DE2156150A1 - Adhesive compositions - Google Patents

Description

Dr. F. Zumsteln sen. - Dr. E. Assmann Dr. R. Koenlgsberger - Dlpl.-Fhys. R. Holzbauer - Dr. F. Zumsteln Jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 225341

TELEX 529979

TELEGRAMS: ZUMPAT CHECK ACCOUNT: MUNICH 91139

BANK ACCOUNT: BANK H. HOUSES

8 MUNICH 2,

BRÄUHAUSSTRASSE 4 / III

97/90 / white

Case 3-7231 / AKL 177

GIBA - GEIGY A.G., Basel / Switzerland

Adhesive composition

The present invention relates to adhesive compositions based on epoxy resins, the use of such compositions and structures associated with it.

The utility and versatility of epoxy resin adhesive compositions are known. Such compositions consist of two essential components, the epoxy resin (ie a substance which contains more than one 1,2-epoxy group per average molecule) and a catalyst or hardener, which causes the epoxy resin to crosslink or itself reacts with the resin, whereby a hard solid forms with a high specific adhesion to a wide variety of substrates. Particularly useful adhesives are those that at room temperature, ie about 25 ⁰ C, or at moderate iDemperatüren, that is approximately below 60 ⁰ C, to cure.

Most of the epoxy resin adhesive compositions available to date lack it ("green strength ¹ ·), ie they are not tacky before they set, so that surfaces which are to be bonded with the aid of the adhesive have *" holding power "20982 3 ^ 099 4

with the help of jigs, clamps, presses or others Temporary fasteners must be held together while tightening. Attempts have been made to overcome this disadvantage, like solving "certain High molecular weight polymers in one or more components of the composition to act as tackifiers works. For example, U.S. Patent 3,310,603 describes the use of a homogeneous mixture of epoxy resin and one Chloroprene-acrylonitrile copolymers .. This composition, however, like other compositions, according to the prior art the disadvantage that the mixture of added polymers and epoxy resin is viscous and almost immediately becomes tacky, which is the case with its mixing with other components of the composition and when applied in a layer leads to difficulties. To overcome these drawbacks, volatile solvents could be incorporated, but solvents containing solvents could be incorporated Compositions not always in layers of the desired one Thickness spread, the solvent can attack the object to be glued and many kinds of Solvents bring fire and loxicity hazards with them.

It has now been found that the desired objectives, namely the production of an epoxy resin adhesive, which liquid or is paste-like and can be easily mixed, spread and spread, and which during use without the application of heat tackiness, usually without the need for the addition of a volatile solvent, can be achieved by use certain combinations of epoxy resins and hardeners with finely divided, solid polymers, which slowly move into one or the other component of the adhesive if necessary in the presence of a solubilizer, dissolve.

The present invention thus relates to compositions which can be spread at room temperature, are curable without the application of heat and which are for use as Adhesives are suitable, which are characterized in that they

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(a) a polyepoxide which has more than one 1,2-epoxy group of the general formula per average molecule

RR ¹ R ²

ι I 1

- CH - c - σ -

which are directly connected to an oxygen, sulfur or nitrogen

ρ atom is bonded and where if R and R are hydrogen atoms represent, R is a hydrogen atom or a methyl group

or when R and R together represent the group -CHg-CH ₂ -, R is a hydrogen atom ", contains,

(B) a polyamine with at least 3 Aminöwassersto ff atoms per Molecule as hardener for the compounds mentioned under (a)

(c) a finely divided, solid vinyl polymer and if necessary

(d) contain a solubilizer, the vinyl polymer initially at least partly in a liquid mixture of (a) and (b) is insoluble but swells therein and, if necessary, dissolves therein in the presence of (d), while the composition becomes firm to achieve greater tack.

The invention also relates to a method for producing a tacky adhesive composition which is characterized is that you have a finely divided, solid vinyl polymer, a polyepoxide, as explained above, a polyamine, such as explained above, and optionally mixing a solubilizer to obtain a spreadable composition, and the vinyl polymer swells and dissolves.

