WO2019101728A1

WO2019101728A1 - Reactive adhesive film having improved adhesive strength

Info

Publication number: WO2019101728A1
Application number: PCT/EP2018/081898
Authority: WO
Inventors: Uwe Schümann; Clementine PRADIER
Original assignee: Tesa Se
Priority date: 2017-11-22
Filing date: 2018-11-20
Publication date: 2019-05-31
Also published as: TW201927983A; DE102017220861A1

Abstract

The invention relates to a reactive adhesive film A and a reactive adhesive film B, comprising (a) a polymeric film-former matrix, (b) at least one first reactive monomer or reactive resin, (c) at least one second reactive monomer and (d) a reagent, selected from: reactive adhesive film A: an initiator, in particular a radical initiator, or alternatively reactive adhesive film B: an activator, characterized in that the at least one second reactive monomer (c) comprises one or more organofunctional silanes of general structure (I) (R1O-)xSi(R2)y(R3)z (I), wherein moieties R1 represent, independently of each other, a C1-C4-alkyl moiety, a C1-C4-alkoxy-C1-C6-alkyl moiety or an acetyl moiety; moiety R2 represents a moiety containing one or more carbon-carbon double bonds; moieties R3 represent, independently of each other, a C1-C18-alkyl moiety; and x = 1, 2 or 3; Y = 1 and z = 4 –x –y, and reactive adhesive systems comprising a reactive adhesive film A and/or a reactive adhesive film B for adhesively bonding various materials, such as metal, glass and/or plastic, with improved adhesive strength, in particular measured in the push-out test in the case of adhesive bonds of anodized aluminum against polycarbonate after a brief storage time of the finished adhesive bond at 23°C and 50% relative humidity.

Description

Reactive adhesive film with improved bond strength

description

Technical field of the invention

The present invention relates to a reactive adhesive film A and a reactive adhesive film B as well as reactive adhesive systems for bonding various materials, such as e.g. Metal, wood, glass and / or plastic. Adhesive film A and adhesive film B comprise in each case (a) a polymeric film former matrix and (b) at least one first reactive monomer or reactive resin, (c) at least one second reactive monomer, wherein the at least one second reactive monomer comprises at least one organofunctional silane with carbon Carbon double bond (s). Adhesive film A comprises at least one initiator, in particular a radical initiator, and adhesive film B comprises at least one activator.

The reactive adhesive systems comprise a reactive adhesive film A according to the invention and a reactive adhesive film B according to the invention, or a reactive adhesive film A according to the invention and a component B comprising an activator or a reactive adhesive film B according to the invention and a component A comprising an initiator, in particular a radical initiator. Furthermore, a method for producing a reactive adhesive film of the present invention as described above is provided.

General state of the art

Two-component adhesive systems have been generally known for years and described in detail in the literature. In these systems, a two-component adhesive system is applied to the parts to be bonded, usually two liquid components are used. For example, in chemically-reactive polymerization adhesive systems, one component consists of one radical-forming substance (also called hardener or initiator) and the monomers to be polymerized and the other component of an activator and the monomers to be polymerized. After mixing or at least contacting the two components, the radical-forming substance is split by the activator into two radicals and the polymerization reaction of the monomers to be polymerized begins. The radical polymerization of the monomers then takes place until a chain termination and the adhesive cures, whereby a permanent bonding of the parts to be bonded is achieved.

Disadvantage of such liquid polymerization adhesive systems is that their application is often dirty, since the two components usually liquid to pasty on the parts to be bonded must be applied.

Alternatively, EP 0 300 847 A1, WO 2014 202 402 A1 and WO 2015 062 809 propose polymerization adhesive systems in the form of films or adhesive tapes. Although the fundamental disadvantage of the liquid systems is thus eliminated, these adhesive systems also do not meet certain requirements. For example, in applications of the electronic industry there is often a demand to achieve high bond strengths on anodized aluminum. The counter substrate is usually a plastic, often polycarbonate. The bond strength is usually measured in the push-out test. In this case, a round sample disc made of said plastic is glued against a square perforated plate made of anodized aluminum. Both the activation and the curing of the adhesive system should preferably be carried out at room temperature. To test the bond strength after complete curing, a mandrel is pressed through the hole in the perforated plate perpendicular to the round specimen until the bond dissolves. The pressure acting immediately before releasing is the push-out value. As a rule, push-out values of greater than or equal to 3.5 N / mm ² are required, which are not achieved with the known polymerization adhesive systems in the form of films or adhesive tapes.

Object of the present invention

The present invention is based on the object to provide an improved, reactive two-component adhesive system. Against this background beats the present invention provides a reactive adhesive film A or B improved in terms of the achievable adhesive strength. The reactive adhesive films A and B together form or are part of an improved reactive adhesive system to circumvent the above-described problems of the known liquid two-component adhesive systems as well as the known polymerization adhesive systems in the form of films or adhesive tapes.

In particular, a reactive adhesive film A or B is provided, which is easy to handle, ideally already has pressure-sensitive adhesive, so that there is no slippage during application to the substrates to be bonded and a more accurate bonding than in the liquid polymerization adhesive systems, which in the Technology are known is enabled.

More particularly, the reactive adhesive system of the present invention is characterized by having improved bond strength in bonding anodized aluminum to polycarbonate as measured by the push-out test.

Summary of the invention

The present invention relates to a reactive adhesive film A and a reactive adhesive film B, as well as reactive adhesive systems comprising at least one of these reactive adhesive films. The reactive adhesive film A and the reactive adhesive film B each comprise (a) a polymeric film former matrix and (b) at least a first reactive monomer or reactive resin, (c) at least one second reactive monomer, and (d) a reagent, the at least one second reactive monomer one or more organofunctional silanes of the general structure (I)

(R ¹ O-) x Si (R ² ) y (R ³ ) _z (I), wherein

each R ^{1 is} independently a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ alkoxy C ₁ -C ₆ alkyl radical or an acetyl radical;

the radical R ^{2 is} a radical containing one or more carbon-carbon double bond (s);

the radicals R ³ independently of one another are a C ¹ -C 6 -alkyl radical; and

x = 1, 2 or 3; Y = 1 and z = 4 - x - y; The reagent (d) in the case of the reactive adhesive film A comprises an initiator, in particular a radical initiator, in the case of the reactive adhesive film B, an activator.

