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Title:

Value or security document, method for producing an adhesive bond between a security element and the surface of the value or security document and the use of a one-component adhesive

Child code:

A1

Abstract:

Inventors:

STASIAK MICHAEL (DE)
GAHLBECK JEFFRY (DE)
SINGER STEFAN (DE)
HAUG TIMM (DE)

Application Number:

DE102015208534A

Publication Date:

11/10/2016

Assignee:

BUNDESDRUCKEREI GMBH (Berlin, DE)
DELO IND KLEBSTOFFE GMBH & CO KGAA (Windach, DE)

Domestic Patent References:

DE102010033049A1N / A2012-02-02
DE102008019871B3N / A2009-11-05
DE69030981T2N / A1997-10-23

Other references:

ISO / IEC 7810
ISO 14443
DIN EN ISO 2409
DIN EN ISO 7500

Attorney, Agent or Firm:

Patent Attorneys Bressel und Partner mbB (Berlin, DE)

Claims:

1. Value or security document (), comprising a carrier () and a security element () connected to the carrier () by means of a one-component adhesive (), characterized, that the one-component adhesive () has an adhesive composition with the following components:
(A) at least one oligomeric 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 () according to claim 1, characterized, that the security element () is formed by a diffraction element.

3. Value or security document () according to one of the preceding claims, characterized, that the security element () is formed by a holographic data carrier.

4. Value or security document () according to one of the preceding claims, characterized, that the carrier () is formed from a material containing polycarbonate and formed from polycarbonate, at least on one surface () on which the security element () is connected to the carrier (14).

5. Value or security document () according to one of the preceding claims, characterized, that the security element () is formed at least on one side () with which it is connected to a surface () of the carrier () from a material which contains a polymer or is formed from a polymer which is selected from a group including polyethylene terephthalate, polyvinyl acetate and fluoropolymers.

6. Value or security document () according to one of the preceding claims, characterized, that at least one of the at least one radiation-curing compound has at least two functional groups for radiation curing.

7. A method for producing an adhesion promoter composite between a carrier () of a value or security document () and a security element () by means of a one-component adhesive () which is curable with actinic radiation, the security element () by means of the one-component adhesive () the surface () of the carrier () is glued on, characterized, that the one-component adhesive () has an adhesive composition with the following components:
(A) at least one oligomeric urethane (meth) acrylate based on a polycarbonate;
(B) at least one radiation curing compound; and
(C) at least one photoinitiator.

8. A method for producing an adhesion promoter composite according to claim 7, characterized, that at least one of the at least one radiation-curing compound has at least two functional groups for radiation curing.

9. A method for producing an adhesion promoter composite according to one of claims 7 and 8, characterized, 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. A method for producing an adhesion promoter composite according to claim 9, characterized, that the at least one radiation-curing compound is selected from a group comprising poly (meth) acrylates, this compound having more than two acrylate groups, in particular pentaerythritol tri (meth) acrylate.

11. A method for producing an adhesion promoter composite according to any one of claims 7 to 10, characterized, that the at least one oligomeric urethane (meth) acrylate is obtained
(a) by reacting at least one polycarbonate diol and at least one polyfunctional isocyanate to form an isocyanate-functionalized polycarbonate diol in a first synthesis step; and
(b) by reacting the isocyanate-functionalized polycarbonate diol obtained in the first synthesis step 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, in a second synthesis step .

12. A method for producing an adhesion promoter composite according to claim 11, characterized, that the reaction of the at least one polycarbonate diol with the at least one polyfunctional isocyanate is carried out in the presence of a diluent.

13. A method for producing an adhesion promoter composite according to claim 12, characterized, that the diluent is a (meth) acrylate 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-dioxan-5-yl) methyl (meth) acrylate, 1 , 6-hexanediol (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, octyl (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate and cyclotrimethylolpropaneformyl (meth ) acrylate.

14. A method for producing an adhesion promoter composite according to any one of claims 7 to 13, characterized, that the components of the one-component adhesive (300) in the following quantities in the adhesive (300) include:
(A) 5 to 70 parts by mass of the at least one oligomeric urethane (meth) acrylate;
(B) 5 to 90 parts by mass of the at least one radiation-curing compound; and
(C) 0.1 to 20 parts by mass of the at least one photoinitiator,
based on 100 parts by mass of the adhesive composition,
where the sum of the mass fractions of components A, B and C is a maximum 100 Mass fractions results.

15. A method for producing an adhesion promoter composite according to any one of claims 7 to 14, characterized, that the one-component adhesive (300) also contains other substances serving as modifiers.