The invention further relates to a method for creating j & wei surfaces to connect with each other, which is characterized in that one or on both surfaces one Composition applies, which consists of a finely divided, solid vinyl polyamide, a polyepoxide, as explained above,

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a polyamine, as explained above, and optionally a solubilizer, the composition becomes sticky can be, brings the two surfaces in contact with each other and allows the composition to cure.

The finely divided, solid vinyl polymer can be incorporated when the epoxy resin and its hardener are mixed together, or it can already have been dispersed in one of the components beforehand. In the latter case, the polymer should of course be mixed with that component of the epoxy resin adhesive in which it is essentially insoluble under the given storage conditions. By choosing Gefe appropriated formulations, Ze can. ·., Cdauer during which the tack is designed to be kept long enough to make the resin and hardener to easily raitein & ider mix and can easily spread to you surface. before the ropes are put together. The developed tack will then hold the assembly together as crosslinking proceeds and the adhesive composition solidifies.

The vinyl polymers are preferably prepared by emulsion polymerization Manufactured because this process produces small, spherical, dense lights. However, other methods could also be used those used to manufacture materials of similar physical Form are suitable for use. These polymers ™ are preferably based on methyl vinyl ether, vinyl alcohol, Vinyl acetate or styrene? Tfömonomere, such as acrylonitrile, Acrylic esters or acrylic acid can also be used. A particularly preferred vinyl polymer is polyvinyl acetate, in particular a polyvinyl acetate containing some free carboxyl groups. The largest diameter of the polymer particles is typically in the range from 1 to 200 μm and preferably in the range from 5 to 125 μm. The polymers usually dissolve only slowly in the epoxy resin, but faster in the hardener, and / or in the solubilizer, if any.

The amount of vinyl polymer used depends on its solubility in the other components will, in general, be

2 0 9 8 ? 3/0 9 9 h

however 5 to 150 and preferably 15 to 75 parts by weight of vinyl polymer per 100 parts by weight of epoxy resin (expressed on the basis of a 100% content of resin-forming materials) used.

According to the usual processes for the production of epoxy resins, mixtures of compounds with different molecular weights obtained, these mixtures generally containing a proportion of compounds whose epoxy groups are a partial hydrolysis have been received. The average number of 1, 2-epoxy groups per molecule of the resin does not need one to be an integer of at least 2. In general it is a fractional 7-ahl, but it is in any case greater than 1.0 have to be.

Examples of resins that can be used are Polyglycidyl and poly (ß-methylglycidyl) esters produced by reaction a substance 'with 2 or more carboxyl groups with epichloro-

hydrin, glycerol dichlorohydrin or ß-methyl epichlorohydrin insind.
Available in the presence of alkali / "Such polyglycidyl esters can be derived from aliphatic carboxylic acids, such as oxalic acid, succinic acid, adipic acid, sebacic acid or dimerized or trimerized linoleic acid, from cycloaliphatic carboxylic acids, such as hexahydrophthalic acid, 4-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, l'etrahydrophthalic acid, hydrophthalic acid and 4-methylrophthalic acid Carboxylic acids such as phthalic acid, isophthalic acid and iCerephthalic acid.

Other epoxy resins which can be used include polyglycidyl and poly (β-methylglycidyl) ethers, as described by Reaction of a substance with 2 or more alcoholic hydroxyl groups or 2 or more phenolic hydroxyl groups with one suitable epichlorohydrin or glycerol dichlorohydrin under alkaline conditions or, alternatively, in the presence of an acidic one Catalyst can be obtained with subsequent treatment with alkali. Such polyglycidyl ethers can be derived from aliphatic Derive alcohols, such as from ethylene glycol and

