamines, such as dipropylene triamine, or polyoxypropylene polyamines and diamines of the general formula H 2 N.CH 2 -X-CH 2 .NH 2 , where X is the divalent radicals means.
  • preferred compounds of component B are xylylenediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2,2,4- (2,4,4, -) - trimethylhexamethylene diamine or polyoxypropylene polyamine and mixtures thereof. It is possible to react all of the amines mentioned with the monounsaturated compound C of the type before the reaction with the epoxy-polyalkylene polyether polyol adduct to convert to so-called cyanoethylated amines and then use them instead of the pure polyamines. However, the route described below is more common. Before the reaction product of polyamines and the epoxy-polyalkylene polyether polyol adduct is reacted with the monounsaturated compound, it may be diluted with water to a solids content of 50.0 to 90% by weight.
  • the reaction with the monounsaturated compound is carried out by adding z. B. acrylonitrile at 20 to 70 ° C, wherein after the addition a residence time at elevated temperature, preferably 50 to 70 ° C is appropriate.
  • Acrylonitrile or methacrylonitrile are the preferred compounds of component C.
  • BF 3 -benzylamine, BF 3 -mono-ethylamine, BF 3 -propylamine and BF 3 -n-butylamine are preferably used.
  • a g equivalent of a hydroxyl group to be reacted with a g equivalent of an epoxy group 100 to 1, preferably 15 to 2 mmol, of the BF 3 amine complex are used.
  • the reaction of the hydroxyl groups with the epoxy groups can be carried out in the temperature range from 20 to 200 ° C.
  • the reaction temperature depends on the respective BF 3 amine complex.
  • the reaction temperature when using BF 3 monoethylamine or BF 3 benzylamine is around 130 ° C.
  • the mixtures of hydroxyl groups and epoxy group-containing compounds to be reacted are therefore expediently heated to the temperature at which the reaction proceeds at a sufficient rate, ie in 30 minutes to 15 hours.
  • the reaction is expediently followed by increasing the epoxy equivalent, which indicates a decrease in the epoxide groups.
  • the reaction can be stopped by cooling below the reaction temperature.
  • Part of the BF 3 amine complex is consumed during the reaction by incorporating the fluoride ions into the reaction product. Any excess of the BF 3 amine complex can be rendered harmless after the reaction has ended by adding basic-acting substances such as bleaching earth, calcium oxide, calcium hydroxide, barium oxide and barium hydroxide to the complex.
  • the basic substances are removed together with the products resulting from them and the BF 3 amine complexes by filtration.
  • the reaction of the adduct, which still contains reactive epoxy groups, with the polyamine or the adduct of polyamine and component C is carried out at 20 to 100 ° C., preferably 20 to 40 ° C. Thereafter, a holding time at elevated temperature, preferably 50 to 80 ° C., with stirring for 1 to 3 hours is appropriate.
  • the curing agents according to the invention are used, if appropriate together with emulsifying agents, for the preparation of aqueous curable epoxy resin dispersions which are used as coating or coating agents.
  • the epoxy resins curable with the curing agents according to the invention can contain further additives, such as, for. B. wetting agents, preferred wetting agents are the commercially available, non-ionic wetting agents based on modified alkylphenol, such as. B. alkylphenoxypoly (ethyleneoxy) ethanol, a condensate of nonylphenol and ethylene oxide, containing 9-10 moles of ethylene oxide per mole of nonylphenol, etc.
  • modified alkylphenol such as. B. alkylphenoxypoly (ethyleneoxy) ethanol, a condensate of nonylphenol and ethylene oxide, containing 9-10 moles of ethylene oxide per mole of nonylphenol, etc.
  • the epoxy resins are generally introduced into water, so that the dispersion preferably contains up to 50% by weight of water. If a combination of epoxy resin and curing agent according to the invention is used as block filler or if pigments are present, the water content can even be 90% by weight. If colored coating mixtures are produced from epoxy resins and curing agents according to the invention, various additives can be added to the dispersion of epoxy resin and the curing agent according to the invention. These include pigments such as titanium dioxide, iron oxide, fillers such as asbestos, talc, mortar and other cement-like substances, pigment dispersants and other conventional coloring and coating aids.
  • the dispersion of epoxy resins and water-based hardening agents according to the invention can be used in any known manner. Suitable methods include: brushing, rolling, spraying, pouring, dipping, squeegees, pressing, filling, electrodeposition, screen printing, etc.
  • the dispersion of epoxy resins and hardening agents according to the invention can be used as a base coat, filler, clear sealer, protective coating, coatings, seals, thin mortar, mortar, etc. Their use is particularly expedient where corrosion resistance is desired.
  • the dispersions can also be used with epoxy resin / thermoplastic mixtures such as coal tar, vinyl polymers, etc. It can be used as a binder for pressed carbon, conductive floor coverings and leveling compounds, as an adhesive for wood, fabric, leather and metal and for various types of substrates such as cemented floors, walls, swimming pools, glass, glazed bricks etc.
  • the epoxy resin dispersion can be mixed with mortar or cement, the water being used as an emulsion to make the cement pasty.
  • the water in the cement mixture can be used as a solvent for the epoxy resin dispersion.
  • Addition of the hardening agent according to the invention enables uniform mixing of cement and epoxy resin hardener dispersion. It is thus possible to obtain epoxy resin hardener dispersion hardened cement.
  • the viscosities are measured at 25 ° C. in a falling ball viscometer according to Höppler.
  • the character ⁇ -_ means «approximately» and EV epoxy equivalent weight.
  • the viscosity of the product is 9600 mPa.s. This product is used as a preliminary product for the production of the curing agents according to the invention.
  • the curing agent obtained is now 82%, has an HAV of 159 and a viscosity of 2330 mPa.s.
  • Example 1A was repeated. After a 4.5 hour hold time at 170 ° C, an EV value of 391 was obtained.
  • the curing agent obtained is now 81.5%, has an HAV of 197 and a viscosity of 13450 m.Pa.s.
  • Example 4 C The procedure was as described in Example 3 C.
  • the curing agent obtained is 81.5%, has an HAV of 197 and a viscosity of 13120 mPa.s.
  • Example 3 A and B were repeated.
  • Example 1 A and B Example 1 A and B were repeated.
  • Example 12 C 590 g of the 80% solution are now reacted with 53 g of acrylonitrile (0.2 val per hydrogen amine) as described under Example 1 C.
  • the HAV is now 161
  • the viscosity is 3940 mPa.s. 1.25 val each, based on epoxy groups, of the precursors listed under Example 13 A to 19 A were followed up with 136 g xylylenediamine (2 val) and 170 g 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (2 val)
  • Example 3 B implemented.
  • Products 13B to 19B were implemented according to Example 3C.
  • the dispersions showed excellent stability within the processing time (i.e. until the start of the crosslinking reaction between the resin and hardener components), which was 30 minutes to 5 hours.
  • the aqueous dispersions using epoxy resin A were applied in a layer thickness of approximately 200 pm to phosphated iron sheets and asbestos-cement plates.
  • the dispersions showed excellent stability within the processing time (i.e. until the start of the crosslinking reaction between the resin and hardener components), which was 30 minutes to 3 hours.
  • the emulsion paint produced with epoxy resin A and the films produced therefrom showed test results similar to those with epoxy resin C.
  • pot life was used to denote the time which elapsed until a dispersion composed of 50 g of the epoxy resin, 50 g of water and an equivalent amount of the particular curing agent according to the invention, Example 1 C to 19 C, or until the viscosity of the dispersion was so strong it has increased that their proper processing is no longer possible.
  • a mixture consisting of 80 g of fine-grained quartz sand (grain size 0.5 mm), 160 g of coarse-grained quartz sand, 80 g of cement, 11 g of epoxy resin B and 11.7 g of the curing agent according to Example 3 C according to the invention were mixed homogeneously in a mixer and mixed with 80 g Water mixed to a pasty consistency.
  • This mass was processed with a squeegee to an approximately 5mm thick concrete floor covering, which after curing had excellent oil and water resistance.
  • the tensile, compressive and flexural strengths of the concrete mixture are improved by the addition of the epoxy resin hardener dispersion by approx. 20%.

Description

Es ist bekannt, dass Polyamidoamine, die freie Aminogruppen enthalten und die aus Alkylenpolyaminen und polymerisierten ungesättigten, natürlichen Fettsäuren hergestellt werden, zum Härten von Epoxidharzen verwendet werden können. (Vergl. Epoxydverbindungen und Epoxydharze von Dr. Alfred Paquin, Springer-Verlag Berlin/Göttingen/Heidelberg 1958, Seiten 511 bis 516 und Lee & Neville «Handbook of Epoxy Resins» Mc Graw-Hill Book Co., New York, 1967, 10, 1.-10, 12.).It is known that polyamidoamines containing free amino groups and made from alkylene polyamines and polymerized unsaturated natural fatty acids can be used to cure epoxy resins. (Compare epoxy compounds and epoxy resins by Dr. Alfred Paquin, Springer-Verlag Berlin / Göttingen / Heidelberg 1958, pages 511 to 516 and Lee & Neville "Handbook of Epoxy Resins" Mc Graw-Hill Book Co., New York, 1967, 10 , 1-10, 12.).

Die Härtung von Epoxidharzen mit Addukten, die aus Polyamidoaminen und Polyepoxiden gebildet werden, in Abwesenheit von Wasser ist ebenfalls durch die US-A-3280054 bekannt. Zwar wurde in der DE-A-1520918 erwähnt, härtbare, wässerige Dispersionen aus diesen Addukten und Epoxidharzen herzustellen, die hierbei erhaltenen Ergebnisse sind jedoch häufig nicht zufriedenstellend wie eigene Prüfungen ergeben haben. So sind in einigen Fällen die Addukte, besonders die aus aromatischen Polyepoxiden hergestellten, halbfest und nicht vollständig in wässrigem Milieu dispergierbar, während wässrige Dispersionen, die ein aromatisches Epoxidharz und ein aus einem aliphatischen Polyepoxid hergestellte Addukt enthalten, häufig unerwünschtes thixotropes Verhalten besitzen.The curing of epoxy resins with adducts formed from polyamidoamines and polyepoxides in the absence of water is also known from US-A-3280054. Although it was mentioned in DE-A-1520918 to prepare curable, aqueous dispersions from these adducts and epoxy resins, the results obtained here are often unsatisfactory, as our own tests have shown. In some cases, the adducts, especially those made from aromatic polyepoxides, are semi-solid and not completely dispersible in an aqueous medium, while aqueous dispersions containing an aromatic epoxy resin and an adduct made from an aliphatic polyepoxide often have undesirable thixotropic behavior.

In der US-A-3383347 ist angegeben, phenolmodifizierte Amine, die Reaktionsprodukte einer primären Aminogruppe eines aliphatischen Polyamins mit einem Phenol oder Reaktionsprodukte eines aliphatischen Polyamins mit einem Phenol und einem Aldehyd sein können, als Härtungsmittel zu verwenden. Diese Härtungsmittel führen jedoch zu Epoxidharz-Härter-Emulsionen mit nicht ausreichender Verarbeitungszeit, die sehr spröde Beschichtungen bilden und die ausserdem in Gegenwart von Eisen unerwünschte rostbraune Verfärbungen aufweisen.US-A-3383347 states that phenol-modified amines, which can be reaction products of a primary amino group of an aliphatic polyamine with a phenol or reaction products of an aliphatic polyamine with a phenol and an aldehyde, are used as curing agents. However, these hardeners lead to epoxy resin hardener emulsions with insufficient processing time, which form very brittle coatings and which, in addition, have undesirable rust-brown discoloration in the presence of iron.

