DE2446108A1 - PROCESS FOR GENERATING DETERMINABLE INFORMATION RECORDS AND THE MATERIALS USED FOR THEREFORE - Google Patents

Description

,.-., · ink pen

Energy Conversion Devices, Inc.

1675 West Maple Road, Troy , Michigan 48084 (V.St.A.)

Process for the creation of accessible information records and the materials used for this

The present invention relates to improvements in the field of information recording and image formation.

There are several methods of creating images or image duplicates known. The image-providing materials used are in certain cases certain inorganic ones Compounds and in other cases certain organic compounds. Some of the previously known Methods use mixtures of inorganic compounds, e.g. silver halides, with one or more specific ones Types of organic compounds as sensitizers. So it is in particular from the German patent 2 022 260 became known to generate images by that one is on a substrate such as paper, glass or a

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synthetic polymer, inorganic light-sensitive substances such as cupric oxide, bismuth subchloride, mercury chloride and tellurium dihalides, for example tellurium dichloride, tellurium dibromide, tellurium chlorobromide and tellurium iodobromide, as a coating or depositing it thereon. As stated there, the tellurium dihalides are produced by first producing the tetrahalide, e.g. TeCl ₂ P TeBr ₂ ^ or TeJ ₁ ^, and then melting the said tetrahalide with metallic tellurium powder and comminuting the melt to a powder which is generally yellow-gray or black. The resulting tellurium dihalides are applied to an adhesive strip, which is then moistened with acetone, ethanol, isopropanol or another organic liquid and exposed to an energy source such as a xenon fluorescent tube to create a visible image. The patent teaches the development of images produced according to the invention described therein with the aid of liquid developers such as an aqueous solution of sodium hydroxide or other alkali hydroxides or aqueous solutions of mineral acids or organic acids such as sulfuric acid, nitric acid, phosphoric acid, acetic acid , Citric acid, formic acid, and also with other liquid developers such as ethyl alcohol, ethyl ether, chloroform and the like. Such procedures are - generally speaking - laborious to carry out, in some cases dangerous, time-consuming and technically unsatisfactory. For example, tellurium dichloride is black in color, whereas tellurium tetrachloride is white in color. When exposed to the image-generating energy, the last-mentioned substance turns black in the areas of the surface exposed to said energy

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and leaves a white background in the unexposed parts of the surface, a situation that occurs in the event the use of tellurium dichloride does not occur.

The present invention relates to a new imaging system using certain tellurium tetrahalides are used, namely those where the halide is at least one member of the group consisting of chlorine and bromine, especially chlorine. Certain representatives of this imaging materials can be made by the formula

- ^TeC1 n ^Br m

in which η is an integer worth 2 to 4 and m represents an integer from 0 to 2 with the proviso that the sum of η and m is 4. Two particularly important embodiments of the invention the aforementioned imaging material is converted into a matrix or base material together with a sensitizer incorporated, as explained in detail below. The resulting combination of materials is then deformed into a thin film or layer, who is able to create a latent image when he or she receives an image-generating energy, e.g. electromagnetic radiation. The resulting latent image can then easily become an image of Excellent contrast can be developed by using it as a development energy source usually in the form of Exposing thermal energy.

Accordingly, the present invention provides a new method and new masses for creating inferred informational records, for example from BiI-

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dam and duplicates of existing images available, which are based on a layer that contains certain tellurium tetrahalides as image-providing materials, which have a detectable characteristic and which are capable of chemical conversion when responding to the addressing imaging energy applied to it in order to produce a material from a different one chemical nature or composition to produce which has another detectable characteristic. According to The method will apply the imaging energy to at least a certain part of that containing the material Layer brought into action to the chemical conversion in the image-providing material in that of the energy to bring about exposed part of the layer, wherein the chemically converted material at least one detectable Has characteristics that are different from the characteristics of the original image-providing material, and this difference in the detectable characteristics either perceived visually or by means of some suitable display or reading device can be detected. The material that has an altered chemical nature or composition and different detectable characteristics, that at the imaging step is sometimes referred to below as an image generator.

As noted above, the imaging materials employed in the practice of the present invention are comprised of tellurium tetrahalides such as TeCl ₂ , * TeBr ₂ ,, TeCIpBr ₂ , TeCl, Br and TeClBr- ,, where TeCl ₂₊ for the inventive

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is particularly well suited to moderate purposes. They are supposed to be in the matrix material, which is described in more detail below will be soluble or homogeneously dispersible.

If tellurium tetrahalide is dissolved in an organic solvent, E.g. tetrahydrofuran (THF) is dissolved and the solution is then used to coat a substrate and the organic solvent only partially evaporated to leave the surface wet or damp, and the material then exposed to radiation exposed to an imaging energy such as ultraviolet light through a mask, then the image is formed and development by heat and the like energy is unnecessary and does not bring about a reinforcing effect. These Method thus represents a "wet process" and it can be appropriately referred to here. It is not a sensitizer required if, for example, ultraviolet light is applied as image-generating energy. Other Tellurium tetrahalides give significantly less satisfactory results than tellurium tetrahalide when this wet process is applied.

It is particularly advantageous, however, to use the tellurium tetra-chloride or to use another tellurium tetrahalide in the form of a dry film by putting it in association with a sensitizer incorporated into a matrix and then the same in the form of a dry to the touch thin Film applies in particular to a substrate. In this form, the material is image-forming through a mask Exposed to energy to create an image or a latent image, which is then subjected to heat or development effecting energy source is developed in order to

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to win a good picture. The imaging energy can be ultraviolet light depending on the sensitizer used or visible light or one of the other energy sources explained in more detail below.

The matrix materials, which are solids at room temperature, can be selected from a relatively large number of materials. As mentioned above, they should desirably be at least partially amorphous in character, and it is particularly desirable that they be vitreous, amorphous materials which have a glass transition temperature which is preferably not above 200 ° C and down to 50 ° C or - better still - should be between about 8o and 12O ° C. As a rule, they are polymeric materials. Examples include cyanoethylated starches, celluloses and amylose, which have a degree of cyanoethylation of z £ 2; Polyvinylbenzophenone; Polyvinylidene chloride; Polyethylene terephthalate ("Mylar"); Polyvinyl carbazole; Polyvinyl chloride; Polyvinyl methyl ketone; Polyvinyl pyrrolidone; Polyvinyl methyl ether; Hydroxypropyl cellulose ("Klucel"; manufactured by Hercules Chemical Company); Copolymers of polyvinyl methyl ether and maleic anhydride; various commercial grades of polyvinyl formal resins, such as the so-called 12/85, 6/95 E, 15/95 S, 15/95 E, B-79, B-98 and similar products, as they are under the trade name " FORMVAR "(Manufacturer: Monsanto Company). "Polyvinyl formal 15/95 E", which is a white, free-flowing powder which has a molecular weight of 24,000 to 40,000 and a formal content, expressed as% polyvinyl formal, is particularly useful

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82 % . These resins and their production belong to the state of the art per se. It should also be pointed out that matrix materials which contain groups which complex with the image-providing materials are not suitable for use in the practice of the present invention.

