WO2010057472A1

WO2010057472A1 - Preparation for producing a cover layer for an electroluminescent security element of a security document and/or value document

Info

Publication number: WO2010057472A1
Application number: PCT/DE2009/001631
Authority: WO
Inventors: Oliver Muth
Original assignee: Bundesdruckerei Gmbh
Priority date: 2008-11-19
Filing date: 2009-11-19
Publication date: 2010-05-27
Also published as: CN105440783B; EP2346954A1; EP2346954B1; DE102008058260A1; CN105440783A; CN102216402A

Abstract

The invention relates to a preparation comprising A) 0.1 to 40 % by weight of a binder having a polycarbonate derivative on the basis of a geminally disubstituted dihydroxy diphenyl cycloalkane, B) 60 to 99.9 % by weight of an organic solvent or solvent mixture, C) 0 to 10 % by weight, relative to the dry mass, of a colorant or colorant mixture, D) 0 to 10 % by weight of a functional material or a mixture of functional materials, E) 0 to 30 % by weight of additives and/or adjuvants, or a mixture of such materials, and F) 0.1 to 20 % by weight of a UV blocker, wherein the sum of the components A) through F) is always 100% by weight.

Description

Preparation for producing a cover layer for an electroluminescent security element of a

Security and / or value document

Field of the invention

The invention relates to a preparation for producing a cover layer of a security and / or value document comprising: A) 0.1 to 40 wt .-% of an organic polymer, B) 60 to 99.9 wt .-% of a solvent, C) 0 up to 10% by weight, based on dry matter, of a colorant or colorant mixture, D) 0 to 10% by weight of a functional material or a mixture of functional materials, E) 0 to 30% by weight

Additives and / or auxiliaries, or a mixture of such substances, wherein the sum of the components A) to E) always gives 100 wt .-%.

The invention further relates to uses of such a preparation, a security and / or valuable document having a cover layer, produced with such a preparation and a method for producing a security and / or value document using such a preparation.

Background of the invention and prior art

Security and / or value documents may have security elements which contain electroluminescent substances. However, such substances usually also show photoluminescence. Therefore, unauthorized persons can determine the presence and location of such a security element in a rather simple manner, for example by exposure of the security and / or value document of a light source, in particular a UV source.

Although the above problem seems to be solved in that areas with electroluminescent

Substances are covered with a visible in the most transparent, but UV blocking topcoat. However, experiments with professional screen printing varnishes, which were mixed with UV blockers, even with a loading of 15 wt .-% of the UV blocker and / or the admixture of titanium dioxide not sufficient shading of the security element in the UV range. Consequently, the areas with the electroluminescent substances were readily recognizable. In addition, the topcoat was easy to scrape off and showed an undesirable yellowish tinge.

From the document EP 0 688 839 Bl screen printing inks of the aforementioned composition are known. This reference also discloses methods of making such polycarbonates. This reference is hereby incorporated in full in the disclosure of the present application. The use of UV blockers, however, is not described in this reference. The same applies to the publications DE 44 24 106 Al and DD 297 605 A5. Technical problem of the invention

The invention is therefore based on the technical problem of providing a (covering) covering layer for a substrate containing an electroluminescent substance, which shields this substance in the UV range to such an extent that photoluminescence of the substance is not readily apparent, and also high Has adhesion and freedom from color casts.

Basic principles of the invention and preferred embodiments

To solve this technical problem, the invention teaches a preparation comprising: A) from 0.1 to 40% by weight of a binder with a polycarbonate derivative based on a geminally disubstituted dihydroxydiphenylcycloalkane, B) from 60 to 99.9% by weight of a preferably organic one

C) 0 to 10% by weight, based on dry matter, of a colorant or colorant mixture, D) 0 to 10% by weight of a functional material or a mixture of functional materials, E) 0 to 30% by weight Additives and / or auxiliaries, or a mixture of such substances, and F) 0.1 to 20 wt .-% of a UV blocker, wherein the sum of components A) to F) always gives 100 wt .-%.

The invention is based on the surprising finding that the combination of conventional UV blockers specifically with Coating agents or paints containing polycarbonate derivatives used according to the invention on the one hand to a very good shading of security elements in the UV range and on the other hand to a very good adhesion and optically flawless

Appearance, especially freedom from color casts, the top layer leads.

UV blockers are all substances which, when used as an additive to a coating agent, increase the extinction of at least 0.1, better at least 0.3, preferably at least 1.0, in the wavelength range 330 to 370 nm with a layer thickness of the dried Coating agent of 5 microns causes compared to the absorbance measured under the same conditions, but in the absence of the UV blocker.

