EP1767988A1 - Security material with reversible and irreversible photochemical components and coating methods - Google Patents

Abstract

The material has a carrier and a photochromic protein and/or a mutein of the photochromic protein. An irreversible photosensitive layer is provided on the carrier, and the photochromic protein and/or mutein is provided in the photosensitive layer and/or in an optional additional layer. A color photographic copying and displaying materials are provided. A retinal protein is provided in a photochromic substance. Independent claims are also included for the following: (1) a method of manufacturing a protective material (2) a method of chemical treating of a protective material.

Description

Technical area

The invention relates to materials comprising a support and at least one photochromic protein and / or a mutein of a photochromic protein in a layer thereon, as well as processes for their preparation including their chemical processing, and the use of such materials.

State of the art

Security applications to ensure the authenticity of documents or items include the use of appropriate security features or authentication markers. The use of photochromic materials for such safety applications has already been recognized. Application examples are z. In US 4,927,180 described. The photochromic identification feature is visualized in the known examples by the use of UV light. For the eyes of the authenticity-verifier is due to the use of UV light, a suitable protection necessary, which also never provides complete security. The use of UV light to identify security features may therefore be considered unfavorable. A similar prior art is in US 5,807,625 explained. Again, UV light is used to visualize the security feature.

Out DE 199 14 702 A1 For example, there is known a method of securing the authenticity of objects using a photochromic preparation in the form of an ink containing bacteriorhodopsin. From example 7 of the cited DE 199 14 702 A1 It is also known to print objects, for example normal paper or photographic paper, with the photochromic preparation and then to laminate them. However, printing requires an additional manufacturing step and increases the cost of manufacturing the security material. Even more seriously, this can lead to a safety gap if the printing with the photochromic composition is carried out as often customary only after imaging with the end customer, because in this case, the photochromic composition must be issued to a much larger customer base, not only at the manufacturer of the security material itself. In addition, the possibility offers the remove photochromic paint from the surface of the material and reinsert it for counterfeiting other documents.

One way to avoid this problem is over DE 199 61 841 is known, and is to embed the photochromic substance in the substrate itself. In addition, in WO 03/052701 , A2 describes a method in which a photochromic material can be introduced into the substrate base material and in which the thereby detectable random inhomogeneities of the substrate are read out and used as a safety data record.

However, the introduction of the photochromic material in the substrate has the consequence that for each variant of the photochromic substance, a separate pad must be made, rather than that a standard Trügermaterial can be used, which makes the production more expensive. In addition, it greatly restricts the nature of the support material, since it must be compatible with the photochromic substance during manufacture and should be sufficiently transparent and undyed to allow the desired effect.

A specific embodiment of the introduction into the substrate is shown in FIG US 5,346,789 in which a preparation comprising polyvinyl alcohol (PVA) and bacteriorhodopsin (BR) is adjusted to a high pH and then a film is produced therefrom. The same goes for it US 5,854,710 a BR-containing gel solidified between two glass plates to produce a BR-containing film.

Finally is off US 5,518,858 discloses a photochromic material consisting of a support and a photochromic composition thereon, the photochromic composition comprising a bakleriorhodopsin suspension, at least one organic N-containing compound and a binder.

Object of the invention

Since counterfeiting attempts are always carried out more complex, a further increase in the security against counterfeiting of known security materials is desired. The invention is therefore based on the object to find a security material that has a very high security against counterfeiting. In addition, the abovementioned disadvantages of known safety materials are to be eliminated.

Brief description of the invention

It has now surprisingly been found that these objectives can be achieved by using as the safety material an irreversibly photosensitive material in which a photochromic protein or a mutein of a photochromic protein within the layer structure is contained as a security feature.

Although the proteins or muteins mentioned are very complex biomolecules with many functional groups, it has surprisingly been found in the context of the present invention that the function of the biomolecules is retained even if the proteins or muteins are already incorporated into the safety material during production to be built in. Contrary to what was to be expected, the self-photoactive substances do not appreciably affect the exposure process, and the photochromic proteins and muteins contained in the layer structure survive even the action of solvents and chemicals necessary for processing which irreversibly affect the isolated photochromic protein or mutein of a photochromic protein can.

Subject of the invention

The invention therefore relates to a security material comprising a carrier and at least one photochromic protein and / or a mutein of a photochromic protein, characterized in that the security material on the carrier has at least one irreversibly photosensitive layer and wherein the at least one photochromic protein and / or mutein at least in the at least one photosensitive layer and / or in an optional additional layer.

The incorporation of the photochromic protein and / or mutein of a photochromic protein, also collectively referred to as a photochromic biomolecule, can be carried out directly in the production of the safety material and by introducing directly into a layer, it is not possible to derive the photochromic biomolecule in usable form. thus preventing an important point of attack for counterfeiters. In addition, the photochromic biomolecule does not have to be delivered to a large clientele. The material according to the invention can thus hardly be produced by a counterfeiter because of the hardly available photochromic biomolecule and can not be copied by conventional methods, since the For example, reproduction produced by photographic or electrophotographic methods shows no photochromic behavior.

For the purposes of the invention, an irreversible photosensitive layer is to be understood as any layer in which an irreversible change occurs by exposure, which is either directly detectable or visually perceptible, or which is initially only latent and detectable only after chemical processing is visually perceptible.

Examples of irreversible photosensitive layers in the sense of the invention in which an irreversible change, which is directly detectable by exposure, are e.g. Layers of dyes which are destructible and bleachable by exposure, especially UV light, or photopolymerizable layers, e.g. find use in photoresist materials or printing plates.

For the present invention, irreversible light-sensitive layers are preferred, in which exposure leads to an irreversible change which initially only exists latently and is detectable or visually perceptible only after chemical processing. Such materials have i.a. the advantage of a higher light sensitivity, which allows a lower exposure intensity and thus the photochromic protein and / or Mutein little to no harm. Materials containing such layers are also called photographic materials.

In a preferred embodiment of the present invention, the security material is a photographic material having at least one photochromic biomolecule in at least one layer. Especially preferred are black-and-white and especially silver halide based photographic materials, e.g. for photographic films and copying materials are known.

In the context of the present invention, it has surprisingly been found that, despite the complex layer structure and the associated high number of layers, particularly good results can be achieved if the security material is a color photographic copy material (eg photographic paper) suitable for high-speed processing suitable and its Total silver halide emulsions consist of at least 95 mol% of silver chloride. Surprisingly, the photochromic biomolecules and in particular bacteriorhodopsins were particularly stable with respect to the substances present in such a layer structure and the high-speed processing accelerated in this case.

Documents with photographic layers allow you to quickly and cheaply display high-quality images together with any other characters, patterns or colors. Thus, e.g. German ID cards as well as German passports are made from a substrate containing photographic layers.

The present invention moreover permits an elegant combination of the reversible photochromic effect with the irreversible, photogenerated effect. The images, characters, patterns or colors that can be produced by exposure influence the photochromic process, which can be visually recognized with test equipment and significantly increases the number of safety variants.

The carrier according to the present invention may be e.g. be such of paper, plastic coated paper, cardboard, plastic, metal, glass or a mixture of such materials (so-called "compounds"), which may be transparent or non-transparent. It is preferably a flexible support which can be rolled up and down, in particular one that can be rolled up to a radius of less than 10 cm without breaking.

