DE2021951B2 - FILLER-CONTAINING, NON-SETTING EPOXY RESIN MIXTURE - Google Patents

Description

35

40

Where R and the anion have the meaning given above, R 'is a monovalent hydrocarbon radical having 1 to 20 carbon atoms, b the value 1, 2 or 3; c denotes the value 0 to 2 and X a divalent alkylene radical, a divalent hydroxyl-substituted alkylene radical or a divalent hydroxyl-substituted alkylene-carbonoxy radical with oxygen in the ether bond, each with 1 to 12 carbon atoms, and customary fillers, and optionally organic solvents and customary additives.

It is known that epoxy resins containing fillers have the disadvantage that the filler when igern discontinues. For example, a mixture of an epoxy resin and one is used in storage silicon dioxide from the latter, d. H. sinks / around the bottom of the container and forms a Irte packed mass. It is extremely difficult if not impossible to redisperse these settled aces prior to use. the currently of those containing a filler

R - N - R

Anion

where the radicals R can be identical or different and are hydrogen or monovalent organic radicals with 1 to 24 carbon atoms and where the anion is a halogen, a carboxylic acid radical, a Denotes nitrate, sulfate, sulfonate or hydroxyl radical; or at least one cationic quaternary Polysiloxane-ammonium compound in which the siloxane is a siloxane unit of the general formula

and at least one siloxane unit of the general formula

R,

where R and the anion have the meaning given above. R 'is a monovalent hydrocarbon radical with 1 to 20 carbon atoms, b the value!, 2 or 3; c denotes the value 0 to 2 and X a divalent alkylene radical, a divalent hydroxyl-substituted alkylene radical or a divalent hydroxyl-substituted alkylene-carbonoxy radical with oxygen in the ether bond, each with 1 to 12 carbon atoms, and conventional fillers, and optionally organic solvents and usual Additives.

Preferred polyepoxides include the polyglyeidyl ethers of polyhydric phenol, e.g. B. the polyglyeidyl ethers of mononuclear polyhydric phenols, such as resorcinol, catechol and hydroquinone and pyrogallol, as well as di- or polynuclear phenols, such as naphthols and bisphenols. They also include the polyglyeidyl ethers of polyphenols, such as the novolac condensation products of a phenol and a saturated or unsaturated aldehyde containing 3 to 20 or more phynylene radicals in the

Molecule included. Examples are polyphenylenes from a phenol and an unsaturated aldehyde, such as acrolein, such as. B. triphenylenes, pentaphenylenes and kepiaphenylenes. The phenols can also contain substituents, e.g. B. alkyl radicals, ring-shaped aryl radicals, halogens. These include alkyl reserves. Tribromoresorcinol and those diphenols which contain alkyl and halogen substituents on the aromatic ring. The polyhydric polynuclear phenols can contain two or more phenol radicals which are linked to one another by groups such as methylene, alkylene or sulfone - hydroxyphenyl) dimethyl methane, dihydroxydiphenyl sulfone and the like _IS

The polyglycidyl ethers of polyhydric aliphatic alcohols or polyfunctional alcohols are also suitable Amines or aliphatic alcohols substituted by amine radicals.

Further suitable polyepoxides are the polyglycidyl esters of polycarboxylic acids obtained by reacting polycarboxylic acids with a halohydrin such as epichlorohydrin or dichlorohydrin. Such polyesters can be derived from aliphatic polycarboxylic acid such as oxalic acid, suecic acid. Glutaric acid, adipic acid, pimelic acid. Suberic acid, azelaic acid, sebacic acid and the like, or of aromatic polycarboxylic acids such as phthalic acid. Isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, Diphenylorthodicarboxylic acid. Orthodicarboxylic acid, ethylene glycol bis (paracarbüxyphenyl) ether and the like

Polyglycidyl compounds obtained by reacting epichlorohydrin are also suitable with aromatic amines such as aniline, 2,6-dimethylaniline. p-toluidine, m-chloroaniline, p-aminodiphenyl. m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphynyl methane or with aminophenols, such as p-aminophenol, 5-amino-1-naphthol, 4-aminoresorcinol, 2 - methyl - 4 - aminophenol, 2 - chloro-4-aminophenol and the like. fertilizers include N, N-diglycidylaniline, N, N-diglycidyl-2,6-dimethylaniline, Ν, Ν, Ν ', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, the triglycidyl derivatives of p-aminophenol, in which the amino hydrogen and the hydrogen of the hydroxyl groups has been replaced by glycidyl radicals.

