DE2446108C2 - Recording material with a radiation-sensitive layer which contains tellurium halide, a sensitizer and a matrix material which is solid at room temperature - Google Patents

Description

TeCl _n Br _n ,

is provided, where / 7 = 2, 3 or 4, m = 0, 1 or 2 and π + m = 4.

2. Recording material according to claim 1, characterized in that a polymeric matrix material is used.

3. Recording material according to claim 1 or 2, characterized in that an at least partially polar amorphous matrix material is used.

4. Recording material according to one of the preceding claims, characterized in that a vitreous matrix material is used.

5. Recording material according to claim 4, characterized in that a vitreous material is used, the glass transition temperature of which is in the range between 50 and 200 ^c C.

6. Recording material according to claim 5, characterized in that a vitreous matrix material is used, the glass transition temperature of which is in the range between 80 and 120 ^° C.

7. Recording material according to claim 4 or 5, characterized in that a matrix material consists of of the following group is used:

Cyanoethylated starch, cellulose and amylose, which have a degree of cyanoethylation of Have> 2;

Polyvinylbenzophenone; Polyvinylidene chloride;

Polyethylene terephthalate; Polyvinyl carbazole;

Polyvinyl chloride; Polyvinyl methyl ketone;

Polyvinyl pyrrolidone; Polyvinyl methyl ether;

Hydroxypropyl cellulose;

Copolymers from

Polyvinyl methyl ether and maleic anhydride;

Polyvinyl formal resins.

8. Recording material according to claim 7, characterized in that polyvinyl formal with a Molecular weight between 24,000 and 40,000 and a formal content, as a percentage of the polyvinyl formal expressed, is used by about 82% as matrix material.

9. Recording material according to one of the preceding claims, characterized in that dielectric matrix material is used.

10. Recording material according to one of the preceding claims, characterized in that that amorphous tellurium tetrahalide is used.

11. Recording material according to one of the preceding Claims, characterized in that a sensitizer which responds to visible light is used.

12. Recording material according to one of claims 1-10, characterized in that a Sensitizer from the following group is used:

Benzophenone; Acetophenone;

1,5-diphenyl-1,3,5-pentantrione; ninhydrin;

4,4'-dibromobenzophenone and
1,8-dichloroanthraquinone.

13. Recording material according to claim 11, characterized characterized in that phenanthrenequinone is used as a sensitizer

14. Recording material according to one of the preceding claims, characterized in that that the tellurium tetrahalide and / or the sensitizer in the matrix material is largely homogeneous is dispersed.

15. Recording material according to one of the preceding claims, characterized in that that the tellurium tetrahalide and / or the sensitizer is dissolved in the matrix material.

16. Recording material according to one of the preceding Claims, characterized by the following proportions:

more than 50% by weight
7-30% by weight
5-20% by weight

Matrix material

Tellurium tetrahalide

Sensitizers.

17. Recording material according to one of the preceding Claims, characterized in that the layer thickness of the radiation-sensitive Layer is between 100 nm and 1 mm.

18. Use of a recording material according to one of the preceding claims for Recording of information with the proviso that electromagnetic radiation for irradiation serves.

19. Use of a recording material for the purpose stated in claim 18 with the proviso, that UV light is used for irradiation.

20. Use of a recording material for the purpose stated in claim 18 with the proviso, that thermal energy is used for development.

21. Use of a recording material for the purpose stated in claim 18 with the proviso, that the recording material is heated to a temperature for developing which is above the Glass transition temperature of the matrix material is.

22. Use of a recording material according to one of claims 1 to 17 for production of duplicates of microrecords.

23. Use of a recording material according to any one of claims 1-17 for recording of output information from data processing systems.

The invention relates to a recording material with a radiation-sensitive layer, the tellurium halide, contains a sensitizer and a matrix material which is solid at room temperature, as well as on uses of the recording material.

Such a recording material is already known (DE-OS 22 33 868). This is tellurium tetrachloride used as a starting material for the formation of an element-organic imaging material, tellurium has entered into a chemical bond with organic material such as acetophenone. Although such a thing Recording material is very advantageous compared to recording materials which are in the Course of the process of generating an image

Require wet process steps, the known recording material still lacks stability in some cases left to be desired, unless the production is relatively expensive.

In addition, a recording material is known (DE-OS 20 22 260) in which the radiation-sensitive Layer forms a tellurium-II-halide, which immediately applied to a substrate and exposed to visible light in the moistened state, whereupon the development of visible images takes place. The disadvantage of this known recording material is especially in the fact that, if no wet process is used, even after long exposure times practically none of the order of a minute without the initiation of special measures visible light developed. The use of the wet process; H. the use of liquid developers, however, in many cases it is undesirable and even dangerous.

The invention is based on the object of a recording material to improve the aforementioned genus in such a way that despite simple manufacture

can be scaled with low material costs on wet development processes can be dispensed with and good records can still be obtained in a justifiable short time, especially sharp images.

The invention is characterized in claim 1 and further developments are given in subclaims same claimed.