At least one of the reactive adhesive films A or B is part of a reactive adhesive system. The reactive adhesive system thus comprises either a reactive adhesive film A according to the invention and a reactive adhesive film B according to the invention, or a reactive adhesive film A according to the invention and a component B comprising an activator, or a reactive adhesive film B according to the invention and a component A comprising an initiator, in particular a radical initiator ,

By contacting the reactive adhesive films A and B or the reactive adhesive film A and component B or the reactive adhesive film B and component A, the reactive adhesive films cure. If contact is made between two substrates and they are in contact with the reactive adhesive films according to the invention, bonding is produced. Both component A, comprising an initiator, in particular radical initiator, and component B, comprising an activator, can be a film, a substance, a mixture of substances, or a solid or liquid preparation.

Detailed description of the invention

According to the invention, the object described above is achieved by a two-part reactive adhesive system.

In a first variant, the reactive adhesive system comprises a reactive adhesive film A and a reactive adhesive film B.

Adhesive film A comprises an initiator, in particular a radical initiator, while adhesive film B comprises an activator.

When the adhesive films A and B come into contact with each other, the initiator and activator also come into contact with each other, and thus a radical polymerization is initiated. The radical polymerization takes place in both adhesive films and leads to the curing of both adhesive films.

The curing of a reactive adhesive film A or B according to the invention can also be triggered in another way than by bringing these two reactive adhesive films A and B into contact. Adhesive film A may be brought into contact with films, substances, mixtures of substances or solid or liquid preparations containing at least one activator or cured by contacting it with the activator itself. Adhesive film B can be brought into contact with films, substances, mixtures of substances or solid or liquid preparations which contain at least one initiator, in particular free-radical initiator, or are cured by contacting them with the initiator, in particular free radical initiator itself.

The reactive adhesive system thus comprises, in a second variant, a reactive adhesive film A according to the invention and a component B comprising an activator, and in a third variant a reactive adhesive film B according to the invention and a component A comprising an initiator, in particular a radical initiator.

The cure rate depends, inter alia, on the exact composition of the two reactive adhesive films A and B or, if appropriate, the other components A or B. As a rule, the curing proceeds relatively slowly, that is within minutes or hours, rarely within seconds. After the curing has been triggered, thus usually enough time - usually several minutes - to make the bonding. Thus, it is possible to trigger the curing and make the bonding shortly thereafter. Alternatively, it is also possible first to apply adhesive film A or optionally component A to the substrate to be bonded and adhesive film B or optionally component B to the other substrate to be bonded, and then bring A and B into contact with each other and thus to cure.

The reactive adhesive film is characterized by comprising a polymeric film former matrix (a), at least one first reactive monomer or reactive resin (b), at least one second reactive monomer (c), and a reagent (d).

The at least one second reactive monomer comprises one or more organofunctional silanes of the general structure (I)

(R ¹ O-) _x Si (R ² ) y (R ³ ) z (I) wherein

the radicals R ³ independently of one another are a C ₁ -C ₁₈ -alkyl radical; and

x = 1, 2 or 3; Y = 1 and z = 4 - x - y. The reagent (d) in the reactive adhesive film A is selected from an initiator, especially a radical initiator, and the reactive adhesive film B is an activator.

Furthermore, a process for producing a reactive adhesive film A or B according to the invention is disclosed, the process comprising the following steps:

1 . Dissolving and / or finely distributing the ingredients in one or more solvents and / or water,

2. mixing the dissolved or finely divided ingredients,

3. coating a release liner or paper, a carrier material or a pressure-sensitive adhesive with the mixture of dissolved or dispersed ingredients after step 2,

4. Evaporation of the solvent and / or water and

5. Optionally, wind the reactive adhesive film into a roll. wherein the ingredients comprise (a) a polymeric film former matrix, (b) at least one first reactive monomer or reactive resin, (c) at least one second reactive monomer, and (d) a reagent as described.

Steps 1. and 2. can also be done in one step, the ingredients are thus dissolved and / or finely distributed simultaneously.

Furthermore, a composite body is disclosed, which is connected by the reactive adhesive system according to the invention.

Hereinafter, the ingredients of the reactive adhesive film A and B of the present invention and the reactive adhesive system of the present invention will be described in detail.

Polymeric film former matrix

The reactive adhesive films according to the invention basically consist of a matrix which is referred to below as the polymeric film-forming matrix in which the reactive monomers to be polymerized and / or reactive resins are contained. The purpose of this matrix is to form an inert skeleton for the reactive monomers and / or reactive resins, so that they are not - as in the prior art - liquid and thus can trigger the problems mentioned, but are stored in a film or a film. In this way, easier handling is ensured.

Inert in this context means that the reactive monomers and / or reactive resins under suitably selected conditions (eg at sufficiently low temperatures, in particular at room temperature) substantially do not react with the polymeric film former matrix.

Suitable film-forming matrices for use in the present invention are preferably selected from the following list: a thermoplastic polymer, e.g. a polyester or copolyester, a polyamide or copolyamide, a polyacrylic acid ester, an acrylic acid ester copolymer, a polymethacrylic acid ester, a methacrylic acid ester copolymer, thermoplastic polyurethanes and chemically or physically crosslinked substances of the abovementioned compounds. In addition, blends of different thermoplastic polymers can be used.

Furthermore, elastomers and thermoplastic elastomers are conceivable alone or in admixture as a polymeric film-forming matrix. Preference is given to thermoplastic polymers, in particular semicrystalline.

Particularly preferred are thermoplastic polymers with softening temperatures less than 100 ° C. In this context, the term softening point stands for the temperature at which the thermoplastic granules stick to themselves. If the component of the polymeric film former matrix is a semicrystalline thermoplastic polymer, then, in addition to its softening temperature (which is associated with the melting of the crystallites), it very preferably has a glass transition temperature of at most 25 ° C., preferably at most 0 ° C. ,

In a preferred embodiment of the invention, a thermoplastic polyurethane is used. Preferably, the thermoplastic polyurethane has a softening temperature of less than 100 ° C, especially less than 80 ° C.

In a particularly preferred embodiment of the invention Desmomelt® 530 is used as a polymeric film former matrix commercially available from the Covestro AG, 51373 Leverkusen, Germany. Desmomelt® 530 is a hydroxyl-terminated, largely linear, thermoplastic, highly crystallizing polyurethane elastomer.