Other suitable polyepoxides are epoxidized cyclic compounds, such as

"» Ο

1,2,5,6-diepoxydimethyl cyclooctane.

. ^ -Epoxy-o-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carboxylate.

bis- (3,4-epoxydccyclohexanecarboxylate),

bis- (2,3-epoxycyclopentyr; -ether, ss

Vinylcyclohexane dioxide,

Dicyclopentadieride dioxide,

Diethylene glycol bis (3,4-epoxy-6-methylcyclohexanecarboxylate),

^3,4-I:, poxycyclohexylmet hy 1-3,4-1; poxycydo- ho

hexane carboxylate,

M-F.poxy-1-methylcyclohexylmethyl-3.4-L-.poxy-1-methylcyclohexane carboxylate.

l.6-hexanediol bisi- (3,4-epoxycyclohexane carboxylate), 6s

bis (3,4-epoxycyclohexylmethyl) oxalyt,

.W-epoxy-o-methylcyclohexylmethyl-9.10-epoxypentyl-4.5-epoxypcntanoate.

bis- (3,4-epoxy-6-methylcyclohexylmethyl) -

Sebacate,

Diglycidylavetal,
Divinylbenzene dioxide.
Dipentene dioxide.
1,2,5,6-diepoxy-cyclooctane,
bis- (3,4-epoxy-6-methylcyclohexylmethyl) -

Adipate,

Glycidyl ^ I-epoxy cyclopentyl ether.
3,9-bis- (1,2-epoxy-l-methylethyl) -Spirobi-

(Metadio.xan).

bis (3,4-epoxycyclohexyl) sulfone,
Glycidyl-2,3-epoxybutyl ether,
bis- (2,3-epoxy-2-methylpropyl) -ether,
1,1 bis (2,3 epoxy-2-methylpropoxy) ethane,
Di- (6-methyl-3,4-epoxycyclohexylmethyl) -ether, (o-methyl-S ^ epoxycyclohexylmethyl) -

(3,4-epoxycyclohexyimethyl) ether.
2.3-epoxycyclopentyl phenyl glycidyl ether

and the like, especially those that have no amino, amido, Contain carboxyl and anhydride groups.

The epoxy compounds having an internal 1,2-epoxy group include suitable diolefins. Serve or cyclic dienes, such as 1,2: 5,6-diepoxyhexane, 1.2: 4.5 - diepoxycyclohexane. Dicyclopentadiene diepoxide. Dipentene diepoxide, vinylcyclohexene diepoxide. just like the epoxidized diolefinically unsaturated ones Esters of carboxylic acids such as methyl 9,10: 12,13-diepoxystearate. the dimethyl ester of 6.7: 10.11-diepoxyhexadecane-Uo-dicarboxylic acid and the like. Epoxidized monoethers can also be mentioned. Dieters and polyethers, monoesters, diesters and polyesters. Monoacetals, diacetals and polyacetals which have at least one cycloaliphatic 5- or 6-membered Contain ring to which at least one 1,2-epoxy group is connected. Other suitable Connections with an inner one. 1,2-epoxy groups are epoxidized polymeric diolefins, like the polymers of butadiene or cyclopentadiene, and epoxidized fatty acids, fatty oils and fatty acid esters.

Preferred polymers of butadiene are epoxidized copolymers with styrene, acrylonitrile and adducts with toluene or xylene.

The maximum level of polyepoxides in the system is immaterial. As a rule, such polyepoxides are used preferred that are already liquid at room temperature. But if the polyepoxide is at room temperature is solid, it can be easily converted into a liquid form by dissolving in a usual Solvent for polyepoxides or in a mixture of solvents which are inert, d. H. chemically inactive are compared to the other components of the mixture.