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Polyoxyethylene glycols such as diethylene glycol and triethylene glycol, propylene glycol and polyoxypropylene glycols, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6 , -trio] glycerine, 1,1,1-irimethylolpropane and pentaerythritol; of cycloaliphatic alcohols, v / ie quinite, 1, i-bis (hydroxymethyl) cyclohex-3-ene, bis (4-hydroxycyclohexyl) methane and 2,2-bis (4-hydroxycyclohexyl) propane; and of alcohols with aromatic nuclei, such as IV, N-bis (2-hydroxyethyl) aniline and 4.4 ^! -Bis- (2-hydroxyethylamino) -diphenylmethane. The polyglycidyl ethers are preferably derived from substances which contain 2 or more phenolic hydroxyl groups, such as resorcinol, porridge catechol, hydroquinone, bis (4-hydroxyphenyl) methane, 1,1,2,2-a! Etrakis (4-hydroxyphenyl) -ethane, 4,4'-dihydroxydiphenyl, bis- (4-h; / ärüxj phenyl) -sulfone, phenol-formaldehyde and cresol-eorraaldehyde Novolakli & .rEse, 2,2-bis- (4-hydroxyphenyl) -propane (known as bisphenol A) and 2,2-bis- (3,5-dibromo-4-hydroxyplxHnyl) propane.

Poly-N-glycidyl compounds can also be used, such as, for example, in the dehydrohalogenation of the reaction products of epichlorohydrin and amines, which contain at least 2 hydrogen atoms directly bound to nitrogen, such as aniline, n-butylcmin, Bis (4-aminophenyl) methane, bis (4 ~ aminophenyl) sulfone and Bis (4-methylaminophenyl) methane is obtained. Other poly-glycidyl compounds which can be used include! driglycidyl isocyanurate, lijif'-diglycidyl derivatives of cyclic Alkylene ureas such as ethylene urea and 1, ^ - propylene urea and ITjiP diglycidyl derivatives of hydantoins, such as 5 * 5-diraethylhydantoin, a.

Compounds of the general formula I in which R and R together represent the group -CH ₂ -CH ₂ - and R ^{1 represents} a hydrogen atom include bis- (2,3-epoxideyclopenty.l) -ether, 2,3-EpoTtdcyclopentyl glycidyl ether and 1,2-bis (2 ^f ^ '- epoxidcyclnpentyX-oxy) ethane.

209823/0994

Particularly suitable epoxy resins are polyglycidyl ethers of 2,2-bis- (4-hydroxyphenyl) propane or from a novolak Phenol (which is substituted in the ring by a chlorine atom or by an alkyl group with 1 Ms 4 carbon atoms. .. can be ated) and Formaldel ^ d, which have an epoxide content of have at least 1.0 epoxy equivalent per kg.

Polyamines, which can be used to make epoxy resins Cure at room temperature are usually aliphatic polyamines, like the alkyleneamines of the general formula

r4 - II (CH-CH ₂ M) ₁₀ - E * L *

where R is a hydrogen a ¹ IOm or a methyl group,

m is an integer of at least 1 and at most 6, and • R ^ a V / hydrogen atom, the 2-hydroxyethyl, 2-hydroxypropyl or 2-Cyanoäthylgruppfc mean,

on condition that at least 3 of the R groups represent hydrogen atoms,
or the general phrase

H ₂ H (X) NH ₂

wherein X is an alkylene hydrocarbon chain with at least 3 and at most 12 carbon atoms.

Examples of such amines are diethylenetriamine and hexane-1,6-diamine and its 2, 2, 4-trimethyl and 2,3 »3 _} -irimethyl analogs.

Polyaminoamides that can be used are those which in a known manner by reaction of a molar excess of such an aliphatic polyamine with a polycarboxylic acid, in particular a dimerized or trimerized ethylenically

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- 8 unsaturated fatty acids can be produced.

Other suitable polyamines are cycloaliphatic and cycloaliphatic-aliphatic Amines, such as bis (4-aminocyclohexyl) methane, Bis (4-amino-3-methylcyclohexyl) methane and 3,5 »5-3} rimethyl-3 - (aminomethyl ) -cyclohexylamine.