In principle, any substances known for this purpose, for example from the cosmetic field, can be used as UV blockers. Preferably, lipophilic UV blockers are used. In particular, the UV blocker may be selected from the group consisting of butylmethoxydibenzoylmethanes, octyl methoxycamates, octyl salicylates, homosalates, menthylantranilates, octocrylenes, benzophenones-3, octyl-dimethyl-PABA, A-methylbenzilidenes, and mixtures of two or more of such substances. These substance names are INCI names. But also UV blockers, as described for example in the reference DE 101 59 373 Al, can be used. In detail, the polycarbonate derivative may contain functional carbonate structural units of the formula (I),

wherein ^R: and R ² are independently hydrogen, halogen, preferably chlorine or bromine, Ci-C ₈ alkyl, C ₅ -C _O - cycloalkyl, C ₆ -C ₀ aryl, preferably phenyl, and C ₇ -C ₂ - Aralkyl, preferably phenyl-Ci-Cj-alkyl, in particular benzyl; m is an integer from 4 to 7, preferably 4 or 5; R ³ and R ^{4 are} individually, independently for each X, independently hydrogen or C ₁ -C ₆ -alkyl; X is carbon and n is an integer large 20, with the proviso that on at least one atom X, R ³ and R ^{4 are} simultaneously alkyl.

It is preferred for X, R ³ and R ^{4 to be} simultaneously alkyl at 1 to 2 atoms, in particular only at one atom. R ³ and R ⁴ may be in particular methyl. The X atoms alpha to the diphenyl-substituted C atom (Cl) may not be dialkyl-substituted. The X atoms in beta position to Cl can be disubstituted with alkyl. Preferably m = 4 or 5. The polycarbonate derivative can For example, based on Monmeren such as 4, 4 '- (3,3, 5- trimethyl-1, 1-diyl) diphenol, 4, ^4' - (3, 3-dimethylcyclohexane-1, 1-diyl) diphenol, or 4,4 '- (2,4,4-trimethylcyclopentane-1, 1-diyl) diphenol.

According to the reference DE 38 32 396.6, a polycarbonate derivative used according to the invention can be prepared from diphenols of the formula (Ia), the disclosure content of which is hereby included in full in the disclosure of this description.

It is possible to use both a diphenol of the formula (Ia) to form homopolycarbonates and a plurality of diphenols of the formula (Ia) to form copolycarbonates (meaning of radicals, groups and parameters, as in formula I).

Ia;

In addition, the diphenols of the formula (Ia) can also be used in the

Mixture with other diphenols, for example with those of the formula (Ib)

HO - Z - OH Ib), be used for the preparation of high molecular weight, thermoplastic, aromatic polycarbonate derivatives.

Suitable other diphenols of the formula (Ib) are those in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted, and aliphatic radicals or cycloaliphatic radicals other than those of the formula (II) Ia) or heteroatoms may contain as bridge members.

Examples of the diphenols of the formula (Ib) are: hydroquinone, resorcm, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ether, (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, alpha, alpha 'bis (hydroxyphenyl) -dusopropylbenzenes and their ring-alkylated and ring-halogenated compounds.

These and other suitable diphenols are e.g. m the

US Pat. Nos. 3,028,365, 2,999,835, 3,148,172, 3,275,601, 2,991,273, 3,271,367, 3,062,781, 2,970,131 and 2,999,846, in the publications DE-A 1 570 703, 2 063 050, 2 063 052, 2 211 956, Fr-A 1 561 518 and in the monograph "H. Schnell, Chemistry and Physics of

Polycarbonates, Interscience Publishers, New York 1964 ", which are hereby incorporated in full in the disclosure of the present application. Preferred other diphenols are, for example: 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- ( 4-hydroxyphenyl) -cyclohexane, alpha, alpha -bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (3-methyl) chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3, 5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1, 1-bis (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, alpha, alpha -bis (3, 5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and 2,2-bis - (3, 5-dibromo-4-hydroxyphenyl) -propane.

Particularly preferred diphenols of the formula (Ib) are, for example: 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3, 5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis - (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane and 1,1-bis- (4-hydroxyphenyl) -cyclohexane. In particular, 2, 2-bis (4-hydroxyphenyl) propane is preferred. The other diphenols can be used both individually and in a mixture.

