DE102017204525A1 - Laminated laminates for flexible packaging - Google Patents

Abstract

Disclosed are composite films which have a first and at least one second film, which are bonded together via an adhesive coating, wherein the adhesive coating contains at least one polymerizable vinyl compound selected from methylene malonates, Methylenbetaketoestern and Methylenbetadiketonen. The first and / or second film has a precoat adjacent to the adhesive coating. The precoat comprises at least one precoat polymer containing a plurality of basic groups selected from polymers having amino groups and aqueous dispersions of anionic polyurethanes. The adhesive coating has a thickness of 10 μm and less and the pre-coating has a thickness of 5 μm and less. The composite films are suitable for the production of flexible packaging.

Description

The invention relates to composite films which have a first and at least one second film which are bonded to one another via a specific adhesive coating, wherein the adhesive coating contains at least one polymerizable vinyl compound selected from methylene malonates, methylene beta tetoesters and methylene beta-diketones. The first and / or second film has a precoat adjacent to the adhesive coating. The precoat comprises at least one specific precoat polymer containing a plurality of basic groups. The composite films are suitable for the production of flexible packaging.

Laminate laminating adhesives, for example, for flexible food packaging, are often based on two-part adhesive polymer systems which generally require a crosslinker for sufficient adhesion, chemical resistance or heat resistance.

For this, the laminating adhesives are often formulated with isocyanate crosslinkers together with polyol components. The application of these systems can be carried out as solvent and water-free, 100% systems or as adhesive solutions based on organic solvent or as water-based, aqueous polymer dispersions.

In this case, a first film, for example made of plastic, aluminum or paper, applied to the adhesives and laminated after subsequent evaporation of solvent or water with a second film under pressure and usually elevated temperatures.

The disadvantage here is that these formulations have a relatively short pot life (so-called pot life) and may be questionable because of the reactive isocyanate crosslinker. Thus, it is desirable to provide alternative isocyanate-free laminating adhesives for flexible packaging. Moreover, conventional aqueous polymer dispersions require larger amounts of emulsifier to stabilize the dispersion. The disadvantage is that high quantities of emulsifier can reduce the immediate tackiness of aqueous laminating adhesive formulations.

Laminated products used for food packaging often contain gas barrier layers based on inorganic oxides such as SiOx or AlOx. Such surfaces are difficult to bond with conventional adhesives.

In the WO 2013/149168 For example, laminates made with methylene malonates, methylene beta tetoesters or laminating adhesives containing methylene beta-diketones are described, with fairly large amounts of adhesive used in the examples.

The object was to provide flexible film composite films made with an alternative, isocyanate-free, laminating adhesive. The adhesive is a one-component adhesive, but it could also be a two-component adhesive. The laminating adhesive should have a long pot life and develop a high bond strength in a short time at low application strength also for films comprising layers of inorganic oxides.

It has been found that the object can be achieved by the composite films described below. The invention relates to a composite film which has a first and at least one second film which are adhesively bonded to one another via an adhesive coating, wherein the adhesive coating contains at least one polymerizable vinyl compound selected from methylene malonates, methylene beta tetoesters and methylenebetadiketones,
wherein the first and / or second foil has a precoat adjacent to the adhesive coating, and
wherein the precoat comprises at least one precoat polymer, wherein the precoat polymer contains a plurality of basic groups and is selected from polymers having amino groups, aqueous dispersions of anionic polyurethanes, and
wherein the adhesive coating has a thickness of 10 microns and less and the pre-coating has a thickness of 5 microns and less.

The invention also provides a use of the composite film for the production of flexible packaging.

The invention furthermore relates to a corresponding process for producing composite films, in which a first film and at least one second film are bonded to one another via an adhesive coating, the adhesive coating containing at least one polymerizable, monofunctional or polyfunctional vinyl compound selected from methylene malonates, methylene beta tetoesters and methylene beta-diketones.
wherein the first and / or second foil has a precoat adjacent to the adhesive coating, and
wherein the precoat comprises at least one precoat polymer, wherein the precoat polymer contains a plurality of basic groups and is selected from polymers having amino groups, aqueous dispersions of anionic polyurethanes, and
wherein the adhesive coating has a thickness of 10 microns and less and the pre-coating has a thickness of 5 microns and less.

The molar ratio of the basic groups on the precoating monomer to the vinyl groups on the polymerizable vinyl compound is preferably 1 to 10 to 1 to 1 million, more preferably 1 to 20 to 1 to 10,000.

Methylenmalonates are compounds with at least one group ~OC (O) -C (C = CH ₂ ) -C (O) -O-

Methylene beta tetoesters are compounds having at least one group ~C (O) -C (C = CH ₂ ) -C (O) -O ~

Methylene betadiketones are compounds with at least one group ~ C (O) -C (C = CH ₂₎ -C (O) ~

Preferred methylene malonates are compounds of the formula R ^{1 is} -OC (O) -C (C =CH ₂ ) -C (O) -OR ²

Preferred methylene beta tetoesters are compounds of the formula R ¹ -C (O) -C (C =CH ₂ ) -C (O) -OR ²

Preferred methylene betadiketones are compounds of the formula R ¹ -C (O) -C (C =CH ₂ ) -C (O) -R ² wherein R ¹ , R ^{2 are} independently C 1 -C 15 alkyl, C 2 -C 15 alkenyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C1-C15-alkyl), aryl, aryl- (C1-C15-alkyl), heteroaryl or heteroaryl- (C1-C15-alkyl), or alkoxy- (C1-15-alkyl), each optionally substituted by C1- C 15 alkyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, esters or sulfonyl;
or where R ¹ and R ^2, together with the atoms which connect them, are optionally substituted by C 1 -C 15 -alkyl, halogeno (C 1 -C 15 -alkyl), C 3 -C 6 -cycloalkyl, halogeno (C 3 -C 6 -cycloalkyl), heterocyclyl, Heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl substituted 5-7-membered heterocycle form.

wobei R¹, R² unabhängig voneinander für C1-C15-Alkyl, C2-C15-Alkenyl, Halogen-(C1-C15-alkyl), C3-C6-Cycloalkyl, Halogen-(C3-C6-cycloalkyl), Heterocyclyl, Heterocyclyl-(C1-C15-alkyl), Aryl, Aryl-(C1-C15-alkyl), Heteroaryl oder Heteroaryl-(C1-C15-alkyl), oder Alkoxy-(C1-15-alkyl), jeweils gegebenenfalls substituiert durch C1-C15-Alkyl, Halogen-(C1-C15-alkyl), C3-C6-Cycloalkyl, Halogen-(C3-C6-cycloalkyl), Heterocyclyl, Heterocyclyl-(C1-C15-alkyl), Aryl, Aryl-(C1-C15-alkyl), Heteroaryl, C1-C15-Alkoxy, C1-C15-Alkylthio, Hydroxyl, Nitro, Azido, Cyano, Acyloxy, Carboxy, Ester oder Sulfonyl; oder wobei R¹ und R² zusammen mit den sie verbindenden Atomen einen gegebenenfalls durch C1-C15-Alkyl, Halogen-(C1-C15-alkyl), C3-C6-Cycloalkyl, Halogen-(C3-C6-cycloalkyl), Heterocyclyl, Heterocyclyl-(C1-C15-alkyl), Aryl, Aryl-(C1-C15-alkyl), Heteroaryl, C1-C15-Alkoxy, C1-C15-Alkylthio, Hydroxyl, Nitro, Azido, Acyloxy, Carboxy, Ester oder Sulfonyl substituierten 5-7-gliedrigen Heterocyclus bilden.
[A]- für -(CR^AR^B)_n-, -(CR^AR^B)_n-O(C=O)-(CH₂)_1-15-(C=O)O-(CR^AR^B)_n–,
-(CH₂)_n-[CY]-(CH₂)_n, eine verknüpfende Polybutadienylgruppe, eine verknüpfende Polyethylenglykolgruppe, eine verknüpfende Polyethergruppe, eine verknüpfende Polyurethangruppe, eine verknüpfende Epoxidgruppe, eine verknüpfende Polyacrylgruppe oder eine verknüpfende Polycarbonatgruppe steht; R^A oder R^B jeweils unabhängig voneinander für H, C₁-C₁₅-Alkyl, C₂-C₁₅-Alkenyl, eine Gruppierung entsprechend der Formel:

worin L eine Verknüpfungsgruppe ausgewählt aus der Gruppe bestehend aus Alkylen, Alkenylen, Halogenalkylen, Cycloalkylen, Cycloalkylen, Heterocyclylen, Heterocyclylalkylen, Arylalkylen, Heteroarylen oder Heteroaryl-(alkylen), oder Alkoxy-(alkylen), die jeweils gegebenenfalls verzweigt sein können und jeweils gegebenenfalls durch Alkyl, Halogenalkyl, Cycloalkyl, Halogencycloalkyl, Heterocyclyl, Heterocyclyl-(alkyl), Aryl, Aryl-(alkyl), Heteroaryl, C₁-C₁₅-Alkoxy, C₁-C₁₅-Alkylthio, Hydroxyl, Nitro, Azido, Cyano, Acyloxy, Carboxy, Ester, die jeweils gegebenenfalls verzweigt sein können, substituiert sein können, bedeutet, stehen,
R₃ unabhängig davon aus der oben bei R₂ definierten Gruppe ausgewählt ist,
[CY] für eine Alkyl-, Alkenyl-, Halogenalkyl-, Cycloalkyl-, Halogencycloalkyl-, Heterocyclyl-, Heterocyclyl-(alkyl)-, Aryl-(alkyl)-, Heteroaryl- oder Heteroaryl-(alkyl)- oder Alkoxy-(alkyl)gruppe steht;
n eine ganze Zahl von 1 bis 25 und
m eine ganze Zahl von 1 bis 25, vorzugsweise von 2 bis 25, bedeuten
und Q jeweils unabhängig für -O- oder eine direkte Bindung steht.The polymerizable vinyl compounds may be monofunctional, ie have only a single vinyl group, or they may have polyfunctionally two or more than two vinyl groups. Preferred polyfunctional polymerizable vinyl compounds correspond to the formula:

wherein R ¹ , R ^{2 are} independently C 1 -C 15 alkyl, C 2 -C 15 alkenyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C1-C15-alkyl), aryl, aryl- (C1-C15-alkyl), heteroaryl or heteroaryl- (C1-C15-alkyl), or alkoxy- (C1-15-alkyl), each optionally substituted by C1- C 15 alkyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, esters or sulfonyl; or where R ¹ and R ^2, together with the atoms which connect them, are optionally substituted by C 1 -C 15 -alkyl, halogeno (C 1 -C 15 -alkyl), C 3 -C 6 -cycloalkyl, halogeno (C 3 -C 6 -cycloalkyl), heterocyclyl, Heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl substituted 5-7-membered heterocycle form.
[A] - for - (CR ^A R ^B ) _n -, - (CR ^A R ^B ) _n -O (C = O) - (CH ₂ ) _1-15 - (C = O) O- (CR ^A R ^B ) _n -,
- (CH ₂ ) _n - [CY] - (CH ₂ ) _n , a linking polybutadienyl group, a linking polyethylene glycol group, a linking polyether group, a linking polyurethane group, a linking epoxy group, a linking polyacrylic group, or a linking polycarbonate group; R ^A or R ^{B are} each independently H, C ₁ -C ₁₅ alkyl, C ₂ -C ₁₅ alkenyl, a moiety corresponding to the formula:

wherein L is a linking group selected from the group consisting of alkylene, alkenylene, haloalkylene, cycloalkylene, cycloalkylene, heterocyclylene, heterocyclylalkylene, arylalkylene, heteroarylene or heteroaryl (alkylene), or alkoxy (alkylene), each of which may optionally be branched and optionally by alkyl, haloalkyl, cycloalkyl, halocycloalkyl, heterocyclyl, heterocyclyl (alkyl), aryl, aryl (alkyl), heteroaryl, C ₁ -C ₁₅ -alkoxy, C ₁ -C ₁₅ -alkylthio, hydroxyl, nitro, azido, cyano , Acyloxy, carboxy, esters, each of which may be optionally branched, means
R _{3 is} independently selected from the group defined above for R ₂ ,
[CY] is an alkyl, alkenyl, haloalkyl, cycloalkyl, halogenocycloalkyl, heterocyclyl, heterocyclyl (alkyl), aryl (alkyl), heteroaryl or heteroaryl (alkyl) or alkoxy ( alkyl) group;
n is an integer from 1 to 25 and
m is an integer from 1 to 25, preferably from 2 to 25
and each Q is independently -O- or a direct bond.

Process for the preparation of methylenmalonates are described in WO 2014/110388 . WO 2012/054616 and WO 2012/054633 described. Processes for the preparation of methylenebetadiketones are described in WO 2013/059479 described. Processes for the preparation of methylenebetaketoesters are described in WO 2013/066629 described. Processes for the preparation of multifunctional vinyl compounds are disclosed in WO 2013/059473 described.

The precoat polymer has several basic groups. Examples of basic groups which may be considered are primary, secondary or tertiary amino groups. Also to be mentioned as basic groups are deprotonated acid groups such as carboxylate groups, sulfonate groups or phosphate groups.

The precoat polymer may be a polymer having multiple amino groups (amino polymer). The amino groups may be present in the form of substituents or as part of the polymer chain. They may also be part of an aromatic or non-aromatic ring system. As polymers, homopolymers of monomers having amine functionality or copolymers of monomers having amine functionality and monomers containing no amine functionality may be considered.

• (a) Polymere mit einpolymerisierten Vinylamineinheiten (Vinylaminpolymere),
• (b) Polymere mit einpolymerisierten Ethylenimineinheiten (Ethyleniminpolymere),
• (c) Polymere von verseiften Vinylformamid,
• (d) Polymere mit einpolymerisierten Vinylimidazoleinheiten (Vinylimidazolpolymere),
• (e) Polymere mit einpolymerisierten Vinylpyridineinheiten (Vinylpyridinpolymere),
• (f) Polymere mit einpolymerisierten Dialkylaminoalkylacrylateinheiten und/oder mit einpolymerisierten Dialkylaminoalkylmethacrylateinheiten sowie
• (g) Polymere mit einpolymerisierten Dialkylaminoalkylacrylamideinheiten und/oder mit einpolymerisierten Dialkylaminoalkylmethacrylamideinheiten,
• (h) Polyurethane mit Aminogruppen.

Examples of suitable amino copolymers are those from the following group:

• (a) polymers with polymerized vinylamine units (vinylamine polymers),
• (b) polymers with copolymerized ethyleneimine units (ethyleneimine polymers),
• (c) polymers of saponified vinylformamide,
• (d) polymers with copolymerized vinylimidazole units (vinylimidazole polymers),
• (e) polymers with polymerized vinylpyridine units (vinylpyridine polymers),
• (F) polymers with copolymerized Dialkylaminoalkylacrylateinheiten and / or with copolymerized Dialkylaminoalkylmethacrylateinheiten and
• (g) polymers with copolymerized dialkylaminoalkylacrylamide units and / or with copolymerized dialkylaminoalkylmethacrylamide units,
• (h) polyurethanes with amino groups.

Examples of preferred amino copolymers are
Polyvinylamine as a homopolymer,
Polyethyleneimine as a homopolymer,
Polydimethylaminoethyl acrylate, polydimethylaminoethyl methacrylate,
Copolymers of acrylamide and dimethylaminoethyl acrylate and copolymers of acrylamide and
Dimethylaminoethyl methacrylate and
Polydimethylaminoethylacrylamide, polydimethylaminoethylmethacrylamide and
Copolymers of acrylamide and dimethylaminoethylacrylamide.

The weight-average molecular weights M _{w of} the aminopolymers are preferably at least 500. For example, they are in the range of 500 to 1 million, preferably from 1000 to 500,000, or from 2,000 to 100,000.

• (a) Polyvinylamine eines gewichtsmittleren Molekulargewichts M_w von 500 bis 1 Millionen und
• (b) Polyethylenimine eines gewichtsmittleren Molekulargewichts M_w von 500 bis 1 Millionen.

The following are preferably suitable as amino polymers:

• (a) polyvinylamines having a weight-average molecular weight M _w of 500 to 1 million and
• (b) Polyethyleneimines having a weight-average molecular weight M _w of 500 to 1 million.

Polymers containing vinylamine units are obtainable by polymerizing N-vinylformamide optionally in the presence of comonomers and hydrolysing the vinylformamide polymers with elimination of formyl groups to form amino groups. The degree of hydrolysis of the polymers can be for example 1 to 100% and is usually in the range of 60 to 100%. The weight average molecular weights M _w can be up to 1 million. Vinylamine units containing polymers are sold, for example as Catiofast ^® of BASF SE.

