Adhesives with latent reactivity for identification documents

FIELD: printing.

SUBSTANCE: group of inventions relates to production of identification documents, made of thermoplastic material and a method of their manufacture. The identification document comprises the layers A), B) and C), at that the layer A) is thermoplastic, the layer B) is made of a storage-stable adhesive with latent reactivity, and the layer C) is thermoplastic, at that the adhesive comprises an aqueous dispersion comprising a diisocyanate or polyisocyanate with a melting point or, respectively, softening point above +30°C and the polymer reactive towards isocyanates, which is polyurethane composed of crystallised polymer chains which, according to the study results, by thermomechanic method at temperatures below +110°C decrystalise partially or completely.

EFFECT: exclusion of layers stratifying.

11 cl, 8 ex, 8 tbl

The present invention relates to an identification document comprising the layers A), b) and C)and the layer (a) is a thermoplastic layer) made of the stability during storage of the adhesive with latent reactivity and the layer (C) is a thermoplastic.

In the manufacture of identification documents based on polycarbonate issue with the destruction complex (e) elements and diffractive structures (in particular, holograms) in the laminating process, if they are not equipped with a flexible packaging. Such problems until recently avoided through the creation of a directly around the subject lamination element filled cavities or through the use of thermoelasticity/thermoplastic buffer layers consisting, for example, of thermoplastic polyurethane. Such "soft" layer is designed to reduce mechanical stresses in the laminating process. The material of such layer on the chemical nature different from the material from which is comprised the identification document, that is, in principle, it is an alien body that is a weak point of identification documents with a high degree of protection against forgery.

With the introduction of identification documents polycarbonate based electronic components, primarily the integral is s circuits (chips), if too thin semiconductor structures arises the problem of premature destruction of the element in the laminating process. In the case of known manufacturing smart cards polycarbonate, carried out by lamination of the individual film layers, it comes to the fact that the polycarbonate film is directly above the chip. In accordance with the industrial technology pre-prepared components such cards pressed into the corresponding "quasimonopoly" block under the simultaneous effect of temperature and pressure. Since the polycarbonate due to the characteristic of the heat transfer coefficient does not immediately softened, directly on the chip operates high blood pressure, which in most cases determines its mechanical destruction.

In the case of supply of electronic elements self-adhesive film, they can be bonded with the card. However, the respective adhesive layers usually are the weak point of the structure of such maps: water vapor and the air is easier to diffuse inside her over the edge, which may lead to subsequent delamination of the map. The delamination of the card, and, consequently, its unfit for further use can be attributed to other influences of the external environment, primarily variable temperature is dependent.

Adhesives with latently reactivity known, for example, from European patent application EP-A-0922720. Such adhesives in principle contain two solid phases, such as a mixture of two crystalline substances at room temperature or normal ambient conditions do not interact with each other. These substances enter into chemical interaction with each other only when activated by, for example, by heating.

In accordance with German patent DE 3112054, DE 3228723 and DE 3228724 carry out surface deactivation powdered finely dispersed solid polyisocyanates with a particle diameter of 150 μm. Surface treatment provides a constant content of isocyanate groups and the reactivity of these polyisocyanates, and stable one-component system formed in water or water-containing solvents.

In accordance with German patent DE 3228724 and DE 3230757 surface deactivated powder diisocyanate combined with polyols and water dispersions containing the functional group of the polymer, having a stable when stored reactive pasta. By heating such water-containing paste to 140°C., i.e. to a temperature higher than the temperature of the entry MDI in response, going on the t followed by the binding interaction of both components with the formation of the slightly foamed elastic coating.

Method of preparation of stable dispersions of finely dispersed isocyanate with deactivated surface is described in German patent DE 3517333. The resulting stable dispersion suitable for use as cross-linking agents.

On the application of aqueous dispersions of surface-deactivated finely dispersed solid polyisocyanates as crosslinking agents in pigment pastes and dye solutions for printing on textile is reported in the German patent DE 3529530. Upon completion of the process of applying pigment pastes and dyeing solutions they are fixed on the fabric by means of hot air or steam.

The disadvantage described in the cited publications systems is the lack of a separate implementation of the business operations of their application and curing, respectively stitching that for economic and logistical reasons, obviously, it is desirable for many applications of such systems.

Separate implementation of these operations, for example, would be applied to the substrate layer or powder stable during storage of the adhesive with latent reactivity in a place where there is suitable equipment, to store the obtained semi-finished product for a specified period of time, and then transport it to the place of processing in other intermediate products which you or a final product.

