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
  • C08G59/40—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 characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4042—Imines; Imides

Definitions

• the invention relates to the field of epoxy resin compositions, and their uses, in particular for coatings, coatings and paints.
• Two-part epoxy resin compositions and their use as coatings are known. They usually consist of a resin component which contains an epoxy resin, and a hardener component which has compounds reactive with epoxide groups, usually predominantly polyamines. The two components are mixed for use and cure at ambient temperature.
• Epoxy resins especially the most widely used bisphenol-based types, are viscous liquids or solids. For use in two-part epoxy resin coating compositions, they are usually diluted to achieve good miscibility of the two components and good processability at ambient temperatures. For dilution, often low-viscosity epoxides, so-called epoxide reactive diluents, are used. But these are expensive, often very irritating and can increase the strength of the
• Epoxy resins can also be diluted with organic solvents. However, these are usually volatile organic
• VOC Volatile Organic Compund
• Secondary amino groups generally show no spontaneous reaction with CO2, or their carbonates and carbamates are not stable. Polyamines with predominantly secondary amino groups therefore rarely lead to blushing in epoxy resin compositions. However, only secondary amino-containing polyamines are rarely used, since they are usually expensive to produce and lead to long curing times. Often, however, be used with diepoxides adducted polyamines, as well as so-called polyamidoamines. Both have predominantly secondary and primary amino groups and show little blushing; However, they are usually so viscous that they must be diluted, which in turn brings the mentioned disadvantages. Presentation of the invention
• the resin component is surprisingly low viscosity, since the aldehyde is surprisingly very well tolerated with the epoxy resin and this well diluted, especially when the aldehyde is liquid at room temperature.
• blushing effects scarcely occur with the composition according to the invention, even when applied over a large area, since the aldehyde reduces the content of primary amino groups during the mixing of the components by chemical reaction to such an extent that they no longer noticeably react with CO 2.
• the aldehyde is covalently bound in the composition. Curing produces largely clear, glossy and tack-free films with excellent mechanical properties.
• the invention thus makes it possible in particular to obtain high-grade epoxy resin coatings which have no or a markedly reduced content of VOC and epoxide reactive diluents.
• the invention relates to a two-component epoxy resin composition consisting of
• a hardener component K2 which contains at least one polyamine A1 having at least one primary amino group.
• the resin component K1 preferably has an aldehyde content of at least 1% by weight, preferably at least 3% by weight.
• the two-component epoxy resin composition is suitable, in particular, as a coating.
• substance names such as polyamine, polyol or polyepoxide starting with "poly” designate substances which formally contain two or more of the functional groups per molecule occurring in their name
• Epoxide groups called.
• glycol ether an ether of 2,3-epoxy-1-propanol (glycidol) is referred to.
• EW epoxide equivalent weight
• an NH 2 - group is bound, which is bonded to an organic radical
• the "secondary” amino group is an NH group referred to two organic radicals, which also be part of a ring together can, is bound.
• room temperature is referred to in this document a temperature of 23 ° C.
• dilute in this document refers to the reduction of the viscosity of a liquid.
• the bold marks such as K1, K2, A1, A2, ALD or the like in the present document are for the convenience of reading and identification only.
• the resin component K1 of the two-part epoxy resin composition contains at least one epoxy resin.
• Epoxy resins which are customary in epoxychemia are suitable as the epoxy resin. These are obtained in a known manner, for example from the oxidation of the corresponding olefins or from the reaction of
• Epichlorohydrin with the corresponding polyols, polyphenols or amines.
• liquid resin So-called polyepoxide liquid resins, hereinafter referred to as "liquid resin”, which have a glass transition temperature which is usually below 25.degree. C., in contrast to the so-called solid resins which have a glass transition temperature above 25.degree can be crushed to 25 ° C pourable powders.
• the liquid resin is an aromatic polyepoxide. Suitable for this purpose are, for example, liquid resins of the formula I),
• the liquid resins of the formula (I) are diglycidyl ethers of bisphenol A, bisphenol F and bisphenol A / F, where A is acetone and F is formaldehyde, which serve as starting materials for the preparation of these bisphenols. Accordingly, a bisphenol A liquid resin has methyl groups, a bisphenol F liquid resin hydrogen atoms, and a bisphenol A / F liquid resin has both methyl groups and hydrogen atoms as R 'and R "in formula (I) In the case of bisphenol-F Positional isomers may also be present, in particular derived from 2,4'- and 2,2'-hydroxyphenylmethane. Further suitable aromatic liquid resins are the glycidylation products of
• Dihydroxybenzene derivatives such as resorcinol, hydroquinone and pyrocatechol;
• bisphenols or polyphenols such as bis (4-hydroxy-3-methyl-phenyl) -methane, 2,2-bis (4-hydroxy-3-methyl-phenyl) -propane (bisphenol-C) bis (3,5 -dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) - propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) -propane, 2,2-bis (4-hydroxyphenyl) -butane (bisphenol-B), 3,3-bis (4 -hydroxyphenyl) pentane, 3,4-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane , 2,4-bis- (3,5-dimethyl-4-hydroxyphen
• aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine (MDA), 4,4'-methylenediphenyl-di (N-methyl) -amine, 4,4 '- [1, 4- Phenylenebis (1-methylethylidene)] bisaniline (bisaniline-P), 4,4 '- [1,3-phenylene bis (1-methyl-ethylidene)] bisaniline (bisaniline-M).
