DE4205860A1 - Reactive hot-melt adhesive and coating material - comprises mixt. of amino-terminated co:polyamide(s) and bis-maleimide(s) - Google Patents

Abstract

The use of a mixt. (I) contg. copolyamide(s) with at least one terminal amino gp. (II) and bis-maleimide(s) (III) as a reactive hot-melt adhesive or reactive coating material is claimed. Pref. (I) contains 80-99 (pref. 90-98, esp. pref. 92-97) wt.% (II) and 1-20 (pref. 2-10, esp. pref. 3-8) wt% (III). (II) has Mn 2000-20,000 and melting range 50-180 (pref. 60-130) deg.C, and is derived from at least 2 monomers comprising (a) alpha, omega-amino-carboxylic acids and/or lactams thereof or (b) equimol. amts. of prim. and/or sec. 2-20C diamines and/or polyoxyalkylene-diamines and 2-44C aliphatic diacids (up to 20 wt.% of which can be replaced by aromatic diacids). (III) are cpds. of formula (III) (where R = 2-20C linear, branched and/or cyclic alkylene, 6-50C aromatic aromatic/aliphatic or aromatic/cycloaliphatic hydrocarbylene, or a polyoxyalkylene gp. of formula -((CH2)a-O)b-(CH2)a- (IVA), -CHMe-CH2-(O-CH2-CHMe)c- (IVB), -CHM3-CH2-(O-CHMe-CH2)d-(O-CH2CH2)e-(O-CH2-CHMe)f- (IVC) or -CHMe-CH2-(O-CH2-CHMe)g-NH-CO-NH-(CHMe-CH2-O)g-CH2-CHMe- (IVD) (with a = 2-4; b = 1-100; c = 2-70; d + f = 2-3; e = 8-140; g 2-70)). USE/ADVANTAGE - For bonding and coating various materials (see below). (I) is used in the form of a powder, film or aq. dispersion, and is heated for 10-60 (pref. 20-40) secs. at 120-180 (pref. 140-160) deg.C (claimed). Also claimed are materials bonded with (I), namely textiles, wood fibre materials, plastics and/or metals, and materials coated with (I), esp. metals. W.r.t. prior-art copolyamide-based materials, (I) have improved heat resistance and are therefore suitable for a wider range of applications; (I) also have good chemical resistance and can be applied at very low temp.

Description

The invention relates to the use of a mixture which one or several copolyamides containing at least one terminal amino group, and one or more bismaleimides, as reactive hot melt adhesive or Reactive coating agent, as well as with the reactive hot melt adhesive or Reactive coating agents glued or coated substances.

The use of hot melt adhesives for gluing materials has gained importance in various fields. So is the use of Adhesives in the automotive industry for the production of composite parts widespread. In addition to the use of adhesives for engine compartment encapsulation In the automotive industry, hot melt adhesives are manufactured at position of composite parts in the interior of the vehicle (e.g. car sky, parcel shelf etc.).

In both cases, heat resistance of more than about 120 ° C, and a deformability of the composite material following the Gluing process required. Furthermore, such adhesives Deep drawing ability of the bonded composites, resistance to the in the plasticizers to be glued and optimal Adhesion to not - e.g. by plasma etching or radiation - pretreated materials required.

DE-C-27 01 431 describes the use of a hot melt adhesive Polyamide-based fabric film for gluing covering material with Polyurethane foam for automotive interior materials. However, the polyurethane foam must be covered with a PVC cover film be coated.

Hot melt adhesive compositions for bonding substrates Olefin polymers are made by fusing copolymers onto propylene base, ethylene copolymers with acrylic acid and / or their esters, and one Addition of binary copolymers based on ethylene and / or copolyamides obtained and are described in DE-A-39 08 953.  

It is also known to use copolyamides as hot melt adhesives in particular Use of textiles. This is how DE-C-23 24 160 describes it Copolyamides, process for their preparation and their use for Heat sealing. DE-A-32 48 776 also uses Copolyamides for heat sealing textiles described. Also disclosed DE-C-37 30 504 copolyamides containing caprolactam and laurolactam, Process for their preparation and their use for heat sealing Textiles.