The present invention relates to a new imaging system in which such tellurium tetrahalogoni- ; de are used in which the halide at least is a member of the group consisting of chlorine and bromine, especially chlorine. These representatives of the imaging materials are made by the formula

TcCl "Br",

10

15th

20th

30th

35

, in which π is an integer from 2 to 4 and m is an integer from 0 to 2, with the proviso that the sum of η and m is 4. In the embodiments of the invention, the aforementioned imaging material is incorporated into a matrix material together with a sensitizer, as will be explained in detail below. The resulting combination of materials is then deformed into a thin film or layer which is capable of producing a latent image when exposed to imaging energy, e.g. B. is exposed to electromagnetic radiation. The resulting latent image can then easily be developed into an image of excellent contrast by exposure to a source of development energy, usually in the form of thermal energy.

Accordingly, the invention makes new means for generating records, e.g. B of pictures and Duplicates of existing images available based on a layer containing certain tellurium tetrahalides contains as image-providing materials which have a detectable characteristic and that of a former Conversion are capable when you click on the image drawing Energy that is brought to act upon them to address a material from a different one chemical nature or composition to produce which has another detectable characteristic According to the method, the imaging energy is applied to at least a certain part of the Material-containing layer brought into action to the chemical conversion in the image-providing To bring about material in the part of the layer exposed to the energy, the chemically converted Material has at least one detectable characteristic different from the characteristics of the image-providing Starting material is different, and this difference in the detectable characteristics either visually or detected by any suitable display or reading device can. The material that has a changed chemical nature or composition and different detectable Has characteristics that result in the image forming step is hereinafter sometimes referred to as Designated Image Formers.

As noted above, the imaging materials used in the practice of the present invention are comprised of tellurium tetrahalides such as TeCU, TeChBr? _{and TeCbBr, the known (DE-OS 22 33 868) TeCI 4,} which is known per se as a starting material for the production of element-organic compounds, is particularly well suited. These halides should be homogeneously dispersible in the matrix material, which is described in more detail below.

It is particularly advantageous to use the tellurium tetrachloride or another tellurium tetrahalide in the form of a to use dry film: it is incorporated into a matrix together with a sensitizer and then in the form of a dry-to-touch thin film, in particular on a substrate upset. In this form the material is exposed to the image-generating energy through a mask, to create an image or a latent image, which is then subjected to heat or development causing energy source is developed to win the finished image. The image-generating energy can ultraviolet light or visible light or one of the others, depending on the sensitizer used 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 already mentioned above, they should desirably be at least in part of amorphous character and it is especially desirable that they glassy, are amorphous materials having a Glasteinperatur that is not recommended to be above 200 ⁰ C and be down to 5O ⁰ C or - even better - should be between about 80 and 12O ⁰ C. As a rule, they are polymeric materials. Examples include: cyanoethylated starches, celluloses and amylose, which have a degree of cyanoethylation of>2;Polyvinylbenzophenone; Polyvinylidene chloride; Polyethylene terephthalate: polyvinyl carbazole; Polyvinyl chloride; Polyvinyl methyl ketone; Polyvinyl pyrrolidone; Polyvinyl methyl ether; Hydroxypropyl cellulose; Copolymers of polyvinyl methyl ether and maleic anhydride; various commercial grades of polyvinyl formal resins. Particularly useful is a polyvinyl formal resin which is a white, free-flowing powder having a molecular weight of 24,000 to 40,000 and a formal content, expressed as% polyvinyl formal resin, of approximately 82%. These resins and their manufacture belong to the state of the art.

The sensitizers required to be used in the practice of the invention for the purpose of creation useful for dry-to-the-touch films

can be selected from a large group of substances. They should be soluble or in the matrix material be homogeneously dispersible. Your selections for use in any particular image providing Composition is determined in part by the spectral sensitivity ranges that are desired. So are z. B. in the case of the in the ultraviolet (UV) light and in visible light sensitizing substances List of usable sensitizers listed below, their approximate sensitization range (nm) is given at the same time:

Sensitizer

spectral sensitivity range (nm)
UV light; visible light

o-naphthoquinone

4,5-pyrenquinone

4,5,9,10-pyrenequinone

9,10-phenanthrenequinone

Difurylglyoxal

1-phenyl-1,2-propanedione

U'-dibenzoyiferrocene

up to about 560
up to about 530
up to about 550
up to about 530
400 to 480
400 to 500
400 to 600

10

15th

20th

25th

The following substances are, for example, suitable sensitizers that operate in a range up to sensitize about 400 nm and can therefore only be used in the ultraviolet range: Benzophenone; Acetophenone; 1,5-diphenyl-1,3,5-pentantrione; Ninhydrin; 4,4'-dibromobenzophenone and 1,8-dichloroanthraquinone.

In the image-forming compositions of matter or masses, the proportions of the image-forming material Material and the matrix as well as the sensitizer are variable. Generally speaking, in any case, except when using an organic solvent, if this is provided in the dry touching films are to be produced, which are the particularly preferred embodiment of the present Invention embody the matrix material, which is a normally solid material, i. H. one at room temperature solid material, represents, - at least in most cases - used in amounts opposite each of the other materials are in excess and which are also in a predominant amount, i.e. H. in in an amount greater than 50% by weight, broadly in an amount up to 90% by weight, preferably about 70% by weight of the total of the materials present in the imaging composition. That Image-providing material, namely tellurium tetrahalide, also a normally solid material, is common the next largest ingredient and usually makes about 7 to about 30% by weight, typically about 15 to 20% by weight, of the image-providing composition. The sensitizer that is common for is a solid, but can also be a liquid at room temperature, will usually be in lower amounts Amounts used, commonly on the order of about 5 to 20 weight percent, typically about 6 up to 15% by weight, based on the mass of the image, although in certain cases the amounts of it can be considerably higher and the amounts of the image-providing material can approximate or even slightly exceed it.

