MXPA06005371A - Laminates, their production and use - Google Patents

Abstract

A description is given of laminates comprising sheetlike substrate and film joined to the substrate by means of an adhesive which comprises a polymer dispersion prepared by free-radical emulsion polymerization and an organosilane which is incorporated into the polymer during the polymerization and/or is added subsequently and which in addition to at least one silane group has at least one primary, secondary or tertiary amino group or at least one epoxide group or which comprises at least one ethylenically unsaturated group and at least one silane group. Through the addition of an organosilane it is possible to produce laminates which can be processed rapidly and which are distinguished by improved embossing strength.

Description

LAMINAR UNITS. YOUR PRODUCTION AND USE DESCRIPTIVE MEMORY The present invention relates to laminar units produced by agglutinating with selected polymer dispersions. The use of aqueous polymer dispersions as adhesives or as binders in aqueous adhesive preparations is known to those skilled in the art. Compared to solvent-based adhesives, these polymer dispersions offer the advantage of allowing the emission of solvents to be avoided when used. Since organic solvents are generally flammable or even easily incinerable, aqueous adhesives of this type also offer a distinct safety advantage during use. Adhesives comprising polymer dispersions and organosilane additions are already known. EP-A-215,518 discloses an aqueous polymer dispersion comprising an aminosilane. The dispersion is used as an adhesive or paint for buildings with improved moisture resistance. JP-A-10 / 178,931 discloses emulsion paints comprising epoxysilane compounds. The coatings produced using these paints present high resistance to weathering, chemicals and water. US-A-2002/0037964 discloses a reaction product of selected polyisocyanates with aminosilanes. It can be used as an adhesion promoter in sizing materials. US-A-4,032,487 discloses an adhesive composition comprising a selected acrylate copolymer and an interlayer containing epoxide and alkoxysilane functionalities. US-A-2005/0038152 discloses a pressure sensitive adhesive based on an aqueous dispersion comprising a polyacrylate modified with silane and a compound which is coupled with the silane. This adhesive is easily separated from the temporary backing film. JP-A-2002/241, 725 discloses an aqueous dispersion comprising a silane modified polyacrylate and finely divided filler attached thereto. The dispersion can be used as a pressure sensitive adhesive. JP-A-2003 / 321,660 discloses an additional pressure sensitive adhesive comprising an aqueous dispersion comprising a polyacrylate modified with silane and also an aminosilane. Additionally, laminar units that have been produced using adhesives comprising polymer components and organosilane additions have already been described. US-A-2004/0092689 discloses a selected acrylic resin that preferably comprises a silane and is used to produce laminar units for optical applications, such as for producing LCDs. EP-A-1, 283,232 describes a two-part adhesive for producing laminar units comprising a hardening component, comprising polyisocyanate and silane coupler, and a base component, comprising polyol. JP-A-11 / 245,346 describes a laminated film for packaging. This film is composed of two films having non-absorbent surfaces, namely a laminated polyvinylidene film to a support film. The adhesive used is an aqueous dispersion of a polyester-polyurethane resin to which a silane adhesion promoter has been added. JP-A-09 / 125,039 describes an adhesive for wood-metal laminar units. This adhesive comprises a water soluble polymer or an aqueous polymer dispersion, a filler, an isocyanate interleaver, and a silane coupling agent. The laminar wood-metal units described are not noteworthy. DE 198 38 667 A1 describes the use of aqueous polyacrylate dispersions selected as laminating adhesives. During the preparation of the dispersions, it is possible to use regulators. Among the given examples of regulators is mercaptopropyltrimethoxysilane. For the production of laminar units, a multiplicity of different requirements are imposed on the lamination adhesive. For example, it is desired that the laminating adhesives be suitable for bonding different materials, such as polymer films, thin foils of metal or metallized polymer films, to paper and to coated paper or cardboard. Lamination adhesives must adhere well to these substrates and must produce high and durable strength in the assembly in as short a time as possible after lamination. Adhesives are also expected to have problem-free processing even on high-speed machinery, which means that even the dispersion used as a binder must already have high shear stability and good flow properties. In the special case of high-gloss film lamination, a transparent polymer film is first coated with the liquid adhesive. The adhesive is dried and then the adhesive coated film is laminated under heat and pressure to the substrate, generally a printed paper or a printed board. The laminated unit thus produced is frequently processed subsequently in a relatively short time after lamination, and is embossed, bent or grooved. The deformation of the laminar unit that this entails must not be accompanied, in any case whatsoever, by the detachment of the film from the substrate. In order to avoid these cases of detachment, the adhesive layer is generally entangled. This can take place by incorporating a chemical entanglement system in the dispersion, as described in EP-A-148,386 or EP-A-644,902, or by the addition of water-soluble isocyanate hardeners or by incorporation of UV crosslinking groups, as described in DE-A-101 35 379. In view of the fact that chemically crosslinkable adhesives take time to cure, it is necessary with these systems to wait for a certain period of storage before the laminated systems they can be processed later. This disadvantage can be solved by using UV curing adhesives. However, these systems need an additional irradiation station in the rolling mill, and there are restrictions in terms of the films that can be used, since matte films or films that are not transparent to UV light can not be used. Based on this prior art, the object of the invention was to provide a laminar unit that without the incorporation of additional equipment in the lamination plant has an increased resistance to enhancement in a short time after lamination without damaging other properties of the unit. laminate. It has now been found that adhesives comprising aqueous polymer dispersions can be used, through the addition of organosilanes, to produce laminated assemblies exhibiting improved enhancement capability. The present invention provides enhanceable laminar units comprising a) a sheet-shaped substrate having at least one absorbent surface b) a film c) is bonded to the substrate by means of an adhesive comprising a polymer dispersion prepared by emulsion polymerization of free radicals and an organosilane is incorporated into the polymer during the polymerization and / or subsequently added and which in addition to at least one silane group has at least one primary, secondary or tertiary amino group or at least one epoxide group or comprising at least one ethylenically unsaturated group and at least one silane group. The laminar units of the invention must be capable of realization - that is, they can be capable of forming a pattern by means of appropriate pressure treatment of selected parts of the surface. The laminar units of the invention need not have been patterned by enhancement. However, preferably, these laminar units have at least one embossed surface. The laminar units of the invention are produced using sheet-like substrates having at least one absorbent surface. In the context of this descriptionThese substrates are flexible and rigid substrates which are composed of paper, cardboard or other fiber materials, examples being glass fibers, polymer fibers or natural fibers. The substrates can be composed of one or more materials or can themselves be laminated, such as polymeric laminar units having at least one absorbent surface, which if desired can also carry printed circuits. Particular preference is given to the use of substrates that are sheet-like and at the same time flexible and have absorbent surfaces. Examples of such substrates are papers, including paperboard and cardboard, and other fiber strips. These materials can also be printed and / or coated. In order to produce the laminar units of the invention, it is possible to use any desired films.