Ethyleneimine units containing polymers, for example, polyethyleneimines, are also commercial products. They are sold for example under the name Polymin® ^® from BASF SE, for example Polymin® ^® SK. These polymers are polymers of ethyleneimine prepared by polymerizing ethyleneimine in an aqueous medium in the presence of small amounts of acids or acid forming compounds such as halogenated hydrocarbons such as chloroform, carbon tetrachloride, tetrachloroethane or ethyl chloride or condensation products of epichlorohydrin and amino groups containing compounds such as mono- and polyamines, for example dimethylamine, diethylamine, ethylenediamine, diethylenetetramine and triethylenetetramine or ammonia. They have, for example, weight average molecular weights M _w of 500 to 1 million, preferably from 1000 to 500,000.

This group of polymers also includes graft polymers of ethyleneimine on compounds having a primary or secondary amino group, for example polyamidoamines of dicarboxylic acids and polyamines. If desired, the polyamidoamines grafted with ethyleneimine can also be reacted with bifunctional crosslinking agents, for example with epichlorohydrin or with bischlorohydrin ethers of polyalkylene glycols.

Suitable aminopolymers are (polymerized) dialkylaminoalkyl acrylate units and / or polymers containing dialkylaminoalkyl methacrylate units. These monomers can be used in the form of the free bases, but preferably in the form of the salts with mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid in the polymerization. From these monomers, both homopolymers and copolymers can be prepared. Suitable comonomers are, for example, acrylamide, methacrylamide, N-vinylformamide, N-vinylpyrrolidone, methyl acrylate, ethyl acrylate, methyl methacrylate and mixtures of the monomers mentioned.

Suitable aminopolymers are (polymerized) dimethylaminoethylacrylamide units and / or dimethylaminoethylmethacrylamide units containing polymers. These may be homopolymers and copolymers. Examples are homopolymers of dimethylaminoethylacrylamide, homopolymers of dimethylaminoethylmethacrylamide.

As the amino copolymers, there are exemplified copolymers of diallyldimethylammonium chloride and dimethylaminoethyl acrylate, copolymers of diallyldimethylammonium chloride and dimethylaminoethyl methacrylate, copolymers of diallyldimethylammonium chloride and diethylaminoethylacrylate, copolymers of diallyldimethylammonium chloride and dimethylaminopropylacrylate, copolymers of diallyldimethylammonium chloride and dimethylaminoethylacrylamide, and copolymers of diallyldimethylammonium chloride and dimethylaminopropylacrylamide.

The following amino copolymers are preferably used:
Polyethyleneimines having a weight-average molecular weight of 25,000 to 800,000
Polyvinylamines having a weight-average molecular weight M _w of 1000 to 500,000.

• – Copolymerisate aus Acrylamid, Dimethylaminoethylacrylat und Acrylsäure, die mindetens 5 mol% mehr Dimethylaminoethylacrylat als Acrylsäure einpolymerisiert enthalten;
• – hydrolysierte Copolymerisate aus N-Vinylformamid und einer ethylenisch ugesättigten C₃-C₅-Carbonsäure, vorzugsweise Acrylsäure oder Methacrylsäure, mit einem um mindestens 5 mol% höheren Gehalt an Vinylamineinheiten als Einheiten an ethylenisch ungesättigten Carbonsäuren; und
• – Copolymerisate aus Vinylimidazol, Acrylamid und Acrylsäure, wobei der pH-Wert so gewählt ist, dass mindestens 5 mol% mehr Vinylimidazol kationisch geladen ist als Acrylsäure einpolymerisiert ist.

In addition to these polymers, which are composed solely of amino monomers or of amino monomers and neutral monomers, it is also possible to use amphoteric polymers as amino copolymers, provided that the amount of amino groups exceeds that of the acid groups or that acid groups are neutralized. The excess of amino groups with respect to acid groups in the amphoteric polymers is, for example, at least 5 mol%, preferably at least 10 mol%, and is usually in the range from 15 to 95 mol%. Examples of amphoteric polymers with an excess of amino groups are

• - Copolymers of acrylamide, dimethylaminoethyl acrylate and acrylic acid containing at least 5 mol% more dimethylaminoethyl acrylate copolymerized as acrylic acid;
• Hydrolyzed copolymers of N-vinylformamide and an ethylenically unsaturated C ₃ -C ₅ -carboxylic acid, preferably acrylic acid or methacrylic acid, with at least 5 mol% higher content of vinylamine units than units of ethylenically unsaturated carboxylic acids; and
• - Copolymers of vinylimidazole, acrylamide and acrylic acid, wherein the pH is selected so that at least 5 mol% more vinylimidazole is cationically charged than acrylic acid is copolymerized.

Polyethyleneimine is preferred as the amino polymer. Polyethyleneimines are polymers containing ethyleneimine units. Preferably, they are branched. The polyethyleneimines can be used (partially) neutralized in the form of the salts with suitable acids, but they are preferably used in unneutralized form.

In one embodiment of the invention, the polyethylenimine is selected from highly branched or dendritic polyethylenimines. Highly branched polyethyleneimines are characterized by their high degree of branching DB. The degree of branching DB can be determined by ¹³ C-NMR spectroscopy, preferably in D ₂ O, and is defined as follows: DB = D + T / (D + T + L) where D (dendritic) corresponds to the number of tertiary amine groups, L (linear) to the number of secondary amine groups and T (terminal) to the number of primary amine groups. Highly branched polyethyleneimines according to the invention have a degree of branching DB preferably from 0.1 to 0.95 or from 0.25 to 0.9, more preferably from 0.30 to 0.80 and most preferably from at least 0.5. Dendritic polyethylenimines have a structurally and molecularly uniform constitution (DB = 1).

The weight-average molecular weight of the polyethyleneimines is at least 2500 g / mol, more preferably at least 10000 g / mol, for example 25000 to 3 million g / mol or 100000 to 2 million g / mol. The charge density of the polyethyleneimines is preferably from 1 to 35 meq / g, more preferably from 5 to 25 meq / g. To determine the charge density, one can titrate aqueous solutions of polyethyleneimine with potassium polyvinyl sulfate (KPVS) at pH 4.5 against toluidine blue as an indicator.

As the amino polymers are polymers of ethyleneimine, which are prepared by polymerizing ethyleneimine in an aqueous medium in the presence of small amounts of acids or acid-forming compounds such as halogenated hydrocarbons, eg chloroform, carbon tetrachloride, tetrachloroethane or ethyl chloride or condensation products of epichlorohydrin and amino-containing compounds such for example, mono- and polyamines, for example dimethylamine, diethylamine, Ethylenediamine, diethylenetriamine and triethylenetetramine or ammonia. They have, for example, molecular weights M _{w of} from 25,000 to 3 million, preferably from 100,000 to 2 million g / mol.

This group of aminopolymers also includes graft polymers of ethyleneimine on compounds which have a primary or secondary amino group, for example polyamidoamines of dicarboxylic acids and polyamines. If desired, the polyamidoamines grafted with ethyleneimine can also be reacted with bifunctional crosslinking agents, for example with epichlorohydrin or with bischlorohydrin ethers of polyalkylene glycols.

In one embodiment, the polyethyleneimine is crosslinked. All crosslinking agents which have at least two functional groups which can covalently bond with amine groups of the polyethyleneimine are suitable for this purpose. Suitable crosslinking agents are, for example, alkyldialdehydes having preferably 3 to 20 C atoms, such as glutaric dialdehyde (1,5-pentanedial).

In one embodiment, the precoat polymer is a polyurethane having basic groups that can undergo reaction with the polymerizable vinyl compound as a base. The basic groups are again amino groups (aminopolyurethane) or anionic groups such as neutralized acid groups (anionic polyurethane). The polyurethanes are preferably used in dispersed form as aqueous dispersions.

The amount of the basic (preferably anionic) groups based on dry substance is preferably 50 mmol / kg to 450 mmol / kg. Preferred anionic groups are selected from carboxylate groups, sulfonate groups and phosphate groups.

An anionic polyurethane contains either anionic groups and no cationic or amino groups or both anionic and amino or cationic groups, wherein the number of anionic groups at least equal to the amount of the amino groups. An aminopolyurethane contains either amino groups and no anionic groups or both anionic groups and amino groups, with the number of amino groups predominating.

The aminopolyurethanes are preferably composed of a) polyisocyanates, preferably at least one diisocyanate, b) polyols, preferably at least one polyester diol or at least one polyether diol, and c) optionally further mono- or polyvalent compounds having reactive groups, for example selected from alcoholic hydroxy groups, primary amino groups, secondary amino groups and isocyanate groups, at least one of the constituent components having one or more than one amino group.

The anionic polyurethanes are preferably composed of a) polyisocyanates, preferably at least one diisocyanate, b) polyols, preferably at least one polyester diol or at least one polyether diol, and c) optionally further, mono- or polyvalent compounds having reactive groups, for example selected from alcoholic hydroxy groups , primary amino groups, secondary amino groups and isocyanate groups, at least one of the constituent components having one or more than one anionic group.

