Application Number: 16155767 Application Date: 15.02.2016
Publication Number: 3205682 Publication Date: 16.08.2017
Publication Kind : A1
IPC:
C08G 59/56
Applicants: SIKA TECH AG
Inventors: KASEMI EDIS
KRAMER ANDREAS
STADELMANN URSULA
BURCKHARDT URS
Priority Data: 16155767 15.02.2016 EP
Title: (FR) ​CURING AGENT FOR LOW-EMISSION EPOXY RESIN COMPOSITIONS 
(EN) HARDENER FOR LOW-EMISSION EPOXY RESIN COMPOSITIONS
(DE) ​CURING AGENT FOR LOW-EMISSION EPOXY RESIN COMPOSITIONS 
Abstract:

(DE) ​The present invention relates to a curing agent for epoxy resin compositions comprising at least one amine of the formula (I) and at least one amine of the formula (II). The hardener is low-odor, low-viscosity, of low toxicity and has a low tendency to carbamerization and a high reactivity towards epoxy resins ​It enables low-odor and low-emission epoxy resin products, which can be processed well and, even at low temperatures and high air humidity, rapidly and without disruption to high-quality plastics of high hardness and likewise, non-tacky surface with high gloss. 

[0001]   The invention relates to the field of curing agents for epoxy resins, epoxy resin compositions, and their use, in particular as a coating, covering or paint.

State of the art

[0002]   the lowest possible viscosity for coating purposes should have suitable epoxy resin compositions so that they are readily processable at ambient temperature. Furthermore, they should cure as quickly and trouble-free, even in humid and cold conditions, thereby forming an even surface without clouding, spots or craters. Finally, the cured coating should have a high hardness and low brittleness to resist mechanical stress as well as possible. For optically demanding applications, such as floor coverings of floors, a coating is said to have also a high gloss and a low tendency to yellowing on exposure to light.

[0003]  To achieve these properties, curing agents in epoxy resin coatings according to the prior art typically used which is based on high-viscosity adducts of polyamines with diepoxides or highly viscous Mannich bases. Mannich bases are the condensation products of phenols with aldehydes, especially formaldehyde, and polyamines. Especially popular are also referred to as phenalkamines Mannich bases of cardanol, a product obtained from the oil of the cashew nut shell alkenylphenol mixture are. Mannich bases have the advantage that they are capable of epoxy resins in a very rapid reaction and thus allow epoxy resin products, which even at low ambient temperatures, for example at 8 ° C,

[0004]  Such Mannich bases alone are too thick for themselves for their use in epoxy coatings. To reduce the viscosity low molecular weight amines can be added to them. Such amines are usually foul-smelling, strong skin and eye irritation and sensitization, will lead to Blushing effects. Furthermore diluent such as benzyl alcohol, glycols or alkylphenols may be employed. Such thinner improve the processability and surface quality of the coating by reducing the occurrence of Blushing effects. but they are non-reactive with epoxy resins at room temperature and are therefore not installed in the hardening in the resin matrix. Nowadays, however, low-emission products are increasingly desired, which after curing have a low content of releasable by evaporation or diffusion processes substances. For low-emission epoxy coatings such thinners can therefore not only be used in small quantity or. Further Mannich bases are prone to problems with yellowing, which is problematic for Beschichtunsanwendungen often. Phenalkamines with a high content of free alkylphenols also only achieve a low final hardness.

[0005]   US 6,262,148 describes phenalkamines based on cardanol and MXDA and their use as curing agents for coatings. The hardeners described have little inclination to Blushing effects and rapid curing. However, they are too viscous for good processability in coating applications without further dilution.

Summary of the Invention

[0006]   The object of the invention is to provide a low-odor, low toxicity, low viscosity, fast curing agents for epoxy resins are available, which enables emission products which cure rapidly even at relatively low temperatures, and thereby high-quality films or bodies with even, glossy surface and form high strength and which are particularly suitable for coatings, coverings or coatings.

[0007]  This object is achieved with a curing agent described in claim. 1 The hardener is low odor, low toxicity and low viscosity, has a low tendency to Carbamatisierung and is very reactive with epoxy resins. It allows epoxy resin products that use little or no solvents or thinners and yet are surprisingly thin. Such epoxy resin products are odorless and emission, very easily processable and show even under unfavorable curing conditions hardly Blushing-related errors. They also cure at low temperatures such as 8 ° C rapidly and form high-quality plastic materials of high hardness, provide moderate non-tacky surface with high gloss and low tendency to yellowing. Surprisingly, the curing agent epoxy resin products permits a higher ultimate hardness and as a comparative curing agent without amine of formula (II) or with other added amines. Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are subject of the dependent claims.

Ways of carrying out the invention

[0008]   The present invention is a curing agent for epoxy resins comprising

  • at least one amine of the formula (I),

    wherein

    1 is an alkylene radical having 2 to 15 C atoms, which optionally cycloalkyl or aryl rings and optionally ether oxygen or amine nitrogen contains and which is not 1,2-propylene, standing,

    1 stands for a hydrogen radical or alkyl radical having 1 to 8 carbon atoms or phenyl radical,

    X represents identical or different radicals selected from the group consisting of hydroxyl, alkyl, alkenyl and alkoxy having in each case 1 to 18 C atoms, which optionally contain ether or hydroxyl oxygen or amine nitrogen, is,

    m is 0 or 1 or 2, and

    n is 1 or 2 or 3; and

  • at least one amine of the formula (II),

    wherein

    2 represents an alkylene radical selected from 1,2-ethylene and 1,2-propylene,

    2 stands for a hydrogen atom or methyl or phenyl radical,

    Q is a five-, six- or seven-membered, in the ring optionally contains an oxygen, sulfur or nitrogen atom-containing cycloalkyl or aryl radical having from 4 to 7 carbon atoms,

    Y is identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino each having 1 to 18 carbon atoms, and

    p is 0 or 1 or 2 or 3.

[0009]   starting with “poly” substance names such as polyamine, polyol or polyepoxide designate substances which formally contain two or more occur in their name functional groups per molecule.

[0010]   As the “primary amino group” is an amino group which is bound to a single organic residue, and carries two hydrogen atoms; as a “secondary amino group” is an amino group is referred to, which is attached to two organic radicals, which may be part of a ring and together and carries a hydrogen atom; and “tertiary amino group” is an amino group is referred to, which is bonded to three organic radicals, which may also be in twos or threes part of one or more rings and bears no hydrogen atom.

[0011]   As the “amine hydrogen”, the hydrogen atoms of primary and secondary amino groups are referred to.

[0012]   As the “amine hydrogen equivalent weight” is the mass of an amine or an amine-containing composition containing a mole equivalent of amine hydrogen, respectively.

[0013]   A “diluent” refers to a soluble in an epoxy resin and which has a viscosity-lowering substance, which is not covalently incorporated into the resin matrix during the curing of the epoxy resin.

[0014]   As the “viscosity” refers to the dynamic viscosity or shear viscosity, represented by the ratio between the shear stress and the shear rate (velocity gradient) is defined and determined as described in the embodiments.

[0015]   As the “molecular weight” refers to the molar mass (in grams per mole) of a molecule. As “average molecular weight” is the number average M n of an oligomeric or polymeric mixture of molecules referred to which (GPC) is determined with respect to polystyrene as a standard usually by gel permeation chromatography.

[0016]   As the “room temperature” refers to a temperature of 23 ° C.

[0017]   The curing agent for epoxy resins containing at least one amine of the formula (I).

[0018]   Preferably, A 1 represents identical or different radicals selected from the group consisting of 1,2-ethylene, 1,3-propylene, 2-methyl-1,5-pentylene, 1,6-hexylene, 2,2 ( 4), 4-trimethyl-1,6-hexylene, 1,3-cyclohexylene-bis (methylene), 1,3-phenylene-bis (methylene), (1,5,5-trimethylcyclohexan-1-yl) methane 1,3, 3-aza-1,5-pentylene, 3,6-diaza-1,8-octylene, 3,6,9-triaza-1,11-undecylene, 4-aza-1,7-heptylene, 3-aza-1,6-hexylene, 4,7-diaza-1,10-decylene and 7-aza-1,13-tridecylene.

[0019]   Particularly preferred radicals A 1 are 1,3-phenylene-bis (methylene), 3-aza-1,5-pentylene or 3,6-diaza-1,8-octylene.

[0020]   It is very particularly preferably 1,3-phenylene-bis (methylene).

[0021]   Preferably, R 1 is a hydrogen radical or an alkyl radical having 1 to 4 C-atoms, in particular methyl, ethyl or isopropyl, or a phenyl radical.

[0022]   Particularly preferred R 1 for a hydrogen residue or for a methyl residue.

[0023]   Most preferably, R 1 for a hydrogen radical.

[0024]   Preferably, X represents identical or different radicals selected from the group consisting of hydroxyl, alkyl, alkenyl and alkoxy each having 1 to 15 carbon atoms, optionally containing ether oxygen, hydroxyl oxygen or amine nitrogen.

[0025]   Particularly preferably, X is selected from the group consisting of hydroxy, methyl, methoxy, tert-butyl, nonyl, dodecyl, pentadeca-8-enyl, pentadeca-8,11-dienyl, pentadeca-8,11,14-trienyl , N, N-dimethylaminomethyl, N, N-diethyl-aminomethyl, N-methyl-N-ethylaminomethyl, N-methyl-N-butylaminomethyl, N, N-bis (hydroxyethyl) aminomethyl, N-methyl-N-hydroxyethylaminomethyl, N ethyl-N-hydroxyethylaminomethyl, N-butyl-N-hydroxyethylaminomethyl, N-pyrrolidinylmethyl, N-piperidinylmethyl, N-morpholinylmethyl, (3- (N, N-dimethylamino) propyl) aminomethyl, or (3- (3- (N, N-dimethylamino) propyl) aminopropyl) aminomethyl, in particular for pentadeca-8-enyl or pentadeca-8,11-dienyl or pentadeca-8,11,14-trienyl.