According to the invention, the amount of the polymeric film-forming agent matrix is in the range of about 10 to 90% by weight, preferably about 20 to 50% by weight, based on the total mixture of the constituents of the reactive adhesive film. More preferably, from 25 to 45 weight percent, most preferably from about 30 to 40 weight percent of the polymeric film former matrix, based on the total blend of the reactive adhesive component components, is employed. The total mixture of the constituents of the reactive adhesive film here stands for the total amount of the polymeric film former matrix (a) used, the reactive first monomers or reactive resins (b), the reactive second monomers (c) of the reagent (d) and other optional substances , which is obtained as the sum (in% by weight).

First reactive monomer or reactive resin

As used herein, the first reactive monomer or reactive resin is intended to be a monomer or resin that is particularly capable of radical polymerization.

According to the invention, a suitable, first reactive monomer is selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, vinyl compounds and / or oligomeric or polymeric compounds having carbon-carbon double bonds, furthermore nitrogen-containing vinyl compounds and / or nitrogen-containing, oligomeric or polymeric Compounds with carbon-carbon double bond (s). The term "compound having carbon-carbon double bond (s)" as used herein means a compound having one or more double bonds.

In a preferred embodiment, the first reactive monomer is one or more members selected from the group consisting of: methyl methacrylate (CAS No. 80-62-6), methacrylic acid (CAS No. 79-41-4), cyclohexyl methacrylate (CAS No. 101-43-9), tetrahydrofurfuryl methacrylate (CAS No. 2455-24-5), 2-phenoxyethyl methacrylate (CAS No. 10595-06-9), hydroxyalkyl methacrylates, 2-hydroxyethyl methacrylate (CAS No. 868-77-9), 2-hydroxypropyl methacrylate (CAS Nos. 923-26-2 and 27813-02-1), 4-hydroxybutyl methacrylate (CAS Nos. 29008-35-3 and 997-46-6), di- (ethylene glycol) methyl ether methacrylate (CAS No. 45103-58-0) and / or ethylene glycol dimethacrylate (CAS No. 97-90-5) ,

Particular preference is given to using N-vinylcaprolactam (CAS No. 2235-00-9) and / or N-vinylpyrrolidone (CAS No. 88-12-0) as the first reactive monomers to be polymerized.

In a particularly preferred embodiment of the invention, the reactive adhesive film A or B comprises a mixture of 2-phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-vinylcaprolactam and ethylene glycol dimethacrylate as the first reactive monomers to be polymerized.

In addition, more reactive resin (s) may be present, such. B. oligomeric mono-, di-, tri- and higher functionalized (meth) acrylates. They are very advantageously used in admixture with at least one first reactive monomer as described above.

Each of these preferred embodiments can be used according to the invention with a thermoplastic polyurethane, e.g. Desmomelt® 530 can be combined as a polymeric film former matrix.

The amount of the first reactive monomer (s) of the reactive resin (s) in the present invention is in the range of about 10-90% by weight, preferably about 40-70% by weight, based on the total mixture of reactive adhesive component components. Most preferably, about 45-65 weight percent of the first reactive monomer (s) / reactive monomer (s) based on the total blend of the reactive adhesive component (s) is employed. The total mixture of the components of the reactive adhesive film here stands for the total amount of the polymeric film former matrix (a), the first reactive monomers or reactive resins (b), the second reactive monomer (s) (c), the reagent (i.e. ) and other optional substances, which is obtained as a sum (in% by weight).

Second reactive monomer

As used herein, the second reactive monomer is also intended to mean a monomer capable of radical polymerization in particular. The at least one second reactive monomer comprises one or more organofunctional silanes of the general structure (I)

(R ¹ O-) _x Si (R ² ) y (R ³ ) z (I) wherein

x = 1, 2 or 3; Y = 1 and z = 4 - x - y.

The radicals R ¹ in preferred embodiments are methyl or ethyl groups, isopropyl groups, n-propyl groups, tert-butyl groups, methoxyethyl groups or acetyl radicals.

The radical R ² in a preferred embodiment represents a vinyl group, a methacryloxypropyl group, a methacryloxymethyl group, an acryloxypropyl group or an acryloxymethyl group.

The radicals R ³ are in preferred embodiments for methyl or ethyl groups.

In a preferred embodiment, the organofunctional silane comprises one or more members selected from the group consisting of: vinyltrimethoxysilane (CAS No. 2768-02-7), vinyldimethoxymethylsilane (CAS No. 16753-62-1), vinyltriethoxysilane (CAS No. 78-08-0), vinyldimethylethoxysilane (CAS No. 5356-83-2), vinylmethyldiethoxysilane (CAS No. 5507-44-8), vinyltrisisopropoxysilane (CAS No. 18023-33-1), vinyl tris (2-methoxyethoxy) silane (CAS No. 1067-53-4), vinyltriacetoxysilane (CAS No. 4130-08-9), 3-methacryloxypropyltrimethoxysilane (CAS No. 2530-85-0), 3 -

Methacryloxypropylmethyldimethoxysilane (CAS No. 14513-34-9),

Methacryloxymethyltrimethoxysilane (CAS No. 54586-78-6), methacryloxymethyl) methyldimethoxysilane (CAS No. 121 177-93-3), 3-methacryloxypropyltriethoxysilane (CAS No. 21 142-29-0), 3- Methacryloxypropylmethyldiethoxysilane (CAS No. 65100-04-1), 3-acryloxypropyltrimethoxysilane (CAS No. 4369-14-6) and / or 3-methacryloxypropyltriacetoxysilane (CAS No. 51772-85-1). In a particularly preferred embodiment of the invention, the reactive adhesive film A or B contains vinyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane as the second reactive monomer to be polymerized.

The amount of organofunctional silanes of the general structure (I)

is according to the invention in the range of about 0.1 to 10.0 wt.%, Preferably about 0.5 to 5.0 wt.%, Based on the total mixture of the components of the reactive adhesive film. The total mixture of the components of the reactive adhesive film here stands for the total amount of the polymeric film former matrix (a), the first reactive monomers or reactive resins (b), the second reactive monomer (s) (c), the reagent (i.e. ) and other optional substances, which is obtained as a sum (in% by weight).

Initiator, in particular radical initiator

As used herein, the term initiator, especially radical initiator (or hardener), is a compound that can initiate a polymerization reaction or crosslinking of the adhesive. However, the initiator, in particular free-radical initiator, takes part in the reaction process to a very small extent and consequently does not form a polymer component which determines the properties of the bond.