Suitable diisocyanates are, for example, those of the formula X (NCO) ₂ , where X is an aliphatic hydrocarbon radical having 4 to 15 C atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 C atoms or an araliphatic hydrocarbon radical having 7 to 15 C atoms stands. Examples of such diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane, trimethylhexane diisocyanate, 1 , 4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-isocyanatocyclohexyl) methane (HMDI), for example, the trans / trans isomer, the cis / cis isomer and the cis / trans isomer, and mixtures consisting of these compounds. Such diisocyanates are available commercially. Particularly suitable mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane; in particular, the mixture of 80 mol% of 2,4-diisocyanatotoluene and 20 mol% of 2,6-diisocyanatotoluene is suitable. Furthermore, the mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, wherein the preferred mixing ratio of aliphatic to aromatic isocyanates at 1 to 9 to 9 to 1 , in particular at 1 to 4 to 4 to 1.

For the construction of the polyurethanes can be used as polyisocyanate compounds except the aforementioned also isocyanates, in addition to the free isocyanate groups further capped isocyanate groups, such as uretdione wear.

Preferably, the polyurethanes are each at least 40 wt .-%, more preferably at least 60 wt .-% and most preferably at least 80 wt .-% of diisocyanates, polyether diols and / or polyester diols constructed. Preferably, the polyurethanes contain polyester diols or polyether diols or mixtures thereof in an amount of more than 10 wt .-%, more preferably greater than 30 wt .-%, in particular greater than 40 wt .-% or greater than 50 wt .-%, most preferably greater 60 wt .-%, based on the polyurethane.

Particularly suitable polyester diols are relatively high molecular weight diols which have a molar mass of more than 500 to 5000 g / mol, preferably about 1000 to 3000 g / mol. Polyether diols preferably have a molar mass of 240 to 5000 g / mol. These are the number average molar mass Mn. Mn is determined by determining the number of end groups (OH number).

Polyester diols are known, for example, from Ullmanns Enzyklopadie der technischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterdiols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally substituted, for example by halogen atoms, and / or unsaturated. Examples of these are: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dimer fatty acids. Preference is given to dicarboxylic acids of the general formula HOOC- (CH ₂ ) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable dihydric alcohols for the preparation of the polyester diols are, for example, ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol , Pentane-1,5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol, methylpentanediols, and diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol , Polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration. Alcohols of the general formula HO- (CH ₂ ) _x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred. Examples of these are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Further preferred is neopentyl glycol.

In addition to the polyesterdiols or to the polyetherdiols, polycarbonatediols, as can be obtained, for example, by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for thepolyesterpolyols, may also be used. Optionally, it is also possible to use lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably hydroxyl-terminated addition products of lactones onto suitable difunctional starter molecules. Preferred lactones are those which are derived from compounds of the general formula HO- (CH ₂ ) _z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also denoted by a C ₁ - to C _4- alkyl radical may be substituted. Examples are ε-caprolactone, β-propiolactone, γ-butyrolactone and / or methyl-ε-caprolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as a builder component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

Polyetherdiols are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF ₃ or by addition of these compounds optionally in admixture or successively to starter components with reactive hydrogen atoms, such as alcohols or amines, for example water , Ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-bis (4-hydroxyphenyl) propane or aniline. Particularly preferred are propylene oxide and polytetrahydrofuran having a number average molecular weight of 240 to 5000 and especially 500 to 4500. Preference is given to polyether diols which consist of less than 20 wt .-% of ethylene oxide.

Optionally, it is also possible to use polyhydroxyolefins, preferably those having two terminal hydroxyl groups, for example α, ω-dihydroxypolybutadiene, α, ω-dihydroxypolymethacrylate or α, ω-dihydroxypolyacrylic esters as monomers (c1). Such compounds are for example from the EP-A 622 378 known. Further suitable polyols are polyacetals, polysiloxanes and alkyd resins.

Preferably, the polyether diols are selected from polytetrahydrofuran and polypropylene oxide. Preferably, the polyester diols are selected from reaction products of dihydric alcohols with dibasic carboxylic acids and lactone-based polyester diols.

The hardness and the modulus of elasticity of the polyurethanes can be increased, if necessary, if, in addition to the polyester diols or in addition to the polyether diols, there are still various low molecular weight monomeric diols having a molar mass of about 60 to 500 g / mol, preferably of 62 up to 200 g / mol. The low molecular weight monomeric diols used are, in particular, the synthesis components of the short-chain alkanediols mentioned for the preparation of polyesterpolyols, preference being given to the unbranched diols having 2 to 12 C atoms and an even number of C atoms and also pentane-1,5-diol and neopentyl glycol become. Examples are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1,5- diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes, such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol and methylpentanediols, further include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration. Alcohols of the general formula HO- (CH ₂ ) _x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred. Examples of these are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Further preferred is neopentyl glycol. Preferably, the proportion of the polyester diols or of the polyether diols based on the total amount of all diols 10 to 100 mol% and the proportion of low molecular weight monomeric diols based on the total amount of all diols 0 to 90 mol%. The ratio of the polymeric diols to the monomeric diols is particularly preferably 0.1: 1 to 5: 1, in particular 0.2: 1 to 2: 1.

In order to achieve a water-dispersibility of the polyurethanes, the polyurethanes may additionally contain monomers as the synthesis component which carry at least one isocyanate group or at least one isocyanate-reactive group and moreover at least one hydrophilic group or a group which can be converted into a hydrophilic group. In the following text, the term "hydrophilic groups or potentially hydrophilic groups" is abbreviated to "(potentially) hydrophilic groups". The (potentially) hydrophilic groups react much more slowly with isocyanates than the functional groups of the monomers which serve to build up the polymer main chain. The proportion of components with (potentially) hydrophilic groups on the total amount of all the structural components of the polyurethanes is generally such that the molar amount of the (potentially) hydrophilic groups, based on the total weight of the monomers, 30 to 1000 mmol / kg, preferably 50 to 500 mmol / kg and more preferably 80 to 300 mmol / kg. The (potentially) hydrophilic groups may be nonionic or, preferably, (potentially) ionic hydrophilic groups. Suitable nonionic hydrophilic groups are, in particular, polyethylene glycol ethers of preferably 5 to 100, preferably 10 to 80, ethylene oxide repeat units. The content of polyethylene oxide units is generally 0 to 10 wt .-%, preferably 0 to 6 wt .-%, based on the amount by weight of all monomers. Preferred monomers having nonionic hydrophilic groups are polyethylene oxide diols containing at least 20% by weight of ethylene oxide, polyethylene oxide monools, and the reaction products of a polyethylene glycol and a diisocyanate carrying a terminally etherified polyethylene glycol radical. Such diisocyanates and processes for their preparation are in the patent documents US-A 3,905,929 and US-A 3,920,598 called.

The anionic polyurethanes contain monomers with anionic groups as structural components. Anionic groups are especially the sulfonate, the carboxylate and the phosphate group in the form of their alkali metal or ammonium salts. The aminopolyurethanes contain monomers with amino groups as constituent components. In the context of the invention, anionic groups are also understood to mean potentially anionic groups which can be converted into the abovementioned ionic hydrophilic groups by simple neutralization or hydrolysis reactions, that is to say, for example, carboxylic acid groups. (Potentially) ionic monomers are for example in Ullmanns Enzyklopadie der technischen Chemie, 4th Edition, Volume 19, pp. 311-313 and for example in the DE-A 1 495 745 described in detail.