In der DE-A-1925941 werden Epoxidharz-Härter-Emulsionen beschrieben, die als Härterkomponente ein Aminoamid-Addukt enthalten, welches ein Aminoamid einer Fettsäure und eines Alkylenpolyamins darstellt und welches das Reaktionsprodukt des Aminoamids mit 10-40 Gewichtsprozent, (bezogen auf das Gewicht der schwer flüchtigen Aminoamid-Addukt-Anteile) Monoepoxid ist, welches aus einem aliphatischen Monoepoxid mit 2-12 C-Atomen oder aus einem durch einen Phenylrest substituierten Monoepoxid besteht.DE-A-1925941 describes epoxy resin hardener emulsions which contain, as hardener component, an aminoamide adduct which is an aminoamide of a fatty acid and an alkylene polyamine and which is the reaction product of the aminoamide with 10-40 percent by weight (based on the weight the highly volatile aminoamide adduct components) is monoepoxide, which consists of an aliphatic monoepoxide with 2-12 C atoms or of a monoepoxide substituted by a phenyl radical.

Diese Epoxidharz-Härter-Emulsionen weisen eine relativ grosse Instabilität auf und scheiden schon innerhalb der Verarbeitungszeit Wasser aus. Die damit hergestellten Beschichtungen bleiben relativ weich und gegenüber mechanischen Einflüssen stark empfindlich, so dass sich damit keine ausreichend stabilen Schutzüberzüge herstellen lassen.These epoxy resin hardener emulsions have a relatively high instability and excrete water within the processing time. The coatings produced in this way remain relatively soft and highly sensitive to mechanical influences, so that it is not possible to produce sufficiently stable protective coatings with them.

In der CH-A-487955 werden härtbare, wässerige Dispersionen beschrieben, die einen bei Raumtemperatur flüssigen Härter für das Epoxydharz enthalten, wobei im Härter der Wasserstoff direkt am Stickstoff gebunden ist, der durch Addition aus nicht aliphatischem Epoxyd, das nur eine endständige 1,2-Epoxydgruppe pro Molekül enthält, oder aliphatischem Epoxyd, das im Durchschnitt eine oder mehr als eine endständige, 1,2-Epoxydgruppe pro Molekül enthält, und einem stöchiometrischen Überschuss eines Poly(aminoamid)-Kondensationsproduktes, welches aus einem Alkylenpolyamin der Formel

Figure imgb0001
worin der Alkylenrest der Äthylen-, Propylen-, Butylen-, Pentylen oder Hexylenrest sein kann, n eine ganze Zahl grösser als Null bedeutet, und einem Mischpolymerisat einer konjugiert ungesättigten Fettsäure oder eines amidbitdenden Säurederivates mit einer aromatischen Vinylverbindung, erhältlich ist.CH-A-487955 describes curable, aqueous dispersions which contain a hardener for the epoxy resin which is liquid at room temperature, the hydrogen being bound directly to the nitrogen in the hardener, which is formed by addition of non-aliphatic epoxide, which is only a terminal 1, Contains 2-epoxy group per molecule, or aliphatic epoxy, which contains on average one or more than one terminal, 1,2-epoxy group per molecule, and a stoichiometric excess of a poly (aminoamide) condensation product, which consists of an alkylene polyamine of the formula
Figure imgb0001
 wherein the alkylene radical can be the ethylene, propylene, butylene, pentylene or hexylene radical, n is an integer greater than zero, and a copolymer of a conjugated unsaturated fatty acid or an amide-dying acid derivative with an aromatic vinyl compound is available.

Diese wässerigen Dispersionen enthalten vorzugsweise ferner einen Beschleuniger zur Härtung. Diese Beschleuniger sind Verbindungen, die wenigstens ein tertiäres Aminostickstoffatom und eine phenolische Hydroxylgruppe enthalten: Ausserdem enthalten die Dispersionen Orthophosphorsäure oder eine flüssige aliphatische Monocarbonsäure, z. B. Essigsäure. Auch diese Epoxyd-Härter-Dispersionen weisen noch eine ungenügende Stabilität auf und liefern nur relativ weiche und mechanisch empfindliche Schutzüberzüge. Ferner führt die Anwesenheit der dissoziierenden Säuren zu einer Instabilität der Dispersion, da das Säureanion (A ) mit der Epoxydgruppe nach folgendem Schema reagieren kann und Epoxydgruppen verbraucht:

Figure imgb0002
OThese aqueous dispersions preferably also contain an accelerator for curing. These accelerators are compounds which contain at least one tertiary amino nitrogen atom and one phenolic hydroxyl group. In addition, the dispersions contain orthophosphoric acid or a liquid aliphatic monocarboxylic acid, e.g. B. acetic acid. These epoxy hardener dispersions also have insufficient stability and only provide relatively soft and mechanically sensitive protective coatings. Furthermore, the presence of the dissociating acids leads to instability of the dispersion, since the acid anion (A) can react with the epoxy group according to the following scheme and consumes epoxy groups:
Figure imgb0002
 O

In der DE-A-2332177 werden Härtungsmittel für wässerige Epoxydharz-Dispersionen beschrieben, die Assoziate sind, aufgebaut aus:

  • 1. Polyamidoamin-Epoxyd-Addukten (1) mit einem stöchiometrischen Überschuss eines Polyamidoamins (1a) aus einem Polyalkylenpolyamin (worin der Alkylenrest aus dem Äthylen-, Propylen-, Butylen-, Pentylen- oder Hexylenrest besteht) und mono-, di- und/oder trimerisierten Fettsäuren oder einem Mischpolymerisat konjugiert ungesättigter Fettsäuren oder amidbildender Fettsäurederivate (worin die Fettsäuren bzw. Fettsäurederivate in der monomeren Form 8 bis 24 Kohlenstoffatome enthalten) davon mit einer aromatischen Vinylverbindung und 5 bis 35 Gew.-%, bezogen auf das eingesetzte Polyamidoamin, einer aliphatischen Epoxydverbindung (1b) mit mehr als 2 endständigen, jedoch höchstens 6 Epoxydgruppen und
  • 2. 5 bis 30 Gew.-%, bezogen auf das eingesetzte Polyamidoamin, eines Phenol-Formaldehyd-Polyamin-Kondensationsproduktes (2) (wobei das aliphatische, araliphatische, cycloaliphatische oder heterocyclische Polyamin mindestens 2, jedoch höchstens 8 direkt am Stickstoff gebundene Wasserstoffatome enthält) besteht.
DE-A-2332177 describes curing agents for aqueous epoxy resin dispersions, which are associates, composed of:
  • 1. polyamidoamine-epoxy adducts (1) with a stoichiometric excess of a polyamidoamine (1a) from a polyalkylene polyamine (in which the alkylene radical consists of the ethylene, propylene, butylene, pentylene or hexylene radical) and mono-, di- and / or trimerized fatty acids or a copolymer of conjugated unsaturated fatty acids or amide-forming fatty acid derivatives (in which the fatty acids or fatty acid derivatives in the monomeric form contain 8 to 24 carbon atoms) thereof with an aromatic vinyl compound and 5 to 35% by weight, based on the polyamidoamine used, an aliphatic epoxy compound (1b) with more than 2 terminal but not more than 6 epoxy groups and
  • 2. 5 to 30% by weight, based on the polyamidoamine used, of a phenol-formaldehyde poly amine condensation product (2) (where the aliphatic, araliphatic, cycloaliphatic or heterocyclic polyamine contains at least 2 but not more than 8 hydrogen atoms directly bonded to the nitrogen).

Für die Herstellung von Überzügen ist es jedoch erforderlich, dem Gemisch von Epoxyharzpräpolymer und Härtungsmittel organische wasserverdünnbare Lösungsmittel zuzusetzen, um die Viskosität der Masse zu verringern und sie leichter anwendbar zu machen. Diese organischen Lösungsmittel erleichtern zwar die Anwendung der Massen und ergeben Filme mit guten Eigenschaften, bieten aber eine Reihe schwerwiegender Probleme. Die Lösungsmittel sind kostspielig und gewöhnlich giftig oder entzündlich. Verunreinigungen durch das Lösungsmittel während Herstellung, Lagerung, Transport und letztlicher Verwendung der Massen, Lösungsmitteldämpfe, Lösungsmittelabfälle von Reinigungsanlagen und Verspritzen von Lösungsmittel sind weitere Probleme, deren Lösung oft schwierig und kostspielig ist. Durch diese Nachteile wird die Verwendung der bekannten Epoxydüberzugsmassen beträchtlichen Beschränkungen unterworfen, insbesondere wenn sie im Zusammenhang mit dem Umgang oder der Herstellung von Nahrungsmitteln verwendet werden sollen. Ausserdem ist die Reinigung einer Anlage, die mit solchen Überzügen in Kontakt gestanden hat, von beträchtlichen Schwierigkeiten begleitet.For the production of coatings, however, it is necessary to add organic water-dilutable solvents to the mixture of epoxy resin prepolymer and curing agent in order to reduce the viscosity of the composition and to make it easier to use. Although these organic solvents facilitate the application of the compositions and produce films with good properties, they offer a number of serious problems. The solvents are expensive and are usually toxic or flammable. Contamination from the solvent during the manufacture, storage, transportation and ultimate use of the masses, solvent vapors, solvent waste from cleaning plants and spraying of solvents are further problems which are often difficult and costly to solve. These disadvantages place considerable restrictions on the use of the known epoxy coating compositions, in particular if they are to be used in connection with the handling or production of foods. In addition, the cleaning of a plant that has been in contact with such coatings is accompanied by considerable difficulties.

In der FR-A-2068390 werden wasserverdünnbare Hilfsmittel zum Emulgieren und Härten von Epoxydharzen beschrieben, die aus Umsetzungsprodukten aus Glycidyläthern von Polyalkylenpolyätherpolyolen und Polyaminen bestehen.FR-A-2068390 describes water-dilutable auxiliaries for the emulsification and curing of epoxy resins which consist of reaction products from glycidyl ethers of polyalkylene polyether polyols and polyamines.

Die dort beschriebenen Produkte sind jedoch nicht auf der Basis einer zusätzlichen additionsfähigen ungesättigten Verbindung aufgebaut. Ausserdem geht dieses bekannte Verfahren von einem Monoepoxyd, nämlich Epichlorhydrin und einem Alkylenglykol aus, wobei als Katalysator Zinntetrachlorid verwendet wird. Bei diesem bekannten Verfahren würde der erfindungsgemäss eingesetzte BF3-Amin-Komplex überhaupt nicht wirksam werden.However, the products described there are not based on an additional, unsaturated compound capable of addition. In addition, this known process is based on a monoepoxide, namely epichlorohydrin and an alkylene glycol, tin tetrachloride being used as the catalyst. In this known method, the BF 3 amine complex used according to the invention would not be effective at all.

Die FR-A-2128773 beschreibt ein Härtungsmittel für Epoxydharze in Form eines Reaktionsprodukts aus a) mindestens einem Diamin, b) einem polyfunktionellen Polymeren, z. B. einem Butadien-Homo- oder Copolymerisat und gegebenenfalls c) einem Polyepoxyd. Der Anteil des Amins a) beträgt hierbei 20-80%, bezogen auf das Reaktionsprodukt aus a), b) und c). Diese Mischungen werden jedoch nur in organischen Lösungsmittelsystemen verwendet. Ferner sind die dort eingesetzten polymeren Komponenten b) keine Polyalkylen-polyäther-polyole und der Aminüberschuss liegt dort wesentlich höher als in den erfindungsgemässen Härtungsmitteln.FR-A-2128773 describes a curing agent for epoxy resins in the form of a reaction product of a) at least one diamine, b) a polyfunctional polymer, e.g. B. a butadiene homo- or copolymer and optionally c) a polyepoxide. The proportion of amine a) is 20-80%, based on the reaction product from a), b) and c). However, these mixtures are only used in organic solvent systems. Furthermore, the polymeric components b) used there are not polyalkylene-polyether-polyols and the amine excess there is significantly higher than in the curing agents according to the invention.