In the production of the films or the thin layers of the image-providing material combinations, which are generally produced in the form of solutions or homogeneous dispersions and then onto a substrate applied or deposited on it, it is particularly advisable to combine the ingredients in one to dissolve organic solvents or to disperse them homogeneously therein. As examples of suitable Solvents must be listed dimethylformamide (DMF), chloroform, tetrahydrofuran (THF), dimethylacetamide (DMA), dioxane and ethylene dichloride or mutually compatible mixtures of such organic Solvents with other organic solvents. After the solution or the homogeneous Dispersion has been applied to a substrate in any convenient manner as a film the organic solvent or solvents are evaporated, preferably at a proportionate rate low temperature and - as may occasionally be desirable - sub-atmospheric Printing or in a vacuum until the film or coating is essentially dry to the touch, and such Coatings with a dry touch are particularly desirable for handling and processing purposes. The film thicknesses are variable, but are usually in the range from about 1 to about 35 μm, the range from 5 to about 15 μίτι a good average value is. The production of the imaging material compositions, the coating and the handling and Processing operations are classified as appropriate to the extent necessary Lighting conditions carried out.

In practical use of the films or layers according to the invention, these are e.g. B. exposed to the imaging energy through a suitable or desired mask, for example by irradiation with ultraviolet or visible light, depending on the specific imaging material used and the sensitizer, so as to produce a latent image which is normally not visible to the eye, unless excessive light energy is used. In a case, such as that explained in Example E below, in which the exposure is carried out with a xenon lamp, the energy density supplied to the film surface can be in the general range from 3 × ^{10 5} to 10 ⁶ erg / cm ^{2 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, e.g. B. at a temperature of about 130 to 160 ^° C., preferably about 150 ^° C. Such thermal development can be accomplished by various means, for example with the aid of a hot plate, hot mineral oil or an infrared lamp. The result is the creation of a dark image, e.g. B. from an OD 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 is used that is present in the matrix composition is reduced to metallic tellurium. After developing is in the case of forming dry-touch films using a matrix and a Sensibiiisators the film or the layer subjected to a fixing stage, which serves to remove the To effect sensitizer and inactivate the unreacted imaging compound. Although this can be done in a number of ways, a particularly effective procedure is to put the film in a chloroform / toluene solution (volume ratio

20:80), which is saturated with organic amines to wash. This removes the sensitizer and inactivates the imaging material no image is formed after exposure and heating, and so the film is stabilized. As examples of organic amines that can be used include. to mention trimethylamine, triethylamine, Diethylamine, triisopropylamine, aniline and benzylamine (e.g. as 10% solutions in various solvents, as listed above).

The following examples are intended to produce films or layers according to the teaching of the present invention Explain the invention. They are in no way intended to limit the scope of the invention, as are numerous other films or layers following the principles of the invention and applying those disclosed herein Teaching can be produced.

Example A.

50 mg TeCl ₄ , 250 mg polyvinyl formal, 20 mg o-naphthoquinone and 3 ml DMF are stirred together at room temperature until a homogeneous, yellow, viscous solution has formed. It is then χ on a polyethylene terephthalate film on the format 76,2 101,6 mm cast to form a film or a layer of a thickness of about 10 μηι and then in a drying cabinet for approximately 30 to 45 minutes at 5O ⁰ C heated, after which time the film or the layer feels dry.

Example B.

It is carried out according to the working method described in Example A. worked with the modification that chloroform is used instead of DMF. The movie will dried in a well-ventilated hood for 30 minutes at room temperature to get a dry touch Form film.

Example C

The working method of Example A is used with the modification that instead of DMF a mixture of DMF and chloroform in a volume ratio 20:80 is applied. A film with a dry feel is obtained.

Example D

50 mg TeCl ₂ Br ₂ , 250 mg polyvinyl formal. 20 mg of 9,10-phenanthrenequinone and 3 ml of DMF are stirred together at room temperature until a homogeneous, viscous solution has formed. This is then poured onto a sheet of polyethylene terephthalate and dried as described in Example B to form a clear, dry-touching film.

Example E.

50 mg TeCl ₄ , 200 mg cyanoethylated starch, 16 mg 4,5,9,10-pyrenquinone and 2.8 ml DMF are stirred together at room temperature until a homogeneous, viscous solution is formed cast from the format 76.2x101.6 mm to form a film or a layer with a thickness of about 10 μτη, and the whole thing is then ^{heated to 50 0} C in a drying cabinet for about 30 to 45 minutes, after which time the The film or the layer feels dry to the touch.

Example F

50 mg TeCl ₄ , 250 mg polyvinyl formal, 20 mg 4,5-pyrenquinone and 3 ml DMF are stirred together at room temperature until a homogeneous, yellow, viscous solution has formed. This is then poured onto the sheet of format 76.2 χ 101.6 mm to form a yellow, clear film or a layer with a thickness of about 10 μίτι, and the whole thing is then about 30 to 45 minutes in one drying cabinet heated to 5O ⁰ C, after which time handles to dry the film or the layer.