16. A method for producing an adhesion promoter composite according to claim 15, characterized, that the components of the one-component adhesive (300) in the following amounts in the adhesive (300) include:
(A) 5 to 80 parts by mass of the at least one oligomeric urethane (meth) acrylate;
(B) 5 to 90 parts by mass of the at least one radiation-curing compound;
(C) 0.1 to 20 parts by mass of the at least one photoinitiator; and
(D) 0 to 10 parts by mass of the at least one modifier,
based on 100 parts by mass of the adhesive composition,
where the sum of the mass fractions of components A, B, C and D gives 100 mass fractions.

17. A method for producing an adhesion promoter composite according to one of claims 7 to 16, characterized, that the one-component adhesive (300) with a printing process on the security element (200) and / or on the surface (101) of the carrier (110) applied and the security element (200) and the carrier (110) are brought into contact with each other.

18.Use of a one-component adhesive (300) for the production of a value or security document (100), where the adhesive (300) has an adhesive composition with the following components:
(A) at least one oligomeric urethane (meth) acrylate based on a polycarbonate;
(B) at least one radiation curing compound; and
(C) at least one photoinitiator.

Description:
Field of the invention:

The present invention relates to a value or security document which has a security element connected to it 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 an adhesive bond between a carrier 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:

Valuable or security products, in particular value 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 surrender of a product or the provision of a service. To this end, it must be ensured that the product cannot be imitated, falsified or adulterated, or only with considerable effort. The product therefore contains security features that are extremely difficult or even practically impossible to imitate. For example, like banknotes, the product is made of a material that is not readily available. Additionally or alternatively, security features can be formed by special colors, for example luminescent or optically variable colors, optical elements such as holograms, tilt images, cinegraphic objects, lens or prism arrays, as well as guilloches, mottled fibers, security threads and others. Furthermore, it is also necessary that the value or security documents can be easily produced.

Optical security elements can, for example, be produced separately and then glued as patches, security threads, security strips or the like to an external surface on the valuable or security product or to an internal surface in the valuable or security product. Such security elements can be optically variable elements, so that visually perceptible phenomena generated therewith are either recognizable and / or can assume different shapes depending on the angle at which the value or security document is viewed.

To attach a security element to a surface on the inside of the value or security document or on the outside of the document, adhesion promoters are used with which the security element is glued to a surface of the value or security document. To do this there DE 10 2008 019 871 B3 For example, a multilayer security document has a printable carrier material, a photopolymer film connected to the carrier material on a first side and a first cover film connected to the photopolymer film or a first cover film composite connected to the photopolymer film. The photopolymer film is connected to the carrier material via a first adhesive film. A volume hologram is exposed in at least one area of ​​the photopolymer film. A so-called transfer adhesive film is used to connect the photopolymer film to the carrier material. It is an acrylate-based adhesive material. The carrier is formed, for example, from polyethylene or polyethylene terephthalate. The adhesive film can be activated by pressure and / or thermally.

Out DE 10 2010 033 049 A1 discloses a laminate composite with a first polymer layer, a second polymer layer and a security element which is laminated between the first polymer layer and the second polymer layer, a layer of a reactive adhesive being arranged at least between the security element and the first polymer layer. To laminate in 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. The first polymer layer and the security element are then positioned with respect to one another and connected to one another. The adhesive is then crosslinked, and finally the first and the second polymer layer, including the security element, are laminated to one another under the action of pressure and heating. One-component systems in particular are used as reactive adhesives, namely heat-crosslinkable systems with a base polymer and a heat-activated crosslinker, for example epoxies, urethanes, polyesters and polyimides, and also radiation-crosslinkable systems, which are usually based on acrylate, and systems that crosslink through moisture, for example cyanoacrylates and Urethanes. Alternatively, two-component systems can also be used.

Definitions:

Insofar as the term “(meth) acrylic” or “(meth) acrylate” is used below in the description and in the claims, this includes both an acrylic or acrylate group and, alternatively, a methacrylate or methacrylate group understand.

Insofar as the term “actinic radiation” is used below in the description and in the claims, this is understood to mean radiation which is suitable for curing the one-component 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-rays, synchrotron radiation and the like, and on the other hand, corpuscle radiation with a suitable wavelength, for example electron beams.

To the extent that the term “C1- to C12-Alkyl ‘is used, it is to be understood as meaning a saturated linear or branched-chain monovalent hydrocarbon radical having 1 to 12 carbon atoms, where the alkyl radical can optionally be independently substituted by one or more substituents.

Insofar as the term “alkylene” is used in the description and in the claims below, it is to be understood as meaning a saturated linear or branched-chain divalent hydrocarbon radical with one to twelve carbon atoms, where the alkylene radical can optionally be independently substituted with one or more substituents. Examples of alkylene groups include, but are not limited to, methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH (CH3) CH2-), and the same.