All of the aforementioned hot melt adhesives based on copolyamides common that their heat resistance and their application temperature is determined by the melting range of the copolyamides. It means that such hot melt adhesive based on gopolyamide, which has a high heat resistance possess strength while maintaining a high application temperature demand what often disadvantages, for example with heat-sensitive substrates brings itself.

An attempt to address the disadvantages of copolyamides in terms of their heat resistance To achieve strength is undertaken in DE-A-23 07 346, the aqueous dispersions for high temperature resistant hot melt adhesives based of copolyamides, alkoxylated diamine resins and acidic catalysts for Gluing metal and / or rubber parts describes. These hot melt adhesive described have the disadvantage that they are only as aqueous dispersions and only with acidic catalysts, such as phosphoric acid or p-toluenesulfonic acid can be applied, making her Area of application is limited.

Bismaleinimide z. B. Found in the curing of poly olefins, polyurethanes and polyamides. So z. B. m-phenlenebismalein imid as hardener for chlorosulfonated polyethylene (Hypalon®) and Neoprene® used.

The modification of polyamide molding compounds from polyamide 6.10 with Bismaleinimiden is described by A.T. Voloschin et al. Zh. Prikl. Khim. (Leningrad) 60 (1987) 7, 1607-1610. In particular, the Reaction mechanism discussed, which both an addition of amino also allows amide groups on the maleimide double bond. With this Modification will improve the physical-mechanical  Properties such as B. the tensile strength is reached. The described Procedure for performing the modification (heating for 10 minutes 280 ° C) is unsuitable for the reactive systems described here. This also applies to the homopolyamide molding compositions described there Basis of polyamide 6.10, which is also for use in Reactive systems according to the invention are unsuitable.

The object of the present invention was to use copolyamides Due to their low heat resistance, only limited so far Scope z. B. was possible when heat sealing textiles, a wide one Use as reactive hot melt adhesive or reactive coating agent for Production of temperature-resistant bonds or coating compounds to make accessible, the application at very low Temperatures can take place.

The inventors could now surprisingly show that this task by using a mixture which contains one or more copoly amides containing at least one terminal amino group, and one or several bismaleimides, as reactive hot melt adhesive or coating can be solved.

The mixture used according to the invention contains, based on the Total amount of copolyamides and bismaleimides used, advantageously 80 up to 99% by weight of the copolyamides and 1 to 20% by weight of the bismaleimides. A mixture is preferably used, the 90 to 98 wt .-% of the copolyamides and contains 2 to 10% by weight of the bismaleimides. Is particularly preferred the use of a mixture with 92 to 97% by weight of the copolyamides and 3 up to 8% by weight of the bismaleimides. The percentages by weight are based on the Total amount of copolyamides and bismaleimides used.

The copolyamides according to the invention expediently have a number average molecular weight ( _s ) of 2,000 to 20,000, preferably at least 4,000 to at most 14,000.

They are expediently made up of at least two monomers which are selected from the group consisting of:

• a) α, ω-aminocarboxylic acids and / or their lactam form,  
• b) equimolar amounts of primary and / or secondary C ₂ - to C ₂₀ -diamines and / or ether diamines and aliphatic C ₂ - to C ₄₄ -dicarboxylic acids, which in an amount of up to 20 wt .-%, based on the total weight of the dicarboxylic acids can be replaced by aromatic dicarboxylic acids.

As the diamine component, cyclic and are common in the copolyamide sector acyclic aliphatic diamines and dicyclic aliphatic diamines, whose rings have branched or straight-chain alkylene radicals with 1 to 6 Carbon atoms can be linked, as well as corresponding polyoxy alkylene diamines can be used. Examples are hexamethylenediamine, piperazine, Isophoronediamine, dodecanediamine, methylpentamethylenediamine, trimethylhexa methylenediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane and polyoxyalkylene diamines of the formulas I ′ to IV ′:

H₂N - [(CH₂) _a O] _b - (CH₂) _a -NH₂ I ′,

in which a can be from 2 to 4 and b from 1 to 100, or

in which c can be from 2 to 70, or

in which the sum d + f can be from 2 to 3 and e from 8 to 140, or

in which g can be from 2 to 70.

As dicarboxylic acids which can usually be used in the production of Copolyamides or polyamides used, preferably straight-chain  Dicarboxylic acids are used. Be exemplary here Alkylene dicarboxylic acids with 4 to 10 methylene units such as adipic acid, Azelaic acid, sebacic acid and decanedicarboxylic acid, dimerized Fatty acids with up to 44 carbon atoms, as well as aromatic Dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid called.