Aufgabe der vorliegenden Erfindung ist es, ein lösungsmittelfreies Härtungsmittel für wässerige Epoxydharz-Dispersionen zur Verfügung zu stellen, das die genannten Nachteile nicht hat und überraschend widerstandsfähige Schutzüberzüge in Verbindung mit wässerigen Epoxydharz-Dispersionen liefert.It is an object of the present invention to provide a solvent-free curing agent for aqueous epoxy resin dispersions which does not have the disadvantages mentioned and which provides surprisingly resistant protective coatings in conjunction with aqueous epoxy resin dispersions.

Durch die Abwesenheit organischer Lösungsmittel entfallen die durch Geruch, Giftigkeit und Entzündlichkeit verursachten Probleme; ferner können alle Anlagen, die mit Epoxydharzen in Kontakt kommen, durch Waschen mit Wasser gereinigt werden.The absence of organic solvents eliminates the problems caused by smell, toxicity and flammability; Furthermore, all systems that come into contact with epoxy resins can be cleaned by washing with water.

Gegenstand der Erfindung sind Hähungsmittel für wässrige Epoxydharz-Dispersionen, bestehend aus einem Umsetzungsprodukt, erhältlich aus

  • A) 20 bis 80 Gew.-% eines Adduktes aus a1) mindestens einer Polyepoxydverbindung und a2) mindestens eines Polyalkylenpolyätherpolyols mit einem mittleren Molekulargewicht von 200 bis 10000 durch Umsetzung im Äquivalentverhältnis von a1 :a2 = 2:(0,1 bis 1,5) mit
  • B) 80 bs 20 Gew.-% eines aliphatischen, cycloaliphatischen, araliphatischen oder heterocyclischen Polyamins oder Polyamingemisches, wobei das eingesetzte Amin in einer solchen Menge verwendet wird, dass die am Stickstoff befindlichen H-Atome in einem 2- bis 10-fachen Überschuss, bezogen auf die zur Umsetzung befähigten Epoxydgruppen, vorhanden sind, die dadurch gekennzeichnet sind, dass an die reaktiven Gruppen des Polyamins b1) noch C) zur Addition befähigte ungesättigte Verbindungen vom Typ
    Figure imgb0003
    -CH3 und X=-CN, -COOH, -COOCH3, -COOC2H5, -COOC3H7, -COOC4H9, -CONH2, -COONHCH3, CON(CH3)2 bedeuten, addiert sind.
The invention relates to waxing agents for aqueous epoxy resin dispersions, consisting of a reaction product, obtainable from
  • A) 20 to 80% by weight of an adduct of a1) at least one polyepoxide compound and a2) at least one polyalkylene polyether polyol with an average molecular weight of 200 to 10,000 by reaction in the equivalent ratio of a1: a2 = 2: (0.1 to 1.5 ) With
  • B) 80 to 20% by weight of an aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamine or polyamine mixture, the amine used being used in such an amount that the H atoms on the nitrogen are in a 2 to 10-fold excess, based on the epoxy groups capable of reaction, which are characterized in that unsaturated compounds of the type capable of addition are added to the reactive groups of the polyamine b1)
    Figure imgb0003
     -CH 3 and X = -CN, -COOH, -COOCH 3 , -COOC 2 H 5 , -COOC 3 H 7 , -COOC 4 H 9 , -CONH 2 , -COONHCH 3 , CON (CH 3 ) 2 , are added.

Nach einer Ausführungsform der Erfindung ist das Addukt aus 2 bis 4 Äquivalenten der Komponente a1) und 0,2 bis 1,5 Äquivalenten der Komponente a2) mit 80-20 Gew.-% der Komponente B) und bis 0,5, vorzugsweise 0,1 bis 0,3 Äquivalenten der Komponente C) erhältlich. Vorzugsweise werden A) 50 bis 70 Gew.-% eines Adduktes aus 2,3 bis 3,0 Äquivalenten a1) und 0,3 bis 0,8 Äquivalenten a2) mit B) 50 bis 30 Gew.-% der Komponente eines aliphatischen, cycloaliphatischen, araliphatischen und/oder heterocyclischen Polyamins oder Polyamingemisches, wobei die eingesetzte Aminmenge in einem 5 bis 8-fachen Überschuss, bezogen auf die zur Umsetzung befähigten Epoxyd-und Aminwasserstoffgruppen, vorliegt, umgesetzt. Vorzugsweise ist a1 wasserunlöslich und a2 wasserlöslich.According to one embodiment of the invention, the adduct is composed of 2 to 4 equivalents of component a1) and 0.2 to 1.5 equivalents of component a2) with 80-20% by weight of component B) and up to 0.5, preferably 0 , 1 to 0.3 equivalents of component C) available. A) 50 to 70% by weight of an adduct of 2.3 to 3.0 equivalents a1) and 0.3 to 0.8 equivalents a2) with B) 50 to 30% by weight of the component of an aliphatic, cycloaliphatic, araliphatic and / or heterocyclic polyamines or polyamine mixtures, the amount of amine used being present in a 5 to 8-fold excess, based on the epoxy and amine hydrogen groups capable of reaction. A1 is preferably water-insoluble and a2 is water-soluble.

Ein weiterer Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung der Härtungsmittel, wie es in den Patentansprüchen 5 bis 7 beschrieben ist. Bevorzugt erfolgt die Umsetzung der Hydroxylgruppen des Polyalkylenpolyätherpolyols mit den Epoxydgruppen bei 20 bis 200°C.Another object of the invention is also a method for producing the hardening agents, as described in claims 5 to 7. The hydroxyl groups of the polyalkylene polyether polyol are preferably reacted with the epoxy groups at 20 to 200.degree.

Gegenstand der Erfindung ist auch die Verwendung der nach den vorstehend genannten Verfahren erhaltenen Härtungsmittel zusammen mit polyfunktionellen Epoxydverbindungen und Wasser sowie gegebenenfalls Emulgiermitteln zur Herstellung von aushärtbaren gegebenenfalls filmbildenden Dispersionen als Beschichtungs-oder Überzugsmittel.The invention also relates to the use of the curing agents obtained by the abovementioned processes together with polyfunctional epoxy compounds and what water and optionally emulsifiers for the production of curable, optionally film-forming dispersions as coating or coating agents.

Aus der grossen Zahl der polyfunktionellen Epoxydverbindungen a1), die mehr als eihe.1,2-Epoxydgruppe im Molekül enthalten, seien genannt:From the large number of polyfunctional epoxy compounds a1) which contain more than one 1,2-epoxy group in the molecule, the following may be mentioned:

Die Epoxyde mehrfach-ungesättigter Kohlenwasserstoffe (Vinylcyclohexen, Dicyclopentadien, Cyclohexadien, Cyclododecadien, Cyclododecatrien, Isopren, 1,5-Hexadien, Butadien, Polybutadiene, Divinylbenzole und dergleichen), Oligomere des Epichlorhydrins und ähnliche, Epoxyäther mehrwertiger Alkohole (Äthylen-, Propylen- und Butylenglykole, Polyglykole, Thiodiglykole, Glycerin, Pentaerythrit, Sorbit, Polyvinylalkohol, Polyallylalkohol und ähnliche), Epoxyäther mehrwertiger Phenole (Resorcin, Hydrochinon, Bis-(4-hydroxyphenyl)-methan, Bis-(4-hydroxy-3-methylphenyl)-methan, Bis-(4-hydroxy-3,5-dibromphenyl)-methan, Bis-(4-hydroxy-3,5-difluorphenyl)-methan, 1,1-Bis-(4-hydroxyphenyl)-äthan, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis-(4-hydroxy-3-methylphenyl)-propan, 2,2-Bis-(4-hydroxy-3-chlorphenyl)-propan, 2,2-Bis-(4-hydroxy-3,5-dichtor- phenyl)-propan, 2,2-Bis-(4-hydroxy-3,5-dichlorphenyl)-propan, Bis-(4-hydroxyphenyl)-phenylmethan, Bis-(4-hydroxyphenyl)-diphenylmethan, Bis-(4-hydroxyphenyl)-4'-methylphenylmethan, 1,1-Bis-(4-hydroxyphenyl)-2,2,2-trichloräthan, Bis-(4-hydroxyphenyl)-(4-chlorphenyl)-methan, 1,1-Bis-(4-hydroxyphenyll-cyclohexan, Bis-(4-hydroxyphenyl)-cyclohexylmethan, 4,4'-Dihydroxydiphenyl, 2,2'-Dihydroxydiphenyl, 4,4'-Dihydroxydiphenylsulfon sowie deren Hydroxyäthyläther, Phenoi-Formaldehyd-Kondensationsprodukte, wie Phenolalkohole, Phenolaldehydharze und ähnliche, S- und N-haltige Epoxyde, (N,N-Diglycidylanilin, N,N'-Dimethyldiglycidyl-4,4-Diaminodi-. phenylmethan) sowie Epoxyde, welche nach üblichen Verfahren aus mehrfach ungesättigten Carbonsäuren oder einfach ungesättigten Carbonsäureestern ungesättigter Alkohole hergestellt worden sind, Glycidylestern, Polyglycidylester, die durch Polymerisation oder Mischpolymerisation von Glycidylestern ungesättigter Säuren gewonnen werden können oder aus anderen sauren Verbindungen (Cyanursäure, Diglycidylsulfid, cyclischem Trimethylentrisulfon bzw. deren Derivaten und anderen) erhältlich sind.The epoxies of polyunsaturated hydrocarbons (vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadienes, divinylbenzenes and the like), oligomers of epichlorohydrin and the like, epoxy ethers and polyhydric alcohols Butylene glycols, polyglycols, thiodiglycols, glycerin, pentaerythritol, sorbitol, polyvinyl alcohol, polyallyl alcohol and the like), epoxy ether of polyhydric phenols (resorcinol, hydroquinone, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane , Bis (4-hydroxy-3,5-dibromophenyl) methane, bis (4-hydroxy-3,5-difluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2.2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2 Bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, bis (4-hydroxyphenyl) phenylmethane, bis - (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) - 4'-methylphenylmethane, 1,1-bis- (4-hydroxyphenyl) -2,2,2-trichloroethane, bis- (4-hydroxyphenyl) - (4-chlorophenyl) methane, 1,1-bis- (4- hydroxyphenyll-cyclohexane, bis- (4-hydroxyphenyl) cyclohexylmethane, 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylsulfone and their hydroxyethyl ether, pheno-formaldehyde condensation products such as phenol alcohols, phenol aldehyde resins and the like , S- and N-containing epoxies, (N, N-diglycidylaniline, N, N'-dimethyldiglycidyl-4,4-diaminodi-. phenylmethane) and epoxides, which have been prepared by conventional processes from polyunsaturated carboxylic acids or monounsaturated carboxylic acid esters of unsaturated alcohols, glycidyl esters, polyglycidyl esters which can be obtained by polymerizing or copolymerizing glycidyl esters of unsaturated acids or from other acidic compounds (cyanuric acid, diglycidyl sulfide, Trimethylene trisulfone or its derivatives and others) are available.