An effective amount of the hardener is used. As is well known, this depends on the chemical composition the hardener and the epoxy resin and the desired properties of the adhesive composition and the cured one Product. In general, 0.8 to 1.2 amino-hydrogen equivalents de · * - Hart er s per 1,2-epoxy group equivalent of epoxy resins ·? used.

"Iiöslichmacher" Bind compounds other than a Polyepoxxd (a) or a polyamine (b), welohe at room temperature, the sources and a parzielle solution of the vinyl polymer in the other components favoring, composition to the tacky within 2 hours after mixing with the curable Zv to accomplish. They are relatively non-volatile compounds, ie they boil above 150 ⁰ C (but usually below 30O ⁰ C) at atmospheric pressure and are relatively inert to the polyepoxide (a) and / or the Polyarain (b), under normal storage conditions. Usually, the amount of the solubilizer used is 15 to 60, especially 20 to 50 parts by weight per 100 parts by weight of the epoxy resin. Substances which have been found to be effective include ϊϊ, Ιί-dimethylpropane-1,3-diamine, Η, Η-diethylpropane-1, 3-diamine, iT-benzyldimethylamine, 2,4,6-! Ris- (dimethylaminomethyl) - phenol, phenylglycidyl ether, ^ "- butyrolactone, p-ionylphenol, di-n-butyl phthalate, n-butylbenzyl phthalate, 3» 4-dihydro-2H-pyran-2-ylmethyl-3,4-dihydro-2H-pyran-? - carboxylate , Isooctyl monoglycidyl ether and cresyl glycidyl ether.

The compositions can also contain accelerators to aid in their hardening, especially when polyaminoamides be used. Examples of such accelerators are aliphatic

209823/099 U

tables amines which contain at least one tertiary amino group and contain at least one primary amino group, v / ie F, H-dialkylethane-1,2-diamine and M, iY-I) alkylpropane-1,3-diamine, in particular the Μ ', Η-dimethyl and ΙΫ, Η-diethyl derivatives and also Mannich bases the general formula

R ⁵ (CH ₂ HR ⁶ R ⁶ )

where y is an integer of at least 1 and preferably 3

or 4 »
5
R · ^ a mononuclear or polynuclear, monovalent

or polyvalent phenol radical, the y free valences

"owns, and each
R is an alkyl or hydroxyalkyl group with up to 4 carbon atoms

". A preferred Mannich base is ^, 4) 6 ~ 'i'r: i3" (dimethylaminomethyl) phenol. Some of these accelerators are also solubilizers.

Plasticizers which are known to be used in the new compositions include dibutyl phthalate, dioctyl phthalate and Irieresy! phosphate. Some of these substances can also be called Solubilizers act. Other inert diluents can also be present and also so-called reactive diluents, in particular monoepoxides, such as butyl glycidyl ether, iso- ■ oetylglyeidylether, phenylglycidylether, cresylglycidylether, Glycidyl acrylate, glycidyl methacrylate and glyeidyl ester of synthetic, highly branched, predominantly tertiary, aliphatic monocarboxylic acids. The compositions can also contain fillers, Colorants, flow control agents and flame inhibitors. Suitable extenders and fillers are asphalt, bitumen, glass fiber, mica, quartz powder, cellulose, kaolin, and WCLlastonite and colloidal silicon dioxide with a large specific surface, as it is available under the registered trade name "Aerosil" is available. Depending on the solubility of the polyvinyl polymer in the hardener, in the epoxy resin or in one

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- ίο -

other component of the composition may be the composition according to the present invention can be supplied as a two- or three-part package. The polyvinyl polymer can dem Epoxy resin or the hardener or "both.

The following examples illustrate the invention. Unless otherwise stated, the parts given are parts by weight.

"Epoxy Resin I" denotes a polyglycidyl ether of 2,2-bis ~ (4-hydroxyphenyl) propane having a viscosity in the range of 200 to 400 poise at 21 ⁰ C and an epoxide content of 5.1 iquiv./kg.