The monovalent organic radicals R of the quaternary ammonium compound can only be carbon and contain hydrogen, d. H. Be hydrocarbon residues. But you can also use other atoms, such as oxygen. Two or three of the radicals R with the nitrogen atoms can also be a heterocyclic one Form a ring. The radicals R are preferably hydrocarbon radicals, such as alkyl radicals. Cycloalkyl radicals, Aryl radicals or alkaryl radicals or monovalent Hydroxyalkyl radicals such as / • / -hydroxyethyl, / i-hydroxypropyl u. dg !. Typical residues of monovalent hydrocarbon groups are methyl, ethyl, propyl, Isopropyl, butyl, isobiityl, tertiary butyl, pentyl, Hexyl, octyl, 2-ethylhexyl, decyl, 2-ethyl

. • yclohexyl-. Phenyl, benzyl, ethylbenzyl, dimethyloenzyl, Mesityl, cumyl, naphthyl, lauryl. Myristyle. Stearyl, tetracosyl radicals and the like.

To the typical cationic quaternary ammonium compounds belong

Ammonium chloride,

Tetramethylammonium chloride.

Di ~ iyldimethylammonium chloride, benzyltrimethylammonium chloride, Distearyl dimethyl ammonium chloride.

Octyl stearyl dimethyl ammonium chloride.

Dicetyl dimethyl ammonium chloride.

Cetostearyldimethylammonium bromide.

Dilauryldimethylammonium chloride, P-ethylbenzyllauryldimethylammonium nitrate.

p-ethylbenzylstearyldimethylammonium sulfate.

3.5-dimethylbenzyl lauryl dimethylbenzenesulfonate.

3,5-dimethylbenzylstearyldimethylammonium chloride.

Benzyl lauryl dimethyl ammonium chloride. Benzyl stearyl dimethyl ammonium bromide. Lauryl trimethyl ammonium chloride. Stearyl trimethyl ammonium chloride. 2-methylquinoline-N-cetylammonium chloride, 2-methylquinoline-N-tetradecylammonium chloride,

Cctyltrimethylammonium chloride, Tctracesyltrimethylammonium chloride. Benzyl trimethyl ammonium chloride. Benzyltrimethylammonium acetate. Benzyl triethylammonium formate, Benzyl tripropylammonium stearate. Benzyl tributylammonium acetate. Ethylenebistrimethylammonium chloride. Octyltrimethylammonium chloride. / i-Hydroxyethyltrimethylammonium hydroxide. Benzyltrimethylammonium hydroxide. Tetramethylammonium hydroxide

and the like. Preferred cationic quaternary ammonium compounds are Dilauryldimethylammoniumchlorid and their Cholinebasc, and // - Hydroxyäthyltrimethylammoniumhydroxyd.

Among the preferred cationic organic silicon compounds belong to those of the general

formula C ₃ H ₆ OCH ₂ CH (OH) CHjN (CH ₃ ).,

! Anion "

(CH. ^ JSiOlSiO ^ CSKCHjJjOlj.SKCH.,).,

In this formula, χ has a mean value from 1 to about 50. y has a mean value from 0 to about 250. The ratio of y to χ is no more than about 20: 1. The anion is the same as in the first formula, especially chlorine. The most preferred compounds of this type are those with the general formula

(Me, Si ()) _: MeSiC., H ₍₁ OCHjCH (OH) CHjNMc, CI and the general formula

C, H "OCn ₂ CH (OH) CHjNMe ₃ Cl

Me., SiO (Si ()) _{: o} | MeSiO], _{7 (} , SiMe,

Me
Me here denotes a methyl radical (CH,).

Of these compounds are the silicon-free quaternary organic ammonium compounds preferred, \ νείϊ they are cheaper. The addition of quaternary organic silicon compounds can also produce a haze in the mixture, which does not occur with silicon-free organic quaternary ammonium compounds.

Any inorganic fillers can be used, which are also otherwise known as polyepoxy resins clogs. These fillers can be used alone or in various combinations will. These include, for example, asbestos. Asphalt. Bitumen. Glass fibers, magnesium carbonate. different Clays such as kaolin and the like, lime, slate. Titanium-

[5 dioxide, various metal powders such as aluminum powder and the like, talc, mica, blanc-fix. RuB. Diatomy Earth. Pumice stone, precipitated silicon dioxide. a silicon dioxide in airgel form. Quartz. Sand and the like. The preferred filler is silica.

The preferred amount of the quaternary ammonium compounds is between about 0.02 and 0.09 "- ■» Very good results have been achieved with amounts of about 0.075 "Ό of the ammonium compound, based on

2s the weight of the polyepoxide or hardener. the upper limit of 0.1% is critical, since larger amounts lead to premature crosslinking of the polyepoxide being able to lead.