Like substrates, these films can be composed of any of a very wide variety of materials, such as, for example, plastics, metals, wood veneer or paper. Metal films (thin films) or polymers are preferred, especially transparent polymer films. Examples of thin sheets of metal used preferably are thin sheets of aluminum. Examples of polymer films used are preferably polyurethane (PE), polypropylene (PP) films, especially oriented polypropylene (OPP), polystyrene (PS), cellulose acetate (CA), polyvinyl chloride (PVC), polylamide (PA) ) and polyethylene terephthalate (PET). Examples of transparent polymer films used with particular preference are films of oriented polypropylene (monoaxially or biaxially oriented) or cellulose acetate. Particular preference is given to laminar units where the substrate surface is printed and the polymeric film is transparent. Another preferred laminar unit has enhancement on the side of the film. The adhesives used in accordance with the invention comprise polymer dispersions prepared by free radical emulsion polymerization of ethylenically unsaturated monomers. Adhesives of this type are known as such. The selection of ethylenically unsaturated monomers suitable for preparing the polymer dispersions is not critical as such. All monomers commonly used to prepare polymer dispersions are suitable, which can be rationally combined with one another according to the requirements of the art. Preferred primary monomers are vinyl esters of carboxylic acids having 1 to 18 carbon atoms, complete esters or monoesters of monocarboxylic acids and C3-C8 dicarboxylic acids ethylenically unsaturated with C18 alkanols, and aromatic or aliphatic, ethylenically unsaturated hydrocarbons , optionally substituted with halogen. As vinyl esters of carboxylic acids having 1 to 18 carbon atoms, it is possible to use all monomers that are known to those skilled in the art. However, particular preference is given to vinyl esters of carboxylic acids having from 1 to 4 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl pivalate and vinyl 2-ethylhexanoate.; vinyl esters of saturated, branched monocarboxylic acids having 9, 10 or 11 carbon atoms in the acid radical (© Versatic acids (versatic acids)); vinyl esters of saturated and unsaturated fatty acids of larger chain, such as vinyl esters of fatty acids having 8 to 18 carbon atoms, such as vinyl laurate and vinyl stearate; vinyl esters of benzoic acid or of p-tert-butylbenzoic acid, and also mixtures thereof, such as, for example, mixtures of vinyl acetate and a versatic acid or of vinyl acetate and vinyl laurate. Vinyl acetate is especially preferred. As full esters or monoesters of C3-C8 ethylenically unsaturated monocarboxylic and dicarboxylic acids with C-i-C-is alkanols, it is possible to use all monomers which are known to those skilled in the art. Preference is given here to the complete esters and monoesters of monocarboxylic acids and dicarboxylic acids of C3-C8, which are energetically unsaturated, with C - - C 2 2 alkanols, and C?-C8 alkanols or C5-C8 cycloalkanols are particularly preferred. Examples of suitable CrC 8 alkanols are methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, sobutanol, tert-butanol, n-hexanol, 2-ethylhexanol, lauryl alcohol and stearyl alcohol. Examples of suitable cycloalkanols are cyclopentanol and cyclohexanol. Particular preference is given to esters of acrylic acid, methacrylic acid or crotonic acid, maleic acid, itaconic acid, citraconic acid and fumaric acid. Special preference is given to esters of acrylic acid and / or methacrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( meth) isobutyl acrylate, 1-hexyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and also the esters of fumaric acid and maleic acid, such as dimethyl fumarate , dimethyl maleate, di-n-butyl maleate, di-n-octyl maleate, di-2-ethylhexyl maleate. Where appropriate, the indicated esters can also be substituted by epoxy and / or hydroxyl groups. Examples of aromatic or aliphatic, ethylenically unsaturated hydrocarbons, optionally substituted by halogen, are ethene, propene, 1-butene, 2-butene, sobutene, styrene, vinyl toluene, vinyl chloride and vinylidene chloride, preference being given to ethene and styrene. In addition to these major monomers, it is possible to use functional monomers. These include ionic monomers and non-ionic monomers having functional groups. The ionic monomers include those compounds which carry at least one carboxylic, sulfonic, phosphoric or phosphonic acid group in direct vicinity to the double bond unit or are linked to said unit by a separator. Examples that may be mentioned include the following: ethylenically unsaturated C3-C8 monocarboxylic acids, ethylenically unsaturated Cs-C8 dicarboxylic acids and their anhydrides, and ethylenically unsaturated C4-C8 dicarboxylic acid monoesters. Preference is given to unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid and also their anhydrides; unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid and citraconic acid, and also their monoesters with C -C-2 alkanols, such as monomethyl maleate and mono-n-butyl maleate, for example. Other preferred ethylenically unsaturated ionic monomers are ethylenically unsaturated sulfonic acids such as vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloyloxyethanesulfonic acid and 2-methacryloyl-oxietanesulfonic acid, 3-acryloyloxy- and 3-methacryloyloxypropanesulfonic acid, vinylbenzenesulfonic acid and ethylenically unsaturated phosphonic acids, such as vinylphosphonic acid. Additionally, as well as the indicated acids, it is also possible to use their salts, preferably their alkali metal or ammonium salts, and most preferably their sodium salts, such as the sodium salts of vinylsulfonic acid and 2-acrylamidopropanesulfonic acid. , for example. Additional suitable ethylenically unsaturated ionic monomers include monomers with cationic functionality, such as monomers that are based, for example, on quaternary ammonium groups. However, anionic monomers are preferred. The nonionic ethylenically unsaturated functional monomers include, for example, the amides of the carboxylic acids specified in connection with the ethylenically unsaturated ionic monomers, such as, for example, methacrylamide and acrylamide, and also water-soluble N-vinyl lactams such as N-vinylpyrrolodone, for example, and also compounds containing polyethylene glycol units covalently linked as ethylenically unsaturated compounds, such as, for example, monoallyl or diallyl polyethylene glycol ethers or the esters of ethylenically unsaturated carboxylic acids with polyalkylene glycols. In addition, additional ethylenically unsaturated nonionic functional monomers which are suitable are nitriles of ethylenically unsaturated C3-C8 carboxylic acids, such as acrylonitrile and methacrylonitrile, and also adhesion and crosslinking promoter monomers. It is also possible to use C4-C8 conjugated dienes, such as 1,3-butadiene, isoprene and chloroprene, as monomers. The adhesion promoting monomers include not only compounds having an acetoacetoxy unit covalently linked to the double bond system but also compounds containing covalently linked urea groups. The compounds mentioned first include, in particular, acetoacetoxyethyl (meth) acrylate and allyl acetoacetate. The compounds containing urea groups include, for example, N-vinylurea and N-arylurea, and also imidazolidin-2-one derivatives, such as N-vinyl- and N-allyl-imidazolyl-2-one, N-vinyloxyethylimidazolidin- 2-one, N- (2- (meth) acrylamidoethyl) imidazolid-2-one, N- (2- (meth) acryloyloxyethyl) imidazolidin-2-one, N- (2- (met) -acyloxy-acetamidoethyl) midazolidin-2-one, and additional adhesion promoters known to those skilled in the art and based on urea or imidazolidin-2-one. Also suitable for improving adhesion is diacetone acrylamide in combination with a subsequent addition of adipic dihydrazide to the dispersion. As crosslinking monomers, it is possible to use not only difunctional but also polyfunctional monomers. Examples thereof are diallyl phthalate, diallyl maleate, triallyl cyanurate, tetraalyloxyethane, divinylbenzene, butane di (meth) acrylate-1,4-diol, triethylene glycol di (meth) acrylate, divinyl adipate, (meth) allyl acrylate, vinyl crotonate, methylenebisacrylamide, hexanediol diacrylate, pentaerythritol diacrylate and trimethylolpropane triacrylate. Functional monomers may be used where appropriate in amounts of 0.1% to 25% by weight, preferably 0.5% to 10% > by weight, based on the total amount of the monomers. The crosslinking monomers are used where appropriate in amounts of 0.02% to 5% by weight, preferably from 0.02% to 1% by weight, based on the total amount of the monomers. When selecting the appropriate monomers or combinations of monomers, it is necessary to take into account the general knowledge prospects related to the preparation of dispersions that are used to prepare adhesives. Therefore, it is necessary in particular to ensure that the polymers are formed which, under the drying conditions contemplated for the coating, form an adhesive film, and that the selection of the monomers for preparing copolymers is made in such a way that the formation of copolymers is probably in view of the position of the polymerization parameters. Preference is given to the use of polymer dispersions derived from acrylates, methacrylates and / or vinyl esters of aliphatic carboxylic acids. Mixtures of preferred monomers