The photochromic biomolecule is preferably used in the security materials according to the present invention in such a small amount that it is no longer detectable by the naked eye but only analytically, so that it disturbs the irreversibly produced images as little as possible.

However, it can also be used in higher amounts and is then visually perceptible. The amount required depending on the desired effect can be determined by a person skilled in the art by conventional experiments. If a clear visual perception is desired, about 500 mg or more of the photochromic biomolecule should be used per square foot of security material, yielding about 0.2 optical density measured in reflection.

At these densities, the photochromic biomolecule results in a significant color cast in images, e.g. Passport photos. In this case, it is preferable that the security material is a color photographic material and the color cast is compensated for by a (filtered) photographic exposure adapted thereto so as to produce a neutral gray background. In this way, the observer does not notice the natural color of the protein even in higher concentrations, but only a gray color is perceived.

In a preferred embodiment of the present invention, the photochromic protein is a retinal protein, in particular bacteriorhodopsin. By way of example, the production and modification of bacteriorhodopsin for the purpose of the invention will be described, but the statements apply analogously to other retinal proteins.

From microorganisms of the genus Halobacterium salinarum, the protein bacteriorhodopsin can be obtained in large quantities. The wild-type bacteriorhvdopsin is well known to those skilled in the art in its basic photochemical and physical properties as a photochromic material which, when activated by light, undergoes a cyclic series of intermediates. An overview of the mentioned properties of the bacteriorhodopsin is found, for example, in DE 199 14 702 al, NN Vsevolodov, "Biomolecular Electronics: An Introduction via Photosensitive Protein", Birkhäuser, Boston, 1998 ; in D. Oesterhelt, C. Bräuchle, N. Hampp, "Bacteriorhodopsin: A Biological Material for Information Processing", Quarterly Review of Biophysics, 24 (1991) 425-478 and N. Hampp, "Bacteriorhodopsin as a Photochromic Retinal Protein for Optical Memories", Chemical Reviews, 100 (2000) 1755-1776 ,

It is also known to the person skilled in the art that there are a whole series of variants of bacteriorhodopsin which, although having the same initial charge as the wild type, sometimes differ considerably in the kinetics of their photocycle. A preferred example is the variant BR-D96N. Their properties are described in various publications, eg. In A. Miller, D. Oesterhelt. "Kinetic Optimization of Bacteriorhodopsin by Aspartic Acid 96 as to Internal Proton Donor", Biochim: Biophys. Acta 1020 (1990) 57-64 ,

To model the photochromic properties of bacteriorhodopsins, a highly simplified photocycle is used that contains only two states, called the B and M states.

ist hoch reversibel und ermöglicht eine gegenüber anderen photochromen Substanzen sehr hohe Zahl von über 10⁵ Schaltzyklen, was sowohl für Schaltzyklen mit thermischem Schritt II als auch mit photochemischem Schritt II gilt. Da jeder Schaltzyklus einem Prüfungsvorgang entspricht, ermöglicht das Bakteriorhodopsin entsprechend auch eine viel höhere Anzahl Prüfungsvorgänge als andere photochrome Substanzen. Ein weiterer Vorteil liegt darin, dass zum Farbwechsel Licht sichtbarer Wellenlänge eingesetzt werden kann. weshalb kein UV-Licht und deshalb weder Schutzvorrichtungen noch Speziallampen benötigt werden. Zudem weisen beide Schaltzustände eine detekticrbare Eigenfärbung auf.The purple B-state can advantageously be photochemically bleached with visible light, in particular a wavelength of 500 to 600 nm, for example 568 nm. In this bleaching, the bacteriorhodopsin is converted to the yellow-colored M state. The return of the bacteriorhodopsin to the initial state (B state) can then be achieved photochemically by thermal relaxation and / or by irradiation of light of a second wavelength range. The photochemical variant can be used, for example, in safety terminals to speed up the switching process. Wavelengths in the range of 400 to 450 nm, eg 412 nm, are advantageously used for this second wavelength range. The overall process (switching cycle) according to scheme (I): $$\mathrm{B}-\mathrm{Status}\left(\mathrm{purple}\right)\stackrel{\mathrm{step}\mathrm{}\mathrm{I}}{\to }\mathrm{M}-\mathrm{Status}\left(\mathrm{yellow}\right)\stackrel{\mathrm{step}\mathrm{}\mathrm{I}\mathrm{I}}{\to }\mathrm{B}-\mathrm{Status}\left(\mathrm{purple}\right)$$

is highly reversible and allows a very high number of over 10 ⁵ switching cycles over other photochromic substances, which applies to both thermal step II and photochemical step II switching cycles. As each switching cycle corresponds to a test procedure, the bacteriorhodopsin also allows a correspondingly higher number of test procedures than other photochromic substances. Another advantage is that light of visible wavelength can be used for the color change. why no UV light and therefore neither protections nor special lamps are needed. In addition, both switching states have a detectable intrinsic color.

The visible bleaching of bacteriorhodopsin under irradiation is the easier to detect the higher the lifetime of the M-state. Typically, a bleaching of about 90% of the bacteriorhodopsin material is achieved with light outputs less than 100 mW / cm ² at 532 nm.

In a particularly preferred embodiment of the present invention, bacteriorhodopsin (BR) is in the so-called purple membrane form, in this form it occurs in the microorganisms of the genus Halobacterium salinarum. The preparation and isolation of bacteriorhodopsin in purple membrane form is technically well known, eg from EP 0 406 850 B1 , Although bacteriorhodopsin is known to be particularly thermodynamically stable in this form, its particular stability to the abovementioned aggressive chemical processing conditions found in the context of the present invention was not to be expected.

In a preferred embodiment of the present invention, at least one Baktorhodopsin Funlctionsvariante and / or at least one bacteriorhodopsin derivatization variant and / or at least one bacteriorhodopsin chromophore variant and / or at least one bacteriorhodopsin sequence variant is used. These variants allow, for example, a flexible adaptation to the requirements of the test method and in particular allow a correction of the property changes, which may result from the incorporation into the safety material according to the invention. In addition, the variants are difficult to fake and thus offer increased security. A special feature of the variants is also that, in addition to the easily detectable security feature according to scheme (I), so-called high-security features can also be provided, as described in particular in US Pat DE 199 14 702 A1 , Sp. 3 Z. 54 to Sp. 4 Z. 30 and that the combination of these security features enables an easy-to-use system that nevertheless meets the highest security requirements.

The use of at least two bacteriorhodopsin variants results in advantageous effects for an analysis in that the analysis can be carried out in two dimensions.