The sensitizers necessary for use in practice Embodiments of the present invention are useful for producing dry-touch films, can be selected from a large group of materials. They should be soluble or homogeneously dispersible in the matrix material be. Your selection for use in any particular imaging composition becomes partial determined by the spectral sensitivity ranges that are desired. For example, in the case of Sensitizing in ultraviolet (UV) light and in visible light Substances to list the usable sensitizers compiled below, their approximate Sensitization area (n m) is indicated at the same time:

Sensitizer

ο-naphthoquinone 4,5-pyrenequinone 4, 5 * 9 * 10-pyrenequinone 9,10-phenanthrenehinone di fury1glyoxal 1-phenyl-1,2-propanedione 1,1 * -dibenzoylferroeen

spectral sensitivity range (nm)

UV light; visible light

up to about 56O up to about 5JO up to about 550 up to about 550 400 to 480 400 to 500 400 to 600

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For example, the following substances are suitable Sensitizers are which sensitize in a range up to about 400 η m and therefore only in the ultraviolet range the following can be used: Benzophenoni Acetophenone; 1,5-diphenyl-1,3,5-pentantrione; Ninhydrin; ^, ^ '- Dibromobenzophenone and 1,8-diehloranthraquinone.

In the image-generating compositions or masses, the proportions of the image-providing material and the matrix and the sensitizer - if one is also used - are variable. Generally speaking, in any case, with the exception of the use of an organic solvent, if this is provided, in which films with a dry feel are to be produced, which embody the particularly preferred embodiment of the present invention, the matrix material, which is a normally solid material, ie a material which is solid at room temperature, is - at least in most cases - used in amounts which are in excess of each of the other materials and which are also broadly expressed in a predominant amount, ie in an amount of more than 50 wt .- ^ are present in an amount up to 90% by weight , preferably about 70% by weight, of the total of the materials which are present in the imaging composition. The image-providing material, namely tellurium tetrahalide, also a normally solid material, is usually the next largest constituent and normally makes up about 7 to about 30% by weight , usually about 15 to 20% by weight , of the image-providing composition the end. The sensitizer, which is usually a solid but can also be a liquid at room temperature, is typically used in lesser amounts, commonly on the order of

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about 5 to 20 wt .- ^, usually about 6 to 15 wt .- ^, in relation to the image-providing mass, although the quantities of the same are in certain cases considerably higher can be and the amount of image-providing material can approximate or even exceed them somewhat.

In the manufacture of the films or the thin layers of the image-forming material combinations, in general generated in the form of solutions or homogeneous dispersions and then applied to or on a substrate are deposited, it is particularly advisable to dissolve the ingredients in an organic solvent or to disperse them homogeneously therein. Examples of suitable solvents are dimethylformamide (DMF), chloroform, tetrahydrofuran (THF), dimethylacetamide (DMA), dioxane and ethylene dichloride or compatible mixtures of such organic solvents with other organic solvents. After this the solution or homogeneous dispersion coated on a substrate in any convenient manner as a film has been, the organic solvent or solvents are evaporated, preferably at a relatively low temperature and - like it Occasionally it may be desirable - under subatmospheric pressure or in a vacuum until the film or the The coating is essentially dry to the touch, and such dry touch coatings are particularly desirable for handling and processing purposes. Film thicknesses are variable, but are usually in the range of about 1 to about 55 / U, with the range from 5 to about ' 15 / U is a good average. The manufacture of the

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imaging material compositions, coating and the handling and processing operations are to the extent necessary under the appropriate Lighting conditions carried out *

In those cases in which the approach of the wet process is followed, in which case, as already mentioned, all that is required is to dissolve the tellurium tetrahalide in an organic solvent and use the solution to bring suitable substrate into contact or to impregnate it with it and then preferably if necessary To evaporate only part of the organic solvent, the solvents used should be compatible with the tellurium tetrahalide. The solvents mentioned play a crucial role in relation on the intensity of the image obtained. To illustrate this, it should be mentioned that solvents such as diethyl ether, Tetrahydrofuran (THF) and bis (raethoxyethyl) ether Provide images of high intensity, whereas images of lower intensity when using Solvents such as tetrahydrofurfuryl alcohol, pinacolone, Methyl ethyl ketone, acetone, acetophenone, benzene, ethylene glycol, butyl acetate, methyl isobutyl ketone and anisole are formed. On the other hand, the use of incompatible solvents has the consequence that no images or im essentially no images are produced, and some cause the tellurium tetrahalide to precipitate, and as Examples of such incompatible solvents are pyridine, aniline * Ν, Ν-dimethylaniline, phenyl ether, -W - iiMfliyi fm iiiilllllii. Ethylenediamine, tributylamine, diethylamine and dimethyl phthalate. The compatibility of a specific solvent can easily be determined by simple preliminary searches.

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It should also be mentioned that all tellurium tetrahalides are not usable with the same effectiveness and they can work with different effectiveness, what depends on whether it is used for the wet process method or for the production of a film that is dry to the touch Using a matrix and a sensitizer can be used. For example, TeBr ^ has no value, when used for the wet process method, however, gives satisfactory results in the field of self dry touch film.

In practical use of the films or layers of the present invention, they are, for example, replaced by a suitable one or exposed the desired mask to the imaging energy, for example by exposure to ultraviolet or visible light, depending on the specific imaging material used and the sensitizer, in order to create a latent image that is normally not visible to the naked eye, provided that excessive light energy is not used. In a case such as that in Example E explained below, in which the exposure is carried out with a xenon lamp, that applied to the film surface Energy density in the general range of

(T £ p

3 χ ICK to 10 ergs / cm of film. The subsequent development - if one is carried out to develop the image - is recommended to be carried out by exposure to heat for several seconds, for example 3 to 15 or 20 seconds, for example at a temperature of about 10 to 160 ° C., preferably about 150 ⁰ C. Such a thermal development can be achieved by means of various

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Means are accomplished, for example with help a hot plate, hot mineral oil or an infrared lamp. The result is the creation of a dark image, e.g. from an O.D. of 1, only in the exposed area, while the background usually remains clear.