Die vorstehenden polyfunktionellen Epoxydverbindungen, dieser Ausdruck schliesst auch den Begriff Epoxydharz ein, können einzeln oder im Gemisch, gegebenenfalls in Gegenwart von Lösungsmitteln oder Weichmachern, nach dem vorliegenden Verfahren umgesetzt oder zur Herstellung von Dispersionen verwendet werden. Sie können auch in Gemischen mit Monoepoxyden eingesetzt werden. So finden beispielsweise die folgenden Monoepoxyde im Gemisch mit den vorgenannten Epoxydverbindungen Verwendung: epoxydierte ungesättigte Kohlenwasserstoffe (Butylen-, Cyclohexen-, Styroloxyd und andere), halogenhaltige Epoxyde, wie z. B. Epichlorhydrin, Epoxyäther einwertiger Alkohole (Methyl-, Äthyl-, Butyl-, 2-Äthylhexyl-, Dodecylalkohol und andere), Epoxyäther einwertiger Phenole (Phenol, Kresol sowie andere in o- oder p-Stellung substituierte Phenole), Glycidylester ungesättigter Carbonsäuren, epoxydierte Ester von ungesättigten Alkoholen bzw. ungesättigten Carbonsäuren sowie die Acetale des Glycidaldehyds.The above polyfunctional epoxy compounds, this term also includes the term epoxy resin, can be reacted individually or in a mixture, if appropriate in the presence of solvents or plasticizers, by the present process or used to prepare dispersions. They can also be used in mixtures with monoepoxides. For example, the following monoepoxides are used in a mixture with the aforementioned epoxy compounds: epoxidized unsaturated hydrocarbons (butylene, cyclohexene, styrene oxide and others), halogen-containing epoxides, such as. B. epichlorohydrin, epoxy ether of monohydric alcohols (methyl, ethyl, butyl, 2-ethylhexyl, dodecyl alcohol and others), epoxy ether of monohydric phenols (phenol, cresol and other phenols substituted in the o- or p-position), glycidyl esters of unsaturated carboxylic acids , epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids and the acetals of glycidaldehyde.

Als bevorzugte mehrwertige Phenole werden eingesetzt: Resorcin und verschiedene Bisphenole, die man durch Kondensation von Phenol mit Aldehyden und Ketonen wie z. B. Formaldehyd, Acetaldehyd, Aceton, Methyläthylketon u. a., erhält. Harze dieser Art sind in den US-A-2855159 und 2589245 beschrieben.The preferred polyhydric phenols are: resorcinol and various bisphenols, which can be obtained by condensing phenol with aldehydes and ketones such as, for. B. formaldehyde, acetaldehyde, acetone, methyl ethyl ketone and. a., receives. Resins of this type are described in US-A-2855159 and 2589245.

Besonders bevorzugte Epoxydharze sind Polyphenol-Glycidyl-äther, z.B. das Reaktionsprodukt aus Epichlorhydrin und 2,2-Bis-(4-hydroxyphenyl-)propan (=Bisphenol A), welches Epoxydharz folgende theoretische Strukturformel besitzt:

Figure imgb0004
bzw. das Analogon auf Basis von Bisphenol F:
Figure imgb0005
einzeln oder im Gemisch mit Bisphenol A, worin n 0 oder eine ganze Zahl bis 10 bedeutet. Normalerweise ist n nicht grösser als 2 oder 3 und vorzugsweise 1 oder weniger. Das Epoxydharz hat ein Epoxyd-Äquivalent von 160-500.Particularly preferred epoxy resins are polyphenol glycidyl ether, for example the reaction product of epichlorohydrin and 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), which epoxy resin has the following theoretical structural formula:
Figure imgb0004
 or the analog based on bisphenol F:
Figure imgb0005
 individually or in a mixture with bisphenol A, in which n denotes 0 or an integer up to 10. Usually n is not greater than 2 or 3, and preferably 1 or less. The epoxy resin has an epoxy equivalent of 160-500.

Zu geeigneten Polyalkylenpolyätherpolyolen b), die für die erfindungsgemässe Herstellung der Härtungsmittel angewandt werden können, gehören beispielsweise die Anlagerungsprodukte eines Alkylenoxyds oder eines Alkylenoxyds mit einem mehrwertigen Alkohol. Geeignete Alkylenoxyde sind beispielsweise Äthylenoxyd, Propylenoxyd, Butylenoxyd, Amylenoxyd und Hetero- oder Blockcopolymere dieser Oxyde, vorzugsweise aber Äthylenoxyd. Als mehrwertige Alkohole sind sowohl aliphatische Alkohole einzeln oder im Gemisch geeignet, z.B. Äthylenglykol, 1,3-Propylenglykol, 1,2-Propylenglykol, 1,4-Butylenglykol, 1,3-Butylenglykol, 1,2-Butylenglykol, 1,5-Pentandiol, 1,4-Pentandiol, 1,3-Pentandiol, 1,6-Hexandiol, 1,7-Heptandiol, Glycerin, 1,1,1-Trimethylolpropan, 1,1,1-Trimethyloläthan, Hexan-1,2,6-triol, a-Methylglucosid, Pentaerythrit und Sorbit.Suitable polyalkylene polyether polyols b) which can be used for the preparation of the curing agents according to the invention include, for example, the adducts of an alkylene oxide or an alkylene oxide with a polyhydric alcohol. Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, butylene oxide, amylene oxide and hetero- or block copolymers of these oxides, but preferably ethylene oxide. Suitable polyhydric alcohols are both aliphatic alcohols individually or in a mixture, e.g. Ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, hexane-1,2,6-triol, a-methylglucoside, pentaerythritol and sorbitol.

Die Polyalkylenpolyätherpolyole können auch aus anderen Ausgangsstoffen hergestellt werden, z. B. aus Tetrahydrofuran und Alkylenoxid-Tetrahydrofuran-Copolymeren; Epihalogenhydrinen, z.B. Epichlorhydrin sowie Aralkylenoxyden, z.B. Styroloxyd.The polyalkylene polyether polyols can also be prepared from other starting materials, for. B. from tetrahydrofuran and alkylene oxide-tetrahydrofuran copolymers; Epihalohydrins, e.g. Epichlorohydrin and aralkylene oxides, e.g. Styrene oxide.

Die Polyalkylenpolyätherpolyole können entweder primäre oder sekundäre Hydroxylgruppen aufweisen und sind vorzugsweise Polyäther, die aus Alkylenoxyden mit 2 bis 6 Kohlenstoffatomen hergestellt werden, z. B. Polyäthylenätherglykole, Polypropylenätherglykole und Polybutylenätherglykole. Die Polyalkylenpolyätherpolyole können nach jedem bekannten Verfahren hergestellt werden, z. B. nach dem Verfahren, das von Wurtz 1859 angegeben wurde und in Encyclopedia of Chemical Technology, Bd. 7, S. 257 bis 262, Interscience Publishers, Inc (1951) oder in der US-A-1922459 beschrieben ist. Die mittlere Molmasse der Komponente a2 beträgt 200 bis 10000, vorzugsweise 800 bis 1200.The polyalkylene polyether polyols can have either primary or secondary hydroxyl groups and are preferably polyethers made from alkylene oxides having 2 to 6 carbon atoms, e.g. B. polyethylene ether glycols, polypropylene ether glycols and polybutylene ether glycols. The polyalkylene polyether polyols can be prepared by any known method, e.g. B. by the method specified by Wurtz 1859 and described in Encyclopedia of Chemical Technology, Vol. 7, pp. 257 to 262, Interscience Publishers, Inc (1951) or in US-A-1922459. The average molar mass of component a2 is 200 to 10,000, preferably 800 to 1200.

Gemäss der Erfindung können aliphatische, cycloaliphatische, araliphatische und heterocyclische Amine oder deren Gemische als Komponente B mit den Epoxyd-Polyalkylenpolyätherpolyol-Addukten umgesetzt werden.According to the invention, aliphatic, cycloaliphatic, araliphatic and heterocyclic amines or mixtures thereof can be reacted as component B with the epoxy-polyalkylene polyether polyol adducts.

Als Beispiele seien genannt: aliphatische, gesättigte oder ungesättigte, bifunktionelle Amine, z. B. niedere aliphatische Alkylen-Polyamine, wie z.B. Äthylendiamin, 1,2-Propylendiamin; 1,3-Propylendiamin, 1,4-Butylendiamin, Hexamethylendiamin, 2,2,4-(2,4,4-)Trimethylhexamethylendiamin oder Polyalkylen-Polyamine, z. B. homologe Polyäthylen-Polyamine, wie Diäthylentriamin, Triäthylentetramin, Tetraäthylenpentamin oder analoge Polypropylen-Polyamine, wie z.B. Dipropylentriamin, oder Polyoxypropylenpolyamine und Diamine der allgemeinen Formel H2N.CH2-X-CH2.NH2, wobei X die zweiwertigen Reste bedeutet.

Figure imgb0006
Examples include: aliphatic, saturated or unsaturated, bifunctional amines, e.g. B. lower aliphatic alkylene polyamines, such as ethylenediamine, 1,2-propylenediamine; 1,3-propylene diamine, 1,4-butylene diamine, hexamethylene diamine, 2,2,4- (2,4,4-) trimethyl hexamethylene diamine or polyalkylene polyamines, e.g. B. homologous polyethylene-polyamines, such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or analogous polypropylene polyamines, such as dipropylene triamine, or polyoxypropylene polyamines and diamines of the general formula H 2 N.CH 2 -X-CH 2 .NH 2 , where X is the divalent radicals means.
Figure imgb0006

Im einzelnen seien 1,2-, 1,3- und 1,4-Bis(ämino- methyl)-benzol, bzw. Gemische der Isomeren, 1,2-, 1,3- und 1,4-Bis-(aminomethyl-)cyclohexan bzw. Gemische der Isomeren, erwähnt. Weiter können Isophorondiamin (= 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan) und N-Amino- äthylpiperazin eingesetzt werden. Bevorzugte Verbindungen der Komponente B sind jedoch Xylylendiamin, 1-Amino-3-aminomethyl-3,5,5-trimethyl-cyclohexan, 2,2,4-(2,4,4,-)-Trimethylhexamethylendiamin oder Polyoxypropylenpolyamin sowie deren Gemische. Es ist möglich, alle genannten Amine vor der Umsetzung mit dem Epoxyd-Polyalkylenpolyätherpolyol-Addukt mit der einfach ungesättigten Verbindung C vom Typ

Figure imgb0007
zu sogenannten cyanäthylierten Aminen umzusetzen und diese dann statt der reinen Polyamine einzusetzen. Nachfolgend beschriebener Weg ist jedoch gebräuchlicher. Bevor das Umsetzungsprodukt aus Polyaminen und dem Epoxyd-Polyalkylenpoly-ätherpolyol-Addukt mit der einfach ungesättigten Verbindung umgesetzt wird, kann ggf. mit Wasser auf einen Festkörpergehalt von 50,0 bis 90 Gew.-% verdünnt werden.In particular, 1,2-, 1,3- and 1,4-bis (aminomethyl) benzene, or mixtures of the isomers, 1,2-, 1,3- and 1,4-bis (aminomethyl) -) Cyclohexane or mixtures of the isomers mentioned. Isophoronediamine (= 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane) and N-aminoethylpiperazine can also be used. However, preferred compounds of component B are xylylenediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2,2,4- (2,4,4, -) - trimethylhexamethylene diamine or polyoxypropylene polyamine and mixtures thereof. It is possible to react all of the amines mentioned with the monounsaturated compound C of the type before the reaction with the epoxy-polyalkylene polyether polyol adduct
Figure imgb0007
 to convert to so-called cyanoethylated amines and then use them instead of the pure polyamines. However, the route described below is more common. Before the reaction product of polyamines and the epoxy-polyalkylene polyether polyol adduct is reacted with the monounsaturated compound, it may be diluted with water to a solids content of 50.0 to 90% by weight.

Die Umsetzung mit der einfach ungesättigten Verbindung erfolgt durch Zugabe von z. B. Acrylnitril bei 20 bis 70°C, wobei nach der Zugabe eine Verweilzeit bei erhöhter Temperatur, bevorzugt 50 bis 70°C angebracht ist. Acryl- oder Methacrylnitril bilden die bevorzugten Verbindungen der Komponente C.The reaction with the monounsaturated compound is carried out by adding z. B. acrylonitrile at 20 to 70 ° C, wherein after the addition a residence time at elevated temperature, preferably 50 to 70 ° C is appropriate. Acrylonitrile or methacrylonitrile are the preferred compounds of component C.