The copolyamides can be prepared in a manner known per se. It is e.g. B. described in DE-C-23 24 160 and DE-A-32 48 776. It is usually preferred at temperatures from about 200 to 300 ° C about 250 ° C to 290 ° C, and optionally at pressures up to about 50 bar, preferred 10 to 30 bar precondensed. It is then reduced to normal pressure and with nitrogen gas purge for a few more hours, preferably post-condensed at 250 to 300 ° C for about 1 to 3 hours. The Amino termination of the copolyamides is carried out in a manner known per se Addition of a mono- or diamine component achieved as a chain terminator.

The copolyamides expediently have a melting range between 50 and 180 ° C, preferably from 60 to 130 ° C, - measured on a KOFLER- Heating table microscope - on.

Compounds of the following are expediently used as bismaleimides general formula used:

where R can be one of the following groups:

• - Straight-chain, branched and / or cycloaliphatic alkylene radicals with 2 up to 20 carbon atoms,
• - aromatic or aromatic / aliphatic or aromatic / cycloalipha table hydrocarbon residues with 6 to 50 carbon atoms,  
• - Polyoxyalkylene groups of the formulas I to IV: - [(CH₂) _a O] _b - (CH₂) _a - I,

in which a can be from 2 to 4 and b from 1 to 100, or

in which c can be from 2 to 70, or

in which the sum d + f can be from 2 to 3 and e from 8 to 140, or

in which g can be from 2 to 70.

Aromatic or aromatic / aliphatic or aromatic / cycloaliphatic Hydrocarbon residues with 6 to 50 carbon atoms are preferred from selected from the group consisting of 4,4'-diphenylmethane, 4,4'-diphenylpropane, 4,4'-diphenylsulfone, 4,4'-diphenyl ether, 2,4-tolylene, 1,3-phenylene, 1,4-phenylene residues and indane derivatives, such as. B. 6-maleimide-1- (4'- maleinimidphenyl) -1,3,3-trimethylindane. Is particularly preferred the use of 4,4'-diphenylmethane bismaleimide (matrimide 5292 A, Commercial product from Ciba-Geigy) and from m-phenylene bismaleimide (HVA-2, commercial product from Dupont).

The mixture according to the invention can be dry in a known manner mixture or melt blend, as a film or in the form of aqueous Dispersions can be used. When making the melt blend care should be taken to ensure that processing is below temperature occurs in which an undesirable reaction between the components entry.  

The mixture according to the invention can, depending on the application, if necessary other common additives, such as processing aids, Colorants, antioxidants and / or flammability reducing agents contain. A large number of such agents are known to those skilled in the art as Commercial products are known.

If powders or dispersions are used, they can also be used known machines applied to one of the substrates to be bonded and are sintered by using elevated temperatures, so that the Reactive adhesive adheres firmly to the substrate. It is important to ensure that the sintering temperature is below the temperature at which one undesirable reaction of the component takes place. The substrate can do so can be stored and shipped and later with the desired other Substrate are glued. But it can also be glued immediately of the substrates.

Gluing with the reactive hot melt adhesive according to the invention takes place in usually by pressing the substances to be bonded at temperatures of 120 to 180 ° C for a period of 10 to 60 seconds. Especially bonding temperatures of 140 to 160 ° C. and one are preferred Pressure time from 20 to 40 seconds. You get temperature-resistant Hot melt adhesive compositions whose melting point is greater than about 200 ° C is. In contrast, the copolyamides used have a melting point range between 50 and 180 ° C.

Coating with the reactive coating agent according to the invention takes place in a manner known per se, for. B. electrostatically or after Vortex sintering process under basically the same conditions as that Gluing.

Another advantage of the bonds or Coatings are their chemical resistance. With a reactive hot melt adhesive according to the invention can be various substances such. B. glued textile fabrics, wood fiber materials, plastics or metals will.

In particular, with the reactive coating agent according to the invention Metals are coated.  