The molar ratio of diphenols of the formula (Ia) to the optionally used other diphenols of the formula (Ib) should be between 100 mol% (Ia) to 0 mol% (Ib) and 2 mol% (Ia) to 98 mol -% (Ib), preferably between 100 mol% (Ia) to 0 mol% (Ib) and 10 mol% (Ia) to 90 mol% (Ib) and especially between 100 mol% (Ia) to 0 mol% (Ib) and 30 mol% (Ia) to 70 mol% (Ib). The high molecular weight polycarbonate derivatives from the diphenols of the formula (Ia), if appropriate in combination with other diphenols, can be prepared by the known polycarbonate production processes. The various diphenols can be linked together both statistically and in blocks.

The polycarbonate derivatives used according to the invention can be branched in a manner known per se. If the branching is desired, by condensing small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used), of trifunctional or more than trifunctional in a known manner

Compounds, especially those having three or more than three phenolic hydroxyl groups, can be achieved. Some branching agents having three or more than three phenolic hydroxyl groups are: phloroglucinol, 4,6-dimethyl-2,4,4-tris (4-hydroxyphenyl) -heρten-2,4,6-dimethyl-2,4,6 tri- (A-hydroxyphenyl) -heptane, 1,3,5-Tn- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) - phenylmethane, 2,2-bis- [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, 2,6-iso- (2 -hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, hexa- [4- (4-hydroxyphenyl-isopropyl) -phenyl] - orthoterephthalic acid ester, tetra (4-hydroxyphenyl) methane, tetra- [4- (4-hydroxyphenyl-isopropyl) -phenoxy] -methane and 1,4-bis- [4 ', 4 "-dihydroxytriphenyl) -methyl] -benzene , Some of the other trifunctional compounds are 2,4- Dihydroxybenzoic acid, trimesic acid, cyanurchloπd and

3,3-Bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

As chain terminators known per se regulation of the molecular weight of the polycarbonate derivatives are monofunctional compounds in conventional concentrates. Suitable compounds are e.g. Phenol, tert-butylphenols or other alkyl-substituted phenols. For controlling the molecular weight, in particular small amounts of phenols of the formula (Ic) are suitable

(Ic) where R is a branched Ce- and / or C ₉ -alkyl radical.

Preferably, in the alkyl radical R, the proportion of CH ₃ protons between 47 and 89% and the proportion of CH and CH ₂ - protons between 53 and 11%; also preferably R is in the o- and / or p-position to the OH group, and more preferably the upper limit of the ortho-portion is 20%. The chain terminators are generally used in amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on diphenols used.

The polycarbonate derivatives may preferably be prepared according to the phase boundary behavior (compare H. Schnell "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. Page 33ff., Interscience Publ. 1964) m be prepared in a conventional manner.

In this case, the diphenols of the formula (Ia) are dissolved in an aqueous alkaline phase. For production of

Copolycarbonates with other diphenols are mixtures of diphenols of the formula (Ia) and the other diphenols, for example those of the formula (Ib) used. To regulate the molecular weight, chain terminators of, for example, the formula (Ic) can be added. Then, in the presence of an inert, preferably polycarbonate losenden, organic phase reacted with phosgene by the method of interfacial condensation. The reaction temperature is between 0 ⁰ C and 40 ⁰ C.

The optionally used branching agents (preferably from 0.05 to 2.0 mol%) can be initially charged with the diphenols m in the aqueous alkaline phase or added to the organic solvent dissolved before the phosgenation. In addition to the diphenols of the formula (Ia) and, if appropriate, other diphenols (Ib), it is also possible to use their mono- and / or bis-chlorocarbonic esters, these being added dissolved in organic solvents. The amount of chain terminators and of branching agents then depends on the molar amount of diphenolate radicals corresponding to formula (Ia) and optionally formula (Ib); When using chlorocarbonic acid esters, the amount of phosgene can be reduced accordingly in a known manner. Suitable organic solvents for the chain terminators and optionally for the branching agents and the chlorocarbonic acid esters are, for example, methylene chloride, chlorobenzene and in particular mixtures of methylene chloride and chlorobenzene. Optionally, the chain terminators and branching agents used can be dissolved in the same solvent.

The organic phase used for the phase boundary polycondensation is, for example, methylene chloride,

Chlorobenzene and mixtures of methylene chloride and chlorobenzene.

As wassπge alkaline phase is used, for example, NaOH solution. The production of the polycarbonate derivatives by the phase boundary process can be catalyzed in the usual way by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts of 0.05 to 10 mol%, based on moles of used

Diphenols, are used. The catalysts can be added before the beginning of the phosgenation or during or after the phosgenation.