Usually the qualernary ammonium compound is used in the form of a solution as it is available as such. But this is not necessary when the ammonium compound is already liquid.

The content of organic fillers in both systems is insignificant and only depends on it.

Xs what the cured polyepoxy resin is used for shall be. Fillers in an amount up to the amount of the polyepoxide or the amine hardener can be used can be successfully prevented from weaning. Usually the amount of filler is between about 1 and 500 percent by weight based on the weight of the total mixture.

It is immaterial in what type and order the individual components of the invention Mixtures are brought together. In the end

4s nis a liquid mixture is obtained.

Mixtures according to the invention can also contain other customary additives. So z. B. a Mixture with a content of a polycapoxide hardener such as polyfunctional amines. Polycarboxylic acids, Anhydrides of polycarboxylic acids, polyols, polythiols, polyisocyanates, polythioisocyanates. Polyacyl halides and the like included. Furthermore, all of these mixtures can contain coloring substances, such as pigments or Dyes, also plasticizers, the combustion

5s inhibiting substances, lubricants, etc. contain.

The following examples illustrate the invention. The quantities given are weight everywhere parts or percentages by weight, if nothing else! is said.

f> o To check the settling of the organic lull substance from the mixtures according to the invention, the following procedure was used:

The device includes a piston with a piston rod, the upper half of which is calibrated. At

A perforated shoe is attached to the lower end at the top there is a small disc on which weights can be placed. The whole before direction is on a tripod. With

of the tripod, the device is spread apart onto a container in which there is a mixture with a settled filler. The perforated Disc acts as a probe. You wildly under gradual increase in the load of weights in depressed for certain periods of time. The loading with the weights is continued until the perforated disc touches the bottom of the container or until a maximum load is reached and the Disk cannot penetrate through the settled filler. That can be read on the calibrated piston rod. Such devices are described in detail in an article by Pat ton. "Simple Pigment-Settling Gage and a Simple Anti-Sag Test" in Official Digest, Jan. 1957. is the Federation of Paint and Varnish Production Clubs.

example 1

20th

Hin mixture of the curable diglycidyl ether of 2,2-bis- (Parahydroxyphcnyl) -propane with a Epoxy equivalent weight of about 190 and a viscosity of about 12,000 cntipoise at 25 ° C was mixed with 5 (K) g of a filler made of silicon dioxide (p-quartz) and deaerated.

Example 2

A mixture was prepared according to Example i, ν the 0.75 g of dimethyldilaurylammonium chloride was added became.

Example 3

A mixture according to Example 1 was prepared. the 0.75 g of a 50% solution of the choline base of 'i'-Hydroxyälhyltrimethylamrnojiiumhydroxid in Methanol was added.

Example 4

The mixtures according to Examples 1 to 3 were stored. After 30 days the thickness of the layer became of the deposited filler measured with the device described above. The results are in the Table I included.

Table 1 ,. ,,,,

Example 1 3.2 cm

Example 2 0.025 cm

Example 3 0.125 cm

The results show that less than 0.1 percent by weight of the cationic quaternary Ammonium compounds are sufficient to prevent the filler from settling.

Example 5

Similar results were obtained when mar followed the procedure of Example 3 and da; Polyepoxide mentioned there replaced by other polyepoxides, such as by the diglycidyl ether of bis (Parahydroxyphenyl) methane, the diglycidyl ether of dihydroxyphenyl sulfone, the polyglycidyl ethers of ethylene glycol. the polyglycidyl ether of ethy lenediamine. the polyglycidyl ester of oxalic acid and the like

Example 6

440 g of a curable polyepoxy according to Example 1, 60 g of butyl glycidyl ether with one epoxy equivalent of about 130 and a viscosity of about 20 centi poise at 25 C, with 500 g of a filler: mixed according to example 1 and vented.

example

A mixture according to Example 6 was 0.75 g of a 50% ethanol solution of a polysiloxane de formula

((CH ₃ I ₃ SiO) ₂ CH ₃ SiC ₃ H ,, OCH ₂ CH (OH) CH ₂ NlCH ₃ I ₃ Cr was added. The mixture was then vented.

example

A mixture according to Example 6 was 0.75 g of a 50% ethanolic solution of a polysiloxane dei formula

(CH, I ₃ SiOI (CH ₃ 1 ₂ SiO) ₁ -,

O -

CH ₃ SIC ₃ H ^ OCH (OH) Ch ₂ N (CH ₃ I ₃

, 0Si (CH ₃ I ₃ CI

was added and the mixture was deaerated.