In the present invention, an initiator, especially a radical initiator, is added to the reactive adhesive film A.

Preference is given to radical initiators. It can be used all known in the art radical initiators. Preferred free-radical initiators are peroxides, hydroperoxides and azo compounds.

In a particularly preferred embodiment of the invention, the free-radical initiator is an organic hydroperoxide, especially α, α-dimethylbenzyl hydroperoxide, also known as cumene hydroperoxide (CAS No. 80-15-9), diisopropylbenzene hydroperoxide (CAS No. 26762-93 -6), tert-amyl hydroperoxide (CAS No. 3425-61-4), p-menthane hydroperoxide (CAS No. 26762-92-5), and 1,1,3,3-tetramethylbutyl hydroperoxide ( CAS No. 5809-08-5). Most preferably, a, a- Dimethylbenzyl hydroperoxide, diisopropylbenzene hydroperoxide and tert-amyl hydroperoxide.

The amount of the radical initiator according to the invention is in the range of about 1 to 20 wt.%, Preferably about 3 to 15 wt.%, Based on the total mixture of the components of the reactive adhesive film. Most preferably, about 5 to 12% by weight of the radical initiator, based on the total mixture of the constituents of the reactive adhesive film, is used. The total mixture of the components of the reactive adhesive film here stands for the total amount of the polymeric film former matrix (a), the first reactive monomers or reactive resins (b), the second reactive monomer (s) (c), the reagent (i.e. ) and other optional substances, which is obtained as a sum (in% by weight).

activator

As used herein, the term activator stands for a compound that enables or accelerates the polymerization process even at very low concentrations. Activators can also be called accelerators or accelerators. In particular, what is meant here is a substance which activates it by contacting it with an initiator such that polymerization is initiated in the presence of polymerizable monomers.

In the present invention, an activator is added to the reactive adhesive film B.

Suitable activators for use in the present invention when a radically polymerizable system is to be activated are, for example, selected from the group consisting of: an amine, a dihydropyridine derivative, a transition metal salt or a transition metal complex. In particular, tertiary amines and / or transition metal complexes are used for activating the radical-forming substance.

In one embodiment of the invention, the activator is 3,5-diethyl-1,2-dihydro-1-phenyl-2-propylpyridine (also called PDHP, CAS No. 34562-31 -7). In a further embodiment of the invention, a complex compound having a manganese, iron or cobalt ion as the central atom and a compound containing carbon-nitrogen double bonds is used as the ligand. The compound containing carbon-nitrogen double bonds is anionic in the complex compound. The manganese, iron or cobalt ion is doubly positively charged in the complex compound, while the compound containing carbon-nitrogen double bonds is doubly negatively charged. The manganese, iron or cobalt ion replaces in the complex compound in each case two hydrogen atoms which the ligand has carried to the nitrogen atoms before the conversion to the complex compound.

In a preferred embodiment of the invention, the ligand has a cyclic structure, preferably a porphyrin, porphyrazine or phthalocyanine ring structure. These structures are to be understood as framework structures. The ligands may optionally bear substituents in place of the carbon atoms bonded to H atoms. In this case one speaks of derivatives of these connections. Suitable substituents are selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, -OH, -NH 2, -NO 2 ·

A particularly suitable activator comprises manganese (II) phthalocyanine (CAS No. 14325-24-7), iron (II) phthalocyanine (CAS No. 132-16-1) or cobalt (II) phthalocyanine (CAS No. No. 3317-67-7). Most preferably, ferrous phthalocyanine (CAS No. 132-16-1) is used as the activator.

The amount of activator according to the invention is in the range of greater than 0 to about 10 wt.%, Preferably about 0.1 -5.0 wt.%. Most preferably, about 0. 2-3.0 wt.%, More preferably 0.5-2.0 wt.% Activator, based on the total mixture of the constituents of the reactive adhesive film, is used. The total mixture of the constituents of the reactive adhesive film is for this purpose the total amount of the polymeric film former matrix (a), the first reactive monomer or reactive resin (b), the second reactive monomer / second reactive monomer (c), the reagent (d). and other optional substances, which is obtained as a sum (in% by weight).

crosslinkers As used herein, the term crosslinker refers to chemical compounds capable of providing linear molecular chains with reactive functional groups to allow the linear structures to form three-dimensionally crosslinked structures through intermolecular bridge formation.

Typical examples of crosslinkers are chemical compounds which have two or more identical or different functional groups within the molecule or at the two molecule ends and consequently can crosslink together molecules of identical or different structures. In contrast to the initiator or activator, as described above, a crosslinker does not initiate polymerization but is a monomer, oligomer or reactive resin to be polymerized and is thus incorporated into the polymer network.

In a particularly preferred embodiment of the invention, ethylene glycol dimethacrylate (CAS No. 97-90-5) is used as crosslinker and / or additional reactive monomer.

Preferred crosslinkers are also diacrylates, dimethacrylates, triacrylates, trimethacrylates, higher functional acrylates and / or higher functional methacrylates.

Other components of the reactive adhesive film

The reactive adhesive films of the present invention may optionally contain other additives and / or adjuvants known in the art. Here, for example, fillers, dyes, nucleating agents, rheological additives, blowing agents, adhesive-enhancing additives (adhesion promoters, tackifier resins), compounding agents, plasticizers and / or aging, light and UV protection agents, for example in the form of primary and secondary antioxidants call.

Reactive adhesive film

As used herein, the term "adhesive film" (or adhesive layer or adhesive film) is intended to include a wholly or partially provided application of the particular ingredient mixture, as described below. Thus, for example, a point-like application of the constituent mixture, the to adhesive substrate surface (s) not completely covered, also lead to a permanent bonding in the context of the present invention.

In a preferred embodiment according to the invention, the reactive adhesive film A comprises a mixture of the following constituents: thermoplastic polyurethane, in particular Desmomelt® 530, 2-phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-vinylcaprolactam, ethylene glycol dimethacrylate, vinyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane and diisopropylbenzene - hydroperoxide ..

A preferred embodiment of the reactive adhesive film A according to the invention contains about 10 to 90% by weight of thermoplastic polyurethane, about 10 to 90% by weight of first reactive monomer (s), about 0.1 to 10.0% by weight. % organofunctional silanes of general structure (I) and about 1 to 20 weight percent diisopropylbenzene hydroperoxide, preferably about 20 to 50 weight percent thermoplastic polyurethane, about 40 to 70 weight percent first (s) monomer (s) ), about 0.5 to 5.0% by weight of organofunctional silanes of the general structure (I) and about 3 to 15% by weight of diisopropylbenzene-hydroperoxide, based on the total mixture of the constituents of the reactive adhesive film.