By bacteriorhodopsin functional variants are to be understood in particular variants that differ in their absorption spectrum and / or their photocycle of bacteriorhodopsin wild type and which are obtainable by applying genetic engineering methods. A known functional variant is z. Example, the variant D96N, in which the aspartic acid is replaced at position 96 by asparagine. This bacteriorhodopsin functional variant and some others are described in: H. Otto, T. Marti, M. Holz, T. Mogi, M. Lindau, HG Khorana and MP Heyn, Proc. Natl. Acad. Sci. USA. 86 (1989), pp. 9228-9232 and TE Thorgeirsson, SJ Milder, LJW Miercke, MC Betlach, RF Shand, RM Stroud and DS Kliger, Biochemistry 30 (1991). Pp. 9133-9142 ,

Bacteriorhodopsin derivatization variants are to be understood as meaning, in particular, bacteriorhodopsin variants which differ from the wild type by virtue of the covalent coupling of molecules. Such molecules may, for example, have the task of increasing the molecular weight of bacteriophodopsin in order to be able to identify such a molecule in mass spectroscopy or to be a colored molecule so as to change the absorption spectrum of the bacteriorhodopsin. Preferably, this is a fluorescent or phosphorescent molecule, so as to be able to observe a luminescence coupled to the bacteriorhodopsin, the emission of which represents an additional safety feature. By properly selecting the location of the emission, suppression of luminescence can be achieved when the bacteriorhodopsin material is in the unbleached state. This is achieved when the location of the initial bacteriorhodopsin absorption and the emission of the fluorescent or phosphorescent material strongly overlap. In this case, the bacteriorhodopsin material absorbs the emitted photons and no luminescence is perceptible to the naked eye. The luminescence only becomes visible when the bacteriorhodopsin material is photochemically bleached.

Likewise, the bacteriorhodopsin material may also be covalently coupled to a polymer. The coupling reaction can, for. B. after Chignell & Chignell, Biophys. Biochem. Res. Commun. 62 (1975), pp. 136-143 and after Renthal et al., Biochemistry 22 (1983), pp. 12-12 be performed.

Link molecules can be coupled to the bacteriorhodopsin, which in turn allow additional compounds to be coupled to them. Molecules that can be coupled to the objects of the invention serve to increase the molecular weight of Baktehorhodopsin in order to identify such a molecule in mass spectroscopy.

Bacteriorhodopsin chromophore variants should be understood as meaning, in particular, bactetiorhodopsin variants which differ from the wild type by the removal or exchange of the chromophoric retinylidene group by another molecule, so-called retina! -Containing molecules. The retinal analog molecule may be covalently linked to bacteriorhodopsin via lysine-216.

Bacteriorhodopsin sequence invertants are to be understood as meaning in particular those bacteriorhodopsin variants which differ from the wild-type by the Loss or replacement or the addition of one or more amino acids, but do not lead to a significant influence on the photocycle. Sequence variants of bacteriorhodopsin are z. B. D36C or variants in which amino acids are attached to the N-terminus or C-terminus. The combination of the modifications of the abovementioned variants leads to new, preferred variants, which makes possible an enormous number of different bacteriorhodopsin preparations. Because of the enormous number of possible "codes", only a minimal fraction of all possible "codes" in a production will ever be usable. Even if the method of coding by specific sequences is known, a false one misses the information which codes have ever been used.

The bacteriorhodopsin preparation may further contain, in addition to bacteriorhodopsin, a conventional, non-photochromic pigment, and / or a fluorochrome and / or another photochromic pigment. By mixing with bacteriorhodopsin, the pigment or fluorochrome may be hidden within the security tag. In such an embodiment, it may further be useful to use UV light in addition to the visible light.

As mentioned, other possibilities for producing bacteriorhodopsin variants by replacing the chromophoric retinylidene group are possible. In this case, a modification of the photophysical properties is achieved, wherein preferably dihydroretinal or 4-ketoretinal can be used.

The examination of the composition of the applied bacteriorhodopsin material can be carried out by determining in whole or in part the amino acid sequence of the bacteriorhodopein material by means of microanalytical sequencing or by measuring the reaction with a specific antibody by means of immunological methods.

In a preferred embodiment of the present invention, the security material contains bacteriorhodopsin vectors mt specifically altered amino acid sequences, wherein the sequence change not the photophysical. Properties bceinfluBt and / or with chemically bound molecules. Particularly preferred are combinations of two or more of the above bacteriorhodopsin variant types.

In a further embodiment of the present invention, the photochromic biomolecule is a bacteriorhodopsin in which a) the area necessary to form the purple membrane form of the protein is unchanged from the bacteriorhodopsin wild type, or b) in loops and / or C-terminus and / or the N-terminus of the polypeptide chain at least one amino acid exchange to the wild-type bacteriorhodopsin, comprising deletions, additions, insertions and / or substitutions, wherein these amino acid substitutions do not result in a change by the photochromic region lead to certain photochromic properties of Baktorhodopsins.

In the bacteriorhodopsin characterized in this way, at least one amino acid is preferably added at the C-terminus.

Furthermore, it is preferred if the Bäkteriorhodopsin variant contains at least one cysteine and / or has a different wild-type photocycle or a different initial color from wild type.

When incorporating the bacteriorhodopsin, as a solvent, e.g. Water or organic solvents, such as. As those based on alcohol.

In addition to the preferred purple membrane form of bacteriorhodopsin, the inventive safety material may additionally contain bacteriorhodopsin in solubilized form.

Bacteriorhodopsin in solubilized form can be obtained by the bacteriorhodopsin gene in a host such. BE coli is expressed and reconstituted with added retinal aldehyde. Another possibility is that bacteriorhodopsin is obtained from purple membrane by removing the lipids. For this purpose a Purpurmembran- suspension (OD ₅₇₀ <5), for example placed in water or buffer with 1% Triton-X 100 and 1 h sonicated continuously at a microprobe a sonifier. The supernatant obtained after centrifugation contains bacteriorhodopsin in solubilized form.

In a preferred embodiment of the present invention, the safety material contains UV-absorbing substances. It has proven to be advantageous to accommodate these UV absorbers within and more preferably above the layer containing the photochromic biomolecule. With above is means a location in the stratiform that is farther from the support than the layer containing the photochromic biomolecule. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292 , in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 et seq and in Research Disclosure 38957, Parts VI, VIII, IX and X (1996), pp. 607 and 610 et seq , UV absorber-containing security materials according to the present invention are particularly preferred for open-end credentials and those that also contain fluorescent dyes that need to be excited with UV light

A further increase in protection against counterfeiting and increased protection against environmental influences can be achieved by lamination of the security materials, which can be done in particular with transparent plastic films. The lamination can be one-sided, but increased protection is achieved by double-sided lamination. The major surfaces of the ID materials can be covered by the laminate only partially or accurately fitting, a particularly high level of protection is achieved by supernatant laminate films whose protruding edges are welded or glued. In the context of the present invention, it has been found that the per se known lamination effect is particularly pronounced for the materials according to the invention, since the layer structure has a somewhat lower adhesion to the layer containing the photochromic biomolecile and it is therefore practically impossible to apply the lamination film without Destruction of the material to be replaced.

The layer comprising the photochromic biomolecule may contain the usual layer additives known for photographic materials in order to achieve good casting quality, adhesion and scratch resistance. In addition to water, e.g. a binder, especially an inert gelatin, wetting agents, e.g. Fluorosurfactants or manoxol; and viscosity modifiers, e.g. Polystyrenesulfonic acid (PSS).