Embodiments of the invention will now be explained with reference to the drawings; thereby shows

1 shows a schematic partial cross-section through an initial structure of the invention, which consists of a layer which contains an image-providing material of the type proposed according to the invention, in particular TeCl ₄ , and which is selectively exposed to the image-generating energy through the cutout of a mask;
FIG. 2 shows a partial cross-section, analogous to FIG. 1, illustrating the image formed by the selective action of the image-generating energy;

Fig. 3 shows a cross section similar to Fig.2, in which the The mask is removed and developmental energy is applied to the structure;

Fig. 4 is a cross section similar to Fig. 1 showing the now reproduces fully developed structures, and

F i g. 5 is a schematic representation of a photomicrograph showing part of a Illustrates area containing a deposit of a crystalline imager.

The structure shown in Fig. 1 consists of a substrate 12, for. B. glass on which a thin, translucent layer 14 is deposited. which consists of a matrix of a vitreous amorphous material, such as polyvinyl formal or cyanoethylated starch, and contains TeCl ₄ 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 22 falls through the transparent surface 20 of the mask onto that part of the layer 14 which lies under the surface 20 of the mask. The electromagnetic radiation is brought into effect in the form of short-pulse radiation. In Fig. 2 is the structure of FIG. 1 shown in the state in which it is present after the end of the action of the electromagnetic radiation. In the layer 14, the presence of the latent image 24 is indicated by the small wavy lines, although this latent image is not necessarily visible to the eye.

In Fi g. 3 is the structure of the Fi g. 2 with the latent image 24 in the central portion of the layer 14. The mask 15 is removed. The structure is shown hanging above the radiant heat source 26, the z. B. may be an electrical heating element, the temperature of which to the desired range, e.g. B. one of 130 to 150 ⁰ C, is regulated. It is illustrated how the radiant heat energy 28 penetrates the substrate 12 in order to heat the layer 14. As the layer 14 is heated, a chemical reaction occurs in the area containing the latent image 24 through which the tellurium in the above mentioned

image-providing material released from its bonds and deposited in layer 14 in elemental form will. The tellurium is in the area corresponding to the latent image 24 in the layer 14 in the form of Crystals of extremely small size present. What the structure looks like after the heating stage has ended, is in Fig. 4, the structure having an opaque section 30 in the center where the electromagnetic Radiation impinges on the layer 14, and one permeable to the electromagnetic radiation Has section 32 which corresponds to the surfaces 18 of the iMaske 16 (FIG. 1).

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

Is the substrate 12 a non-transparent, but highly reflective material, such as white paper, and is the Layer 14 is translucent according to its basic nature when viewed, so 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 Figure 4 is in Photographed at 2000x magnification. The appearance of the microphotograph thus obtained is in F i g. 5 shown schematically. The dividing line between the transparent and opaque surfaces is represented by the arrow at 34. No or only a few occur on the left in the translucent surface 32 larger crystals 35 of tellurium, whereas clouds of tiny particles 36 are observed on the right can. The in area 30 of FIG. Particles 36 shown in FIG. 5 form only a few layers on which the microscope is in focus. When looking visually under the microscope one can see that crystal particles of the tellurium are scattered in the layer 14, which cause the opacity of the surface 30.

In the one shown in FIG. The example of the image shown in FIG. 5 has the tellurium particles, which form the image in the area 30 represent an average diameter of approximately 0.2 µm. It deserves special mention to become that the image-forming particles have a very narrow particle size distribution. There are essentially all image-forming particles of the same size. This is an extremely favorable characteristic of the imaging material of the present invention as it enables the manufacture of high quality Allows images of uniform properties. It also enables the creation of a well balanced Grayscale. The above-specified 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 adjusting the image generation 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 generator can be regulated. Ever extremely small grain sizes, e.g. B. in the order of magnitude of 0.1 μίτι or below, reach or also larger grain sizes, e.g. B. of about ί μπι or above it up to 10 μΐη or more, achieve. Depending on underlying mechanism is in certain cases with increasing grain size the relative density and the contrast increases, but the resolution potential of the system decreases. 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 selection of the particular one to be used within the teachings of the present invention Imaging material that has variable chemical reactivity enables the creation of a new photographic system, which in terms of resolving power, sensitivity im ordinary light of the environment, the photographic sensitivity, the speed of development and the accessibility to the image fills various gaps in demand for which the photographic systems are used Time can be used or put to good use.

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 being used as a dry-to-the-touch film 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 of the image-generating energy has been exposed, the imaging material apparently decomposes with the release of metallic material Tellurium. After the development stage, the metallic tellurium seems to remain behind as such, albeit the Particle size and shape cause modifications due to nucleation and probably other forces, whose exact nature and exact character cannot yet be precisely described. the Particle size and the nature of the metallic tellurium are evidenced by circumstances such as the thickness of the forming film, the character and viscosity of the matrix and the temperature at which the winding takes place is carried out and which also has an effect on the color of the finished image.