In a preferred embodiment according to the invention, the reactive adhesive film B comprises a mixture of the following constituents: thermoplastic polyurethane, in particular Desmomelt® 530, 2-phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-vinylcaprolactam, ethylene glycol dimethacrylate, vinyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane and iron (II) phthalocyanine.

A preferred embodiment of the reactive adhesive film B according to the invention contains about 10 to 90% by weight of thermoplastic polyurethane, about 10 to 90% by weight of first reactive monomer (s), about 0.1 to 10.0% by weight. % organofunctional silanes of the general structure (I) and greater than 0 to about 10% by weight of iron (II) phthalocyanine, preferably from about 20 to 50% by weight thermoplastic polyurethane, from about 40 to 70% by weight first (s) reactive (s ) Monomer (s), about 0.5 to 5.0% by weight of organofunctional silanes of the general structure (I) and about 0.1 to 5% by weight of iron (II) phthalocyanine, based on the total mixture of the constituents of the reactive adhesive film. As used herein, the total mixture of the components of the reactive adhesive film A or B refers to the total amount of the polymeric film former matrix (a), the first reactive monomer / monomer and / or the reactive resin / reactive resin (b) used, the second reactive monomer (s) (c), the reagent (d) and other optional substances obtained as the sum (in% by weight).

The reactive adhesive film of the invention generally has a layer thickness in the range of about 20 to 200 μm, preferably about 30 to 100 μm, more preferably about 40 to 60 μm and particularly preferably about 50 μm. For producing larger layer thicknesses, it may be advantageous to laminate several adhesive film layers together.

In addition, the reactive adhesive film according to the invention is characterized in that it preferably has pressure-sensitive adhesive properties. According to Römpp, such viscoelastic adhesives are defined as pressure-sensitive adhesives (Römpp Online 2013, document identifier RD-08-00162), whose set, dry film is permanently tacky at room temperature and remains tacky. The pressure-sensitive adhesive is applied by light pressure immediately on almost all substrates. As a light contact pressure here is a contact pressure of greater than 0 bar, which is exercised for a duration of greater than 0 seconds meant.

Reactive adhesive system

According to the invention, reactive adhesive films A or B, as described above, are used for a reactive adhesive system. In a first variant, the reactive adhesive system comprises a reactive adhesive film A and a reactive adhesive film B.

In addition, the invention provides a reactive adhesive system comprising two or more reactive adhesive films A and B, as defined above, characterized in that a first reactive adhesive film A contains an initiator, in particular a radical initiator, and a second reactive adhesive film B contains an activator and these two reactive ones Adhesive films A and B are alternately present.

In a second variant, the reactive adhesive system comprises a reactive adhesive film A and a component B comprising an activator as described above. The Component B may be a film, cloth, mixture of substances or a solid or liquid preparation containing at least one activator or the activator itself.

In a third variant, the reactive adhesive system comprises a reactive adhesive film B and a component A comprising an initiator, in particular a radical initiator, as described above. Component A may be a film, substance, mixture of substances or a solid or liquid preparation which contains at least one initiator, in particular free-radical initiator, or the initiator itself, in particular free-radical initiator.

The reactive adhesive systems are cured by contacting adhesive film A with adhesive film B or component B or adhesive film B with adhesive film A or component A.

The bringing into contact takes place over a wide area under moderate pressure, in particular at 1 to 10 bar, preferably at 3 bar, at room temperature (23 ° C). Optionally, higher or lower temperatures are also possible. The contact time is according to the invention at room temperature for a few seconds to a few minutes, preferably 60 to 240 seconds. The print can be applied by machine or manually.

If the reactive adhesive film A, as described above, previously applied to the substrate to be bonded, and the reactive adhesive film B, as described above, previously applied to the other substrate to be bonded, comes by contacting and thus initiated curing reaction a permanent bonding of the substrates to conditions. Alternatively, it is also possible to apply adhesive film A to the substrate to be bonded and component B to the other substrate to be bonded. Furthermore, alternatively, component A can also be applied to the one substrate to be bonded and adhesive film B to the other substrate to be bonded.

A further alternative procedure provides that adhesive film A is first applied to the one substrate to be bonded and applied to adhesive film A adhesive film B or a component B. Subsequently, the other substrate to be bonded is then applied to adhesive film B or component B. Instead of adhesive film A, it is also possible first to apply component A to the substrate to be bonded and to apply adhesive film B to component A.

As an alternative, it is also possible first to apply adhesive film B to the substrate to be bonded and to adhesive film B adhesive film A or a component A. be applied. Subsequently, the second substrate to be bonded is then applied to the adhesive film A or component A. Instead of adhesive film B, it is also possible initially to apply component B to the one substrate to be bonded and to apply adhesive film A to component B.

Furthermore, the reactive adhesive system of the invention may comprise further films, layers, adhesives as well as permanent and / or temporary supports.

Suitable support materials are known to a person skilled in the art. For example, films (polyester, PET, PE, PP, BOPP, PVC, polyimides), nonwovens, foams, fabrics and / or fabric films can be used as permanent substrates. Temporary supports should be provided with a release layer, wherein the release layer is usually made of a silicone release varnish or a fluorinated release varnish or has polyolefinic character (HDPE, LDPE).

Optionally, it may be necessary to pretreat the surfaces of the substrates to be bonded by a physical, chemical and / or physico-chemical process. Here, for example, the application of a primer or a primer composition is advantageous.

substrates

Suitable substrates which are suitable for bonding by means of the reactive adhesive system according to the invention are metals, glass, wood, concrete, stone, ceramic, textile and / or plastics. The substrates to be bonded may be the same or different.

The reactive adhesive system according to the invention is preferably used for the bonding of metals, glass and plastics. Particularly preferably, anodized aluminum is bonded to polycarbonate using the reactive adhesive system according to the invention. In this case, both the reactive adhesive film A and the reactive adhesive film B can be applied to the anodized aluminum. The metal substrates to be bonded can generally be made from all common metals and metal alloys. Preferably, metals such as aluminum, stainless steel, steel, magnesium, zinc, nickel, brass, copper, titanium, ferrous metals and alloys are used. The parts to be bonded can also be made of different metals.