In the imaging and development stages, only a very small percentage of the imaging material present in the matrix composition to metallic Tellurium reduced. After developing, in the case of the production of dry-to-the-touch films, under Using a matrix and a sensitizer, the film or the layer is subjected to a fixing step which is necessary for this serves to effect the removal of the sensitizer and inactivate the unreacted imaging compound. While this can be done in a number of ways, a particularly effective procedure is to use the film in a chloroform / toluene solution (volume ratio 20 j 80), which is saturated with organic amines. This will remove the sensitizer and that Imaging material is inactivated, so that no image is formed on subsequent exposure and heating and so the film is stabilized. As examples of organic amines that can be used are i.a. to mention trimethylamine, triethylamine, diethylamine, triisopropylamine, Aniline and benzylamine (e.g. as 10 # solutions in various solvents, as described above are listed).

The following examples are intended to demonstrate the production of films or layers according to the teaching of the present invention explain. They are in no way intended to reduce the

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Limit the invention, as numerous other films or layers can also be used if the basic principle of the invention is followed and application of the teaching disclosed here can be produced.

Example A. Making a wet film

0.1 g of TeCl ₁ are dissolved in 5 ml of tetrahydrofuran in order to obtain a pale yellow, clear, homogeneous solution. The solution is applied to an inert substrate, for example paper, fabric, wood or the like; Then, while the film is still wet, it is irradiated with ultraviolet light through a mask. An image is immediately generated in the exposed area without further treatment, said image consisting of tellurium particles. The X-ray analysis shows that the resulting black image consists of metallic tellurium, not TeCIp. The intensity of the image varies with the degree of evaporation of the tetrahydrofuran solvent, in the sense that as evaporation of said solvent increases, there is a decrease in intensity.

Example B.

50 mg TeCl ₄ , 250 mg polyvinyl formal ("FORMVAR" 15/95 E), · 20 ng o-naphthoquinone and J> ml DMF are stirred together at room temperature until a homogeneous, yellow, viscous solution is formed. It is then poured onto a sheet of "MYLAR" 76.2 101.6 mm (3 " χ k ⁿ ) to form a film or layer approximately 10 / U thick and then in one Drying cabinet, for example

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50 to 45 minutes warmed to 50 ° C, after which time the film or the layer is dry to the touch.

Example C

The working method described in Example B is followed, with the modification that chloroform is used instead of DMF. The film is dried in a well-ventilated hood for 30 minutes at room temperature to form a film that has a dry feel.

Example D

The working method of Example B is followed with the modification ^ that a mixture is used instead of DMF obtained from DMF and chloroform in a volume ratio of 20-180. It will be dry to the touch Film received.

Example E.

50 mg TeCl ₂ Br ₂ , 250 mg polyvinyl formal ("FORMVAR" 15/95 E), 20 mg 9-10 phenanthrenequinone and 3 ml DMF are stirred together at room temperature until a homogeneous, viscous solution has formed. This is then cast onto a sheet of "MYLAR" and dried as described in Example B to form a clear, dry feeling film.

Example F

50 mg TeBr ^, 25O mg polyvinyl formal ("FORMVAR" 15/95 E), 20 mg of 9 * 10-phenanthrenequinone and 3 ml of DMF are mixed with one another mixed and then applied to "MYLAR" and

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heated to form a clear, dry feeling film in the manner described in Example B.

Example G

50 mg TeCl ^, 200 mg eyanethylated starch, 16 mg 4,5,9,10-pyrenequinone and 2.8 ml IMIF are mixed together at room temperature Stirred until a homogeneous, viscous solution is obtained. This is then put on a sheet of "MYLAR" 76.2 χ 101.6 mm (3 "χ 4") format to form a film or layer approximately 10 / rev thick form, and the whole thing will then take about 30 to 45 minutes heated in a drying cabinet to 50 ° C, after which Time the film or the layer is dry to the touch.

Example H

50 mg TeCl ^, 250 mg polyvinyl formal ("FORMVAR" 15/95 E), 20 mg 4,5-pyrenequinone and 3 ml DMF are stirred together at room temperature until a homogeneous, yellow, viscous solution is formed. This is then poured onto a sheet of "MYLAR" of the format 76.2 χ 101.6 mm (3 "χ 4") to form a yellow, clear film or layer with a thickness of about 10 / U, ^{and the whole thing is then heated to 50 °} C. in a drying cabinet for about 30 to 45 minutes, after which «
Layer dry to the touch.

heated to 50 ⁰ C, after which time the film or the

The invention will now be further explained with reference to the accompanying drawings, which have the following meanings:

Figure 1 shows a schematic partial cross section an initial structure of the invention, which consists of a layer which is an image-providing material of the

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proposed type according to the invention, in particular TeCl ^,
contains and selectively through the cutout of a mask
exposed to the imaging energy.

FIG. 2 shows a partial cross-section analogous to FIG again, that through the selective action of the image-generating Illustrates energy formed image.

FIG. 5 shows a cross section analogous to FIG. 2, in which the mask is removed and development energy is on
the structure is brought into action.

Figure 4 is a cross-section similar to Figure 1, showing the structure now fully developed.

Figure 5 is a schematic representation of a photomicrograph showing, at 2000 times magnification, a portion
illustrates an area containing a deposit of a crystalline imager.

As far as the drawing is concerned in detail, the structure shown in FIG. 1 consists of a substrate 12, for example glass, on which a thin, translucent
Layer 14 is deposited, consisting of a matrix
a vitreous amorphous material, such as polyvinyl formal or cyanoethylated starch, and contains TeCIh as an image-providing material and 9,10-phenanthrenequinone as a sensitizer distributed therein. An image mask 16, which consists of light-impermeable opaque surfaces 18 and the light-permeable surface 20, is placed on the layer 14 of the structure. The electromagnetic radiation falls through the transparent surface 20 of the mask
on the part of the layer 14 which lies under the surface 20 of the mask. The electromagnetic radiation is in shape

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brought into effect a short pulse radiation. In Figure 2, the structure of Figure 1 is shown in the state, in which it is present after the end of the exposure to electromagnetic radiation. In the Sohicht the presence of the latent image 24 is indicated by the small wavy lines, albeit this latent image is not necessarily visible to the eye.

