EP3291995B1 - Value or security document, and method for producing an adhesion promoter connection between a security element and the surface of the value or security document, and use of a single-component adhesive - Google Patents

Description

Field of the invention:

The present invention relates to a value or security document which has a security element connected thereto by means of a one-component adhesive, in particular a diffraction element, for example a holographic data carrier. Furthermore, the present invention also relates to a method for producing a primer bond between a support of a value or security document and a security element by means of a one-component adhesive. Finally, the present invention also relates to a use of the one-component adhesive.

Prior art and background of the invention:

Value or security products, in particular securities or security documents, serve to verify the identity of a person or thing or a claim, for example, for payment of a sum of money or for the issue of a product or service. For this purpose, it must be ensured that the product can not be imitated, counterfeited or falsified with considerable effort. The product therefore contains security features whose imitation is extremely difficult or even practically impossible. For example, the product, such as banknotes, consists of a not readily available material. Additionally or alternatively, security features may be formed by special colors, for example luminescent or optically variable colors, optical elements, such as holograms, tilt images, kinegraphic objects, lens or prism arrays, also guilloches, mottled fibers, security threads and others. Furthermore, it is also necessary that the value or security documents are easy to produce.

For example, optical security elements may be manufactured separately and then adhered as patches, security threads, security strips or the like to an exterior surface on the security or security product or to an interior surface in the security or security product. Such security elements may be optically variable elements such that visually perceivable phenomena produced therewith may either be discernible and / or take different shapes depending on the angle at which the asset or security document is viewed.

For securing a security element on a surface inside or on the document in the value or security document, adhesion promoters are used with which the security element is adhered to a surface of the security or value document. There are DE 10 2008 019 871 B3 For example, a multi-layered security document comprising a printable substrate, a photopolymer film bonded to the substrate on a first side, and a first cover film bonded to the photopolymer film or a first cover film composite bonded to the photopolymer film. The photopolymer film is connected to the carrier material via a first adhesive film. In at least a portion of the photopolymer film, a volume hologram is imprinted. To connect the photopolymer film with the carrier material, a so-called transfer adhesive film is used. It is an acrylate-based adhesive material. The carrier is formed, for example, from polyethylene or polyethylene terephthalate. The adhesive film may be pressure and / or thermally activated.

Out DE 10 2010 033 049 A1 discloses a laminate composite having a first polymer layer, a second polymer layer and a security element laminated between the first polymer layer and the second polymer layer, wherein a layer of a reactive adhesive is disposed at least between the security element and the first polymer layer. For lamination of the security element, at least one side of the security element or the side of the first polymer layer facing the security element is coated with a reactive adhesive. Then, the first polymer layer and the security element are positioned to each other and connected to each other. Thereafter, the adhesive is crosslinked, and finally, the first and second polymer layers are laminated together with the inclusion of the security element under pressure and heating. In particular, one-component systems are used as reactive adhesives, namely heat-crosslinkable systems comprising a base polymer and a heat-activated crosslinker, for example epoxides, urethanes, polyesters and polyimides, furthermore radiation-crosslinkable systems, which are usually based on acrylate, and systems which crosslink by moisture, for example cyanoacrylates and urethanes. Alternatively, two-component systems can also be used.

From document WO 99/29754 A1 is an adhesive known with multi-stage curing.

definitions:

Insofar as the term '(meth) acryl' or '(meth) acrylate' is used below in the description and in the claims, it includes both an acrylate or acrylate group and, alternatively, a methacrylic or methacrylate group understand.

As used hereinafter in the specification and claims, the term 'actinic radiation' means radiation which is capable of curing the one-part adhesive according to the present invention. This includes, on the one hand, electromagnetic radiation, for example radiation in the UV and / or visible (VIS) spectral range or higher-energy radiation, such as X-ray radiation, synchrotron radiation and the like, and, on the other hand, body radiation with a suitable wavelength, for example electron beams.

Insofar as the term 'C _{1 to} C ₁₂ alkyl' is used below in the description and in the claims, it is to be understood as meaning a saturated linear or branched chain monovalent hydrocarbon radical having 1 to 12 carbon atoms, the alkyl radical optionally being independent of one or more Substituents may be substituted. Examples of alkyl groups include, but are not limited to, methyl (-CH ₃ ), ethyl (-CH ₂ CH ₃ ), 1-propyl (-CH ₂ CH ₂ CH ₃ ), 2-propyl (-CH (CH ₃ ) ₂ ), 1-butyl (-CH ₂ CH ₂ CH ₂ CH ₃ ), 2-methyl-1-propyl (-CH ₂ CH (CH ₃ ) ₂ ), 2-butyl (-CH (CH ₃ ) CH ₂ CH ₃ ), 2-methyl-2-propyl (-C (CH ₃ ) ₃ ), 1-pentyl (-CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ), 2-pentyl (-CH (CH ₃ ) CH ₂ CH ₂ CH ₃ ), 3-pentyl (-CH (CH ₂ CH ₃ ) ₂ ), 2-methyl-2-butyl (-C (CH ₃ ) ₂ CH ₂ CH ₃ ) 3-methyl-2-butyl (-CH (CH ₃ ) CH (CH ₃ ) ₂ ), 3-methyl-1-butyl (-CH ₂ CH ₂ CH (CH ₃ ) ₂ ), 2-methyl-1-butyl (-CH ₂ CH (CH ₃ ) CH ₂ CH ₃ ), 1-hexyl (-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ), 2-hexyl (-CH (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₃ ) 3-hexyl (-CH ( CH ₂ CH ₃ ) (CH ₂ CH ₂ CH ₃ )), 2-methyl-2-pentyl (-C (CH ₃ ) ₂ CH ₂ CH ₂ CH ₃ ), 3-methyl-2-pentyl (-CH (CH ₃ ) CH (CH ₃ ) CH ₂ CH ₃ ), 4-methyl-2-pentyl (-CH (CH ₃ ) CH ₂ CH (CH ₃ ) ₂ ), 3-methyl-3-pentyl (-C (CH ₃ ) (CH ₂ CH ₃ ) ₂ ), 2-methyl-3-pentyl (-CH (CH ₂ CH ₃ ) CH (CH ₃ ) ₂ ), 2,3-dimethyl-2-butyl (-C (CH ₃ ) ₂ CH (CH ₃ ) ₂ ), 3,3-dimethyl-2-butyl (-CH (CH ₃ ) C (CH ₃ ) ₂ ), 1-heptyl, 1-octyl and the like.

Insofar as the term 'alkylene' is used below in the description and in the claims, it is a saturated linear or branched chain divalent among them Hydrocarbon radical having one to twelve carbon atoms to understand, wherein the alkylene radical may optionally be independently substituted with one or more substituents. Examples of alkylene groups include, but are not limited to, methylene (-CH ₂ -), ethylene (-CH ₂ CH ₂ -), propylene (-CH ₂ CH ₂ CH ₂ - or -CH (CH ₃ ) CH ₂ -) , and the same.

As used hereinafter in the specification and claims, the term 'alkylene oxide' is to be understood as meaning a saturated linear or branched chain group having the general formula - (alkylene-O) _q -, where q is an integer, the value thereof For example, it is determined that the number of carbon atoms of the alkylene groups is in a range of 12 to about 500, for example.

As used hereinafter in the specification and claims, the term 'substituent' is taken to mean a monovalent chemical radical selected from a group comprising C ₁ to C ₁₂ alkyl, Hal (F, Cl, Br , I), -OR ¹ , -NR ¹ R ² , -COOR ¹ , -CONR ¹ R ² , wherein R ¹ and R ^{2 are} independently H and C ₁ - to C ₆ alkyl. Similarly, in the term 'substituted' to understand.

Insofar as the terms 'polyol' and 'polyisocyanate' are used below in the description and in the claims, these are to be understood as meaning chemical compounds which have more than one functional group, for example two, three, four or even more functional groups, in this case or isocyanate groups.