Stable during storage masses or layers of latent reactivity described in international application WO 93/25599. Such masses or layers consist of reactive towards isocyanate polymers with a melting point above 40°C and surface-deactivated polyisocyanates. With the aim of producing a mixture of these components is melted at temperatures that are much higher than the softening temperature of the polymer. This technology in addition to the high cost of energy is a significant cost of equipment for the manufacture and application of these masses. In addition, to ensure the stability and the possibility of processing in such a system can be used only superficially deactivated polyisocyanates, temperature stitching which exceeds 80°C. Along with this object cited application is targeted and controlled inhomogeneous mixing of the components. However, it requires the implementation of appropriate expensive labour operations.

Based on the foregoing, the present invention was based on the task to propose a new identification documents with improved protection against forgery, and the method of their manufacture. In the first place was to reduce the tendency of identification documents to delamination

According to the invention this task is solved through an identification document, comprising the layers A), b) and C)and the layer (a) is a thermoplastic layer) made of the stability during storage of the adhesive with latent reactivity and the layer (C) is a thermoplastic.

In accordance with the present invention under identification document imply having the flat shape of the multilayer document, with protective signs, such as chips, photographs, biometric data, and the like. Such protective signs should be visually distinct, or at least read from the external side of the identification document. Identification document usually has a size intermediate between the size of a Bank card and passport. Identification document may be part of a multi-part document, for example, it may be composed of a polymeric material identification document as part of the passport, including the paper or cardboard parts.

The present invention in another embodiment, implementation refers to the identification document, wherein the adhesive consists of an aqueous dispersion containing a diisocyanate or polyisocyanate with a melting point, respectively RASMAG the tion, above 30°C, and reactive towards isocyanate polymer.

The present invention in another embodiment, implementation refers to the identification document, wherein the adhesive consists of an aqueous dispersion, the viscosity of which is at least 2000 mPas.

The present invention in another embodiment, implementation refers to the identification document, wherein the reactive towards isocyanate polymer is a polyurethane, comprising crystallizing polymer chains, which according to the research thermomechanical method at temperatures below +110°C, preferably below +90°C, partially or fully decrystallization. Thermo-mechanical method is used to control the crystallinity, as specified in ISO 11359, part 3, "temperature Determination of penetratie".

The present invention in another embodiment, implementation refers to the identification document, wherein the diisocyanate or polyisocyanate is selected from the group comprising a product of the dimerization, trimerization product and urea derivatives diisocyanate, respectively isophorondiisocyanate.

The present invention in another embodiment, implementation refers to the identification document, wherein the adhesive with which the Association is made in the following way: at first be used for bonding the substrate to cause a variance under paragraph 1 of the claims, which is then dried, the dried adhesive layer is subjected to testing by briefly heating, the duration of which is preferably less than 5 minutes, to a temperature greater than 65°C, preferably in the range from 80 to 110°C, and in decrystallization able to connect with the second subject to the bonding substrate.

In accordance with the present invention under thermoplastic mean a thermoplastic polymer, such as polycarbonate, polymethylmethacrylate, polystyrene or copolymer of styrene, for example, preferably transparent polystyrene or copolymer of styrene with Acrylonitrile, transparent thermoplastic polyurethanes, and polyolefins, for example, preferably transparent grades of polypropylene or polyolefins based on cyclic olefins (e.g., TOPAS^®company Topas Advanced Polymers, polycondensation products or copolycondensation terephthalic acid, for example, preferably polyethylene terephthalate, spriterenderer or modified glycol terephthalate, polietilenglikolsuktsinata or transparent polysulfones.

The present invention in another embodiment, implementation refers to the identification document, wherein thermoplastic polymer layer (A) and layer (C) independently from each other selected from the group including polycarbonate, polycondensation products or copolycondensation terephthalic acid, for example, preferably polyethylene terephthalate, spriterenderer or modified glycol terephthalate.

Thus, laminates, used primarily for the manufacture of identification documents with a high degree of protection against forgery and including at least one stable during storage layer with latent reactivity, can be manufactured through the use of mostly water dispersion containing at least one surface-deactivated the polyisocyanate and at least one reactive towards isocyanates, dispersed or dissolved polymer.

The object of the present invention is also a method of manufacturing a layered materials, at least one stable during storage and having latent reactivity layer, in accordance with which:

A.) predominantly aqueous dispersion or solution of at least one reactive towards isocyanate polymer is mixed

b.) at least one predominantly suspended in water, surface-deactivated solid, finely dispersed polyisocyanate,

C) the mixture when neo is needed to be applied on the substrate layer of specified thickness, and

d.) present in a mixture of water are removed at a temperature below the entry of isocyanate in the reaction,

in the result that are mainly dry and waterless layers or masses, which at temperatures below the temperature of the MDI interaction with the polymer are stable during storage and latent reactivity.