Example 9

A mixture according to Example 6 was 0.75 g of a 50% ethanol solution of a compound de formula

(CH ₃ I ₃ SiOl (CH ₃ I ₂ SiO) ₁ -,

CH ₁ SAFE ₁ OCH ₂ CH (OHiCH ₁ N (HI (CH,);

Si (CH ₃ I ₁ CH ₁ COO

zimesetzt. whereupon the mixture was vented.

ίο

dragonfly 11

Line 47 repayment W) Tu μι- I.UTügi 27 repayment (cml lone) I em I Ium) 4.0 0.0 0.0 1.0 1.5 0.1 0.0 0.075 1.0 0.02.5 0.05 0.0

Example 10

A mixture according to Example 6 was 0.75 g
added to a 50% isopropanolic solution of trihydrocarbon ammonium chloride, wor- 5
on the mixture was vented.

Example 6 Example 11 Example 7

A mixture according to Example 6 was given 0.75 g, 0 ^Bels P ^{lcl 8}
Dimethyldilaurylammonium chloride added, Example 9
on the mixture was vented. Example 10

Example 11 Example 12 Example 12

A mixture according to the example (> were 0.75 g The table shows that less than 0.1 weight

a 50% methanolic solution of 7% of a cationic quaternary ammonium hydroxyethyltrimethylammonium hydroxide added, compound the hard settling of the filler from whereupon the mixture was deaerated. prevent the mixture. Although according to the two

20 play 9 and 11 cut certain layer thicknesses

Example 13, the constituents could be identified by simply *

Stir gently to be mixed again. At the Mi

The mixtures according to Examples 6 to 12 were made according to Example 6, but this was not the case.
stored and then examined as in Example 4

is described. The results are shown in Table 11 25 B e i s ρ i e 1 14

contain. A mixture according to Example 6 was prepared.

Example 15

A mixture according to Example 14 was given 0.75 g of a 50% strength methanolic solution of the choline base von / i - Hydroxyäthyltrimethyiammoniumhydroxyd added, whereupon the mixture was deaerated.

Example 16

A mixture according to Example 14 was given 0.75 g of a 50 "own ethanoiischen solution of a polysiloxane the formula below

((CHj) ₃ SiO) ₂ CH ₃ SiC ₃ H ₆ OCH ₂ CH (OH) CH ₂ N (CHj) ₃ Cr
was added and the mixture was deaerated.

Example 17

A mixture according to Example 14 was 0.75 g of a 50% ethanol solution; of a polysiloxane of the formula ^{b y} '

K ₃ SiC ₃ H ₁ OCH ₂ CH (OH) CH ₂ N (CH ₃ Ij | _2n - Si (CHj) ₃ Cl
was added and the mixture was deaerated.

Example 18

A mixture according to Example 14 was 0.25 g of a 50% ethanoiischen solution of a polysiloxane formula

(ICHjI ₃ SiO) XH ₃ SiC ₃ HOCH ₂ CH (OH) CH ₂ N (CHj) ₃ Cr
was added and the mixture was deaerated.

Example 19

The mixtures according to Examples 14b, s 18 were stored and according to the method described checked. The results are given in Table III.

11th

Tabel III / hurry 5 days I .W I K) St (J. I cm ι (cm I. I cm I 2.54 0.63 0.0 0.25 example 14th 0.0 0.75 1.2 example 15th 0.0 0.0 0.5 example 16 0.0 3.2 example 17th 0.0 example 18th

IXS! .Ige

Sufficient in connection to prevent settling of the filler from the mixture. According to Example 18, even about 0.02 percent by weight is sufficient. In the mixtures according to Examples 16 and 1 , a certain settling was observed, but the constituents could be mixed again by simple stirring. This was not the case with the mixture according to Example 14.

Example 20

1.5

The results show that weight percent of the cationic

500 grams of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate with an epoxy equivalent of about 135 and a viscosity of about 400 centi-

less than 0.1 ge 15 poise at 25 ^C C were treated with 500 g of silicon dioxide as

quaternary ammo filler mixed and deflated.