of the monomers to prepare poly (meth) acrylates, together where appropriate with vinyl esters, are vinyl acetate / butyl acrylate, vinyl acetate / dibutyl maleate, vinyl acetate / fuma of dibutyl, vinyl acetate / 2-ethylhexyl acrylate, vinyl acetate / ethene / butyl acrylate, vinyl acetate / ethene / dibutyl maleate, vinyl acetate / ethene / dibutyl fumarate, vinyl acetate / ethene / acrylate of 2-ethylhexyl, methyl methacrylate / butyl acrylate, methyl methacrylate / 2-ethylhexyl acrylate, styrene / butyl acrylate, styrene / 2-ethylhexyl acrylate, methyl methacrylate / isobutyl acrylate and methyl methacrylate / acrylate of isopropyl. Additional preferred monomer mixtures of the monomers for preparing polyvinyl esters, where appropriate, together with additional functional monomers are vinyl acetate / vinyl chloride / ethene, vinyl acetate / vinyl laurate / ethene, vinyl acetate / laurate vinyl / ethene / vinyl chloride, vinyl acetate / versic acid vinyl ester / ethene / vinyl chloride, versic acid vinyl ester / ethene / vinyl chloride, vinyl acetate / versic acid / ethene vinyl ester, and acetate of vinyl / ethene, the vinyl acetate / ethene combination being particularly preferred. The adhesive used is particularly preferably a polymer dispersion prepared by free radical emulsion polymerization which is a homopolymer or copolymer derived from acrylate and / or methacrylate as the main monomer ("polyacrylate") or is a homopolymer or copolymer derived from vinyl ester as the main monomer, ("polyvinyl ester"), preferably a polyacrylate or a polyvinyl ester having a glass transition temperature below 15 ° C. The glass transition temperature of the polymer can be adjusted by the person skilled in the art by appropriate selection of the monomer combinations. The dispersion used according to the invention is established by protective colloids and / or by emulsifiers. Protective colloids are polymeric compounds with molecular weights, for example, greater than 2000 g / mol, wherein the emulsifiers are low molecular weight compounds whose relative molecular weights, for example, are below 2000 g / mol. These compounds are added during the actual polymerization and, where appropriate, they can also be added again after the polymerization. Examples of protective colloids are starch, gum arabic, alginates or tragacanth, methyl-, ethyl-, hydroxyethyl-, or carboxymethyl-cellulose, or corn starch modified with saturated acids or epoxides and also synthetic substances such as polyvinyl alcohol (with or without residual acetyl content), or polyvinyl alcohol that has been partially esterified or acetalized or etherified with saturated radicals, and also polypeptides such as gelatin, but also polyvinylpyrrolidone, polyvinylmethylacetamide or poly (meth) acrylic acid. Polyvinyl alcohol is preferred. The weight fraction of said protective colloids when present, based on the total amount of monomers used for the preparation, it is generally up to 15%. Additionally, in many cases it may be advantageous to use nonionic and / or ionic emulsifiers during the preparation of the dispersions, in addition to or instead of the protective colloids. Suitable nonionic emulsifiers are araliphatic and aliphatic nonionic emulsifiers, such as ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C4 to Cg), ethoxylates of long-chain alcohols ( of EO: 3 to 50, alkyl radical: Cs to C36), and also polyethylene oxide / polypropylene oxide block copolymers. Preference is given to the use of long chain alkanol ethoxylates (alkyl radical: C-io to C22l average degree of ethoxylation: 3 to 50) and of these, particular preference is given to those based on natural alcohols, Guerbet alcohols or alcohols processed with oxo having a straight or branched C-t2-C? alkyl radical and an ethoxylation degree of from 8 to 50. Additional suitable emulsifiers are found in Houben-Weyl, Methoden der organischen Chemie [Methods of organic chemistry], Volume XIV / 1, Macromolekulare Stoffe [macromolecular compounds], Georg-Thieme-Verlag, Stuttgart, 1961, p. 192-208). Suitable ionic emulsifiers include both anionic and cationic emulsifiers. Anionic emulsifiers include alkali metal salts and ammonium salts of alkyl sulphates (alkyl radical: Cs to C-? 8), alkyl phosphonates (alkyl radical: Cβ to C-is), sulfur monoesters or monoesters and phosphoric diesters with ethoxylated alkanols (EO grade: 2 to 50, alkyl radical: C8 to C22) and ethoxylated alkylphenols (EO grade: 3 to 50) , alkyl radical: C4 to C9), of alkylsulfonic acids (alkyl radical: C | 2 to C? 8), of alkylarylsulfonic acids (alkyl radical: Cg to C-is), of sulfosuccinic monoesters and sulfosuccinic diesters of alkanols (alkyl radical) : C8 to C22) and ethoxylated alkanols (EO grade: 2 to 50, alkyl radical: C8 to C22), and also to ethoxylated and non-ethoxylated alkylphenols (EO grade: 3 to 50, alkyl radical: C4 to C9). In general, the listed emulsifiers are useful as technical mixtures, the alkyl radical length and EO chain length statements referring to the respective maximum of the distributions rring within the mixtures. Examples of the indicated classes of emulsifiers are © Texapon K12 (Cognis sodium lauryl sulphate), © Emulsogen EP (C13-C17 alkylsulfonate from Clariant), © Maranil A 25 IS (n-alkyl (C? OC-i3) -benzenesulfonate sodium of Cognis), © Genapol liquid ZRO (alkyl sulfate of C- | 2 / C14 sodium with 3 units EO, of Clariant), © Hostapal BVQ-4 (sodium salt of an ether sulphate of nonylphenol with 4 EO units, from Clariant), Aerosol MA 80 (sodium dihexylsulfosuccinate from Cytec Industries), Aerosol A-268 (disodium isodecylsulfosuccinate from Cytec Industries) and Aerosol A-103 (disodium salt from a monoester of sulfosuccinic acid with an ethoxylated nonylphenol , from Cytec Industries). Cationic emulsifiers include, for example, alkylammonium acetates (C 8 to C 12 alkyl radical), quaternary compounds containing ammonium groups and pyridinium compounds. With regard to the choice of ionic emulsifiers, it must of course be ensured that the incompatibilities in the resulting polymer dispersion, which would lead to coagulation, are regulated. Therefore, it is preferred to use anionic emulsifiers in combination with anionic monomers or to use cationic emulsifiers in combination with cationic monomers, the combination of anionic emulsifiers and anionic monomers being particularly preferred. The amounts of the emulsifiers, where used, are within the normally observable limits. In general, therefore, up to about 10% by weight, preferably up to 5% by weight, is used, based on the total amount of the monomers used to prepare the dispersions. In general, mixtures of ionic and nonionic emulsifiers are used, although it is also possible to use ionic and nonionic emulsifiers alone in order to further stabilize the dispersions. The aqueous polymer dispersions used according to the invention typically have solid content of 20% to 70%, preferably 30% to 65%, and most preferably 40% to 60% by weight. The polymer dispersions used according to the invention further comprise, if desired, further adjuvants which are customary as such. Additional additives and constituents that may be used include film-forming auxiliaries such as white spirit, Texanol®, TxiB®, butyl glycol, butyl diglycol, butyl dipropylene glycol and butyltripropylene glycol; plasticizers, such as dimethyl phthalate, diisobutyl phthalate, diisobutyl adipate, Coasol B®, and Plastilit 3060®; wetting agents, such as AMP 90®, TegoWet.280®, Fluowet PE®; thickeners such as polyacrylates or polyurethanes, such as Borchigel L75® and Tafigel PUR 60®; defoamers, being defoaming examples of mineral oil or silicone defoamers; UV stabilizers, such as Tinuvin 1130®, emulsifiers or retro-added stabilizing polymers, such as polyvinyl alcohol or cellulose ethers, rheology modifiers, examples being polyacrylate or polyurethane thickeners, and other additives and auxiliaries as used in the formulation of adhesives The minimum film-forming temperature of the adhesives used according to the invention is typically below 25 ° C, preferably below 15 ° C. The film formation temperature can be modified and adjusted by adding conventional coalescents. The polymer dispersion used according to the invention is prepared by emulsion polymerization of free radicals. This can be carried out by means of an intermittent process, a feeding procedure, an intermittent / combined feeding method or a continuous process. However, preference is given to operating in a combined intermittent and feeding procedure, or with particular preference, in a feeding process, in which generally a portion of the monomers (1% to 15% by weight) is initially introduced for start the polymerization. The dosage of the monomers can take place either together or in separate feeds. In addition, it may be advantageous in certain embodiments to carry out a seed polymerization in order to set specific particle sizes and specific particle size distributions. Examples of free radical initiators used include the following: hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide, isopropylcumyl hydroperoxide, potassium, sodium and ammonium persulfates, saturated monovalent aliphatic carboxylic acid peroxides of even number with a length of chain of Cs-C? 2, tert-butyl hydroperoxide, diter-butyl peroxide, diisopropyl percarbonate, azoisobutyrenitrile, acetylcyclohexansulfonyl peroxide, terbutyl perbenzoate, tert-butyl peroctoate, bis-3,5,5 peroxide -trimethexanoyl, tert-butyl