• MDA 4,4'-methylenediphenyldiamine
• N-methyl N-methyl
• aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine (MDA), 4,4'-methylenediphenyl-di (N-methyl) -amine, 4,4 '- [1, 4- Phenylenebis (1-methylethylidene)] bisaniline (bisaniline-P), 4,4 '- [
• an epoxy resin is an aliphatic or cycloaliphatic polyepoxide, such as, for example
• a glycidyl ether of a saturated or unsaturated, branched or unbranched, cyclic or open-chain C2 to C30-D10IS such as, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, octane diol, a polypropylene glycol, dimethylolcyclohexane, neopentyl glycol or dibromo-neopentyl glycol;
• a glycidyl ether of a tri- or tetrafunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain polyol such as castor oil, trimethylolpropane, trimethylolethane, pentaerythrol, sorbitol or glycerol, as well as alkoxylated glycerol or alkoxylated
• N-glycidyl derivative of amides or heterocyclic nitrogen bases such as triglycidyl cyanurate and triglycidyl isocyanurate, as well as reaction products of epichlorohydrin and hydantoin.
• an epoxy resin is a bisphenol A, F or -A / F solid resin which has a similar structure to the already mentioned liquid resins of the formula (I) but has a value of from 2 to 12 instead of the index s and has a glass transition temperature above 25 ° C.
• epoxide resins from the oxidation of olefins for example from the oxidation of vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene, are also suitable as the epoxy resin.
• the epoxy resin are liquid resins based on a bisphenol, in particular based on bisphenol A, bisphenol F or bisphenol A / F, as are commercially available, for example, from Dow, Huntsman and Hexion, these optionally being used in combination with
• Bisphenol A solid resin or bisphenol F novolac epoxy resin are present.
• the epoxy resin may contain a reactive diluent, in particular an epoxy reactive diluent.
• Suitable epoxide reactive diluents are low-viscosity mono- and polyepoxides, such as, for example, the glycidyl ethers of monohydric or polyhydric phenols and aliphatic or cycloaliphatic alcohols, in particular the polyglycidyl ethers of diols or polyols already mentioned, and also, in particular, phenylglycidyl ethers , Cresyl glycidyl ether, p-butylphenyl glycidyl ether, p-tert-butyl-phenylglycidyl ether ethers, nonylphenyl glycidyl ethers, allyl glycidyl ethers, butyl glycidyl ethers, hexyl glycidyl
• the resin component K1 preferably contains only a low content of epoxide reactive diluents, or in particular is free of epoxide-reactive thinner.
• the resin component K1 of the two-part epoxy resin composition further contains at least one aldehyde.
• Aldehydes which are particularly suitable as aldehyde are, on the one hand, aldehydes which are liquid at room temperature, in particular propanal, 2-methylpropanal, butanal, 2-methylbutanal, 2-ethylbutanal, pentanal, pivalaldehyde, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,3-dimethylpentanal, Hexanal, 2-ethylhexanal, heptanal, octanal, nonanal, decanal, undecanal, 2-methyl-undecanal, dodecanal, methoxyacetaldehyde, cyclopropanecarboxaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 2,2-dimethyl-3-phenylpropanal; 1 -naphthaldehyde, benzaldehyde or substituted benzal
• aldehydes of the formula (II) are particularly suitable as aldehyde.
• R 3 represents a hydrogen atom or an arylalkyl or cycloalkyl or
• Z is an ester, ether, tertiary amino or amido group having up to 31 C atoms, these optionally having additional ether oxygens.
• R 1 and R 2 each represent a methyl radical.
• R 3 is a hydrogen atom.
• Z is preferably a radical of the formula (III) or (IV)
• each represent a monovalent aliphatic, cycloaliphatic or arylaliphatic radical having 1 to 20 C atoms, which optionally contains heteroatoms in the form of ether oxygen or tertiary amine nitrogen, or together for a bivalent aliphatic radical having 3 to 20 C atoms, which is part of an optionally substituted heterocyclic ring having 5 to 8, preferably 6, ring atoms and, in addition to the nitrogen atom optionally further heteroatoms in the form of ether oxygen or tertiary amine nitrogen.
• R 5 is preferably a linear or branched alkyl radical having 6 to 30, in particular having 1 to 30, C atoms, optionally with cyclic moieties and optionally with at least one heteroatom, or a mono- or polyunsaturated, linear or branched hydrocarbon radical 6 to 30, in particular with 1 1 to 30, carbon atoms.
• R 5 is a linear or branched alkyl radical having 6 to 30, in particular having 1 1 to 30, carbon atoms, optionally with cyclic moieties and optionally with at least one heteroatom.