In FIG. 3, the structure of FIG. 2 is shown with the latent image 24 in the middle section of the layer 14. The mask 16 is removed. The resultant structure is shown suspended above the radiant heat source 26, for example, an electrical heating element may be, whose temperature is such of 130, adjusted to 150 ⁰ C to the desired range, eg. It is illustrated how the radiant heat energy 28 penetrates the substrate 12 to heat the layer 14. As the layer 14 is heated, a chemical reaction occurs in the area containing the latent image 24, by which the tellurium in the aforementioned image-providing material is released from its bonds and is deposited in the layer 14 in elemental form. The tellurium is present in the surface part corresponding to the latent image 24 in the layer 14 in the form of crystals of extremely small size. How the structure looks after completion of the heating stage is shown in FIG. 4, the structure having an opaque section 30 in the middle, where the electromagnetic radiation strikes the layer 14, and one for the electromagnetic radiation. Has radiation-permeable section J2, which corresponds to the areas l8 of the mask l6 (Figure 1).

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If the substrate 12 is translucent or transparent, such as glass, when viewed through the structure, the surface 30 appears as dark or essentially non-translucent, whereas the surfaces 32 are highly translucent. Such a structure therefore represents a transparent image.

The substrate 12 is a non-transparent, but highly reflective material, such as white paper, and is the layer 14 according to its basic nature when viewed translucent, the surface 32 appears white and thus shows the reflectivity of the paper, whereas the surface 30 does not reflect and when it is reflective Look at dark or black looks.

The dividing line 34 in the structure of FIG. 4 has been photographed at a magnification of 2000 times. The appearance of the microphotograph obtained in this way is shown schematically in FIG. The dividing line between the transparent and opaque surfaces is shown by the arrow at 34. No or only a few larger crystals 35 of tellurium appear on the left in the translucent surface 32, whereas clouds of tiny particles 36 can be observed on the right. The particles 36 shown in area 30 of FIG. 5 form only a few layers on which the microscope is focused. By visual inspection under a microscope one can determine that the crystal particles of tellurium dispersed in the layer 14 are _p which produce the opacity of the surface thirtieth

In the example shown in Figure 5, the Tellurium particles, which represent the image-former in the area 30, have an average diameter of approximately 0.2 microns. It particularly deserves

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to be raised that the image-forming particles one have a very narrow particle size distribution. Essentially all of the image-forming particles are the same Size. This is an extremely favorable characteristic of the imaging material of the present invention, as it enables the production of high quality images of uniform properties. she also enables a well-balanced gray scale to be produced. The above particle size of the image former is of course only to be understood as an example. By varying the composition of the image-providing Material in the vitreous matrix material and / or by modifying the amount of sensitizer and by Adjustment of the image formation and development conditions, such as the intensity and duration of exposure to the image-generating energy and the intensity and duration of the development energy, the particle size of the image-former can be be regulated. Depending on the intended use of the picture, extremely small grain sizes, e.g. in the order of 1/10 micron or less, or even larger grain sizes, e.g. of about 1 micron or above to 10 microns or more. Depending on the underlying mechanism, in In certain cases, with increasing grain size, the relative density and contrast increase, but the resolution potential of the system is reduced. In other cases increase larger grain sizes, even if they leave everything else the same, the photographic amplification and the photographic Acceleration of the system. The choice of the particular one to be used in accordance with the teachings of the present invention Image-providing material, which has a variable previous reactivity, enables the creation of a new one

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photographic system that, in terms of resolution, sensitivity in ordinary light of the Environment, photographic sensitivity, speed of development and accessibility to the image fills various gaps in demand for which the photographic systems currently in use or useful be recycled.

Even if the image-providing materials are used for the Production of the image-providing film used, generally have a crystalline character, so the unused fresh film seems like it is a dry-to-the-touch film that is also used a matrix and a sensitizer is applied to the substrate prior to initiating the imaging step to be generally or usually non-crystalline, at least as shown by the examination the X-ray diffraction spectrum can be determined. After the film is exposed to the imaging energy has been, the imaging material apparently decomposes with the release of metallic tellurium. After The metallic tellurium as such seems to remain behind in the development stage, although the particle size and -form due to nucleation and probably other forces cause modifications, their exact nature and exact character cannot yet be precisely described. The particle size and the nature of the metallic Tellurium are manifested by circumstances such as the thickness of the film providing the image, the character and the viscosity the matrix and the temperature at which the development is carried out and which at the same time also affect the Color of the finished picture acts, influences.

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Depending on the desired result in the particular system that is being used, the thickness of layer 14 (Figure l) can be varied within wide limits in the structure according to the invention, as already mentioned above. The layer, which contains the imaging material can be as thin as 1000 Angstrom units or less, and it can also be 1 mm or more thick. Layer thicknesses are used to create transparent images or reflective copies from about 20 microns down to 0.2 microns typically extremely beneficial. The recommended in each case The thickness of the layer depends on factors such as the concentration of the imaging material in the matrix, the Size of the particles of the image generator, the desired maximum density, the desired reflection differential or transparency differential, and numerous other factors. In any system can be based on the consideration of these factors, the technically most favorable layer thickness can easily be determined. For other uses, such as information recording in data processing devices, or for special purposes, such as electrostatic printing, the layers of image-providing material may be thicker or thinner than indicated above. The formation of the germs and the preferred image-forming crystallites are influenced to some extent by the thickness of the film. Obviously, surface effects and interfacial effects in the nucleation reaction and in the Reaction leading to the small image-forming crystallites should be considered. So it must be with the Determination of the technically most advantageous film thickness of the image-providing layer takes into account all of the factors mentioned will.

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Similar considerations apply to the choice of concentration of the imaging material in the matrix material. In general, it is recommended to use the imaging material to be used in as high a concentration as possible. The matrix material acts as a binder to cause the imaging material to adhere to the substrate and to give durability in use and wear resistance to the finished images. Usually is it is desirable that the imaging material - of whatever kind it is as such - in the imaging material Layer exists in a non-crystalline form. This can be done by the mass a sufficient amount of a plasticizer or solvent that a polymer for the image-providing Material can be clogging. It is advantageous if the matrix material, in particular the material of a vitreous, amorphous character, also as a plasticizer or loser for the image-providing material. The matrix material is said to be compatible with the imaging material be miscible and it is particularly desirable that it actually dissolve the imaging material. This compatibility these two materials generally contribute to the sensitivity of a given system and provides better images or better contrasts and higher densities. In fact, the degree of tolerance of the vitreous matrix material and the image-providing material that are used, in each case as means to regulate the size of the separated particles of the image-maker - represented by the released tellurium - be used effectively.

