EP0000605B1 - Härtungsmittel für wässerige Epoxydharzdispersionen, deren Herstellung und Verwendung - Google Patents

Härtungsmittel für wässerige Epoxydharzdispersionen, deren Herstellung und Verwendung 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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EP
European Patent Office
Prior art keywords
adduct
weight
polyamine
component
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78200101A
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German (de)
English (en)
French (fr)
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EP0000605A1 (de
Inventor
Wilhelm Dr. Becker
Horst Karasmann
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Hoechst AG
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Hoechst AG
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Classifications

    • 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%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP78200101A 1977-07-18 1978-07-17 Härtungsmittel für wässerige Epoxydharzdispersionen, deren Herstellung und Verwendung Expired EP0000605B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH8853/77 1977-07-18
CH885377 1977-07-18

Publications (2)

Publication Number Publication Date
EP0000605A1 EP0000605A1 (de) 1979-02-07
EP0000605B1 true EP0000605B1 (de) 1983-04-06

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EP78200101A Expired EP0000605B1 (de) 1977-07-18 1978-07-17 Härtungsmittel für wässerige Epoxydharzdispersionen, deren Herstellung und Verwendung

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Country Link
US (1) US4197389A (ja)
EP (1) EP0000605B1 (ja)
JP (1) JPS5456700A (ja)
DE (1) DE2862222D1 (ja)
IT (1) IT1097871B (ja)

Cited By (22)

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EP0387418A2 (de) * 1989-03-13 1990-09-19 Rütgerswerke Aktiengesellschaft Härtungsmittel für Epoxidverbindungen, ihre Herstellung und Verwendung
EP0610787A2 (de) * 1993-02-08 1994-08-17 Hoechst Aktiengesellschaft Härtungsmittel für wässrige Epoxidharz-Dispersionen
EP0618245A2 (de) * 1993-03-29 1994-10-05 Hoechst Aktiengesellschaft Polyol-Epoxid Additionsprodukte zur Verwendung als Emulgator für flüssige Epoxidharze
EP0694579A2 (de) 1994-06-30 1996-01-31 Hoechst Aktiengesellschaft Stabile, wässrige Epoxidharz-Dispersion, Verfahren zu deren Herstellung und deren Verwendung
DE19525826C1 (de) * 1995-07-15 1996-10-24 Herberts Gmbh Wäßriges zweikomponentiges Überzugsmittel und dessen Verwendung bei Verfahren zur Herstellung von Mehrschichtlackierungen
EP0768348A2 (de) * 1995-09-29 1997-04-16 Vianova Resins GmbH Wässrige Beschichtungsmittel auf der Basis lösemittelarmer modifizierter Epoxidharz-Dispersionen
US5670612A (en) * 1994-10-28 1997-09-23 Mitsubishi Gas Chemical Company, Inc. Polyamine/epoxy-containing polyoxyethylene/hydrophobic epoxy adduct curing agent
US5854312A (en) * 1992-04-21 1998-12-29 Air Products And Chemicals, Inc. Aqueous hardeners for epoxy resin systems
US5906864A (en) * 1996-06-25 1999-05-25 Herberts Gesellschaft Mit Beschrankter Haftung Aqueous coating composition and its use to produce filler coats
US6008314A (en) * 1996-06-25 1999-12-28 Herberts Gmbh Aminourethane hardeners, epoxide-based coating media and the use thereof
EP0995767A2 (de) * 1998-10-19 2000-04-26 U. Prümmer Polymer-Chemie GmbH Härtungsmittel für wässrige Epoxidharzdispersionen
US6235931B1 (en) 1998-12-30 2001-05-22 Shell Oil Company Partial oxidation of polyoxyalkylene polyol compositions to polycarboxylic acid compositions
US6387988B1 (en) 1998-07-07 2002-05-14 Cognis Deutschland Gmbh Epoxy resin hardener from aminopolyalkylene oxide/unsaturated ester, polyepoxide and amine
US6387989B1 (en) 1998-07-07 2002-05-14 Cognis Deutschland Gmbh Hardeners for epoxy resins, processes for producing the same and methods of using the same
US6395806B1 (en) 1998-07-07 2002-05-28 Cognis Deutschland Gmbh Hardeners for epoxy resins, processes for producing the same and methods of using the same
US6653436B2 (en) 2000-12-08 2003-11-25 Resolution Performance Products Llc Water dispersible epoxy resins
US6653369B2 (en) 2001-06-15 2003-11-25 Solutia Austria Gmbh Water dilutable amine curing agents for aqueous two component epoxy resin systems
US6911490B2 (en) 2001-11-30 2005-06-28 Solutia Austria Gmbh Aqueous curing agents for aqueous epoxy resin dispersions
EP1803760A1 (en) 2005-12-30 2007-07-04 Cytec Surface Specialties Austria GmbH Aqueous aminic curing agent for epoxy resins
EP2520599A1 (en) 2011-05-05 2012-11-07 Cytec Austria GmbH Multifunctional primary amine, process for its preparation, and use thereof
EP2727968A1 (en) 2012-11-06 2014-05-07 ALLNEX AUSTRIA GmbH Multifunctional primary amine, process for its preparation, and use thereof
WO2019097039A1 (en) 2017-11-19 2019-05-23 Allnex Austria Gmbh Multi-layer coatings and coating compositions therefor

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US4748167A (en) * 1984-08-01 1988-05-31 Ppg Industries, Inc. Water-based coating compositions comprising epoxy-containing acrylic polymers an polyfunctional water-soluble amines
US4608405A (en) * 1985-05-06 1986-08-26 Celanese Corporation Aqueous based epoxy resin curing agents
US5593770A (en) * 1989-10-25 1997-01-14 Thiokol Corporation Chemorheologically tailored matrix resin formulations containing anhydride curing agents
US5545278A (en) * 1989-10-25 1996-08-13 Thiokol Corporation Method for increasing fiber strength translation in composition pressure vessels using matrix resin formulations containing anhydride curing agents and surface-active agents
US5232961A (en) * 1991-08-19 1993-08-03 Murphey Joseph R Hardenable resin compositions and methods
JPH0543096U (ja) * 1991-11-15 1993-06-11 株式会社和工 スコアカウンタ−付き腕時計
DE4344510A1 (de) * 1993-12-24 1995-06-29 Hoechst Ag Flüssige Zweikomponenten-Überzugsmittel
WO1996003452A1 (en) * 1994-07-25 1996-02-08 Henkel Corporation Curing agents for aqueous epoxy resins
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US5576416A (en) * 1994-12-13 1996-11-19 Air Products And Chemicals, Inc. Amide-containing self-emulsifying epoxy curing agent
US5527839A (en) * 1994-12-13 1996-06-18 Air Products And Chemicals, Inc. Self-emulsifying epoxy curing agent based on the reaction product of epoxy resin and polyether polyol
WO1996020970A1 (en) * 1994-12-29 1996-07-11 Henkel Corporation Aqueous self-dispersible epoxy resin based on epoxy-amine adducts
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DE2862222D1 (en) 1983-05-11
IT7825810A0 (it) 1978-07-17
EP0000605A1 (de) 1979-02-07
JPS6140688B2 (ja) 1986-09-10
IT1097871B (it) 1985-08-31
JPS5456700A (en) 1979-05-07
US4197389A (en) 1980-04-08

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