Suitable amino monomers are, for example, monomers having tertiary amino groups, for example: tris (hydroxyalkyl) amines, N, N-bis (hydroxyalkyl) alkylamines, N-hydroxyalkyldialkylamines, tris (aminoalkyl) amines, N, N-bis (aminoalkyl) alkylamines and N -Aminoalkyldialkylamine, wherein the alkyl radicals and alkanediyl moieties of these tertiary amines independently of one another from 1 to 6 carbon atoms. Furthermore, tertiary nitrogen atoms containing polyether having preferably two terminal hydroxyl groups, such as, for example, by alkoxylation of two bonded to amine nitrogen hydrogen atoms containing amines, eg methylamine, aniline or N, N'-dimethylhydrazine, are accessible in per se conventional manner into consideration. Such polyethers preferably have a molar mass Mn of 500 to 6000 g / mol

Particularly preferred synthesis components for aminopolyurethanes are N, N-bis (aminoalkyl) alkylamines, in particular N, N-bis (aminopropyl) methylamine, and N, N-bis (hydroxyalkyl) alkylamines, in particular N, N-bis (2-hydroxyethyl) methylamine ,

in welcher R¹ und R² für eine C₁-C₄-Alkandiyl-Einheit und R³ für eine C₁-C₄-Alkyl-Einheit stehen, und vor allem Dimethylolpropionsäure (DMPA) bevorzugt. Ferner eignen sich entsprechende Dihydroxysulfonsäuren und Dihydroxyphosphonsäuren, wie 2,3-Dihydroxypropanphosphonsäure. Ansonsten geeignet sind Dihydroxyverbindungen einer molaren Masse über 500 bis 10 000 g/mol mit mindestens zwei Carboxylatgruppen, die aus der DE-A 39 11 827 bekannt sind. Sie sind auch durch Umsetzung von Dihydroxyverbindungen mit Tetracarbonsäuredianhydriden wie Pyromellitsäuredianhydrid oder Cyclopentantetracarbonsäuredianhydrid im Molverhältnis 2 zu 1 bis 1,05 zu 1 in einer Polyadditionsreaktion erhältlich. Als Dihydroxyverbindungen eignen sich insbesondere die oben als Kettenverlängerer aufgeführten Monomere sowie die oben genannten Diole.Suitable monomers with (potentially) anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least one alcoholic hydroxyl group or at least one primary or secondary amino group. Preference is given to dihydroxyalkylcarboxylic acids, especially those having 3 to 10 carbon atoms, as they are also known in the US-A 3,412,054 are described. In particular, compounds of the general formula (c1)

in which R ¹ and R ^{2 are} a C ₁ -C ₄ alkanediyl moiety and R ^{3 is} a C ₁ -C ₄ alkyl moiety, and especially dimethylolpropionic acid (DMPA) is preferred. Also suitable are corresponding dihydroxysulfonic acids and dihydroxyphosphonic acids, such as 2,3-dihydroxypropanephosphonic acid. Otherwise suitable are dihydroxy compounds having a molar mass of from 500 to 10,000 g / mol with at least two carboxylate groups which are selected from DE-A 39 11 827 are known. They are also obtainable by reacting dihydroxy compounds with tetracarboxylic dianhydrides such as pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride in a molar ratio of 2: 1 to 1.05: 1 in a polyaddition reaction. Particularly suitable dihydroxy compounds are the monomers listed above as chain extenders and the abovementioned diols.

Particularly preferred anionic synthesis components have carboxy groups. The carboxy groups can be introduced into the polyurethanes by the abovementioned aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids bearing at least one alcoholic hydroxy group or at least one primary or secondary amino group. Preference is given to dihydroxyalkylcarboxylic acids, in particular having 3 to 10 C atoms, in particular dimethylolpropionic acid.

A particularly preferred structural component for anionic polyurethanes is 2,2-bis (hydroxymethyl) propionic acid (dimethylolpropionic acid, DMPA).

As further anionic synthesis components with isocyanate-reactive amino groups are aminocarboxylic acids such as lysine or β-alanine or in the DE-A 20 34 479 mentioned adducts of aliphatic diprimary diamines to a, ß unsaturated carboxylic or sulfonic acids into consideration. Such compounds obey, for example, the formula (c2) H ₂ NR ₄ -NH-R ₅ -X c2) in which R ⁴ and R ⁵ independently of one another are a C ₁ -C ₆ -alkanediyl unit, preferably ethylene, and X is COOH or SO ₃ H. Particularly preferred compounds of the formula (c2) are N- (2-aminoethyl) -2-aminoethanecarboxylic acid and also N- (2-aminoethyl) -2-aminoethanesulfonic acid or the corresponding alkali metal salts, Na being particularly preferred as the counterion. Also particularly preferred are the adducts of the abovementioned aliphatic diprimary amines with 2-acrylamido-2-methylpropanesulfonic acid, as described, for example, in US Pat DE-B 1 954 090 are described.

If monomers with potentially ionic groups are used, their conversion into the ionic form may take place before, during, but preferably after the isocyanate polyaddition, since the ionic monomers are often difficult to dissolve in the reaction mixture. Neutralizing agents are, for example, ammonia, NaOH, triethanolamine (TEA), triisopropylamine (TIPA) or morpholine or its derivatives. The sulfonate or carboxylate groups are particularly preferably present in the form of their salts with an alkali ion or an ammonium ion as the counterion.

For crosslinking or chain extension of the polyurethanes, it is possible to use further, polyvalent monomers. These are generally more than dihydric non-phenolic alcohols, amines having two and / or more primary or secondary amino groups, and compounds bearing one or more than one alcoholic hydroxy group or more than one primary and / or secondary amino group. Alcohols of higher valency than 2, which can serve to set a certain degree of branching or crosslinking, are, for example, trimethylolpropane, glycerol or sugar. Also suitable are polyamines having 2 or more primary and / or secondary amino groups and monoalcohols which, in addition to the hydroxy group, carry a further isocyanate-reactive group, for example the monoalcohols having one or more primary and / or secondary amino groups, e.g. Monoethanolamine. The polyurethanes preferably contain 1 to 30 mol%, particularly preferably 4 to 25 mol%, based on the total amount of all structural components, of a polyamine having at least 2 isocyanate-reactive amino groups. For the same purpose higher than divalent isocyanates can be used. Commercially available compounds are, for example, the isocyanurate or the biuret of hexamethylene diisocyanate.

Monovalent monomers which are optionally included are monoisocyanates, monoalcohols and monoprimary and secondary amines. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers. The monofunctional compounds usually carry further functional groups such as, for example, olefinic groups or carbonyl groups and serve to introduce functional groups into the polyurethane which make possible the dispersion or the crosslinking or further polymer-analogous reaction of the polyurethane. For this purpose, monomers such as isopropenyl-α, α-dimethylbenzyl isocyanate (TMI) and esters of acrylic or methacrylic acid, e.g. Hydroxyethyl acrylate or hydroxyethyl methacrylate.

In the field of polyurethane chemistry, it is well known how the molecular weight of the polyurethanes can be adjusted by selecting the proportions of the monomers reactive with each other and the arithmetic mean of the number of reactive functional groups per molecule. Normally, the components and their respective molar amounts are chosen so that the ratio A to B with
A is the molar amount of isocyanate groups and
B is the sum of the molar amount of the hydroxyl groups and the molar amount of the functional groups which can react with isocyanates in an addition reaction,
at 0.5 to 1 to 2 to 1, preferably 0.8 to 1 to 1.5 to 1 and more preferably 0.9 to 1 to 1.2 to 1. Most preferably, the ratio of A to B is as close as possible to 1 to 1. The monomers used usually carry on average 1.5 to 2.5, preferably 1.9 to 2.1 and particularly preferably 2.0 isocyanate groups or functional groups which can react with isocyanates in an addition reaction.

The polyaddition of the synthesis components for the preparation of the polyurethane is preferably carried out at reaction temperatures of up to 180 ° C, preferably up to 150 ° C, under atmospheric pressure or under autogenous pressure. The preparation of polyurethanes and of aqueous polyurethane dispersions is known to the person skilled in the art.

The polyurethanes are preferably in the form of an aqueous dispersion and are used in this form.

• a) Diisocyanaten,
• b) Polyesterdiolen einer molare Massen größer 500 bis 5000 g/mol und/oder Polyetherdiolen einer molaren Masse von 240 bis 5000 g/mol,
• c) Diolen mit Carbonsäuregruppen sowie
• d) gegebenenfalls weiteren von a)–c) verschiedenen mono- oder polyfunktionellen Verbindungen mit reaktiven Gruppen, ausgewählt aus alkoholischen Hydroxygruppen, primären Aminogruppen, sekundären Aminogruppen und Isocyanatgruppen.

Preferably, the anionic polyurethane is composed of

• a) diisocyanates,
• b) polyester diols of a molar mass greater than 500 to 5000 g / mol and / or polyether diols of a molar mass of 240 to 5000 g / mol,
• c) diols with carboxylic acid groups as well
• d) optionally further of a) -c) different mono- or polyfunctional compounds having reactive groups selected from alcoholic hydroxy groups, primary amino groups, secondary amino groups and isocyanate groups.

• a) Diisocyanaten,
• b) Polyesterdiolen einer molaren Masse größer 500 bis 5000 g/mol und/oder Polyetherdiolen einer molaren Masse von 240 bis 5000 g/mol,
• c) Verbindungen, welche mindestens eine tertiäre Amingruppe und 1, 2 oder 3 funktionelle Gruppen ausgewählt aus Hydroxygruppen, primären Amingruppen und sekundären Amingruppen aufweisen und
• d) gegebenenfalls weiteren von a)–c) verschiedenen mono- oder polyfunktionellen Verbindungen mit reaktiven Gruppen ausgewählt aus alkoholischen Hydroxygruppen, primären Aminogruppen, sekundären Aminogruppen und Isocyanatgruppen.