The safety material according to the invention usually contains a binder which is cured in the preparation by the addition of a curing agent, in particular a Soforthartungsmittels and only withstands the high temperatures during chemical processing. In the presence of the photochromic biomolecules, it has been found that, relative to the total amount of binder, the amount of hardener must be increased significantly to provide a comparable layer stability to the material without the photochromic To obtain biomolecule. Preferably, the security material according to the present invention contains at least 0.05 g of hardener per g of binder, more preferably at least 0.1 g of hardener per g of binder.

In and adjacent to the layer containing the photochromic biomolecule, it has proved to be advantageous if there are as few organic solvents as possible in the preparation as well as in the finished material, as are e.g. Usually be used for the introduction of non-water-soluble substances. If, for this purpose, the amount of organic solvent is reduced as much as possible by the substances e.g. instead of being used as solutions or EmuJgate instead of solutions or where possible water-soluble compounds are used, the photochromic activity is hardly adversely affected despite incorporation into the layer structure.

The photochromic biomolecule may according to the present invention be in one or more arbitrary layers of the security material, but surprisingly it has been found that the photochromic activity increases when it is located closer to the support and thus covered by a large part of the layer structure. Particularly preferably, the layer containing the photochromic biomolecule is arranged directly on the carrier or merely removed from the carrier by a layer which contains a binding agent as its essential constituent.

In order to improve the photochromic switching behavior, it has proven to be advantageous to admix one or more of the following substances, alone or in combination, with any layer, preferably a layer adjacent to the BR layer and in particular with the BR layer itself: organic amines and ammonium Compounds, peptides and amino acids and the chemical derivatives of said compounds, preferably amine derivatives of aromatics and alkanes, in particular substances having primary, secondary, tertiary or quaternary amino groups; particularly preferably triethanolamine, alkylamine, diaminotoluene, betaine, serine, threonine, cysteine, lysine, arginine, tyrosine, asparagine, glutamine, histidine, polyethyleneamine, aminohydroxypyridine and aminomethoxypyridine. Most preferred is arginine. The substances mentioned lead in particular to a reduced climate dependence of the photochromic behavior and enable an outgrowing photochromism even at low relative humidity. The security materials of the invention preferably give in the range of 30 to 100% relative humidity, preferably from 50 to 80% relative Humidity, a measurable photochromism and this behavior can be controlled by using the aforementioned substances. For use in photographic security materials, this results in the advantage that the material can be dried well and then, for example, be welded in, thus gaining stability.

Further advantages could be achieved by the fact that the safety material according to the present invention contains substances which react with the developer oxidation product resulting from the chemical processing. In addition to eg color mask and white couplers, these include in particular scavengers, which are known to the person skilled in the art of photographic materials. Surprisingly, the photochromic activity can be increased by such substances. The substances which react with the developer oxidation product are preferably used in the layer containing the photochromic biomolecule or above, in particular above, wherein in each case preferably from 0.03 to 0.5 g / m ² , in particular from 0.1 to 0.25 g / m ^{2 of} such substances are used. A high content is favorable for the photochromic effect, but the amount should not be increased too much so as not to impair the adhesion between the layers. The optimum amount can be determined by one of ordinary skill in the art by conventional experimentation.

In a preferred embodiment of the present invention, a barrier layer which is largely impermeable to the developer oxidative product is disposed above the layer containing the photochromic bioluminescent molecule. This can e.g. can be achieved in that the Bameieschicht contains at least one of the aforementioned substances which react with the developer oxidation product, but can also, for example, be achieved by binders and a particularly strong hardening in the barrier layer, whereby the swelling and thus the diffusion of the developer is reduced.

High demands are placed on the stability of ID materials, which also applies to the stability against bacterial or fungal attack, because such materials are often touched with the fingers and can easily be contaminated. However, the bactericides and fungicides known for photographic materials can not be used without restriction for the security materials according to the present invention. Thus, it has surprisingly been found that some of the known bactericides and fungicides significantly increase the photochromic activity reduce. However, the selection of suitable biocides can be easily made by a test in which the substance to be tested is added to the safety material according to the present invention and the material is exposed to a temperature of 60 ° C for 48 hours without controlling the relative humidity. Thereafter, the photochromism and the cycle number are determined. Materials which, after this stress test, continue to have photochromic activity which can be adequately deectected for the intended purpose are suitable as security materials according to the invention and the biocides tested in this way are suitable for this purpose.

The invention also provides a process for producing a security material comprising a carrier and at least one photochromic protein and / or a mutein of a photochromic protein, characterized in that the security material on the carrier has at least one irreversibly photosensitive layer, wherein the at least one photochromic protein and / or mutein is present at least in the at least one light-sensitive layer and / or in an optional additional layer, and wherein the layer or layers are applied as flowable preparations, in particular as aqueous preparations, to the support.

The application can be carried out by any known methods, ie, for example, by brushing or spreading, but it is preferably carried out with continuous casting process, in particular cascade and Vorhangbeguß, as are known for photographic materials. In this case, it is particularly preferred to apply a plurality of layers simultaneously, in particular all layers at the same time, to the carrier. With the continuous casting processes, very uniform layers are possible and it has been shown that the layer adhesion problems that result from introducing photochromic biomolecules into the layer structure can be considerably reduced compared to non-continuous methods. In addition, it has surprisingly been found that with this continuous casting process, the photochroic activity is improved, which could be due to the cleaner layer separation, whereby the layer with the photochromic biomolecule contains no compounds from other layers, which can reduce the activity. The casting parameters such as viscosity and surface tension can be adjusted by conventional methods of the desired casting method and the casting speed. For casting speeds around 50 m / min For example, using a cascade caster viscosities of the casting solution between 80 and 120 cPa have proved favorable; however, using a curtain caster and casting speeds of over 300 m / min, viscosities of 300 cPa and higher have been found. The pH of the preparation with the photochromic biomolecule (the casting solution) is preferably from 4 to 7, in particular from 5 to 5.5.

In another embodiment of the present invention, the security material is manufactured in two passes. In the first pass, the carrier is provided only with the layer containing the photochromic biomolecule. This has the advantage, for example, that subbed carriers of this kind can be produced in large quantities directly by the manufacturer of the carrier. The preparation can be carried out in a known manner as described above in the prior art by pouring the preparation with the photochromic biomolecule onto a stationary support. However, it has not been possible to apply this method to continuous casting processes that allow rational production on a large scale. Despite the usual setting attempts of the casting, it was not possible to pour a preparation containing a photochromic biomolecule directly on a support continuously and with acceptable casting quality. Only the introduction of an additional layer, which contains at least one binder, between the support and the layer with the photochromic biomolecule, enabled a continuous coating of the support. Such an intermediate layer is not necessary if the material with all layers, including the at least one irreversibly photosensitive layer, is cast continuously simultaneously in one machine pass. For this simultaneous pouring cascade and curtain casters are preferably used, which are equipped with a casting head having as many pouring slots, as the material contains layers, but it can also be arranged two or more casting heads in a row, which together have the required number of pouring slots , As a machine passage, the scope of the present invention is the unrolling of the web to be coated, its casting with one or more layers and its drying. After the drying stretch, a further pourer together with a downstream drying section can be provided, which allows the second machine passage without interruption, but the dried material can also be wound up after the first or further machine passes. The dried web thus obtained may then be in one or more If further machine passes are intended, it has proven to be advantageous to apply an additional layer as the top layer in the preceding pass, which serves as a bonding layer for the layer or coating applied in the further machine pass. applied layers and preferably comprises at least one binder and / or at least one thickening agent, in particular a thickener.