perpivalate, hydroperoxypin and p-menthane hydroperoxide. The aforementioned compounds can also be used as part of a reduction oxide system including transition metal salts such as iron (II) salts or other reducing agents. As reducing agents or regulators it is possible to use alkali metal salts of oximetansulfinic acid, mercaptans of chain length of C10-Ci4, but-1-en-3-ol, salts of hydroxylamine, dialkyldithiocarbamate sodium, sodium bisulfite, bisulfite ammonium, sodium dithionite, diisopropylxanthogen disulfide, ascorbic acid, tartaric acid, isoascorbic acid, boric acid, urea and formic acid. However, it is preferred to use water-soluble persulfates, especially ammonium persulfate or sodium persulfate, to initiate the polymerization. The emulsifier and / or protective colloid used for stabilization may alternatively also be added in its entirety at the beginning of the polymerization, included in the initial charge, or partially included in the initial charge and dosed partially in, or fully metered during the polymerization . The pH of the dispersion is typically between 2 and 7, preferably between 2.5 and 6. The polymerization temperature is typically within the range of 20 to 120 ° C, preferably in the range of 30 to 110 ° C, and most preferably in the range of Range from 45 to 95 ° C. After the end of the polymerization it is possible, for purposes of demonomerization, to add an additional post-treatment, preferably chemical, in particular using oxide-reduction catalysts, such as combinations of the oxidizing agents and reducing agents mentioned above, for example. In addition, it is possible to remove residual monomer that is present by any means, such as by physical demonomerization, i.e., removal by distillation (in particular steam distillation) or by separation with an inert gas. A combination of physical and chemical methods is particularly efficient and allows a reduction in residual monomers to very low levels (<; 1000 pp, preferably < 100 ppm). The amount of the polymer in the adhesive used according to the invention is typically from 50% to 99.9% by weight, preferably from 80 to 99.8% by weight, based on the solids content of the adhesive. The adhesive used according to the invention comprises at least one organosilane. The silane may be present during the actual preparation of the polymer dispersion and / or may be added subsequently. The amount of organosilane compound is typically 0.05% or 20% by weight, preferably 0.05% to 5% by weight, based on the solids content of the adhesive. It is possible to use some organosilanes which in addition to at least one silane group have at least one primary, secondary or tertiary amino group or at least one epoxide group or which comprises ethylenically unsaturated groups and silane groups. Possible compounds are both those that are incorporated into the polymer during polymerization and those that are present throughout the polymer as a separate component in the dispersion. The organosilanes used according to the invention preferably include compounds of the formula I or II a) an organofunctional silane wherein R 1 is - (CH 2) n -NH-R 4, - (CH 2) n -NH - [(CH 2) m -NH] 0 -R 4 (CH2) n-0-R5 or - (CH2), - CH = CH2, R2 is hydrogen, - (CH2) n-CH3 or R1, R3 is hydrogen, - (CH2) n-CH3 or R2, R4 is hydrogen , - (CH2) n-CH3 or -CO- (CH2) m-CH3, and R5 is hydrogen, - (CH2-CH2-O) m-R4 or n and m each independently of the other being an integer between 0 and 12, and o being an integer between 0 and 5. The additional silanes used with preference are polyfunctional silanes. These include, in particular, compounds which in addition to at least one silane group have at least one primary, secondary or tertiary amino group or at least one epoxide group, or polyfunctional silanes containing two or more ethylenically unsaturated groups in the molecule . Particularly preferred compounds of this group are compounds of the formulas III, IV, V or VI (Re6-0) 3-Si- (CH2) p-NH- (CH2) p-Si- (0-R6) 3 (III) , (Re6-O) 3-Si- (CH2) pN [- (CH2) p-Si- (O-R6) 2 (IV), (Re6-O) 3-Si- (CH2) pO-R7 (V ), (Re6-O) 3-Si- (CH2) p-NR8R9 (VI), in which R6 independently at each occurrence is hydrogen or C-? -C6 alkyl, preferably methyl, ethyl or propyl, R7 is a glycidyl radical (1,2-epoxypropyl), R8 and R9 independently of one another are hydrogen or C6 alkyl, and p is an integer between 1 and 12. The particularly preferred silanes of formulas III and IV are the following compounds: CH3-CH2-O) 3-Si- (CH2) p-NH- (CH2) p-Si- (O-CH2-CH3) 3, (CH3-O) 3-S- (CH2) p-NH ~ (CH2) pS- (O-CH3) 3, (CH3-CH2-O) 3-Si- (CH2) pN [- (CH2) p-Si- (O-CH2-CH3) 3] 2, (CH3) -O) 3-Si- (CH 2) pN [- (CH 2) p-Si- (O-CH 3) 3] 2 in which p is as defined above The silanes can be used as individual compounds or as mixtures. Examples that can be mentioned of compounds d The silane of the above-mentioned types which are commercially available include the following: Silanes of the trade name Dynasylan® (Degussa), of the trade names ADDID® or Geniosil® (Wacker), or of the trade name Silquest® (Crompton). The organosilanes that are incorporated into the polymer include ethylenically unsaturated monomers containing silane groups and are of the formula R11Si (CH3) or-2 (OR12) 3- ?, wherein R1 has the definition CH2 = CR13 (CH2) 0- ? or CH2 = CR13CO2- (CH2) 1.3, R12 is an unsubstituted or substituted, unbranched or branched alkyl radical having 1 to 12 carbon atoms and can be uninterrupted or interrupted by an ether group, and R13 is hydrogen or methyl. Preferred silanes are of the formulas CH2 = CR13 (CH2) or-? Si (CH3) or.? (OR12) 3- = and CH2 = CR13CO2- (CH2) 3Si (CH3) or -? (OR12) 3-2 , wherein R12 is an unsubstituted or substituted, unbranched or branched alkyl radical having 1 to 12 carbon atoms and R13 is hydrogen or methyl. Preferred silanes are vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane, vinylmethyldisopropoxysilane, vinylmethyldi-n-butoxysilane, vinylmethyldi-sec-butoxysilane, vinylmethyldi-tert-butoxysilane, vinylmethyldi (2-methoxyisopropyloxy) silane, and vinylmethyldioctyloxysilane. Especially preferred silanes are of the formula CH2 = CR13 (CH2) 0-? Si (OR14) 3 and CH2 = CR13CO2- (CH2) 3Si (OR14) 3, wherein R14 is a branched or unbranched alkyl radical having 1 to 4 carbon atoms and R13 is hydrogen or methyl. Examples thereof are α- (meth) acryloyloxypropyltris (2-methoxyethoxy) silane, α- (meth) acryloyloxypropyltrismethoxysilane, α- (meth) acryloyloxy-propyl-isomethoxysilane, α- (meth) acryloxy-1-oxlpropyltri-3-propaxysilane,? - (meth) acryloyloxypropyltrisisopropoxy silane,? - (meth) acryloyloxypropyltrisbutoxy silane,? -acyloxypropyltris (2-methoxyethoxy) silane,? -acyloyloxypropyltrismethoxysilane,? - acryloyloxypropyltrisetoxysilane,? -acyloxypropyltris-n-propoxysilane,? -acryloyloxypropyl -trisisopropoxysilane,? -acyloxypropyltrisbutoxysilane and vinyltris (2-methoxy-ethoxy) silane, vinyltrismethoxysilane, vinyltrisetoxysilane, vinyltris-propoxysilane, vinyltrisisopropoxysilane and vinyltrisbutoxysilane. The indicated silane compounds, where appropriate, they can also be used in the form of their hydrolysates (partial). Particularly preferred silanes are primary and secondary aminoalkyl ethoxy silanes, bis (3-triethoxysilylpropyl) amine, trifunctional propyltrimethoxysilane (NH2 (CH2) 2-NH- (CH2) 2NH- (CH2) 3-Si (OCH3) 3], vinyltriethoxysilane (CH2 = CH-Si (OC2H5) 3], vinyltrimethoxysilane (CH2 = CH-Si (OCH3) 3], 3-glycidyloxy-propyltriethoxysilane, 3-aminepropyltrimethoxysilane, oligomeric diaminosilane system, glycidyltrimethoxy-functionalsilane, vinyltrietoxy -functional silane, glycidyltriethoxy-functionalsilane, vinyltrials (2-methoxyethoxy) silane, (3-glycidyloxy-propyl) trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, N - (2-aminoethyl) (3-aminopropyl) methyldimethoxy-silane, (3-aminopropyl) trimethoxysilane, (methacryloyloxymethyl) methyldimethoxysilane, (methacryloyloxymethyl) trimethoxysilane and / or (methacryloyloxy-methyl) methyldiethoxysilane. In the adhesive used according to the invention, the organosilane is typically present in an amount of 0.001% to 20% by weight, based on the solids content of the adhesive. Preferably, the organosilane is used in an amount of 0.001% to 10% by weight. Silane compounds, as is known, are also used to promote adhesion. The promotion of adhesion, however, does not necessarily lead to an improvement in resistance to enhancement in connection with the production of laminar units. For improved compatibility between polymer dispersion and silane compound it may be necessary to stabilize the polymer dispersion by adding surfactants or protective colloid prior to the addition of the organofunctional silane. The invention also provides a method for producing the above-described laminar unit, comprising the steps of i) coating at least one absorbent surface of a substrate with an adhesive comprising a polymer dispersion prepared by free radical emulsion polymerization and a organosilane which is incorporated into the polymer during the polymerization and / or subsequently added and which in addition to at least one silane group has at least one primary, secondary or tertiary amino group or at least one epoxide group or which comprises at least one less an ethylenically unsaturated group and at least one silane group, i) laminate a film to the surface coated with adhesive in a conventional manner, and iii) if desired, enhance the laminar unit on the side laminated with the film.