Geeignete BF3-Aminkomplexe sind beispielsweise diejenigen, die aus folgenden Aminen (pKb-Werte in Klammern) und BF3 gebildet werden: n-Amylamin (10,63), Anilin (4,63), β-Phenylalanin = 2-Aminoäthylbenzol (9,84), 2-Äthylbenzimidazol (6,18), Benzylamin (9,33), trans-Bornylamin (10,17), 1-Amino-3-Methylbutan (10,60), 1,4-Diaminobutan (11,15), n-Butylamin (10,77), t.-Butylamin (10,83), n-Butylcyclohexylamin (11,23), Cyclohexylamin (10,66), n-Decylamin (10,64), Diäthylamin (10,49), Diisobutylamin (10,91 Diisopropylamin (10,96), Dimethylamin (10,73), n-Dodecanamin = Laurylamin (10,63), 2-Aminoäthanol (9,50), Äthylamin (10,81), Hexadecanamin (10,63), 1-Aminoheptan (10,66), 2-Aminoheptan (10,88), n-Hexylamin (10,56), 2,4-Dimethylimidazol (8,36), Morpholin (8,33), Methylamin (10,66), n-Nonylamin (10,64), Octadecanamin (10,60), Octylamin (10,65), 3-Aminopentan (10,59), 3-Amino-3-Methylpentan (11,01), n-Pentadecylamin (10,61), Piperazin (9,83), Propylamin (10,71), Pyrrolidin (11,27), Tetradecanamin = Myristylamin (10,62), Tridecanamin (10,63), Triäthylamin (11,01), ), Trimethylamin (9,81).Suitable BF 3 -amine complexes are, for example, those which are formed from the following amines (pK b values in brackets) and BF 3 : n-amylamine (10.63), aniline (4.63), β-phenylalanine = 2-aminoethylbenzene (9.84), 2-ethylbenzimidazole (6.18), benzylamine (9.33), trans-bornylamine (10.17), 1-amino-3-methylbutane (10.60), 1,4-diaminobutane ( 11.15), n-butylamine (10.77), t-butylamine (10.83), n-butylcyclohexylamine (11.23), cyclohexylamine (10.66), n-decylamine (10.64), diethylamine (10.49), diisobutylamine (10.91 diisopropylamine (10.96), dimethylamine (10.73), n-dodecanamine = laurylamine (10.63), 2-aminoethanol (9.50), ethylamine (10.81 ), Hexadecanamine (10.63), 1-aminoheptane (10.66), 2-aminoheptane (10.88), n-hexylamine (10.56), 2,4-dimethylimidazole (8.36), morpholine (8 , 33), methylamine (10.66), n-nonylamine (10.64), octadecanamine (10.60), octylamine (10.65), 3-aminopentane (10.59), 3-amino-3-methylpentane (11.01), n-pentadecylamine (10.61), piperazine (9.83), propylamine (10.71), pyrrolidine (11.27), tetrade canamin = myristylamine (10.62), tridecanamine (10.63), triethylamine (11.01),), trimethylamine (9.81).

Bevorzugt werden BF3-Benzylamin, BF3-Mono- äthylamin, BF3-Propylamin und BF3-n-Butylamin eingesetzt.BF 3 -benzylamine, BF 3 -mono-ethylamine, BF 3 -propylamine and BF 3 -n-butylamine are preferably used.

Für ein g-Äquivalent einer mit einem g-Äquivalent einer Epoxydgruppe umzusetzenden Hydroxylgruppe werden 100 bis 1, bevorzugt 15 bis 2 mMol, des BF3-Aminkomplexes eingesetzt. Die Umsetzung der Hydroxylgruppen mit den Epoxydgruppen kann im Temperaturbereich von 20 bis 200°C vorgenommen werden. Die Umsetzungstemperatur ist abhängig von dem jeweiligen BF3-Aminkomplex. Beispielsweise liegt die Umsetzungstemperatur bei Verwendung von BF3-Mo- noäthylamin oder BF3-Benzylamin um 130°C. Man erwärmt deshalb zweckmässig die umzusetzenden Gemische aus Hydroxylgruppen und Epoxydgruppen enthaltenden Verbindungen bis zu derjenigen Temperatur, bei der die Umsetzung mit ausreichender Geschwindigkeit, d.h. in 30 Minuten bis 15 Stunden, abläuft. Die Umsetzung verfolgt man zweckmässig über die Zunahme des Epoxydäquivalents, das eine Verminderung der Epoxydgruppen anzeigt.For a g equivalent of a hydroxyl group to be reacted with a g equivalent of an epoxy group, 100 to 1, preferably 15 to 2 mmol, of the BF 3 amine complex are used. The reaction of the hydroxyl groups with the epoxy groups can be carried out in the temperature range from 20 to 200 ° C. The reaction temperature depends on the respective BF 3 amine complex. For example, the reaction temperature when using BF 3 monoethylamine or BF 3 benzylamine is around 130 ° C. The mixtures of hydroxyl groups and epoxy group-containing compounds to be reacted are therefore expediently heated to the temperature at which the reaction proceeds at a sufficient rate, ie in 30 minutes to 15 hours. The reaction is expediently followed by increasing the epoxy equivalent, which indicates a decrease in the epoxide groups.

Die Reaktion kann durch Kühlung unter die Reaktionstemperatur abgebrochen werden.The reaction can be stopped by cooling below the reaction temperature.

Ein Teil des BF3-Amin-Komplexes wird während der Reaktion durch Einbau der Fluoridionen in das Umsetzungsprodukt verbraucht. Ein etwaiger Überschuss des BF3-Amin-Komplexes kann nach Reaktionsablauf durch Zugabe von basisch wirkenden Substanzen wie Bleicherde, Calcjumoxyd, Calciumhydroxyd, Bariumoxyd und Bariumhydroxyd im Überschuss zum Komplex unschädlich gemacht werden. Die basisch wirkenden Substanzen werden zusammen mit den aus ihnen und den BF3-Aminkomplexen entstehenden Produkten durch Filtration entfernt. Die Umsetzung des Adduktes, welches noch reaktionsfähige Epoxydgruppen enthält, mit dem Polyamin oder dem Addukt aus Polyamin und Komponente C wird bei 20 bis 100°C, vorzugsweise 20 bis 40°C durchgeführt. Danach ist eine Haltezeit bei erhöhter Temperatur, bevorzugt 50 bis 80°C, unter Rühren für 1 bis 3 Stunden angebracht.Part of the BF 3 amine complex is consumed during the reaction by incorporating the fluoride ions into the reaction product. Any excess of the BF 3 amine complex can be rendered harmless after the reaction has ended by adding basic-acting substances such as bleaching earth, calcium oxide, calcium hydroxide, barium oxide and barium hydroxide to the complex. The basic substances are removed together with the products resulting from them and the BF 3 amine complexes by filtration. The reaction of the adduct, which still contains reactive epoxy groups, with the polyamine or the adduct of polyamine and component C is carried out at 20 to 100 ° C., preferably 20 to 40 ° C. Thereafter, a holding time at elevated temperature, preferably 50 to 80 ° C., with stirring for 1 to 3 hours is appropriate.

Die erfindungsgemässen Härtungsmittel werden, gegebenenfalls zusammen mit Emulgiermittein, zur Herstellung von wässrigen härtbaren Epoxydharzdispersionen verwendet, die als Beschichtungs- oder Überzugsmittet eingesetzt werden.The curing agents according to the invention are used, if appropriate together with emulsifying agents, for the preparation of aqueous curable epoxy resin dispersions which are used as coating or coating agents.

Die mit den erfindungsgemässen Härtungsmitteln härtbaren Epoxydharze können weitere Zusätze, wie z. B. Netzmittel, enthalten, bevorzugte Netzmittel sind die im Handel erhältlichen, nicht ionischen Netzmittel auf der Basis von modifiziertem Alkylphenol, wie z. B. Alkylphenoxypoly-(äthylenoxy-)äthanol, ein Kondensat aus Nonylphenol und Äthylenoxyd, enthaltend 9-10 Mol Äthylenoxyd pro Mol Nonylphenol, usw.The epoxy resins curable with the curing agents according to the invention can contain further additives, such as, for. B. wetting agents, preferred wetting agents are the commercially available, non-ionic wetting agents based on modified alkylphenol, such as. B. alkylphenoxypoly (ethyleneoxy) ethanol, a condensate of nonylphenol and ethylene oxide, containing 9-10 moles of ethylene oxide per mole of nonylphenol, etc.

Die Epoxydharze, gegebenenfalls versetzt mit Verdünnungsmitteln und/oder Netzmitteln, werden im allgemeinen in Wasser eingetragen, so dass die Dispersion vorzugsweise bis zu 50 Gew.-% Wasser enthält. Wenn eine Kombination aus Epoxydharz und erfindungsgemässem Härtungsmittel als Blockfüllstoff benutzt wird oder wenn Pigmente zugegen sind, kann der Wassergehalt sogar 90 Gew.-% betragen. Wenn farbige Überzugsmischungen aus Epoxydharzen underfindungsgemässen Härtungsmitteln hergestellt werden, können verschiedene Zusatzstoffe zu der Dispersion aus Epoxydharz und dem erfindungsgemässen Härtungsmittel zugesetzt werden. Diese schliessen Pigmente wie Titandioxyd, Eisenoxyd, Füllstoffe wie Asbest, Talkum, Mörtel und andere zementähnliche Stoffe, Pigment-Dispergierstoffe und andere herkömmliche Farb- und Überzugshilfsstoffe ein. Die Dispersion aus Epoxydharzen und erfindungsgemässen Härtungsmitteln auf der Basis von Wasser kann in jeder beliebigen bekannten Weise verwendet werden. Geeignete Methoden schliessen ein: Bürstenanwendung, Rollen, Sprühen, Giessüberziehen, Eintauchen, Rakel, Pressen, Spachteln, Elektroabscheidung, Siebdruck usw.The epoxy resins, optionally mixed with diluents and / or wetting agents, are generally introduced into water, so that the dispersion preferably contains up to 50% by weight of water. If a combination of epoxy resin and curing agent according to the invention is used as block filler or if pigments are present, the water content can even be 90% by weight. If colored coating mixtures are produced from epoxy resins and curing agents according to the invention, various additives can be added to the dispersion of epoxy resin and the curing agent according to the invention. These include pigments such as titanium dioxide, iron oxide, fillers such as asbestos, talc, mortar and other cement-like substances, pigment dispersants and other conventional coloring and coating aids. The dispersion of epoxy resins and water-based hardening agents according to the invention can be used in any known manner. Suitable methods include: brushing, rolling, spraying, pouring, dipping, squeegees, pressing, filling, electrodeposition, screen printing, etc.

