MXPA00006203A - Laminating adhesives hardenable by radiation - Google Patents

Abstract

The invention relates to the use of an adhesive containing components A, B and C, where component A contains a compound with at least one epoxy group, component B contains a compound with at least 3 OH groups and component C contains a photo-initiator which after irradiation with light at a wave length of between 100 and 600 nm initiates a polymerisation of components A and B, for the production of films and materials. Use of the adhesive according to the invention yields composite films presenting high heat-resistance, low migration and high flexibility.

Description

RADIATION HARDENED LAMINATION ADHESIVES The present invention relates to the use of an adhesive containing three components A, B and C for the production of composite film materials. The component A found in the adhesive contains at least one compound with at least one epoxy group, the component B contains at least one compound with at least three OH groups and a molecular weight of less than 400, and the compound C contains at least a photoinitiator that, after irradiation with light of wavelength from 100 to 600 nm, initiates a polymerization of components A and B. Within the field of adhesives, especially in the case of flat lamination materials, there is an increasing demand for short hardening times and a shorter "response time" (faster use capacity) of the adhesives used for lamination. Common commercial systems are based, in general terms, on polyurethane, acrylate or epoxy binders that harden through a reaction with additional hardeners or with moisture through relatively slow crosslinking. The usual hardening time of commercial systems is from about 4 to about 21 days. However, a period of this type until the final hardening and therefore until reaching the greatest possible strength of composite film materials is not desirable. Composite film materials are subjected to a series of stresses during manufacture, treatment and use, to which other glued materials are usually not exposed or not as intensely as is the case with composite film materials. During the manufacture of composite film materials, materials having different flexibility and different surface structure are used. In general terms, these are flat materials made of paper, plastics with metal or metal oxides, especially plastic sheets with transition metal oxides or metal sheets, especially aluminum sheets. The composite film materials are subjected during processing, treatment and use to a series of mechanical stresses that pose high requirements to the adhesive that constitutes the union between the materials with respect to the mechanical properties of the adhesive. Since in general, in the case of adhesive flat materials of high flexibility materials which are constantly subjected during manufacture, preparation and use to detachment and bending movements, the adhesive must have a sufficiently high flexibility to be able to withstand the forces without damage or separation of the adhesive bond.

In addition, the adhesive must also have a sufficient peel strength such that it can withstand orthogonal peel forces relative to the sheet joining surface without separation of the constituents. To the tendency to crystallization and coloration, present a series of criteria that exceed the performance characteristics of adhesives for usual adhesions.So, for example, in the case of the adhesion of transparent plastic films, it must be ensured that the union of the films present a transparent transparency without clouding due to the crystallisation.Furthermore, the adhesive must also present, even in the case of a long storage of the films, for example in the case of UV irradiation, a tendency as low as possible to the formation of colored by-products.The composite film materials must in addition s present in the shortest time as possible temperature resistance. This property is especially important in the case for example of products with a short production and packaging cycle that must be packaged with composite film materials while still at an elevated temperature. The heat resistance characteristic is however also important when materials at least partially wrapped in a composite film material must be subjected to heating. The union of sheets that do not have the necessary transparency required to initiate the polymerization reaction of the adhesive presents, in general terms, a problem. When dealing with sheets of non-transparent material, in general terms, the sheet covered with adhesive on the adhesive side must be irradiated before applying a second sheet on this side. This method requires that the connection with the second sheet be carried out at a time when the polymerization of the adhesive, ie the hardening of the adhesive, has not yet been fully completed. The adhesive must, however, at this time present sufficient adhesion so that the second sheet can adhere. While the radical polymerization adhesive systems often exhibit too fast hardening and too limited initial adhesion, the cationic polymerization adhesive systems allow a lamination process in which a sheet in which a layer is applied is first irradiated of adhesive and then the second sheet is applied. This is