Insofar as the term “alkylene oxide” is used in the description and claims below, this includes a saturated linear or branched-chain group with the general formula - (alkylene-O)q- to be understood where q is an integer whose value is determined by the fact that the number of carbon atoms of the alkylene radicals is in a range from 12 to about 500, for example.

If the term “substituent” is used below in the description and in the claims, this is to be understood as a monovalent chemical radical selected from a group comprising C1- to C12-Alkyl, Hal (F, Cl, Br, I), -OR1, -NO1R.2, -COOR1, -CONR1R.2where R1 and R2 independently of each other H and C1- to C6-Alkyl are. The term “substituted” is to be understood in a corresponding manner.

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 hydroxy or isocyanate groups.

Tasks on which the invention is based:

To apply and permanently connect a security element to the carrier of a value or security document, various requirements must be met: On the one hand, it must be provided that the adhesive is easy to process, ie has a sufficiently long pot life under normal daylight conditions, while at the same time ensuring that the Curing with actinic radiation also takes place quickly through the security element. Furthermore, the viscosity of the adhesive must be sufficiently low to ensure that it can be applied to the connection partner or partners without the formation of air bubbles and streaks.This also includes that the adhesive wets the connection partner (s) sufficiently securely in order to achieve an all-over and gap-free coating of its surface. Furthermore, in order to ensure that the visually recognizable security element should be recognizable through the adhesive layer without impairment, the adhesive must be transparent and as colorless as possible, which also requires the adhesive to be used during the curing process and / or during aging, in particular UV light does not yellow or otherwise change 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 a high degree of flexibility in order to prevent the security element from tearing or flaking off.

Finally, the adhesive must of course ensure a very high peel strength of the security element on the carrier, i.e. a very high bond strength between the connection partners. This presupposes 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.

Principles of the invention and preferred embodiments:

According to a first aspect of the present invention, these objects are achieved by the value or security document according to the invention, which has a carrier and a security element connected to the carrier by means of a one-component adhesive, the one-component adhesive being characterized in that it has an adhesive composition at least with the has the following components:

  • (A) at least one oligomeric urethane (meth) acrylate based on a polycarbonate;
  • (B) at least one radiation curing compound; and
  • (C) at least one photoinitiator.

Furthermore, according to a second aspect of the present invention, these objects are also achieved by the method according to the invention for producing an adhesion promoter composite between the security element and the carrier of the value or security document by using a one-component adhesive that is curable with actinic radiation for connecting the security element to the carrier is used. For this purpose, the security element is glued to the surface of the carrier by means of the one-component adhesive. The one-component adhesive has an adhesive composition with at least the aforementioned constituents (components) A, B and C.

Finally, these objects are also achieved by using the aforementioned one-component adhesive for producing the value or security document.

By optimizing the adhesive composition of the adhesive, the requirements mentioned at the beginning 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 bond strength of materials containing polycarbonate or formed from polycarbonate with other polymers, for example polyethylene terephthalate, polyvinyl acetate or fluoropolymers, is achieved.

The adhesive forms a hardenable mass which is liquid at room temperature and has a dynamic viscosity at room temperature (20 ° C.) which is in the range from 500 to 3000 mPas (measured with a rotary viscometer with cylinder-cup geometry). The dynamic viscosity is preferably 1000 mPas (20 ° C.). This ensures that the adhesive mass can be applied without streaks or bubbles and that it wets the surfaces to be connected well.

Furthermore, the adhesive has a high level of transparency and is, if necessary, completely colorless, so that the security element itself can be easily recognized visually through the adhesive without impairment. The adhesive has excellent stability against the effects of moisture. Water does not change the physical and chemical properties of the adhesive, for example its transparency, color and bond strength. Finally, the one-component adhesive according to the present invention is also sufficiently stable in storage. In addition, the adhesive is highly flexible.

The one-component adhesive is preferably solvent-free, which results 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 in such a way that the resistance of the adhesive connection is as great as possible. Furthermore, the one-component adhesive also has sufficient flexibility, i.e. the adhesive or the adhesive layer ideally does not show any breaks or cracks under the given conditions.

The one-component adhesive contains as at least one component A in each case an oligomeric urethane (meth) acrylate based on a polycarbonate diol, ie based on an oligomeric compound with a polycarbonate chain which forms the basic structure for the urethane (meth) acrylate, the polycarbonate chain at least on the Chain ends with radical polymerizable groups, in particular (meth) acrylic groups, is functionalized.

In a particularly preferred embodiment of the present invention, the at least one oligomeric urethane (meth) acrylate can be obtained using a process with the following process steps:

  • (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 synthesis step; and
  • (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 synthesis step.

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. To produce a polycarbonate diol, a polyol can, for example, be reacted with a dialkyl carbonate, diaryl carbonate or phosgene, or a polyol can be reacted with several different compounds selected from dialkyl carbonates, diaryl carbonates and phosgene, or several different polyols can be reacted with a dialkyl carbonate , Diaryl carbonate or phosgene are reacted, or several different polyols can be reacted with several different compounds selected from dialkyl carbonates, diaryl carbonates and phosgene.