The aminopolyurethane is preferably composed of

• a) diisocyanates,
• b) polyester diols of a molar mass greater than 500 to 5000 g / mol and / or polyether diols of a molar mass of 240 to 5000 g / mol,
• c) compounds which have at least one tertiary amine group and 1, 2 or 3 functional groups selected from hydroxy groups, primary amine groups and secondary amine groups, and
• d) optionally further of a) -c) different mono- or polyfunctional compounds having reactive groups selected from alcoholic hydroxy groups, primary amino groups, secondary amino groups and isocyanate groups.

In accordance with the invention, adhesive coating and precoating serve to produce laminates, i. as preparations for the bonding of large-area substrates, in particular the production of composite films.

The application of the precoating substances on one or more of the film substrates can be carried out, for example, as a solution or dispersion in a suitable solvent with subsequent drying. In this case, the application of the precoating only shortly before laminating the two film substrates "in-line", but you can also apply the vinyl compounds well before lamination and store the precoated films until lamination ("off-line").

The present invention thus also provides a process for producing composite films in which a first film and at least one second film are bonded to one another via an adhesive coating, wherein the adhesive coating contains at least one polymerizable, monofunctional or polyfunctional vinyl compound selected from methylene malonates, methylene beta tetoesters and methylene beta-diketones wherein the first and / or second film has a precoat adjacent to the adhesive coating and wherein the precoat comprises at least one precoat polymer, wherein the precoat polymer contains a plurality of basic groups and is selected from polymers having amino groups aqueous dispersions of anionic polyurethanes, and wherein the adhesive coating is over a thickness of 10 microns and less and the pre-coating has a thickness of 5 microns and less.

Adhesive coating material and precoating agent can be used after formulation with typical auxiliaries and additives. Typical auxiliaries and additives include, for example, wetting agents, thickeners, protective colloids, UV protectants, light stabilizers, biocides, defoamers, tackifiers, antioxidants, metal deactivators, antistatics, reinforcing agents, fillers, antifogging agents, blowing agents, plasticizers, lubricants, emulsifiers, colorants, pigments , Rheology modifiers, impact modifiers, adhesion modifiers, optical brighteners, flame retardants, anti-drip agents, nucleants, protective colloids, water, organic solvents, reactive thinners, etc. According to the method of making composite films, at least two films are coated using the adhesive coating on at least one of the films and the precoat connected to at least one of the foils.

According to the novel process for the production of composite films, adhesive coating material and precoating material or correspondingly prepared preparations are applied to the large-area substrates to be bonded, for example by knife coating, brushing, spraying, etc. The usual coating methods may be used, such as roll coating, reverse roll coating, gravure roll coating, countergraduate roll coating, brush coating, bar brushing, spray coating, airbrush coating, meniscus coating, curtain coating or dip coating. After a short time to deaerate the dispersion water or solvent (preferably after 1 to 60 seconds), the coated substrate can then be laminated with a second substrate, the temperature for example 20 to 200 ° C, preferably 20 to 100 ° C, under pressure For example, 0.1 to 3000 kN / m ² , preferably 0.2 to 10 kN / m ² may be.

The application of the adhesive coating can be carried out, for example, in amounts of from 0.1 to 20 g / m ² , preferably in amounts of from 1 to 7 g / m ² . The layer thickness of the adhesive coating is preferably 1 .mu.m to less than 10 .mu.m, for example 1 to 7 .mu.m. The layer thickness of the precoating is preferably 0.1 to less than 5 μm or 0.5 μm and less, for example 0.01 to 1 μm or 0.01 to 0.5 μm. Adhesive coating and precoating add up in the layer thickness preferably to less than 15 microns. In this case, the layer thickness in the case of solvents (eg water or organic solvent) containing coating formulations refers to the dried coating after evaporation of the solvent.

The polymer dispersion according to the invention is preferably used as one-component agent, ie without additional crosslinking agents, in particular without isocyanate crosslinkers. At least one of the films may be printed or metallized on the adhesive coated side. Suitable substrates are, for example, polymer films, in particular polyethylene (PE), oriented polypropylene (OPP), unstretched polypropylene (CPP), polyamide (PA), polyethylene terephthalate (PET), polyacetate, cellophane, with metal, eg aluminum, coated or vapor-deposited Polymer films (short metallized films) or metal foils, for example made of aluminum. The films mentioned can be bonded together or with a film of another type, for example polymer films with metal foils, different polymer films, etc. The films mentioned can also be printed with printing inks, for example. The substrate films may be, for example, 5 to 100 .mu.m, preferably 5 to 40 .mu.m thick.

One embodiment of the invention relates to a composite film in which the material of the first film of OPP, CPP, PE, PET and PA and the material of the second film of OPP, CPP, PE, PET, PA and metal foil is selected. According to one embodiment of the invention, the first film and / or the second film on the respective side, which is coated with the polymer dispersion according to the invention, printed or metallized.

A surface treatment of the film substrates is not absolutely necessary before the coating according to the invention. However, better results can be achieved if the surface of the film substrates is modified prior to coating. In this case, conventional surface treatments can be used, such as a corona treatment to enhance the adhesion. The corona treatment or other surface treatments are performed to the extent necessary for adequate wettability with the coating composition. Usually, a corona treatment of about 10 watts per square meter per minute is sufficient for this purpose. Alternatively or additionally, it is optionally also possible to use primers or intermediate layers between the film substrate and the adhesive coating or precoating. In addition, the composite films may have additional, additional functional layers, for example barrier layers, printed layers, paint or lacquer layers or protective layers. The functional layers may be external, i. on the side facing away from the adhesive coated side of the film substrate or inside, between film substrate and adhesive layer.

The curing of the adhesive is preferably carried out at temperatures below 100 ° C, most preferably at 15 to 30 ° C or at ambient temperature.

A preferred embodiment relates to a composite film according to the invention, wherein the first and / or the second film further comprises at least one barrier layer comprising at least one inorganic oxide. The barrier layer performs its barrier function to oxygen or water vapor, i. it improves a barrier effect with respect to water vapor and / or oxygen. In this case, the at least one barrier layer is designed to adjoin the adhesive coating, because the barrier layer can cause an increased bond strength of the laminated composite film and / or a shortened curing time, in particular with a content of inorganic oxides. The barrier layer preferably has a layer thickness of from 5 to 500 nm or from 5 to 300 nm, particularly preferably from 10 to 100 nm, very particularly preferably from 20 to 80 nm, and is preferably transparent.

The barrier layer is made up of one of inorganic oxides such as silicon oxide (SiOx) or aluminum oxide (AlOx). However, it is also possible to use other inorganic substances such as SiNxOy, ZrO, TiO2, ZnO or FexOy. The inorganic oxides are selected from the group consisting of silica and alumina.

Preferred SiO x layers are those in which x is dimensioned so that the ratio of silicon and oxygen is 1: 1 to 1: 2, more preferably 1: 1.3 to 1: 1.7. A preferred silica coating conforms to the formula SiO x Cy where the carbon in the formula is covalently bonded and x moves between 0.1 and 2.5 and y can range between 0.1 and 2.5. Such carbon-containing coatings have gas barrier properties as well as improved water vapor barrier properties. Another preferred coating is a silica coating of the formula SiOxCyNz in which the carbon and nitrogen atoms are covalently bonded and x is from 0.1 to 2.5, y is from 0.1 to 2.5, and z is from 0 , 1 to 2.5 moves. A sole coating of SiOxCyNz preferably has a layer thickness of 5 to 100 nm and is vapor-deposited in the PECVD process by plasma-assisted chemical vapor deposition from a process gas mixture containing an organosilicon compound and nitrogen as the carrier gas.

AlOx layers are preferably those in which x is from 1.0 to 1.5, preferably Al2O3. Preferably, such an AlOx layer is 5 to 100 nm, preferably 5 to 30 nm thick.

The application of the inorganic oxides can be carried out in a technically well-known manner, such as by physical vacuum deposition (PVD, eg electron beam method or thermal method), sputtering, reactive or chemical vapor deposition (CVD), particularly preferably by plasma enhanced chemical vapor deposition (PECVD), wherein metal - or silicon compounds are deposited under oxidizing conditions on the substrate and thus forms an amorphous layer of metal or silicon oxide. Other possibilities are flame treatment, plasma treatment or corona treatment.