• R 9 and R 10 each independently represent a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-ethylhexyl, cyclohexyl, benzyl or alkoxyethyl group, or they together form - with the inclusion of the nitrogen atom - a ring, in particular a pyrrolidine, piperidine, morpholine or N-alkylpiperazine ring, this ring being optionally substituted.
• R 9 and R 10 each independently represent a benzyl or methoxyethyl group, or form
• Aldehydes of the formula (II) which, as the radical Z, have a radical of the formula (III), are esters of aliphatic, cycloaliphatic or arylaliphatic 2,2-disubstituted 3-hydroxyaldehydes, in particular 2,2-dimethyl-3 -hydroxypropanal, with suitable carboxylic acids, wherein as carboxylic acids in particular the following are suitable: saturated
• aliphatic carboxylic acids in particular formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, 2-ethylcaproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid ; monounsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, erucic acid; polyunsaturated aliphatic carboxylic acids such as linoleic acid, linolenic acid, elaeostearic acid, arachidonic acid; cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid; arylaliphatic carboxylic
• rapeseed oil for example, rapeseed oil, sunflower oil, linseed oil, olive oil, coconut oil, oil palm kernel oil and oil palm oil; and dicarboxylic acid monoalkyl and aryl esters, as obtained from the simple esterification of dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, maleic acid, fumaric acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3, 6,9-tri- oxaundecanedioic acid and similar derivatives of polyethylene glycol, with
• Alcohols such as methanol, ethanol, propanol, butanol, higher homologues and isomers of these alcohols can be obtained.
• carboxylic acids having at least 7 C atoms, in particular those having 12 to 31 C atoms, in particular lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. Particularly preferred is lauric acid.
• the aldehyde is preferably selected from the group consisting of 2-ethylbutanal, pentanal, pivalaldehyde, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,3-dimethylpentanal, hexanal, 2-ethyl-hexanal, heptanal, Octanal, methoxyacetaldehyde, 2,2-dimethyl-3-phenylpropanal, benzaldehyde, 1-naphthaldehyde, salicylaldehyde and aldehydes of the formula (II), in particular 3-acetoxy-2,2-dimethylpropanal, 2,2-dimethyl-3-lauroyloxypropanal, 2,2-dimethyl-3- (N-morpholino) -propanal and 2,2-dimethyl-3-bis (methoxyethyl) -amino-propanal.
• the aldehyde is particularly preferably selected from the group consisting of benzaldehyde, salicylaldehyde, 2,2-dimethyl-3-phenylpropanal, 3-acetoxy-2,2-dimethylpropanal, 2,2-dimethyl-3-lauroyloxypropanal and 2,2-dimethyl -3- (N-morpholino) propanal.
• aldehydes are aldehydes of the formula (II) which, as the radical Z, have a radical of the formula (III) in which R 5 has 1 1 to 30 C atoms, in particular 1 1 to 20 C atoms.
• Such aldehydes are used in the
• aldehydes ALD are odorless substances.
• An "odor-free" substance is understood to mean a substance which is not palpable for most human individuals, ie which has no perceptible odor, When using such aldehydes ALD, resin components K1 are available which are odor-free and VOC-free.
• Preferred aldehyde ALD is 2,2-dimethyl-3-lauroyloxypropanal.
• the hardener component K2 of the two-component epoxy resin composition comprises at least one polyamine A1 having at least one primary amino group.
• Suitable polyamines A1 are, in particular, the following polyamines: aliphatic, cycloaliphatic or arylaliphatic primary diamines, for example ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethylamine 1, 3-propanediamine, 1, 3-butanediamine, 1, 4-butanediamine, 1, 3-pentanediamine (DAMP), 1, 5-pentanediamine, 1, 5-diamino-2-methylpentane (MPMD), 2-butyl 2-ethyl-1, 5-pentanediamine (C1 1 -Neodiamin), 1, 6-hexanediamine, 2,5-dimethyl-1, 6-hexanediamine, 2,2,4- and 2,4,4-trimethyl-hexamethylenediamine (TMD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-no nandiamin, 1, 10-decanediamine, 1, 1 1-und
• Ether group-containing aliphatic primary diamines for example bis (2-aminoethyl) ether, 3,6-dioxaoctane-1, 8-diamine, 4,7-dioxadecane-1, 10-diamine, 4,7-dioxadecane-2.9 diamine, 4,9-dioxadodecane-1, 12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1, 13-diamine and higher oligomers of these diamines, bis- (3-aminopropyl) polytetrahydrofurans and others
• the latter are typically products of the amination of polyoxyalkylene diols and are available, for example, under the name Jeffamine® (from Huntsman), under the name Polyetheramine (from BASF) or under the name PC Amine® (from Nitroil).