Unexpectedly, it was found that the removal of water and drying the above mixture can be made:

i) in the temperature interval from room temperature to the softening temperature of the polymer with functional groups, or

ii) at a temperature exceeding the softening temperature of the polymer with functional groups,

provided that none of these cases, the temperature does not exceed the temperature of the joining surface Deaktivierung MDI reaction. Regardless, in accordance with any of paragraphs (i) or (ii) perform drying, surface-deactivated solid, finely dispersed polyisocyanates after drying are present in essentially anhydrous polymer in intact and unreacted state, respectively distributed in anhydrous layer or powder and implemented in their state. Dispersion, suspension or solution of the polymer and the suspended surface-deactivated isocyanate moving in the wrong is on-going phase unstitched polymer, in which suspended unreacted surface deactivated, fine isocyanates.

In case (i) are formed waterless dry film or waterless dry powder with latent reactivity, suitable for storage at room or slightly higher temperature. In such case, provide the ability of surface-deactivated isocyanate to interact with the functional groups of the polymer.

In case (ii) after evaporation of the water formed by the fused system. An example of such technology is the manufacture of the laminated material by bonding films. When this surface-deactivated isocyanate also remain unchanged and retain their reactivity. The bonding in the first place due to thermoplastic properties of the polymer.

In both cases, the binding system, in which it becomes infusible and insoluble, occurs only at temperatures exceeding the temperature of the joining surface Deaktivierung isocyanate in the reaction. Crosslinking occurs after a specified period of time.

In some cases, to initiate the crosslinking reaction is sufficient to briefly exceed the temperature of the joining surface Deaktivierung of the cyanate reaction. The temperature enters the deactivated polyisocyanates in the reaction or increase their viscosity should be in the range from 30 to 180°C., preferably from 40 to 150°C.

The temperature increase of the viscosity or the entry deactivated polyisocyanates in the reaction means the temperature at which the surface-deactivated layer of isocyanate dissolved in the polymer or destroyed otherwise. When this occurs, the release of MDI and its dissolution in the polymer. Final curing occurs due to diffusion of MDI and its interaction with the functional groups of the polymer, followed by increased viscosity and crosslinking. Depending on the type of surface Deaktivierung MDI temperature increasing the viscosity or the entry of isocyanate in the reaction is above or below the softening temperature of the polymer.

The stability of unreacted system, as well as temperature and reaction are determined by the type MDI, type, and quantity of surface stabilizer, the solubility parameters of the polymer with functional groups, as well as catalysts, plasticizers and other auxiliary materials. These products are discussed in detail in the references cited at the beginning of the present description publications.

In addition, what bhakta of the present invention is the processing of the substrate, implemented after applying a layer or powder. We are talking about the final processing of the substrate, for example, by punching, cutting, bending, jointing, laminating, or other methods. At this unexpected circumstance was also proposed processing in the invention of film or powder in a plastic condition. After days or even months layer or the powder can be heated to a temperature exceeding the softening temperature of the polymer, without interaction of the functional groups of the last surface with empty isocyanates. Recycling in the plastic state of the layer or powder can be made after repeated heating and cooling.

In accordance with a preferred embodiment of the invention, films or powders are having latent reactivity and stability during storage of the adhesive systems.

Drawing on electronic items such self-adhesive film with latent reactivity enough to hold them with the relevant identification documents. With the invention of the adhesive layers are not the weak point in the structure of the past, because the water vapor and air can diffuse through the edge and cause delamination of the documents. PR is this attached to the document electronic element cannot be separated from it without failure.

For carrying out the invention method as polyisocyanates you can use any of the diisocyanates, polyisocyanates or mixtures thereof, provided that the temperature of their melting point greater than 40°C and that they can be well-known methods translated in powder form with a particle size less than 200 microns. Suitable are aliphatic, cycloaliphatic, heterocyclic or aromatic polyisocyanates. Examples of such compounds are difenilmetana-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, dimeric 1-methyl-2,4-delete the entry, 3,3'-diisocyanato-4,4'-dimethyl-N,N'-diphenylacetone, the product of the merger of two moles of 1-methyl-2,4-phenylenediamine to one pray 1,2-ethanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol or ethanolamine, and isocyanurate isophorondiisocyanate.

The above mentioned addition products allow you to achieve the benefits in case of their use for carrying out the invention method not only in the form of aqueous dispersions. The addition products of 1-methyl-2,4-phenylene-diisocyanate to 1,4-butanediol or 1,2-ethanediol also have very favorable properties when used in solid and liquid systems, whether or not containing solvent. Such systems are primarily distinguished low is the temperature of curing, accordingly stitching, which corresponds to the temperature region below 90°C. In this regard, highly preferred is the use of such a mixture mainly water or polyol as one basis for use on temperature-sensitive substrates and bonding.

Response surface stabilization can be realized by the following methods.

By dispersing powder of isocyanate in the solution of deactivator.