Die Dispersion aus Epoxydharzen und erfindungsgemässen Härtungsmitteln kann verwendet werden als Grundlack, Füllstoff, Klarsiegier, Schutzanstrich, Überzüge, Dichtungen, dünne Mörtel, Mörtel usw. Ihre Anwendung ist dort besonders zweckmässig, wo Korrosionsbeständigkeit erwünscht ist. Die Dispersionen können auch mit EpoxydharzlThermoplast-Mischungen, wie Kohlenteer, Vinylpolymerisaten usw. verwendet werden. Sie kann als Bindemittel für Presskohle, leitende Bodenbeläge und Spachtelmassen, als Klebstoff für Holz, Gewebe, Leder und Metall und für verschiedenartige Schichtträger, wie zementierte Fussböden, Wände, Schwimmbäder, Glas, glasierte Ziegel usw. benutzt werden. Weiter kann die Epoxydharz-Dispersion mit Mörtel oder Zement gemischt werden, wobei das Wasser als Emulsion benutzt wird, um den Zement anzuteigen. Umgekehrt kann das Wasser in der Zementmischung als Lösungsmittel für die Epoxydharz-Dispersion benutzt werden. Ein Zusatz des erfindungsgemässen Härtungsmittels ermöglicht gleichmässiges Mischen von Zement und Epoxydharz-Härter-Dispersion. So ist es möglich, Epoxydharz-Härtungsmittel-Dispersion-gehärteten Zement zu erhalten.The dispersion of epoxy resins and hardening agents according to the invention can be used as a base coat, filler, clear sealer, protective coating, coatings, seals, thin mortar, mortar, etc. Their use is particularly expedient where corrosion resistance is desired. The dispersions can also be used with epoxy resin / thermoplastic mixtures such as coal tar, vinyl polymers, etc. It can be used as a binder for pressed carbon, conductive floor coverings and leveling compounds, as an adhesive for wood, fabric, leather and metal and for various types of substrates such as cemented floors, walls, swimming pools, glass, glazed bricks etc. Furthermore, the epoxy resin dispersion can be mixed with mortar or cement, the water being used as an emulsion to make the cement pasty. Conversely, the water in the cement mixture can be used as a solvent for the epoxy resin dispersion. Addition of the hardening agent according to the invention enables uniform mixing of cement and epoxy resin hardener dispersion. It is thus possible to obtain epoxy resin hardener dispersion hardened cement.

In den Beispielen werden die Viskositäten bei 25°C im Kugefallviskosimeter nach Höppler gemessen. Das Zeichen ^-_ bedeutet «ungefähr» und EV Epoxydäquivalentgewicht.In the examples, the viscosities are measured at 25 ° C. in a falling ball viscometer according to Höppler. The character ^ -_ means «approximately» and EV epoxy equivalent weight.

BeispieleExamples Herstellung der HärtungsmittelManufacture of curing agents

1 A) 300g Polyäthylenglykol, mittlere Molmasse 1000 (A- 0,6 Val), 470g Bisphenol A-Diglycidyl- äther/Bisphenol F-Diglycidyläther-Gemisch im Verhältnis 60:40 Gew.-Teilen mit einem EV-Wert von 180 (

Figure imgb0008
2,6 Val) und 2g BF3-Amin-Komplex (z. B. Anchor 1040) werden in einen 2 I-Dreihalskolben, der mit einem Thermometer und Rührer versehen ist, eingewogen. Der Kolben wird über einen Abscheider an einen Kühler angeschlossen. Unter Stickstoff als Inertgas heizt man in 30' auf 80°C, wobei sich eine homogene Mischung bildet.1 A) 300g polyethylene glycol, average molecular weight 1000 (A- 0.6 Val), 470g bisphenol A diglycidyl ether / bisphenol F diglycidyl ether mixture in a ratio of 60:40 parts by weight with an EV value of 180 (
Figure imgb0008
2.6 Val) and 2 g BF 3 amine complex (e.g. Anchor 1040) are weighed into a 2 l three- necked flask equipped with a thermometer and stirrer. The piston is connected to a cooler via a separator. With nitrogen as the inert gas, the mixture is heated to 80 ° C. in 30 minutes, a homogeneous mixture being formed.

Danach heizt man auf 170°C und hält diese Temperatur bis der theoretische EV-Wert von 385±+10 erreicht ist. Nach 5 Stunden Haltezeit bei 170°C erhielt man einen EV-Wert von 378. Die Viskosität des Produktes beträgt 9600 mPa.s. Dieses Produkt wird als Vorprodukt für die Herstellung der erfindungsgemässen Härtungsmittel weiterverwendet.Then heat to 170 ° C and keep this temperature until the theoretical EV value of 385 ± + 10 is reached. After a holding time of 5 hours at 170 ° C., an EV value of 378 was obtained. The viscosity of the product is 9600 mPa.s. This product is used as a preliminary product for the production of the curing agents according to the invention.

1 B) In einem 1 I-Dreihalskolben werden 272g Xylylendiamin (4 Val) vorgelegt, Stickstoff wird übergeleitet und bei Raumtemperatur werden unter Rühren 378g (1 Val) Vorprodukt nach Beispiel 1 A in 15 bis 30' zugesetzt. Nach Beendigung der Zugabe wird noch 1 Stunde verrührt, wobei die Temperatur auf ca. 60°C ansteigt. Nach Abfallen der Temperatur auf ca. 80°C geheizt und 1 Stunde dort gehalten. Das Wasserstoffäquivalentgewicht (HAV) beträgt 93. Dieses Produkt wird mit Wasser 80%ig verdünnt, das HAV beträgt nun 116.1 B) 272 g of xylylenediamine (4 eq) are placed in a 1 l three-necked flask, nitrogen is passed over and 378 g (1 eq) of the precursor according to Example 1A are added at room temperature with stirring in 15 to 30 minutes. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60 ° C. After the temperature has dropped to about 80 ° C. and held there for 1 hour. The hydrogen equivalent weight (HAV) is 93. This product is 80% diluted with water, the HAV is now 116.

1 C) 813g dieser 80%igen wässrigen Lösung enthalten 7 aktive Aminwasserstoffatome. Bei 60°C addiert man durch Zutropfen in 30' 74g Acrylnitril, das entspricht 0,2 Val Acrylnitril pro Aminwasserstoff. Nach Beendigung der Zugabe hält man noch 1 Std. bei 60°C.1 C) 813 g of this 80% aqueous solution contain 7 active amine hydrogen atoms. At 60 ° C are added dropwise in 30 '74g acrylonitrile, which corresponds to 0.2 val acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 60 ° C. for 1 hour.

Das erhaltene Härtungsmittel ist nun 82%ig, hat einen HAV von 159 und eine Viskosität von 2330 mPa.s.The curing agent obtained is now 82%, has an HAV of 159 and a viscosity of 2330 mPa.s.

2 B) In einem 2 1-Dreihalskolben werden 272g Xylylendiamin (4 Val) vorgelegt, Stickstoff wird übergeleitet und bei Raumtemperatur werden unter Rühren 173g (1,25 Val) Vorprodukt nach Beispiel 1 A in 15 bis 30' zugesetzt. Nach Beendigung der Zugabe wird noch 1 Stunde verrührt, wobei die Temperatur auf ca. 60°C ansteigt. Nach Abfallen der Temperatur wird auf 80°C geheizt und 1 Std. dort gehalten. Das HAV beträgt 111. Dieses Produkt wird mit Wasser 80%ig verdünnt, das HAV beträgt nun 138.2 B) 272 g of xylylenediamine (4 Val) are placed in a 2 1 three-necked flask, nitrogen is passed over and, at room temperature, 173 g (1.25 Val) of the preliminary product according to Example 1A are added in 15 to 30 minutes. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60 ° C. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The HAV is 111. This product is 80% diluted with water, the HAV is now 138.

2 C) 932g dieser 80%igen wässrigen Lösung enthalten 6,75 aktive Aminwasserstoffatome. Bei 60°C addiert man durch Zutropfen in 30' 71,5g Acrylnitril, das entspricht 0,2 Val Acrylnitril pro Aminwasserstoff. Nach Beendigung der Zugabe hält man noch 1 Std. bei 60°C. Das erhaltene Härtungsmittel ist nun 81 %ig, hat einen HAV von 186 und eine Viskosität von 5150 mPa.s.2 C) 932 g of this 80% aqueous solution contain 6.75 active amine hydrogen atoms. At 60 ° C., 71.5 g of acrylonitrile are added by dropwise addition in 30 ', which corresponds to 0.2 val acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 60 ° C. for 1 hour. The curing agent obtained is now 81%, has an HAV of 186 and a viscosity of 5150 mPa.s.

3 A) Beispiel 1 A wurde wiederholt. Nach 4,5 Std. Haltezeit bei 170°C erhielt man einen EV-Wert von 391.3A) Example 1A was repeated. After a 4.5 hour hold time at 170 ° C, an EV value of 391 was obtained.

3 B) In einem 2 I-Dreihalskolben werden 136g Xylylendiamin (2 Val) und 170g 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan (2 Val) vorgelegt, Stickstoff wird übergeleitet und bei Raumtemperatur werden unter Rühren 489g (1,25 Val) Vorprodukt nach Beispiel 3 A in 15' bis 30' zugesetzt. Nach Beendigung der Zugabe wird noch 1 Stunde verrührt, wobei die Temperatur auf ca. 60°C ansteigt. Nach Abfallen der Temperatur wird auf 80°C geheizt und 1 Stunde dort gehalten. Das HAV beträgt 118. Dieses Produkt wird mit Wasser 80%ig verdünnt, das HAV beträgt 147.3 B) 136 g of xylylenediamine (2 val) and 170 g of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (2 val) are placed in a 2 l three-necked flask, nitrogen is passed over and 489 g ( 1.25 Val) intermediate product according to Example 3 A in 15 'to 30' added. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60 ° C. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The HAV is 118. This product is 80% diluted with water, the HAV is 147.

3 C) 994g dieser 80%igen wässrigen Lösung enthalten 6,75 aktive Aminwasserstoffatome. Bei 60°C addiert man durch Zutropfen in 30' 71,5g Acrylnitril, das entspricht 0,2 Val Acrylnitril pro Aminwasserstoff. Nach Beendigung der Zugabe hält man noch 1 Std. bei 60°C.3 C) 994 g of this 80% aqueous solution contain 6.75 active amine hydrogen atoms. At 60 ° C., 71.5 g of acrylonitrile are added dropwise in 30 ', which corresponds to 0.2 val acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 60 ° C. for 1 hour.

Das erhaltene Härtungsmittel ist nun 81,5%ig, hat einen HAV von 197 und eine Viskosität von 13450 m.Pa.s.The curing agent obtained is now 81.5%, has an HAV of 197 and a viscosity of 13450 m.Pa.s.

4 A) Es wurde das Produkt aus Beispiel 3 A eingesetzt.4 A) The product from Example 3 A was used.

4 B) In einen 2 I-Dreihalskolben werden 489g (1,25 Val) Vorprodukt nach Beispiel 3 A vorgelegt, Stickstoff wird übergeleitet und bei Raumtemperatur werden unter Rühren nacheinander 136g Xylylendiamin (2 Val) und 170g 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan (2 Val) in 10-15 Minuten zugesetzt. Nach Beendigung der Zugabe wird noch 1 Stunde verrührt, wobei die Temperatur auf ca. 65°C ansteigt. Nach Abfallen der Temperatur wird auf 80°C geheizt und 1 Stunde dort gehalten. Das HAV beträgt 118. Dieses Produkt wird mit Wasser 80%ig verdünnt, das HAV beträgt 147.4 B) 489 g (1.25 val) of the preliminary product according to Example 3A are placed in a 2 l three-necked flask, nitrogen is passed over and 136 g of xylylenediamine (2 val) and 170 g of 1-amino-3-aminomethyl- 3,5,5-trimethylcyclohexane (2 Val) added in 10-15 minutes. After the addition has ended, the mixture is stirred for a further 1 hour, during which the temperature rises to approx. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The HAV is 118. This product is 80% diluted with water, the HAV is 147.

4 C) Es wurde wie unter Beispiel 3 C beschrieben verfahren. Das erhaltene Härtungsmittel ist 81,5%ig, hat einen HAV von 197 und eine Viskosität von 13120 mPa.s.4 C) The procedure was as described in Example 3 C. The curing agent obtained is 81.5%, has an HAV of 197 and a viscosity of 13120 mPa.s.