Suitable plastic substrates include acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonates (PC), ABS / PC blends, PMMA, polyamides, glass fiber reinforced polyamides, polyvinyl chloride, polyvinyl fluoride, cellulose acetate, cycloolefin copolymers, liquid crystal polymers (LCP), polylactide , Polyether ketones, polyetherimide, polyethersulfone, polymethacrylmethylimide, polymethylpentene, polyphenyl ether, polyphenylene sulfide, polyphthalamide, polyurethanes, polyvinyl acetate, styrene acrylonitrile copolymers, polyacrylates or polymethacrylates, polyoxymethylene, acrylic ester-styrene-acrylonitrile copolymers, polyethylene, polystyrene, polypropylene and / or polyesters, such as eg Polybutylene terephthalate (PBT) and / or polyethylene terephthalate (PET).

Substrates can be painted, printed, steamed or sputtered.

The substrates to be bonded may take any form required for the use of the resulting composite. In the simplest form, the substrates are flat. In addition, three-dimensional substrates, e.g. are inclined to be bonded with the reactive adhesive film system according to the invention. The substrates to be bonded can also assume a wide variety of functions, such as, for example, housings, viewing windows, stiffening elements, etc.

Process for the preparation of a reactive adhesive film

The reactive adhesive films according to the invention are prepared by the process described below:

In a first step, the ingredients in one or more solvent (s) and / or water are dissolved or finely distributed. Alternatively, no solvent and / or water is necessary because the ingredients are already completely soluble in each other (possibly under the action of heat and / or shear). Suitable solvents are in the state of Technique known, wherein preferably solvents are used, in which at least one of the ingredients has a good solubility. Particularly preferred is acetone.

As used herein, the term ingredient includes the polymeric film former matrix, at least one first reactive monomer or reactive resin, at least one organofunctional silane of general structure (I), and a reagent in the reactive adhesive film A selected from an initiator, especially a radical initiator reactive adhesive film B selected from an activator, also optionally further additives and / or auxiliaries, as defined above.

Subsequently, the dissolved or finely divided ingredients are mixed in a second step. To prepare the mixture, conventional stirring devices are used. If necessary, the solution is also heated. Possibly. the ingredients are dissolved or dispersed at the same time and mixed.

Subsequently, in a third step, a release liner which preferably separates on both sides, a release paper which preferably separates on both sides, a carrier material or a precoated pressure-sensitive adhesive is coated with the mixture of the dissolved or finely divided ingredients according to step 2. The coating is done by the usual techniques known in the art.

After coating, the solvent and / or water is removed by evaporation in a fourth step.

Optionally, the reactive adhesive film can be wound into a roll in a further step.

For storage, the reactive adhesive films according to the invention can be covered with a further release liner or paper.

Kit for providing a reactive adhesive system according to the invention In addition, the invention provides a kit for providing a reactive adhesive system. This kit comprises in a first variant a reactive adhesive film A as described above and a reactive adhesive film B as described above.

In a second variant, the kit comprises a reactive adhesive film A and a component B comprising an activator as described above. The component B may be a film, substance, mixture of substances or a solid or liquid preparation containing at least one activator or be the activator itself.

In a third variant, the kit comprises a reactive adhesive film B and a component A comprising an initiator, in particular a radical initiator, as described above. Component A may be a film, substance, mixture of substances or a solid or liquid preparation which contains at least one initiator, in particular free-radical initiator, or the initiator itself, in particular free-radical initiator.

Typically, the kit according to the invention is used as follows:

The reactive adhesive film A is applied to the surface of the one substrate to be bonded. The reactive adhesive film B is applied to the surface of the other substrate to be bonded. Adhesive film A and adhesive film B are brought into contact and kept in contact for a few seconds to several minutes at room temperature (23 ° C) for periods of time, thereby starting the polymerization reaction and curing the adhesive system.

Alternatively, it is also possible to apply adhesive film A to the substrate to be bonded and component B to the other substrate to be bonded. Furthermore, alternatively, component A can also be applied to the one substrate to be bonded and adhesive film B to the other substrate to be bonded.

A further alternative procedure provides that adhesive film A is first applied to the one substrate to be bonded and applied to adhesive film A adhesive film B or a component B. Subsequently, the other substrate to be bonded is then applied to adhesive film B or component B. Instead of adhesive film A, it is also possible first to apply component A to the substrate to be bonded and to apply adhesive film B to component A. As an alternative, it is also possible first to apply adhesive film B to the one substrate to be bonded and to apply adhesive film A or a component A to adhesive film B. Subsequently, the second substrate to be bonded is then applied to the adhesive film A or component A. Instead of adhesive film B, it is also possible initially to apply component B to the one substrate to be bonded and to apply adhesive film A to component B.

Optionally, the above-described method may be repeated so as to achieve adhesion of the layers of substrate A-B-A-B substrate or substrate B-A-B substrate or substrate A-B-A substrate, etc. This can be advantageous if different pronounced adhesive properties between the substrates to be bonded and the adhesive films or components A and B are given.

composite body

Finally, according to the present invention, there is provided a composite body joined by the reactive adhesive film A or B of the present invention, the reactive adhesive system of the present invention as defined above or the kit of the present invention as defined above.

Experimental part

The following examples serve to illustrate the present invention, but should not be construed as limiting the scope of protection.

Preparation of a solution of the film former matrix

PU solution:

A 20% acetone solution of the film-forming polymer is prepared by first weighing 120 g of Desmomelt® 530 and 480 g of acetone into a screw-cap jar and sealing the screw-on glass. By several days of winding the screw jar on a roll bar, the Desmomelt® 530 is completely in solution brought. Depending on the rolling speed, the process takes about one to seven days.

Alternatively, the acetone solution may also be prepared by stirring the Desmomelt® 530 granules in acetone with a commercial laboratory stirrer.

example 1

Preparation of the reactive adhesive film A comprising a radical initiator

150.0 g of the 20% strength by weight acetone solution of Desmomelt® 530 (PU solution) are mixed with 26.7 g of 2-phenoxyethyl methacrylate, 18.7 g of 2-hydroxyethyl methacrylate, 12.6 g of 2-hydroxypropyl methacrylate, 1.0 g vinyltrimethoxysilane, 3.0 g of ethylene glycol dimethacrylate and 10.0 g of Peroxan® IHP-50 (50% strength by weight solution of diisopropyl hydroperoxide in diisopropylbenzene, Pergan) mixed with a commercial laboratory stirrer for 30 minutes.