Another object of the present invention is thus a material having at least two layers on a support, characterized in that at least one layer contains at least one photochromic biomolecule and between this layer and the support at least one other layer is arranged, which wetting the carrier with the at least one photochromic biomolecule containing layer improves and leads to a better adhesion of this layer. Thus, a uniformly coated material with little or no casting defects such as e.g. Strips are obtained. The at least one layer between support and photochromic biomolecule-containing layer preferably contains at least one binder, in particular a curable binder such. inert gelatin and / or at least one thickener and / or at least one wetting agent. This material can be cured if it is no longer to be continuously watered, to which one of the said layers or preferably in a separate curing layer, a curing agent is added, which is suitable for the binder used. Particularly preferred hardening agents used are the instant hardening agents known for photographic materials.

In the context of the present invention, however, it is preferable not to cure the material obtained as described above, but to provide an uppermost layer removed furthest from the support with an additional adhesive layer as described above. Such a material is eminently suitable as a basis for a second or further machine passes to arrive at the photochromic security material according to the present invention.

Another object of the present invention is therefore a process for the preparation of a security material comprising a support and at least one photochromic protein and / or a mutein of a photochromic protein, characterized in that the security material on the support at least one wherein the at least one photochromic protein and / or mutein is contained in at least the at least one photosensitive layer and / or in an optional additional layer, and wherein the layer or layers are applied continuously in one, two or more machine passes ,

An object of the present invention is also a method for the chemical processing of the security material according to the present invention, characterized in that the processing takes place according to the character of the material. Surprisingly, it has been found that the processing can be carried out according to the methods known for the corresponding materials without the photochromic biomolecule. For photographic materials, processing usually involves their development, bleaching, fixing and stabilizing and / or watering, bleaching and fixing often being able to occur in one processing step.

In the context of the present invention, however, it has been found that the development can change the photochromic behavior and, in particular, reduce the photochromic activity. However, this intrinsically undesirable effect can also be utilized in that a processing process e.g. with certain processing parameters, e.g. Development temperatures and times is developed, which changes the photochromic behavior in a certain way. Such experiments can be easily performed by one skilled in the art. In addition, if the processing conditions so specified are kept secret and disclosed only to a very small group of people, this increases the safety, since even a precisely replicated material can not be processed by a wrong person and thus differs from the legally produced and processed material.

In a preferred embodiment of the present invention, therefore, the processing conditions differ from those typical and typical of the material without the photochromic biomolecule such that there is a measurable change in photochromic behavior. For example, if the material according to the present invention is a silver halide-based photographic paper containing a photochromic biomolecule, it is preferably processed by a process that differs from the known type processes for minilabs and large laboratories such that a measurable Change in photochromic activity.

The customary development conditions are preferably modified in such a way that the damaging effect of the processing is reduced, so that the color, structure and function of the photochromic biomolecule does not change significantly and a maximum photochromic activity is achieved. Thus, in spite of the processing, a clear color transition can be detected which, depending on the requirements of the material, is also visually perceptible given a sufficient amount of photochromic biomolecule.

It has proved to be advantageous, at least one processing bath alone or in combination to add certain N-containing compounds, which have already been mentioned above as preferred layer additives: organic amines and ammonium compounds, peptides and amino acids and the chemical derivatives of said compounds, preferably Amine derivatives of aromatics and alkanes, in particular substances with primary, secondary, tertiary or quaternary amino groups; particularly preferably triethanolamine, alkylamine, diaminotuluol, betaine, serine, threonine, cysteine, lysine, arginine, tyrosine, asparagine, glutamine, histidine, polyethyleneamine, aminohydroxypyridine and aminomethoxypyridine. Arginine is particularly preferred. These additives may be incorporated into the material prior to processing, e.g. by passing the material before the first processing step through a solution, in particular an aqueous solution of such a compound. However, the additives can also be added to one or more of the processing baths. Particularly preferably, the said compound is introduced by means of the final bath, which may be a stabilizing bath or a simple washing bath. By such additives, the Schaltvetfialten is significantly improved and the speed of color changes can be selectively influenced. Preference is also given to using combinations of said compounds in one or more baths, e.g. Arginine and triethanolamine.

As a further preferred measure for improving the photochromic switching behavior, it has been found that the salts commonly used in the baths, in particular in the developer, in particular buffer substances which frequently have the potassium ion as the counterion, e.g. Potassium carbonate, replace with those with sodium ions.

In addition, it has proven to be beneficial to dispense in the baths as possible to organic solvents and in at least one, in several or all baths based on the total amount of solvent in the respective bath to a proportion of at least 20% by weight, in particular at least 50% by weight, more preferably at least 80% by weight and, if possible, 100% by weight of water. If organic solvents can not be dispensed with, preference is given to using those which are particularly compatible with BR, which can be easily determined by simple processing experiments.

Preferably, at least one treatment bath, in particular the final stabilization bath, at least one bactericidal and / or at least one fungicidal component is added. Preference is given to using those substances which have passed the stress test described above.

The invention also provides the use of the security material according to the invention in processed or unprocessed form for customizable documents with increased security requirements, e.g. in the field of product protection, goods traffic or e.g. in the field of identity cards, passports, ID cards, visas and other security-related documents.

Products which are provided with the feature according to the invention are easily protected against imitation. The photochromic feature authenticates the product with visual and / or machine inspection.

A personalized document, a card system or other object used to authenticate an access right or right of use of a room or a device can be easily obtained with the inventive feature. The feature may require authentication after machine verification of the visually perceptible or visually imperceptible photochromism.

A document or card system or product incorporating a feature of the invention may be inspected not only visually but also with the aid of devices which detect a color change or absorption change due to a change in lighting conditions for the feature. This can be done for example by the illumination of the feature with different LEDs or other light sources and the detection of the reflected or transmitted light via a photodiode or other detector. The material changes eg when irradiated with light one LED with an emission maximum in the green or yellow range, its color from purple to yellow. This is particularly easy to detect if the entire surface is not irradiated and, in particular, if the photographic material in this area has either a slight staining or a staining produced by exposure and processing which, in combination with the color of the photochromic biotope molecule, becomes easily detectable or visually discernible color change fUhn. Without further ado, after a few seconds to minutes, depending on the preparation used, the purple color returns and the initial state is restored. Alternatively, by irradiating light of a light emitting diode having an emission maximum in the blue range, the purple color can be restored immediately. The technical effort for the test is minimal. The user can follow the color change with the naked eye, but the measuring process can preferably also be carried out by machine.

The security material according to the present invention may preferably be provided with a security barrier, e.g. can be generated easily and yet in a very complex form via the photographic layered composite. When exposed, the security marker changes color and after a short time of approximately 30 to 60 seconds and / or exposure to blue wavelength light, the original purple color returns.