The polycarbonate derivatives can be prepared by the known method in the homogeneous phase, the so-called "Pyridmverfahren" as well as by the known melt transesterification process using, for example, diphenyl carbonate instead of phosgene. The polycarbonate derivatives may be linear or branched, they are homopolycarbonates or copolycarbonates based on the diphenols of the formula (Ia).

By arbitrary composition with other diphenols, in particular with those of the formula (Ib), the polycarbonate properties can be varied in a favorable manner. In such copolycarbonates, the diphenols of the formula (Ia) are present in amounts of from 100 mol% to 2 mol%, preferably in amounts of from 100 mol% to 10 mol% and in particular in amounts of from 100 mol% to 30 mol% %, based on the total amount of 100 mol% of Diphenolemheiten contained in polycarbonate derivatives.

A particularly advantageous embodiment of the invention is characterized in that the polycarbonate derivative contains a copolymer, in particular consisting of monomer units M1 based on the formula (Ib), preferably bisphenol A, and monomer units M2 based on the geminally disubstituted dihydroxydiphenylcycloalkane, preferably of the 4, 4 ^' - (3, 3, 5-trimethylcyclohexane-l, 1-diyl) diphenol, wherein the molar ratio M2 / M1 is preferably greater than 0.3, in particular greater than 0.4, for example greater than 0.5. Because in such copolymers was surprisingly found that the glass transition temperature can be increased after a first heating cycle of T _g below 150 ⁰ C in a second heating cycle, which can significantly increase the stability of the resulting composite. It is preferred that the polycarbonate derivative has a weight average molecular weight of at least 10,000, preferably from 20,000 to 300,000.

The component B may in principle be substantially organic or aqueous. Substantially aqueous means that up to 20% by weight of component B) can be organic solvents. Substantially organic means that up to 5% by weight of water may be present in component B). Preferably, component B contains or consists of a liquid aliphatic, cycloaliphatic, and / or aromatic hydrocarbon, a liquid organic ester, and / or a mixture of such substances.

Component B) contains or consists, for example, of organic hydroxyfatty acids and / or esters of fatty acids or hydroxyfatty acids with monoalcohols and / or glycols. Examples of fatty acids are saturated unbranched fatty acids having 1 to 30, in particular 3 to 20, carbonated, branched fatty acids, such as isobutyric or isovaleric acid, monounsaturated unbranched fatty acids, such as acrylic, croton, palmitoleic or oleic acid, and diunsaturated unbranched fatty acids, such as sorbic or linoleic acid, optionally with one or more -OH functions in the molecule, in question. Suitable alcohols are, for example, monoalcohols having 1 to 20 C atoms, linear or branched, glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, and 1,3-butylene glycol. The molecular weight of the esters used is preferably below 400, especially below 300 there.

The organic solvents used are preferably halogen-free organic solvents. In particular, come into question in particular aliphatic, cycloaliphatic, aromatic hydrocarbons, such as mesitylene, 1,2,4-tnmethylbenzene, cumene and solvent naphtha, toluene, xylene; (organic) esters, such as methyl acetate, ethyl acetate, butyl acetate,

Methoxypropyl acetate, ethyl 3-ethoxypropionate. Preferred are mesitylene, 1, 2, 4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene, methyl acetate, ethyl acetate, methoxypropyl acetate. Ethyl 3-ethoxypropionate, butyl glycol acetate. Very particular preference is given to mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, cumene (2-phenylpropane), solvent naphtha and ethyl 3-ethoxypropionate.

A suitable solvent mixture comprises, for example, Ll) 0 to 10 wt .-%, preferably 1 to 5 wt .-%, in particular 2 to 3 wt .-%, mesitylene, L2) 10 to 50 wt .-%, preferably 25 to 50 wt .-%, in particular 30 to 40 Gew. -%, l-Methoxy-2-propanolacetat, L3) 0 to 20 Gew. -%, preferably 1 to 20 wt .-%, in particular 7 to 15 wt .-%, 1, 2, 4-trimethylbenzene, L4) 10 to 50 wt .-%, preferably 25 to 50 wt .-%, in particular 30 to 40% by weight, ethyl 3-ethoxypropionate, L5) 0 to 10% by weight, preferably 0.01 to 2% by weight, in particular 0.05 to 0.5% by weight, cumene, and Lβ) 0 to 80 wt .-%, preferably 1 to 40 wt .-%, in particular 15 to 25 wt .-%, solvent naphtha, wherein the sum of the components Ll to L6 always gives 100 wt .-%. Instead of L2 and / or L4 or additionally, the solvent mixture may also contain L7) with 10 to 50 wt .-%, preferably 25 to 50 wt .-%, in particular 30 to 60 wt .-%, butyl glycol acetate, wherein the sum the components used Ll to L7 always yields 100 wt .-%.