• Particularly suitable polyoxyalkylene diannines are Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® XTJ-51 1, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine ® XTJ-568, Jeffamine® XTJ-569, Jeffamine® XTJ-523, Jeffamine® XTJ-536, Jeffamine® XTJ-542, Jeffamine® XTJ-559, Jeffamine® EDR-104, Jeffamine® EDR-148, Jeffamine® EDR -176; Polyetheramine D 230, polyetheramine D 400 and polyetheramine D 2000, PC Amine® DA 250, PC
• aliphatic, cycloaliphatic or arylaliphatic primary triamines such as 4-aminomethyl-1, 8-octanediamine, 1, 3,5-tris (aminomethyl) benzene, 1, 3,5-tris (aminomethyl) cyclohexane, tris (2 -aminoethyl) amine, tris (2-aminopropyl) amine, tris (3-aminopropyl) amine;
• - primary polyoxyalkylene triamines which are typically products from the amination of polyoxyalkylene triols and available for example under the trade name Jeffamine ® (from Huntsman), under the name polyetheramine (from BASF) or under the name PC amines ® (of Nitroil) such as Jeffamine ® T403, Jeffamine ® T-3000, polyetheramine T403 and PC amines ® TA 403;
• tertiary amino group-containing polyamines such as N, N'-bis (aminopropyl) piperazine, N, N-bis (3-aminopropyl) methylamine, N, N-bis (3-aminopropyl) ethylamine, N, N Bis (3-aminopropyl) propylamine N, N-bis (3-aminopropyl) cyclohexylamine, N, N-bis (3-aminopropyl) -2-ethyl-hexylamine, and the products of the double cyanoethylation and subsequent reduction of fatty amines, which are derived from natural fatty acids, such as N, N-bis (3-aminopropyl) dodecylamine, and N, N-bis (3-aminopropyl) -talgalkyl- amine, available as Triameen ® Y12D and Triameen ® YT (from Akzo Nobel); polyamines having secondary
• polyamidoamines which reaction products of a mono- or polyhydric carboxylic acid, or their esters or anhydrides, especially a dinner fatty acid, and an aliphatic, cycloaliphatic or aromatic used in stoichiometric excess Polyamine, in particular a polyalkyleneamine such as DETA or triethylenetetramine (TETA), in particular the commercially available polyamidoamines Versamid ® 100, 125, 140 and 150 (from
• Euretek ® 530 (from Huntsman), Beckopox EH ® 651, 654 EH, EH 655, EH 661 and EH 663 (Cytec);
• Polyamines A2 with at least one primary and at least two secondary amino groups are preferred.
• polyamine A2 As the polyamine A2, the following are particularly suitable:
• polyalkyleneamines having two primary and at least two secondary amino groups
• polyalkyleneamines such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), polyethylenepolyamine having from 5 to 7 ethyleneamines units (so-called "higher ethylenepolyamine", HEPA) and N, N'-bis (3-aminopropyl) ethylenediamine
• TETA triethylenetetramine
• TEPA tetraethylenepentamine
• PEHA pentaethylenehexamine
• polyethylenepolyamine having from 5 to 7 ethyleneamines units so-called "higher ethylenepolyamine", HEPA) and N, N'-bis (3-aminopropyl) ethylenediamine
• Such polyalkyleneamines are prepared, for example, from 1,2-dichloroethane and ammonia, or from the cyanoethylation or cyanobutylation and subsequent hydrogenation of primary polyamine
• polyethyleneimines are branched polymeric amines from the polymerization of ethyleneimine.
• a suitable polyethyleneimine typically has an average molecular weight in the range of 250 to 25 ⁇ 00 g / mol and contains tertiary, secondary and primary amino groups.
• Polyethyleneimines are available, for example under the trade name Lupasol ® (from BASF), for example, the types Lupasol ® FG, Lupasol ® G20 and Lupasol ® PR 8515;
• Amine / polyepoxide adducts which have at least one primary and at least two secondary amino groups, in particular the adducts of polyalkyleneamines with diepoxides in a molar ratio of at least 2/1, in particular in a molar ratio of 2/1 to 6/1, where as polyalkyleneamine in particular DETA, DPTA, BHMT, 3- (2-aminoethyl) aminopropylamine, N3- (3-aminopentyl) -1,3-pentanediamine, N5- (3-aminopropyl) -2-methyl-1,5-pentanediamine, N5- 3-amino-1-ethylpropyl) -2-methyl-1,5-pentanediamine, TETA, TEPA, PEHA, HEPA and N, N'-bis (3-aminopropyl) ethylenediamine; - Polyamidoamine, which have at least one primary and at least two secondary amino groups, such as the reaction
• the polyamine A1 is a polyamine A2 having at least one primary and at least two secondary amino groups.
• the polyamine A2 is selected from the group consisting of TETA, TEPA, PEHA, HEPA, N, N'-bis (3-aminopropyl) ethylenediamine;
• polyamine A1 Also suitable as polyamine A1 are mixtures of different polyamines, in particular mixtures of at least one polyamine A2 and at least one further polyamine with at least one primary
• the ratio of the number of aldehyde groups in the resin component K1 with respect to the number of primary amino groups in the hardener component K2 is in the range of 0.1 to 1 .1.
• the ratio of the number of aldehyde groups in the resin component K1 with respect to the number of primary amino groups in the hardener component K2 is preferably in the range of 0.1 to 0.5.