The laminar units of the invention can be used, for example, to produce packaging boxes and other packaging materials, book spines, brochures, advertising media, postcards, training cards, and also identity cards and chip cards. . These uses are probably provided by the present invention. In addition, the present invention provides the use of adhesives comprising an organosilane and a polymer dispersion prepared by free radical emulsion polymerization to bond polymeric films to porous substrates and for high gloss film lamination. The examples that follow elucidate the invention without restricting it.

EXAMPLE 1 An aqueous dispersion of an acrylate copolymer based on methyl methacrylate and 2-ethylhexyl acrylate, with the glass transition temperature, Tg of -18 ° C, was mixed with 0.5% or an emulsifier (Emulsogen EPN 287) and 0.5% of an aminosilane (N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane). The initial dispersion and the mixture were each adjusted, after dilution with water, to a viscosity of about 100 mPa * s (Brookfield RVT, Spindle 1120 rpm, 23 ° C) and used to laminate an OPP film (20 μm thickness, penetrated by crown action on one side; Trespaphan NND 20) to a sheet of paper (100 g / m2) printed in deep black.

The lamination was carried out in a laminating unit in which the adhesive was applied by air brush to the penetrated side of the OPP film. After the application of adhesive, the film passed through a drying tunnel operated at a temperature of 60-70 ° C. The lamination of the film and printing medium was carried out with thermal activation after passing through the drying tunnel, between a silicone roller and a roller heated to 80 ° C. In a portion of the laminated specimens, measurements of the peel strength and the heat stability at 80 ° C were made, in direct comparison. The results for peel strength were reported for different release rates, as averages of the three measurements in each case, in N / 2.5 cm. The results for heat stability are reported as the time after which a detachment length of 5 cm was reached at 80 ° C in a 2.5 cm wide sample under a load of 100 g or 200 g. Here again, the figure reported was the average of three individual measurements. A second portion of the laminated specimens was subjected to an enhancement test (flax pattern), 24 hr after rolling, in a roller enhancement unit, the pressure being set at a level such that there was no fiber elevation of paper on the raised edges. A self-assessment was made, 24 h after the enhancement, there were signs of, for example, gray coloration visible by delamination. These tests were always carried out in direct comparison.