For the deposition of coatings of inorganic oxide, such by the PECVD method is preferably used due to cost advantages and the achieved advantageous barrier and flexibility properties of the coating, but other vapor deposition methods, ie any reactive evaporation or electron beam reactive evaporation method or any heat evaporation method, according to the invention, feasible. These processes are usually batch processes which require a reaction chamber under vacuum or vacuum for reactive evaporation. In the U.S. Patent 5,224,441 For example, a PECVD method will be described in more detail. On the other hand, deposition by a normal pressure plasma process has also been found to be advantageous and desirable because of a continuous coating mode which allows easier control and logistics for the production of the coated film. Another continuous and highly desirable atmospheric pressure deposition process is the so-called flame application or CCVD (Combustion Chemical Vapor Deposition) process.

A barrier layer of a different kind is an organic-inorganic hybrid layer, available under the trade name Ormocer ^®, developed by Fraunhofer ISC. The material is condensed in the sol-gel process and used in various functions, for example as a migration barrier. A third type is a fully organic barrier layer: Such types are used, for example, in WO 2013/182444 and WO 2012/175433 described. Both coatings can be applied in the same way as other aqueous coatings, and after drying they provide good barriers to oxygen and water, which makes them ideal pre-coatings for flexible packaging.

The invention further provides a packaging container comprising a composite film according to the invention as described above. The packaging container may be filled with a food or beverage product, especially when equipped with a barrier layer as described above. Base film materials for packaging containers and composite films for food packaging are preferably selected from polyethylene terephthalate (PET) and polyamide (PA).

It is an advantage of the invention that a wide variety of substrates are glued together, i. can be laminated, wherein the adhesive coating and the precoat according to the invention ensure good adhesion of the adhesive preparation to the substrates and cause high strength of the bonded composite.

• – ermöglicht isocyanatfreie und vernetzerfreie Zubereitungen zur Herstellung von flexiblen Verpackungen
• – ermöglicht 1K-Klebstoffsysteme mit langer Topfzeit
• – hohe Sofortfestigkeit
• – zusätzliche Verbesserung im Aufbau der Verbundfestigkeit für Laminate mit Gasbarriereschichten auf Basis von anorganischen Oxiden

Particular advantages of the products according to the invention are in particular:

• - allows isocyanate-free and crosslinker-free preparations for the production of flexible packaging
• - enables 1K adhesive systems with long pot life
• - high instant strength
• - Additional improvement in composite strength build-up for laminates with inorganic oxide based gas barrier layers

Examples

Monomer 1:

Monomer 2:

Monomer 3:

Monomer 4:

General procedure for the preparation of composite films (unless stated otherwise): The adhesive coating compositions are applied to commercially available polymer films at a dry film thickness of 1-3 g / m ² (based on solids content). The films coated in this way are rolled up with a second polymer film and the composite films are then stored for one day at room temperature under standard conditions.

General procedure for determining the peel strength:
To determine the peel strength, the composite films are cut into 15 mm wide strips. The strips are then stripped off at 23 ° C. in a universal peel strength test machine from Zwick (type 1120.25.01) at a speed of 100 mm / min at an angle of 2 × 90 ° (180 °) and the force required in Newton measured.

Example 1:

Monomer 2 was coated at 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (OPP 20 microns thick) was corona treated, with a 1% aqueous solution of Lupasol ^® P (polyethyleneimine) coated 3 micron wet and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 4 hours the peel strength was determined to be 0.5 N / 15 mm. After 24 hours, the laminate was no longer separable. Instead, material breakage was observed in the OPP film.

Example 2:

Monomer 1 and 2 were applied in a weight ratio of 60/40 with 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (OPP 20 microns thick) was corona treated, with a 1% aqueous solution of Lupasol ^® P (polyethyleneimine) coated 3 micron wet and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 4 hours the peel strength was determined to be 0.1 N / 15 mm. After 24 hours, the laminate was no longer separable. Instead, material breakage was observed in the OPP film.

Example 3:

Two OPP film (20 microns thick with fresh corona treatment) (polyethyleneimine) were coated 3 micron wet and dried with a 1% aqueous solution of Lupasol ^® P. A film was coated with 3 g / m ^{2 of} a mixture of monomer 1 and monomer 2 in a weight ratio of 60/40 and the second Place the film on the coated first film and press the laminate twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 4 hours the peel strength was determined to be 0.4 N / 15 mm. After 24 hours, the laminate was no longer separable. Instead, material breakage was observed in the OPP film.

Example 4:

Two OPP film (20 microns thick with fresh corona treatment) (polyethyleneimine) were coated 3 micron wet and dried with a 1% aqueous solution of Lupasol ^® P. A film was coated with 3 g / m ^{2 of} monomer 2 and the second film was placed on the coated first film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 4 hours the peel strength was determined to be 1.4 N / 15 mm.

After 24 hours, the laminate was no longer separable. Instead, material breakage was observed in the OPP film.

Example 5:

Monomer 2 was coated at 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (CPP 54 micrometers thick, Amcor) was corona treated with a 1% aqueous solution of Lupasol ^® P (polyethyleneimine) coated 3 micron wet and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 4 hours the peel strength was determined to be 0.7 N / 15 mm. After 24 hours, the peel strength was 2.7 N / 15 mm.

Example 6:

Monomer 1 and 2 were applied in a weight ratio of 60/40 with 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (CPP 54 micrometers thick, Amcor) was corona treated with a 1% aqueous solution of Lupasol ^® P (polyethyleneimine) coated 3 micron wet and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 4 hours the peel strength was determined to be 2.7 N / 15 mm ("Zippy"). After 24 hours, the peel strength was 5 N / 15 mm ("zippy").

Example 7:

Monomer 2 was coated at 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (CPP 54 μm thick, Amcor) was corona treated, wet-coated 3 μm with 10% strength by weight aqueous polyurethane dispersion according to Example 9 and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 24 hours the peel strength was determined to be 2.1 N / 15 mm.

Example 8

Monomer 1 and 2 were applied in a weight ratio of 60/40 with 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (CPP 54 μm thick, Amcor) was corona treated, wet-coated 3 μm with 10% strength by weight aqueous polyurethane dispersion according to Example 9 and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 24 hours the peel strength was determined to be 2 N / 15 mm with adhesion breakage to PET.

Example 9: aqueous polyurethane dispersion

A dispersion was after EP 1853639, Example 1 prepared.

The solids content was adjusted to 50%. A sample was diluted to 10% w / w with ethanol.

Example 10: PUD 2

A dispersion was prepared according to DE 2645779, Example 1 prepared. The solids content was adjusted to 39%. A sample was diluted with water to 10% w / w and 0.1% w / w tel quel Lumiten ^® ISC (BASF) was added.

Example 11:

Monomer 2 was coated at 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (cPP 54 μm thick, Amcor) was corona treated, wet-coated 3 μm with 10% PUD solution according to Example 10 and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and after 5 hours the seal strength was determined to be 1.8 N / 15 mm and after 24 hours 2.2 N / 15 mm.

Example 12:

A monomer mixture (20% of monomer 1, 20% Monomer 3, 20% Monomer 4, 40% Monomer 2) (weight ratio) was coated at 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (CPP 54 micrometers thick, Amcor) was corona treated with a 1% aqueous solution of Lupasol ^® P (polyethyleneimine) coated 3 micron wet and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was cut into 15 mm wide strips and the seal strength determined to be 2.1 N / 15 mm after 24 hours. After 72 hours, the seal strength was 5-8 N / 15 mm ("zippy").

Comparative Example 1: no precoating

Monomer 1 and 2 were applied in a weight ratio of 60/40 with 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (CPP 54 μm thick, Amcor) was corona treated. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was checked after 4 hours and 24 hours, but the adhesive was still liquid. After 5 days, the glue was completely gone and the slides were easy to separate.

Comparative Example 2: Sodium benzoate precoating

Monomer 2 was coated at 3 g / m ² on a PET film (Hostaphan ^® RN 36). A second film (CPP 54 μm thick, Amcor) was corona treated, wet-coated 3 μm with 1% solution of sodium benzoate in ethanol and dried. This film was placed on the coated PET film and the laminate was pressed twice with a 1 kg roller. The laminate was inspected after 24 hours and the peel strength was determined to be 0.2 N / 15 mm with PP-sided adhesion fracture.