The polycarbonate derivative typically has a weight average molecular weight of at least 10,000, preferably from 20,000 to 300,000.

The preparation may contain in detail: A) 10 to 40 wt .-%, in particular 15 to 30 wt .-%, of a binder with a polycarbonate derivative based on a gem-disubstituted dihydroxydiphenylcycloalkane, B) 60 to 90 wt .-%, in particular 70 to 85% by weight of an organic solvent or solvent mixture, C) 0 or 0.1 to 6% by weight, in particular 0.5 to 4% by weight, of a colorant or colorant mixture, D) 0 or 0.001 to 6 Wt .-%, in particular 0.1 to 4 wt .-%, of a functional material or a mixture of functional materials, E) 0 or 0.1 to 30 wt .-%, in particular 1 to 20 wt .-%, additives and / or auxiliaries, or a mixture of such substances, and F) 1 to 20 wt .-%, in particular 5 to 15 wt .-% of a UV blocker.

As component C, if a colorant is to be provided at all, in principle any colorant or colorant mixture comes into question. Colorants are all colorants. This means it can be both dyes (a Overview of Dyes is provided by ullmann's Encyclopedia of Industrial Chemistry, Electronic Release 2007, Wiley Publishing, Chapter "Dyes, General Survey", as well as pigments (for a review of organic and inorganic pigments, see Ulimann's Encyclopedia of Industrial Chemistry,

Dye should be soluble or (stably) dispersible or suspendable in the solvents of component B. The colorants may be used either directly as a dye or as a dye ,

Pigment are added or as a paste, a mixture of dye and pigment together with another binder. This additional binder may differ from the binder used in the invention (e.g., be a polyester), but should be chemically compatible with the others

Components of the inventive preparation be. If such a paste is used as a colorant, the amount of component B refers to the colorant without the other components of the paste. These other components of the paste are then subsumed under the component E.

Component D comprises substances that can be seen directly by the human eye or by the use of suitable detectors using technical aids. Here are meant the materials well known to those skilled in the art (see also van Renesse, Optical document secυπty, 3rd ed., Artech House, 2005) which are used to secure value and security documents. In addition, luminescent substances pay

(Dyes or pigments, organic or inorganic) such as For example, photoluminophores, Elektrolummophore, Antistokes luminophores, fluorophores but also magnetizable, photoacoustically addressable or piezoelectric materials. Furthermore, Raman-active or Raman-enhancing materials can be used, as well as so-called Barcode Mateπalien. Again, the preferred criteria in particular the solubility in the component B. Functional materials can be added directly or via a paste, ie mixture with another binder, which is then part of the

Component E, or the binder of the component A used according to the invention.

Component E comprises in the case of paints, inks or coating compositions conventionally prepared substances such as antifoams, leveling agents, wetting agents, surfactants, flow agents, dryers, catalysts, (light) stabilizers, preservatives, biocides, surfactants, organic polymers for the production of viscosity, buffer systems, etc. As adjusting agents are professional dosing salts in question. An example of this is sodium lactate. As biocides, all commercially available preservatives which are used for inks come into question. Examples are Proxel®GXL and Parmetol® A26. Suitable surfactants are all commercially available surfactants which are used for inks. Preferred are amphoteric or nonionic surfactants.

Of course, it is also possible to use special anionic or cationic surfactants which do not alter the properties of the dye.

Examples of suitable surfactants are betame, ethoxylated DaoIe etc. Examples are the product series Surfynol® and Tergitol®. A buffer system can be set up which stabilizes the pH in the range from 2.5 to 8.5, in particular in the range from 5 to 8. Suitable buffer systems are lithium acetate, borate buffer, triethanolamine or acetic acid / sodium acetate. Em buffer system is particularly in the case of a substantially aqueous component B come into question. To adjust the viscosity (possibly water-soluble) polymers can be provided. Here all suitable for conventional ink formulations polymers come into question. Examples are water-soluble starch, in particular with an average molecular weight of 3,000 to 7,000, polyvinylpyrolidone, in particular with an average molecular weight of 25,000 to 250,000, polyvinyl alcohol, in particular with an average molecular weight of 10,000 to 20,000, xanthan gum, carboxymethyl cellulose, ethylene oxide / propylene oxide Block copolymer, especially having an average molecular weight of 1,000 to 8,000. An example of the latter block copolymer is the

Pluronic® product line. The proportion of biocide, based on the total amount, may be in the range of 0 to 0.5% by weight, preferably 0.1 to 0.3% by weight. The proportion of surfactant, based on the total amount, may be in the range of 0 to 0.2% by weight. The proportion of adjusting agents, based on the total amount, 0 to 1 wt .-%, preferably 0.1 to 0.5 wt .-%, amount.