Preferably, m is 0 or. 1

[0026]   In a particularly preferred embodiment, m is 1 and X is pentadeca-8-enyl or pentadeca-8,11-dienyl or pentadeca-8,11,14-trienyl, wherein the X radical in the 3-position and the other residues in the 2- and / or 4 and / or 6-position relative standing on the phenolic OH.

[0027]   Such amines of formula (I) are also referred to as phenalkamines. They are contained in commercially available curing agents for epoxy resins such as Cardolite® ® NC 540, NC 557, NC 558, NC 566, Lite 2002, GX 6019, GX-6013, NX-4943, NX-5607 or NX -5608 (from Cardolite) or Aradur ® 3440, 3441, 3442, 3460 or 3462 (from Huntsman).

[0028]   A most preferred amine of the formula (I), m is 1, X is pentadeca-8-enyl or pentadeca-8,11-dienyl or pentadeca-8,11,14-trienyl, R 1 is a hydrogen radical, and A 1 is selected from 1,3-phenylene-bis, 3-aza-1,5-pentylene (methylene) and 3,6-diaza-1,8-octylene.

[0029]   The preferred amines of formula (I) are distinguished by a particularly good manufacturability, a particularly low viscosity and particularly good properties for the described uses.

[0030]   An appropriate amine of formula (I) is obtainable from the reaction of at least one primary diamine of formula (III), at least one aldehyde of formula (IV) and at least one phenol compound of the formula (V) with elimination of water ,

[0031]   In the formulas (III), (IV) and (V) have A 1 , R 1 , X and m have the meanings already mentioned on.

[0032]   Preference is given here, m is 0 or 1, in particular for 1 hour.

[0033]   In this reaction, it is a Mannich reaction. The reaction conditions are that only one of the two amino groups of the diamine of formula (III) is alkylated and thus minimize polynuclear compounds are formed advantageously selected.

[0034]   From such a Mannich reaction produces a reaction product mainly containing amines of formula (I) which are substituted in the 2- and / or 4- and / or 6-position relative to the phenolic OH and different values for having n. Typically, the reaction product also contains a certain proportion of unreacted starting compounds, ie diamine of formula (III) and phenol compound of the formula (V), and in addition a certain amount of polynuclear Mannich bases of the double or multiple alkylation of diamines of the formula (III).

[0035]   The diamine of the formula (III) in a molar excess with respect to the phenol compound of formula (V) are used, preferably in a molar ratio of at least 2/1, preferably at least 3/1. In this way, a reaction product is obtained which mainly contains amines of the formula (I) with n = 2 or 3 and has a low content of unreacted phenol compound.

[0036]   The diamine of the formula (III) but also can be used in substoichiometric with respect to the phenol compound. Here, a comparatively low-viscosity reaction product is obtained which mainly contains amines of the formula (I) with n = 1 as well as a certain amount of unreacted phenol compound. This procedure is preferred especially for cardanol as a phenol compound, as cardanol is less toxic than other phenolic compounds typically used, such as phenol, tert-butylphenol or nonylphenol.

[0037]   The diamine of the formula (III) can also be used in form of a mixture of two or more diamines of the formula (III), whereby the reaction product obtained amines of the formula (I) with different A radicals 1 contains.

[0038]   Suitable aldehydes of the formula (IV) is, in particular formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, 2-ethylhexanal and benzaldehyde. Formaldehyde is preferred.

[0039]   is suitable as a primary diamine of formula (III) is a primary aliphatic diamine having 2 to 15 C atoms, which optionally has at least one cycloalkyl or aryl ring and optionally containing ether oxygen or amine nitrogen, with the exception of 1,2-propylene diamine.

[0040]   Preferably, the primary diamine of formula (III) selected from the group consisting of 1,2-ethylenediamine, 1,3-propylenediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,2 (4), 4-trimethyl-1,6-hexyandiamin, 1,3-bis (aminomethyl) cyclohexane, benzene, 1,3-bis (aminomethyl), 3-aminomethyl-3,5,5-trime-thylcyclohexylamin, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), 3- (2-aminoethyl) aminopropylamine (N3-amine), N, N’-bis (3-aminopropyl) ethylenediamine (N4-amine ) and bis (hexamethylene) triamine (BHMT).

[0041]   Particularly preferred are 1,3-bis (aminomethyl) benzene, DETA or TETA. Most particularly preferred is 1,3-bis (aminomethyl) benzene.

[0042]   Suitable phenolic compound of formula (V) is in particular phenol, o-cresol, m-cresol, p-cresol, 4-tert-butylphenol, 4-nonylphenol, 4-dodecylphenol, cardanol (composed mainly of 3- (pentadeca-8-enyl) phenol, 3- (pentadeca-8,11-dienyl) phenol and 3- (pentadeca-8,11,14-trienyl) phenol), 2,3-dimethylphenol (o-xylenol), 2 , 4-dimethylphenol (m-xylenol), 2,5-dimethylphenol (p-xylenol), 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2-methoxyphenol (guaiacol), 3-methoxyphenol, 4-methoxyphenol, 2,6-dimethoxyphenol, pyrocatechol, resorcinol, hydroquinone or pyrogallol.

[0043]  Bevorzugt ist Phenol, o-Kresol, m-Kresol, p-Kresol, 4-tert.Butylphenol, 4-Nonylphenol, 4-Dodecylphenol, Cardanol, o-Xylenol, m-Xylenol, p-Xylenol, Guajacol, 3-Methoxyphenol, 4-Methoxyphenol, Resorcin oder Hydrochinon. Besonders bevorzugt ist Phenol, o-Kresol, m-Kresol, p-Kresol, Cardanol oder Resorcin, insbesondere Phenol oder Cardanol.

[0044]   Very particularly preferred phenolic compound of formula (V) is Cardanol. The reaction products thus obtained are free of phenol or small alkyl phenols such as cresol, tert-butylphenol or nonylphenol. They typically have a certain amount of unreacted cardanol.

[0045]   Preferred reaction products of the described Mannich reaction include in particular amines of the formula (I a),

wherein

a is 0 or 1, b is 0 or 1 and c is 0 or 1, wherein at least one index a or b or c is 1;

and A 1 has the meanings already described.

[0046]   Amines of formula (Ia) are also referred to as phenalkamines.

[0047]   A preferred amine of the formula (Ia) as A 1 are each a 1,3-phenylene-bis (methylene) moiety.

[0048]   An appropriate amine of formula (I) is further obtainable from the reaction of at least one primary diamine of formula (III) and at least one Mannich base of the formula (VI) with elimination of amine of the formula R 3 -NH-R 4 .

[0049]   In the formula (VI) has R 1 have the meanings already mentioned, and R 3 and R 4 are each identical or different alkyl, cycloalkyl, or aralkyl radicals having 1 to 4 carbon atoms, which optionally ether oxygen or amine nitrogen contain, or together represent an alkylene radical with 4 to 8 C atoms, which optionally contains ether oxygen or amine nitrogen.

[0050]   Preferably, R 3 and R 4 each represent methyl or ethyl or butyl or isobutyl, in particular each methyl.

[0051]   This reaction is a transamination. In this case the liberated amine of the formula R 3 -NH-R 4 preferably removed during the reaction from the reaction mixture, particularly by distillation. The reaction conditions in the transamination are that only one of the two amino groups of the diamine of formula (III) is alkylated and thus minimize polynuclear byproducts advantageously selected.

[0052]   In the transamination results in a reaction product, which typically contains units of amines of the formula (I) in which X is

in particular N, N-dimethylaminomethyl, is.

[0053]   As a Mannich base of the formula (VI) is preferably 2,4,6-tris (N, N-dimethylaminomethyl) phenol. It is particularly easy to manufacture from inexpensive raw materials and is commercially available in high purity. In addition, the released therefrom dimethylamine can be removed because of its relatively low boiling point by distillation particularly well from the reaction mixture.

[0054]   Preferred reaction products of the described transamination include in particular amines of the formula (Ib),

wherein A 1 has the meanings already mentioned.

[0055]   An appropriate amine of formula (I) is further obtainable from the reaction of at least one primary diamine of formula (III) with at least one aldehyde or ketone of formula (VII) and hydrogen.

[0056]   In the formula (VII) have R 1 , X, m and n have the meanings already mentioned on.

Preferably, m stands for 0 or 1, in particular for the 0th

N preferably stands for 1 h.

X is preferably methyl or methoxy or hydroxy.

[0057]  This reaction is a reductive alkylation. The reductive alkylation can be performed directly with molecular hydrogen or indirectly by hydrogen transfer from other reagents. molecular hydrogen is preferably used. The reaction conditions are that only one of the two amino groups of primary diamine of formula (III) with good selectivity is easily alkylated and the aromatic ring is not hydrogenated advantageously selected. , A temperature of 40 to 120 ° C and in the presence of a suitable catalyst is preferably at a hydrogen pressure of 5 to 100 bar worked. are as a catalyst preferably palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams catalyst or Raney nickel, in particular palladium on carbon or Raney nickel.