The materials of the invention also provide high copy protection. Will such a safety material; such as. For example, if a badge is duplicated by a photocopier, exposure to light during the copying process bleaches the photosensitive bacteriorhodepsin material and irreversibly freezes that state in the copy, thereby clearly distinguishing the copy from the original. For this effect to be exploited, the amount of photochromic biomolecule should be high enough to allow visual recognition. The copy protection effect can be further enhanced by imprinting in a purple color, similar to that of the photochromic biomolecule, a pattern that becomes visible only when the photochromic biomolecule transitions to its M state.

Preferred embodiments of the present invention can be found in the subclaims.

Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process, or the silver bleaching process. An overview can be found in Research Disclosure 37038 (1995 ) and Research Disclosure 38957 (1996 ).

The photographic materials consist of a support on which at least one light-sensitive silver halide emulsion layer is applied. Suitable supports are, in particular, thin films and films. An overview of carrier materials and auxiliary layers applied to their front and back is in Research Disclosure 37254, Part 1 (1995), p. 285 and in Research Disclosure 38957, Part XV (1996), p. 627 shown.

The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and optionally intermediate layers and protective layers.

• Farbfotografische Filme wie Colomegarivfilme und Colorumkehrfilme weisen in der nachfolgend angegebenen Reihenfolge auf dem Träger 2 oder 3 rotempfindliche, blaugrünkuppelnde Silberhalogenidemulsionsschichten, 2 oder 3 grünempfindliche, purpurkuppelnde Silberhalogenidemulsionsschichten und 2 oder 3 blauempfindliche, gelbkuppelnde Silberhalogenidemulsionsschichten auf. Die Schichten gleicher spektraler Empfindlichkeit unterscheiden sich in ihrer fotografischen Empfindlichkeit, wobei die weniger empfindlichen Teilschichten in der Regel näher zum Träger angeordnet sind als die höher empfindlichen Teilschichten.

Depending on the type of photographic material, these layers may be arranged differently. This is illustrated for the main products:

• Color photographic films such as colombarge films and color reversal films have on the support 2 or 3 red sensitive cyan coupling silver halide emulsion layers, 2 or 3 green sensitive magenta coupling silver halide emulsion layers and 2 or 3 blue sensitive yellow coupling silver halide emulsion layers on support 2 in the order given below. The layers of equal spectral sensitivity differ in their photographic sensitivity, with the less sensitive sublayers generally being located closer to the carrier than the higher sensitive sublayers.

Between the green-sensitive and blue-sensitive layers there is usually a yellow filter layer attached, which prevents blue light from entering the underlying layers.

The possibilities of the different layer arrangements and their effects on the photographic properties are discussed in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183-193 and in Research Disclosure 38957 Part XI (1996), p. 624 described.

Color photographic paper, which is generally much less photosensitive than a color photographic film, typically has a blue-sensitive yellow coupling silver halide emulsion layer, a green-sensitive, magenta coupling silver halide emulsion layer and a red-sensitive, cyan-coupling silver halide emulsion layer in the order listed below on the support; the yellow filter layer can be omitted.

Deviations from the number and arrangement of the photosensitive layers can be made to achieve certain results. For example, all the high-speed layers may be combined into one layer package and all the low-speed layers combined into another layer packet in a photographic film to increase sensitivity ( DE-25 30 645 ).

Essential constituents of the photographic emulsion layers are binders, silver halide grains and color couplers.

Information about suitable binders can be found in Research Disclosure 37254, Part 2 (1995), p. 286 and in Research Disclosure 38957, Part II.A (1996), p. 598 ,

Information on suitable silver halide emulsions, their preparation, ripening, stabilization and spectral sensitization, including suitable spectral sensitizers, can be found in US Pat Research Disclosure 37254, Part 3 (1995), p. 286 , in Research Disclosure 37038, Part XV (1995), p. 89 and in Research Disclosure 38957, Part VA (1996), p. 603 ,

Photosensitive camera materials typically contain silver bromoiodide emulsions, which may also contain minor amounts of silver chloride. Photographic copying materials contain either silver chloride bromide emulsions containing up to 80 mol% AgBr or silver chlorobromide emulsions containing greater than 95 mol% AgCl.

Information about the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 , in Research Disclosure 37038, Part II (1995), p. 80 and in Research Disclosure 38957, Part XB (1996), p. 616 , The maximum absorption of the dyes formed from the couplers and the color developer oxidation product is preferably in the following ranges: yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan coupler 630 to 700 nm.

In color photographic films, to improve sensitivity, graininess, sharpness, and color separation, compounds which release compounds that are photographically active, e.g., in reaction with the developer oxidation product, are often used. DIR couplers which cleave a development inhibitor.

Information on such compounds, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 , in Research Disclosure 37038, Part XIV (1995), p. 86 and in Research Disclosure 38957, Part XC (1996), p. 618 ,

The mostly hydrophobic color couplers, but also other hydrophobic constituents of the layers, are usually dissolved or dispersed in high-boiling organic solvents. These solutions or dispersions are then emulsified in an aqueous binder solution (usually gelatin solution) and after drying the layers are present as fine droplets (0.05 to 0.8 μm in diameter) in the layers.

Suitable high-boiling organic solvents, methods for incorporating them into the layers of a photographic material, and other methods of incorporating chemical compounds in photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292 ,

The non-photosensitive interlayers, which are usually disposed between layers of different spectral sensitivity, may contain means which prevent unwanted diffusion of developer oxidation products from one photosensitive layer to another photosensitive layer with different spectral sensitization.

Suitable compounds (white couplers, scavengers or EOP scavengers) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 , in Research Disclosure 37038, Part III (1995), p. 84 and in Research Disclosure 38957, Part XD (1996), p. 621 et seq.

The photographic material may further include whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, plasticizers (latices), biocides and additives to improve coupler and dye stability, to reduce color fog, and to reduce yellowing and others contain. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292 , in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 et seq and in Research Disclosure 38957, Parts VI, VIII, IX and X (1996), pp. 607 and 610 et seq.

The layers of color photographic materials are usually cured, that is, the binder used, preferably gelatin, is crosslinked by suitable chemical techniques.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 , in Research Disclosure 37038, Part XII (1995), page 86 and in Research Disclosure 38957, Part II.B (1996), p. 599 ,

After imagewise exposure, color photographic materials are processed according to their character according to different processes. Details of the procedures and required chemicals are available in Research Disclosure 37254, Part 10 (1995), p. 294 , in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 et seq and in Research Disclosure 38957, parts XVIII, XIX and XX (1996). P. 630 ff published together with exemplary materials.

Examples

The Baktorhodopsin suspension (BR suspension) used in the examples was tested by the University of Marburg, Prof. Dr. med. Hampp provided. The content data in mg refer to the amount of bacteriorhodopsin used itself.

example 1

A color photographic imaging material suitable for a rapid processing process was prepared by applying the following layers in a cascade coater in the order given on a polyethylene-coated paper backing. The quantities are in each case based on 1 m ² . For the silver halide application, the appropriate amounts of AgNO ₃ are given.