The invention is illustrated by the following examples:

I. Reactive hot melt adhesive compositions Comparative Example 1 (Acid-Terminated Copolyamide)

The following monomers were weighed out in a commercially available autoclave:

4800 g caprolactam
4800 g laurolactam
1336.9 g adipic acid
1063.1 g hexamethylenediamine
120 g water
124.8 g adipic acid as a chain terminator

The loaded autoclave was heated to 290 ° C. with the exclusion of air, an internal pressure of 25 bar being established. The agitator was set to 50 rpm at a pressure of 25 bar. After the temperature of 290 ° C. had been reached, it was precondensed at 25 bar for two hours. The mixture was then reduced to normal pressure and split off for a total of 90 minutes while flushing with nitrogen gas. The acid-terminated copolyamide thus produced has a number average molecular weight ( _s ) of 14,000 (determined by titration of the end groups) and melts at 115-125 ° C. To produce the bonds, the product is ground with liquid nitrogen while cooling and sieved to 0-200 µm.

Comparative Example 2 (acid-terminated copolyamide + bismaleimide)

95 parts by weight of the ground copolyamide powder from Comparative Example 1 with 5 parts by weight of m-phenylene bismaleimide (HVA-2, commercial product from Dupont) and homogeneous in a commercial mixer mixed (dry blend).

Comparative Example 3 (Diamond-terminated copolyamide without bismaleimide)

The procedure is as in Comparative Example 1, but 154.7 g of hexamethylenediamine are used as chain terminators instead of adipic acid. The diamond-terminated copolyamide thus produced has a number average molecular weight ( _n ) of 9,000 and melts at 115-120 ° C. To produce the bonds, the product is ground with liquid nitrogen while cooling and sieved to 0-200 µm.

example 1

The procedure is as in Comparative Example 1, but 99.5 g of hexamethylenediamine are used as chain terminators instead of adipic acid. The diamond-terminated copolyamide thus produced has a number average molecular weight ( _n ) of 14,000 and melts at 115-125 ° C. The product is ground with liquid nitrogen while cooling and sieved to 0-200 µm. To produce the reactive hot melt adhesive, 95 parts by weight of this powder are mixed with 5 parts by weight of 1,3-phenylenebismaleinimide (HVA-2) and mixed as in Comparative Example 2.

Example 2

The procedure is as in Comparative Example 1, but 231.6 g of hexamethylenediamine are used as chain terminators instead of adipic acid. The diamond-terminated copolyamide thus produced has a number average molecular weight ( _n ) of 6000 and melts at 118-121 ° C. The product is ground with liquid nitrogen while cooling and sieved to 0-200 µm. To produce the reactive hot melt adhesive, 95 parts by weight of this powder are mixed with 5 parts by weight of HVA-2 and mixed homogeneously.

Example 3

The procedure is as in Example 2, but 95 parts by weight of the Copolyamide powder for the production of the reactive hot melt adhesive with 5% by weight Parts of dodecamethylene bismaleimide are added and mixed homogeneously.

Example 4

The following monomers were weighed out in a commercially available autoclave:

2400 g caprolactam
910.8 g hexamethylenediamine
1489.2 g azelaic acid
2400 g of aminoundecanoic acid
491.3 g triethylene glycol diamine (H₂N-CH₂-CH₂ (-O-CH₂-CH₂) ₂-NH₂) (Jeffamine EDR 148, commercial product of TEXACO)
1908.7 g Empol 1008® (commercial product from Quantum Chemical Corporation; dimerized C-18 fatty acids of the general formula X (-R₁) (- R₂) (- R₃-COOH) (- R₄-COOH); exact structure unknown)
174 g of hexamethylenediamine as a chain terminator

The procedure followed was as in Comparative Example 1, which gave a diamine-terminated copolyamide with a number average molecular weight ( _s ) of 8,000. The melting range was 70-78 ° C. The product was ground with liquid nitrogen while cooling and sieved to 0-200 μm. To produce the reactive hot melt adhesive, 95 parts by weight of the powder were then mixed with 5 parts by weight of 4,4'-bismaleimidodiphenyl methane (MATRIMID 5292 A, commercial product from CIBA GEIGY) and mixed homogeneously.

Example 5

The procedure is as in Example 3, but the reactive powder mixture dissolved in methanol / dichloromethane (2: 1) under reflux. After cooling down The room temperature is poured onto a fat-free glass plate and brought to 200 µm layer thickness using a doctor blade. After this Evaporation of the solvent mixture gives a reactive one Hot melt adhesive film with a layer thickness of approx. 50 µm.