[0058]  As aldehyde or ketone of formula (VII) are particularly suitable 2-hydroxybenzaldehyde (salicylaldehyde), 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-3-methylbenzaldehyde, 2-hydroxy-5-methylbenzaldehyde, 4-hydroxy-3,5 -dimethylbenzaldehyd, 2-hydroxy-3-methoxybenzaldehyde (o-vanillin), 2-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 4-hydroxy-2-methoxybenzaldehyde , 4-hydroxy-3-methoxybenzaldehyde (vanillin), 6-hydroxy-2,4-dimethoxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde (β-resorcinaldehyde), 2,5-dihydroxybenzaldehyde (Gentisinaldehyd), 3, 4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2′-hydroxyacetophenone, 3′-hydroxyacetophenone, 4′-hydroxyacetophenone, 4′-hydroxy-3 ‘-methoxyacetophenon (Acetovanillon), 4′-Hydroxy-3′,5′-dimethoxyacetophenon, 2′,4′-Dihydroxyacetophenon (Resacetophenon), 2′,5′-Dihydroxyacetophenon (Chinacetophenon), 2′,6′-Dihydroxyacetophenon (2-Acetylresorcin), 2′,4’-Dihydroxyacetophenon, 4-Hydroxybenzophenon oder 2-Hydroxy-4-methoxy-benzophenon.

[0059]  Davon bevorzugt ist Salicylaldehyd, 3-Hydroxybenzaldehyd, 4-Hydroxybenzaldehyd, o-Vanillin, Isovanillin, Vanillin, β-Resorcinaldehyd, Gentisinaldehyd, 3,4-Dihydroxybenzaldehyd, 2′-Hydroxyacetophenon, 3′-Hydroxyacetophenon, 4′-Hydroxyacetophenon, Acetovanillon oder Resacetophenon.

[0060]   It is particularly preferred salicylaldehyde or 2′-hydroxyacetophenone.

[0061]   Preferred reaction products of the above reductive alkylation include in particular amines of the formula (Ic),

wherein R 1 and A 1 have the meanings already mentioned.

[0062]   Amines of formula (Ic) are particularly reactive towards epoxy resins, since they have a relatively high content of phenol groups.

[0063]   The amine of formula (I) is thus preferably in the form of a reaction product from a reaction selected from the group consisting of

  1. (I) reacting
    • at least one primary diamine of formula (III),
    • at least one aldehyde of formula (IV)
    • and at least one phenol compound of the formula (V)

    with elimination of water,

  2. (Ii) Reaction of
    • at least one primary diamine of formula (III) and
    • at least one Mannich base of the formula (VI)

    with elimination of amine of the formula R 3 -NH-R 4 , and

  3. (Iii) reacting
    • at least one primary diamine of formula (III),
    • at least one aldehyde or ketone of formula (VII)
    • and hydrogen

    with elimination of water
    used.

[0064]   A reaction product from the reaction (i) ( “Mannich reaction”) has the advantage that it can be produced in a simple and inexpensive process for a variety of industrially available starting compounds in a wide structural diversity. In the (co-) use of cardanol as a phenol compound of formula (V) is the reaction product also largely or entirely free of low molecular weight, toxic phenols such as phenol itself or alkylphenols such as cresol, tert-butylphenol or nonylphenol.

[0065]   A reaction product from the reaction (ii) ( “transamination”) has the advantage that it is free from low-molecular weight, toxic phenols such as phenol itself or alkylphenols such as cresol, tert-butylphenol or nonylphenol, and that particularly in the (, N-dimethylaminomethyl N) phenol inexpensive and easy to manufacture using the commercially available in high purity 2,4,6-tris.

[0066]   A reaction product from the reaction (iii) ( “reductive alkylation”) has the advantage that it is particularly pure and particularly low viscosity, has particularly highly reactive amines of the formula (I) and no low-molecular weight, toxic phenols such as phenol itself or includes alkylphenols such as cresol, tert-butylphenol or nonylphenol.

[0067]   Preferably, the primary diamine of formula (III) in each case selected from the group consisting of 1,2-ethylenediamine, 1,3-propylenediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2 , 2 (4), 4-trimethyl-1,6-hexyandiamin, 1,3-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) benzene, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, diethylenetriamine ( DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), 3- (2-aminoethyl) aminopropylamine (N3-amine), N, N’-bis (3-aminopropyl) ethylenediamine (N4-Amin) and bis (hexamethylene) (BHMT) triamine.

[0068]   The amine of formula (I) allows hardener for epoxy resins which at low ambient temperatures, for example at 8 ° C, allowing a particularly rapid curing. But it is not efficient dilution too viscous for many epoxy resin products and tends to yellow.

[0069]   The curing agent for epoxy resins further contains at least one amine of the formula (II).

[0070]   A 2 is preferably 1,2-propylene. These amines of formula (II) are particularly prone to little Carbamatisieren and allow epoxy resin compositions with particularly beautiful surfaces.

[0071]   R 2 preferably represents a hydrogen radical or methyl, in particular for a hydrogen radical. These amines of the formula (II) are particularly easily accessible and allowing particularly low-viscosity curing agent and epoxy resin compositions.

[0072]   Preferably, Q is an optionally substituted phenyl radical Y. These amines enable fast curing and a particularly attractive surface.

[0073]   Y preferably represents identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino each having 1 to 12, especially 1 to 4, carbon atoms. Particularly preferably, Y is methyl or methoxy, or dimethylamino. Very particularly preferably, Y is methoxy or dimethylamino.

[0074]   Preferably, the radical Y is in the meta and / or para position. In the case of p = 1 is the radical Y is in particular in the para position.

[0075]   p preferably represents 0 or 1 or 2, especially 0 or 1. Especially preferably p is 0. These amines enable especially low-viscosity epoxy resin compositions.

[0076]   For the case where p is 1, Q is in particular a substituted phenyl group with Y, and Y is, in particular methoxy or dimethylamino. These amines provide epoxy resin compositions with particularly rapid curing.

[0077]   particularly preferably A 2 is 1,2-propylene, R 2 for a hydrogen radical, Q is a phenyl radical and p is 0. Such an amine permits epoxy resin compositions having a particularly good processability, very rapid curing and particularly beautiful surfaces.

[0078]   The amine of formula (II) is preferably selected from the group consisting of N-benzyl-1,2-ethanediamine, N- (4-methoxybenzyl) -1,2-ethanediamine, N- (4- (dimethylamino) benzyl) -1,2-ethanediamine, N 1 -benzyl-1, 2-propanediamine or N 2 -benzyl-1,2-propanediamine or a mixture of these isomers, N 1 – (4-methoxybenzyl) -1,2-propanediamine or N 2 – (4-methoxybenzyl) -1,2-propanediamine or a mixture of these isomers, N 1 – (4- (dimethylamino) benzyl) -1,2-propanediamine or N 2 – (4- (dimethylamino) benzyl) -1,2-propanediamine or a mixture of these isomers.
Of these, preferred is N 1 -benzyl-1,2-propanediamine or N 2-benzyl-1,2-propanediamine or a mixture of these isomers referred to, hereinafter also referred to as N-benzyl-1,2-propanediamine.

[0079]   The preferred amines of formula (II) are distinguished by particularly good accessibility, particularly low viscosity and good properties in the novel use of, in particular fast curing, high end hardness and little tendency to Blushing effects.

[0080]   The amine of formula (II) is preferably obtained from the simple alkylation of 1,2-ethylenediamine or 1,2-propylenediamine with a suitable alkylating agent such as an organic halide or a carbonyl compound.

[0081]   Preference is produced the amine of formula (II) by reductive alkylation of 1,2-ethylenediamine or 1,2-propylenediamine with an aldehyde or ketone of formula (VIII) and hydrogen,

wherein R 2 , Q, Y and p have the meanings already mentioned. This preparation proceeds particularly selective and leads to reaction products of particularly high purity, that is, a high content of amines of the formula (II).

[0082]   The amine of formula (II) is thus preferably used in the form of a reaction product from the reductive alkylation of 1,2-ethylenediamine or 1,2-propylenediamine with at least one aldehyde or ketone of formula (II) and hydrogen.
Such a reaction product is particularly pure and without expensive purification steps, ie it contains a high content of amine of formula (II). It is therefore particularly low in viscosity and reactive, and thus particularly suitable as a constituent of the hardener described.

[0083]   The amine of formula (II) in the form of a reaction product from the alkylation of 1,2-ethylenediamine or 1,2-propylenediamine, and in particular from the reductive alkylation with an aldehyde or ketone of formula (VIII) and hydrogen is particularly preferred used. Preferably, the reaction product is purified by distillation. A purified by distillation reaction product allows particularly rapid cure rates and particularly high hardness.

[0084]   The inventive curing agent comprising a combination of amine of formula (I) and the amine of formula (II) allows epoxy resin products having a surprisingly low viscosity, which are good processable thus, in particular as a self-leveling coating with a fast curing, especially in the cold, and a surprisingly high final hardness, which, like turbid show little Blushing-related errors or sticky surface or reduced final hardness and yellowing only slightly.

[0085]   The hardener may contain, in addition to at least one amine of the formula (I) and at least one amine of the formula (II) in addition at least one other amine which does not correspond to the formula (I) or (II), and / or at least one accelerator ,
The additional amine is in particular not a reactant or by-product from the production of the amine of formula (I) and / or the amine of formula (II).