Layer structure 101

Layer 1a:

(Auxiliary layer 1) according to Table 1
1.84 g of gelatin

Layer 1b:

(Substrate layer)
Gelatine according to Table 1.
BR suspension according to Table 1

Layer 1c:

(Auxiliary layer 2) according to Table 1
0.05 g of thickener VM = 1

Layer 2:

(blue-sensitive layer)
blue-sensitive silver halide emulsion (99.94 mole% chloride,
0.06 mol% bromide, medium Konidurchmesser 0.85 μ m) of 0.39 g AgNO. ₃
0.94 g of gelatin
0.375 g yellow coupler GH-1
0.125 g yellow coupler GB-2
0.30 g of dibutyl phthalate (DBP)
0.10 g stabilizer ST-1

Layer 3:

(Intermediate layer)
1.24 g of gelatin
BR suspension according to Table 1
0.155 g EOP scavenger SC-1
0.028 g EOP scavenger SC-2
0.155 g DBP
0.028 g tricresyl phosphate (TKP)

Layer 4:

(green-sensitive layer)
green-sensitive silver halide emulsion (99.9 mole% chloride,
0.1 mol% bromide, average grain diameter 0.48 μ m) from 0.18 g AgNO ₃
0.75 g of gelatin
0.14 g magenta coupler according to Table 1
0.15 g stabilizer ST-2
0.20 g Stabilizer ST-3
0.186g CPM

Layer 5:

(UV protective layer)
1.13 g of gelatin
0.40 g UV-Abgorber UV-1
0.70 g UV absorber UV-2
0.125 g EOP scavenger SC-1
0.021 g EOP scavenger SC-2
0.125 g DBP
0.021 g TKP

Layer 6:

(red-sensitive layer)
red-sensitive silver halide emulsion (99.7 mole% chloride,
0.3 mol% bromide, mean diameter 0.48 μ m) from 0.30 g AgNO ₃ .
0.73 g of gelatin
0.35 g cyan coupler BG-1
0.35 g TKP

Layer 7:

(UV protective layer)
0.45 g of gelatin
0.148 g UV absorber UV-1
0.026 g UV absorber UV-2
0.05g EOP-Ablet SC-1
0.05 g DBP

Layer 8:

(Protective layer)
0.62 g of gelatin
0.059 g whitener WT-1
1.20 ml of silicone oil.
2.50 mg polymethylmethacrylate spacer, average particle size 0.8 μ m

Layer 9:

(Hardening)
0.113 g of thickener VM-1
Hardener H-1 according to Table 1

In layer structure 101, the following compounds are used:

The other layer structures differ from 101 as shown in Table 1. For layer structures 101 and 102, layer 1b or layers 1a to 1c were first applied to the substrate, the material dried and the remaining layers applied in a separate machine passage. In contrast, the layer structures 103 to 105 were cast in a machine passage. <b> Table 1 </ b> Layer construction Layer 1a available Quantity BR in layer 1b in mg / m ² Amount of gelatin in layer 1b in g / m ² Layer 1c present Quantity BR in layer 3 in mg / m ² Amount of H-1 in layer 9 in mg / m ² 101 No 150 1.92 No 0 500 invention 102 Yes 150 1.92 Yes 0 646 invention 103 No 150 0.23 No 0 303 invention 104 No 150 0.23 No 0 646 invention 105 No 0 0.23 No 150 646 invention 106 No 0 0.23 No 0 303 comparison

Layered structure 106 is a photographic copy material that does not contain a photochromic biomolecule and therefore does not exhibit photochromic behavior. The casting quality, the layer adhesion and the scratch resistance are both unprocessed and processed very well.

Layer structure 103 differs from 106 only in that the BR suspension is contained in substrate layer 1b. The casting quality is still good, but the layer adhesion and scratch resistance satisfy only very low demands, which at the high temperatures of the short-term processing can lead to a floating of the layer structure. For a Kurizeitverarbeitung such a material is therefore less suitable.

Although the same amount of gelatin is contained in layer structure 103 as in layer structure 106, in layer structure 104, the amount of hessor usually customarily adjusted to the amount of binder was increased to more than the doppler value. Surprisingly, the layer adhesion was significantly improved and the scratch resistance increased.

Layer structure 105 differs from 104 in that the BR suspension was introduced into layer 3. Film adhesion and scratch resistance were comparable to film build 104, except that a scratch on the scratch tests now occurred above the yellow layer and not above the backing as in build 104.

The layer structures 101 and 102 have been produced by an alternative production method, in which the carrier material was subbed in a first pass with the BR suspension, in order then to be doused with the residual layer structure in a separate machine pass. The first passage may e.g. also be carried out directly by the manufacturer of the support material, whereby the proliferation of the photochromic biomolecules is further restricted and which also allows to use the substrate thus subbed with the photochromic biomolecule for purposes other than the security material according to the present invention.

Surprisingly, the 1st machine passage for the layer structure 101 provided only a very unsatisfactory casting quality in the case of the continuous casting by means of a cascade caster, although a significantly better casting quality was obtained in a preliminary test with a conventional doctor blade caster. The poor casting quality was noticeable by clear streaks, which remain visible even after the second machine pass, whereby a material produced in this way is acceptable only for very low quality requirements. Only after embedding the BR-suspension layer through the Auxiliary layers 1a and 1b could be a good casting quality can be achieved, which is also comparable in terms of adhesion and scratch resistance with the layer structure 104.

Chemical processing

All samples were processed with a short-term process as follows. The composition of the processing bath, the process time and the process temperature are given.
a) color developer, 27s, 39 ° C DEHX soln. (Diethylhydroxylamine, 85% strength by weight, aqueous) 35 ml sodium 0.5 g CD3, base 31 g diethylene glycol 30 ml whiteners 7 g Polymaleic anhydride, 50 wt .-% aq. solution 15 ml Adjust potassium carbonate to pH 13.5 with KOH and make up to 5 liters with water. 100 g b) Bleach-fix, 27 s, 35 ° C Ammonium thiosulfate solution, 58% by weight 100 ml sodium metabisulfite 15 g Add ammonium iron EDTA, 48% by weight with water to 1000 ml, adjust the pH to 6.0 with ammonia or acetic acid. 100 ml c) Stabilizer, 54 s, 33 ° C water 900 ml sodium 2 g Hydroxyethandiphosphonsäuredinatriumsalz 4 g Add sodium benzoate to 1000 ml with water, adjust the pH to 7 with acetic acid. 0.5 g d) drying

The processing took place in each case in an AgfaPhoto Minilab of the type d.lab 2.

The layer structures 101 to 106 were examined for their photochromic properties using a test device (terminal) developed at the University of Marburg. The material is bleached for several seconds with LED light of 640 nm and switched back with LED light of 405 nm. Then one obtains an averaged relative measured value "delta PC", which stands for the photochromic effectiveness and must be at least 50 in order to enable a reliable state differentiation. The results are shown in Table 2 under "Photochromic effect" Delta-PC "after standard processing". The processing experiments were repeated but with the difference that the stabilizer contained 4% by weight of arginine. The results thus obtained are shown in Table 2 under "Photochromic effect" delta-PC "with arginine".