The polyols used are polyhydric, preferably saturated or unsaturated, aliphatic, cycloaliphatic or araliphatic alcohols with at least two hydroxyl groups, it being possible for the hydroxyl groups to be both primary and secondary. It is also possible to use polyols with more than two hydroxyl groups, such as glycerol, trimethylolethane, trimethylolpropane, di (trimethylolpropane) dimethylolpropionic acid, trimethylolethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and anhydroenneaheptitol. It is also possible to use mixtures of two or more of the polyols mentioned.

The polycarbonate diol has a molar mass of 500 to 10,000 g / mol, preferably 1,000 to 5,000 g / mol and very particularly preferably 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 name Desmophen® C2200 from Bayer MaterialScience AG.

In the first synthesis step, the polycarbonate diol is reacted with a polyfunctional, preferably difunctional, isocyanate compound (ii), i.e. a diisocyanate compound, resulting in 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.

At least one compound is selected as the polyfunctional isocyanate 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 -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 from 1: 1.8 to 1: 2.2, very particularly preferably in a ratio of 1: 2.

The reaction can be carried out in a customary manner in an aprotic solvent, for example in a halogen-containing organic solvent. However, preference is given to solvents which do not contain halogen, for example acetone, methyl isobutyl ketone or ethyl acetate. The reaction temperature can be room temperature. However, the temperature of the reaction mixture can usually be increased, for example to 40 to 80.degree. C., to accelerate the reaction mixture. If necessary, the catalysts common in polyurethane chemistry, in particular organometallic compounds, can also be added to the reaction mixture to accelerate the reaction, for example at least one compound selected from a group comprising dibutyltin laurate (DBTL), dibutyltin acetate or dibutyltin versate, tin octoate, iron (II) - chloride, zinc chloride and lead octoate. Tin salts are preferably used, for example tin dioctoate, tin diethylhexoate and dibutyltin-bis-dodecyl-mercaptide. It is also possible to use lead salts, for example lead phenylethyldithiocarbaminate, bismuth salts, for example triaryl bismuth compounds, oxides of these compounds and phenates and carboxylates of bismuth. 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% by weight.

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

In a preferred development of the present invention, the reaction of the at least one polycarbonate diol with the at least one polyfunctional isocyanate is carried out 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-dioxan-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 cyclotrimethylolpropaneformyl (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 then reacted with at least one compound (iii) which carries a functional group which can react with isocyanates , and which has a double bond crosslinkable by radical polymerization as a further functional group. 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. It is, 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 products of polyalcohols such as pentaerythritol, glycerol or trimethylolpropane with (meth) acrylic acid and also esters and amides bearing SH groups 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 radical polymerizable groups are preferably used in a molar ratio (isocyanate-functionalized polycarbonate to compound (iii)) in a range from 1: 1.8 to 1: 2.2, very particularly preferably in a molar ratio of 1: 2.

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

The second constituent 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.e. a compound that polymerizes radically 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 which contain up to 20 radiation-reactive groups. It is very particularly preferred if the at least one component B1 carries up to 5 radiation-reactive groups. Optionally, a mixture of such monomers and / or oligomers and / or polymers can also be used. In a most preferred embodiment of the present invention, at least one of the components B3 contains to 5 radiation-reactive groups.

It is particularly preferred if, for the at least one component B, radiation-curing compounds are selected from a group which comprises (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 are substituted with radiation-curing groups, such as (meth) acrylic acid esters. The polyols specified above for the formation of the polycarbonate backbone of the at least one component A can be used as polyols (in this respect reference is made to the disclosure there). Polyurethanes which can be used are reaction products of the diisocyanates mentioned above for the formation of the isocyanate-functionalized polycarbonate backbone (in this respect reference is made to the disclosure therein) and other higher-value polyisocyanates (tri-, tetraisocyanates) with the above-mentioned polyols (in this respect reference is again made to the disclosure there ) can be used. When using higher-quality polyols or when using polyols reacted to produce the polyurethanes, for example tri-, tetra- or penta-alcohols, dendrimers are formed which - reacted with radiation-curing groups - can also 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.

Acid amides with radiation-reactive groups are particularly suitable as component (s) B, 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 similar compounds.

In addition, acids with radiation-reactive groups are also suitable, from 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). Furthermore, (meth) acrylates of polyols, for example pentaerythritol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, ) acrylate, suitable.

In a particularly preferred embodiment of the present invention, components B are selected from a 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 with more than two acrylate groups being very particularly preferred. It should be pointed out that these polyfunctional acrylate compounds can also be used in combination with single- and / or double-functional acrylate compounds, for example in order to specifically control the crosslinkability of the adhesive composition.