"Epoxy resin II" denotes a polyglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane with an Epc: cid content of 4.5 to 4> 7 equiv. / kg.

"Epoxy Resin III" identifies a Epoxiclnovolac, .- which is semi-solid at 21 ⁰ C and an epoxide content 5.5 to 5.7 Iquiv./ has kg.

"Epoxy resin IV" denotes bis [p- (diglycidylamino) phenyl] methane.

"Epoxy resin V" denotes diglycidyl tetrahydrophthalate.

"Polyarainoamid I" denotes a polyaminoamide, which by Reaction of diethylenetriamine with a commercial mixture of dimerized and trimerized unsaturated fatty acids was obtained. Its amine value is 350 to 400 mg KOH / g.

"Polyaminoamides II and III" denote polyeminoamides, which are similar to "polyaminoamide I", but with amine values of 230 up to 246 mg KOH / g or 210 to 220 mg EOH / g.

The shear strength of joints was determined using 1.63 mm thick strips of aluminum

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alloy available under the name "2L 73 Alcad". The strips were degreased, pickled according to the procedure given in the British Ministry of Technology Aircraft Process Specification DQH) -SM 5B, washed under running water and dried at room temperature. ( "Alcad" is a registered trademark.) Simple Überlappungsverbindungostellen of 12.7 x 25.4 were prepared, and the adhesive was cured for 2 hours at 21 ⁰ C and cured by heating for 30 minutes at 100 ⁰ C.

example 1

The vinyl polymer used (hereinafter referred to as "vinyl polymer I") was "Polystyrene R3612", which was obtained from Vinyl Products Limited, Carahalton, Surrey. Per maximum diameter of $ 90 its particles ranged from 20 to 80 pm. When mixing mV. Epoxy resin I (1: 0.5 ropes) did not change and the mixture remained ^{stable for longer than 2 months at 15 to 20 °} C.. When 0.75 parts of N, H-dimethylpropane-1,3- diamine to 15 'files of a mixture of epoxy resin I and vinyl polymer I, however, the mixture became tacky within an hour at room temperature.For comparison purposes, 0.75 part of N, Η-dimethylpropane-1,3-diamine in 10 parts of epoxy resin I was added at room temperature The mixture did not become noticeably stickier during its pot life.

An adhesive was prepared by mixing together 100 parts of epoxy resin I, 25 parts of di-n-butyl phthalate, 50 parts Vinyl polymer I and 25 parts of polyaminoamide I at room temperature and then stirring in 7> 5 parts of Η, ϊί-dimethylpropane-1,3-diamine. The mixture became sticky within 45 minutes at room temperature.

The shear strength of the mix treated this adhesive hardened joints was 21.3 newtons (xl ') / mm.

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- 12 Example 2

"Vinyl polymer II" denotes a styrene-aeryl copolymer which was obtained from Vinyl Products Limited under the designation "R1OO65". The maximum diameter of 90 ^c ß> of its particles was in the range from 10 to 60 μm. When mixed with epoxy resin I (1: 0.5 parts), the dissolution was extremely slow at room temperature and the mixture gelled after 9 days.

A similar mixture, which was freshly prepared and which 0.2 part of Ν, ϊΓ-diraethylpropane-i, 3-diamine or JJ, H-diethylpropane-1,3-diamine or 0.25 part of if-butyrοlactone or 3,4-DihydrO '5H-pyran-2-ylmethyl-3,4-dihydro-2H-pyran-2-carboxylate was added, but was at in less than 1 hour Sticky at room temperature.

An adhesive composition was prepared as in Example 1, replacing the vinyl polymer I with the vinyl polymer II (50 parts). The composition became tacky within 25 minutes to butt joints which were not caused by heating were post-cured, withstood loads of 14 · kl \ f / qu without to crawl. The shear strength of simply overlapped joints was 29.6 IT / mm.