• the ratio of the number of aldehyde groups in the resin component K1 with respect to the number of primary amino groups of this polyamine A2 in the hardener component K2 preferably in the range of 0.5 to 1 .0, in particular in
• the hardener component K2 of the two-component epoxy resin composition may contain, in addition to the polyamine A1, further compounds which are reactive toward epoxide groups, in particular compounds containing mercapto groups, such as in particular
• Liquid mercaptan-terminated polysulfide polymers known under the
• Mercaptan-terminated polyoxyalkylene ethers obtainable, for example, by reaction of polyoxyalkylene diols and triols with either epichlorohydrin or with an alkylene oxide, followed by sodium hydrogen sulfide;
• Polyesters of thiocarboxylic acids for example pentaerythritol tetramer capoacetate, trimethylolpropane trimercaptoacetate, glycol dimercaptoacetate, penic acid taerythritol tetra- (3-mercaptopropionate), trimethylolpropane tri- (3-mercaptopropionate) and glycol di (3-mercaptopropionate), as well as the esterification products of polyoxyalkylene diols and triols, ethoxylated trimethylol propane and polyester diols with thiocarboxylic acids such as thioglycolic acid and 2- or 3-mercaptopropionic acid;
• thiocarboxylic acids for example pentaerythritol tetramer capoacetate, trimethylolpropane trimercaptoacetate, glycol dimercaptoacetate, penic acid taerythritol tetra-
• Both the resin component K1 and the hardener component K2 may contain other auxiliaries and additives, such as:
• Solvents, film-forming aids or extenders such as toluene, xylene, methylethyl ketone, 2-ethoxyethanol, 2-ethoxyethyl acetate, benzyl alcohol, ethylene glycol, diethylene glycol butyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, N-methylpyrrolidone, propylene glycol butyl ether, propylene glycol phenyl ether, diphenylmethane, diisopropylnaphthalene, Petroleum fractions such as Solvesso types (exxon), aromatic hydrocarbon resins, especially phenolic group-containing types, sebacates, phthalates, organic phosphoric and sulphonic acid esters and sulphonamides; Reactive diluents, for example epoxy reactive diluents, as they are
• Polymers such as polyamides, polysulfides, polyvinylformal (PVF), polyvinylbutyral (PVB), polyurethanes (PUR), polymers with carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene copolymers, homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth) acrylates,
• chlorosulfonated polyethylenes and fluorine-containing polymers in particular, chlorosulfonated polyethylenes and fluorine-containing polymers, sulfonamide-modified melamines and purified montan waxes; inorganic and organic fillers, for example ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barite, talc, quartz flour, quartz sand, dolomites, wollastonites, kaolins, mica (potassium aluminum silicate), Molecular sieves, aluminum oxides, aluminum hydroxides, silicas, cements, gypsum, flyash, soot, graphite, metal powders such as aluminum, copper, iron, silver or steel, PVC powder or hollow spheres;
• inorganic and organic fillers for example ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barite, talc, quartz flour, quartz sand,
• Pigments for example titanium dioxide and iron oxides
• Accelerators which accelerate the reaction between amino groups and epoxide groups for example acids or acids
• hydrolyzable compounds for example organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids such as phosphoric acid, or mixtures of the abovementioned acids and acid esters ; furthermore tertiary amines such as 1,4-diazabicyclo [2.2.2] octane, benzyldimethylamine, ⁇ -methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, salts of such tertiary amines, quaternary ammonium salts such as, for example, benzyltrimethylammonium chloride, phenols, in particular bisphenols, phenol resins and Mannich bases such
• Rheology modifiers in particular thickeners, for example phyllosilicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silicas, cellulose ethers and hydrophobically modified polyoxyethylenes;
• thickeners for example phyllosilicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silicas, cellulose ethers and hydrophobically modified polyoxyethylenes;
• Adhesion promoters for example organoalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl ] ethylene diamine, 3-ureidopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, vinyl trimethoxysilane, or the corresponding organosilanes having ethoxy groups in place of the methoxy groups;
• organoalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxys
• flame-retarding substances in particular compounds such as aluminum hydroxide (Al (OH) 3 , also called ATH for "aluminum trihydrate"), magnesium hydroxide (Mg (OH) 2 , also called MDH for "magnesium dihydrate”), ammonium sulfate ((NH) 2 SO 4 ) Boric acid (B (OH) 3 ), zinc borate, melamine borate and melamine cyanurate; Phosphorus-containing compounds such as ammonium phosphate ((NH) 3 PO 4 ), ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, triphenyl phosphate, diphenyl cresyl phosphate, tricresyl phosphate, triethyl phosphate, tris (2-ethylhexyl) phosphate, trioctyl phosphate, mono-, bis- and Tris (isopropylphenyl) phosphate, resorcinol bis (dip
• Biocides such as algicides, fungicides or fungal growth inhibiting substances.
• the two-component epoxy resin composition preferably comprises further auxiliaries and additives, in particular wetting agents, Flow control agents, defoamers, stabilizers, pigments and accelerators, in particular salicylic acid or 2,4,6-tris (dimethylaminomethyl) phenol.