based, in general terms, on the fact that the cationic system in comparison with the radical polymerization systems have a slower hardening speed. The drawback is that frequently in the case of the systems that can be obtained in the market, the period until a complete hardening of the adhesive compound is too long for an economical use of this adhesion technique. A quality criterion that is becoming increasingly important for composite film materials is represented by the absence of migrant elements as much as possible. By migrating elements, we mean low molecular weight constituents of composite film materials that are not fixed within the composite material, that is, they can move within the composite material, and on the other hand can eventually be diffused from the composite material. towards the material wrapped in said composite material. Since such low molecular weight constituents can be hazardous to the health of living beings, especially humans, it is desirable to prepare composite film materials with the least possible amount of migrating elements. DE-U 94 20 640.6 relates to compositions curable by irradiation with a content of OH-terminated polyurethanes, an epoxy compound and a photoinitiator. A one-step, irradiatable, curable adhesive composition having both high initial adhesion and high final adhesion when used as a lamination adhesive is described. EP-A 0 668 804 discloses multiple component, cationic hardening epoxy masses as well as method for hardening. Said document discloses cationic hardening epoxide masses in various embodiments which, as a fundamental part, generally contain a mixture of compounds made from the irradiation of Lewis acids and / or Brónsted acids, monomers containing cationically polymerizable epoxide groups. as at least one additional component selected from the group of flexibilizing agents, retardants, radical polymerizable monomers, accelerators or modifiers. As flexibilizing agents, retarders, radically polymerizable monomers, accelerators or modifiers. As flexibilizing agents we mentioned glycol alcohols with a molecular weight of at least 200 to 20,000 g / mol. DE-A 43 40 949 discloses light-initiating cationic epoxide masses and their use. The document describes a light-initiated cationic hardening epoxy mass containing at least one retarder, at least one accelerator, at least one ferrocenium complex salt and at least one compound containing epoxide, cycloaliphatic groups, as well as auxiliaries and additives usual. The adhesives represented in the state of the art present, in general terms, the disadvantage that they do not meet all the requirements that an adhesive is required for the production of composite film materials. Thus, although fast hardening adhesives can be made from epoxy and polyurethane polyol compounds, however, its resistance to heat does not meet the requirements, for example in the case of food preparation or in the case of sterilization of medical instruments. Accordingly, it is an object of the present invention to provide an adhesive system for the manufacture of composite film materials which can withstand the high requirements during the manufacture, preparation and use of such composite film materials and which also exhibit a fast hardening time. as well as a high resistance to detachment and cutting. Furthermore, the object of the present invention is to provide an adhesive for the production of composite film materials with which composite film materials with high heat resistance and low content of migrating elements (for example low molecular weight polyols) can be obtained. . The object of the present invention is achieved through an adhesive containing at least three components A, B and C, which will be described below within the framework of this text. The object of the present invention is the use of an adhesive containing at least three components A, B and C for the production of composite film materials, where a) component A contains a compound with at least one epoxy group and b) component B contains a compound with at least three OH groups and has a molecular weight of less than 400 and c) component C contains a photoinitiator which, after irradiation with light of a wavelength of 100 to 600 nm initiates a polymerization of components A and B. In a first embodiment of the present invention, an adhesive is used for the production of composite film materials containing components A, B and C. Component A is at least one compound with at least one group epoxy, or a mixture of two or more compounds of this type. As an epoxy group, "within the scope of the present invention, it is meant a functional group having an oxirane ring, said epoxy groups can be polymerized by cationic initiation as is known to those skilled in the art. of the present invention may contain a compound with at least one epoxy group as an exclusive part; however, a mixture of two or more compounds with at least one epoxy group can also be used as component A. For the formation of the polymers it is sufficient that as part of component A the aforementioned compound with at least one epoxy group present only one epoxy group. However, to achieve a higher degree of crosslinking in the adhesive film, at least partially one or more compounds with more