Example 21

One. The mixture according to Example 20 was 0.75 g of a 50% strength ethanolic solution of a polysiloxane Formula +

((CH ₃ I ₃ SiO) ₂ CH ₃ SiC ₃ H _n CH ₂ CH (OH) CH ₂ N (CH ₃ ) JCr

was added and the mixture was deaerated. phenyl) methyne and the like, and by replacing the above

Similar mixtures were obtained by replacing the 25 described quaternary ammonium compound

of the polyepoxide mentioned by other polyepoxides. through other quaternary compounds, such as / i-Hy-

as by the polyepoxides of bis- (2,3-epoxy-cycloxyäthyltrimethylammoniumhydroxyd. Dimethyl-

penthyl) ether, bis (3,4-epoxy-6-methylcyclohexyldilaurylammonium chloride and the like. methyl), the diglycidyl ether of bis- (parahydroxy-

Example 22

A mixture according to Example 20 was 0.75 g of a 50% ethanolic solution of a polysiloxane formula

((CH ₃ I ₃ SiO) ₂ CH ₃ SiC ₃ FL ₁ CH ₂ CH (OH) CH ₂ N (CH ₃ J ₃ Cr

was added and the mixture was deaerated.

Example 23

Examples 20-22 were stored and tested according to the procedure described above. the Results are given in Table IV.

Table IV Time 39 days 60 days 190 days 14 days (cml learn) (cm) lcml 1.3 1.5 4.8 1.5 0.13 0.5 2.0 Example 20 0.0 0.0 0.18 1.5 Example 21 0.0 Example 22

Example 24

500 g of a mixture of bis (2,3-epoxycyclopenthyl) ether and an epoxidized novolac having an epoxy equivalent of about 135 and a viscosity of about 5000 centipoise at 25 ^: C was mixed with 500 g of silica filler and deaerated.

Example 25

A mixture according to Example 24 were 0.75 g of a 50'Oipen ethanolic solution of a cationic Polysiloxane of the formula

Added ((CH ₃ I ₃ SIO) ₂ CH ₃ SIC ₃ H ^ CH ₂ OCH ₂ CH (OHiCH ₂ N (CH ₃ ) JCI and the mixture was vented.

13 14

Example 26

A mixture according to Example 24 was given 0.75 g of a 50% ethereal solution of a polesilo formula

was added and the mixture was deaerated.

Example 29

The mixtures according to Examples 24 to 26 were stored and according to the V described above checked. The results are given in Table V.

Table V

14'lagt- V) days «) days IWI agc learn) lemi (cm 1 icml

Example 24 0.13 0.63

Example 25 0.0 0.0

Example 26 0.0 0.0

0.75 1.75 0.0 0.0 0.0 0.0

Claims (1)

Claim: Filler-containing, non-settling epoxy resin mixture, characterized in that there :; Mixture of at least one curable Polyepoxide with more than one epoxy group in the molecule and in an amount less than 0.1 percent by weight, based on the weight of the polyepoxide, of at least one quaternary cationic ammonium compound of the general formula R-N -R Anion where the radicals R can be identical or different and denote hydrogen or a few organic radicals having 1 to 24 carbon atoms and where anion is a halogen, a carboxylic acid radical. a nitrate, sulphate, sulfonate or Hyd ^r-oxyl radical; or at least one cationic quaternary polysiloxane-ammonium compound, in which the siloxane is a siloxane unit of the general formula R ^ SiO ₄ _ " And at least one siloxane unit the more general. formula R, R - N - X - SiO, _, Preliminary products is very short, usually only for a few days. Since these preliminary products can no longer be stored, it is necessary that the filler is only added to such a system and mixed with it shortly before it is used. It is clear "that this creates disadvantages and high costs due to separate transport and separate storage.
The object of the invention is a filler-containing ίο Epoxy mixture from which the filler is not made or settles so slowly that the mixture can be stored for a long time without hesitation. According to the invention, this object is achieved in that the mixture consists of at least one curable Polyepoxide with more than one epoxy group in the molecule and in an amount of less than 0.1 percent by weight, based on the weight of the polyepoxide, at least one quaternary cationic Ammonium compound of the general formula