• the two-component epoxy resin composition preferably has less than 10% by weight, preferably less than 5% by weight, of benzyl alcohol.
• the two-part epoxy resin composition is free of benzyl alcohol.
• the resin component K1 and the hardener component K2 may each be in a suitable package or assembly, such as a keg, a hobbock, a bag, a bucket, a can, a cartridge or a tube, for several months prior to their use be stored for a year or longer without changing their respective properties to a degree relevant to their use.
• a suitable package or assembly such as a keg, a hobbock, a bag, a bucket, a can, a cartridge or a tube
• the resin component K1 and the hardener component K2 are mixed together.
• the mixing ratio between the resin component K1 and the hardener component K2 is preferably selected such that the groups reactive with epoxide groups in the hardener component K2 are in a suitable ratio to the epoxy groups in the resin component K1.
• the ratio of the number of groups reactive with epoxide groups in the hardener component K2 compared to the number of epoxy groups in the resin component K1 in the range of 0.5 to 1 .5, in particular 0.8 to 1 .2, wherein so many primary amino groups not to be counted relative to epoxy groups reactive groups, as in the resin component K1 aldehyde groups are present.
• the mixing ratio between the resin component K1 and the hardener component K2 is usually in the range of 1:10 to 10: 1.
• the mixing of the two components takes place by means of a suitable method; it can be continuous or batchwise. If mixing takes place before application, care must be taken that there is not too much time between blending the components and the application, as this can lead to disturbances, such as a slow or incomplete build-up of adhesion to the substrate.
• the mixing takes place in particular at ambient temperature, which is typically in the range of about 5 to 50 ° C, preferably at about 10 to 30 ° C.
• the aldehyde groups of the aldehyde from the resin component K1 react rapidly with primary amino groups of the polyamine A1 from the hardener component K2 to form aldimino groups and water (condensation reaction). In this way, reacted primary amino groups of the polyamine A1 are then for a reaction with epoxide groups at the given reaction conditions therefore largely no longer available.
• the reaction of benzaldehyde with PEHA in the M l ratio of 2: 1 in the following equation (V) is shown here by way of example.
• a hardener with four secondary amino groups is formally formed after the reaction, which is free of primary amino groups.
• the resulting in the condensation reaction water remains in the mixed composition and may there during curing under certain circumstances exercise accelerating influence. Depending on the ambient humidity and the temperature, the water evaporates more or less rapidly from the composition.
• the curing takes place in particular at ambient temperature, which is typically in the range of about 5 to 50 ° C, preferably at about 10 to 30 ° C.
• the curing typically takes a few days to go
• the duration depends among other things on the temperature, the reactivity of the constituents and their stoichiometry as well as the presence of
• the present invention also describes a cured composition obtained by blending the resin component K1 and the hardener component K2 of a two-part epoxy resin composition as described above.
• the application of the described epoxy resin composition is carried out on at least one substrate, wherein as substrate the following are particularly suitable:
• ABS butadiene-styrene copolymers
• SMC Sheet Molding Compounds
• PC polycarbonate
• PA polyamide
• PA poly (methyl methacrylate)
• PMMA poly(methyl methacrylate)
• PUR polyurethanes
• POM polyoxymethylene
• POM polyolefins
• PE polyethylene
• PP polypropylene
• EPM ethylene / propylene copolymers
• EPDM ethylene / propylene / diene terpolymers
• the plastics may preferably be surface-treated by means of plasma, corona or flame ;
• coated substrates such as powder-coated metals or alloys; as well as paints and varnishes.
• the substrates can be pretreated before applying the epoxy resin composition.
• pretreatments include in particular physical and / or chemical cleaning methods, For example, sanding, sandblasting, shot peening, brushing or the like, with resulting dusts are advantageously removed by suction, and further treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer.
• the two-component epoxy resin composition is especially suitable for surface applications.
• the epoxy resin composition described can be used in particular as a coating, floor covering, paint, lacquer, primer or primer, and as an adhesive, sealant or potting compound.
• their excellent properties such as waterproofness, corrosion protection, adhesion, chemical resistance and / or hardness and toughness come into play.
• They can be used, for example, in civil engineering, for example as a floor covering or coating either for interiors such as offices, industrial halls, gymnasiums or cold rooms, or outdoors for balconies, terraces, parking decks, bridges or roofs, as well as for concrete or concrete Metals, in particular as protective coatings against corrosion.
• it can be used for the manufacture or repair of industrial goods or consumer goods.
• the described two-part epoxy resin composition has several advantages.
• the resin component K1 is relatively low viscosity because the epoxy resin is surprisingly diluted by the aldehyde, especially when it is liquid at room temperature.
• a low intrinsic viscosity is an important prerequisite for ensuring a good flow behavior and thus good applicability.
• the epoxy liquid resins typically have a rather high viscosity and usually need to be diluted for application in coatings.
• the epoxide-reactive diluents commonly used for dilution in the prior art are expensive, often have a strong irritating effect and can trigger allergies.