Depending on the desired result in the particular system that is being used, the thickness of the Layer 14 (Fig. 1) in the structure according to the invention can be varied within wide limits, as has already been done above is mentioned. The layer containing the imaging material can be thin down to 100 nm units or less, and it can also be 1 mm or more thick. For creating transparencies or Reflection copies are layer thicknesses of about 20 μm down to 0.2 μm, as a rule, extremely advantageous. The recommended 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 former, the desired maximum density, the desired Reflection differential or transparency differential, and numerous other factors. In each By taking these factors into account, the system can easily find the technically most favorable layer thickness to be determined. For other purposes, such as recording information in data processing devices, or for special purposes such as electrostatic printing, the layers of imaging material be thicker or thinner than indicated above. The formation of the germs and the preferred image-forming ones Crystallite is affected to some extent by the thickness of the film. Obviously need to too Surface effects and interface effects in the

Nucleation reaction and the reaction that leads to small image-forming crystallites into consideration to be pulled. When determining the technically most advantageous film thicknesses, the image-providing film must be used Layer all of the factors mentioned should be taken into account.

Similar considerations apply to the choice of the concentration of the imaging material in the matrix material. In general, it is advisable to use the imaging material in such a high concentration to apply as much as possible. The matrix material acts as a binder to prevent the image-providing material from adhering on the substrate and to give the finished images durability in use and wear resistance to rent. As a rule, it is desirable that the imaging materia! - in what way it as such whatever - is present in the image-providing layer in a non-crystalline form. This can be accomplished by the fact that the mass a sufficient amount of a plasticizer or Solvent, which can be a polymer for the image-providing material, is added. It is advantageous if the matrix material, in particular the material of vitreous, amorphous character, also used as a plasticizer or solver for the image-providing material. The matrix material is said to match the imaging material be miscible and it is particularly desirable that it actually dissolve the imaging material. This compatibility these two materials generally add to the sensitivity of a given system and provides better images or better contrasts and higher densities. In fact, the degree of tolerability can be the vitreous matrix material and the image-providing material used in in each case as a means of regulating the size of the deposited particles of the image-forming device - by the released tellurium shown - can be used effectively.

Another important fact that should be taken into account is the relationship between the glass transition temperature the matrix material and the temperature at which the cleavage of the molecule of the used imaging material in each case under the particular reaction conditions and in their respective Environment takes place. For example, if the molecule of the imaging material is at a temperature begins to decompose or split, which is much lower than that of the film, secondary reactions can be localized take place which inactivate all or part of the decomposition products of the image-providing material, thus reducing the effectiveness of the particular imaging system in certain systems it may be desirable that the cleavage of the image-providing material be initiated at a temperature which is much lower than the glass transition temperature of the matrix material, so that initially secondary reactions can be facilitated by the supply of heat in order to release the metallic tellurium. Will the glass temperature reached at the development stage, the secondary reaction product migrates to the nucleation sites and supplies the atoms of the metallic tellurium for the construction of the particles of the image formers. So can through 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 that occur after Freeing up the atoms of the metallic part and leaving the reaction towards equilibrium favor or not favor the metallic tellurium. In general, polar meet amorphous matrix materials, such as polyvinyl formal or organoethylated starch, meet these requirements in an outstanding manner Way. By varying the amount of free polar groups and by introducing changing amounts of substituents in the polar groups as well as by changing the nature of the substituents the physical properties of the polar matrix material can be varied to a large extent, in order to make it extremely useful in combination with the image-providing material.

As mentioned above, according to the present invention, an image providing material is proposed here Type - dissolved or dispersed in an amorphous film in association with a sensitizer - converted into an image formed by microcrystalline particles of metallic tellurium. In the grainless amorphous film, nucleation is triggered in the areas on which the light strikes, and the seeds can be further developed to form a crystalline phase. This fact makes it is possible to use different reading methods, which the differences in reflectivity, in transparency, opacity, in electrical properties, in the ability to carry electrical charges to hold on, etc. exploit.

One of the advantages is that the light acts as a heterogeneous nucleating agent, which is important has that background conversions are only possible to a minimal extent and that a large one Number of nucleation sites as desired in response to light energy in those exposed Area parts can be generated while only a few nuclei are formed in the non-exposed areas will.

For those imaging purposes in which a transparency is to be created or in which the If the image is to be recognizable as a reflection image, it is occasionally recommended that both the matrix of the amorphous material as well as the image-providing material is transparent or at least translucent and only has faint or no coloring. On the other hand, it may be desirable to use the layer of the image-providing Material with some color, so as to absorb the energy of a certain wavelength to favor. Accordingly, the sensitizers used can be so selected that they contribute to the fulfillment of the wishes mentioned. So they can be of a type that colored is, or a guy. which turns out to be colorless and transparent or translucent Decomposition products.

As for the substrates mentioned above, some of which are exemplified it should be noted that the substrate can be made of any material capable of a 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 it gives him a sufficient degree of responsiveness is absent so that it does not interfere with the imaging reaction.