5 A und B) Beispiel 3 A und B wurden wiederholt.5 A and B) Example 3 A and B were repeated.

5 C) 882g der 80%igen Lösung, wie unter Beispiel 3 B beschrieben, enthalten 6,0 aktive Aminwasserstoffatome. Bei 60°g addiert man durch Zutropfen in 30 Minuten 79,5g Acrylnitril, das entspricht 0,25 Val Acrylnitril pro Aminwasserstoff. Nach Beendigung der Zugabe hält man noch 1 Std. bei 70°C. Das erhaltene Härtungsmittel ist nun 82%ig, hat einen HAV von 216 und eine Visko- . sität von 14520 mPa.s.5 C) 882 g of the 80% solution, as described under Example 3 B, contain 6.0 active amine hydrogen atoms. At 60 ° g, 79.5 g of acrylonitrile are added dropwise in 30 minutes, which corresponds to 0.25 eq of acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 70 ° C. for 1 hour. The curing agent obtained is now 82%, has an HAV of 216 and a viscous. of 14520 mPa.s.

6 A und B) Beispiel 1 A und B wurden wiederholt.6 A and B) Example 1 A and B were repeated.

6 C) 696g der 80%igen Lösung, wie unter Beispiel 1 B beschrieben, enthalten 6,0 aktive Aminwasserstoffatome. Bei 50°C addiert man durch Zutropfen in 30 Minuten 79,5g Acrylnitril, das entspricht 0,25 Val Acrylnitril pro Aminwasserstoff. Nach Beendigung der Zugabe hält man noch 1,5 Std. bei 70°C. Das erhaltene Härtungsmittel ist nun 82%ig, hat einen HAV von 175 und eine Viskosität von 3150 mPa.s.6 C) 696 g of the 80% solution, as described under Example 1 B, contain 6.0 active amine hydrogen atoms. At 50 ° C., 79.5 g of acrylonitrile are added dropwise in 30 minutes, which corresponds to 0.25 val of acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 70 ° C. for a further 1.5 hours. The curing agent obtained is now 82%, has an HAV of 175 and a viscosity of 3150 mPa.s.

7 C) 932g der 80%igen Lösung, wie unter Beispiel 2 B beschrieben, werden mit 89,5g Acrylnitril (0,25 Val pro Aminwasserstoff) wie unter Beispiel 5C beschrieben umgesetzt. Das erhaltene Härtungsmittel ist nun 82%ig, hat einen HAV von 202 und eine Viskosität von 5900 m.Pa.s.7 C) 932 g of the 80% solution, as described in Example 2 B, are reacted with 89.5 g of acrylonitrile (0.25 Val per hydrogen amine) as described in Example 5C. The curing agent obtained is now 82%, has an HAV of 202 and a viscosity of 5900 m.Pa.s.

8-11)

Figure imgb0009
8-11)
Figure imgb0009

12 A) Es wurden 300g Polyäthylenglykol, mittlere Molmasse 1000(A- 0,6 Val),482g Bisphenol A-Diglycidyläther mit einem EV-Wert von 185 (Viskosität 9800 mPa.s) und 2g BF3-Amin-Komplex wie unter Beispiel 1 A beschrieben umgesetzt.12 A) 300 g of polyethylene glycol, average molar mass 1000 (A-0.6 Val), 482 g of bisphenol A diglycidyl ether with an EV value of 185 (viscosity 9800 mPa.s) and 2 g of BF 3 -amine complex were obtained as in Example 1 A described implemented.

Das Produkt hatte folgende Kenndaten:

  • EV-Wert: 388
  • Viskosität: 13750 mPa.s
The product had the following characteristics:
  • EV value: 388
  • Viscosity: 13750 mPa.s

12 B) 388g dieses Produktes wurden mit 272g Xylylendiamin wie unter Beispiel 1 B beschrieben umgesetzt. Die 80%ige Lösung in Wasser hat einen HAV von 118.12 B) 388 g of this product were reacted with 272 g of xylylenediamine as described under Example 1 B. The 80% solution in water has an HAV of 118.

12 C) 590g der 80%ige Lösung werden nun wie unter Beispiel 1 C beschrieben mit 53g Acrylnitril (0,2 Val pro Aminwasserstoff) umgesetzt. Das HAV beträgt nun 161, die Viskosität beträgt 3940 mPa.s.

Figure imgb0010
Je 1,25 Val, bezogen auf Epoxydgruppen, der unter Beispiel 13 A bis 19 A aufgeführten Vorprodukte wurden mit 136g Xylylendiamin (2 Val) und 170g 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan (2 Val) nach Beispiel 3 B umgesetzt.
Figure imgb0011
Die Produkte 13B bis 19B wurden nach Beispiel 3C umgesetzt.
Figure imgb0012
 12 C) 590 g of the 80% solution are now reacted with 53 g of acrylonitrile (0.2 val per hydrogen amine) as described under Example 1 C. The HAV is now 161, the viscosity is 3940 mPa.s.
Figure imgb0010
 1.25 val each, based on epoxy groups, of the precursors listed under Example 13 A to 19 A were followed up with 136 g xylylenediamine (2 val) and 170 g 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (2 val) Example 3 B implemented.
Figure imgb0011
 Products 13B to 19B were implemented according to Example 3C.
Figure imgb0012

20) In einen 2 I-Dreihalskolben werden 136g Xylylendiamin (2Val) und 170g 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan (2 Val) vorgelegt und Stickstoff wird übergeleitet. Bei 60°C addiert man durch Zutropfen in 30' 71,5g Acrylnitril. Nach Zugabeende hält man noch 1 Std. bei 60°C.20) 136 g of xylylenediamine (2Val) and 170g of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (2 Val) are placed in a 2 l three-necked flask and nitrogen is passed over. At 60 ° C., 71.5 g of acrylonitrile are added dropwise in 30 '. After the addition has ended, the mixture is kept at 60 ° C. for 1 hour.

Zu dieser cyanäthylierten Polyamin-Mischung werden bei Raumtemperatur unter Rühren 489g (1,25 Val) Vorprodukt nach Beispiel 3 A in 15' bis 30' zugesetzt. Nach Beendigung der Zugabe wird noch 1 Std. verrührt, wobei die Temperatur auf ca. 60°C ansteigt. Nach Abfallen der Temperatur wird auf 80°C geheizt und 1 Std. dort gehalten. Danach wird mit Wasser auf 81,5% Festkörper verdünnt. Das erhaltene Härtungsmittel hat einen HAV von .197 und eine Viskosität von 13300 mPa.s.489 g (1.25 eq) of the precursor according to Example 3 A in 15 'to are added to this cyanoethylated polyamine mixture at room temperature with stirring 30 'added. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60.degree. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The mixture is then diluted to 81.5% solids with water. The curing agent obtained has a HAV of .197 and a viscosity of 13300 mPa.s.

Herstellung der Epoxydharz-DispersionenProduction of the epoxy resin dispersions

Epoxydharz-Dispersionen, die mit den erfindungsgemässen Addukten als Härtungsmittel kombiniert werden können, sind u.a. in folgenden Patentschriften beschrieben:

  • Österreichische Patentschrift 286647 (= Britische Patentschrift 1.244.424) und Japanische Patentschrift 29.625/71, sowie die Schweizerische Patentschrift 603738.
Epoxy resin dispersions which can be combined with the adducts according to the invention as curing agents are described, inter alia, in the following patents:
  • Austrian patent specification 286647 (= British patent specification 1.244.424) and Japanese patent specification 29.625 / 71, as well as Swiss patent specification 603738.

Folgende Epoxydharze wurden bevorzugt eingesetzt:

  • 21) Epoxydharz A (EV-Wert ca. 195)
  • 72 g eines Epoxydharz-Emulgatorgemisches, bestehend aus
  • 66 g einer Mischung aus 88 Gew.-% eines Epoxydharzes auf Basis von Bisphenol A und Epichlorhydrin mit einem Epoxyd- äquivalent von ca. 186 und einer Viskosität von 9000 mPa.s, und 12 Gew.-% 2- Äthylhexylglycidyläther, wurde in der Wärme mit
  • 6 g eines Emulgatorgemisches, bestehend aus
  • 2,67 g eines Anlagerungsproduktes von 25-30 Molen Äthylenoxyd an 1 Mol Abietinsäure,
  • 1 g eines Anlagerungsproduktes von 30 Molen Äthylenoxyd an 1 Mol p-Nonylphenol
  • 1 g eines Anlagerungsproduktes von 10 Molen Äthylenoxyd an 1 Mol p-Nonylphenol
  • 1,33 g n-Dodecylalkohol vermischt
The following epoxy resins were preferably used:
  • 21) Epoxy resin A (EV value approx. 195)
  • 72 g of an epoxy resin-emulsifier mixture consisting of
  • 66 g of a mixture of 88 wt .-% of an epoxy resin based on bisphenol A and epichlorohydrin with an epoxy equivalent of about 186 and a viscosity of 9000 mPa.s, and 12 wt .-% 2-ethylhexylglycidyl ether, was in the Warmth with
  • 6 g of an emulsifier mixture consisting of
  • 2.67 g of an adduct of 25-30 moles of ethylene oxide with 1 mole of abietic acid,
  • 1 g of an adduct of 30 moles of ethylene oxide with 1 mole of p-nonylphenol
  • 1 g of an adduct of 10 moles of ethylene oxide with 1 mole of p-nonylphenol
  • 1.33 g of n-dodecyl alcohol mixed

(Diese Mischung entspricht dem Epoxydharz-Emulgator-Gemisch aus Beispiel 7 der CH-A-603738.

  • 22) Epoxydharz B (EV-Wert ca. 185)
    • 80 g eines Epoxydharz-Emulgatorgemisches, bestehend aus
    • 75,2 g einer Mischung aus 60 Gew.-% eines Epoxydharzes auf Basis Bisphenol A und Epichlorhydrin und 40 Gew.-% eines Epoxydharzes auf Basis Roh-Bisphenol F und Epichlorhydrin mit einem Misch-Epoxydäquivalent von ca. 180 und einer Viskosität von 6500 mPa.s wurde in der Wärme mit
    • 4,8 g eines Emulgatorgemisches, bestehend aus
    • 2,14 g eines Anlagerungsproduktes von 25-30 Molen Äthylenoxyd an 1 Mol Abietinsäure,
    • 0,8 g eines Anlagerungsproduktes von 4 Molen Äthylenoxyd an 1 Mol p-Nonylphenol
    • 0,8 g eines Anlagerungsproduktes von 10 Molen Äthylenoxyd an 1 Mol p-Nonylphenol
    • 1,06 g n-Dodecylalkohol vermischt
  • 23) Epoxydharz C
    • 100 g einer Mischung bestehend aus 60 Gew.-% eines Epoxydharzes auf Basis Bisphenol A und Epichlorhydrin und 40 Gew.-% eines Epoxydharzes auf Basis Roh-Bisphenol F und Epichlorhydrin mit einem Misch-Epoxydäquivalent von ca. 180 und einer Viskosität von 6500 mPa.s.
  • 24) Epoxydharz D
    • Epoxydharz auf Basis von Bisphenol A und Epichlorhydrin mit einem Epoxyd- äquivalent von ca. 185 und einer Viskosität von 9000 mPa.s.
  • 25) Je 100g der bevorzugt eingesetzten Epoxydharze A, B, C und D wurden mit Hilfe eines Rührers mit den erfindungsgemässen Härtungsmitteln der Beispiele 1 C bis 19 C, 20 und 1 B bis 3 B äquivalent vermischt. Es wurde soviel Wasser zugesetzt, bis die Dispersionen 60%ig waren. Die Mengen sind der nachfolgenden Tabelle zu entnehmen.
Figure imgb0013
 (This mixture corresponds to the epoxy resin-emulsifier mixture from Example 7 of CH-A-603738.
  • 22) Epoxy resin B (EV value approx. 185)
    • 80 g of an epoxy resin-emulsifier mixture consisting of
    • 75.2 g of a mixture of 60% by weight of an epoxy resin based on bisphenol A and epichlorohydrin and 40% by weight of an epoxy resin based on crude bisphenol F and epichlorohydrin with a mixed epoxy equivalent of approx. 180 and a viscosity of 6500 mPa.s was in the warmth with
    • 4.8 g of an emulsifier mixture consisting of
    • 2.14 g of an adduct of 25-30 moles of ethylene oxide with 1 mole of abietic acid,
    • 0.8 g of an adduct of 4 moles of ethylene oxide and 1 mole of p-nonylphenol
    • 0.8 g of an adduct of 10 moles of ethylene oxide with 1 mole of p-nonylphenol
    • 1.06 g of n-dodecyl alcohol mixed
  • 23) epoxy resin C
    • 100 g of a mixture consisting of 60% by weight of an epoxy resin based on bisphenol A and epichlorohydrin and 40% by weight of an epoxy resin based on crude bisphenol F and epichlorohydrin with a mixed epoxy equivalent of approx. 180 and a viscosity of 6500 mPa .s.
  • 24) epoxy resin D
    • Epoxy resin based on bisphenol A and epichlorohydrin with an epoxy equivalent of approx. 185 and a viscosity of 9000 mPa.s.
  • 25) 100 g of the epoxy resins A, B, C and D used with preference were mixed with the aid of a stirrer with the curing agents according to the invention of Examples 1 C to 19 C, 20 and 1 B to 3 B in an equivalent manner. So much water was added until the dispersions were 60%. The quantities are shown in the table below.
Figure imgb0013