• the dilution effect of the aldehyde makes it possible to a large extent or completely dispensed with the use of epoxy reactive diluents or in particular solvents.
• the presence of the aldehyde in the resin component K1 and any pigmentation of the resin component K1 also cause an increase in the volume of the same, which can be a great advantage for setting a suitable mixing ratio for the practice.
• the hardener component is often poured into the container of the resin component and the two components are mixed therein and applied therefrom. In such an application, it is advantageous if the mixing ratio is set so that the resin component has a rather large volume and the hardener component has a rather small volume, otherwise the resin component in a container with relatively much
• odorless aldehydes ALD has additional advantages. These are odorless substances with a relatively high molecular weight and a surprisingly good dilution effect, which are not considered VOCs. As a result, resin components K1 are accessible, which are odorless and VOC-free, and in which under certain circumstances can be completely dispensed with a reactive epoxy diluent.
• Reaction conditions namely at low curing temperature and high humidity. It is therefore possible, largely or entirely, to dispense with the addition of blushing-reducing additives of the prior art which are not covalently bound in the composition during curing and outgas as VOCs, in particular benzyl alcohol.
• the aldehyde is covalently bound in the reaction with the primary amino groups and thus remains permanently in the cured composition, even in the presence of water. There is thus hardly any outgassing of the aldehyde from the hardening or hardened composition, which has a very favorable effect on the emission values and on the abrasion resistance of the cured composition.
• the composition described can thus be used particularly advantageously also indoors.
• the water formed in the reaction between aldehyde and primary amino groups can accelerate the cure.
• VOC Compounds (VOC) or are VOC-free.
• the aldehyde is a constituent of the resin component K1 and not the hardener component K2. Namely, would the aldehyde as part of the hardener component K2
• Another object of the present invention is the use of an aldehyde for diluting an epoxy resin or a
• aldehyde particularly suitable as aldehyde are the aldehydes described above, in particular benzaldehyde or an aldehyde of the formula (II).
• Another object of the present invention is a method for reducing blushing effects in the curing of a two-component epoxy resin composition whose hardener component contains at least one polyamine having at least one primary amino group by adding an aldehyde to the resin component.
• polyamine having at least one primary amino group the previously described polyamines A1 are suitable, in particular the previously described polyamines A2 having at least one primary and at least two secondary amino groups.
• aldehyde are the previously described
• Aldehydes in particular benzaldehyde or an aldehyde of the formula (II).
• the viscosity was measured on a Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10-100 s -1 ).
• Araldite® GY 250 bisphenol A diglycidyl ether, EEW approx.
• Araldite® DY-E (Huntsman) monoglycidyl ether of a C 12 to C 4 alcohol
• Pentaethylene hexamine technical molecular weight about 232 g / mol
• N4-amine BASF
• N4-amine BASF
• N4-amine N, N'-bis (3-aminopropyl) ethylenediamine
• IPDA hexane
• MXDA Gas chem.
• a resin component and a hardener component having the ingredients shown in Table 1 were separately prepared in the indicated amounts (in parts by weight) (by mixing if the component consisted of more than one ingredient) and then the resin Component mixed with the hardener component by means of a centrifugal mixer (SpeedMixer TM DAC 150, FlackTek Inc.).
• a centrifugal mixer SpeedMixer TM DAC 150, FlackTek Inc.
• the film's aspect was judged to be "flawless", which was clear and had a hard, glossy and tack-free surface with no texture.
• structure refers to any form of drawing or pattern on the surface, as well as the king hardness (pendulum hardness according to König, measured according to DIN EN ISO 1522) of the films after 14 days ("Königshärte (14d)”) Weeks ("Königshärte (4w)”) or after 5 Months ("royal hardness (5mt)”).
• king hardness pendulum hardness according to König, measured according to DIN EN ISO 1522
• Composition was assessed twice by smelling the nose at a distance of 1 cm, the first time 15 minutes after mixing the two components ("odor (15 ')") and the second time after one
• Almond-smelling substance is, which is even in the smallest concentrations still perceptible.
• a resin component and a hardener component with the ingredients shown in Table 2 were prepared separately in the stated amounts (in parts by weight) and then mixed as described for Example 5.
• the mixed compositions in each case three films in a layer thickness of 500 ⁇ each mounted on a glass plate and these glass plates at different
• the other two glass plates were stored in a circulating air oven at 80 ° C. After 3, 7 and 14 days, after cooling off from these plates, the plates were weighed ("(28d)") 2 hours in NK the weight loss ("(3d)” or “(7d)” or “(14d)”), based on the same initial weight, determined by reweighing. In the same manner as described for Example 5, the aspect and the king hardness of the plates were determined.
• Example 8 Composition and properties of Example 8 and Comparative Examples 9 to 11.
• "nm” stands for "not measurable” 1 from aldimine formation 2 bubbles distort the measurements
• Example 8 only slightly more than that in the reaction of benzaldehyde with the primary amines.
• the water produced by PEHA loses weight at 80 ° C storage. This slight weight loss is a clear indication that the benzaldehyde is bound to the cured epoxy polymer and therefore does not evaporate at 80 ° C.