Vinyl ethers and maleimides and bismaleimides are also suitable. 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, US), 1,4-cyclohexanedimethanol divinyl ether (available under the trade name RAPI-CURE® CHVE, International Specialty Products), trimethylolpropane trivinyl ether (available under the name TMPTVE from BASF Corp., US), divinyl ether resins (such as VECTOMER 2010, VECTOMER 2020, VECTOMER 4010, VECTOMER 4020) and similar materials and mixtures thereof.

Preferred maleimides which can be used as component (s) B according to the present invention have the following general chemical formula (I): wherein:
R.8 in each of the two residues N (CO)2CH (R8) CH2 is selected independently of the other radical from a group comprising hydrogen and C1- to C12-Alkyl and
X is a divalent radical which is selected from a group comprising branched-chain alkylene and alkylene oxide radicals having from about 12 to about 500 carbon atoms in the basic structure, and which can represent a group which has the structure with the general chemical formula (II): has, in which:
p is 0, 1, 2 or 3;
y is 0 or 1;
Ar in each of the residues O (CO)yAr is independently selected from a group comprising monosubstituted and trisubstituted rings, each of which can be aromatic or heteroaromatic and 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.

One or more components B can be present, mixtures of the abovementioned compounds being used in the latter case.

As component (s) C, the adhesive composition according to the present invention also contains at least one photoinitiator for free-radical polymerization. The usual, commercially available compounds can be used as photoinitiators of this type, which decompose into reactive radicals under the action of preferably UV radiation and / or radiation in the visible spectral range, provided that the adhesive according to the invention can be cured through the security element, ie that the security element is transparent to the actinic radiation required for curing. Furthermore, with regard to 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 when using artificial light).

The following compounds, for example, can be used as photoinitiator (s): α-hydroxy ketones, benzophenone, α-aminoketones, benzophenone derivatives such as 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and 2-hydroxy-2-methylpropiophenone , also 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 in each case be used alone or in combination of two or more of the compounds mentioned.

You can also use the Irgacure®Types from BASF, for example the Irgacure types® 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.e. radical polymerization takes place when irradiated in the UV spectral range. 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. The initiator CGI 277, available from BASF SE, is particularly suitable. It is an α-aminoketone.

In a most preferred embodiment of the present invention, the adhesive composition contains 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.

Furthermore, the adhesive composition according to the present invention can contain at least one further substance serving as a 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.

All commercially available compounds and mixtures of compounds which are soluble or at least miscible in the mixture of components A, B and C can be used as dyes and pigments. In particular, cationic, anionic or neutral colorants can be used. For example, brilliant black C.I. No. 28440, chromogenic black C.I. No. 14645, direct deep black E C.I. No. 30235, Fast Black Salt B C.I. No. 37245, Fast Black Salt K C.I. No. 37190, Sudan Black HB C.I. 26150, naphthol black C.I. No. 20470, Bayscript® Black liquid, C.I. Basic Black 11, C.I., Basic Blue 154, Cartasol® Turquoise K-ZL liquid, Cartasol® Turquoise K-RL liquid (C.I. Basic Blue 140), Cartasol® Blue K5R liquid, Hostafine® Black TS liquid, Bayscript® Black liquid, Cartasol® Black MG liquid (C.I. Basic Black 11), Flexonyl®black PR 100 (E C.I. No. 30235), Cartasol® Orange K3 GL, Cartasol® Yellow K4 GL, Cartasol® K GL, or Cartasol® Red K-3B, where Bayscript® a trademark of Lanxxess, DE, Cartasol® and flexonyl® Brands of Clariant, DE and Hostafine® are a trademark of Hoechst GmbH, DE. Anthraquinone, azo, quinophthalone, coumarin, methine, perinone and / or pyrazole dyes can also be used as soluble colorants.

All commercially available compounds and compound mixtures which are soluble in the mixture of components A, B and C can also be used as luminescent agents. The luminescent means 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.

Hindered amine light stabilizers and triazole compounds can be used as stabilizers. Silane compounds can be used as moisture scavengers and adhesion promoters. For example, silane compounds with the chemical structural formula (III) can be used: As polymeric thickeners, water-soluble starches, in particular with an average molecular weight of 3,000 to 7,000 g / mol, polyvinylpyrolidone, in particular with an average molecular weight of 25,000 to 250,000 g / mol, polyvinyl alcohol, in particular with an average molecular weight of 10,000 to 20,000 g / mol, Xanthan gum, carboxy methyl cellulose, ethylene oxide / propylene oxide block copolymer, in particular with an average molecular weight of 1,000 to 8,000 g / mol, can be used. An example of the latter block copolymer is the Pluronic range® from BASF, DE. Phthalates, citric acid esters and other substances known for this purpose can be used as plasticizers.