Suitable substrates include glass, mica, polyamides, polyesters, polystyrenes, hardened condensation polymers, for example of the epoxy type and the like. There are numerous heat resistant

Polymers are commercially available which meet these requirements in an excellent manner therefore excellently useful in the imaging formations of the present invention are. For most technical applications of the invention For imaging materials, it is desirable that the substrate be flexible and so is the use of the image-providing material in the form of endless rolls in printing and reading devices will. Shall be in a specific imaging system To produce transparencies, it is of course desirable that the substrate be translucent on the other hand, copies should be made, which can be read by viewing in reflected light, then it is recommended to use a substrate that has a high reflectivity, such as ζ. B. White or colored filler containing Cardboard paper and other similar materials.

In some cases, the substrate can be used if desired omitted and the layer 14 used as a self-supporting structure on which then the image is generated and developed, for example, being placed on a temporary support base can. In this case, the matrix material can serve as a film former and can also be viewed in the direction of this film-forming and self-supporting properties are selected, and the finished image structure exists then only from a thin film of the amorphous, vitreous matrix material which is incorporated into it the image-providing material to the sensitistor as well as the material selected from it and converted into it Contains image builder.

As mentioned above, a variety of forms of energy can be used as a source of image-forming energy and development energy. These include electromagnetic radiation, heat, electrons, electric current, etc. Which of these forms of energy is used depends in certain cases on whether a separate image generation stage and a separate development stage or both stages are carried out at the same time. The preferred energy also depends on whether the negative or positive working system described above is used. If a separate image generation stage is carried out, electromagnetic radiation is preferably used for this stage, although other forms of energy can also be used. The radiating electromagnetic radiation is usually best suited to create an image by projection or by the use of a mask and the like. It is also generally best for producing an image of desired gray scale or tonal gradation. The type of electromagnetic radiation or other radiant energy and of which wavelengths are used in a particular case depends on the task to be solved and the particular sensitivity of the material providing the image. Many imaging materials used in accordance with the present invention are sensitive to actinic radiation, including laser energy and the like. If a given, selected imaging material does not exhibit its optimum sensitivity at a wavelength of electromagnetic radiation used or available for imaging, then appropriately selected sensitizers are added to shift the sensitivity into the desired range. In this way, for example, one can use an imaging material which has its maximum sensitivity in the UV wavelength range to a sensitivity in the range of visible light or X-rays, etc. Similar considerations apply with regard to the energy used in the development stage. It is highly recommended and also beneficial to use thermal energy for development. This can be radiant heat, e.g. B. infrared radiation or microwaves or hot air or heat supplied by contact and convection from a heated body. The use of heat for development has the advantage that the heat can be easily regulated in terms of intensity and duration. Heat is also readily available at a low cost from an inexpensive source. However, if desired, any other energy source can be used to effect the development of the exposed supplying material provided that it is accessible to that form of energy.

In each of the image generation and development stages a combination of different forms of energy ai can also be used. This is especially true also in the case where image formation and development are carried out at the same time. In this case it is it is advisable to combine the most effective energy with respect to image generation with that with respect to to apply the most effective energy to development. The heat for development can also come from the heat which is generated when the electromagnetic radiation is absorbed, as in the case of laser radiation. A combination of electromagnetic radiation and heat is also available from sources such as strong incandescent lamps, infrared lamps, laser beams, electronic or bulb photo flash units, mercury-vapor quartz lamps, accessible. These and other sources can also be used to advantage for image generation alone, if, for example, the development is carried out in a separate heat treatment stage.

The energy can be applied for different times, depending on the intensity of the the energy source used. For high energy imaging power sources, pulses are 1 microsecond or even shorter duration up to a few milliseconds or more usually sufficient, to complete the imaging. With energy sources of lesser intensity, longer times, like z. B. those from fractions of a second to several seconds can be used. Depending on the intended Purpose of the pictures and depending on whether they are insensitive to daylight Is desired or not, one will choose one or the other image-providing material and the image formation 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 to a certain extent on the intensity of the action Development energy, although in this case there is usually a threshold energy, which must be exceeded. This threshold value is one of the intensity - the temperature in the Trap of heat energy - and must be exceeded in order to bring about the development. With attention

This prerequisite is the development in 1 second or in a few seconds or in a slightly longer one Zeil, e.g. B. in 15 to 20 seconds, what ends of the The way in which the energy is brought into action and the nature of the material providing the picture as well as the Matrix material that is used also depends on the thickness of the layer of image-providing The material and the thickness of the substrate can influence the time required for development. In all However, development is rapid in cases, so the image-providing materials and method of the invention make the finished stable image quickly accessible.

For example, depending on the composition of the image-providing material, it may be desirable to do the development to be carried out at a predetermined temperature. As already mentioned, the development temperature should be above the threshold value Area to be regulated in which the reaction that lead to the formation of the image-forming agent, namely the deposition of the metallic tellurium. On the other hand, the temperature should not be so high that a l 'thermally induced nucleation and a reaction is triggered in the surface areas that are not the image-generating ones Have been exposed to energy. Usually the range is between these two temperature limits quite large, and the temperature can easily be regulated so that it is in the intermediate appropriate area falls. If you take these requirements into account, the image becomes strong Contrast achieved with essentially no nucleation in the background.

It is noteworthy that the latent image formed in the image forming step is general is completely permanent and stable. It is usually not decomposed, even if the material which is the latent Image contains a considerably long time, e.g. B. is stored for a day or so. The development through Heat after prolonged storage of the imaged material provides an image of high contrast with no apparent evidence of latent image degradation.