• Comparative Examples 9 to 11 lose significantly more weight at 80 ° C storage. Since the benzyl alcohol is not bound to the epoxy polymer, it largely vaporizes from the films. In Comparative Examples 9 and 10, which already had bubbles in the film, they were significantly larger at 80 ° C storage. Comparative Examples 12 and 13 and Examples 14 to 18
• a resin component and a hardener component having the ingredients shown in Table 3 were prepared separately in the stated amounts (in parts by weight) and then mixed as described for Example 5.
• a film in a layer thickness of 500 ⁇ m was mounted on a glass plate and this was stored in the NC, or cured. After 5 months, the aspect of films and royal hardness were determined in the same manner as described for Example 5.
• PEHA aldimine-1 was prepared as follows:
• Comparative Examples 12 and 13 contain benzaldehyde as
• a resin component and a hardener component with the ingredients shown in Table 4 were prepared separately in the stated amounts (in parts by weight) and then mixed as described for Example 5. With the mixed compositions, in each case a film in a layer thickness of 500 ⁇ m was applied to a glass plate and this was stored in the NC, or cured. After 4 weeks, the aspect of the films and the royal hardness were determined in the same manner as described for Example 5. The results are shown in Table 4.
• Table 4 Composition and properties of Examples 19 to 24.
• Examples 19 to 22 which have as a hardener a combination of PEHA and IPDA, or MXDA, or Jeffamine ® D-230, and in which benzaldehyde, or L-Ald, each stoichiometrically with respect dosed to the primary amino groups of PEHA, to cure to good quality films. Furthermore, it can be seen from Table 4 that also Examples 23 and 24, which each have a hardener component without secondary amino groups, cure to give films of good quality.
• a resin component and a hardener component with the ingredients shown in Table 5 were prepared separately in the stated amounts (in parts by weight) and then mixed as described for Example 5. With the mixed compositions, in each case one film in a layer thickness of 500 ⁇ m was applied to a glass film. plate mounted and stored this in the NK, or cured. After 5 months, the aspect of films and royal hardness were determined in the same manner as described for Example 5.
• Table 5 Composition and properties of Examples 25 to 31.
• a resin component and a hardener component with the ingredients shown in Table 6 were prepared separately in the stated amounts (in parts by weight) and then mixed as described for Example 5. With the mixed compositions, in each case a film in a layer thickness of 500 ⁇ was mounted on a glass plate and this stored in the NK, or cured. After 4 weeks, the aspect of the films and the royal hardness were determined in the same manner as described for Example 5. The results are shown in Table 6.
• the adduct 1 was prepared as follows:
• the adduct 2 was prepared as follows:
• adduct 1 20.0 g were mixed with 1 1 .2 g of benzaldehyde. It formed a clear liquid with a viscosity at 20 ° C of 76.8 Pa-s.
• the adduct 3 was prepared as follows:
• Araldite ® GY-250 are mixed and kept at 60 ° C for 2 hours. It formed a clear liquid with a viscosity at 20 ° C of 3.5 Pa-s.
• Example 6 Composition and properties of Examples 32 to 35. Example 36
• Example 5 With the composition of Example 5, in each case a film in a layer thickness of 500 ⁇ m was applied to a glass plate 6 times and these plates were stored under different conditions, as described below.
• Plate # 1 was stored in the NK for 21 days (designated " ⁇ " in Table 7).
• Plate # 2 was stored for 1 day in NK, then immersed in water for 7 days, and then stored for 3 days in NK (labeled "NK, H 2 O" in Table 7).
• Plate No. 3 was stored for 1 day in NK, then for 7 days at 70 ° C and 100% relative humidity, and then again for 3 days in NK (indicated by "NK, 70/100" in Table 7).
• the plate No. 4 was stored for 4 days in the NK, then for 7 days in a convection oven at 80 ° C, and then again for 10 days in the NK (indicated by "80 ° C" in Table 7).
• Plates # 5 were stored in the NK for 4 days, then in a forced air oven at 80 ° C for 7 days, then immersed in water for 7 days, and then stored in the NK for 3 days (in Table 7 with "80 ° C, H” 2 ”) 0 ").
• Plate No. 6 was stored for 4 days in NK, then for 7 days in a convection oven at 80 ° C, then for 7 days at 70 ° C and 100% relative humidity, and then again 3 days in NK (in Table 7 with " 80 ° C, 70/100 ").
• Table 8 Composition and viscosity of Examples 37 and 38 and
• a resin component was prepared with the ingredients shown in Table 9 in the stated amounts (in parts by weight), then the Viscosity of each composition at 20 ° C measured (in Table 9 with "visc. Start) ”) and then filled each composition in two aluminum tubes and sealed airtight.
• the second tube was stored for 7 days at 60 ° C and then each of the viscosity measured at 20 ° C (in Table 9 with "Visc. (7d 60 ° C)").
• Table 9 Composition and properties of Examples 41 to 43 and Comparative Examples 44 and 45.

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