Another significant fact that is worth considering is the relationship between the glass transition temperature

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the matrix material and the temperature at which the cleavage of the molecule of the imaging material used in each case takes place under the particular reaction conditions and in their respective surroundings. if for example, the molecule · of the imaging material to decompose or split at a temperature which is much lower than that of the film, secondary reactions can take place locally, which inactivate all or part of the cleavage products of the image-providing material, thus resulting in the Degrades the effectiveness of the particular imaging system. In certain systems it may be desirable that the cleavage of the image-providing material is initiated at a temperature much lower than that Glass temperature of the matrix material is so that initially Secondary reactions are facilitated by the supply of heat for the purpose of releasing the metallic tellurium. If the glass transition temperature is reached during the development stage, the secondary reaction product migrates the nucleation sites and supplies the atoms of the metallic tellurium for the construction of the particles of the image-forming agents. Thus, by carefully adjusting these factors, better imaging performance can be achieved. Further factors are, of course, the ability of the matrix material to absorb the fission products, which after the release of the atoms of the metallic tellurium and the direction of an equilibrium of the reaction favor or not favor the metallic tellurium. In general, polar amorphous Matrix materials such as polyvinyl formal or organoethylated Strength to meet these requirements in an excellent manner. By varying the amount of free polar groups and by introducing changing amounts of substances

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tuenten in the polar groups and by modifying the nature of the substituents can change the physical properties of the polar matrix material can be varied to a large extent in order to combine it with the image-providing material To make material extremely useful.

As mentioned above, according to the present invention, an image providing material is proposed as proposed herein Type - dissolved or dispersed in an amorphous film in association with a sensitizer - in converted to an image formed by microcrystalline particles of metallic tellurium. In the grainless one amorphous film is triggered in the surface areas on which the light strikes, nucleation, and the nuclei can be further developed to form a crystalline phase. This fact makes it possible for various To apply reading methods that highlight the differences in reflectivity, transparency, Take advantage of opacity, electrical properties, ability to hold electrical charges, etc.

One of the advantages is that the light acts as a heterogeneous nucleating agent, which is important has that background conversions are minimal and that a large number of Nucleation sites generated as desired in response to the light energy in the exposed parts of the surface while there are few germs in the unexposed Surfaces are formed.

For those image generation purposes in which a transparency is to be created or in which the image is used as a

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If the reflection image is to be recognizable, it is sometimes recommended that both the matrix of the amorphous material as well as the image-providing material is transparent or at least translucent and only a weak one or has no color at all. On the other hand, it may be desirable to use the layer of image-providing material with some color to favor the absorption of the energy of a certain wavelength. Accordingly, the sensitizers used can be selected to meet the requirements contribute to the wishes mentioned. So they can be of a type that is colored or of a type that is colored decomposes to form colorless and transparent or translucent decomposition products.

As for the substrates mentioned above, some of which are exemplified, so it should be noted that the substrate may be made of any material capable of film or to form a plate provided that it has a melting point or a softening point which is higher than the temperature used in the development stage for the development of the latent image must be, and further provided that he lacks sufficient responsiveness that it does not interfere with the imaging reaction. Suitable substrates include glass, mica, polyamides, Polyesters, polystyrenes, cured condensation polymers, for example of the epoxy type and the like. There are numerous heat-resistant polymers available on the market, which meet these requirements.

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in the manner described, which for this reason are in the imaging formations of the present invention are excellently useful. For the most technical Applications of the. imaging materials of the invention it is desirable that the substrate be flexible and so the use of the image-providing material in the form of endless Roles in printing and reading devices is made possible. Should transparencies in a certain imaging system are generated, it is of course desirable that the substrate be transparent. Should on the other hand, copies are made which are read by viewing in reflected light, then it is recommended to use a substrate that has high reflectivity, such as containing filler white or colored cardboard and other similar materials.

In, in some cases, the substrate can be omitted if desired and the layer 14 can be used as a self-supporting structure on which the image is then generated and is developed, for example, it can be placed on a temporary support base. In this case The matrix material can serve as a film former and can also be film-forming and self-supporting with a view to this Properties are selected, and the finished image structure then consists only of a thin film the amorphous, vitreous matrix material incorporating therein the image-providing material and the sensitizer as well as the image-maker precipitated from it and converted into it.

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As mentioned above, a variety of forms of energy can be used as a supplier of the image-generating energy and the Developmental energy can be used. These include electromagnetic radiation, heat, electrons, the electric current etc. Which of these forms of energy is used, depends in certain cases on whether there is a separate image generation stage and a separate Development stage used or whether both stages are carried out at the same time, - the preferred one in question Energy also depends on whether one uses the negative or positive work system described above. Will if a separate imaging step is performed, then preferably electromagnetic radiation is used for this stage, although other forms of energy are also used Can find application. The radiating electromagnetic radiation is usually best suited to to form an image by projection or by applying a mask and the like. It is also in general best suited to create an image of desired grayscale or tonal gradation. Which type of electromagnetic radiation or some other radiation energy and of which wavelengths one is in a particular case depends on the task to be solved and the particular sensitivity of the supplying material. Numerous imaging materials made in accordance with the present invention are sensitive to actinic radiation including laser energy and the like. If a given, selected image-providing material its optimal sensitivity does not have a wavelength of electromagnetic radiation that is used for image generation or is

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28- 24A6108

can be added, then appropriately selected sensitizers are added, in order to shift the sensitivity into the desired range for x-rays etc. Similar considerations apply to the energy used in the developmental stage. Highly recommended and it is also advantageous to land ^ for the development of thermal energy ,, This may be radiant heat _fl eg, infrared radiation or microwaves or hot air or heat supplied through contact and convection from a heated body. The application of heat to the development offers the advantage that the heat can be easily regulated, ims the intensity and the duration terms. Heat is also readily available at a low cost from a non-costly source. That it is accessible, however, this form of energy Gewünsehtenfalls, any other energy sources can be applied to _fl bewerkstelllgen dieEntwicklung to the exposed image-providing material provided *.

In each of the imaging and development stages a combination of different forms of energy can also be used. This also applies in particular to the case in which the image formation and the development are carried out at the same time. In this case it is recommended to use a Combination of the most effective energy in terms of image generation with the most effective energy in terms of development

apply energy. The heat for development can also be supplied by the heat generated during absorption the electromagnetic radiation is generated, as in the case of laser radiation. A combination of electromagnetic Radiation and heat is also from sources such as strong incandescent lamps, infrared lamps, laser beams, electronic or bulb photo flash units, mercury vapor quartz lamps. These and others Sources can also be used to advantage for image generation alone, if the development, for example is carried out in a separate heat treatment stage. .