In a preferred embodiment of the present invention, the constituents of the one-component adhesive are contained in the adhesive in the following amounts:

  • (A) 5 to 70 parts by mass of the at least one oligomeric urethane (meth) acrylate (component (s) A);
  • (B) 5 to 90 parts by mass of the at least one radiation-curing compound (component (s) B); and
  • (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 components A, B and C results in a maximum 100 Mass fractions. If only the components A, B and C are contained in the adhesive composition, the sum of the mass fractions of these three components gives exactly 100 Mass fractions. 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, where 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).

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:

  • (A) 5 to 80 parts by mass of the at least one oligomeric urethane (meth) acrylate (component (s) A);
  • (B) 5 to 90 parts by mass of the at least one radiation-curing compound (component (s) B);
  • (C) 0.1 to 20 parts by mass of the at least one photoinitiator (component (s) C); and
  • (D) 0 to 10 parts by mass of the at least one modifier (component (s) D),
based on 100 Mass fractions of the adhesive composition.

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

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

For this purpose, the one-component adhesive can be applied to the at least one connection surface in a conventional manner, for example by means of printing, brushing, pouring, roller coating, curtain casting, spin coating, knife coating, dipping, dispensing or other coating techniques. The layer thickness produced depends on the viscosity of the adhesive, the wettability of the at least one connecting surface, the application method and other parameters. The layer thickness can preferably be 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 can preferably be a maximum of 1,000 μm, more preferably a maximum of 500 μm, even more preferably a maximum of 50 μm and most preferably a maximum of 30 μm. In the case of double-sided application to the connection surfaces of both connection partners, the individual adhesive layers can be thinner, for example in the range from 1 to 20 μm.

After the security element has been placed on the carrier at the connection point at which it is to be connected to the carrier on its surface, the security element is brought into contact with and connected to the carrier surface at the connection point.

The adhesive is then cured by exposure to actinic radiation. For this purpose, actinic radiation is used, which activates the at least one photoinitiator. The actinic radiation is thus matched to the at least one photoinitiator in terms of its spectral distribution and intensity. The at least one photoinitiator is preferably adapted to the available actinic radiation. The spectral distribution is to be determined in such a way that the actinic radiation is absorbed by the at least one photoinitiator. The intensity of the actinic radiation should be set so high that the radical polymerization is promoted. The actinic radiation is preferably in the UV spectral range, but can alternatively or additionally also lie in another spectral range, for example in the visible (VIS) or IR spectral range. UV radiation is advantageous because it enables processing in normal daylight if the adhesive composition cannot also be cured by exposure to electromagnetic radiation in the VIS spectral range.

The curing step by means of the actinic radiation creates a very firm and non-releasable connection between the security element and the carrier of the value or security document.

The curing time can be short or long depending on the effect of the actinic radiation on the one-component adhesive. For example, the curing time is in a range from 0.5 s to 5 h, preferably from 1 s to 30 min, more preferably from 2 s to 1 min and most preferably from 5 s to 20 s.

The adhesive layer is preferably irradiated through the security element. Irradiation through the carrier of the value or security document is also possible. For this purpose, it is to be made transparent for the actinic radiation, at least in the connection area.

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

The security element can be in the form of a so-called optically variable element, i.e. 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, for example, zero-order diffraction gratings, diffraction gratings with a rainbow effect, and relief and volume holograms, as well as microlenses and lens grids.

The security element is typically produced separately and is applied to the carrier of the value or security document as a patch, security thread, security strip or the like. The structure of a semifinished product that can be used to apply the security element to the carrier depends on its type. In general, the semi-finished product is multilayered. For example, it can have a base on which a functional layer is located, 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 layer forms the actual security element, which is ultimately located on the carrier. The base 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 it is applied to the carrier. These two auxiliary layers can consist, for example, 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 only covers a partial area of ​​the value or security document, for example 0.5 to 75%. , preferably 1 to 50% and most preferably 2 to 25% of the area of ​​the value or security document. One or more security elements can be applied to one side of the value or security document, or one or more security elements can be applied to both sides of the value or security document.

In a preferred embodiment of the present invention, the carrier of the value or security document is formed from a material comprising polycarbonate and formed from polycarbonate, at least on one surface on which the security element is connected to the carrier. The one-component adhesive according to the present invention is particularly well suited for producing a permanent, firmly bonded connection between the security element and a surface of the carrier which contains or consists of polycarbonate.