than one epoxy group in the molecule can be used as part of component A. The compounds used as part of component A within the framework of the present invention which are useful have from 1 to 4 epoxy groups per molecule. It is especially preferred when the average epoxy group content of the global component A is from about 1 to about 2.5, especially from about 1.5 to about 2.0. Basically, as a compound with at least one epoxy group, a low molecular weight epoxide can be used, however, high molecular weight epoxies or mixtures of high and low molecular weight epoxides can also be used as component A. By "low molecular weight" "Within the framework of the present text we understand compounds containing at least one epoxy group, which have a molecular weight not greater than about 400. Compounds with at least one epoxy group and having a molecular weight greater than 400 are known within the framework of the present text as "high molecular weights". High molecular weight compounds with at least one epoxy group may have, for example, the epoxy group at the end of the chain of a polymer chain, the epoxy group can however also be within the structure of the polymer or be laterally bound to the polymer structure. polymer structure. In the case of compounds with more than one epoxy group the corresponding high molecular weight compound can also have epoxy groups in two or more of the configurations described with respect to the polymer backbone. For example, a compound with more than one epoxy group can for example have an end epoxy group and a side epoxy group or an epoxy group within the structure of the polymer and an epoxy group in the side position. Among the compounds which can be used as component A within the framework of the present invention with at least one epoxy group are, for example, cycloaliphatic epoxides. Examples of cycloaliphatic epoxides are bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate or bis (3,4-epoxycyclohexylmethyl)) piptelato, it being possible also to use mixtures of two or more of the mentioned compounds. Also suitable are 3-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, for example 3,4-epoxycyclohexylmethyl-3, -epoxycyclohexanecarboxylic acid, 3-epoxy-1-methylcyclohexylmethyl-3, 4-epoxy-1-methylcyclohexanecarboxylic acid, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3, -epoxycyclohexanecarboxylic acid, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylic acid, 3,4-epoxy-5- acid methylcyclohexylmethyl-3, 4-epoxy-5-methylcyclohexanecarboxylic acid, or the like, or mixtures of two or more of them. Other suitable epoxides that can be used within the scope of the present invention include glycidyl ethers, such as those obtainable from polyvalent phenols, for example 2,2'-bis (2,3-epoxypropoxyphenyl) propane diglycidyl ether. Advantageously, it is also possible to use compounds with at least one epoxy group which are commercially available. Examples are octadecylene oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ether of bisphenol-A (for example, EPON 828, EPON 1004 and EPON 1010, manufacturer: Shell Chemical Co .; 331, DER-332 and DER-334, manufacturer: Dow Chemical Co.), vinylcyclohexene dioxide (e.g. ERL-4206, manufacturer: Union Carbide Corp.), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate (e.g., ERL-4221, manufacturer: Union Carbide Corp.), 3,4-epoxy-6-methylcyclohexylmethyl carboxylate, 3, 4-epoxy-6-methylcyclohexene (e.g., ERL-4201, manufacturer: Union Carbide Corp.), bis (3, -epoxy-6-methyclohexylmethyl) adipate (e.g., ERL-4289, manufacturer: Union Carbide Corp.) ), bis (2,3-epoxycyclopentyl) ether (for example, ERL-0400, manufacturer: Union Carbide Corp.), aliphatic epoxy resin modified with polypropylene glycol (for example ERL-4050 or ERL-4052, manufacturer: Union Carbide Corp) .), dipentene dioxide (e.g. ERL-4269, manufacturer: Union Carbide Corp.), epoxidized polybutadiene (e.g. OXIRON 2001, manufacturer: FMC Corp.), silicone resin with an epoxy-functional content, flame-retardant epoxy resins ( for example DER-580, manufacturer: Dow Chemical Co.), diglycidyl ether of 1,4-butanediol of phenolformaldehydonovolak (for example either DEN-31 or DEN-438, manufacturer: Dow Chemical Co.,) as well as resorcinol diglycidyl ether (for example, KOPOXITE, manufacturer: Koppers Co., Inc.). Also, as compounds with at least one epoxy group that can be used, mention may be made of polymers carrying epoxy groups such as, for example, ethylenically unsaturated epoxy compounds bearing epoxy groups obtainable by polymerization. Examples of such ethylenically unsaturated compounds bearing epoxy groups are the esters of acrylic acid of glycidol, for example, glycidyl acrylate or glycidyl methacrylate. Advantageously, these compounds are copolymerized with at least one additional ethylenically unsaturated compound which does not have an epoxy group. Polyurethanes carrying epoxy groups are also suitable. Such polyurethanes are obtained, for example, by the reaction of polyesters carrying OH groups or polyethers carrying OH group with polyfunctional isocyanates, whereby the stoichiometric ratio between the isocyanate groups and the OH groups is selected in such a way that the corresponding polyurethane it has at least one free isocyanate group