The objects underlying the invention:

For the application and permanent connection of a security element to the support of a security or security document, various requirements must be fulfilled. First, it must be provided that the adhesive is easy to process, ie has a sufficiently long pot life under normal daylight conditions, while ensuring that the Curing with actinic radiation also passes quickly through the security element. Furthermore, the viscosity of the adhesive must be sufficiently low to ensure that it can be applied to the bonding partner or compounds without the formation of air bubbles and streaks. This also includes the fact that the adhesive sufficiently wets the connection partner or partners sufficiently to achieve a full-surface and seamless coating of the surface. Furthermore, the adhesive must be used to ensure that the visually recognizable security element is not compromised by the Adhesive layer should be recognizable by, transparent and to be as colorless as possible transparent, which also presupposes that the adhesive does not nachgilbt during the curing process and / or aging, especially when exposed to UV light or otherwise changes the color. The adhesive must also not attack the carrier and the security element and lead to a color shift, for example, in the material of the security element. In addition, the adhesive must have high flexibility to prevent tearing or flaking of the security element.

Finally, of course, the adhesive must have a very high peel strength of the security element on the support, i. a very high adhesion between the partners, ensure. This requires good chemical compatibility with the materials of the carrier and the security element and also includes the requirement that the adhesive strength and all other requirements must be maintained over a longer period of 10 to 15 years.

Not all of these requirements can be met with the known methods and adhesive systems.

Broad features of the invention and preferred embodiments:

These objects are achieved according to a first aspect of the present invention by the inventive value or security document according to claim 1.

Furthermore, according to a second aspect of the present invention, these objects are also achieved by the method according to the invention for producing a primer bond between the security element and the support of the security document according to claim 7.

Finally, these objects are also achieved by use of the abovementioned one-component adhesive for producing the value or security document according to claim 18.

By optimizing the adhesive composition of the adhesive, the requirements mentioned above are met. In particular, it is ensured that the security element is securely and permanently attached while maintaining the flexibility. In particular, an exceptionally stable composite strength of polycarbonate-containing or polycarbonate-formed materials is achieved with other polymers, for example polyethylene terephthalate, polyvinyl acetate or fluoropolymers.

The adhesive forms a curable composition that is liquid at room temperature and has a dynamic viscosity at room temperature (20 ° C) that is in the range of 500 to 3000 mPa · s (measured with a cylinder-cup geometry rotary viscometer). Preferably, the dynamic viscosity is 1000 mPa · s (20 ° C). This ensures that the adhesive mass can be applied without streaks and bubbles and that it wets the surfaces to be bonded well.

Furthermore, the adhesive has a high transparency and is optionally completely colorless, so that the security element itself is easily visually recognizable without being impaired by the adhesive. The adhesive has excellent stability to moisture. Water does not alter the physical and chemical properties of the adhesive, such as its transparency, color and bond strength. Finally, the one-component adhesive according to the present invention is also sufficiently storage-stable. In addition, the adhesive is highly flexible.

The one-component adhesive is preferably solvent-free, resulting in advantageous properties with regard to the processability of the adhesive. By using an additional radiation-curing compound (crosslinker), the adhesive is irreversibly crosslinked under the action of actinic radiation. The properties of the adhesive composition are optimized so that the durability of the adhesive bond is as great as possible. Furthermore, the one-component adhesive also has sufficient flexibility, ie the adhesive or the adhesive layer ideally shows under the given conditions, no breaks and cracks.

The one-component adhesive contains, as at least one component A, an oligomeric urethane (meth) acrylate based on a polycarbonate diol, i. based on an oligomeric compound having a polycarbonate chain which forms the backbone for the urethane (meth) acrylate, wherein the polycarbonate chain is functionalized at least at the chain ends with radically polymerizable groups, in particular (meth) acrylic groups.

1. (a) Umsetzen von mindestens einem Polycarbonatdiol (Verbindung (i)) und mindestens einem polyfunktionellen Isocyanat (Verbindung (ii)) unter Bildung eines Isocyanat-funktionalisierten Polycarbonatdiols in einem ersten Syntheseschritt; und
2. (b) Umsetzen des im ersten Syntheseschritt (a) erhaltenen Isocyanat-funktionalisierten Polycarbonatdiols mit mindestens einem Ester oder Amid einer α,β-ungesättigten Carbonsäure mit einem oder mehreren niedermolekularen, aliphatischen Alkoholen, die zusätzlich eine weitere OH- oder SH-Gruppe aufweisen (Verbindung (iii)), in einem zweiten Syntheseschritt.

The at least one oligomeric urethane (meth) acrylate is obtainable in a particularly preferred embodiment of the present invention by a process comprising the following process steps:

1. (a) reacting at least one polycarbonate diol (compound (i)) and at least one polyfunctional isocyanate (compound (ii)) to form an isocyanate-functionalized polycarbonate diol in a first step of the synthesis; and
2. (b) reacting the isocyanate-functionalized polycarbonate diol obtained in the first synthesis step (a) with at least one ester or amide of an α, β-unsaturated carboxylic acid with one or more low molecular weight, aliphatic alcohols which additionally have a further OH or SH group ( Compound (iii)) in a second step of the synthesis.

The at least one polycarbonate diol (compound (i)) can be synthesized in a known manner by polycondensation of polyols and dialkyl carbonates suitable for their preparation, for example dimethyl carbonate, diaryl carbonates, such as diphenyl carbonate, or phosgene. For the preparation of a polycarbonate diol, a polyol may be reacted with, for example, a dialkyl carbonate, diaryl carbonate or phosgene, or a polyol may be reacted with a plurality of different compounds selected from dialkyl carbonates, diaryl carbonates and phosgene, or several different polyols with a dialkyl carbonate , Diaryl carbonate or phosgene, or several different polyols can be reacted with several various compounds selected from dialkyl carbonates, diaryl carbonates and phosgene.

Polyols used are polyhydric, preferably saturated or unsaturated, aliphatic, cycloaliphatic or araliphatic alcohols having at least two hydroxyl groups, it being possible for the hydroxyl groups to be bonded both primarily and secondarily. Suitable polyols are, for example, polyols having two hydroxyl groups, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butenediol, 1, 4-butynediol, 1,5-pentanediol and the isomeric pentanediols, including neopentyl glycol, also pentene diols or pentynediols or mixtures of two or more thereof, 1,6-hexanediol, and the isomeric hexanediols, hexenediols or hexynediols or mixtures of two or more thereof , 1,7-heptanediol and the isomeric heptane, heptene or heptynediols, 1,8-octanediol and the isomeric octane, octene or octynediols, 2-butyl-2-ethyl-1,3-propanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2.5 Hexanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanediol, 1,7-heptanediol, 2,4-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, further Polybutadienediol, hydrogenated polybutadiene diol, bisphenol A, a bisphenol A-alkylene oxide adduct kt, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, diethylene glycol, triethylene glycol, tetraethylene glycol, polytetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, propylene oxide, poly (oxytetramethylene) diols, 1,3- Dimethanol cyclohexane, 1,4-dimethanol cyclohexane, bis (hydroxymethyl) cyclohexane, 1,2-bis (hydroxyethyl) cyclohexane and dimethanol tricyclodecane. It is also possible to use polyols having more than two hydroxyl groups, such as glycerol, trimethylolethane, trimethylolpropane, di (trimethylolpropane) -dimethylolpropionic acid, trimethylolethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and anhydroeneneaheptitol. Furthermore, mixtures of two or more of said polyols can be used.

The polycarbonate diol has a molar mass of 500 to 10,000 g / mol, preferably from 1,000 to 5,000 g / mol, and most preferably from 1,500 to 2,500 g / mol. Most preferred is a molar mass of about 2,000 g / mol.

Polycarbonate diols are also commercially available, for example under the trade names Desmophen® C2200 from Bayer MaterialScience AG.

The polycarbonate diol is reacted in the first step of the synthesis with a polyfunctional, preferably difunctional, isocyanate compound (ii), i. a diisocyanate compound to yield an isocyanate-functionalized polycarbonate diol. Alternatively, several different polycarbonate diols can be reacted with a polyfunctional isocyanate, or a polycarbonate diol can be reacted with several different polyfunctional isocyanates, or several different polycarbonate diols can be reacted with several different polyfunctional isocyanates.