[0086]  suitable for use as accelerators are substances which accelerate the reaction between amino groups and epoxy groups, in particular acids or hydrolysable to acid compounds, in particular 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- dodecylbenzene sulfonic acid, sulfonic acid ester, other organic or inorganic acids such as, in particular phosphoric acid, or mixtures of the aforementioned acids and acid esters; tertiary amines such as in particular 1,4-diazabicyclo [2.2.2] octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethyl aminopropyl amine, imidazoles such as especially N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, Salts of such tertiary amines, quaternary ammonium salts such as benzyltrimethylammonium chloride particular, amidines such as in particular 1,8-diazabicyclo [5.4.0] undec-7-ene, guanidines such as 1,1,3,3-tetramethylguanidine in particular, phenols, in particular bisphenols, phenol resins or Mannich bases and in particular 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol or polymers of phenol, formaldehyde and N, N-dimethyl-1,3-propanediamine, phosphites such as in particular di- or triphenyl phosphites, or mercapto containing compounds. preferred as the accelerator acids, tertiary amines or Mannich bases. Phenols, in particular bisphenols, phenolic resins or Mannich bases and in particular 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol or polymers of phenol, formaldehyde and N, N-dimethyl-1,3-propanediamine , compounds having phosphites such as in particular di- or triphenyl phosphites, or mercapto groups. preferred as the accelerator acids, tertiary amines or Mannich bases. Phenols, in particular bisphenols, phenolic resins or Mannich bases and in particular 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol or polymers of phenol, formaldehyde and N, N-dimethyl-1,3-propanediamine , compounds having phosphites such as in particular di- or triphenyl phosphites, or mercapto groups. preferred as the accelerator acids, tertiary amines or Mannich bases.
Most preferred is salicylic acid or 2,4,6-tris (dimethylaminomethyl) phenol or a combination thereof.

[0087]   are as a further amine preferably polyamines, which have at least two, in particular at least three, reactive toward epoxide amine hydrogens, and in particular the following:

  • Polyamines having one or two secondary amino groups, especially products from the reductive alkylation of primary aliphatic polyamines with aldehydes or ketones which do not correspond to the formula (II), such as in particular N, N’-dibenzyl-1,2-ethanediamine, N, N ‘dibenzyl-1,2-propanediamine, N-benzyl-1,3-bis (aminomethyl) benzene, N, N’-dibenzyl-1,3-bis (aminomethyl) benzene, N-2-ethylhexyl-1,3 -bis (aminomethyl) benzene, N, N’-bis (2-ethylhexyl) -1,3-bis (aminomethyl) benzene, or partially styrenated polyamines such as styrenated in particular 1,3-bis (aminomethyl) benzene (available as gas fireplaces ®240 from Mitsubishi gas Chemical);
  • aliphatic, cycloaliphatic or arylaliphatic primary diamines, in particular 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2 -butyl-2-ethyl-1,5-pentanediamine (C11-Neodiamin), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2 (4), 4-trimethylhexamethylenediamine (TMD), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecane diamine, 1,2-, 1,3- or 1,4- diaminocyclohexane, bis (4-aminocyclohexyl) methane (H 12-MDA), bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3,5-dimethylcyclohexyl) methane, bis (4-amino-3- ethyl-5-methylcyclohexyl) methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine or IPDA), 2- or 4-methyl-1,3-diaminocyclohexane or mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA), 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 2,6 ] decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-menthane diamine, 3,9-bis (3-aminopropyl) -2 , 4,8,10-tetraoxaspiro [5.5] undecane, 1,3-bis (aminomethyl) benzene (MXDA) or 1,4-bis benzene (aminomethyl);
  • Ether-containing aliphatic primary di- or triamines, in particular 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 or higher oligomers of these diamines, bis ( 3-aminopropyl) polytetrahydrofurans or other Polytetrahydrofurandiamine, cycloaliphatic diamines containing ether groups of the propoxylation and subsequent amination of 1,4-dimethylolcyclohexane, available in particular as Jeffamine ®RFD-270 (Huntsman) or polyoxyalkylenedi- or triamines, which typically represent products from the amination of polyoxyalkylene or triols 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 or triamines are Jeffamine ® D-230, Jeffamine ® D-400, Jeffamine ® D-2000, Jeffamine ® EDR-104, Jeffamine ® EDR-148, Jeffamine ® EDR-176, Jeffamine ® T-403, Jeffamine ® T-3000, Jeffamine ®T-5000, or the corresponding amines by BASF or Nitroil;
  • secondary amino groups, polyamines with two primary aliphatic amino groups, such as in particular 3- (2-aminoethyl) aminopropylamine, bis (hexamethylene) triamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) or higher homologues of linear polyethylene amines such as polyethylene polyamine having from 5 to 7 ethylene amine units (so-called “higher ethylenepolyamine” HEPA), products made of multiple cyanoethylation or cyanobutylation and subsequent hydrogenation of the primary di- and polyamines having at least two primary amino groups such as dipropylenetriamine (DPTA) , N- (2-aminoethyl) -1,3-propanediamine (N3-amine), N, N’-bis (3-aminopropyl) ethylenediamine (N4-amine), N, N’-bis (3-aminopropyl) – 1,4-diaminobutane,N5-(3-Aminopropyl)-2-methyl-1,5-pentandiamin, N3-(3-Aminopentyl)-1,3-pentandiamin, N5-(3-Amino-1-ethylpropyl)-2-methyl-1,5-pentandiamin oder N,N’-Bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentandiamin;
  • aliphatic, cycloaliphatic or arylaliphatic primary triamines, in particular 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 or tris (3-aminopropyl) amine;
  • aromatic polyamines, such as especially m- and p-phenylenediamine, 4,4′-, 2,4′- and / or 2,2′-diaminodiphenylmethane, 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA), 2 , 4- and / or 2,6-toluene diamine, mixtures of 3,5-dimethylthio-2,4- and -2,6-toluene diamine (available as Ethacure ®300 from Albermarle), mixtures of 3,5-diethyl-2 , 4- and 2,6-toluenediamine (DETDA, available as Ethacure ® 100 von Albermarle), 3,3′,5,5′-Tetraethyl-4,4′-diaminodiphenylmethan (M-DEA), 3,3′,5,5′-Tetraethyl-2,2′-dichloro-4,4′-diaminodiphenylmethan (M-CDEA), 3,3′-Diisopropyl-5,5′-dimethyl-4,4′-diaminodiphenylmethan (M-MIPA), 3,3′,5,5′-Tetraisopropyl-4,4′-diaminodiphenylmethan (M-DIPA), 4,4′-Diaminodiphenylsulfon (DDS), 4-Amino-N-(4-aminophenyl)benzolsulfonamid, 5,5′-Methylendianthranilsäure, Dimethyl-(5,5′-methylendianthranilat), 1,3-Propylen-bis(4-aminobenzoat), 1,4-Butylen-bis(4-aminobenzoat), Polytetramethylenoxid-bis(4-aminobenzoat) (erhältlich als Versalink® von Air Products), 1,2-Bis(2-aminophenylthio)ethan, 2-Methylpropyl-(4-chloro-3,5-diaminobenzoat) oder tert.Butyl-(4-chloro-3,5-diaminobenzoat);
  • Polyamidoamines, in particular reaction products of a mono- or polybasic carboxylic acid, or their esters or anhydrides, in particular a dimer fatty acid, with an inserted in a stoichiometric excess aliphatic, cycloaliphatic or aromatic polyamine, in particular a polyalkylene amine such as DETA or TETA, in particular the polyamidoamines commercially available Versamid ® 100, 125, 140 or 150 (from Cognis), Aradur ® 223, 250 or 848 (from Huntsman), Euretek ® 3607 or 530 (from Huntsman) or Beckopox ® EH 651, EH 654, EH 655, EH 661 or EH 663 (Cytec);
  • or adducts of polyamines with epoxides or epoxy resins, in particular adducts with diepoxides in a molar ratio of about 2/1, or adducts with monoepoxides in a molar ratio of about 1/1, or reaction products of polyamines and of epichlorohydrin, in particular that of 1,3-bis (aminomethyl ) benzene, commercially available as gas fireplaces ® 328 (from Mitsubishi gas Chemical).

[0088]   It may be advantageous if the hardener according to the invention contains a combination of two or more other amines.

[0089]   As another amine especially preferred are polyamines having one primary and one secondary amino group which do not correspond to the formula (II), in particular N-benzyl-1,3-bis (aminomethyl) benzene, N-2-ethylhexyl-1, 3-bis (aminomethyl) benzene or styrenated 1,3-bis (aminomethyl) benzene.

[0090]   As another amine further, particularly preferred are primary diamines having a molecular weight of at least 120 g / mol, in particular at least 150 g / mol, preferably TMD, H 12 -MDA, IPDA, 2- or 4-methyl-1,3- diamino-cyclohexane, or mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, NBDA, MXDA or BHMT, especially TMD, H 12 -MDA, IPDA, NBDA, or BHMT

[0091]   As another amine are still more preferably containing ether groups, aliphatic primary di- or triamines, in particular polyoxyalkylene or – triamine having an average molecular weight in the range of 200 to 500 g / mol, especially Jeffamine ® D-230 or Jeffamine ® T -403 (both available from Huntsman), or cycloaliphatic diamines containing ether groups of the propoxylation and subsequent amination of 1,4-dimethylolcyclohexane, especially Jeffamine ® RFD-270 (from Huntsman).