Example 6

The procedure is as in Example 2, but hexamethylene bismaleimide used instead of HVA-2.

Example 7

The procedure is as in Example 1, but using 5 parts by weight of a bismaleimide from triethylene glycol diamine (H ₂ N-CH ₂ -CH ₂ (-O-CH ₂ -CH ₂ ) ₂ -NH ₂ ; Jeffamine EDR 148 from TEXACO) instead of HVA-2.

Example 8

The procedure is as in Example 1, but 5 parts by weight of hexa are used methylene bismaleimide instead of HVA-2.

Example 9

The following monomers were weighed out in a commercially available autoclave:

180 g aminoundecanoic acid
284.8 g piperazine
123.85 g azelaic acid
611.35 g dodecanedioic acid
17.2 g piperazine as chain terminator

The procedure was further as in Comparative Example 1, which gave a diamine-terminated copolyamide with a number average molecular weight ( _n ) of 6,000. The melting range was 111-115 ° C. The product was ground with liquid nitrogen while cooling and sieved to 0-200 μm. To produce the reactive hot melt adhesive, 95 parts by weight of this powder were then mixed with 5 parts by weight of HVA-2 and mixed homogeneously.

Example 10

The following monomers were weighed out in a commercially available autoclave:

432 g caprolactam
240 g AH salt (salt from adipic acid and hexamethylene diamine)
528 g of aminoundecanoic acid
17 g octadecylamine as chain terminator
30 ml of deionized water

The procedure followed was as in Example 1, which gave a monoamine-terminated copolyamide with a number average molecular weight ( _n ) of 13,000. The melting range was 115-120 ° C. The product was ground with liquid nitrogen while cooling and sieved to 0-200 μm. To produce the reactive hot melt adhesive, 95 parts by weight of this powder were then mixed with 5 parts by weight of HVA-2 and mixed homogeneously.

Example 11

The procedure was as in Example 10, but 44 g of octadecylamine were used as chain terminators. A monoamine-terminated copolyamide having a melting range of 115-120 ° C. and a number average molecular weight ( _s ) of 5000 was thus obtained. The product was ground and sieved as described in Example 10 and 95 parts by weight of it were mixed with 5 parts by weight of HVA -2 mixed.

Example 12

97 parts by weight of the copolyamide from Example 4 were in an extruder 100 ° C mixed with 3 parts by weight of HVA-2, extruded into a thread and then granulated. The speed of the extruder was 30 rpm. A Crosslinking during the incorporation of the bismaleimide could not be found in the melt.

Example 13

The copolyamide from Example 1 was used. However, 97% by weight Parts of the 0-200 µm powder are only mixed homogeneously with 3 parts by weight of HVA-2.

II. Adhesion experiments 1) Heat resistance of a composite textile / wood fiber boards a) Production of the bonds

The (reactive) hot melt adhesive from comparative examples 1 to 3 and from Examples 1 to 4, 6 and 10 to 13 were made from a substrate sprinkled with a wood fiber material and on a heatable on one side Press with a textile outer fabric at 150 ° C and 0.35 bar 30 seconds long pressed. Before starting the measurements, the mixture was left in a climate of 20 ° C / 65% for 24 h relax relative humidity. In the case of the cast film from Example 5  this was placed between the two substrates mentioned above and on pressed in the same way under the same conditions.

b) Measurement of the heat resistance

A statement about the heat resistance of the manufactured Bonding was made at different temperatures.

Test specimen of the bonds described above with a width of 50 mm have been produced. The flexible, textile outer fabric was made on one Distance of 10 mm peeled off. The test specimen was placed vertically in a Circulating air heat level placed and on the peeled off part of the upper body a weight of 50 g was hung, the peeling at an angle of 180 °. The temperature in the oven is increased from 120 to 160 ° C, with a temperature increase of 10 ° C after every 30 minutes. It was measured whether and how many cm the outer fabric is torn off.

The results are summarized in the tables.

In the samples from Examples 1 to 6 and 10 to 13 were also after Not noticed any changes (peeling) for 24 hours at 160 ° C, while the samples from Comparative Examples 1 to 3 already Peel off completely at 120 ° C, so no heat-resistant bonds delivered.