By introducing a molten low-melting MDI in solution deactivator in nerastvorim the polyisocyanate liquid dispersant.

By adding deactivator or his solution to the dispersion of solid fine isocyanates.

The concentration of deactivator should be from 0.1 to 25% EQ., preferably from 0.5 to 8% EQ. in terms of the total number of isocyanate groups.

For implemented according to the invention using powder polyisocyanates it is often necessary to set the size of the particles in the range from 0.5 to 20 μm, for which the polyisocyanates after synthesis is subjected to fine dispersion or grinding in the wet state. For this purpose, suitable dissolvers, dispersal device type rotor-stator, ball mills with a stirrer, a bead mill, a mill for grinding sand, ball grounding the Itza and kraskoterke, operating at temperatures below 40°C. depending on the type of MDI and its use grinding Deaktivierung MDI perform in the presence of deactivator, directionspanel the dispersant or water with subsequent deactivation. Ground and surface stabilized polyisocyanate you can also select from the resulting grinding dispersion and subjected to drying.

For the regulation of surface deactivate and the crosslinking reaction can also use catalysts. Preferred are catalysts resistant to hydrolysis in aqueous solution or dispersion and, therefore, able to accelerate subsequent thermally activated reaction. Examples of suitable urethane catalysts synthesis are organic compounds of tin, iron, lead, cobalt, bismuth, antimony, or zinc, and mixtures thereof. Due to the increased resistance to hydrolysis preferred catalysts are allylmercaptan connection dibutylamine.

For special purposes or in combination with catalysts based on metals it is possible to use tertiary amines, such as dimethylbenzylamine or databaseconnect, as well as non-volatile catalysts foaming of polyurethanes based on tertiary amines, but it may mean the ing to the loss of catalytic activity due to the interaction with airborne carbon dioxide.

The concentration of catalyst is in the range from 0.001 to 3%, preferably from 0.01 to 1% in terms of the reactive system.

Water dispersion to offer in the invention compositions contain (preferably in the form of reactive towards isocyanates dispersed polymer) polyurethane, respectively polycarbamide dispersion with crystalline plasticizer segments complicated polyester. Especially preferred are dispersions of reactive towards isocyanate polyurethanes with crystal, respectively semi-crystalline polymer chains that are at least partially loses defined thermomechanical method crystallinity in the temperature interval from 50 to 120°C.

If necessary, you can also enter dispersions of polyacrylates, however, it is preferable to use polyurethane, respectively polycarbamide dispersions with crystal plasticizing segments complicated polyester.

As proposed in the invention of reagents that interact with polyisocyanates, use water-soluble or water-dispersible emulsion or dispersion polymers with functional groups which are reactive towards isocyanates. On the one polymers get known from the prior art methods of polymerization refinancing monomers in solution, emulsion or suspension. Film-forming polymers contain from 0.2 to 15%, preferably from 1 to 8% of monomer units with reactive towards isocyanate groups, such as hydroxyl group, amino group, carboxyl group or urea group.

Examples of these monomers with functional groups are allyl alcohol, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, potentialtheorie, ethoxylated or propoxycarbonyl acrylates or methacrylates, N-methylolacrylamide, tert-butylmethacrylate, acrylic acid, methacrylic acid, maleic acid and esters of maleic acid. As co monomer can also be used glycidylmethacrylate or allylglycidyl ether. The latter contain an epoxy group, which is implemented by additional stages of interaction with amines or aminoalcohols, for example, ethylamine, ethylhexylamine, isononylphenol, aniline, toluidine, xylidine, benzylamine, ethanolamine, 3-amino-1-propanol, 1-amino-2-propane, 5-amino-1-pentanol, 6-amino-1-hexanol or 2-(2-aminoethoxy)ethanol can be converted into the secondary amino group.

The specified transformation increases the reactivity of the functional groups of the polymer with respect to sociality groups, reducing the likelihood of adverse reactions with water.

Suitable are water-soluble binder with a hydroxyl functional groups, such as polyvinyl alcohol, partially saponified polyvinyl acetate, hydroxyethyl cellulose, hydroxypropylcellulose, and water-dispersible polyesters and culpability with hydroxyl functional groups of the polyurethane dispersion and dispersion polyamidoamine containing carboxyl groups, hydroxyl groups and primary or secondary amino group.

In addition, you can use get in a colloidal mill aqueous colloidal dispersions or colloidal solutions of thermoplastic polymers with reactive towards isocyanate groups. An example of such products are high molecular weight solid epoxy resin, a copolymer of ethylene with vinyl alcohol and a copolymer of ethylene and acrylic acid with a particle size in the range from 1 to 100 nm.