As the polyfunctional isocyanate, at least one compound is selected from a group comprising isophorone diisocyanate (IPDI: 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane), 1,5-naphthylene diisocyanate, diphenylmethane diisocyanate (MDI), namely 2,2 '. Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, hydrogenated MDI (H12MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1.3 Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate (TDI), 1-methyl-2,4-diisocyanato-cyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, tetramethoxybutane-1,4-diisocyanate (HDI) , Dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, dimer fatty acid diisocyanate and uretdione, biuret and isocyanurates of diisocyanates.

The polycarbonate diol is reacted with the polyisocyanate preferably in a molar ratio (polycarbonate diol to polyisocyanate) in a range of 1: 1.8 to 1: 2.2, most preferably in a ratio of 1: 2.

The reaction can be carried out in the usual manner in an aprotic solvent, for example in a halogenated organic solvent. However, preference is given to solvents which are not halogen-containing, for example acetone, methyl isobutyl ketone or ethyl acetate. The reaction temperature may be at room temperature. For acceleration, however, the temperature of the reaction mixture can usually be increased, for example to 40 to 80 ° C. If appropriate, it is also possible to add to the reaction mixture the catalysts known in polyurethane chemistry, in particular organometallic compounds, for example at least one compound selected from a group comprising dibutyltin laurate (DBTL), dibutyltin acetate or dibutyltin versat, tin octoate, iron (II) chloride, zinc chloride and Lead octoate. Tin salts are preferably used, for example Zinndioctoat, Zinndiethylhexoat and dibutyltin-bis-dodecyl-mercaptide. It is also possible to use lead salts, for example lead phenyl ethyldithiocarbamate, bismuth salts, for example triaryl bismuth compounds, oxides of these compounds and also bismuth phenates and carboxylates. Other organometallic salts are derived from compounds of iron, titanium and zirconium. The catalysts can be used in the reaction mixture in a concentration, for example, from 0.1 to 5 wt .-%.

Further, the reaction may be conducted to form the isocyanate-functionalized polycarbonate diol in the presence of stabilizers, for example in the presence of butylated hydroxytoluene (BHT) and hydroquinone monomethyl ether (HQMME).

The reaction of the at least one polycarbonate diol with the at least one polyfunctional isocyanate is carried out in a preferred development of the present invention in the presence of a diluent.

In a further development of the present invention, the diluent used is a (meth) acrylate which is selected from a group comprising 3,3,5-trimethylcyclohexyl (meth) acrylate, tert- butylcyclohexyl (meth) acrylate, 2- (2- Ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (5-ethyl-1,3-dioxane-5 yl) methyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, octyl (meth) acrylate, 3-methyl-1,5- pentanediol (meth) acrylate and cyclotrimethylolpropane formyl (meth) acrylate.

In a second synthesis step, in which the at least one oligomeric urethane (meth) acrylate (component A) is formed, all NCO groups present are subsequently reacted with at least one compound (iii) which carries a functional group which reacts with isocyanates can, and which has as a further functional group a crosslinkable by free-radical polymerization double bond. These compounds usually have a molecular weight of at most 1000 g / mol (at least 100 g / mol). These compounds can be selected from a group comprising esters and amides of α, β-unsaturated carboxylic acids with one or more low molecular weight, aliphatic alcohols or amines, which additionally have a further OH or SH group. These are, for example, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, reaction products of glycidyl ethers and glycidyl esters with acrylic or methacrylic acid, partial transesterification of polyalcohols, such as pentaerythritol, glycerol or trimethylolpropane with (meth) acrylic acid and also SH-bearing esters and amides according to the above examples.

The isocyanate-functionalized polycarbonate obtained by reacting the at least one polycarbonate diol with the at least one polyfunctional isocyanate and the compound (iii) containing the radically polymerizable groups are preferably used in a molar ratio (isocyanate-functional polycarbonate to compound (iii)) in a range from 1: 1.8 to 1: 2.2, most preferably in a molar ratio of 1: 2 used.

The reaction conditions for the reaction of the isocyanate-functionalized polycarbonate diol with the compound (iii) are basically the same as in the reaction of the compounds (i) and (ii) (see above).

The second component of the adhesive composition according to the present invention is formed by the at least one component B. It is a radiation curing compound, i. a compound which undergoes radical polymerization under the influence of actinic radiation.

According to a preferred embodiment of the present invention, the at least one radiation-curing compound is selected from a group comprising monomers, oligomers and polymers containing up to 20 radiation-reactive groups. It is very particularly preferred if the at least one component B carries 1 to 5 radiation-reactive groups. Optionally, a mixture of such monomers and / or oligomers and / or polymers may be used. In a most preferred embodiment of the present invention, at least one of the components B contains 3 to 5 radiation-reactive groups.

It is particularly preferred for the at least one component B radiation-curing compounds are selected from a group comprising (meth) acrylic acid esters, (meth) acrylic acid amides, vinyl ethers and bismaleimides. Further preferred free-radically polymerizable compounds are prepolymers based on polyols or polyurethanes which react with radiation-curing groups, such as (meth) acrylic esters, are substituted. As polyols, the polyols specified above for the formation of the polycarbonate backbone of the at least one component A can be used (in this regard, reference is made to the disclosure therein). As polyurethanes, reaction products of the diisocyanates mentioned above for the formation of the isocyanate-functionalized polycarbonate backbone (to which extent reference is made to the disclosure therein) and further higher-value polyisocyanates (tri-, tetraisocyanates) with the abovementioned polyols (in this respect, reference is again made to the disclosure there ) are used. When using polyols of higher value or when using polyurethanes reacted for preparing the polyurethanes, for example tri-, tetra- or penta-alcohols, dendrimers are formed which, likewise reacted with radiation-curing groups, can be used as component (s) B.

In a preferred embodiment of the present invention, at least one, for example one, two, three or even more, preferably all, of the at least one radiation-curing compound (component B) has at least two, for example two, three, four, five, six or even more, functional groups for radiation curing, in particular at least two, for example two, three, four, five, six or even more, unsaturated bonds, in particular ethylenically unsaturated bonds.

As component (s) B, especially acid amides with radiation-reactive groups are / are suitable, for example (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N- tert- butyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N-phenyl (meth ) acrylamide, N - ((meth) acryloyl) morpholine, N - ((meth) acryloyl) piperidine, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N-1,1,3,3 Tetramethylbutyl (meth) acrylamide, dimethylene bis (meth) acrylamide, tetramethylene bis (meth) acrylamide, tri (meth) acryloyldiethylenetriamine and like compounds.

Furthermore, acids with radiation-reactive groups are also suitable, of which, for example, the abovementioned (meth) acrylamides are derived, namely, for example, (meth) acrylic acid and the like (in this respect, reference is made to the above list of acrylamides). Also suitable are (meth) acrylates of polyols, for example pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritolhexa (meth) acrylate, tripentaerythritol (meth ) acrylate, suitable.

In a particularly preferred embodiment of the present invention, the components B are selected from the group consisting of poly (meth) acrylates (di (meth) acrylates, tri (meth) acrylates, tetra (meth) acrylates, penta (meth) acrylates, etc.) of polyols, in particular pentaerythritol tri (meth) acrylate, poly (meth) acrylates having more than two acrylate groups being very particularly preferred. It should be noted that these polyfunctional acrylate compounds can also be used in combination with mono- and / or di-functional acrylate compounds, for example in order to specifically control the crosslinkability of the adhesive composition.