which will react, for example, with 1-hydroxy-2,3-epoxypropane or another suitable epoxide. Component A generally contains up to about 30% by weight, preferably up to about 10% by weight, of a compound with only one epoxy group. The part of compounds with two or more epoxy groups reaches up to about 50% by weight, preferably from about 10% to about 40% by weight, so that the part of trifunctional epoxies or with a higher functionality in component A represents up to about 10% by weight. In relation to the entire adhesive, the part of the component A represents from about 5% by weight to about 60% by weight, preferably from about 10% by weight to about 40% by weight. The component B found in the adhesives used within the framework of the present invention has a compound with at least three OH groups and a molecular weight of less than 400. The trifunctional compound part, ie, a compound with three OH groups represents from about 1% by weight to about 10% by weight, relative to the total adhesive. Compounds carrying suitable OH groups are, for example, alcohols with higher functionality such as glycerin, trimethylolpropane, pentaerythritol and sugar alcohols, as well as oligomeric ethers of the aforementioned compounds or oligomeric ethers of a mixture of two or more the mentioned compounds. In addition, the products of the reaction of polyfunctional alcohols of low molecular weights with alkylene oxides having up to 4 carbon atoms can be used as polyol components for the preparation of the polyesters. For example, the products of the reaction of polyfunctional alcohols, such as glycerin, are suitable., trimethylolethane and / or trimethylolpropane, pentaerythritol or sugar alcohols with the alkylene oxides named in oligoether polyols with a molecular weight of not more than about 400. As component C, the adhesive to be used according to the present invention contains a photoinitiator, or well a mixture of two or more photoinitiators. The photoinitiator can initiate the polymerization induced by irradiation of the epoxy groups. Especially suitable are photoinitiators which create Lewis acids or Bronstedt acids under the effect of electromagnetic irradiation, especially light irradiation. As photoinitiators that cause the creation of Lewis acids and / or Brónsted acids with the effect of light, within the framework of the present invention, preferably onium compounds are used. Basically, all sulfonium salts or photosensitive aromatic iodonium salts are suitable for the light-induced initiation of the polymerization. Particularly suitable are trisarylsulfonium hexafluoroantimonates, trisarylsulfonium hexafluorophosphates, such as those obtainable, for example, from Cyracure® UVI-6974 and UVI-6990 (manufacturer: UCC, Danbury, United Kingdom), or bis (4, '-dimethylbenzyl) iodoniotetra (pentafluorophenyl) borate (UV CATA 200, manufacturer: Rhone-Poulenc, Saint-Fons, FR). The photoinitiator employed within the framework of the present invention can initiate the polymerization of component A after irradiation with light of a wavelength of about 100 to about 600 nm. In a preferred embodiment of the present invention the initiation is effected through irradiation with a light of a wavelength of about 150 to about 500 nm, for example about 200 to about 480 nm. Component component D, the adhesive to be used according to the present invention may contain a compound with at least two OH groups and with a molecular weight of at least 400, or a mixture of two or more compounds of this type. For use as component D, for example, polyester polyols, polyether polyols, polyurethane polyols, polycarbonate polyols, polyvinylacetal polyols, polyacrylate polyols, polymethacrylate polyols, or copolyols from suitable acrylates and methacrylates or mixtures of two or more of the aforementioned polyols are suitable. Preferably, the compounds used as component D have a molecular weight of more than about 400 to about 10,000, with a molecular weight of greater than about 400 to about 2,000 being preferred. Within the framework of the present invention, it is especially preferred to use polyester polyols, polyether polyols or polyurethane polyols as component D. Polyester polyols which can be used as component D are preferably polyesters with a molecular weight (Mn) of more than about 400 to about 10,000. Preferred polyester polyols are prepared, for example, by the reaction of alcohols with low molecular weights, especially ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerin or trimethylolpropane by condensation with a polycarboxylic acid or a mixture of two or more of these acids. For example, difunctional and / or trifunctional alcohols can be condensed in polyesters with dicarboxylic and / or tricarboxylic acids or their reactive derivatives. Suitable dicarboxylic acids are, for example, succinic acid and its higher homologues with up to 16 carbon atoms, in addition unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and aromatic dicarboxylic acids, especially isomeric italic acids such as phthalic acid, acid isophthalic or terephthalic acid. Suitable tricarboxylic acids are, for example, citric acid or trimethyl acid. Also suitable are aliphatic polycarboxylic acids such as adipic acid, glutamic acid, pimelic acid, aromatic acids such as naphtalindicarboxylic acid, cycloalkyl acids such as for example cyclohexanedicarboxylic acid, or acids with a content of heteroatoms such as S or N, for example diglycolic acid, 2,2-dicarboxylic acid ethyl ether or thiodiglycolic acid. Also suitable as polyols for the preparation of the polyesters are aliphatic alcohols with two to four OH groups per molecule. The OH groups are preferably primary, but they can also be secondary. Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, butanediol-1,4, pentanediol-1,5, hexanediol-1,6,6-heptanediol-1,7,7-octanediol-1,8 and their higher homologues and isomers, as they are obtained in a manner known to the person skilled in the art through a progressive prolongation of the hydrocarbon chain each time in a CH2 group or with the introduction of amplifications in the carbon chain. Also suitable are alcohols with higher functionality, such as, for example, glycerin, trimethylolpropane, pentaerythritol, as well as oligomeric ethers of the mentioned substances with themselves or in a mixture from two or more of the aforementioned ethers. In addition, the low molecular weight, polyfunctional alcohols which are products of the reaction can be used with alkylene oxides having up to four carbon atoms as polyol components for the preparation of the polyesters. Suitable, for example, are products of the reaction of ethylene glycol, propylene glycol, of the isomeric butanediols or of hexanediols with ethylene oxide, propylene oxide and / or butylene oxide. Furthermore, products of the reaction of polyfunctional alcohols such as glycerin, trimethylolethane and / or trimethylolpropane, pentaerythritol or sugar alcohols with the alkylene oxides mentioned for polyether polyols are also suitable. Furthermore, the products of the reaction of low molecular weight polyfunctional alcohols with alkylene oxides having up to four carbon atoms can be used as the polyol component for the production of the polyester. Suitable reaction products are, for example, ethylene glycol, propylene glycol, butanediols or isomeric hexanediols with ethylene oxide, propylene oxide and / or butylene oxide. In addition, the reaction products of polyfunctional alcohols such as, for example, glycerin, trimethylolethane and / or trimethylolpropane, pentaerythritol or sugar alcohols with the algeny oxides in polyester polyols are also suitable. Especially suitable as polyols for the production of polyesters are polyether polyols with a molecular weight of from about 100 to 5,000, preferably from about 200 to about 3,000. Especially preferred within the scope of the present invention is propylene glycol with a molecular weight of from about 300 to about 2,500. Polyester polyols are also suitable, such as are obtained, for example, by the polymerization of tetrahydrofuran. A group of preferred polymers employed as component D according to the present invention preferred within the framework of said invention are the polyurethane polyols. By polyurethane polyols we understand compounds which can be obtained by the polyaddition of divalent alcohols and / or alcohols with a higher valence and polyisocyanates within the scope of the present invention. As polyols for the manufacture of the polyurethanes, polyesters and / or polyethers with a molecular weight of from about 300 to 10,000, preferably from about 800 to about 5,000 and with at least two OH groups are typically chosen. As polyesters for the preparation of the polyurethanes which can be used within the framework of the present invention, all polyesters terminated in OH groups which can react with at least one difunctional isocyanate with chain elongation are suitable. Among these we can mention for example the aforementioned polyesters. Additional dihydroxy compounds which can be used as a representation of the polyol components which can be used for the preparation of the polyurethanes are, for example, butanediol-1, 3, butanediol-1, butanediol-2, 3, 2,2-diethylpropan-l, 3-diol, 2-methyl-2-propylpropan-l, 3-diol, isomeric octandiols, ethylenically unsaturated divalent compounds, for example heptadiol, octendiol as well as divalent compounds with a content of N or S heteroatoms, for example diethylene glycol, triethylene glycol, thioethylene glycol, diethanolamine or N-methyldiethanolamine, or mixtures of two or more of them. The diols react in general terms for the preparation of the polyurethanes with corresponding at least difunctional isocyanates. The isocyanates used within the framework of the present invention may be aliphatic or aromatic and may have from about 4 to about 40 carbon atoms. Examples of suitable isocyanates are hexamethylene diisocyanate (HDI), 1,8-octanediisocyanate, 1,10-decanediisocyanate, diisocyanates such as those obtained from dimerization of fatty acids and corresponding functionalization, phenylene diisocyanate-1,4, tetramethylxylylene diisocyanate (TMXDI), 2,4- and 2,6-toluene diisocyanate and mixtures thereof, 1,5-naphthylene diisocyanate, 2,4'-diisocyanate or 4'-diphenylmethane (MDI) and their mixtures, isophorone diisocyanate (IPDI), cyclobutan-1,3-diisocyanate, cyclohexane-1, 3- and -1,4-diisocyanate, 2,4- and 2,6-dihydro-hexahydrotoluylene diisocyanate, hexahydro-1-diisocyanate, 3- or -1, 