The homogenous mixture obtained is spread with the aid of a commercial laboratory coating table (for example from SMO (Sondermaschinen Oschersleben GmbH)) with a doctor blade on a siliconized polyester film (release liner). Subsequently, the acetone is evaporated at 60 ° C in a convection oven for 10 minutes. The gap width during spreading is adjusted so that after evaporation of the solvent, a 50 pm thick film is obtained. The adhesive-tacky, reactive adhesive film A obtained is covered and stored with a second siliconized polyester film until it is adhesively bonded.

Preparation of the reactive adhesive film B comprising an activator

150.0 g of the 20% strength by weight acetone solution of Desmomelt® 530 (PU solution) are mixed with 29.9 g of 2-phenoxyethyl methacrylate, 21.0 g of 2-hydroxyethyl methacrylate, 14.1 g of 2-hydroxypropyl methacrylate, 1.0 g Vinyltrimethoxysilane, 3.0 g of ethylene glycol dimethacrylate and 1, 0 g of iron (II) phthalocyanine (quality: Sigma-Aldrich, purity about 90%) mixed with a commercial laboratory stirrer for 30 minutes, so that a mixture with dissolved portions.

The resulting mixture is spread on a siliconized polyester film (release liner) using a commercially available laboratory coating table with a doctor blade. Subsequently, the acetone is evaporated at 60 ° C in a convection oven for 10 minutes. The gap width during spreading is adjusted so that after evaporation of the solvent, a 50 pm thick film is obtained. The adhesive-tacky, reactive adhesive film B obtained is covered and stored with a second siliconized polyester film until it is adhesively bonded.

The percentage compositions of the reactive adhesive films A and B and of the previous solutions are listed in the following table together with the described initial weights:

Example 1, Solution and Reactive Adhesive Film A

Example 1, Solution and Reactive Adhesive Film B

In an analogous manner as in Example 1, the solutions and reactive adhesive films A and B of the further examples and comparative examples are prepared.

The following tables provide information on the compositions of the solutions and reactive adhesive films A and B in the further examples and comparative examples.

Example 2, Solution and Reactive Adhesive Film A

Example 2, Solution and Reactive Adhesive Film B

Example 3, Solution and Reactive Adhesive Film A

21

Example 3, Solution and Reactive Adhesive Film B

Example 4, Solution and Reactive Adhesive Film A

Example 4, Solution and Reactive Adhesive Film B

Example 5, Solution and Reactive Adhesive Film A

Example 5, Solution and Reactive Adhesive Film B

Example 6, Solution and Reactive Adhesive Film A

Example 6, Solution and Reactive Adhesive Film B

Example 7, Solution and Reactive Adhesive Film A

Example 7, component B

Unlike in the previous examples, component B is not spread on a siliconized polyester film (release liner) but thinner with a brush Layer applied directly to the open side of the reactive adhesive film A, after this was previously glued to one of the substrates to be bonded and the siliconized polyester film was removed. Afterwards, the other substrate is glued on within five minutes.

Example 8, Solution and Reactive Adhesive Film A

Example 8, component B

Component B is applied with a brush in a thin layer directly on the open side of the reactive adhesive film A, after this was previously glued to one of the substrates to be bonded and the siliconized polyester film was removed. Afterwards, the other substrate is glued on within five minutes.

Example 9, Component A.

Component A is applied with a brush in a thin layer directly on the open side of the reactive adhesive film B after it has been previously glued to one of the substrates to be bonded and the siliconized polyester film was removed. Afterwards, the other substrate is glued on within five minutes.

Example 9, Solution and Reactive Adhesive Film B

Comparative Example 1, Solution and Reactive Adhesive Film A

Comparative Example 1, Solution and Reactive Adhesive Film B

Comparative Example 2, Solution and Reactive Adhesive Film A

Comparative Example 2, Solution and Reactive Adhesive Film B

Comparative Example 3, Solution and Reactive Adhesive Film A

Comparative Example 3, Solution and Reactive Adhesive Film B

Comparative Example 4, Solution and Reactive Adhesive Film A

Comparative Example 4, Solution and Reactive Adhesive Film B

Comparative Example 5, Solution and Reactive Adhesive Film A

Comparative Example 5, Solution and Reactive Adhesive Film B

Push out test

The push-out test provides information on the bond strength of a double-sided adhesive product in the direction of the adhesive layer normal.

Sample preparation for the push-out test

From the reactive adhesive films A and B to be examined, which are each covered on both sides with a release liner, round die-cuts with a diameter of 21 mm are punched out. The T rennliner are then deducted from each side of a punched. The diecuts A or B are placed on a round sample disc made of polycarbonate ("Disc", first substrate, first specimen) with a diameter of 21 mm. The diecuts now adhere to the "disc". Subsequently, the still remaining on the diecuts release paper is peeled off. The discs are now equipped with the reactive adhesive films A or B.

The curing reaction is started by contacting the die-cuts A or B adhering to the "discs" with the die-cuts or counter-components.

If Punch A is on the "Disc", Punch B will be placed on Punch A exactly. Alternatively, component B is applied thinly to stamped sheet A with a brush stroke.

If stamped B is on the "Disc", then stamped stamping A will be placed on stamped blank B. Alternatively, component A is applied thinly to stamped B with a brushstroke.

After the start of the curing reaction, the subsequent bonding with the second substrate must take place within a maximum of one hour, since the curing reaction is now proceeding. In practice, the bonding takes place within five minutes. For further preparation of the bonds, if appropriate, the last remaining release liners still remaining on the diecuts are removed, so that the diecuts are in each case open.

Bonding for the push-out test

The second substrate (second specimen) is a square perforated plate made of anodized aluminum. The side lengths are each 40 mm. The hole is arranged centrally and round, the hole diameter is 9 mm.

The round specimens ("discs") equipped with the diecuts in the curing reaction are positioned on the perforated plate with the exposed side of the diecuts in such a way that the center of the round specimen and the center of the hole of the perforated plate lie one above the other. Subsequently, the composite of square perforated plate, stamped A / stamped B or stamped B / stamped A or stamped A / component B or stamped B / component A and the "disc" held together by the pressure-sensitive tackiness of the stamped pieces is placed in a pneumatic pressing device. It is exerted a pressing pressure of 3 bar. The composite is exposed to this pressure in each case 60 seconds (compression time) at 23 ° C. Then the pressure is released. The composite is then stored for three days at 23 ° C and 50% relative humidity. This leads to a gradually progressing hardening reaction within the diecuts and to a gradually increasing adhesion between the diecuts and to the substrates (test specimens). It thus comes to a bond with a gradual increase in strength over time.