Also suitable are vinyl ethers and maleimides and bismaleimides. Typical examples of vinyl ether monomers are methyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, tert- butyl vinyl ether, isobutyl vinyl ether, triethylene glycol divinyl ether (available under the trade name RAPI-CURE® DVE-3 from International Specialty Products, U.S.A.), 1,4-cyclohexanedimethanol divinyl ether (available under the trade name RAPI-CURE® CHVE, International Specialty Products), trimethylolpropane trivinyl ether (available as TMPTVE from BASF Corp., US), divinyl ether resins (such as VECTOMER 2010, VECTOMER 2020, VECTOMER 4010, VECTOMER 4020), as well as similar materials and blends thereof.

worin:

R⁸

in jedem der beiden Reste N(CO)₂CH(R⁸)CH₂ unabhängig von dem anderen Rest aus einer Gruppe ausgewählt ist, umfassend Wasserstoff und C₁- bis C₁₂-Alkyl und

X

ein zweiwertiger Rest ist, der ausgewählt ist aus einer Gruppe, umfassend verzweigtkettige Alkylen- und Alkylenoxidreste mit etwa 12 bis etwa 500 Kohlenstoffatomen im Grundgerüst, und der eine Gruppe darstellen kann, die die Struktur mit der allgemeinen chemischen Formel (II):

hat, worin:
p 0, 1, 2 oder 3 ist;
y 0 oder 1 ist;
Ar in jedem der Reste O(CO)_yAr unabhängig ausgewählt ist aus einer Gruppe, umfassend monosubstituierte und trisubstituierte Ringe, die jeweils aromatisch oder heteroaromatisch sein und 3 bis 10 Kohlenstoffatome enthalten können;
Z eine verzweigtkettige Alkylen- oder Alkylenoxid-Gruppe ist, die etwa 12 bis etwa 500 Kohlenstoffatome in ihrem Grundgerüst aufweist.

Preferred maleimides which can be used according to the present invention as component (s) B have the following general chemical formula (I):

wherein:

R ⁸

in each of the two radicals N (CO) ₂ CH (R ⁸ ) CH _{2 is} independently selected from the other radical from a group comprising hydrogen and C ₁ - to C ₁₂ alkyl and

X

is a divalent radical selected from a group comprising branched chain alkylene and alkylene oxide radicals having from about 12 to about 500 carbon atoms in the backbone, and which may represent a group having the structure of general chemical formula (II):

has, in which:
p is 0, 1, 2 or 3;
y is 0 or 1;
Ar in each of the radicals O (CO) _y Ar is independently selected from a group comprising monosubstituted and trisubstituted rings, each of which may be aromatic or heteroaromatic and may contain from 3 to 10 carbon atoms;
Z is a branched chain alkylene or alkylene oxide group having from about 12 to about 500 carbon atoms in its backbone.

There may be one or more components B, in which case mixtures of the abovementioned compounds are used.

As component (n) C, the adhesive composition according to the present invention further contains at least one photoinitiator for radical polymerization. As such photoinitiators, it is possible to use the customary commercially available compounds which, upon the action of preferably UV radiation and / or radiation in the visible spectral region, decompose into reactive radicals, provided that the adhesive according to the invention is curable through the security element, i. the security element is transparent to the actinic radiation needed for curing. Further, as for the selection of the at least one photoinitiator, it is also required that the adhesive has a sufficiently long processing time in daylight, for example, 1 hour (at least 30 minutes using artificial light).

The following compounds can be used as photoinitiator (s): α-hydroxyketones, benzophenone, α-aminoketones, benzophenone derivatives, such as 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and 2-hydroxy-2-methylpropiophenone , benzyl dimethyl ketals, acyl phosphine oxides, for example diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (available as Lucirin® TPO-L from BASF), phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone. The photoinitiators mentioned can each be used alone or in combination of two or more of the named compounds.

Furthermore, the Irgacure® types from BASF, for example the types Irgacure® 184, Irgacure® 500, Irgacure® 1173, Irgacure® 651, Irgacure® 369, Irgacure® 127, Irgacure® 907, Irgacure® 1300, CGI 277, can be used , These photoinitiators are UV photoinitiators, i. the radical polymerization takes place when irradiated in the UV spectral region. The initiators Irgacure® 2022, Irgacure® 2100, Irgacure® TPO and Irgacure® TPO-L can only be used in small amounts of less than 1% by weight, based on the adhesive composition, since the processing time in daylight is otherwise too short , Particularly suitable is the initiator CGI 277, available from BASF SE. It is an α-amino ketone.

The adhesive composition in a most preferred embodiment of the present invention comprises an oligomeric urethane (meth) acrylate based on a polycarbonate as component A, pentaerythritol triacrylate as component B, and a mixture of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2-hydroxy 2-methylpropiophenone as components C.

Further, the adhesive composition according to the present invention may contain at least one other modifier as component (s) D. The modifiers are preferably selected from a group comprising fillers, dyes, pigments, luminescent agents, stabilizers, moisture scavengers, accelerators, adhesion promoters, crosslinkers, flexibilizers, polymeric thickeners, flame retardants, corrosion inhibitors, plasticizers and tackifiers.

For example, quartz, hollow glass spheres (density = 1) and hydrophilic or hydrophobic thixotropic agents can be used as fillers.

As dyes and pigments, it is possible to use all commercially available compounds and compound mixtures which are soluble or at least miscible in the mixture of components A, B and C. In particular, cationic, anionic or neutral colorants can be used. For example, brilliant black CI No. 28440, chromogen black CI No. 14645, direct deep black E CI No. 30235, Genuine black salt B CI No. 37245, true black salt K CI No. 37190, Sudan black HB CI 26150, Naphtol black CI No. 20470, Bayscript® Black Liquid, CI Basic Black 11, CI, Basic Blue 154, Cartasol® Turquoise K-ZL liquid, Cartasol ® Turquoise K-RL liquid (CI Basic Blue 140), Cartasol® Blue K5R liquid, Hostafine® Black TS liquid, Bayscript® Black liquid, Cartasol® Black MG liquid (CI Basic Black 11), Flexonyl® black PR 100 (E CI No. 30235), Cartasol® Orange K3 GL, Cartasol® Yellow K4 GL, Cartasol® K GL, or Cartasol® Red K-3B, where Bayscript® is a trademark of Lanxxess, DE, Cartasol® and Flexonyl® trademarks of Clariant, DE and Hostafine® are a trademark of Hoechst GmbH, DE. Furthermore, anthraquinone, azo, quinophthalone, coumarin, methine, perinone, and / or pyrazole dyes can be used as soluble colorants.

As the luminescent agent, it is also possible to use all commercially available compounds and compound mixtures which are soluble in the mixture of components A, B and C. The luminescent agents are in particular photoluminophores, electroluminophores, Antistokes luminophores, fluorophores and magnetizable, photoacoustically addressable and piezoelectric materials. For example, fluorescein, 2 ', 7'-dichlorofluorescein, xanthene dyes and rosamines and rhodamines, for example rhodamine B, can be used.

worin:
R¹, R², R³ und R⁴ unabhängig voneinander sind:
H, OH, Cl, F, C₄- bis C₂₀-Alkyl; C₁- bis C₂₀-Ether; C₁- bis C₂₀-Alkyl mit einem N, O oder S enthaltenden Substituenten; C₂- bis C₂₀-Akenyl mit einem N, O oder S enthaltenden Substituenten; C₂- bis C₂₀-Alkinyl mit einem N, O oder S enthaltenden Substituenten; C₁- bis C₂₀-Ester, C₁- bis C₂₀-Hydroxyl, C₂- bis C₂₀-Alkenyl; oder C₂- bis C₂₀-Alkinyl; ein cyclisches Molekül, enthaltend 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 oder mehr Ringe, die wahlweise eine oder mehrere Seitenketten enthalten, die einen linearen, verzweigten, cyclischen Rest oder deren Kombinationen von C₁- bis C₂₀-Alkyl; C₁- bis C₂₀-Ether; C₁-bis C₂₀-Alkyl mit einem N, O oder S enthaltenden Substituenten; C₂- bis C₂₀-Alkenyl mit einem N, O oder S enthaltenden Substituenten; C₂- bis C₂₀-Alkinyl mit einem N, O oder S enthaltenden Substituenten; C₂- bis C₂₀-Ester; C₁- bis C₂₀-Hydroxyl, C₂- bis C₂₀-Alkenyl oder C₂- bis C₂₀-Alkinyl enthalten. Insbesondere können (3-Glycidyloxypropyl)-trimethoxysilan, Vinyltrimethoxysilan und 3-Trimethoxysilylpropylmethacrylat (erhältlich von Evonik, DE) verwendet werden.As stabilizers, hindered amine light stabilizers and triazole compounds can be used. As moisture scavenger and adhesion promoter silane compounds can be used. For example, silane compounds having the chemical structural formula (III) can be used:

wherein:
R ¹ , R ² , R ³ and R ^{4 are} independently of one another:
H, OH, Cl, F, C ₄ to C ₂₀ alkyl; C ₁ to C ₂₀ ether; C ₁ to C ₂₀ alkyl with an N, O or S-containing substituent; C ₂ to C ₂₀ alkenyl with an N, O or S-containing substituent; C ₂ to C ₂₀ alkynyl with an N, O or S-containing substituent; C ₁ - to C ₂₀ -ester, C ₁ - to C ₂₀ -hydroxyl, C ₂ - to C ₂₀ -alkenyl; or C ₂ to C ₂₀ alkynyl; on cyclic molecule containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more rings optionally containing one or more side chains containing a linear, branched, cyclic radical or combinations thereof of C ₁ - to C ₂₀ alkyl; C ₁ to C ₂₀ ether; C _{1 to} C ₂₀ alkyl having an N, O or S-containing substituent; C ₂ to C ₂₀ alkenyl with an N, O or S-containing substituent; C ₂ to C ₂₀ alkynyl with an N, O or S-containing substituent; C ₂ to C ₂₀ ester; C ₁ - to C ₂₀ -hydroxyl, C ₂ - to C ₂₀ -alkenyl or C ₂ - to C ₂₀ -alkynyl. In particular, (3-glycidyloxypropyl) trimethoxysilane, vinyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate (available from Evonik, DE) can be used.

Water-soluble starch, in particular having an average molecular weight of 3,000 to 7,000 g / mol, polyvinylpyrolidone, in particular having an average molecular weight of 25,000 to 250,000 g / mol, polyvinyl alcohol, in particular having an average molecular weight of 10,000 to 20,000 g / mol, can be used as the polymeric thickener. Xanthan gum, carboxy-methyl cellulose, ethylene oxide / propylene oxide block copolymer, especially having an average molecular weight of 1,000 to 8,000 g / mol. An example of the latter block copolymer is the product series Pluronic® from BASF, DE. As plasticizers, phthalates, citric acid esters and other substances known for this purpose can be used.

1. (A) 5 bis 70 Massenanteile des mindestens einen oligomeren Urethan(meth)acrylats (Komponente(n) A);
2. (B) 5 bis 90 Massenanteile der mindestens einen strahlungshärtenden Verbindung (Komponente(n) B); und
3. (C) 0,1 bis 20 Massenanteile des mindestens einen Photoinitiators (Komponente(n) C),

bezogen auf 100 Massenanteile der Klebstoffzusammensetzung.In a preferred embodiment of the present invention, the constituents of the one-component adhesive are contained in the adhesive in the following amounts:

1. (A) 5 to 70 parts by mass of the at least one oligomeric urethane (meth) acrylate (component (s) A);
2. (B) 5 to 90 parts by mass of the at least one radiation-curing compound (component (s) B); and
3. (C) 0.1 to 20 parts by mass of the at least one photoinitiator (component (s) C),

based on 100 parts by mass of the adhesive composition.

The sum of the mass fractions of the components A, B and C gives a maximum of 100 mass fractions. If only components A, B and C are included in the adhesive composition, the sum of the mass fractions of these three components is exactly 100 parts by mass. If further additional components are included, the sum of the mass fractions of the three components A, B and C is less than 100 mass fractions, wherein the difference between 100 mass fractions and the sum of the mass fractions of the three components A, B and C is given by the mass fraction of the further component (s).

1. (A) 5 bis 80 Massenanteile des mindestens einen oligomeren Urethan(meth)acrylats (Komponente(n) A);
2. (B) 5 bis 90 Massenanteile der mindestens einen strahlungshärtenden Verbindung (Komponente(n) B);
3. (C) 0,1 bis 20 Massenanteile des mindestens einen Photoinitiators (Komponente(n) C); und
4. (D) 0 bis 10 Massenanteile des mindestens einen Modifikators (Komponente(n) D),

bezogen auf 100 Massenanteile der Klebstoffzusammensetzung.In a particularly preferred embodiment of the present invention, the constituents of the one-component adhesive are contained in the adhesive in the following amounts:

1. (A) 5 to 80 parts by mass of the at least one oligomeric urethane (meth) acrylate (component (s) A);
2. (B) 5 to 90 parts by mass of the at least one radiation-curing compound (component (s) B);
3. (C) 0.1 to 20 parts by mass of the at least one photoinitiator (component (s) C); and
4. (D) 0 to 10 parts by mass of the at least one modifier (component (s) D),

based on 100 parts by mass of the adhesive composition.

The sum of the mass fractions of the components A, B, C and D is 100 parts by mass, if not further constituents are contained in the adhesive composition, for example a solvent. If the sum of the mass fractions of the components A, B, C and D corresponds to less than 100 parts by mass of the adhesive composition, the difference between 100 parts by mass and the sum of the mass fractions of the four components A, B, C and D is given by the mass fraction of further constituents ,

For use, the adhesive composition is applied to at least one bonding surface of the two bonding partners, namely the security element and / or the backing.

For this purpose, the one-component adhesive can be applied in a conventional manner to the at least one bonding surface, for example by means of printing, brushing, casting, rollercoating, curtain casting, spincoating, knife coating, dipping, dispensing or other coating techniques. The layer thickness produced depends on the viscosity of the adhesive, on the wettability of the at least one bonding surface, the application method and on other parameters. The layer thickness can preferably at least 1 μm, more preferably at least 2 μm, even more preferably at least 5 μm, and most preferably at least 7 μm. The layer thickness may preferably be at most 1000 μm, more preferably at most 500 μm, even more preferably at most 50 μm and most preferably at most 30 μm. In the case of two-sided application to the connecting surfaces of both connection partners, the individual adhesive layers may be thinner, for example in the range of 1 to 20 microns.

After placing the security element on the carrier at the connection point at which it is to be connected to the carrier on the surface thereof, the security element is brought into contact with the carrier surface at the connection point and connected thereto.

Subsequently, the adhesive is cured by irradiation of actinic radiation. For this purpose, actinic radiation is used which causes activation of the at least one photoinitiator. The actinic radiation is thus matched in terms of their spectral distribution and intensity to the at least one photoinitiator. Preferably, the at least one photoinitiator is adapted to the available actinic radiation. The spectral distribution is to be determined so that the actinic radiation is absorbed by the at least one photoinitiator. The intensity of the actinic radiation must be set so high that radical polymerization is promoted. The actinic radiation is preferably in the UV spectral range, but may alternatively or additionally also be in another spectral range, for example in the visible (VIS) or IR spectral range. UV radiation is advantageous because it allows for processability under normal daylight if the adhesive composition is not curable by irradiation of electromagnetic radiation in the VIS spectral range.

The curing step by means of the actinic radiation creates a very strong and irreversible connection between the security element and the carrier of the security document.

The curing time may be short or long, depending on the effect of actinic radiation on the one-part adhesive. For example, the curing time ranges from 0.5 seconds to 5 hours, preferably from 1 second to 30 minutes, more preferably from 2 seconds to 1 minute, and most preferably from 5 seconds to 20 seconds.

The irradiation of the adhesive layer is preferably carried out through the security element. Also possible is irradiation by the wearer of the value or security document. For this purpose, this is transparent form at least in the connection region for the actinic radiation.

The method according to the invention can be used in particular for applying a security element to a carrier of a security or security document, in particular a security or security document.

The security element may be in the form of a so-called optically variable element, i. an element that has a different appearance depending on the viewing direction. The security element is preferably formed by a diffraction element, very particularly preferably by a holographic data carrier. The security element can be formed for example by diffractive structures, such as zero-order diffraction gratings, rainbow-effect diffraction gratings and relief and volume holograms, as well as microlenses and lenticular grids.