By mixing or dispersing in the resulting viscous paste or low viscosity mixture, you can enter additional inert or functional additives. Such functional additives include powdered or liquid, low-molecular or high-molecular compounds with functional hydroxyl or amino groups, which is the contrasted to interact with the solid polyisocyanates at temperatures above the temperature of the last entry in the response. Such functional additives should be used in the appropriate stoichiometric number. Under low-molecular functional additives include compounds with a molecular weight in the range from 40 to 500 g/mol, while the molecular weight of high molecular weight functional additives corresponds to the interval from 500 to 10000 g/mol. The concern of low-molecular or high-molecular liquid polyols and/or polyamines, and solid polyfunctional polyols and/or aromatic polyamines. Examples of suitable functional additives are triethanolamine, butanediol, trimethylolpropane, ethoxylated bisphenol-a, polypropylenglycol with ethoxylated terminal groups, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2-6-diamine, polytetramethylene-di(p-aminobenzoate), trihydroxide-isocyanurate, bishydroxyethyl ether of hydroquinone, pentaerythritol, 4,4'-diaminobenzanilide and 4,4'-Methylenebis(2,6-diethylaniline).

To inert additives include, for example, wetting agents, organic or inorganic thickeners, plasticizers, fillers, polymer powders, pigments, dyes, light stabilizers, antioxidants, anti-corrosion, fire-proof means, the pore-formers, resins to improve adhesion, organovo clonally silanes, staple fiber, and optionally minor quantities of inert solvents.

The advantages of the present invention are the ability to separate the operation of applying a water dispersion and reaction of crosslinking, i.e. the final curing. Because of this, for example, in a certain place can be applied to wood, glass or other substrates or base adhesive film, and then store the corresponding pre-manufactured semi-finished products and/or send them to another location for curing to the final product.

Another advantage of the invention method and application of relevant products is the use of water as a dispersion medium. Preparation of aqueous dispersions requires little power consumption. They contain the minimum amount of organic solvent, which is a prerequisite for favorable impact on the environment processing.

The original aqueous polymer dispersion allows to achieve additional advantages, which is the ability to smooth the introduction of the mixture is also surface-deactivated polyisocyanates, melting point which is in the range from 40 to 150°C. the temperature of the stitching can be from to 90°C. Due to the low temperature crosslinking given the opportunity bonding of such one-component system under the action of heat is also temperature sensitive substrates.

Made from an aqueous suspension, dispersion or solution layer or the powder can be stored for months. However, the length of storage at room or slightly higher temperature may vary depending on the ability of a solid film dissolving the polyisocyanate. Storage duration proposed in the invention system in anhydrous and unstitched condition, at least three times, usually more than 10 times higher compared to a similar mixture containing the same polyisocyanates, however, are not subjected to surface deactivation. Storage proposed in the invention of layers or powders at +2°C, they retain their stability and suitability for implemented according to the invention, the processing for at least six months, whereas in the case of storage at room temperature for a period of preservation of source properties is at least one month. The term "latent reactivity" is used to denote a condition predominantly anhydrous layer or powder in which the surface-deactivated the polyisocyanate and reactive in respect of which the isocyanate polymer are mainly in unstitched form.

Required for thermoplastic processing, as well as for stitching the heat can be summed preferably in the form of heat convection or heat radiation. Storable aqueous suspension, dispersion or solution of surface fine deactivated polyisocyanates and dispersed or water-soluble polymers containing reactive towards isocyanate groups, can be applied to the surface of the glue or supplied adhesive substrate primarily by smearing brush, spraying, splashing through squeegee, filling, watering, dipping, extruding, by the roll or by the method of printing.

Substrates suitable for making proposed in the invention of layered materials are thermoplastic polymers, such as polycarbonates or copolycarbonates based diphenols, polyacrylates, copolymers of acrylates, polymethacrylates or copolymers of methacrylates, for example, preferably polymethylmethacrylate, polymers or copolymers of styrene, for example, preferably transparent polystyrene or copolymer of styrene with Acrylonitrile, transparent thermoplastic polyurethanes, polyolefins, for example, preferably transparent grades of polypropylene or polyolefins based on cyclic olefins (e.g., TOPAS^{® company Topas Advanced Polymers, polycondensation products or copolycondensation terephthalic acid, for example, preferably polyethylene terephthalate, spriterenderer modified with glycol terephthalate or polietilenglikolsuktsinata and transparent polysulfones.}

^{The bonding of the substrates can be accomplished in one of the following methods.}

^{1. The bonding pressing, providing for the connection of the mating surfaces at room temperature, heated to a temperature higher than the softening temperature of the polymer, but lower than reaction temperature, and then cooled to room temperature. Receive a composite material with latent reactivity. This material can be subjected to further processing and molding, including, if the polymer is plastic, respectively thermoplastic condition. The final cross-linked state provide heated to a temperature higher than the temperature increase of the viscosity or the temperature of the reaction.}