Then the push-out tests are carried out.

Performing the push-out test

It is pressed by means of a clamped in a tensile testing machine through the hole in the perforated plate at a constant speed of 10 mm / min perpendicular to the round specimen ("disc") (ie parallel to the normal vector on the Prüfkörper-level, centered on the center of the hole Centered) until the bond dissolves so far that a pressure drop of 50% is registered. The pressure acting immediately before the pressure drop is the maximum pressure P _max . This value corresponds to the push out value [N / mm ² ] specified in the table. All measurements are carried out in an air-conditioned room at 23 ° C and 50% relative humidity. Results

Push-out test

discussion of the results

In the push-out test, when bonding polycarbonate "discs" to anodized aluminum, the required values of greater than or equal to 3.5 N / mm ^{2 are} achieved, the conditions being that the bonds occur at room temperature and a pressure of 3 bar and a pressing time of 60 seconds is applied. The values are achieved after a storage time of the bonded bond of 3 days. The storage conditions are 23 ° C and 50% relative humidity.

Comparative samples without organofunctional silane or with another silane only achieve significantly lower values. The fracture patterns on anodized aluminum are predominantly adhesive. By adding N-vinylcaprolactam, the fracture patterns can be improved somewhat in the direction of a cohesive fracture pattern. Likewise, slight improvements in the push-out values can thus be achieved.

Claims

claims

A reactive adhesive film A or B comprising (a) a polymeric film former matrix, (b) at least one first reactive monomer or reactive resin, (c) at least one second reactive monomer, and (d) a reagent selected from:

reactive adhesive film A: an initiator, in particular a radical initiator, or alternatively

reactive adhesive film B: an activator,

characterized in that

the at least one second reactive monomer (c) one or more organofunctional silanes of the general structure (I)

(R ¹ O-) x Si (R ² ) y (R ³ ) _z (I), wherein

the radicals R ¹ independently of one another are a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -alkyl radical or an acetyl radical;

the radicals R ³ independently of one another are a C ¹ -C 6 -alkyl radical; and x = 1, 2 or 3; Y = 1 and z = 4 - x - y.

2. Reactive adhesive film A or B according to claim 1, characterized in that the one or more organofunctional silanes of the general structure (I) are vinyl-containing silanes or silanes containing acryloxy or methacryloxy groups.

3. Reactive adhesive film A or B according to any one of claims 1 or 2, characterized in that

the at least one first reactive monomer or reactive resin at least one member selected from acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, preferably methyl methacrylate, methacrylic acid, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, a hydroxybutyl methacrylate isomers,

Di (ethylene glycol) methyl ether methacrylate and / or ethylene glycol dimethacrylate, a nitrogen-containing vinyl compound and / or a nitrogen-containing, oligomeric or polymeric compound having carbon-carbon double bond (s), in particular N-vinylcaprolactam and / or N-vinylpyrrolidone.

4. Reactive adhesive film A or B according to any one of the preceding claims, characterized in that

the polymeric film former matrix comprises a thermoplastic polymer, preferably a thermoplastic polyurethane, or an elastomer or a thermoplastic elastomer.

5. Reactive adhesive film A or B according to one of the preceding claims, characterized in that

the radical initiator comprises a peroxide, preferably a hydroperoxide, particularly preferably a, a-dimethylbenzyl hydroperoxide, diisopropylbenzene hydroperoxide or tert-amyl hydroperoxide.

6. Reactive adhesive film A or B according to any one of the preceding claims, characterized in that

the activator comprises a transition metal-phthalocyanine complex, preferably iron (II) phthalocyanine, manganese (II) phthalocyanine or cobalt (II) phthalocyanine.

7. Reactive adhesive film A or B according to any one of the preceding claims, characterized in that it has pressure-sensitive adhesive properties.

8. A reactive adhesive film A or B according to any one of the preceding claims, comprising

10 to 90% by weight of polymeric film former matrix,

From 10 to 90% by weight of at least one first reactive monomer or reactive resin,

0.1 to 10.0% by weight of organofunctional silanes of the general structure (I) and:

reactive adhesive film A: 1 to 20% by weight of radical initiator, or alternatively

reactive adhesive film B: greater than 0 to 10% by weight activator,

preferably

From 20 to 50% by weight of polymeric film former matrix, From 40 to 70% by weight of at least one first reactive monomer or reactive resin,

0.5 to 5.0% by weight of organofunctional silanes of the general structure (I) and:

reactive adhesive film A: 3 to 15% by weight of radical initiator; or alternatively

Reactive adhesive film B: 0.1 to 5% by weight of activator.

9. A reactive adhesive system comprising a reactive adhesive film A, comprising an initiator, in particular radical initiator according to one of the preceding claims, and a reactive adhesive film B, comprising an activator according to any one of the preceding claims.

10. A reactive adhesive system comprising a reactive adhesive film A, comprising an initiator, in particular radical initiator according to one of the preceding claims and a component B, comprising an activator.

1 1. A reactive adhesive system comprising a reactive adhesive film B, comprising an activator according to any one of the preceding claims and a component A, comprising an initiator, in particular radical initiator.

12. A reactive adhesive system according to claim 9, 10 or 1 1, comprising further films, layers, adhesives, carriers, release papers and / or release liners.

13. Use of a reactive adhesive film A or B according to any one of claims 1 to 8 and / or a reactive adhesive system according to any one of claims 9 to 12 for the bonding of materials made of metal, wood, glass and / or plastics.

14. A process for producing a reactive adhesive film A or B according to any one of claims 1 to 8, said process comprising the steps of:

1. Dissolving and / or finely distributing the ingredients in one or more solvents and / or water,

2. mixing the dissolved or finely divided ingredients,

4. Evaporation of the solvent and / or water and

5. Optionally, winding the reactive adhesive film into a roll, the ingredients selected from (a) a polymeric film former matrix, (b) at least one first reactive monomer or reactive resin, (c) at least one second reactive monomer, and (d) a reagent from an initiator, in particular free-radical initiator, or alternatively an activator, and optionally further additives and / or auxiliaries.

15. A composite body joined by the reactive adhesive system of any one of claims 9 to 12.