The security element is typically manufactured separately and applied to the backing of the security or security document as a patch, security thread, security strip or the like. The structure of a semifinished product which can be used for applying the security element to the carrier depends on its type. In general, the semi-finished product is multilayered. It can, for example, have a base on which there is a functional layer, and a protective layer can be located above the functional layer so that the functional layer is arranged between the base and the protective layer. The functional position forms the actual security element, which is finally located on the carrier. The pad and the protective layer serve to handle and protect the functional layer during the manufacturing process of the security element and to protect it when applied to the carrier. These two auxiliary layers may for example consist of polyvinyl alcohol, a fluoropolymer, a polyester such as polyethylene terephthalate, or an acrylate polymer or contain one of these materials. In the application process, the auxiliary layers are typically removed from the functional layer so that only the functional layer remains on the carrier after application. The dimensions of the security element can be arbitrary and are adapted to the application. For example, the security element can be as large as the value or security document to which it is applied, so that it covers the entire surface, or it is smaller, so that it is only a partial surface of the value or Security document covers, for example, 0.5 to 75%, preferably 1 to 50% and most preferably 2 to 25% of the surface of the security document. One or more security elements may be applied to one side of the security or security document, or one or more security elements may be applied to either side of the security or value document.

In a preferred embodiment of the present invention, the support of the security or security document is formed from a polycarbonate-containing material formed from polycarbonate at least on a surface on which the security element is connected to the carrier. The one-part adhesive according to the present invention is particularly well-suited for producing a stable adherent bond between the security element and a polycarbonate-containing or polycarbonate surface of the support.

The value or security document may in particular be a passport, identity card, driving license, an access control card or other ID card, a vehicle registration document, vehicle registration document, visa, check, means of payment, in particular a banknote, a check, bank, credit or cash card, Customer card, health card, chip card, company card, credentials, membership card, gift or shopping voucher, bill of lading or other credentials, tax stamp, postage stamp, ticket, token, sticky label (for example for product security) or other document. The document may be, for example, a smart card. The value or security document may be in ID 1, ID 2, ID 3, or any other normalized or non-normalized format, such as a booklet form, such as a passport-like item. A value or security document is generally a laminate of several document layers, which have been connected in register under the influence of heat and under increased pressure. These documents should meet the standardized requirements, for example ISO 10373, ISO / IEC 7810, ISO 14443. For example, the document layers are made of a material suitable for lamination.

The security or security document may be formed from a polymer selected from a group comprising polycarbonate (PC), especially bisphenol A polycarbonate, polyethylene terephthalate (PET), their derivatives such as glycol modified PET (PETG), polyethylene naphthalate (PCT). PEN), polyvinyl chloride (PVC), polyvinyl butyral (PVB), polymethylmethacrylate (PMMA), polyimide (PI), polyvinyl alcohol (PVA), polystyrene (PS), polyvinylphenol (PVP), polypropylene (PP), polyethylene (PE), thermoplastic elastomers (TPE), in particular thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene copolymer (ABS) and their derivatives, and / or paper. In addition, the document may also be made of several of these materials. It preferably consists of PC or PC / TPU / PC. The polymers may be either unfilled or filled. In the former case, they are preferably transparent or translucent. If the polymers are filled, they are opaque. The above information relates both to films to be bonded together and to liquid formulations applied to a precursor, such as a resist. Preferably, the document is made from 3 to 12, preferably 4 to 10, films (including the carrier of a data communication device contained therein). A laminate formed in this way can finally be coated on one or both sides with a protective lacquer. Overlay layers formed in this way protect security features arranged underneath and / or give the document the required abrasion resistance. The security element according to the present invention may also be arranged protected under an overlay position. Likewise, the security element can alternatively also be integrated into an inner laminate plane by lamination.

To produce a value or security document according to the invention in the form of a laminate of a plurality of polymer films, a stack of a plurality of polymer films can first be collected. The films of the stack are then laminated under the action of a pressing pressure and at an elevated temperature. In lamination, the stack is laminated in a hot press typically at 190 to 200 ° C and a pressure of, for example, 350 N / cm ² and in a cold press at a pressure of 600 N / cm ² when the document layers are made of polycarbonate. The security element, for example a holographic data carrier, can then be glued onto the carrier produced in this way in accordance with the invention. So that the security element is protected, the laminate can then be provided with a protective varnish. At least the outer polymer film on which the security element is attached is preferably a polycarbonate film.

Alternatively, the security element can also first be applied to a carrier film and fixed there with the method according to the invention. This polymer film is preferably formed from polycarbonate. This carrier film with the security element applied thereon can then be combined with other polymer films, for example likewise polycarbonate films or films of different materials, into a stack be collected. The films in the stack are then laminated together. The security element may in this case be arranged inside in the laminate stack. So that the security element is visually recognizable from the outside, the film layers arranged between a viewer's point of view and the security element are transparent and preferably colorless. Optionally, there may be apertured print layers between the viewer's point of view and the security element.

The further document layers in the laminate may contain additional security features, such as a photograph of the document owner and / or security printing features and functional colors. The stack can also contain a film layer with an RFID circuit with RFID chip and RFID antenna. Outwardly, the stack may be completed by cover sheet layers (overlays) or coated with a protective varnish. These cover sheet layers or the protective lacquer are preferably transparent, thereby allowing the view of underlying document layers and security features. The overlays protect the underlying document layers and / or offer the possibility of optical laser personalization and generation of text and image information. In order to form a value or security document, the carrier film layer and the further document layers can have, for example, additional security features.

After completion of the laminate, the document can be equipped with further security features. The further security features can be either individualizing or not individualizing. Other security features include guilloches, watermarks, embossing prints, a security thread, microfilm, tipping, Durchlichtpasser and the like. Furthermore, the document may also comprise electronic components, for example an RFID circuit with antenna and RFID microchip, electronic display elements, LEDs, touch-sensitive sensors and the like. For example, the electronic components may be hidden between two opaque layers of the document.

Detailed description of the invention:

Fig. 1

zeigt ein erfindungsgemäßes Wert- oder Sicherheitsdokument in einer isometrischen Darstellung;

Fig. 2

zeigt das erfindungsgemäße Wert- oder Sicherheitsdokument von Fig. 1 in einer seitlichen Schnittansicht.

To further illustrate the present invention, the following figures and examples are provided, the figures and examples being merely exemplary in nature and do not represent a limitation on the scope of the described invention:

Fig. 1

shows an inventive value or security document in an isometric view;

Fig. 2

shows the value or security document according to the invention of Fig. 1 in a side sectional view.

In the figures, like reference numerals designate elements having the same function or elements.

The value or security document according to the invention, shown in FIG Fig. 1, 2 , an identity card can be 100. The identity card has an upper side 101 and a lower side (not shown). In the example shown, the identity card is essentially formed from a carrier 110 which has been produced by lamination of one or more polymer layers 111, 112. The upper polymer layer 111 can be made of polycarbonate, for example, and the lower polymer layer 112 of another polymer, such as polyethylene terephthalate, or also of polycarbonate.

In a first surface area, a passport photo 120 is printed on the top side 101 of the identity card 100. In a second area of the identity card, a security element 200, for example a hologram patch, is laminated on top by gluing. This, too, when viewed at a certain angle, shows the facial image of the person to whom the identity card is associated. The hologram patch may for example be formed from two layers, for example from a first carrier facing the first layer 210 and a second layer 220, which forms the actual functional position, in the present case, the hologram. The hologram patch is applied to a contact side 211 facing the carrier 110 of the identity card. The first layer may preferably consist of polycarbonate. To bond the hologram patch to the carrier, there is an adhesive layer 300 between the hologram patch and the carrier 110.

To further illustrate the invention, examples are given below, which, however, are also merely exemplary of the operation of the invention and in no way limit the scope of the invention:

Beispielzusammensetzunaen:

To compare an adhesive composition according to the present invention with adhesive compositions which are not in accordance with the invention, mixtures of a prepolymer (corresponding to component A according to the present invention) with a plurality of radiation-curing compounds (corresponding to components B according to the present invention) and a plurality of photoinitiators (corresponding to US Pat the components C according to the present invention). In addition, other ingredients are included, namely a primer and UV light stabilizers.