[0092]   As another amine further comprises at least three amine hydrogens are particularly preferred containing adducts of at least one polyamine having from 2 to 12 carbon atoms and at least one epoxide.
As an epoxide adduct of such monoepoxides are preferred, especially aromatic monoepoxides in particular cresyl glycidyl ether, the glycidyl ether of cardanol or tert.Butylphenylglycidylether. Particularly preferred is glycidyl ether. Suitable as cresyl glycidyl ether are all isomeric cresyl glycidyl ether, or mixtures thereof, in particular commercially erhältiche types such as in particular Araldite ® DY-K (from Huntsman), Polypox ™ R6 (from Dow), Heloxy ™ KR (from Hexion) or Erisys ®GE-10 (CVC Spec. Chem.) As epoxy adduct of such a preferred are further diepoxides, in particular, aromatic diepoxides, in particular bisphenol-A or bisphenol F or bisphenol A / F diglycidyl ether or resorcinol diglycidyl ether, in particular commercially available liquid resins.
Particularly preferred is an at least three amine hydrogens exhibiting adduct of at least one polyamine with at least one aromatic monoepoxide which are reacted in a molar ratio of about 1/1. During the reaction, the polyamine is present in excess and in particular have been removed after the reaction by distillation.
For such adduct the aromatic monoepoxide is a glycidyl ether are preferred, especially orto-glycidyl ether.
For such adduct the polyamine is preferably 1,2-ethylene diamine, 1,2-propylene, 1,3-propylene or MPMD, particularly preferably 1,2-propylene or MPMD.

[0093]  The hardener may further comprise at least one diluent, and in particular xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Ethylenglykoldiphenylether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butylylether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, N- methylpyrrolidone, diphenylmethane, diisopropylnaphthalene,Petroleum fractions such as Solvesso® grades (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, cardanol, or (product of cashew shell oil containing as the main component parts of 3- (pentadeca-8-enyl) phenol, 3- (pentadeca-8,11- dienyl) phenol and 3- (pentadeca-8,11,14-trienyl) phenol), available for example as Cardolite ® NC-700 or Cardolite ®NX-2026 (both available from Cardolite), styrenated phenol, bisphenols, aromatic hydrocarbon resins, especially phenol-group-containing types, alkoxylated phenol, particularly ethoxylated or propoxylated phenol, in particular 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphoric acid or sulfonic acid or sulfonamides. Benzyl alcohol, dodecyl phenol, tert-butylphenol, styrenated phenol, ethoxylated phenol, or phenol group-containing aromatic hydrocarbon resins, in particular the Novares are preferred ® types LS 500, LX 200, LA 300 or LA 700 (from Rutgers).

[0094]   The curing agent preferably contains no or only a low content of diluents, preferably less than 25% by weight, more preferably less than 15% by weight, more preferably less than 10% and especially less than 5% by weight.

[0095]   The hardener may further toward epoxide groups contain reactive substances, for example, monoamines such as hexylamine or benzylamine, or mercapto-containing compounds, in particular the following:

  • liquid mercaptan-terminated polysulfide polymers, known under the trade name Thiokol ® (from Morton Thiokol, for example, available from SPI Supplies, or by Toray Fine Chemicals), in particular the types of LP-3, LP-33, LP-980, LP-23 , LP-55, LP-56, LP-12, LP-31, LP-32 or LP-2; and also known under the brand name Thioplast ® (ex Akzo Nobel), in particular the types of G 10, G 112, G 131, G 1, G 12, G 21, G 22, G 44 or G 4;
  • Mercaptan-terminated polyoxyalkylene ethers, obtainable for example by reacting polyoxyalkylene diols or triols either with epichlorohydrin or an alkylene oxide, followed by sodium hydrogen sulfide;
  • Mercaptan-terminated compounds in the form of polyoxyalkylene derivatives known under the trademark Capcure ® (from Cognis), in particular the types WR-8, LOF, or 3-800;
  • Polyesters of thiocarboxylic acids, for example Pentaerythritoltetramercaptoacetat, trimethylolpropane trimercaptoacetate, glycol dimercaptoacetate, Pentaerythritoltetra- (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate) or Glykoldi- (3-mercaptopropionate), or esterification products of polyoxyalkylene diols or triols, ethoxylated trimethylolpropane or polyester diols with thiocarboxylic such as thioglycolic acid or 2- or 3-mercaptopropionic acid; or
  • more mercapto compounds having, in particular 2,4,6-trimercapto-1,3,5-triazine, 2,2 ‘- (ethylenedioxy) -diethanthiol (triethylene glycol dimercaptan), or ethanedithiol.

[0096]   The curing agent is preferably substantially free of amines having a molecular weight below 150 g / mol, in particular below 120 g / mol. Preferably, it contains less than 2% by weight, in particular less than 1% by weight, amines having a molecular weight below 150 g / mol, in particular below 120 g / mol. Such a curing agent is toxicologically and odor particularly advantageous and allows coatings with particularly beautiful surfaces.

[0097]   The inventive hardener preferably contains as much of amine of the formula (I), that 15 to 80%, particularly preferably 20 to 70%, of the total of the hardener amine hydrogens of the amine of the formula (I) as submitted.

[0098]   The inventive hardener preferably contains as much of the amine of formula (II), that 20 to 70%, particularly preferably 30 to 60%, of the total of the hardener amine hydrogens of the amine of formula (II) come from.

[0099]   contains A particularly preferred curing agent as a further amine, at least one at least three amine hydrogens exhibiting adduct of at least one polyamine having from 2 to 12 carbon atoms and at least one epoxide.
In such a curing agent, the amine of formula (I), the amine of formula (II), the adduct and optionally other amines are present in an amount such that the total contained in the hardener amine hydrogens

15 to 50% of amines of the formula (I),

30 to 60% of amines of the formula (II),

15 to 50% having at least three amine hydrogens adducts

and 0 to 10% of other amines derived.

One of such hardener is odorless, has a low viscosity and is in contact with air hardly turbidity or crusts. Compared with epoxy resins, it has a high dilution effect in particularly good compatibility. It thus allows emission epoxy resin compositions which are easy to process, particularly quick and largely cure without blushing effects and also very form films of high gloss and high hardness.

[0100]   Another object of the invention is an epoxy resin composition comprising

  • a resin component containing at least an epoxy resin and
  • a hardener component a hardener comprising at least one amine of the formula (I) and at least one amine of the formula (II), containing as described previously.

The resin and the hardener component are typically in separate containers and are each storage-stable in itself. They are not mixed until immediately before application with each other so that their reactive groups come into contact and curing the composition.

[0101]   conventional industrial epoxy resins are suitable as 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.
The epoxy resin are particularly suitable so-called polyepoxide liquid resins, hereinafter referred to as “liquid resin”. These have a glass transition temperature below 25 ° C.
Also possible as the epoxy resin are so-called solid resins which have a glass transition temperature above 25 ° C and let crush to pourable at 25 ° C powders.

[0102]   Suitable epoxy resins are in particular, aromatic epoxy resins, in particular the Glycidylisierungsprodukte of:

  • Bisphenol-A, bisphenol-F or bisphenol-A / F, where A is acetone and F for formaldehyde, which served as starting materials for the preparation of these bisphenols. In the case of bisphenol F and position isomers may be present, especially derived from 2,4′- or 2,2′-hydroxyphenylmethane.
  • Dihydroxybenzene derivatives such as resorcinol, hydroquinone or catechol;
  • other bisphenols or polyphenols, such as bis (4-hydroxy-3-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) 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), 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-hydroxyphenyl) -2-methylbutane, 1,1 bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis (4-hydroxyphenyl) – 1-phenylethane, 1,4-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol P), 1,3-Bis[2-(4-hydroxyphenyl)-2-propyl]benzol (Bisphenol-M), 4,4′-Dihydroxydiphenyl (DOD), 4,4′-Dihydroxybenzophenon, Bis(2-hydroxynaphth-1-yl)methan, Bis(4-hydroxynaphth-1-yl)methan, 1,5-Dihydroxynaphthalin, Tris(4-hydroxyphenyl)methan, 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethan, Bis(4-hydroxyphenyl)ether oder Bis(4-hydroxyphenyl)sulfon;
  • Condensation products of phenols with formaldehyde which are obtained under acid conditions such as phenol novolacs or cresol novolacs;
  • aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4′-diphenylmethanediamine, 4,4′-Methylendiphenyldi- (N-methyl) amine, 4,4 ‘- [1,4-phenylenebis (1-methylethylidene)] bisaniline (bisaniline-P) or 4,4 ‘- [1,3-phenylene-bis (1-methylethylidene)] bisaniline (bisaniline-M).

[0103]   Other suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular

  • Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C 2 to C 30 alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, Dibromoneopentylglykol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or alkoxylated alkoxylated glycerol or trimethylolpropane;
  • a hydrogenated bisphenol A, F or A / F liquid resin, or the Glycidylisierungsprodukte of hydrogenated bisphenol-A, -F, or -A / F;
  • a N-glycidyl derivative of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin.
  • Epoxy resins from the oxidation of olefins, such as in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene, or divinylbenzene.

[0104]   is as epoxy resin in the resin component is preferably a liquid resin based on a bisphenol, especially a diglycidyl ether of bisphenol-A, bisphenol-F or bisphenol-A / F, such as are commercially available for example from Dow, Huntsman or Momentive , These liquid resins have a low viscosity and good for epoxy resins in the cured state properties as a coating. They may contain amounts of bisphenol A solid resin or phenol novolaks.