After development, in cases where fixing is necessary or desired, fixing can be carried out can be applied, for example by wiping, brushing or dipping, etc. in the one described above Way. The imaging systems of the present invention thus render a permanent image in a short time Time, usually in a few or several seconds, calculated from the time the image was generated, accessible.

The imaging material can be constructed to provide an image or record of the desired Information through the one-time action of the energy, e.g. B. a combination of light and Heat or any other desired effective energy. However, it is as above notes, it is generally recommended that the energy be brought into action in two stages, whereby the imaging energy is applied in a first stage to the layer that provides the image Contains material therein for the purpose of forming a latent image. The chemical transformation that the material produced by 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 radiation are brought into action according to the image; and into the development stage can then heat or some other electrical energy that effectively brings about the development be applied. Since a latent image is formed in the imaging stage, the energy in of the stage of development cannot be brought into effect according to the image, but can extend over the entire Extend across layer. In certain cases, the development stage can also function as the fixer stage fulfill, if this is desired or necessary.

The image-providing material can in itself be sensitive to the radiant energy used for the purpose the image generation is brought into action. In this case, the imaging energy can e.g. Am Form a photon to generate a free radical or an electron deficit in the image-providing material .call to create carriers which are then frozen or trapped and the latent image form. In the later stage of development, the molecules become mobile, for example due to the fact that that the surrounding matrix becomes plastic or rubbery and allows them to come close to the To move the carrier. The carriers can be released from the confinement by the developmental energy. The wearer thereby initiates a secondary reaction which creates the real image as it is in closer detail Details will be explained below.

It was found in accordance with the present invention, and it is already mentioned quite generally above, that the formation of a developable latent image by the imaging energy is thereby strong it is promoted that the image-providing material is incorporated into a matrix of a vitreous, amorphous material which has a glass transition temperature. One can assume that the photons that are in the image-generating Radiant energy contained, will be absorbed by the image-providing material when this is opposite sensitive to the particular radiation that is exposed. The image-providing material or a certain part of it, which absorbs a photon, is activated and will probably remain so because it has become immobile due to the fact that it is embedded in a vitreous amorphous material or a reactive intermediate is not deactivated. Becomes the vitreous, amorphous material later in a development stage to a temperature which is above the glass transition temperature, so are the activated molecules (or the activated atoms or carriers) are set to migrate. Through this secondary reactions are initiated that form the real picture or record of the information form.

In summary it can be said that in the case of a dry-to-the-touch film in which a matrix material and a sensitizer can be used, an imaging material of the type described above imaging energy is exposed to form what may be considered a latent image, and the metallic tellurium originally written out is then further precipitated or its character is modified in the areas in which the image was created, namely in a development stage, in the z. B. Heat is brought into action as developmental energy. If there is a

winding energy, ζ. Β. Warmth of a temperature which is below the thermal decomposition temperature of the original image-providing compound is used, so the reaction does not take place in those areas for which the imaging energy does not received even if the heat for development is not imagewise on the layer in its entirety is brought to action. Is development energy, e.g. B. Heat from a temperature that is above the thermal decomposition temperature of the original image-providing compound, to act brought, the image-providing compound decomposes and also sets the metallic tellurium in the non-exposed areas free. In general, however, it seems to be the case that the metallic tellurium crystals, which are excreted in the non-exposed parts of the area, are fewer and larger than the crystals, which excreted in the exposed areas so that an image of excellent contrast is formed.

In the reaction mechanisms under discussion here, the generation of the metallic tellurium can be used as

. Image-formers in the surface parts, which the image-generating energy have received, are increased by the fact that an acceptor is also used. The matrix of the vitreous amorphous material appears to serve as an acceptor and it works to do the Brings precipitation of the metallic tellurium to the complete end.

_ 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 due to this fact. These can turn into crystals of more handsome Grow in size because there is no competition from nearby nucleation sites. It was found, that those few crystals that are present in the surface parts are not of the imaging energy were exposed, despite their relatively large size, microscopic and wide Distance from each other are present so that they do not affect the transparency or reflection of these surfaces affect. In addition, careful handling of the image-providing material from the beginning its production up to the formation of the image and by effectively keeping away the carrier-forming energy of detrimental intensity from the material prior to exposure to the imaging energy to time the development, the number of these crystals in the non-image areas be further reduced.

It has been observed that the image-providing material is capable of undergoing conversion to form metallic Tellurium only through the application of developmental energy, such as heat, and without the material To expose, deposit or release a source of an image-generating energy. In general, in order to To bring about this reaction, such an amount of developmental energy exerted as greater is than that which is required in order to achieve the above-described, selective, imagewise development of the layer accomplish. Preferably, the intensity - such. B. the temperature - the development energy, which is necessary to bring about this reaction is chosen to be higher than that which is used in the development stage for the development of an irradiated layer, where the development is mainly in the Area portions that have received the imaging energy is desired. The one just described Uniform development of the layer of the image-providing material is particularly possible in those cases in which the imaging material is embedded in a vitreous matrix that is above the glass transition temperature softens and thereby gives the molecules mobility for the image-providing material and thus the Λ41-gration of the molecules to the nuclei for the excretion of the released metallic tellurium in the above makes possible

The phenomenon just described is based on the phenomenon that radicals or other reactive intermediates or carriers are thermally formed above a certain threshold of energy intensity, for example above a certain temperature in the case where heat is used as developmental energy is applied and which is characteristic of the image-providing material This phenomenon and the threshold nature the reaction can be used for imaging purposes according to the teaching of the method of the invention be exploited.