As a prepolymer, a bifunctional aliphatic urethane acrylate based on polycarbonate and isophorone diisocyanate (SUO 1200, Polygon Chemie AG) is used for the inventive example.

Also used as prepolymers (component A) for the comparative examples 1 to 3 are bifunctional aliphatic urethane acrylates, but not based on polycarbonate, or polyester (meth) acrylates, namely on the basis of an aliphatic urethane acrylate based on a polyether (CN 9002 by Sartomer Arkema Group), a polyether-based aliphatic urethane acrylate (UV-3300B from Nippon Gohsei) or a mixed polyether obtained by ring-opening polymerization from two cyclic monomers (diol-6000-DMA (dimethacrylate)).

The radiation-curable compounds (components B) are mono- and polyfunctional acrylate monomers.

The photoinitiator (components C) used is CGI 277 from BASF.

The compositions are given in Table 1. The adhesives with these compositions were prepared by mixing the components with the photoinitiator added under yellow light conditions. The amounts of the ingredients are given in wt .-%.

As is apparent from Table 1, the adhesive compositions of Comparative Examples 1, 2 and 3 also contain a prepolymer based on an oligomeric urethane acrylate, but not on the basis of polycarbonate, but on the basis of polyethers or a prepolymer based on a polyester (meth) acrylate. The Compositions of Comparative Examples 4 and 5 as well as the composition of the example according to the invention contain a urethane acrylate based on a polycarbonate as component A.

The product SUO-1200IB20 used in the composition of the example of the invention additionally contains isobornyl acrylate. For this reason, the total amount of the radiation-curing compounds constituting the components B in this composition is 64.1% by weight as in the case of Comparative Examples 1, 2 and 3. The proportion of the urethane acrylate is 32.8% by weight in the composition of the present invention as well as in the compositions of Comparative Examples 1, 2 and 3 for the same reason. The compositions of Comparative Examples 4 and 5 differ in the composition of the radiation-curing compounds (Components B). The composition of Comparative Example 5 contains a total of 59.1% by weight of isobornyl acrylate (partially contained in SUO-1200IB20) while the composition of Comparative Example 4 Contains 50.9 wt .-% of the compound 3,3,5-trimethylcyclohexanol acrylate. The former compound is much more hydrophobic than the latter. The content of isobornyl acrylate in the compositions of the inventive example and comparative examples 1, 2, 3 and 4 is the same (8.2% by weight) and thus significantly lower than in the composition of comparative example 5 (50.9% by weight). %).

Properties of adhesive compositions:

To evaluate the properties of the adhesive compositions described above, the inclusion of media (solvents) in a cured adhesive, the adhesive strength of the cured adhesive on a substrate, the compressive shear strength of the cured adhesive, the viscosity of the uncured adhesive composition, and the reactivity of the adhesive composition in the Light curing examined.

To determine the media pick-up, DIN circular disks (diameter 50 mm, height 5 mm) were produced from the adhesive compositions. For this purpose, the compositions were each cured on both sides for 60 s at an intensity of 60 mW / cm ² , then dried for 72 hours in a desiccator, weighed and then stored for 24 hours at 21 ° C in the media. The media used were DELOTHEN® EP (acetone / isopropanol mixture, hydrohilic solvent) and DELOTHEN® NK1 (Hydrocarbon mixture, hydrophobic solvent) used by DELO Industrial Adhesives. After storage in these media, the surface of the respective round disc was dried with filter paper. The round disc was weighed after drying within one minute. The measurement resulted in a mass difference between the specimen mass after storage and the specimen mass before storage. The respective media intake for the adhesive compositions according to the inventive example and the comparative examples as a quotient of this mass difference and the initial mass is given in Table 2.

For the determination of the adhesive strength, the respective adhesive composition was applied to a substrate (polycarbonate) and cured as described above. The adhesion was carried out with the cross-cut test according to DIN EN ISO 2409. The results of these measurements are also given in Table 2 for the adhesive compositions according to the example of the invention and the comparative examples. A high adhesive strength is then represented by a test value Gt 0, while a test value Gt 2 indicates a lower adhesive strength.

To determine the compressive shear strength of cured adhesive compositions, in each case two test specimens of polycarbonate (PC) measuring 20 × 20 × 5 mm ³ with an overlap of 5 × 20 mm ² were glued together. The specimens were examined in a tensile testing machine according to DIN EN ISO 7500. The results of these measurements are also given in Table 2 for the adhesive compositions according to the example of the invention and the comparative examples.

To determine the viscosity of the uncured adhesive compositions, the complex viscosity was determined using a Physica MCR301 rheometer from Anton Paar. The measurement was carried out with a standardized measuring cone PP20 and a 200 μm gap at 23.5 ° C. The viscosity was determined at a shear rate of 1 / s. The results of these measurements are also given in Table 2 for the adhesive compositions according to the example of the invention and the comparative examples.

Finally, the reactivity of the adhesive compositions in light cure was also determined. For this purpose, a Bohlin CS rheometer CVO PP 9 with photorheology device and a DELOLUX® 80/400 LED lamp from DELO Industrie Klebstoffe, DE was used. The LED lamp was at an intensity of 200 mW / cm ² operated. The exposure start took place 10 s after the start of the measurement. The reaction time is defined as the time value at the intersection of the tangents of the maximum slope and the final viscosity. A continuous oscillation with 10 Hz, a temperature of 23.5 ° C., a layer thickness of 100 μm and a nominal deformation of 5% were set. The results of these measurements are also given in Table 2 for the adhesive compositions according to the example of the invention and the comparative examples, the photocuring being shown as duration in [s].

Results:

The adhesive composition according to the invention has a substantially lower media uptake both in a relatively polar solvent (DELOTHEN® EP) and in a non-polar solvent (DELOTHEN® NK1). This indicates that a dissolution by these solvents is lower than in the case of the compositions according to the comparative examples. This applies not only to compositions in which the proportion of component A (prepolymer) is the same as in the case of the composition of the invention but also for cases in which this proportion is significantly higher (Comparative Examples 4, 5).

The adhesive strength of a non-solvent-impaired adhesive bond determined by the cross-cut test is very good in the case of the adhesive composition according to the invention and comparable to the compositions of the comparative examples.

The compressive shear strength of a specimen obtained with the adhesive composition of the invention is also still higher than in the case of the compositions compared therewith.

Although the viscosity of the adhesive composition according to the invention is somewhat higher than in the case of the comparative samples, it is within the usual range.

Finally, the photocuring is much faster than in the case of the compositions according to the comparative examples, so that a higher cycle time can be achieved in the production of adhesive bonds.

Thus, not only are the properties of an adhesive bond with the adhesive composition according to the invention superior to the compositions according to the comparative examples, but also the processability of the adhesive composition according to the invention is very good.

Ausführunasbeispiel:

The adhesive composition according to the present invention, which is shown in Table 1, is prepared and applied, for example, by means of a flexographic printing process over the entire surface of a substrate, preferably of polycarbonate. After applying the adhesive composition, a hologram / ldentigram (photopolymer) film is laminated to the substrate wetted with the adhesive composition with a laminating roller. The adhesive composition is then cured / polymerized by UV radiation through the hologram / ldentigram sheet. There is obtained a very strong bond between the hologram / ldentigramm film and the substrate, which is not affected even after prolonged exposure to hydrocarbon solvents or polar solvents such as acetone and / or ethanol. Table 1: Adhesive compositions (amounts in [% by weight]) example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Component A: SUO-1200IB20 ¹ ) 41 41 41 CN9002 ² ) 32.8 UV-3300B ³ ) 32.8 Diol 6000 DMA ⁴ ) 32.8 Component B: Pentaerythritol triacrylate ⁵ ) 20 20 20 20 5 3,3,5-trimethylcyclohexanol acrylate ⁶ ) 30.9 30.9 30.9 30.9 50.9 Acryloylmorpholine ⁷ ) 5 5 5 5 5 5 Isobornyl acrylate ⁸ ) 8.2 8.2 8.2 50.9 Component C: CGI277 ⁹ ) 2.5 2.5 2.5 2.5 2.5 2.5 Haftvermeittler: (Glycidyloxypropyl) trimethoxysilane ¹⁰ ) 0.5 0.5 0.5 0.5 0.5 0.5 UV light stabilizer: Tinuvin 123 ¹¹ ) 0.05 0.05 0.05 0.05 0.05 0.05 Tinuvin 384 ¹² ) 0.05 0.05 0.05 0.05 0.05 0.05 TOTAL 100 100 100 100 100 100 Explanatory notes to Table 1:
¹ ) bifunctional aliphatic urethane acrylate based on polycarbonate and isophorone diisocyanate containing 20% by weight of isobornyl acrylate, available from Shin A T & C
² ) bifunctional aliphatic urethane acrylate based on a polyether available from Sartomer
³ ) bifunctional aliphatic urethane acrylate based on a polyether available from Nippon Gohsei
⁴ ) bifunctional dimethacrylate based on a copolymer of two cyclic ethers obtained by ring-opening polymerization (molecular weight 6000)
⁵ ) available from Sartomer
⁶ ) available from Sartomer
⁷ ) available from Rahn GmbH
⁸ ), for example, available from Sartomer
⁹ ) available from BASF
¹⁰ ) available from Evonik Industries
¹¹ ) hindered amine light stabilizer, available from BASF
¹² ) Hydroxyphenylbenzotriazole based light stabilizer available from BASF example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 media recording Media Recording DELOTHEN® EP [%] 2.2 12.0 8.0 12.4 14.4 8.2 Media Image DELOTHEN® NK1 [%] 0.1 6.0 4.2 8.1 14 4.7 adhesiveness Cross-cut test Gt 0 Gt 0 Gt 0 Gt 2 Gt 2 Gt 0 Compression shear strength DSF PC-PC [MPa] 29 10 21 11 26 23 viscosity Viscosity [mPas] 990 510 940 520 540 640 Reactivity Reactivity light curing [s] 1.5 2 1.5 2 3.5 3

LIST OF REFERENCE NUMBERS

100

Value or security document, identity card

101

Top, surface

110

carrier

111

polymer layer

112

polymer layer

120

Passphoto

200

Security element, hologram patch

210

first location

211

(Contact) side

220

second location

300

Adhesive (layer)

Claims (18)

1. Value or security document (100), comprising a support (110) and a security element (200) connected to the support (110) by means of a single-component adhesive (300), wherein the single-component adhesive (300) has an adhesive composition comprising the following constituents:

   (A) at least one oligomer urethane(meth)acrylate based on a polycarbonate;

   (B) at least one radiation-curing compound; and

   (C) at least one photoinitiator.
2. Value or security document (100) according to claim 1, characterised in that the security element (200) is formed by a diffraction element.
3. Value or security document (100) according to any one of the preceding claims, characterised in that the security element (200) is formed by a holographic data carrier.
4. Value or security document (100) according to any one of the preceding claims, characterised in that the support (110) is formed, at least at a surface (101) at which the security element (200) is connected to the support (110), from a material containing polycarbonate and formed from polycarbonate.
5. Value or security document (100) according to any one of the preceding claims, characterised in that the security document (200) is formed, at least on a side (211) with which it is connected to a surface (101) of the support (110), from a material that contains a polymer, or is formed from a polymer, which is selected from a group comprising polyethyleneterephthalate, polyvinyl acetate, and fluropolymers.
6. Value or security document (100) according to any one of the preceding claims, characterised in that at least one of the at least one radiation-curing compound comprises at least two functional groups for the radiation curing.
7. Method for producing an adhesion promoter connection between a support (110) of a value or security document (100) and a security element (200) by means of a single-component adhesive (300), which can be cured by actintic radiation, wherein the security element (200) is adhesively bonded onto the surface (101) of the support (110) by means of the single-component adhesive (300), wherein the single-component adhesive (300) has an adhesive composition comprising the following constituents:

   (A) at least one oligomer urethane(meth)acrylate based on a polycarbonate;

   (B) at least one radiation-curing compound; and

   (C) at least one photoinitiator.
8. Method for producing an adhesion promoter connection according to claim 7, characterised in that at least one of the at least one radiation-curing compound comprises two functional groups for the radiation curing.
9. Method for producing an adhesion promoter connection according to one of claims 7 and 8, characterised in that the at least one radiation-curing compound is selected from a group comprising (meth)acrylates of polyols, preferably poly(meth)acrylates of polyols.
10. Method for producing an adhesion promoter connection according to claim 9, characterised in that the at least one radiation-curing compound is selected from a group comprising poly(meth)acrylates, wherein the compound comprises more than two acrylate groups, in particular pentaerythritoltri(meth)acrylate.
11. Method for producing an adhesion promoter connection according to any one of claims 7 to 10, characterised in that the at least one oligomer urethane(meth)acrylate is obtained:

    (a) by reacting at least one polycarbonate diol and at least one polyfunctional isocyanate, with the formation of an isocyanate-functionalised polycarbonate diol in a first synthesis step; and

    (b) by reacting the isocyanate-functionalised polycarbonate diol obtained in the first synthesis step with at least one ester or amide of an α, β non-saturated carboxylic acid with one or more low-molecular aliphatic alcohols, which additionally comprise a further OH or SH group, in a second synthesis step.
12. Method for producing an adhesion promoter connection according to claim 11, characterised in that reacting the at least one polycarbonate diol with the at least one polyfunctional isocyanate is done in the presence of a dilutant.
13. Method for producing an adhesion promoter connection according to claim 12, characterised in that the dilutant is a (meth)acrylate, which is selected from a group comprising 3,3,5-trimethylcyclohexyl(meth)acrylate, tert-butylcyclohexyl(meth)acrylate, 2(2-ethoxyethoxy)ethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate,2-phenomethyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl(meth)acrylate, (5-ethyl-1,3-dioxan-5-yl)methyl(meth)acrylate, 1,6-hexandiol(meth)acrylate, lauryl(meth)acrylate, isodecyl(meth)acrylate, isooctyl(meth)acrylate, octyl(meth)acrylate, 3-methyl-1,5-pentandioldi(meth)acrylate, and cyclotrimethylolpropanformyl(meth)acrylate.
14. Method for producing an adhesion promoter connection according to any one of claims 7 to 13, characterised in that the constituents of the single-component adhesive (300) are contained in the following quantities in the adhesive (300):

    (A) 5 to 70 parts by weight of the at least one oligomer urethane(meth)acrylate;

    (B) 5 to 90 parts by weight of the at least one radiation-hardening compound; and

    (C) 0.1 to 20 parts by weight of the at least one photoinitiator,

    related to 100 parts by weight of the adhesive composition,
    wherein the sum of the parts by weight of the constituents A, B, and C results in a maximum of 100 parts by weight.
15. Method for producing an adhesion promoter connection according to any one of claims 7 to 14, characterised in that the single-component adhesive (300) additionally contains further substances serving as modifiers.
16. Method for producing an adhesion promoter connection according to claim 15, characterised in that the constituents of the single-component adhesive (300) are contained in the following quantities in the adhesive (300):

    (A) 5 to 80 parts by weight of the at least one oligomer urethane(meth)acrylate;

    (B) 5 to 90 parts by weight of the at least one radiation-hardening compound; and

    (C) 0.1 to 20 parts by weight of the at least one photoinitiator; and

    (D) 0 to 10 parts by weight of the at least one modifier,

    related to 100 parts by weight of the adhesive composition,
    wherein the sum of the parts by weight of the constituents A, B, C and D results in a maximum of 100 parts by weight.
17. Method for producing an adhesion promoter connection according to any one of claims 7 to 16, characterised in that the single-component adhesive (300) is applied with a printing method onto the security element (200) and/or onto the surface (101) of the support (110), and the security element (200) and the support (110) are brought into contact with one another.
18. Use of a single-component adhesive (300) for producing a value or security document (100), wherein the adhesive (300) has an adhesive composition comprising the following constituents:

    (A) at least one oligomer urethane(meth)acrylate based on a polycarbonate;

    (B) at least one radiation-curing compound; and

    (C) at least one photoinitiator.

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