The energy can be applied for different times, depending on the intensity of the used Depends on the energy source. With high-energy image generation energy sources are pulses of 1 microsecond or even shorter duration up to a few milliseconds or more usually sufficient to complete the imaging. With energy sources of lower intensity Longer times, such as those from fractions of a second to several seconds, can be used. Depending on the intended use of the pictures and depending on whether an insensitivity to the If daylight is desired or not, one will choose one or the other image-providing material and the image generation time and the intensity and type of imaging energy meet the requirements placed on the selected Image-providing material are provided, adjust accordingly.

The duration of the development also depends in a certain amount Degree of the intensity of the action

/ 1 0 4 p

Development energy, although in this case there is usually a threshold energy which is exceeded must become. This threshold value is one of intensity - temperature in the case of thermal energy and must be exceeded in order to bring about the development. If this requirement is observed, the development in 1 second or in a few seconds or in a slightly longer time, e.g. in 15 to 20 seconds, ends what of the way in which one brings the energy to act and of the nature of the material providing the picture as well as the matrix material used. Likewise, the thickness of the layer of the Image-providing material and the thickness of the substrate may affect the time required for development. In however, in all cases development is rapid, so the imaging materials and method of the Invention to make the finished stable image quickly accessible.

For example, depending on the composition of the image-providing material, it may be desirable to carry out development at a predetermined temperature. As already mentioned, the development temperature should be regulated to a range above the threshold value in which the reactions that lead to the formation of the image former, namely the deposition of the metallic tellurium, take place. On the other hand, the temperature should not be so high that a thermlsch _s induced nucleation, and a reaction is triggered in the surface parts, which the imaging energy have not been exposed. Usually the range between these two temperature limits is quite large, and the temperature

temperature can easily be adjusted to fit in the suitable area in between falls. If these conditions are taken into account, a picture of high contrast with essentially no nucleation in the background.

It is noteworthy that the latent image formed in the image forming step is generally is completely durable and stable. It is usually not decomposed, even if the material which is the latent Image is stored for a considerable length of time, e.g., a day or so. The development through Heat after prolonged storage of the imaged material provides a strong image Contrast with no apparent evidence of latent image degradation.

After development, where fixing is necessary or desired, fixing can be used , for example by wiping, brushing or dipping, etc. in the manner described above. The imaging systems of the present invention make such a permanent picture in a short time, usually in a few or several seconds, of the time of the image generation, accessible.

The imaging material can be constructed to provide an image or record of the desired information through the one-time effect of the energy, e.g. a combination of light and heat or any other desired effective energy, forms. However, as noted above, it is generally recommended

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it is worthwhile that the energy be applied in two stages is brought, wherein the imaging energy is applied in a first stage to the layer that contains the image-providing material for the purpose of forming a latent image therein. The chemical conversion, which produces the material of a different chemical composition or character, is then brought about in a subsequent separate stage, which is the development stage. In the image generation stage - as has already been explained in general above - radiation energy, such as infrared radiation, visible light, ultraviolet radiation, X-rays or gamma rays or particle radiation or electron beams, image-wise brought into action; and in the development stage then heat or some other electrical energy that effectively induces development can be applied will. Since a latent image is formed in the image forming step, the energy is needed in the developing step can not be brought into action according to the image, but can extend over the entire layer. The development stage can in certain cases also fulfill the function of the fixation stage, provided that this is the case is desired or required.

The image-providing material can in itself be sensitive to the radiant energy used for the purpose of Imaging is brought into action. In this case, the imaging p-energy may be in the form of a photon, for example generate a free radical or cause an electron deficiency in the image-providing material, so as to carrier

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to create frozen or trapped intestines and form the latent image. In the later stage of development, the molecules become mobile, for example by the fact that the surrounding matrix becomes plastic or rubbery and allows them to to move near the carrier. The carriers can be released from the confinement by the developmental energy will. The wearers thereby initiate a secondary reaction that creates the real image like it is explained in more detail below.

It has been found in accordance with the present invention, and it has already been mentioned in a very general manner above, that through the formation of a developable latent image the imaging energy is greatly promoted in that the image-providing material is a matrix of a glass-like, amorphous material is incorporated, which has a glass temperatur. One can assume that the photons involved in the imaging radiation energy are contained, are absorbed by the image-providing material if this is opposite to the specific Radiation that is exposed to it is sensitive. The material providing the picture or a certain part that which absorbs a photon is activated and remains so, presumably because it is that it is embedded in a vitreous amorphous material has become immobile, or a reactive intermediate is not deactivated. If the glassy, amorphous material later in a development stage to a temperature which is above the glass transition temperature is heated, the activated molecules (or the activated atoms or carriers) are put into the state,

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to hike. This initiates secondary reactions that affect the real image or recording of information.

In summary, in the case of a dry touch film in which a matrix material and a sensitizer are used, an imaging material of the type described above is exposed to the imaging energy to form what is known as a latent image and the originally precipitated metallic tellurium is then precipitated further or its character modified in the areas in which the image was created, namely in a development stage in which, for example, heat is brought into action as development energy will. If development energy, for example heat at a temperature below the thermal decomposition temperature of the original image-forming compound, is applied, the reaction does not take place in those areas which have not received the image-forming energy, even if the heat for the Development is not caused to act on the layer in its entirety in accordance with the image. If development energy, for example heat, is brought into action at a temperature above the thermal decomposition temperature of the original image-providing compound, the image-providing compound decomposes and the metallic tellurium is also released in the unexposed parts of the surface. In general, however, it seems that the metallic tellurium crystals precipitated in the unexposed planar portions are fewer and larger than the crystals precipitated in the exposed planar portions, so that an image of excellent contrast is formed .

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In the reaction mechanisms under discussion here, the generation of the metallic tellurium can act as an image generator in the surface parts which the imaging energy have received, can be increased by the fact that an acceptor is also used .. The matrix of the glass-like Amorphous material seems to serve as an acceptor and it works in such a way that it can precipitate the metallic Brings Tellurium to its full completion.

As mentioned above, in the non-exposed or non-image surface parts, no or only very few carriers are formed or are present. Given very few nuclei are formed from this fact. These can grow into crystals of sizable size, because there is no competition from nearby nucleation sites. It was found that these few Crystals present in the surface portions which have not been exposed to the imaging energy were, despite their relatively large size, microscopic and far apart are present so that they do not affect the transparency or reflection of these surfaces. About that In addition, careful handling of the image-providing material from the beginning of its manufacture through to image formation and by effectively keeping the carrier-forming energy of harmful intensity away from the material, before it is exposed to the image-forming energy until the time of development, the number of these crystals can be further reduced in the non-image areas.