[0105]  The resin component may contain a reactive diluent, particularly a least one epoxide group-containing reactive diluent. suitable as reactive diluents are especially the glycidyl ethers of mono- or polyhydric phenols, or aliphatic or cycloaliphatic alcohols, in particular the aforementioned polyglycidyl ethers of di- or polyols, or furthermore phenyl glycidyl ether, cresyl glycidyl ether, Guaiacolglycidylether, 4-methoxyphenyl glycidyl ether, p-butylphenyl glycidyl ether, p-tert .Butylphenylglycidylether, 4-nonylphenyl glycidyl ether, 4-Dodecylphenylglycidylether, Cardanolglycidylether, benzyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, or glycidyl ethers of natural alcohols, such as especially C8 – to C 10 -Alkylglycidylether or C 12 to C 14 -Alkylglycidylether. The addition of a reactive diluent for epoxy resin causes a reduction in viscosity, and / or a reduction in the glass transition temperature and / or the mechanical properties.

[0106]   Optionally, the epoxy resin composition contains additional ingredients commonly used, especially in epoxy resin compositions auxiliaries and additives, for example the following:

  • Solvent, thinner or extender, in particular the thinner already mentioned;
  • Reactive diluents, especially epoxide groups reactive diluents, as mentioned previously, epoxidized natural oils such as soybean oil, linseed oil or palm kernel oil, or acetoacetate groups-containing compounds, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes, and furthermore isocyanates or reactive group-containing silicones;
  • Polymers, in particular polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers having carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene copolymers, homo- or copolymers of unsaturated monomers, particularly from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular chlorosulfonated polyethylenes or fluorine-containing polymers, sulfonamide-modified melamine or purified montan waxes;
  • inorganic or organic fillers, in particular ground or precipitated calcium carbonates, which optionally are coated with fatty acids, especially stearates, barite (barite), talcs, silica flour, silica sand, iron mica, dolomite, wollastonite, kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silica, cements, plasters, fly ash, carbon black, graphite, metal powders such as aluminum, copper, iron, zinc, silver or steel, PVC-powder or hollow balls;
  • Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or synthetic fibers such as polyamide fibers or polyethylene fibers;
  • Pigments, especially titanium dioxide and / or iron oxides;
  • the aforementioned accelerator;
  • Rheology modifiers, particularly anti-settling agents, thickeners or;
  • Coupling agents, particularly organoalkoxysilanes;
  • Stabilizers against oxidation, heat, light or UV radiation;
  • flame-retardant substances, in particular aluminum hydroxide (ATH), magnesium dihydroxide (MDH), (antimony trioxide, antimony pentoxide, boric acid B (OH) 3), Zinkborat, Zinkphosphat, Melaminborat, Melamincyanurat, Ammoniumpolyphosphat, Melaminphosphat, Melaminpyrophosphat, polybromierte Diphenyloxide oder Diphenylether, Phosphate wie insbesondere Diphenylkresylphosphat, Resorcinol-bis(diphenylphosphat), ResorcinoldiphosphatOligomer, Tetraphenylresorcinoldiphosphit, Ethylendiamindiphosphat oder Bisphenol-A-bis(diphenylphosphat), Tris(chloroethyl)phosphat, Tris(chloropropyl)phosphat oder Tris(dichloroisopropyl)phosphat, Tris[3-bromo-2,2-bis-(bromomethyl)propyl]phosphat, Tetrabromo-Bisphenol-A, Bis(2,3-dibromopropylether) von Bisphenol A, bromierte Epoxidharze, Ethylen-bis(tetrabromophthalimid), Ethylen-bis(dibromonorbornandicarboximid), 1,2-Bis(tribromophenoxy)ethan, Tris(2,3-dibromopropyl)isocyanurat, Tribromophenol, Hexabromocyclododecan,Bis (hexachlorocyclopentadieno) cyclooctane or chlorinated paraffins;
  • surface-active substances, in particular wetting agents, leveling agents, devolatilizers or defoamers;
  • Biocides such as algicides, fungicides or substances which inhibit fungal growth.

[0107]   Preferably, the epoxy resin composition contains other auxiliaries and additives, in particular wetting agents, leveling agents, defoamers, stabilizers, pigments and / or accelerators, in particular salicylic acid and / or 2,4,6-tris (dimethylaminomethyl) phenol.
Preferably, the epoxy resin composition contains no or only a low content of diluents, preferably at most 10% by weight, in particular at most 5% by weight.

[0108]   In the epoxy resin composition, the ratio of the number of groups reactive toward epoxide groups relative to the number of epoxy groups preferably in the range of 0.5 to 1.5, in particular 0.7 to 1.2.

[0109]  The two components of the epoxy resin composition are each mounted in a separate container. Other components of the epoxy resin composition may be present as a component of the resin or the hardener component, is reactive toward epoxide other ingredients preferably are a part of the hardener component. A suitable container for storing the resin or the hardener component is in particular a drum, a pail, a pouch, a bucket, a can, a cartridge or a tube. The components can be stored, which means that they can be stored before they are used for several months to a year or longer without having to change in their respective properties in a relevant for its use degree. To apply the epoxy resin composition, the resin and the hardener component are mixed together shortly before or during the application. The mixing ratio between the two components is preferably selected so that the are reactive toward epoxide groups of the hardener component in an appropriate ratio to the epoxy groups of the resin component, as previously described. 1: in parts by weight, the mixing ratio between the resin component and the curative component typically in the range of 1:10 to 10. that the reactive toward epoxide groups of the curing component are in an appropriate ratio to the epoxy groups of the resin component, as previously described. 1: in parts by weight, the mixing ratio between the resin component and the curative component typically in the range of 1:10 to 10. that the reactive toward epoxide groups of the curing component are in an appropriate ratio to the epoxy groups of the resin component, as previously described. 1: in parts by weight, the mixing ratio between the resin component and the curative component typically in the range of 1:10 to 10.
The mixing of the two components is carried out by a suitable method; they can be continuous or batch-wise. If the mixing is carried out before the application must be taken to ensure that between the mixing of the components and the application does not pass too much time as it such as can a slow or incomplete structure of the adhesion to the substrate come, thereby disorders. The mixing takes place in particular at ambient temperature, which typically is in the range of about 5 to 50 ° C, preferably at about 10 to 30 ° C.
When mixing the resin and the curing agent component, the curing begins by chemical reaction. The epoxy groups react with the amine hydrogen carrying amino groups and optionally present further reactive toward epoxide groups to ring opening to give amino alcohol units. Other epoxide react with itself to anionic polymerization. As a result of these reactions, the composition to a crosslinked plastic hardens. The skilled worker is known that primary amino groups over epoxy groups are difunctional and a primary amino group thus than two counts toward epoxide-reactive groups.
Curing takes place in particular at ambient temperature. They typically extends over several days to weeks until it has largely been completed under the given conditions. The time depends on factors including the temperature, the reactivity of the components and their stoichiometry and the presence of accelerators.
Another object of the invention is a cured composition obtained from the curing of an epoxy resin composition described.

[0110]   The application of the epoxy resin composition is carried out on at least one substrate, the following are particularly suitable:

  • Glass, glass ceramic, concrete, mortar, brick, tile, plaster, or natural stone such as granite or marble;
  • Metals or alloys such as aluminum, iron, steel or non-ferrous metals, or surface-coated metals or alloys such as galvanized or plated metals;
  • Leather, textiles, paper, wood, with resins such as phenolic, melamine or epoxy resins, bonded wood materials, resin-textile composite materials, or other so-called polymer composites;
  • Plastics, in particular hard or soft PVC, ABS, polycarbonate (PC), polyamide (PA), polyester, PMMA, epoxies, PUR, POM, PO, PE, PP, EPM or EPDM, and the plastics, if appropriate, by means of plasma, corona or flames are surface treated;
  • Fiber-reinforced plastics such as carbon fiber reinforced plastics (CFRP), glass fiber-reinforced plastics (FRP) or sheet molding compounds (SMC);
  • coated substrates, such as powder-coated metals or alloys;
  • Paint or varnish.

[0111]   The substrates may be pretreated prior to the application of the epoxy resin composition, if necessary. Such pretreatments include in particular physical and / or chemical cleaning processes, for example grinding, sand blasting, shot blasting, brushing and / or blowing, and further treatment with detergents or solvents, or the application of an adhesion promoter, an adhesion promoter solution or a primer.

[0112]   The described epoxy resin composition is advantageously used as a fiber composite matrix for fiber composites (composites) such as in particular carbon fiber or fiberglass, or as a potting compound, sealant, adhesive, coating, coating, paint, varnish, sealer, primer or primer. It is particularly useful as a potting compound, for example as Elektrovergussmasse, or as an adhesive, in particular as Karrosserieklebstoff, sandwich element adhesive, half-shell adhesive for rotor blades of wind turbines, bridge element anchoring adhesive or adhesive.
it is particularly useful to continue as a covering, coating, paint, varnish, sealer, primer or primer for construction and industrial applications, in particular as floor covering or floor coating for indoor environments such as offices, industrial halls, gymnasiums or refrigeration rooms or in the outdoor area for balconies, terraces, parking decks , bridges and roofs, as a protective coating for concrete, cement, metals, plastics or wood, for example, for surface sealing of wooden structures, vehicles, loading platforms, tanks, silos, shafts, pipes, pipelines, machines or steel structures such as ships, piers, offshore platforms, lock gates, hydroelectric power stations, river works, swimming pools, wind power plants, bridges, chimneys, cranes or sheet piling.
It is particularly useful as a primer further, primer, adhesive paint or anti-corrosion primers.
A further coating, another pad, or another coating can be applied to the fully or partially cured epoxy resin composition in particular be applied when used as a coating, covering or paint, which may also act in this further layer is an epoxy resin composition , but also other material, in particular a polyurethane or polyurea coating. Particularly advantageously, the described epoxy resin composition is used as coating.