^{2. The bonding pressing, providing for the connection of the mating surfaces at room temperature, heated to a temperature higher than the softening temperature of the polymer, forming a homogeneous adhesive film which wets the mating surface is knosti and stick to it, heated to a temperature higher than the temperature increase of the viscosity or the temperature of the reaction, and the final stitching.}

^{3. Translation of the mating surfaces in thermoplastic state, implemented by heating to a temperature exceeding the softening temperature of the polymer, the connection with the second substrate and the pressing is carried out by heating to a temperature exceeding the temperature increase of the viscosity or the temperature of the reaction. If necessary, in a thermoplastic state of a system can be subjected to further processing.}

^{In accordance with a second embodiment of the method is stable when stored water dispersion of surface-deactivated finely dispersed polyisocyanates and dispersed or water-soluble polymers with reactive towards isocyanate groups shape the adhesive film, adhesive tape, adhesive non-woven material or adhesive fabric with latent reactivity, which may be double-sided adhesion. With the aim of producing systems without substrate, such as an adhesive film or adhesive tapes offered in the invention dispersion is applied on neuzgesinama substrate in the form of a tape or on the separating paper and at room temperature or at temperatures below the softening temperature poly the EPA evaporated water. After cooling, the adhesive film can be separated from the substrate, without which it can be stored until use. In another embodiment, the adhesive film can be stored together with a paper backing.}

^{In the case of adhesive non-woven material or adhesive fabric reactive dispersion is applied by spraying, sprinkling, by squeegee, spray, dipping, add on, by the roll or by the method of printing, at room temperature or at temperatures below the softening temperature of the polymer evaporated water with or impregnated with an adhesive layer with a latent reactive adhesive non-woven material or adhesive fabric store to use.}

^{Adhesive tapes, adhesive tapes, adhesive non-woven material or adhesive fabric used as located between the substrates, the adhesive layer. In addition, adhesive film, adhesive non-woven material or adhesive fabric can be applied to the surface which is in plastic condition of the substrate or sintering with him. Such laminated material can be stored at room temperature before the final bonding surface of the second substrate.}

^{In accordance with a third embodiment of the method is stable when stored water dispersion of surface-deactivated finely dispersed polyisocyanates and dispergirovany the or water-soluble polymers with reactive towards isocyanate groups shape having latent reactivity of the powder. Such powders can be used as adhesives with latent reactivity or for the manufacture of coatings, such as powder lacquer coating.}

^{For the manufacture of powders of the invention dispersions of the latter can be sprayed in the spray dryer. The temperature of feed in the lower part of the spray drier air should be below the softening temperature of the polymer and the temperature of the joining surface is blocked MDI in response.}

^{In another embodiment of the proposed invention in the dispersion can be sprayed or applied with a method of printing on neuzgesinama surface rotating in a continuous loop tape. After the water evaporates dry particles are separated from the specified tape, if necessary, sieved and sorted, and stored until use.}

^{Powders with latent reactivity can be produced by crushing films or tapes without substrate, which optionally implement at low temperatures. Such powders are used as thermally activated stitched powdered adhesives or as powder coatings. Appropriate devices and application methods known in the art, and technology.}

^{Pre-manufactured proposed in the invention by way of layers with latents the Oh reactivity is preferably used as susceptible to temperature effects of adhesive joints for flexible or rigid substrates, for example, such as metals, polymeric materials, glass, wood, wood composite materials, cardboard, film materials, synthetic products flat shape or textile materials.}

^{Manufactured according to the invention the reactive powders for coatings can be processed also by the methods used for applying powder coating. Stitching should be done in dependent type MDI low temperature, thus avoiding thermal damage temperature sensitive substrates, such as polymeric materials, textiles and wood. Proposed in the invention method also allows to perform only the sintering of powders for coatings on the surface of the substrate or melting, ensuring the formation of a continuous layer. In this case, complete crosslinking is carried out at the subsequent heat treatment, if necessary after addition of the realized operation of mechanical or thermal processing.}

^Examples

^{A) Used trade products}

^{Dispercoll®U 53}

Polyurethane dispersion from Bayer MaterialScience AG 51368 Leverkusen) with a solids content of about 40% of the mass. (reactive towards isocyanates unbranched polyurethane). After drying the dispersion and cooling the film to 23 which the polymer is in the crystalline state. According to the study of film thermomechanical method at temperatures below +65°C it basically decrystallization.

Desmodur^®DN

Does not contain solvents hydrophilic modified crosslinking isocyanate-based trimer of hexamethylenediisocyanate. The content of NCO-groups of about 20%, viscosity at 23°C to about 1200 mPas.