To the aids and other components are paid, such as acetic acid, formic acid or n-methylpyrolidone or other polymers from the dye solution or paste used.

With regard to substances which are suitable as component E, supplementary reference is made, for example, to Ullmann 's

Encyclopedia of Chemical Industry, Electronic Release 2007, Wiley Publishing, Chapter "Paints and Coatings", section "Paint Additives".

The invention furthermore relates to the use of a preparation according to the invention as a coating agent, in particular as a printing ink, for example as a screen printing ink or ink jet printing ink, and to the use for producing a cover layer on a substrate comprising an electroluminescent substance, the preparation being applied to the substrate and dried. In principle, all professional printing techniques, but also other application techniques, such as brushing, doctoring, spraying, etc., can be used for the job.

The term of the cover layer designates in the context of the invention a layer which over a

Security element is arranged with an electroluminescent and this covers. It may be a top layer arranged in the finished product, but it is also possible to provide further layers on the cover layer.

Furthermore, the invention relates to a security and / or value document with a substrate, wherein the substrate at least one area containing an electroluminescent substance, and wherein at least the area covered with the electroluminescent substance is covered with a cover layer, which can be produced by means of a erfmdungsgemaßen preparation. The thickness of the (dried) cover layer is in the range 0.01 to 10 .mu.m, in particular 0.05 to 5 microns.

Finally, the invention relates to a method for producing such a safety and / or

Value document, wherein the cover layer by application of the

Preparation, for example by means of a printing process, in particular a screen printing process, is produced.

The order of the preparation can be repeated several times, for example 2 - 5-fold, take place between each order the

Preparation can be dried. But also the job wet in wet is possible.

Examples of security and / or value documents are: identity cards, passports, ID cards,

Access control cards, visas, tax stamps, tickets, driver's licenses, motor vehicle papers, banknotes, checks, postage stamps, credit cards, any chip cards and self-adhesive labels (eg for product security). Such security and / or valuable documents typically have at least one substrate and a cover layer which is mostly in partial areas or completely transparent. Substrate and cover layer may in turn consist of a plurality of layers. A substrate is a support structure on or in which a print layer is usually applied with information, images, patterns and the like. The substrate also contains security elements, inter alia within the scope of the invention, at least one security element with an electroluminophore. Examples of suitable Elektrolummophore are Zinsulfldische Elektrolummophore, as described in the reference WO 2001/034723 and the references cited therein. In addition, reference is made to the reference by Renesse, Optical document security, 3rd ed., Artech House, 2005, for other electro-phonophores. These electroluminescent pores can be arranged in the substrate or directly on its surface, for example in the context of a printing layer.

Suitable materials for a substrate are all suitable materials based on paper and / or (organic) polymers in question. Preparations according to the invention are also independent of the present invention, in particular also for

Coating of paper-based substrates suitable, regardless of the presence or absence of Elektrolummophore in the substrate and / or UV blockers in the preparation.

In the following the invention will be explained in more detail by means of examples.

Example 1 Preparation of Polycarbonate Derivatives Useful According to the Invention Example 1.1: Preparation of a first

Polycarbonatdeπvats

205.7 g (0.90 mol) of bisphenol A (2,2-bis (4-hydroxyphenyl) propane, 30.7 g (0.10 mol) of 1,1-bis (4-hydroxyphenyl) -3 , 3, 5-trimethylcyclohexane, 336.6 g (6 mol) of KOH and 2700 g of water are dissolved in an inert gas atmosphere while stirring, then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added 198 g (2 mol) of phosgene were introduced into the stirred solution at pH 13 to 14 and 21 to 25 ° C. Thereafter, 1 ml of ethyl piperidine was added and the mixture was stirred for another 45 minutes washed neutral with water and freed from the solvent.

The polycarbonate derivative showed a relative solution viscosity of 1.255. The glass transition temperature was determined to be 157 ° C. (DSC).

Example 1.2: Preparation of a second

polycarbonate derivative

Analogously to Example 1, a mixture of 181.4 g (0.79 mol) of bisphenol A and 63.7 g (0.21 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane converted to the polycarbonate derivative. The polycarbonate derivative showed a relative solution viscosity of 1.263. The glass transition temperature was determined to be 167 ° C. (DSC).