TABLE 1 Results of rolling tests EXAMPLE 2 An aqueous dispersion of an acrylate copolymer based on methyl methacrylate and 2-ethylhexyl acrylate, with the glass transition temperature, Tg, of -18 ° C, was mixed with 1% or of an epoxysilane (gamma-glycidyloxypropyltrimethoxysilane) . The initial dispersion and the mixture were each adjusted, after dilution with water, to a viscosity of about 100 mPa * s (Brookfield RVT, Spindle 1120 rpm, 23 ° C) and used to laminate an OPP film (20 μm) of thickness, penetrated by the action of a crown on one side, Trespaphan NND 20) to a sheet of paper (100 g / m2) printed in deep black.

The lamination and the measurement of the properties of the laminated specimens were carried out in the same manner as for Example 1. The results are shown in Table 2.

TABLE 2 Results of rolling tests EXAMPLE 3 An aqueous dispersion of an acrylate copolymer based on methyl methacrylate and butyl acrylate, with the glass transition temperature, Tg of -20 ° C, was mixed with 0.5% of an epoxysilane (gamma-glycidyloxypropyltrimethoxysilane). The initial dispersion and the mixture were each adjusted, after dilution with water, to a viscosity of about 100 mPa * s (Brookfield RVT, Spindle 1120 rpm, 23 ° C) and used to laminate an OPP film (20 μm) of thickness, penetrated by crown action on one side, Trespaphan NND 20) to a sheet of paper (100 g / m2 printed in deep black) Lamination and measurement of the properties of the laminated specimens were carried out from the same way than for the example 1. The results are shown in table 3.