Dispercoll^®BLXP 2514

The suspension surface Deaktivierung toluylenediisocyanate-uretdione (toluylene diisocyanate dimer) in water with a solids content of about 40%.

Dispercoll^®U VP KA 8755

Polyurethane dispersion from Bayer MaterialScience AG 51368 Leverkusen) with a solids content of about 40% of the mass.(reactive towards isocyanates unbranched polyurethane). After drying the dispersion and film cooling to 23°C. the polymer is in the crystalline state. According to the study of film thermomechanical method at temperatures below +65°C it basically decrystallization.

Borchi^®Gel L 75 N

Non-ionic liquid aliphatic thickener based on polyurethane with a viscosity at 23°C less than 9000 MPa·s and a content of non-volatile components of about 50 wt%.

Aqua Press^®ME

Trading milky-white dispersion of firm Pröll.

Borchi^®Gel ALA

An aqueous solution of anionic thickener on acrylate basis with Vascos the d at 20°C from 25,000 to 60,000 MPa·s (o'hare Chicago MARRIOTT, LVT, hydrometer IV, 6 rpm) and the content of non-volatile components about 10% of the mass.

Dispercoll KRAU 2756 K-1 (laboratory product)

Polyurethane dispersion from Bayer MaterialScience AG 51368 Leverkusen) with a solids content of about 45% of the mass. (reactive towards isocyanates linear polyurethane).

After drying the dispersion and film cooling to 23°C. the polymer is in a partially crystalline state. According to the study of film thermomechanical method at temperatures below +65°C it basically decrystallization.

Study of thermo-mechanical method was performed according to ISO 11359, part 3, "temperature Determination of penetration".

C) storage Options

Option a

Application of the dispersion at room temperature, the maximum removal of water by evaporation at room temperature (measured on the film), the laminating adhesive surfaces to a maximum of 3 hours at 90°or 120 ° C (object temperature), followed by crosslinking reaction. Cooling and storage of material within 24 hours under normal conditions.

Option

Application of the dispersion at room temperature, the maximum removal of water by evaporation at room temperature (measured on the film), storage under normal conditions for one day, followed by laminating at 90 or 120°C (object temperature) followed by crosslinking reaction. Cooling and storage of material within 24 hours under normal conditions.

Option

Application of the dispersion at room temperature, the maximum removal of water by evaporation at room temperature (measured on the film), storage under normal conditions for at least 7 days, followed by laminating at 90 or 120°C (object temperature), followed by crosslinking reaction. Cooling and storage of material within 24 hours under normal conditions.

Option D

Application of the dispersion at room temperature, the maximum removal of water by evaporation at room temperature. Excerpt provided with adhesive surfaces on the air for 21 days. Subsequent lamination at 90 or 120°C (object temperature), followed by crosslinking reaction. Cooling and storage of material within 24 hours under normal conditions.

C) Preparation of specimens and test methods

The resistance to delamination of the two glued films was determined according to DIN 53357.

The sample size of 200×50×0.15 mm³produced by bonding two films overlap by pressing. Leave free the plots of films with a length of about 40 mm was secured in the clamps of the machine for tensile test. The bonding area was about 160 x 50 mm². Resistance to delamination was measured at 120°C.

Below on the other test conditions and their deviation from the standard.

D) Application and testing of dispersions of reactive glue

Used dispersion glue

General method of preparation of dispersions of adhesive

First, by adding a thickener to increase the viscosity of the dispersion Dispercoll U.

Then under stirring to 100 mass Dispercoll U 53 add from 5 to 10 mass Deaktivierung MDI, receiving water suspension of the following composition.

Through dissolver carried out the preparation of the reactive dispersion adhesive with the following the following polyisocyanates:

Example 5 (comparative, not according to invention)

Commercial aqueous one-component adhesion promoter Aqua Press^®(firm Pröll KG, Weisenburg).

Example 6

The adhesive mixture from examples 1-5 by spiral doctor blade inflicted on structured on both sides special polycarbonate film for identification is ocuments Makrofol ^®ID 6-2 Bayer Material-Science AG with a thickness of 150 μm (6-I page: roughness R₃z about 9 μm; 2-I page: R₃z about 4 microns) layer of a thickness of 100 μm (wet). The film was dried under normal conditions.

Each of the supplied adhesive films once implemented in accordance with the options a-C storage was eliminirovali film Makrofol^®ID 6-2 thickness of 150 μm without the adhesive layer, and then performing tests of the material as specified in section C). Lamination (bonding pressing) was performed at 90 and 120°C With a compressing force of 2 kgf/cm².

Then determined the mechanical strength of the bonding depending on the storage option And-S (storage duration) and temperature lamination.

The determination of the stability of the films with the adhesive during storage continued for the best of the above systems (from example 3).