2) Peel strength and tensile shear strength of a composite SMC / PU film a) Production of the bonds

An SMC molded body and, on the other hand, a Polyurethane film (PU film) reinforced on one side by textile outer material used. The commercially available SMC (sheet molding compound) consists of a filled polyester resin. The substrate surfaces were cleaned with isopropanol and the hot melt adhesive powder on the PU side of the Scattered. Then the one-sided was covered with textile Reinforced polyurethane film with the PU side with the SMC part at 0.5 bar pressed together for one minute at a joint temperature of 160 ° C.  

b) Measurement of the peel strength and tensile shear strength Peel strength

The bonds of the SMC molded body with the polyurethane side of the Polyurethane film reinforced on one side by textile outer fabric with the (Reactive) hot melt adhesives from Example 1 and Comparative Example 1 were as prepared above and the peel strengths were determined by peeling the bonded substrates from each other at a 180 ° angle and the necessary force in N / cm with an INSTRON® tensile testing machine measures.

The results are summarized in the tables.

The reactive hot melt adhesive from Example 1 shows a very good one Peel strength, while a conventional non-reactive hot melt adhesive material is not sufficient for this application.

Tensile shear strength

Measurement at 20 ° C and 65% relative humidity based on DIN 53 283.

Bonding of the SMC molded body to the polyurethane side of the polyurethane film reinforced on one side by textile outer material with the (reactive) hot melt adhesives of Examples 2, 6, 7, 8, 9 and Comparative Example 1 was produced as described above and the bonds were left for 48 hours before the start of the tests Relax for a long time at 20 ° C and 65% relative humidity and then measure the tensile shear strength by shearing the substrates with the help of an INSTRON® tensile testing machine and measuring the force required in N / cm ² . The test speed was 100 mm / min.

The results are summarized in the tables.

The bonds with the reactive hot melt adhesives showed very good ones Tensile shear strengths, while a conventional hot melt adhesive (Ver same example 1) has a low tensile shear strength.  

3) Metal coating by fluidized bed sintering

An 80-200 µm powder fraction of the reactive hot melt adhesive Example 1 was placed in a plunge pool, with the bottom from Air was flowed through. This created a fluidized one Powder-air mixture. In this sintered pool a was Degreased aluminum sheet heated to 200 ° C for 5 seconds immersed. The reactive adhesive powder sintered to the hot surfaces and then melted to an approx. 1 mm thick film, while curing took place at the same time. Man thus received a solvent-resistant metal coating Corrosion protection, good adhesion and temperature resistance, during the same coating, carried out with the powder Comparative Example 1, no solvent and temperature resistance as well as poorer corrosion protection.

Table 1

Legend to the tables

Mol. Weight: The molecular weight of the copolyamides produced was determined by potentiometric titration of the end groups.
End groups: end groups of the copolyamides.
Melting range of the copolyamides: Melting range of the copolyamides measured with a KOFLER hot stage microscope.
Bismaleinimide: The information in brackets explains how much wt .-% bismaleinimide based on the total amount of copolyamide and bismaleinimide contains the reactive hot melt adhesive. The abbreviations used are explained below:
HVA-2: m-phenylene bismaleimide (commercial product from Dupont)
C ₁₂ -BM: dodecamethylene bismaleimide (based on Ref. 1)
Matr.A: 4,4′-diphenylmethane-bismaleimide (Matrimid 5292 A, commercial product from Ciba Geigy)
C ₆ -BM: hexamethylene bismaleimide (based on Ref. 1)
EDR 148: bismaleimide from triethylene glycol diamine (EDR 148; commercial product from Texaco), produced based on literature 1
Bonding conditions (T / t): T indicates the temperature in ° C during bonding. t indicates the duration of the gluing in seconds. The pressure when gluing was 0.5 bar.
Gel content: Films were pressed from the substances of the comparative examples and examples under the bonding conditions given in the tables, the reaction taking place. The resulting films were extracted with methanol / dichloromethane (1: 1) for 8 hours. The weight difference before and after extraction was then determined. The insoluble fraction was referred to as the gel content and was regarded as a measure of the degree of crosslinking and the resistance to solvents.
1 N HCl at 80 ° C:
As described under "Gel content", foils were pressed and treated with 1 N HCl at 80 ° C. for 4 h. The solubility or insolubility illustrates the resistance to hydrolysis and the resistance in 1 N HCl.
Heat resistance:
Was determined as described under II 1) b) and is given in cm.
Peel strength: at RT (DIN 53357)
Peel strength measured in accordance with DIN 53 357. The bond was allowed to relax for 48 hours at 20 ° C. and 65% relative atmospheric humidity before the start of the measurements and the peel strength was then measured as described under II 2) b).
Peel strength: 144/40/95 (DIN 53 357)
Peel strength measured in accordance with DIN 53 357. The test specimens were stored at 40 ° C. and 95% relative atmospheric humidity for 144 h and then the peel strength was determined as described under II 2) b).
Tensile shear strength: (DIN 53 283)
was determined as described under II 2) b) based on DIN 53 283.
Ref. 1:
S. Takeda, H. Akiyama, H. Kakiuchi, J. Appl. Pole. Sci. 35, 1341 (1988).