[0113]   Another object of the invention is accordingly a coating containing an epoxy resin composition as described previously.
Thereby applied flat coverings of all kinds are used as coating understood, in particular paints, varnishes, sealants, primers or primers, as previously described, or floor coverings or protective coatings, in particular those for heavy duty corrosion protection. Especially advantageous is the described epoxy resin composition in low-emission coatings eco-quality seals, for example after Emicode (EC1 Plus), AgBB, DIBt, Blue Angel, AFSSET, RTS (M1) and US Green Building Council (LEED) was used.

[0114]  As coating the epoxy resin composition is advantageously used in a method for coating, wherein it has a liquid consistency having a low viscosity and good flow properties and is applied in particular as a self-leveling or thixotropic coating to predominantly flat surfaces or as a paint. Preferably, the epoxy resin composition in this application immediately after mixing the resin and the hardener component a viscosity, measured at 20 ° C, in the range of 300 to 4’000 mPa · s, preferably in the range of 300 to 2 ‘ 000 mPa.s, particularly preferably in the range from 300 to 1,500 mPa.s at. The mixed composition is applied within the working time surface as a thin film having a film thickness typically of about 50 microns to about 5 mm on a substrate, typically at ambient temperature. Administration is carried out in particular by pouring onto the substrate to be coated and subsequent uniform distribution using, for example, a doctor blade or a notched trowel. The application can also be carried out with a brush or roller or spray application, for example as a corrosion protective coating on steel. Administration is carried out in particular by pouring onto the substrate to be coated and subsequent uniform distribution using, for example, a doctor blade or a notched trowel. The application can also be carried out with a brush or roller or spray application, for example as a corrosion protective coating on steel. Administration is carried out in particular by pouring onto the substrate to be coated and subsequent uniform distribution using, for example, a doctor blade or a notched trowel. The application can also be carried out with a brush or roller or spray application, for example as a corrosion protective coating on steel.
During curing typically substantially clear, glossy and non-tacky films of high hardness, which have good adhesion to variety of substrates arise.

[0115]   The application of the epoxy resin composition, an article is formed comprising the cured composition from curing the above epoxy resin composition. The cured composition lies in particular in the form of a coating.

[0116]   The described epoxy resin composition is characterized by advantageous properties. It is odorless and low emission, low viscosity and therefore easy to process and display even under unfavorable curing conditions hardly Blushing-related errors. They also cures at relatively low temperatures, for example at 8 ° C, rapidly and forms high-quality plastics from high hardness and even, non-tacky surface with high gloss and low yellowing tendency.

Examples

[0117]   Embodiments are given which serve to illustrate the invention described in detail. Of course, the invention is not limited to these embodiments described.
“AHEW” represents the amine hydrogen equivalent weight.
“EEW” stands for epoxy equivalent weight.
As “standard air” is a temperature of 23 ± 1 ° C and a relative humidity of 50 ± 5%, respectively. “NK” stands for “standard climate”.

Description of Measurement Methods:

[0118]   The viscosity was measured on a thermostated cone-plate viscometer Rheotec RC30 (0.05 mm, shear rate 10 U / min cone diameter 50 mm, cone angle 1 °, cone tip distance).

[0119]   The amine number was determined by titration (with 0.1 N HClO 4 in acetic acid using crystal violet).

Substances used containing amines of the formula (I):

 

Cardolite ® GX-6013:

[0120]   phenalkamine hardener from Cardolite with AHEW 180 g / mol containing 20 to 30% by weight of cardanol and about 1% by weight of 1,3-bis (aminomethyl) benzene.

Substances used containing amines of formula (II):

 

N-Benzyl-1,2-propandiamin:

[0121]   In a round bottom flask was charged at room temperature 444.8 g (6 mol) of 1,2-propanediamine under a nitrogen atmosphere. With good stirring, a solution of 212.2 g (2 mol) of benzaldehyde was slowly added dropwise in 1,500 ml of isopropanol and stirred for 2 hours. The reaction mixture was then bar at a hydrogen pressure of 90, is hydrogenated at a temperature of 85 ° C and a flow rate of 5 ml / min on a continuously operating hydrogenation with Pd / C-fixed bed catalyst. To check the reaction was checked by IR spectroscopy that the Iminbande at about 1665 cm -1had disappeared. Subsequently, the hydrogenated solution was concentrated on a rotary evaporator at 65 ° C, whereby unreacted 1,2-propanediamine and isopropanol were removed. This gave a clear, slightly yellowish liquid. Of which 300 g were distilled at 80 ° C under vacuum to give 237.5 g of distillate at a vapor temperature of 60 to 63 ° C and collected 0:08 to 0:09 bar were. Was obtained a colorless liquid with an amine number of 682 mg KOH / g, which according to 1 H NMR a mixture of N 1 -benzyl-1,2-propanediamine and N 2 -benzyl-1,2-propanediamine in the ratio of about 2/1 represented and had a GC purity of> 97%.

Used other substances:

[0122]

Araldite ® GY 250:
Bisphenol-A-Diglycidylether, EEW 187.5 g/Eq (von Huntsman)
Araldite® DY-E:
Monoglycidyl ethers of C 12 – to C 14 -alcohols, EEW 290 g / eq (from Huntsman)
EP-adduct 1:
Reaction product of 1,5-diamino-2-methylpentane and Araldite ® DY-K, prepared as described below, AHEW 106.5 g / eq
EP-adduct 2:
Reaction product of 1,2-propylenediamine and Araldite ® DY-K, prepared as described below, AHEW 90.0 g / eq
Araldite® DY-K:
Corrupted Kresylglycidylether, 182 g / eq (Huntsman)
Gaskam to ® 240:
Styrenated 1,3-bis (aminomethyl) benzene, AHEW 103 g / eq (by Mitsubishi Gas Chemical)
MXDA:
1,3-bis (aminomethyl) benzene, AHEW 34 g / eq (by Mitsubishi Gas Chemical)
Ipda:
3-aminomethyl-3,5,5-trimethylcyclohexylamine, 42.6 AHEW g / Eq (Vestamin ® IPD from Evonik)
TMD
2.2 (4), 4-trimethylhexamethylenediamine, AHEW 39.6 g / Eq (Vestamin ® TMD from Evonik)
1,3-BAC
1,3-bis (aminomethyl) cyclohexane, AHEW 35.5 g / Eq (by Mitsubishi Gas Chemical)
MCDA:
2-methylcyclohexane-1,3 (5) diamine, AHEW 32 g / Eq (Baxxodur ® EC 210 from BASF)

[0123]   The EP-1 adduct was prepared by adding 4.65 kg of 1,5-diamino-2-methylpen tan-(Dytek ® submitted A from Invista) under a nitrogen atmosphere, heated to 70 ° C and then with good stirring slowly with 1.83 kg Araldite ® DY-K was added, keeping the temperature of the reaction mixture was 70 to 80 ° C. After 1 hour at 80 ° C, the reaction mixture was cooled and 1,5-diamino-2-methylpentane and other volatile constituents by distillation using a thin film evaporator (0.5-1 mbar, jacket temperature 160 ° C).

[0124]   The EP-adduct 2 was prepared by mixing 04.15 kg presented 1,2-propylenediamine under a nitrogen atmosphere, heated to 70 ° C and then slowly treated with 2.93 kg of Araldite with good stirring ® DY-K was added, keeping the temperature of the reaction mixture 70 to 80 ° C was. After 1 hour at 80 ° C, the reaction mixture was cooled and 1,2-propylenediamine, and other volatile constituents removed by distillation using a thin film evaporator (0.5-1 mbar, jacket temperature 115 ° C).

Preparation of hardeners and epoxy resin compositions:

[0125]   For each example, the ingredients specified in Table 1 or 2 in the amounts indicated (in parts by weight) of the hardener component by means of a centrifugal mixer (Speed Mixer ™ DAC 150, FlackTek Inc.) were mixed, and stored under exclusion of moisture.
Similarly, the ingredients of the resin component specified in Table 1 or 2 were processed and stored. Subsequently, the two components were each composition processed by the centrifugal mixer to form a homogeneous liquid and tested them immediately as follows:

10 minutes after the mixing, the viscosity was determined at 20 ° C ( “viscosity (10 ‘) ).

A first film was coated in a thickness of 500 micrometers on a glass plate and this stored under standard conditions or cured. This film was King hardness (König pendulum hardness, measured according to DIN EN ISO 1522) after 1 day ( “King hardness (1d NK)”), after 2 days ( “King hardness (2d NK)”), (4 Days “King hardness (4d NK) “), after 7 days (” King hardness (7d NK) “) and after 14 days (” King hardness (14d NK) “) was determined. After 14 days, the aspect of the film was evaluated (in the table with “aspect (NK)” hereinafter). When it was “beautiful” doing a film called, which was clear and had a glossy and non-tacky surface without structure. As a “structure”
A second film was coated in a thickness of 500 micrometers on a glass plate and the cured immediately after application for 7 days at 8 ° C and 80% relative humidity and then stored for 14 days in NK, respectively. 24 hours after the application, a bottle cap of polypropylene was attached to the film, under which a damp sponge was placed. After another 24 hours the sponge and the lid was removed and placed in a new location of the film where it was placed again removed and reinstalled after 24 hours, a total of 4 times. Subsequently, the aspect of this film has been described (in the tables, “aspect (8 ° / 80%)” hereinafter), in the same manner as for the aspect (NK) evaluated. In this case, the number of markings in each case was specified, which were visible in the film by the wet sponge and / or the fitted lid. in turn the king hardness was determined on the thus cured films after 7 days at 8 ° C and 80% relative humidity ( “King hardness (7d 8 ° / 80%)”), (, then (after a further 2 days in NK “König hardness + 2d NK) “), 7 days in NK (” King hardness (7d + NK) “) and 14d (in the NK” König hardness (14d + NK) “).
As a measure for the yellowing of the color change after exposure in a weathering tester was further determined. For this purpose, another film in a layer thickness of 500 microns was coated on a glass plate and this stored under standard conditions for 2 weeks and cured, and then in a weathering tester of the type Q-Sun Xenon Xe-1 with optical filter Q-SUN Daylight-Q and a xenon lamp with a light intensity 0.51 W / m 2 at 340 nm at a temperature of 65 ° C for 72 hours load ( Q-Sun (72h)). Subsequently, the color difference .DELTA.E of the thus-loaded film compared to the corresponding non-loaded film by means of a colorimeter NH310 of Shenzhen 3NH Technology Co. LTD, equipped with silicone Photoelectric Diode Detector Light Source A, Color Space Measurement Interface CIE L * a * b * C * H *, determined. A high value AE stands for a big color difference or severe yellowing.
The results are shown in Tables 1 and 2. FIG.