The previous discussion of the present invention makes it clear that it is an excellent Imaging system makes it widely available for a variety of imaging tasks can be used technically. The materials according to the invention can be used in the camera for checking purposes and for duplicating images, for making duplicate copies of Micro recordings and other micro representations (microfiche) for recording output information a computer and the output data of other data storage and access systems. the The broad usefulness of the novel imaging system of the invention relies on this quick and convenient access to permanent copies of the information of the record or image. The recordings and images are sharp and have excellent resolution. The practical Materials used in the practice of the invention can range from a very low level of contrast up to can be varied to a very high degree of contrast, as required and desired in each individual case.

In this regard, the new imaging system has - generally speaking - the versatility of the permanent constituent silver halide systems, which by appropriate selection of the emulsions and development conditions also allow a wide variability of the degrees of contrast. However needed the image generation system peculiar to the present invention and also the development system, as can be easily seen from the above, none of the conventional wet treatments, and it gives quick access to the final stable image, which in many cases is the case with silver halide images is not the case. As a result, the new system proves to be the solid one, especially in these cases Consists of proper silver halide systems as superior.

The various other imaging systems that have already been suggested by the notice are that they do not require a wet treatment are usually associated with the disadvantage that they are on based on the use of a single photosensitive material and only to a very limited extent it is possible to modify the character of the material, for example the degree of contrast of the Image to vary. You may therefore be useful for a particular application, but are for

not suitable for any other purpose. The materials used in the imaging system of the present invention are on the other hand, generally speaking, cheap and can easily be used with the help of cheap methods, see above that with the invention of the professional world an overall inexpensive image generation system was made available will.

The present invention does not require vacuum deposition or sputter evaporation, to knock down an ebmental image-maker on a substrate. The picture-providing mixtures of substances can easily be in the form of a solution, for example by brushing, centrifugal or squeegee application and the like are applied. The images generated according to the teachings of the present invention can be saved as Original or mother-imprints are used, for example, when an imager has been used that has the ability to capture and capture of electrical charges and thereby differs from the usual matrix material. In this Case, the images can e.g. B. on a paper or cardboard substrate can be generated in order to obtain an inexpensive, disposable original impression. after the Once the desired number of copies has been made, the original print is simply discarded.

For an electrostatic printing or copying system of this type, an electrically conductive substrate, for example an aluminum foil or a sheet of paper or cardboard paper, which is coated with an electrically conductive layer, can be used. A layer of the image-providing material is then deposited on the conductive layer in embedding in a dielectric matrix material, said image-providing material depositing a conductive, particulate image-forming agent. The electrical matrix material is preferably composed of one which is easily removed by the action of energy, e.g. B. heat, volatilized or decomposed. The material is then subjected to the imaging process in the manner described above, e.g. B. by exposing selected areas of the image-generating energy, such as electromagnetic radiation. The image is then developed, for example by subjecting the material to moderate heat, as described above. The developed image, which consists of highly reflective surfaces of the dielectric matrix material with the aluminum foil as the back and of opaque surfaces, which are formed by the precipitated, conductive particles of the metallic tellurium, is then the heat radiation energy, e.g. B. to infrared radiation of short duration and high intensity exposed. The opaque, dark areas in which the tellurium metal has precipitated absorb the heat, which causes the tellurium metal and the surrounding matrix to heat up to the point at which the matrix evaporates or is otherwise destroyed by the heat. As a result, the tellurium metal particles consolidate or flow together to form a conductive surface with the electrically conductive layer below. In the areas in which no opaque particles were 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 areas made of a dielectric material! exist, and also has surfaces that are electrically conductive and are in conductive connection with the electrically conductive sublayer. When a charge is applied, for example by using a device that generates a corona discharge, static electrical charges are generated in the surfaces made up of the dielectric, and no charges are retained by the electrically conductive surfaces. The charged plate is then treated in the usual manner with a toner or a dry ink, which is then transferred to paper and fixed thereon in order to produce an impression. Many impressions can be made from one plate. If an impression is no longer required, it is simply discarded. On this we ^; There is no need for cleaning and stripping of charge from a permanent drum as is currently done with electrostatic replication processes. As a result, the apparatus for imaging and making replicas can be of a much simpler type and much cheaper to manufacture than is the case with prior art devices.

The layer made up of surface parts with strong dielectric properties and surface parts with good electrical conductivity can also be used in the imaging Film or plate are produced by using an imaging material, which reacts with the matrix material during development to form a highly conductive layer, while in the areas that have not been exposed, the layer remains non-conductive and its dielectric Maintains properties. A plate produced in this way has the same good properties and can be used in the same way as previously described.

For this purpose 2 sheets of drawings

Claims (1)

Patent claims: 1. Recording material with a radiation-sensitive layer which is a tellurium halide Contains a sensitizer and a matrix material which is solid at room temperature, characterized in that that as a tellurium halide