Example 3

The vinyl polymer ("Vinylpolyineres III") of this example was obtained from Vinyl Products Limited under the designation "Styrene copolymer R1O653". The maximum diameter of 90 ° β> of its particles was in the range from 15 to 60 μm.

A mixture of 2 parts of epoxy resin I and one part of vinyl polymers III had no egg clicks at room temperature for 2 months Retained signs of reaction. A freshly made mixture (10 parts), the 0.66 part of Ν, ίΤ-dimethylpropane-1,3-diamine on the other hand, became sticky within 1 hour.

2098?, 1/099 / *

An adhesive composition was prepared as in the example 1 "described," but replacing the vinyl polymer I durclj vinyl polymer III (50 parts) and use of 35 parts instead of di-n-butyl phthalate. The time the composition at room temperature it took 30 minutes to become tacky. The shear strength of the hardened overlapped Joints was 16.8 ij "/ mm.

Example 4

The vinyl polymer used was polyvinyl acetate, 90 % of the particles having a maximum diameter between 25 and 100 μm. This polymer ("Vinvlinlymeres IV") was obtained from Vinyl Products Limited under the designation "R10688".

When mixing polyepoxide I with vinyl polymer IV (1: 0.5 iDeile) the Gothic slowly gelled at room temperature after 3 days. Freshly prepared mixtures (10 parts) became one of the following within 1 hour after adding 0.2 parts Solubilizer sticky:

p-u'onylphenol, n-butylbenzyl phthalate, phylglycidyl ether, N-benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) puenol or Ν, Ν, -dimethylpropane-I, 3-diamine

An adhesive composition was prepared as in the example 3, but replacing the vinyl polymer III with the same amount by weight of the vinyl polymer IV. The stickiness developed within 12 minutes.

The shear strength of the overlapped joints was 8.3 H "/ mm ² .

Ex iel 5

"Vinyl polymer V" denotes a polyvinyl acetate with free Carboxyl groups with a particle size of 5 to 150 μm, which is available under the name R 11151 from Vinyl Products Limited was obtained. This polymer (20 parts) was with

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100 parts of the epoxy resin II mixed to form a stable suspension. An adhesive composition was prepared by mixing this suspension with a mixture consisting of 20 parts of an adduct of triethylenetetramine and propylene oxide (1: 1 mol), 50 parts of polyarainoamide II and 30 parts of cresylglycidyl ether. The tack developed within 32 minutes, and the shear strength of a joint obtained with this adhesive was 22.0 N / mra ² .

Example 6

25 parts of the vinyl polymer III were mixed with 100 parts of the epoxy resin III to form a stable suspension and this was with 7.5 parts ίΓ, ϊί-dimethylpropane-i, 3-diamine, 50 parts of polyarainoamide II and 50 parts of isooctylglyeidyl ether mixed. The stickiness developed within 7 minutes and the joint shear strength was 11.0 H / mm.

Example 7

"Vinyl polymer VI" denotes a styrene-acrylic acid copolymer with free carboxyl groups and with a particle size of 5 to 150 μm, which is available under the designation R10784 by Vinyl Products Limited. 20 parts of this polymer were added to 100 parts of the epoxy resin IV under Formation of a stable suspension, which with 12 parts of triethylenetetramine, 50 parts of polyaminoamide II and 50 parts of cresyl glycidyl ether were mixed. The stickiness developed within 15 minutes and the shear strength of the joint was 14 »3 H / mm.

Example 8

"Vinyl polymer VII" denotes a styrene-acrylic acid copolymer with free carboxyl groups and with a particle size of 5 to 150 µm, which is known under the designation R11O63 by the

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Vinyl Products Limited. 40 parts of this polymer were mixed with 100 ropes of the epoxy resin III and the resulting stable suspension was mixed with 11 ropes 2,4 »6- £ ris- (dimethylaminomethyl) -phenol, 40 ropes of polyaminoamide II and ropes of di-n-butyl phthalate mixed. The stickiness developed within 1 hour and the shear strength of the joint was 16.0 N / rara.