The adhesive mixtures of examples 7-8 through a spiral doctor blade inflicted on smooth on both sides special polycarbonate film for identification documents Makrofol^®ID 1-1 Bayer MaterialScience AG with a thickness of 250 μm layer thickness of 50 μm (wet). The film was dried in a vacuum drying Cabinet at 50°C.

Each of the supplied adhesive films once implemented in accordance with options a and D storage was eliminirovali film Makrofol^®ID 1-1 thickness of 250 μm without the adhesive layer, and then performed tests, as specified in section C). Lamination (bonding pressing) was performed at 120 and 135°With the compressing force of 2 kgf/cm².

Then determined the mechanical strength of the bonding depending on the storage option a or D (storage duration) and temperature lamination.

Laminated materials with the adhesive compositions of examples 7 and 8 even after storage for 21 days remain suitable for the formation of extremely durable adhesive bonding. At a temperature activated adhesive 135°To achieve higher bonding strength than 120°C.

After determination of the resistance of the glued film exfoliation their surfaces are so badly damaged that the possibility of their further use is excluded. Therefore, achieved the main use of identification documents with protection from forgery: elimination of thermal stratification films, glued by the glue and made according to the invention of examples, without damage.

1. Identification document comprising the layers A), b) and C)and the layer (a) is a thermoplastic layer) made of stabilin the th during storage of the adhesive with latent reactivity and the layer (C) is a thermoplastic, moreover, the adhesive consists of an aqueous dispersion containing a diisocyanate or polyisocyanate with a melting point or softening above +30°C, and reactive towards isocyanate polymer which is a polyurethane, comprising crystallizing polymer chains, which, according to the results of the study thermomechanical method, at temperatures below +110°C partially or fully decrystallized.

2. The identification document according to claim 1, characterized in that the reactive towards isocyanate polymer is a polyurethane, comprising crystallizing polymer chains, which, according to the results of the study thermomechanical method, at temperatures below +90°C partially or fully decrystallized.

3. The identification document according to claim 1, characterized in that the diisocyanate or polyisocyanate is selected from the group comprising a product of the dimerization, trimerization product and urea derivatives diisocyanate, or respectively isophorondiisocyanate.

4. The identification document according to claim 1, characterized in that thermoplastic layer a) and layer (C) independently from each other selected from the group including polycarbonate, polymethyl methacrylate, polystyrene, copolymers of styrene, for example, preferably transparent polystyrene or copolymer of styrene with Smoot is onitrile, transparent thermoplastic polyurethanes, polyolefins, for example, preferably transparent grades of polypropylene or polyolefins based on cyclic olefins, for example, TOPAS^®company Topas Advanced Polymers, polycondensation products or copolycondensation terephthalic acid, for example, preferably polyethylene terephthalate, spriterenderer or modified glycol terephthalate, polietilenglikolsuktsinata and transparent polysulfones.

5. The identification document according to claim 1, characterized in that thermoplastic layer a) and layer (C) independently from each other selected from the group comprising polycarbonate and polycondensation products or copolycondensation terephthalic acid, for example, preferably polyethylene terephthalate, spriterenderer or modified glycol terephthalate.

6. The identification document according to claim 1, characterized in that it contains an electronic element.

7. The identification document according to claim 1, wherein the electronic element is an integrated circuit chip.

8. A method of manufacturing an identification document according to claim 1, comprising the following stages:
i) mixing a predominantly aqueous dispersion or solution containing(s)reactive toward isocyanates, the polymer is suspended in water with a surfactant, Deactive ofanim a diisocyanate or polyisocyanate, moreover, the diisocyanate or polyisocyanate has a melting point or softening above +30°C, and reactive towards isocyanate polymer is a polyurethane, comprising crystallizing polymer chains, which, according to the results of the study thermomechanical method, at temperatures below +110°C partially or fully decrystallized.
ii) application received at stage i) of the mixture on the layer (A),
iii) removing water from the obtained in stage i) mixture at a temperature below the entry of the diisocyanate or MDI in the reaction, followed by formation of a layer),
iv) applying a layer (C) formed in stage (iii) layer).

9. The method according to claim 8, characterized in that water is removed at a temperature below the entry of isocyanate in the reaction, and therefore formed, mainly dry and solid layers at temperatures below the temperature of the MDI interaction with polymers, possess latent reactivity.

10. The method according to claim 8, characterized in that between the layers (A) and (C) carry out adhesive bonding due to the fact that the dried stage iii) layer) is subjected to testing by briefly heating, the duration of which is preferably less than 5 minutes, to a temperature above +65°C, preferred is compulsory in the interval above +80°C but below +110°C, and, in decrystallization condition, combined with the layer (C).

11. The use of stable storage of the adhesive with latent reactivity as a layer of the identification document according to claim 1.