4-phenylene, 2,2'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate or mixtures of two or more of the aforementioned diisocyanates. Likewise, within the framework of the present invention, as isocyanates that can be used for the production of the polyurethanes contained in component A, we can mention trivalent or higher valence polyisocyanates, such as those obtainable, for example, by oligomerization of diisocyanates. Examples of such trivalent polyisocyanates or with a higher valency are the triisocyanurates of HDI or IPDI or their mixed triisocyanurates. In general terms, the average molecular weight of the polymers used as component D should not be less than 400. Since polymers, in general terms, have a statistical molecular weight distribution dependent on the chosen synthesis method, the concept "molecular weight" "average" refers to the number (Mn) of molecular weight of the polymers contained in component A. This includes that individual polymer molecules whose molecular weight is below the value of 400 can also be found. In addition to the components A, B , C and optionally D, the adhesive to be used in accordance with the present invention may also contain an additional component E. The component E contains at least one compound or a mixture of two or more compounds having a cationically polymerizable functional group which does not It is an epoxy group. Examples are olefins, vinyl ethers, vinylarenes, especially styrene, and heterocyclic compounds - such as ethers, thioethers, esters or acetals. Preferred within the scope of the present invention are vinyl ethers such as those obtainable from the etherification of alcohols, preferably polyols and vinyl ethers (in fact in the case of the technical preparation of vinyl ethers, one generally initiates). from acetylene), and vinylstyrene. The compounds which can be used as component E within the framework of the present invention having at least one cationically polymerizable functional group, which is not an epoxy group, can have one or preferably several cationically polymerizable groups. It can be, in the case of the compound used as component E of a low molecular weight compound, that is, of a compound with a molecular weight of up to about 400, however it can also be a high molecular weight compound with a weight molecular from about 400 to about 10, 000 or eventually even more. The component E employed in the adhesive to be used in the present invention may contain a single compound, however it may also contain a mixture of two or more compounds bearing cationically polymerizable groups which are not epoxy groups. Within the framework of the present invention, the use of vinyl ethers as component A is especially preferred. As vinyl ethers of low molecular weights, for example monofunctional or difunctional vinyl ethers can be used, for example, hydroxybutyl vinyl ether, divinyl ether. of triethylene glycol, divinyl ether of cyclohexanedimethanol, propylenecarbonate propenyl ether, dodecyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, diethylene glycol divinyl ether, 2-ethylhexyl vinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, ether hexyndiol, octadecyl vinyl ether or butanediol divinyl ether It is also possible to use divinyl ethers of higher functional alcohols as component E. Examples are glycerin monovinyl ether, glycerin divinyl ether, trivinyl ether and glycerin, monovinyl, divinyl or trivinyl ether of trimethylpropane, monovinyl, divinyl, trivinyl or tetravinyl ether of pentaerythritol or vinyl ether of alcohols with more than four OH groups for example vinyl ether of sugar alcohols. The mentioned compounds can be used alone as component E, however, as component E, mixtures of two or more of the mentioned vinyl ethers can also be used. Within the framework of the present invention, the use of divinyl ether of butanediol as component E is preferred. When a higher molecular weight compound is used as component E, it is preferably a polymer which carries as end groups or optionally lateral with respect to the polymer backbone a cationically polymerizable group which is not an epoxy group. Such compounds which are preferably used individually or as mixtures of two or more of them as component E within the framework of the present invention for the adhesive to be used are obtained, for example, from the polyol components of higher molecular weights such as as those described within the framework of the present text as component D. For example, it is possible to prepare a vinylstyrene-terminated polymer by reacting an OH-terminated polymer with 4-styrene isocyanate. As OH-terminated polymers, a polyester polyol or a polyether polyol or a polyurethane is preferably used. It is also possible to present a wide variation of polymers containing vinyl ether groups. Furthermore, for example, a polymer containing OH groups reacts with at least a double excess of diisocyanates (relative to the OH groups). The polymer made in this way that has free NCO groups reacts with hydroxyvinyl ethers. It is thus also possible to prepare polymers containing vinyl ethers by first reacting a vinyl ether containing OH groups with an equimolar amount of diisocyanate and then the reaction product reacts with a polymer terminated with OH groups.