Example 9

A mixture of 25 ropes of vinyl polymer VII and 100 ropes of epoxy resin V was incorporated into a mixture consisting of 7-5 ropes of N, IT-Dime * h; v ::. Propane-1,3-diamine and 20 ropes of polyamino arid III . Tack developed within 10 minutes and the joint shear strength was 16.0 ii / mm ² .

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Claims (26)

Claims 1. Adhesive compositions, characterized in that they (a) a polyepoxide, which per average molecule more than one 1,2-epoxy group of the general Eorinel RR ¹ R ² -CH-C-C-H I which are directly connected to an oxygen, sulfur or nitrogen P atom is bonded and where, when R and R are hydrogen atoms Ί
represent, R be a hydrogen atom or a methyl group ~ ρ
or when R and R together represent the group -CH ₉ -CHo- represent, R denotes a hydrogen atom, contains, (b) a polyamine having at least 3 amino hydrogen atoms per Molecule as hardener for the compounds mentioned under (a) (c) a finely divided, solid vinyl polymer and if necessary (d) contain a solubilizer, the vinyl polymer initially at least for the iCeil in a liquid mixture (a) and (b) is insoluble but, if necessary, dissolves therein in the presence of (d) to while the composition becomes firm to achieve greater tack. 2. Compositions according to claim 1, characterized gekennzeiclmet, that the polyepoxide is a polyglyeidyl ether of 2,2-bis (^ - hydroxyphenyl) propane or a novolak made of phenol, which is in the ring by a chlorine atom or an alkyl group with 1 to 4 carbon atoms can be substituted, and formaldehyde with an epoxide content of at least 1.0 equiv. / Kg. 209823/099 3. Compositions according to claims 1 or 2, thereby characterized in that the polyamine is an alkylene amine of the general formula -E * Ε * "5 is where R is a hydrogen atom or a methyl group, m is an integer of at least 1 and at most 6, and R ^{4 is} a hydrogen atom, the 2-hydroxyethyl, 2-hydroxypropyne or 2-cyanoethyl group ", with the proviso that at least 3 of the R groups represent hydrogen atoms, or the general formula H ₂ N (X) wherein X is an alkylene hydrocarbon chain with at least 3 and means at most 12 carbon atoms is. 4. Compositions according to claims 1 or 2, thereby characterized in that the polyamine is a polyaminoamide, which in a known manner by reaction of a molar excess of an aliphatic polyamine according to claim 3 with a polycarboxylic acid was produced. 5. Compositions according to claims 1 or 2, characterized in that the polyamine is a cycloaliphatic or is a cycloaliphatic aliphatic amine. 6. Compositions according to one of the preceding claims 1 to 5, characterized in that 0.8 to 1.2 amino hydrogen equivalents of hardener per 1,2-epoxy group equivalent of the epoxy resin is used. 209823/0994 7. Compositions according to any one of the claims 1 Ms 6, characterized in that the maximum diameter of the Vinylpolymeri full particles in the range of 1 his 200 µm. 8, Compositions 1 in accordance with one of the entitlement to benefits to 7 »characterized in that it up to 150 parts by weight of vinyl polymer per 100 parts by weight epoxy resin, expressed on the basis of a content of 100 follow harzMldenden materials containing 5". 9. Compositions according to one of the claims "" before 1 Με 3, characterized in that the Viny! is one obtained by emulsion polymerization. 10. Compositions according to one of the claims. . ciie 1 to 9, characterized in that the vinyl polymer a polymer based on methyl vinyl ether, vinyl alcohol, Yinylaootate or styrene or a copolymer of these Compounds with acrylonitrile or acrylic acid. 11. Compositions according to claim 10, characterized in that the vinyl polymer is polyvinyl acetate. 12. Compositions according to claim 11, characterized in that the polyvinyl acetate contains free carboxyl groups. 13. Compositions according to one of the preceding claims 1 to 11, characterized in that the solubilizer has a boiling point of over 150 ⁰ O and is inert to the polyepoxide and the polyamine under normal storage conditions. 