The value or security document can in particular be a passport, identity card, driver's license, an access control card or another ID card, a vehicle registration document, vehicle registration document, visa, check, means of payment, in particular a bank note, a check, bank, credit or cash card, Customer card, health card, chip card, company ID, proof of eligibility, membership card, gift or shopping voucher, waybill or other proof of authorization, tax code, postage stamp, ticket, (game) token, adhesive label (e.g. for product security) or another document. The document can be a smart card, for example. The value or security document can be in ID 1, ID 2, ID 3 or in any other standardized or non-standardized format, for example in booklet form, as in the case of a passport-like object. A value or security document is generally a laminate made up of several document layers that have been joined to one another over a large area under the action of heat and under increased pressure. These documents should meet the standardized requirements, for example ISO 10373, ISO / IEC 7810, ISO 14443. The document layers consist, for example, of a material that is suitable for lamination.

The value or security document can be formed from a polymer selected from a group comprising polycarbonate (PC), in particular bisphenol A polycarbonate, polyethylene terephthalate (PET), their derivatives, such as glycol-modified PET (PETG), polyethylene naphthalate ( PEN), polyvinyl chloride (PVC), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), polyimide (PI), polyvinyl alcohol (PVA), polystyrene (PS), polyvinyl phenol (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 can also be made from several of these materials. It preferably consists of PC or PC / TPU / PC. The polymers can 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 that are applied to a preliminary product, such as a protective varnish. The document is preferably produced from 3 to 12, preferably 4 to 10, films (including the carrier of a data transmission device contained therein). A laminate formed in this way can then 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 can also be arranged in a protected manner under an overlay layer. 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 from several polymer films, a stack of several polymer films can first be brought together. The foils of the stack are then laminated under the action of a compression pressure and at an elevated temperature. When laminating the stack in a hot press typically at 190 to 200 ° C and a pressure of, for example, 350 N / cm2 and in a cooling press at a pressure of 600 N / cm2 laminated if the document layers are made of polycarbonate. The security element, for example a holographic data carrier, can then be glued to the carrier produced in this way in the manner according to the invention. So that the security element is protected, the laminate can then be provided with a protective varnish. At least the external 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 fastened there using 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 further polymer films, for example likewise polycarbonate films or films made of different materials, to form a stack. The foils in the stack are then laminated together. In this case, the security element can be arranged on the inside of the laminate stack. So that the security element can be visually recognized from the outside, the film layers arranged between an observer's point of view and the security element are transparent and preferably colorless. If necessary, there can be perforated printed layers between the viewer's point of view and the security element.

The further document layers in the laminate can contain additional security features, for example a photograph of the owner of the document and / or security printing features and functional colors. The stack can also contain a film layer with an RFID circuit with an RFID chip and an RFID antenna. The stack can be closed to the outside by layers of cover film (overlays) or covered with a protective varnish. These cover film layers or the protective varnish are preferably transparent and thus allow the document layers and security features underneath to be viewed. The overlays protect the document layers arranged below and / or offer the possibility of optical laser personalization and the 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, for example, have additional security features.

After the laminate has been completed, the document can be equipped with further security features. The further security features can either be individualizing or non-individualizing. Guilloches, watermarks, embossed prints, a security thread, microscript, tilt images, transparency register and the like come into consideration as further security features. Furthermore, the document can also have electronic components, for example an RFID circuit with antenna and RFID microchip, electronic display elements, LEDs, touch-sensitive sensors and the like. The electronic components can be arranged hidden between two opaque layers of the document, for example.

Detailed description of the invention:

The following figures and examples serve to illustrate the present invention in more detail, whereby the figures and examples are merely exemplary and do not represent any restriction with regard to the scope of the invention described:

1 shows a value or security document according to the invention in an isometric representation;

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

In the figures, the same reference symbols denote elements with the same function or the same elements.

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

A first surface area is on top 101 the identity card 100 a passport photo 120 imprinted. In a second area of ​​the identity card there is a security element on the upper side 200, for example a hologram patch, laminated by gluing. When viewed from a certain angle, this also shows the facial image of the person to whom the identity card is assigned. The hologram patch can for example be formed from two layers, for example from a first first layer facing the carrier 210 and a second layer 220, which forms the actual functional layer, in the present case the hologram. The hologram patch is with a contact side 211that the carrier 110 the identity card is facing is applied to this. The first layer can preferably consist of polycarbonate. There is an adhesive layer to connect the hologram patch to the carrier 300 between the hologram patch and the wearer 110.

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

Example compositions:

To compare an adhesive composition according to the present invention with adhesive compositions that are not according to the invention, mixtures of a prepolymer (corresponding to component A according to the present invention) with several radiation-curing compounds (corresponding to component B according to the present invention) and several photoinitiators (corresponding to components C according to the present invention). In addition, other components are included, namely an adhesion promoter and UV light stabilizers.

A bifunctional aliphatic urethane acrylate based on polycarbonate and isophorone diisocyanate (SUO 1200, Polygon Chemie AG) is used as the prepolymer for the example according to the invention.