Example 1.3: Making a third

polycarbonate derivative

Analogously to Example 1, a mixture of 149.0 g (0.65 mol) of bisphenol A (2, 2-bis (4-hydroxyphenyl) propane and 107.9 g (0.35 mol) of 1, 1-bis - (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane reacted to polycarbonate derivative.

The polycarbonate derivative showed a relative solution viscosity of 1.263. The glass transition temperature was determined to be 183 ^° C. (DSC).

Example 1.4: Preparation of a fourth Polycarbonatdeπvats

Analogously to Example 1, a mixture of 91.6 g (0.40 mol) of bisphenol A and 185.9 g (0.60 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane converted to the polycarbonate derivative.

The polycarbonate derivative showed a relative solution viscosity of 1.251. The glass transition temperature was determined to be 204 ^° C. (DSC). Example 1.5: Preparation of a fifth polycarbonate derivative

As in Example 1, a mixture of 44.2 g (0.19 mol) of bisphenol A and 250.4 g (0.81 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-methylcyclohexane converted to polycarbonate.

The polycarbonate derivative showed a relative solution viscosity of 1.248. The glass transition temperature was determined to be 216 ° C. (DSC).

Example 2: Preparation of a liquid preparation for the production of a topcoat

A liquid preparation was prepared from 25 parts by weight of the polycarbonate derivative from Example 1.3 and 75 parts by weight of a sol. Mixture prepared according to Table I.

Table I

A colorless solution was obtained. To 9 g of the solution was added 1 g of butyl methoxydibenzoylmethane and dissolved overnight at room temperature and with stirring.

Example 3: Preparation of an Inventive

Security and / or value document

First, a substrate, typically a multilayer, is prepared in the usual way, which contains a security element with a zinc sulfide electroluminophore. On the area with the security element, a layer of a preparation of Example 2 is applied, for example by means of double screen printing (79er sieve). Thereafter, the applied layer was dried to form the finished cover layer.

The resulting security and / or value document was then exposed to a UV light source, the

Security element was not visible. By contrast, the electroluminescence of the security element was completely preserved. The cover layer, which was arranged at the top in the exemplary embodiment, had no yellow cast and was also extremely resistant to abrasion.

Claims

claims:

1. Preparation for the preparation of a topcoat of a

Security and / or value document containing

A) 0.1 to 40% by weight of a binder with a polycarbonate derivative based on a gem-disubstituted dihydroxydiphenylcycloalkane,

B) 60 to 99.9% by weight of a solvent or solvent mixture,

C) 0 to 10 wt .-%, based on dry matter, of a colorant or colorant mixture,

D) 0 to 10% by weight of a functional material or a mixture of functional materials,

E) 0 to 30 wt .-% of additives and / or auxiliaries, or a mixture of such substances, and

F) 0.1 to 20 wt .-% of a UV blocker

the sum of components A) to F) always being 100% by weight.

2. Preparation according to claim 1, wherein the

Polycarbonate derivative has a weight average molecular weight of at least 10,000, preferably from 20,000 to 300,000.

3. A preparation according to any one of claims 1 or 2, wherein the polycarbonate derivative contains functional carbonate structural units of formula (I),

wherein

R ¹ and R are independently hydrogen, halogen, preferably chlorine or bromine, Ci-C ₈ alkyl, C ₅ -C ₆ - cycloalkyl, C ₆ -Cio-aryl, preferably phenyl, and C ₇ -C ₂ - aralkyl, preferably Phenyl-C] -C ₄ -alkyl, in particular benzyl,

m is an integer from 4 to 7, preferably 4 or 5,

R ³ and R ^{4 are} individually selectable for each X, independently of one another hydrogen or C 1 -C 6 -alkyl

X carbon and mean an integer of big 20,

with the proviso that on at least one atom X, R ^J and R ^{4 are} simultaneously alkyl.

4. A preparation according to claim 3, wherein at 1 to 2 atoms

X, in particular only on one atom X, R ³ and R ^{4 are} simultaneously alkyl.

5. A preparation according to claim 3 or 4, wherein R ³ and R ^{4 are} methyl.

6. A preparation according to any one of claims 3 to 5, wherein the X atoms in the alpha position to the diphenyl-substituted C atom (Cl) are not dialkylsubstituiert.

7. A preparation according to any one of claims 3 to 6, wherein the X atoms are disubstituted in the beta position to Cl with alkyl.

8. Preparation according to one of claims 3 to 7, wherein m

= 4 or 5.