It has been observed that the image-providing material is capable of undergoing conversion to form metallic Tellurium only through the use of developmental energy,

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like heat, and without the material of a source of an image-generating Exposing, secreting or releasing energy. In general, in order to effect this reaction, brought into action such an amount of developmental energy which is greater than that which is required to accomplish the above-described, selective, imagewise development of the layer. Preferably becomes the intensity - such as the temperature of the developmental energy that is used to bring about this Reaction required to be chosen higher than that required in the development stage to develop an irradiated Layer is applied where the development mainly occurs in the parts of the surface which produce the image Received energy is desired. The uniform development of the layer just described of the imaging material is possible in particular in those cases in which the imaging material is in a vitreous matrix is embedded, which softens above the glass transition temperature and thereby the molecules , provides mobility for the image-providing material and thus the migration of the molecules to the germs for the Precipitation of the released metallic tellurium makes possible in the manner described above.

The phenomenon just described is based on the phenomenon that radicals or other reactive intermediates or Carriers are formed thermally above a certain threshold of energy intensity, for example above a certain temperature in the case where heat is used as developmental energy and that for the image-forming energy Material is characteristic. This phenomenon and the threshold nature of the response may vary according to the Teaching of the method according to the invention can be used for image generation purposes.

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For the sake of explanation and in view of what has been said above, it should be emphasized again that when an image-generating Material structure, such as that of Example A, is used in practice and this is left somewhat moist and then subjecting it to the imaging energy of ultraviolet light, an image in a single stage and no separate development stage is required. In this case, it is caused by the ultraviolet light The energy emitted does indeed develop at the same time as the image is generated, although the length of time in which the Material exposed to ultraviolet light is very short.

The foregoing discussion of the "present invention" shows that it is an excellent imaging system makes it available that is widely used technically for a variety of imaging tasks can be. The materials according to the invention can be used in the camera for testing purposes and for duplicating images, making duplicate copies of micro-recordings and other micro-images (microfiche), for recording the output information of one computer and the output data of others Data storage and access systems. The broad utility of the new imaging system the invention relies on quick and convenient access to permanent copies of the information the recording or the image. The recordings and images are sharp and have excellent resolution. The materials used in practicing the invention can be of a very low level of contrast can be varied up to a very high degree of contrast, as required and desired in each individual case.

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In this regard, the new imaging system has, generally speaking, the versatility of the fixed Consistent silver halide systems, which by appropriate selection of the emulsions and development conditions also enable a wide variability of the degrees of contrast. However, this requires the present The image forming system peculiar to the invention, and also the developing system, as easy from the above none of the conventional wet treatments, and it opens up quick access to it produce a stable image, which in many cases is not the case with silver halide images. Through this The new system proves itself particularly in these cases with the permanent silver halide systems than superior.

The various other imaging systems that or have recently been suggested with the indication that they are not a wet treatment require, are usually associated with the disadvantage that they rely on the use of a single photosensitive Material and with them there is only a very limited possibility of changing the character of the material to modify, for example to vary the degree of contrast of the image. You may therefore like for a particular one Intended use, but are not suitable for any other uses. The materials, used in the imaging system of the present invention are broadly stated cheap, and they can be conveniently applied by cheap methods, so that with the invention a generally inexpensive image generation system is made available to experts.

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The present invention does not require vacuum deposition or sputter evaporation to deposit an elemental imager on a substrate. The image-providing material mixtures can easily be converted into In the form of a solution, for example, applied by brushing on, centrifugal or squeegee application and the like will. The images generated according to the teaching of the present invention can be used as an original or mother print be used when, for example, an imager has been used that has the ability to capture and for retaining electrical charges and thereby differs from the matrix material. In this In this case, the images can be generated on a paper or cardboard substrate, for example, in order to save money Receive an original disposable impression. After the desired number of copies have been made of it, will the original print simply discarded.

For an electrostatic copier system of this type, one can use an electrically conductive substrate, e.g. Use an aluminum foil or a sheet of paper or cardboard paper that is electrically conductive Layer is coated. A layer of the image-providing material is then applied to the conductive layer Embedding deposited in a dielectric matrix material, said image-providing material being a conductive, particulate image-forming agent is deposited. The dielectric matrix material is preferably made from one that can easily be volatilized or decomposed by the action of energy, e.g. heat. That Material is then subjected to the imaging process in the manner described above, e.g.

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2U6108

selected parts of the surface are exposed to the image-generating energy, such as electromagnetic radiation. Thereafter the image is developed, for example by subjecting the material to moderate heat, such as it is described above. The developed image made up of highly reflective surfaces of the dielectric matrix material with the aluminum foil as the back and made of opaque surfaces, which are separated by the conductive Particles of metallic tellurium are formed, thereafter the radiant heat energy, e.g. short duration and high intensity infrared radiation. The opaque, dark areas in which the tellurium metal is precipitated, absorb the heat, causing the tellurium metal to heat up and the surrounding matrix to the point where the matrix evaporates or otherwise passes through the heat is destroyed. As a result, the tellurium metal particles consolidate or flow together, in order to form a conductive surface with the electrically conductive layer underneath. In the , Areas in which no opaque particles have been deposited, the radiant heat is reflected and the dielectric matrix material is essentially not heated and thus remains intact. In this way a plate is obtained which has image-patterned surfaces made of a dielectric material, and in addition has surfaces which are electrically conductive and in conductive connection with the electrically conductive Stand underclass. If a charge is applied, for example by using a device that If a corona discharge is generated, static electrical charges will be generated in the areas that result from the Dielectric exist, and no charges are retained by the electrically conductive surfaces. The recorded

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The loaded plate is then treated in the usual way with a toner or a dry ink, which is then applied to paper transferred and fixed thereon to produce an impression. Many impressions can be made from one plate will. If an imprint is no longer required, it is simply discarded. That way there is no need to cleaning and removing the charge from a permanent drum, as is currently the case with the electrostatic impression process is carried out. As a result, the technical equipment for the Image generation and the production of prints are of a far simpler design and are manufactured much cheaper, than is the case with prior art devices.

The layer made up of planar parts with strong dielectric Properties and consists of surface parts with good electrical conductivity, can also be used in the image-generating Foil or plate are produced by using an image-forming material which is at the development reacts with the matrix material to form a highly conductive layer while in the Areas that have not been exposed, the layer remains non-conductive and its dielectric properties maintains. A plate produced in this way has the same good properties and can be used in can be used in the same manner as previously described.