14. Compositions according to claim 12, characterized in that the solubilizing agent has a boiling point above 150 ⁰ C and is inert to the polyepoxide and the polyamine under normal storage conditions. 209823/0994 15. Compositions according to. Claim 13 »characterized in that that the solubilizer N, IT-dimethylpropane-1,3-diamine, ^, If-diethylpropane-1,3-diamine, N-benzyldimethylarain, phenylglycidyl ether, f-butyrolactone, p-monyl phenol, n-butyl benzyl phthalate or 3,4-dihydro-2H-pyran-2-ylmethyl ~ 3 j 4-dihydro-2H-pyran-2-carboxylate eats. 16. Compositions according to claim 12 or 14 »thereby made ' indicates that the solubilizer Ν, Ν-dimethylpropane-I, 3-diamine, K, N-diethylpropane-1,3-diaraine, N-benzyldimethylamine, Phenyl glycidyl ether, ^ f-butyrolactone, p-nonylphenol, n-butyl- "benzyl phthalate, 3,4-dihydro-2H-pyran ~ 2-ylmethyl-3,4-dihydro-2H-pyran-2-carboxylate, 2,4,6-triss- (dimethylaminomethyl) phenol, Di-n-butyl phthalate, isooctyl glycidyl ether or cresyl glycidyl ether is. 17 · Compositions according to any one of claims 1 to 11 or 13, characterized in that the solubilizer 2,4,6-tris (dimethylarainomethyl) phenol, di-n-butyl phthalate, iBOOctyl glycidyl ether or cresyl glycidyl ether. 18. Compositions according to any one of claims 1 to 17 » characterized in that they contain 15 to 60 parts by weight of the solubilizer per 100 parts by weight of the epoxy resin. 19. Terpackung, consisting of 2 parts, characterized in that the ingredients contained in them when mixing forming a composition according to any one of claims 1 to 11, 13 and 15, one part being the epoxy resin and the other rope contains the hardener and wherein the polyvinyl polymer is contained in one or in both parts. 20. Packaging, consisting of 2 parts, characterized in that that the constituents contained in them form a composition according to any one of claims 12, 14 and 16 to 18, one part containing the epoxy resin and the other part containing the hardener and wherein the polyvinyl polymer in one or in both Share is included. 209823/0994 21.. A method of making a tacky adhesive composition, characterized in that a finely divided, solid vinyl polymer according to one of Claims 1 and 7 to 11 with a polyepoxide according to claims 1 or 2, a polyamine according to any one of claims 1 and 3 to 6, and optionally a solubilizer according to any one of claims 1, 13 and 15 a spreadable composition is mixed, whereupon the yinyl polymer is caused to swell and dissolve. 22. A process for preparing a tacky adhesive composition, characterized in that a finely divided solid Viny! Polymer according to claim 12 mit'einem polyepoxide according to claims 1 or 2, a polyamine ö according einerr. ^R. ^ Claims 1 and 3 to 6, and optionally a solubilizer geiaai * one of claims 14, 16 or 17 ^ ¹ J. is mixed with a spreadable composition, whereupon the vinyl polymer is caused to swell and dissolve. 23. A method for connecting 2 surfaces to one another, characterized in that a composition according to Claims 1 to 11, 13 and 15 are applied to one or both surfaces, whereupon the composition becomes tacky leaves, the two surfaces are placed against each other and the composition is allowed to harden. 24. A method for connecting 2 surfaces to one another, characterized in that a composition according to a of claims 12, 14, 16 to 18 is applied to one or both surfaces, whereupon the composition becomes sticky leaves, the two surfaces are placed against each other and the composition is allowed to harden. 25. Structure, characterized in that their surfaces are interconnected by means of a composition according to any one of claims 1 to 11, 13 and 15. 26. Structures, characterized in that their surfaces by means of a composition according to one of claims 12, 14, 16 to 18 are connected to each other, 20982 3/0994,