TABLE 3 Results of rolling tests EXAMPLE 4 An aqueous dispersion of an acrylate copolymer based on methyl methacrylate and butyl acrylate (Acronal® A 310) was mixed with 1% of an epoxysilane (gamma-glycidyloxypropyltrimethoxysilane). The initial dispersion and the mixture were each adjusted, after dilution with water, to a viscosity of about 100 mPa * s (Brookfield RVT, Spindle 1120 rpm, 23 ° C) and used to laminate an OPP film (20 μm) of thickness, penetrated by the action of a crown on one side, Trespaphan NND 20) to a sheet of paper (100 g / m2) printed in deep black. Lamination and measurement of the properties of the laminated specimens were carried out in the same way as for example 1. The results are shown in table 4.

TABLE 4 Results of the rolling tests EXAMPLE 5 A dispersion of finely divided anionically stabilized copolymer, with 25% methyl methacrylate and 75% butyl acrylate as main monomers (solids content: 50.5% or, pH: 8.2, Tg: -21 ° C, size distribution of particle: Mastersizer, evaluation of multimodal MiE: dn = 220 nm, dw = 260 nm) was mixed with 1% > of aminosilane (N- (2-amino-ethyl) (3-aminopropyl) trimethoxylane). The initial dispersion and the mixture were each adjusted, after dilution with water, to a viscosity of about 100 mPa * s (Brookfield Rv: r, Spindle 1120 rpm, 23 ° C) and used to laminate an OPP film ( 20 μm thick, penetrated by corona on one side, Trespaphan NND 20) onto a sheet of paper (100 g / m2) printed in deep black. Lamination and measurement of the properties of the laminated specimens were carried out in the same manner as for Example 1. The results are shown in Table 5.

TABLE 5 Results of rolling tests EXAMPLE 6 A dispersion of finely divided anionically stabilized copolymer with 30% methyl methacrylate and 70% 2-ethylhexyl acrylate as main monomers (solids content: 52.3%, pH: 8.0, Tg: -18 ° C, size distribution) of particle: Mastersizer, evaluation of multimodal MiE: dn = 190 nm, dw = 200 nm) was mixed with 1% epoxysilane (gamma-glycidyloxypropyltrimethoxysilane). The initial dispersion and the mixture were each adjusted, after dilution with water, to a viscosity of about 100 mPa * s (Brookfield RVT, Spindle 1/20 rpm, 23 ° C) and used to laminate an OPP film ( 20 μm thick, penetrated by a crown on one side; Trespaphan NND 20) to a sheet of paper (100 g / m2) printed in deep black. Lamination and measurement of the properties of the laminated specimens were carried out in the same manner as for example 1. The results are shown in table 6.

TABLE 6 Results of rolling tests

Claims (22)

NOVELTY OF THE INVENTION CLAIMS

1. - An expandable laminar unit comprising: a) a substrate in the form of a sheet having at least one absorbent surface, b) a film c) is attached to the substrate by means of an adhesive comprising a polymer dispersion prepared by polymerization in free radical emulsion and an organosilane which is incorporated into the polymer during the polymerization and / or subsequently added and which in addition to a silane group has at least one primary, secondary or tertiary amino group or at least one epoxide group or comprising at least one ethylenically unsaturated group and at least one silane group.

The laminar unit according to claim 1, further characterized in that said substrate is selected from the group consisting of papers, cardboards, cartons and other fiber strips.

3. The laminar unit according to claim 2, further characterized in that the substrate is printed and / or coated.

4. The laminar unit according to claim 1, further characterized in that the film is selected from the group consisting of thin sheets of metal or polymeric films.

5. The laminar unit according to claim 4, further characterized in that the substrate is printed and wherein the polymer film transmits the light.

6. The laminar unit according to claim 1, further characterized in that the polymer dispersion prepared by free radical emulsion polymerization is a polyacrylate or a polyvinyl ester, preferably a polyacrylate or a polyvinyl ester having a transition temperature of glass below 15 ° C.

7. The laminar unit according to claim 1, further characterized in that the polymer dispersion prepared by free radical emulsion polymerization is derived from the main monomers vinyl acetate / butyl acrylate, vinyl acetate / dibutyl maleate, vinyl acetate / dibutyl fumarate, vinyl acetate / 2-ethylhexyl acrylate, vinyl acetate / ethene / butyl acrylate, vinyl acetate / ethene / dibutyl maleate, vinyl acetate / ethene / dibutyl fumarate, acetate vinyl / ethene / 2-ethylhexyl acrylate, methyl methacrylate / butyl acrylate, methyl methacrylate / 2-ethylhexyl acrylate, styrene / butyl acrylate, styrene / 2-ethylhexyl acrylate, methyl methacrylate / butyl isoacrylate or methyl methacrylate / isopropyl acrylate.

8. The laminar unit according to claim 1, further characterized in that the polymer dispersion prepared by free radical emulsion polymerization is derived from the main monomers vinyl acetate / vinyl chloride / ethene, vinyl acetate / laurate vinyl / ethene, vinyl acetate / vinyl laurate / ethene / vinyl chloride, vinyl acetate / versic acid vinyl ester / ethene / vinyl chloride, versic acid vinyl ester / ethene / vinyl chloride, vinyl acetate / Versatic acid / ethene vinyl ester, and vinyl acetate / ethene, the vinyl acetate / ethene combination being particularly preferred.

9. The laminar unit according to claim 1, further characterized in that said organosilane is a compound of the formula I or II (H), in which R1 is - (CH2) n-NH-R4, - (CH2) n -NH - [(CH2) m -NH] o -R4, - (CH2) nO-R5 or - (CH2 )? - CH = CH2, R2 is hydrogen, - (CH2) n-CH3 or R1, R3 is hydrogen, - (CH2) n-CH3 or R2, R4 is hydrogen, - (CH2) n- CH3 or -CO- (CH2) m-CH3, and R5 is hydrogen, - (CH2-CH2-O) m-R4 or n and m each independently of the other being an integer between 0 and 12, and o being an integer between 0 and 5.

10. The laminar unit according to claim 1, further characterized in that said organosilane is a compound which in addition to at least one silane group has at least one primary, secondary or tertiary amino group or at least one epoxide group.