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

Mono- and polyfunctional acrylate monomers are used as radiation-curing compounds (component B).

CGI 277 from BASF is used as the photoinitiator (component C).

The compositions are given in Table 1. The adhesives with these compositions were made by mixing the components with the photoinitiator added under yellow light conditions. The amounts of the constituents are given in% by weight.

As can be seen 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 based on polycarbonate, but based on polyethers or a prepolymer based on a polyester (meth) acrylate. The compositions of Comparative Examples 4 and 5, like the composition of the example according to the invention, contain a urethane acrylate based on a polycarbonate as component A.

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

Properties of the adhesive compositions:

To assess the properties of the adhesive compositions described above, the absorption 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 not yet cured adhesive composition and the reactivity of the adhesive composition in the Investigated light curing.

To determine the media uptake, DIN round disks (diameter 50 mm, height 5 mm) were produced from the adhesive compositions. For this purpose, the compositions were in each case on both sides for 60 s at an intensity of 60 mW / cm2 hardened, then dried in a desiccator for 72 hours, weighed and then stored in the media for 24 hours at 21 ° C. The media were DELOTHEN® EP (acetone / isopropanol mixture, hydrohilic solvent) and DELOTHEN® NK1 (hydrocarbon mixture, hydrophobic solvent) used by DELO Industrial Adhesives. After storage in this media, the surface of the respective round disc was dried with filter paper. After drying, the circular disk was weighed within one minute. The measurement resulted in a mass difference between the test body mass after storage and the test body mass before storage. The respective media uptake obtained for the adhesive compositions according to the inventive example and the comparative examples as the quotient of this mass difference and the initial mass is given in Table 2.

To determine the adhesive strength, the respective adhesive composition was applied to a substrate (polycarbonate) and cured as described above. The adhesive strength was determined using the cross-cut test DIN EN ISO 2409 carried out. The results of these measurements are also given in Table 2 for the adhesive compositions according to the inventive example 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, two test specimens made of polycarbonate (PC) measuring 20 × 20 × 5 mm were used3 with an overlap of 5 × 20 mm2 glued together. The test specimens were tested in a tensile testing machine DIN EN ISO 7500 examined. The results of these measurements are also given in Table 2 for the adhesive compositions according to the inventive example and the comparative examples.

To determine the viscosity of the not yet cured 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 according to the invention and the comparative examples.

Finally, the reactivity of the adhesive compositions during light curing was also determined. For this purpose, a Bohlin CS rheometer CVO PP 9 with a photorheology device and a DELOLUX LED lamp was used® 80/400 used by DELO Industrial Adhesives, DE. The LED lamp was at an intensity of 200 mW / cm2 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 at 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 according to the invention and the comparative examples, the light curing being shown as the duration in [s].

Results:

The adhesive composition according to the invention has a significantly lower media absorption both in a relatively polar solvent (DELOTHEN® EP) as well as in a non-polar solvent (DELOTHEN® NK1). This indicates that partial dissolution by these solvents is less 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 just as high as in the case of the composition according to the invention, but also to cases in which this proportion is significantly higher (Comparative Examples 4, 5).

In the case of the adhesive composition according to the invention, the adhesive strength of an adhesive bond not impaired by solvents, which was determined using the cross-cut test, is very good and comparable to the compositions of the comparative examples.

The compressive shear strength of a test specimen obtained with the adhesive composition according to the invention is also even 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 comparison samples, it is within the usual range.

Finally, the light curing is significantly 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 connections.

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.

Embodiment:

The adhesive composition according to the present invention, which is given in Table 1, is produced and applied over the entire area to a substrate, preferably made of polycarbonate, for example by means of a flexographic printing process. After the adhesive composition has been applied, a hologram / identigram film (photopolymer) is laminated onto the substrate wetted with the adhesive composition using a laminating roller. The adhesive composition is then cured / polymerized through the hologram / identigram film by means of UV radiation. A very strong connection is obtained between the hologram / identigram film and the substrate, which is not impaired even after prolonged exposure to hydrocarbon solvents or polar solvents such as acetone and / or ethanol.

List of reference symbols

100
Value or security document, identity card
101
Top, surface
110
carrier
111
Polymer layer
112
Polymer layer
120
Passport photo
200
Security element, hologram patch
210
first position
211
(Contact) page
220
second layer
300
Adhesive (layer)

QUOTES INCLUDED IN THE DESCRIPTION

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

Patent literature cited

  • DE 102008019871 B3 [0004]
  • DE 102010033049 A1 [0005]

Non-patent literature cited

  • ISO 10373 [0074]
  • ISO / IEC 7810 [0074]
  • ISO 14443 [0074]
  • DIN EN ISO 2409 [0097]
  • DIN EN ISO 7500 [0098]