Claims (15)

1. Use of a mixture which comprises one or more copolyamides, containing at least one terminal amino group, and one or comprises several bismaleimides, as reactive hot melt adhesive or Reactive coating agent. 2. Use of a mixture according to claim 1, characterized in that that the mixture, based on the total amount of used Copolyamides and bismaleimides, 80 to 99 wt .-% of copolyamides and Contains 1 to 20 wt .-% of bismaleimides. 3. Use of a mixture according to claims 1 to 2, characterized characterized in that the mixture, based on the total amount of used copolyamides and bismaleimides, 90 to 98 wt .-% of Contains copolyamides and 2 to 10 wt .-% of bismaleimides. 4. Use of a mixture according to claims 1 to 3, characterized characterized in that the mixture, based on the total amount of used copolyamides and bismaleimides, 92 to 97 wt .-% of Contains copolyamides and 3 to 8 wt .-% of bismaleimides. 5. Use of a mixture according to claims 1 to 4, characterized in that the copolyamide has a number average molecular weight ( _s ) of 2000 to 20,000. 6. Use of a mixture according to claims 1 to 5, characterized in that the copolyamide is composed of at least two monomers which are selected from the group consisting of:

• a) α, ω-amino carboxylic acids and / or their lactam form,
• b) equimolar amounts of primary and / or secondary C ₂ - to C ₂₀ - diamines and / or polyoxyalkylenediamines and aliphatic C ₂ - to C ₄₄ -dicarboxylic acids, in an amount of up to 20% by weight, based on the total weight of the Dicarboxylic acids, can be replaced by aromatic dicarboxylic acids.

7. Use of a mixture according to claims 1 to 6, wherein the Copolyamides have a melting range of 50 to 180 ° C, preferably 60 to 130 ° C. 8. Use of a mixture according to claims 1 to 6, wherein the bismaleimides are compounds of the general formula: where R can be one of the following groups:

• straight-chain, branched and / or cycloaliphatic alkylene radicals having 2 to 20 carbon atoms,
• aromatic or aromatic / aliphatic or aromatic / cyclo aliphatic hydrocarbon radicals having 6 to 50 carbon atoms,
• - Polyoxyalkylene groups of the formulas I to IV: - [(CH₂) _a -O] _b - (CH₂) _a - I, in which a can be from 2 to 4 and b from 1 to 100, or in which c can be from 2 to 70, or in which the sum d + f can be from 2 to 3 and e from 8 to 140, or in which g can be from 2 to 70.

9. Use of a mixture according to claims 1 to 8, characterized characterized in that the mixture in the form of a powder, in the form of a Film or in the form of an aqueous dispersion. 10. Use of a mixture according to claims 1 to 9, characterized characterized in that the mixture for hot melt gluing or coating heated to a temperature of 120 to 180 ° C for 10 to 60 seconds becomes. 11. Use of a mixture according to claims 1 to 10, characterized characterized in that the mixture for hot melt gluing or coating heated to a temperature of 140 to 160 ° C for 20 to 40 seconds becomes. 12. Glued with a reactive hot melt adhesive according to claims 1 to 11 Fabrics. 13. Bonded fabrics according to claim 12, characterized in that the bonded fabrics textile fabrics, wood fiber materials, plastics and / or metals. 14. With a reactive coating agent according to claims 1 to 11 be layered fabrics. 15. Coated fabrics according to claim 14, characterized in that the coated fabrics are metals.