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Claims (1)

Claims j 1. Process for the creation of accessible information records, characterized in that one starts from a layer which is an image-providing material in the form of a tellurium tetrahalide, in which at least one representative of the halogen atoms is selected from that of chlorine and bromine is selected, and said imaging material contains a detectable one Has characteristic and it is able to undergo a chemical transformation when responding to the action one energy producing a material of different chemical character, the other Has detectable characteristic, and one has the image-forming energy at least to a certain extent Part of said layer brings about the chemical transformation in said image-providing To bring about material in said certain part of said layer and thus said material of different chemical character and to record the desired information in said layer. 2. The method according to claim 1, characterized in that that said image-generating energy from a. electromagnetic radiation. J). A method according to claim 1, characterized in that a sensitizer is also incorporated into said layer for the purpose of modifying the sensitivity of said imaging material to a given imaging energy. 509813/1046 4. The method according to claim J, characterized in that that said image-providing material and the sensitizer in a polymer which is at least partially is amorphous in character, is dissolved or dispersed. 5. The method according to claim 4, characterized in that there stands. that said image-providing material made of TeCl ₂ , Process for generating an image, characterized in that one starts from a layer which has a image-providing material of the formula in which η is an integer from 2 to 4 and m is an integer from 0 to 2 with the Provided that the sum of η and m is equal to 4, one contains at least a certain part of the mentioned Layer for the purpose of decomposing the aforementioned image-providing material to form a latent image an image-generating energy to act and one then converts the said latent image into a developed one Image transferred through the action of a developmental energy. 7. The method according to claim 6, characterized in that said image-providing material consists of TeCl ₂ ^. 8. The method according to claim 7, characterized in that said layer for the purpose of modifying the Sensitivity of said imaging material 509813/1046 ORIGINAL BATHROOM as opposed to an image-generating energy, a sensitizer is also incorporated. 9. The method according to claim 8, characterized in that that said image-providing material and the sensitizer in a polymer which is at least partially is amorphous in character, is dissolved or dispersed. 10. The method according to claim 9 *, characterized in that that the imaging material is sensitive to visible light. 11. The method according to claim 9 *, characterized in that the image-providing material to ultraviolet light is sensitive. 12. The method according to claim 9, characterized in that the image-generating energy consists of electromagnetic Energy exists and warnings are brought into effect as developmental energy. 13. Process for the creation of accessible information records, characterized in that a layer in the form of a matrix of a vitreous, emanates from amorphous material, which has a glass transition temperature and a sensitizer and an image-providing Material contains which of the formula TeCl _n Br _1n corresponds, in which η is an integer from 2 to and m is an integer from 0 to 2 with the Provided that the sum of η and m is equal to 4, one on 509813/1046 BATH ORIGINAL brings at least a certain part of said layer to the action of electromagnetic energy a chemical transformation in said image-providing material in said certain part of those mentioned Bring about a layer and produce a material of different chemical character and so to record the desired information in said layer. 14. The method according to claim Ij5 *, characterized in that that the energy mentioned, which has been brought into action on the layer mentioned, creates a latent one Image is created and this latent image is then generated by exposure to heat at a temperature above the glass transition of said vitreous, amorphous material lying temperature is developed. 15. The method according to claim 14, characterized in that that the vitreous amorphous material consists of polyvinyl formal. 16. The method according to claim 15, characterized in that the image-providing material consists of TeCl ₂ . 17. Process for the creation of accessible information records, characterized by applying a solution of an image-providing material to a substrate applies in order to deposit a layer of said image-providing material on said substrate, where is the image-providing material of the formula TeCl _n Br _1n corresponds to, in which η is an integer from 2 to 509813/1046 ORIGINAL BATHROOM and m is an integer value from 0 to 2 with with the proviso that the sum of η and m is equal to 4, one thereafter, while said layer of said Solution is still moist, an image-generating electromagnetic energy on at least one certain part of the layer mentioned "brings about a" chemical transformation in the said layer to bring about image-providing material in said certain part of said layer and a material of different chemical character and thus the desired information in the mentioned Record shift. l8. Method according to claim 17, characterized in that the image-providing material consists of a group of substances consisting _{of TeCl ^ and TeCIgBr 2.} 19. Method according to claim 18, characterized in that ultraviolet light is used as electromagnetic energy is brought to action. 20. Process for generating accessible information records, characterized in that a matrix is deposited on eil substrate, which a contains image-providing material and a sensitizer, said matrix being composed of a polymer Consists of material that is at least partially amorphous and the aforementioned image-providing material consists of TeCl ^, one brings an image-generating energy to act on a part of the mentioned layer in order to achieve a 509813/1046 ORIGINAL BATHROOM To cause decomposition of said image-providing material and metallic tellurium and a latent one Generate image in those surface parts on which the aforementioned image-generating energy to act has been brought. 21. The method according to claim 20, characterized in that that heat is applied to the latent image to bring about the development of the same. 22. The method according to claim 21, characterized in that the sensitizer consists of phenanthrenequinone. 23. The method according to claim 1, characterized in that that radiation energy serves as image-generating energy, which at the same time with the development energy in the form of Heat is brought into action. 24. The method according to claim 1, characterized in that the image-generating energy consists of radiant energy and that after exposure to the imaging radiant energy, heat to induce the development is brought into effect. 25. The method according to claim 1, characterized in that the image-providing layer is the image-forming material in amorphous form and the said imaging material due to the energy in metallic Tellurium is transformed by crystalline structure. 26. To generate an accessible information record certain object, thereby 509813/1046 indicates that it consists of a layer of an image-providing material on a substrate, the said image-providing material in turn consists of a tellurium tetrahalide, in which the halide consists of at least one member of the group comprising chlorine and bromine and said image-providing Material has at least one detectable characteristic and it is capable of chemical conversion to respond to the action of an energy producing a material of various kinds chemical character which has another detectable characteristic. 27. The article according to claim 26, characterized in that the image-providing material consists of TeCl ^. 28. To generate an accessible information record specific and in the form of a dry itself gripping film or a dry touching layer of the present object, characterized in that, that it consists of a matrix containing an image-providing material and a sensitizer, said matrix in turn consisting of a polymeric material which is at least partially is amorphous, and said image-providing material consists of a tellurium tetrahalide in which the Halide consists of at least one member of the group comprising chlorine and bromine, furthermore that mentioned Imageable material has at least one detectable characteristic and it is capable of having one undergo chemical conversion when responding to 509813/1046 2U6108 the action of an energy producing a material of different chemical character, which has a different detectable characteristic. 29. The article according to claim 28, characterized in that the image-providing material consists of TeCl ^. JO. Article according to claim 29, characterized in that that the sensitizer consists of phenanthrenequinone. 509813/1046