11. The laminar unit according to claim 10, further characterized in that said organosilane is a compound of formula III, IV, V or VI: (Re6-O) 3-Si- (CH2) p-NH- (CH2) p-Si- (O-R6) 3 ( lll), (Re6-O) 3-Si- (CH2) pN [- (CH2) p-Si- (O-R6] 2 (IV), (Re6-O) 3-Si- (CH2) PO-R7 (V), (Re6-O) 3-S i- (CH 2) P-NR 8 R 9 (VI), in which R 6 independently at each occurrence is hydrogen or C 1 -C 7 alkyl, preferably methyl, ethyl or propyl, R 7 is a glycidyl radical (1,2-epoxypropyl), R8 and R9 independently of one another are hydrogen or alkyl of CI-CT, and p is an integer between 1 and 12.

12. The laminar unit accog to claim 11, characterized in addition because said organosilane is a compound of the formulas (CH3-CH2-O) 3-Si- (CH2) p-NH- (CH2) p-Si- (O-CH2-CH3) 3, (CH3-O) 3 -Si- (CH2) p -NH- (CH2) pSi- (O-CH3) 3, (CH3-CH2-O) 3 -Si- (CH2) pN [- (CH2) p-Si- ( O-CH2-CH3) 3] 2, and / or (CH3-O) 3-Si- (CH2) pN [- (CH2) p-Si- (O-CH3) 3] 2, in which p is as is defined in claim 11.

13. The laminar unit accog to claim 1. 1, further characterized in that said organosilane is an ethylenically unsaturated compound containing silane groups of the formula R11Si (CH3) or-2 (OR12) 3- ?, wherein R11 has the definition CH2 = CR13 (CH2) or-? or CH2 = CR13CO2- (CH2)? -3, R12 is an unsubstituted or substituted, unbranched or branched alkyl radical having 1 to 12 carbon atoms and can be Uninterrupted or interrupted by an ether group, and R13 is hydrogen or methyl.

14. The laminar unit accog to claim 1, further characterized in that said organosilane is an ethylenically unsaturated compound containing silane groups and of the formulas CH2 = CR13 (CH2) or-? S1 (CH3) or -? (OR12 ) 3-2 and CH2 = CR13CO2- (CH2) 3Si (CH3) or -? (OR12) 3- 2, wherein R12 is an unsubstituted or substituted, unbranched or branched alkyl radical having 1 to 12 carbon atoms and R13 is hydrogen or methyl.

15. The laminar unit accog to claim 14, further characterized in that said organosilane is a compound selected from the group consisting of vinylmethyldimethoxysilane, vinylnietyldiethoxysilane, vinylmethyl-propoxysilane, vinylmethyldisopropoxysilane, vinylmethyldi-n-butoxysilane, vinylmethyldi-sec-butoxysilane. , vinylmethyldi-tert-butoxysilane, vinylmethyldi (2-methoxyisopropyl-oxy) silane and / or vinylmethyldioctyloxysilane.

16. The laminar unit accog to claim 14, further characterized in that said organosilane is a compound of the formula CH2 = CR13 (CH2) o-? Si (OR14) 3 and CH2 = CR13CO2- (CH2) 3Si (OR14) ) 3, wherein R14 is a branched or unbranched alkyl radical having 1 to 4 carbon atoms and R13 is hydrogen or methyl.

17. The laminar unit accog to claim 16, further characterized in that said organosilane is a compound selected from the group consisting of? - (meth) acryloyloxypropyltris (2-methoxyethoxy) silane,? - (meth) acryloyloxypropyltrismethoxysilane ,? - (meth) acryloyloxypropyltrisetoxy-silane,? - (meth) acryloyloxypropyltris-n-propaxysilane,? - (meth) acryloyloxypropyltrisaminepropoxysilane,? - (meth) acryloxypropyltris - butoxysilane, -acriloiloxipropiltris (2-methoxyethoxy) silane,? -? acriloiloxipropiltrismetoxisilano, -acriloiloxipropiltrisetoxisilano, n-propoxysilane -acriloiloxipropiltris-, -acríloiloxipropíltrisisopropoxisilano, -acriloiloxipropiltrisbutoxisilano and vinyltris (2-methoxyethoxy) silane, viniltrismetoxisiiano, viniltrisetoxisilano, vinyltris??? -n-propoxysilane, vinyltrisisopropoxysilane and vinyltrisbutoxysilane.

18. The laminar unit accog to claim 1, further characterized in that the organosilane is a compound selected from the group consisting of primary and secondary aminoalkyl-ethoxysilanes, bis (3-triethoxy-1-propyl) amine, Trifunctional propyltrimethoxysilane (NH2 (CH2) 2-NH- (CH2) 2NH- (CH2) 3-Si (OCH3) 3], vinyltriethoxysilane vinyltrimethoxysilane (CH2 = CH-S i (OCH3) 3], 3-glycidyloxy-propyltriethoxysilane, -aminapropyltrimethoxysilane, oligomeric diaminosilane system, glycidyltrimethoxy-functionalsilane, vinyl-triethoxy-funclionalsilane, glycidyl-triethoxy-functional-silane, vinyltris (2-methoxyethoxy) silane, (3-glycidyloxy-propyl) trimethoxysilane, N- (2-amynoethyl) (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane , N- (2-aminophenyl) (3-aminopropyl) methyldimethoxysilane, (3-aminopropyl) trimethoxysilane, (methacryloyloxymethyl) methyldimethoxysilane, (methacryloyloxymethyl) trimethoxysilane and / or (methacryloyloxymethyl) methyldiethoxysilane.

19. The laminar unit according to claim 1, further characterized by having an enhancement on the side of the film.

20. A process for producing the laminar unit according to claim 1, comprising the steps of: i) coating at least one absorbent surface of a substrate with an adhesive comprising a polymer dispersion prepared by emulsion polymerization free radicals and an organosilane which is incorporated into the polymer during the polymerization and / or is subsequently added and which in addition to at least one silane group has at least one primary, secondary or tertiary amino group or at least one epoxide group or comprising at least one ethylenically unsaturated group and at least one silane group, i) laminating a film to the surface coated with adhesive in a conventional manner, and i) if desired, enhancing the laminar unit on the side laminated with the film.

21. The use of the laminar unit according to claim 1, to produce packaging boxes, other packaging materials, book spines, brochures, advertising media, postcards, training cards, identity cards and cards. chips

22. The use of adhesive comprising a polymer dispersion prepared by free radical emulsion polymerization and an organosilane which is incorporated into the polymer during the polymerization and / or subsequently added and which in addition to at least one silane group has at least one primary, secondary or tertiary amino group or at least one epoxide group or which comprises at least one ethylenically unsaturated group and at least one silane group for bonding polymer films to porous substrates or for film lamination. high brightness.