Because of the poor adhesion or quality of the coating, the layer structures 101 and 103 were not evaluated accordingly. <b> Table 2 </ b> layer structure Photochromic effect "Delta-PC" after standard processing Photochromic effect "Delta-PC" with arginine 102 113 165 invention 104 117 131 invention 105 106 112 invention 106 0 0 comparison

It is clear from the results that, surprisingly, the materials according to the invention, despite their integration into the layer structure and despite the chemical processing, exhibit a pronounced photochromic effect, which is suitable for use as a security feature; that this effect is particularly great when the BR suspension is introduced between the carrier and the layer structure; and that the effect is considerably improved by the arginine treatment, which has a particularly marked effect on the materials in which the BR suspension is contained between carrier and layer structure.

Example 2 processing variants

The layer structure 102 was according to the variants 201 to 206 loud. Table 3 processed. <b> Table 3 </ b> Processing variant Summary "Delta-PC" without arginine "Delta-PC" with 4 wt .-% arginine in Stabibad "Delta-PC" with 4% by weight arginine in water 201 Na instead of K. 141 172 205 202 without solvents 144 185 205 203 Na instead of K; without solvents 158 186 230 204 Triethanolamine as a solvent 133 169 210 205 Na instead of K; Triethanol as solvent 145 174 219 206 default 121 176 201

Variant 206 and "Delta-PC" without arginine "are the processing described above, which was also used for the results according to Table 2. Variants 201 to 205 differ only in the composition of the color developer bath the potassium carbonate contained therein was replaced by sodium carbonate and the pH was adjusted with NaOH, the diethylene glycol was omitted for variant 202 and the variants of variants 201 and 202 were combined for variant 203. For variant 204, the diethylene glycol was replaced by the same amount of triethanol Variant 205 represents a combination of the measures according to variants 201 and 204. The results thus obtained are reproduced in the column "" Delta-PC "without arginine." The test series was repeated with the difference that the stabilizer bath was 4% by weight. The results thus obtained are shown in Table 3 in the column "" Delta-PC "with 4% by weight of arginine in the S tabibad " played. In another series of experiments, the Stabibad was replaced by water containing 4 wt .-% arginine. The results thus obtained are shown in Table 3 in the column "" Delta-PC "with 4 wt% a arginine in water". It is clear from Table 3 that the best results are obtained with variant 203, ie without solvent and with sodium ions instead of potassium ions. However, as processing chemicals are often sent and stored as concentrated solutions, the addition of an organic solvent is often indispensable to avoid irreversible precipitations frequently. In such a case, variants 204 and 205 are a good solution in which the organic solvent poorly compatible with the photochromic biomolecule has been replaced by a more compatible one, in the case shown by triethanolamine. The treatment with arginine leads to a significant improvement of the photochromic behavior, which is particularly pronounced when a watering is carried out instead of Stabibades.
Experiments 201-206 were repeated as 211-216, except that 2% by weight, instead of 4% by weight, of arginine was contained in the stabilizer bath or water bath. The results are summarized in Table 4.
In a further series, the experiments 201 to 206 were repeated as 221 to 226, with the difference that in the stabilizer bath or the water bath 1 wt .-% instead of 4 wt .-% arginine were included. The results are summarized in Table 5.
From the comparison of Tables 3 to 5 shows that arginine even in lower amounts than 4 wt .-% acts, this amount is preferred for maximum effect. <b> Table 4 </ b> processing variant Summary "Delta-PC" without arginine in the Stabibad "Delta-PC" with 2 wt% arginine in the Stabibad "Delta-PC" with 2% by weight arginine in water 211 Na instead of K. 141 160 188 212 without solvents 144 168 202 213 Na instead of K; without solvents 158 169 207 214 Triethanolamine as a solvent 133 164 208 215 Na instead of K; Triethanol as solvent 145 159 187 216 default 121 175 185 processing variant Summary "Delta-PC" without arginine in the Stabibad "Delta-PC" with 1 wt .-% arginine in Stabibad "Delta-PC" with 1 wt% arginine in water 211 Na instead of K. 141 155 185 212 without solvents 144 160 200 213 Na instead of K; without solvents. 158 160 193 214 Triethanolamine as a solvent 133 159 195 215 Na instead of K; Triethanol as solvent 145 158 186 216 default 121 154 175

Claims (21)

A security material comprising a support and at least one photochromic protein and / or a mutein of a photochromic protein, characterized in that the security material on the support has at least one irreversibly photosensitive layer and wherein the at least one photochromic protein and / or mutein is at least in the at least one photosensitive Layer and / or contained in an optional additional layer. Safety material according to claim 1, characterized in that it is a color photographic copy material. A security material according to any one of the preceding claims, characterized in that the total contained silver halide emulsions consist of at least 95 mol% of silver chloride. Safety material according to one of the preceding claims, characterized in that it is an ID material. Safety material according to one of the preceding claims, characterized in that the photochromic substance is a retinal protein. Safety material according to one of the preceding claims, characterized in that the photochromic substance is a bacteriorhodopsin. Safety material according to one of the preceding claims, characterized in that it contains UV-absorbing substances inside and / or above the layer containing the photochromic substance. Safety material according to one of the preceding claims, characterized in that the layer containing the photochromic substance is arranged directly on the carrier or removed from the carrier only by a layer. Safety material according to one of the preceding claims, characterized in that it contains alone or in combination substances from the following group of compounds: organic amines and ammonium compounds, peptides and amino acids and the chemical derivatives of said compounds. Safety material according to one of the preceding claims, characterized in that it contains, alone or in combination, substances from the following group of compounds: triethanolamine, alkylamine, diaminotoluoi, betaine, serine, threonine, cysteine, lysine, arginine, tyrosine, asparagine, glutamine, histidine , Polyethylene amine, Aminvhydroxypyudin and Aminomethoxypytidin. A method for producing a security material according to any one of claims 1 to 10, characterized in that the layer or layers are applied as flowable preparations on the carrier. A process for the preparation of a material comprising a support and at least one photochromic protein and / or mutein of a photochromic protein contained in a layer, and which material may consist of further layers, characterized in that the layer (s) is continuous Casting process can be produced. A method according to claim 12, characterized in that a material according to any one of claims 1 to 10 is produced. A method according to claim 12, characterized in that a material is prepared which has directly on a support a layer comprising a binder and / or a thickening agent and above a layer containing a photochromic biomolecule. A material comprising, directly on a support, a layer comprising a binder and / or a thickener and, above, a layer containing a photochromic biomolecule. Material according to claim 15, characterized in that it has an adhesive layer as a further layer above the photochromic layer. Process for the chemical processing of a security material according to claim 1, characterized in that the processing takes place in accordance with the character of the material. A method according to claim 17, characterized in that the processing comprises the steps of development, bleaching, fixing and stabilizing and / or Wässem, wherein the bleaching and fixing can also be done in one step. Method according to one of claims 17 to 18, characterized in that at least one processing solution alone or in combination contains substances from the following group of compounds: organic amines and ammonium compounds, peptides and amino acids and the chemical derivatives of said compounds. A method according to claim 19, characterized in that at least one processing solution alone or in combination contains substances from the following group of compounds: triethanolamine, alkylamine, diaminotoluene, betaine, serine, threonine, cysteine, lysine, arginine, tyrosine, asparagine, glutamine, histidine , Polyethylene amine, aminohydroxypyridine and aminomethoxypyridine. Use of the security material according to one of claims 1 to 10 in processed or unprocessed form for individualizable documents with increased security requirements.