[0126]   In the epoxy resin compositions EZ-1 to EZ-3 is examples of the invention. In the epoxy resin compositions Ref-1 to Ref-7 are comparative examples.

Table 1: Composition and Properties of EZ-1 to SR-3 and Ref-1 .

example EZ-1 EZ-2 EZ-3 Ref-1
Resin component:
Araldite ® GY-250 167.2 167.2 167.2 167.2
Araldite® DY-E 31.8 31.8 31.8 31.8
Hardener component:
Cardolite ® GX-6013 90.0 45.0 45.0 180.0
N-Benzyl-1,2-propandiamin 27.4 27.4 27.4
EP-adduct 1 26.6
EP-adduct 2 22.5
Viscosity (10 ‘) [Pa · s] 1.3 1.0 1.1 4.4
Königshärte [s] (1d NK) 76 63 66 91
(2d NK) 120 116 119 118
(4d NK) 141 137 148 132
(7d NK) 154 153 164 139
(14d NK) 162 169 181 133
Aspect (NK) beautiful beautiful beautiful beautiful
Q-Sun (72h) ΔE 30 26 27 47
Königshärte [s] (7d 8 ° / 80%) 56 53 59 78
(+ 2d NK) 119 125 134 122
(+ 7d NK) 125 143 144 137
(+ 14d NK) 161 161 174 143
Aspect (8 ° / 80%) beautiful beautiful beautiful beautiful
number marks one one one no

Table 2: Composition and Properties of Ref-2 to Ref. 7

example Ref-2 Ref-3 Ref-4 Ref-5 Ref-6 Ref-7
Resin component:
Araldite ® GY-250 167.2 167.2 167.2 167.2 167.2 167.2
Araldite® DY-E 31.8 31.8 31.8 31.8 31.8 31.8
Hardener component:
Cardolite ® GX-6013 117.0 90.0 90.0 90.0 90.0 90.0
Gaskam to ® 240 36.1
MXDA 17.0
Ipda 21.3
TMD 19.8
1,3-BAC 8.17
MCDA 16.0
Viscosity (10 ‘) [Pa · s] 2.4 2.2 2.6 2.1 2.5 2.1
Königshärte [s] (1d NK) 66 109 105 98 120 101
(2d NK) 99 129 140 129 144 143
(4d NK) 120 144 154 134 150 160
(7d NK) 132 147 167 140 168 168
(14d NK) 140 151 165 148 157 167
Aspect (NK) beautiful matt cloudy beautiful beautiful Drawing light. beautiful
Q-Sun (72h) ΔE 34 26 30 33 29 26
Königshärte [s] (7d 8 ° / 80%) 53 87 83 57 80 74
(+ 2d NK) 95 106 94 74 111 109
(+ 7d NK) 99 129 140 78 119 122
(+ 14d NK) 132 129 147 99 139 144
Aspect (8 ° / 80%) beautiful matt cloudy matt matt slightly dull beautiful
number marks one 2nd 3 one one 3
Claims

1.  hardener for epoxy resins comprising

– at least one amine of the formula (I),

wherein

1 is an alkylene radical having 2 to 15 C atoms, which optionally cycloalkyl or aryl rings and optionally ether oxygen or amine nitrogen contains and which is not 1,2-propylene, standing,

1 stands for a hydrogen radical or alkyl radical having 1 to 8 carbon atoms or phenyl radical,

X represents identical or different radicals selected from the group consisting of hydroxyl, alkyl, alkenyl and alkoxy having in each case 1 to 18 C atoms, which optionally contain ether or hydroxyl oxygen or amine nitrogen, is,

m is 0 or 1 or 2, and

n is 1 or 2 or 3; and

– at least one amine of the formula (II),

wherein

2 represents an alkylene radical selected from 1,2-ethylene and 1,2-propylene,

2 stands for a hydrogen atom or methyl or phenyl radical,

Q is a five-, six- or seven-membered, in the ring optionally contains an oxygen, sulfur or nitrogen atom-containing cycloalkyl or aryl radical having from 4 to 7 carbon atoms,

Y is identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino each having 1 to 18 carbon atoms, and

p is 0 or 1 or 2 or 3.


2.  Hardener according to claim 1, characterized in that A 1 represents identical or different radicals selected from the group consisting of 1,2-ethylene, 1,3-propylene, 2-methyl-1,5-pentylene, 1,6- hexylene, 2,2 (4), 4-trimethyl-1,6-hexylene, 1,3-cyclohexylene-bis (methylene), 1,3-phenylene-bis- (methylene), (1,5,5-trimethylcyclohexane -1-yl) methane-1,3, 3-aza-1,5-pentylene, 3,6-diaza-1,8-octylene, 3,6,9-triaza-1,11-undecylene, 4-aza -1,7-heptylene, 3-aza-1,6-hexylene, 4,7-diaza-1,10-decylene and 7-aza-1,13-tridecylene stands.
3.  Hardener according to one of claims 1 or 2, characterized in that X ausgewählt ist aus der Gruppe bestehend aus Hydroxy, Methyl, Methoxy, tert.Butyl, Nonyl, Dodecyl, Pentadeca-8-enyl, Pentadeca-8,11-dienyl, Pentadeca-8,11,14-trienyl, N,N-Dimethylaminomethyl, N,N-Diethylaminomethyl, N-Methyl-N-ethylaminomethyl, N-Methyl-N-butylaminomethyl, N,N-Bis(hydroxyethyl)aminomethyl, N-Methyl-N-hydroxyethylaminomethyl, N-Ethyl-N-hydroxyethylaminomethyl, N-Butyl-N-hydroxyethylaminomethyl, N-Pyrrolidinylmethyl, N-Piperidinylmethyl, N-Morpholinylmethyl, (3-(N,N-Dimethylamino)propyl)aminomethyl oder (3-(3-(N,N-Dimethylamino)propyl)aminopropyl)aminomethyl.
4. Härter gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dassm is 1 and X is pentadeca-8-enyl or pentadeca-8,11-dienyl or pentadeca-8,11,14-trienyl stand, wherein the radical X is in the 3-position and the other radicals in the 2- and / or 4 – and / or 6-position relative to the phenolic OH stand.
5.  hardener according to any one of claims 1 to 4, characterized in that the amine of formula (I) is used in the form of a reaction product of a reaction selected from the group consisting of

(I) reacting

– at least one primary diamine of formula (III)

NH 2 -A 1 -NH 2      (III)

– at least one aldehyde of formula (IV)

– and at least one phenol compound of the formula (V)

with elimination of water,

(Ii) Reaction of

– at least one primary diamine of formula (III) and

– at least one Mannich base of the formula (VI)

with elimination of amine of the formula R 3 -NH-R 4 , and

(Iii) reacting

– at least one primary diamine of formula (III),

– at least an aldehyde or ketone of formula (VII)

– and hydrogen, with elimination of water.


6.  hardener according to any one of claims 1 to 5, characterized in that A 2 stands for 1,2-propylene.
7.  hardener according to any one of claims 1 to 6, characterized in that Q stands for an optionally substituted phenyl radical Y.
8.  hardener according to any one of claims 1 to 7, characterized in that A 2 is 1,2-propylene, R 2 stand for a hydrogen radical, Q is a phenyl radical and p is the 0th
9.  hardener according to any one of claims 1 to 8, characterized in thatthe amine of formula (II) is used in the form of a reaction product from the reductive alkylation of 1,2-ethylenediamine or 1,2-propylenediamine with an aldehyde or ketone of formula (VIII) and hydrogen.

10.  hardener according to any one of claims 1 to 9, characterized in that in addition at least one other amine which does not correspond to the formula (I) or (II), and / or at least one accelerator is included.
11.  hardener according to any one of claims 1 to 10, characterized in that so much of amine of the formula (I) is that 15 to 80% of the total amine hydrogen of the curing agent of the amine of the formula (I) as submitted.
12.  hardener according to any one of claims 1 to 11,characterized in that so much is of amine of formula (II), that 20 to 70% of the total amine hydrogen of the curing agent of the amine of formula (II) come from.
13.  epoxy resin composition comprising

– a resin component containing at least an epoxy resin and

– a curative component comprising a curing agent according to any one of claims 1 to 12th


14.  coating comprising an epoxy resin composition as described in claim. 13
15.  A cured composition obtained from the curing of an epoxy resin composition according to claim 13 or a coating according to claim fourteenth