Die Dispersionen zeigten eine ausgezeichnete Stabilität innnerhalb der Verarbeitungszeit (d.h. bis zum Beginn der Vernetzungsreaktion zwischen Harz- und Härterkomponente), die 30 Minuten bis 5 Stunden betrug.The dispersions showed excellent stability within the processing time (i.e. until the start of the crosslinking reaction between the resin and hardener components), which was 30 minutes to 5 hours.

Die wässrigen Dispersionen unter Verwendung des Epoxydharzes A wurden in ca. 200pm Schichtstärke auf phosphatierte Eisenbleche und Asbest-Zementplatten aufgetragen.The aqueous dispersions using epoxy resin A were applied in a layer thickness of approximately 200 pm to phosphated iron sheets and asbestos-cement plates.

Die anwendungstechnischen Ergebnisse sind in der folgenden Tabelle 5 zusammengefasst, wobei die Numerierung der Dispersionen mit der Kennzeichnung der Härtungsmittel identisch ist. Als Antrocknung wird der Zeitpunkt bezeichnet, an dem bei Berührung mit dem Finger keine Oberflächenklebrigkeit mehr festgestellt werden kann.

Figure imgb0014
Figure imgb0015
 The application results are summarized in Table 5 below, the numbering of the dispersions being identical to the labeling of the curing agents. Drying is the point at which no surface stickiness can be determined when touched with the finger.
Figure imgb0014
Figure imgb0015

Die mit den Epoxydharzen B, C und D hergestellten Dispersionen und die daraus hergestellten Filme, lieferten ähnliche Eigenschaften wie mit Epoxydharz A.The dispersions produced with the epoxy resins B, C and D and the films produced therefrom gave properties similar to those with epoxy resin A.

26) Je 100g der bevorzugt eingesetzten Epoxydharze A und C wurden auf einer Walze mit 150g nichtkreidendem Titandioxyd vom Rutiltyp und 5g hochdisperser Kieselsäure abgerieben. Mit Hilfe eines Rührers wurden äquivalente Mengen der Härtungsmittel gemäss Beispiel 1 C bis 12 C und soviel Wasser zugesetzt, dass 55%ige Dispersionen erhalten werden. Die Mengen sind der nachfolgenden Tabelle 6 zu entnehmen.

Figure imgb0016
Figure imgb0017
 26) 100 g each of the preferred epoxy resins A and C were rubbed on a roller with 150 g non-chalking rutile-type titanium dioxide and 5 g highly disperse silica. With Hil For a stirrer, equivalent amounts of the curing agents according to Example 1 C to 12 C and sufficient water were added to give 55% dispersions. The amounts are shown in Table 6 below.
Figure imgb0016
Figure imgb0017

Die Dispersionen zeigten eine ausgezeichnete Stabilität innerhalb der Verarbeitungszeit (d. h. bis zum Beginn der Vernetzungsreaktion zwischen Harz- und Härterkomponente), die 30 Minunten bis 3 Stunden betrug.The dispersions showed excellent stability within the processing time (i.e. until the start of the crosslinking reaction between the resin and hardener components), which was 30 minutes to 3 hours.

Die wässrigen Dispersionsfarben unter Verwendung des Epoxydharzes C wurden in ca. 100µ Schichtstärke auf phosphatierte Eisenbleche und Asbest-Zementplatten aufgetragen. Die anwendungstechnischen Ergebnisse sind in der folgenden Tabelle 7 zusammengefasst:

Figure imgb0018
Figure imgb0019
 The aqueous emulsion paints using the epoxy resin C were applied in a layer thickness of approx. 100µ on phosphated iron sheets and asbestos cement plates. The application results are summarized in Table 7 below:
Figure imgb0018
Figure imgb0019

Die mit dem Epoxydharz A hergestellte Dispersionsfarbe und die daraus hergestellten Filme zeigten ähnliche Prüfergebnisse wie mit Epoxydharz C.The emulsion paint produced with epoxy resin A and the films produced therefrom showed test results similar to those with epoxy resin C.

Mit dem Ausdruck «Topfzeit» wurde die Zeit bezeichnet, die verstreicht, bis eine Dispersion aus 50g des Epoxydharzes, 50g Wasser und einer äquivalenten Menge des jeweiligen erfindungsgemässen Härtungsmittels Beispiel 1 C bis 19 C geliefert ist, bzw. bis die Viskosität der Dispersion so stark angestiegen ist, dass ihre sachgemässe Verarbeitung nicht mehr möglich ist.The term “pot life” was used to denote the time which elapsed until a dispersion composed of 50 g of the epoxy resin, 50 g of water and an equivalent amount of the particular curing agent according to the invention, Example 1 C to 19 C, or until the viscosity of the dispersion was so strong it has increased that their proper processing is no longer possible.

27) Eine Mischung, bestehend aus 80g feinkörnigem Quarzsand (Korngrösse 0,5 mm), 160g grobkörnigem Quarzsand, 80g Zement, 11 g des Epoxydharzes B und 11,7g des erfindungsgemässen Härtungsmittels gemäss Beispiel 3 C wurden in einem Mischgerät homogen gemischt und mit 80g Wasser zu einer pastösen Konsistenz verrührt. Diese Masse wurde mit einem Rakel zu einem etwa 5mm starken Betonbodenbelag verarbeitet, der nach dem Durchhärten eine ausgezeichnete Öl- und Wasserfestigkeit aufwies. Zug-, Druck-, und Biegefestigkeiten der Betonmischung werden durch den Zusatz der Epoxydharz-Härtungsmittel-Dispersion um ca. 20% verbessert.27) A mixture consisting of 80 g of fine-grained quartz sand (grain size 0.5 mm), 160 g of coarse-grained quartz sand, 80 g of cement, 11 g of epoxy resin B and 11.7 g of the curing agent according to Example 3 C according to the invention were mixed homogeneously in a mixer and mixed with 80 g Water mixed to a pasty consistency. This mass was processed with a squeegee to an approximately 5mm thick concrete floor covering, which after curing had excellent oil and water resistance. The tensile, compressive and flexural strengths of the concrete mixture are improved by the addition of the epoxy resin hardener dispersion by approx. 20%.

Claims (8)

1. Hardening agent for aqueous epoxy resin dispersions, consisting of a reaction product obtainable from
A) 20 to 80% by weight of an adduct of
a1) at least one epoxide compound and
a2) at least one polyalkylene polyether polyol with an average molecular weight of from 200 to 10000 by reaction in an equivalent ratio of a1 : a2 = 2: (0.1 bis 1.5) with
B) 80 to 20% by weight of an aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamine or a mixture of polyamines, wherein the amine employed is used in such an amount, that the hydrogen atoms attached to the nitrogen are present in a 2 to 10 times excess, relative to the epoxide groups capable of being reacted, characterized in that there are further added to the reactive groups of polyamine B)
C) unsaturated compounds which are capable of being added and have the formula
Figure imgb0021
wherein R1 is H, -CH3, - C2H5, R2 is H, -CH3 and X is -CN, -COOH, -COOCH3, -COOC2H5, -COOC3H7, -COOC4H9, -CONH2, COONHCH3, CON(CH3)2.
2. Hardening agent according to claim 1, characterized in that per hydrogen atom attached to the nitrogen of a), the reaction product of a1), a2) and B, or of β) the excess of B) over the amount essential for the reaction with the adduct of a1) and a2) respectively, up to 0,5, preferably of from 0,1 to 0,3 equivalents of component C) are added.
3. Hardening agent according to claim 1 or 2, characterized in that the component a1) is a water- insoluble polyepoxide compound and the component a2) is a water-soluble polyalkylene polyether polyol.
4. Hardening agent according to one or more of claims 1 to 3, characterized in that the reaction product consists of
A) 50 to 70% by weight of the adduct derived from
a1) 2.3 to 3 equivalents of the polyepoxide compound and
a2) 0.3 to 0.8 equivalents of the polyalkylene polyether polyol with
B) 50 to 30% by weight of the polyamine or the mixture of polyamines, wherein the amine employed is used in such an amount that the hydrogen atoms, attached to the nitrogen atom are present in a 5- to 8-times excess.
5. Process for the preparation of hardening agents for aqueous epoxy resins dispersions consisting of a reaction product, obtainable from
A) 20 to 80% by weight of an adduct of
a1) at least one polyepoxide compound and
a2) at least one polyalkylene polyether polyol with an average molecular weight of from 200 to 10000 by reaction in an equivalent ratio of a1 : a2 -2.10.1 bis 1.5) with
B) 80 to 20% by weight of an aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamine or a mixture of polyamines, wherein the amine employed is used in such an amount that the hydrogen atoms, attached to the nitrogen are present in a 2 to 10 times excess, relative to the epoxide groups, capable of being reacted, characterized in that
I) at first the adduct A) of a1) and a2) is prepared in the presence of a BF3-amine complex as catalyst and this product is reacted subsequently with an adduct of a polyamine B) with C) an unsaturated component of formula HC(R1) = C(R2)-X, wherein Ri, R2 and X have the meaning mentioned above or
II) the reaction product of components a1), a2) with a polyamine B) is reacted with C) an unsaturated component of formula HC(R1) = C(R1)-X wherein R1, R2 and X have the meaning mentioned above, the reactions with the use of component C) being carried out at a temperature of from 20 to 70° C.
6. Process according to claim 5, characterized in that the reaction of a1) with a2) is carried out at a temperature of from 20 to 200°C and that of the adduct obtained with the polyamine adduct of component C) at a temperature of from 20 to 100°C, preferably of from 20 to 40°C.
7. Process according to claim 5 or 6, characterized in that polyphenol glycidyl ether is employed as component a1).
8. Use of hardening agents according to one or more of claims 1 to 4 together with polyfunctional epoxide compounds a1) and water for the preparation of hardenable dispersions with up to 90, preferably up to 50% by weight of water content as coverings or coating compositions.
EP78200101A 1977-07-18 1978-07-17 Hardeners for aqueous dispersions of epoxy resins, their preparation and use Expired EP0000605B1 (en)

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IT1097871B (en) 1985-08-31
EP0000605A1 (en) 1979-02-07
JPS5456700A (en) 1979-05-07
DE2862222D1 (en) 1983-05-11
IT7825810A0 (en) 1978-07-17
JPS6140688B2 (en) 1986-09-10
US4197389A (en) 1980-04-08

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