As vinyl ethers containing OH groups, hydroxybutyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, and cyclohexanedimethanol monovinyl ether are preferred within the scope of the present invention. The adhesive to be used according to the present invention contains the component E preferably in an amount of up to 20% by weight. In a preferred embodiment, the adhesive to be used according to the present invention contains the component E for example in an amount of 0.1% by weight to approximately 10% by weight, for example from approximately 1% by weight to approximately 8% by weight, in relation to the total adhesive. The adhesives to be used according to the present invention can also contain additives such as accelerators, dyes, pigments, fillers, reinforcers, thixotropic agents, initiators, stabilizers, inhibitors or adhesion agents. Accelerators are used in general terms to accelerate the course of polymerization. This can be achieved either by accelerating the start of the reaction under the influence of irradiation or to the extent that the polymerization itself, ie the addition of individual monomers one after the other is supported. The additives can be used in the adhesive according to the present invention in a general amount of up to about 20% by weight, preferably in a general amount of up to about 10% by weight, for example from about 1% by weight to about 8% by weight. % by weight or from about 3% by weight to about 5% by weight relative to the total adhesive. The adhesive compositions according to the present invention can usually be made through the mixture of the mentioned components. The application on the sheets to be glued can be achieved through machines that are used for this purpose, such as, for example, by conventional laminating machines. The application of the adhesives in liquid state on one of the sheets to be glued to form the laminate is an especially suitable procedure. When in the case of at least one of the sheets to be glued on the surface of composite film material is a transparent sheet, the sheet receiving a layer of adhesive can be laminated immediately on the second sheet. Then the composite sheets can be subjected to irradiation in an irradiation zone where the irradiation of the transparent side of the sheet with ultraviolet radiation initiates the polymerization reaction, ie the crosslinking of the individual components of the adhesive. When in the case of the sheets to be bound, these are non-transparent materials for the irradiation that initiates the polymerization, in general terms the sheet receiving the adhesive must be subjected to irradiation before placing on this side a second sheet. This method requires that the bonding with the two sheets be carried out at a time when the polymerization of the adhesive, ie the hardening has not yet completely finished. The adhesive must still be able to develop sufficient adhesion at this time so that the second sheet can adhere. The described gluing and laminating process can be repeated several times in such a way that laminates consisting of more than two bonded layers can be manufactured. Among the materials that can be adhered, we mention, for example, paper, cellulose hydrate, plastics such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, vinyl chloride and vinylidene chloride copolymers, copper acetate copolymers. • vinyl / olefins, polyamides or metal sheets, for example aluminum, lead or copper. The following examples serve to explain the invention with greater precision but do not have the purpose of limiting said invention. Examples Abbreviations used: PPG: polypropylene glycol Poly-THF: polytetrahydrofuran CAPA: polycaprolactone MDI: 4, '-difenilmeta or HBVE diisocyanate: hydroxybutyl vinyl ether Preparation example Cycloaliphatic epoxide PPG 7.1% base with OH in aromatic polyester position 39.8! final, use of MDI CAPA 8.7% low molecular weight and cycloaliphatic epoxide 28.9i vinyl ether layer 2.9% divinyl ether 9.1% initiator 3.5% 100%

Claims (1)

1. CLAIMS The use of an adhesive, containing at least three components A, B and C, for the manufacture of composite film materials, where a) component A contains a compound with at least one epoxy group and b) component B contains a composed with at least three OH groups and with a molecular weight of less than 400 and c) component C contains a photoinitiator which, after irradiation with light of a wavelength of 100 to 600 nm, initiates a polymerization of components A and B The use according to claim 1, characterized in that the adhesive contains a component D, where d) the component D is a compound with at least two OH groups and with a molecular weight of at least 400. The use in accordance with claim 1 or according to claim 2, characterized in that the component A has a molecular weight of less than 400. The use according to claim 1 or according to the claim n 2, characterized in that component A has a molecular weight greater than 400. The use according to one of the preceding claims, characterized in that, as component B, there is an alcohol with 3 to 6 OH groups. The use according to one of the preceding claims, characterized in that as component B there is an alcohol selected from the group containing glycerin, triethylolpropane, trimethylolpropane or pentaerythritol, or a mixture of two or more of them. The use according to one of the preceding claims, characterized in that a photoinitiator selected from the group consisting of triarylsulfonium salts or diaryliodonium salts is present as component C. Use according to one of claims 2 to 7, characterized in that a compound selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols or polyurethane polyols is selected as component D. The use according to one of the preceding claims, characterized in that the adhesive contains: from 1% by weight to 98% by weight of component A from 1% by weight to 10% by weight of component B and 1% by weight at 10% by weight of component C. The use according to one of the preceding claims, characterized in that the adhesive contains an E component, where: e) as component E there is a compound or a mixture of two or more compounds that have a cationically polymerizable functional group which is not an epoxy group.