Examples 1 to 8, 11 and 12 according to the invention show a high peel strength after 24 h. Comparative Examples 1 and 2 show no or very low peel strength after 24 hours.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2013/149168 [0007]
• WO 2014/110388 [0020]
• WO 2012/054616 [0020]
• WO 2012/054633 [0020]
• WO 2013/059479 [0020]
• WO 2013/066629 [0020]
• WO 2013/059473 [0020]
• EP 622378A [0054]
• US 3905929 A [0057]
• US 3920598 A [0057]
• DE 1495745A [0058]
• US Pat. No. 3,412,054 A [0061]
• DE 3911827 A [0061]
• DE 2034479 [0064]
• DE 1954090 B [0064]
• US 5224441 PS [0088]
• WO 2013/182444 [0089]
• WO 2012/175433 [0089]
• EP 1853639 [0104]
• DE 2645779 [0106]

Cited non-patent literature

• Ullmanns Enzyklopadie der technischen Chemie, 4th Edition, Volume 19, pp. 311-313 [0058]

Claims (15)

Composite film comprising a first and at least one second film, which are bonded together via an adhesive coating, wherein the adhesive coating contains at least one polymerizable vinyl compound selected from methylene malonates, Methylenbetaketoestern and Methylenbetadiketonen wherein the first and / or second foil has a precoat adjacent to the adhesive coating, and wherein the precoat comprises at least one precoat polymer, wherein the precoat polymer contains a plurality of basic groups and is selected from polymers having amino groups and aqueous dispersions of anionic polyurethanes, and wherein the adhesive coating has a thickness of 10 microns and less and the pre-coating has a thickness of 5 microns and less. Composite film according to claim 1, in which the coating thickness of the adhesive coating is 1 μm to less than 10 μm and in the precoating 0.01 to 1 μm. A composite film according to any one of the preceding claims, wherein the precoat polymer is selected from polymers having copolymerized vinylamine units, polymers comprising polymerized ethylenimine units, saponified vinylformamide polymers, polymers having copolymerized vinylimidazole units, polymers having polymerized vinylpyridine units, polymers having dialkylaminoalkyl acrylated units polymerized in and / or copolymerized dialkylaminoalkylmethacrylate units and Polymers with copolymerized Dialkylaminoalkylacrylamideinheiten and / or with copolymerized Dialkylaminoalkylmethacrylamideinheiten and polyurethanes with amino groups. The composite film of any one of the preceding claims, wherein the precoat polymer is a branched polyethylenimine and the weight average molecular weight of the polyethyleneimine is 2,500 to 3 million g / mol and / or the charge density of the polyethyleneimine is 1 to 35 meq / g. A composite film according to claim 1 or 2, wherein the precoat polymer is selected from aqueous dispersions of anionic polyurethanes, the polyurethanes having a dry matter-related amount of anionic groups of from 50 mmol / kg to 450 mmol / kg and wherein the anionic groups are selected from Carboxylate groups, sulfonate groups and phosphate groups. A composite film according to claim 1, 2 or 5, wherein the anionic polyurethane is composed of a) diisocyanates, b) polyester diols of a molar mass and / or greater than 500 to 5000 g / mol, polyether diols of a molar mass of 240 to 5000 g / mol, c) diols with carboxylic acid groups as well d) optionally further of a) -c) different mono- or polyfunctional compounds having reactive groups selected from alcoholic hydroxyl groups, primary amino groups, secondary amino groups and isocyanate groups composed. Composite foil according to one of the preceding claims, comprising as the polymerizable vinyl compound a methylene malonate selected from compounds of the formula R ^{1 is} -OC (O) -C (C =CH ₂ ) -C (O) -OR ² or containing as the polymerizable vinyl compound a Methylenbetaketoester selected from compounds of the formula R ¹ -C (O) -C (C =CH ₂ ) -C (O) -OR ² or containing as the polymerizable vinyl compound a Methylenbetadiketon selected from compounds of the formula R ¹ -C (O) -C (C =CH ₂ ) -C (O) -R ² wherein R ¹ , R ^{2 are} independently C 1 -C 15 alkyl, C 2 -C 15 alkenyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C1-C15-alkyl), aryl, aryl- (C1-C15-alkyl), heteroaryl or heteroaryl- (C1-C15-alkyl), or alkoxy- (C1-15-alkyl), each optionally substituted by C1- C 15 alkyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, esters or sulfonyl; or where R ¹ and R ^2, together with the atoms which connect them, are optionally substituted by C 1 -C 15 -alkyl, halogeno (C 1 -C 15 -alkyl), C 3 -C 6 -cycloalkyl, halogeno (C 3 -C 6 -cycloalkyl), heterocyclyl, Heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl substituted 5-7-membered heterocycle form. A composite film according to any one of the preceding claims, wherein the polymerizable vinyl compound is selected from compounds of the formula:

wherein R ¹ , R ^{2 are} independently C 1 -C 15 alkyl, C 2 -C 15 alkenyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C1-C15-alkyl), aryl, aryl- (C1-C15-alkyl), heteroaryl or heteroaryl- (C1-C15-alkyl), or alkoxy- (C1-15-alkyl), each optionally substituted by C1- C 15 alkyl, halo (C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo (C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or sulfonyl; or where R ¹ and R ^2, together with the atoms which connect them, are optionally substituted by C 1 -C 15 -alkyl, halogeno (C 1 -C 15 -alkyl), C 3 -C 6 -cycloalkyl, halogeno (C 3 -C 6 -cycloalkyl), heterocyclyl, Heterocyclyl (C 1 -C 15 alkyl), aryl, aryl (C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl substituted Form 5-7 membered heterocycle; [A] - for - (CR ^A R ^B ) _n -, - (CR ^A R ^B ) _n -O (C = O) - (CH ₂ ) _1-15 - (C = O) O- (CR ^A R ^B ) _n -, - (CH ₂ ) _n - [CY] - (CH ₂ ) _n , a linking polybutadienyl group, a linking polyethylene glycol group, a linking polyether group, a linking polyurethane group, a linking epoxide group, a linking polyacrylic group, or a linking polycarbonate group ; R ^A or R ^{B are} each independently H, C ₁ -C ₁₅ alkyl, C ₂ -C ₁₅ alkenyl, a moiety corresponding to the formula:

wherein L is a linking group selected from the group consisting of alkylene, alkenylene, haloalkylene, cycloalkylene, cycloalkylene, heterocyclylene, heterocyclylalkylene, arylalkylene, heteroarylene or heteroaryl (alkylene), or alkoxy (alkylene), each of which may optionally be branched and optionally by alkyl, haloalkyl, cycloalkyl, halocycloalkyl, heterocyclyl, heterocyclyl (alkyl), aryl, aryl (alkyl), heteroaryl, C ₁ -C ₁₅ -alkoxy, C ₁ -C ₁₅ -alkylthio, hydroxyl, nitro, azido, cyano , Acyloxy, carboxy, esters, each of which may be optionally branched, means; R _{3 is} independently selected from the group defined above for R ₂ ; [CY] is an alkyl, alkenyl, haloalkyl, cycloalkyl, halogenocycloalkyl, heterocyclyl, heterocyclyl (alkyl), aryl (alkyl), heteroaryl or heteroaryl (alkyl) or alkoxy ( alkyl) group; n is an integer from 1 to 25 and m is an integer from 1 to 25, and each Q is independently -O- or a direct bond. A composite film according to any one of the preceding claims, wherein the material of the first film and the second film is independently selected from polyethylene films, oriented Polypropylene films, unstretched polypropylene films, polyamide films, polyethylene terephthalate films, polyacetate films, cellophane, metal-coated polymer films, and metal foils. Composite film according to one of the preceding claims, wherein the first and / or the second film further comprises at least one barrier layer comprising at least one inorganic oxide. Composite film according to one of the preceding claims, wherein the barrier layer exerts its barrier function to oxygen or water vapor and the at least one barrier layer rests against the adhesive coating. A composite foil according to claims 10 to 11, wherein said inorganic oxide is selected from the group consisting of silica and alumina. Use of the composite film according to one of the preceding claims for the production of flexible packaging. A packaging container comprising a composite film according to any one of claims 1 to 12, wherein the packaging container is optionally filled with a food or drink. A process for producing composite films in which a first film and at least one second film are bonded to one another via an adhesive coating, the adhesive coating containing at least one polymerizable, monofunctional or polyfunctional vinyl compound selected from methylene malonates, methylene beta tetoesters and methylenebetadiketones, wherein the first and / or second foil has a precoat adjacent to the adhesive coating, and wherein the precoat comprises at least one precoat polymer, wherein the precoat polymer contains a plurality of basic groups and is selected from polymers having amino groups and aqueous dispersions of anionic polyurethanes, and wherein the adhesive coating has a thickness of 10 microns and less and the pre-coating has a thickness of 5 microns and less.