9. Preparation according to one of claims 3 to 8, wherein the Polycarbonatdeπvat based

4, 4 ^' - (3, 3, 5-methylcyclohexane-1,1-diyl) -diphenol, 4,4 ^' - (3,3-dimethylcyclohexane-1,1-diyl) -diphenol, or 4,4 - (2, 4, 4-trimethylcyclopentane-l, 1-diyl) diphenol

is.

10. Preparation according to one of claims 1 to 9, wherein the polycarbonate derivative comprises a copolymer, in particular consisting of, monomer units M1 based on the formula (Ib), for example based on bisphenol A, and monomer units M2 based on the geminally disubstituted Dihydroxydiphenylcyclo- alkane, Preferably, the 4,4 - (3, 3, 5-tnmethylcyclo-hexane-1, 1-diyl) diphenol, wherein the molar ratio M2 / M1 is preferably greater than 0.3, in particular greater than 0.40, preferably greater than Is 0.50.

11. A preparation according to any one of claims 1 to 10, wherein component B) is halogen-free.

12. Preparation according to one of claims 1 to 11, wherein component B) consists of a liquid aliphatic, cycloaliphatic, and / or aromatic hydrocarbon, a liquid organic ester, and / or a mixture of such substances.

13. A preparation according to claim 12, wherein the hydrocarbon and / or the organic ester is selected from the group consisting of

"Mesitylene, 1,2,4-t-methylbenzene, cumene, solvent naphtha, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl 3-ethoxypropionate, butyl glycol acetate".

14. A preparation according to claim 13, wherein component B) consists of:

Ll) 0 to 10 wt .-%, preferably 1 to 5 wt .-%, in particular 2 to 3 wt .-%, mesitylene, L2) 10 to 50 wt .-%, preferably 25 to 50 wt .-%, in particular 30 to 40% by weight, 1-methoxy-2-propanol acetate, L3) 0 to 20% by weight, preferably 1 to 20% by weight, in particular 7 to 15% by weight, 1,2,4- Trimethylbenzene, LA) 10 to 50% by weight, preferably 25 to 50% by weight, in particular 30 to 40% by weight, of ethyl 3-ethoxypropionate,

L5) 0 to 10 wt .-%, preferably 0.01 to 2 wt .-%, in particular 0.05 to 0.5 wt .-%, cumene, and L6) 0 to 80 wt .-%, preferably 1 to 40% by weight, in particular 15 to 25% by weight, of solvent naphtha, wherein the sum of the components Ll to L6 always amounts to 100%.

15. A preparation according to any one of claims 1 to 14, wherein the preparation contains:

A) 10 to 40 wt .-%, in particular 15 to 30 wt .-%, of a binder with a polycarbonate derivative based geminal disubstituted

Dihydroxydiphenylcycloalkane,

B) 60 to 90% by weight, in particular 70 to 85% by weight, of an organic solvent or solvent mixture,

C) 0 or 0.1 to 6 wt .-%, in particular 0.5 to 4 wt .-%, of a colorant or colorant mixture,

D) 0 or 0.001 to 6% by weight, in particular 0.1 to 4% by weight, of a functional material or a mixture of functional materials,

E) 0 or 0.1 to 30 wt .-%, in particular 1 to 20

% By weight, additives and / or auxiliaries, or a mixture of such substances, and

F) 1 to 20 wt .-%, in particular 5 to 15 wt .-% of a UV blocker.

16. A preparation according to any one of claims 1 to 15, wherein the UV blocker is selected from the group consisting of Butylmethoxydibenzoylmethane, octyl Methoxycinnamate, octyl salicylates, homosalates,

Menthyl antranilates, octocrylenes, benzophenones-3, octyl-dimethyl-PABA, 4-methylbenzilidenes, and mixtures of two or more of such substances.

17. Use of a preparation according to one of Claims 1 to 16 a of a coating composition, preferably as a printing composition, in particular as a printing ink or a tinting ink.

18. Use of a preparation according to one of claims 1 to 16 for the production of a cover layer on a substrate containing an electroluminescent substance, wherein the preparation is applied to the substrate and dried.

19. A security and / or valuable document with a substrate, wherein the substrate contains at least one area with an electroluminescent substance, and wherein at least the area with the electroluminescent substance is covered with a cover layer, which is prepared by means of a preparation according to one of claims 1 to 16 can be produced.

20- security and / or document of value according to claim 19, wherein the thickness of the cover layer in the range 0.01 to 10 .mu.m, in particular 0.05 to 5 microns, is located.

21. Method for producing a security and / or

Value document according to claim 19 or 20, wherein the cover layer is produced by applying the preparation by means of a coating method, preferably a printing method, in particular a screen printing method.